Relationship between electrical resistivity and particle dispersion state for carbon black filled poly (ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate)/poly (<Emphasis Type="SmallCaps">L</Emphasis>-lactic acid) blend

It is known that the electrical volume resistivity of insulating polymers filled with conductive fillers suddenly decreases at a certain content of filler. This phenomenon is called percolation. Therefore, it is known that controlling resistivity in the semi-conductive region for carbon black (CB) filled composites is very difficult. When poly (ethylene-co-vinyl acetate) (EVA) is used as a matrix, the percolation curve becomes gradual because CB particles disperse well in EVA. In this study, the relationship between the dispersion state of CB particles and electrical resistivity for EVA/poly (L-lactic acid) (PLLA) filled with CB composite was investigated. The apparent phase separation was seen in the SEM photograph. It was predicted that the CB particles located into the EVA phase in the light of thermodynamical consideration, which was estimated from the wetting coefficient between polymer matrix and CB particles. The total surface area per unit mass of dispersed CB particles in the polymer blend matrix was estimated from small-angle X-ray scattering and the volume resistivity decreased with increasing CB content. The values of the surface area of CB particles in CB filled EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) polymer blends showed a value similar to that of the CB filled EVA single polymer matrix. In electrical volume resistivity measurement, moreover, the slopes of percolation curves of EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) filled with CB composite are similar to that of EVA single polymer filled with CB composite. As a result, it was found that CB particles selectively locate in the EVA phase, and then the particle forms conductive networks similar to the networks in the case of EVA single polymer used as a matrix.     

Influence of thermoplastic spacer on the mechanical,electrical, and thermal properties of carbon black filled epoxy adhesives

A new approach of mimicking the selective localization mechanism of conductive filler into one phase of immiscible polymer blend system is proposed here, where a moderate fine of polymethylmethacrylate (PMMA) powder is prepared and used as the spacer in the carbon black (CB) filled epoxy adhesives system that can be applied at room temperature. The main purpose of PMMA‐spacer is to promote the formation of conductive networks via aiding the 3D self‐assembly of CB filler, selectively in the continuous phase of epoxy. PMMA‐spacer content ranged from 10, 20, 30, 40, and 50 vol.% were investigated under electrical, mechanical, and thermal properties for both unfilled and 15 vol.% CB filled system. With the incorporation of 10 vol.% PMMA‐spacer, the filled system shows promising improvement in electrical conductivity, with three order of magnitude increment at 15 vol.% CB loading. Toughening mechanism of epoxy was observed, where crack deflection upon the PMMA‐spacer is observed under scanning electron microscopy characterization and agreed by fracture toughness calculation. Thermal stability and coefficient of thermal expansion were improved at the minimum addition of PMMA‐spacer content, at 10 vol.%, while a small reduction in flexural strength is observed because of the poor interface interaction between the PMMA‐spacer and epoxy matrix. Interestingly, a limited interaction between the PMMA‐spacer with epoxy at the curing temperature of 100°C is observed, indicating the solubility of PMMA‐spacer in epoxy before crosslinking process occurred. Copyright © 2016 John Wiley & Sons, Ltd.     

Nanostructured carbon black filled polypropylene/polystyrene blends containing styrene-butadiene-styrene copolymer: Influence of morphology on electrical resistivity

This paper is part of a comprehensive study on using selective localization of carbon black (CB) at the interface of immiscible polymer blends in order to reduce the percolation threshold concentration and enhance the conductivity of the blends. CB was successfully localized at the interface of polypropylene/polystyrene (PP/PS) blend by introducing styrene-butadiene-styrene (SBS) tri-block copolymer to the blend. In CB-PP/PS/SBS blends, CB has higher affinity for the polybutadiene (PBD) section of the SBS copolymer, whereas in CB-PP/PS blends, CB prefers the PS phase. PP/PS interface is one of the preferred locations for the SBS copolymer in the (PP/PS) blend; at which the PBD section of the SBS copolymer forms a few nanometers thick layer able to accommodate the CB nano-particles. The influence of SBS addition on the morphology and electrical properties of various PP/PS blends filled with 1 vol% CB were studied. SBS influence on the conductivity of PP/PS blends was found to be a function of the PP/PS volume ratio and SBS loading. The most dramatic increase in conductivity was found in the (60/40) and (70/30) PP/PS blends upon the addition of 5 vol% SBS. 5 vol% SBS was found to be the optimum loading for most blends. Using 10 vol% of SBS was reported to deteriorate electrical conductivity of the conductive co-continuous PP/PS blends. For all blends studied, SBS addition was found to compatibilize the blends. Finer morphologies were obtained by increasing SBS loading.     

Interface stabilization and micelle formation in blends with a block copolymer

The phase separation behavior of ternary blends of two homopolymers, PMMA and PS, and a block copolymer of styrene and methylmethacrylate, P(S-b-MMA), was studied. The homopolymers were of equal chain length and were kept at equal amounts. Two copolymers were used with blocks of equal length, which exceeded or equaled that of the homopolymer chains. Varied was the copolymer contentf. Films were cast from toluene, which is a nonselective solvent. The morphologies of the cast films were compared with the structure of the critical fluctuations in solution, which were calculated in mean field approximation. The axis of blend compositionsf can be divided into parts of dominating macrophase and microphase separation. Above a transition concentrationf _o, all copolymer chains are found in phase interfaces. Belowf _o, part of them form micelles within the homopolymer phases.     

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.     

Sensing of liquids by electrically conductive immiscible polypropylene/thermoplastic polyurethane blends containing carbon black

Immiscible polymer blends based on polypropylene/thermoplastic polyurethane (PP/TPU) are interesting host multiphase systems for the incorporation of low concentrations of conductive carbon black (CB) particles. The enhancement of conductivity (and the lower critical CB content for percolation) in the PP/TPU blend is achieved via double percolation, that is, structural and electrical. The CB particles form chainlike network structures within the TPU phase, which exhibit phase continuity of elongated particles within the PP matrix. Moreover, scanning electron microscopy and dynamic mechanical thermal analysis studies indicated that the incorporation of CB particles into the PP/TPU blend has a “compatibilizing” effect, resulting in an enhanced interaction between the two polymers. Extruded PP/TPU/CB filaments produced by a capillary rheometer process at various shear rates were examined as sensing materials for a homologous series of alcohols, that is, methanol, ethanol, and 1‐propanol. All filaments displayed increasing resistance upon exposure to the various alcohols combined with excellent reproducibility and recovery behavior. An attempt is made to identify the dominant mechanisms controlling the sensing process in a CB‐containing immiscible polymer blend characterized by a double‐continuity structure. The interphase region, its quantity, and continuity played a significant role in the liquid‐transport process. Blend composition, filaments' extrusion temperature, and production shear rate level were considered as significant parameters determining the structure and the resultant sensing properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1428–1440, 2003     

Poly(ethylene-co-vinyl alcohol) and poly(methyl methacrylate) blends: Phase behavior and morphology

In this work blends of poly(ethylene-co-vinyl alcohol) (EVOH) with different ethylene contents (27, 32, 38 and 44 mol%) and poly(methyl methacrylate) (PMMA) were prepared by mechanical mixing in the melted state. The miscibility and melting behavior as a function of blend composition and the ethylene content in EVOH copolymers were investigated by means of differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The morphology of the cryofractured surfaces was examined by scanning electron microscopy (SEM). DSC and DMTA data show that EVOH/PMMA blends are immiscible, independent of EVOH and blend composition. The SEM analysis in agreement with DMTA analysis indicates that the morphology of phases depends on the blend composition, with phase inversion occurring as the concentration of one or other polymer component increases. However, the copolymer composition apparently does not affect the domain size distribution for blends containing 20 wt% of EVOH or 20 wt% of PMMA. A better phase adhesion is observed mainly for blends with 50 wt% of each polymer component.     

Enthalpy relaxations in polymer blends and block copolymers: Influence of domain size

It is now well known that enthalpy relaxation measurements can be used to establish polymer-polymer blend phase behavior when the glass transition temperatures of the two polymers are virtually coincident. In the most simple cases, the aging kinetics of an immiscible blend will be representative of the pure polymers superimposed upon each other. However, in many cases the situation is more complicated because of the presence of interface material. In this paper the relation between enthalpy recovery peak separation, domain size and interface thickness is considered. The discussion is based on relaxation experiments involving di-block copolymers of styrene and 2-vinyl pyridine, blends of polystyrene and poly(2-vinyl pyridine) and blends of poly(vinyl chloride) and poly(isopropyl methacrylate). If the amount of material in the interface is too large due to either a small average domain size or a thick interface no peak separation will occur. The first situation is found for the microphase separated block copolymer system whereas the second possibility occurs for blends of polymers which are on the verge of miscibility like poly(vinyl chloride) and poly(isopropyl methacrylate).Presented in part at the Sixth International Seminar on Polymer Physics Relaxation in Polymers, Gomadingen, October 3–8, 1988, F.R.G.     

Thermo-optical analysis as a complementary method in the study of phase transitions of thermotropic liquid crystalline polymer and its blends with polycarbonate

Differential scanning calorimetry (DSC) and thermo-optical analysis (TOA) were applied to study the phase transitions phenomena of thermotropic liquid crystalline polymer and its blends with polycarbonate. It was found that both methods are complementary. Glass transition temperatures of the blends of polycarbonate with liquid crystalline polymer were measured and discussed.     

Competition between crystallization and phase separation in polymer blends I. Diffusion controlled supermolecular structures and phase morphologies in poly(ɛ-caprolactone)/polystyrene blends

The type of supermolecular structure and the morphology in binary polymer blends with one crystallizable component and with a miscibility gap are strongly influenced by the relative rate of crystallization and demixing. Depending on the composition of the blend and on the relative position of the crystallization curve and the miscibility gap in the phase diagram, demixing-induced crystallization as well as crystallization-induced demixing can occur. Both these approaches lead to new and interesting structures. Additionally, the interaction of the two mentioned kinds of phase transition can under circumstances affect the growth rates of adjacent spherulites. This results in anisotropic concentration distribution or phase-separation morphology around their surfaces.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday.Presented at the Frühjahrstagung des FA Polymerphysik der DPG, Bad Nauheim, FRG, April 1990.     

Kinetics of nonisothermal crystallization and melting of normal high density and ultra-high molecular weight polyethylene blends

The kinetics of nonisothermal crystallization and melting of blends of ultra-high molecular weight polyethylene (UHMWPE) and polyethylene high density with normal molecular weight (NMWPE) are investigated by means of differential scanning calorimetry (DSC). Mixing the components at a temperature below the flow temperature of UHMWPE (215 °C) results in increased crystallization/melting rates of the individual components in the blends above the corresponding additive values. The morphological observations of the blends, carried out by means of polarization microscopy, show that a strong boundary of both types of structures (UHMWPE non-flowing aggregates and NMWPE spherulite structures) does not exist. The NMWPE spherulites' dimensions decrease on increasing the UHMWPE concentration in the blends, but their number increases. The facilitation of the crystallization/melting of the components in the blends is explained in terms of mutual influence exhibited by the components with respect to each other. It is due to the inner stresses in nonflowing UHMWPE characterized with a lot of entangled tie molecules and to the partial co-crystallization of NMWPE molecules with the flowing part of UHMWPE. At mixing temperatures above 215 °C the melting/crystallization integral kinetic curves have only one linear part in contrast to these of the same blend (11 ratio of components), prepared at 190 °C. The rates of melting/crystallization remain almost constant with the increase of the mixing temperatures.     

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.     

Evaluation of carbon black distribution in different phases of compatible blend of EVA/NBR through electrical,mechanical and morphological test

The paper reveals the influence of different methods of carbon black (CB) incorporation in the compatible blend of 50/50 (wt %) Ethylene vinyl acetate (EVA) and Acrylonitrile butadiene elastomer (NBR) on different properties of vulcanized blend compounds. The partitioning of two types of CB in two different phases of the blend was estimated from dynamic mechanical analysis (DMA). The distribution of CBs due to preferential addition in different phases of the blend affects property variations in different degrees. From the analysis of SEM, TEM, AFM and electrical property measurements, it is found that mixing method significantly affects the electrical properties, morphology, and surface topography. The variation in AC conductivity and surface resistance study confirms the formation of different conductive network of CB with variation in mixing technique and it is supported by morphology analysis. The DMA have shown that CB has higher affinity towards less viscous EVA phase. This is further corroborated by the surface energy measurement, which in turn controls the electrical conductivity behaviour as well as mechanical properties of the blends.     

Polymerization of acrylamide in nonionic microemulsions: Characterization of the microlatices and polymers formed

Free radical polymerization of acrylamide was carried out in nonionic microemulsions of water, an isoparaffinic oil, Isopar M and a blend of nonionic emulsifiers: a sorbitan sesquioleate and a polyoxyethylene sorbitol hexaoleate (HLB of the mixture: 9.3). The size and the stability of the latex particles formed after polymerization were studied as a function of monomer, emulsifier and electrolyte concentration. High emulsifier and high monomer contents favor obtaining high molecular weight polyacrylamides. It is shown that both the number of polymer chains contained in each latex particle and the size of the particles are essentially controlled by the acrylamide/emulsifier weight ratio.     

Deformation and fracture behavior of polystyrene ionomer and ionomer blends

The deformation and fracture behavior of sulphonated polystyrene ionomers, and of blends of these with polystyrene have been investigated. The microstructure of the ionomer, which varies with ion content, appears to have a significant effect on mechanical properties. Both tensile strength and toughness increase appreciably at ion contents near 5 mol%, where clusters become dominant over ion pairs and multiplets. In blends of the ionomers and polystyrene, phase separation occurs and the ionomer component appears in the form of fine particles dispersed in the polystyrene matrix. These particles possess a greater effective entanglement density than the matrix, as a result of ionic crosslinking, and they provide reinforcement against early craze breakdown and fracture. Tensile strength and fracture energy increase rapidly as the ionomer concentration in the blend is increased and they become essentially independent of blend ratio above about 10 wt% of the ionomer. Tests carried out on thin film specimens of the blends show that the dispersed ionomer particles adhere well to the matrix and contribute to the fracture energy both by inducing matrix crazing and by internal fibrillation within the particles.Dedicated to Professor Hans-Henning Kausch on the occasion of his 60th birthday.     

Simultaneous enhancement of electrical conductivity and impact strength via formation of carbon black‐filler network in PP/EPDM Blends

The electrical conductivity and impact strength of polypropylene(PP)/EPDM/carbon black ternary composites were investigated in this paper. Two processing methods were employed to prepare these ternary composites. One was called one‐step processing method, in which the elastomer and the filler directly melt blended with PP matrix. Another one was called two‐step processing method, in which the elastomer and the filler were mixed first, and then melt blended with pure PP. To get an optimal phase morphology that favors the electrical conductivity and impact strength, controlling the distribution of CB in PP/EPDM blend was a crucial factor. Thus the interfacial tension and the work of adhesion were first calculated based on the measurement of contact angle, and the results showed that CB tended to be accumulated around EPDM phases to form filler‐network structure. Expectably, the filler‐network structure was observed in PP/EPDM/CB(80/20/3) composite prepared by two‐step processing method. The formation of this filler‐network structure decreased the percolation threshold of CB particles in polymer matrix, and the electrical conductivity as well as Izod impact strength of the composite increased dramatically. This work provided a new way to prepare polymer composites with both improved conductivity and impact strength. Copyright © 2009 John Wiley & Sons, Ltd.     

Spontaneous film formation from a polymer solution

An unusual continuous film formation process of lateral pentyloxy substituted poly(p-phenylene terephthalate)s (s-PPPT) and poly(carbonate) (PC) is observed. A liquid film of polymer solution creeps over the surface of water dropped into the polymer solution. By vaporization of the solvent a solid polymer film is formed on the water surface and can be removed. The driving force for the film formation mechanism is assumed by the reduction of the surface tension of water. Experiments verify this mechanism by increasing the film formation speed using a gas stream, by reducing the formation speed through lowering the surface tension by rinsing agents, and by lowering the solubility of the polymer. As expected, no effects are found by variation of the pH-value of water. Necessary conditions for the film formation process are: good solubility of the polar polymers in organic solvents having a high vapor pressure, complete phase separation, solution density higher than water density, and a surrounding gas phase unsaturated with solvent vapor.The thickness of the mechanically stable films is less than 0.5 m. The films are amorphous by microscopical, FT-IR, x-ray, and DTA investigations.     

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.     

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     

Volume‐exclusion effects in polyethylene blends filled with carbon black,graphite, or carbon fiber

Conductive polymer composites possessing a low percolation‐threshold concentration as a result of double percolation of a conductive filler and its host phase in an immiscible polymer blend afford a desirable alternative to conventional composites. In this work, blends of high‐density polyethylene (HDPE) and ultrahigh molecular weight polyethylene (UHMWPE) were used to produce ternary composites containing either carbon black (CB), graphite (G), or carbon fiber (CF). Blend composition had a synergistic effect on electrical conductivity, with pronounced conductivity maxima observed at about 70–80 wt % UHMWPE in the CB and G composites. A much broader maximum occurred at about 25 wt % UHMWPE in composites prepared with CF. Optical and electron microscopies were used to ascertain the extent to which the polymers, and hence filler particles, are segregated. Differential scanning calorimetry of the composites confirmed that the constituent polymers are indistinguishable in terms of their thermal signatures and virtually unaffected by the presence of any of the fillers examined here. Dynamic mechanical analysis revealed that CF imparts the greatest stiffness and thermal stability to the composites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1013–1023, 2002