Do X-ray Binary Spectral State Transition Luminosities Vary
xrd衍射及应用
X射线衍射的方法及应用从1912年,马克思·冯·劳埃发现晶格中晶面的距离与X射线相近,晶体材料可以作为X射线天然的三维光栅以来。
X射线衍射逐渐发展成为了一种有效的高科技无损检测技术来分析许许多多的材料,包括流体、矿物、聚合物、药物、薄膜材料、陶瓷、半导体等等。
X射线衍射可以提供直观的材料的结构信息,如相、织构和平均晶粒尺寸、缺陷、结晶度等结构参数。
X-Ray Diffraction: Instrumentation and Applications(ANDREI A. BUNACIU; ELENA GABRIELA UDRI¸STIOIU; HASSAN Y. ABOUL-ENEIN. Critical Reviews in Analytical Chemistry.2015,45,289-299)这篇文章首先简单介绍了关于X射线衍射的基础理论,之后着重介绍了X射线衍射仪的原理构造、样品制备以及XRD技术在制药生产、法医学、地质学、微电子工业、玻璃制造以及腐蚀分析六个领域的应用。
Micro-XRD study of beta–titanium wires and infrared soldered joints(Masahiro Iijimaa,∗, William A. Brantleyb, Naoki Babac, Satish B. Alapatid,Toshihiro Yuasaa, Hiroki Ohnoe, Itaru Mizoguchia。
Dental Materials.2007,23,1051–1056)针对红外焊接的beta-Ti丝接头做了微区X射线衍射分析。
X-Ray Diffraction: Instrumentation and Applications(ANDREI A. BUNACIU; ELENA GABRIELA UDRI¸STIOIU; HASSAN Y. ABOUL-ENEIN. Critical Reviews in Analytical Chemistry.2015,45,289-299)中基础理论部分包括布拉格方程、X射线的发生以及测角仪的原理和光学布置等等,文章大致阐述了一下XRD的原理,这些与我们在课本上学到的基本一致。
基于氮掺杂碳量子点的水体氟离子选择性荧光开启检测
DOI:10.7524/j.issn.0254-6108.2022090802陈倍宁, 王恩语, 杨正爽, 等. 基于氮掺杂碳量子点的水体氟离子选择性荧光开启检测[J ]. 环境化学, 2024, 43(3): 875-884.CHEN Beining, WANG Enyu, YANG Zhengshuang, et al. Rapid and selective “turn-on ” fluorescent detection of fluoride ion in aqueous solution using nitrogen-doped carbon quantum dots [J ]. Environmental Chemistry, 2024, 43 (3): 875-884.基于氮掺杂碳量子点的水体氟离子选择性荧光开启检测 *陈倍宁 王恩语 杨正爽 付翯云 **(南京大学环境学院,污染控制与资源化研究国家重点实验室,南京,210093)摘 要 本论文以柠檬酸为碳源、尿素为氮源,通过水热法制备了氮掺杂碳量子点(NCDs ),将其作为荧光探针用于检测水体中的氟离子(F –). 利用透射电镜(TEM )、X 射线光电子能谱(XPS )、红外光谱(FT-IR )、紫外-可见光谱(UV-vis )、荧光光谱等表征手段分析了NCDs 的结构和光谱学性质. 考察了探针检测氟离子的灵敏度、稳定性和选择性,及其在天然水体样品中的适用性. 结果表明,NCDs 可在紫外光激发下产生蓝色荧光,且具有较高的荧光量子产率(41%). NCDs 富含羧基、羟基等含氧官能团,可与铝离子(Al 3+)发生反应,这一过程会导致其荧光淬灭;而F –与Al 3+的配位反应可置换出与NCDs 结合的Al 3+,使NCDs 的荧光恢复,产生荧光“开启”效应.NCDs 荧光恢复的程度与F –浓度线性正关系(R 2 = 0.995),表明该方法可用于定量检测F –. 进一步研究显示,NCDs 在检测F –时具有较快的响应时间(约1.0 min )、较宽的线性范围(20—300 μmol·L −1)、较低的检出限(0.65 μmol·L −1)和良好的选择性(水体常见阴阳离子对检测过程的影响低于5%). 此外,NCDs 还具有良好的稳定性,在中性到弱碱性环境(pH 6.0—9.0)中均能有效检出F –. 在实际水体分析过程中,NCDs 显示了良好的F –加标回收率(88.2%—105.0%)和检测精密度(相对标准偏差低于3.0%),表明其具有较好的应用潜能.关键词 氮掺杂碳量子点,氟离子,荧光检测,荧光开启.Rapid and selective “turn-on” fluorescent detection of fluoride ion inaqueous solution using nitrogen-doped carbon quantum dotsCHEN Beining WANG Enyu YANG Zhengshuang FU Heyun **(School of Environment, State Key Laboratory of Pollution and Resource Reuse, Nanjing University, Nanjing, 210093, China )Abstract Nitrogen-doped carbon quantum dots (NCDs) were synthesized by a facile hydrothermal method using citric acid as the carbon source and urea as the nitrogen source, and were applied as a novel “turn-on” fluorescent probe for the detection of fluoride ions (F –) in water. The structural and spectroscopic properties of the NCDs were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-vis), and fluorescence spectroscopy. The sensitivity, stability and selectivity of the NCDs probe to detect F – as well as its applicability in natural water samples were investigated. NCDs showed blue fluorescence emission under ultraviolet light irradiation, and had a high fluorescence quantum yield of 41%. The NCDs can react with aluminium ions (Al 3+) via the surface oxygen-2022 年 9 月 8 日 收稿(Received :September 8,2022).* 江苏省自然科学基金(BK20190059)和国家自然科学基金(21976086)资助.Supported by the Natural Science Foundation of Jiangsu Province (BK20190059) and National Natural Science Foundation of China (21976086).* * 通信联系人 Corresponding author ,E-mail :***************.cn876环 境 化 学43 卷containing groups, which would quench the fluorescence emission of NCDs. Due to the strong coordination affinity, F– can compete with NCDs for Al3+ and thus recover the fluorescence of NCDs.There existed a good linear relationship between the recovery ratio of NCDs fluorescence and F–concentration (R2 = 0.995), suggesting the possibility of NCDs in F– quantification. The NCDs-based fluorescence method for F– detection exhibited a short response time (approximately1.0 min), wide linear range (20—300 μmol·L−1), low detection limit (0.65 μmol·L−1), good selectivity(influences of common ions below 5%), and satisfactory stability in environmentally relevant pH range (pH 6.0—9.0). Finally, the proposed method was successfully applied in the analysis of F– in real water samples with high recoveries (88.2%—105.0%) and precision (relative standard deviations lower than 3.0%).Keywords nitrogen-doped carbon dots,fluoride ion,fluorescent detection,turn-on.氟是常见的水体污染物,过量摄入会导致氟中毒,不但会损害人体骨骼和牙齿健康,还可能使人体肾脏受损和甲状腺激素紊乱[1 − 2]. 氟污染已对全球多个国家造成了严重威胁,全球有超过2亿人处于氟中毒的危险中,我国是氟中毒较为严重的国家之一[3 − 4]. 由于严重的毒副作用,世界卫生组织(WHO)规定饮用水中的氟离子(F–)浓度不得超过1.5 mg·L−1(ISBN 978-92-4-154995-0),我国《生活饮用水卫生标准》规定水中氟化物不应超过1.0 mg·L−1(GB 5749-2006). 因此,对水体中的F–进行监测和管理是保障水环境安全的重要内容,研究准确、快速、高灵敏度的水体F–检测方法十分必要.目前F–的检测方法主要包括离子选择电极法、离子色谱法、分子吸收光谱法、比色法和荧光检测法等[5 − 8]. 其中,荧光检测法因其灵敏度高、检测实时、操作简便等优点,近年来引起了研究者的广泛关注[8 − 11]. 荧光检测技术的关键是其探针,探针的性能很大程度上决定了方法的检测灵敏度、速度和选择性. 目前可用于F–检测的荧光探针以硅基/硼基/脲基有机合成小分子或聚合物、无机半导体量子点为主[8, 12 − 15]. 这些探针不但种类较为有限,还存在着合成过程复杂、F–响应时间长、检测限高,以及在水溶液中适用性较差等问题[12 − 14].碳量子点是一种新兴的零维荧光碳纳米材料,具有荧光性质可控、稳定性高、水溶性好、合成方法简单、毒性低等优点[16 − 20],在荧光检测领域显示了巨大的应用潜力. 在环境分析方面,碳量子点已被成功用于检测水体、血液等环境样品中的污染物[21 − 25]. 但目前关于碳量子点的荧光检测研究主要集中于重金属等阳离子型污染物[21 − 23],对F–等阴离子型污染物的研究相对较少.本文以柠檬酸为碳源、尿素为氮源,采用简单的水热法制备了掺氮荧光碳量子点(NCDs),并利用多种表征技术对其结构组成和光学性质进行了表征. NCDs与铝离子(Al3+)作用后会发生荧光淬灭,而F–与Al3+的配位反应可置换出与NCDs结合的Al3+,使NCDs荧光恢复. 利用荧光“开启”效应,建立了F–的快速检测方法,研究了方法的灵敏度、选择性和稳定性,以及其在实际水体样品中的应用性能.1 实验部分(Experimental section)1.1 化学试剂分析纯一水合柠檬酸(C6H8O7·H2O)、尿素(CH4N2O)、无水乙醇(C2H5OH)、氢氧化钠(NaOH)、盐酸(HCl)和硫酸(H2SO4)购自国药集团化学试剂有限公司. 分析纯六水合氯化铝(AlCl3·6H2O)、氟化钠(NaF)、氯化钠(NaCl)、溴化钠(NaBr)、硝酸钠(NaNO3)、溴酸钠(NaBrO3)、碳酸钠(Na2CO3)、氯化钾(KCl)、氯化镁(MgCl2)、氯化钙(CaCl2)购自上海Sigma-Aldrich公司. 生物试剂级硫酸奎宁购自上海阿拉丁生化科技股份有限公司.1.2 NCDs的制备利用水热法制备NCDs,具体制备过程如下:将0.21 g一水合柠檬酸和0.18 g尿素溶于5 mL去离子水中,超声至形成澄清溶液. 将上述溶液转移至含有聚四氟乙烯内衬的高压反应釜中,置于鼓风烘箱中加热,于160 ℃反应4 h. 离心收集反应产物,经乙醇洗涤、冷冻干燥后,得到固体NCDs样品.3 期陈倍宁等:基于氮掺杂碳量子点的水体氟离子选择性荧光开启检测877NCDs储备液配置于纯水中,并于4 ℃避光保存.1.3 NCDs的表征采用JEM-2100型透射电子显微镜(TEM,日本JEOL公司)观察NCDs形貌. 利用Vario MICRO cube型元素分析仪(德国Elementar公司)测定NCDs中碳、氮、氧、氢等元素含量. 使用NEXUS870型傅里叶变换红外光谱仪(FT-IR,美国Nicolet公司)解析NCDs的官能团性质. 利用PHI5000 VersaProbe型X射线光电子能谱仪(XPS,日本ULVAC-PHI公司)分析NCDs的表面元素组成和元素形态. 使用Zetasizer Nano ZS型纳米粒度电位仪(英国Malvern公司)测定NCDs的Zeta电位. 采用UV-2700型紫外-可见分光光谱仪(日本Shimadzu公司)和Aqualog型荧光光谱仪(日本Horiba公司)分别采集NCDs的紫外-可见吸收光谱(UV-vis)和荧光光谱. 以硫酸奎宁的H2SO4溶液为标准样品,采用参比法测定NCDs的荧光量子产率. 使用FLS-980型稳态瞬态荧光光谱仪分析(英国Edinburgh公司)测定NCDs的荧光寿命.1.4 NCDs对F–的荧光检测性能研究在10 mL离心管中加入适量NCDs溶液和AlCl3溶液,使溶液中NCDs浓度为1 mg·L−1、Al3+浓度为0—140 μmol·L−1,并用NaOH将溶液pH值调节为7.0. 溶液配置完成1 min后,采集上述溶液在激发波长(E x)为340 nm处的二维荧光光谱. 利用相同的方法配置NCDs、AlCl3和NaF的混合溶液(pH 7.0),使NCDs浓度为1 mg L−1、Al3+浓度为100 μmol·L−1、F–浓度范围为0—500 μmol·L−1,并在E x为340 nm处采集溶液的荧光光谱. 为研究NCDs荧光检测F–的稳定性和选择性,考察了光照、溶液pH值,以及常见水体阴阳离子对检测过程的影响. 在光稳定性实验中,持续采集NCDs、NCDs/Al3+、NCDs/Al3+/F–混合溶液在E x为340 nm、发射波长(E m)为440 nm处的荧光强度,采集时长为1 h,采集频率为每分钟1次. 在pH影响实验中,采用NaOH和HCl调节溶液pH值,pH值设定范围为4.0—9.0.在阴阳离子影响实验中,氯离子(Cl–)、溴离子(Br–)、硝酸根(NO3–)、硫酸根(SO42–)、溴酸根(BrO3–)、碳酸根(CO32–)、钾离子(K+)、镁离子(Mg2+)、钙离子(Ca2+)等离子的浓度为50 μmol·L−1和300 μmol·L−1.所有实验均设置3组平行样.2 结果与讨论(Results and discussion)2.1 NCDs表征结果2.1.1 NCDs的形貌和粒径图1a为NCDs的TEM图像,可以看出本研究所合成的NCDs具有类球形结构,且颗粒分散性良好、尺寸较为均一(粒径范围为1.5—5.0 nm). 对NCDs的粒径进行统计分析,得到平均粒径为3.4 nm.2.1.2 NCDs的元素组成和官能团性质元素分析结果显示,NCDs中氮质量分数高达40.80% wt.,证实了氮元素的成功掺杂. NCDs中其它主要元素分别为碳(35.18%)、氧(17.65%)和氢(6.37%). 图1b为NCDs的FT-IR图谱. NCDs在1580 cm−1处的C=C伸缩振动峰和1440、1400、1340 cm−1处的C—H弯曲振动峰来源于其碳骨架结构[26];1260 cm−1处的吸收峰对应于C—N的伸缩振动,验证了NCDs中氮元素及含氮官能团的存在[27];1690 cm−1和1180 cm−1处的峰分别来源于C=O和C—O的伸缩振动[26, 28],表明NCDs还具有羧基、羟基等含氧官能团.NCDs的XPS分析结果如图1c和d所示. 在NCDs的XPS全谱扫描图中出现了3个尖锐的特征结合能峰(图1c),分别对应于C1s(285 eV)、N1s(400 eV)和O1s(532 eV),表明NCDs表面富含碳、氮、氧元素. C1s峰可进一步分为4个子峰(图1d),对应于不同化学状态的碳原子,具体为:非氧化碳原子(C=C/C—C,结合能为284.5 eV)、与氮相连的碳原子(C—N,结合能为285.7 eV)、羟基/烷氧基中的碳原子(C—O,结合能为286.8 eV)和羰基/羧基中的碳原子(C=O,结合能为288.5 eV)[26, 28]. 结果与FT-IR表征结果一致,进一步证明了NCDs中存在含氮官能团以及羟基、羧基等含氧官能团.图 1 NCDs 的(a )TEM 图和粒径分布直方图(插图)、(b )FT-IR 光谱图、(c )XPS 全扫描谱图和(d )C1s 高分辨率谱图Fig.1 (a ) TEM image and histogram of particle size distribution, (b ) FT-IR spectrum, and (c ) full scan and (d ) C1s XPSspectra of NCDs2.1.3 NCDs 的光谱学性质图2a 为NCDs 的UV-vis 光谱图. 在低于230 nm 和300—380 nm 的波段范围内,NCDs 均具有明显光吸收;其中小于230 nm 的吸收峰归因于C=C 基团的π-π*跃迁,通常不产生强荧光信号[29];而峰值位于340 nm 处的吸收峰则可能伴随着荧光发射的产生. NCDs 的三维荧光光谱分析结果印证了这一点. 如图2b 所示,当E x 为300—380 nm 时,NCDs 产生了很强的荧光发射,E m 范围为400—500 nm.NCDs 的荧光峰值位于E x = 340 nm/E m = 440 nm 处,可能是产生于NCDs 表面态电子-空穴对的辐射复合[17]. 值得注意的是,当E x 在300 nm 至380 nm 之间变化时,NCDs 的E m 峰始终位于440 nm 左右,没有明显位移,说明NCDs 具有不依赖于E x 的荧光发射特性,这可能源于其较为均一的粒径和表面状态分布[17]. 碳量子点的荧光量子产率是衡量其发光性能的重要指标. 以硫酸奎宁为参比,根据NCDs 荧光强度与吸光度的关系,测定了NCDs 的荧光量子产率(图2c ),发现NCDs 的量子产率高达41%,表明其具有优异的荧光发射本领.图 2 NCDs 溶液的(a )UV-vis 光谱图和(b )三维荧光光谱图;(c )NCDs 荧光强度积分与吸光度的线性关系Fig.2 (a ) UV-vis absorption and (b ) 3D fluorescence spectra of NCDs aqueous solution; (c ) linear relationship betweenfluorescence intensity integral and absorbance of NCDs878环 境 化 学43 卷3 期陈倍宁等:基于氮掺杂碳量子点的水体氟离子选择性荧光开启检测8792.2 NCDs的F–检测性能2.2.1 检测灵敏度碳量子点通常带负电,故绝大多数基于碳量子点的荧光传感器被用于检测阳离子型污染物 [21 − 23] .研究显示,通过与碳量子点官能团的作用,金属等阳离子可引发量子点的荧光淬灭. 若能利用阴离子与金属的强配位作用,使金属离子从碳量子点脱附,则可恢复碳量子点的荧光,进而实现阴离子的荧光“开启”检测. Al3+作为一种环境友好的金属离子,与F–之间存在极强的配位能力. 基于此,以Al3+为介导离子,设计了NCDs检测F–的实验.首先研究了Al3+对NCDs荧光的影响. 如图3a所示,当Al3+的浓度从0逐渐增加至140 μmol·L−1时,NCDs的荧光强度逐渐降低,证实了Al3+对NCDs的荧光淬灭效应.图3b显示了加入F–后,NCDs/Al3+溶液(Al3+浓度为100 μmol·L−1)的荧光变化情况. 可以看出,随着F–浓度的升高,NCDs/Al3+溶液的荧光强度逐渐变强,表明F–确实能够恢复NCDs被Al3+淬灭的荧光.图 3 (a)Al3+和(b)F–对NCDs溶液荧光光谱的影响(E x= 340 nm);(c)不同浓度F–存在下NCDs在E x = 340 nm/E m = 440 nm处的荧光恢复率;(d)NCDs在E x = 340 nm/E m = 440 nm处的荧光恢复率与F–的相关关系Fig.3 Fluorescence spectra of NCDs solution at E x 340 nm upon the addition of (a) Al3+ and (b) F–; (c) fluorescence recovery efficiency of NCDs at E x = 340 nm/E m = 440 nm as a function of F– concentration; (d) relationship between fluorescence recovery efficiency of NCDs at E x = 340 nm/E m = 440 nm and F– concentration 根据NCDs荧光峰值处(E x = 340 nm,E m = 440 nm)的变化情况,可通过下式计算F–存在下NCDs的荧光恢复率:其中,F0为NCDs溶液的原始荧光强度,F Al和F分别为加入Al3+和F–后的NCDs荧光强度. 由图3c可以发现,NCDs荧光恢复率先随着F–浓度的升高而稳步上升,并在F–浓度超过300 μmol·L−1后逐渐平稳,说明已达NCDs荧光恢复的上限. 在20—300 μmol·L−1浓度范围内,NCDs的荧光恢复率与F–浓度具有很好的线性关系(R2 = 0.995,图3d),表明该NCDs/Al3+体系可用于定量检测水中的F–. 该方法对F–的检出限(LOD)为0.65 μmol·L−1(即0.012 mg L−1),远低于WHO和我国规定的饮用水F–浓度限值,也低于多数已报道F–荧光检测法的LOD值(见表1)[8, 10 − 12, 28 − 31],表明NCDs/Al3+方法具有良好的F–灵敏度.表 1 文献报道F–荧光检测法的分析性能Table 1 Analytical performances of reported fluorescence methods for F– detection探针Probe 检出限/(μmol·L−1)LOD线性范围/(μmol·L−1)Linear Range响应时间/minResponse time文献References基于内部电荷转移的荧光探针80500—2800025[8]基于Si—O键断裂的荧光探针180—100045[12]含有多面体低聚硅氧烷的纳米粒子1010—100 1.67[13]基于硼酸的荧光碳点1100—26700 5.0[14]蒽基荧光受体 2.02—120NA a[30]基于1,1’-联萘基支架的荧光探针 1.86 5.0—45.0200[31]基于壳聚糖凝胶的荧光碳点 6.6 6.6—50.6 2.0[32]基于羧酸桥联二铁络合物的荧光探针 6.70—30NA a[33] NCDs0.6520—300 1.0本论文 注:a “NA” 文中未提及. a “NA ” Not available.2.2.2 检测速度图4a显示了加入Al3+和F–后NCDs的荧光强度随时间的变化. 可以看出,Al3+淬灭NCDs荧光的速度极快,几乎在加入NCDs溶液的瞬时即达到淬灭平衡. F–恢复NCDs荧光的速度略慢于Al3+的淬灭速度,但也可在约1.0 min之内达到恢复平衡. 与文献报道的荧光方法相比(表1),NCDs/Al3+对F–的响应时间更短,具有更快的F–检测速度.图 4 NCDs的(a)荧光响应速度和(b)荧光稳定性随时间的变化;溶液pH值对NCDs的(c)荧光强度和(d)荧光恢复率的影响(Al3+浓度为100 μmol·L−1,F–浓度为300 μmol·L−1)Fig.4 Fluorescence intensity of NCDs solution in the presence of Al3+ (100 μmol·L−1) and/or F– (300 μmol·L−1) as a function of (a) incubation time and (b) irradiation time; effect of solution pH on NCDs (c) fluorescence intensity and (d) fluorescencerecovery efficiency by F–2.2.3 检测稳定性由于荧光探针是依靠荧光强度的改变来达到检测目的,因此探针在激发光下的荧光稳定性是其至880环 境 化 学43 卷3 期陈倍宁等:基于氮掺杂碳量子点的水体氟离子选择性荧光开启检测881关重要的性能指标. 如图4b所示,在激发光下连续照射1 h后,NCDs、NCDs/Al3+和NCDs/Al3+/F–溶液的荧光发射强度均未发生明显波动,表明该NCDs检测体系具有较强的荧光稳定性.图4c和d为溶液pH值对NCDs检测F–性能的影响. 在溶液pH4.0时,NCDs表现出较弱的荧光发射,这可能是由于NCDs表面的含氧官能团在酸性条件下解离程度较低,NCDs疏水性较高,易因聚集产生荧光淬灭[34]. 当溶液pH由4.0升至9.0时,随着NCDs表面官能团解离程度的提高,NCDs的荧光强度逐渐上升,并在中性至弱碱性pH范围内(6.0—9.0)保持稳定(图4c). 在此pH范围内,Al3+和F–对NCDs荧光的淬灭和恢复程度也基本相同(图4d),表明NCDs有良好的pH适应性,在中性至弱碱性环境中均能保持稳定的荧光性能.2.2.4 检测选择性进一步考察NCDs/Al3+体系对F–的选择性,研究了水体常见阴离子(Cl–、Br–、NO3–、SO42–、BrO3–、CO32–)和阳离子(K+、Mg2+、Ca2+)对F–检测的影响. 如图5a和c所示,在浓度相同的情况下,F–恢复NCDs荧光的效率明显高于其它离子. 例如,低浓度(50 μmol·L−1)和高浓度(300 μmol·L−1)F–分别将NCDs的荧光恢复了10%和60%,而除CO32–外的其它离子的恢复率不足2%和5%.CO32–在两个浓度下的恢复效率分别为5%和25%,稍高于其它干扰离子,这可能是因为CO32–能够与Al3+在溶液中发生双水解反应. 尽管如此,CO32–的荧光恢复效率仍明显低于F–. 研究了F–与相同浓度干扰离子共存时,NCDs的荧光恢复效率(图5b和d). 在低浓度共存条件下,F–对NCDs的荧光恢复仅受CO32–微量影响(恢复率由10%增至14%);而当共存浓度较高时,所有测试离子均不影响NCDs检测F–. 结果表明, NCDs/Al3+体系对F–具有优秀的选择性. 该体系的F–选择性主要源于F–远高于其它离子的Al3+配位能力,F–的存在更容易使Al3+从NCDs上脱附.图 5 (a)低浓度(50 μmol·L−1)和(c)高浓度(300 μmol·L−1)离子存在下NCDs的荧光恢复率;(b)低浓度(50 μmol·L−1)和(d)高浓度(300 μmol·L−1)干扰离子和F–共存时的NCDs荧光恢复率Fig.5 Fluorescence recovery efficiency of NCDs in the presence of different ions at (a) low (50 μmol·L−1) and (c) high concentrations (300 μmol·L−1), and in the coexistence of F– and other ions at (b) low (50 μmol·L−1) and (d) highconcentrations (300 μmol·L−1)2.3 NCDs的F–检测机制为探究NCDs对F–的检测机制,考察了Al3+和F–对NCDs荧光寿命的影响. 如图6a所示,NCDs、NCDs+Al3+、NCDs/Al3++F–的荧光衰减曲线几乎重叠,3个体系中NCDs的荧光寿命分别为7.01 ns、7.06 ns、7.02 ns,表明Al3+和F–对NCDs的荧光寿命无明显影响,二者不是通过能量转移过程影响NCDs荧光发光. 由此推测Al3+对NCDs荧光的淬灭机制为静态淬灭,即NCDs与Al3+发生相互作用,形成NCDs/Al3+静态复合物;当F–存在时,F–会与Al3+发生配位反应,使NCDs/Al3+复合物中的Al3+脱附,进而恢复NCDs荧光. 为了验证此假设,进一步分析了加入Al3+和F–后NCDs的表面电荷和FT-IR光谱变化. NCDs表面含有丰富含氧官能团,原始NCDs带负电,Zeta电位为-6.41 mV;加入Al3+后,由于Al3+与含氧官能团发生配位作用,因此NCDs的Zeta电位升至+1.40 mV;而加入F–后,F–与Al3+的配位导致NCDs表面的Al3+脱附,NCDs的Zeta电位又降至-3.97 mV. FT-IR光谱分析结果也印证了这一机制. 如图6b所示,与NCDs相比,NCDs/Al3+的FT-IR光谱在1120 cm−1处出现1个新强峰,对应于Al—OH的弯曲振动,证实了Al3+与NCDs的结合[35 − 36];加入F–后,Al—OH吸收峰的强度显著下降,表明F–的存在使Al3+从NCDs表面脱附.图 6 加入Al3+(100 μmol·L−1)和F–(300 μmol·L−1)前后NCDs的(a)荧光衰减曲线和(b)FT-IR光谱Fig.6 (a) Time-resolved fluorescence decay and (b) FT-IR spectra of NCDs solution in the absence and presence of Al3+(100 μmol·L−1) and/or F– (300 μmol·L−1)2.4 NCDs对实际水样中F–的检测性能为了评估NCDs/Al3+的可应用性,将其用于检测实际水体中的F–浓度. 所测试实际水样分别取自实验室自来水龙头和太湖,过0.45 μm滤膜后直接进行分析. 结果显示,两个水样中的F–浓度均低于方法的LOD值. 论文进一步开展了梯度加标回收实验(加标浓度为20、40、60、80、100 μmol·L−1,表2),测得F–回收率范围为88.2%—105.0%,与常规离子色谱法的检测回收率相当(91.4%—111.9%). 此外,NCDs/Al3+方法也具有较好的精密度,多次检测的相对标准偏差在2.67%以内(n=3),表明可利用NCDs检测实际水样中的F–.表 2 基于NCDs的荧光法对实际水样中F–的检测结果(%, n=3)Table 2 Analytical results for the determination of F– in real water samples加标浓度/(μmol·L−1)Spiked concentration自来水样加标回收率Tap water recoveries太湖水样加标回收率Taihu Lake water recoveries荧光法离子色谱法荧光法离子色谱法2088.2 ± 2.24111.7 ± 0.7688.5 ± 2.66111.9 ± 1.274092.1 ± 2.6398.5 ± 2.0694.7 ± 2.01107.2 ± 1.936095.7 ± 2.6794.0 ± 0.33105.0 ± 1.9799.9 ± 1.758096.9 ± 1.9092.0 ± 1.2197.3 ± 2.2094.7 ± 0.25100101.6 ± 1.5891.4 ± 1.13103.7 ± 2.0191.5 ± 1.053 结论(Conclusion)本文利用简单的水热法成功地制备了具有优异荧光性能的掺氮碳量子点(NCDs). 该量子点能够882环 境 化 学43 卷以铝离子(Al 3+)为介导,通过荧光“关闭”—“开启”模式选择性检测水体中的氟离子(F –). 与已报道的F –荧光检测方法相比,本论文基于NCDs 的检测体系具有更低的F –检测限(0.65 μmol·L −1)和更快的检测速度(F –响应时间约1.0 min ). 此外,NCDs 还具有优异的荧光稳定性和F –选择性,在实际水样的F –分析中也显示了良好的应用性能. 本论文的研究结果可为水体F –的快速检测提供技术支持,也有助于拓展碳量子点材料在荧光检测中的应用.参考文献(References)AOBA T, FEJERSKOV O. 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Design and fabrication of carbon dots for energy conversion and storage [J ]. Chemical Society Reviews,2019, 48(8): 2315-2337.[19]傅鹏, 周丽华, 唐连凤, 等. 碳量子点的制备及其在能源与环境领域应用进展 [J ]. 应用化学, 2016, 33(7): 742-755.FU P, ZHOU L H, TANG L F, et al. Progress in preparation of carbon quantum dots and its application in the fields of energy and environment [J ]. Chinese Journal of Applied Chemistry, 2016, 33(7): 742-755(in Chinese ).[20]PENG D, ZHANG L, LIANG R P, et al. Rapid detection of mercury ions based on nitrogen-doped graphene quantum dots acceleratingformation of Manganese porphyrin [J ]. ACS Sensors, 2018, 3(5): 1040-1047.[21]3 期陈倍宁等:基于氮掺杂碳量子点的水体氟离子选择性荧光开启检测883LIU H, LI R S, ZHOU J, et al. Branched polyethylenimine-functionalized carbon dots as sensitive and selective fluorescent probes forN -acetylcysteine via an off-on mechanism [J ]. Analyst, 2017, 142(22): 4221-4227.[22]ZHENG M, XIE Z G, QU D, et al. On-off-on fluorescent carbon dot nanosensor for recognition of chromium(VI) and ascorbic acidbased on the inner filter effect [J ]. ACS Applied Materials & Interfaces, 2013, 5(24): 13242-13247.[23]CHEN B B, LIU M L, ZHAN L, et al. Terbium (III) modified fluorescent carbon dots for highly selective and sensitive ratiometry ofstringent [J ]. Analytical chemistry, 2018, 90(6): 4003-4009.[24]ZHANG Z, ZHANG D, SHI C, et al. 3, 4-Hydroxypyridinone-modified carbon quantum dot as a highly sensitive and selectivefluorescent probe for the rapid detection of uranyl ions [J ]. Environmental Science:Nano, 2019, 6(5): 1457-1465.[25]TANG L, JI R, LI X, et al. Deep ultraviolet to near-infrared emission and photoresponse in layered N-doped graphene quantumdots [J ]. ACS nano, 2014, 8(6): 6312-6320.[26]LI H, KONG W, LIU J, et al. Fluorescent N-doped carbon dots for both cellular imaging and highly-sensitive catechol detection [J ].Carbon, 2015, 91: 66-75.[27]QU D, ZHENG M, ZHANG L G, et al. Formation mechanism and optimization of highly luminescent N-doped graphene quantumdots [J ]. Scientific Reports, 2014, 4: 5294.[28]LI L B, YU B, YOU T. Nitrogen and sulfur co-doped carbon dots for highly selective and sensitive detection of Hg (Ⅱ) ions [J ].Biosensors and Bioelectronics, 2015, 74: 263-269.[29]HUANG W W, LIN H, CAI Z, et al. A novel anthracene-based receptor: Highly sensitive fluorescent and colorimetric receptor forfluoride [J ]. Talanta, 2010, 81(3): 967-971.[30]DONG M, PENG Y, DONG Y M, et al. A selective, colorimetric, and fluorescent chemodosimeter for relay recognition of fluoride andcyanide anions based on 1, 1'-binaphthyl scaffold [J ]. Organic Letters, 2012, 14(1): 130-133.[31]BARUAH U, GOGOI N, MAJUMDAR G, et al. β-Cyclodextrin and calix[4]arene-25, 26, 27, 28-tetrol capped carbon dots for selectiveand sensitive detection of fluoride [J ]. Carbohydrate Polymers, 2015, 117: 377-383.[32]ZHOU Y H, DONG X L, ZHANG Y X, et al. Highly selective fluorescence sensors for the fluoride anion based on carboxylate-bridgeddiiron complexes [J ]. Dalton Transactions, 2016, 45(16): 6839-6846.[33]WANG H, WANG Y, GUO J, et al. A new chemosensor for Ga 3+ detection by fluorescent nitrogen-doped graphitic carbon dots [J ].RSC Advances, 2015, 5(17): 13036-13041.[34]SHI L H, WANG Q, ZHANG C, et al. Tricolor emission carbon dots for label-free ratiometric fluorescent and colorimetric recognitionof Al 3+ and pyrophosphate ion and cellular imaging [J ]. Sensors and Actuators B:Chemical, 2021, 345: 130375.[35]LIU C S, SHIH K, GAO Y X, et al. Dechlorinating transformation of propachlor through nucleophilic substitution by dithionite on thesurface of alumina [J ]. Journal of Soils and Sediments, 2012, 12(5): 724-733.[36]884环 境 化 学43 卷。
光电子学第5章_光电探测器
When a photon with an energy greater than the bandgap Eg is incident, it becomes absorbed to photogenerate a free EHP. Usually, the photogeneration takes place in the depletion layer. The field E in the depletion layer separates the EHP and drifts them in opposite directions until they reach the neutral regions. Drifting carriers generate a current, called photocurrent Iph, in the external circuit that provides the electrical signal. The photocurrent Iph depends on the number of EHPs photogenerated and the drift velocities of the carriers while they are transiting the depletion layer. The photocurrent in the external circuit is due to the flow of electrons, not to both electrons and holes.
Photodetectors
• • • • • • • • • 5.1 Principle of the pn Junction Photodiode 5.2 Ramo’s theorem and external photocurrent 5.3Absorption Coefficient and Photodiode Materials 5.4 Quantum Efficiency and Responsivity 5.5 The pin Photodiode 5.6 Avalanche Photodiode 5.7 Heterojunction Photodiodes 5.8 Phototransistors 5.9 Noise In Photodetectors
XRF检测原理
XRF检测原理·12009-11-16 12:29原理(XRF)仪器由激发源(X射线管)和探测系统构成。
X射线管产生入射X 射线(一次射线),激励被测样品。
样品中的每一种元素会放射出的二次X射线,并且不同的元素所放出的二次射线具有特定的能量特性。
探测系统测量这些放射出来的二次射线的能量及数量。
然后,仪器软件将控测系统所收集的信息转换成样品中的各种元素的种类及含量。
利用X射线荧光原理,理论上可以测量元素周期表中的每一种元素。
在实际应用中,有效的元素测量范围为11号元素(钠Na)到92号元素(铀U)。
全反射X-光荧光分析仪(Total-reflection X-ray Fluorescence Spectrometer,TXRF )传统X-光荧光分析仪(X-ray Fluorescence Spectrometer, XRF )系利用X-光束照射试片以激发试片中的元素,当原子自激发态回到基态时,侦测所释放出来的荧光,经由分光仪分析其能量与强度后,可提供试片中组成元素的种类与含量,具有快速、非接触、非破坏性及多元素分析等特点;然而X-光荧光分析仪分析的灵敏度受到试片基质散射效应及入射X-光与试片基座反应产生的制动幅射的限制,尔后逐渐发展出全反射X-光荧光分析仪,才大幅提高X-光荧光分析仪的灵敏度。
XRF是一项非破坏性的元素定性和定量分析的技术,其原理是根据被入射X 光提升到激发态的样品,在回复到基态时,所放射的X光荧光,具有因元素种类和含量不同而有不同的波长X光射线的特性。
当X光照射样品时,有两种主要的现象发生,即:散射现象(Scattering)和光电吸收(Photoelectric Absorption)。
前者为当入射X光弹性碰撞到晶体样品中的原子时,入射X光的波长λ,和晶格平面间距d,绕射程度n,以及绕射角度θ,有下列的关系:nλ=2dsinθ(1)(1)式即为布拉格定律(Bragg's Law)。
X-ray复习
一、材料X射线应力测试1、三种应力及衍射效应材料现代分析方法X射线内应力的测定第I类应力(σⅠ):在物体宏观较大体积或多晶粒范围内存在并保持平衡的应力。
此类应力释放,会使物体宏观体积或形状发生变化,称之为“宏观应力”或“残余应力”。
衍射效应:能使衍射线产生位移。
产生原因:比如零件在热处理、焊接、表面处理、塑性变形加工。
第II类内应力(σⅡ):在一个或少数个晶粒范围内存在并保持平衡的内应力。
衍射效应:引起线形变化(峰宽化)。
产生原因:由于弹性变形时晶格会发生弹性的弯曲、扭转、拉伸等,变形消失后残留的内应力,或者由于温度变化引起。
第III类应力(σⅢ):在若干原子范围存在并保持平衡的内应力。
衍射效应:能使衍射强度减弱。
产生原因:由于不同种类的原子的移动、扩散、原子的重新排列使晶格畸变所造成的。
第Ⅱ类应力和第Ⅲ类应力称为:“微观应力”。
2、应力测定原理通过测定弹性应变量推算应力(σ=Eε)。
通过晶面间距的变化来表征应变(σ=Eε=E△d/d0)晶面间距的变化与衍射角2θ的变化有关。
因此,只要知道试样表面上某个衍射方向上某个晶面的衍射线位移量△θ,即可计算出晶面间距的变化量△d/d,进一步通过胡克定律计算出该方向上的应力数值。
1)、对于单轴应力测定的思路:是在单轴应力作用下,垂直于应力方向的晶面间距变小,通过X-ray衍射求出晶面间距的变化值,便可算出应变(ε=△d/d ),通过εx= -γεy ,求出应力方向的应变,从而求出应力σy=Eεy。
布拉格方程微分得d/d=-cosθ*△θ,推出2)宏观应力测定方法:由应力测定的基本公式:可知,若测得M,根据测试条件取应力常数K,即可求得测定方向平面内的宏观应力值因此关键是M的测定。
一般步骤如下:(1)使X射线从几个不同的ψ角入射(ψ角已知),并分别测取各自的2θ(衍射角)。
(2)作出2θ- sin2ψ的曲线,求出斜率M,求出σφ。
3、衍射仪法测定2θ- sin2ψ曲线常用方法有两种:①sin2ψ法为尽量避免测量时的误差,多取ψ方位进行测量,用最小二乘法求出2θ-sin2ψ直线的最佳斜率。
用正电子湮没研究纳米碲化铋的缺陷及其对热导率的影响
(AR), NaOH (AR), NaH4 B (96%) 和蒸馏水. 将原 材料混合在一起放入高压反应釜里, 并在 150 ◦ C 下反应 24 h. 将反应产物用蒸馏水和无水乙醇洗涤 后放入真空干燥箱里并在 110 ◦ C 下真空干燥 6 h. 然后将制备得到的粉末在 20 MPa 的压强及 300, 350, 400, 450 和 500 ◦ C 的温度下分别进行 5 min 的等离子烧结. 将不同温度 下进行烧结的样 品 分别命名为 SPS-300, SPS-350, SPS-400, SPS-450, SPS-450 和 SPS-500. 将制备的样品进行 X 射线衍射 (XRD) 测试 (用 Cu Kα 光谱). 正电子寿命测量使用快 - 快符合 正电子寿命谱仪, 时间分辨率约为 220 ps. 正电子 源为 22 Na, 强度约为 20 µCi. 热扩散系数 D 和比 热 Cp 分别采用 NETCH LFA457 和 TA Instrument Q20 测量, 而密度 d 利用阿基米德原理测定. 最后 材料的热导率利用公式 κ = DdCP 计算得到.
关键词: Bi2 Te3 , 正电子, 空位型缺陷, 热导率 PACS: 78.70.Bj, 51.20.+d, 84.60.Rb DOI: 10.7498/aps.64.207804
低晶格热导率. 研究表明, 掺杂原子和主体原子
1 引
言
之间的质量差 ∆M 对晶格热导率的降低起着关键 作用 [6−8] , 散射因子是影响晶格热导率的重要参 数 [6] , 且散射因子 (A) 的表达式如下: ∆M 2 Ωo x(1 − x) , (1) 2 4πυ M 其中, Ωo , υ , x, ∆M 和 M 分别表示晶胞的自由体 A= 积、 晶格的声速、 掺杂原子的比例、 掺杂原子与主 体原子之间的质量差及平均原子质量. 根据 (1) 式 得知, 散射因子越大表明晶格对声子的散射作用 越强, 并且质量差越大散射因子就越大. 在一个或 多个晶格位置引入空位型缺陷可以使原子质量差 ∆M 达到最大值, 从而使晶格热导率得到最大限度 的降低. 最近, 已有一些关于空位型缺陷对热导率 及热电优值 ZT 影响的报导. Pei 和 Morelli [9] 的研 究表明, 在 In2 Te3 -InSb 固溶体中引入 In 空位可使 晶格热导率得到大幅度的降低. Kurosaki 等 [10] 也 有类似的发现, 对于 Ga2 Te3 块体材料, 空位型缺陷 引起的声子散射能够降低热导率. 在其他热电材料
x射线荧光光谱法 英文
x射线荧光光谱法英文X-Ray Fluorescence Spectrometry (XRF)。
X-ray fluorescence spectrometry (XRF) is an analytical technique used to determine the elemental composition of materials by measuring the X-rays emitted by the material when it is exposed to a high-energy X-ray beam. This method is widely used in various fields, including geology, environmental science, forensic science, archaeology, and materials science.Principle of Operation.XRF is based on the principle that when a material is irradiated with high-energy X-rays, electrons in the atoms of the material are excited and ejected from their orbits. The resulting vacancies are filled by electrons from higher energy levels, releasing X-rays with energiescharacteristic of the elements present in the material.The energy of the emitted X-rays is specific to each element, and the intensity of the X-rays is proportional to the concentration of the element in the material. By measuring the energies and intensities of the emitted X-rays, it is possible to identify and quantify the elements present in the sample.Instrumentation.A typical XRF spectrometer consists of the following components:X-ray source: Generates high-energy X-rays that bombard the sample.Sample chamber: Holds the sample to be analyzed.Detector: Converts X-rays into electrical signals.Multichannel analyzer (MCA): Digitizes and analyzes the electrical signals from the detector.Types of XRF Spectrometers.There are several types of XRF spectrometers, each with its own advantages and limitations:Energy-dispersive XRF (EDXRF): Uses a solid-state detector to measure the energies of the emitted X-rays. EDXRF is relatively inexpensive and easy to operate, but it has lower energy resolution compared to other types of XRF spectrometers.Wavelength-dispersive XRF (WDXRF): Uses a crystal monochromator to separate the emitted X-rays by wavelength. WDXRF offers higher energy resolution than EDXRF, but it is more complex, expensive, and time-consuming to operate.Total reflection XRF (TXRF): Utilizes total reflection conditions to enhance the sensitivity for analyzing trace elements in liquids. TXRF is highly sensitive, but it requires sample preparation and is not suitable for solid samples.Applications of XRF.XRF is a versatile analytical technique with a wide range of applications:Geochemistry: Determining the elemental composition of rocks, minerals, and soils.Environmental science: Monitoring pollutants in air, water, and soil.Forensic science: Analyzing trace evidence, such as gunshot residue and paint chips.Archaeology: Studying the composition of artifacts and ancient materials.Materials science: Characterizing the elemental composition of metals, alloys, and other materials.Advantages of XRF.Nondestructive: Does not damage the sample being analyzed.Multi-elemental: Can identify and quantify multiple elements simultaneously.Rapid: Provides real-time analysis results.Sensitive: Can detect elements at trace levels.Versatile: Can be applied to various sample types, including solids, liquids, and powders.Limitations of XRF.Limited sensitivity: Cannot detect elements present in very low concentrations.Matrix effects: The presence of other elements in the sample can affect the accuracy of the analysis.Sample preparation: May require sample preparation,such as grinding or homogenization.Cost: XRF spectrometers can be expensive, especially WDXRF systems.Conclusion.X-Ray Fluorescence Spectrometry is a powerful analytical technique that provides valuable information about the elemental composition of materials. It is widely used in various fields and offers advantages such as non-destructiveness, multi-elemental analysis, and rapid results. However, it has limitations in sensitivity and potential matrix effects, which should be considered when selecting this technique for specific applications.。
少数载流子瞬态光谱(mcts)
少数载流子瞬态光谱(MCTS)是一种用于研究半导体材料中载流子动力学特性的先进技术。
通过测量材料中载流子的寿命和迁移率等参数,可以深入了解材料的电学性质,对半导体材料的研究和应用具有重要意义。
1. MCTS的原理和方法少数载流子瞬态光谱是使用激光脉冲来激发半导体材料,然后通过光电探测器测量样品的光学响应。
在这个过程中,材料中的载流子会发生非平衡状态的激发和复合过程,这些过程会导致材料的光学性质发生变化。
通过对这些变化的测量和分析,可以得到材料中载流子的寿命、迁移率等重要参数。
MCTS通常包括时间分辨和频率分辨两种方法。
时间分辨MCTS主要通过测量载流子在光激发后的动力学过程来研究载流子的特性,而频率分辨MCTS则通过对不同频率激发光的响应来获得频率依赖的载流子动力学信息。
2. MCTS在半导体材料研究中的应用MCTS在半导体材料研究中具有广泛的应用价值。
它可以帮助研究人员深入了解材料的电学性质,包括载流子的寿命、迁移率、复合过程等。
这些参数对于半导体材料的电子器件性能具有重要影响,因此MCTS 可以为新材料的研发和性能优化提供重要参考。
MCTS还可以用于研究半导体材料中的缺陷和杂质。
通过分析载流子动力学的变化,可以推断出材料中的缺陷类型和浓度等信息,这对于材料的质量控制和改进具有重要意义。
另外,MCTS也可以用于研究半导体材料中的光学特性和光电器件的工作原理。
通过对载流子动力学的研究,可以更好地理解材料的光吸收、发光等过程,为新型光电器件的设计和优化提供重要参考。
3. MCTS的发展和未来随着半导体材料和器件的不断发展,MCTS技术也在不断完善和拓展。
近年来,一些新型的光子学和超快光学技术被应用到MCTS中,如二维电子谱学、高阶谐波产生等,使得 MCTS 在时间和频率分辨能力上有了新的突破。
这些进展为更深入地研究和理解半导体材料的载流子动力学提供了新的途径,也为半导体光电器件的性能优化提供了更多可能性。
X-ray photoelectron spectroscopy - Wikipedia, the free encyclopedia
Basic components of a monochromatic XPS system.X-ray photoelectron spectroscopyFrom Wikipedia, the free encyclopedia"ESCA" redirects here. For the grape disease, see Esca (grape disease).X-ray photoelectron spectroscopy(XPS) is a surface-sensitivequantitative spectroscopic techniquethat measures the elementalcomposition at the parts perthousand range, empirical formula,chemical state and electronic stateof the elements that exist within amaterial. XPS spectra are obtainedby irradiating a material with abeam of X-rays while simultaneouslymeasuring the kinetic energy andnumber of electrons that escape from the top 0 to 10 nm of the materialbeing analyzed. XPS requires highvacuum (P ~ 10−8 millibar) or ultra-high vacuum (UHV; P < 10−9 millibar)conditions, although a current area of development is ambient-pressure XPS, in which samples are analyzed at pressures of a few tens of millibar.XPS is a surface chemical analysis technique that can be used to analyze the surface chemistry of a material in its as-received state, or after some treatment, forexample: fracturing, cutting or scraping in air or UHV to expose the bulk chemistry,ion beam etching to clean off some or all of the surface contamination (with mild ion etching) or to intentionally expose deeper layers of the sample (with moreextensive ion etching) in depth-profiling XPS, exposure to heat to study the changes due to heating, exposure to reactive gases or solutions, exposure to ion beamimplant, exposure to ultraviolet light.XPS is also known as ESCA (Electron Spectroscopy for Chemical Analysis), anabbreviation introduced by Kai Siegbahn's research group to emphasize thechemical (rather than merely elemental) information that the techniqueprovides.In principle XPS detects all elements. In practice, using typical laboratory-scale X-ray sources, XPS detects all elements with an atomic number (Z ) of 3(lithium) and above. It cannot easily detect hydrogen (Z = 1) or helium (Z =2).Detection limits for most of the elements (on a modern instrument) are in theparts per thousand range. Detection limits of parts per million (ppm) arepossible, but require special conditions: concentration at top surface or very long collection time (overnight).XPS is routinely used to analyze inorganic compounds, metal alloys,semiconductors, polymers, elements, catalysts, glasses, ceramics, paints,papers, inks, woods, plant parts, make-up, teeth, bones, medical implants, bio-materials, viscous oils, glues, ion-modified materials and many others.XPS is less routinely used to analyze the hydrated forms of some of the abovematerials by freezing the samples in their hydrated state in an ultra pureenvironment, and allowing or causing multilayers of ice to sublime away priorWide-scan or survey spectrum of a somewhat dirty silicon wafer, showing all elements present. A survey spectrum is usually the starting point of most XPS analyses because it shows all elements present on the sample surface and allows one to set up subsequent high-resolution XPS spectra acquisition. The inset shows a quantification table indicating all elements observed, their binding energies, and their atomic percentages.to analysis. Such hydrated XPS analysis allows hydrated sample structures,which may be different from vacuum-dehydrated sample structures, to be studied in their more relevant as-used hydrated structure. Many bio-materials such ashydrogels are examples of such samples.Contents1 Measurements2 History3 Basic physics4 Surface sensitivity5 Components of a commercialsystem6 Uses and capabilities7 Capabilities of advancedsystems8 Chemical states andchemical shift9 Industrial use10 Routine limits10.1 Quantitativeaccuracy and precision10.2 Analysis time10.3 Detection limits10.4 Measured area10.5 Sample size limits10.6 Degradation duringanalysis10.7 General summary ofuse11 Materials routinelyanalyzed12 Analysis details12.1 Charge compensationtechniques12.2 Sample preparation13 Data processing13.1 Peak identification13.2 Charge referencinginsulators13.3 Peak-fitting13.3.1 FWHMs13.3.2 Chemicalshifts13.3.3 Peak shapes13.3.4 Instrumentdesign factors13.3.5 Experimentsettings13.3.6 Samplefactors14 Advanced instrumentationHigh-resolution spectrum of an oxidized silicon wafer in the energy range of the Si 2p signal.The raw data spectrum (red) is fitted with five components or chemical states, A through E. Themore oxidized forms of Si (SiO x , x = 1-2) appearat higher binding energies in the broad featurecentered at 103.67 eV. The so-called metallicform of silicon, which resides below an upperlayer of oxidized silicon, exhibits a set ofdoublet peaks at 100.30 eV (Si 2p 1/2) and 99.69eV (Si 2p 3/2). The fact that the metallic silicon signal can be seen "through" the overlayer of oxidized Si indicates that the silicon oxide layer is relatively thin (2-3 nm). Attenuation of XPS signals from deeper layers by overlayers is often used in XPS to estimate layer thicknesses and depths.aspects14.1 Hemisphericalelectron energy analyzer14.2 Cylindrical mirroranalyser14.3 Synchrotron basedXPS15 Electron detectors15.1 Older styleelectron detector16 Theoretical aspects16.1 Quantum mechanicaltreatment16.2 Theory of corelevel photoemission ofelectrons17 See also17.1 Related methods18 References19 Further reading20 External links Measurements XPS is used to measure:elemental composition of the surface (top 0–10 nm usually)empirical formula of pure materials elements that contaminate a surface chemical or electronic state of each element in the surfaceuniformity of elementalcomposition across the top surface (or line profiling or mapping)uniformity of elemental composition as a function of ion beam etching (or depth profiling)XPS can be performed using a commercially built XPS system, a privately built XPSsystem, or a synchrotron-based light source combined with a custom-designed electron energy analyzer. Commercial XPS instruments in the year 2005 used either a focused 20- to 500-micrometer-diameter beam of monochromatic Al K α X-rays, or a broad 10-to 30-mm-diameter beam of non-monochromatic (polychromatic) Al K α X-rays or Mg K αX-rays. A few specially designed XPS instruments can analyze volatile liquids orgases, or materials at pressures of roughly 1 torr (1.00 torr = 1.33 millibar), but there are relatively few of these types of XPS systems. The ability to heat or cool the sample during or prior to analysis is relatively common.Because the energy of an X-ray withparticular wavelength is known (forAl Kα X-rays, E photon = 1486.7 eV),and because the emitted electrons'kinetic energies are measured, theelectron binding energy of each ofthe emitted electrons can bedetermined by using an equation thatis based on the work of ErnestRutherford (1914):Rough schematic of XPS physics - "PhotoelectricEffect.where E binding is the binding energy (BE) of the electron, E photon is the energy ofthe X-ray photons being used, E kinetic is the kinetic energy of the electron as measured by the instrument and is the work function dependent on both the spectrometer and the material. This equation is essentially a conservation of energy equation. The work function term is an adjustable instrumental correction factor that accounts for the few eV of kinetic energy given up by the photoelectron as it becomes absorbed by the instrument's detector. It is a constant that rarely needs to be adjusted in practice.HistoryIn 1887, Heinrich Rudolf Hertz discovered but could not explain the photoelectric effect, which was later explained in 1905 by Albert Einstein (Nobel Prize in Physics 1921). Two years after Einstein's publication, in 1907, P.D. Innes experimented with a Röntgen tube, Helmholtz coils, a magnetic field hemisphere (an electron kinetic energy analyzer), and photographic plates, to record broad bands of emitted electrons as a function of velocity, in effect recording the first XPS spectrum. Other researchers, including Henry Moseley, Rawlinson and Robinson, independently performed various experiments to sort out the details in the broad bands. World Wars I and II halted research on XPS.After WWII, Kai Siegbahn and his research group in Uppsala (Sweden) developed several significant improvements in the equipment, and in 1954 recorded the first high-energy-resolution XPS spectrum of cleaved sodium chloride (NaCl), revealing the potential of XPS.[1] A few years later in 1967, Siegbahn published a comprehensive study of XPS, bringing instant recognition of the utility of XPS, which he referred to as ESCA (Electron Spectroscopy for Chemical Analysis). In cooperation with Siegbahn, a small group of engineers (Mike Kelly, Charles Bryson, Lavier Faye, Robert Chaney) at Hewlett-Packard in the USA, produced the first commercialmonochromatic XPS instrument in 1969. Siegbahn received the Nobel Prize for Physics in 1981, to acknowledge his extensive efforts to develop XPS into a usefulanalytical tool.[2]In parallel with Siegbahn's work, David Turner at Imperial College (and later at Oxford University) in the UK developed ultraviolet photoelectron spectroscopy (UPS) on molecular species using helium lamps.[3]Basic physicsA typical XPS spectrum is a plot of the number of electrons detected (sometimes per unit time) (Y-axis, ordinate) versus the binding energy of the electrons detected (X-axis, abscissa). Each element produces a characteristic set of XPS peaks at characteristic binding energy values that directly identify each element that exists in or on the surface of the material being analyzed. These characteristic spectral peaks correspond to the electron configuration of the electrons within the atoms, e.g., 1s, 2s, 2p, 3s, etc. The number of detected electrons in each of the characteristic peaks is directly related to the amount of element within the XPS sampling volume. To generate atomic percentage values, each raw XPS signal must be corrected by dividing its signal intensity (number of electrons detected) by a "relative sensitivity factor" (RSF), and normalized over all of the elements detected. Since hydrogen is not detected, these atomic percentages exclude hydrogen. To count the number of electrons during the acquisition of a spectrum with a minimum of error, XPS detectors must be operated under ultra-high vacuum (UHV) conditions because electron counting detectors in XPS instruments are typically one meter away from the material irradiated with X-rays. This long path length for detection requires such low pressures.Surface sensitivityXPS detects only those electrons that have actually escaped from the sample into the vacuum of the instrument, and reach the detector. In order to escape from the sample into vacuum, a photoelectron must travel through the sample. Photo-emitted electrons can undergo inelastic collisions, recombination, excitation of the sample, recapture or trapping in various excited states within the material, all of which can reduce the number of escaping photoelectrons. These effects appear as an exponential attenuation function as the depth increases, making the signals detected from analytes at the surface much stronger than the signals detected from analytes deeper below the sample surface. Thus, the signal measured by XPS is an exponentially surface-weighted signal, and this fact can be used to estimate analyte depths in layered materials.Components of a commercial systemThe main components of a commercially made XPS system include a source of X-rays, an ultra-high vacuum (UHV) stainless steel chamber with UHV pumps, an electron collection lens, an electron energy analyzer, Mu-metal magnetic field shielding, anAn inside view of an old-type, non-monochromatic XPS system.electron detector system, a moderate vacuum sample introduction chamber, sample mounts, a sample stage, and a set of stage manipulators.Monochromatic aluminium K-alpha X-rays are normally produced by diffracting and focusing a beam of non-monochromatic X-rays off of a thin disc of natural,crystalline quartz with a <1010>orientation. The resulting wavelength is8.3386 angstroms (0.83386 nm) whichcorresponds to a photon energy of 1,486.7eV. Aluminum K -alpha X-rays have anintrinsic FWHM of 0.43 eV, centered on1,486.7 eV (E /ΔE = 3,457). For a welloptimized monochromator, the energy width of the monochromated aluminum K -alpha X-rays is 0.16 eV, but energy broadening incommon electron energy analyzers(spectrometers) produces an ultimate energy resolution on the order of FWHM=0.25 eV which, in effect, is the ultimate energy resolution of most commercial systems. When working under practical, everyday conditions, high-energy-resolution settings will produce peak widths (FWHM) between 0.4–0.6 eV for various pure elements and somecompounds. For example, in a spectrum obtained in 1 minute at a pass energy of 20 eV using monochromated aluminum K -alpha X-rays, the Ag 3d 5/2 peak for a clean silver film or foil will typically have a FWHM of 0.45 eV.Non-monochromatic magnesium X-rays have a wavelength of 9.89 angstroms (0.989 nm)which corresponds to a photon energy of 1253 eV. The energy width of the non-monochromated X-ray is roughly 0.70 eV, which, in effect is the ultimate energy resolution of a system using non-monochromatic X-rays. Non-monochromatic X-raysources do not use any crystals to diffract the X-rays which allows all primary X-rays lines and the full range of high-energy Bremsstrahlung X-rays (1–12 keV) to reach the surface. The ultimate energy resolution (FWHM) when using a non-monochromatic Mg K -alpha source is 0.9–1.0 eV, which includes some contribution from spectrometer-induced broadening.Uses and capabilitiesXPS is routinely used to determine:What elements and the quantity of those elements that are present within thetop 1-12 nm of the sample surfaceWhat contamination, if any, exists on the surface or in the bulk of the sample Empirical formula of a material that is free of excessive surface contamination The chemical state identification of one or more of the elements in the sample and also give information on local bonding of atomThe binding energy of one or more electronic statesThe thickness of one or more thin layers (1–8 nm) of different materialswithin the top 12 nm of the surfaceThe density of electronic statesCapabilities of advanced systemsMeasure uniformity of elemental composition across the top the surface (or line profiling or mapping)Measure uniformity of elemental composition as a function of depth by ion beam etching (or depth profiling)Measure uniformity of elemental composition as a function of depth by tilting the sample (or angle-resolved XPS)Chemical states and chemical shiftThe ability to produce chemical state information (as distinguished from merely elemental information) from the topmost few nm of any surface makes XPS a unique and a valuable tool for understanding the chemistry of any surface, either as received, or after physical or chemical treatment(s). In this context, "chemical state" refers to the local bonding environment of a species in question. The local bonding environment of a species in question is affected by its formal oxidation state, the identity of its nearest-neighbor atom, its bonding hybridization to that nearest-neighbor atom, and in some cases even the bonding hybridization between the atom in question and the next-nearest-neighbor atom. Thus, while the nominal binding energy of the C 1s electron is 284.6 eV (some also use 285.0 eV as the nominal value for the binding energy of carbon), subtle but reproducible shifts in the actual binding energy, the so-called chemical shift, provide the chemical state informationreferred to here.Chemical-state analysis is widely used for the element carbon. Chemical-state analysis of the surface of carbon-containing polymers readily reveals the presence or absence of the chemical states of carbon shown in bold, in approximate order of increasing binding energy, as: carbide (-C2−), silicone (-Si-C H3),methylene/methyl/hydrocarbon (-C H2-C H2-, C H3-CH2-, and -C H=C H-), amine (-C H2-NH2), alcohol (-C-OH), ketone (-C=O), organic ester (-C OOR), carbonate (-C O32−), monofluoro-hydrocarbon (-C FH-CH2-), difluoro-hydrocarbon (-C F2-CH2-), and trifluorocarbon (-CH2-C F3), to name but a few examples.Chemical state analysis of the surface of a silicon wafer readily reveals chemical shifts due to the presence or absence of the chemical states of silicon in its different formal oxidation states, such as: n-doped silicon and p-doped silicon (metallic silicon in figure above), silicon suboxide (Si2O), silicon monoxide (SiO), Si2O3, and silicon dioxide (SiO2). An example of this is seen in the figure above: High-resolution spectrum of an oxidized silicon wafer in the energy range of the Si 2p signal.Industrial useAdhesionAgricultureAutomotiveBatteryBiomaterialsBiomedicalBiotechnologyCanningCatalystCeramicChemicalComputerCosmeticsElectronicsEnergyEnvironmentalFabricsFoodFuel cellsGeologyGlassLaserLightingLubricationMagnetic storageMineralogyMiningNanotechnologyNuclearPackagingPaintingPaper and woodPlatingPolymer and plasticPrintingRecordingSemiconductorSteelTextilesThin-film coatingWeldingRoutine limitsQuantitative accuracy and precisionXPS is widely used to generate an empirical formula because it readily yields excellent quantitative accuracy from homogeneous solid-state materials.Quantification can be divided into two categories: absolute quantification and relative quantification. The former generally requires the use of certified (or independently verified) standard samples, is generally more challenging, and is generally less common.Relative quantification is more common and involves comparisons between several samples in a set for which one or more analytes are varied while all othercomponents (the sample matrix) are held constant.Quantitative accuracy depends on several parameters such as: signal-to-noise ratio, peak intensity, accuracy of relative sensitivity factors, correction for electron transmission function, surface volume homogeneity, correction forenergy dependence of electron mean free path, and degree of sample degradation due to analysis.Under optimum conditions, the quantitative accuracy of the atomic percent (at%) values calculated from the Major XPS Peaks is 90-95% for each major peak. If a high level quality control protocol is used, the accuracy can be furtherimproved.Under routine work conditions, where the surface is a mixture of contamination and expected material, the accuracy ranges from 80-90% of the value reported in atomic percent values.The quantitative accuracy for the weaker XPS signals, that have peakintensities 10-20% of the strongest signal, are 60-80% of the true value, and depend upon the amount of effort used to improve the signal-to-noise ratio (for example by signal averaging).Quantitative precision (the ability to repeat a measurement and obtain the same result) is an essential consideration for proper reporting of quantitativeresults. Standard statistical tests, such as the Student's t test forcomparison of means, should be used to determine confidence levels in theaverage value from a set of replicate measurements, and when comparing theaverage values of two or more different sets of results. In general, a p value (an output of the Student's t test) of 0.05 or less indicates a level ofconfidence (95%) that is accepted in the field as significant.Analysis timeTypically ranging 1–20 minutes for a broad survey scan that measures theamount of all detectable elements, typically 1–15 minutes for high resolution scan that reveal chemical state differences (for a high signal/noise ratio for count area result often requires multiple sweeps of the region of interest), 1–4 hours for a depth profile that measures 4–5 elements as a function ofetched depth (this process time can vary the most as many factors will play a role).Detection limits0.1–1.0 at% (0.1 at% = 1 part per thousand = 1000 ppm). (Ultimate detectionlimit for most elements is approximately 100 ppm, which requires 10–16 hours.) Measured areaMeasured area depends on instrument design. The minimum analysis area ranges from 10 to 200 micrometres. Largest size for a monochromatic beam of X-rays is 1–5 mm. Non-monochromatic beams are 10–50 mm in diameter. Spectroscopicimage resolution levels of 200 nm or below has been achieved on latest imaging XPS instruments using synchrotron radiation as X-ray source.Sample size limitsInstruments accept small (mm range) and large samples (cm range), e.g. wafers. Limiting factor is the design of the sample holder, the sample transfer, and the size of the vacuum chamber. Large samples are laterally moved in x and y direction to analyse a larger area.Degradation during analysisDepends on the sensitivity of the material to the wavelength of X-rays used, the total dose of the X-rays, the temperature of the surface and the level of the vacuum. Metals, alloys, ceramics and most glasses are not measurablydegraded by either non-monochromatic or monochromatic X-rays. Some, but notall, polymers, catalysts, certain highly oxygenated compounds, variousinorganic compounds and fine organics are degraded by either monochromatic or non-monochromatic X-ray sources.Non-monochromatic X-ray sources produce a significant amount of high energyBremsstrahlung X-rays (1–15 keV of energy) which directly degrade the surface chemistry of various materials. Non-monochromatic X-ray sources also produce a significant amount of heat (100 to 200 °C) on the surface of the samplebecause the anode that produces the X-rays is typically only 1 to 5 cm (2 in) away from the sample. This level of heat, when combined with the Bremsstrahlung X-rays, acts synergistically to increase the amount and rate of degradation for certain materials. Monochromatic X-ray sources, because they are far away (50–100 cm) from the sample, do not produce any heat effects.Monochromatic X-ray sources are monochromatic because the quartz monochromator system diffracts the Bremsstrahlung X-rays out of the X-ray beam, which means the sample is only exposed to one narrow band of X-ray energy. For example, if aluminum K-alpha X-rays are used, the intrinsic energy band has a FWHM of 0.43 eV, centered on 1,486.7 eV (E/ΔE = 3,457). If magnesium K-alpha X-rays areused, the intrinsic energy band has a FWHM of 0.36 eV, centered on 1,253.7 eV (E/ΔE = 3,483). These are the intrinsic X-ray line widths; the range ofenergies to which the sample is exposed depends on the quality and optimization of the X-ray monochromator.Because the vacuum removes various gases (e.g., O2, CO) and liquids (e.g.,water, alcohol, solvents, etc.) that were initially trapped within or on the surface of the sample, the chemistry and morphology of the surface willcontinue to change until the surface achieves a steady state. This type ofdegradation is sometimes difficult to detect.General summary of useXPS is, in effect, a non-destructive technique that measures the surfacechemistry of most any material, however non-dry, outgassing, radioactive orhighly magnetic materials can pose serious challenges.Materials routinely analyzedInorganic compounds, metal alloys, semiconductors, polymers, pure elements, catalysts, glasses, ceramics, paints, papers, inks, woods, plant parts, make-up, teeth, bones, human implants, biomaterials,[4] viscous oils, glues, ion modified materialsAnalysis detailsCharge compensation techniquesLow-voltage electron beam (1-20 eV) (or electron flood gun)UV lightsLow-voltage argon ion beam with low-voltage electron beam (1-10 eV)Aperture masksMesh screen with low-voltage electron beamsSample preparationSample handlingSample cleaningSample mountingData processingPeak identificationThe number of peaks produced by a single element varies from 1 to more than 20. Tables of binding energies (BEs) that identify the shell and spin-orbit of each peak produced by a given element are included with modern XPS instruments, and can be found in various handbooks [citations] and websites.[5] Because these experimentally determined BEs are characteristic of specific elements, they can be directly used to identify experimentally measured peaks of a material with unknown elemental composition.Before beginning the process of peak identification, the analyst must determine if the BEs of the unprocessed survey spectrum (0-1400 eV) have or have not been shifted due to a positive or negative surface charge. This is most often done by looking for two peaks that due to the presence of carbon and oxygen. {tbc}Charge referencing insulatorsCharge referencing is needed when a sample suffers either a positive (+) or negative (-) charge induced shift of experimental BEs. Charge referencing is needed to obtain meaningful BEs from both wide-scan, high sensitivity (low energy resolution) survey spectra (0-1100 eV), and also narrow-scan, chemical state (high energy resolution) spectra.Charge induced shifting causes experimentally measured BEs of XPS peaks to appear at BEs that are greater or smaller than true BEs. Charge referencing is performed by adding or subtracting a "Charge Correction Factor" to each of the experimentally measured BEs. In general, the BE of the hydrocarbon peak of the C (1s) XPS signal is used to charge reference (charge correct) all BEs obtained from non-conductive (insulating) samples or conductors that have been deliberately insulated from the sample mount.Charge induced shifting is normally due to: a modest excess of low voltage (-1 to-20 eV) electrons attached to the surface, or a modest shortage of electrons (+1 to +15 eV) within the top 1-12 nm of the sample caused by the loss of photo-emitted electrons. The degree of charging depends on various factors. If, by chance, the charging of the surface is excessively positive, then the spectrum might appear as a series of rolling hills, not sharp peaks as shown in the example spectrum.The C (1s) BE of the hydrocarbon species (moieties) of the "Adventitious" carbonthat appears on all, air-exposed, conductive and semi-conductive materials is normally found between 284.5 eV and 285.5 eV. For convenience, the C (1s) of hydrocarbon moieties is defined to appear between 284.6 eV and 285.0 eV. A value of 284.8 eV has become popular in recent years. However, some recent reports indicate that 284.9 eV or 285.0 eV represents hydrocarbons attached on metals, not thenatural native oxide. The 284.8 eV BE is routinely used as the "Reference BE" for charge referencing insulators. When the C (1s) BE is used for charge referencing, then the charge correction factor is the difference between 284.8 eV and the experimentally measured C (1s) BE of the hydrocarbon moieties.When using a monochromatic XPS system together with a low voltage electron flood gun for charge compensation the experimental BEs of the C (1s) hydrocarbon peak is often 4-5 eV smaller than the reference BE value (284.8 eV). In this case, all experimental BEs appear at lower BEs than expected and need to be increased by adding a value ranging from 4 to 5 eV. Non-monochromatic XPS systems are not usually equipped with a low voltage electron flood gun so the BEs will normally appear at higher BEs than expected. It is normal to subtract a charge correction factor from all BEs produced by a non-monochromatic XPS system.Conductive materials and most native oxides of conductors should never need charge referencing. Conductive materials should never be charge referenced unless the topmost layer of the sample has a thick non-conductive film.Peak-fittingThe process of peak-fitting high energy resolution XPS spectra is still a mixture of art, science, knowledge and experience. The peak-fit process is affected by instrument design, instrument components, experimental settings (aka analysis conditions) and sample variables. Most instrument parameters are constant while others depend on the choice of experimental settings.Before starting any peak-fit effort, the analyst performing the peak-fit needs to know if the topmost 15 nm of the sample is expected to be a homogeneous material or is expected to be a mixture of materials. If the top 15 nm is a homogeneous material with only very minor amounts of adventitious carbon and adsorbed gases, then the analyst can use theoretical peak area ratios to enhance the peak-fitting process.Variables that affect or define peak-fit results include:FWHMsChemical ShiftsPeakshapesInstrument design factorsExperimental settingsSample factorsFWHMsWhen using high energy resolution experiment settings on an XPS equipped with a monochromatic Al K-alpha X-ray source, the FWHM of the major XPS peaks range。
电感耦合等离子体发射光谱法的英文简称
电感耦合等离子体发射光谱法的英文简称全文共3篇示例,供读者参考篇1Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) is a powerful analytical technique used in many scientific fields. This technique utilizes the high temperature of a plasma to atomize and excite samples for elemental analysis. ICP-OES provides high sensitivity, accuracy, and precision, making it a popular choice for analyzing trace elements in various sample types.The process of ICP-OES involves generating a plasma by applying a high-frequency radio frequency (RF) current to a flowing gas, typically argon. The intense heat of the plasma vaporizes the sample and excites the atoms to emit characteristic light at specific wavelengths. This emitted light is then dispersed by a spectrometer and detected by a charged-coupled device (CCD) detector. The intensity of the emitted light is proportional to the concentration of the element in the sample, allowing for quantitative analysis.ICP-OES is widely used in environmental monitoring, pharmaceutical analysis, forensic science, and materials science, among other areas. It can detect a wide range of elements, from alkali metals to rare earth elements, with detection limits as low as parts per billion. Additionally, ICP-OES can analyze multiple elements simultaneously, making it a fast and efficient tool for elemental analysis.Overall, ICP-OES is a versatile and reliable technique for elemental analysis, providing accurate and precise results for a wide range of sample types. Its high sensitivity and ability to analyze multiple elements simultaneously make it an essential tool in many research and industrial laboratories.篇2Title: ICP-OES: The Technique Behind Inductively Coupled Plasma Optical Emission SpectroscopyIntroductionInductively Coupled Plasma Optical Emission Spectroscopy, commonly abbreviated as ICP-OES, is a powerful analytical technique used for the quantitative analysis of elements present in a sample. This technique utilizes the principles of inductively coupled plasma (ICP) and optical emission spectroscopy (OES) toprovide accurate and precise measurements of the elemental composition of a sample. In this article, we will explore the fundamentals of ICP-OES and its applications in various fields.Principles of ICP-OESICP-OES operates by generating a high-temperature plasma consisting of ionized gas atoms by introducing a sample into an argon gas stream. The plasma is sustained by an induction coil, which induces an electric current that generates heat, forming a high-energy environment capable of atomizing and ionizing the sample components. As the atoms and ions return to their ground state, they emit light at characteristic wavelengths, which can be measured by a spectrometer to identify and quantify the elements present in the sample.Advantages of ICP-OESICP-OES offers several advantages over other analytical techniques, making it a preferred choice for elemental analysis in various industries. Some of the key advantages of ICP-OES include:- High sensitivity and detection limits: ICP-OES can detect elements at trace levels, making it suitable for a wide range ofapplications, including environmental monitoring and pharmaceutical analysis.- Multi-element analysis: ICP-OES is capable of analyzing multiple elements simultaneously, providing comprehensive information on the elemental composition of a sample.- Wide dynamic range: ICP-OES can analyze elements across a wide concentration range, from parts-per-billion to percent levels, making it suitable for diverse sample types.- Speed and efficiency: ICP-OES offers rapid analysis times, allowing for high sample throughput and increased productivity.- Minimal sample preparation: ICP-OES requires minimal sample preparation, saving time and reducing the risk of sample contamination.Applications of ICP-OESICP-OES is widely used in various industries and research fields for elemental analysis due to its versatility and accuracy. Some common applications of ICP-OES include:- Environmental analysis: ICP-OES is used for the analysis of trace elements in soil, water, and air samples to assess environmental contamination levels.- Geological analysis: ICP-OES is employed in the analysis of rocks, minerals, and ores to determine their elemental composition and identify valuable mineral deposits.- Pharmaceutical analysis: ICP-OES is used in the pharmaceutical industry for the analysis of drug formulations, determining the elemental impurities present in pharmaceutical products.- Food and beverage analysis: ICP-OES is utilized for the analysis of food and beverage products to ensure compliance with regulatory standards and assess product safety.ConclusionICP-OES is a versatile and reliable technique for elemental analysis, offering high sensitivity, multi-element capabilities, and rapid analysis times. With its wide range of applications in various fields, ICP-OES has become an essential tool for researchers, analysts, and industry professionals seeking accurate and precise elemental analysis. As technology continues to advance, ICP-OES is expected to play a key role in shaping the future of analytical chemistry and elemental analysis.篇3Inductively Coupled Plasma Emission Spectroscopy (ICP-ES) is a powerful analytical technique widely used in various fields including environmental monitoring, pharmaceutical analysis, and material science. This technique is based on the inductively coupled plasma (ICP) as the excitation source and the emission spectroscopy for detecting and quantifying elements present in a sample.ICP-ES offers several advantages over other analytical methods. Firstly, it provides a high sensitivity, allowing for the detection of trace elements at parts per billion or even parts per trillion levels. This makes ICP-ES ideal for analyzing samples with low concentrations of elements of interest. Secondly, ICP-ES has a wide dynamic range, enabling the simultaneous analysis of multiple elements present in a sample. This feature is particularly useful when analyzing complex samples containing a diverse range of elements. Additionally, ICP-ES offers excellent precision and accuracy, making it a reliable technique for quantitative analysis.The principle of ICP-ES involves the generation of ahigh-temperature plasma by inducing an electric current in a gas (typically argon) using a radiofrequency source. The plasma reaches temperatures of up to 10,000 Kelvin, causing the sampleto be atomized and ionized. As a result, the atoms and ions emit characteristic radiation when transitioning from excited states to ground states. The emitted radiation is then dispersed and detected by a spectrometer, allowing for the identification and quantification of elements based on their unique emission spectra.The use of inductively coupled plasma as the excitation source offers several advantages over other excitation sources, such as flame atomic absorption spectroscopy and graphite furnace atomic absorption spectroscopy. Firstly, the high temperature of the plasma ensures complete atomization and ionization of the sample, leading to higher sensitivity and lower detection limits. Secondly, the plasma provides a stable and robust excitation source, resulting in reliable and reproducible analytical results. Additionally, the high energy density of the plasma allows for the analysis of refractory elements that are difficult to atomize using other excitation sources.ICP-ES is a versatile technique that can be used for the analysis of a wide range of samples, including liquids, solids, and gases. It is commonly used for the analysis of environmental samples, such as water, soil, and air, to monitor the levels of toxic elements and pollutants. In the pharmaceutical industry, ICP-ESis used for the analysis of drug formulations to ensure compliance with regulatory standards. In material science, ICP-ES is employed for the analysis of metals, alloys, and ceramics to determine their elemental composition and purity.In conclusion, Inductively Coupled Plasma Emission Spectroscopy (ICP-ES) is a powerful analytical technique that offers high sensitivity, wide dynamic range, and excellent precision for the analysis of trace elements in various samples. Its use of inductively coupled plasma as the excitation source provides several advantages over other excitation sources, making it a popular choice in analytical laboratories worldwide. With its versatility and reliability, ICP-ES is a valuable tool for research, quality control, and environmental monitoring applications.。
不同科技学科单词
colon n.冒号dash n.连接号comma n.逗号underscore n.下划线discipline n.学科fundamental s n.基本原理corollary n.推论assume v.假设assessment n.评估assignment n.任务access n.通道入口v.接近accurate adj.准确的精确的analysis n.分析elementary adj.基础的algebra n.代数calculus n.微积分probability n.概率论prescribe v.规定指示开药方protocol n. (数据传输)协议laboratory n. 实验课conduct v.组织实施指挥enforce v.实施强迫fundamental adj.基本的comprehensive adj.综合的comprehension n.理解力complement n.补充second half 下半场revise v.复习修正reinforce v.增强review v.复习notify v.通知公告notification n. 通知subsequent adj.随后的curriculum n.课程circuit n.电路v. 环行router n.路由器server n.服务器projector n.投影仪analogous adj.类似的analogue adj.模拟的n.类似物analogy n.类比propagate v.传播普及繁衍accelerate v.加速framework n.结构框架dispensable adj.非必需的indispensable adj.必不可少的terminology n.术语deploy v.部署有效利用module n.单元模块modulate v.调制调节modulation n.调制model n/v. 模型做模型建模modem 等于modulator-demodulator n.调制解调器cellular adj.蜂窝的细胞的interference n.干涉干扰slide n.幻灯片v.滑动降低slice v./n.薄片切precise adj.精确的heterogeneous adj.多种多样由不同组成的homogeneous adj.同类的由相同组成的(uniform)无线通信:spectrum n.谱频谱声谱spectral adj.domain n.范围领域定义域域time domain时域frequency domain频域transmit v.传输传播发射transmitter n.发射机receiver n.接收机binary adj.二进制的bipolar adj.两极的双极性的repeater n.中继器转发器electromagnetic noise电磁干扰electromagnetic wave 电磁波interfere v.干扰阻碍interference n.interval n.间隔conjugate adj.共轭的distort v.扭曲失真distortion n.失真variance n.方差变化不一致variation n.变化mean n.平均值standard deviation 标准差covariance n.协方差integration n.积分integrate v.使结合一体化求积分derivation n.导数derivate v.派生衍生求导derive v.导出源于获得corrupted adj.损坏的腐败的modulation n.调制demodulation n.解调amplitude n.振幅广阔丰富detection n.检测检波imaginary part 虚部real part 实部imaginary adj.虚构的想象的虚部的proximity n.接近临近proximate adj.近似的最接近的obstruct v.阻塞阻碍obstructed adj. unobstructed adj.decay v.腐朽衰败衰落attenuation n.衰减attenuate v.antenna gain 天线增益unitless 无单位的partition n./v.分裂隔板隔开random variable 随机变量conductor n.导体指挥检票员fluctuate v.波动carrier n.载波inter-symbol interference 符号间干扰ISIreplica n.复制副本overlap n./v.重叠convolution n.卷积convolute v.回旋卷绕discrete system 离散系统decompose v.分解腐烂sequence n.序列impulse n.脉冲一般指冲激信号velocity n.速率threshold n.阈值临界值coherent adj.相干的连贯的synchronize v.同步同时发生synchronization n.phase n.相位phasor n.矢量相量(包括幅度和角度)amplify v.放大增强dashed line虚线millisecond n.毫秒hexagon n.六角形prone adj.有...的倾向的易于...的deteriorate v.恶化退化sectorial adj.扇形的sectorization n.分段化扇形化sector n.扇形align v.校准对其一致alignment n.电信网络:topology n.拓扑学memory n.内存buffer n./v.缓存缓冲allocate v.分配指定拨出slot n./v.空挡位置idle adj./v.空闲的闲置的懒惰的congestion n.拥挤充血占线音congest v. busy tone 忙音processor n.处理器nodal adj.节点的encapsulation n.封装encapsulate v.压缩封入内部decapsulate v.解封装intermittent adj.间歇性的retrieve v.检索,恢复,取回identifer n.标识符proprietary adj.专有的专利的specification n.说明规范cleartext password 明文密码encrypt v.加密encryption n.intact adj.完好无损的integrate v.整合adj.完全的hierarchical adj.分层次的分等级的iterate v.迭代iteration n.recursive adj.递归的congest v.充血拥塞congestion n.idle adj./v.空闲的懒惰的encapsulate v.封装constrain v.约束constraint n.约束条件consent n./v.同意准许collision n.冲突collide v.reassemble v.重新装配fragment v./n.碎片片段payload n.有效负荷净负荷enumerate v.枚举列举数学相关:diagram n.图表v.用图表法histogram n.直方图柱状图exponential adj.指数的exponent n.指数orthogonal adj.正交的proportional adj.成比例的statistical adj.统计的integer n.整数constant n.常数variable n.变量symmetrical adj.对称的biased adj.偏的有偏见的bias n.偏见偏差arithmetic n./adj.算数算数的computation n.计算formula n.公式megabyte n.1MB mega百万10^6multi前缀多…multiple adj.多重的复杂的n.倍数multiply v.乘繁殖domain定义域range 值域slope n.斜率parameter n.参数加and/plus/added to 减minus/taken from/subtracted from subtraction减法4 plus 6 equals to 10. 8 minus 3 is 5.4 added to 6 is 10. 3 taken(subtracted) from 8 leaves 5.乘time/multiplied by 除divided to/into3 times 5 is 15. 8 into 24 equals 3.3 multiplies by 5 is 15. 24 divided by 8 is 3.3/4 three fourth s24/25 twenty-four twenty-fifth s10^7 the 7th power of 10 10 to the 7th powerx分之y y over xtranspose v.移项变换顺序转置multiplication n.相乘power n.幂4 to the power of 3. 4的3次方exponential adj./n.指数的logarithm n.对数logarithmic adj.initialization n.初始化probability n.概率proportional adj.成比例的linear adj.线性的nolinear adj.非线性的equation n.方程式fraction n.分数比例率coefficient n.系数denote v.表示指代(记为)threshold n.临界值阈值门槛converge v.趋于收敛于diameter n.直径weighted adj.加权的directed adj.有向的time-varying adj.时变的bifurcate v./adj. 分叉分支chaotic adj.无序的混沌的mutual adj.相互的共有的internal adj.内部的国内的external adj.外部的国外的fractal n.不规则形分形adjacent adj.相邻的shift v.移动替换transition n.转变过渡discrete adj.离散的分离的column n.列圆柱row n.行cylinder n.圆柱体identical adj.同一的identity n.同一性身份identify v.识别等同于geometric n.几何的denominator n.分母numerator n.分子2D continuous function 二维连续函数origin n.原点开端起源coordinate system 坐标系diagonal n./adj.对角线斜线density n.密度dense adj.稠密的密度大的normalized adj.标准化归一化dimensionless n.无穷小量dimension n.方面维3Dinverse adj./n.相反的倒转的倒数reciprocal n./adj.倒数的相互的交互的product n.乘积normal distribution 正态分布square n./adj.平方正方形monotonic adj.单调的argument n.自变量binomial n./adj. 二项式binomial distribution 二项分布inequality n.不等式不平等intersection n.交集交叉点intersect v.相交交叉横穿union n.并集编程相关:syntax n.语法句法tuple n. 数组set n.集合array n.数组package n.软件包extract n./v.提取摘录matrix n.矩阵loop n.循环iterate v.迭代execute v.执行function n.函数parameter n.参数segment n.段部分v.分割划分algorithm n.算法conjecture n.猜想theory n.理论theorem n.定理colon n.冒号interface n.界面v.连接交流图像处理:format n.格式v.格式化formation n.形成组成extract v.提取convert v.转变转换merge v.合并split v.分离划分slice v.切割RGB和BGR蓝绿红ROI: region of interestpixel n.像素photosite n.像素attribute n.属性variable n.变量element n.元素要素degrade v.退化降低degradation n.compress v.压缩compression n.压缩deburr v.清理毛刺blur n./v.模糊motion n./v.运动移动Spatial quantization 空间的量化intensity n.强度intense adj.强烈的紧张的激烈的inpainting n.图像修复texture n.质地实质纹理segment v.分割划分segmentation n.分割partition v.分割partitioning n.extract v.提取storage n.储存transmit v.传输发送transfer v.转移translate v.翻译shift v.转移换convert v.转变换算transition n.过渡转变transit v.运送经过lossy adj.有损耗的lossy compression 有损压缩acquire v.获得acquisition n.获得采集capture v.采集捕捉引起sensor n.传感器individual n.个人adj.单独的charge v./n.收费充电电荷accumulate v.累积horizontal adj./n.水平的水平面horizon n.地平线vertical adj./n.垂直的垂直线vertex n.顶点voltage n.电压volume n.体积amplify v.放大增强register v./n.注册登记显示shift register n.移位寄存器interpolate v.篡改插入mosaic n./v.马赛克demosaic v.去马赛克illuminate v.照亮阐明illumination n.光源灯饰启示illustrate v.举例说明digital adj.数字的digitize v.数字化analog n./adj.模拟analog image 模拟图像index n.索引(复数indexes/indices)denote v. 表示指示标志imply v.表示暗示donate v.捐赠sample n./v. 采样取样quantization n.量化quantize v.scan v./n.扫描discrete adj.分离的离散的continuous adj.连续的coordinate v.协作搭配n.坐标coordinate system 坐标系resolution n.解决决心分辨率interpolation n.插入插值填写interpolate v.resize v.调整大小real-time 实时的ultrasound n.超声波capacitor n.电容器circuit n.电路回路环线circuitry n.电路电路图prism n.棱镜棱柱contour n./v.轮廓边界线abrupt adj.突然的不连贯的tuple n.元组hue n.色调saturation n.饱和度offset n.偏移量gain n.增益clip v.剪掉裁剪template n.样板模板intermediate adj./n.中间的中间事物intermediate image 中间过渡图像eliminate v.消除淘汰flip v.反转打开overlap v.重叠superimpose v.叠加magnitude n.大小数值periodic adj.周期的series n.级数系列mitigate v.减轻缓和ramp n.斜坡坡道渐变notate v.以符号标记notation n.记法符号conjugate v./adj./n.共轭complex conjugate 复共轭harmonics n.谐波impulse train冲击序列translation v.平移翻译replica n.复制副本dilated adj.扩大膨胀dilate v. dilation n.sinusoid 正弦曲线aliasing n.混叠wrap v./n.包裹环绕围巾卷饼wraparound error 环绕错误suppress v.抑制阻止mitigate v.使减轻使缓和transition n.过渡转变transit v.运输经过agenda n.议程表待议日程arithmetic n.算数运算arithmetical adj. algorithm n.算法geometry n.几何geometric adj. medium adj.中间的五分熟的平均的median adj./n.中间值中位数prior adj.先前的正式的prior probability先验概率matrix n.矩阵metric n.度量标准adj.十进制的trim v.修剪调整emit v.发出发射beam n.光线波束project v.投射预测projection n.投影diffuse v./adj.扩散弥漫漫反射传播synchronous adj.同步的synchrony n.intercept n./v.截距拦截截断slope n./v.斜率倾斜斜坡vector n.矢量向量unit vector单位向量prime n.上标撇slash n.斜杠arbitrary adj.任意的recap n.扼要重述preliminary adj./n.初步的预赛transpose n./v.转置调换erode v.腐蚀削弱erosion n.腐蚀dilate v.膨胀扩大dilation n.膨胀shrink v.缩水缩小减少fracture v.断裂破碎duality n.二元性对偶性optimize v.优化optimal adj.最佳的合适的speckled adj.有斑点的speckle n./v.斑点色斑做标记多维数据:regress v./n..倒退回归regression n.回归set v.放n.集合anomaly n.异常asymmetric adj.不对称的sparse adj.稀疏的sparsity n.稀疏性symmetry n.对称相似induce v.引起诱使inductive adj.归纳的诱导的induction n.归纳感应deduct v.演绎扣除deduction n.推论split v./n.分割划分sort v./n.分类排序permute v.改变顺序permutation n.categorize v.分类category n. categorical adj.分类的绝对的numeric adj.数值的quantitative adj.定量的数量的qualitative adj.定性的质量的autocorrelation 自相关temporal autocorrelation 时间自相关temporal adj.时间的暂时的redundant adj.多余的冗余converge v.收敛聚集convergence n.复杂网络:homogeneous adj.单一的均匀的同质的isomorphic adj.同构的同形的isomorphism n.bipartite adj.双向的二分的invertible adj.可逆的traverse v.穿过横越yield v./n.产生出产产量skeleton n.骨骼框架梗概backbone n.脊柱骨干initial adj.最初的首字母outlier n.离群值异常值局外人consensus n.共识一致看法counterclockwise 逆时针clockwise顺时针equilibrate v.使平衡equilibrium n.均衡平衡rational adj.理智的hierarchies n.层级分层分类sparse adj.稀疏的稀少的benchmark n.比较基准synchrony n.同步synchronization n.同时性同步性consensus n.共识检测估计:hypothesis n.假设猜想scenario n.场景terminology n.术语interpolate v.插入篡改defect n.缺点v.背叛crude adj.粗略的粗糙的abrupt adj.突然的陡峭的唐突的asymptotic adj.渐进的渐近线的marginal adj.边缘的微不足道的marginal probability边缘概率prior probability先验概率conditional probability条件概率posterior probability后验概率hypothesis testing假设检验ground truth真实值decision region决策域disjoint adj.不相交的overlap adj.重叠的curvature n.弧线曲率concave adj.凹的power spectral density能量谱密度inner product 内积点积norm 模transpose v.调换n.转置矩阵determinant n./adj.决定因素行列式subscript n./adj.下标注脚Wide Sense Stationary 广义平稳time invariant时不变discretize v.离散discrete adj.离散的distort v.失真扭曲superimpose v.叠加compose v.组成构成移动APP:tablet n.药片平板电脑agenda n.待议事项议事日程kernel n.核内核compiler n.编译器compile v.汇编编译搜集manifest adj./n.表明显示清单configurate v.配置使形成obfuscate v.使模糊混淆refine v.改进精炼virtual adj.虚拟的实际上的device driver 设备驱动程序accelerate v.加速促进template n.模板样板compact adj./n.紧凑的简洁的deploy v.部署调动配置refactor v./n.重构configure v.配置config=configuration n.配置install v.安装icon n.图标palette n.调色板选项板compatible adj.兼容的可共处的execute v.执行实施prototype v./n.原型雏形widget n.小工具窗口小部件toggle n./v.切换转换(键)embed v.嵌入内置portrait adj.纵向的n.肖像描绘纵向打印格式vertical adj.垂直的纵向的landscape adj.横向打印格式n.风景横向打印格式v.景观美化horizontal adj.水平的chaos n.混乱无序状态chaotic adj.混乱的enclose v.封装围住封上nest v./n.鸟巢嵌套一套物件align v.对齐使一致margin v./n.边缘利润余地custom n.顾客惯例adj.定做的自定义的current adj.当前的流行的n.水流concurrency n.并发性并行性thread n.线程v.穿起来asynchronous adj.异步的instantiate v.举例说明invoke v.调用提及引起sequential adj.按顺序的相继发生的dispatch n./v.派遣发送迅速处理parse v.分析解析immutable adj.不可改变的mutable adj.可变的易变的explicit adj.明确的详述的implicit adj.含蓄的facilitate v.促进使便利synchronize v.同步grant v./n.承认给予授予engage v.从事雇佣pane n.玻璃窗格repository n.数据库储藏室资源库retrieve n.找回检索refactor v./n.重构resume v.恢复重新开始customize v.定制排队论:stochastic adj.随机的stochastic process 随机过程swap v.交换替换constraint n.约束条件constrain v.约束限制强迫moderate adj.适中的温和的中等的regime n.制度状态机制ethical adj.道德的plagiarize v.抄袭剽窃plagiarism n.mutually exclusive events 互斥事件mutual adj.相互的exclusive adj.昂贵的独有的排斥的rigorous adj.严格的严密的novel n.小说novelty adj./n.新颖的新奇的事物intersection n.交集相交交点在B的条件下A的概率the probability of A given Bposterior probability后验概率posterior adj.其次的较后的prior probability先验概率prior adj.先前的优先的axiom n.公理定理binomial n./adj.二项分布geometric n./adj.几何分布uniform distribution均匀分布recursion n.递归循环recur v.再发生反复出现arbitrary adj.任意的estimator n.估计量估计函数revise v./n.修正复习denominator n.分母numerator n.分子numerous adj.许多的fraction n.分数decimal n.小数integer n.整数expected value 期望standard deviation 标准差covariance n.协方差preliminary n./adj.初步的预备的准备工作identity n.身份特征同一性identical adj.同一的完全相同的stationary adj.不动的平稳的strictly stationary严格平稳ergodicity n. 遍历性各态历经性ergodic adj.multivariate adj.多元的多变量的superpose v.叠加叠放superposition n.叠加lag v./n.掉队延迟滞后consecutive adj.连续的derive v.起源于获得导出derivation n.求导导数validate v.正式确认生效物联网:mindset n.思维模式trend n.趋势风尚curriculum n.课程combat v.战斗争论block diagram 狂徒converge v.集中汇集convergence n.汇集融合immersive adj.沉浸式immerse v.沉浸于浸没resistor n.电阻resistance n.电阻(值)accelerate v.加速促进acceleration n.加速度accelerometer n.加速度计acoustic adj./n.声音的声学appliance n.家用电器actuator n.执行器驱动器actuate v.驱动促使velocity n.速度displacement n.位移gravity n.重力coordinate v./n.协调坐标magnetometer n.磁力计magnetic adj.磁性的axis n.轴对称轴calibrate v.校准calibration n.校准刻度vibrate v.震动vibration n.震动oscillate v.振荡oscillation n.振荡gearbox n.变速箱utilize v.利用使用日常:obsess v.痴迷blackout v.断电propagate v.传播繁殖grid n.格子lattice n.格子pervade v.遍及弥漫prominent adj.突出的杰出的tremendous adj.极大的极棒的intrinsic adj.内在的disordered adj.杂乱的错乱的convention n.约定协定condense v.压缩浓缩eliminate v.消除淘汰consensus n.一致同意initial adj.最初的字首的initialization n.初始化interrelated adj.相互关联的interpersonal adj.人与人之间的split v.分离skip v.跳过conform v.遵守符合顺应cluster n.群formation n.形成formative adj.形成的有重大影响的format v.格式化n.格式subtle adj.细微的敏感的verify v.核实查证vary v.变化variation n.变化variant adj.变化的vertical adj.垂直的duplicate n./v./adj.完全一样的复制implement v.实施penalty n.惩罚penalize v.惩罚capital n./adj.大写lowercase n./adj.小写specify v.具体指出specific adj.明确的特定的respective adj.各自的分别的estimate v.估计assign v.赋值分配assignment n.任务作业execute v.执行valid adj.有效的合法的vivid adj.生动的鲜艳的dynamic adj.动态的有活力的compose v. 组成撰写排版decompose v.分解腐烂spectrum n.范围频谱光谱perceptual adj.感知的有知觉的perception n.认知知觉洞察力absorb v.吸收掌握scope n.范围视野dissipate v.驱散挥霍mandatory adj.强制的tedious adj.单调乏味的allude v.略微提到暗指discern v辨别了解recognize v.识别承认decompose v.分解腐烂衰变deficient adj. deficiency n.不足缺陷interval n.间隔desirable adj.令人满意的满足需要的complement n./v.补充pros and cons(拉丁语) 优缺点nuts and bolts(螺母和螺栓) 基本组成部分aka (also known as)又叫做ultimate adj.最终的最重要的configuration n.布局配置configure v.安装形成hybrid n./adj.混合杂种immune adj.免疫的不受影响的layman n.外行门外汉exceed v.超越超过incoming adj.进来的进入的income n.收入alter v.改变修改alternate v./adj.交替轮流alternative adj./n.可选择的二选一alternatively adv.要不二择一on-demand adj.按需的emphasize v.强调negligible adj.可以忽略的precede v. 在之前的领先experiment v./n.实验尝试arbitrary adj.任意的suffice v.足够有能力sufficient adj.elastic adj.弹性的灵活的essentially adv.本质上实质上essential adj.必须的基本的excess adj./n.超额的过多的violate v.违反侵犯compose v.撰写组成排版compromise n./v.折中妥协intuitive adj.直觉的intuition n.直觉lengthy adj.冗长的过于详尽的grasp v./n.握紧领会characterize v.描述刻画convention n.习俗公约conventional adj.依照惯例的criterion n.标准规范criteria 复数interpret v.解释口译interpretation n.解释notation n.符号标记法mutual adj.相互的sketch v./n.绘制草图outage n.断电中断in all walks of life 在各行各业frontier n./adj.边境前沿embark v.开始着手上船possess v.具备拥有insight n.了解洞察力encounter v.遭遇碰到inherent adj.固有的内在的与生俱来的inherently adv. commonality n.共性sophisticated adj.复杂精妙的水平高的stepping stone 跳板垫脚石bracket n.括号圆括号square bracket 方括号superscript n.上角标hypothesis n.猜想假设submarine v./n./adj.海底的潜水艇。
jstd035声学扫描
JOINT INDUSTRY STANDARDAcoustic Microscopy for Non-HermeticEncapsulatedElectronicComponents IPC/JEDEC J-STD-035APRIL1999Supersedes IPC-SM-786 Supersedes IPC-TM-650,2.6.22Notice EIA/JEDEC and IPC Standards and Publications are designed to serve thepublic interest through eliminating misunderstandings between manufacturersand purchasers,facilitating interchangeability and improvement of products,and assisting the purchaser in selecting and obtaining with minimum delaythe proper product for his particular need.Existence of such Standards andPublications shall not in any respect preclude any member or nonmember ofEIA/JEDEC or IPC from manufacturing or selling products not conformingto such Standards and Publications,nor shall the existence of such Standardsand Publications preclude their voluntary use by those other than EIA/JEDECand IPC members,whether the standard is to be used either domestically orinternationally.Recommended Standards and Publications are adopted by EIA/JEDEC andIPC without regard to whether their adoption may involve patents on articles,materials,or processes.By such action,EIA/JEDEC and IPC do not assumeany liability to any patent owner,nor do they assume any obligation whateverto parties adopting the Recommended Standard or ers are alsowholly responsible for protecting themselves against all claims of liabilities forpatent infringement.The material in this joint standard was developed by the EIA/JEDEC JC-14.1Committee on Reliability Test Methods for Packaged Devices and the IPCPlastic Chip Carrier Cracking Task Group(B-10a)The J-STD-035supersedes IPC-TM-650,Test Method2.6.22.For Technical Information Contact:Electronic Industries Alliance/ JEDEC(Joint Electron Device Engineering Council)2500Wilson Boulevard Arlington,V A22201Phone(703)907-7560Fax(703)907-7501IPC2215Sanders Road Northbrook,IL60062-6135 Phone(847)509-9700Fax(847)509-9798Please use the Standard Improvement Form shown at the end of thisdocument.©Copyright1999.The Electronic Industries Alliance,Arlington,Virginia,and IPC,Northbrook,Illinois.All rights reserved under both international and Pan-American copyright conventions.Any copying,scanning or other reproduction of these materials without the prior written consent of the copyright holder is strictly prohibited and constitutes infringement under the Copyright Law of the United States.IPC/JEDEC J-STD-035Acoustic Microscopyfor Non-Hermetic EncapsulatedElectronicComponentsA joint standard developed by the EIA/JEDEC JC-14.1Committee on Reliability Test Methods for Packaged Devices and the B-10a Plastic Chip Carrier Cracking Task Group of IPCUsers of this standard are encouraged to participate in the development of future revisions.Contact:EIA/JEDEC Engineering Department 2500Wilson Boulevard Arlington,V A22201 Phone(703)907-7500 Fax(703)907-7501IPC2215Sanders Road Northbrook,IL60062-6135 Phone(847)509-9700Fax(847)509-9798ASSOCIATION CONNECTINGELECTRONICS INDUSTRIESAcknowledgmentMembers of the Joint IPC-EIA/JEDEC Moisture Classification Task Group have worked to develop this document.We would like to thank them for their dedication to this effort.Any Standard involving a complex technology draws material from a vast number of sources.While the principal members of the Joint Moisture Classification Working Group are shown below,it is not possible to include all of those who assisted in the evolution of this Standard.To each of them,the mem-bers of the EIA/JEDEC and IPC extend their gratitude.IPC Packaged Electronic Components Committee ChairmanMartin FreedmanAMP,Inc.IPC Plastic Chip Carrier Cracking Task Group,B-10a ChairmanSteven MartellSonoscan,Inc.EIA/JEDEC JC14.1CommitteeChairmanJack McCullenIntel Corp.EIA/JEDEC JC14ChairmanNick LycoudesMotorolaJoint Working Group MembersCharlie Baker,TIChristopher Brigham,Hi/FnRalph Carbone,Hewlett Packard Co. Don Denton,TIMatt Dotty,AmkorMichele J.DiFranza,The Mitre Corp. Leo Feinstein,Allegro Microsystems Inc.Barry Fernelius,Hewlett Packard Co. Chris Fortunko,National Institute of StandardsRobert J.Gregory,CAE Electronics, Inc.Curtis Grosskopf,IBM Corp.Bill Guthrie,IBM Corp.Phil Johnson,Philips Semiconductors Nick Lycoudes,MotorolaSteven R.Martell,Sonoscan Inc. Jack McCullen,Intel Corp.Tom Moore,TIDavid Nicol,Lucent Technologies Inc.Pramod Patel,Advanced Micro Devices Inc.Ramon R.Reglos,XilinxCorazon Reglos,AdaptecGerald Servais,Delphi Delco Electronics SystemsRichard Shook,Lucent Technologies Inc.E.Lon Smith,Lucent Technologies Inc.Randy Walberg,NationalSemiconductor Corp.Charlie Wu,AdaptecEdward Masami Aoki,HewlettPackard LaboratoriesFonda B.Wu,Raytheon Systems Co.Richard W.Boerdner,EJE ResearchVictor J.Brzozowski,NorthropGrumman ES&SDMacushla Chen,Wus Printed CircuitCo.Ltd.Jeffrey C.Colish,Northrop GrummanCorp.Samuel J.Croce,Litton AeroProducts DivisionDerek D-Andrade,Surface MountTechnology CentreRao B.Dayaneni,Hewlett PackardLaboratoriesRodney Dehne,OEM WorldwideJames F.Maguire,Boeing Defense&Space GroupKim Finch,Boeing Defense&SpaceGroupAlelie Funcell,Xilinx Inc.Constantino J.Gonzalez,ACMEMunir Haq,Advanced Micro DevicesInc.Larry A.Hargreaves,DC.ScientificInc.John T.Hoback,Amoco ChemicalCo.Terence Kern,Axiom Electronics Inc.Connie M.Korth,K-Byte/HibbingManufacturingGabriele Marcantonio,NORTELCharles Martin,Hewlett PackardLaboratoriesRichard W.Max,Alcatel NetworkSystems Inc.Patrick McCluskey,University ofMarylandJames H.Moffitt,Moffitt ConsultingServicesRobert Mulligan,Motorola Inc.James E.Mumby,CibaJohn Northrup,Lockheed MartinCorp.Dominique K.Numakura,LitchfieldPrecision ComponentsNitin B.Parekh,Unisys Corp.Bella Poborets,Lucent TechnologiesInc.D.Elaine Pope,Intel Corp.Ray Prasad,Ray Prasad ConsultancyGroupAlbert Puah,Adaptec Inc.William Sepp,Technic Inc.Ralph W.Taylor,Lockheed MartinCorp.Ed R.Tidwell,DSC CommunicationsCorp.Nick Virmani,Naval Research LabKen Warren,Corlund ElectronicsCorp.Yulia B.Zaks,Lucent TechnologiesInc.IPC/JEDEC J-STD-035April1999 iiTable of Contents1SCOPE (1)2DEFINITIONS (1)2.1A-mode (1)2.2B-mode (1)2.3Back-Side Substrate View Area (1)2.4C-mode (1)2.5Through Transmission Mode (2)2.6Die Attach View Area (2)2.7Die Surface View Area (2)2.8Focal Length(FL) (2)2.9Focus Plane (2)2.10Leadframe(L/F)View Area (2)2.11Reflective Acoustic Microscope (2)2.12Through Transmission Acoustic Microscope (2)2.13Time-of-Flight(TOF) (3)2.14Top-Side Die Attach Substrate View Area (3)3APPARATUS (3)3.1Reflective Acoustic Microscope System (3)3.2Through Transmission AcousticMicroscope System (4)4PROCEDURE (4)4.1Equipment Setup (4)4.2Perform Acoustic Scans..........................................4Appendix A Acoustic Microscopy Defect CheckSheet (6)Appendix B Potential Image Pitfalls (9)Appendix C Some Limitations of AcousticMicroscopy (10)Appendix D Reference Procedure for PresentingApplicable Scanned Data (11)FiguresFigure1Example of A-mode Display (1)Figure2Example of B-mode Display (1)Figure3Example of C-mode Display (2)Figure4Example of Through Transmission Display (2)Figure5Diagram of a Reflective Acoustic MicroscopeSystem (3)Figure6Diagram of a Through Transmission AcousticMicroscope System (3)April1999IPC/JEDEC J-STD-035iiiIPC/JEDEC J-STD-035April1999This Page Intentionally Left BlankivApril1999IPC/JEDEC J-STD-035 Acoustic Microscopy for Non-Hermetic EncapsulatedElectronic Components1SCOPEThis test method defines the procedures for performing acoustic microscopy on non-hermetic encapsulated electronic com-ponents.This method provides users with an acoustic microscopy processflow for detecting defects non-destructively in plastic packages while achieving reproducibility.2DEFINITIONS2.1A-mode Acoustic data collected at the smallest X-Y-Z region defined by the limitations of the given acoustic micro-scope.An A-mode display contains amplitude and phase/polarity information as a function of time offlight at a single point in the X-Y plane.See Figure1-Example of A-mode Display.IPC-035-1 Figure1Example of A-mode Display2.2B-mode Acoustic data collected along an X-Z or Y-Z plane versus depth using a reflective acoustic microscope.A B-mode scan contains amplitude and phase/polarity information as a function of time offlight at each point along the scan line.A B-mode scan furnishes a two-dimensional(cross-sectional)description along a scan line(X or Y).See Figure2-Example of B-mode Display.IPC-035-2 Figure2Example of B-mode Display(bottom half of picture on left)2.3Back-Side Substrate View Area(Refer to Appendix A,Type IV)The interface between the encapsulant and the back of the substrate within the outer edges of the substrate surface.2.4C-mode Acoustic data collected in an X-Y plane at depth(Z)using a reflective acoustic microscope.A C-mode scan contains amplitude and phase/polarity information at each point in the scan plane.A C-mode scan furnishes a two-dimensional(area)image of echoes arising from reflections at a particular depth(Z).See Figure3-Example of C-mode Display.1IPC/JEDEC J-STD-035April1999IPC-035-3 Figure3Example of C-mode Display2.5Through Transmission Mode Acoustic data collected in an X-Y plane throughout the depth(Z)using a through trans-mission acoustic microscope.A Through Transmission mode scan contains only amplitude information at each point in the scan plane.A Through Transmission scan furnishes a two-dimensional(area)image of transmitted ultrasound through the complete thickness/depth(Z)of the sample/component.See Figure4-Example of Through Transmission Display.IPC-035-4 Figure4Example of Through Transmission Display2.6Die Attach View Area(Refer to Appendix A,Type II)The interface between the die and the die attach adhesive and/or the die attach adhesive and the die attach substrate.2.7Die Surface View Area(Refer to Appendix A,Type I)The interface between the encapsulant and the active side of the die.2.8Focal Length(FL)The distance in water at which a transducer’s spot size is at a minimum.2.9Focus Plane The X-Y plane at a depth(Z),which the amplitude of the acoustic signal is maximized.2.10Leadframe(L/F)View Area(Refer to Appendix A,Type V)The imaged area which extends from the outer L/F edges of the package to the L/F‘‘tips’’(wedge bond/stitch bond region of the innermost portion of the L/F.)2.11Reflective Acoustic Microscope An acoustic microscope that uses one transducer as both the pulser and receiver. (This is also known as a pulse/echo system.)See Figure5-Diagram of a Reflective Acoustic Microscope System.2.12Through Transmission Acoustic Microscope An acoustic microscope that transmits ultrasound completely through the sample from a sending transducer to a receiver on the opposite side.See Figure6-Diagram of a Through Transmis-sion Acoustic Microscope System.2April1999IPC/JEDEC J-STD-0353IPC/JEDEC J-STD-035April1999 3.1.6A broad band acoustic transducer with a center frequency in the range of10to200MHz for subsurface imaging.3.2Through Transmission Acoustic Microscope System(see Figure6)comprised of:3.2.1Items3.1.1to3.1.6above3.2.2Ultrasonic pulser(can be a pulser/receiver as in3.1.1)3.2.3Separate receiving transducer or ultrasonic detection system3.3Reference packages or standards,including packages with delamination and packages without delamination,for use during equipment setup.3.4Sample holder for pre-positioning samples.The holder should keep the samples from moving during the scan and maintain planarity.4PROCEDUREThis procedure is generic to all acoustic microscopes.For operational details related to this procedure that apply to a spe-cific model of acoustic microscope,consult the manufacturer’s operational manual.4.1Equipment Setup4.1.1Select the transducer with the highest useable ultrasonic frequency,subject to the limitations imposed by the media thickness and acoustic characteristics,package configuration,and transducer availability,to analyze the interfaces of inter-est.The transducer selected should have a low enough frequency to provide a clear signal from the interface of interest.The transducer should have a high enough frequency to delineate the interface of interest.Note:Through transmission mode may require a lower frequency and/or longer focal length than reflective mode.Through transmission is effective for the initial inspection of components to determine if defects are present.4.1.2Verify setup with the reference packages or standards(see3.3above)and settings that are appropriate for the trans-ducer chosen in4.1.1to ensure that the critical parameters at the interface of interest correlate to the reference standard uti-lized.4.1.3Place units in the sample holder in the coupling medium such that the upper surface of each unit is parallel with the scanning plane of the acoustic transducer.Sweep air bubbles away from the unit surface and from the bottom of the trans-ducer head.4.1.4At afixed distance(Z),align the transducer and/or stage for the maximum reflected amplitude from the top surface of the sample.The transducer must be perpendicular to the sample surface.4.1.5Focus by maximizing the amplitude,in the A-mode display,of the reflection from the interface designated for imag-ing.This is done by adjusting the Z-axis distance between the transducer and the sample.4.2Perform Acoustic Scans4.2.1Inspect the acoustic image(s)for any anomalies,verify that the anomaly is a package defect or an artifact of the imaging process,and record the results.(See Appendix A for an example of a check sheet that may be used.)To determine if an anomaly is a package defect or an artifact of the imaging process it is recommended to analyze the A-mode display at the location of the anomaly.4.2.2Consider potential pitfalls in image interpretation listed in,but not limited to,Appendix B and some of the limita-tions of acoustic microscopy listed in,but not limited to,Appendix C.If necessary,make adjustments to the equipment setup to optimize the results and rescan.4April1999IPC/JEDEC J-STD-035 4.2.3Evaluate the acoustic images using the failure criteria specified in other appropriate documents,such as J-STD-020.4.2.4Record the images and thefinal instrument setup parameters for documentation purposes.An example checklist is shown in Appendix D.5IPC/JEDEC J-STD-035April19996April1999IPC/JEDEC J-STD-035Appendix AAcoustic Microscopy Defect Check Sheet(continued)CIRCUIT SIDE SCANImage File Name/PathDelamination(Type I)Die Circuit Surface/Encapsulant Number Affected:Average%Location:Corner Edge Center (Type II)Die/Die Attach Number Affected:Average%Location:Corner Edge Center (Type III)Encapsulant/Substrate Number Affected:Average%Location:Corner Edge Center (Type V)Interconnect tip Number Affected:Average%Interconnect Number Affected:Max.%Length(Type VI)Intra-Laminate Number Affected:Average%Location:Corner Edge Center Comments:CracksAre cracks present:Yes NoIf yes:Do any cracks intersect:bond wire ball bond wedge bond tab bump tab leadDoes crack extend from leadfinger to any other internal feature:Yes NoDoes crack extend more than two-thirds the distance from any internal feature to the external surfaceof the package:Yes NoAdditional verification required:Yes NoComments:Mold Compound VoidsAre voids present:Yes NoIf yes:Approx.size Location(if multiple voids,use comment section)Do any voids intersect:bond wire ball bond wedge bond tab bump tab lead Additional verification required:Yes NoComments:7IPC/JEDEC J-STD-035April1999Appendix AAcoustic Microscopy Defect Check Sheet(continued)NON-CIRCUIT SIDE SCANImage File Name/PathDelamination(Type IV)Encapsulant/Substrate Number Affected:Average%Location:Corner Edge Center (Type II)Substrate/Die Attach Number Affected:Average%Location:Corner Edge Center (Type V)Interconnect Number Affected:Max.%LengthLocation:Corner Edge Center (Type VI)Intra-Laminate Number Affected:Average%Location:Corner Edge Center (Type VII)Heat Spreader Number Affected:Average%Location:Corner Edge Center Additional verification required:Yes NoComments:CracksAre cracks present:Yes NoIf yes:Does crack extend more than two-thirds the distance from any internal feature to the external surfaceof the package:Yes NoAdditional verification required:Yes NoComments:Mold Compound VoidsAre voids present:Yes NoIf yes:Approx.size Location(if multiple voids,use comment section)Additional verification required:Yes NoComments:8Appendix BPotential Image PitfallsOBSERV ATIONS CAUSES/COMMENTSUnexplained loss of front surface signal Gain setting too lowSymbolization on package surfaceEjector pin knockoutsPin1and other mold marksDust,air bubbles,fingerprints,residueScratches,scribe marks,pencil marksCambered package edgeUnexplained loss of subsurface signal Gain setting too lowTransducer frequency too highAcoustically absorbent(rubbery)fillerLarge mold compound voidsPorosity/high concentration of small voidsAngled cracks in package‘‘Dark line boundary’’(phase cancellation)Burned molding compound(ESD/EOS damage)False or spotty indication of delamination Low acoustic impedance coating(polyimide,gel)Focus errorIncorrect delamination gate setupMultilayer interference effectsFalse indication of adhesion Gain set too high(saturation)Incorrect delamination gate setupFocus errorOverlap of front surface and subsurface echoes(transducerfrequency too low)Fluidfilling delamination areasApparent voiding around die edge Reflection from wire loopsIncorrect setting of void gateGraded intensity Die tilt or lead frame deformation Sample tiltApril1999IPC/JEDEC J-STD-0359Appendix CSome Limitations of Acoustic MicroscopyAcoustic microscopy is an analytical technique that provides a non-destructive method for examining plastic encapsulated components for the existence of delaminations,cracks,and voids.This technique has limitations that include the following: LIMITATION REASONAcoustic microscopy has difficulty infinding small defects if the package is too thick.The ultrasonic signal becomes more attenuated as a function of two factors:the depth into the package and the transducer fre-quency.The greater the depth,the greater the attenuation.Simi-larly,the higher the transducer frequency,the greater the attenu-ation as a function of depth.There are limitations on the Z-axis(axial)resolu-tion.This is a function of the transducer frequency.The higher the transducer frequency,the better the resolution.However,the higher frequency signal becomes attenuated more quickly as a function of depth.There are limitations on the X-Y(lateral)resolu-tion.The X-Y(lateral)resolution is a function of a number of differ-ent variables including:•Transducer characteristics,including frequency,element diam-eter,and focal length•Absorption and scattering of acoustic waves as a function of the sample material•Electromechanical properties of the X-Y stageIrregularly shaped packages are difficult to analyze.The technique requires some kind offlat reference surface.Typically,the upper surface of the package or the die surfacecan be used as references.In some packages,cambered packageedges can cause difficulty in analyzing defects near the edgesand below their surfaces.Edge Effect The edges cause difficulty in analyzing defects near the edge ofany internal features.IPC/JEDEC J-STD-035April1999 10April1999IPC/JEDEC J-STD-035Appendix DReference Procedure for Presenting Applicable Scanned DataMost of the settings described may be captured as a default for the particular supplier/product with specific changes recorded on a sample or lot basis.Setup Configuration(Digital Setup File Name and Contents)Calibration Procedure and Calibration/Reference Standards usedTransducerManufacturerModelCenter frequencySerial numberElement diameterFocal length in waterScan SetupScan area(X-Y dimensions)Scan step sizeHorizontalVerticalDisplayed resolutionHorizontalVerticalScan speedPulser/Receiver SettingsGainBandwidthPulseEnergyRepetition rateReceiver attenuationDampingFilterEcho amplitudePulse Analyzer SettingsFront surface gate delay relative to trigger pulseSubsurface gate(if used)High passfilterDetection threshold for positive oscillation,negative oscillationA/D settingsSampling rateOffset settingPer Sample SettingsSample orientation(top or bottom(flipped)view and location of pin1or some other distinguishing characteristic) Focus(point,depth,interface)Reference planeNon-default parametersSample identification information to uniquely distinguish it from others in the same group11IPC/JEDEC J-STD-035April1999Appendix DReference Procedure for Presenting Applicable Scanned Data(continued) Reference Procedure for Presenting Scanned DataImagefile types and namesGray scale and color image legend definitionsSignificance of colorsIndications or definition of delaminationImage dimensionsDepth scale of TOFDeviation from true aspect ratioImage type:A-mode,B-mode,C-mode,TOF,Through TransmissionA-mode waveforms should be provided for points of interest,such as delaminated areas.In addition,an A-mode image should be provided for a bonded area as a control.12Standard Improvement FormIPC/JEDEC J-STD-035The purpose of this form is to provide the Technical Committee of IPC with input from the industry regarding usage of the subject standard.Individuals or companies are invited to submit comments to IPC.All comments will be collected and dispersed to the appropriate committee(s).If you can provide input,please complete this form and return to:IPC2215Sanders RoadNorthbrook,IL 60062-6135Fax 847509.97981.I recommend changes to the following:Requirement,paragraph number Test Method number,paragraph numberThe referenced paragraph number has proven to be:Unclear Too RigidInErrorOther2.Recommendations forcorrection:3.Other suggestions for document improvement:Submitted by:Name Telephone Company E-mailAddress City/State/ZipDate ASSOCIATION CONNECTING ELECTRONICS INDUSTRIESASSOCIATION CONNECTINGELECTRONICS INDUSTRIESISBN#1-580982-28-X2215 Sanders Road, Northbrook, IL 60062-6135Tel. 847.509.9700 Fax 847.509.9798。
x-ray检测工作原理
x-ray检测工作原理嗨,亲爱的朋友!今天咱们来唠唠X - ray检测这个超酷的东西的工作原理吧。
你知道吗,X - ray就像是一个超级透视眼。
想象一下,有一双眼睛可以看穿东西,是不是特别像超人的超能力呀?其实X - ray检测就有点这个意思哦。
X - ray呢,它是一种电磁波,这电磁波可神奇啦。
它的波长超级短,能量可不小呢。
当我们要检测一个物体的时候,就像要看看一个包裹里面装了啥,或者是检查身体里有没有小毛病的时候,就会用到X - ray检测。
我们先来说说在医疗方面的情况吧。
当你去医院做X - ray检查,比如说拍个胸片。
那X - ray机器就会发射出这些X - ray射线。
这些射线就像一群小小的、看不见的精灵,它们会穿过你的身体。
你身体里不同的组织对X - ray的吸收能力是不一样的哦。
像骨头这种比较致密的组织,就像是一个很厉害的小盾牌,它会吸收很多的X - ray,而像肌肉、脂肪这些比较软的组织呢,就比较“弱”啦,它们吸收的X - ray就少一些。
那这些X - ray穿过身体之后呢,就会到达一个特殊的板子上,这个板子就像是一个小画家的画布一样。
X - ray多的地方,在这个板子上就会显示出白色或者浅色,就像骨头在胸片上是白色的。
而X - ray穿过去比较多的地方,也就是那些软的组织的地方,就会显示出黑色或者深色。
这样,医生就可以通过这个胸片看到你的骨头有没有骨折啦,肺有没有什么异常啦。
是不是很有趣呢?再说说在工业上的X - ray检测吧。
比如说有个小零件,我们想看看它里面有没有小裂缝或者缺陷。
这个时候,X - ray检测就登场啦。
X - ray射线会朝着这个小零件射过去。
如果这个小零件内部结构完好无损,那X - ray就会比较均匀地穿过它,在检测的屏幕上就会显示出比较规则的图像。
但是,如果这个小零件里面有裂缝或者有气泡之类的缺陷呢,那这些地方对X - ray的吸收就和周围不一样啦。
就好像是一群小士兵(X - ray)在行军,遇到了一个小陷阱(缺陷),那这个小陷阱的地方就会和周围的行军路线不一样,在检测图像上就会显示出不同的颜色或者形状。
乙腈不同温度下的表面蒸气压_概述及解释说明
乙腈不同温度下的表面蒸气压概述及解释说明1. 引言1.1 概述乙腈(化学式CH3CN)是一种常用的有机溶剂,广泛应用于化学实验室、工业生产和科研领域。
乙腈的表面蒸气压是其在不同温度下从液态向气态转变时产生的压强。
了解乙腈在不同温度下的表面蒸气压变化规律对于科学研究及工业应用有着重要意义。
1.2 文章结构本文将首先介绍乙腈的物性特点,包括分子结构、物理性质和化学性质等方面。
接着将对表面蒸气压的概念进行解释,并探讨影响乙腈表面蒸气压变化的因素。
最后,通过实验方法与结果分析,详细讨论不同温度下乙腈表面蒸气压的变化规律,并总结归纳实验结果。
1.3 目的本文旨在深入探讨乙腈在不同温度下的表面蒸气压变化规律,并通过实验结果分析验证相关理论模型。
通过研究乙腈的表面蒸气压,可以拓宽我们对乙腈及相关有机溶剂的认识,并为实验室操作、工业生产以及科学研究提供技术参考和应用前景展望。
2. 正文2.1 乙腈的物性介绍乙腈是一种常见的有机溶剂,化学式为CH3CN。
它具有无色、透明、有刺激性气味以及良好的溶解性等特点,在化工、制药等多个领域广泛应用。
乙腈的分子量为41.05 g/mol,密度为0.786 g/cm^3。
它的沸点为81.6°C,熔点为-45°C。
2.2 表面蒸气压的概念和影响因素表面蒸气压指在一定温度下,液体与其饱和蒸气之间达到动态平衡时所对应的气相压强。
表面蒸气压受多种因素影响,包括温度、分子间吸引力以及液体分子挥发速率等。
较高温度和较强分子间相互作用力会提高液体表面上的分子挥发速率,从而增加表面蒸气压。
2.3 不同温度下乙腈表面蒸气压的变化规律随着温度升高,乙腈的表面蒸气压将增加。
根据饱和蒸气压与温度之间的关系,一般而言,液体的饱和蒸气压随着温度的升高而增加。
对于乙腈来说也是如此。
以常规大气压下为例,乙腈在25°C时的表面蒸气压约为76.15 mmHg,在50°C时增至131.3 mmHg。
X-ray Absorption Spectroscopy (XAS)
X-ray Absorption Spectroscopy (XAS)When the x-rays hit a sample, the oscillating electric field of the electromagnetic radiation interacts with the electrons bound in an atom. Either the radiation will be scattered by these electrons, or absorbed and excite the electrons.xA narrow parallel monochromatic x-ray beam of intensity I 0 passing through a sample of thickness x will get a reduced intensity I according to the expression: ln (I 0 /I) = µ x (1)where µ is the linear absorption coefficient , which depends on the types of atoms and the density ρ of the material. At certain energies where the absorption increases drastically, and gives rise to an absorption edge . Each such edge occurs when the energy of the incident photons is just sufficient to cause excitation of a core electron of the absorbing atom to a continuum state, i.e . to produce a photoelectron. Thus, the energies of the absorbed radiation at these edges correspond to the binding energies of electrons in the K, L, M, etc, shells of the absorbing elements. The absorption edges are labelled in the order of increasing energy , K, L I , L II , L III , M I ,…., corresponding to the excitation of an electron from the 1s (2S ½), 2s (2S ½), 2p (2P ½), 2p (2P 3/2), 3s (2S ½), … orbitals (states), respectively. Bohr Atomic Modeled K L L L Continuumge: 2 S ½2P ½2P 32IIIII IWhen the photoelectron leaves the absorbing atom, its wave is backscattered by the neighbouring atoms. The figure below shows the sudden increase in the x-ray absorption of the platinum Pt L III edge in K 2[Pt(CN)4] with increasing photon energy. The maxima and minima after the edge correspond to the constructive and destructive interference between the outgoing photoelectron wave and backscattered wave. 11300115001170011900121001230012500Energy (eV)µ (E )An x-ray absorption spectrum is generally divided into 4 sections: 1) pre-edge (E < E 0); 2) x-ray absorption near edge structure (XANES ), where the energy of the incident x-ray beam is E = E 0 ± 10 eV; 3) near edge x-ray absorption fine structure (NEXAFS ), in the region between 10 eV up to 50 eV above the edge; and 4) extended x-ray absorption fine structure (EXAFS ), which starts approximately from 50 eV and continues up to 1000 eV above the edge.The minor features in the pre-edge region are usually due to the electron transitions from the core level to the higher unfilled or half-filled orbitals (e.g, s → p , or p → d ). In the XANES region, transitions of core electrons to non-bound levels with close energy occur. Because of the high probability of such transition, a sudden raise of absorption is observed. In NEXAFS, the ejected photoelectrons have low kinetic energy (E-E 0 is small) and experience strong multiple scattering by the first and even higher coordinating shells. In the EXAFS region, the photoelectrons have high kinetic energy (E-E 0 is large), and single scattering by the nearest neighbouring atoms normally dominates.11400.00.51.01.52.001150011600117001180011900Multiple scatteringSingle scatteringHome Research Publications Synchrotron XANES EXAFS XAS Measurement。
p区金属氧化物Ga_(2)O_(3)和Sb_(2)O_(3)光催化降解盐酸四环素性能差异
收稿日期:2020⁃09⁃29。
收修改稿日期:2020⁃12⁃28。
国家自然科学基金(No.21875037,51502036)和国家重点研发计划(No.2016YFB0302303,2019YFC1908203)资助。
*通信联系人。
E⁃mail :***************.cn ,***************第37卷第3期2021年3月Vol.37No.3509⁃515无机化学学报CHINESE JOURNAL OF INORGANIC CHEMISTRYp 区金属氧化物Ga 2O 3和Sb 2O 3光催化降解盐酸四环素性能差异毛婧芸1黄毅玮2黄祝泉1刘欣萍1薛珲*,1肖荔人*,3(1福建师范大学环境科学与工程学院,福州350007)(2福建师范大学生命科学学院,福州350007)(3福建师范大学化学与材料学院,福州350007)摘要:对沉淀法合成的p 区金属氧化物Ga 2O 3和Sb 2O 3紫外光光催化降解盐酸四环素的性能进行了研究,讨论了制备条件对光催化性能的影响。
最佳制备条件下得到的Ga 2O 3⁃900和Sb 2O 3⁃500样品光催化性能存在巨大差异,通过X 射线粉末衍射、傅里叶红外光谱、N 2吸附-脱附测试、荧光光谱、拉曼光谱、电化学分析及活性物种捕获实验等对样品进行分析,研究二者光催化降解盐酸四环素的机理,揭示影响光催化性能差异的本质因素。
结果表明,Ga 2O 3和Sb 2O 3光催化性能差异主要归结于二者不同的电子和晶体结构、表面所含羟基数量及光催化降解机理。
关键词:p 区金属;氧化镓;氧化锑;光催化;盐酸四环素中图分类号:O643.36;O614.37+1;O614.53+1文献标识码:A文章编号:1001⁃4861(2021)03⁃0509⁃07DOI :10.11862/CJIC.2021.063Different Photocatalytic Performances for Tetracycline Hydrochloride Degradation of p ‑Block Metal Oxides Ga 2O 3and Sb 2O 3MAO Jing⁃Yun 1HUANG Yi⁃Wei 2HUANG Zhu⁃Quan 1LIU Xin⁃Ping 1XUE Hun *,1XIAO Li⁃Ren *,3(1College of Environmental Science and Engineering,Fujian Normal University,Fuzhou 350007,China )(2College of Life and Science,Fujian Normal University,Fuzhou 350007,China )(3College of Chemistry and Materials Science,Fujian Normal University,Fuzhou 350007,China )Abstract:The UV light photocatalytic performances of p ⁃block metal oxides Ga 2O 3and Sb 2O 3synthesized by a pre⁃cipitation method for the degradation of tetracycline hydrochloride were explored.The effects of synthesis conditions on the photocatalytic activity were discussed.The Ga 2O 3⁃900and Sb 2O 3⁃500samples prepared under optimal condi⁃tions exhibited a remarkable photocatalytic activity difference,which were characterized by X⁃ray diffraction,Fouri⁃er transform infrared spectroscopy,N 2adsorption⁃desorption tests,fluorescence spectrum,Raman spectrum,electro⁃chemical analysis and trapping experiment of active species.The photocatalytic degradation mechanisms of tetracy⁃cline hydrochloride over the photocatalysts were proposed and the essential factors influencing the difference of pho⁃tocatalytic performance were revealed.The results show that the different photocatalytic activities observed for Ga 2O 3and Sb 2O 3can be attributed to their different electronic and crystal structures,the amount of hydroxyl groupin the surface and the photocatalytic degradation mechanisms.Keywords:p ⁃block metal;Ga 2O 3;Sb 2O 3;photocatalysis;tetracycline hydrochloride无机化学学报第37卷0引言盐酸四环素(TC)作为一种四环素类广谱抗生素,被广泛应用于治疗人体疾病及预防畜禽、水产品的细菌性病害,其在世界范围的大量使用致使其在环境中积累[1]。
X-射线单晶衍射仪XtaLAB_Pro_的低温系统改造
大型仪器功能开发 (227 ~ 229)X -射线单晶衍射仪XtaLAB Pro 的低温系统改造马 宣,孙爱君,张 云(中国科学院 南海海洋研究所,广东 广州 510301)摘要:X -射线单晶衍射作为一种可以精确测定分子三维空间结构的物理方式,是现代化学研究中重要的技术手段之一,广泛应用于生物、化学等领域. 低温系统是X -射线单晶衍射仪中重要的配件系统,晶体在低温液氮条件下测试,能够避免风化和开裂,同时减少晶体中原子的热运动,从而得到更好的测试数据. 改造了一款X -射线单晶衍射仪XtaLAB Pro 的低温系统,实现了实时监测杜瓦瓶内液氮液位高度、液氮自动补给以及远程报警功能,减少频繁手动添加液氮的麻烦,提升效率,节省时间与成本.关键词:X -射线单晶衍射;低温系统;改造;自动补液;远程报警中图分类号:O657 文献标志码:B 文章编号:1006-3757(2023)02-0227-03DOI :10.16495/j.1006-3757.2023.02.014Modification of Cryogenic System of X -ray Single CrystalDiffractometer XtaLAB ProMA Xuan , SUN Aijun , ZHANG Yun(South China Sea Institute of Oceanology , Chinese Academy of Sciences , Guangzhou 510301, China )Abstract :X -ray single crystal diffractometer is a physical method that can accurately determine the three-dimensional structure of molecules. It is one of the important technical means in modern chemical research and is widely used in biology, chemistry and other fields. The cryogenic system is an important accessory system in the X -ray single crystal diffractometer. Crystals tested under low-temperature liquid nitrogen conditions can avoid the weathering and cracking,and reduce the thermal movement of atoms in the crystal, thus better test data are obtained. The cryogenic system of XtaLAB Pro, an X -ray single crystal diffractomete was modified to realize the real-time monitoring of liquid nitrogen in the Dewar flask, the automatic rehydration and the remote alarm, which reduce the frequently manual addition of liquid nitrogen, improve the efficiency, save time and cost.Key words :X -ray single crystal diffractometer ;cryogenic system ;modification ;automatic rehydration ;remote alarmX -射线单晶衍射仪是化学和生命科学领域用来解析小分子和酶等生物大分子结构的有力工具. 通过X -射线单晶衍射仪可以获得原子的种类、化合状态、位置分布,原子间相互结合的方式,准确的原子坐标、键长键角等信息,特别是手性绝对构型、分子构象等其他表征手段难以提供的精确信息,从而进行价态分析、功能研究等,广泛用于无机小分子化合物、复杂天然有机小分子绝对构型测定以及生物大分子(蛋白、核酸、糖类)研究领域[1-3]. 低温冷却系统是单晶衍射仪的重要组成部分,某些不稳定的晶体在常温下测试会出现开裂、风化等问题,在试验过程中产生的衍射点被拉长或者呈粉末化,无法得到理想的试验数据[4]. 因此在低温条件下,晶体较稳定,而且低温可以减少化合物中原子的热运动,有助于消除或减少无序性[5].目前,常用的低温系统主要采用低温液氮对晶收稿日期:2023−02−20; 修订日期:2023−04−13.作者简介:马宣(1991−),女,工程师,主要从事质谱光谱等仪器测试与管理工作,E-mail :.第 29 卷第 2 期分析测试技术与仪器Volume 29 Number 22023年6月ANALYSIS AND TESTING TECHNOLOGY AND INSTRUMENTS June 2023体降温,低温系统主要包括以下几个模块:(1)液氮存储供应模块,(2)低温泵模块,(3)流量控制器,(4)干燥气系统,(5)Cryoscream 冷头. 其中,液氮存储供应模块主要是杜瓦瓶,瓶内液氮为低温系统提供冷源. 低温泵模块将液氮从无压的杜瓦瓶中通过灵活的真空绝缘传输线,流入Cryoscream 冷头. 液氮通过加热器,大部分液体被蒸发成气体,气体沿着热交换器的一条路径向外流动,通过温度和流量控制器到达泵. 此时气体流回Cryostream 冷头,沿着热交换器的第二条路径重新冷却,气体温度在进入Cryostream 喷嘴前由加热器和传感器调节,沿着等温喷嘴流动,在样品上方流出. 仪器长时间运作,需要不断向杜瓦瓶内加入液氮保证低温系统正常运行. 杜瓦瓶要求无压,瓶口处密封性不强,当杜瓦瓶内充满液氮时,由于液氮温度较低,易挥发,导致杜瓦瓶口一直处于结冰的状态. 每次手动向瓶内加入液氮打开瓶口时,瓶口的冰块很容易掉入瓶底,冰块被吸入到液氮管路,堵塞管路,此时整个低温系统无法达到降温的目的. 需要将杜瓦瓶中的液氮管拿出,在室温或者加热条件下使冰块融化,频繁加液氮导致管路堵塞的频率会更高,此过程会浪费大量的时间. 另外,在试验过程中,由于不能实时监测杜瓦瓶内液氮使用情况,当剩余液氮量较少时,无法及时补充液氮,迫使试验终止,影响试验进度.本文主要对仪器的低温系统液氮存储模块进行简单改造,能够实时监测杜瓦瓶内液氮液面高度,达到杜瓦瓶内液氮自动补给并远程报警的目的.1 试验部分1.1 仪器X -射线单晶衍射仪XtaLAB Pro ,日本理学公司生产.1.2 低温系统改造低温系统改造后的示意图如图1所示,主要包括6个方面:(1)自增压液氮罐. 增加液氮存储体积,延长液氮使用时间. (2)电磁阀. 在自增压液氮罐出口处安装电磁阀,电磁阀连通补液灌和控制器. 当液位低于设置的补液液位时,电磁阀打开,开始补液. 当液位到达设置的停止补液液位时,电磁阀关闭,停止补液,从而实现液氮的自动补给. (3)液位传感器. 电容式液位计,能够在低温容器中对液氮等低温液体进行连续的高度测量,通过金属杆内的液位传感器感应当前液位,为控制器提供当前液位值.(4)法兰. 在杜瓦瓶瓶口安装法兰盖,法兰盖上面设置液氮出口、入口、液位传感器与安全阀接口,减少液氮瓶口频繁打开. (5)远程报警模块. 当杜瓦瓶内的液氮液面高度低于设置的液面高度时,控制器会触发报警,同时远程报警模块将远程发送信息或打电话提醒仪器管理人员. (6)控制器系统. 控制器是一切的终端,LED 触摸屏直接显示当前液位,可以设置补液液位和停止补液液位.以上配件中自增压液氮罐生产厂家为成都米兰低温科技有限公司;电磁阀为ASCO 品牌,型号为2/2-210系列;液位计型号为LL-445,由四川赛尔电磁阀自增压液氮罐红色虚线框内为改造部分控制器报警模块杜瓦瓶杜瓦瓶口法兰设计3∶20仪器进液管出液管液位传感器安全阀接口16ϕ7510700液氮出口液氮入口出气口排气口液位计设置告警(a)(b)图1 (a )低温系统改造后示意图,(b )图(a)中蓝色框部分的尺寸和具体构造Fig. 1 (a) Diagram of modification of cryogenic system, (b) size and construction of blue section in figure (a)228分析测试技术与仪器第 29 卷微讯科技有限公司定制;法兰型号为FT-B45、远程报警模块型号为BMT/GSM-2、控制器系统型号为MLT-200B ,均由广州倍玛特仪器设备有限公司生产.2 结果与讨论低温系统在样品测试过程中发挥着重要的作用,小分子以及蛋白大分子样品在低温下测试,减少晶体开裂,提高数据质量. 针对该仪器低温系统存在的不足加以改进,并增加了其他功能,与改造前相比:(1)改造前液氮3~5 d 需手动添加一次,改造后2周添加一次,延长液氮使用时间,减少液氮补充次数. (2)改造后通过控制器界面可实时查看杜瓦瓶内的液氮液位高度. (3)由手动向杜瓦瓶中添加液氮升级为自动补充. (4)实现远程报警功能,当杜瓦瓶内液氮低于补液液位时,报警模块会触发报警,通过电话或短信告知仪器管理者. (5)此设计不需要打开杜瓦瓶口就能够向瓶内添加液氮,因此避免了冰块堵塞液氮管的风险,相关测试结果已表明(如图2所示).3 结论本文主要改造了X -射线单晶衍射仪低温系统中的液氮存储模块,解决了测试过程中冰块堵塞管路问题,防止因管路堵塞或者无法及时补充液氮导致试验终止的现象,节省了时间,提高了效率,同时实现液氮液位监测与自动补充的目的. 目前仪器公司对于X -射线单晶衍射仪的改进部分主要集中在主机部分,但其他配件对于仪器的运行也非常重要,例如低温系统、循环冷却系统等,其存在的问题可能会影响仪器的正常运行. 本文改造的低温系统能够保证单晶样品(尤其是不稳定样品以及大分子蛋白晶体等)的稳定性(防止开裂和风化)与测试数据的高质量性. 测试结果表明改造后的低温系统能够流畅运行,具有较高的实用性,对其他领域类似仪器低温系统使用者具有借鉴意义.参考文献:李国武. CCD 平面探测X 射线单晶衍射新技术开发及在调制结构研究中的应用[D ]. 北京: 中国地质大学,2005. [LI Guowu. New techniques development for CCD detector X -ray single crystal diffraction and ap-plication in modulated structure [D ]. Beijing: China University of Geosciences, 2005.][ 1 ]武佳颖, 于碧辉. X 射线单晶衍射仪远程控制系统消息通信系统[J ]. 计算机系统应用,2017,26(2):43-50. [WU Jiaying, YU Bihui. Communication system of X -ray single crystal diffraction remote control system [J ]. Computer Systems & Applications ,2017,26(2):43-50.][ 2 ]陈小明, 蔡继文. 单晶结构分析原理与实践[M ]. 第2版. 北京: 科学出版社, 2007.[ 3 ]杨培菊, 沈志强, 黄晓卷, 等. X -射线单晶衍射仪易风化晶体低温显微上样系统的研制[J ]. 分析测试技术与仪器,2019,25(2):111-113. [YANG Peiju, SHEN Zhiqiang, HUANG Xiaojuan, et al. Development of mi-croscopic selecting and sampling system in low-temper-ature environments for single crystal X -ray diffractomet-er to test weathering-suspected crystals [J ]. Analysis and Testing Technology and Instruments ,2019,25 (2):111-113.][ 4 ]Muller P, Herbst-Irmer R, Spek A L, 等. 晶体结构精修:晶体学者的SHELXL 软件指南[M ]. 陈昊鸿, 译. 北京:高等教育出版社, 2010.[ 5 ]出气口安全阀液氮入口液位计法兰杜瓦瓶(d)液氮出口至仪器图2 相关测试情况(a )杜瓦瓶内液氮实时液位,(b )设置自动补液高度与停止补液高度,(c )法兰实物图,无需打开法兰即可添加液氮,(d )远程报警短信Fig. 2 Results of relevant test(a) liquid level of liquid nitrogen in Dewar vessel, (b) set automatic fluid replenishment height and stop fluid replenishment height, (c) physical design of flange cover, no need to open flange cover to add liquid nitrogen, (d) remotealarm message第 2 期马宣,等:X -射线单晶衍射仪XtaLAB Pro 的低温系统改造229。
核磁共振中常用的英文缩写和中文名称
NMR 中常用的英文缩写和中文名称收集了一些NMR 中常用的英文缩写,译出其中文名称,供初学者参考,不妥之处请指出,也请继续添加.相关附件NMR 中常用的英文缩写和中文名称APT Attached Proton Test 质子连接实验ASIS Aromatic Solvent Induced Shift 芳香溶剂诱导位移BBDR Broad Band Double Resonance 宽带双共振BIRD Bilinear Rotation Decoupling 双线性旋转去偶(脉冲)COLOC Correlated Spectroscopy for Long Range Coupling 远程偶合相关谱COSY ( Homonuclear chemical shift ) COrrelation SpectroscopY (同核化学位移)相关谱CP Cross Polarization 交叉极化CP/MAS Cross Polarization / Magic Angle Spinning 交叉极化魔角自旋CSA Chemical Shift Anisotropy 化学位移各向异性CSCM Chemical Shift Correlation Map 化学位移相关图CW continuous wave 连续波DD Dipole-Dipole 偶极-偶极DECSY Double-quantum Echo Correlated Spectroscopy 双量子回波相关谱DEPT Distortionless Enhancement by Polarization Transfer 无畸变极化转移增强2DFTS two Dimensional FT Spectroscopy 二维傅立叶变换谱DNMR Dynamic NMR 动态NMRDNP Dynamic Nuclear Polarization 动态核极化DQ(C) Double Quantum (Coherence) 双量子(相干)DQD Digital Quadrature Detection 数字正交检测DQF Double Quantum Filter 双量子滤波DQF-COSY Double Quantum Filtered COSY 双量子滤波COSYDRDS Double Resonance Difference Spectroscopy 双共振差谱EXSY Exchange Spectroscopy 交换谱FFT Fast Fourier Transformation 快速傅立叶变换FID Free Induction Decay 自由诱导衰减H,C-COSY 1H,13C chemical-shift COrrelation SpectroscopY 1H,13C 化学位移相关谱H,X-COSY 1H,X-nucleus chemical-shift COrrelation SpectroscopY 1H,X- 核化学位移相关谱HETCOR Heteronuclear Correlation Spectroscopy 异核相关谱HMBC Heteronuclear Multiple-Bond Correlation 异核多键相关HMQC Heteronuclear Multiple Quantum Coherence 异核多量子相干HOESY Heteronuclear Overhauser Effect Spectroscopy 异核Overhause 效应谱HOHAHA Homonuclear Hartmann-Hahn spectroscopy 同核Hartmann-Hahn 谱HR High Resolution 高分辨HSQC Heteronuclear Single Quantum Coherence 异核单量子相干INADEQUATE Incredible Natural Abundance Double Quantum Transfer Experiment 稀核双量子转移实验(简称双量子实验,或双量子谱)INDOR Internuclear Double Resonance 核间双共振INEPT Insensitive Nuclei Enhanced by Polarization 非灵敏核极化转移增强INVERSE H,X correlation via 1H detection 检测1H 的H,X 核相关IR Inversion-Recovery 反(翻)转回复JRES J-resolved spectroscopy J-分解谱LIS Lanthanide (chemical shift reagent ) Induced Shift 镧系(化学位移试剂)诱导位移LSR Lanthanide Shift Reagent 镧系位移试剂MAS Magic-Angle Spinning 魔角自旋MQ(C)Multiple-Quantum ( Coherence )多量子(相干)MQF Multiple-Quantum Filter 多量子滤波MQMAS Multiple-Quantum Magic-Angle Spinning 多量子魔角自旋MQS Multi Quantum Spectroscopy 多量子谱NMR Nuclear Magnetic Resonance 核磁共振NOE Nuclear Overhauser Effect 核Overhauser 效应(NOE)NOESY Nuclear Overhauser Effect Spectroscopy 二维NOE 谱NQR Nuclear Quadrupole Resonance 核四极共振PFG Pulsed Gradient Field 脉冲梯度场PGSE Pulsed Gradient Spin Echo 脉冲梯度自旋回波PRFT Partially Relaxed Fourier Transform 部分弛豫傅立叶变换PSD Phase-sensitive Detection 相敏检测PW Pulse Width 脉宽RCT Relayed Coherence Transfer 接力相干转移RECSY Multistep Relayed Coherence Spectroscopy 多步接力相干谱REDOR Rotational Echo Double Resonance 旋转回波双共振RELAY Relayed Correlation Spectroscopy 接力相关谱RF Radio Frequency 射频ROESY Rotating Frame Overhauser Effect Spectroscopy 旋转坐标系NOE 谱ROTO ROESY-TOCSY Relay ROESY-TOCSY 接力谱SC Scalar Coupling 标量偶合SDDS Spin Decoupling Difference Spectroscopy 自旋去偶差谱SE Spin Echo 自旋回波SECSY Spin-Echo Correlated Spectroscopy 自旋回波相关谱SEDOR Spin Echo Double Resonance 自旋回波双共振SEFT Spin-Echo Fourier Tran sform Spectroscopy (with J modulati on)(J-调制)自旋回波傅立叶变换谱SELINCOR SELINQUATE SFORD SNR or S/NSelective Inverse Correlation 选择性反相关Selective INADEQUA TE 选择性双量子(实验)Single Frequency Off-Resonance Decoupling 单频偏共振去偶Signal-to-noise Ratio 信/ 燥比SQF Single-Quantum Filter 单量子滤波SRTCF TOCSY TORO TQF WALTZ-16 Saturation-Recovery 饱和恢复Time Correlation Function 时间相关涵数Total Correlation Spectroscopy 全(总)相关谱TOCSY-ROESY Relay TOCSY-ROESY 接力Triple-Quantum Filter 三量子滤波A broadband decoupling sequence 宽带去偶序列WATERGATE Water suppression pulse sequence 水峰压制脉冲序列WEFTZQ(C) ZQF T1T2 tmWater Eliminated Fourier Transform 水峰消除傅立叶变换Zero-Quantum (Coherence) 零量子相干Zero-Quantum Filter 零量子滤波Longitudinal (spin-lattice) relaxation time for MZ 纵向(自旋- 晶格)弛豫时间Transverse (spin-spin) relaxation time for Mxy 横向(自旋-自旋)弛豫时间T C rotational correlation time 旋转相关时间。
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a r X i v :a s t r o -p h /0308036v 1 2 A u g 2003Astronomy &Astrophysics manuscript no.H4592February 2,2008(DOI:will be inserted by hand later)Do X-ray Binary Spectral State Transition Luminosities Vary?Thomas J.MaccaroneAstrophysics Sector,Scuola Internazionale Superiore di Studi Avanzati,via Beirut,n.2-4,Trieste,Italy,34014andAstronomical Institute “Anton Pannekoek,”University of Amsterdam,Kruislaan 403,1098SJ Amsterdam,The NetherlandsAbstract.We tabulate the luminosities of the soft-to-hard state transitions of all X-ray binaries for which there exist good X-ray flux measurements at the time of the transition,good distance estimates,and good mass estimates for the compact star.We show that the state transition luminosities are at about 1-4%of the Eddington rate,markedly smaller than those typically quoted in the literature,with a mean value of 2%.Only the black hole candidate GRO J 1655-40and the neutron star systems Aql X-1and 4U 1728-34have measured state transition luminosities inconsistent with this value at the 1σlevel.GRO J 1655-40,in particular,shows a state transition luminosity below the mean value for the other sources at the 4σlevel.This result,combined with the known inner disk inclination angle (the disk is nearly parallel to the line of sight)from GRO J 1655-40’s relativistic jets suggest that the hard X-ray emitting region in GRO J 1655-40can have a velocity of no more than about β=0.68,with a most likely value of about β=0.52,and a minimum speed of β=0.45,assuming that the variations in state transition luminosities are solely due to relativistic beaming effects.The variance in the state transition luminosities suggests an emission region with a velocity of ∼0.2c .The results are discussed in terms of different emission models for the low/hard state.We also discuss the implications for measuring the dimensionless viscosity parameter α.We also find that if its state transitions occur at typical luminosities,then GX 339-4is likely to be at a distance of at least 7.6kpc,much further than typically quoted estimates.Key words.accretion,accretion disks –binaries,close –stars:neutron –black hole physics1.IntroductionEarly on,it was discovered that the spectral energy distri-butions of X-ray binaries showed variations with luminos-ity.At low luminosities,these systems typically show hard X-ray spectra,dominated by a power-law like component with a photon spectral index of about 1.8and a cutoffat a few hundred keV (the low/hard state).At higher lumi-nosities,they typically show spectra dominated by a soft quasi-thermal component with a characteristic tempera-ture of about 1keV (the high/soft state).These quasi-thermal spectra are generally fairly well described by mod-els of a geometrically thin,optically thick accretion disk (Shakura &Sunyaev 1973;Novikov &Thorne 1973).The low/hard state spectra are usually described in terms of thermal Comptonization models in a geometrically thick,optically thin medium (e.g.Shapiro,Lightman &Eardley 1976).The optically thin region has an electron tempera-ture of ∼70keV,with the high temperature maintained either by magnetic reconnections (Haardt &Maraschi 1991;Nayakshin &Melia 1997;Di Matteo et al.1999)or simply by inefficient cooling of the gas at particularly low accretion rates (e.g.Rees et al.1982;Narayan &Yi 1994).2Maccarone:State Transition Luminositiestransitions thus holds great potential for helping us un-derstand the radiation mechanisms and the accretion ge-ometry in the individual spectral states(see e.g.Esin et al.1997;Poutanen et al.1997;Merloni2003).A systematic study of the luminosities at which these transitions occur and the possible variations in these lumi-nosities is a necessary,but generally unavailable piece of the puzzle for understanding state transitions.Flux mea-surements at or near the state transitions and compar-isons of the low/hard state and high/soft state luminosi-ties have been presented for some individual sources(see e.g.Zhang et al.1997;Zdziarski et al.2002as well as the observations discussed below),and the transition lu-minosity has been estimated in Eddington units for one source(Sobczak et al.2000),but never before has a large sample been collected and analyzed in one place.The gen-eral lore has held that state transitions occur at about 8%of the Eddington luminosity(Esin et al.1997),and that the state transition luminosities do not vary much. Recent work has shown hysteresis effects in many low mass X-ray binary systems,where the soft-to-hard state tran-sitions occur at higher luminosities than the hard-to-soft state transitions(e.g.Miyamoto et al.1995;Nowak et al. 2002;Barret&Olive2002;Maccarone&Coppi2003a). Furthermore,since some models for the low/hard state come from regions with bulk relativistic velocities away from the accretion disk(e.g.Beloborodov1999;Markoffet al.2001),while others come from regions without such motions(e.g.Shapiro et al.1976;Rees et al.1982;Narayan &Yi1994),the presence of inclination angle effects on state transition luminosities may be an important diag-nostic for understanding the accretion geometry of the low/hard states.With these aims in mind,we collect from the literature and/or derive from archival data the masses, distances,and state transitionfluxes for all x-ray binaries where such data is available and reliable.We discuss the observations used in Section2and discuss the implica-tions of the mean value,the variance in the values and the possible effects of inclination angle in Section3.2.ObservationsWe have compiled from the literature the data for the sources where the mass of the compact object,distance to the binary system,and state transition luminosity have all been measured.Where the distances come from opti-cal measurements of the mass donor,we use the quoted errors.We have also included several neutron star sources whose distances have been measured from the luminosities of their type I bursts.For these sources,we have set the distance estimate errors to be30%in accordance with the results of Kuulkers et al.(2003).The distance uncertain-ties are discussed in greater detail below.We also discuss below which sources which are known transients were not included in our sample and why they have not been in-cluded.For a few additional sources,the data exist except for the state transitionflux.In these cases,we have es-timated the state transitionflux,either from existingfits to the data or by downloading the appropriate data from HEASARC andfitting it.The sources of data for each system are discussed below,and the relevant parameters are all listed in Table1.We have,in general,chosen the data with the best temporal sampling among data sets capable of measur-ing the state transition.In some cases,this means using a narrower bandpass instrument than the most broad-band instrument which observed the state transition.This choice is justified,however,by the fact that the luminosi-ties can change rather quickly for X-ray transients,but the spectral shapes of low/hard state black hole accretors are rather constant.That is to say,the difference in luminosity caused by observing a source a week after its state tran-sition is generally larger than the uncertainty introduced by extrapolating2-20keV data in order to measure the bolometric luminosity.There is greater variation in the spectral shapes of the neutron star accretors,but given that RXTE has generally provided the best broadband spectroscopy and the best temporal sampling,the choice need not be made for the neutron star sources included in our sample.We have focused here on the soft-to-hard state tran-sitions.There are two major reasons for this.Firstly,the luminosities of X-ray binaries in outbursts oftenfit a fast-rise/exponential decay profile,so,with the source luminos-ity changing more slowly during the decaying than during the rising part of the outburst,errors in determining the exact time of the state transition will cause smaller errors in the overall luminosity.Secondly,hysteresis has been found to be ubiquitous in the state transition luminosities of X-ray binaries,with the transition from the hard state to the soft state occurring at a higher luminosity that the soft-to-hard state transition.Since one possible ex-planation for this hysteresis effect is that the soft-to-hard state transitions occur in quasi-equilibrium states,while the hard-to-soft occur in violently unstable states,there may be instrinsic variations in the hard-to-soft state tran-sition luminosities that do not occur in the soft-to-hard state transition luminosities(Maccarone&Coppi2003a).Nova Muscae1991.The measurement of the X-rayflux is taken from the Ginga All-Sky Monitor light curve of Kitamoto et al.(1992),with the state transition estimated to have occurred on day135.The black hole mass and distance estimates come from Gelino et al.(2001).XTE J1550-564.The measurement of the X-rayflux comes from Sobczak et al.(2000),with the assumption that the state transition occurred at the luminosity mea-sured in observation number205.The black hole mass and distance estimate come from Orosz et al.(2002).The state transition luminosity was estimated by Sobczak et al.(2000)to occur at about0.02L EDD,but the estimate was made before the mass and distance of the black hole had been measured and bolometric corrections to that lu-minosity estimate were not made.GS2000+251.Like Nova Mus91,the measurement of the X-rayflux is taken from the Ginga All-Sky MonitorMaccarone:State Transition Luminosities3light curve of Kitamoto et al.(1992),with the state tran-sition estimated to have occurred on day135.The black hole mass and distance estimates come from Callanan et al.(1996).Cyg X-1.The X-rayflux measurements come from afit to the spectral data from the September2,1996data,the first low/hard state observed by RXTE after the high/soft state seen in the spring/summer of1996.The3-20keV spectrum shows aflux of1.5×10−8ergs/second/cm2when aΓ=1.9absorbed power law plus Gaussian(tofit the iron emission line)model isfit.The mass measurement comes from Herrero et al.(1995),assuming an inclination angle of30degrees and the distance estimate comes from from Gies&Bolton(1986).GRO J1655-40.The measurement of the X-rayflux comes from Sobczak et al.(1999),with the state transition occurring on August14,1997.The mass estimates come from Greene et al.(2001).We note that the high proper motions seen in the relativistic jets of GRO J1655-40 (Hjellming and Rupen1995),place afirm upper limit on the distance of3.5kpc(Fender2003).The distance de-terminations for this sources thus have two constraints-one from the optical measurements,which suggest that d=3.8±0.7kpc(Greene et al.2001),and the other that d<3.5kpc(Fender2003).We therefore combine these two pieces of information andfind that d=3.3±0.2kpc.LMC X-3.This source was long thought to be steadily in the high/soft state until the discovery of occasional, brief state transitions by Wilms et al.(2001).Luminosities are not quoted for the state transitions,but the dates dur-ing which the source was in the hard state are identified by Wilms et al.(2001).The hard state observation closest to the soft-to-hard transition was taken on May29,1998 (RXTE ObsID30087-02-07-00).We have downloaded the data for this ObsID andfit an absorbed power law model to the PCA and HEXTE data from3-200keV,using the standard HEASARC screening criteria.The bestfitting model gives a power law index of1.8±0.1and aflux of 5.0×10−11ergs/sec/cm2.The distance is assumed to be the standard distance to the Large Magellenic Cloud,51 kpc(Keller&Wood2002).As a persistent,high mass system,ellipsoidal light curve variations have not been measured in LMC X-3,so the system’s inclination angle is not well-constrained.The black hole’s mass estimates come from Cowley et al.(1983)and Paczynski(1983).Aql X-1.This system is an accreting neutron star,and its mass is assumed to be the standard1.4M⊙values for neutron stars.Theflux at the state transition comes from Maccarone&Coppi(2003a).The distance of this system is a debated point;the estimate in the paper presenting thefirst optical spectrum is2.5kpc(Chevalier et al.1999) while other work has suggested a distance of4-6.5kpc (Rutledge et al.2001).We have adopted the smaller value here as it is based entirely on optical measurements,but also present alternative calculations for the higher value.4U1608-52.The distance to4U1608-52is estimated to be3.6kpc on the basis of radius expansion type I X-ray bursts(Nakamura et al.1989).As a neutron star,the mass of the central object is assumed to be1.4solar masses.Theflux is taken from the well-sampled RXTE PCA/HEXTE data set in the November2001outburst. The source wasfirst observed in a hard spectral state early on20November2001(ObsID60052-02-06-00).Thefirst observed hard stateflux is2.7×10−9ergs/sec/cm2(2-20 keV);after correcting for neutral hydrogen absorption and making the bolometric spectral correction(the spectrum has a photon indexΓ=1.72,and a cutoffenergy of50.6 keV),wefind that the bolometricflux is about5.6×10−9 ergs/sec/cm2.At the quoted distance of3.6kpc,the lu-minosity is8.1×1036ergs/sec,which corresponds to4.2% of the Eddington luminosity for a1.4M⊙neutron star.4U1728-34.The distance to this source is estimated to be4.3±0.5kpc on the basis of neutron star atmo-sphere modeling of a sample of Type I bursts(Foster et al.1986-FRF).The state transition with the best tem-poral sampling is found to have occurred on22February 1996.Theflux at this transition is2-200keVflux at this transition is found to be4.6×10−9ergs/sec/cm2,with an optical depth of0.75and a temperature of36keV for the Comptonizing region.The bolometric luminosity is then 9.6×1036ergs/sec,corresponding to5%of the Eddington luminosity,assuming that the model for the distance es-timate is correct.Additional confidence in the distance estimate was ascribed to its consistency with the distance of a putative globular cluster associated with4U1728-34 (Grindlay&Hertz1981),whose existence has since been refuted(van Paradijs&Isaacman1989).Given the lack of this confirmation of the distance estimate and the fact that FRF did not consider the effects of changing the chemi-cal composition of the accreted gas,we have increased the uncertainty in the distance estimate to this source to the 30%found by Kuulkers et al.(2003)to be the rough sys-tematic error.2.1.Sources not includedThere are several soft X-ray transients with suspected black hole primaries which are not included in this work. The reasons vary-typically there is either no mass esti-mate,no distance estimate,or the X-ray data at the time of the state transitions lack either the necessary spectral or spatial resolution.We note that this is much more likely to be the case for neutron star systems than black hole systems;the state transitions and the changes in lumi-nosity are much more rapid for neutron stars than for black holes,perhaps because the timescale for luminos-ity change scales with the mass of the accreting object; therefore,while sampling a few times a week may be suf-ficient to measure the state transitions of black hole sys-tems,it will generally not be sufficient for the neutron star systems.This is compounded by the fact that the sampling of black hole systems has generally been better at the times of state transitions than the sampling of the neutron star systems,presumably because the black hole systems have been much brighter in the all-sky monitors4Maccarone:State Transition Luminositiesand hence have attracted more attention.There are also several neutron star sources not included in the sample for various reasons-generally because a transition to a full low/hard state was not seen with sufficient temporal sam-pling,or because of extreme uncertainties in the source distance.Below we discuss the observations for all sources listed as atoll sources in the most recent“van Paradijs catalog”(Liu et al.2001)that have not been included in the analysis as described above.Only the atoll sources are included because the Z sources are thought to all be ac-creting steadily at luminosities well above the soft/hard transition level and the unclassified neutron star sources are unclassified for the simple reason that they have not shown spectral state phenemenology.2.1.1.Neutron stars not included4U1705-44.The transitionflux for this source has been estimated to be between7×1036and2.1×1037ergs/sec (Barret&Olive2003),with the distance assumed to be 7.4kpc(as estimated from non-radius expansion bursts by Haberl&Titarchuk1995).However,it seems from the spectralfits to the data presented in this paper,that a full low/hard state is not reached;the optical depth in the Comptonization model(using the COMPTT model in XSPEC;Hua&Titarchuk1995)never drops below5.5 and the temperature never rises above14.1keV(com-pare,for example with Aql X-1where the Comptonization modelfits show a drop in the coronal optical depth to τ≈1and a rise in the coronal temperature to above80 keV-Maccarone&Coppi2003b).It is commonly held lore that the cutoffenergies of neutron star spectra in hard states are typically lower than those for black hole spectra,and typically about30keV or less(Zdziarski et al.1998).In fact,for many systems,the true low/hard state occurs and the spectrum takes a form quite similar to the low/hard states of black holes(Barret et al.2000). While clearly substantial hardening to the spectrum has occured in4U1705-44,the spectrum has entered only an intermediate state,and after this point,the luminosity be-gins rising and the spectrum begins softening again.Based on this data,we can say only that the state transition luminosity should be less than about7×1036ergs/sec. Furthermore,if the accreted material is helium rich,the distance estimate of Haberl&Titarchuk(1995)drops to 7.0kpc,and the luminosity drops to6.3×1036ergs/sec, which corresponds to3.3%of the Eddington luminosity for a1.4M⊙neutron star.Because a full state transition is not seen,we do not include this source in either the table or any of the calculations based on the table.4U0614+09.There does not exist a particularly well-sampled state transition for this source,but evidence seems to suggest that the hysteresis effects for it are rather mild.Barret&Grindlay(1995)found that the source was in a low/hard type state during two EXOSAT observa-tions where theflux was1.1&1.2×10−9ergs/sec/cm2 from1-20keV,in an intermediate state when theflux was1.5×10−9ergs/sec/cm2and in a much softer state at3.5×10−9ergs/sec/cm2.We thus take the transition flux to be1.3±0.2×10−9ergs/sec/cm2.The distance has only an upper limit of3kpc from sub-Eddington Type I bursts.When correcting to the bolometric luminosity,we assume that the spectrum has a cutoffenergy of about 60keV,in agreement with typical results from other neu-tron star systems,and use the measured power law pho-ton index ofΓ=1.9.The bolometric luminosity is then 2×1036(d/3kpc)2ergs/sec,or less than about1%of the Eddington luminosity.4U1820-30.This source has a known distance due to its association with the globular cluster NGC6624. Its transition luminosity cannot be measured,however, because the sampling of the pointed RXTE observations of it is insufficient.It did appear to show a state transi-tion in1997,but the timespan between the last high/soft state observation and thefirst low/hard state observation was about20days,sufficient time for a rather largeflux change.Given that the count rate did not continue de-creasing after the source entered the low/hard state,one cannot even be certain that the transitionflux is between the two observedfluxes.This source is a good candidate for future monitoring campaigns,as its distance is well known and it is known to exhibit state transitions.SLX1732-304.This system represents a similar case to4U1820-30.It is a globular cluster source,located in Ter1(Parmar et al.1989),but has been poorly sampled by RXTE;only four observations have been made,all in a lowflux state,and showing similar X-ray spectra(Molkov et al.2001).Observations from Granat did show a spec-tral state transition,but there were only two observations made,a month apart in time,and a factor of four apart in flux(Pavlinsky et al.2001).Using the typically quoted5.2 kpc distance to the globular cluster(Ortolani et al.1999), and the3-20keVfluxes of6.95×10−10and1.64×10−10 erg/sec/cm2,the luminosities are found to be2.25×1036 ergs/sec and5.0×1035ergs/sec respectively,indicating a state transition between1%and0.25%of the Eddington rate.However,no bolometric corrections have been made to these values,and given the rather large neutral hy-drogen columns to the sources,the corrections are rather uncertain,but should be of order a factor of2-4.Given that the spectral data and the sampling in time are insuf-ficient to make accurate measurements,we choose not to include these transition luminosities in the analysis.KS1731-260.This source has been assumed to lie at the Galactic Center.Neutron star model atmospheres for this source in quiescence are consistent with a distance of about8kpc,but the bestfitting value is half that distance, assuming a neutron star radius of12km(Rutledge et al. 2000).We adopt a distance of4±2kpc for this source based on the neutron star model atmospheres.Its tran-sition appears to have occured at a luminosity of about 3.3×1036ergs/sec,based on the PCA/HEXTE measure-ments taken on May25,1999.However,with the distance uncertainty of a factor of∼2,we do not include this source in calculations.Maccarone:State Transition Luminosities54U1636-53.State transitions werefirst seen in4U 1636-53with EXOSAT(e.g.Prins&van der Klis1987), but only the hard-to-soft transition was seen in these data.A more recent campaign(RXTE proposal60032) shows some evidence that a soft-to-hard state transition probably occurred between17September2001and30 September2001,as the count rate is dropping and the spectrum is hardening in the well sampled region of the lightcurve leading up to17September2001.The spec-trum on17September2001is well represented by a ther-mal Comptonization model with a temperature of3.7keV and an optical depth of4.7,so the source is clearly still in an intermediate state.Unfortunately,no observations were taken between17and30September,and the count rate had again started rising by September30,so the tran-sition cannot even be said to have occurred in aflux range bracketed by the values of thefluxes on these dates.We can thus estimate only an upper limit on the transition flux for this source of the1.5×10−9ergs/sec/cm2seen on17September2001.Given the5.5kpc distance to the source,estimated from radius expansion Type I bursts (van Paradijs et al.1986;van Paradijs&White1995),we estimate that the state transition luminosity occurs at no more than4.8×1036ergs/sec,implying that the Eddington fraction of the state transition is less than2.5%.Cir X-1Circinus X-1is an extremely unusual sys-tem.It has been tentatively classified as an atoll source (Oosterbroek et al.1995),but shows much larger luminos-ity variations than most systems in its class.Furthermore, its mass accretion rate seems to vary due to the eccentric-ity of its orbit,and not due to disk or mass transfer insta-bility effects that affect most other neutron star systems.GX3+1This system has not been the subject of a reg-ular,finely sampled monitoring campaign by RXTE.The only regular monitoring,in Proposal60022,was roughly monthly.4U1735-44This system is thought to be at a distance of9.2kpc(van Paradijs&White1995)from Type I X-ray bursts,but again there are no well sampled state transi-tions observed.Furthermore,the ASM lightcurves show that the luminosity,assuming this distance,seems not to drop below about15%of the Eddington rate,so in fact,it seems likely that no state transition has occurred during the RXTE mission.The persistently bright Galactic Center sources.Four atoll sources near the Galactic Center,GX3+1.GX9+1, GX9+9,and GX13+1have generally been found only in the banana branches after rather detailed studies(see Homan et al.1998and references within).These sources hence do not undergo state transitions,and some have even sometimes been classified as Z sources rather than as atoll sources(see e.g.Schulz et al.1989).These sources are thus rather similar to4U1735-444.XTE J2123-058.This source is a new transientfirst detected with RXTE in June of1998.It was observed with the pointed instruments on RXTEfive times,includ-ing on either side of a state transition.Unfortunately,the flux dropped by a factor of15between the lowest soft state and highest hard state points(Tomsick et al.1999). Given theflux measurements of1.1×10−9and7.3×10−10 respectively,along with the distance estimate of8±3kpc (Zurita et al.2000),wefind that the transition occurred between14%and0.2%of the Eddington rate(accounting for both the distance andflux uncertainties).This range is not particularly useful,so we exclude this source.XTE J1806-276This source has no reliable distance estimate;there is a only a tentative association with an X-ray burster(Marshall et al.1998),and there is only a “likely”optical counterpart(Hynes et al.1998).4U1915-05This system was monitored by RXTE with quite good sampling in May of1996,but the well sampled part of the light curve showed only the upper and lower banana states(Boirin et al.2000).The other data for this source is sampled typically monthly.Thus no state tran-sition has been observed in a well sampled data set.4U1724-30This system is in Terzan2,a globular cluster about9.5kpc away.During the RXTE mission it reached a rather large luminosity(about10%of the Eddington rate),where it was observed rather frequently (P20170,PI:Jung),but did not show a state transition;the spectrum always remained hard,even at the peak(as de-termined from the long-timescale lightcurve in Emelyanov et al.(2002),being wellfit by a thermal Comptonization model with an optical depth of about0.5and a tempera-ture of about45keV.4U1746-37This is another globular cluster system lacking a well-sampled state transition luminosity mea-surement.There are two well sampled RXTE campaigns on this source,P30701(PI:van Paradijs)and P60044 (PI:Smale),but P30701has been shown to be in the island state all the time(Jonker et al.2000),and an inspection of the data from P60044has shown that the same is true here.An additional set of observations,P10112,that was less well sampled showed the source only in an island state, and occurred well before the other two campaigns(Jonker et al.2000).2.1.2.Black hole sources with insufficient optical data GX339-4.GX339-4is in some ways the best candidate for studying state transitions-it is one of the few sources which has been well studied in the X-rays in all the canoni-cal spectral states.However,its optical counterpart is very faint,and its lowest luminosity observations are still dom-inated by the accretionflow in the optical and infrared. Thus no mass measurement has been possible and the dis-tance measurements to this source are based primarily on the absorbing medium.Recent optical studies(Hynes et al.2003)of the source in outburst have allowed the mea-surement of a mass function,i.e.a lower limit on the mass, which are sufficient to prove that the primary is a black hole under the standard assumptions about the neutron star equation of state,but the mass and distance estimates remain insufficient for estimating the Eddington luminos-ity of the state transitions.6Maccarone:State Transition LuminositiesXTE J1859+226.This source lacks an inclination an-gle estimate,a distance estimate,and is the subject of a debated period.The mass function is hence uncertain and regardless of its certainty,it cannot be converted to a mass measurement.GRS1009-45.Three problems exist for this source. The inclination angle is extremely uncertain,so the con-version from mass function to mass is likewise uncertain. The Hαemission does not follow the spectroscopic phase in the conventional manner,suggesting that the orbital period may be in error.Finally,the spectral type of the mass donor is highly uncertain,so there is no distance estimate(Fillipenko et al.1998).2.1.3.Black hole sources with insufficient X-ray data 4U1543-47.This source is a dynamically confirmed black hole candidate,and has shown three strong X-ray out-bursts.Unfortunately,thefirst occurred in1971,when it was monitored once a month over the entire outburst,the second in1983,when it was monitored more frequently, but only during the high/soft state,and the third occurred in1992,where the only publicly available data set comes from BATSE,which is not well-suited to measuring the bolometric luminosity,and whose data results are avail-able only as1week averages.It is currently in its fourth outburst,and the current outburst is likely to provide use-ful data.A0620-00.This source was well observed for two months during its outburst,but its spectrum only soft-ened throughout the outburst.This softening is generally consistent with the decrease in temperature of an accre-tion disk which is dominating the X-ray spectrum.Hence the state transition was not observed in the well-sampled portion of the light curve and the transitionflux cannot be estimated.XN Oph77.This system was monitored during its out-burst by Ariel V,but the published results present only count rates.Hence the state transition cannot be detected and itsflux cannot be estimated.V404Cyg.This source was observed only by Ginga. The data are not public,and the published results (Kitamoto et al.1989)are insufficient for determining a time of the state transition.It appears that the time reso-lution of the observations is regardless insufficient for de-termining a transition luminosity.2.1.4.Black hole sources which do not show thenecessary state transitionsA handful of black hole X-ray transients have not shown the full phenomenology of spectral states seen in the typ-ical soft X-ray transients.As a result,there is no soft-to-hard state transition for these systems,so the measure-ment obviously cannot be made.GRO J0422+32&XTE J1118+480.Both these sys-tems exhibited“mini-outbursts”in which the luminosity never reached a high enough level to trigger a high/soft state.V4641Sgr.This source was seen to spend a large amount of time in the low/hard state in the period be-fore a very rapid,very bright outburst on September15-16,1999.It may have entered the high/soft state on the way down from the∼L EDD peak,but the luminosity de-cay was so rapid that even the several pointings per day from the RXTE All Sky Monitor provide insufficient time resolution to determine whether,or at what luminosity,a state transition occurred.GRS1915+105.Since its discovery by Granat(Castro-Tirado et al.1992),GRS1915+105has shown a lumi-nosity consistently sufficient to place it in the high/soft state,the very high state,or an unstableflaring state.In fact,its lowest luminosity observations are those in the high/soft state.At times,it enters into a state commonly referred to as its“low/hard”state,but the spectral in-dex of the power law component in this state is typically aboutΓ=2.5,much softer than any of the other low/hard states.It has been suggested that at high fractions of the Eddington luminosity,flows with high viscosities may see a large fraction of their energy dissipated in a hot corona (Merloni2003);in this picture,in fact,two solutions,a disk-dominated and a corona dominated one,are possi-ble at every accretion rate above a critical fraction of the Eddington rate which is a function of the viscosity pa-rameterα.The properties of these corona are still not well studied,but the presence of an alternative means of explaining a power-law dominated spectrum at high ac-cretion rates lends credence to the suggestion that the GRS1915+105“low/hard”state is fundamentally differ-ent than that seen in other systems.2.2.Bolometric correctionsBolometric corrections are applied to the data assuming a spectrum of dN。