PMVS/SiO2复合体系中粒子表面处理对动态粘弹特性的影响

粘弹性是高分子材料最本质的特征,其与高分子结构的关系一直是多组分高分子材料研究的热点。目前,对于填料增强聚硅氧烷体系的研究主要集中于填料在聚合物中的分散以及增强机理等方面,而有关不同填料表面特性体系的粘弹响应的研究报道尚不多见．在前文报道未经表面处理的超细SiO2填充聚甲基乙烯基硅氧烷(Polymethylvinylsiloxane,PMVS)的粘弹性研究的基础上,本文采用双(γ-三乙氧基硅基丙基)四硫化物IBis(3-triethoxysilyl)tetrasul{ane,TESPT]对SiO2进行表面处理,并采用溶液共混法制备样品,研究了经表面处理的SiO2填充PMVS体系的动态粘弹行为,并探讨了其结构变化与粘弹响应的关系。     

核/壳纳米复合粒子填充聚苯乙烯的流变行为

采用细乳液聚合制备了以偶联剂改性纳米二氧化硅粒子(SiO2)为核、交联聚苯乙烯(PS)为壳的SiO2@PS复合纳米粒子(SCCSN).采用透射电子显微镜(TEM)、动态光散射(DIS)法考察了SCCSN的粒子形貌特征,发现SCCSN呈球形,粒径约90 nm,均匀分散;采用热失重(TG)、调制式差示扫描量热(MDSC)与动态力学分析(DMA)研究了SCCSN的结构特征,发现PS包覆率随交联剂含量增加而升高,且玻璃化转变温度(Tg)显著升高.交联壳层不仅能够将聚合物锚固在SiO2表面,屏蔽SiO2粒子与基体PS间相互作用,而且阻止PS壳层与基体PS分子链间的缠结.MDSC结果显示,SiO2与SCCSN填充可降低复合物Tg.动态流变结果表明,填充PS熔体非线性流变行为与PS分子链解缠结有关,SiO2与SCCSN均不影响填充熔体非线性流变机理.SCCSN的SiO2核对PS的增强效应略优于SiO2,且增强效应与壳层交联度有关.     

纳米SiO_2填充PMMA/PS复合物共连续范围的研究

采用流变法、抽提法以及扫描电镜3种表征方法研究了亲水性纳米二氧化硅粒子SiO2填充对聚甲基丙烯酸甲酯(PMMA)/聚苯乙烯(PS)不相容体系共连续范围的影响.对于未填充PMMA/PS体系,3种方法测得的共连续范围基本一致.而对于粒子填充体系,SEM与溶剂抽提法均表明随着粒子含量的增加,体系的共连续范围变宽,这是由于亲水性SiO2粒子选择性填充在极性PMMA相中,导致PMMA相的熔体粘度和弹性均有大幅提高,从而减缓了破坏共连续结构的纤维断裂或回缩等松弛过程.与SEM法和溶剂抽提法相反,流变法测得的共连续范围随粒子含量增加明显变窄,这主要是因为加入SiO2粒子后,PMMA/PS体系的弹性模量和黏度大大提高(加入7vol%的SiO2后分别增加近50倍和5倍),导致填充试样在装样和设定间距之后需要更长的松弛时间才能开始流变测试.试样在测试前长时间处于高温熔体状态时,其共连续结构很容易在界面张力的驱动下发生粗化和破碎,所以得到的共连续反而变窄.SEM和溶剂抽提法比流变法更适合用来判断粒子填充PMMA/PS体系特别是其高填充体系的共连续范围.     

硅烷偶联剂对SSBR/SiO_2混炼胶体系动态流变行为的影响

研究了高填充白炭黑(SiO2)补强溶液聚合丁苯橡胶(SSBR)混炼胶体系的动态流变特性,分别考察了在2个混炼温度(120℃、160℃)下添加3种不同偶联剂(TESPT、TESPD、NXT)对其体系中SiO2粒子表面改性的效果.结果表明,在较低混炼温度下添加偶联剂,不利于SiO2粒子表面改性.在较高混炼温度下,偶联剂TESPT、PESPD、NXT均对SiO2粒子表面有改性效果,但同时引起混炼胶不同程度的焦烧,其中以TESPT最明显.随SiO2粒子表面改性程度的提高,出现“Payne效应”的临界应变(γc)值以及低频率(ω)区域lgG′-lgω曲线的斜率值均增大,反映出偶联剂对SiO2与SSBR相互作用的促进以及SiO2粒子分散的改善.     

粒子填充HDPE复合体系动态流变行为研究

研究了炭黑(CB)和石墨(GP)填充高密度聚乙烯(HDPE)复合体系的动态流变行为.发现高填料含量时出现似固体行为,并认为它归因于无机粒子网络逾渗结构的形成.在相同聚合物基体条件下,粒子种类和粒子几何参数(粒子形状、大小、粒径分布)对低频区域流变行为、流变参数的逾渗行为和逾渗阈值(φ_c)有决定性影响,且种类的影响相比于粒子几何参数更为显著.此外,高表面活性及高比表面积(大径厚比、小尺寸)粒子填充体系具有较低的φ_c.     

电响应聚合物薄膜的表面图案化

研究了炭黑(CB)和石墨(GP)填充高密度聚乙烯(HDPE)复合体系的动态流变行为.发现高填料含量时出现似固体行为,并认为它归因于无机粒子网络逾渗结构的形成.在相同聚合物基体条件下,粒子种类和粒子几何参数(粒子形状、大小、粒径分布)对低频区域流变行为、流变参数的逾渗行为和逾渗阈值(φc)有决定性影响,且种类的影响相比于粒子几何参数更为显著.此外,高表面活性及高比表面积(大径厚比、小尺寸)粒子填充体系具有较低的φc.     

SSBR/SiO_2混炼胶的动态黏弹行为

研究了白炭黑(SiO2)填充溶液聚合丁苯橡胶(SSBR)的动态流变行为,考察了时间-浓度叠加(time-concentration superposition,TCS)原理在粒子填充橡胶中的应用,获得以未填充SSBR为基准的流变叠加曲线.流变叠加曲线在低频下呈现模量平台,复数黏度呈现剪切变稀行为,而损耗因子tanδ在特定频率下出现峰值.基于刚性粒子所导致的应变放大效应以及SiO2粒子间SSBR分子的受限运动,探讨了TCS模量平移因子AG与频率平移因子Aω随SiO2体积分数φ的变化.AG与Aω均为φ的标度函数,但AG～φ关系不符合粒子聚集体团聚(cluster-cluster aggregation,CCA)模型.讨论了偶联剂3-辛酰基硫代-1-丙基三乙氧基硅烷(NXT)对动态流变行为的影响.NXT不影响性叠加曲线的低频平台模量与剪切变稀幂律指数.然而,与不含偶联剂的混炼胶相比,NXT造成SSBR特征弛豫时间缩短,稠度与A增大.     

SiO2纳米颗粒与聚氧乙烯对Pickering乳液的协同稳定作用简

研究了聚氧乙烯(PEO)与SiO2纳米颗粒对水/二甲苯体系Pickering乳液的协同稳定作用. 实验发现,PEO的存在减小了乳液液滴的平均直径,抑制了乳液的相反转,有效阻止了乳液的熟化,使乳液具有更好的稳定性. 进一步对纳米颗粒膜的流变性质进行研究,结果表明,PEO高分子促进了纳米颗粒形成更大尺寸的聚集结构,提高了其在界面上的吸附性,增强了颗粒膜的力学性能,在较小颗粒用量条件下使得Gibbs稳定性判据得到满足.     

加工工艺对气相生长碳纤维填充聚苯乙烯复合体系导电逾渗与动态流变特性的影响

研究了加工工艺对气相生长碳纤维(VGCF)填充聚苯乙烯(PS)复合体系导电逾渗与动态流变特性的影响.结果表明,低转速、短时间混合有利于VGCF形成较为完善的逾渗网络结构,其复合体系逾渗阈值低、导电性能好.使用作者提出的两相模型描述VGCF/PS复合体系的流变特性,发现低转速、短时间(30 r/min、5 min)混合条...     

基于剪切增稠液体防护装甲的研究

综述了剪切增稠液体(Shear Thickening Fluid,即STF)的基本性质、组成成分、流变机理,影响STF流变性能的诸多因素以及对STF流变性能的研究方法,介绍了STF中聚乙二醇(PEG)/纳米SiO2颗粒体系和SiO2的制备方法,对PEG/SiO2的增稠机理进行了讲解。在对STF研究的基础上,阐述了STF-织物组成的液体防护装甲的优异防护性能、防弹和防刺(防锥、防刀)机理,讲述了STF-Kevlar构成的液体防护装甲及防刺机理,介绍了动态防刺测试和准静态防刺测试,最后对液体防护装甲未来研究方面进行了展望。     

二氧化硅分散体系在应力剪切过程中粘弹性及能耗研究

通过动态应力剪切研究了以乙二醇、丙二醇和丁二醇为分散介质的雾化二氧化硅分散体系的粘弹性以及能耗. 研究发现, 随着应力的增大, 体系都经历了线性粘弹区、剪切变稀区以及剪切增稠区. 在线性粘弹区, 储能模量(G′)、耗能模量(G′′)随着应力(σ)的增大保持不变；在剪切变稀区, G′随着σ的增大而减小, 且乙二醇、丙二醇、丁二醇分散体系的减小幅度依次递减, 而G′′基本保持不变；在剪切增稠区, G′、G′′都随着σ的增大而增大. 在所研究的应力范围内, G′′都大于G′, 体系主要体现粘性, 消耗能量为主. 同时还发现在低剪切应力区, 体系所消耗的能量(Ed)都随着最大应变(γ0)成二次方关系增长, 而在剪切增稠区, 当n=2.79、4.93、4.88时, EG/SiO2、PG/SiO2、BG/SiO2的Ed分别随γ0以指数关系增长.     

Preparation and properties of magnetic alumina microspheres with a γ-Fe_2O_3/SiO_2 core and Al_2O_3 shell

Magnetic alumina composite microspheres with γ-Fe 2 O 3 core/Al 2 O 3 shell structure were prepared by the oil column method. A dense silica layer was deposited on the surface of γ-Fe 2 O 3 particles (denoted as γ-Fe 2 O 3 /SiO 2 ) with a desired thickness to protect the iron oxide core against acidic or high temperature conditions. γ-Fe 2 O 3 /SiO 2 /Al 2 O 3 particles with about 85 wt% Al 2 O 3 were obtained and showed to be suitable for practical applications as a magnetic catalyst or catalyst support due to their magnetic properties and pore structure. The products were characterized with scanning electron microscope (SEM) and transmission electron microscope (TEM), nitrogen adsorption-desorption, and vibrating sample magnetometer (VSM). The specific surface area and pore volume of the γ-Fe 2 O 3 /SiO 2 /Al 2 O 3 composite microspheres calcined at 500 ? C were 200 m 2 /g and 0.77 cm 3 /g, respectively.     

Preliminary Study on the Dynamic Properties of PMVS Filled with Surface-treated Silica

Dynamic properties of polymethylvinylsiloxane (PMVS) filled with surface-treatedsilica (SiO2) were studied using an advanced rheometric expansion system (ARES). The results revealed that the coupling agent, bis (3-triethoxysilylpropyl) tetrasulfane (TESPT) exerted a pronounced effect on the storage modulus (G‘), and the effect of TESPT involved a frequency-dependent relation.     

负载型La0.8Sr0.2MnO3燃烧催化剂的载体效应

Combustion catalysts La0.8Sr0.2MnO3 supported on γ-Al2O3, α-Al2O3, cordierite (2MgO•2Al2O3•5SiO2) and ZrO2 were compared. Further investigation was focused on LSM/ γ-Al2O3 catalyst. It was observed that LSM/γ－Al2O3 catalyst loaded with 20% (mass fraction) LSM (La0.8Sr0.2MnO3 or corresponding oxides), heated at 750℃ or above, perovskite-type oxides were found by XRD examination, whereas, the same catalyst loaded with 10% or less LSM, perovskite oxides were absent, calcination temperature about 750℃ is necessary for the formation of perovskite structure in LSM/γ-Al2O3 catalysts. High activity of complete oxidation of xylen will be obtained when perovskite-type oxides.
Investigation of TPR showed that neat LSM or LSM/γ-Al2O3(20%) was reduced by H2-N2 mixed gas. Two degradation processes took place. In the first, reduced temperature peak was about 350 - 450℃. If reduction ended at 400℃, perovskite structure was retained, which may be due to the reduction of Mn3+to Mn2+ on the surface of LSM only. In the second process, perovskite structure was destroied, and La2O3, Mn2O3, Mn - Sr - O oxides could be obtained, which took place in the temperature range 685 - 750℃ and ended at 800℃. This was proved by TPR experiments (Fig. 3, 5) and XRD patterns (Fig. 4)
Catalysts LSM/γ-Al2O3(10% or 20%) heated at 500℃ have only one TPR peak, i. e. lower temperature peak. This is due to the absence of perovskite-type oxides in the catalysts. However, neat LSM or LSM/γ-Al2O3(20%) heated 750℃ or above, not only the first low temperature TPR peak but also the second peak, which is contributed by the perovskite-type oxides in these catalysts appeared. Therefore, the second TPR peak, i. e. the higher temperatue peak is a characteristic peak for perovskite-type oxides in the reduced process. When LSM/ γ-Al2O3 (10%) catalys is heated at 750℃, no perovskite-type oxides were detected by XRD, and the second reduction peak was absent also in TPR process. \
The order of the second reduction peak temperature(characteristic peak of perovskite - type ox- ides) is: neat LSM(750℃）> LSM/γ-Al2O3 20% (685-698℃) -deposited LSM/γ-Al2O3 (698℃) > LSM/γ-Al2O3 15% (677 - 680℃) >(LSM/γ-AL2O3 10% 620 - 630℃, for Mn - Al - O medium oxides on surface). It is correleted with the increasing of the effect of support sequentially.
When LSM/γ-Al2O3 catalysts were heated at 900℃, more stable phase, spinel MnAl2O4 appeared, which could be proved by TPR of model catalyst MnAl2O4/γ-Al2O3.     

聚醚型氨酯酰亚胺/二氧化硅杂化材料的合成与性能研究

利用Sol Gel共聚合反应制备出聚醚型氨酯酰亚胺 (PUI) /二氧化硅 (SiO2 )杂化材料 .利用NMR、FTIR、TG、DSC及SEM等测试手段对性能进行了基本表征 .FTIR研究结果发现在 10 0℃下能同时完成有机相PUI的亚胺化和无机相SiO2 凝胶网络的Sol Gel转变 .TG及SEM发现SiO2 含量为 9wt%时SiO2 聚集相粒径在 0 2～1 0 μm之间 ,耐热性明显提高并达到最佳 ;发现SiO2 含量的增加其颗粒粒径不断增大 ,并不断聚集成大粒径SiO2 相 ,有机和无机相分离明显 .DSC研究显示 ,SiO2 相的引入 ,对杂化材料聚醚软段富集相的Tg 不产生明显影响 .     

甲基三乙氧基硅烷修饰的Ti3+/SiO2复合薄膜的发光性能

采用溶胶-凝胶(Sol-Gel)法, 以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为先驱物, 盐酸为催化剂, 用二步水解法制备了Ti3+/SiO2薄膜和甲基三乙氧基硅烷修饰的Ti3+/SiO2复合薄膜. 采用红外光谱仪、X射线衍射仪、椭偏仪、荧光光谱仪等对膜层性质进行了分析. 结果表明, 掺杂Ti3+的SiO2薄膜分别在250 nm附近有一弱的激发峰, 294 nm附近有一强的激发峰, 在393 nm附近出现一强的发射峰. IR光谱发现, MTES修饰的Ti3+/SiO2复合薄膜的Si—OH的吸收峰强度比Ti3+/SiO2薄膜的略减小, Si—O—Si的吸收峰明显增强, 表明复合薄膜硅氧网络结构更规则, 有利于Ti3+的均匀分散. Ti3+/SiO2薄膜与复合薄膜的孔隙率分别为13.64%和6.66%, 表明MTES的加入使薄膜更致密. 在空气中陈放30 d后, Ti3+/SiO2薄膜已经检测不到荧光发射峰, 而MTES修饰的Ti3+/SiO2复合薄膜荧光强度只下降了18%. 在氮气中陈放30 d后, 普通薄膜与复合薄膜的荧光强度均仅下降了10%. 表明Ti3+的荧光猝灭的主要原因是由于Ti3+被氧化造成的. 溶胶中加入MTES后, 薄膜表面结构得到改善, 有效地防止了Ti3+的氧化, 荧光强度更稳定.     

DMFCs用磺化聚醚醚酮/功能化二氧化硅复合质子交换膜

在磺化度(DS)为55.1%的磺化聚醚醚酮(SPEEK)中掺杂功能化二氧化硅(吸湿性SiO2溶胶及带有磺酸基团的二氧化硅(SiOx-S)粒子)制备SPEEK/SiO2和SPEEK/SiOx-S复合质子交换膜.SiO2和SiOx-S的掺杂能有效提高复合膜的抗溶胀、阻醇性能及高温低湿情况下的电导率.纯SPEEK膜在80℃溶胀为52.6%,而SiO2和SiOx-S掺杂量为15%的复合膜在此温度下分别仅有26.2%和27.3%的溶胀.在室温至80℃范围内,SPEEK/SiO2(20 wt%)和SPEEK/SiOx-S(20 wt%)复合膜的甲醇透过系数比Nafion115膜小近2个数量级.在120℃、相对湿度(RH)为40%情况下,SPEEK纯膜的电导率仅为2.6×10-4S.cm-1,SPEEK/SiO2(20 wt%)复合膜约为2.0×10-3S.cm-1,而SPEEK/SiOx-S(20 wt%)复合膜高达1.0×10-2S.cm-1,与Nafion115相当.SPEEK/SiO2(20 wt%)和SPEEK/SiOx-S(20 wt%)2种复合膜的尺寸稳定性较高,膜电极无催化剂与膜分离现象,其DMFCs单电池性能好于SPEEK膜.     

Metal-modified silica adsorbents for removal of humic substances in water

As novel adsorbents for humic substances, Fe-, Mg-, and Ca-modified silica gels SiO(2)Fe, SiO(2)Mg, and SiO(2)Ca were prepared, and their adsorbabilities to humic and fulvic acids were evaluated in water at 25 degrees C for 20 h. Among these adsorbents, SiO(2)Fe indicated the highest adsorbability, in which removing humic substances in water was accomplished to 80-97%. By calcination at 600 degrees C and washing with water, adsorbabilities of the silica adsorbents deteriorated except for the case of calcination of SiO(2)Ca. This is due to changing metal modification structures and losing chlorine, judging from elemental analysis, TG-DTA, and XPS. Especially, the modifier Fe was tightly fixed on the silica surface of SiO(2)Fe, since the metal content was almost constant even after the calcination and water washing unlike the other adsorbents. Therefore, we found that SiO(2)Fe is the most useful adsorbent among the silica adsorbents and that its modification structure is composed of SiOFe, FeCl, and FeOH. In addition, the adsorption mechanism is explained by an interaction between Fe and humic substance molecule having carboxylate and phenolate groups, accompanied with anion exchange of chloride ion Cl(-) for the humic substance molecule via the silica pores. SiO(2)Fe may be applied to an adsorbent alternative for charcoal in water purification plants, and the used SiO(2)Fe may be further reused as a fertilizer since humic substances have plant-glowing ability and silica strengthens plant parts.     

荧光素掺杂的溶胶凝胶SiO2/甲基硅油复合薄膜的制备和光谱特性

采用溶胶-凝胶(Sol-Gel)法制备了掺杂荧光素(FL)的SiO₂/甲基硅油(MSO)复合薄膜,并且测定了这种薄膜的光谱特性.实验表明,荧光素掺杂的SiO₂薄膜在350nm~450nm波长范围内激发,在520nm附近有最强的荧光发射峰;与常规SiO₂膜相比较,SiO₂/甲基硅油(MSO)复合薄膜的荧光发射强度可增加50%;在70℃下的加速老化实验表明,常规SiO₂薄膜20天后开始出现严重的荧光猝灭现象,而复合膜放置一个月后荧光强度仅下降了15%.