非对称嵌段共聚物PI-b-PB对IR/BR并用胶相形态与性能的影响

主要研究非对称嵌段共聚物PI-b-PB(液体橡胶LIR-390)对异戊橡胶/顺丁橡胶(IR/BR)共混体系相形态、加工性能和力学性能的影响。采用原子力显微镜(AFM)表征IR/BR并用胶的相形态,结果显示,LIR-390能够细化分散相(BR)的尺寸,且使分散相分布更加均匀;但加入过量LIR-390(7份)则会减弱其增容作用,使BR的相尺寸增大。通过哈克旋转流变仪测试IR/BR未硫化胶的流变特征,发现LIR-390能够降低未硫化胶的储能模量(G′),得出在橡胶共混过程中加入LIR-390可以减少加工能耗。利用裂纹生长测试平台分析并用胶的抗疲劳裂纹生长性能,结果表明,LIR-390的增容作用有助于减小分散相的尺寸,从而降低裂纹生长速率;而加入过量LIR-390则会致使开裂加快。     

混炼工艺对SBR/BR/CB共混硫化胶性能的影响

为了研究混炼工艺对最终硫化胶性能的影响,利用HAAKE转矩流变仪对不同配比的丁苯橡胶/顺丁橡胶/炭黑进行混炼,混炼采用两种不同的混炼顺序——一种是炭黑首先与丁苯橡胶(SBR)混炼,然后加入顺丁橡胶(BR)混炼;另一种是BR与炭黑混炼之后再加入SBR进行混炼。对制得共混物进行结合胶含量、拉伸以及动态力学性能测试。结果显示,在相同配比下,炭黑首先跟份数多的富相橡胶混炼可以得到较多的结合胶,有利于体系的补强;动态力学测试结果表明硫化胶的粘弹特性受第一段混炼所用橡胶的影响较大,炭黑与柔顺性较好的BR先混炼,共混体系工艺相容性较好。     

混炼工艺对SBR/BR/CB共混硫化胶性能的影响EI北大核心

为了研究混炼工艺对最终硫化胶性能的影响,利用HAAKE转矩流变仪对不同配比的丁苯橡胶/顺丁橡胶/炭黑进行混炼,混炼采用两种不同的混炼顺序——一种是炭黑首先与丁苯橡胶(SBR)混炼,然后加入顺丁橡胶(BR)混炼;另一种是BR与炭黑混炼之后再加入SBR进行混炼。对制得共混物进行结合胶含量、拉伸以及动态力学性能测试。结果显示,在相同配比下,炭黑首先跟份数多的富相橡胶混炼可以得到较多的结合胶,有利于体系的补强;动态力学测试结果表明硫化胶的粘弹特性受第一段混炼所用橡胶的影响较大,炭黑与柔顺性较好的BR先混炼,共混体系工艺相容性较好。     

增容作用和动态固化对聚丙烯/环氧树脂共混物形态结构的影响

研究了增容作用和动态固化对聚丙烯(PP)/环氧树脂(EP)共混物形态结构的影响。实验结果表明,PP/EP共混物是不相容共混体系,当环氧树脂含量小于50%时,共混物中环氧树脂以分散相存在,PP为连续相。反之,则共混物的相态发生相反转,即环氧树脂为连续相,PP为分散相。加入马来酸酐接枝聚丙烯(M AH-g-PP)促进环氧树脂与PP的相容性,使得分散相的颗粒明显变小。与PP/EP和PP/M AH-g-PP/EP共混物不同,当环氧树脂含量大于50%时,动态固化PP/EP和PP/M AH-g-PP/EP共混物仍是环氧树脂分散相和PP连续相结构,未出现相反转。对于相同含量环氧树脂的共混物,动态固化PP/M AH-g-PP/EP共混物中环氧树脂分散相尺寸明显小于动态固化PP/EP共混物中环氧树脂分散相尺寸。     

天然橡胶/顺丁橡胶共混胶体系裂纹生长行为的形态演变机理

研究了不同共混比例的顺丁橡胶(BR)与天然橡胶(NR)组成的共混胶的裂纹尖端生长行为。采用裂纹扩展在线研究平台(DMA-Crack Growth)、超高速摄像仪、扫描电子显微镜和扫描探针显微镜对裂纹尖端进行实时追踪观测,拍摄不同共混比例的橡胶裂纹尖端的裂纹扩展动态图像。结果表明,共混比例达到m(BR)/m(NR)=50/50时,韧带均匀分布在裂纹尖端,韧带多而细且均匀,可以有效减缓橡胶裂纹扩展速度;橡胶开裂的断面随着BR共混比例的增加,表面形貌由类三角形向扇形形貌过渡。最后讨论了裂纹增长的机理。     

共混型热塑性弹性体的形态结构研究

本文介绍了一种用透射电镜研究共混型热塑性弹性体的制样方法,其与传统方法的不同之处是在染色前先用具有双键的溶剂将试样溶胀。此制样方法对于完全硫化共混型热塑性弹性体是有效的。研究结果证实了SBR/BR/LDPE完全硫化共混型热塑性弹性体是以塑料为连续相,交联了的橡胶颗粒为分散相的形态特征。     

高乙烯基聚丁二烯橡胶与顺丁橡胶共混的研究

研究了不同配比高乙烯基聚丁二烯橡胶(HVBR)与顺丁橡胶(BR)共混体系的性能,并用透射电镜和扭辫分析法考察了共混胶的结构形态。结果表明,两胶共混容易,相容性好,各自的加工性能可通过并用得到改善。BR的加入,使HVBR的低温性能、弹性和耐磨性等得到明显改善,同时保持了HVBR耐老化性好、生热低和抗湿滑性强等优点。共混胶性能非常类似于中乙烯基聚丁二烯橡胶。     

OMMT/PEO-PP复合材料相形态及其透光性能

通过熔融共混制备了有机蒙脱土 (OMMT)/聚氧化乙烯(PEO)- 聚丙烯(PP)复合材料, 采用TEM、 SEM、 DSC、 透光率分析等手段研究了OMMT在PEO-PP共混物中的分布及OMMT对共混物相形态、 OMMT含量对复合材料透光率的影响。结果表明, OMMT选择性分布在PEO分散相内部及两相界面, 对PEO-PP共混物起到增容作用, OMMT 的加入使PEO相粒径得到细化, 粒径尺寸趋于均匀, PP球晶尺寸明显减小, 复合材料的透明性显著增加。      

动态保压注射成型中POE-g-MAH 对PA1010-PP 共混物的增容作用

以马来酸酐接枝乙烯-辛烯共聚物(POE-g-MAH)作为增容剂, 采用熔体共混的方法制备了PA1010-PP共混物, 通过扫描电镜(SEM)、 力学性能和差示扫描量热(DSC)测试, 研究了动态保压注射成型中POE-g-MAH对PA1010-PP共混物的增容作用。力学性能测试结果表明, 在注射成型过程中施加剪切应力, 明显提高了共混物的拉伸和冲击性能。SEM结果表明, 剪切诱导制品产生多层次结构, 而且分散相相区尺寸显著减小, 分散更趋均匀, 相界面更加模糊。DSC结果表明, 剪切应力作用下, 当POE-g-MAH的质量分数达到15%时, PP出现2个结晶峰, 即出现异相成核结晶和均相成核结晶, PP均相成核结晶的出现从另一个方面表明动态试样中分散相PP尺寸小于静态试样。剪切应力作用下增容作用的提高归因于剪切应力作用下独特相形态的形成。      

共混顺序对非对称两嵌段共聚物增容体系微观形貌的影响和机理探究

研究了熔融共混过程中共混顺序对非对称的聚苯乙烯-b-聚甲基丙烯酸甲酯嵌段共聚物(PS-b-PMMA,分别命名为SM1和SM2)增容聚苯乙烯/聚甲基丙烯酸甲酯(PS/PMMA)共混体系微观形貌的影响.扫描电镜(SEM)结果发现:合适的共混顺序可以导致分散相相尺寸的明显降低.为研究其增客机理,还选择了聚甲基丙烯酸环己酯/聚甲基丙烯酸甲酯(PCHMA/PMMA)共混体系,并以SM1为增容剂.透射电镜(TEM)结果发现:当SM1首先与连续相PCHMA混合再与PMMA混合,几乎全部的嵌段共聚物分散在共混界面上,增容效率极大提高;反之,SM1首先与分散相PMMA混合再与PCHMA共混,胶束形成并存在于PMMA相内,未起到增容作用.     

SiO2含量和共混方法对NR/PP共混型热塑性弹性体的影响

采用两种共混方法制备天然橡胶(NR)/聚丙烯(PP)/纳米二氧化硅(SiO2)热塑性弹性体,采用透射电镜(TEM)、动态热机械(DMA)分析、橡胶加工分析仪(RPA)和力学性能测试研究了共混方法和SiO2的填充量对NR/PP/SiO2热塑性弹性体力学性能、形态结构和流变行为的影响。研究结果表明,当纳米SiO2的填充量较低(<3phr),共混方法对SiO2的分散影响较大,当SiO2主要分散在PP基体相中时,其对热塑性弹性体的补强作用明显;随着纳米SiO2的填充量的增加(≥3phr)时,SiO2趋向于分散在NR相中,共混方法对SiO2的分散影响不大。     

Poly(ether ether ketone) with pendent methyl groups as a toughening agent for amine cured DGEBA epoxy resin

A diglycidyl ether of bisphenol-A (DGEBA) epoxy resin was modified with poly(ether ether ketone) with pendent methyl groups (PEEKM). PEEKM was synthesised from methyl hydroquinone and 4,4′-difluorobenzophenone and characterised. Blends of epoxy resin and PEEKM were prepared by melt blending. The blends were transparent in the uncured state and gave single composition dependent T _g. The T _g-composition behaviour of the uncured blends has been studied using Gordon–Taylor, Kelley–Bueche and Fox equations. The scanning electron micrographs of extracted fracture surfaces revealed that reaction induced phase separation occurred in the blends. Cocontinuous morphology was obtained in blends containing 15 phr PEEKM. Two glass transition peaks corresponding to epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum of the blends. The crosslink density of the blends calculated from dynamic mechanical analysis was less than that of unmodified epoxy resin. The tensile strength, flexural strength and modulus were comparable to that of the unmodified epoxy resin. It was found from fracture toughness measurements that PEEKM is an effective toughener for DDS cured epoxy resin. Fifteen phr PEEKM having cocontinuous morphology exhibited maximum increase in fracture toughness. The increase in fracture toughness was due to crack path deflection, crack pinning, crack bridging by dispersed PEEKM and local plastic deformation of the matrix. The exceptional increase in fracture toughness of 15 phr blend was attributed to the cocontinuous morphology of the blend. Finally it was observed that the thermal stability of epoxy resin was not affected by the addition of PEEKM.     

Preparation of composite dispersed phase morphologies in incompatible and compatible blends during melt processing

Most processing/morphology studies of multi-phase polymer blends have been concerned with controlling the size and shape of the dispersed phase. The dispersed phase is generally a pure homo- or copolymer (apart from low levels of interfacial modifier). This paper describes the preparation during melt processing of a complex polymer blend morphology known as a composite dispersed phase system. Microscopically this structure can be seen to be composed of three parts: two distinct phases with sub-inclusions within one of the phases. This system is a type of blend within a blend. Various microscopic techniques are used to show that a composite multi-phase morphology can be prepared in an incompatible polypropylene/ polycarbonate (PP/PC) blend as well as in a compatible polyethylene copolymer/polyamide blend. This structure has been generated at two compositions for polypropylene/ polycarbonate through melt blending. At 50% volume fraction (near the region of dual-phase continuity), simultaneous addition of components results in co-continuous polypropylene and polycarbonate phases with the latter containing small PP spherical sub-inclusions. At 25% PC (volume fraction) the generation of a composite dispersed phase in a polypropylene matrix is obtained by imposing phase inversion followed by controlling the mixing time. The morphology in this case consists of a polypropylene matrix, a polycarbonate dispersed phase and spherical polypropylene sub-inclusions within the dispersed polycarbonate. Partial stabilization of the composite morphology in incompatible blends with mixing time can be obtained through control of the viscosity of the dispersed phase. Polyethylene copolymer/polyamide blends have also been prepared by the phase inversion process and show that strong interfacial interactions between the polyamide sub-inclusions and polyethylene copolymer dispersed phase material results in complete stabilization of the composite dispersed phase morphology with very high retention of sub-inclusions persisting even after long mixing times.     

Morphology, mechanical and thermal behavior of acrylate rubber/fluorocarbon elastomer/polyacrylate blends

Novel thermoplastic elastomers derived from binary and ternary blends of polyfunctional acrylates, acrylic rubber (ACM) and fluorocarbon rubber (FKM) were analyzed by using Transmission Electron Microscopy (TEM), Differential Scanning Calorimetry (DSC), Dynamic Mechanical Thermal Analysis (DMTA) and mechanical tests. TEM revealed the presence of a single-phase structure for both acrylate rubber/fluorocarbon elastomer (ACM/FKM) and ACM/polyacrylate binary blends. Increase of FKM concentration in the ACM/FKM/polyacrylate ternary blend resulted in phase separation of FKM from the ternary blend. The FKM formed a dispersed phase with polynodal particle distribution and irregular shape ranging from ellipsoidal to highly elongated form with inclusion of ACM. The FKM/polyacrylate binary blend showed complete phase separation. Ageing of the blend increased the domain size of the dispersed phase. Differential scanning calorimetric (DSC) and DMTA studies showed no major changes in the T _gs of individual polymers in the blend, although the peak tan values were affected on changing the composition of the blends. Vulcanization of the thermoplastic elastomer (TPE) changed the phase morphology with increase in particle size. There is a distinct difference in morphology of statically and dynamically vulcanized blends.     

Effect of liquid additives on morphology and properties of thermoplastic elastomers prepared from phase-modified EPDM elastomer and isotactic polypropylene blends

Thermoplastic elastomers (TPEs) were prepared from ternary blends of ethylene propylene diene poly methylene rubber (EPDM), isotactic polypropylene (PP), and low loadings (5–10 phr) of different types of interfacial phase modifiers (like maleated EPDM, styrene-ethylene-co-butylene-styrene block copolymer, and maleated PP). These showed much improved physico-mechanical properties compared to the binary blend of EPDM-PP. The effects of non-polar paraffin oil and polar di-octyl phthalate liquid additives (5–20 phr) were investigated in these phase-modified ternary and binary EPDM-PP blends. Only 5 phr of liquid additives provided synergistic improvement in physical properties (maximum stress, modulus, and elongation at break) and generated improved finer morphology of the ternary blends as revealed from scanning electron and atomic force microscopy studies. Enhanced physical properties and dynamic mechanical properties of these blends were explained with the help of better phase morphology and enhanced crystallinity of the blends.     

High-shear effects on the nano-dispersed structure of the PVDF/PA11 blends

The fabrication of miscible or nanostructured polymer blends or alloys raises much hope, but poses significant scientific and industrial challenges over the past several decades. Here, we propose a novel strategy using high-shear processing and demonstrate the high-shear effects on the nanodispersed structure formed in the poly(vinylidene fluoride) (PVDF)/polyamide 11 (PAll) blends, in which PA11 domains with a size of several tens of nanometers are dispersed in the PVDF phase. For the blend of PVDF/PA11 = 65/35, the TEM image shows that many nanometer-sized PAl1 particles are dispersed in the PVDF domain to form a special type of domain-in-domain morphology. In contrast, no PVDF nano-dispersion was observed in the PA11 phase. The effects of both the screw rotation speed and the mixing time on the blend structure were systematically studied. It shows that the extruder screw rotation speed and the mixing time are two critical factors to prepare the nanostructured blends. In addition, the investigations on the thermal behavior of the obtained blends indicate the improved miscibility between PVDF and PAl1 by the high shear processing.     

Microstructural,thermal and rheological correlations to mechanical response of polyamide-6(glass filled)/polyetherimide blend: effect of ethylene-octene copolymer on toughening of blend

Melt mixed glass-filled polyamide 6(PA6)/polyetherimide (PEI) blends were prepared in a co-rotating twin screw extruder over the entire composition range of 0–100 wt% of polyamide 6. These blends were characterized by structural, rheological, mechanical and thermal properties. Crystallization behavior and phase morphology of the blends were also investigated. The blend with the composition PA6/PEI 75/25 showed overall improved mechanical properties along with low resultant viscosity which can be processed on standard equipment. Shear viscosity along with shear stress of the blends were analyzed using shear rheometer which concluded that the blends can be processed on standard equipment due to resultant low viscosity. Scanning electron microscope micrographs revealed that the morphology of the blends showed a two phase structure in which the minor phase was dispersed as domains in the continuous phase. Polyolefin elastomer (POE) as impact modifier was added to the above composition in the range of 0–15 phr to study its effect. The thermal characteristics of PA6, PEI, and PA6/PEI blends with and without POE were investigated using DSC and TGA which revealed that the melting temperature and crystallization temperature of the blend remained unchanged while XRD results showed percent crystallinity was increased slightly. Furthermore, it can be said that the blend with composition PA6/PEI 75/25 with 10 phr impact modifier loading was suitable for high end applications because it combines the high mechanical properties of glass-filled PA6 with inherent flame-retardant property of PEI while POE overcomes the physical weakness of moisture absorption.     

Gamma irradiation aging of NBR/CSM rubber nanocomposites

The effect of gamma-irradiation on the acrylonitrile butadiene/chlorosulphonated polyethylene rubber blends (NBR/CSM) based nanocomposites containing carbon black (CB) and silica filler (Si) were investigated by TG-DTG and ATR-FTIR techniques. The silica (with primary particle size of 22 nm) was added in content of 0, 10, 20 and 30 phr and carbon black (with primary particle size 40–48 nm) was added in content of 30 phr and rubber blend compounds were prepared. The obtained elastomeric materials were aging to different γ-irradiation doses (100, 200 and 400 kGy). The cure and mechanical properties of obtained nanocomposites were determined. Incorporating 20 phr of silica to the control NBR/CSM rubber blends containing 30 phr CB resulted 152% increase in tensile strength, 116%, in elongation at break and 142% modulus at 100% elongation, according to synergistic effect between the fillers. FTIR measurements of aged samples estimated the formation of alcohols, ethers and small amounts of lactones, anhydrides, esters and carboxylic acids after exposure to lower doses of γ-radiation (100 kGy). On the basis of the obtained spectra the formation of shorter polyene sequences and aromatic rings in aged elastomeric samples are assumed. The results show that 30 phr of carbon black (CB) and 20 phr of silica are needed for the best gamma aging resistance of NBR/CSM rubber nanocomposites. The result of radiation exposure is decrease in mechanical properties. The dose at which ultimate mechanical properties decreased was at 200 kGy. TG-DTG measurements estimated decrease in thermal stability of gamma-irradiated NBR/CSM rubber blend based nanocomposites. Silica reinforced NBR/CSM rubber blend had better radiation resistant than carbon black. Rough and heterogeneity of fracture surfaces has been observed for NBR/CSM rubber blends filled with silica. More uniform morphology of fracture surfaces according to high polymer–filler interaction and low filler–filler interaction has been observed for CB/Si filled NBR/CSM rubber blend.     

Effect of crosslinking on morphology and phase inversion of EPDM/PP blends

This study investigates the effect of cross-linking on morphology and phase inversion of EPDM/PP blends. Several EPDM/PP blends without and with cross-linking agent were prepared in a Haake batch mixer under constant conditions. The morphology was studied by electronic microscopy (SEM and TEM), and cross-linking was followed by EPDM gel content and swelling. The results showed that the position of the phase inversion region is essentially governed by composition, being independent of the viscosity ratio of the EPDM/PP blend. The TPVs’ morphology of the EPDM/PP blend, with 70 and 50 wt% of PP, consists of EPDM cross-linked particles dispersed in the PP matrix. For EPDM-rich composition (30 wt% of PP), the TPVs’ morphology appears to be co-continuous. Even though dynamic vulcanisation of the rubber phase always improves the dispersion of the EPDM phase, complete phase inversion (from fully dispersed PP in the EPDM matrix to EPDM fully dispersed in the PP matrix) was achieved only with low viscosity EPDM.