Blow-up and stability of semilinear PDEs with Gamma generators
上半空间高次分数阶Laplace方程解的不存在性
上半空间高次分数阶Laplace方程解的不存在性李冬艳;陈文雄【摘要】Nonexistence of positive solutions for equations involving higher order fractional Laplacians with Navier conditions in an upper-half space is considered.Narrow region principle of higher-order fractional Laplacian equations is established by using iterative method.And then with method of moving planes,nonexistence of positive solutions for equations involving higher-order fractional Laplacians with Navier conditions is proved.%研究上半空间中带Navier条件的高次分数阶Laplace方程正解的不存在性.借助迭代法,建立高次分数阶方程的狭窄区域原理;然后结合移动平面法,证明具有Navier条件的高次分数阶方程正解的不存在性.【期刊名称】《纺织高校基础科学学报》【年(卷),期】2017(030)001【总页数】5页(P18-22)【关键词】高次分数阶Laplace方程;Navier条件;狭窄区域极值原理;解不存在性【作者】李冬艳;陈文雄【作者单位】西安工程大学理学院,陕西西安710048;叶史瓦大学,美国纽约10033【正文语种】中文【中图分类】O175分数阶Laplace算子是一个非局部拟微分算子,定义为其中α为0与2之间的任意实数,且近年来,分数阶Laplace方程问题倍受关注,它在描述一系列物理现象中有着重要的作用,如不规则扩散现象[1-2]、气象学中的准地转流[3-4]、湍流模型、分子动力学以及相对量子力学[5-6]等,甚至在金融和概率方面[7-8]也有着广泛的应用.在基础研究方面,对测度椭圆问题、非一致椭圆问题[9]以及势梯度问题[10]也不可或缺.为克服分数阶Laplace的非局部性,Caffarelli-Silvestre引进了延拓法[11],将非局部问题转化成更高维Rn×[0,∞)中的局部问题,从而成为研究带有分数阶Laplace算子方程的有力工具.后来,Chen等[12]提出了一种直接对分数阶方程进行的移动平面法,这种方法对有界区域及无界区域均有效,成为证明分数阶非线性方程正解的对称性、单调性及不存在性的有力工具.在式(1)的基础上,定义如下高次的分数阶Laplace算子.当0<α<2时,式(1)可以等价的写为其中Sr(x)是以x为中心,r为半径的球面.当r充分小且y∈Sr(x)时,因为,做Taylor 展开可得由对称性得从而有显然,该积分当α<2时收敛,当α>2时发散.因此,当2<α<4时,为使积分收敛,定义高次的分数阶Laplace算子为当,类似地,由Taylor展开及对称性,则有该积分当α<4时收敛,当α>4时发散.本文考虑上半空间{x=(x1,x2,…xn)|xn≥0}中具有Navier条件的高次分数阶非线性方程其中,,0<α<2.移动平面法已在证明方程正解对称性[13],不存在性[14]及解的先验估计[15]等方面发挥过重要作用.但目前为止,移动平面法还不能被直接应用到高次分数阶方程上.因此,本文先将高次分数阶方程化成低次方程组,然后再应用移动平面法.为此,需要以下两个引理,其在后续证明中起着重要作用.引理1 设H={x∈Rn|0<xn<λ,λ∈R}是Σ内的一个无界区域.设,且U,V在上下半连续.若其中c(x)<0,且当|x|充分大时,c(x)则存在常数R0>0,使得若那么引理2[16] 设Ω⊂∑λ={x∈Rn|xn<λ}是有界狭窄区域,不失一般性,假设Ω包含在狭窄区域{x∈Rn|λ-l<xn<λ}中,l充分小.考虑方程组其中ci(x)≤0,i=1,2有界,在中下半连续.则当l充分小时,有对无界区域Ω,若U(x),V(x)→0, |x|→∞,式(3)仍成立.并且,若存在一点x0∈Ω,使得U(x0)=0或V(x0)=0,则基于狭窄区域原理,可以沿xn方向做移动平面,证明正解关于xn单调,从而得到以下结论.定理1 设(m>0)是方程(2)的正解,f(t)满足以下条件:(Ⅰ) 关于t单调增且Lipschitz连续;(Ⅱ).则u(x)≡0.为方便证明,采用以下记号.设Tλ={x∈Rn|xn=λ},Σλ={x∈Rn|xn<λ},且xλ={(x1,x2,…,2λ-xn)|x=(x1,x2,…,xn)∈Rn}是点x关于平面Tλ的对称点.定理1的证明令-Δu=v,则方程(2)可以写成如下两个方程:及设uλ(x)=u(xλ), Uλ(x)=uλ(x)-u(x), Vλ(x)=vλ(x)-v(x). 则有Step 1 证明当λ充分小时,有因为取引理2中的Ω为,则当λ充分小时,Ω为狭窄区域,且当λ固定时,当|x|→+∞时,|xλ|→+∞.从而由可知,u(x)→0, |x|→∞且uλ(x)→0, |x|→∞.所以当x∈Σλ时, 同理,可证则由引理2可得其中,c1(x)=-1, c2(x)=c(x).由f(x)为Lipschitz连续性,c2(x)是有界的,而f(x)的单增性保证了c2(x)≤0.Step 2 由式(4),从xn=0附近开始移动平面Tλ,只要Uλ(x)≥0, Vλ(x)≥0成立,则一直沿xn轴移动平面.定义接下来证明利用反证法.如若λ0<+∞,则必有由式(5)可知,平面xn=2λ0是边界关于平面Tλ0的对称平面.由边界条件及uλ0关于Tλ0的对称性知,在xn=2λ0上有u(x)=0,这与u(x)>0矛盾.从而λ0=+∞. 即方程正解u(x)关于变量xn单调增加.这与在无穷远处矛盾,从而方程无正解.现在证明式(5)成立.假设式(5)不成立,则由强极值原理,有则可以继续沿xn方向移动平面Tλ0,说明存在一个ε>0,使得∀λ∈[λ0,λ0+ε),有成立.这与λ0的定义矛盾,从而式(5)成立.接下来证明式(7)成立.假设式(7)不成立,即存在点,使得则从而存在一点,使得由条件(Ⅰ)、(Ⅱ)知,因此,c(x)满足引理1中的条件,从而存在R0,使得固定R0,则对任意小的δ>0,由式(6)知,存在常数C,使得即但由引理2知,在狭窄区域(Σλ\Σλ0-δ)∩BR0(0)内,矛盾,即式(7)成立.定理1证毕.E-mail:************LI Dongyan,CHEN Wenxiong.Nonexistence of positive solutions for higher order fractional Laplacians in an upper-half space[J].Basic Sciences Journal of Textile Universities,2017,30(1):18-22.【相关文献】[1] METZLER R,KLAFTER J.The random walk′s guide to anomalous diffusion:A fractional dynamics approach[J].Physics Reports-Review Section of Physics Letters,2000,339(1):1-77.[2] MELLET A,MISCHLER S,MOUHOT C.Fractional diffusion limit for collisional kinetic equations[J].Archive of Rational Mechanics and Analysis,2011,199(2):493-525.[3] CAFFARELLI L,VASSEUR A.Drift diffusion equations with fractional diffusion and the quasi-geostrophic equation[J].Annals of Mathematics,2010,171(3):1903-1930.[4] CORDOBA D.Nonexistence of simple hyperbolic blow-up for the quasi-geostrophic equation[J].Annals of Mathematics,1998,148(3):1135-1152.[5] BOUCHARD J P,GEORGES A.Anomalous diffusion in disordered media,statistical mechanics,models and physical applications[J].Physics Reports,1990,195(4/5):127-293. [6] TARASOV V,ZASLASVKY G.Fractional dynamics of systems with long-range interaction[J].Communications in Nonlinear Science & NumericalSimulation,2006,11(8):885-889.[7] APPLEBAUM D.L′evy processes and stochastic calculus[M].2ndedition.Cambridge:Cambridge University Press,2009.[8] CONT R,TANKOV P.Financial modelling with jump processes[M].Boca Raton:Chapman & Hall/CRC Financial Mathematics Series,2004.[9] ESPOSITO L,LEONETTI F,MINGIONE G.Sharp regularity for functionals with (p,q) growth[J].Journal of Differential Equations,2004,204(1):5-55.[10] MINGIONE G.Gradient potential estimates[J].Journal of the European Mathmatical Society,2011,13(2):459-486.[11] CAFFARELLI L,SILVESTRE L.An extension problem related to the fractional Laplacian[J].Communications in Partial Differential Equations,2007,32(8):1245-1260. [12] CHEN Wenxiong,LI Congming,LI Yan.A direct method of moving planes for thefractional Laplacian[J].Advances in Mathematics,2017,308:404-437.[13] ZHANG Lizhi.Symmetry of solutions to semilinear equations involving the fractional Laplacian[J].Communication on Pure and Applied Analysis,2015,14(6):2393-2409. [14] CHEN Wenxiong,FANG Yanqin,YANG Ray.Semilinear equations involving the fractional Laplacian on a half space[J].Advances in Mathematics,2015,274(8):167-198. [15] CHEN Wenxiong,LI Congming.A priori estimates for prescribing scalar curvature equations[J].Annals of Mathematics,1997,145(3):547-564.[16] ZHUO Ran,LI Yan.A Liouville theorem for the higher order fractionalLaplacian[J].arXiv:1609.04105[math.AP].。
One-step strategy to three-dimensional graphene_
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Huanwen Wang, Huan Yi, Xiao Chen and Xuefeng Wang*
A facile one-step strategy has been developed to prepare 3D graphene/VO2 nanobelt composite hydrogels, which can be readily scaled-up for mass production by using commercial V2O5 and graphene oxide as precursors. During the formation of the graphene/VO2 architecture, 1D VO2 nanobelts and 2D flexible graphene sheets are self-assembled to form interconnected porous microstructures through hydrogen bonding, which facilitates charge and ion transport in the electrode. Due to the hierarchical network framework and the pseudocapacitance contribution from VO2 nanobelts, the hybrid electrode demonstrates excellent capacitive performances. In the two-electrode configuration, the graphene/VO2 nanobelt composite hydrogel exhibits a specific capacitance of 426 F gÀ1 at 1 A gÀ1 in the potential range of À0.6 to 0.6 V, which greatly surpasses that of each individual counterpart (191 F gÀ1 and 243 F gÀ1 at 1 A gÀ1 for VO2 nanobelt and graphene hydrogel, respectively). The hybrid electrode also shows an improved rate capability and cycling stability, which is indicative of a positive synergistic effect of VO2 and graphene on the improvement of electrochemical performance. These findings reveal the importance and great potential of graphene composite hydrogels in the development of energy storage devices with high power and energy densities.
用初中英语简要介绍双缝实验
用初中英语简要介绍双缝实验The Double-Slit ExperimentThe double-slit experiment is a fundamental experiment in quantum mechanics that demonstrates the wave-particle duality of light and other quantum particles. It was first performed by the English physicist Thomas Young in 1801, and it has since become one of the most famous experiments in the history of science.The basic setup of the double-slit experiment is as follows. A source of light, such as a laser or a monochromatic light source, is directed towards a barrier that has two narrow slits cut in it. The light passing through the slits is then projected onto a screen or a detector. When the light passes through the two slits, it creates an interference pattern on the screen, with alternating bright and dark regions.This interference pattern is a clear demonstration of the wave-like nature of light. If light were simply a stream of particles, one would expect to see two separate bright spots on the screen, corresponding to the two slits. However, the interference pattern shows that the light is behaving like a wave, with the waves from the two slits interfering with each other.The double-slit experiment can also be performed with other quantum particles, such as electrons or atoms. When these particles are directed towards the double slit, they also exhibit an interference pattern, indicating that they too have a wave-like nature.The wave-particle duality of quantum particles is a fundamental concept in quantum mechanics. It means that particles can exhibit both wave-like and particle-like properties, depending on the experiment being performed. This is a departure from the classical view of the world, where objects were either waves or particles, but not both.The double-slit experiment has been used to demonstrate the wave-particle duality of various quantum particles, including electrons, neutrons, atoms, and even large molecules. In each case, the interference pattern observed on the screen is a clear indication of the wave-like nature of the particles.One of the most interesting aspects of the double-slit experiment is the role of the observer. When the experiment is set up to detect which slit the particle goes through, the interference pattern disappears, and the particles behave like classical particles. This suggests that the act of measurement or observation can affect the behavior of quantum particles.This is a concept known as the "observer effect" in quantum mechanics, and it has profound implications for our understanding of the nature of reality. It suggests that the very act of observing or measuring a quantum system can alter its behavior, and that the observer is not a passive participant in the experiment.The double-slit experiment has also been used to explore the concept of quantum entanglement, which is another fundamental concept in quantum mechanics. Quantum entanglement occurs when two or more quantum particles become "entangled" with each other, such that the state of one particle is dependent on the state of the other.In the double-slit experiment, the interference pattern can be used to demonstrate the phenomenon of quantum entanglement. For example, if two particles are entangled and then directed towards the double slit, the interference pattern observed on the screen will depend on the state of the entangled particles.Overall, the double-slit experiment is a powerful and versatile tool for exploring the fundamental nature of reality at the quantum level. It has been used to demonstrate the wave-particle duality of light and other quantum particles, the observer effect, and the phenomenon of quantum entanglement. As such, it remains one ofthe most important and influential experiments in the history of science.。
通常的化合物结晶是通过降温实现,但这篇钙钛矿的结晶是通过升温实现的,而且速度超快,还是单晶-2015-NC
of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 2 Department of Chemistry, Faculty of Science, Mansoura University, Mansoura 35516, Egypt. 3 Mathematical Institute, University of Oxford, Woodstock Road, Oxford OX2 6GG, UK. 4 Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. 5 Imaging and Characterization Lab, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia. * These authors contributed equally to this work. Correspondence and requests for materials should be addressed to O.M.B. (email: osman.bakr@.sa).
光谱法研究药物小分子与蛋白质大分子的相互作用的英文
Spectroscopic Study of the Interaction between Small Molecules and Large Proteins1. IntroductionThe study of drug-protein interactions is of great importance in drug discovery and development. Understanding how small molecules interact with proteins at the molecular level is crucial for the design of new and more effective drugs. Spectroscopic techniques have proven to be valuable tools in the investigation of these interactions, providing det本人led information about the binding affinity, mode of binding, and structural changes that occur upon binding.2. Spectroscopic Techniques2.1. Fluorescence SpectroscopyFluorescence spectroscopy is widely used in the study of drug-protein interactions due to its high sensitivity and selectivity. By monitoring the changes in the fluorescence emission of either the drug or the protein upon binding, valuable information about the binding affinity and the binding site can be obt本人ned. Additionally, fluorescence quenching studies can provide insights into the proximity and accessibility of specific amino acid residues in the protein's binding site.2.2. UV-Visible SpectroscopyUV-Visible spectroscopy is another powerful tool for the investigation of drug-protein interactions. This technique can be used to monitor changes in the absorption spectra of either the drug or the protein upon binding, providing information about the binding affinity and the stoichiometry of the interaction. Moreover, UV-Visible spectroscopy can be used to study the conformational changes that occur in the protein upon binding to the drug.2.3. Circular Dichroism SpectroscopyCircular dichroism spectroscopy is widely used to investigate the secondary structure of proteins and to monitor conformational changes upon ligand binding. By analyzing the changes in the CD spectra of the protein in the presence of the drug, valuable information about the structural changes induced by the binding can be obt本人ned.2.4. Nuclear Magnetic Resonance SpectroscopyNMR spectroscopy is a powerful technique for the investigation of drug-protein interactions at the atomic level. By analyzing the chemical shifts and the NOE signals of the protein in thepresence of the drug, det本人led information about the binding site and the mode of binding can be obt本人ned. Additionally, NMR can provide insights into the dynamics of the protein upon binding to the drug.3. Applications3.1. Drug DiscoverySpectroscopic studies of drug-protein interactions play a crucial role in drug discovery, providing valuable information about the binding affinity, selectivity, and mode of action of potential drug candidates. By understanding how small molecules interact with their target proteins, researchers can design more potent and specific drugs with fewer side effects.3.2. Protein EngineeringSpectroscopic techniques can also be used to study the effects of mutations and modifications on the binding affinity and specificity of proteins. By analyzing the binding of small molecules to wild-type and mutant proteins, valuable insights into the structure-function relationship of proteins can be obt本人ned.3.3. Biophysical StudiesSpectroscopic studies of drug-protein interactions are also valuable for the characterization of protein-ligandplexes, providing insights into the thermodynamics and kinetics of the binding process. Additionally, these studies can be used to investigate the effects of environmental factors, such as pH, temperature, and ionic strength, on the stability and binding affinity of theplexes.4. Challenges and Future DirectionsWhile spectroscopic techniques have greatly contributed to our understanding of drug-protein interactions, there are still challenges that need to be addressed. For instance, the study of membrane proteins and protein-protein interactions using spectroscopic techniques rem本人ns challenging due to theplexity and heterogeneity of these systems. Additionally, the development of new spectroscopic methods and the integration of spectroscopy with other biophysical andputational approaches will further advance our understanding of drug-protein interactions.In conclusion, spectroscopic studies of drug-protein interactions have greatly contributed to our understanding of how small molecules interact with proteins at the molecular level. Byproviding det本人led information about the binding affinity, mode of binding, and structural changes that occur upon binding, spectroscopic techniques have be valuable tools in drug discovery, protein engineering, and biophysical studies. As technology continues to advance, spectroscopy will play an increasingly important role in the study of drug-protein interactions, leading to the development of more effective and targeted therapeutics.。
全氧烧嘴-速焰英国
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Industrial Burners Handbook
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21.2.1.1 High Flame Temperature and Heat Transfer High adiabatic flame temperature and high heat release rate and transfer are the main benefits for which traditional applications of oxy-fuel burners were developed. Welding with an oxy-acetylene flame, flame polishing of glass surfaces, and oxygen cutting of steel plates are some of examples of applications that take advantage of these oxy-fuel flame characteristics. 21.2.1.2 Fuel Savings The use of oxygen in a heating process eliminates the nitrogen introduced with combustion air from the process and hence eliminates the energy required to heat the nitrogen from inlet temperature to outlet temperature. For high-temperature processes (>2200°F or 1200°C) with no heat recovery, fuel savings when using oxygen can exceed 50%. As heat recovery is employed with the air combustion system, the savings achievable when switching to oxy-fuel combustion are reduced. A simple heat and mass balance on the furnace under each operating condition can provide accurate
单分子综述-NATURE NANOTECHNOLOGY-Single-molecule junctions beyond electronic transport-2013
Stimulated by the initial proposal that molecules could be used as the functional building blocks in electronic devices 1, researchers around the world have been probing transport phenomena at the single-molecule level both experimentally and theoretically 2–11. Recent experimental advances include the demonstration of conductance switching 12–16, rectification 17–21, and illustrations on how quantum interference effects 22–26 play a critical role in the electronic properties of single metal–molecule–metal junctions. The focus of these experiments has been to both provide a fundamental understanding of transport phenomena in nanoscale devices as well as to demonstrate the engineering of functionality from rational chemical design in single-molecule junctions. Although so far there are no ‘molecular electronics’ devices manufactured commercially, basic research in this area has advanced significantly. Specifically, the drive to create functional molecular devices has pushed the frontiers of both measurement capabilities and our fundamental understanding of varied physi-cal phenomena at the single-molecule level, including mechan-ics, thermoelectrics, optoelectronics and spintronics in addition to electronic transport characterizations. Metal–molecule–metal junctions thus represent a powerful template for understanding and controlling these physical and chemical properties at the atomic- and molecular-length scales. I n this realm, molecular devices have atomically defined precision that is beyond what is achievable at present with quantum dots. Combined with the vast toolkit afforded by rational molecular design 27, these techniques hold a significant promise towards the development of actual devices that can transduce a variety of physical stimuli, beyond their proposed utility as electronic elements 28.n this Review we discuss recent measurements of physi-cal properties of single metal–molecule–metal junctions that go beyond electronic transport characterizations (Fig. 1). We present insights into experimental investigations of single-molecule junc-tions under different stimuli: mechanical force, optical illumina-tion and thermal gradients. We then review recent progress in spin- and quantum interference-based phenomena in molecular devices. I n what follows, we discuss the emerging experimentalSingle-molecule junctions beyond electronic transportSriharsha V. Aradhya and Latha Venkataraman*The id ea of using ind ivid ual molecules as active electronic components provid ed the impetus to d evelop a variety of experimental platforms to probe their electronic transport properties. Among these, single-molecule junctions in a metal–molecule–metal motif have contributed significantly to our fundamental understanding of the principles required to realize molecular-scale electronic components from resistive wires to reversible switches. The success of these techniques and the growing interest of other disciplines in single-molecule-level characterization are prompting new approaches to investigate metal–molecule–metal junctions with multiple probes. Going beyond electronic transport characterization, these new studies are highlighting both the fundamental and applied aspects of mechanical, optical and thermoelectric properties at the atomic and molecular scales. Furthermore, experimental demonstrations of quantum interference and manipulation of electronic and nuclear spins in single-molecule circuits are heralding new device concepts with no classical analogues. In this Review, we present the emerging methods being used to interrogate multiple properties in single molecule-based devices, detail how these measurements have advanced our understanding of the structure–function relationships in molecular junctions, and discuss the potential for future research and applications.methods, focusing on the scientific significance of investigations enabled by these methods, and their potential for future scientific and technological progress. The details and comparisons of the dif-ferent experimental platforms used for electronic transport char-acterization of single-molecule junctions can be found in ref. 29. Together, these varied investigations underscore the importance of single-molecule junctions in current and future research aimed at understanding and controlling a variety of physical interactions at the atomic- and molecular-length scale.Structure–function correlations using mechanicsMeasurements of electronic properties of nanoscale and molecu-lar junctions do not, in general, provide direct structural informa-tion about the junction. Direct imaging with atomic resolution as demonstrated by Ohnishi et al.30 for monoatomic Au wires can be used to correlate structure with electronic properties, however this has not proved feasible for investigating metal–molecule–metal junctions in which carbon-based organic molecules are used. Simultaneous mechanical and electronic measurements provide an alternate method to address questions relating to the struc-ture of atomic-size junctions 31. Specifically, the measurements of forces across single metal–molecule–metal junctions and of metal point contacts provide independent mechanical information, which can be used to: (1) relate junction structure to conduct-ance, (2) quantify bonding at the molecular scale, and (3) provide a mechanical ‘knob’ that can be used to control transport through nanoscale devices. The first simultaneous measurements of force and conductance in nanoscale junctions were carried out for Au point contacts by Rubio et al.32, where it was shown that the force data was unambiguously correlated to the quantized changes in conductance. Using a conducting atomic force microscope (AFM) set-up, Tao and coworkers 33 demonstrated simultaneous force and conductance measurements on Au metal–molecule–metal junc-tions; these experiments were performed at room temperature in a solution of molecules, analogous to the scanning tunnelling microscope (STM)-based break-junction scheme 8 that has now been widely adopted to perform conductance measurements.Department of Applied Physics and Applied Mathematics, Columbia University, New York, New York 10027, USA. *e-mail: lv2117@DOI: 10.1038/NNANO.2013.91These initial experiments relied on the so-called static mode of AFM-based force spectroscopy, where the force on the canti-lever is monitored as a function of junction elongation. I n this method the deflection of the AFM cantilever is directly related to the force on the junction by Hooke’s law (force = cantilever stiff-ness × cantilever deflection). Concurrently, advances in dynamic force spectroscopy — particularly the introduction of the ‘q-Plus’ configuration 34 that utilizes a very stiff tuning fork as a force sen-sor — are enabling high-resolution measurements of atomic-size junctions. In this technique, the frequency shift of an AFM cantilever under forced near-resonance oscillation is measuredas a function of junction elongation. This frequency shift can be related to the gradient of the tip–sample force. The underlying advantage of this approach is that frequency-domain measure-ments of high-Q resonators is significantly easier to carry out with high precision. However, in contrast to the static mode, recover-ing the junction force from frequency shifts — especially in the presence of dissipation and dynamic structural changes during junction elongation experiments — is non-trivial and a detailed understanding remains to be developed 35.The most basic information that can be determined throughsimultaneous measurement of force and conductance in metalThermoelectricsSpintronics andMechanicsOptoelectronicsHotColdFigure 1 | Probing multiple properties of single-molecule junctions. phenomena in addition to demonstrations of quantum mechanical spin- and interference-dependent transport concepts for which there are no analogues in conventional electronics.contacts is the relation between the measured current and force. An experimental study by Ternes et al.36 attempted to resolve a long-standing theoretical prediction 37 that indicated that both the tunnelling current and force between two atomic-scale metal contacts scale similarly with distance (recently revisited by Jelinek et al.38). Using the dynamic force microscopy technique, Ternes et al. effectively probed the interplay between short-range forces and conductance under ultrahigh-vacuum conditions at liquid helium temperatures. As illustrated in Fig. 2a, the tunnel-ling current through the gap between the metallic AFM probe and the substrate, and the force on the cantilever were recorded, and both were found to decay exponentially with increasing distance with nearly the same decay constant. Although an exponential decay in current with distance is easily explained by considering an orbital overlap of the tip and sample wavefunctions through a tunnel barrier using Simmons’ model 39, the exponential decay in the short-range forces indicated that perhaps the same orbital controlled the interatomic short-range forces (Fig. 2b).Using such dynamic force microscopy techniques, research-ers have also studied, under ultrahigh-vacuum conditions, forces and conductance across junctions with diatomic adsorbates such as CO (refs 40,41) and more recently with fullerenes 42, address-ing the interplay between electronic transport, binding ener-getics and structural evolution. I n one such experiment, Tautz and coworkers 43 have demonstrated simultaneous conduct-ance and stiffness measurements during the lifting of a PTCDA (3,4,9,10-perylene-tetracarboxylicacid-dianhydride) molecule from a Ag(111) substrate using the dynamic mode method with an Ag-covered tungsten AFM tip. The authors were able to follow the lifting process (Fig. 2c,d) monitoring the junction stiffness as the molecule was peeled off the surface to yield a vertically bound molecule, which could also be characterized electronically to determine the conductance through the vertical metal–molecule–metal junction with an idealized geometry. These measurements were supported by force field-based model calculations (Fig. 2c and dashed black line in Fig. 2d), presenting a way to correlate local geometry to the electronic transport.Extending the work from metal point contacts, ambient meas-urements of force and conductance across single-molecule junc-tions have been carried out using the static AFM mode 33. These measurements allow correlation of the bond rupture forces with the chemistry of the linker group and molecular backbone. Single-molecule junctions are formed between a Au-metal sub-strate and a Au-coated cantilever in an environment of molecules. Measurements of current through the junction under an applied bias determine conductance, while simultaneous measurements of cantilever deflection relate to the force applied across the junction as shown in Fig. 2e. Although measurements of current throughzF zyxCantileverIVabConductance G (G 0)1 2 3Tip–sample distance d (Å)S h o r t -r a n g e f o r c e F z (n N )10−310−210−11110−110−210−3e10−410−210C o n d u c t a n c e (G 0)Displacement86420Force (nN)0.5 nm420−2F o r c e (n N )−0.4−0.200.20.4Displacement (nm)SSfIncreasing rupture forcegc(iv)(i)(iii)(ii)Low HighCounts d9630−3d F /d z (n N n m −1)(i)(iv)(iii)(ii)A p p r o a chL i ft i n g110−210−4G (2e 2/h )2051510z (Å)H 2NNH 2H 2NNH 2NNFigure 2 | Simultaneous measurements of electronic transport and mechanics. a , A conducting AFM set-up with a stiff probe (shown schematically) enabled the atomic-resolution imaging of a Pt adsorbate on a Pt(111) surface (tan colour topography), before the simultaneous measurement of interatomic forces and currents. F z , short-range force. b , Semilogarithmic plot of tunnelling conductance and F z measured over the Pt atom. A similar decay constant for current and force as a function of interatomic distance is seen. The blue dashed lines are exponential fits to the data. c , Structural snapshots showing a molecular mechanics simulation of a PTCDA molecule held between a Ag substrate and tip (read right to left). It shows the evolution of the Ag–PTCDA–Ag molecular junction as a function of tip–surface distance. d , Upper panel shows experimental stiffness (d F /d z ) measurements during the lifting process performed with a conducting AFM. The calculated values from the simulation are overlaid (dashed black line). Lower panel shows simultaneously measured conductance (G ). e , Simultaneously measured conductance (red) and force (blue) measurements showing evolution of a molecular junction as a function of junction elongation. A Au point contact is first formed, followed by the formation of a single-molecule junction, which then ruptures on further elongation. f , A two-dimensional histogram of thousands of single-molecule junctionrupture events (for 1,4-bis(methyl sulphide) butane; inset), constructed by redefining the rupture location as the zero displacement point. The most frequently measured rupture force is the drop in force (shown by the double-headed arrow) at the rupture location in the statistically averaged force trace (overlaid black curve). g , Beyond the expected dependence on the terminal group, the rupture force is also sensitive to the molecular backbone, highlighting the interplay between chemical structure and mechanics. In the case of nitrogen-terminated molecules, rupture force increases fromaromatic amines to aliphatic amines and the highest rupture force is for molecules with pyridyl moieties. Figure reproduced with permission from: a ,b , ref. 36, © 2011 APS; c ,d , ref. 43, © 2011 APS.DOI: 10.1038/NNANO.2013.91such junctions are easily accomplished using standard instru-mentation, measurements of forces with high resolution are not straightforward. This is because a rather stiff cantilever (with a typical spring constant of ~50 N m−1) is typically required to break the Au point contact that is first formed between the tip and sub-strate, before the molecular junctions are created. The force reso-lution is then limited by the smallest deflection of the cantilever that can be measured. With a custom-designed system24 our group has achieved a cantilever displacement resolution of ~2 pm (com-pare with Au atomic diameter of ~280 pm) using an optical detec-tion scheme, allowing the force noise floor of the AFM set-up to be as low as 0.1 nN even with these stiff cantilevers (Fig. 2e). With this system, and a novel analysis technique using two-dimensional force–displacement histograms as illustrated in Fig. 2f, we have been able to systematically probe the influence of the chemical linker group44,45 and the molecular backbone46 on single-molecule junction rupture force as illustrated in Fig. 2g.Significant future opportunities with force measurements exist for investigations that go beyond characterizations of the junc-tion rupture force. In two independent reports, one by our group47 and another by Wagner et al.48, force measurements were used to quantitatively measure the contribution of van der Waals interac-tions at the single-molecule level. Wagner et al. used the stiffness data from the lifting of PTCDA molecules on a Au(111) surface, and fitted it to the stiffness calculated from model potentials to estimate the contribution of the various interactions between the molecule and the surface48. By measuring force and conductance across single 4,4’-bipyridine molecules attached to Au electrodes, we were able to directly quantify the contribution of van der Waals interactions to single-molecule-junction stiffness and rupture force47. These experimental measurements can help benchmark the several theoretical frameworks currently under development aiming to reliably capture van der Waals interactions at metal/ organic interfaces due to their importance in diverse areas includ-ing catalysis, electronic devices and self-assembly.In most of the experiments mentioned thus far, the measured forces were typically used as a secondary probe of junction prop-erties, instead relying on the junction conductance as the primary signature for the formation of the junction. However, as is the case in large biological molecules49, forces measured across single-mol-ecule junctions can also provide the primary signature, thereby making it possible to characterize non-conducting molecules that nonetheless do form junctions. Furthermore, molecules pos-sess many internal degrees of motion (including vibrations and rotations) that can directly influence the electronic transport50, and the measurement of forces with such molecules can open up new avenues for mechanochemistry51. This potential of using force measurements to elucidate the fundamentals of electronic transport and binding interactions at the single-molecule level is prompting new activity in this area of research52–54. Optoelectronics and optical spectroscopyAddressing optical properties and understanding their influence on electronic transport in individual molecular-scale devices, col-lectively referred to as ‘molecular optoelectronics’, is an area with potentially important applications55. However, the fundamental mismatch between the optical (typically, approximately at the micrometre scale) and molecular-length scales has historically presented a barrier to experimental investigations. The motiva-tions for single-molecule optoelectronic studies are twofold: first, optical spectroscopies (especially Raman spectroscopy) could lead to a significantly better characterization of the local junction structure. The nanostructured metallic electrodes used to real-ize single-molecule junctions are coincidentally some of the best candidates for local field enhancement due to plasmons (coupled excitations of surface electrons and incident photons). This there-fore provides an excellent opportunity for understanding the interaction of plasmons with molecules at the nanoscale. Second, controlling the electronic transport properties using light as an external stimulus has long been sought as an attractive alternative to a molecular-scale field-effect transistor.Two independent groups have recently demonstrated simulta-neous optical and electrical measurements on molecular junctions with the aim of providing structural information using an optical probe. First, Ward et al.56 used Au nanogaps formed by electromi-gration57 to create molecular junctions with a few molecules. They then irradiated these junctions with a laser operating at a wavelength that is close to the plasmon resonance of these Au nanogaps to observe a Raman signal attributable to the molecules58 (Fig. 3a). As shown in Fig. 3b, they observed correlations between the intensity of the Raman features and magnitude of the junction conductance, providing direct evidence that Raman signatures could be used to identify junction structures. They later extended this experimental approach to estimate vibrational and electronic heating in molecu-lar junctions59. For this work, they measured the ratio of the Raman Stokes and anti-Stokes intensities, which were then related to the junction temperature as a function of the applied bias voltage. They found that the anti-Stokes intensity changed with bias voltage while the Stokes intensity remained constant, indicating that the effective temperature of the Raman-active mode was affected by passing cur-rent through the junction60. Interestingly, Ward et al. found that the vibrational mode temperatures exceeded several hundred kelvin, whereas earlier work by Tao and co-workers, who used models for junction rupture derived from biomolecule research, had indicated a much smaller value (~10 K) for electronic heating61. Whether this high temperature determined from the ratio of the anti-Stokes to Stokes intensities indicates that the electronic temperature is also similarly elevated is still being debated55, however, one can definitely conclude that such measurements under a high bias (few hundred millivolts) are clearly in a non-equilibrium transport regime, and much more research needs to be performed to understand the details of electronic heating.Concurrently, Liu et al.62 used the STM-based break-junction technique8 and combined this with Raman spectroscopy to per-form simultaneous conductance and Raman measurements on single-molecule junctions formed between a Au STM tip and a Au(111) substrate. They coupled a laser to a molecular junction as shown in Fig. 3c with a 4,4’-bipyridine molecule bridging the STM tip (top) and the substrate (bottom). Pyridines show clear surface-enhanced Raman signatures on metal58, and 4,4’-bipy-ridine is known to form single-molecule junctions in the STM break-junction set-up8,15. Similar to the study of Ward et al.56, Liu et al.62 found that conducting molecular junctions had a Raman signature that was distinct from the broken molecu-lar junctions. Furthermore, the authors studied the spectra of 4,4’-bipyridine at different bias voltages, ranging from 10 to 800 mV, and reported a reversible splitting of the 1,609 cm–1 peak (Fig. 3d). Because this Raman signature is due to a ring-stretching mode, they interpreted this splitting as arising from the break-ing of the degeneracy between the rings connected to the source and drain electrodes at high biases (Fig. 3c). Innovative experi-ments such as these have demonstrated that there is new physics to be learned through optical probing of molecular junctions, and are initiating further interest in understanding the effect of local structure and vibrational effects on electronic transport63. Experiments that probe electroluminescence — photon emis-sion induced by a tunnelling current — in these types of molec-ular junction can also offer insight into structure–conductance correlations. Ho and co-workers have demonstrated simultaneous measurement of differential conductance and photon emissionDOI: 10.1038/NNANO.2013.91from individual molecules at a submolecular-length scale using an STM 64,65. Instead of depositing molecules directly on a metal sur-face, they used an insulating layer to decouple the molecule from the metal 64,65 (Fig. 3e). This critical factor, combined with the vac-uum gap with the STM tip, ensures that the metal electrodes do not quench the radiated photons, and therefore the emitted photons carry molecular fingerprints. Indeed, the experimental observation of molecular electroluminescence of C 60 monolayers on Au(110) by Berndt et al.66 was later attributed to plasmon-mediated emission of the metallic electrodes, indirectly modulated by the molecule 67. The challenge of finding the correct insulator–molecule combination and performing the experiments at low temperature makes electro-luminescence relatively uncommon compared with the numerous Raman studies; however, progress is being made on both theoretical and experimental fronts to understand and exploit emission pro-cesses in single-molecule junctions 68.Beyond measurements of the Raman spectra of molecular junctions, light could be used to control transport in junctions formed with photochromic molecular backbones that occur in two (or more) stable and optically accessible states. Some common examples include azobenzene derivatives, which occur in a cis or trans form, as well as diarylene compounds that can be switched between a conducting conjugated form and a non-conducting cross-conjugated form 69. Experiments probing the conductance changes in molecular devices formed with such compounds have been reviewed in depth elsewhere 70,71. However, in the single-mol-ecule context, there are relatively few examples of optical modula-tion of conductance. To a large extent, this is due to the fact that although many molecular systems are known to switch reliably in solution, contact to metallic electrodes can dramatically alter switching properties, presenting a significant challenge to experi-ments at the single-molecule level.Two recent experiments have attempted to overcome this chal-lenge and have probed conductance changes in single-molecule junctions while simultaneously illuminating the junctions with visible light 72,73. Battacharyya et al.72 used a porphyrin-C 60 ‘dyad’ molecule deposited on an indium tin oxide (I TO) substrate to demonstrate the light-induced creation of an excited-state mol-ecule with a different conductance. The unconventional transpar-ent ITO electrode was chosen to provide optical access while also acting as a conducting electrode. The porphyrin segment of the molecule was the chromophore, whereas the C 60 segment served as the electron acceptor. The authors found, surprisingly, that the charge-separated molecule had a much longer lifetime on ITO than in solution. I n the break-junction experiments, the illuminated junctions showed a conductance feature that was absent without1 μm Raman shift (cm –1)1,609 cm –1(–)Source 1,609 cm–1Drain (+)Low voltage High voltageMgPNiAl(110)STM tip (Ag)VacuumThin alumina 1.4 1.5 1.6 1.701020 3040200400Photon energy (eV)3.00 V 2.90 V 2.80 V 2.70 V 2.60 V2.55 V 2.50 VP h o t o n c o u n t s (a .u .)888 829 777731Wavelength (nm)Oxideacebd f Raman intensity (CCD counts)1,5001,00050000.40.30.20.10.01,590 cm −11,498 cm −1d I /d V (μA V –1)1,609 cm –11,631 cm–11 μm1 μmTime (s)Figure 3 | Simultaneous studies of optical effects and transport. a , A scanning electron micrograph (left) of an electromigrated Au junction (light contrast) lithographically defined on a Si substrate (darker contrast). The nanoscale gap results in a ‘hot spot’ where Raman signals are enhanced, as seen in the optical image (right). b , Simultaneously measured differential conductance (black, bottom) and amplitudes of two molecular Raman features (blue traces, middle and top) as a function of time in a p-mercaptoaniline junction. c , Schematic representation of a bipyridine junction formed between a Au STM tip and a Au(111) substrate, where the tip enhancement from the atomically sharp STM tip results in a large enhancement of the Raman signal. d , The measured Raman spectra as a function of applied bias indicate breaking of symmetry in the bound molecule. e , Schematic representation of a Mg-porphyrin (MgP) molecule sandwiched between a Ag STM tip and a NiAl(110) substrate. A subnanometre alumina insulating layer is a key factor in measuring the molecular electroluminescence, which would otherwise be overshadowed by the metallic substrate. f , Emission spectra of a single Mg-porphyrin molecule as a function of bias voltage (data is vertically offset for clarity). At high biases, individual vibronic peaks become apparent. The spectra from a bare oxide layer (grey) is shown for reference. Figure reproduced with permission from: a ,b , ref. 56, © 2008 ACS; c ,d , ref. 62, © 2011 NPG; e ,f , ref. 65, © 2008 APS.DOI: 10.1038/NNANO.2013.91light, which the authors assigned to the charge-separated state. In another approach, Lara-Avila et al.73 have reported investigations of a dihydroazulene (DHA)/vinylheptafulvene (VHF) molecule switch, utilizing nanofabricated gaps to perform measurements of Au–DHA–Au single-molecule junctions. Based on the early work by Daub et al.74, DHA was known to switch to VHF under illumina-tion by 353-nm light and switch back to DHA thermally. In three of four devices, the authors observed a conductance increase after irradiating for a period of 10–20 min. In one of those three devices, they also reported reversible switching after a few hours. Although much more detailed studies are needed to establish the reliability of optical single-molecule switches, these experiments provide new platforms to perform in situ investigations of single-molecule con-ductance under illumination.We conclude this section by briefly pointing to the rapid pro-gress occurring in the development of optical probes at the single-molecule scale, which is also motivated by the tremendous interest in plasmonics and nano-optics. As mentioned previously, light can be coupled into nanoscale gaps, overcoming experimental chal-lenges such as local heating. Banerjee et al.75 have exploited these concepts to demonstrate plasmon-induced electrical conduction in a network of Au nanoparticles that form metal–molecule–metal junctions between them (Fig. 3f). Although not a single-molecule measurement, the control of molecular conductance through plas-monic coupling can benefit tremendously from the diverse set of new concepts under development in this area, such as nanofabri-cated transmission lines 76, adiabatic focusing of surface plasmons, electrical excitation of surface plasmons and nanoparticle optical antennas. The convergence of plasmonics and electronics at the fundamental atomic- and molecular-length scales can be expected to provide significant opportunities for new studies of light–mat-ter interaction 77–79.Thermoelectric characterization of single-molecule junctions Understanding the electronic response to heating in a single-mole-cule junction is not only of basic scientific interest; it can have a tech-nological impact by improving our ability to convert wasted heat into usable electricity through the thermoelectric effect, where a temper-ature difference between two sides of a device induces a voltage drop across it. The efficiency of such a device depends on its thermopower (S ; also known as the Seebeck coefficient), its electric and thermal conductivity 80. Strategies for increasing the efficiency of thermoelec-tric devices turned to nanoscale devices a decade ago 81, where one could, in principle, increase the electronic conductivity and ther-mopower while independently minimizing the thermal conductiv-ity 82. This has motivated the need for a fundamental understandingof thermoelectrics at the single-molecule level 83, and in particular, the measurement of the Seebeck coefficient in such junctions. The Seebeck coefficient, S = −(ΔV /ΔT )|I = 0, determines the magnitude of the voltage developed across the junction when a temperature dif-ference ΔT is applied, as illustrated in Fig. 4a; this definition holds both for bulk devices and for single-molecule junctions. If an addi-tional external voltage ΔV exists across the junction, then the cur-rent I through the junction is given by I = G ΔV + GS ΔT where G is the junction conductance 83. Transport through molecular junctions is typically in the coherent regime where conductance, which is pro-portional to the electronic transmission probability, is given by the Landauer formula 84. The Seebeck coefficient at zero applied voltage is then related to the derivative of the transmission probability at the metal Fermi energy (in the off-resonance limit), with, S = −∂E ∂ln( (E ))π2k 2B T E 3ewhere k B is the Boltzmann constant, e is the charge of the electron, T (E ) is the energy-dependent transmission function and E F is the Fermi energy. When the transmission function for the junction takes on a simple Lorentzian form 85, and transport is in the off-resonance limit, the sign of S can be used to deduce the nature of charge carriers in molecular junctions. In such cases, a positive S results from hole transport through the highest occupied molecu-lar orbital (HOMO) whereas a negative S indicates electron trans-port through the lowest unoccupied molecular orbital (LUMO). Much work has been performed on investigating the low-bias con-ductance of molecular junctions using a variety of chemical linker groups 86–89, which, in principle, can change the nature of charge carriers through the junction. Molecular junction thermopower measurements can thus be used to determine the nature of charge carriers, correlating the backbone and linker chemistry with elec-tronic aspects of conduction.Experimental measurements of S and conductance were first reported by Ludoph and Ruitenbeek 90 in Au point contacts at liquid helium temperatures. This work provided a method to carry out thermoelectric measurements on molecular junctions. Reddy et al.91 implemented a similar technique in the STM geome-try to measure S of molecular junctions, although due to electronic limitations, they could not simultaneously measure conductance. They used thiol-terminated oligophenyls with 1-3-benzene units and found a positive S that increased with increasing molecular length (Fig. 4b). These pioneering experiments allowed the iden-tification of hole transport through thiol-terminated molecular junctions, while also introducing a method to quantify S from statistically significant datasets. Following this work, our group measured the thermoelectric current through a molecular junction held under zero external bias voltage to determine S and the con-ductance through the same junction at a finite bias to determine G (ref. 92). Our measurements showed that amine-terminated mol-ecules conduct through the HOMO whereas pyridine-terminatedmolecules conduct through the LUMO (Fig. 4b) in good agree-ment with calculations.S has now been measured on a variety of molecular junctionsdemonstrating both hole and electron transport 91–95. Although the magnitude of S measured for molecular junctions is small, the fact that it can be tuned by changing the molecule makes these experiments interesting from a scientific perspective. Future work on the measurements of the thermal conductance at the molecu-lar level can be expected to establish a relation between chemical structure and the figure of merit, which defines the thermoelec-tric efficiencies of such devices and determines their viability for practical applications.SpintronicsWhereas most of the explorations of metal–molecule–metal junc-tions have been motivated by the quest for the ultimate minia-turization of electronic components, the quantum-mechanical aspects that are inherent to single-molecule junctions are inspir-ing entirely new device concepts with no classical analogues. In this section, we review recent experiments that demonstrate the capability of controlling spin (both electronic and nuclear) in single-molecule devices 96. The early experiments by the groups of McEuen and Ralph 97, and Park 98 in 2002 explored spin-depend-ent transport and the Kondo effect in single-molecule devices, and this topic has recently been reviewed in detail by Scott and Natelson 99. Here, we focus on new types of experiment that are attempting to control the spin state of a molecule or of the elec-trons flowing through the molecular junction. These studies aremotivated by the appeal of miniaturization and coherent trans-port afforded by molecular electronics, combined with the great potential of spintronics to create devices for data storage and quan-tum computation 100. The experimental platforms for conducting DOI: 10.1038/NNANO.2013.91。
湍流燃烧模型
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195 2. Balance equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
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D. Veynante, L. Vervisch / Progress in Energy and Combustion Science 28 (2002) 193±266
6. Tools for turbulent combustion modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212 6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212 6.2. Scalar dissipation rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214 6.3. Geometrical description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214 6.3.1. G-®eld equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214 6.3.2. Flame surface density description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 6.3.3. Flame wrinkling description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 6.4. Statistical approaches: probability density function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 6.4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 6.4.2. Presumed probability density functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219 6.4.3. Pdf balance equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219 6.4.4. Joint velocity/concentrations pdf . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221 6.4.5. Conditional moment closure (CMC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221 6.5. Similarities and links between the tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
半导体一些术语的中英文对照
半导体一些术语的中英文对照离子注入机ion implanterLSS理论Lindhand Scharff and Schiott theory 又称“林汉德—斯卡夫—斯高特理论".沟道效应channeling effect射程分布range distribution深度分布depth distribution投影射程projected range阻止距离stopping distance阻止本领stopping power标准阻止截面standard stopping cross section 退火annealing激活能activation energy等温退火isothermal annealing激光退火laser annealing应力感生缺陷stress-induced defect择优取向preferred orientation制版工艺mask—making technology图形畸变pattern distortion初缩first minification精缩final minification母版master mask铬版chromium plate干版dry plate乳胶版emulsion plate透明版see—through plate高分辨率版high resolution plate,HRP超微粒干版plate for ultra-microminiaturization 掩模mask掩模对准mask alignment对准精度alignment precision光刻胶photoresist又称“光致抗蚀剂”。
负性光刻胶negative photoresist正性光刻胶positive photoresist无机光刻胶inorganic resist多层光刻胶multilevel resist电子束光刻胶electron beam resistX射线光刻胶X-ray resist刷洗scrubbing甩胶spinning涂胶photoresist coating后烘postbaking光刻photolithographyX射线光刻X-ray lithography电子束光刻electron beam lithography离子束光刻ion beam lithography深紫外光刻deep-UV lithography光刻机mask aligner投影光刻机projection mask aligner曝光exposure接触式曝光法contact exposure method接近式曝光法proximity exposure method光学投影曝光法optical projection exposure method 电子束曝光系统electron beam exposure system分步重复系统step-and—repeat system显影development线宽linewidth去胶stripping of photoresist氧化去胶removing of photoresist by oxidation等离子[体]去胶removing of photoresist by plasma 刻蚀etching干法刻蚀dry etching反应离子刻蚀reactive ion etching, RIE各向同性刻蚀isotropic etching各向异性刻蚀anisotropic etching反应溅射刻蚀reactive sputter etching离子铣ion beam milling又称“离子磨削”。
Principles of Plasma Discharges and Materials Processing9
CHAPTER8MOLECULAR COLLISIONS8.1INTRODUCTIONBasic concepts of gas-phase collisions were introduced in Chapter3,where we described only those processes needed to model the simplest noble gas discharges: electron–atom ionization,excitation,and elastic scattering;and ion–atom elastic scattering and resonant charge transfer.In this chapter we introduce other collisional processes that are central to the description of chemically reactive discharges.These include the dissociation of molecules,the generation and destruction of negative ions,and gas-phase chemical reactions.Whereas the cross sections have been measured reasonably well for the noble gases,with measurements in reasonable agreement with theory,this is not the case for collisions in molecular gases.Hundreds of potentially significant collisional reactions must be examined in simple diatomic gas discharges such as oxygen.For feedstocks such as CF4/O2,SiH4/O2,etc.,the complexity can be overwhelming.Furthermore,even when the significant processes have been identified,most of the cross sections have been neither measured nor calculated. Hence,one must often rely on estimates based on semiempirical or semiclassical methods,or on measurements made on molecules analogous to those of interest. As might be expected,data are most readily available for simple diatomic and polyatomic gases.Principles of Plasma Discharges and Materials Processing,by M.A.Lieberman and A.J.Lichtenberg. ISBN0-471-72001-1Copyright#2005John Wiley&Sons,Inc.235236MOLECULAR COLLISIONS8.2MOLECULAR STRUCTUREThe energy levels for the electronic states of a single atom were described in Chapter3.The energy levels of molecules are more complicated for two reasons. First,molecules have additional vibrational and rotational degrees of freedom due to the motions of their nuclei,with corresponding quantized energies E v and E J. Second,the energy E e of each electronic state depends on the instantaneous con-figuration of the nuclei.For a diatomic molecule,E e depends on a single coordinate R,the spacing between the two nuclei.Since the nuclear motions are slow compared to the electronic motions,the electronic state can be determined for anyfixed spacing.We can therefore represent each quantized electronic level for a frozen set of nuclear positions as a graph of E e versus R,as shown in Figure8.1.For a mole-cule to be stable,the ground(minimum energy)electronic state must have a minimum at some value R1corresponding to the mean intermolecular separation (curve1).In this case,energy must be supplied in order to separate the atoms (R!1).An excited electronic state can either have a minimum( R2for curve2) or not(curve3).Note that R2and R1do not generally coincide.As for atoms, excited states may be short lived(unstable to electric dipole radiation)or may be metastable.Various electronic levels may tend to the same energy in the unbound (R!1)limit. Array FIGURE8.1.Potential energy curves for the electronic states of a diatomic molecule.For diatomic molecules,the electronic states are specifiedfirst by the component (in units of hÀ)L of the total orbital angular momentum along the internuclear axis, with the symbols S,P,D,and F corresponding to L¼0,+1,+2,and+3,in analogy with atomic nomenclature.All but the S states are doubly degenerate in L.For S states,þandÀsuperscripts are often used to denote whether the wave function is symmetric or antisymmetric with respect to reflection at any plane through the internuclear axis.The total electron spin angular momentum S (in units of hÀ)is also specified,with the multiplicity2Sþ1written as a prefixed superscript,as for atomic states.Finally,for homonuclear molecules(H2,N2,O2, etc.)the subscripts g or u are written to denote whether the wave function is sym-metric or antisymmetric with respect to interchange of the nuclei.In this notation, the ground states of H2and N2are both singlets,1Sþg,and that of O2is a triplet,3SÀg .For polyatomic molecules,the electronic energy levels depend on more thanone nuclear coordinate,so Figure8.1must be generalized.Furthermore,since there is generally no axis of symmetry,the states cannot be characterized by the quantum number L,and other naming conventions are used.Such states are often specified empirically through characterization of measured optical emission spectra.Typical spacings of low-lying electronic energy levels range from a few to tens of volts,as for atoms.Vibrational and Rotational MotionsUnfreezing the nuclear vibrational and rotational motions leads to additional quan-tized structure on smaller energy scales,as illustrated in Figure8.2.The simplest (harmonic oscillator)model for the vibration of diatomic molecules leads to equally spaced quantized,nondegenerate energy levelse E v¼hÀv vib vþ1 2(8:2:1)where v¼0,1,2,...is the vibrational quantum number and v vib is the linearized vibration frequency.Fitting a quadratic functione E v¼12k vib(RÀ R)2(8:2:2)near the minimum of a stable energy level curve such as those shown in Figure8.1, we can estimatev vib%k vibm Rmol1=2(8:2:3)where k vib is the“spring constant”and m Rmol is the reduced mass of the AB molecule.The spacing hÀv vib between vibrational energy levels for a low-lying8.2MOLECULAR STRUCTURE237stable electronic state is typically a few tenths of a volt.Hence for molecules in equi-librium at room temperature (0.026V),only the v ¼0level is significantly popula-ted.However,collisional processes can excite strongly nonequilibrium vibrational energy levels.We indicate by the short horizontal line segments in Figure 8.1a few of the vibrational energy levels for the stable electronic states.The length of each segment gives the range of classically allowed vibrational motions.Note that even the ground state (v ¼0)has a finite width D R 1as shown,because from(8.2.1),the v ¼0state has a nonzero vibrational energy 1h Àv vib .The actual separ-ation D R about Rfor the ground state has a Gaussian distribution,and tends toward a distribution peaked at the classical turning points for the vibrational motion as v !1.The vibrational motion becomes anharmonic and the level spa-cings tend to zero as the unbound vibrational energy is approached (E v !D E 1).FIGURE 8.2.Vibrational and rotational levels of two electronic states A and B of a molecule;the three double arrows indicate examples of transitions in the pure rotation spectrum,the rotation–vibration spectrum,and the electronic spectrum (after Herzberg,1971).238MOLECULAR COLLISIONSFor E v.D E1,the vibrational states form a continuum,corresponding to unbound classical motion of the nuclei(breakup of the molecule).For a polyatomic molecule there are many degrees of freedom for vibrational motion,leading to a very compli-cated structure for the vibrational levels.The simplest(dumbbell)model for the rotation of diatomic molecules leads to the nonuniform quantized energy levelse E J¼hÀ22I molJ(Jþ1)(8:2:4)where I mol¼m Rmol R2is the moment of inertia and J¼0,1,2,...is the rotational quantum number.The levels are degenerate,with2Jþ1states for the J th level. The spacing between rotational levels increases with J(see Figure8.2).The spacing between the lowest(J¼0to J¼1)levels typically corresponds to an energy of0.001–0.01V;hence,many low-lying levels are populated in thermal equilibrium at room temperature.Optical EmissionAn excited molecular state can decay to a lower energy state by emission of a photon or by breakup of the molecule.As shown in Figure8.2,the radiation can be emitted by a transition between electronic levels,between vibrational levels of the same electronic state,or between rotational levels of the same electronic and vibrational state;the radiation typically lies within the optical,infrared,or microwave frequency range,respectively.Electric dipole radiation is the strongest mechanism for photon emission,having typical transition times of t rad 10À9s,as obtained in (3.4.13).The selection rules for electric dipole radiation areDL¼0,+1(8:2:5a)D S¼0(8:2:5b) In addition,for transitions between S states the only allowed transitions areSþÀ!Sþand SÀÀ!SÀ(8:2:6) and for homonuclear molecules,the only allowed transitions aregÀ!u and uÀ!g(8:2:7) Hence homonuclear diatomic molecules do not have a pure vibrational or rotational spectrum.Radiative transitions between electronic levels having many different vibrational and rotational initial andfinal states give rise to a structure of emission and absorption bands within which a set of closely spaced frequencies appear.These give rise to characteristic molecular emission and absorption bands when observed8.2MOLECULAR STRUCTURE239using low-resolution optical spectrometers.As for atoms,metastable molecular states having no electric dipole transitions to lower levels also exist.These have life-times much exceeding10À6s;they can give rise to weak optical band structures due to magnetic dipole or electric quadrupole radiation.Electric dipole radiation between vibrational levels of the same electronic state is permitted for molecules having permanent dipole moments.In the harmonic oscillator approximation,the selection rule is D v¼+1;weaker transitions D v¼+2,+3,...are permitted for anharmonic vibrational motion.The preceding description of molecular structure applies to molecules having arbi-trary electronic charge.This includes neutral molecules AB,positive molecular ions ABþ,AB2þ,etc.and negative molecular ions ABÀ.The potential energy curves for the various electronic states,regardless of molecular charge,are commonly plotted on the same diagram.Figures8.3and8.4give these for some important electronic statesof HÀ2,H2,and Hþ2,and of OÀ2,O2,and Oþ2,respectively.Examples of both attractive(having a potential energy minimum)and repulsive(having no minimum)states can be seen.The vibrational levels are labeled with the quantum number v for the attrac-tive levels.The ground states of both Hþ2and Oþ2are attractive;hence these molecular ions are stable against autodissociation(ABþ!AþBþor AþþB).Similarly,the ground states of H2and O2are attractive and lie below those of Hþ2and Oþ2;hence they are stable against autodissociation and autoionization(AB!ABþþe).For some molecules,for example,diatomic argon,the ABþion is stable but the AB neutral is not stable.For all molecules,the AB ground state lies below the ABþground state and is stable against autoionization.Excited states can be attractive or repulsive.A few of the attractive states may be metastable;some examples are the 3P u state of H2and the1D g,1Sþgand3D u states of O2.Negative IonsRecall from Section7.2that many neutral atoms have a positive electron affinity E aff;that is,the reactionAþeÀ!AÀis exothermic with energy E aff(in volts).If E aff is negative,then AÀis unstable to autodetachment,AÀ!Aþe.A similar phenomenon is found for negative molecular ions.A stable ABÀion exists if its ground(lowest energy)state has a potential minimum that lies below the ground state of AB.This is generally true only for strongly electronegative gases having large electron affinities,such as O2 (E aff%1:463V for O atoms)and the halogens(E aff.3V for the atoms).For example,Figure8.4shows that the2P g ground state of OÀ2is stable,with E aff% 0:43V for O2.For weakly electronegative or for electropositive gases,the minimum of the ground state of ABÀgenerally lies above the ground state of AB,and ABÀis unstable to autodetachment.An example is hydrogen,which is weakly electronegative(E aff%0:754V for H atoms).Figure8.3shows that the2Sþu ground state of HÀ2is unstable,although the HÀion itself is stable.In an elec-tropositive gas such as N2(E aff.0),both NÀ2and NÀare unstable. 240MOLECULAR COLLISIONS8.3ELECTRON COLLISIONS WITH MOLECULESThe interaction time for the collision of a typical (1–10V)electron with a molecule is short,t c 2a 0=v e 10À16–10À15s,compared to the typical time for a molecule to vibrate,t vib 10À14–10À13s.Hence for electron collisional excitation of a mole-cule to an excited electronic state,the new vibrational (and rotational)state canbeFIGURE 8.3.Potential energy curves for H À2,H 2,and H þ2.(From Jeffery I.Steinfeld,Molecules and Radiation:An Introduction to Modern Molecular Spectroscopy ,2d ed.#MIT Press,1985.)8.3ELECTRON COLLISIONS WITH MOLECULES 241FIGURE 8.4.Potential energy curves for O À2,O 2,and O þ2.(From Jeffery I.Steinfeld,Molecules and Radiation:An Introduction to Modern Molecular Spectroscopy ,2d ed.#MIT Press,1985.)242MOLECULAR COLLISIONS8.3ELECTRON COLLISIONS WITH MOLECULES243 determined by freezing the nuclear motions during the collision.This is known as the Franck–Condon principle and is illustrated in Figure8.1by the vertical line a,showing the collisional excitation atfixed R to a high quantum number bound vibrational state and by the vertical line b,showing excitation atfixed R to a vibra-tionally unbound state,in which breakup of the molecule is energetically permitted. Since the typical transition time for electric dipole radiation(t rad 10À9–10À8s)is long compared to the dissociation( vibrational)time t diss,excitation to an excited state will generally lead to dissociation when it is energetically permitted.Finally, we note that the time between collisions t c)t rad in typical low-pressure processing discharges.Summarizing the ordering of timescales for electron–molecule collisions,we havet at t c(t vib t diss(t rad(t cDissociationElectron impact dissociation,eþABÀ!AþBþeof feedstock gases plays a central role in the chemistry of low-pressure reactive discharges.The variety of possible dissociation processes is illustrated in Figure8.5.In collisions a or a0,the v¼0ground state of AB is excited to a repulsive state of AB.The required threshold energy E thr is E a for collision a and E a0for Array FIGURE8.5.Illustrating the variety of dissociation processes for electron collisions with molecules.collision a0,and it leads to an energy after dissociation lying between E aÀE diss and E a0ÀE diss that is shared among the dissociation products(here,A and B). Typically,E aÀE diss few volts;consequently,hot neutral fragments are typically generated by dissociation processes.If these hot fragments hit the substrate surface, they can profoundly affect the process chemistry.In collision b,the ground state AB is excited to an attractive state of AB at an energy E b that exceeds the binding energy E diss of the AB molecule,resulting in dissociation of AB with frag-ment energy E bÀE diss.In collision b0,the excitation energy E b0¼E diss,and the fragments have low energies;hence this process creates fragments having energies ranging from essentially thermal energies up to E bÀE diss few volts.In collision c,the AB atom is excited to the bound excited state ABÃ(labeled5),which sub-sequently radiates to the unbound AB state(labeled3),which then dissociates.The threshold energy required is large,and the fragments are hot.Collision c can also lead to dissociation of an excited state by a radiationless transfer from state5to state4near the point where the two states cross:ABÃðboundÞÀ!ABÃðunboundÞÀ!AþBÃThe fragments can be both hot and in excited states.We discuss such radiationless electronic transitions in the next section.This phenomenon is known as predisso-ciation.Finally,a collision(not labeled in thefigure)to state4can lead to dis-sociation of ABÃ,again resulting in hot excited fragments.The process of electron impact excitation of a molecule is similar to that of an atom,and,consequently,the cross sections have a similar form.A simple classical estimate of the dissociation cross section for a level having excitation energy U1can be found by requiring that an incident electron having energy W transfer an energy W L lying between U1and U2to a valence electron.Here,U2is the energy of the next higher level.Then integrating the differential cross section d s[given in(3.4.20)and repeated here],d s¼pe24021Wd W LW2L(3:4:20)over W L,we obtains diss¼0W,U1pe24pe021W1U1À1WU1,W,U2pe24021W1U1À1U2W.U28>>>>>><>>>>>>:(8:3:1)244MOLECULAR COLLISIONSLetting U2ÀU1(U1and introducing voltage units W¼e E,U1¼e E1and U2¼e E2,we haves diss¼0E,E1s0EÀE11E1,E,E2s0E2ÀE1EE.E28>>>><>>>>:(8:3:2)wheres0¼pe4pe0E12(8:3:3)We see that the dissociation cross section rises linearly from the threshold energy E thr%E1to a maximum value s0(E2ÀE1)=E thr at E2and then falls off as1=E. Actually,E1and E2can depend on the nuclear separation R.In this case,(8.3.2) should be averaged over the range of R s corresponding to the ground-state vibrational energy,leading to a broadened dependence of the average cross section on energy E.The maximum cross section is typically of order10À15cm2. Typical rate constants for a single dissociation process with E thr&T e have an Arrhenius formK diss/K diss0expÀE thr T e(8:3:4)where K diss0 10À7cm3=s.However,in some cases E thr.T e.For excitation to an attractive state,an appropriate average over the fraction of the ground-state vibration that leads to dissociation must be taken.Dissociative IonizationIn addition to normal ionization,eþABÀ!ABþþ2eelectron–molecule collisions can lead to dissociative ionizationeþABÀ!AþBþþ2eThese processes,common for polyatomic molecules,are illustrated in Figure8.6.In collision a having threshold energy E iz,the molecular ion ABþis formed.Collisionsb andc occur at higher threshold energies E diz and result in dissociative ionization,8.3ELECTRON COLLISIONS WITH MOLECULES245leading to the formation of fast,positively charged ions and neutrals.These cross sections have a similar form to the Thompson ionization cross section for atoms.Dissociative RecombinationThe electron collision,e þAB þÀ!A þB Ãillustrated as d and d 0in Figure 8.6,destroys an electron–ion pair and leads to the production of fast excited neutral fragments.Since the electron is captured,it is not available to carry away a part of the reaction energy.Consequently,the collision cross section has a resonant character,falling to very low values for E ,E d and E .E d 0.However,a large number of excited states A Ãand B Ãhaving increasing principal quantum numbers n and energies can be among the reaction products.Consequently,the rate constants can be large,of order 10À7–10À6cm 3=s.Dissocia-tive recombination to the ground states of A and B cannot occur because the potential energy curve for AB þis always greater than the potential energycurveFIGURE 8.6.Illustration of dissociative ionization and dissociative recombination for electron collisions with molecules.246MOLECULAR COLLISIONSfor the repulsive state of AB.Two-body recombination for atomic ions or for mol-ecular ions that do not subsequently dissociate can only occur with emission of a photon:eþAþÀ!Aþh n:As shown in Section9.2,the rate constants are typically three tofive orders of magnitude lower than for dissociative recombination.Example of HydrogenThe example of H2illustrates some of the inelastic electron collision phenomena we have discussed.In order of increasing electron impact energy,at a threshold energy of 8:8V,there is excitation to the repulsive3Sþu state followed by dissociation into two fast H fragments carrying 2:2V/atom.At11.5V,the1Sþu bound state is excited,with subsequent electric dipole radiation in the ultraviolet region to the1Sþg ground state.At11.8V,there is excitation to the3Sþg bound state,followedby electric dipole radiation to the3Sþu repulsive state,followed by dissociation with 2:2V/atom.At12.6V,the1P u bound state is excited,with UV emission tothe ground state.At15.4V,the2Sþg ground state of Hþ2is excited,leading to the pro-duction of Hþ2ions.At28V,excitation of the repulsive2Sþu state of Hþ2leads to thedissociative ionization of H2,with 5V each for the H and Hþfragments.Dissociative Electron AttachmentThe processes,eþABÀ!AþBÀproduce negative ion fragments as well as neutrals.They are important in discharges containing atoms having positive electron affinities,not only because of the pro-duction of negative ions,but because the threshold energy for production of negative ion fragments is usually lower than for pure dissociation processes.A variety of pro-cesses are possible,as shown in Figure8.7.Since the impacting electron is captured and is not available to carry excess collision energy away,dissociative attachment is a resonant process that is important only within a narrow energy range.The maximum cross sections are generally much smaller than the hard-sphere cross section of the molecule.Attachment generally proceeds by collisional excitation from the ground AB state to a repulsive ABÀstate,which subsequently either auto-detaches or dissociates.The attachment cross section is determined by the balance between these processes.For most molecules,the dissociation energy E diss of AB is greater than the electron affinity E affB of B,leading to the potential energy curves shown in Figure8.7a.In this case,the cross section is large only for impact energies lying between a minimum value E thr,for collision a,and a maximum value E0thr for8.3ELECTRON COLLISIONS WITH MOLECULES247FIGURE 8.7.Illustration of a variety of electron attachment processes for electron collisions with molecules:(a )capture into a repulsive state;(b )capture into an attractive state;(c )capture of slow electrons into a repulsive state;(d )polar dissociation.248MOLECULAR COLLISIONScollision a 0.The fragments are hot,having energies lying between minimum and maximum values E min ¼E thr þE affB ÀE diss and E max ¼E 0thr þE af fB ÀE diss .Since the AB Àstate lies above the AB state for R ,R x ,autodetachment can occur as the mol-ecules begin to separate:AB À!AB þe.Hence the cross section for production of negative ions can be much smaller than that for excitation of the AB Àrepulsive state.As a crude estimate,for the same energy,the autodetachment rate is ffiffiffiffiffiffiffiffiffiffiffiffiffiM R =m p 100times the dissociation rate of the repulsive AB Àmolecule,where M R is the reduced mass.Hence only one out of 100excitations lead to dissociative attachment.Excitation to the AB Àbound state can also lead to dissociative attachment,as shown in Figure 8.7b .Here the cross section is significant only for E thr ,E ,E 0thr ,but the fragments can have low energies,with a minimum energy of zero and a maximum energy of E 0thr þE affB ÀE diss .Collision b,e þAB À!AB ÀÃdoes not lead to production of AB Àions because energy and momentum are not gen-erally conserved when two bodies collide elastically to form one body (see Problem3.12).Hence the excited AB ÀÃion separates,AB ÀÃÀ!e þABunless vibrational radiation or collision with a third body carries off the excess energy.These processes are both slow in low-pressure discharges (see Section 9.2).At high pressures (say,atmospheric),three-body attachment to form AB Àcan be very important.For a few molecules,such as some halogens,the electron affinity of the atom exceeds the dissociation energy of the neutral molecule,leading to the potential energy curves shown in Figure 8.7c .In this case the range of electron impact ener-gies E for excitation of the AB Àrepulsive state includes E ¼0.Consequently,there is no threshold energy,and very slow electrons can produce dissociative attachment,resulting in hot neutral and negative ion fragments.The range of R s over which auto-detachment can occur is small;hence the maximum cross sections for dissociative attachment can be as high as 10À16cm 2.A simple classical estimate of electron capture can be made using the differential scattering cross section for energy loss (3.4.20),in a manner similar to that done for dissociation.For electron capture to an energy level E 1that is unstable to autode-tachment,and with the additional constraint for capture that the incident electron energy lie within E 1and E 2¼E 1þD E ,where D E is a small energy difference characteristic of the dissociative attachment timescale,we obtain,in place of (8.3.2),s att¼0E ,E 1s 0E ÀE 1E 1E 1,E ,E 20E .E 28>><>>:(8:3:5)8.3ELECTRON COLLISIONS WITH MOLECULES 249wheres 0%p m M R 1=2e 4pe 0E 1 2(8:3:6)The factor of (m =M R )1=2roughly gives the fraction of excited states that do not auto-detach.We see that the dissociative attachment cross section rises linearly at E 1to a maximum value s 0D E =E 1and then falls abruptly to zero.As for dissociation,E 1can depend strongly on the nuclear separation R ,and (8.3.5)must be averaged over the range of E 1s corresponding to the ground state vibrational motion;e.g.,from E thr to E 0thr in Figure 8.7a .Because generally D E (E 0thr ÀE thr ,we can write (8.3.5)in the forms att %p m M R 1=2e 4pe 0 2(D E )22E 1d (E ÀE 1)(8:3:7)where d is the Dirac delta ing (8.3.7),the average over the vibrational motion can be performed,leading to a cross section that is strongly peaked lying between E thr and E 0thr .We leave the details of the calculation to a problem.Polar DissociationThe process,e þAB À!A þþB Àþeproduces negative ions without electron capture.As shown in Figure 8.7d ,the process proceeds by excitation of a polar state A þand B Àof AB Ãthat has a separ-ated atom limit of A þand B À.Hence at large R ,this state lies above the A þB ground state by the difference between the ionization potential of A and the electron affinity of B.The polar state is weakly bound at large R by the Coulomb attraction force,but is repulsive at small R .The maximum cross section and the dependence of the cross section on electron impact energy are similar to that of pure dissociation.The threshold energy E thr for polar dissociation is generally large.The measured cross section for negative ion production by electron impact in O 2is shown in Figure 8.8.The sharp peak at 6.5V is due to dissociative attachment.The variation of the cross section with energy is typical of a resonant capture process.The maximum cross section of 10À18cm 2is quite low because autode-tachment from the repulsive O À2state is strong,inhibiting dissociative attachment.The second gradual maximum near 35V is due to polar dissociation;the variation of the cross section with energy is typical of a nonresonant process.250MOLECULAR COLLISIONS。
A New Equation of State for Carbon Dioxide Covering the Fluid Region
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Melting Pressure. . . . . . . . . . . . . . . . . . . . . . .. Sublimation Pressure. . . . . . . . . . . . . . . . . . . .. Vapor Pressure ....................... " Saturated Liquid Density. . . . . . . . . . . . . . . .. Saturated Vapor Density. . . . . . . . . . . . . . . . .. Caloric Data on the Liquid-Vapor Phase Boundary. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. Experimental Basis of the New Equation of State. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 4.1 Thermal Properties .................... " 4.2 Specific Isobaric Heat Capacity. . . . . . . . . . .. 4.2.1 Experimental Results for the Specific Isobaric Heat Capacity. . . . . . . . . . . . .. 4.2.2 Results for the Specific Isobaric Heat
法布里珀罗基模共振英文
法布里珀罗基模共振英文The Fabryperot ResonanceOptics, the study of light and its properties, has been a subject of fascination for scientists and researchers for centuries. One of the fundamental phenomena in optics is the Fabry-Perot resonance, named after the French physicists Charles Fabry and Alfred Perot, who first described it in the late 19th century. This resonance effect has numerous applications in various fields, ranging from telecommunications to quantum physics, and its understanding is crucial in the development of advanced optical technologies.The Fabry-Perot resonance occurs when light is reflected multiple times between two parallel, partially reflective surfaces, known as mirrors. This creates a standing wave pattern within the cavity formed by the mirrors, where the light waves interfere constructively and destructively to produce a series of sharp peaks and valleys in the transmitted and reflected light intensity. The specific wavelengths at which the constructive interference occurs are known as the resonant wavelengths of the Fabry-Perot cavity.The resonant wavelengths of a Fabry-Perot cavity are determined bythe distance between the mirrors, the refractive index of the material within the cavity, and the wavelength of the incident light. When the optical path length, which is the product of the refractive index and the physical distance between the mirrors, is an integer multiple of the wavelength of the incident light, the light waves interfere constructively, resulting in a high-intensity transmission through the cavity. Conversely, when the optical path length is not an integer multiple of the wavelength, the light waves interfere destructively, leading to a low-intensity transmission.The sharpness of the resonant peaks in a Fabry-Perot cavity is determined by the reflectivity of the mirrors. Highly reflective mirrors result in a higher finesse, which is a measure of the ratio of the spacing between the resonant peaks to their width. This high finesse allows for the creation of narrow-linewidth, high-resolution optical filters and laser cavities, which are essential components in various optical systems.One of the key applications of the Fabry-Perot resonance is in the field of optical telecommunications. Fiber-optic communication systems often utilize Fabry-Perot filters to select specific wavelength channels for data transmission, enabling the efficient use of the available bandwidth in fiber-optic networks. These filters can be tuned by adjusting the mirror separation or the refractive index of the cavity, allowing for dynamic wavelength selection andreconfiguration of the communication system.Another important application of the Fabry-Perot resonance is in the field of laser technology. Fabry-Perot cavities are commonly used as the optical resonator in various types of lasers, providing the necessary feedback to sustain the lasing process. The high finesse of the Fabry-Perot cavity allows for the generation of highly monochromatic and coherent light, which is crucial for applications such as spectroscopy, interferometry, and precision metrology.In the realm of quantum physics, the Fabry-Perot resonance plays a crucial role in the study of cavity quantum electrodynamics (cQED). In cQED, atoms or other quantum systems are placed inside a Fabry-Perot cavity, where the strong interaction between the atoms and the confined electromagnetic field can lead to the observation of fascinating quantum phenomena, such as the Purcell effect, vacuum Rabi oscillations, and the generation of nonclassical states of light.Furthermore, the Fabry-Perot resonance has found applications in the field of optical sensing, where it is used to detect small changes in physical parameters, such as displacement, pressure, or temperature. The high sensitivity and stability of Fabry-Perot interferometers make them valuable tools in various sensing and measurement applications, ranging from seismic monitoring to the detection of gravitational waves.The Fabry-Perot resonance is a fundamental concept in optics that has enabled the development of numerous advanced optical technologies. Its versatility and importance in various fields of science and engineering have made it a subject of continuous research and innovation. As the field of optics continues to advance, the Fabry-Perot resonance will undoubtedly play an increasingly crucial role in shaping the future of optical systems and applications.。
Flow patterns and draining films created by inclined coherent water jets impinging on vertical walls
Flow patterns and draining films created by horizontal and inclined coherent water jets impinging on vertical wallsT.Wang,D.Faria,L.J.Stevens,J.S.C.Tan,J.F.Davidson,D.I.Wilson nDepartment of Chemical Engineering &Biotechnology,University of Cambridge,New Museums Site,Pembroke Street,Cambridge CB23RA,UKH I G H L I G H T SFlow patterns created by liquid jets impinging at angles off horizontal are studied. Little effect of gravity and contact angle at flow rates studied.Width and height of radial impingement region are predicted by the model. Falling film width is correlated with film jump radius.Formation of dry patches in falling film is predicted by the model.a r t i c l e i n f oArticle history:Received 1June 2013Received in revised form 11August 2013Accepted 24August 2013Available online 4September 2013Keywords:CleaningContact angle Fluid flow Impinging jet Surface tensiona b s t r a c tThe flow patterns created by coherent water jets created by solid stream nozzles impinging on vertical polymethylmethacrylate (Perspex)and glass surfaces were studied for nozzles with diameters 2–4mm at angles up to 7451from the horizontal.The flow rates studied ranged from 7.1to 133g s À1(26–480L h À1;jet velocities 2.6–10.6m s À1).The width and height of the film jump marking the limit of the radial flow zone were compared with models based on that developed by Wilson et al.(2011),modi fied to include the effect of gravity and the angle of inclination for non-horizontal jets (incorporat-ing the flow distribution model reported by Kate et al.(2007.Journal of Fluid Mechanics 573,247–263)).The location of the film jump and the flow pattern around the impingement point were sensitive to the nature of the substrate at low flow rates,but insensitive to substrate nature at higher flow rates.The models predicted the film jump location with reasonable accuracy,and the width of the wetted region at the mid-plane was found to follow a simple relationship to the film jump width there.A first-order model for the width of the rope of liquid draining around the film jump gave a lower bound estimate of this dimension.The falling film generated below the impingement point exhibited three forms of behaviour:a wide film,termed gravity flow ;a narrowing film,termed rivulet flow ,and a wide film which split into two with the formation of a dry patch .The transition to form a dry patch was found to obey the minimum wetting rate criterion reported by Hartley and Murgatroyd (1964),once loss of liquid due to splashback was accounted for.Dry patch formation within the falling film was only observed with upwardly impinging jets,and the tendency to form dry patches was predicted with some success by a simple two-stream model.&2013Elsevier Ltd.All rights reserved.1.IntroductionLiquid jets are widely used to remove surface soiling (fouling)layers when cleaning process equipment (Jensen,2011).Their use for cleaning the internals of tanks and other vessels is increasing as they offer several advantages over simple ‘fill and soak ’strategies in employing smaller volumes of liquid.Mechanical energy is required for pumping but this is usefully dissipated bythe liquid,usually water-based,as it flows over the soil:the flow imposes a shear stress which enhances soil break-down and increases convective heat transfer as well as mass transfer of soluble species into the liquid.The performance of jet cleaning systems such as spray balls,solid-stream nozzles,jet heads and rotating spray arms (e.g .in dishwashers)depends strongly on the wetting patterns of the liquid on the wall.For cases where cleaning arises primarily from the chemical or detergent action of the liquid,it is important to be able to predict whether the design will achieve complete coverage of the target area with liquid.For cases where cleaning also requires a high shear stress,knowledge of the shear stressContents lists available at ScienceDirectjournal homepage:/locate/cesChemical Engineering Science0009-2509/$-see front matter &2013Elsevier Ltd.All rights reserved./10.1016/j.ces.2013.08.054nCorresponding author.Tel.:þ441223334791.E-mail address:diw11@ (D.I.Wilson).Chemical Engineering Science 102(2013)585–601distribution is required.Both instances require a working knowl-edge of theflow patterns created by the liquid jet.This paper investigates theflow patterns created by coherent liquid jets impinging on vertical surfaces,such as are created by solid stream nozzles and by spray balls before the jet breaks up(caused by Rayleigh instabilities).Studies of spray jets in cleaning have been presented by Leu et al.(1998)and Meng et al.(1998).Theflow patterns generated by coherent liquid jets impinging vertically downwards on horizontal surfaces,giving circular regions of rapid,radialflow terminating with an abrupt change infilm height called the hydraulic jump,have been studied for over50years.The phenomenology,including the formation of surface waves and influence of surface tension,has been estab-lished and modelled by successive workers(e.g.Watson,1964; Bush and Aristoff,2003).The case of a non-vertical jet impinging on a horizontal plate and forming a non-circular hydraulic jump has been modelled by Blyth and Pozrikidis(2005),Kibar et al. (2010)and by Kate et al.(2007).Button et al.(2010)reported an elegant study and model of the less common case,where a liquid jetflowing vertically upwards impinges on a horizontal plate, spreads radially outwards and falls downwards to form a‘water bell’.The behaviour of jets impinging on vertical or near-vertical surfaces has received less attention despite its importance in cleaning.Morison and Thorpe(2002)reported a study of the contact region,drainingfilm and cleaning behaviour generated by individual spray ball jets operating at industrialflow rates.They studied jets created by spray ball holes with diameters1.6–2.4mm at pressures up to 3.6barg at velocities ranging from7to 28m sÀ1.Atomisation was not observed in their tests.On a vertical wall,the liquidflows radially outwards from the point of impingement until a feature resembling a hydraulic jump occurs, which is here termed thefilm jump.Knowledge of the location of thefilm jump is important as this is the boundary of the radialflow zone(RFZ)where the highest shear stresses are generated.Wilson et al.(2011)analysed Morison and Thorpe's data sets as well as new experimental data and showed that the size of the RFZ could be predicted by a simplified model derived from the work by Button et al.;in this simplified model thefilm jump occurs when the radially outwardflow of momentum is balanced by surface tension at radial location R(see Fig.1),given byR¼0:276_m3μργð1ÀcosβÞ"#1=4ð1Þwhere_m is the massflow rate,μis the liquid kinematic viscosity,ρits density,γis the gas–liquid surface tension andβthe contact angle.Beyond thefilm jump theflow pattern is complex.Fig.1shows schematics of three types of behaviour observed in this work.The pattern above the plane of impingement is common to all,where beyond thefilm jump the liquid falls circumferentially in a rope until it reaches the plane of impingement,beyond which it falls downwards.The width of the rope and RFZ at the impingement plane(labelled X–X)is2R c.An a priori prediction for R c is currently not available.Wilson et al.(2011)and Wang et al.(2013)observed that R c E2R at lowerflow rates and approached R c E4R/3at higherflow rates(above11g sÀ1for a3mm nozzle).Theflow rate at which the transition in R c/R behaviour occurred depended on the substrate and thus the contact angle.In the case where downward momentum dominates surface tension(Fig.1(a)),theflow forms a stable fallingfilm of width W, which is here termed gravityflow.Thefilm width may change gradually.In cases where surface tension is significant,two behaviours can arise:rivuletflow,Fig.1(b),where the liquid forms a narrow tail,and dry patch formation,Fig.1(c),where the falling film splits.Both rivuletflow and dry patch formation are undesir-able for cleaning applications.Wilson et al.studied waterflow rates which were low com-pared to those used in industrial cleaning jets,up to2.0g sÀ1,and observed either gravity or rivuletflow.They found that the occurrence of stable widefilms,of width W,could be predicted by the criterion for the minimum wetting rate,Γmin,for stable fallingfilms developed for evaporators by Hartley and Murgatroyd (1964)viz.Γ¼_m=W Z1:69ðμρ=gÞ0:2½γð1ÀcosβÞ 0:6¼Γminð2Þwhere g is the gravitational acceleration.The reliability of this criterion for higherflow rates is explored here.Wang et al.(2013)studied the effect of a surfactant,Tween20, for similarflow rates and found the presence of surfactant to have little influence on the size of thefilm jump,but strongly affected fallingfilm behaviour.This was attributed to dynamic contact angle effects:in the fallingfilm there was sufficient time for the surfactant to accumulate at the wetting line and influence the contact angle.The contact angle is also determined by the nature of the substrate.Wang et al.(2013)reported results for jets impinging on vertical glass and Perspex(polymethylmethacrylate)substrates, which have different water contact angles.At lowerflow rates (o11g sÀ1at201C),the location of thefilm jump was sensitive to substrate nature but at higherflow rates,obtained by Wang et al. using larger nozzles,thefilm jump location was insensitive to substrate nature.Drainingfilm behaviour continued to be sensitive to the substrate and static contact angle.XFig.1.Schematics offlow patterns,viewed from behind target in Fig.2,generated by a jet impinging on a vertical plate.O is the jet impingement point,R is the radius of the film jump,R c is the radius of the corona or rope at the impingement level(X–X).Z r is the height of inner radial zone above O;Z t is the maximum height of thefilm above O. The grey arrows show theflow pattern:radial from O to the jump;tangential around the rim.The polar coordinate isθ.Flow regimes below X–X are(a)Gravityflow,with a drainingfilm of width W at z,where z is the distance measured downwards from O.(b)Rivuletflow.(c)Gravityflow,with dry patch formation.T.Wang et al./Chemical Engineering Science102(2013)585–601586This paper reports an investigation of coherent water jets impinging on vertical walls at higher flow rates than those reported by Wilson et al.and Wang et al.The flow rates employed are at the low end of those used in industrial cleaning nozzle devices 1and establish some of the fundamental aspects of the flows in these devices.Wilson et al.'s model is modi fied to include gravitational effects as well as the case where the jet impinges at an oblique angle,i.e .the jet is not horizontal.2.Materials and methodsTwo apparatuses were used in this work.The majority of the results reported here were generated using the system in Fig.2,which consisted of a 1.2m Â1.2m Â1.7m high chamber with Perspex walls containing a vertical nozzle locating rail and a vertical target.The test liquid was tap water at room temperature.Cambridge water is hard (315ppm as calcium carbonate)and its surface tension was measured at 74.671mN m À1(Wilson et al.,2011).Water was pumped from a 26L holding tank through one of two rotameters,thereby covering the range of mass flow rates in the range 7–133g s À1(400–8000mL min À1).A flexible hoseallowed the elevation and angle of the nozzle on the locating rail to be adjusted as desired.The nozzles were fabricated from cylindrical brass blanks 9mm in diameter,and 30mm in length (see Fig.3).The dimensions of the nozzles are summarised in Table 1.The ori fice sizes,d N ,(i.d.2,3and 4mm)were selected to lie in the range of commercial cleaning-in-place (CIP)nozzles.The nozzle was connected to the entry pipe of inner diameter 7.5mm with a 150mm long straigh-tening section.The liquid jet from the nozzle impinged on the vertical target surface at a horizontal distance l away from the nozzle.For the tests reported here,l was approximately 50mm and the Reynolds number in the pipe upstream of the nozzle,Re pipe ,ranged from 1450to 10,800,while those in the nozzle throat,Re jet ,varied from 4300to 20,300.Re jet is calculated from Re jet ¼U o r o =ν,where U o and r o are the jet velocity and radius,respectively,and νis the liquid dynamic viscosity.Also shown in Table 1are the values of the coef ficient of velocity,C v ,for each nozzle.C v is de fined as the ratio of the actual velocity to the theoretical velocity calculated assuming plug flow across the nozzle cross-section.The actual velocity was deter-mined by a simple measurement of how high a vertical jet rose in air before gravity caused it to stop rising and cascade downwards.The results show that for d N ¼3mm and 4mm,covering the majority of tests reported here,C v ¼1and thus r o ¼d N /2.The target was a vertical plate of float glass (height 1000mm,width 800mm)mounted on an aluminium alloy frame.Water impinged on one side and the resulting flow pattern was photo-graphed using a Nikon 12megapixel camera located behind the target as shown in Fig.2.Transparent ruled tape was attached to the dry side of the target to allow distances to be read off photographs reliably.The width of the falling film at a given point,W ,was measured horizontally.The wetting rate at that point,Γ,was calculated from Γ¼_m=W .A separate Perspex plate could be attached to the frame.The advancing contact angle of the tap water on the glass was measured using a Kruss DSA 100S drop shape analyser as 39751;the value on Perspex was 72.5751.Surface roughness,R a ,was measured using a pro filometer.This gave R a for the glass of 0.008μm and that of the Perspex $0.02μm.At high flow rates there was noticeable splattering where liquid splashed back off the surface following impact.Splattering does not affect the velocity of the liquid in the radial flow zone,but it reduces the flow rate in the falling film and thus the wetting rate.The amount of splattering was measured by weighing the liquid which accumulated in the collection tray (Fig.2)over a set time and comparing this with the nozzle feed rate.The nozzle feed rate was measured separately by a catch and weigh method.The fraction splattered,ξ,was evaluated from ξ¼1À_mðcollected Þ_ð3ÞThe results in Fig.4show that there was little noticeable splatter-ing until Re jet reached 12,000for all three nozzles tested.Thenegative values on the plot at low Re jet values result from the uncertainty in the method for collecting the flow.At higher velocities ξincreased almost linearly with Re jet ,independentofFig.2.Schematic diagram of the apparatus for jet impinging onto a verticalsurface.Fig.3.Nozzle cross-section.Table 1Nozzle dimensions (see Fig.3)and flow parameters.Nozzle diameter,d N (mm)Internal diameter d i (mm)Inlet length,L i (mm)Throat length,L t (mm)Re pipeRe jetC v29 2.50.7580–57802170–17,1000.839 2.60.6580–79401440–19,8001492.40.82890–10,8005300–20,30011For example,a typical industrial 4mm diameter rotary jet cleaning head operating at 5barg would deliver water at a flow rate of 400g s À1.T.Wang et al./Chemical Engineering Science 102(2013)585–601587nozzle diameter.However,Fig.4(b)shows that the amount of splash back increased signi ficantly for upwardly inclined jets,with the largest amount of splash back at the greatest upward impinge-ment angle.The data were also compared with the models for splattering reported by Bhunia and Lienhard (1994)and Lienhard et al.(1992)for jets generated by flow through a long capillary striking a rigid flat surface.Those models did not give reliable predictions of the amount of splattering observed here,which is attributed to the use of convergent nozzles and a relatively short pipe entry length in this work.3.Model developmentTheoretical developments are presented in two sections.Section 1outlines models for predicting the size of the radial flow zone in the presence of gravity,the rope width,and the effect of jet inclination.Section 2describes an approach for predicting the formation of dry patches in the falling liquid film resulting from an inclined jet.3.1.Effect of gravity on the radial flow region for a horizontal jet impinging on a vertical surfaceFig.5(a)shows a schematic of a horizontal liquid jet with radius r oand volumetric flow rate,Q ,striking a vertical surface atimpingement point O.The jet is in plug flow with velocity U o ,where Q ¼πr 2o U o .The liquid flows radially away from the point of impingement:at a distance r (4r o )the film thickness is h and the local mean velocity is U .Following the analysis presented by Wilson et al.(2011),a momentum balance on a streamline gives d dr ðMr Þ¼d dr 65ρhU 2r¼Àτr Àrh ρg cos θð4Þwhere M is the momentum flux per unit width,ρis the liquid density,τthe wall shear stress and θis the angle of inclination of the streamline to the vertically upwards direction (see Fig.1(a)).Surface tension does not appear in (4)as it does not create a resultant force.In the RFZ the liquid film is assumed to have a well-developed laminar velocity pro file.The distance required to develop this pro file is discussed by Watson (1964)and Yeckel and Middleman (1987).For a Newtonian fluid the wall shear stressisFig.4.Effect of jet Reynolds number on splattered fraction ξ;no splattering is indicated by the horizontal dashed line,ξ¼0.The distance from the nozzle to the target plate is l ¼50mm.for (a)horizontal jets,d N ¼2,3and 4mm;(b)Effect of jet inclination angle,ϕ,with d N ¼3mm.Solid symbols –downward jet,ϕo 901;open symbols,upward jet,ϕZ 901.Data in (b)provided by Atkinson and Suddaby (2013).ϕValues indegrees.Fig. 5.Schematic of (a)horizontal liquid jet impinging on a vertical surface,showing geometry of radial film (b)surface tension forces involved in termination of the radial film.T.Wang et al./Chemical Engineering Science 102(2013)585–601588given by (Nusselt,1916)τ¼3μU hð5ÞAssuming no loss due to splashback or spray formation,the local film thickness at r may be calculated from Q ¼2πhrUð6ÞCombining Eqs.(4)–(6)gives d dr QU 2π ¼À5πνU 2r 2Q À56Qg cos θ2πU ð7ÞSimplifyingd U ¼À10π2νU 2r 2Q À5g cos θð8ÞThe local velocity U at location r is obtained by integrating (8)subject to the boundary condition U ¼U o at r ¼r o .This analysis differs from that presented by Wilson et al.(simpli fied model)in the inclusion of the gravity term.The in fluence of gravity can be estimated by comparing the two terms on the right hand side.This implies that the deceleration of liquid moving vertically above thepoint of impingement is larger if gravity is included.The contribu-tion from gravity increases as U decreases,i.e .at large r .The flow stops spreading outwards at R when the radial momentum is matched by the force due to surface tension,shown in Fig.5(b).A force balance gives,as a boundary condition 6ρU 2Rh R ¼γð1Àcos βÞð9ÞSubstituting for h R using (6)with h ¼h R and r ¼R ,yields U R ¼5π3γð1Àcos βÞρQRð10ÞR is found by integrating (8)to give U (r )and finding the radial position which satis fies (10).This requires integration and is solved numerically to find R .The effect of θon R is compared with experimental observations in Section 4.2.At higher flow rates (such as shown later in Fig.15for _m¼50g s À1),the rope becomes less stable and the precise location of the termination of outward flow may be obscured by liquid from the rope falling down across the surface under the in fluence of gravity.This gravity model (Eqs.(8)–(10))indicates that the radial flow zone should be non-circular since the component of g acting in the direction of the streamline varies from –9.81m s À2to zero as the streamlines move from the vertical to the horizontal.This aspect was not considered by Wilson et al.(2011)in their study as their focus was on the width of the falling film generated by the impinging jet.The above analysis is not expected to apply to the flow below the impingement plane (labelled X –X in Fig.1)as gravity causes the flow to accelerate downwards and the boundary condition for the film jump is in fluenced by liquid draining from above.Eq.(9)does not include these effects.3.2.Flow in the ropeFig.6(a)describes a simple model for predicting the width of the rope region.The photograph in Fig.6(b)shows that the flow in this region is unstable:this model provides a first order descrip-tion of the phenomenon.The rope consists of liquid falling under gravity after its radial flow is terminated.The liquid descends,flowing around the edge of the film jump radius,r in ,while collecting more liquid from the radial flow.The rope width,r out Àr in ,increases from the crown down to the impingement plane.Below the latter the rope spreads out into the draining film.In this model,the radial flow zone is assumed to be circular and symmetrical.The values of r in and r out at θ¼01(i.e .the crown)are labelled Z r and Z t ,respectively,and are compared with experi-mental data in Fig.18(discussed later),while the corresponding values at θ¼901are labelled R and R c .Flow in the rope is assumed to increase uniformly with angle θup to 901.The rope width,D ,is small such that the average radius,r avg ¼1=2ðr in þr out Þ%r in .The cross section of the rope is assumed to be semi-circular,as shown in the inset in Fig.6(a),so that the width of the rope can be calculated from the cross sectional area,A .This shape assumption is unlikely to be accurate and the rope is expected to be wider than that calculated.The liquid flow is deemed to be proportional to the angular coordinate,θ,soAu ¼Q θ ¼Q θð11Þwhere u is the tangential velocity within the rope and θis inradians.A momentum balance on an element of rope,assuming negligible wall shear,then gives ρgAr in d θsin θ¼d ðρAu 2Þ¼ρQ2πd ðu θÞð12ÞFig. 6.(a)Schematic of the geometry and flow in the rope.Inset shows the assumed rope cross-section.(b)Photograph of the rope.Dashed line indicates location of the film jump.T.Wang et al./Chemical Engineering Science 102(2013)585–601589Combining(11)and(12),eliminating A,givesd dθðuθÞ22!¼gr inθ2sinθð13ÞIntegrating with the boundary condition uθ¼0atθ¼01gives the mean velocity as a function of the angular position,viz.u2 2gr in ¼2sinθθþ2ðcosθÀ1Þθ2Àcosθ¼f ropeðθÞð14ÞSubstituting u from(14)to(11)and assuming r in¼R gives an expression for A(θ)which can then be related to the width of the rope,D at that position,fromDðθÞ¼2ffiffiffiffiffiffiffiffiffiffiffiffiffiQffiffiffiffiffiffiffiffiffi2gRpsffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiθffiffiffiffiffiffiffiffiffiffiffiffiffiffiffif ropeðθÞqv uu tð15Þ3.3.Obliquely impinging jets(oblique jet model)The analysis is extended to non-horizontal jets impinging on a vertical surface,employing theflow distribution model presented by Kate et al.(2007)for jets impinging obliquely on a horizontal surface.The angle of impingement,α,is defined as positive if approaching the impingement point from above,see Fig.7(a).The geometry is simplified if the angle to the vertical,labelledϕ,is used,whereαþϕ¼π/2.The following paragraphs summarise the Kate et al.model.The circular jet forms an elliptical zone on impact,as shown in Fig.7(b).Kate et al.showed that in the initial impingement zone liquid moves radially outward from a source,labelled S,located a distance r o cotϕfrom the point of impingement,O.Applying Bernoulli's equation in this(small)impingement zone shortly after the start of thefilm implies that the mean velocity in thefilm is U o at the edge of the ellipse.Beyond this ellipse the liquidflows radially but loses energy against wall friction,as in model I.A.S lies at one of the foci of the ellipse,and the radial distance from S to the edge of the impingement zone where u¼U o,r e,at angleθto the major axis(as shown in thefigure)is given byr e r o ¼sinϕ1þcosϕcosθð16ÞKate et al.also showed that the height of thefilm,h p,at the radial distance of a point,r p,located on the plate,is given byh p¼r2esinϕ2r pð17ÞBeyond the edge of the ellipse,radialflow is assumed to continue. Applying continuity to the element offlow dQ along a streamline at angleθyieldsdQ¼U o h e r e dθ¼Uhrdθr Z r eð18ÞSubstituting(17)in(18)gives1 2U o r2esinϕ¼rhUð19ÞThe momentum balance on a streamline(Eq.(8))can then be written asdρU r 2eU o sinϕ¼À5μUr2rUo e À5ρg cosθU o r2esinϕð20ÞThis simplifies todU dr ¼À10νU2or4esin2ϕr2U2À56g cosθUð21Þwhich collapses to Eq.(8)forϕ¼π/2.This needs to be integratednumerically,as in I.A.,if gravity is considered.Gravity is ignored in the following analysis to enable ananalytical solution to be obtained:Eq.(21)then givesÀZ UU odUU¼10νU2or4esinϕZ rr er2drð22Þwhich yields the analytical result1À1o¼10ν3U2or4esinϕðr3Àr3eÞð23ÞThe location of the jump at locations above point of impingementis given by the force balance(Eq.(10)),which is now written asU Rθ¼53γð1ÀcosβÞU oρr2e sinϕRθð24Þwhere the subscriptθis used to emphasise that the location of thejump depends on the value of the angle.Equating(23)and(24)togfilmjumpOFig.7.Geometry of impinging jet.(a)Side view,(b)end view.O marks the point ofimpingement.T.Wang et al./Chemical Engineering Science102(2013)585–601590find r ¼R θgives1R θ¼1θ3U o ρr 2e sin ϕ¼1o þ10ν3r 4e U 2osin ϕðR 3θÀr 3eÞð25ÞSubstituting (16)and (19)into (25)eliminating r e and takingU ¼U R in (19)and _m¼ρU o πr o 2gives R 4θ¼r o sin ϕ3À0:3r 2o _m sin 6ϕπμð1þcos ϕcos θÞ"#R θþ0:18_msin 9ϕπ3ρμγð1Àcos βÞð1þcos ϕcos θÞð26ÞThis quartic in R θcan be solved numerically or analytically (seeWang et al.,2013).A useful approximation for illustrative purposes is obtained by setting 1/U o and r e 3to zero from (25)and using (16)to eliminate r e ,giving R 4θ¼950r 6e U 3o sin 3ϕρ2μγð1Àcos βÞ¼sin 9ϕð1þcos ϕcos θÞ9U 3or 6o ρ2μγð1Àcos βÞð27ÞFor the conditions considered in this paper,Eq.(27)gives close agreement with numerical solutions to (26),con firming that the above assumptions are justi fied.The effect of impingement angle is plotted in Fig.8(a)for the case of a 4mm diameter water jet impinging on Perspex (contact angle ¼72.51)at a flow rate of 0.1kg s À1.The location of the film jump is plotted in Cartesian co-ordinates with O as the origin,where x ¼R θsin θand y ¼R θcos θÀr o cot ϕ.The plots show that a jet inclined downwards (ϕo 901)projects a small fraction of the flow above the plane of impingement,whereas those inclined upwards project a larger fraction upwards,so that the film jump is located further uptheFig.8.Effect of impingement angle on predicted film jump shape for 100g s À1water jet from 4mm nozzle impinging on a vertical Perspex surface.(a)Ignoring gravity;(b)considering gravity.Cartesian co-ordinates centred on the point of impingement.ϕValues indegrees.Fig.9.Predicted maximum half-width of impingement zone for obliquely impinging jets.d N ¼4mm,Perspex surface,gravity neglected.(a)Downward jet,(b)upward jet.ϕValues in degrees.T.Wang et al./Chemical Engineering Science 102(2013)585–601591。
Principles of Plasma Discharges and Materials Processing第2章
CHAPTER 2BASIC PLASMA EQUATIONS AND EQUILIBRIUM2.1INTRODUCTIONThe plasma medium is complicated in that the charged particles are both affected by external electric and magnetic fields and contribute to them.The resulting self-consistent system is nonlinear and very difficult to analyze.Furthermore,the inter-particle collisions,although also electromagnetic in character,occur on space and time scales that are usually much shorter than those of the applied fields or the fields due to the average motion of the particles.To make progress with such a complicated system,various simplifying approxi-mations are needed.The interparticle collisions are considered independently of the larger scale fields to determine an equilibrium distribution of the charged-particle velocities.The velocity distribution is averaged over velocities to obtain the macro-scopic motion.The macroscopic motion takes place in external applied fields and in the macroscopic fields generated by the average particle motion.These self-consistent fields are nonlinear,but may be linearized in some situations,particularly when dealing with waves in plasmas.The effect of spatial variation of the distri-bution function leads to pressure forces in the macroscopic equations.The collisions manifest themselves in particle generation and loss processes,as an average friction force between different particle species,and in energy exchanges among species.In this chapter,we consider the basic equations that govern the plasma medium,con-centrating attention on the macroscopic system.The complete derivation of these 23Principles of Plasma Discharges and Materials Processing ,by M.A.Lieberman and A.J.Lichtenberg.ISBN 0-471-72001-1Copyright #2005John Wiley &Sons,Inc.equations,from fundamental principles,is beyond the scope of the text.We shall make the equations plausible and,in the easier instances,supply some derivations in appendices.For the reader interested in more rigorous treatment,references to the literature will be given.In Section2.2,we introduce the macroscopicfield equations and the current and voltage.In Section2.3,we introduce the fundamental equation of plasma physics, for the evolution of the particle distribution function,in a form most applicable for weakly ionized plasmas.We then define the macroscopic quantities and indicate how the macroscopic equations are obtained by taking moments of the fundamental equation.References given in the text can be consulted for more details of the aver-aging procedure.Although the macroscopic equations depend on the equilibrium distribution,their form is independent of the equilibrium.To solve the equations for particular problems the equilibrium must be known.In Section2.4,we introduce the equilibrium distribution and obtain some consequences arising from it and from thefield equations.The form of the equilibrium distribution will be shown to be a consequence of the interparticle collisions,in Appendix B.2.2FIELD EQUATIONS,CURRENT,AND VOLTAGEMaxwell’s EquationsThe usual macroscopic form of Maxwell’s equations arerÂE¼Àm0@H@t(2:2:1)rÂH¼e0@E@tþJ(2:2:2)e0rÁE¼r(2:2:3) andmrÁH¼0(2:2:4) where E(r,t)and H(r,t)are the electric and magneticfield vectors and wherem 0¼4pÂ10À7H/m and e0%8:854Â10À12F/m are the permeability and per-mittivity of free space.The sources of thefields,the charge density r(r,t)and the current density J(r,t),are related by the charge continuity equation(Problem2.1):@rþrÁJ¼0(2:2:5) In general,J¼J condþJ polþJ mag24BASIC PLASMA EQUATIONS AND EQUILIBRIUMwhere the conduction current density J cond is due to the motion of the free charges, the polarization current density J pol is due to the motion of bound charges in a dielectric material,and the magnetization current density J mag is due to the magnetic moments in a magnetic material.In a plasma in vacuum,J pol and J mag are zero and J¼J cond.If(2.2.3)is integrated over a volume V,enclosed by a surface S,then we obtain its integral form,Gauss’law:e0þSEÁd A¼q(2:2:6)where q is the total charge inside the volume.Similarly,integrating(2.2.5),we obtaind q d t þþSJÁd A¼0which states that the rate of increase of charge inside V is supplied by the total currentflowing across S into V,that is,that charge is conserved.In(2.2.2),thefirst term on the RHS is the displacement current densityflowing in the vacuum,and the second term is the conduction current density due to the free charges.We can introduce the total current densityJ T¼e0@E@tþJ(2:2:7)and taking the divergence of(2.2.2),we see thatrÁJ T¼0(2:2:8)In one dimension,this reduces to d J T x=d x¼0,such that J T x¼J T x(t),independent of x.Hence,for example,the total currentflowing across a spatially nonuniform one-dimensional discharge is independent of x,as illustrated in Figure2.1.A generalization of this result is Kirchhoff’s current law,which states that the sum of the currents entering a node,where many current-carrying conductors meet,is zero.This is also shown in Figure2.1,where I rf¼I TþI1.If the time variation of the magneticfield is negligible,as is often the case in plasmas,then from Maxwell’s equations rÂE%0.Since the curl of a gradient is zero,this implies that the electricfield can be derived from the gradient of a scalar potential,E¼Àr F(2:2:9)2.2FIELD EQUATIONS,CURRENT,AND VOLTAGE25Integrating (2.2.9)around any closed loop C givesþC E Ád ‘¼ÀþC r F Ád ‘¼ÀþC d F ¼0(2:2:10)Hence,we obtain Kirchhoff’s voltage law ,which states that the sum of the voltages around any loop is zero.This is illustrated in Figure 2.1,for which we obtainV rf ¼V 1þV 2þV 3that is,the source voltage V rf is equal to the sum of the voltages V 1and V 3across the two sheaths and the voltage V 2across the bulk plasma.Note that currents and vol-tages can have positive or negative values;the directions for which their values are designated as positive must be specified,as shown in the figure.If (2.2.9)is substituted in (2.2.3),we obtainr 2F ¼Àre 0(2:2:11)Equation (2.2.11),Poisson’s equation ,is one of the fundamental equations that we shall use.As an example of its application,consider the potential in the center (x ¼0)of two grounded (F ¼0)plates separated by a distance l ¼10cm and con-taining a uniform ion density n i ¼1010cm 23,without the presence of neutralizing electrons.Integrating Poisson’s equationd 2F d x 2¼Àen i eFIGURE 2.1.Kirchhoff’s circuit laws:The total current J T flowing across a nonuniform one-dimensional discharge is independent of x ;the sum of the currents entering a node is zero (I rf ¼I T þI 1);the sum of voltages around a loop is zero (V rf ¼V 1þV 2þV 3).26BASIC PLASMA EQUATIONS AND EQUILIBRIUMusing the boundary conditions that F ¼0at x ¼+l =2and that d F =d x ¼0at x ¼0(by symmetry),we obtainF ¼12en i e 0l 22Àx 2"#The maximum potential in the center is 2.3Â105V,which is impossibly large for a real discharge.Hence,the ions must be mostly neutralized by electrons,leading to a quasi-neutral plasma.Figure 2.2shows a PIC simulation time history over 10210s of (a )the v x –x phase space,(b )the number N of sheets versus time,and (c )the potential F versus x for 100unneutralized ion sheets (with e /M for argon ions).We see the ion acceleration in (a ),the loss of ions in (b ),and the parabolic potential profile in (c );the maximum potential decreases as ions are lost from the system.We consider quasi-neutrality further in Section 2.4.Electric and magnetic fields exert forces on charged particles given by the Lorentz force law :F ¼q (E þv ÂB )(2:2:12)FIGURE 2.2.PIC simulation of ion loss in a plasma containing ions only:(a )v x –x ion phase space,showing the ion acceleration trajectories;(b )number N of ion sheets versus t ,with the steps indicating the loss of a single sheet;(c )the potential F versus x during the first 10210s of ion loss.2.2FIELD EQUATIONS,CURRENT,AND VOLTAGE 2728BASIC PLASMA EQUATIONS AND EQUILIBRIUMwhere v is the particle velocity and B¼m0H is the magnetic induction vector.The charged particles move under the action of the Lorentz force.The moving charges in turn contribute to both r and J in the plasma.If r and J are linearly related to E and B,then thefield equations are linear.As we shall see,this is not generally the case for a plasma.Nevertheless,linearization may be possible in some cases for which the plasma may be considered to have an effective dielectric constant;that is,the “free charges”play the same role as“bound charges”in a dielectric.We consider this further in Chapter4.2.3THE CONSERVATION EQUATIONSBoltzmann’s EquationFor a given species,we introduce a distribution function f(r,v,t)in the six-dimensional phase space(r,v)of particle positions and velocities,with the interpret-ation thatf(r,v,t)d3r d3v¼number of particles inside a six-dimensional phasespace volume d3r d3v at(r,v)at time tThe six coordinates(r,v)are considered to be independent variables.We illus-trate the definition of f and its phase space in one dimension in Figure2.3.As particles drift in phase space or move under the action of macroscopic forces, theyflow into or out of thefixed volume d x d v x.Hence the distribution functionaf should obey a continuity equation which can be derived as follows.InFIGURE2.3.One-dimensional v x–x phase space,illustrating the derivation of the Boltzmann equation and the change in f due to collisions.time d t,f(x,v x,t)d x a x(x,v x,t)d t particlesflow into d x d v x across face1f(x,v xþd v x,t)d x a x(x,v xþd v x,t)d t particlesflow out of d x d v x across face2 f(x,v x,t)d v x v x d t particlesflow into d x d v x across face3f(xþd x,v x,t)d v x v x d t particlesflow out of d x d v x across face4where a x v d v x=d t and v x;d x=d t are theflow velocities in the v x and x directions, respectively.Hencef(x,v x,tþd t)d x d v xÀf(x,v x,t)d x d v x¼½f(x,v x,t)a x(x,v x,t)Àf(x,v xþd v x,t)a x(x,v xþd v x,t) d x d tþ½f(x,v x,t)v xÀf(xþd x,v x,t)v x d v x d tDividing by d x d v x d t,we obtain@f @t ¼À@@x(f v x)À@@v x(fa x)(2:3:1)Noting that v x is independent of x and assuming that the acceleration a x¼F x=m of the particles does not depend on v x,then(2.3.1)can be rewritten as@f @t þv x@f@xþa x@f@v x¼0The three-dimensional generalization,@f@tþvÁr r fþaÁr v f¼0(2:3:2)with r r¼(^x@=@xþ^y@=@yþ^z@=@z)and r v¼(^x@=@v xþ^y@=@v yþ^z@=@v z)is called the collisionless Boltzmann equation or Vlasov equation.In addition toflows into or out of the volume across the faces,particles can “suddenly”appear in or disappear from the volume due to very short time scale interparticle collisions,which are assumed to occur on a timescale shorter than the evolution time of f in(2.3.2).Such collisions can practically instantaneously change the velocity(but not the position)of a particle.Examples of particles sud-denly appearing or disappearing are shown in Figure2.3.We account for this effect,which changes f,by adding a“collision term”to the right-hand side of (2.3.2),thus obtaining the Boltzmann equation:@f @t þvÁr r fþFmÁr v f¼@f@tc(2:3:3)2.3THE CONSERVATION EQUATIONS29The collision term in integral form will be derived in Appendix B.The preceding heuristic derivation of the Boltzmann equation can be made rigorous from various points of view,and the interested reader is referred to texts on plasma theory, such as Holt and Haskel(1965).A kinetic theory of discharges,accounting for non-Maxwellian particle distributions,must be based on solutions of the Boltzmann equation.We give an introduction to this analysis in Chapter18. Macroscopic QuantitiesThe complexity of the dynamical equations is greatly reduced by averaging over the velocity coordinates of the distribution function to obtain equations depending on the spatial coordinates and the time only.The averaged quantities,such as species density,mean velocity,and energy density are called macroscopic quantities,and the equations describing them are the macroscopic conservation equations.To obtain these averaged quantities we take velocity moments of the distribution func-tion,and the equations are obtained from the moments of the Boltzmann equation.The average quantities that we are concerned with are the particle density,n(r,t)¼ðf d3v(2:3:4)the particlefluxG(r,t)¼n u¼ðv f d3v(2:3:5)where u(r,t)is the mean velocity,and the particle kinetic energy per unit volumew¼32pþ12mu2n¼12mðv2f d3v(2:3:6)where p(r,t)is the isotropic pressure,which we define below.In this form,w is sumof the internal energy density32p and theflow energy density12mu2n.Particle ConservationThe lowest moment of the Boltzmann equation is obtained by integrating all terms of(2.3.3)over velocity space.The integration yields the macroscopic continuity equation:@n@tþrÁ(n u)¼GÀL(2:3:7)The collision term in(2.3.3),which yields the right-hand side of(2.3.7),is equal to zero when integrated over velocities,except for collisions that create or destroy 30BASIC PLASMA EQUATIONS AND EQUILIBRIUMparticles,designated as G and L ,respectively (e.g.,ionization,recombination).In fact,(2.3.7)is transparent since it physically describes the conservation of particles.If (2.3.7)is integrated over a volume V bounded by a closed surface S ,then (2.3.7)states that the net number of particles generated per second within V ,either flows across the surface S or increases the number of particles within V .For common low-pressure discharges in the steady state,G is usually due to ioniz-ation by electron–neutral collisions:G ¼n iz n ewhere n iz is the ionization frequency.The volume loss rate L ,usually due to recom-bination,is often negligible.Hencer Á(n u )¼n iz n e (2:3:8)in a typical discharge.However,note that the continuity equation is clearly not sufficient to give the evolution of the density n ,since it involves another quantity,the mean particle velocity u .Momentum ConservationTo obtain an equation for u ,a first moment is formed by multiplying the Boltzmann equation by v and integrating over velocity.The details are complicated and involve evaluation of tensor elements.The calculation can be found in most plasma theory texts,for example,Krall and Trivelpiece (1973).The result is mn @u @t þu Ár ðÞu !¼qn E þu ÂB ðÞÀr ÁP þf c (2:3:9)The left-hand side is the species mass density times the convective derivative of the mean velocity,representing the mass density times the acceleration.The convective derivative has two terms:the first term @u =@t represents an acceleration due to an explicitly time-varying u ;the second “inertial”term (u Ár )u represents an acceleration even for a steady fluid flow (@=@t ;0)having a spatially varying u .For example,if u ¼^xu x (x )increases along x ,then the fluid is accelerating along x (Problem 2.4).This second term is nonlinear in u and can often be neglected in discharge analysis.The mass times acceleration is acted upon,on the right-hand side,by the body forces,with the first term being the electric and magnetic force densities.The second term is the force density due to the divergence of the pressure tensor,which arises due to the integration over velocitiesP ij ¼mn k v i Àu ðÞv j Àu ÀÁl v (2:3:10)2.3THE CONSERVATION EQUATIONS 31where the subscripts i,j give the component directions and kÁl v denotes the velocity average of the bracketed quantity over f.ÃFor weakly ionized plasmas it is almost never used in this form,but rather an isotropic version is employed:P¼p000p000p@1A(2:3:11)such thatrÁP¼r p(2:3:12) a pressure gradient,withp¼13mn k(vÀu)2l v(2:3:13)being the scalar pressure.Physically,the pressure gradient force density arises as illustrated in Figure2.4,which shows a small volume acted upon by a pressure that is an increasing function of x.The net force on this volume is p(x)d AÀp(xþd x)d A and the volume is d A d x.Hence the force per unit volume isÀ@p=@x.The third term on the right in(2.3.9)represents the time rate of momentum trans-fer per unit volume due to collisions with other species.For electrons or positive ions the most important transfer is often due to collisions with neutrals.The transfer is usually approximated by a Krook collision operatorf j c¼ÀXbmn n m b(uÀu b):Àm(uÀu G)Gþm(uÀu L)L(2:3:14)where the summation is over all other species,u b is the mean velocity of species b, n m b is the momentum transfer frequency for collisions with species b,and u G and u L are the mean velocities of newly created and lost particles.Generally j u G j(j u j for pair creation by ionization,and u L%u for recombination or charge transfer lossprocesses.We discuss the Krook form of the collision operator further in Chapter 18.The last two terms in(2.3.14)are generally small and give the momentum trans-fer due to the creation or destruction of particles.For example,if ions are created at rest,then they exert a drag force on the moving ionfluid because they act to lower the averagefluid velocity.A common form of the average force(momentum conservation)equation is obtained from(2.3.9)neglecting the magnetic forces and taking u b¼0in theÃWe assume f is normalized so that k f lv ¼1.32BASIC PLASMA EQUATIONS AND EQUILIBRIUMKrook collision term for collisions with one neutral species.The result is mn @u @t þu Ár u !¼qn E Àr p Àmn n m u (2:3:15)where only the acceleration (@u =@t ),inertial (u Ár u ),electric field,pressure gradi-ent,and collision terms appear.For slow time variation,the acceleration term can be neglected.For high pressures,the inertial term is small compared to the collision term and can also be dropped.Equations (2.3.7)and (2.3.9)together still do not form a closed set,since the pressure tensor P (or scalar pressure p )is not determined.The usual procedure to close the equations is to use a thermodynamic equation of state to relate p to n .The isothermal relation for an equilibrium Maxwellian distribution isp ¼nkT(2:3:16)so thatr p ¼kT r n (2:3:17)where T is the temperature in kelvin and k is Boltzmann’s constant (k ¼1.381Â10223J /K).This holds for slow time variations,where temperatures are allowed to equilibrate.In this case,the fluid can exchange energy with its sur-roundings,and we also require an energy conservation equation (see below)to deter-mine p and T .For a room temperature (297K)neutral gas having density n g and pressure p ,(2.3.16)yieldsn g (cm À3)%3:250Â1016p (Torr)(2:3:18)p FIGURE 2.4.The force density due to the pressure gradient.2.3THE CONSERVATION EQUATIONS 33Alternatively,the adiabatic equation of state isp¼Cn g(2:3:19) such thatr p p ¼gr nn(2:3:20)where g is the ratio of specific heat at constant pressure to that at constant volume.The specific heats are defined in Section7.2;g¼5/3for a perfect gas; for one-dimensional adiabatic motion,g¼3.The adiabatic relation holds for fast time variations,such as in waves,when thefluid does not exchange energy with its surroundings;hence an energy conservation equation is not required. For almost all applications to discharge analysis,we use the isothermal equation of state.Energy ConservationThe energy conservation equation is obtained by multiplying the Boltzmannequation by12m v2and integrating over velocity.The integration and some othermanipulation yield@ @t32pþrÁ32p uðÞþp rÁuþrÁq¼@@t32pc(2:3:21)Here32p is the thermal energy density(J/m3),32p u is the macroscopic thermal energyflux(W/m2),representing theflow of the thermal energy density at thefluid velocityu,p rÁu(W/m3)gives the heating or cooling of thefluid due to compression orexpansion of its volume(Problem2.5),q is the heatflow vector(W/m2),whichgives the microscopic thermal energyflux,and the collisional term includes all col-lisional processes that change the thermal energy density.These include ionization,excitation,elastic scattering,and frictional(ohmic)heating.The equation is usuallyclosed by setting q¼0or by letting q¼Àk T r T,where k T is the thermal conduc-tivity.For most steady-state discharges the macroscopic thermal energyflux isbalanced against the collisional processes,giving the simpler equationrÁ32p u¼@32pc(2:3:22)Equation(2.3.22),together with the continuity equation(2.3.8),will often prove suf-ficient for our analysis.34BASIC PLASMA EQUATIONS AND EQUILIBRIUMSummarySummarizing our results for the macroscopic equations describing the electron and ionfluids,we have in their most usually used forms the continuity equationrÁ(n u)¼n iz n e(2:3:8) the force equation,mn @u@tþuÁr u!¼qn EÀr pÀmn n m u(2:3:15)the isothermal equation of statep¼nkT(2:3:16) and the energy-conservation equationrÁ32p u¼@@t32pc(2:3:22)These equations hold for each charged species,with the total charges and currents summed in Maxwell’s equations.For example,with electrons and one positive ion species with charge Ze,we haver¼e Zn iÀn eðÞ(2:3:23)J¼e Zn i u iÀn e u eðÞ(2:3:24)These equations are still very difficult to solve without simplifications.They consist of18unknown quantities n i,n e,p i,p e,T i,T e,u i,u e,E,and B,with the vectors each counting for three.Various simplifications used to make the solutions to the equations tractable will be employed as the individual problems allow.2.4EQUILIBRIUM PROPERTIESElectrons are generally in near-thermal equilibrium at temperature T e in discharges, whereas positive ions are almost never in thermal equilibrium.Neutral gas mol-ecules may or may not be in thermal equilibrium,depending on the generation and loss processes.For a single species in thermal equilibrium with itself(e.g.,elec-trons),in the absence of time variation,spatial gradients,and accelerations,the2.4EQUILIBRIUM PROPERTIES35Boltzmann equation(2.3.3)reduces to@f @tc¼0(2:4:1)where the subscript c here represents the collisions of a particle species with itself. We show in Appendix B that the solution of(2.4.1)has a Gaussian speed distribution of the formf(v)¼C eÀj2m v2(2:4:2) The two constants C and j can be obtained by using the thermodynamic relationw¼12mn k v2l v¼32nkT(2:4:3)that is,that the average energy of a particle is12kT per translational degree offreedom,and by using a suitable normalization of the distribution.Normalizing f(v)to n,we obtainCð2p0d fðpsin u d uð1expÀj2m v2ÀÁv2d v¼n(2:4:4)and using(2.4.3),we obtain1 2mCð2pd fðpsin u d uð1expÀj2m v2ÀÁv4d v¼32nkT(2:4:5)where we have written the integrals over velocity space in spherical coordinates.The angle integrals yield the factor4p.The v integrals are evaluated using the relationÃð10eÀu2u2i d u¼(2iÀ1)!!2ffiffiffiffipp,where i is an integer!1:(2:4:6)Solving for C and j we havef(v)¼nm2p kT3=2expÀm v22kT(2:4:7)which is the Maxwellian distribution.Ã!!denotes the double factorial function;for example,7!!¼7Â5Â3Â1. 36BASIC PLASMA EQUATIONS AND EQUILIBRIUMSimilarly,other averages can be performed.The average speed vis given by v ¼m =2p kT ðÞ3=2ð10v exp Àv 22v 2th !4p v 2d v (2:4:8)where v th ¼(kT =m )1=2is the thermal velocity.We obtainv ¼8kT p m 1=2(2:4:9)The directed flux G z in (say)the þz direction is given by n k v z l v ,where the average is taken over v z .0only.Writing v z ¼v cos u we have in spherical coordinatesG z ¼n m 2p kT 3=2ð2p 0d f ðp =20sin u d u ð10v cos u exp Àv 22v 2th v 2d v Evaluating the integrals,we findG z ¼14n v (2:4:10)G z is the number of particles per square meter per second crossing the z ¼0surfacein the positive direction.Similarly,the average energy flux S z ¼n k 1m v 2v z l v in theþz direction can be found:S z ¼2kT G z .We see that the average kinetic energy W per particle crossing z ¼0in the positive direction isW ¼2kT (2:4:11)It is sometimes convenient to define the distribution in terms of other variables.For example,we can define a distribution of energies W ¼12m v 2by4p g W ðÞd W ¼4p f v ðÞv 2d vEvaluating d v =d W ,we see that g and f are related byg W ðÞ¼v (W )f ½v (W ) m (2:4:12)where v (W )¼(2W =m )1=2.Boltzmann’s RelationA very important relation can be obtained for the density of electrons in thermal equilibrium at varying positions in a plasma under the action of a spatially varying 2.4EQUILIBRIUM PROPERTIES 3738BASIC PLASMA EQUATIONS AND EQUILIBRIUMpotential.In the absence of electron drifts(u e;0),the inertial,magnetic,and fric-tional forces are zero,and the electron force balance is,from(2.3.15)with@=@t;0,en e Eþr p e¼0(2:4:13) Setting E¼Àr F and assuming p e¼n e kT e,(2.4.13)becomesÀen e r FþkT e r n e¼0or,rearranging,r(e FÀkT e ln n e)¼0(2:4:14) Integrating,we havee FÀkT e ln n e¼constorn e(r)¼n0e e F(r)=kT e(2:4:15)which is Boltzmann’s relation for electrons.We see that electrons are“attracted”to regions of positive potential.We shall generally write Boltzmann’s relation in more convenient unitsn e¼n0e F=T e(2:4:16)where T e is now expressed in volts,as is F.For positive ions in thermal equilibrium at temperature T i,a similar analysis shows thatn i¼n0eÀF=T i(2:4:17) Hence positive ions in thermal equilibrium are“repelled”from regions of positive potential.However,positive ions are almost never in thermal equilibrium in low-pressure discharges because the ion drift velocity u i is large,leading to inertial or frictional forces in(2.3.15)that are comparable to the electricfield or pressure gra-dient forces.Debye LengthThe characteristic length scale in a plasma is the electron Debye length l De.As we will show,the Debye length is the distance scale over which significant charge densities can spontaneously exist.For example,low-voltage(undriven)sheaths are typically a few Debye lengths wide.To determine the Debye length,let us intro-duce a sheet of negative charge having surface charge density r S,0C/m2into an。
BLOW-UP AND BLOW-UP RATE FOR A COUPLED SEMILINEAR PARABOLIC SYSTEM WITH NONLOCAL BOUNDARIES
B LOW -U P AN D B LOW -UP R AT E F O R AC OU P LED SE M ILIN E A R P A R A BO LIC S YST EMW IT H N ON LO CA L B OU N DA R IE SZhengqiu Ling(I nstitute of Ma th.and I nfor ma tion Science,Yulin Nor ma l Un iver sity,Yulin 537000,Guan gxi,E-m ail:lingzq00@ )Ann.of Di .Eqs.29:2(2013),151-158Ab st ra ctT his pa per dea ls wit h t he blow-up pr op ert ies of p ositive solut ions to a coupled sem ilinear par a bolic system wit h nonlin ear nonloca l sour ces a nd nonloca l b oun dar ie s.Und er a ppr op riat e hypoth eses,th e global exist ence a nd nite tim e blow-u p of solut ions a r e pr oved.M oveover ,t he upp er b ou nd of blow-up r a te is obt a ined.K e yw or d s p ar ab olic system ;global exist ence;blow-u p;blow-up r a te 2000M a t h e m a t ic s S u b je c t C la ss i c a t io n 35K40;35K55;35B 401In t r o d u ct io nIn t his paper,we st udy t he blow-up and t he blow-up rat e of posit ive solut ion t o t he following sem ilinear parabolic system coupled wit h nonlinear nonlocal sources and nonlocal boundariesu i t =u i +∫u p ii +1(x,t)dx,i =1,,k,u k +1:=u 1,x ∈,t >0,u i (x,t )=∫ψi (x,y)u i (y,t )dy,i =1,,k,x ∈,t >0,u i (x,0)=u i ,0(x),i =1,,k,x ∈,(1.1)where R N is a bounded domain wit h smoot h boundary ;exponent s p i >0,ψi (x,y)isa cont inuous and nonnegat ive funct ion de ned for ×;u i ,0(x)∈C 2,ν()wit h 0<ν<1,u i ,0(x)≥0sat is es t he compat ibilit y conditions,i =1,2,,k.The semilinear parabolic syst em like (1.1)const it ut es a simple coupled example of react ion-di usion syst em,such as heat propagat ions in a t wo-com ponent com bustible m ix-t ure [1]for k =2,where u 1and u 2represent t he t emperat ures of two di erent mat erials during a propagat ion.When k =1or k =2,many import ant result s concerning t he blow-up and global existence of solut ions have been est ablished.At rst ,in the case of a single equat ionu t =u +f (u),(1.2)t he blow-up properties of positive solution have been studied ext ensively,see for exam ple,[2-4].In particular,Souplet [3]st udied a di usion equat ion wit h space int egral source terms or space-t ime int egral source terms,and int roduced a m et hod t o investigat e t he pro le ofTh is work was suppor ted by t he NNSF of China (11071100).Ma nusc ript r eceived Augu st 15,2012;R evised Decem ber 19,2012151152ANN.OF DIF F.E QS.Vol.29blow-up solut ions t hen observed t he asym pt ot ic blow-up behaviors of t he solut ions.As for k =2,Escobedo and Herrero [5]considered t he blow-up of t he solut ions t o t he following syst emu t =u +v p ,v t =v +u q (1.3)in a bounded domain wit h null Dirichlet boundary condit t ely,Zheng [6]and Kong[7]extended t he result s of [5],where t hey st udied syst emsu t =u +u p 1v q 1,v t =v +u p 2v q 2,(1.4)u t =u +∫u m v n dx,v t =v +∫u p v q dx,(1.5)respect ively.Several int erest ing result s about t he condit ions for blow-up and global exist ence have been est ablished.For t he systemsu it =u i +u pii +1,i =1,,k,u k+1:=u 1,(1.6)t here have been many results for t he blow-up rat es and blow-up set ,see for exam ple,[8-10].For t he ot her relat ed works,we refer t he readers t o [11,12]and references therein.Mot ivat ed by t he above result s,in t his paper we st udy t he blow-up rat e and t he pro le of t he posit ive solution t o (1.1).Moreover,we assume that k ≥3.2M ax im u m P rin cip leIn this sect ion,we give t he maximum principle and comparison principle.For conveni-ence,set Q T =×(0,T),Q T =×[0,T),S T =×(0,T).On t he ot her hand,we use t hat C or C i t o denot e a generic const ant depending only on t he st ruct ural dat a of problem,and it m ay be di erent even in t he sam e formula.D e n it i on 1A pair of funct ions (u 1(x,t ),,u k (x,t ))is called a super-solution t o(1.1),if u i (x,t)∈C 2,1(Q T )∩C (Q T )sat is esu i t ≥u i +∫u pi i +1(x,t)dx,i =1,,k,u k +1:=u 1,(x,t )∈Q T ,u i (x,t)≥∫ψi (x,y)u i (y,t )dy,i =1,,k,(x,t )∈S T ,u i (x,0)≥u i ,0(x),i =1,,k,x ∈.(2.1)A sub-solut ion can be de ned in a similar w ay.Lem m a 1(Maximum principle)Suppos e that c i (x,t )and d i (x,t )are continuous,nonne-gative funct ions de ned on Q T and ×,respecti vely.ωi (x,t )∈C 2,1(Q T )∩C (Q T )sati s es M (ωi ):=ωi t ωi ∫c i (x,t)ωi +1(x,t)dx ≥0,i =1,,k,(x,t )∈Q T ,ωi (x,t )≥∫d i (x,y)ωi (y,t )dy,i =1,,k,(x,t )∈S T ,ωi (x,0)≥0,i =1,,k,x ∈,(2.2)where ωk +1:=ω1.For any t ∈[0,T ),x ∈,if the functions c i (x,t )and d i (x,y)satisfy 0≤∫c i (x,t )dx ≤C i ,0≤∫d i (x,y)dy <1,i =1,,k,respectively.Then ωi (x,t)≥0(i =1,,k)in Q T .No.2Z.Q.Ling,BLOW-UP AND BLOW-UP RAT E 153P r oof The proof of t he maxim um principle for parabolic equations is quit e st andard.Here we shall sket ch t he argum ent for convenience.Suppose that t he st rict inequalit ies of (2.2)hold,t hen we assert t hat ωi (x,t )>0(i =1,,k)on Q T .According t o ωi (x,0)>0,x ∈,by cont inuit y,t here exist s a δ>0such t hat ωi (x,t )>0for all x ∈,0≤t ≤δ.Let A ={δ≤T :ωi (x,t )>0,(x,t )∈×[0,δ],i =1,,k}and t =sup A,t hen 0<t ≤T.If t <T,t hen ωi (x,t)≥0holds in ×(0,t ],and at least one of ω1,,ωk vanishes at (x,t )for some x ∈.Furt hermore,by the boundary condit ions we know t hat x ∈.Wit hout loss of generalit y,we suppose ω1(x,t )=0.In view of t he boundary condit ions,we know t hat ω1>0on ×(0,t].So ω1t akes the nonnegat ive m inimum on Q t at (x,t).T henM (ω1)(x,t)=ω1t (x,t )ω1(x,t)∫c 1(x,t)ω2(x,t)dx ≤0.This contradict s (2.2).Hence t =T ,t hat is ωi (x,t)>0(i =1,,k)on Q T .Now,w e consider t he general case.Take a const ant K satisfyingK ≥k ∑i =1∫c i (x,t )dxand set v i =ωi +εe K t ,i =1,,k,where εis any xed posit ive const ant.In view of (2.2),we can getM (v i )=M (ωi )+εe K t(K ∫c i (x,t)dx )>0,i =1,,k,(x,t)∈Q T ,v i (x,t)>∫d i (x,y)v i (y,t )dy,i =1,,k,(x,t)∈S T ,v i (x,0)>0,i =1,,k,x ∈.(2.3)Therefore,we have v i (x,t )>0on Q T .Let ε→0+,it follows t hat ωi (x,t )≥0(i =1,,k)on Q T .Based on t he above lemma,we obt ain t he following comparison principle.Lem m a 2Assume that ∫ψi (x,y)dy <1(i =1,,k)for all x ∈.L et (u 1,,u k )and (u 1,,u k )be t he sub-solution and the super -solut ion t o problem (1.1)on Q T ,re-spect ively.If (u 1(x,0),,u k (x,0))≤(u 1(x,0),,u k (x,0))in ,then (u 1,,u k )≤(u 1,,u k )in Q T .Sim ilar t o t he analysis of Theorem 3.1in [4],we have the following lemm a.Lem m a 3L et ω0(x)and f (x,y)be t he cont inuous and nonnegative functions on and ×,respectively.Assume that t he nonnegative const ant s θi j sat isfy 0<θi1+θi 2≤1,i =1,,k.Then the solution t o t he nonlocal problemωt =ω+k∑i =1ωθi 1(x,t )∫ωθi 2(x,t )dx,x ∈,t >0,ω(x,t)=∫f (x,y)ω(y,t)dy,x ∈,t >0,ω(x,0)=ω0(x),x ∈(2.4)exis ts globally.154ANN.OF DIF F.E QS.Vol.293G lob al E x ist en ce a n d B low-u pWe assume t hat is a bounded domain in R N wit h C2boundary.In t his sect ion,λ1 andφ1(x)denot e t he rst eigenvalue and t he rst eigenfunct ion of t he following eigenvalue problemφ(x)=λφ(x),x∈;φ(x)=0,x∈,(3.1) andφ1(x)sat is es t he posit ivit y conditionφ1(x)>0,x∈,∫φ1(x)dx= 1.By const ruct ing t he super-solut ion and sub-solut ion,we obt ain t he global exist ence andblow-up result s.T he or em1Assume that ∫ψi(x,y)dy<1(i=1,,k)for all x∈.If theexponents p i(i=1,,k)satisfy p1p2p k≤1,then the s olution to(1.1)exists globally for any nont rivi al nonnegat ive i niti al condition.P r oof From p1p2p k≤1,t here exist a i∈(0,1),i=1,,k,such t hatp1≤a1a2,p2≤a2a3,,p k≤a ka1.(3.2)That is a1≥p1a2,,a k1≥p k1a k,a k≥p k a1.Denot ea=1a1+1a2++1a kand let(x,y)≥max{ψi(x,y),i=1,,k}be a cont inuous funct ion de ned on×and z(x,t)be a solut ion t o t he following problemz t=z+ak∑i=1z1a i(x,t)∫z a i(x,t)dx,x∈,t>0,z(x,t)=(k∑i=1g i(x))∫(x,y)z(y,t)dy,x∈,t>0,z(x,0)=1+k∑i=1u1a ii,0(x),x∈,(3.3)whereg i(x)=(∫(x,y)dy)1a ia i,i=1,...,k,x∈.In view of Lem ma3,z(x,t)exist s globally,and t he m aximum principle implies that z(x,t)>1in×[0,∞).Setu1(x,t)=z a1(x,t),u2(x,t)=z a2(x,t),,u k(x,t)=z a k(x,t).By a simple com put ation t oget her wit h(3.2),(3.3),we haveu i t≥u i+∫u p i i+1(x,t)dx,i=1,,k,u k+1:=u1,x∈,t>0,u i(x,t)≥∫ψi(x,y)u i(y,t)dy,i=1,,k,x∈,t>0,u i(x,0)≥u i,0(x),i=1,,k,x∈.No.2Z.Q.Ling,BLOW-UP AND BLOW-UP RAT E 155Therefore,(u 1,,u k )is a super-solut ion t o problem (1.1).In virt ue of Lemm a 2,(u 1,,u k )≤(u 1,,u k )on ×(0,∞).So (u 1,,u k )exist s globally.T he or em 2Assume that ∫ψi (x,y)dy <1(i =1,,k)for all x ∈.If exponents p i (i =1,,k)sat isfy p 1p 2,,p k 1p k ,p k p 1>1,then the solution t o (1.1)blow s up in nit e time for a large enough initial da ta.P r oof By p 1p 2,,p k 1p k ,p k p 1>1,there exist m 1,m 2,,m k >1such t hat1+p 11+p 2=m 1m 2,,1+p k 11+p k =m k 1m k,1+p k 1+p 1=m k m 1.(3.4)Hencep 1>m 1m 2,,p k1>m k 1m k ,p k >m km 1,namely,p 1m 2m 1=p 2m 1m 2>0,,p k1m km k1=p k m k1m k >0,p k m 1m k =p 1m km 1>0.(3.5)Denot e γ1=p 1m 2m 1+1,,γk1=p k1m km k1+1,γk =p k m 1m k +1and b 1=1m 1∫φp 1m 21(x)dx,,b k1=1m k1∫φp k1m k1(x)dx,b k =1m k∫φp km11(x)dx.Let γ=min{γ1,γ2,,γk },b =min{b 1,b 2,,b k },t hen γ> 1.Denot e s (t )be t he unique posit ive solut ion t o t he C auchy problem{s ′(t )=λs (t )+bs γ(t ),s(0)=s 0>0.(3.6)Due t o t he solution s (t)blows up in anit e t im e T (s 0)for sucient ly large s 0,setu 1(x,t )=sm 1(t )φm11(x),,u k (x,t)=sm k(t )φmk1(x).By a simple comput at ion t oget her with (3.1)and (3.6),we can getu i t ≤u i +∫u p ii+1(x,t )dx,i =1,,k,u k+1:=u 1,(x,t)∈Q T (s 0),u i (x,t)=0≤∫ψi (x,y)u i (y,t)dy,i =1,,k,(x,t)∈S T (s 0).(3.7)Therefore,t he init ial data u i ,0(x)is suciently large and sat is esu 1(x,0)=s m 10φm 11(x)≤u 1,0(x),,u k (x,0)=s m k 0φmk1(x)≤u k,0(x),x ∈.In view of Lemma 2,we can get (u 1,,u k )≤(u 1,,u k ).So t he solut ion (u 1,,u k )t o(1.1)blows up in a nite t ime.4B low-u p R at e E st im at eIn t his sect ion,under t he hypot heses p 1p 2,,p k1p k ,p k p 1>1and∫ψi (x,y)dy <1156ANN.OF DIF F.E QS.Vol.29(i =1,,k)for all x ∈,we discuss the blow-up rat e of solut ions t o problem (1.1).Denot ef i (t )=∫u p ii +1(x,t )dx,F i (t )=∫tf i (s )ds ,i =1,,k,u k+1:=u 1.Sim ilar t o Lem mas 4.1and 4.2,Theorem s 4.1and 4.2in [4],we rst show some propert iesof t he solut ion t o (1.1).Lem m a 4Let (u 1,,u k )be the classical solut ion to (1.1)in ×(0,T),which blows up in nit e time T.T hen we have(1)C 1≤u i ≤m ax {sup 0≤s ≤tf i (s ),C 1},i =1,,k,in ×[T/2,T)for some C 1>0;(2)0≤u i (x,t)≤C 2+F i (t),i =1,,k,in ×[T/2,T )for some C 2>0;(3)lim t →T u i (x,t)F i (t )=lim t →T ∥u i (t )∥∞F i (t)=1,i =1,,k,uniformly on com pact subset s of ;(4)lim t →T u it (x,t )f i (t )=1,lim t →T u i (x,t )f i (t )=0,i =1,,k,uniformly on compa ct subsets ofif u i ,0(x)+∫u p ii +1,0(x)dx ≥0in.In addit ion,by C ram er principle of linear syst em,we have t he following lem ma.Lem m a 5The fol lowing linear system1p 100001p 200..................0001p k1p k1α1α2...αk 1αk=11 (11)(4.1)has a unique posit ive s olution (α1,,αk )T which is given by αi =1+p i +k +i 2∑l =i +1p i p l 12k,p k+l :=p l ,and p i αi +1=1+αi ,i =1,,k.DenoteM i (t ):=sup ×[0,t ]u i (x,s ),i =1,,k.(4.2)Next ,we est ablish a relat ionship among M i (t ),and t hen give t he est im ates of u i near t he blow-up t ime T.Lem m a 6Let (u 1,,u k )be the cla ssical solut ion to (1.1)in ×(0.T),w hi ch blows up in nit e time T.T hen t here exi st T 1<T and δ∈(0,1)such t hatδm ax jM 1αjj(t )≤min iM 1αii(t),t ∈(T 1,T),(4.3)where (α1,,αk )is t he solution to (4.1).P r oof As in [10],we argue by cont radict ion.Without loss of generalit y,we assume t hat there exist s a sequence {t n }wit h t n →T as n →+∞and l ∈{2,3,,k}such t hatM 1α11(t n )=max jM 1αjj(t n ),M 1αll(t n )M 1α11(t n )→0.(4.4)No.2Z.Q.Ling,BLOW-UP AND BLOW-UP RAT E157 For each t n choose an(x n,t n)∈×(0,t n]such t hatu1(b x n,b t n)≥12M1(t n).Obviously,M1(t n)→+∞,hence,b t n→T.On t he ot her hand,from Lemma4,we know t hat t here exist a T1<T,such t hatu i t(x,t)≥0,(x,t)∈×(T1,T),(4.5)u i(x,t)≤2u i(b x n,t),(x,t)∈×(T1,T).(4.6) Choose a const ant A≥1and letλn:=λ(t n):=(12AM1(t n))12α1and funct ionsi,λn (y,s)=λ2αinu i(λ23n y+b x n,λ43n s+b t n),(y,s)∈n×I n(t n),i=1,,k,(4.7)wheren ={y|λ23n y+b x n∈},I n(t n)=(λ43n b t n,λ43n(t b t n)).Clearly,λn→0as n→∞,and(1,λn ,,k,λn)solves(i)s=i+∫n p ii+1(y,s)dy,i=1,,k,k+1:=1,(y,s)∈n×I n(T),(4.8)also1,λn (0,0)≥A.Moreover,when(y,s)∈n×(λ4/3nb tn,0]and t n≤T1,we have0≤1,λn(y,s)=λ2α1nu1(λ23n y+b x n,λ43n s+b t n)≤2λ2α1nu1(b x n,λ43n s+b t n)≤2λ2α1nu1(b x n,b t n)≤2(2A),(4.9)0≤i,λn(y,s)≤2(2A)αiα1,i=2,,k,(4.10)0≤l,λn(y,s)≤2(2A)αlα1(M1αll(t n)Mlα11(t n))αl.(4.11)It follows from t he parabolic est imat es in[13]t hat t here is a∈(0,1)such t hat for any K>0,∥i,λn ∥C2+,1+/2(n∩|y|≤K×[K,0])≤C K,where t he const ant C K is independent of n.Hence,w e obt ain a sequence converging t o a solut ion t o(4.8)in R N+×(∞,0]such t hat1(0,0)≥A and l≡0,which leads t o a cont radict ion.This prove(4.3)for t≥T1.Now we can easily derive the est imat e of t he blow-up rat e from Lemma6.T he or em3Let(u1,,u k)be t he classical solution to(1.1)in×(0,T),which blowsup in nite tim e T.Ifu i,0(x)+∫u p ii+1,0(x)dx≥0,i=1,,k,in,t hen t here exis ts a constant C>0s uch thatu i(x,t)≤C(T t)αi,i=1,,k,(x,t)∈×(0,T),(4.12) where(α1,,αk)is solution t o(4.1).158ANN.OF DIF F.E QS.Vol.29 P r oof It follows from(4)Lemm as4and6t hat there exist s a T2<T such t hatu i t(x,t)≤2f i(t)=2∫u p ii+1(x,t)dx,T2≤t<T,(4.13)M i+1(t)≤δαi+1Mαi+1αii(t),T2≤t<T.(4.14)Again by(4.13)we getM it(t)≤C M p i i+1(t),T2≤t<T.(4.15)Therefore,M i t(t)≤Cδp iαi+1Mp iαi+1αii(t)=Cδ1αi M1+αiαii(t).(4.16)Int egrat ing t his inequalit y,we ndM i(t)≤C(T t)αi,i=1,,k,T2≤t<T,and we conclude(4.12).R eferen ces[1] E.Esc obe do,M.A.He rr ero,Bounde dness a nd blow-up f or a semilinea r r ea ction-di usionsyst em,J.Di.E qua tions,89(1991),176-202.[2]L.Wa ng,Q.C hen,The asymp totic be havior of blow-up solut ion of loca lized nonlinea r equat ion,J.Ma th.Ana l.Appl.,200(1996),315-321.[3]P.Souplet,Un iform blow-up pro les a nd bounda r y b ehavior for di usion equa tion s wit h non-loca l nonlinear sour ce,J.Di.E quations,153(1999),374-406.[4]Z.G.Lin,Y.R.Liu,Uniform blow-up pr o les for di usion equa tions with nonlocal sour ce a ndnonloca l b ou ndar 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a sem iline ar pa r ab olic syst em wit h nonlocalbounda ries,Acta Ma th.Sci.,32A(2012),433-440.[12]K.Deng,B low-up ra tes for pa r ab olic system s,Z.Angew.M at h.P hys.,47(1996),132-143.[13] dyzenska ja,V.A.Solonnikov a nd N.Ur a l’ceva,Linear and Oua siline ar E quat ions ofP ar a bolic Typ e,Am er.M at h.Soc.,P r ovidence,RI,1968.(edited by Liangwei Huang)。
具对数源项的四阶双曲方程解的爆破
第42卷第1期吉林师范大学学报(自然科学版)Vol.42ꎬNo.1㊀2021年2月JournalofJilinNormalUniversity(NaturalScienceEdition)Feb.ꎬ2021收稿日期:2020 ̄12 ̄15基金项目:吉林省科技发展计划项目(20180520025JH)ꎻ吉林省教育厅 十三五 科学计划项目(JJKH20190547KJ)第一作者简介:初㊀颖(1984 )ꎬ女ꎬ吉林省长春市人ꎬ讲师ꎬ博士ꎬ硕士生导师.研究方向:偏微分方程.doi:10.16862/j.cnki.issn1674 ̄3873.2021.01.011具对数源项的四阶双曲方程解的爆破初㊀颖ꎬ程㊀镱(长春理工大学理学院ꎬ吉林长春130022)摘㊀要:主要研究了一类具对数源项的四阶双曲方程.首先利用Galerkin逼近得到了弱解的局部存在性ꎬ然后借助位势井方法证明了一定条件下解在无穷远处的爆破性.关键词:双曲方程ꎻ对数源项ꎻ位势井ꎻ爆破中图分类号:O175.2㊀㊀文献标志码:A㊀㊀文章编号:1674 ̄3873 ̄(2021)01 ̄0057 ̄040㊀引言考虑如下四阶双曲型方程:utt+Δ2u=uln|u|ꎬxɪΩꎬt>0ꎻu(xꎬt)=Δu(xꎬt)=0ꎬxɪƏΩꎬt>0ꎻu(xꎬ0)=u0(x)ꎬut(xꎬ0)=u1(x)ꎬxɪΩ.ìîíïïï(1)其中Ω⊂n(nȡ1)是具光滑边界ƏΩ的有界区域.近年来ꎬ非线性发展方程的研究已成为国内外众多数学工作者所关注的热点问题之一[1 ̄7]ꎬ尤其是具对数源项的发展方程解的爆破性质研究已取得很多重要结果[3 ̄7].C.Qu和W.Zhou[8]研究了四阶方程ut+D4u=|u|p-1u-1|Ω|ʏΩ|u|p-1udxꎬ利用位势井方法[9]ꎬ证明了一定条件下整体弱解的存在性和爆破结果.P.Li和C.Liu[3]考虑了一类具对数源项的抛物方程ut+Δ2u=|u|q-2uloguꎬ获得了弱解的存在唯一性及弱解在有限时刻的爆破结果.受上述文献的启发ꎬ一个自然的问题是如果考虑具对数源项的双曲方程ꎬ其解的性质会怎样?抛物方程解的性质研究较完善ꎬ但具对数源项的四阶双曲方程解的存在性和爆破性质还没有任何结果ꎬ这正是本文的研究方向ꎬ我们补充和推广了现有的研究结果.1㊀预备知识为了获得本文主要结果ꎬ首先引入一些记号㊁基本定义和重要引理.令1ɤpɤ+ɕꎬ对任意uɪLp(Ω)ꎬ u p表示u的Lp(Ω)的范数ꎬ以( ꎬ )表示L2(Ω)空间中的内积.记X=H10(Ω)ɘH2(Ω)ꎬX0=X\{0}.定义泛函:吉林师范大学学报(自然科学版)第42卷E(t)=12 ut 22+12 Δu 22-12ʏΩ|u|2ln|u|dx+14ʏΩ|u|2dxꎬJ(u)=12 Δu 22-12ʏΩ|u|2ln|u|dx+14ʏΩ|u|2dxꎬI(u)= Δu 22-ʏΩ|u|2ln|u|dx.Nehari流形:N={uɪX0|I(u)=0}ꎬ井深[10]:d=infuɪX0{supλ>0J(λu)}=infuɪNJ(u).(2)由J(u)和I(u)的定义有J(u)=12I(u)+14ʏΩ|u|2dx.(3)本文考虑问题(1)的弱解定义为:定义1㊀令T>0ꎬ如果utɪL2(0ꎬTꎻL2(Ω))ꎬu(xꎬ0)=u0(x)ꎬut(xꎬ0)=u1(x)ꎬ且满足对任意φɪXꎬ有(utꎬφ)+ʏt0(ΔuꎬΔφ)dτ=ʏt0(uln|u|ꎬφ)dτꎬa.e.ꎬtɪ[0ꎬT)ꎬ称u(xꎬt)ɪLɕ(0ꎬTꎻX0)是问题(1)在Ωˑ[0ꎬT)上的弱解.引理1㊀设uɪX0ꎬ有:(1)limλң0+J(λu)=0ꎬlimλң+ɕJ(λu)=-ɕ.(2)存在唯一的λ∗>0ꎬdJ(λu)dλλ=λ∗=0ꎬJ(λu)在0<λɤλ∗上单调递增ꎬ在λ∗<λ<+ɕ上单调递减ꎬ在λ=λ∗处取得最大值.(3)I(λu)>0ꎬλɪ(0ꎬλ∗)ꎬ<0ꎬλɪ(λ∗ꎬ+ɕ)ꎬ{I(λ∗u)=0.此引理的证明参见文献[1ꎬ3 ̄4].引理2㊀设uɪX0ꎬI(u)<0ꎬ则I(u)<2(J(u)-d).证明㊀uɪX0ꎬI(u)<0ꎬ由引理1(3)可知ꎬ存在λ∗ɪ(0ꎬ1)ꎬ使得I(λ∗u)=0.由式(2)和式(3)可得dɤJ(λ∗u)=12I(λ∗u)+14λ2∗ʏΩ|u|2dx<14ʏΩ|u|2dx=J(u)-12I(u)ꎬ故I(u)<2(J(u)-d).2㊀主要结果及证明定理1㊀假设u0ɪX0ꎬu1ɪL2(Ω)ꎬ则问题(1)存在一个局部弱解.证明㊀利用Galerkin逼近结合先验估计来证明弱解的存在性.第一步㊀构造逼近解设{wj(x)}为X中的标准正交基底ꎬ构造问题(1)的逼近解um(xꎬt)=ðmj=1gmj(t)wj(x)ꎬm=1ꎬ2ꎬ ꎬ满足(umtꎬwj)+ʏt0(ΔumꎬΔwj)dτ=ʏt0(umln|um|ꎬwj)dτ+(u1mꎬwj)ꎬj=1ꎬ2ꎬ ꎬmꎻ(4)u0m=um(xꎬ0)=ðmj=1gmj(0)wj(x)ңu0(5)85第1期初㊀颖ꎬ等:具对数源项的四阶双曲方程解的爆破在X中强收敛ꎻu1m=umt(xꎬ0)=ðmj=1gmjt(0)wj(x)ңu1(6)在L2(Ω)中强收敛.由式(4) (6)ꎬ可知在[0ꎬtm)存在局部弱解umꎬ其中0<tmɤTꎬ在下面的步骤中ꎬ利用先验估计来说明tm=T.第二步㊀先验估计对式(4)关于时间变量t求导ꎬ所得方程两端同时乘以gmjt(t)ꎬ并对j从1到m求和得12ddt umt 22+ Δum 22-ʏΩ|um|2ln|um|dx+12ʏΩ|um|2dxæèçöø÷=0ꎬ上式关于时间变量在[0ꎬt]上积分得Em(t)=Em(0).即umt 22+ Δum 22-ʏΩ|um|2ln|um|dx+12ʏΩ|um|2dx= umt(0) 22+ Δum(0) 22-ʏΩ|um(0)|2ln|um(0)|dx+12ʏΩ|um(0)|2dxɤC( u1 22+ u0 2X)-ʏΩ|um(0)|2ln|um(0)|dx.剩下的证明类似于文献[11]的定理1.定理2 设u0ɪX0ꎬu1ɪL2(Ω)ꎬ(u0ꎬu1)>0ꎬ满足E(0)<dꎬI(u0)<0ꎬu(xꎬt)是问题(1)的弱解ꎬ则u(xꎬt)在无穷远处爆破ꎬ即limtң+ɕu 22=+ɕ.证明㊀定义G(t)= u 22ꎬ直接计算可得Gᶄ(t)=2(uꎬut)ꎬGᵡ(t)=2 ut 22+2ʏΩuuttdx=2 ut 22+2ʏΩu2ln|u|dx-2ʏΩ|Δu|2dx=2 ut 22-2I(u).(7)借助于Cauchy ̄Schwarz不等式ꎬ有|Gᶄ(t)|2ɤ4G(t) ut 22.注意到E(t)=E(0)ꎬ计算得Gᵡ(t)G(t)-[Gᶄ(t)]2ȡ2G(t)( ut 22-I(u))-4G(t) ut 22=-2G(t)( ut 22+I(u))ȡ-2G(t)(2E(0)-2J(u)+I(u)).已知E(0)<dꎬ结合引理2ꎬ则2E(0)-2J(u)+I(u)<2d-2J(u)+2J(u)-2d=0.因此ꎬGᵡ(t)G(t)-[Gᶄ(t)]2>0.直接计算得(lnG(t))ᶄ=Gᶄ(t)G(t)ꎬ(8)(lnG(t))ᵡ=Gᶄ(t)G(t)æèçöø÷ᶄ=Gᵡ(t)G(t)-[Gᶄ(t)]2G2(t)>0ꎬ(9)95吉林师范大学学报(自然科学版)第42卷由式(9)可知(lnG(t))ᶄ=Gᶄ(t)G(t)关于t是单调递增的.结合这个事实ꎬ式(8)在[t0ꎬt]上积分得lnG(t)-lnG(t0)=ʏtt0(lnG(t))ᶄdτ=ʏtt0Gᶄ(t)G(t)dτȡGᶄ(t0)G(t0)(t-t0)ꎬ(10)其中0ɤt0<t.不等式(10)等价于G(t)ȡG(t0)eGᶄ(t0)G(t0)(t-t0).(11)由式(7)和引理2得Gᵡ(t)ȡ4(d-E(0))>0ꎬ结合(u0ꎬu1)>0ꎬ取t0足够小ꎬ使得Gᶄ(t0)>0ꎬG(t0)>0.因此ꎬ不等式(11)表明了limtң+ɕ u 22=+ɕ.参㊀考㊀文㊀献[1]GAZZOLAFꎬSQUASSINAM.Globalsolutionsandfinitetimeblowupfordampedsemilinearwaveequations[J].AnnIHPoincare ̄Anꎬ2006ꎬ23(2):185 ̄207.[2]吴秀兰ꎬ朱宏ꎬ徐洪爽ꎬ等.具非标准增长条件和正初始能量p ̄Laplace方程解的爆破[J].吉林师范大学学报(自然科学版)ꎬ2015ꎬ36(3):65 ̄68.[3]LIPꎬLIUC.Aclassoffourth ̄orderparabolicequationwithlogarithmicnonlinearity[J].JInequalApplꎬ2018ꎬ2018(1):1 ̄21. [4]MALꎬFANGZB.Energydecayestimatesandinfiniteblow ̄upphenomenaforastronglydampedsemilinearwaveequationwithlogarithmicnonlinearsource[J].MathMethodsApplSciꎬ2018ꎬ41(7):2639 ̄2653.[5]HEYꎬGAOHꎬWANGH.Blow ̄upanddecayforaclassofpseudo ̄parabolicp ̄Laplacianequationwithlogarithmicnonlinearity[J].ComputMathApplꎬ2018ꎬ75(2):459 ̄469.[6]CHENHꎬTIANS.Initialboundaryvalueproblemforaclassofsemilinearpseudo ̄parabolicequationswithlogarithmicnonlinearity[J].JDifferEquationsꎬ2015ꎬ258(12):4424 ̄4442.[7]NHANLCꎬTRUONGLX.Globalsolutionandblow ̄upforaclassofpseudop ̄Laplacianevolutionequationswithlogarithmicnonlinearity[J].ComputMathApplꎬ2017ꎬ73(9):2076 ̄2091.[8]QUCꎬZHOUW.Blow ̄upandextinctionforathin ̄filmequationwithinitial ̄boundaryvalueconditions[J].JMathAnalApplꎬ2016ꎬ436(2):796 ̄809.[9]SATTINGERDH.Onglobalsolutionofnonlinearhyperbolicequations[J].ArchRationMechAnꎬ1968ꎬ30(2):148 ̄172.[10]刘亚成ꎬ刘萍.关于位势井及其对强阻尼非线性波动方程的应用[J].应用数学学报ꎬ2004ꎬ27(4):523 ̄536.[11]GORKAP.LogarithmicKlein ̄Gordonequation[J].ActaPhysPolonBꎬ2009ꎬ40(1):59 ̄66.BlowupforaclassoffourthorderhyperbolicequationwithlogarithmicsourcetermCHUYingꎬCHENGYi(SchoolofScienceꎬChangchunUniversityofScienceandTechnologyꎬChangchun130022ꎬChina)Abstract:Itwasstudiedforaclassoffourth ̄orderhyperbolicequationswithlogarithmicsourceterm.LocalexistenceoftheweaksolutionwasobtainedbyGalerkinapproximation.Byusingpotentialwellmethodꎬtheblow ̄upresultofthesolutionatinfinityundercertainconditionswasderived.Keywords:hyperbolicequationꎻlogarithmicsourcetermꎻpotentialwellꎻblowup(责任编辑:孙爱慧)06。
Drug Delivery Strategies for Poorly Water-Soluble Drugs chapter 04
4Solid Lipid Nanoparticlesfor Drug DeliverySonja Joseph and Heike Bunjes4.1IntroductionSince many drugs with poor water solubility have lipophilic properties,lipid-based delivery systems are an interesting formulation option for such substances.Colloidal lipid carriers offer the advantage of being,in principle,applicable by virtually any route of administration, nonparenteral as well as parenteral,including pared to other types of nanoparticulate carriers such as,for example,colloidal fat emulsions,liposomes or mixed phospholipid micelles,solid lipid nanoparticles represent a relatively new type of carrier system that has not yet led to a commercial drug product.Thefirst preliminary attempt at preparing solid lipid nanoparticles was reported in1985[1]and thefirst successful approaches were described around1990[2–4].Since then,colloidal lipid suspensions have been under intensive investigation as a new type of carrier system,in particular for the parenteral administration of poorly water-soluble,lipophilic drugs.Solid lipid nanoparticles consist of a core of solid lipids which is surrounded by a shell of stabilizing agents and are usually dispersed in an aqueous medium.According to their classification as a colloidal system,their mean particle size is usually in the range between below100and several hundreds of nanometers.In the majority of cases,glycerides, fatty acids and fatty alcohols are used as matrix components in the preparation of solid lipid nanoparticles.As these substances are components of physiological lipids,they are expected to be well tolerated and are classified as‘generally recognized as safe’(GRAS) by the FDA[5].Matrix lipids based on waxes and solid paraffins are also well known in the preparation of biocompatible colloidal lipid dispersions but may not or may not be as easily biodegradable as the physiological lipids.The choice of matrix material thus Drug Delivery Strategies for Poorly Water-Soluble Drugs,First Edition.Edited by Dennis Douroumis and Alfred Fahr.©2013John Wiley&Sons,Ltd.Published2013by John Wiley&Sons,Ltd.104Drug Delivery Strategies for Poorly Water-Soluble Drugsdepends a lot on the intended type of administration of the formulation of interest.This also applies to the type of emulsifier which has to ensure a good stability of the formulation as well as a good physiological compatibility.The potential toxicity of the components has to be taken into particular consideration with regard to intravenous administration. There are only a few approved emulsifying agents available for parenteral administration, including phospholipids(e.g.lecithin),sodium oleate,sodium glycocholate,poloxamer 188,polysorbate80and sorbitan trioleate[6].Solid lipid nanoparticles were developed in order to improve the drug carrier properties of lipid carriers with a liquid or liquid crystalline matrix.In particular,they can be regarded as a further development of colloidal fat emulsions which are being used in parenteral nutrition(e.g.Intralipid R ,Lipofundin R )and as drug carrier systems(e.g.Disoprivan R , Etomidat-R Lipuro,Lipotalon R ,Stesolid R ).The high mobility of drug molecules in liquid emulsion droplets usually causes a burst release of drug from the carrier in biological fluids.It was hypothesized that the exchange of the liquid with a solid particle core might reduce the mobility of incorporated drug molecules and might thus provide the potential to sustain and/or control drug release.Furthermore,a better physical and chemical sta-bility was expected as a result of the solid physical state of the dispersed lipid phase. Also some advantages concerning the ease of surface modification enabling modification of pharmacokinetics and potential drug targeting were proposed[3,7–9].Not all these expectations have proven realistic(as will be discussed later in this chapter)but solid of lipid nanoparticles still remain an interesting formulation option.This chapterfirst introduces and compares the different methods to prepare solid lipid nanoparticles followed by a short discussion of their general physicochemical properties. Afterwards,the interaction of these carriers with lipophilic drugs is considered and thefinal section of the chapter deals with the administration aspects of these particles with special regard to the oral and parenteral way of administration,as these are the most challenging when dealing with poorly water-soluble substances.4.2Preparation Procedures for Solid Lipid NanoparticlesA broad variety of preparation techniques for solid lipid nanoparticles have been success-fully developed.These techniques can be roughly divided into those involving top-down processes such as dispersion of the lipid phase(melt dispersion,cold homogenization, precipitation from solvent-in-water emulsions)and bottom-up procedures usually involv-ing some kind of precipitation of the lipid particles from homogeneous systems(warm microemulsions,solutions in water-miscible organic solvents).Typically,top-down pro-cesses require rather high energy input whereas bottom-up procedures are lower-energy processes.In the following,the general principles of the different procedures are described, concluding with a comparison and a discussion of their use on different scales.4.2.1Melt Dispersion ProcessesAs most of the lipid matrix materials of interest have a melting point below100◦C,solid lipid nanoparticles can be conveniently prepared by dispersing the liquid melt intofine droplets in a hot,surfactant-containing aqueous phase(Figure4.1).Except for the elevatedSolid Lipid Nanoparticles for Drug Delivery 105Dispersion of solid lipid nanoparticlesCooling&Crystallization T < T crystallization Hot colloidal emulsionHot aqueous phase containing emulsifier Molten matrix lipid + drug (Pre-) Dispersion (a)(Rotor-stator mixer)Hot coarse emulsionT > Tmelt Melt dispersion (a–e)T > T melt (b) Classical high-pressure homogenization (a) High shear rotor-statordevices ω(d) Premix membraneemulsification (e) Ultrasonication(c) Microchannel homogenization30 mmFigure 4.1General processes of melt homogenization for the preparation of solid lipid nanoparticles and variations of the procedure.(a–c,e)Reproduced from [18]with permis-sion from Springer Science and Business Media.(d)Reproduced from [30]with permission from John Wiley and Sons.106Drug Delivery Strategies for Poorly Water-Soluble Drugstemperature required,the droplet generation process is completely analogous to that during the preparation of submicron lipid emulsions.This means that all the technologies estab-lished for emulsion preparation can be used[10].A broad variety of matrix lipids can be employed in melt dispersion processes.Classically,they are of a more nonpolar nature (such as triglycerides,waxes or paraffins)but the processing of more polar matrices such as fatty acids,fatty alcohols or partial glycerides,sometimes in combination with nonpolar ones,has also been described.Lipid soluble drugs are usually processed by dissolving them in the melt prior to droplet dispersion;this process may be supported by using a solution of the drug in a volatile organic solvent.The emulsification process is carried out at tem-peratures above the melting point of the lipid droplets to retain the liquid state.To solidify the particles after generation of the colloidal droplets,a cooling stage is required.The conditions of the cooling process need to be carefully chosen in order to ensure complete crystallization of the lipids.Some lipid matrix materials(e.g.monoacid triglycerides like trimyristin or trilaurin)exhibit extended supercooling in the colloidal state and require ade-quate thermal treatment to be crystallized[7,11].Usually,the cooling process is carried out batch-wise(e.g.in small vials positioned in a thermostat or in a stirred tank)but the use of micro heat exchangers has also been explored in an attempt to provide precisely controlled cooling conditions and to allow continuous processing[12].The physical transformations that take place during crystallization of the particles and potentially following polymorphic transitions of the lipids may impose particular requirements for the formulations of the nanoparticle dispersion.These aspects will be discussed in Section4.3.Melt dispersion of the matrix lipids usually is carried out as a two-step process involving a predispersion step(e.g.by high-shear rotor-stator vortexing)followed by disruption of the predispersed lipid phase into colloidal particles(Figure4.1).A variety of different technical principles,commonly employing high energy input,can be used to perform the second dispersion step(Figure4.1a–e)which will be outlined in the following.4.2.1.1Conventional High Pressure HomogenizationHomogenization with conventional high pressure homogenizers has been used for the preparation of solid lipid nanoparticles since they werefirst described in the beginning of the1990s[3,13].It is currently the most frequently employed preparation process even though special manufacturing equipment is required.Corresponding devices of dif-ferent designs and sizes are commercially available from several manufacturers(e.g.APV, Avestin,Niro Soavi,Microfluidics).In most cases,high pressure homogenizers push the predispersion through a homogenization valve,consisting of a narrow gap in the range of a few microns(Figure4.1(b)).Very high shear and expansion forces in laminarflows, inertia forces through energy dissipating eddies in turbulentflows as well as cavitation forces are responsible for the droplet disruption during the process.Similar processes occur in the microfluidizer which uses narrow channels to achieve droplet break-up[14]. Typically applied homogenization pressures are in the range of several hundred to about 1500–2000bar,and volume fractions of lipid phase of up to more than10%can easily be processed.Process parameters such as,e.g.the homogenization pressure and the number of homog-enization cycles as well as the formulation parameters such as the type of matrix lipid and emulsifier as well as their concentration ratio,the volume fraction of disperse phase and the quality of the predispersion,influence the mean particle size and the particle size distri-bution,which are typically in the range of50–ually,the particle size decreasesSolid Lipid Nanoparticles for Drug Delivery107 with increasing pressure and cycle number reflecting a higher energy input and a more intense droplet break-up.Multiple passes are often preferable to achieve narrower particle size distributions.Smaller particles were also observed with a higher ratio of emulsifier to matrix lipid as well as higher temperatures[15,16].When optimized formulations are processed under adequate conditions,small-size dispersions with narrow size distribution and good storage stability can be obtained.4.2.1.2Melt Dispersion in MicrochannelsAs a variation of the conventional high pressure homogenization process,the hot,coarse dispersion of molten lipids can be forced with high pressures through microchannel sys-tems yielding hot nanoemulsions(Figure4.1c).Customized micro structures of varying geometric principles have been established for the preparation of nanoemulsions[17,18] and further investigated for application in melt homogenization by a single passage[19]. The particle size and the particle size distribution of solid lipid nanoparticles obtained after microchannel homogenization in stainless steel microsystems depend on the homogeniza-tion pressure as well as on the geometric structure of the microchannels.The preparation of narrowly distributed solid lipid nanoparticles in a single passage requires pressures up to1500bar.4.2.1.3Membrane TechniquesMembrane structures can also be used to disrupt the droplets in the coarse pre-emulsion. The so-called premix membrane emulsification method developed in the late1990s[20] is related to the extrusion technique for the preparation of unilamellar liposomes with controlled particle size[21].A predispersed emulsion is extruded several times through the pores of a membrane yielding smaller emulsion droplets(Figure4.1d).In order to prepare uniform particle size products through premix membrane emulsification,the porous membrane must have a narrow pore size distribution and be strong enough not to deform or compact,even if pressure is applied[22].Premix membrane emulsification has been used for the preparation of simple[23]and multiple emulsions[24],solid lipid microcapsules [25],polymer micro-and nanoparticles[26,27]as well as low density lipoprotein(LDL) analogues[28,29].Recently,this technique was also established for the preparation of solid lipid nanoparticles[30,31].Very narrow particle size distributions of the solid lipid nanoparticles were observed in particular when using the membranes in a commercial pump-driven extruder.The process could,however,also be performed in a small-scale (≤1ml),hand-held extruder(as typically used for the preparation of liposomes)which allowed the rapid preparation of a large number of samples with short turn-round times. The processable concentrations of the lipid phase were in the range of those found in high pressure homogenization.The mean particle sizes of the lipid nanoparticle dispersions depended mainly on the membrane pore size and the number of extrusion cycles.Ratios of average pore size to average particle size in the range of1:0.5to1:2.5were obtained[30]. Most experiments were performed with track etched polycarbonate membranes but other types of membranefilters,as well as Shirasu Porous Glass(SPG)membranes could also be used[32,33].A different approach that does not rely on the preparation of a coarse pre-emulsion is used in the classical or‘direct’membrane emulsification process(Figure4.2).The liquid lipid phase is forced by low pressures(e.g.0.15to10bar,depending on the membrane pore size) through the pores of a membrane into the emulsifier-containing aqueous continuous phase.108Drug Delivery Strategies for Poorly Water-SolubleDrugsHot colloidal emulsionPorous MembraneT > T melt Dispersion of solid lipid nanoparticlesCooling &CrystallizationT < T crystallization Pressure(max. 9 bar)Figure 4.2Direct membrane emulsification for the formation of solid lipid nanoparticles.Mechanically robust membranes like glass or ceramic membranes are usually required for this process [22,34,35].Lipid droplets grow at the pore openings at the membrane surface and are stabilized by emulsifiers from the continuous phase.When the droplets reach a certain size,they are detached from the membrane by the stream of the aqueous phase which is recirculated over the membrane surface [22,34].The resulting particle size is primarily controlled by the type and pore size of the membrane and the particle size distributions are very narrow.For emulsions prepared with Shirasu Porous Glass membranes,typical ratios of average pore size to average particle size were obtained in the range from 1:2to 1:10[36,37].Although this process has mainly been used to prepare micron-sized drug delivery systems [22,38,39],there are also a few reports on the preparation of solid lipid nanoparticles [40–43].In these investigations,however,the self-emulsifying matrix lipid Gelucire 44/14was used,which is not likely to form common solid lipid nanoparticles and which does not require a special dispersion process.The processing of lipid materials containing Compritol 888or Precirol ATO 5stabilized with poloxamer 188did not yield fine colloidal dispersions but lipid particles in the upper nanometer range with high instability on storage were obtained [43,44].In principle,however,the preparation of stable,colloidal and narrowly distributed lipid dispersions on the basis of nonpolar lipids can be achieved when membranes with small pore diameters (100nm)are used [32].In most cases,the particles were,however,rather large as a result of the typical pore size to particle size ratios observed in this process.This and the long process times which often still lead to low concentrations of disperse lipid phase make this technique less promising for routine use in solid lipid nanoparticle preparation.4.2.1.4UltrasonicationIn several studies,probe ultrasonication has been reported for the preparation of solid lipid nanoparticles by melt dispersion.In this process,acoustic cavitation is the driving force of droplet disruption [45](Figure 4.1e).Upon collapse of the cavitation bubbles,high energySolid Lipid Nanoparticles for Drug Delivery109 is transferred into the dispersion.In the resulting hot spots,temperatures of approximately 5000◦C and pressures of about500bar have been determined[46].The particle size and the particle size distribution of the ultrasonicated dispersions are influenced by the energy performance of the probe as well as by the composition of the formulation[47,48].For solid lipid nanoparticle formulations,the formation of particles in the adequate size range has been reported[3,49]but the dispersion quality may be compromised due to the pres-ence of submicron-sized particles,resulting in instabilities during storage[3,50,51].More-over,particularly during long process times,the use of ultrasonication carries the risk of metal contamination from the probe[52].4.2.1.5Dispersion by High Shear Rotor-Stator DevicesRotor-stator vortexing(e.g.by UltraTurrax R ),which is commonly employed in the predispersion process,has also been used for the main homogenization stage[53,54] (Figure4.1a).Here,the droplet disruption depends on high shear forces resulting from the high energy input.As the energy input is typically lower than for most of the tech-niques described above,it is,however,rather difficult to produce homogeneous colloidal dispersions of solid lipid particles with this method.The use of optimized combinations of formulation and preparation conditions is crucial to achieve dispersions of accept-able quality[54].Often,rather coarse and heterogeneous lipid dispersions are obtained(e.g.see[55]).4.2.2Other Top-Down Processes4.2.2.1Precipitation from Solvent-in-Water EmulsionsInstead of as a melt,the lipid can also be emulsified as solution in non-water-miscible organic solvents(Figure4.3a).The matrix lipid and the pharmaceutically active ingre-dients are dissolved in a water-immiscible organic solvent and emulsified in the aque-ous phase containing emulsifier.Typically,the mixture is processed in a high-pressure homogenizer yielding a dispersion of nanodroplets by high energy input.Afterwards, the organic solvent is removed by evaporation under reduced pressure to precipitate the solid lipid nanoparticles.This process does not require any heat treatment or low melt-ing point of the lipid matrix materials,and particle sizes far below100nm have been achieved[4,56].However,triglyceride suspensions obtained by this method tended to be physically less stable than dispersions prepared by melt homogenization[56].More-over,residual amounts of organic solvent may lead to toxicological problems during the administration of these colloidal drug carrier systems,which is the major drawback of this preparation procedure.In a modification of the original procedure,Trotta et ed partially water soluble solvents with low toxicity instead of water-immiscible organic solvents[57].The dispersion process was accomplished with rotor-stator equipment.Upon dilution of the resulting emulsion with a large amount of water,colloidal lipid particles precipitated from the organic phase as a result of solvent extraction into the aqueous phase.As this process is dilution-based,relatively low concentrations of particles are obtained.In a further variation, the matrix lipid and drug were dissolved in diethyl ether and injected into a warm(40◦C) agitated,emulsifier-containing aqueous phase.Due to its low boiling point,the diethyl ether evaporated and thus the lipid precipitated from the dispersed droplets[58].110Drug Delivery Strategies for Poorly Water-Soluble Drugs Dispersion of solid lipid nanoparticles Aqueous phase containing emulsifierMatrix lipid + drugin water-immiscible organic solventsSolvent-in-water pre-emulsion Evaporation oforganic solvent&Precipitation ofmatrix lipid Solvent-in-water nanoemulsionCold high-pressure homogenization (a)Dispersion of solid lipid nanoparticlesLipophilic drug (+ emulsifier)CrystallizationSolid lipid/drug mixtureMilling T < T meltLipid microparticles Cold aqueous phase containing emulsifier T < T melt Molten matrix lipid (b)Figure 4.3Precipitation from solvent-in-water emulsions (a)and cold homogenization (b)for the preparation of solid lipid nanoparticles.4.2.2.2Cold HomogenizationA further possibility for the preparation of solid lipid particles is the high-pressure homo-genization of the lipid matrix in the solid state.A coarse dispersion of powdered lipids in the emulsifier-containing aqueous phase is processed below the melting point of the matrix lipid (Figure 4.3b).For drug incorporation,the matrix lipid is melted and the drug is dissolved or dispersed –sometimes with the aid of organic solvents.The solidified mixture is milled into microparticles in liquid nitrogen or using dry ice cooling [59–61].Also this technique allows the processing of the matrix lipid materials with a melting point above 100◦C,which cannot be used in melt homogenization,e.g.cholesterol (melting point ∼148◦C)[60].However,larger particles and rather broad particle size distributions often containing particles in the upper nanometer or even in the micrometer range were observed in spite of comparatively harsh homogenization conditions.Typically,higher pressures (1000–1500bar)and more homogenization cycles (30–40)are required than for melt homogenization[59,62].Due to the high energy input,heating of the dispersion may occur.Friedrich et al .measured product temperatures in the range of the melting point of the matrix lipid after processing at room temperature and observed increasing homogenization efficiency due to the partial melting of the lipids [61].Solid Lipid Nanoparticles for Drug Delivery 1114.2.3Precipitation from Homogeneous SystemsSolid lipid nanoparticles can also be precipitated from homogeneous solutions or colloidal systems.Such processes usually do not require the use of high energy input and can in most cases be performed with conventional laboratory equipment.Often,rather small particles can be obtained but –since supersaturation phenomena are commonly involved –it is sometimes not easy to prevent them from increasing in size.4.2.3.1Precipitation from Warm MicroemulsionsThe solidification of lipid nanoparticles upon precipitation from warm microemulsions introduced by Gasco et al .was the first preparation method published for colloidal solid lipid dispersions [2].This preparation principle is still widely used due to the simple process sequence.In the original process,fatty acids (e.g.stearic acid)were used as matrix con-stituents but the process was later extended also to other lipids [63,64].The molten matrix lipid (containing the drug)is mixed by mechanical stirring with the hot aqueous phase composed of water,emulsifier and cosurfactant.An optically transparent,homogeneous colloidal system is formed spontaneously in the heat and is subsequently diluted with cold water (2–3◦C)to precipitate solid lipid nanoparticles (Figure 4.4).Rather high dilution ratios are often required to obtain small-size dispersions,thus leading to low lipid concen-trations.Moreover,a high concentration of surface active additives (typical examples are phospholipids and bile salts),is usually employed to form the initial microemulsion.In consequence,the process was enhanced continuously:ultrafiltration,dialysis and centrifu-gation were used to concentrate the diluted nanoparticulate systems after precipitation asDispersion of solid lipid nanoparticlesHot aqueous phasecontaining emulsifier and cosurfactant Molten matrix lipid + drugWarm microemulsionDillution with cold wateror cooling & PrecipitationT = 2–3°C T > T Figure 4.4Precipitation from oil-in-water microemulsions for the preparation of solid lipid nanoparticles.112Drug Delivery Strategies for Poorly Water-Soluble Drugswell as to remove most of the cosurfactants [65–67].Freeze drying is typically performed to avoid particle growth in aqueous systems upon storage [68].Systems with modified compositions (usually based on a mixture of fatty alcohols and nonionic surfactants)allow direct cooling of the warm microemulsion to form solid lipid nanoparticles under stirring [69–75].Lipophilic drugs are processed with the lipophilic components of the microemulsion.The size of the resulting nanoparticle dispersion may be affected by drug loading and the composition of the microemulsion may require some adjustment to yield high-quality solid lipid nanoparticle dispersions [73].Although dilution of the microemulsion during precipitation is not required,these dispersions typically contain matrix lipid concentrations below 1%.Upon storage,the aqueous suspensions tend to display particle growth [70,71,76]and thus some kind of stabilization,e.g.by freeze drying,appears to be necessary.4.2.3.2Precipitation from Water-Miscible Organic SolventsThe precipitation of nanoparticulate solid material from water-miscible organic solvents such as acetone or ethanol (Figure 4.5)is becoming increasingly popular.A solution of lipid matrix material,drug and sometimes stabilizers is injected into an agitated,emulsifier-containing aqueous phase.The whole process can be carried out at room temperature [77]or at increased temperatures of the aqueous or organic phase,or both [66,78,79].The use of hot organic solutions may increase the solubility in the organic solvent.To improve dispersion of the lipidic ingredients,ultrasonication or a combination of heat treatment and ultrasonication or vortexing during the solvent injection has been used [80–82].InDispersion of solid lipid nanoparticlesAqueous phase containing emulsifier Matrix lipid + drug in water-miscibleorganic solventT ~ 20°C Injection&Precipitation(solid) Figure 4.5Precipitation from organic solution for the preparation of solid lipid nanoparticles.most cases,organic solvents are later removed from the dispersion,e.g.by evaporation at increased temperature and/or reduced pressure[78,83,84]or by centrifugation and subsequent redispersion of the concentrated solid lipid nanoparticles[79,85].Removal of organic solvents reduces toxicological problems and increases the colloidal stability of the dispersions.While the above-mentioned approaches use batch-wise processing,microchannel tech-niques allow the precipitation of lipid nanoparticles from organic solutions in a continuous process.Microchannel assemblies of different geometry(e.g.a co-flowing assembly with inner and outer capillaries or cross-shaped channels)were employed for the preparation of solid lipid nanoparticles[86–88].The solution of solid lipids in water-miscible solvents and the emulsifier-containing aqueous phase are injected simultaneously into the different channels of the microsystem by separate syringe pumps.When the phases are combined at the junction of the channels,the solvent starts to diffuse into the aqueous phase during the passage along the main,common channel.As a result of supersaturation of the lipid in the aqueous phase,solid lipid nanoparticles are formed.4.2.4Comparison of the Formulation Procedures and Scale-Up FeasibilityAn ideal preparation procedure would lead to the reproducible formation of lipid nanopar-ticle dispersions with narrow particle size distributions and would provide good control over the particle size range obtained.The particle size properties should be retained during storage without further processing steps which would make the process more tedious and expensive.In any case,the preparation method has to be compatible with the physico-chemical properties of the drug to be incorporated.For example,a heat-sensitive active pharmaceutical ingredient should be processed without or with only minimal heat expo-sure.Generally,the whole procedure should be gentle without too much stress on the formulation and its ingredients.The process would be easily scalable and would not require the use of sophisticated equipment.Clearly,the processes described above can only partially meet these criteria.The conventional high-pressure melt homogenization process appears particularly promising with regard to commercial production as it uses well-established instrument-ation that is available for very different scales.Several studies have proven the scaling-up potential of this manufacturing process[89,90].The particle size parameters can be reliably controlled by the homogenization conditions and storage-stable aqueous disper-sions are obtained with appropriate formulations.This also applies to the more recent modi-fications such as the premix membrane or high pressure microchannel emulsification. Concerning potentially negative influences on the formulation,heat and shear stress are parameters that cannot be avoided in the conventional melt homogenization process.For most lipophilic drugs,shear stress should not pose much of a problem.If so,the membrane techniques which involve lower energy densities[91]and typically lead to dispersions with very well-controlled particle size distributions may be an interesting alternative. Thermolabile ingredients may,however,suffer from the heat inevitably present during melt-dispersion processes.The high energy input upon pressurization combined with rather poor energy utilization in the high-pressure homogenization process leads to a temperature increase in the equipment dependent on the homogenization pressure(e.g.15◦C per cycle at 1250bar[92],2.5◦C per100bar for water[93])and the emulsion composition[94].From。
Agilent Bravo 96 固定吸管头 50
Agilent Bravo Liquid Handling Platform: 96 Channel Fixed Tip 50 µL Accuracy and PrecisionTechnical OverviewSummary• Bravo, 96 fi xed tip head, 50 µL capacity • 0.1 µL: 3.9% CV ± 4.4% accuracy• 0.5 µL: 2.0% CV ± 0.9% accuracy• 1.0 µL: 2.1% CV ± 2.1% accuracy• >1 µL: equal or better than 1 µL CVand accuracyIntroductionAutomated liquid handling devices are used in many processes performed in laboratories today. Liquid handling automation increases sample processing and throughput(1) and improves accuracy (desired dispensed volume is equal to the actual dispensed volume) and precision (a narrow distribution of dispensed volume) when compared to a person operating a handheld liquid pipettor. Automated liquid handling devices canalso signifi cantly reduce the occurrence of errors in a process(2). To further the effortto automate routine laboratory processes, Agilent Automation Solutions has developed the Bravo liquid handling platform.Bravo FeaturesThe Bravo has nine deck positions which accommodate any 96-, 384-, or 1,536-well SBS standard microplates. Deck positions can be confi gured with heating, cooling, and shaking stations, as well as maintaining open locations for tip boxes, sample microplates and reservoirs.The Bravo can be used with 8-, 16-, 96-,or 384-channel fi xed tip or disposable tip heads. Heads can be interchanged in a matter of seconds. The Bravo is designedto be used either standalone or as part ofa robotic laboratory automation system. Itis also designed to fi t inside some modelsof laminar fl ow hoods and retain laminarfl ow, thereby opening up cell-based plating and cellular assays to an automated liquid handling platform.Accuracy and Precision TestingThis technical note describes a method tomeasure the accuracy and precision of theBravo in conjunction with a 96 Channel50 µL Fixed Tip Head. The 50 µL fi xed tipswere tested at the lower end of the practicalvolume range (0.1-1 µL). Performance atvolumes > 1 µL meets or exceeds the 1 µLperformance. Measurements are determinedby dispensing a tartrazine/DMSO solutioninto dry microplates, fi lling the plates withwater, and measuring tartrazine absorbance.The product’s performance meets orexceeds CVs of 5% and accuracy of ± 10%of the desired volume across the practicalvolume range.Materials• Bravo with a 96 Channel 50 µL fi xed tiphead (product no. G5498B/G#044)• Agilent 96-well manual fi ll reservoir(product no. G5498B/G#049)• 96-well polystyrene, fl at bottom plates(Greiner 655101)• Tartrazine solution, 0.25% (w/v) dissolvedin dimethylsulfoxide [DMSO]• UV/Vis Spectrophotometer with a 405 nmfi lter (Thermo Multiskan Ascent)Method60 mL of tartrazine solution is poured intoa manual fi ll reservoir. The reservoir isplaced on position 2 of the Bravo. A 96-wellpolystyrene plate is placed on position 5.A VWorks liquid classes for 0.05-1 µLdispenses is utilized. A VWorks protocol iscreated and run in the following manner:1. Tips are primed by mixing 3 µL for10 cycles in the reservoir.2. 0.1, 0.5 or 1.0 µL tartrazine solution isaspirated from the manual fi ll reservoir.Aspirate parameters are 6 mm fromthe bottom of the plate, and precededby a 0 µL, 0.25 µL or 0.5 µL pre-aspiratevolume, respectively.3. 0.1, 0.5 or 1.0 µL tartrazine solutionis dispensed into the 96-well plate.Dispense parameters are 0 mm fromthe bottom of the plate, and followedby dispensing the pre-aspirate volumeof air.Dispensed volumes are diluted to 50 µL bythe addition of water (after washing tips inDMSO). Plates are centrifuged at 1,800 rpmfor 60 seconds to ensure full mixing andconsistent well menisci. Absorbance is readat 405 nm. Accuracy is calculated based onan equation derived from a tartrazine/DMSOcalibration curve consisting of data pointsat 0.05, 0.1, 0.25, 0.5, 1 and 1.5 µL, comparedto the actual absorbance value in each well.The Bravo has nine deck positions and can beconfi gured with interchangeable 8-, 16-, 96-, or 384- fi xedand disposable tip heads./chemThis item is intended for Research Use Only. Not for use in diagnostic procedures.Agilent Technologies shall not be liable for errors contained herein or for incidental or consequentialdamages in connection with the furnishing, performance, or use of this material.This information is subject to change without notice. © Agilent Technologies, Inc., 2015Published in the USA, February 9, 20155989-8844ENAbsorbance values in each well is used to determine the precision of the dispense. Coeffi cient of Variance (CV) calculations were made by dividing the standarddeviation by the mean. The accuracy and precision results are typical, based onaverages of three successive dispenses. Accuracy outliers are an average per plate. Results may vary, depending on individual experimental methods and liquid class optimization.Precision (% CV) 3.9 2.0 2.1% Accuracy (±) 4.40.9 1.5Outliers (± 5%)3122Outliers (± 10%)700Transfer time (seconds/plate)363738ResultsConclusionIn summary, the liquid handling capabilities of the Bravo liquid handling platform in conjunction with a 96 Channel 50 µL fi xed tip head provides precise, accurate and consistent liquid transfers. The 96 channel head can pipette across a broad volume range (0.1-50 µL), making it ideal forapplications requiring precise dispensing at very low volumes. The highly confi gurable deck of the Bravo liquid handling platform along with its compact footprint makes it ideal for many applications in the laboratory including compound sample transfers,genomic applications and cell-based assays.References:1. Sofi a MJ. Leveraging Compound ManagementCapabilities in Support of Drug Discovery: From Sample Archive to Sample Distribution — Driving Effi ciency and Improving Productivity. Laboratory Robotics Interest Group Meeting Oral Presentation, Jan. 2005.2. Holman JW, Miffl in TE, Felder RA, Demers LM. Evaluation of an automated preanalytical robotic workstation at two academic health centers. Clin Chem. 2002 Mar; 48(3): 540-8.Please contact your sales representativeif you have particular questions regarding your specifi c application. Supplemental information (protocol fi les and data analysis spreadsheets) are also available upon request.。
含对流的渗流方程的自相似解
含对流的渗流方程的自相似解邓键;黄锐【摘要】考虑含对流项的渗流方程(E)u/(E)t=△um+x·▽uq的径向自相似解的存在性,其中,q>m>1,x∈RN.注意到该方程具有伸缩不变性,故可考虑形如u(x,t)=t-αφ(t-β|x|)的相似解问题.对该方程建立了相似解的存在性理论,首先确立一个临界指标q* =m+2/N,当对流项的指标q≥q*时,对任意初值A>0,都存在一个单调递减的整体解.而对于m<q<q*的情形,当初值A充分小时,存在有限时刻趋于零的局部解.此外,证明了解关于初值的单调性:若A<B,则φ(r,A)<φ(r,B).【期刊名称】《华南师范大学学报(自然科学版)》【年(卷),期】2016(048)003【总页数】4页(P18-21)【关键词】对流;自相似解;径向解;存在性【作者】邓键;黄锐【作者单位】华南师范大学数学科学学院,广州510631;华南师范大学数学科学学院,广州510631【正文语种】中文【中图分类】O175.2Key words: convection; self-similar solution; radial solution; existence考虑如下含有对流项的渗流方程的自相似解问题其中q>m>1, xN.自相似解在刻画解的正则性与稳定性方面起着重要的作用.1934年,LERAY[1]指出了自相似解研究的重要性.此后,对自相似解的研究一直被人们所关注.对含有各种非线性源项以及吸收项的方程的自相似解的研究已经取得了丰富的成果:对含各种非线性源项的情形的研究[2-4],对含各种非线性吸收项的研究[5-10]. 而对于含有对流项的方程的研究却相对较少.1991年,ESCOBEDO和ZUAZUA[11]考虑了含有对流和吸收项的方程的相似解.2007年,BOUZELMATE等[12]考虑了如下非线性Ornstein-Uhlenbeck方程的径向自相似解的存在性及长时间渐近行为.假设u(x,t)是方程(1)的解,直接计算可以发现,通过伸缩变换其中,α=1/(q-1),β=(q-m)/(2(q-1)),uλ(x,t)仍然是方程(1)的解,因而可以寻找方程(1)的这种伸缩变换下不变的解,即自相似解.在变换(2)中取λ=1/t,则u(x,t)=t-αu(t-βx,1)=t-αφ(t-βx),满足如下方程αφ + βξ▽φ + Δφm+ ξ·▽φq=0(ξN).考虑方程(3)的径向解,即令φ(|ξ|)=φ(ξ), 则方程(3)化为既然解是径向对称的,则φ′(0)=0.为得到方程(4)的自相似解,考虑如下初值问题其中,A是正常数.本文考虑方程(1)的相似解的存在性,得到以下定理:定理1 令φ(r)=φ(r,A)为方程(4)对应初值条件(5)的解,则(i)如果βN≥α,对任意的A>0,方程(4)对应初值条件(5)存在一个单调递减趋于0的整体解,且φ(r)>0 (∀r>0).(ii)如果0<βN<α,则当A适当小时,方程(4)对应初值条件(5)存在一个单调递减趋于0的局部解,即存在r0>0使得φ(r0)=0.且当时,φ(r)>0.进一步可得如下比较结果:如果A<B, 则当φ(r,A)>0时,φ(r,A)<φ(r,B).下面证明自相似解的存在性及比较引理.由方程(4)和初值条件(5)可得利用不动点方法,易得方程(4)对应初值条件(5)存在局部解.下面证明其整体解的存在性.首先有如下引理.引理1 假设φ(r)是方程(4)对应初值条件(5)的解,则φ(r)在到达零点之前严格递减,即如果φ(r)>0,则必有φ′(r)<0.证明由式(6)可知,当r充分小时,φ′(r)<0. 假设存在r0,使得φ′(r0)=0,且当r<r0时, φ′(r)<0;当r≤r0时,φ(r)>0. 则显然有(φm)″(r0)≥0,而由方程(4)可得矛盾. 故引理1成立.证毕.下面将证明一个比较引理(引理3),为此,需要先证明以下引理:引理2 令φ(r)为如下方程对应初值条件(5)的解.则当r → 0+时,有.证明由方程(7)和初值条件(5),利用L’Hopital法则可得即,从0到r积分可得注意到,当g(r)→ 0时,有,则).进一步可得).又由方程(7)可得其中H(r)=∫0r(βNsN-1φ+κNsN-1φq-αsN-1φ)ds. 结合式(9)、(10)可得o(r3).把式(9)、(10)、(12)代入式(11)可得从0到r积分可得.证毕.引理3 令φ(r)=φ(r,A)和ψ(r)=ψ(r,B)是方程(4)对应初值条件(5)的2个解,其中φ(0)=A, ψ(0)=B,0<A<B,则φ(r,A)和ψ(r,B)在到达它们的第1个零点之前不能相交.证明令R1和R2分别表示φ(r)和ψ(r)的第1个零点,其中R1和R2也可能等于∞.假设存在正常数R0<min{R1,R2},使得φ(r)<ψ(r),r[0,R0), φ(R0)=ψ(R0).由引理1可知φ(r)和ψ(r)在[0,R0]上均严格递减.令 (0<k<1),则对某些适当小的k,必有φk(r)>ψ(r),r[0,R0]. 记K=sup{0<k<1;φk(r)>ψ(r),r}.则φK(r)≥ψ(r),r[0,R0]. 注意到φ(0)≥ψ(0),即,显然有K<1. 因而φK(R0)>ψ(R0).下面将证明φK(0)>ψ(0).事实上,若不然,必有φK(0)=ψ(0).注意到φK(r)满足由引理2可得当r>0充分小时,φK(r)<ψ(r),这与K的定义矛盾.进一步可证存在R(0,R0),使得φK(R)=ψ(R).事实上,若不然,则必存在ε>0,使得φK(r)-ψ(r)>ε,r[0,R0],这与K的定义矛盾.由此可得).代入方程(13)的第1个式子,可得即矛盾. 证毕.进一步可得如下存在性结果:引理4 令φ(r)是方程(4)对应初值条件(5)的解,则(i)如果βN≥α,对任意A>0,当r>0时,φ(r)>0;(ii)如果0< βN<α,当A适当小时,存在r0>0,使得φ(r0)=0, 且当时,φ(r)>0.证明(i) 反证法,令r0为φ(r)的第1个零点, 则(φm)′(r0)≤0.又由方程(4)可得对式(14)从0到r0积分可得矛盾.(ii) 由式(14)可得rN-1 (φm)′(r)+βrNφ+rNφq=∫0r(βN-α+Nφq-1)sN-1φds<∫0r(βN-α+NAq-1)sN-1φds.取A充分小使得βN-α+NAq-1<0, 则(φm)′(r)<-βrφ, 即,从0到r积分可得故存在r0>0使得φ(r0)=0.下面证明时,φ(r)>0. 令φ(r)=Aω(η),η=A(q-m)/2r. 则记,则由方程(15)可得,则有即,则η.证毕.由引理4(i)可知当βN≥α时,存在单调递减的整体解.进一步由方程(4)可知,当r→+∞时,φ(r)→ 0,再结合引理3和引理4可知定理1成立.【相关文献】[1] LERAY J.Sur le mouvement d’un liouide visqueux emplissant l’espace[J]. Acta Mathematica,1934,63(1):193-248.[2] GIGA Y, KOHN R V.Asymptotically self-similar blow-up of semilinear heat equations[J]. Communications on Pure and Applied Mathematics,1985,38:297-319.[3] GIGA Y.On elliptic equations related to self-similar solutions for nonlinear heat equations[J]. Hiroshima Mathematical Journal,1986,16:539-552.[4] FILIPPAS S, TERTIKAS A. On similarity solutions of a heat equation with a nonhomogeneous nonlinearity[J]. Journal of Differential Equations,2000,165(2):468-492.[5] BREZIS H,FRIEDMAN A.Nonlinear parabolic equations involving measures as initial conditions[J]. Journal de Mathématiques Pures et Appliquées,1983,62:73-97.[6] PELETIER L A,TERMAN D.A very singular solution of the porous media equation with absorption[J]. Journal of Differential Equations,1986,65(3):396-410.[7] LEONI G.A very singular solution for the porous media equation ut=Δum-uq when0<m<1[J]. Journal of Differential Equations,1996,132(2):353-376.[8] PELETIER L A,WANG J Y.A very singular solution of a quasi-linear degenerate diffusion equation with absorption[J]. Transactions of the American Mathematical Society, 1988,307(2):813-826.[9] CHEN X F,QI Y W,WANG M X.Self-similar singular solutions of a p-Laplacian evolution equation with absorption[J]. Journal of Differential Equations,2003,190(1):1-15.[10]CHEN X F,QI Y W,WANG M X.Singular solutions of parabolic p-laplacian with absorption[J].Transactions of the American Mathematical Society,2007,359(11):5653-5668.[11]ESCOBEDO M,ZUAZUA E.Self-similar solutions for a convection-diffusion equation with absorption in RN[J]. Israel Journal of Mathematics,1991,74(1):47-64. [12]BOUZELMATE A,GMIRA A,REYES G.Radial selfsimilar solutions of a nonlinear ornstein-uhlenbeck equation[J].Electronic Journal of Differential Equations,2007, 67:1-21.。
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failure probabilities of a system undergoing random impacts according to a space-time gamma noise. Notice that the symmetrized generator ˜f (x) = Γ has symbol log(1 + |ξ |) = lim α−1 ((1 + |ξ |)α − 1),
(see e.g. [11]) and can be viewed as the weak limit of α−1 ((I − ∆1/2 )α − I ) as α goes
of (1.3) (finite-time blow up vs existence of global solutions) constitutes a natural follow-up to previous investigations, as it can be considered in a sense as a “limiting case” α → 0. Let us recall that the gamma process belongs to a special class of L´ evy pro-
then (1.1) possesses no global nontrivial solutions, and if d > dc , then (1.1) admits a 1
nontrivial global solution for all sufficiently small initial values. Critical parameters
(0,1]
[x, ∞).
a.s. and the transition kernels Pt−s (x, dy ) := P (Xt ∈ dy |Xs = x) are supported in In contrast with the Brownian and α-stable L´ evy motions, subordinators enjoy in
where ϕ is a nonnegative function, ν , σ and β are positive constants, and Γ is the pseudo-differential operator
∞
Γ f (x) =
0
(f (x + y ) − f (x))
e−y dy, y
BLOW-UP AND STABILITY OF SEMILINEAR PDE’S WITH GAMMA GENERATORS
Jos´ e Alfredo L´ opez-Mimbela
Abstract We investigate finite-time blow-up and stability of semilinear partial differen1+β tial equations of the form ∂wt /∂t = Γ wt + νtσ wt , w0 (x) = ϕ(x) ≥ 0, x ∈ R+ , where Γ is the generator of the standard gamma process and ν > 0, σ ∈ R, β > 0 are constants. We show that any initial value satisfying c 1 x−a1 ≤ ϕ(x), x > x0 for some positive constants x0 , c1 , a1 , yields a non-global solution if a1 β < 1 + σ . If ϕ(x) ≤ c2 x−a2 , x > x0 , where x0 , c2 , a2 > 0, and a2 β > 1 + σ , then the solution wt is global and satisfies 0 ≤ wt (x) ≤ Ct−a2 , x ≥ 0, for some constant C > 0. This complements the results previously obtained in [3, 10, 22] for symmetric α-stable generators. Systems of semilinear PDE’s with gamma generators are also considered.
x ν (dx) < ∞. In particular, the trajectories t → Xt (ω ) are increasing functions
general no scaling or symmetry property, nor dimensional-dependent behavior. This circumstance makes it difficult to carry out the methods in the papers quoted above to investigate (1.1), since most of those methods rely significantly on the symmetry and scaling properties of Gaussian and stable distributions. However, in the case we are considering here the transition densities of the motion process are explicitly given, and, moreover, it is known that the bridges (1.2) are beta distributed. Together with the estimates of [18] for the median of beta distributions, this allows us to obtain lower bounds for the bridge distribution of the gamma subordinator, making it possible to exploit the Feynman-Kac approach of [3] to derive criteria for finite-time blow of (1.3).
Nicolas Privault
Key words: Semilinear partial differential equations, Feynman-Kac representation, blowup of semilinear systems, gamma processes. Mathematics Subject Classification: 60H30, 35K57, 35B35, 60J57, 60E07, 60J75.
cesses called subordinators (see e.g. [2] or [21]), a subordinator being a purely nonGaussian L´ evy process {Xt } in R, whose L´ evy measure ν satisfies ν ((−∞, 0)) = 0 and
It is shown that gt (resp. ht ) grows locally to ∞ if d < dc (resp. if d = dc , and in this
Px (Xs ∈ B |Xt = y ),
0 ≤ s ≤ t,
(1.2)
of (1.1), in dimensions d ≤ dc , then follow from a classical argument that goes back to [12]. Motivated by the method developed in [3], in this paper we investigate finite-time
where L is a L´ evy generator, β > 0 is constant and ϕ ≥ 0, have been investigated
by many authors, specially in the case of the d-dimensional Laplacian L = ∆ (see [13] and [6] for surveys). When L is the fractional power ∆α = −(−∆)α/2 of the Laplacian, 0 < α ≤ 2, it was shown in a series of papers [3, 15, 17, 20, 22] that the critical parameter for blow-up of (1.1) is dc := α/β , meaning that if d ≤ dc
1+β for semilinear equations with time-dependent non-linearities of the form tσ wt (x)
were studied in [3] and [10] for L = ∆α . The case of an elliptic operator L on an exterior domain was investigated in [1] for general time-dependent reaction terms. The approaches developed in the works quoted above use subtle compaobabilistic representations of solutions [3, 15, 17, 20]. In [3] the Feynman-Kac formula is used to construct subsolutions 0 ≤ ft ≤ gt ≤ ht of (1.1), where ft = etL ϕ, and gt , ht are the mild solutions, respectively, of ∂gt = Lgt + ftβ gt , ∂t g0 = ϕ, and ∂ht β = Lht + gt ht , ∂t