Effects of microstructure on crack tip fields and fracture toughness in PC/ABS polymer blends

Numerical simulations are performed in order to gain a better understanding of the effects of various microstructural features and toughening mechanisms in amorphous PC/ABS polymer blends. Crack tip loading under global small-scale yielding conditions is considered with the blend microstructure explicitly resolved in the near-tip process zone. Constitutive models are employed which account for large visco-plastic deformations, the characteristic softening- rehardening behavior of glassy polymers, as well as the effect of plastic dilatancy in the ABS phase due to rubber particle cavitation. The influence of blend composition and morphology on the local stress distribution and the development of the plastic zone at a stationary crack tip are analyzed. Furthermore, crack propagation and the evolution of fracture toughness are studied using different cohesive surface models for failure in the different phases of the blend microstructure.     

PB-g-SAN接枝共聚物的接枝率对ABS树脂结构与性能的影响

采用种子乳液聚合技术在聚丁二烯(PB)乳胶粒子上接枝共聚单体苯乙烯(St)和丙烯腈(AN),通过改变PB的含量合成了一系列具有不同接枝率的PB-g-SAN接枝共聚物(即ABS接枝共聚物),将其与SAN树脂进行熔融共混制得ABS树脂,考察了ABS接枝共聚物的接枝率对ABS树脂结构和性能的影响。结果表明,SAN共聚物在PB橡胶粒子上的接枝可分为‘内接枝’和‘外接枝’,外接枝程度影响PB橡胶粒子在SAN基体中的分散,而内接枝程度显著地影响PB橡胶粒子的内部形态结构。通过抑制内接枝,可提高ABS树脂的冲击韧性和拉伸强度;提高外接枝程度可改善ABS树脂的断裂伸长率。     

阴离子聚合尼龙6/ABS合金的制备与性能

采用缩二脲（HDI）封端端羟基丁腈橡胶预聚物,制备大分子橡胶改性活化剂,以氢氧化钠为催化剂,选择不同配比的ABS树脂加入熔融己内酰胺单体中,确定聚合温度为160℃~180℃,通过阴离子聚合制得ABS/尼龙6（PA6）共混物。在原位合成ABS改性尼龙体系中,以橡胶改性剂作为ABS与尼龙的相容剂,当ABS用量为m（ABS）...     

Computational modeling of rubber-toughening in amorphous thermoplastic polymers: a review

The fracture behavior of rubber-toughened polymers is governed by two dissipative microscopic deformation and damage mechanisms: matrix shear yielding and crazing. These mechanisms are strongly interconnected with the eventual cavitation of the fine dispersed rubber particles. The present work summarizes and discusses a variety of micromechanical–computational modeling approaches undertaken over the past twenty years aiming at an improved understanding of the relation between microstructure and toughening in this class of materials. The focus is on materials such as ABS where both mechanisms are prevalent.     

回收ABS树脂的性能提升

分析了回收ABS树脂在使用过程中的老化机理,老化导致了橡胶相的损失、分子量的降低和相分离,表现为抗冲性能大幅下降,拉伸强度、弯曲模量及热变形温度和耐候性均有一定程度的下降.基于此,提出了高胶粉/无机纳米粒子复合改性方案,添加5%～8%的高胶粉和2%～3%无机纳米粒子,可以大幅提升回收ABS树脂的韧性,同时兼顾了材料的刚...     

ABS增韧树脂的本体法制备和力学性能

以聚丁二烯橡胶为增韧剂,用本体聚合方法合成了一系列丙烯腈-丁二烯-苯乙烯三元共聚物(ABS),并研究其力学性能。结果表明:高顺胶BR9004的增韧效果最好,IZOD缺口冲击强度高达236.1 J/m,与低顺胶700A的复合可使后者的综合力学性能提高(可与高桥8434牌号产品相媲美);随着丙烯腈含量和树脂相分子量的增加,材料的IZOD缺口冲击强度、拉伸强度和断裂伸长率均有所提高;而树脂的拉伸强度则随着橡胶含量的增加而降低;在橡胶含量低于20%时冲击强度随着橡胶含量增长迅速,高于20%时增长缓慢。     

Preparation, microstructure and properties of ABS resin with bimodal distribution of rubber particles

A novel ABS resin with bimodal distribution of rubber particles (BM-ABS) was prepared by bi-seeded emulsion grafting copolymerization (Bi-SEGP) using two different size polybutadiene (PB) particles (320 nm and 575 nm) as seeds. For property comparisons, a model ABS resin with unimodal distribution of rubber particles (UM-ABS) was prepared by only using 320 nm PB particles as seeds. Microscopical morphology of BM-ABS and UM-ABS was observed by transmission electron microscope (TEM). The results showed that BM-ABS possessed higher properties than UM-ABS. Specifically, keeping the same rubber content, BM-ABS had higher toughness than UM-ABS and almost the same rigidity as UM-ABS; keeping the same toughness, BM-ABS had higher rigidity and needed less rubber content than UM-ABS. The synergistic effect of the bigger and the smaller rubber particles was the essential reason why BM-ABS displays improved properties than UM-ABS.     

废旧橡胶热-机械剪切脱硫过程及机理

利用元素分析仪、红外光谱仪研究了废旧橡胶热-机械剪切脱硫过程及其机理。在未加任何脱硫剂的情况下,利用双螺杆挤出机提供的热能和强剪切作用对硫化橡胶进行了脱硫回收,研究发现,硫化橡胶的交联密度下降到71%,恢复了再加工性能,并且微观结构也发生了显著的变化。提出了交联硫键断裂后以活性硫侧挂基形式存在的理论,解释了再生胶脱硫后不需外加硫磺仍可以硫化的现象。溶胶的红外光谱给这一理论提供了有力的证明。根据脱硫反应前后官能团的变化推测出脱硫反应可能的机理。     

Fracture resistance of polyblends and polyblend matrix composites: Part II Role of the rubber phase in Nylon 6,6/ABS alloys

A comprehensive study was undertaken on the specific role of rubber on toughening when other rigid polymer or non-polymer phases were present. Nylon 6,6/SAN blends of various SAN concentrations ranging from pure SAN to pure nylon 6,6 were investigated with and without fibre reinforcements. These results could be compared with the toughness values of unreinforced and fibre-reinforced nylon 6,6/ABS alloys from a previous study in order to elucidate the role of rubber. Fracture behaviour was investigated rigorously by characterizing the fracture initiation toughness, JIC, and the steady-state fracture toughness, Jss. These were then related to the microstructure and failure modes determined by microscopy and fractography methods. It was found that rubber increased both fracture initiation and propagation toughness in the presence of the rigid phase, while the rigid phase toughened the alloy only when the rigid phase/matrix interface was strong enough. The role played by glass fibres was found to be critically related to the fibre/matrix interfacial strength. Toughening was generally observed, both in the presence and absence of rubber, when the interface was strong. In all cases toughening could be related to the enhancement of plasticity in the crack tip by the presence of the rubber phase or the reinforcing glass phase. This revised version was published online in November 2006 with corrections to the Cover Date.     

老化对改性沥青微观结构及疲劳性能的影响

为了研究老化对改性沥青微观结构及疲劳性能的影响,通过沥青常规指标测试试验、动态剪切流变（DSR）试验和AFM测试试验,从宏细观角度分析了老化前后苯乙烯-丁二烯-苯乙烯三嵌段共聚物（SBS）改性沥青和胶粉改性沥青的针入度、延度和软化点及疲劳性能、微观结构的变化情况。结果表明：随着老化程度的加深,两种改性沥青的稠度、硬度增加,高温性能得到改善,而温度敏感性变低,低温抗裂性能变差。综合分析针入度比、延度比和软化点比得出胶粉改性沥青的抗老化性能优于SBS改性沥青;随温度的降低、频率的增大和老化程度的加深,两种改性沥青的抗疲劳性能变差;微观结构观测结果显示,SBS改性沥青具有"蜂型结构",老化后"蜂型结构"的体积增大、高度增加、数量减少;胶粉改性沥青没有"蜂型结构",胶粉颗粒与沥青在共混共融过程中发生溶胀、脱硫和降解等行为会影响沥青中"蜂型结构"的形成;老化前后胶粉改性沥青表面形貌粗糙度和高度变化不大;胶粉改性沥青的抗疲劳、抗老化和高温性能总体优于SBS改性沥青。     

PC／ABS共混物形态的研究

研究了PC/ABS共混物的抗冲击样条的切片形态和取向程度。结果表明:共混物中接技橡胶粒子是包藏在SAN相中的。PC/ABS=25/75时,PC为分散相并呈粒状沿注射方向拉长。PC/ABS=75/25时,ABS为分散相并沿注射方向呈纤维状和层状。PC/ABS=50/50时,PC和ABS都为连续相且沿注射方向呈层状排列。原料对共混物形态和取向有影响,其中以ABS的影响最为显著。     

Fracture resistance of polyblends and polyblend matrix composites Part III Role of rubber type and location in nylon 6,6/SAN composites

The role of rubber particle type, location and morphology on toughening in blends of nylon 6,6 with styrene acrylonitrile (SAN), with and without fibre reinforcements was examined in this study. The rubber used was ethylene propylene diene monomer (EPDM) rubber and the results were compared to a previous study that used butadiene rubber. The compositions of the blends ranged from pure nylon 6,6 to pure SAN. EPDM rubber was chemically compatibilized with one of the matrix phases rather than grafted, as in the ABS. In order to study the effect of rubber location on fracture behaviour, the approach was to compatibilize EPDM with either the minor phase or the major phase component of the blend. Attention was focused on fracture initiation toughness and fracture propagation toughness, measured through the parameters J _IC and J _SS, respectively. J _SS refers to the steady-state, or plateau value of the material R-curve and was therefore a measure of total toughness which included the additional component derived from crack extension. The results indicated that EPDM rubber was not as effective a toughening agent as was butadiene in the Acrylonitrile Butadiene Styrene (ABS) system, primarily due to the morphology of EPDM and its interface character with the nylon 6,6 or SAN matrix. It was demonstrated that the embrittlement effects of a second rigid polymer phase can be mitigated by selectively adding rubber to that phase in the alloy or blend. With regard to the role of fibre reinforcement, a strong fibre matrix interface was found to be essential for toughening. Further, the extent of rubber toughening was larger when fibres were present than when fibres were absent, provided the fibre matrix interface was strong. Fibres also, like rubber, enhanced local matrix plasticity as well as reduced the embrittlement effects associated with a second polymer phase.     

ABS/改性纳米CaCO3复合材料的微观结构和力学性能

制备了改性纳米CaCOa／ABS复合材料,采用SEM和TEM对复合材料的微观结构进行了分析,同时,对复合材料的力学性能进行了考察。结果表明,改性纳米CaCO3可以在ABS塑料中与树脂充分结合,同时改性纳米CaCO3在复合材料中呈纳米分散。复合材料的断面产生了大量的网状结构。分散在丙烯腈一丁二烯一苯乙烯共聚物(ABS)中的改性纳米CaCO3可提高复合材料的裂缝引发能和裂缝增长能。其单缺口冲击强度达到36．77kJ／m^2,与未添加纳米CaCO3的相比提高了44％;邵氏硬度达到34．87N,提高了23．5％。     

PA-6/ABS共混体系中加入SMA的反应型增容作用

加入少量苯乙烯－马来酸酐共聚物,能改善苯不相容的尼龙－６／ＡＢＳ共浊 系的相容性,提高其力学性能。文中共混物的熔体流变性能,ＤＳＣ表征及相结构观察,表明相容性的改善是在熔融共混过程中ＳＭＡ在ＰＡ－６和ＡＢＳ界面的的接枝反应得以实现。     

橡胶件在燃油中腐蚀溶胀性的对比

将丁腈、氢化丁腈、氟橡胶分别浸泡在乙醇、柴油、生物柴油中,测量每组样件的直径、质量和硬度值,计算其变化率,并采用扫描电镜对腐蚀溶胀后的橡胶件进行微观形貌结构分析。结合测量数据与扫描分析结果,分析材料间极性的差异对橡胶腐蚀溶胀的影响。结果表明,样件上述各参数变化率与微观形貌变化一致,氟橡胶在柴油中变化率最低,抗腐蚀溶胀效果最佳。     

胺基化反应增容PC/ABS共混物

采用熔融共混方法制备了ABS树脂接枝马来酸酐接枝共聚物(ABS-g-MAH),将接枝共聚物与1-(2氨乙基)哌嗪反应制备了增容剂,通过红外光谱表征确定了预期反应的发生.将增容剂部分替代聚碳酸酯(PC)/ABS共混物中的ABS树脂,考察了增容剂对PC/ABS共混物的力学性能的影响.结果表明,加入增容剂后,PC/ABS共混...     

Modes of deformation in rubber-modified thermoplastics during tensile impact

Real-time small-angle X-ray scattering (RTSAXS) studies were performed on a series of rubber-modified thermoplastics. Scattering patterns were measured at successive time intervals as short as 1.8 ms and were analysed to determine the plastic strain due to crazing. Simultaneous measurements of the absorption of the primary beam by the sample allowed the total plastic strain to be computed. The plastic strain due to other deformation mechanisms, e.g. particle cavitation and macroscopic shear deformation was determined by the difference. Samples of commercial thicknesses can be studied at high rates of deformation without the inherent limitations of microscopy and its requirement of thin samples (i.e., plane strain constraint is maintained on sample morphology). Contrary to the conclusions drawn from many previous dilatation-based studies, it has been demonstrated that the strain due to non-crazing mechanisms, such as rubber particle cavitation, and deformation of the glassy ligaments between rubber particles, occurs before that due to crazing mechanisms. Crazing accounts for at most only half of the total plastic strain in HIPS (high impact polystyrene) and ABS (rubber-modified styrene-acrylonitrile copolymer) materials. The proportion of strain attributable to crazing can be much less than half the total in thermoplastic systems with considerable shear yield during plastic deformation. The predominant deformation mechanism in polycarbonate-ABS blends is shear in the PC (polycarbonate) with associated rubber gel particle cavitation in the ABS. This cavitation means that there appears to be a direct relationship between gel particle rubber content in the ABS and toughness of the blend. The mechanism is the same whether the tensile stress is in the direction parallel or perpendicular to the injection-moulded orientation, with simply less total strain being reached before fracture in the weaker perpendicular direction. Crazing, although the precursor to final fracture, occurs after the predominant mechanism and contributes only a few per cent to the total plastic deformation.     

ABS塑料表面化学镀镍无钯活化工艺研究

提出了一种非金属表面化学镀镍无钯活化工艺,即在常温下,以NaBH4为还原剂,在ABS塑料上沉积活性镍,以此活性镍为活化中心,进行化学镀镍.研究确定了活化液的最佳配方,并利用均匀设计方法确定了在ABS塑料表面化学镀镍最佳工艺条件为:19g/L Ni(Ac)2·4H2O,22g/LNaH2PO2,0.02 mL/L N2H4·H2O,40 mg/L糖精;镀液pH值5.0～5.6,温度70～80℃.采用SEM、XRD、EDS等手段对镀层的形貌、结构、成分及含量进行了表征.结果表明:所得镀液稳定,镀速快,镀镍层均匀,结合力强,说明在ABS塑料表面用该无钯活化新工艺取代钯活化是可行的.     

有机硅对天然乳胶的改性研究

采用复合阳离子型乳液聚合制备出一种带正电荷的有机硅乳液,通过杂凝聚共混和接枝两种不同的改性方法对带负电荷的天然乳胶进行改性,并比较了两种改性方法对胶膜力学性能、耐溶剂性、耐水性、表面形貌等的改性效果。结果表明,与纯天然乳胶膜相比,改性后胶膜的断裂伸长率均有提高,在石油醚中的增重率降低,表面水接触角增大,改性后胶膜的表面更加平整致密,其中共混改性对水接触角影响较大,接枝改性对力学性能、耐溶剂性、表面形貌的改性效果更为显著。其在工业生产医疗制品,如医用胶管、医用手套及避孕套等领域具有广泛的应用前景。