The experimental results and simulation of temperature dependence of brittle‐ductile transition in PVC/CPE blends and PVC/CPE/nano‐CaCO3 composites

The effect of chlorinated polyethylene (CPE) content and test temperature on the notched Izod impact strength and brittle‐ductile transition behaviors for polyvinylchloride (PVC)/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites is studied. The CPE content and the test temperature regions are from 0–50 phr and 243–363 K, respectively. It is found that the optimum nano‐CaCO₃ content is 15 phr for PVC/CPE/nano‐CaCO₃ ternary composites. For both PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites, the impact strength is improved remarkably when the CPE content or test temperature is higher than the critical value, that is, brittle‐ductile transition content (C_BD) or brittle‐ductile transition temperature (T_BD). The T_BD is closely related to the CPE content, the higher the CPE content, the lower the T_BD. The temperature dependence of impact strength for PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites can be well simulated with a logistic fitting model, and the simulation results can be illustrated with the percolation model proposed by Wu and Jiang. DMA results reveal that both PVC and CPE can affect the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. When the CPE content is enough (20 phr), the CPE is more important than PVC for determining the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. Scanning electron microscopy (SEM) observations reveal that the impact fractured mechanism can change from brittle to ductile with increasing test temperature for these PVC systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of impact load‐temperature conformity on toughening of poly(vinyl chloride) by core‐shell rubber particles

The work focused on the elucidation of several key parameters in toughening poly(vinyl chloride) (PVC) by the methyl methacrylate–butadiene–styrene (MBS) core‐shell particles. Accordingly, blends containing various weight percent of the MBS particles were prepared and characterized by dilute solution viscometry, dynamic light scattering, dynamic mechanical thermal analysis, transmission electron microscopy, and temperature variable impact test. The results showed PVC/MBS solution miscibility in almost all compositions with their maximum thermodynamic affinities at about 17 and 67 wt % of MBS in tetrahydrofurane (THF). In addition, MBS weight percent increase in its blend with the PVC above 10 led to severe impact energy raise with eventual leveling at about 17 wt %. Furthermore, blend toughness and its components miscibility in solution increased in parallel up to 20 wt % of MBS particles. On the other hand, blend toughness declined with test temperature decrease toward impact modifier core T_g at about ?30°C even for the sample with 20 wt % of the MBS particles. Finally, the brittle‐ductile transition of the blend containing 20 wt % of the MBS particles comparison with its matrix tan δ‐temperature correlation implied 2500 J/m impact energy equivalence with 90°C sample temperature rise in secondary relaxation activation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of core‐shell acrylate particles on impact properties of chlorinated polyethylene/polyvinyl chloride blends

The impact properties of core‐shell acrylate (CS‐ACR)/chlorinated polyethylene (CPE)/poly(vinyl chloride) (PVC) blends under different temperatures were investigated. The fracture surface morphologies of the blends were observed by scanning electron microscopy (SEM). The results show that there exists significant synergistic effect between CS‐ACR particles and CPE in toughening PVC, and the impact properties of the blends generally correlate well with SEM morphologies. Besides, with increasing CS‐ACR content, ductile–brittle transition point of the ternary blends remarkably shifts to a lower temperature. Dynamic mechanical analysis exhibited that intensity and area of low‐temperature tan δ peaks of the CPE/PVC blends increase obviously after the addition of CS‐ACR particles, which to some extent are just in line with the changes in impact strength and ductile–brittle transition point of the blends. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Fracture behavior of poly(vinyl chloride)/methyl methacrylate/butadiene/styrene polymer blends

The fracture mode of poly(vinyl chloride)/methyl methacrylate/butadiene/styrene (PVC/MBS) polymer blends can change from ductile to brittle in accordance with the changes in shape of the test specimen or test conditions. Therefore, the mechanisms of impact energy absorption and the main cause of stress whitening are complicated. The following results on PVC/MBS blends were obtained by carrying out fracture experiments at different test speeds and temperatures:

• (1) The ductile/brittle fracture mode of the PVC and PVC/MBS blends can be explained by σ (the craze initiation stress)/σ_y (the shear yield initiation stress), which depends on the strain rates and temperature.
• (2) The fracture behavior of the PVC/MBS blends can be classified into the following types from the standpoints of fracture mode and whitening degree: Fracture I: ductile fracture without whitening; Fracture II: ductile fracture with whitening; and Fracture III: brittle fracture without whitening.
• (3) The following concepts can be estimated from the measurements of yield stress, specific gravity and SEM, TEM and visual observations. In Fracture I, shear yield occurs mainly. In Fracture II, both shear yield and crazing occur. In Fracture III, deformation of the rubber and local crazing occur.
• (4) The main cause of stress whitening in PVC/MBS blends is light scattering by cavities in the rubber particles.
• (5) In Fracture II, at first, crazes with cavities in the rubber particles occur. Then, shear yield occurs. Finally, crazes are healed by the heat, and only the cavities in the rubber remain.

     

Effect of compatibilizer in acrylonitrile‐butadiene‐styrene toughened nylon 6 blends: Ductile–brittle transition temperature

The ductile–brittle transition temperatures were determined for compatibilized nylon 6/acrylonitrile‐butadiene‐styrene (PA6/ABS) copolymer blends. The compatibilizers used for those blends were methyl methacrylate‐co‐maleic anhydride (MMA‐MAH) and MMA‐co‐glycidyl methacrylate (MMA‐GMA). The ductile–brittle transition temperatures were found to be lower for blends compatibilized through maleate modified acrylic polymers. At room temperature, the PA6/ABS binary blend was essentially brittle whereas the ternary blends with MMA‐MAH compatibilizer were supertough and showed a ductile–brittle transition temperature at ?10°C. The blends compatibilized with maleated copolymer exhibited impact strengths of up to 800 J/m. However, the blends compatibilized with MMA‐GMA showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2643–2647, 2003     

氯乙烯共聚弹性体对聚氯乙烯的改性及性能影响

以氯乙烯-丙烯酸丁酯-甲基丙烯酸甲酯共聚弹性体（VCE）增韧改性PVC树脂提高聚氯乙烯（PVC）的抗冲击性能,并与传统抗冲击改性剂甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物（MBS）、ACR及氯化聚乙烯（CPE）改性的PVC材料比较。对改性PVC的流变性能、力学性能、热变形性能及断面结构进行表征和微观观察。结果表明,随着VCE含量的增加,PVC的拉伸强度与弯曲强度逐渐减小,抗冲击强度与断裂伸长率逐渐增加,热变形温度逐渐降低;在相同用量的条件下,VCE对 PVC的改性效果优于ACR及CPE,达到MBS改性PVC的水平,VCE能够增韧PVC,提高PVC的抗冲击性能,是一种性能优异的新型PVC抗冲击改性剂。     

Toughening of polyvinylchloride by methyl methacrylate–butadiene–styrene core–shell rubber particles: Influence of rubber particle size

An analysis was made on the effects of rubber particle size on the mechanical properties and deformation mechanisms of transparent polyvinyl chloride (PVC) blends containing core–shell methyl methacrylate–butadiene–styrene (MBS) impact modifiers. The critical interparticle distance was found not to be the criterion for the brittle‐ductile transition in the blends. In tensile tests, the blends with larger (100–280 nm) rubber particles exhibited intense stress‐whitening, while one blend with small (83 nm) rubber particles showed only slight stress‐whitening. These differences were due to an increase in resistance to cavitation with decreasing rubber particle size. Transmission electron microscopy studies on blends with a bimodal distribution of particle sizes showed that in the whitened zone of Izod specimens the larger rubber particles cavitated and expanded on yielding, while the smaller particles remained intact. However, Izod test results showed that small MBS rubber particles can toughen the PVC matrix very effectively, especially at low temperatures and at low rubber concentrations. The deformation mechanisms responsible for these effects were discussed. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

核—壳共聚物对光盘级聚碳酸酯的增韧研究

研究了甲基丙烯酸甲酯－丁二烯－苯乙烯共聚物（MBS）对光盘级聚碳酸酯的增韧作用，结果表明，MBS对PC增韧效果显著，且MBS分散性越好，达到晚一韧转变时所需的MBS含量越少，求得达到脆－韧转变时的临界粒间距为50nm，对共混物损伤机制的研究表明，MBS增韧PC共混物的增韧机理为MBS粒子的空洞化引发基体的剪切屈服。     

Blends of poly(vinyl chloride) (PVC)/natural rubber‐g‐(styrene‐co‐methyl methacrylate) for improved impact resistance of PVC

To improve the mechanical properties of poly(vinyl chloride) (PVC), the possibility of combining PVC with elastomers was considered. Modification of natural rubber (NR) by graft copolymerization with methyl methacrylate (MMA) and styrene (St) was carried out by emulsion polymerization by using redox initiator to provide an impact modifier for PVC. The impact resistance, dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM) of St and MMA grafted NR [NR‐g‐(St‐co‐MMA)]/PVC (graft copolymer product contents of 5, 10, and 15%) blends were investigated as a function of the amount of graft copolymer product. It was found that the impact strength of blends was increased with an increase of the graft copolymer product content. DMA studies showed that NR‐g‐(St‐co‐MMA) has partial compatibility with PVC. SEM confirmed a shift from brittle failure to ductility with an increase graft copolymer content in the blends. The mechanical properties showed that NR‐g‐(St‐co‐MMA) interacts well with PVC and can also be used as an impact modifier for PVC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1666–1672, 2004     

PVC抗冲改性剂及其进展

介绍了ＰＶＣ抗冲改性剂的国内外状况和技术进展。预计了２０００年我国ＰＶＣ需要抗冲改性剂６．５－７万Ｔ，建议我国搞好ＣＰＥ应用研究大规模生产ＡＣＲ和ＭＢＳ抗入性剂。     

Ductile‐to‐brittle transition behavior of low molecular weight polycarbonate under carbon dioxide

We investigated the stress–strain behavior of low molecular weight polycarbonate for optical disc grade (OD‐PC) under carbon dioxide (CO₂) at various pressures, and compared the results with that under ambient pressure at various temperatures. Elongation at break decreased sharply with increased CO₂ pressure at around 2 MPa, while the elastic modulus decreased gradually up to 6 MPa. These results indicate that the tensile property changed from ductile to brittle with increased CO₂ pressure, although the molecular motion is accelerated due to the plasticization effect of CO₂. Such ductile‐to‐brittle transition is similar to that observed under elevated temperatures caused by chain disentanglement due to accelerated molecular motion. Although the changes of tensile properties were similar, the craze structure obtained by the brittle behavior was different, i.e., a filamented‐craze structure was obtained under high‐pressure CO₂, while a lace‐like one was obtained under elevated temperatures. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

我国PVC抗冲击改性剂的生产及市场概况

叙述了目前国内PVC抗冲击改性剂的生产与需求现状，并对CPE、MBS、ACR、ABS、EVA等常用改性剂的性能、生产现状、发展前景等进行了分析，指出了CPE改性剂在国内仍占主导地位，MBS在未来的生产装置及生产能力都较有较大发展，而ACR在国外的前景看好。     

Impact modification of poly(vinyl chloride) with chlorinated polyethylene I. Blend morphology

The solid state morphology of chlorinated polyethylene (CPE)-modified poly(vinyl chloride) (PVC) and the relationship of blend structure to impact strength and mode of fracture have been investigated. Selective staining of the CPE phase showed that the morphology of the two phase system changes with increasing CPE content from a dispersion of discrete CPE particles to a network structure enveloping the primary PVC particles. The network formation coincides with a transition from brittle to ductile impact fracture. When the blend was mixed for too long a time or above the fusion temperature of the primary PVC particles, the CPE network was destroyed. The resulting indistinct domain structure is associated with a reduction in the impact properties.     

The effects of frequency on fatigue threshold and crack propagation rate in modified and unmodified polyvinyl chloride

The cyclic fatigue crack behavior of polyvinyl chloride (PVC), with (PVC‐M) and without (PVC‐U) chlorinated polyethylene (CPE) impact modifier, was studied. The effect of impact modifier upon fatigue crack growth rate and threshold was evaluated at frequencies of 1, 7, and 20 Hz. It was shown that the addition of CPE lowered the threshold stress intensity factor amplitude for crack growth (ΔK_th) of PVC‐M compared to that of PVC‐U at lower frequencies, and that the effect became more pronounced at lower frequency. At lower stress intensity factor amplitudes (below ΔK = 1 MPa·m^1/2), there was a slight difference between the crack growth rates of U‐ and M‐PVC. The crack advance mechanism is investigated by microscopic observation of the crack tip process zone. Although the zone is relatively large in PVC‐M, associated with higher toughness, it did not improve the fatigue crack growth resistance significantly. Fracture surface observations reveal a higher density of fibrils on the fatigued surface of PVC‐M with the density, relative to that observed in PVC‐U, reducing with frequency. It is therefore hypothesized that accelerated fibril failure is a mechanism of fatigue. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

弹性体/刚性粒子协同增韧PVC研究

研究了不同组成的聚氯乙烯(PVC)树脂/耐热改性剂/(甲基丙烯酸甲酯/丁二烯/苯乙烯)共聚物(MBS)复合体系的力学性能和耐热性能,用扫描电子显微镜分析共混材料的冲击断面微观形态,用动态热机械分析仪测定其动态热力学性能.结果表明,在PVC中添加8份MBS、10份耐热改性剂时共混材料的力学性能和耐热性能达到一个均衡值,冲击断面出现了明显的"须根"现象,PVC材料由脆性断裂转变为韧性断裂,二者协同作用既提高了共混材料的韧性,又改善了其耐热性能.     

The influence of the internal structure of core–shell particles on poly(vinyl chloride)/(methyl methacrylate–butadiene–styrene) blends

Methyl methacrylate–butadiene–styrene (MBS) core–shell particles were prepared by grafting styrene and methyl methacrylate onto polybutadiene seeds via emulsion polymerization. All the MBS particles were designed with the same chemical composition, similar grafting degree but different internal structures. The difference in internal structure was realized by controlling the ratio of ‘external grafting’ and ‘internal grafting’ of styrene. The work focused on the influence of the internal structure of MBS core–shell particles on the properties of poly(vinyl chloride)/MBS blends. From transmission electron microscopy, three different internal structures were observed: rare sub‐inclusions, a large number of small sub‐inclusions and large sub‐inclusions. The results of dynamic mechanical analysis illustrated that the different internal structures greatly affected the glass transition temperature T_g of the rubber phase and the storage modulus of the core–shell particles. The notched Izod impact test results showed that the MBS with large sub‐inclusions had the lowest brittle–ductile transition temperature, while the transparency test revealed that the presence of sub‐inclusions in the rubbery phase reduced the transparency of the blend. Copyright © 2012 Society of Chemical Industry     

PVC抗冲改性机理和新型PVC冲击改性剂的设计

对PVC冲击改性剂——MBS、CPE和ACR的分子组成和分子结构进行了分析,研究了其抗冲改性机理及对PVC制品低温冲击强度、耐候性、维卡软化点、韧性的影响。从高分子热力学的角度分析了CPE和ACR在PVC中分散所形成的制品结构。指明了传统ACR和CPE在PVC改性中所存在的优缺点。在此基础上分析了理想冲击改性剂ACR应具有的结构特点,并设计和开发了新型冲击改性剂ACRHL-56和HL-58,通过试验对其性能与传统冲击改性剂ACR和CPE进行了比较,发现其性能远优于后者。     

Effect of the Shell Thickness of Methacrylate-Butadiene-Styrene Core–Shell Impact Modifier on Toughening Polyvinyl Chloride

The shell thickness of methyl methacrylate-butadiene-styrene (MBS) graft copolymer with a core–shell structure is found to be the most important factor in the toughening of rigid polyvinyl chloride (PVC). When the total shell thickness is too thin, the shell layer is simply unable to fully protect and cover the inner rubbery core, and these MBS particles tend to connect with one another through the partially exposed core, which leads to the aggregation of MBS in PVC and results in the poor toughening efficiency of MBS. However, when the total shell thickness is too thick, the shell thickness results in a hard core of these core–shell MBS particles and the loss of the rubbery nature required of an efficient impact modifier. Both the PMMA thickness and PS thickness in the shell structure have also significantly influenced the toughening efficiency of MBS; the thickness of PMMA and PS should be between the critical values of 4.2 nm ∼ 6.7 nm for PMMA and 7.4 nm∼9.8 nm for PS, and MBS displays high efficiency in toughening rigid PVC. γ _c/V _f ² and γ _y/V _f ², which are relative to the critical characteristic ligament of polymer materials, are used as the criterions of the brittle–ductile transition, and the brittle–ductile transitions of PVC and MBS with various shell structures was investigated in this paper.     

Essential work of fracture (EWF) analysis for short glass fiber reinforced and rubber toughened nylon‐6

The effect of fiber content on the fracture toughness of short glass fiber reinforced and rubber toughened nylon‐6 has been investigated using the essential work of fracture (EWF) analysis under both quasi‐static and impact rates of loading. Under quasi‐static loading rate, matrix plastic deformation played a major role. Addition of 10 wt% of short glass fibers into a rubber toughened nylon‐6 matrix improved the fracture toughness substantially. This is due to the synergistic effect that comes from matrix yielding and fiber related energy absorption such as fiber debonding, fiber pull‐out and fiber fracture. With further increasing the glass fiber content, up to 20 and 30 wt%, even though plastic deformation could still take place on the fracture surfaces, the depth of the fracture process zones was much smaller when compared with the system with 10 wt% of glass fibers. The reduction in fracture process zone caused the reduction in fracture toughness. Under impact loading rate, the unreinforced blend still fractured in a ductile manner with gross yielding in the inner fracture process zone and the outer plastic zone. The unrein‐forced blend therefore possesseed higher fracture toughness. For the fiber reinforced blends, the matrix fractured in brittle manner and so fracture toughness of the reinforced blends decreased dramatically. The impact fracture toughness increased slightly after incorporation of a higher weight percentage of glass fibers.     

Fracture mechanisms in preformed polyphenylene oxide particle‐modified bismaleimide resins

Fracture toughness and failure mechanisms in preformed poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) particle‐modified bismaleimide (BMI) systems are investigated. The fracture toughness of BMI can be significantly improved by incorporating preformed PPO particles without causing significant deterioration in other mechanical and thermal properties. The fracture mechanisms in BMI/PPO appear to be dominated by craze‐like damage. Further investigation of the craze‐like damage zone using transmission electron microscopy reveals that crazes are formed inside the PPO particle phase and dilatation bands, which appear to be triggered by the crazes inside the PPO particle, are formed in the BMI matrix. Particle bridging is also found to contribute to the toughening of BMI/PPO. The benefits of using preformed PPO particles to toughen BMI and other brittle thermosets for composite and adhesive applications are discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2539–2545, 1999