The effect of temperature on the stress-strain behavior of composites based on high-density polyethylene and rubber particles

The failure behavior of composites based on HDPE, which breaks down at the necking stage, and dispersed rubber particles is studied. In was shown that the materials containing at most 8 vol % filler experience the brittle-to-ductile transition with increasing temperature. It was assumed that the ductility retained at elevated temperatures by the composites based on a polymer with unstable neck propagation is due to the interplay of two factors, the decrease in the upper yield point of the matrix polymer and the increase in the polymer draw ratio in the neck. These factors markedly reduce the sensitivity of the materials to the presence of defects and facilitate neck formation and propagation, as well as change the form of the defects from cracks to slitlike pores.     

The brittle-ductile transition in rubber-filled polymers

Composites based on various polymers and rubber particles as a filler were studied. As the filler concentration was increased, the transition from necking to brittle fracture and then to uniform ductile yielding was observed. The criterion for the brittle-ductile transition, which is accompanied by an increase in the elongation at break, is equality between the tensile strength and the upper yield stress of the filled composite. Upon the brittle-ductile transition, the critical concentration of rubber particles is determined by two parameters: the height of the yield drop (difference between the upper and lower yield stresses of matrix polymer) and adhesive strength at the interface between the matrix polymer and filler particles (in the case of good adhesion, tensile strength of rubber particles). The larger the yield drop, the broader the concentration range corresponding to the polymer brittle fracture. The enhancement of adhesion between the matrix and the particles makes it possible to displace the brittle-ductile transition to lower filler contents and, hence, to narrow the region of brittle fracture of the composite.     

The effect of filler content on the lower yield stress of polymer composites

The effect of the concentration of the dispersed elastic filler on the lower yield stress of matrix composites based on plastic polymers is studied. As the matrix polymers, LDPE-HDPE and LDPE-(medium-density PE) are used. The elastic filler is rubber crumb prepared by roll grinding of worn tires or by deformation grinding of ethylene-propylene-diene rubber. Irrespective of the type of filler particles and their adhesion to the polymer matrix, the lower yield stress σ_d of the composite is described by the linear law σ_d = σ_dm(1 ? V _f ), where σ_dm is the lower yield stress of the polymer matrix and V _f is the volume content of the filler. Analysis of the published data shows that this relationship is quite general and describes the effect of rigid inorganic particles on the lower yield stress when adhesion between the filler particles and the matrix is poor.     

Properties of ultrahighly filled composites based on polymers and ground rubber

The stress-strain and strength properties of ultrahighly filled composites based on thermoplastic polymers and ground rubber wastes are studied. The content of the elastic filler is higher than 70 wt%. As is shown, introduction of minor amounts of the plastic polymer, which serves as the binder for the filler particles, makes it possible to improve the strength properties of ultrahighly filled composites and to prepare materials of a desired thickness. A correlation between the stress-strain properties of the plastic polymer-rubber systems and the effective viscosity of the matrix polymer is established. When a polymer with homogeneous deformation and good adhesion to the elastic filler is used as the matrix, the resultant composites are characterized by properties close to those of vulcanized rubbers. A new method is proposed for processing of ground rubber wastes and preparation of materials that are similar to hard rubbers.     

Crazing and shear deformation of polymer alloys

Crazing and/or shear yielding mechanisms in multiphase polymer alloys play a critical role in toughening. The present paper describes the use of finite element models (FEM) to simulate the crazing and shear deformation behaviour around the particles embedded in brittle or ductile matrices. The FEM simulation results on the stress distribution reveal that the dilatational stress within the rubber particles is high enough to cavitate. The stability of craze growth can be reached when the compliant particle is incorporated in a brittle matrix. On the other hand, shear yielding around the particle occurs in the equator of the particle/matrix interface when the stress locally exceeds the yield stress of the matrix. This yield-initiation stress increases with the increase in the elastic modulus and Poisson's ratio of the particles. The toughening mechanism, that cavitation occurs first followed by shear yielding to form a neck between the particles, is discussed based on the simulation results for the two-particle model.     

The effect of glass transition on the self-oscillation regime of tensile drawing of a polymer

The effect of the transition of a polymer into its rubbery state at the glass-transition temperature on the character of the excitation of self-oscillation neck propagation is studied with numerical methods. To describe the rate of plastic yielding near the glass-transition temperature, the Eyring equation is modified by the introduction of the temperature dependence of the parameter related to the free volume. There are three intervals of strain rates. At low strain rates when the yield stress increases with an increase in the strain rate, neck propagation is stable and no oscillations are excited. At high strain rates, when the glass-transition temperature is achieved during stationary neck propagation, the excitation of oscillations shows a mild character and there exists a certain critical length of the samples below which no oscillations are excited. In the intermediate interval of strain rates, the excitation shows a severe character. In this case, the oscillations are excited when, in the transition region, the glass-transition temperature of the polymer is achieved owing to excitations. In strain-rate-sample-length coordinates, the diagram describing the regions of various oscillation behaviors of the samples is constructed.     

Analysis of the debonding process in polypropylene model composites

Polypropylene (PP) model composites were prepared using cross-linked PMMA particles with a very narrow particle size distribution as filler in order to study the micromechanical processes, which take place during deformation. Composites containing a commercial CaCO₃ filler with a broad particle size distribution were also prepared and studied for comparison. The filler loading of the composites was changed from 0 to 0.3 volume fraction in 0.05 volume fraction steps. Measurements of acoustic emission signals during the elongation of PP/PMMA model composites allowed us to assign the debonding process, including its initiation, unambiguously to a well-defined section of the stress vs. strain curve. The number and intensity of the acoustic signals detected during the deformation of the matrix polymer and the composite, respectively, differed considerably, which made possible the separation of the various micromechanical deformation processes occurring in them. At low extensions the composite is deformed elastically, then debonding takes place in a very narrow deformation range, followed by the plastic deformation of the matrix. At small particle content debonding occurs at relatively low stresses, which differ significantly from the yield stress. Considerable plastic deformation of the matrix begins at the yield point. At larger filler content debonding and shear yielding occur simultaneously. Micromechanical deformation processes cannot be separated as clearly in composites prepared from the commercial CaCO₃ filler with a broad particle size distribution. The debonding of particles with different size occurs in a wide deformation range because of the particle size dependence of debonding stress. The analysis of characteristic values derived from acoustic emission experiments proved that the interacting stress fields of neighboring particles influence the deformation process and that even large particles may aggregate or at least associate at large filler content.     

聚合物共混物脆韧转变性能研究 Ⅳ橡胶粒子的分布对PVC/NBR共混物脆韧转变的影响

根据作者已建立的准网络形态模型和推导出的基体层厚度计算公式，从实验上研究了橡胶粒子的分布对聚氯乙烯（ＰＶＣ）／丁氰橡胶（ＮＢＲ）共混物脆韧转变的影响．结果表明，不仅无规形态ＰＶＣ／ＮＢＲ共混物存在脆韧转变主曲线，而且准网络形态ＰＶＣ／ＮＢＲ共混物也存在脆韧转变主曲线．但是两条主曲线明显不重合，表明橡胶粒子的分布对ＰＶＣ／ＮＢＲ共混物脆韧转变有显著影响．而且准网络形态ＰＶＣ／ＮＢＲ共混物的临界基体层厚度比无规形态ＰＶＣ／ＮＢＲ共混物的临界基体层厚度大得多，表明准网络形态比无规形态明显有利于增韧．因此临界基体层厚度不仅是基体的特征参数，还是界面粘结和橡胶粒子分布的函数．     

Effect of temperature on the stress-strain behavior of a polypropylene-particulate rubber composite

Composites based on polypropylene and rubber particles were studied at different temperatures. It was found that, as the temperature is elevated, the type of defects that are formed near large filler particles changes from a crack to a diamond-shaped void and, next, to an elliptical or slit-type void. The change in the defect type predetermines the change of the composite failure mechanism at a constant particulate-filler content from brittle fracture before the yield point to fracture during neck formation or propagation and, finally, to non-uniform plastic drawing with a stable neck growth.     

Toughening of epoxies via craze-like damage

The fracture behavior of a core-shell rubber (CSR) modified epoxy is investigated using both fracture mechanics and microscopy tools. The CSR-modified epoxy is found to be toughened via numerous line-array cavitations of the CSR particles, followed by plastic flow of the epoxy matrix. The toughening effect via the above craze-like damage process is found to be as effective as that of the well-known widespread rubber cavitation/matrix shear yielding mechanisms. The conditions for triggering the craze-like damage appear to be both stress state and rubber concentration dependent. The type of rubber tougheners utilized also plays a critical role in triggering this rather unusual craze-like damage in epoxy systems. © 1993 John Wiley & Sons, Inc.     

Compliant rubber domains in a rigid polymer matrix: Shape and orientation factors related to cavitation and plastic dissipation

The hydrostatic stress in compliant rubber inclusions embedded in a rigid polymer matrix is evaluated for various shapes and orientations of the rubber domains and triaxialities of the remote stress tensor to determine the propensity of the inclusions to undergo cavitation. The first section analyzes the case of rubber particles of an ellipsoidal shape assuming linear elasticity of the matrix and small strains. It is shown that flat shapes, of which the long axis lies perpendicular to the direction of the maximum principal stress, are subjected to the highest levels of hydrostatic stress. The pressure induced by the deviatoric part of the remote stress tensor in the compliant rubber domains depends strongly on their shape and orientation, whereas the pressure induced by the hydrostatic part of the tensor is almost insensitive to the shape and orientation of the compliant domains. The second section examines the stress concentrations for elastoplasticity and plastic dissipation in the matrix. It is found that spherical inclusions ensure the best compromise between the early occurrence of plasticity and large amounts of plastic dissipation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1476–1486, 2004     

Ductile–brittle‐transition phenomenon in polypropylene/ethylene‐propylene‐diene rubber blends obtained by dynamic packing injection molding: A new understanding of the rubber‐toughening mechanism

For a more complete understanding of the toughening mechanism of polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, dynamic packing injection molding was used to control the phase morphology and rubber particle orientation in the matrix. The relative impact strength of the blends increased at low EPDM contents, and then a definite ductile–brittle (D–B) transition was observed when the EPDM content reached 25 wt %, at which point blends should fail in the ductile mode with conventional molding. Wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) were used to investigate the shear‐induced crystal structure, morphology, orientation, and phase separation of the blends. WAXD results showed that the observed D–B transition took place mainly for a constant crystal structure (α form). Also, no remarkable changes in the crystallinity and melting point of PP were observed by DSC. The highly oriented and elongated rubber particles were seen via SEM at high EPDM contents. Our results suggest that Wu's criterion is no longer valid when dispersed rubber particles are elongated and oriented. The possible fracture mechanism is discussed on the basis of the stress concentration in a filler‐dispersed matrix. It can be concluded that not only the interparticle distance but also the stress fields around individual particles play an important role in polymer toughening. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2086–2097, 2002     

橡胶增韧塑料机理

综述了橡胶增韧塑料机理研究的发展与现状,着重探讨了橡增韧机理中有关脆韧转变的定量研究,同时也讨论了分散相的形态参数、界面相容性和韧性测试条件以及分散相与基体的性能等因素对橡胶增韧塑料性能及增韧的影响,最后提出了橡胶增韧塑料研究的发展趋势。     

Thermal stability of CR/CSM rubber blends filled with nano- and micro-silica particles

The properties of filled polymers depend on the properties of the matrix and the filler, the concentration of the components and their interactions. In this research we investigated the rheological and mechanical properties and thermal stability of polychloroprene/chlorosulfonated polyethylene (CR/CSM) rubber blends filled with nano- and micro-silica particles. The density of the nano-silica filled CR/CSM rubber blends was lower than that of the micro-silica filled samples but the tensile strength and elongation at break were much higher. The nano-silica filled CR/CSM rubber blend has higher V _r0/V _rf values than micro-silica composites and show better polymer–filler interaction according to Kraus equation. The nano-silica filled CR/CSM rubber blends were transparent at all filler concentration, and have higher glass transition values than micro-silica filled compounds. The higher values of the glass transition temperatures for the nano- than the micro-filled cross-linked systems are indicated by DMA analysis. The nano-filled cross-linked systems have a larger number of SiO–C links than micro-filled cross-linked systems and hence increased stability.     

Design and control of morphology for high performance polymer alloys

Ductile polymers are significantly toughened by the addition of an elastomeric phase. The rubber phase acts as a stress concentrator, cavitates during the loading process and initiates localized plastic deformation in matrix. This paper deals with the simulation of the deformation behavior of rubber toughened polycarbonate and the fracture process of the embedded rubber particle. A two-dimensional one particle- and two-particle model with varying surface-to-surface interparticle distances are established. The calculation showed that the polymer matrix has plastically deformed before cavitation for the one-particle model whereas cavitation occurs in the elastic state of the matrix for the two-particle model. Cavitation itself is proved to be a change from the particle-system towards a void-system for both cases. The toughness of the post-cavitated void-system is shown to be dependent on the surface-to-surface interparticle distance and the strain-hardening characteristic of the matrix polymer.     

Effect of sol–gel derived in situ silica on the morphology and mechanical behavior of natural rubber and acrylonitrile butadiene rubber blends

Silica particles were generated and grown in situ by sol–gel method into rubber blends comprised of natural rubber (NR) and acrylonitrile butadiene rubber (NBR) at various blend ratios. Silica formed into rubber matrix was amorphous in nature. Amount of in situ silica increased with increase in natural rubber proportion in the blends during the sol–gel process. Morphology studies showed that the generated in situ silica were nanoparticles of different shapes and sizes mostly grown into the NR phase of the blends. In situ silica filled NR/NBR blend composites showed improvement in the mechanical and dynamic mechanical behaviors in comparison to those of the unfilled and externally filled NR/NBR blend composites. For the NR/NBR blend at 40/60 composition, in particular, the improvement was appreciable where size and dispersion of the silica particles into the rubber matrix were found to be more uniform. Dynamic mechanical analysis revealed a strong rubber–in situ silica interaction as indicated by a positive shift of the glass transition temperature of both the rubber phases in the blends.     

低乙烯含量共聚聚丙烯链结构和相结构与应力应变行为的关系

研究了两种典型的低温抗冲共聚聚丙烯(ICPP)的应力应变行为及温度依赖性,其低温应力应变行为揭示ICPP具有优异的低温抗冲性能和综合力学性能的结构本质.从初始弹性模量、屈服应力及断裂伸长随温度变化所显示的变化规律进一步确认了两种ICPP的序列结构特征和相结构特征.断裂伸长变化显示了乙丙橡胶相的增韧作用,屈服应力变化显示了分散相对基质结合紧密程度的影响,弹性模量则与基质的结晶状况和结晶形态有着比较密切的关系,同时也与乙丙橡胶相和聚丙烯基质的玻璃化转变温度密切相关.     

Structure-Property Relationships in Rubber-Modified Styrenic Polymers

Styrenic polymers and copolymers are often impact modified with rubber particles. The efficiency of rubber toughening depends mainly on the size of the rubber particles and the degree of cross-linking. The deformation rate, the temperature, the orientation of the polymer molecules and the efficiency of rubber grafting also influence rubber toughening. It is thought that on impact, cavitation inside the rubber particles occurs which reduces the detrimental dilatational stress in the bulk polymer without forming cracks in the brittle matrix or at the rubber-matrix interface. Crazing and shearing are facilitated if the rubber particles can easily cavitate. This can be achieved by either avoiding too much cross-linking or by adding oil (silicone oil in the case of ABS) into the rubber particles, which acts as nuclei for void formation. An electron spectroscopic imaging method is described which allows visualizing the location of the oil. Already after cooling silicone oil modified ABS samples down to liquid nitrogen temperature rubber cavitation is observed. This cavitation is caused by the thermal stress developing due to the differences in thermal expansion coefficient between the rubber phase and the SAN-matrix and is facilitated by silicone oil. Voiding also leads to an increase of light scattering, which can be detected by an optical microscope using dark field illumination.     

Viscoelastic properties of ionic polymer composites reinforced by soy protein isolate

Both linear and nonlinear viscoelastic properties of ionic polymer composites reinforced by soy protein isolate (SPI) were studied. Viscoelastic properties were related to the aggregate structure of fillers. The aggregate structure of SPI is consisted of submicron size of globule protein particles that form an open aggregate structure. SPI and carbon black (CB) aggregates characterized by scanning electron microscope and particle size analyzer indicate that CB aggregates have a smaller primary particle and aggregate size than SPI aggregates, but the SPI composites have a slightly greater elastic modulus in the linear viscoelastic region than the CB composites. The composite containing 3–40 wt % of SPI has a transition in the shear elastic modulus between 6 and 8 vol % filler, indicating a percolation threshold. CB composites also showed a modulus transition at <6 vol %. The change of fractional free volume with filler concentration as estimated from WLF fit of frequency shift factor also supports the existence of a percolation threshold. Nonlinear viscoelastic properties of filler, matrix, and composites suggested that the filler‐immobilized rubber network generated a G′ maximum in the modulus‐strain curves and the SPI formed a stronger filler network than the CB in these composites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3503–3518, 2005     

Influence of structure on the impact behaviour of nylon-rubber blends

Blends of nylon-6 and EPDM rubber were prepared by reaction blending to study the influence of rubber concentration, rubber particle size and interfacial adhesion on the impact strength. Rubber particles induce a sharp brittle-tough transition which is independent of the glass transition of the nylon matrix. Increasing the rubber concentration or decreasing the particle diameter shifts the brittle-tough transition temperature for notched Izod impact tests to lower values. A toughening mechanism is proposed in which the interparticle distance, the rubber modulus and the temperature play crucial roles.