Phase Equilibria in the Ternary Systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K

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Aspen Plus在三氟乙酸、氯化氢和水共沸精馏研究中的应用

2021年第1期有机氟工业Organo - Fluorine Industry•11•Aspen Plus 在三氟乙酸、氯化氢和水共沸精馏研究中的应用宋昌平1李景通1吴韦韦2王毅3崔永文1李永哲1(1.山东东岳未来氢能材料股份有限公司，山东淄博255000; 2.山东理工大学，山东淄博255000;3.中国石油工程建设有限公司西南分公司，四川成都610000)摘要：利用Aspen P lu s 软件对三氟乙酰氯水解生产三氟乙酸的工艺开展模拟。

借助数据库数据绘制了 HC 1和H 20、 CF 3C 00H 和H 20以及HC 1和CF 3COOH 的二元相图。

根据相图差异，采用“粗分离-共沸精馏-解析精馏”工艺，获得高纯度三氟乙酸产品和达标氯化氢尾气。

模拟结果与试验数据一致，通过计算对工艺进行优化,确定工艺参数以及明确工艺路线。

关键词：Aspen Plus ;三氟乙酸；三氣乙酰氯;共沸精馏；副产盐酸〇刖目1922年，Swarts 教授[1]首次采用铬酸氧化间三氟甲基苯胺获得三氟乙酸，此后三氟乙酸的生产T 艺得到大量的研究与关注。

三氟乙酸是一种重要的含氟中间体，可以用于生产医药、农药、生化试剂和有机合成试剂等产品。

目前，以工业副产的三氟乙酰氯为原料生产三氟乙酸的工艺，已成为很多企业减少三氟乙酰氯污染的首选方案。

Aspen P lu s 软件具有强大的单元操作模型、工程计算能力和多种热力学方法，随着近年来版本的更新，氟化工领域的物性数据库得到了不断的完善，其在氟化工领域的应用得到了扩展[2]。

工业副产三氟乙酰氯水解生产三氟乙酸的工艺，其化学反应式如下：CF3C0C1 + H20 —K ：F3C00H + HC1该反应须确保三氟乙酰氯完全转化，从而减小尾气处理量，减少环保压力。

因此，水在体系内须一直保持过量。

虽然产生的三氟乙酸和氯化氢均可以与水形成共沸物，但利用二者与水形成共沸物的物性差异，可以进行共沸精馏实现氯化氢和水的分离，进而通过解析法获得高纯度三氟乙酸。

Ti–Al–V三元系统中体心立方相的热力学和动力学建模-外文文献及翻译

本科生毕业设计（论文）外文翻译外文原文题目：Thermodynamic and kinetic modeling of bcc phase in the Ti A— ternary system中文翻译题目：Ti - Al - V二兀系统中体心立方相的热力学和动力学建模毕业设计（论文）题目：B 20C新型钛合金热处理工的艺仿真研究姓名：____________ xx _____________________学院：材料学院______________班级：材料成型及控制工程指导教师：_______ xxx __________________Ti — -V三元系统中体心立方相的热力学和动力学建模H. Wan g,N. Warnke n,R.C. Reed（冶金和材料学部，伯明翰大学，伯明翰B15 2TT，UK）摘要：本文利用双亚晶格模型（Ti,AI,V）:（ Ti,AI,V ）进行了Ti-Al二元系统和Ti-Al -V三元系统中有序B2相的热力学优化。

得到的一组自洽参数表明，应用于相平衡的有效实验数据可精确地再现。

通过应用新的热力学数据库计算出的热力学驱动力，分析和优化了Ti-Al-V 三元系统的无序A2相的相互扩散行为。

得出一组描述无序A2相原子迁移率的参数，这些参数将对涉及此无序A2相相变的未来定量模型有一定作用。

关键词：热力学；流动性；优化；Ti -1引言Ti基合金具有较好的强度和韧度，尤其是当我们考虑密度校正时。

然而，这些合金的性质很大程度上取决于其热处理的方式；所以，深刻的理解这些系统中微观组织和合金性能之间关系是很重要的。

尤其是在室温下保留大量体心立方（BCC ）结构的钛合金-比如B钛合金，在这种高强度、高韧度钛合金的范围中很多是应用于航空航天领域的新兴材料。

热力学和动力学数据对B钛合金的设计，许多其它工程合金，可模拟的各种相平衡和相变都非常有帮助。

因此，获得一个完整而深刻的三元Ti -M -系统中体心立方相的热力学和动力学迁移率数据库是很重要的。

由三元相图计算活度

由三元相图计算活度翟玉春【摘要】The activities formulas of all the points, lines and areas were calculated from the eight typical ternary phase diagrams by means of the melting point free energy method, standard free energy of formation method and chemical equilibrium method. No assumptions and approximations were introduced. The eight typical phase diagrams studied almost cover the whole range of ternary phase diagrams. The calculation methods and formulas could be applied to all kinds of complicated ternary phase diagrams. Additionally, this method could also be widely applied to the ternary isothermal section phase diagrams and multi-component phase diagrams.%采用熔化自由能法、标准生成自由能法和化学平衡法推导出利用8种类型的三元相图计算活度的公式,覆盖了三元相图的点、线、面全部范围.公式本身没有引进假设和近似.这8种类型的三元相图涵盖了有液相面各种类型的三元相图.本研究的计算方法和计算公式可以应用于各种复杂的三元相图,该方法也可以推广到三元等温截面相图和三元以上的多元相图.【期刊名称】《中国有色金属学报》【年(卷),期】2011(021)010【总页数】10页(P2687-2696)【关键词】三元相图;活度;计算;熔化自由能法;标准生成自由能法;化学平衡法【作者】翟玉春【作者单位】东北大学材料与冶金学院,沈阳110819【正文语种】中文【中图分类】TF01活度是重要的热力学数据，活度的测量，尤其是高温体系活度的测量费时、费钱、费力，且不易准确。

Al-18Si-5Ti合金中TiAlSi金属间化合物的形成

Al-18Si-5Ti合金中TiAlSi金属间化合物的形成高通;刘相法【摘要】目的选取Al-18Si-5Ti合金为研究对象,研究TiAlSi金属间化合物成分、结构和形貌的形成规律.方法通过调整制备工艺(如熔体反应法、液固反应法),改变制备温度和原料(Ti源),可得到板片状或块状的Ti7Al5Si12或Ti(Al1–x,Six)3相.结果使用海绵Ti为原料时,高的熔炼温度倾向于合成板片状Ti7Al5Si12,而低温则易于形成块状Ti7Al5Si12;当使用K2TiF6、Al-10Ti中间合金或以Al粉、Si粉及Ti 粉为原料时,可通过熔体反应或液固扩散反应合成块状的Ti7Al5Si12或Ti(Al1–x,Six)3相.结论通过对熔体参数调整,可实现Al-Si系合金中TiAlSi相的设计.【期刊名称】《精密成形工程》【年(卷),期】2017(009)005【总页数】7页(P50-56)【关键词】TiAlSi金属间化合物;熔体参数;Ti源;相变【作者】高通;刘相法【作者单位】山东大学材料液固结构演变与加工教育部重点实验室,济南 250061;山东大学材料液固结构演变与加工教育部重点实验室,济南 250061【正文语种】中文【中图分类】TG146.2+1Ti是铝合金中常见的元素。

自20世纪初，工业生产就开始向Al熔体中添加Ti来细化晶粒[1]。

此外，Ti也常作为合金化元素被添加到多种牌号的铝合金中，如铝活塞材料（Al-Si合金）中常含有一定量的Ti元素，其可在合金中形成金属间化合物（记作TiAlSi），使Al-Si系合金的组织发生复杂性变化。

当Al熔体中Ti加入量相对较大时，会形成TiAl3金属间化合物[2]。

TiAl3相属正方晶系，晶格参数a=0.385 nm, c=0.858 nm，依据Al合金的Ti含量、熔炼温度和冷却速度等工艺参数的不同，TiAl3相可表现几种典型形态：板状(plate-like)、片状(flake-like)、花瓣状(petal-like)和块状(block-like)。

CaMnO3热电材料的低温烧结研究

CaMnO3热电材料的低温烧结研究王琴;盛得雪;鲁云;宋少伟;陈建文;金应荣【摘要】It is Proposed to fabricate a thermoelectric generator with P - N structure by sintering the N - type CaMnO3 together with the P - type Ca3 Co4 O9 directly. It is necessary to sinter CaMnO3 ceramic below the phase transition temperature of Ca3 Co4 O9 , 926 癈. In this paper, CaMnO3 powder wsa synthesized using the solid reaction method, then mixed with Bi2O3 and pressed into pellet. Sintering was carried out in air at 900cC for 12h. The microstructure and thermoelectric properties of prepared sample were also investigated. As a result, there was no detectable secondary phase caused by additional Bi2O3; the average electrical conductivity increased and the approximate Seebeck coefficient decreased with increasing adding of Bi2 O3; the average electrical conductivity and the approximate Seebeck coefficient increased with increasing temperature. The addition of Bi2O3 promoted the sintering process and decreased the sintering temperature, and effectively improved the thermoelectric properties of CaMnO3 sample as well.%采用固相反应法制备CaMnO3粉末,加入Bi2O3混合、压块后,在900℃烧结12h得到样品,并对样品的物相、组织和热电性能进行了测试分析.结果表明:制备出的热电材料是单相的CaMnO3,加入Bi2O3后没有形成可观测的第二相；随着Bi2O3加入量的增加,样品的平均电导率增大,温差电势减小；平均电导率随温度的增加而增加,呈半导体特性,温差电势随温度的增加而增大；加入Bi2O3促进了烧结,降低了烧结温度,改善了材料的热电性能.【期刊名称】《西华大学学报（自然科学版）》【年(卷),期】2012(031)006【总页数】4页(P16-19)【关键词】CaMnO3;Bi2O3;热电陶瓷;低温烧结【作者】王琴;盛得雪;鲁云;宋少伟;陈建文;金应荣【作者单位】西华大学材料科学与工程学院,四川成都610039;西华大学材料科学与工程学院,四川成都610039;千叶大学工学部,日本千叶市1-33;西华大学材料科学与工程学院,四川成都610039;西华大学材料科学与工程学院,四川成都610039;西华大学材料科学与工程学院,四川成都610039【正文语种】中文【中图分类】TB3热电器件是一类利用材料的热电效应直接实现热能与电能相互转换的装置，以其无噪音、可靠性高、寿命长和结构简单等特点，在绿色新能源及制冷领域有着广泛的应用前景［1］。

ch21_-_phase_equilibrium_I

2
New Way Chemistry for Hong Kong A-Level Book 2
21.1 Definition of a Phase (SB p.248)
Heterogeneous system ---- system with more than one phase Homogeneous system ---- system consists of one phase only
Only vapour can be found
A phase diagram
10 New Way Chemistry for Hong Kong A-Level Book 2
21.3 Phase Diagram for One-Component System (SB p.251)
One Component System - General
Chapter 21
Phase Equilibrium I: One-Component Systems
21.1 Definition of a Phase 21.2 Phase Equilibrium 21.3 Phase Diagram for OneOneComponent System
1
New Way Chemistry for Hong Kong A-Level Book 2
21.3 Phase Diagram for One-Component System (SB p.253)
(open structure) Contraction in volume
H2O(s)
H2O(l)
By Le Chatelier’s principle, the effect of increasing the pressure will favour a reduction in volume, causing the equilibrium to be shifted to the right.

聚L-谷氨酸-γ-苯甲酯接枝共聚物的合成英文

研究快讯C o mm un i ca ti on 合成橡胶工业,2007-01-15,30(1):66CH I N A SY NTHETI C RUBB ER I N DUST R YSyn the si s of poly(γ2benzyl 2L 2glu t am a te)gra ft copoly m er sB en Jin,L iu Feng 3,Ga o Y un,L in J iaping(Scho ol of Ma teria ls Science and Engi neering,E ast China U niversity of Sci ence a nd Technology ,Shangha i 200237,China )　Pol ypep tide s are synthesized via a m i no ac id or its derivant 1They a re uni que in a s pects of structure and feature s a mong poly me ric m ateria ls[1]1Recently the re has been considerableint e re st in s ynthe sis and charac teriza tion of poly pep tide copo ly m ers 1Poly pep tide copoly me ri c m icelles have been prepared on graft copoly mer s e lf 2a ssembly of poly pepti de which acts asbackb one[2]1Poly (ac rylic ac id )(PAA )is an ani oni c poly 2elec trolyte which was frequently emp l oyed as s caffold for i m 2mobiliza ti on of bi ol ogicall y active molecu l e s 1T he high density carboxylic acid moieties along its backbone can be modified by variety of chem istry t o produce am i des,a lcohols,est e rs,and othe r carbox ylic acid derivati ve s 1Ma p repared m icelles of PAA 2graf t 2polystyrene by direc t injecti on of di oxane sol u ti on of poly me r int o wa t e r conta i ning NaCl [3]1　In this study,we have deve l oped a nov e l me th od f o r graft 2i ng poly (γ2benzyl 2L 2gluta m ate )(PBLG)ont o ca rbox ylicgr oup of PA A mono m er unit f or the first ti me 1The grafting re 2acti on was achieved by reacti ng an a m ino 2te r m ina t ed PBLG with P AA acti va ted by 1,32di cyc l ohexylcarb odi m i de (DCC )to pro mote am ide for m ati on 1　The ty p ical grafting reac ti on p rogram is desc ribed as foll ows :DCC wa s added t o a soluti on of PAA and PBLG with a DCC /PBLG molar rati o of 111/110in di oxane at 25℃1The reacti on wa s a ssu med t o be co mp l e te afte r 3days 1The p re 2cipitate wa s filt e red out 1Then a dialysis m embrane wa s used t o purify the copoly me rs until unreacted P BLG or any s ma ll molecu l e s we re eli m inated via UV dete r m ina ti on 1Afte r s eve ra l days l a ter,the graft co poly m ers we re freeze 2dried 1W e de 2note these poly m ers a s P AA 2g 2PBLG 1　The struc ture of the graf t copoly mer wa s charac terized by 1H nuclea r m ag netic resonance (1H 2N MR ).F r om Fig 1wecan see that the grafting reac ti on is s uccessfully occurred 1It sh ows tha t t he copoly me r conta i ns both t he units of PAA and PBLG 1T he con t ent of PBLG and PAA seg ment molar ra tio is calcula t ed 2216/1001F i g 2is transs m isi on e lectr on m ic r osco pe (TE M )phot o s of PAA 2g 2PBLG (011mg/g)i n NaC l aqueous s oluti on 1Theshell pa rt is the PA A seg ment st a ined by Ph osph otungstic acid 1The core part is PBLG s eg ment 1It is conc luded t hat sy nthesized PA A 2g 2PBLG graf t copol y m er is suit able f o r she ll 2core poly m er m ice lle for m ati on 1Fi g 1　1H 2N MR s pectrum and s tructure of P AA 2g 2P BLG i nC DC l 3/trifl our oacetic acidFig 2　TE M of P AA 2g 2P BLG i n NaC l s oluti onR efer en ces:1　Lin J iaping,L i n Shaoliang.Phas e behavi or of ternary s yste m s in 2vo l ving a confor m ati onall y vari able chain and a random ly co il ed poly m er :Effect of external ori entati onal fiel d [J ].M acro mo l e 2cules ,2004,37(14):546154672　Zhang Suning,Chen Tao,L i n J i ap ing,et al .Studies of s elf 2as 2s emb l y behavi or and drug 2loading p r opertites for amphiphi li c po l y(γ2benzyl L 2gluta m ate )2po l y (et hyl ene glyco l )graft copoly m ers [J ].Act a P o l ymeri ca Sinica,2005(6):9299323　Ma Yanhui,Cao Ti,Webber S E .Polymer m i cell es from po l y(acryl i c aci d )2graft 2polystyrene [J ].Macromolecules ,1998,31(6):17731778 聚(L -谷氨酸-γ-苯甲酯)接枝共聚物的合成贲　进,刘　峰3,杲　云,林嘉平(华东理工大学材料科学与工程学院,上海200237)　以溶液聚合直接合成聚丙烯酸,通过接枝反应将疏水的聚肽链接到聚丙烯酸亲水链段上形成两亲性共聚物,合成了新型聚肽接枝共聚物。

(完整版)ch23_-_phase_equilibrium_III

1 New Way Chemistry for Hong Kong A-Level Book 2
23.1 Partition of a Solute Between Two Immiscible Solvents (SB p.277)
Partition Law
Example
3 components
4 New Way Chemistry for Hong Kong A-Level Book 2
23.1 Partition of a Solute Between Two Immiscible Solvents (SB p.278)
Remark The Partition Law will NOT hold when there is association or dissociation of the solute in one of the solvents. Example The distribution of ethanoic acid between water and benzene. In water, ethanoic acid exists in the form of monomers (it can form intermolecular hydrogen bonds with water molecules). In benzene, ethanoic acid exists in the form of dimers .
2 New Way Chemistry for Hong Kong A-Levef a Solute Between Two Immiscible Solvents (SB p.278)
Some Experimental results

低浓度甲缩醛水溶液-萃取剂液液相平衡数据的测定与关联

低浓度甲缩醛水溶液-萃取剂液液相平衡数据的测定与关联时米东;王利平;何高银;于雪敏;李青松【摘要】在30℃、40℃和大气压力下测定了水-甲缩醛-对二甲苯和水-甲缩醛-甲苯体系的液液相平衡数据.根据实验数据对分配系数和分离因子进行了估算,结果表明两种萃取剂对甲缩醛均具有优异的萃取能力.采用Othmer-Tobias和Hand方程对实验数据的可靠性进行了分析,两个方程的线性相关度R2均在0.99以上,表明实验数据具有良好的可靠性.另外,采用UNIQUAC和NRTL热力学模型对数据进行了关联,结果表明估算值与实验值具有良好的一致性.%Liquid-liquid equilibria (LLE) data for the ternary systems {water + methylal + (p-xylene or toluene)} were measured under atmospheric pressure at 30 and 40℃.The distribution coefficient(D)and separation factor(S)were calculated according to the experimental data, which indicated that p-xylene and toluene showed excellent extraction capacity for methylal. Reliability of the experimental data was determined by Othmer-Tobias and Hand correlation equations with the linear correlation of R2>0.99.Moreover, both UNIQUAC and NRTL models were adopted to correlate the experimental LLE data. The calculated values by the two models showed a good consistency with the measured data.【期刊名称】《天然气化工》【年(卷),期】2018(043)001【总页数】7页(P34-39,46)【关键词】液液相平衡;甲缩醛;对二甲苯;甲苯;水【作者】时米东;王利平;何高银;于雪敏;李青松【作者单位】中国石油大学(华东)化学工程学院重质油国家重点实验室,山东青岛266580;中国石油大学(华东)化学工程学院重质油国家重点实验室,山东青岛266580;中国石油大学(华东)化学工程学院重质油国家重点实验室,山东青岛266580;中国石油大学(华东)化学工程学院重质油国家重点实验室,山东青岛266580;中国石油大学(华东)化学工程学院重质油国家重点实验室,山东青岛266580【正文语种】中文【中图分类】O642甲缩醛是一种重要的溶剂和化工原料[1-5]，可由甲醇与甲醛之间的羟醛缩合得到[6-8]。

Chapter 2 Phase Equilibria in One-Component Systems

Some examples of polymorphic transformation: iron, titanium, uranium. Generally, solid phases existing at high temperatures have less dense structures than those existing at low temperatures. An exception is the most common metal iron.
Chapter 2 Phase Equilibria in One-Component Systems
2.1 General
Phase equilibria are determined by the interaction of state variables, such as temperature, pressure, volume and composition. The direction of equilibria: smallest force (energy). Clausius-Clapeyron equation:
Enantiotropic transformation: Phase transformations between two stable solid phases. It can be carried out on a reversible manner. Monotropic transformation: A metastable solid phase transforms into a stable one. It is nhis line has a negative sign.
The solid phase transformation are connected with volume changes. Thus, the critical temperature depends on pressure. dP H F F dT (T V F )

CdIn2S4相图

Journal of Alloys and Compounds 480(2009)360–364Contents lists available at ScienceDirectJournal of Alloys andCompoundsj o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /j a l l c omPhase equilibria in the quasi-ternary system Ag 2S–In 2S 3–CdS at 870KV.R.Kozer a ,∗,A.Fedorchuk b ,I.D.Olekseyuk a ,O.V.Parasyuk aa Department of General and Inorganic Chemistry,Volyn National University,Voli Ave.13,43025Lutsk,Ukraine bDepartment of Inorganic Chemistry,Lviv National University,Kyryla and Mefodiya St.6,79005Lviv,Ukrainea r t i c l e i n f o Article history:Received 8April 2008Received in revised form 12February 2009Accepted 13February 2009Available online 27February 2009Keywords:Semiconductors Chemical synthesis X-ray diffractiona b s t r a c tAn isothermal section of the quasi-ternary system Ag 2S–CdS–In 2S 3at 870K was investigated using X-ray phase analysis.No quaternary intermediate phase was found.A continuous solid solution series between In 2S 3,AgIn 5S 8and CdIn 2S 4was discovered;a limited solid solution range of CdS is localized along the AgInS 2–CdS section.©2009Published by Elsevier B.V.1.IntroductionThe crystal structure of adamantane semiconductors is charac-terized by the tetrahedral coordination of atoms which allows for the formation of solid solution range of substantial extents.The variations of the compositions of the solid solutions permit a wide range of the control of the properties thus leading to new pos-sibilities of the optimization of the parameters of semiconductor devices.An isothermal section of the quasi-ternary system Ag 2S–CdS–In 2S 3had not been studied in detail until now,and no information was found in literature on the existence of intermediate quater-nary phases in the system.Various authors [1–3]studied only the side sections Ag 2S–CdS,Ag 2S–In 2S 3,In 2S 3–CdS of the quasi-ternary system.The Ag 2S–CdS is of the peritectic type [1]with the peritectic point coordinates 33mol.%CdS and 1166K.A horizontal line at 448K is caused by the polymorphous transition of Ag 2S.A minor solid solubility based on Ag 2S extends to 4mol.%CdS.The latest investigation of the Ag 2S–In 2S 3section was reported in [2].The existence of the compounds AgInS 2(CuFeS 2struc-tural type)and AgIn 5S 8(MgAl 2O 4structural type)was conﬁrmed.The system liquidus consists of four regions of the primary crys-tallization of ␤-Ag 2S,␤-AgInS 2,AgIn 5S 8,␥-In 2S 3.AgInS 2forms incongruently at 1130K.A solid solution range of Ag 2S extends to 8mol.%In 2S 3at 870K.AgIn 5S 8has a large homogeneity region from 81to 100mol.%In 2S 3at 870K as determined by the change of the∗Corresponding author.Tel.:+380332249972;fax:+380332241007.E-mail address:kozer v@mail.ru (V.R.Kozer).unit cell parameters.The AgIn 11S 17compound that was described in detail in [3]is in fact a part of this solid solution range.The con-tinuous solid solution series is formed by the ﬁlling of the existing vacancies in the cation sub-lattice of the binary chalcogenide.The In 2S 3–CdS section was investigated in [1].The section is characterized by a continuous solid solubility between In 2S 3and CdIn 2S 4.The existence of two ternary compounds,CdIn 2S 4and Cd 2In 2S 5,was reported at the section.CdIn 2S 4(MgAl 2O 4structural type)melts congruently at 1398K.Cd 2In 2S 5forms in a solid-state reaction and decomposes above 1283K;the compound is dimor-phous (transition temperature is 1231K).The crystallochemical characteristics of the compounds of the Ag 2S–In 2S 3–CdS system at 870K are presented in Table 1.2.Experimental procedurePhase equilibria of the Ag 2S–In 2S 3–CdS system were investigated using 119sam-ples.The batches were composed of high-purity metals and chalcogene (Ag:99.99wt%;Cd:99.9999wt%;In:99.99wt%;S:99.997wt%).First,the batches were heated in evacuated quartz containers in the oxygen-gas burner ﬂame to complete bonding of elementary sulphur.The alloys were then synthesized by the single-temperature method in a shaft-type furnace.The maximum synthesis temperature was 1473K with 5-h exposure.The alloys were annealed at 870K during 1000h followed by quenching into cold water.XRD spectra were recorded by DRON 4-13diffractome-ter (CuK ␣radiation)in a step-scan mode (10◦≤2Â≤90◦).The diffraction patterns were processed using CSD software package,the phase analysis utilized Powder Cell program [11].3.Results3.1.The In 2S 3–CdS sectionThe inconsistency of the literature data on the In 2S 3–CdS system led us to the re-investigation of this system.The section was studied0925-8388/$–see front matter ©2009Published by Elsevier B.V.doi:10.1016/j.jallcom.2009.02.052V.R.Kozer et al./Journal of Alloys and Compounds 480(2009)360–364361Table 1The crystallochemical characteristics of the compounds of the Ag 2S–In 2S 3–CdS sys-tem at poundSpace group (S.G.)Unit cell parameters (nm)Referencesac ␤-Ag 2S Im 3m 0.4889–[5]␤-CdS P 63mc 0.41340.6749[6]␤-In 2S 3Fd 3m 1.0774–[7]␣-AgInS 2I 42d 0.5879 1.1203[8]AgIn 5S 8Fd 3m 1.0828–[9]CdIn 2S 4Fd 3m1.0843–[10]using 22samples annealed at 870K.The existence of the CdIn 2S 4compound was conﬁrmed,as well as its congruent melting and thecrystal structure of the spinel type (S.G.Fd ¯3m ).A new endothermal ternary compound of an approximate composition Cd 5In 2S 8was discovered.The compound forms peritectically and has a polymor-phous transition at 1265K.The temperature range of the existence of Cd 5In 2S 8is 1205–1390K.The B II 5C III 2X VI 8compounds are not an exception of the In 2S 3–CdS system.An endothermal compound Cd 5Ga 2S 8is known (the range of its existence is 1093–1238K)[1];in the systems HgSe–Ga 2Se 3and HgSe–In 2Se 3,the ordering of the solid solutions occurs below 639K at the compositions Hg 5C III 2Se 8[12].We did not conﬁrm the existence of Cd 8In 2S 11and Cd 2In 2S 5that were reported in [1,4].The sectionCdS–CdIn 2S 4was investigated by XRD of the samples annealed at 870K and by DTA (Fig.1).A horizontal line at 1265K represents the polymorphous transition of Cd 5In 2S 8.The isothermal section at 870K contains a solid solution range of CdS (S.G.P 63mc ),a solid solution range of In 2S 3and CdIn 2S 4Fig. 1.Phase diagram of the CdS–In 2S 3system:(1)L,(2)L +CdS,(3)L +␤-Cd 5In 2S 8,(4)L +CdIn 2S 4,(5)L +␥-In 2S 3,(6)␧+␥-In 2S 3,(7)␥-In 2S 3,(8)␧,(9)␤-Cd 5In 2S 8+CdIn 2S 4,(10)␤-Cd 5In 2S 8,(11)␤-Cd 5In 2S 8+CdS,(12)CdS,(13)␣-Cd 5In 2S 8+CdS,(14)␣-Cd 5In 2S 8,(15)␣-Cd 5In 2S 8+CdIn 2S 4,(16)CdS +CdIn 2S 4,(17)␣-In 2S 3+␧,(18)␣-In 2S 3.Fig.2.The change of the unit cell parameters at the In 2S 3–CdIn 2S 4section at 870K.with the cubic structure (S.G.Fd 3m ),and the two-phase region of their co-existence in the range 52–100mol.%CdS.The alloys in the 0–52mol.%CdS range are single-phase,and crystallize in the cubic structure of spinel.The change of the unit cell parameters within the solid solution range is linear (Fig.2);the a period and the volume of the cubic cell increase linearly with the CdIn 2S 4content.3.2.The AgIn 5S 8–CdIn 2S 4sectionInvestigation of the AgIn 5S 8–CdIn 2S 4section was performed on 11samples.The phase diagram was constructed using XRD and DTA results (Fig.3).The section belongs to Roozeboom Type I,with continuous miscibility in both solid and liquid state.The system below the solidus line forms a continuous ␣-solid solution series of the starting components.Due to the small difference of the melt-ing points of both system components (∼15K),the liquidus and the solidus lines are nearly horizontal at the phase diagram;the thermograms recordedonly one effect during heating and cooling cycle.The change of the unit cell parameters of the investigated alloys is linear (Fig.4).The a period and the cell volume increase linearly with the CdIn 2S 4content.The mechanism of atom substitution in the crystal lattice of the solid solutions was additionally studied.The Wyckoff site 8a is occupied by the statistical mix In +Cd,theFig.3.Phase diagram of the AgIn 5S 8–CdIn2S4system:(1)L,(2)L +␣,and (3)␣.362V.R.Kozer et al./Journal of Alloys and Compounds 480(2009)360–364Table 2Unit cell parameters for the solid solution with the spinel structure (S.G.Fd ¯3m ).mol.%CdIn 2S 40204050608010016CN 6In0.75×0.94=0.705Ag0.25×1.29=0.323In0.78×0.94=0.733Ag0.22×1.29=0.284In0.81×0.94=0.761Ag0.19×1.29=0.245In0.83×0.94=0.780Ag0.17×1.29=0.219In0.86×0.94=0.808Ag0.14×1.29=0.181In0.92×0.94=0.865Ag0.08×1.29=0.103In1.00×0.94=0.940Mean radius 1.028 1.017 1.0060.9990.9890.9680.9408CN 4In1.00×0.76=0.760In0.89×0.76=0.676Cd0.11×0.92=0.101In0.75×0.76=0.570Cd0.25×0.92=0.230In0.66×0.76=0.502Cd0.33×0.92=0.306In0.57×0.76=0.433Cd0.43×0.92=0.396In0.33×0.76=0.251Cd0.66×0.92=0.607Cd1.00×0.92=0.920Mean radius 0.7600.7770.8000.8080.8290.8580.920␦B-S 2.630(4) 2.628(3) 2.627(4) 2.623(5) 2.621(5) 2.618(4) 2.614(4)␦A-S2.484(4) 2.489(3) 2.493(4) 2.501(5) 2.507(5) 2.512(4) 2.529(4)a (nm) 1.0831(3) 1.0832(1)1.0836(2)1.0837(2)1.0839(2)1.0845(2)1.0854(1)16d site is occupied by Ag +In atoms,the 32e site is occupied by S atoms (Table 2).The occupation of all crystallographic sites was unity in the calculation model.Sulphur atoms are tetrahedrally coordinated;the coordination of the statistical mix is a tetrahedron as well,that of Ag +In atoms is an octahedron.Using the ionic radii (which depend on the surrounding),we calculated the averaged radii of the elements in 8(a)and 16(d)sites.As shown in Table 2,the averaged radius in the 16(d)site decreases,while that in the 8(a)site increases.Presenting the structure as the packing of the layers formed of octahedra and tetrahedra along the body axis,the increase of the averaged radius of the element in the 8(a)site which forms tetrahedra leadssimultaneously to the increase of the number of octahedra in this layer.Since octahedra in both layers are formed around the atoms of the same sort,the octahedral layers become thicker,thus the cell dimensions increase (Fig.5).Experimental diffraction patterns of the AgIn 5S 8–CdIn 2S 4sec-tion are presented in Fig.6.3.3.XRD study of the AgInS 2–CdS sectionXRD investigation of the AgInS 2–CdS system utilized 22sam-ples.The solid solubility based on low-temperature modiﬁcation of AgInS 2at 870K is less than 2mol.%CdS.The solid solution range of CdS at 870K is 59–100mol.%CdS (Fig.7).3.4.System AgInS 2-CdIn 2S 4The AgInS 2–CdIn 2S 4is non-quasi-binary both in the solid-state and in the liquidus region (Fig.8).The section liquidus is represented by the single line of the primary crystallization of ␤-solid solutions.The two-phase ﬁeld L +AgIn 5S 8below the liquidus stretches across the entire section.The section solidus is formed by the line of the plane of the invariant peritectic equilibrium at 1123K.The peritectoid process reﬂects the polymorphous transition of AgInS 2.Fig.4.The change of the unit cell parameters at the AgIn 5S 8–CdIn 2S 4section at 870K.The section at the annealing temperature contains the fol-lowing ﬁelds:single-phase regions of AgInS 2and CdIn 2S 4,a two-phase region of CdIn 2S 4+CdS,a three-phase region of ␤-AgInS 2+HPTP+CdS.The section features a minor solid solubility in LT-AgInS 2that does not exceed 3mol.%CdIn 2S 4.The solid solubility in CdIn 2S 4is ∼13mol.%at the annealing temperature.3.5.Isothermal section of the quasi-ternary system Ag 2S–In 2S 3–CdSBased on the XRD results,an isothermal section of the quasi-ternary system Ag 2S–In 2S 3–CdS at 870K was constructed.The chemical and phase composition of the alloys is plotted in Fig.9.The section is characterized by large areas of single-phase and two-phase regions.The triangulating sections of the system at 870K are AgInS 2–CdS and AgIn 5S 8–CdIn 2S 4.They separate the quasi-ternary system into 3sub-systems.The Ag 2S–AgInS 2–CdS sub-system features the equilibrium of ␣-,␤-and ␥-solid solutions.Similarly,the combination of three solid solutions (␤,␥and ␧)deﬁnes the phase equilibria in the AgInS 2–CdS–In 2S 3sub-systems.As AgIn 5S 8,In 2S 3and CdIn 2S 4are isostructural (S.G.Fd 3m ),this leads to the mutual solid solubility of all three compo-Fig.5.Packing of the layers formed of octahedra and tetrahedral the spinel.V.R.Kozer et al./Journal of Alloys and Compounds 480(2009)360–364363Fig.6.Experimental diffraction patterns of the AgIn 5S 8–CdIn 2S 4section.Fig.7.The change of the unit cell parameters across the solid solution range of CdS in the AgInS 2–CdS system at 870K.Fig.8.Phase diagram of the AgInS 2–CdIn 2S 4system:(1)L,(2)L +AgIn 5S 8+CdIn 2S 4,(3)CdIn 2S 4,(4)L +AgIn 5S 8,(5)L +AgIn 5S 8+␤-AgInS 2,(6)AgIn 5S 8+␤-AgInS 2,(7)␤-AgInS 2,(8)␤-AgInS 2+␧+CdS,(9)CdS +CdIn 2S 4,(10)␣-AgInS 2+␤-AgInS 2,(11)␣-AgInS 2,(12)␣-AgInS 2+␧+CdS.Fig.9.Chemical and phase composition of alloys ((I)single-phase alloys,(II)two-phase alloys,and (III)three-phase alloys)and the isothermal section of the Ag 2S–In 2S 3–CdS system at 870K.nents,and thus the AgIn 5S 8–In 2S 3–CdIn 2S 4sub-system issingle-phase.4.ConclusionsPhase equilibria in the quasi-ternary system Ag 2S–In 2S 3–CdS were investigated.The isothermal section of the system at 870K was rge ranges of solid solubility of the binary com-pounds were discovered.The mechanism of the substitution in the solid solutions based on the initial compounds was determined.364V.R.Kozer et al./Journal of Alloys and Compounds480(2009)360–364References[1]V.N.Tomashyk,V.I.Grytsiv,Phase Diagrams of the Systems Based on the Semi-conductor Compounds AIIBVI,Naukova dumka,Kyiv,1982.[2]V.P.Sachanyuk,G.P.Gorgut,V.V.Atuchin,I.D.Olekseyuk,O.V.Parasyuk,J.AlloysCompd.452(2008)348–358.[3]zarev,Z.Z.Kish,Ye.Yu.Peresh,Ye.Ye.Semrad,Complex Chalcogenides inthe A II–B III–C VI Systems,Metallurgy,Moscow,1993.[4]G.D.Guseinov,G.B.Abdullaev,E.M.Kerimova,Mater.Res.Bull.4(1969)807.[5]R.J.Cava,F.Rcidinger,B.J.Wuensh,J.Solid State Chem.31(1980)69.[6]N.K.Abrikosov,V.F.Bakina,L.V.Poretskaya,et al.,Semiconductor Chalcogenidesand their Alloys,Nauka,Moscow,1975.[7]R.Diehl,R.Nitsche,Vapour,J.Cryst.Growth20(1973)38.[8]G.Delgado,A.J.Mora,C.Pineda,T.Tinoco,Mater.Res.Bull.36(2001)2507.[9]A.F.Qasrawi,N.M.Gasanly,Cryst.Res.Technol.36(2001)457.[10]H.Haeuseler,J.Solid State Chem.29(1979)121.[11]L.G.Akselrud,Yu.N.Grin’,P.Yu.Zavalij,V.K.Pecharsky,V.S.Fundamensky,12thEurop.Crystallographic Meet.,Moscow Collected Abstracts Izv.Acad.Nauk SSSR 3,1989.[12]Martina Kerkhoff,Volkmar Leute,J.Alloys Compd.385(2004)148–155.。

化学与制药工程学院教师发表学术论文情况南阳师范学院

郭应臣
陈书阳，包晓玉，邱东方，冯玉全
Chinese J. Struct. Chem
2011.12
SCI
18
Phase Equilibrium of the Ternary System Cadmium Chloride+L-Threonine +Water at 298.15 K and StandardMolar Enthalpy ofFormation ofCd(C4H9NO3)Cl2 3H2O
2011.9
SCI
10
vapor-liquid phase equilibria for CO2+isopentanol binary system at elevated pressures
王琳
曹丰璞，刘珊珊，杨浩
中国化学
2011.8
SCI
11
vapor-liquid phase equilibria for CO2+tertpentanol binary system at elevated pressures
李玉玲
刘克成
Russian Journal of Coordination Chemistry
2011.9
SCI
5
Synthesis and Crystal Structures of the Zinc(II) Complexes with a Tridentate Schiff Base (1-Pyridin-2-ylethylidene)pyridin-2-ylmethylamine (SCI)
2011年化学与制药工程学院教师发表学术论文情况
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小角X射线散射表征AOT水层状溶致液晶的有序性

物理化学学报(Wuli Huaxue Xuebao )SeptemberActa Phys.鄄Chim.Sin .,2005,21(9)：1055~1058Received ：January 11,2005；Revised ：March 28,2005.Correspondent ：CHEN,Xiao(E ⁃mail ：xchen@ ；Tel ：0531⁃8365425).*TheProject Supported by NSFC(20073025,20373035)and Special Research Fund for the Doctoral Program of Higher Education(200220422060)Study of Ordering for AOT/Water Lamellar Lyotropic LiquidCrystal:Small ⁃angle X ⁃ray Scattering Experiments *ZHUANG,Wen ⁃Chang CHEN,Xiao YANG,Chun ⁃Jie WANG,Lu ⁃Yan CHAI,Yong ⁃Cun(Key Laboratory of Colloid and Interface Chemistry ，Ministry of Education,Shandong University,Jinan 250100)AbstractSmall ⁃angle X ⁃ray scattering (SAXS)is utilized to study the ordering of AOT/water lamellar phase.Asincreasing surfactant concentration,temperature or adding cosurfactant in certain range,the arrangement of hydrocarbon chains will change from sparse to dense which results in the structural transformation of lamellar phase from “flexible ”to “planar ”bilayers.The possible mechanism is proposed based on shape factor and molecular interactions.Molecular simulations are also carried out to testify the obtained results.Keywords:SAXS,Molecular simulation,Lamellar phaseLyotropic liquid crystal (LLC),depending on type of molec ⁃ular assembling,is capable to reach special structure of aggre ⁃gation by varying surfactant concentration and temperature [1⁃2].Among them,lamellar phase is widely studied as a good tem ⁃plate due to its stability and long ⁃range periodic structure [3].As a common anionic amphipathic molecule with two hydrophobic chains,sodium ⁃1,4⁃bis (2⁃ethylhexyl)sulfosuccinate (AOT)has been widely used in forming LLC.The AOT/water binary sys ⁃tem has been studied for decades and confirmed to construct the lamellar phase in a broad AOT concentration range [4].Prouzet et al .[5]studied water confined in lamellar structures of AOT using infra ⁃red spectroscopy.Nuclear magnetic resonance experi ⁃ments were done to discuss the influence of mechanical stresses on AOT/water system by Muzzalupo et al .[6].The phase transi ⁃tion boundary of AOT surfactant solution was investigated using rheological techniques by Terentjev et al .[7].The ternary systems of AOT are also extensively studied [8⁃9].However,the detailed ordering of AOT/water binary system is little discussed in previ ⁃ous reports.Especially,there are different opinions about the mechanism of structural transformation [10⁃11].The first observations of diffuse X ⁃ray scattering at small angles,dating back to the early 1930s,were made on solid fibers and colloidal powders.Over the past decades,small ⁃angle X ⁃ray scattering (SAXS)has been developed as an useful tool forstudying organized molecular assemblies [12⁃13].Based on SAXS results,various phases with different Bragg peaks can be char ⁃acterized and their long ⁃range ordering is obtained,so that the interaction between molecules and the stabilization scheme of system can be explored [14⁃15].In this paper,SAXS technique is utilized to characterize the lamellar structures constructed with changing AOT concentration,temperature or adding cosurfac ⁃tant.The structural transition mechanisms,ordering of lamellar phase and interactions between molecules are discussed by ana ⁃lyzing SAXS curves based on shape factor and molecular inter ⁃actions such as van der Waals force,electrostatic force,etc .Molecular simulations are also carried out correspondingly to exhibit definite lamellar phase.1ExperimentalAOT (>98%)was purchased from Sigma.1⁃octanol (A.R.)as cosurfactant was obtained from Hengye Jingxi Chemical Co.LTD and the water used in the experiments was double distilled.The binary system AOT/water and the ternary system AOT/1⁃octanol/water were prepared in glass tubes.The samples were shaken up and centrifuged with 4000r ·min -1for three times,then sealed for 15days at 20℃before further study.The mass fraction of 1⁃octanol was 0.03for all ternary systems.Small ⁃angle X ⁃ray scattering experiments were operated at1055Acta Phys.鄄Chim.Sin.(Wuli Huaxue Xuebao ),2005Vol.21298K by means of a Kratky compact small ⁃angle system equipped with a position sensitive detector(OED 50M from Mbraun,Graz,Austria)containing 1024channels of width 54mm.The range of scattering angle was chosen from h =0.05to 6nm -1,where the magnitude of scattering vector h =2仔sin θ/λ,2θand λbeing,respectively,the scattering angle and incident X ⁃ray wavelength of 0.1542nm.The distance from sample to de ⁃tector was 27.7cm and the exposure time was 600s for each sample.2Results and discussion2.1LLC lamellar structure with varieties ofsurfactant concentrationFig.1shows the scattering curves of AOT/water system as a function of mass fraction φof AOT.There is only one peak at low φshown in Fig.1(a),which cannot be defined as lamellar phase.Two scattering peaks can be distinguished and become sharper with increasing surfactant concentration,which show the appearance of lamellar phase and enhanced ordering.According to shape factor,v /a 0l c ,where v is hydrocarbon volume,a 0is the optimal surface area per molecule and l c is critical chain length,it can be determined that AOT molecules might form micelles (v /a 0l c <0.5)or bilayers (0.5<v /a 0l c <1)[16].The quantity of AOT is small at low φand headgroups contact well with water.This leads to larger a 0and makes the system tend to form micelles.With surfactant concentration increasing,the hydrophobic at ⁃traction will be improved,which may induce molecules to asso ⁃ciate and decrease a 0so that bilayers occur.Fig.1(d)and 1(e)give the scattering curves at φ=0.4and 0.5,respectively.The peaks for φ=0.5are sharper than those for φ=0.4.Therefore the order ⁃ing of the former is better than the latter.This is because the structure of lamellar phase depends not only on the shape factor but also on many interactions,such as van der Waals,electro ⁃static,hydration and steric forces [16].These interactions cannot op ⁃erate in a long distance.For example,van der Waals forces decay with D 2(where D is the distance between bilayers).The lower thickness of water layer is beneficial for van der Waals attraction.The range of hydration forces so far measured between various surfactant bilayers is usually less than 3nm.As shown in Fig.1,the thicknesses of water calculated using a formula suggested by Kotlarchyk [17]between bilayers are about 2.1and 3.4nm for φ=0.5and 0.4respectively.Meanwhile the quantity of ions will increase with AOT concentration that is favorable for the stability of electrostatic double layer.Recently,computer simulation has become a powerful tool for the study of surfactant systems.The dissipative particle dy ⁃namics (DPD)method introduced by Hoogerbrugge and Koelman in 1992[18]is an effective mesoscopic dynamics technique,bridg ⁃ing the gap between atomistic and macroscopic simulation.This technique allows the simulation of hydrodynamic behavior in much larger systems that contain millions of atoms up to mi ⁃crosecond range [18⁃23].The parameters used for carrying out DPD simulation can be obtained from Flory ⁃Huggins ⁃type theory [21].Fig.2shows model structures of AOT/water lamellar phase from molecular simulation using Cerius II .There are only some sphe ⁃rical and plate ⁃like micelles when φ=0.1corresponding to Fig.1(a).As surfactant concentration increases,bilayers appear and the ordering of lamellar phase becomes better,which agree well with SAXS experimental results.However,there is a range around φ=0.4where AOT molecules cannot form well ⁃defined lamellar phase.As shown in Fig.2(d),there are some defective structures at φ=0.4with micelles or surfactant “bridges ”betweenFig.2Molecular simulated phase structures of the AOT/water system with φ=0.1,0.2,0.3,0.4and 0.5for a,b,c,d,and e,respectivelyFig.1Scattering curves of the AOT/water system withφ=0.1,0.2,0.3,0.4and0.5abcde1056No.9CHEN,Xiao et al ：Study of Ordering for AOT/Water Lamellar Lyotropic Liquid Crystal ：Small ⁃angle X ⁃raybilayers.Such deformed lamellar structures result in only a very weak first peak to be observed from SAXS curve (see Fig.1(d))due to much sensitivity of SAXS to small structural fluctuations of lamellae [24],especially to “neighboring ”bilayers.Fontell [11]also reported this phenomenon but he didn ′t explain the possible reason.This will be discussed later.2.2Cosurfactant effect on LLC lamellar structureFig.3illustrates the effect of cosurfactant on AOT orga ⁃nized assemblies.There are two peaks observed obviously at φ=0.2when adding a little 1⁃octanol to form the ternary system as shown in Fig.3(b),which is similar to Fig.1(c)where φ=0.3and no cosurfactant adding.The first scattering peak also occurs with φ=0.4(compared to Fig.1(d))and becomes sharper when φ=0.5than no cosurfactant (see Fig.1(e)).The long ⁃range order ⁃ing of lamellar phase is improved evidently by analyzing the scattering peaks with Scherrer equation [3].This is because the ef ⁃fective hydrocarbon volume,v ,is increased due to the penetra ⁃tion of organic molecule,such as low MW alkanol,into the chain regions.It results in the increased value of v /a 0l c and bi ⁃layer appearance at low φ,as well as the high ordering of lamel ⁃lar phase at high φ.2.3LLC lamellar structure at different temperaturesBoth a 0and l c can be changed with temperature.Such ef ⁃fects are subtle and generally less well understood because a 0usually increases due to the enhanced steric repulsion between headgroups and l c decreases because of the hydrocarbon chain motion involving trans ⁃gauche isomerization as increasing T .Then shape factor v /a 0l c may decrease or increase with temper ⁃ature.As shown in Fig.4,lamellaes occur at φ=0.1and T =278K but vanish when increasing T .It implies that both molecules motion and a 0will be weakened with decreasing T ,which is fa ⁃vorable for larger aggregate such as AOT bilayers.However,the first scattering peak occurs at φ=0.4and sharpens at φ=0.5when T increases from 278to 328K.It shows that the ordering of lamellar phase will be improved.This is because l c is reduced by 0.3and 0.2nm respectively,assuming the thickness of water is constant for the same φat different temperatures.In addition,the curvature modulus of surfactant bilayers may be increased with temperature and the AOT headgroup conformation will change due to dehydration,which will enhance the lamellar phase order [25].All repeated distances measured at different condi ⁃tions are summarized in Table 1.Combined with the effects of AOT concentration and co ⁃surfactant,we think that the surfactant molecules may undergo a reorganization when φ=0.4,where the arrangement of hydro ⁃carbon chains will change from sparse to dense status and mean ⁃while the structure of lamellar phase will transform from “flexi ⁃ble bilayer ”to “planar bilayer ”as shown in Fig.5.Fig.5Schematic description on structural transforma ⁃tion of lamellar phaseFig.3Scattering curves of the AOT/water/1⁃octanolsystem with 渍=0.1,0.2,0.3,0.4and0.5Fig.4Scattering curves of the AOT/water system atdifferenttemperaturesd is the periodic distance of lamellae determined by AOT bilayer(with or without cosurfactant)and water layer.Table 1Repeat distances (d )of AOT/water and AOT/water/1⁃octanol lamellar phasesd /nmφAOT/water AOT/water/1⁃octanolT =278K T =293K T =328K T =293K 0.120.8Non ⁃lamellar Non ⁃lamellar Non ⁃lamellar 0.210.810.610.09.10.37.57.37.1 5.60.4 5.6 5.4 5.3 4.80.54.2 4.1 4.0 3.91057Acta Phys.鄄Chim.Sin.(Wuli Huaxue Xuebao),2005Vol.213ConclusionsHere we analyze SAXS curves of lamellar phases and dis⁃cuss the mechanism of structure transformation based on shape factor and various molecular interaction.Increasing surfactant concentration,temperature and adding cosurfactant in certain range,lamellar phase will change from“flexible bilayers”to “planar bilayers”and the high ordering of LLC will be obtained.References1Burducea,G.Romanian Rep.Phys.,2004,56(1):662Pileni,M.P.Nat.Mater.,2003,2:1453Chen,X.;Efrima,S.;Rege1v,O.;Wang,W.;Niu,L.;Sui,Z.M.;Zhu,B.L.;Yuan,X.B.;Yang,K.Z.Science in China B,2001,44(5):4924Chidichimo,G.;Mesa,C.L.;Ranieri,G.A.;Terenzi,M.Mol.Cryst.Liq.Cryst.,1987,150:2215Boissiere,C.;Brubach,J.B.;Mermet,A.;Marzi,G.D.;Bourgaux,C.;Prouzet,E.;Roy,P.J.Phys.Chem.B,2002,106:10326Coppola,L.;Muzzalupo,R.;Ranieri,G.A.;Terenzi,ngmuir, 1995,11:11167Petrov,P.G.;Ahir,S.V.;Terentjev,ngmuir,2002,18:9133 8Gradzielskl,M.;Hoffmann,H.;Panitz,J.C.;Wokaun,A.J.Colloid &Interf.Sci.,1995,169:1039Nishimi,T.;Miller,ngmuir,2000,16:923310Park,D.;Rogers,J.;Toft,R.W.;Winsor,P.A.J.Colloid&Interf.Sci.,1970,32:8111Fontell,K.J.Colloid&Interf.Sci.,1973,44(2):31812Kratky,O.;Laggner,P.Encyclopedia of physical science and technology.3rd ed.New York：Academic Press,2002:93913Fan,H.Y.;Yang,K.;Boye,M.D.;Sigmon,T.;Malloy,K.J.;Xu,H.F.;Lopez,G.P.;Brinker,C.J.Science,2004,304(23):56714Firestone,M.A.;Wolf,A.C.;Serfert,S.Biomacromoleculars, 2003,4:153915Firestone,M.A.;Williams,D.E.;Serfert,S.;Csencsits,R.Nano Lett.,2001,3(1):12916Israelachvili,J.N.Intermolecular and surface forces.London：Academic Press,1992:36617Kotlarchyk,M.;Sheu,E.Y.;Capel,M.Phys.Rev.A,1992,46:928 18Hoogerbrugge,P.J.;Koelman,J.M.V.A.Europhys.Lett.,1992, 19:15519Koelman,J.M.V.A.;Hoogerbrugge,P.J.Europhys.Lett.,1993, 21:36320Espanol,E.;Warren,P.B.Europhys.Lett.,1995,30:19121Groot,R.D.;Warren,P.B.J.Chem.Phys.,1997,107:442322Ryjkina,E.;Kuhn,H.;Rehage,H.;Muller,F.;Peggau,J.Angew.Chem.Int.Ed.,2002,41:98323Yuan,S.L.;Cai,Z.T.;Xu,G.Y.;Jiang,Y.S.Chem.Phys.Lett., 2002,365:34724Callaghan,P.T.;Soderman,O.J.Phys.Chem.,1983,87:1737 25Li,Z.X.;Lu,J.R.;Thomas,R.K.;Weller,A.;Penfold,J.;Webster,J.R.P.;Sivia,D.S.;Rennie,ngmuir,2001,17(19):5858小角X射线散射表征AOT/水层状溶致液晶的有序性*庄文昌陈晓杨春杰王庐岩柴永存(山东大学胶体与界面化学教育部重点实验室,济南250100)摘要用小角X射线散射研究了AOT/水层状溶致液晶的有序性.通过对散射曲线的解析,讨论了表面活性剂浓度、温度和助表面活性剂等三个方面对溶致液晶层状相结构有序性的影响.在一定的范围内,提高温度,改变表面活性剂浓度和加入少量助表面活性剂可使碳氢链排列由稀疏转变为密实,层状相也相应地由“柔性双层”过渡到更加有序化的“平面双层”.基于形状因子和体系内分子间作用力,提出了层状相形成与有序化的机理,同时采用分子模拟的方法展现了不同浓度下的液晶结构.关键词：小角X射线散射,分子模拟,层状相中图分类号：O6482005⁃01⁃11收到初稿,2005⁃03⁃28收到修改稿.联系人：陈晓(E⁃mail:xchen@；Tel:0531⁃8365425).*国家自然科学基金(20073025,20373035)和高等学校博士点专项科研基金(200220422060)资助项目1058。

化工热力学相平衡综述

《化工热力学理论及应用》课程作业题目：液液相平衡在单一脂肪酸甲酯体系中的应用研究院（系）：化学化工学院专业：化学工程学号：**********姓名：000000指导教师：00000000000000液液相平衡在单一脂肪酸甲酯体系中的应用研究摘要：生物柴油是一种重要的可再生能源,引起人们的广泛研究,但研究大多集中于原料,新型催化剂开发,反应工艺条件的优化等方面。

生物柴油相关体系的液液相平衡数据对于生产工艺中反应器及分离装置的设计非常重要,但仅见少量文献报道。

目前需要积累大量准确有效的相平衡数据,获取有效的相关热力学模型参数,尽量做到以最少量的相平衡实验数据,为今后的计算模拟及装置设计提供依据。

关键词：生物柴油;单一脂肪酸甲酯;液液相平衡1引言目前,对于生物柴油的研究得到了越来越多的关注,逐渐从实验室制备研究转变到工厂生产工艺研究。

这一转变极大的增加了对生物柴油相关体系基础数据的需求。

相平衡数据是设计合适的分离设备所必须的。

故多组分相平衡数据在设计或者优化生产过程中具有基础性的重要性。

此外技术的进步和精炼的过程设计需要高质量的实验数据。

但因为体系的种类很多,并且过程设计需要考虑实际意义,实验数据的数量远远不够。

所以预测混合性质的技术成为了工业计算机模拟中非常重要的一部分。

故需要尽量提供准确大量的数据,丰富相平衡数据库,为进一步的计算和模拟提供数据基础。

目前,对生物柴油的相关研究主要集中于原料、制备工艺的开发和优化、新型催化刑的开发和应用等方面,相关体系相平衡数据在文献中出现较少,应用模型回归和关联实验数据的研究也较少。

本文选取了一系列的生物柴油相关体系,进行了不同温度条件下的相平衡数据的测定,在一定程度上弥补了这方面的空缺。

2液液相平衡的研究进展液液相平衡研究的是达到平衡时,系统的温度、压力、各相的体积、各相的组成以及其他热力学性质间的函数关系。

它是分离技术及分离设备进行开发设计的理论基础。

按照参与相平衡的相的不同,相平衡可以分为气液相平衡(VLE),液液相平衡(LLE),固液相平衡(SLE),它们是化工生产中精馆、吸收、吸附、萃取、结晶等传统分离技术的基础。

铝硅镁合金三元相图

Al-Mg-Si (Aluminum-Magnesium-Silicon)V.RaghavanThe compilation of the experimental data on this ternary system by [1995Vil]includes a liquidus projection and 15vertical sections from [1977Sch]and partial isothermal sections at 1050,800,460,430,427,400,and 300°C from several sources.Subsequent to the thermodynamic assess-ment of this system by [1992Cha],new assessments were reported by [1997Feu,2005Lac].Binary SystemsThe Al-Mg phase diagram [2003Cze]has the following intermediate phases:Mg 2Al 3(cubic,denoted b ),R or e (rhombohedral)and Mg 17Al 12(A 12-type cubic,denoted c ).The Al-Si phase diagram is a simple eutectic system with the eutectic at 577°C and 12.2at.%Si.In the Mg-Si system,[1997Feu]performed calorimetric studies to determine the enthalpies of formation and fusion,and the heat capacity of Mg 2Si and the enthalpy of mixing of liquid Mg-Si alloys.The new experimental results were used in the optimization of the Mg-Si phase diagram by computation.The diagram depicts a stoichiometriccompound Mg 2Si (C 1,CaF 2-type cubic),with negligible terminal solid solubility.[2000Yan]developed a new thermodynamic description of the Mg-Si system that uses fewer model parameters than [1997Feu].More recently,[2004Kev]remodeled the Mg-Si description to obtain a phase diagram without an artiﬁcial miscibility gap in the liquid phase at high temperatures,as found in the descrip-tions of [1997Feu,2000Yan].Ternary Phase EquilibriaWith starting metals of 99.999%Al,99.98%Mg and 99.999%Si,[1997Feu]induction-melted alloy samples under Ar atm.Differential thermal analysis (DTA)was done at heating/cooling rates between 2and 5°C per ing the new data with those in the literature (as selected by [1992Cha]),[1997Feu]reoptimized the thermodynamic parameters.The liquid,the face-centered cubic (fcc)and the close-packed hexagonal (cph)phases were modeled as single-lattice substitutional solutions.The Al-Mg com-pounds,Mg 2Si and Si were treated as stoichiometric phases.Ternary interaction parameters were determined for the liquid phase.The earlier description of the Al-Mg phase diagram [1990Sau],which includes an unconﬁrmed com-pound f ,was used.This,however,did not change the computed results in the Al-rich region.In Fig.1-4,the four vertical sections at 95,90,85and 80mass%AlrespectivelyFig.1Al-Mg-Si computed vertical section at 95mass%Al[1997Feu]Fig.2Al-Mg-Si computed vertical section at 90mass%Al [1997Feu]JPEDAV (2007)28:189–191DOI:10.1007/s11669-007-9027-81547-7037ÓASM InternationalPhase Diagram Evaluations:Section IIJournal of Phase Equilibria and Diffusion V ol.28No.22007189computed by [1997Feu]are compared with their own DTA data on solidiﬁcation temperatures.The agreement with the experimental data is good.[2005Lac]carried out a new thermodynamic assessment of this system,which uses the revised Al-Mg description with only the three intermediate phases,Mg 2Al 3(b ),e and c .They used a larger set of data for the liquid-solid equilibria from the experimental results of [1977Sch,1997Feu].Temperature-independent ternary interaction parameters were obtained for the liquid phase.A partial liquidus projection and three vertical sections at 5and 85mass%Al and 2mass%Si respectively were computed by [2005Lac].The vertical section at 2mass%Si is redrawn in Fig.5.The agreement with the experimental results of [1977Sch,1931Los]is satisfactory.The eutectic maximum (e 3)of the reaction L $ðAl ÞþMg 2Si does not lie on the Al-Mg 2Si join but on the Mg-rich side of this line [1992Cha,1997Feu,2001Bar,2005Lac].The partial liquidus projection in Fig.6depicts the above univariant line determined by [2001Bar].Other recent references on the phase equilibria of this system include [1999Esk,2002Fro,2003Erm,2003Roo,2004Liu,2005Don].References1931Los:L.Losana,The Aluminum-Magnesium-Silicon Ternary System,Metall.Italiana ,1931,23,p 367-382,in Italian1977Sch:E.Schurmann and A.Fischer,Melting Equilibria in the Ternary System Al-Mg-Si,Giessereiforschung ,1977,29(4),p 161-165,inGermanFig.3Al-Mg-Si computed vertical section at 85mass%Al[1997Feu]Fig.4Al-Mg-Si computed vertical section at 80mass%Al[1997Feu]Fig.5Al-Mg-Si computed vertical section at 2mass%Si[2005Lac]Fig.6Al-Mg-Si partial liquidus projection depicting the uni-variant line of L $ðAl ÞþMg 2Si [2001Bar]Section II:Phase Diagram Evaluations190Journal of Phase Equilibria and Diffusion V ol.28No.220071990Sau:N.Saunders,A Review and Thermodynamic assess-ment of the Al-Mg and Mg-Si Systems,CALPHAD,1990, 14(1),p61-701992Cha:N.Chakraborti and H.L.Lukas,Thermodynamic Optimization of the Mg-Al-Si Phase Diagram,CALPHAD, 1992,16(1),p79-861995Vil:P.Villars, A.Prince and H.Okamoto,Al-Mg-Si, Handbook of Ternary Alloy Phase Diagrams,vol4,ASM International,Materials Park,OH,19951997Feu:H.Feufel,T.Godecke,H.L.Lukas,and F.Sommer, Investigation of the Al-Mg-Si System by Experiments and Thermodynamic Calculations,J.Alloys Compd.,1997,247, p31-421999Esk:D.G.Eskin, A.Massardier,and P.Merle,A Study of High Temperature Precipitation of Al-Mg-Si Alloys with an Excess of Silicon,J.Mater.Sci.,1999,34(4), p811-8202000Yan:X.Y.Yan,F.Zhang,and Y.A.Chang,A Thermody-namic Analysis of the Mg-Si System,J,Phase Equilibria,2000, 21(4),p379-3842001Bar:O.M.Barabash,O.V.Sulgenko,T.N.Legkaya,and N.P. Korzhova,Experimental Analysis and Thermodynamic Calcu-lation of the Structural Regularities in the Fusion Diagram of the System of Alloys Al-Mg-Si,J.Phase Equilibria,2001, 22(1),p5-112002Fro:A.G.Froseth,S.J.Andersen, C.D.Marioara,P.M. Derlet,and R.Hoier,Solving the Structure of Phases in theAl-Mg-Si Alloy System with the Help of ab initio Modeling, Mater.Res.Soc.Symp.Proc.,2002,755,p19-242003Cze:T.Czeppe,W.Zakulski,and E.Bielanska,Study of the Thermal Stability of Phases in the Mg-Al System,J.Phase Equilibria,2003,24(3),p249-2542003Erm:S.V.Ermakova,K.D.Savelev,and V.M.Golod, Thermodynamic Study of Equilibrium Solidiﬁcation and Ther-mophysical Properties of Al-Si-Mg System Alloys,Liteinoe Proizvodstvo,2003,9(Suppl.),p9-12,in Russian2003Roo:A.Roosz,J.Farkas,and G.Kaptay,Thermodynamics Based Semi-empirical Description of the Liquidus Surface and Partition Coefﬁcients in Ternary Al-Mg-Si Alloy,Mater.Sci. Forum,2003,414-415,p323-3282004Kev:D.Kevorkov,R.Schmid-Fetzer,and F.Zhang,Phase Equilibria and Thermodynamics of the Mg-Si-Li System and Remodeling of the Mg-Si System,J.Phase Equilib.Diffus., 2004,25(2),p140-1512004Liu:Y.Q.Liu,A.Das,and Z.Fan,Thermodynamic Predic-tions of Mg-Al-M(M=Zn,Mn,Si)Alloy Compositions Amenable to Semisolid Metal Processing,Mater.Sci.Technol., 2004,20(1),p35-412005Don:H.B.Dong and R.Brooks,Determination of Liquidus Temperature in Al-Si and Al-Si-Mg Alloys Using a Single-Pan Scanning Calorimeter,Mater.Sci.Eng.A,2005,A413-A414, p480-4842005Lac:caze and R.Valdes,CALPHAD-type Assessment of the Al-Mg-Si System,Monatsh Chem.,2005,136(11),p1899-1907 Phase Diagram Evaluations:Section IIJournal of Phase Equilibria and Diffusion V ol.28No.22007191。

新型铁电固溶体铌镥酸铅-铌镁酸铅-钛酸铅的制备与表征

新型铁电固溶体铌镥酸铅-铌镁酸铅-钛酸铅的制备与表征刘颖;赖发春;黄志高;沈东全;龙西法【摘要】采用二次合成法制备了纯相钙钛矿结构三元(0.7-x)Pb(Lu1/2Nb1/2)O3-0.3Pb(Mg1/3Nb2/3)O3-xPbTiO3(PLN- PMN-PT)(0.38≤x≤0.46)压电陶瓷,研究了准同型相界(MPB)附近组分的介电、压电和铁电性能。

XRD分析表明PLN-PMN-PT存在准同型相界,且准同型相界区域大致为0.40≤x≤0.44。

MPB附近组分为0.29PLN-0.3PMN-0.41PT陶瓷具有较高的居里温度和相变温度,分别为270℃和135℃,同时该组分表现出较好的铁电压电性能,压电系数达到460 pC/N,矫顽场为14.8 kV/cm,剩余极化强度Pr为34.6μC/cm2。

PLN-PMN-PT材料在压电领域具有潜在的应用前景。

%Ceramics of (0.7-x)Pb(Lu1/2Nb1/2)O3-0.3Pb(Mg1/3Nb2/3)O3-xPbTiO3(PLN-PMN-PT) (0.38≤x≤ 0.46) ternary system were synthesized by means of a two-step columbite precursor method which can effectively suppress the pyro-chlore phase. A morphotropic phase boundary (MPB) region in the ternary systems was found in the range of 0.40≤x≤ 0.44 and the electric properties of the compositions near MPB region were investigated. Those compositions within MPB exhibit good comprehensive piezoelectric properties. The ceramic with composition of 0.29PLN- 0.3PMN-0.41PT shows a high Curie temperature of 270℃ and a high rhombohedral-tetragonal phase transition tem-perature of 135℃, whose piezoelectric coefficientd33, coercive fieldEc and remnant polarizationPr are found to be 460 pC/N, 14.8 kV/cm and 34.6μC/cm2, respectively. The large coercive field and highTc enable it a promising can-didate for application in the piezoelectricity field.【期刊名称】《无机材料学报》【年(卷),期】2014(000)009【总页数】5页(P912-916)【关键词】压电陶瓷;固相法;PLMNT;压电性能【作者】刘颖;赖发春;黄志高;沈东全;龙西法【作者单位】福建师范大学物理与能源学院，福州 350117; 中国科学院福建物质结构研究所，光电材料化学与物理重点实验室，福州 350002;福建师范大学物理与能源学院，福州 350117;福建师范大学物理与能源学院，福州 350117;中国科学院福建物质结构研究所，光电材料化学与物理重点实验室，福州 350002;中国科学院福建物质结构研究所，光电材料化学与物理重点实验室，福州 350002【正文语种】中文【中图分类】TQ174铁电压电陶瓷材料具有压电性、热释电性、铁电性及非线性光学效应等重要特性, 是一类重要的功能材料, 它可用于制作传感器、换能器、储能器、探测器和集成光电器件等新型元器件。

三进制计算机英语

三进制计算机英语In the world of computing, the binary system has long been the standard for representing and processing data. However, in recent years, there has been a growing interest in alternative number systems, such as the ternary system. The ternary system, also known as the base-3 system, uses three symbols (0, 1, and 2) to represent numbers, as opposed to the two symbols (0 and 1) used in the binary system. This shift towards ternary computing has sparked a debate within the computing community, with proponents arguing that it offers several advantages over the traditional binary system, while skeptics remain unconvinced of its practicality and feasibility. One of the key arguments in favor of ternary computing is its potential for higher computational efficiency. Proponents of ternary computing argue that by utilizing three symbols instead of two, it is possible to represent and process larger numbers with fewer digits, leading to potentially faster and more efficient calculations. Additionally, ternary logic gates have been proposed as a way to reduce the complexity and power consumption of digital circuits, which could have significant implications for the design of future computing systems. This potential for improved efficiency has generated a great deal of excitement among researchers and engineers, who see ternary computing as a promising avenue for advancing the capabilities of computing technology. Another advantage of ternary computing is its potential for improved error detection and correction. In the binary system, errors can occur when data is being transmitted or processed, leading to potential issues with accuracy and reliability. However, in the ternary system, the use of three symbols allows for more robust error detection and correction techniques, which could lead to more reliable and secure computing systems. This has led some experts to advocate for the adoption of ternary computing in safety-critical applications, such as aerospace and medical devices, where accuracy and reliability are of paramount importance. Despite these potential advantages, there are also significant challenges and obstacles that must be overcome before ternary computing can become a practical reality. One of the main challenges is the lack of infrastructure and support for ternary computing in the current computing ecosystem. The vastmajority of existing software and hardware is designed to work with binary data,and transitioning to a ternary system would require a massive overhaul of the entire computing infrastructure. This would involve reprogramming existing software, redesigning hardware components, and retraining the workforce, all of which would require significant time, resources, and investment. In addition to the practical challenges, there are also theoretical and conceptual obstacles to overcome in the development of ternary computing. One of the main concerns is the potential for increased complexity in ternary computing systems. While it is true that ternary computing has the potential to represent larger numbers with fewer digits, it also introduces new challenges in terms of logic design, circuitry, and algorithms. This increased complexity could make it more difficult to develop and maintain ternary computing systems, which could limit their practicality and adoption in real-world applications. Furthermore, there are also concerns about the compatibility of ternary computing with existing standards and protocols. The computing industry has long been built around the binary system, and transitioning to a ternary system would require a rethinking of many fundamental concepts and principles. This could lead to compatibility issues with existing software, hardware, and communication protocols, which could further hinder the adoption of ternary computing in the mainstream. In conclusion, while ternary computing holds great promise for improving computational efficiency, error detection and correction, and overall reliability, there are significant challenges and obstacles that must be overcome before it can become a practical reality. The transition to ternary computing would require a massive overhaul of the existing computing infrastructure, as well as the development of new theoretical and conceptual frameworks to support its implementation. While the potential benefits of ternary computing are certainly compelling, it remains to be seen whether these challenges can be overcome, and whether ternary computing will ultimately become a viable alternative to the traditional binary system.。