SiO_2纳米粒子对PMMA/PS共混物共连续相结构退火粗化过程的影响

考察了亲水性纳米SiO2粒子的加入对聚甲基丙烯酸甲酯/聚苯乙烯(PMMA/PS)共混体系的共连续相结构在静态高温退火时形态稳定性的影响,发现静态高温退火条件下,填充体系共连续组成范围变窄幅度较小、特征结构尺寸的粗化速率减慢.流变测试表明纳米SiO2粒子加入之后PMMA/PS共混体系的黏弹性显著提高,从而能减缓破坏构成共连续相结构的纤维断裂或回缩等松弛过程的速率,有效地抑制PMMA/PS共混体系的共连续相结构粗化进程,提高相结构的稳定性.根据现有的两种粗化理论的定性分析表明,在高填充量的共混体系中,加入纳米SiO2粒子导致共混体系的黏弹性的显著改变是影响PMMA/PS共混体系在静态高温退火时共连续相结构粗化速率的主要因素,相对而言界面张力的变化对共连续相结构在静态高温退火时的粗化速率影响则应该较小.     

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.     

MWCNTs与疏水纳米SiO_2填充PMMA/PS共混物的导电与动态流变行为

以多壁碳纳米管(MWCNTs)为导电填料、疏水纳米二氧化硅(SiO2)为非导电填料,填充不相容聚甲基丙烯酸甲酯(PMMA)/聚苯乙烯(PS)(1/1,V/V)共混物,制备(PMMA/SiO2)/(PS/MWCNTs)四元导电高分子复合材料(CPC),研究其导电逾渗与动态流变行为,并与PMMA/(PS/MWCNTs)三元CPC进行对比.发现三元、四元CPC具有类似的导电逾渗行为,且逾渗阈值显著低于PS/MWCNTs二元CPC.在四元CPC中,SiO2粒子可细化相区尺寸,提高熔体模量,但不影响熔体热处理过程中的依时性动态导电逾渗行为.MWCNTs与SiO2均显著影响熔体热处理中的依时性模量逾渗行为,分别缩短、延长四元CPC相粗化起始时间,但均延长相粗化时间区间.     

SiO_2粒子对PMMA/SAN共混体系相分离行为的影响

采用小角激光光散射(SALLS)并结合动态流变学方法,考察了气相法二氧化硅(SiO2)粒子的加入对聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物(PMMA/SAN)共混体系相行为的影响,得到了添加SiO2粒子前后的相图,发现SiO2粒子对基体相行为的影响与基体的组成有关.对PMMA/SAN(60/40)体系,加入SiO2粒子后相分离温度上升,但并未改变相分离机理,仍为亚稳单相分解过程(spinodal decomposition,SD);而对于PMMA/SAN(30/70)体系,加入SiO2粒子后却降低了体系的相分离温度.该现象可能是SiO2粒子和基体组分界面间组成与PMMA/SAN共混物基体组成的差异造成的.     

超细SiO2填充聚甲基乙烯基硅氧烷的动态流变特性

研究粒子填充类聚合物体系的动态粘弹响应，可在较宽应变、温度、频率范围内获得有关体系分散状态及相互作用等结构信息。用粒径小、比表面积大的二氧化硅(SiO2)增强聚硅氧烷时，其独特的化学结构和表面特性对填充体系的静态和动态流变特性有显著影响，Payne等研究了碳黑增强硫化橡胶的动态粘弹性，迄今关于SiO2增强聚硅氧烷，尤其对未硫化体系动态流变特性研究很少报道。本文以超细、高比表面积且具多孔结构的SiO2填充聚甲基乙烯基硅氧烷(Polymethylvinylsiloxane，PMVS)，对室温下不同SiO2含量的SiO2/PMVS体系动态流变特性进行了研究。     

高分散性SiO_2/PMMA复合材料的制备与表征——稀释分散性

以高无机含量SiO2/聚甲基丙烯酸甲酯(PMMA)接枝复合材料为预分散母料,与PMMA树脂进行熔融共混,制得低无机含量的SiO2/PMMA复合材料.通过切片透射电镜(TEM)观察熔融共混过程中预分散母料内堆积SiO2粒子分散状态的演化.发现预分散母料接枝状态对其影响最为显著,不经接枝修饰的SiO2粒子经熔融共混后,不可避免地会在熔体中产生大量亚微米级的立体团聚体;复杂接枝预分散母料内构成以SiO2粒子为交联点的立体交联结构,其中的堆积SiO2粒子不能在剪切场中得到有效解离和释放;只有在使用简单接枝预分散母料时,基体高分子链才能不断地渗透扩散进入预分散母料内,而预分散母料可被不断地溶胀和撕裂,因而其中的堆积SiO2才可不断地向基体相迁移和扩散,并最终在整个复合材料内实现初级粒子形式的高度均匀稳定分散.     

气相生长碳纤维填充聚苯乙烯的熔体动态流变行为

采用修正的两相模型讨论加工条件对不同体积分数(ψ=0～0.05)气相纳米碳纤维(VGCF)填充聚苯乙烯(PS)熔体(200℃)频率(ω)依赖性动态流变的影响.与弱剪切条件(190℃;30 r/min-5 min)下所制备的材料相比,VGCF在强剪切条件(190℃;120 r/min-10 min)下所制备材料中分散均匀,“粒子相”应变放大因子A,(ψ)较低,而松弛指数n较高.将应变(γ)依赖性G″(ω,ψ)应变放大因子A,(ψ,γ)与“粒子相”特征模量G″fψ(,γc),G″f(ψ,γc)引入两相模型,讨论加工条件对γ依赖性非线性流变行为的影响.研究结果表明,两相模型可定量讨论填充熔体动态流变行为.加工条件影响VGCF在基体中的分散性,但不影响“粒子相”弹性贡献R′f(ψ)与n的关系、G′f(ψ,γc)与非线性应变幂律指数x的关系以及G″f(ψ,γc)与非线性应变幂律指数y的关系,说明“粒子相”对填充熔体黏弹性的贡献与其弛豫特性及结构稳定性密切相关.     

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.     

流变-导电同步测试法研究炭黑填充高密度聚乙烯的等温结晶行为

采用流变-导电同步测试法,研究炭黑(CB)填充高密度聚乙烯(HDPE)在124.3～125.3℃范围的等温结晶行为,发现应变、频率与预降温速率均显著影响等温结晶过程中动态流变与导电行为.动态储能模量(G')与电阻均在结晶过程中发生显著变化.其中,CB粒子在熔体中发生扩散,造成原有逾渗网络结构破坏,导致复合体系电阻在结晶诱导期内增大.随结晶度增加,G'在结晶诱导期附近开始显著增大,其临界时间对应1%～2%相对结晶度;同时,CB粒子在无定形区相互聚集而形成渗流网络结构,使得复合体系电阻显著降低.电阻的变化被认为与CB粒子在熔体中的迁移以及在HDPE晶体生长过程中的聚集行为有关,且比依时性动态流变行为更敏感.     

炭黑填充聚苯乙烯熔体流变行为

研究了炭黑(CB)填充聚苯乙烯(PS)熔体的稳态和动态流变行为. CB/PS复合体系在CB体积分数φ=0.06时发生逾渗转变. 结果表明, 低应变区熔体模量降低主要归因于粒子-粒子及粒子-高分子间作用力的破坏, 高应变下模量的急剧下降则主要与高分子链间解缠结有关. 采用“两相”模型拟合线性动态流变行为, 发现应变放大因子A_f(φ)、填充相模量及松弛指数与温度有关. A_f(φ)~φ关系符合Guth方程和扩散控制的粒子簇聚集模型. “粒子相”形状参数与聚集体分维度均随温度升高而有所降低, 说明CB粒子聚集体因团聚而趋于各向同性, 应变放大效应减弱. “粒子相”特征模量G'_f1(φ)和G"_f0(φ)与φ关系满足标度律. 当φ > 0.06时, G'_f1(φ)和G"_f0(φ)及其标度指数均随温度升高而明显降低, 其G'_f1(φ)变化幅度略大于G"_f0(φ), 说明“粒子相”弹性与黏性组分具有不同的温度依赖性. 随着温度升高, 扩散控制的CB粒子团聚过程加快, 应变放大效应减弱.     

玻璃基板作用下高分子共混物薄膜相形态发展过程

研究了玻璃基板作用下极性高聚物为低组分的共混物薄膜在退火条件下相形态的发展过程 .选用聚苯乙烯 (PS) 聚甲基丙烯酸甲酯 (PMMA)与聚苯乙烯 (PS) 聚ε 己内酯 (PCL)两个体系 ,在玻璃基板上Spin Coating成膜后退火 .由于共混物薄膜中极性相对较大的高聚物组分 (PMMA和PCL)相对于极性较小的PS组分对玻璃基板具有更好的润湿性 ,所以在上述的两个共混薄膜体系中其相形态分别显示PMMA和PCL在低组分比例下最终发展成为连续相 .利用扫描电镜以及元素分析很好地验证了以上的结论 ,并且对其机理进行了解释 .此外 ,改变PS的分子量与PCL共混 ,研究了组分粘度对薄膜相形态发展的影响 .结果表明 ,PS组分粘度越大 ,共混物薄膜相结构发展速度越慢     

Difficult reptation of star‐shaped polystyrenes in their blends with poly(methyl methacrylate)

Films of polystyrene/poly(methyl methacrylate) (PS/PMMA) blends are obtained from solution after evaporation of the solvent. The degree of mixing of the two polymers is studied using scanning electron microscopy after selective elimination of the PS phase. Using star‐shaped instead of linear PS, an important degree of mixing is observed. This must be attributed to difficult reptation of the star‐shaped chains due to the high number of entanglements between star‐shaped PS and PMMA compared to the entanglements between linear PS and PMMA.     

Spectroscopic characterization of micro-phase separated blends of polystyrene/polymethyl methacrylate (PS/PMMA)

An investigation of the miscibility behaviour in polystyrene/ polymethyl methacrylate (PS/PMMA) blends of various compositions under different evaporations protocols using Fourier transform infrared (FT-IR) and Raman Spectroscopic techniques took place in the study. Solvent selection and evaporation rates, coupled with variations in the blend composition resulted in completely different miscibility behaviour for these systems. In particular, it was found that blends with low PMMA content result in systems that exhibit PMMA domains of less than 7 microns on average. Finally, depth profiling studies of the PMMA moiety in the PS matrix show that the distribution of the low content phase is highly affected by the solvent selection as well as the blend composition.     

Impact modification of thermoplastics by methyl methacrylate and styrene-grafted natural rubber latexes

The preparation and characterization of polymer blends with structured natural rubber (NR)-based latex particles are presented. By a semicontinuous emulsion polymerization process, a natural rubber latex (prevulcanized or not) was coated with a shell of crosslinked polymethylmethacrylate (PMMA) or polystyrene (PS). Furthermore, core–shell latexes based on a natural rubber/crosslinked PS latex semi-interpenetrating network were synthesized in a batch process. These structured particles were incorporated as impact modifiers into a brittle polymer matrix using a Werner & Pfleiderer twin screw extruder. The mechanical properties of PS and PMMA blends with a series of the prepared latexes were investigated. In the case of PMMA blends, relatively simple core (NR)–shell (crosslinked PMMA) particles improved the mechanical properties of PMMA most effectively. An intermediate PS layer between the core and the shell or a natural rubber core with PS subinclusions allowed the E-modulus to be adjusted. The situation was different with the PS blends. Only core–shell particles based on NR-crosslinked PS latex semi-interpenetrating networks could effectively toughen PS. It appears that microdomains in the rubber phase allowed a modification of the crazing behavior. These inclusions were observed inside the NR particles by transmission electron microscopy. Transmission electron photomicrographs of PS and PMMA blends also revealed intact and well-dispersed particles. Scanning electron microscopy of fracture surfaces allowed us to distinguish PS blends reinforced with latex semi-interpenetrating network-based particles from blends with all other types of particles.     

Surface and interface morphology of polystyrene/poly(methyl methacrylate) thin‐film blends and bilayers

The surface and interface morphologies of polystyrene (PS)/poly(methyl methacrylate) (PMMA) thin‐film blends and bilayers were investigated by means of atomic force microscopy (AFM) and X‐ray photoelectron spectroscopy. Spin‐coating a drop of a PS solution directly onto a PMMA bottom layer from a common solvent for both polymers yielded lateral domains that exhibited a well‐defined topographical structure. Two common solvents were used in this study. The structure of the films changed progressively as the concentration of the PS solution was varied. The formation of the blend morphology could be explained by the difference in the solubility of the two polymers in the solvent and the dewetting of PS‐rich domains from the PMMA‐rich phase. Films of the PS/PMMA blend and bilayer were annealed at temperatures above their glass‐transition temperatures for up to 70 h. All samples investigated with AFM were covered with PS droplets of various size distributions. Moreover, we investigated the evolution of the annealed PS/PMMA thin‐film blend and bilayer and gave a proper explanation for the formation of a relatively complicated interface inside a larger PS droplet. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 9–21, 2006     

Conductivity of Poly(methyl methacrylate)/Polystyrene/Carbon Black and Poly(ethyl methacrylate)/Polystyrene/Carbon Black Ternary Composite Films

Poly(methyl methacrylate)(PMMA)/polystyrene(PS)/carbon black(CB)and poly(ethyl methacrylate)(PEMA)/PS/CB ternary composite films were obtained using solution casting technique to investigate double percolation effect.In both PMMA/PS/CB and PEMA/PS/CB ternary composite films,the CB particles prefer to locate into PS phase based on the results of calculating wetting coefficient,which is also confirmed by SEM images.The conductivity of the films was investigated,and the percolation threshold(￠c)of both ternary composite films with different polymer blend ratios was determined by fitting the McLachlan GEM equation.Conductivity of PMMA/PS/CB ternary composite films showed a typical double percolation effect.However,due to the double emulsion structure of PEMA/PS polymer blends,the PEMA/PS/CB ternary composite films(PEMA/PS=50/50)showed a higher￠c,even CB only located in PS phase,which conflicts with the double percolation effect.A schematic diagram combined with SEM images was proposed to explain this phenomenon.     

基板界面对PS/PMMA溶液共混物溶剂挥发成膜相结构的影响

研究了PS PMMA的共混物溶液溶剂蒸发成膜时的基板界面效应 .利用扫描电子显微镜 (SEM)研究了PS PMMA(5 5 ) (W W) THF高分子共混物溶液在不同基板上通过溶剂挥发成膜的相形态结构 .通过FTIR及ATR FTIR检测了共混物薄膜及其表面的共混组成 .研究结果表明 ,成膜基板对高分子共混物溶液成膜后的相形态有很重要的影响 .控制共混物溶液体系成膜过程中的动力学因素 ,可以调控出所设想的各种复杂的相结构形态     

Use of block copolymer-stabilized cadmium sulfide quantum dots as novel tracers for laser scanning confocal fluorescence imaging of blend morphology in polystyrene/poly(methyl methacrylate) films

This paper describes the first use of polymer-coated quantum dots (QDs) as fluorescent tracers for LSCFM imaging of phase morphology in polymer blends. Cadmium sulfide (CdS) QDs stabilized at the surface with a PS-b-PAA block copolymer are shown to be well dispersed via their polystyrene (PS) brush layer in the PS phase of solvent-cast 40/60 (w/w) PS/PMMA blends. The QDs are excluded from the PMMA phase, providing excellent fluorescence contrast for LSCFM imaging of the phase-separated blends. The presence of PS-b-PAA-stabilized QDs does not appear to affect the blend morphology, since the observed morphologies are the same when the percentage of QDs within the PS phase is varied from 10 to 50 wt %. These QD fluorescent tracers are used to characterize several aspects of blend morphology in solvent-cast 40/60 PS/PMMA blends containing PS homopolymer with either 100 (low molecular weight) or 1250 (high molecular weight) repeat units. In the PS(1250)/PMMA blends, a percolating distribution of PMMA droplets (2-25 mum) in a PS matrix is observed in the bulk, and a distinct inversion in the continuous phase is found near the glass substrate. In the PS(100)/PMMA blends, a "phase-in-phase" morphology is found, consisting of large PS domains (20-100 mum) dispersed in a PMMA continuous phase and small PMMA domains (1-2 mum) scattered throughout the larger PS droplets. The observed change in blend structure is attributed to a lower interfacial tension for the lower molecular weight PS.     

Suppressed coalescence of dispersed viscous poly(methyl methacrylate) phase in polystyrene matrix by glass beads

The effect of glass beads (GB) on morphology of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blends has been studied by scanning electron microscopy (SEM) at different shear rates and during quiescent annealing. For the viscosity ratio of PMMA to PS greater than unity, the dispersed viscous PMMA phase in the blend coalesced during the shear flow or quiescent annealing. However, the domain size of the PMMA phase decreased significantly under shear even though a small amount of GB was added. The PMMA domain size further decreased and the size distribution became narrower with increasing GB content. According to SEM images, the quiescent coalescence of the PMMA phase was effectively inhibited by adding large amounts of GB, and the breakup of PMMA domains in shear flow was greatly favored by the high local shear prevailed between GB. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 25–35, 2009