New insights into the cold crystallization of filled natural rubber

This article is devoted to the cold crystallization of filled natural rubber with different types of filler such as carbon black, silica, and grafted silica. A large set of differential scanning calorimetry data is presented with various scanning rates, times, and temperatures of isothermal crystallization to display the factors affecting natural rubber (NR) crystallization. The crystallization kinetic measurements suggest that fillers can create a region with perturbed mobility where the kinetics of nucleation and/or growth are slowed down, the rest of the matrix being unperturbed. And, the final crystallization level indicates the existence of an excluded region for crystallization close to the filler surface. Furthermore, the presence of fillers appears less unfavorable to NR crystallization than chemical crosslinking. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 955–962, 2007     

The Relationship between Pendant Phosphate Groups and Mechanical Properties of Polyisoprene Rubber

It is still a great challenge to mimic the structure and function of natural rubber by introducing polar components into synthetic polyisoprene. In order to explore the function of phosphate groups on the mechanical properties of polyisoprene rubber, a terminally functionalized compound(PIP-P) containing phosphate groups was synthesized and further vulcanized to prepare the model compound V-PIP-P.Through analyzing the test results, it was found that these phosphate groups formed polar aggregates in non-polar polyisoprene rubber matrix,serving as an additional dynamic cross-linking sites, which increases the cross-linking density and improves mechanical properties. The influence of the phosphate groups on the strain-induced crystallization(SIC) was further investigated via synchrotron wide-angle X-ray diffraction(WAXD)experiment. These phosphate group aggregates not only reduced the onset strain of SIC, but also slowed down the molecular chain mobility,which hinder the crystal lateral growth. The above results help us to gain a deeper understanding for the function of phosphate groups in the formation of "naturally occurring network" and guide the molecular design of next generation polyisoprene rubber.     

Strain‐induced crystallization of natural rubber with high strain rates

Strain‐induced crystallization (SIC) of natural rubber (NR) samples with different strain rates at a fixed strain was investigated by synchrotron radiation X‐ray diffraction measurements, which provided the evolution trends of crystal sizes and crystallinity during the SIC process. It was found that the Avrami index was about 1 during the crystallization of NR after the cessation of stretch, which demonstrated that sporadic nucleation occurred during SIC process. The increase of the crystallinity was attributed to the increase of the number of new crystallites rather than the growth of the crystal size. An unexpected relationship between the final crystallinity and the strain rates was observed. The increase of physical crosslink points originated from either entanglement or crystallite was considered as the reason that leads to the nonmonotonic variation of the final crystallinity with strain rates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Temperature and aging dependence of strain‐induced crystallization and cavitation in highly crosslinked and filled natural rubber

We have investigated the structural changes occurring in highly crosslinked and carbon‐black filled natural rubber under uniaxial extension by small‐ and wide‐angle X‐ray scattering using synchrotron radiation. The experiments focused on strain‐induced crystallization (SIC) and nanocavitation and were carried out on a model series of materials as a function of temperature and aging conditions. We find that for all materials both SIC and cavitation decrease markedly with temperature and aging. However, the presence of carbon black filler shifts the ceiling temperature where SIC is observed to at least 120°C, presumably by a nucleating effect, maintaining the high strength of the elastomers. Interestingly, although in pure elastomers, the cavitation strength decreases with temperature, we find that in these filled elastomers the critical stress for the onset of cavitation increases significantly with temperature strongly suggesting that cavitation is due to the local confinement between fillers and supporting the idea of a glassy layer near the filler. Aging for 10 days at 110°C in oxygen‐free conditions decreases both SIC and cavitation and reduces the strength of the elastomer at high temperature. This is attributed to the formation of sulfur side chains hindering the crystallization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 780–793     

Strain‐induced crystallization and mechanical properties of functionalized graphene sheet‐filled natural rubber

The effects of functionalized graphene sheets (FGSs) on the mechanical properties and strain‐induced crystallization of natural rubber (NR) are investigated. FGSs are predominantly single sheets of graphene with a lateral size of several hundreds of nanometers and a thickness of 1.5 nm. The effect of FGS and that of carbon black (CB) on the strain‐induced crystallization of NR is compared by coupled tensile tests and X‐ray diffraction experiments. Synchrotron X‐ray scattering enables simultaneous measurements of stress and crystallization of NR in real time during sample stretching. The onset of crystallization occurs at significantly lower strains for FGS‐filled NR samples compared with CB‐filled NR, even at low loadings. Neat‐NR exhibits strain‐induced crystallization around a strain of 2.25, while incorporation of 1 and 4 wt % FGS shifts the crystallization to strains of 1.25 and 0.75, respectively. In contrast, loadings of 16 wt % CB do not significantly shift the critical strain for crystallization. Two‐dimensional (2D) wide angle X‐ray scattering patterns show minor polymer chain alignment during stretching, in accord with previous results for NR. Small angle X‐ray scattering shows that FGS is aligned in the stretching direction, whereas CB does not show alignment or anisotropy. The mechanical properties of filled NR samples are investigated using cyclic tensile and dynamic mechanical measurements above and below the glass transition of NR. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Application of the Christensen‐Lo Model to the Reinforcement of Elastomers by Fractal Fillers

This paper is concerned with the development of a hydrodynamic model for the reinforcement of rubber by colloidal fillers such as silica and carbon black. Each fractal aggregate is replaced by an equivalent effective sphere, and the reinforcing ability of the latter is estimated using the Christensen‐Lo solution of the “three‐phase composite sphere model”. With a single adjustable parameter, the model allows a quantitative interpretation of the small‐strain modulus of rubber loaded with up to 50 PHR of N234 carbon black, which falls just below the filler overlap concentration. No additional contributions to the small‐strain modulus by filler–filler “interactions” are needed to interpret the data.

A branched filler aggregate made up of spherical primary particles (black) and the effective sphere replacing it (gray).     

Synthesis,structure, and properties of hybrid organic–inorganic composites based on polysiloxanes. I. Poly(dimethylsiloxane) elastomers containing silica

Various synthetic protocols were used to prepare several classes of polysiloxane–silica filler systems. The structures of these fillers and their interactions with the polysiloxane matrices were studied using small-angle X-ray and neutron scattering. In addition, the mechanical properties of the composites were characterized using equilibrium stress–strain isotherms in elongation. The results indicated that manipulation of the chemical reactions used to generate the filler can lead to a wide range of complex structures and unusual properties. Some of the observed mechanical properties were correlated with information on the composite structures and on elastomer–filler interactions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1167–1189, 1998     

Understanding the effect of filler shape induced immobilized rubber on the interfacial and mechanical strength of rubber composites

Styrene butadiene rubber (SBR) composites with silica, halloysite nanotubes (HNTs) and montmorillonite (MMT) were prepared and the interfacial and mechanical properties were compared to understand the reinforcing behaviours of these fillers based on the results of SEM, DSC, DMA, etc. Due to the formation of interparticle domain, HNTs immobilized more rubber approaching their surface than silica and MMT. Interestingly, only tightly immobilized rubber chains made contribution to the enhancement of interfacial and mechanical strength of SBR composites. This was because the tightly immobilized rubber acted as a bridge in the filler-rubber interface and induced the formation of stretched rubber chains linked filler network when the composites were loaded in tension, while loosely immobilized rubber were easy to slip off from filler surface, causing the separation between filler and bulk rubber. Therefore, silica with more tightly immobilized rubber approaching its surface showed better reinforcing effect on rubber than HNTs and MMT.     

Formation of Network by Carbon Black，Silica and Their Mixing Fillers in Isoprene Rubber北大核心CSCD

The network formed by fillers has great influence on the mechanical properties of rubber materials. To understand the formation of network by carbon black,silica,and carbon black/silica mixing fillers in rubber and its influence on the properties of rubber,isoprene rubber/filler composites with different filler loadings are prepared and their micromorphology,rheological and tensile properties are investigated. It is found that the dispersion of fillers is better in rubber after cure than that in rubber before cure for all three rubber systems,and the filler size of silica is smaller than that of carbon black,but the aggregation is more severe in silica filled rubber system. In mixed filler system,the two fillers tend to aggregate separately, leading to the low modulus at small strain than that in single filler system. With the increase of the filler loading,the tensile strength increases first and then decreases,the elongation at break decreases,and the temperature rise in compression flexometer tests increases. Moreover,the temperature rise in mixed filler system is higher than that in single filler system at high filler loading. © 2022, Science Press (China). All rights reserved.     

Structural evolution during uniaxial deformation of natural rubber reinforced with nano‐alumina

The mechanical properties of natural rubber (NR) were enhanced by the inclusion of nano‐alumina. In order to gain further insights into the reinforcement mechanism, synchrotron wide‐angle X‐ray diffraction (WAXD) was used to monitor the evolution of the molecular structure during stretching in real time, and the tube model theory was applied to study the effect of nanoparticles on rubber network. For the filled rubber, the onset strain of crystallization shifted to much lower value compared with that of the unfilled, indicating the presence of special strain amplification effect, which can be revealed by the reduction of configurational entropy. In addition, the crystallinity increased and the lateral crystallite size decreased after the addition of the nanofiller. During deformation, the crystallites of the filled rubber showed lower orientational fluctuations differing from that of NR reinforced by carbon black. Copyright © 2010 John Wiley & Sons, Ltd.     

The effect of low-temperature crystallization on the mechanical behavior of rubber

In cold climates the correct performance of rubber components such as seismic isolators depends on them maintaining their elastic properties when exposed to prolonged periods at low temperatures. The high damping compounds developed for seismic isolation are normally especially prone to crystallization when exposed to subzero temperatures for periods of a few weeks. The effect of low-temperature crystallization on the mechanical stiffening of natural rubber is evaluated. The relationship between the shear modulus and amount of crystallization is measured using a technique in which the dimensional change and stiffness are monitored simultaneously. The relationship is found to be approximately independent of the crosslink density and the temperature of crystallization. It appears not to be realistically modeled by considering the crystals to behave as rigid filler particles but good qualitative agreement with experiment was obtained by modeling the crystals as a network of threads. Partially crystalline rubbers are found to yield under the application of a large stress like other partially crystalline polymers. Mechanisms for suppressing crystallization in rubber are discussed and the low-temperature stiffening of specially formulated rubber compounds for seismic isolation is presented. These results show that carefully formulated high damping natural rubber compounds can give adequate performance at low temperatures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2181–2190, 2004     

Manipulation of mechanical properties of short pineapple leaf fiber reinforced natural rubber composites through variations in cross-link density and carbon black loading

The aim of this paper is to demonstrate that the stress–strain behavior of natural rubber reinforced with short pineapple leaf fiber (PALF) can easily be manipulated by changing the cross-link density and the amount of carbon black (CB) primary filler. This gives more manageable control of mechanical properties than is possible with conventional particulate fillers alone. This type of hybrid rubber composite displays a very sharp rise in stress at very low strains, and then the stress levels off at medium strains before turning up again at the highest strains. The composites studied here contain a fixed amount of PALF at 10 part (by weight) per hundred rubber (phr) and varying carbon black contents from 0 to 30 phr. To change the cross-link density, the amount of sulfur was varied from 2 to 4 phr. Swelling ratio results indicate that composites prepared with greater amounts of sulfur and carbon black have greater cross-link densities. Consequently, this affects the stress–strain behavior of the composites. The greater the cross-link density, the less is the strain at which the stress upturn occurs. Variations in the rate of stress increase (although not the stress itself) in the very low strain region, while dependent on fillers, are not dependent on the crosslink density. The effect of changes in crosslinking is most obvious in the high strain region. Here, the rate of stress increase becomes larger with increasing cross-link density. Hence, we demonstrate that the use of PALF filler, along with the usual carbon primary filler, provides a convenient method for the manipulation of the stress–strain relationships of the reinforced rubber. Such composites can be prepared with a controllable, wide range of mechanical behavior for specific high performance engineering applications.     

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     

Mechanical properties of polymers containing fillers

The addition of fillers can significantly change the mechanical characteristics of a material. In this paper, a general, mechanistic model is established to determine the moduli, relaxation moduli, break strengths, and break strains for polymer films containing liquid and solid micro fillers. Based on rigorous continuum mechanics principles, this model considers the filler/filler interactions, incorporates the nonlinear synergistic effects of fillers, and provides accurate predictions in comparison with experimental data. The analytical model developed provides information that is not available or extremely difficult to obtain experimentally. The model can be applied to determine the filler/matrix adhesion and filler modulus using measured modulus of a filled polymer film (a filled polymer is a polymer containing fillers). It is found that the compression moduli of polymer films containing liquid fillers differ significantly from the tension moduli, especially when the volume fraction of the filler is high. The difference in compression and tension Young's moduli normalized by the tension Young's modulus is as high as 35%. The relative error in maximum pressure calculation during Hertzian contact caused by using the tension moduli is as high as 48%. The relaxation modulus of a filled polymer film is determined through inverse Laplace transforms of its composite modulus in the s‐space. For a filled polymer film containing liquid phase fillers, a closed form solution for its relaxation modulus has been obtained. It is found that the composite relaxation modulus of the filled polymer is proportional to the relaxation modulus of the matrix polymer multiplied by a factor related to the volume fraction of the liquid filler. The break strength of the filled polymer is found to be proportional to the break strength of the polymer matrix material multiplied by a power function of the modulus ratio of filled polymer to polymer matrix, R. The break strain of the filled polymer is proportional to the break strain of the polymer matrix multiplied by a power function of 1/R. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 155–172, 1999     

Payne effect in silica‐filled styrene–butadiene rubber: Influence of surface treatment

The nonlinear effect at small strains (Payne effect) has been investigated in the case of silica‐filled styrene‐butadiene rubber. The originality of this study lies in the careful preparation of samples in order to fix all parameters except one, that is, the modification of the silica surface by grafting silane (introduced at different concentrations) via reactive mixing. The organosilane can be either a coupling or a covering surface treatment with an octyl alkyl chain. A careful morphological investigation has been performed prior to mechanical characterization and silica dispersion was found to be the same whatever the type and the amount of silane. The increasing amount of covering agents was found to reduce the amplitude of the Payne effect. A similar decrease is observed for low coupling agent concentration. At higher concentrations, the evolution turns through an increase due to the contribution of the covalent bonds between the matrix and the silica acting as additional crosslinking. The discussion of the initial modulus was done in the frame of both the filler–filler and filler–polymer models. It is unfortunately not possible to distinguish both scenarios, because filler–filler and filler–matrix interactions are modified in the same manner by the grafting covering agent. On the other hand, the reversible decrease of the modulus versus strain (Payne effect) is interpreted in terms of debonding of the polymeric chains from the filler surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 286–298, 2007     

Study of electrical,mechanical, and nanoscale free‐volume properties of NBR and EPDM rubber reinforced by bentonite or kaolin

The effect of Na bentonite, Ca bentonite, and kaolin fillers on the macrostructure and microstructure of acrylonitrile butadiene rubber, ethylene propylene diene rubber, and their blend (50/50) was studied through electrical and mechanical measurements, as well as with positron annihilation lifetime spectroscopy. The real part of permittivity (ε′), dielectric loss (ε″), and the crosslinking density were found to increase with increasing filler content. The increase of crosslinking density of the blend with increasing amount of fillers reflects a decrease in the equilibrium swelling up to 21.50 wt % compared with that of the unfilled blends. The mechanical investigation showed pronounced increase in the tensile strength, and in elongation at break with the addition of up to 21.50 wt % of filler. In addition, comparing between different fillers showed that the reinforcing effect of Na bentonite is more effective than Ca bentonite and kaolin but the physico‐mechanical of Ca bentonite is less than that for kaolin. The positron annihilation lifetime measurements revealed that the free‐volume properties were strongly affected by the amount and type of filler, in particular, the free‐volume fraction was dramatically decreased with increasing filler content. Furthermore, correlations were made between the free‐volume parameters and both electrical and mechanical properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1825–1838, 2009     

Unique rheological behavior of rubber based nanocomposites

Montmorillonite clay (N) based nanocomposites were prepared using three different grades of acrylonitrile butadiene rubber (NBR) (19%, 34%, and 50% acrylonitrile contents), styrene butadiene rubber (SBR), and polybutadiene rubber (BR). Rheological study was carried out on these nanocomposites at three different temperatures (110 °C, 120 °C, and 130 °C) over a range of shear rates for comparison. The results showed that the shear viscosity decreased with increasing shear rate and incorporation of the unmodified (N) and the modified (OC) fillers up to a certain loading, when the results were compared with the gum rubber. This effect became more prominent with increasing polarity of the rubber. The die swell, on the other hand, decreased with loading of N and OC. With increasing filler volume fraction, the die swell further decreased. Decrease of viscosity with concomitant decrease of die swell is unique in such systems. Consecutive runs of the same sample over different shear rates increased the viscosity. The results were explained with the help of X‐Ray Diffraction (XRD) data and Transmission Electron Microscopy (TEM).© 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1854–1864, 2005     

Development of internal fine structure in stretched rubber vulcanizates

Small‐angle X‐ray scattering (SAXS) pattern and tensile stress during relaxation of stretched rubber vulcanizates (synthetic polyisoprene) were measured simultaneously at room temperature and at 0 °C. The samples were quickly stretched to the prefixed strain and then allowed to relax for 1 h. In every SAXS pattern, the intensity distribution was elongated along the equator, indicating the formation of structures elongated in the stretching direction. The so‐called two‐spots pattern corresponding to the long period of stacked lamellar crystals did not appear even when the critical strain to induce crystallization was exceeded. On the other hand, even below the critical strain, additional development of equatorial streaks was detected in the differential SAXS patterns. This result suggests the growth of the density fluctuation elongated in the stretching direction, which is not directly related to strain‐induced crystallization. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Electrical and mechanical behavior of filled rubber. III. Dynamic loading and the rate of recovery

Following the earlier articles in this series, the changes in the electrical resistivity and mechanical behavior as a result of static and dynamic deformation have been studied. Cyclic shear and tensile loading were used to follow the changes in stress and resistivity with strain, including the recovery with time from the effects of a large strain as monitored by the small‐strain behavior. The recovery of resistivity from a prestrain was not complete even after 7 days at room temperature or at 50 °C, but swelling with a solvent and subsequent drying produced rapid recovery. It appears from the detailed results that there are two strain regions. Below about 10% the resistance and the modulus are strongly dependent on the filler–filler structure, which can break down and reform fairly readily, but the changes at higher strains are probably influenced by changes in the elastomer matrix and also by slippage at the filler–rubber interface. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1649–1661, 2005     

Multi‐scaled microstructures in natural rubber characterized by synchrotron X‐ray scattering and optical microscopy

Multi‐scaled microstructures induced by natural impurities (i.e., proteins, phospholipids, carbohydrates) in natural rubber (NR) were investigated by synchrotron small‐angle X‐ray scattering (SAXS), wide‐angle X‐ray diffraction (WAXD), and optical microscopy using several kinds of untreated and chemically treated un‐vulcanized samples. These microstructures include large aggregates (size less than 50 μm), well‐defined crystals (size less than a few 10 μm), and micelles (size much less than 10 μm). In un‐vulcanized NR samples, even though the concentrations of natural impurities are relatively low, the dispersion of these microstructures significantly affects the mechanical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2456–2464, 2008