氯化镁/聚乙二醇复配增塑剂热塑加工聚乙烯醇

采用氯化镁和聚乙二醇对聚乙烯醇(PVA)进行增塑改性, 并利用熔融加工方法制备了PVA薄膜.采用傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、差示扫描量热分析(DSC)和热重分析(TGA)方法研究了由氯化镁和聚乙二醇组成的复配增塑剂与PVA的相互作用及复配增塑剂对PVA结晶性能、热性能和力学性能的影响.结果表明, 由氯化镁和聚乙二醇组成的复配增塑剂能有效地破坏PVA自身的氢键, 降低PVA的结晶度和熔融温度, 提高PVA的热稳定性并扩展PVA的热塑加工温度窗口.由复配增塑剂通过热塑加工方法制得的PVA薄膜具有较好的力学性能, 拉伸强度为31 MPa, 断裂伸长率为466%.     

氯化镁增塑改性聚乙烯醇

以氯化镁为增塑剂, 采用流延法制备了增塑改性聚乙烯醇(PVA). 研究了氯化镁与PVA的相互作用以及氯化镁增塑改性PVA的结晶性能、 热性能和机械性能. 研究结果表明, 氯化镁能与PVA大分子发生较强的相互作用, 从而破坏PVA分子链内和链间的氢键, 降低PVA的结晶度. 氯化镁对PVA的热性能影响显著, PVA在加入氯化镁后的热分解过程由纯PVA的两段失重过程转变成三段失重过程. 氯化镁可有效增塑PVA, 其玻璃化转变温度降低, 拉伸强度下降, 断裂伸长率上升, 储能模量下降.     

尿素/乙醇胺复配增塑聚乙烯醇性能的研究

采用尿素/乙醇胺为复合增塑剂,利用流延法制备了增塑改性的PVA膜.通过FTIR法研究了尿素/乙醇胺复合体系与PVA的相互作用,采用XRD、DSC考察了增塑改性PVA膜的结晶性能和热性能.研究结果表明,乙醇胺作为尿素的良溶剂,能有效抑制尿素从PVA基体中析出.由尿素、乙醇胺组成的复合增塑剂能破坏PVA分子中的氢键作用、降低PVA的结晶度和熔点,对PVA的增塑作用显著.增塑改性后的PVA膜在水中的溶胀率(DS)下降,溶失率(S)增加.力学性能测试表明增塑改性后的PVA膜拉伸强度(TS)降低,断裂伸长率(E%)提高.含30phr尿素/乙醇胺的PVA膜的拉伸强度、断裂伸长率分别为23.89MPa和542.88%.     

β-磷酸三钙与聚乙烯醇的相互作用及其对聚乙烯醇热性能和力学性能的影响

以水为增塑剂,利用分子复合和增塑的方法,制备了聚乙烯醇(PVA)/β-磷酸三钙(β-TCP)复合材料,通过傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、差示扫描热分析(DSC)及热重分析(TGA)等手段研究了PVA与β-TCP间的相互作用及其对复合材料热性能和力学性能的影响.结果表明,β-TCP中的Ca2+与PVA中的OH形成配位键,破坏了PVA自身氢键的缔合状态,使PVA中的小分子脱除反应在更高的温度下进行,提高了PVA的热稳定性,当β-TCP质量分数为30%时,复合材料的初始分解温度由PVA的235.4℃提高到268.6℃,增塑剂水可显著降低PVA的熔点,从而获得约138℃的热塑加工窗口.β-TCP在PVA基体中的良好分散及其与PVA基体间的良好界面相互作用使复合材料具有优良的力学性能.     

聚乙烯醇/半纤维素/纤维素纳米晶复合膜的制备和性能

通过碱解醇沉法从玉米芯中提取半纤维素,进而采用溶液共混流延法制备出不同比例的聚乙烯醇(PVA)/半纤维素共混膜,在此基础上加入通过硫酸水解脱脂棉制备的纤维素纳米晶(NCC),制备了NCC增强的复合膜.DSC、TGA、FTIR、SEM和薄膜拉伸等研究表明,复合膜的各组分间形成了氢键作用,相容性良好.在PVA/半纤维素共混膜中,半纤维素的加入大幅度提高了复合膜的断裂伸长率:当PVA与半纤维素质量比为3∶1时,复合膜的断裂伸长率高达380%,比纯PVA的140%增加了1.7倍,而拉伸强度仍能保持在较高的水平;纤维素纳米晶的加入,还可改善复合膜的韧性;半纤维素对PVA组分的结晶性能产生了影响,而刚性结构的NCC则对PVA的结晶起抑制作用.此外半纤维素和NCC的引入也提高了复合膜的热性能,使第二阶段分解速率峰的温度提高了约50℃.     

不同温度下尼龙6性能和结构变化的原位研究

利用拉伸热台对尼龙6在不同温度下的拉伸性能进行了测试和分析.随着拉伸温度的升高,尼龙6样品的屈服强度和杨氏模量逐渐下降.采用了一个阿伦尼乌斯模型来描述尼龙6屈服强度与拉伸温度之间的关系,并描述了尼龙6样品黏度、玻璃化温度对屈服强度的影响.通过原位同步辐射广角衍射分析,我们发现未拉伸的尼龙6样品中的α相与γ相的相对比率随温度升高而下降.在拉伸条件下,随着拉伸温度的升高,样品的结晶部分容易产生滑移或晶区的熔融,有序程度下降,因而样品承载外力的能力下降,体现为屈服强度和杨氏模量的下降.     

表面复合纳米SiO_2和碳纳米管玻璃纤维增强尼龙6的结构与性能

利用静电相互作用在玻璃纤维(GF)表面分别复合纳米二氧化硅(SiO2)和多壁碳纳米管(MWNTs),制备了GF-SiO2、GF-MWNTs复合增强体,并通过转矩流变仪制备了尼龙6(PA6)/GF-SiO2和尼龙6(PA6)/GF-MWNTs复合材料.利用扫描电子显微镜(SEM),示差扫描量热仪(DSC),热机械分析仪(DMA)等手段研究了复合材料的微观结构、热学及力学性能.结果表明,静电复合的方法可以使纳米二氧化硅(nano-SiO2)、多壁碳纳米管(MWNTs)在GF表面达到均匀吸附,复合增强体能加快尼龙6的结晶速度,并使材料的玻璃化温度、动态模量、拉伸强度、结晶温度等明显提高,其中GF-MWNTs对复合材料性能的提高最明显,拉伸强度提升了21%,模量提高了28%.     

拉伸力场主导作用下硫酸钙晶须(CSW)/PBS复合材料的制备与性能研究

利用基于拉伸力场主导作用下的叶片塑化挤出机分别制备硫酸钙晶须(CSW)含量为0、5%(wt)、10%(wt)、15%(wt)、20%(wt)的硫酸钙晶须(CSW)/PBS复合材料,并讨论了CSW的含量对复合材料力学性能、热稳定性、结晶性能的影响。测试结果表明:当CSW的添加量为PBS的15%(wt)时,复合材料的综合力学性能最优,拉伸模量,弯曲模量和弯曲强度分别提高;随着CSW含量的增加,球晶尺寸减小,成核密度增加,结晶温度也有显著提高;引入CSW对PBS的熔融行为没有影响;热失重分析表明CSW有助于提高复合材料的热稳定性。     

改性木纤维/聚乳酸复合材料的制备与性能研究

通过双螺杆挤出机共混制备了不同方法改性的木纤维/聚乳酸可生物降解复合材料,利用DSC、SEM、DMA、冲击和拉伸力学性能测试等手段,对比分析了木纤维的不同改性处理方式对复合材料热性能、界面形态和力学性能的影响.结果表明:复合材料的聚乳酸结晶动力学明显得到改善,木纤维促进了聚乳酸的异相成核过程.改性后的木纤维聚乳酸复合材料界面结合和力学性能均得到明显改善,以性能最优的硅烷偶联剂处理的木纤维和聚乳酸复合材料为例,其拉伸应力(62.1MPa)、杨氏模量(4525.0 MPa)和冲击强度(11.5k J/m~2)比纯聚乳酸分别提高2.9%,36.0%和14.0%.     

一步法制备蒙脱土-石墨烯协同增强聚乙烯醇复合材料

以蒙脱土(MMT)和石墨烯(rGO)为填料,一步法制备了MMT-rGO/PVA纳米复合材料,并研究了不同MMT/rGO比例对PVA复合膜力学性能的影响.结果表明,剥离的MMT片层能够有效阻止石墨烯在被还原过程中的团聚.MMT-rGO二元填料与PVA间形成氢键,极大地改善了填料与聚合物间的界面结合,能够协同提高PVA复合膜的力学性能.1 wt%MMT-GE(2∶1)/PVA复合材料的拉伸强度和杨氏模量最高,分别为85.1 MPa和1627.8 MPa,比纯PVA分别提高了46%和62%.此方法为制备高性能聚合物复合材料提供了有效的途径.     

Analysis and assessment of the occurrence, the fate and the behavior of nanomaterials in the environment

Nanomaterials have one dimension <100 nm and possess physico-chemical properties dictated by their unusually small size, large surface area, shape and chemical composition. New properties of nanomaterials have boosted their production and industrial applications in many fields (e.g., microelectronics, catalysis, fuel cells, materials science, textiles, biotechnology and medicine). In biomedical fields, nanomaterials are of the appropriate dimensions to interact with biological matter. However, they may also have negative effects on biological systems. Nanotechnology is a major, innovative, scientific and economic growth area, but the increasing production and use of nanomaterials have led to calls for more information regarding the potential impacts that their release may have on human health and the environment.This review addresses analytical approaches for characterization and quantification of nanomaterials in the environment and recent studies on their occurrence, fate and behavior.     

New study of the stability and of the spectroscopy of the molecular anions NCO- and CNO-

Using highly correlated wave functions, the ground and the low lying excited states of the molecular NCO(-) and CNO(-) anions have been reinvestigated. The stability of the electronic ground state of the two isomers with respect to dissociation and to electron detachment has been checked along the isomerization pathway. The regions of stability of the excited electronic states have been analyzed and identified and it is shown that only the ground state is stable and the corresponding potential energy surface presents three equilibrium positions. The rovibronic spectroscopy of the X (1)Σ(+) state of both NCO(-) and CNO(-) isomers has been determined by a variational approach leading to remarkable agreement with experimental data.     

McBain and the centenary of the micelle

In 1913, J.W. McBain introduced the word “micelle” into surface and colloid chemistry in the context of the association of surfactant molecules in aqueous solution. This article gives a biographic account of McBain, and reviews the early work on micellar aggregation, leading up to the pioneering ideas of G.S. Hartley who introduced the first model of the spherical micelle that we would recognise today.     

The energy pump and the origin of the non-equilibrium flux of the dynamical systems and the networks

The global stability of dynamical systems and networks is still challenging to study. We developed a landscape and flux framework to explore the global stability. The potential landscape is directly linked to the steady state probability distribution of the non-equilibrium dynamical systems which can be used to study the global stability. The steady state probability flux together with the landscape gradient determines the dynamics of the system. The non-zero probability flux implies the breaking down of the detailed balance which is a quantitative signature of the systems being in non-equilibrium states. We investigated the dynamics of several systems from monostability to limit cycle and explored the microscopic origin of the probability flux. We discovered that the origin of the probability flux is due to the non-equilibrium conditions on the concentrations resulting energy input acting like non-equilibrium pump or battery to the system. Another interesting behavior we uncovered is that the probabilistic flux is closely related to the steady state deterministic chemical flux. For the monostable model of the kinetic cycle, the analytical expression of the probabilistic flux is directly related to the deterministic flux, and the later is directly generated by the chemical potential difference from the adenosine triphosphate (ATP) hydrolysis. For the limit cycle of the reversible Schnakenberg model, we also show that the probabilistic flux is correlated to the chemical driving force, as well as the deterministic effective flux. Furthermore, we study the phase coherence of the stochastic oscillation against the energy pump, and argue that larger non-equilibrium pump results faster flux and higher coherence. This leads to higher robustness of the biological oscillations. We also uncovered how fluctuations influence the coherence of the oscillations in two steps: (1) The mild fluctuations influence the coherence of the system mainly through the probability flux while maintaining the regular landscape topography. (2) The larger fluctuations lead to flat landscape and the complete loss of the stability of the whole system.     

Use of Isotope Effects To Understand the Present and Past of the Atmosphere and Climate and Track the Origin of Life

Stable isotope ratio measurements have been used as a measure of a wide variety of processes, including solar system evolution, geological formational temperatures, tracking of atmospheric gas and aerosol chemical transformation, and is the only means by which past global temperatures may be determined over long time scales. Conventionally, isotope effects derive from differences of isotopically substituted molecules in isotope vibrational energy, bond strength, velocity, gravity, and evaporation/condensation. The variations in isotope ratio, such as ¹⁸O/¹⁶O (δ¹⁸O) and ¹⁷O/¹⁶O (δ¹⁷O) are dependent upon mass differences with δ¹⁷O/δ¹⁸O=0.5, due to the relative mass differences (1 amu vs. 2 amu). Relations that do not follow this are termed mass independent and are the focus of this Minireview. In chemical reactions such as ozone formation, a δ¹⁷O/δ¹⁸O=1 is observed. Physical chemical models capture most parameters but differ in basic approach and are reviewed. The mass independent effect is observed in atmospheric species and used to track their chemistry at the modern and ancient Earth, Mars, and the early solar system (meteorites).     

Isolation and identification of the anti-isohumulones and the anti-acetylhumulinic acids

The anti-isohumulones [5-(3-methylbutanoyl)-2-(3-methylbut-2-enyl)-4-hydroxy-4-(4-methylpent-3-enoyl)-cyclopentane-1,3-diones] and the anti-acetylhumulinic acids [5-(3-methylbutanoyl)-2-(3-methylbut-2-enyl)-4-ethanoyl-4-hydroxy-cyclopentane 1,3-diones] have been isolated from an isomerisation reaction mixture of humulone [2-(3-methylbutanoyl)-4,6-di(3-methylbut-2-enyl)-6-hydroxy-cyclohexane-l,3,5-trione] by counter-current distribution and identified by spectroscopic techniques. The formation mechanism is presented and the stereochemical consequences are discussed. The anti-isohumulones are the most bitter hop compounds presently known.     

Influence of the molecular structure and the nature of the solvent on the absorption and fluorescence characteristics of rhodamines

A study of the equilibrium of the molecular forms of rhodamine 19 in aqueous and ethanolic solution is carried out by determining the absorption and fluorescence characteristics of the zwitterionic and the cationic forms of the dye. The optical properties of rhodamine 19 are compared with those obtained for rhodamine 6G and also with those previously reported for rhodamine 3B and for the molecular forms of rhodamine B in water and ethanol. Different aspects of the molecular structure of the rhodamines and solvent effects are discussed, as well as their influence on the photophysical properties of the rhodamines. The aggregation of the molecular forms of rhodamine 19 is also studied in water and ethanol.     

Decorating step-by-step and independently the surface and the core of dendrons

Dendrons possessing one activated vinyl group at the core and several chlorine atoms at the end of the branches are used as starting materials to study the possibility to react independently the surface functions and the core function. In particular, the most powerful sequence of reactions for decorating them by organometallic complexes as end groups and amine or alcohol at the core has been determined. In the first step, phenol phosphines are grafted as end groups of the dendrons, and they can be used for the complexation of metals. However, these phosphines must be kept free when amines are used to react with the vinyl core in the next step. Depending on the type of phosphine end groups and on the type of function of the core (amine or alcohol), the complexation of ruthenium ([RuCl₂(p-cymene)]₂) and rhodium ([RhCl(COD)]₂) derivatives by the phosphine end groups can occur without side reaction at the core.