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1.
Using Digital Image Correlation on high‐resolution images, the full strain field near the tip of a crack propagating under cyclic loading in an elastomer was characterized. We show unambiguously, and for the first time, the existence of a strongly localized and highly oriented process zone close to the crack tip and propose a simple physical model introducing a local energy release rate glocal = WunloadingH0, where Wunloading is the unloading strain energy density in uniaxial tension at the maximum strain measured at the crack tip, and H0 is the undeformed size of the highly stretched zone in the loading direction. Remarkably, the crack growth rate under cyclic loading is found to fall on a master curve as a function of glocal for three elastomers with different filler contents and crosslinking densities, while the same crack growth rate as a function of the applied macroscopic energy release rate G, differs by two orders of magnitude for the same three elastomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1518–1524, 2011  相似文献   

2.
This study is focused on numerical investigation on fracture behaviors of carbon black (CB) and silica filled elastomeric composites. Finite element analysis (FEA) in compliance with multi-specimen method is used to calculate J-integral and geometry factor of the rubber composites up to a displacement of 20 mm for single edge notch in tension (SENT) and double edge notch in tension (DENT) specimens. An empirical relationship between crack tip opening displacement (CTOD) and crack advancement is established depending on notch to width ratio (NWR). The stress contours across the notches for SENT and DENT specimens is discussed briefly. It is found that fracture propagation resistance of CB filled elastomer is 125% more than that of silica filled elastomer. Although, Silica filled elastomer have good tensile strength and crosslink density but it fails to replace carbon black in terms of fracture properties. The critical J-integral for CB filled elastomer is 18.7% and 32.2% more than silica filled elastomer for SENT and DENT specimens respectively. The effect of specimen type on various fracture properties is also explored. The factor of safety is found to be significantly more in case of CB filled elastomers making them less vulnerable to crack propagation and catastrophic failure.  相似文献   

3.
Crack propagation tests were performed on an amorphous polymer, poly(methyl methacrylate), to investigate fatigue crack propagation mechanisms. A scanning laser microscope with a newly developed tensile testing machine was used to observe in situ crack propagation in compact‐type specimens. A crack usually propagated within the craze located at the crack tip under both static and cyclic loading conditions. When a crack stably propagated into the craze under static loading conditions, bright bands composed of the broken craze were observed at the edges along the crack wakes. However, there were successive ridges and valleys in place of bright bands along the crack wakes under cyclic loading conditions. When stable fatigue cracks were propagated at the loading half‐cycle in each cycle, new craze fragments appeared that were similar to the bright bands under static loading. However, the thickness of these fragments decreased in the following loading cycle, and a new valley was formed. This suggested that the valleys were formed by the contact between the fracture surfaces near the crack tip during unloading. Fatigue crack propagation is thought to be due to fibrils weakened by crack closure between fracture surfaces. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 3103–3113, 2001  相似文献   

4.
Direct experimental access to the monomeric friction coefficient (ζ0) relies on the availability of a suitable polymer dynamics model. Thus far, no method has been suggested that is applicable to filled systems, such as filled rubbers or microphase‐segregated A–B–A thermoplastic elastomers (TPEs) at Tg,B < T < Tg,A. Building upon the procedure proposed by Ferry for entangled and unfilled polymer melts, the Rouse–Bueche theory is applied to an undiluted triblock copolymer to extract ζ0 from the linear behavior in the rubber‐glass transition region, and to estimate the size of Gaussian submolecules. When compared at constant TTg, the matrix monomeric friction factor is consistent with the corresponding value for the homopolymer melt. In addition, the characteristic Rouse dimensions are in good agreement with independent estimates based on the Kratky–Porod worm‐like chain model. These results seem to validate the proposed approach for estimating ζ0 in filled systems. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1437–1442  相似文献   

5.
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  相似文献   

6.
Lifetime spectra of positrons were measured for styrene–butadiene rubber (SBR) vulcanizates filled with carbon black (CB) or silica. At temperatures between 10 and 420 K, no large difference between the size of the open spaces in the CB/SBR vulcanizate and that in the specimen without the filler was observed. Above the glass‐transition temperature (Tg = 230 K), the same was true for the silica/SBR vulcanizate. Below Tg, however, the size of the open spaces was reduced by the incorporation of silica as a result of the suppression of local molecular motions in the SBR. The density of the open spaces was reduced by the incorporation of the fillers. However, above 400 K it started to increase in the silica/SBR vulcanizate. For the CB/SBR vulcanizate, the introduction of open spaces was well suppressed, even at 420 K. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 835–842, 2001  相似文献   

7.
The conductivity of styrene‐butadiene‐styrene block copolymers containing different amounts of extraconductive carbon black (CB) was investigated as a function of the mold temperature. The composites exhibited reduced percolation thresholds (between 1.0 and 2.0 vol % CB). The dynamic mechanical analysis characterization revealed that the glass‐rubber‐transition temperatures of both segments were not affected by the CB addition, although the damping of the polybutadiene phase displayed a progressive drop with an increase in the CB concentration. The normalized curves of tan δ/tan δmax (where tan δ represents the value of the loss tangent at any measurement temperature and tan δmax represents the loss tangent peak value at the corresponding temperature Tmax) versus T/Tmax (where T is the temperature and Tmax is the maximum temperature), corresponding to both polystyrene and polybutadiene phases as well as the activation energy related to the glass‐rubber‐transition process, did not present any significant change with the addition of CB. The dielectric analysis revealed the presence of two relaxation peaks in the composite containing 1.5 vol % CB, the magnitude of which was strongly influenced by the frequency, being attributed to interfacial Maxwell‐Wagner‐Sillars relaxations caused by the presence of different interfaces in the composite. The mechanical properties were not affected by the presence of CB at concentrations of up to 2.5 vol %. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2983–2997, 2003  相似文献   

8.
The morphological structure and mechanical properties of the star‐shaped solution‐polymerized styrene‐butadiene rubber (SSBR) and organically modified nanosilica powder/star‐shaped SSBR co‐coagulated rubber (N‐SSBR) both filled with silica/carbon black (CB) were studied. The results showed that, compared with SSBR, silica powder could be mixed into N‐SSBR much more rapidly, and N‐SSBR/SiO2 nanocomposite had better filler‐dispersion and processability. N‐SSBR/SiO2/CB vulcanizates displayed higher glass‐transition temperature and lower peak value of internal friction loss than SSBR/SiO2/CB vulcanizates. In the N‐SSBR/SiO2/CB vulcanizates, filler was dispersed in nano‐scale resulting in good mechanical properties. Composites filled with silica/CB doped filler exhibited more excellent mechanical properties than those filled with a single filler because of the better filler‐dispersion and stronger interfacial interaction with macromolecular chains. N‐SSBR/SiO2/CB vulcanizates exhibited preferable performance in abrasion resistance and higher bound rubber content as the blending ratio of silica to CB was 20:30. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

9.
The dimensions of reinforcing filler is a key factor in influencing the fracture and fatigue of rubbers. Here, the fracture and fatigue resistance of natural rubber (NR) filled with different dimensional carbon-based fillers including zero-dimensional spherical carbon black (CB), one-dimensional fibrous carbon nanotubes (CNTs) and two-dimensional planar graphene oxide (GO) were explored. To obtain equal hardness, a control indicator in the rubber industry, the amounts of CB, CNTs, and GO were 10.7 vol%, 1.2 vol%, and 1.6 vol%, respectively. J-integral and dynamic fatigue tests revealed that NR filled with CB exhibited the best quasi-static fracture resistance and dynamic crack growth resistance. The much higher hysteresis loss of NR filled with CNTs weakened its fatigue resistance. The planar GO played a limited role in preventing crack growth. Furthermore, digital image correlation revealed that NR filled with CB had the highest strain amplification level and area at the crack tip, which dissipated the most local input energy and then improved the fracture and fatigue performance.  相似文献   

10.
We recently discovered that shearing particle‐reinforced rubbers in oscillation at a frequency fa at a small strain γa (e.g., ~1% strain) for time ta can often produce a spectrum hole or drop in the strain‐dependent dissipation spectra of the materials. The location of the hole (or localized perturbation in the loss modulus or loss tangent) depends on the aging strain amplitude γa. The depth of this hole is influenced by both the oscillatory aging frequency fa and the aging duration ta, and follows a simple power relationship of the product of fa and ta. The exponent for the power relationship is a function of filler concentration. These attributes of the spectral hole in filled rubbers are not sensitive to the frequency used to postanalyze the hole. This new memory effect occurs at very small strains and involves material stiffening during the strain aging, and both of those features are quite different from the Mullins effect in filled elastomers. We interpret this newly discovered memory character of filled rubbers from a much broader concept of structure pinning in a condensed frustrated system and consider that the agglomeration of filler particles in rubber matrix shares common physics with granular materials and glass‐forming materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 859–869, 2010  相似文献   

11.
Environmental stress cracking (ESC) in poly(methyl methacrylate) under different humidity conditions has been investigated. Constant stress‐intensity factor (K) ring‐type specimens were prepared, and all specimens were equilibrated at five different humidity conditions for about two years. ESC tests were carried out under the same humidity as specimens had been stored. Acoustic emission (AE) signals during ESC tests were also measured to examine the crack‐growth behavior. The threshold K value (Kth) tended to increase with increasing humidity. At a relative humidity (RH) of 11%, crack growth occurred gradually until 40 ks under a K value of 0.70 MPam1/2, and then the crack‐growth rate began to increase and AE events were observed. A laser microscopic observation indicated that the crack extended by the coalescence between a main crack and a microcrack ahead of the main crack tip. AE signals generated are considered to be associated with the coalescence. At 98% RH, an incubation period where no crack growth was observed existed under a K value of 0.94 MPam1/2, but the crack began to grow suddenly after that incubation period. This suggests that the craze at the crack tip may become weaker with increasing loading time under high humidity. Although the crack‐growth rate at 98% RH was higher than that at 11% RH, no AE events were observed. This suggests that the crack extended stably in the craze at a crack tip, and sorbed water may make the craze growth easy. All the results suggest that two different ESC mechanisms are activated depending on sorbed water that are varied by humidity. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 1–9, 2002  相似文献   

12.
The influence of an in situ‐grown, sol → gel‐derived silicon oxide filler on mechanical, gas permeation and solvent affinity properties of Surlyn® materials, and melt processibility of Surlyn®/[silicon oxide] hybrid resin, was studied. Tensile modulus increases while elongation‐at‐break decreases with increasing silicon oxide uptake. He gas permeation vs. pressure profiles imply dual mode sorption. Swelling in n‐hexane, 1‐PrOH and xylene decreases as silicon oxide loading increases, the highest uptake being that of xylene. [Surlyn®Zn+2]/[silicon oxide] has better solvent resistance than the H‐form hybrid for each solvent. Affinity of the Zn‐form hybrid for xylene is considerably greater than that for 1‐PrOH and n‐hexane. Melt flow index of the filled H‐form is lower than that of the unfilled H‐form but higher than that of the partially Zn neutralized unfilled form. FTIR analysis of hybrids previously subjected to the melt flow index experiment shows that the silicon oxide phase remained intact but that the high temperatures drove condensation reactions between SiOH groups. After in situ sol–gel reactions and drying [Surlyn®‐H]/[silicon oxide] flakes were passed through an extruder to assess the effect on silicon oxide structure of melt‐processing conditions. All silicon oxide IR fingerprint bands for the processed hybrid persist, the spectrum closely resembling that of a nonextruded hybrid including the signature of Si–OH groups. 29Si solid‐state NMR spectroscopy was used to probe degree of molecular connectivity within the silicon oxide phase. The spectrum is consistent with those of nonextruded hybrids in that Si atom coordination around SiO4 units is predominantly Q3 and Q4, the bias in the distribution toward Q3 being in harmony with the IR results. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 143–154, 1999  相似文献   

13.
A novel core‐shell‐structured carboxylated‐styrene butadiene rubber (XSBR)‐functionalized nanodiamond (ND‐XSBR) was synthesized and characterized. Epoxy (EP) nanocomposites toughened by pristine ND and ND‐XSBR were investigated and compared. The ND‐XSBR‐reinforced nanocomposite exhibited mechanical properties superior to those of the one filled by pristine ND. At a low‐filler loading, the ND‐XSBR exhibited an impressive toughening effect. The maximum flexural strength was shown when the filler loading was as low as 0.1 wt % for the EP/ND‐XSBR nanocomposite. Furthermore, enhanced fracture toughness and fracture energy were shown by surface functionalization, representing enhanced compatibility between the ND‐XSBR and EP matrix. The glass transition temperature (Tg) and storage modulus of the nanocomposites were studied, and the EP/ND‐XSBR0.1 nanocomposite exhibited the highest Tg owing to the stronger interfacial interaction. The EP/ND‐XSBR0.2 exhibited higher storage modulus and Tg than the EP/ND0.2, because the higher interfacial interaction can restrict the molecular mobility of the EP by the functionalized ND‐XSBR. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1890–1898  相似文献   

14.
The sol‐gel reaction of tetraethoxysilane in natural rubber (NR) latex was conducted to produce in situ silica‐filled NR latex, followed by adding sulfur cross‐linking reagents to the latex in a liquid state. The latex was cast and subjected to sulfur curing to result in a unique morphology in the NR composite of a flexible film form. The contents of in situ silica filling were controlled up to 35 parts per one hundred rubber by weight. The silica was locally dispersed around rubber particles to give a filler network. This characteristic morphology brought about the composite of good dynamic mechanical properties. Synchrotron X‐ray absorption near‐edge structure spectroscopy suggested that the sulfidic linkages of the sulfur cross‐linked composites were polysulfidic, Sx (x ≥ 2), and a fraction of shorter polysulfidic linkages became larger with the increase of in situ silica. The present observations will be of use for developing a novel in situ silica‐filled NR composite prepared in NR latex via liquid‐phase soft processing. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

15.
High loading of stable carbon black (CB) dispersion in organic solvent, PGMEA, was prepared by a ball‐milling process when using poly(styrene‐EHA‐HEMA)‐block‐poly(styrene‐EHA‐HEMA‐DMAEMA) (P(SEH)‐b‐P(SEHD)) as a dispersant. The P(SEH)‐b‐P(SEHD) containing P(SEH) as a steric chain and P(SEHD) as an anchoring chain was prepared by TEMPO‐mediated polymerization. The tertiary amine group of DMAEMA in P(SEHD) chain could be adsorbed onto CB by the interaction with the carboxylic acid group on surface of CB and the P(SEH) chain could provide sufficiently steric repulsion force to avoid the aggregation of CB. In addition, a photosensitive dispersant, P(SEH)‐b‐P(SEHD)C?C, containing the methacrylate double bond side group was also synthesized and was used to prepare stable CB dispersion in PGMEA. The effects of the molecular weight between steric and anchoring chains, the content of tertiary amine, and the amount of methacrylate double bond in the dispersant on the particle size of CB were investigated. Furthermore, the influences of various surface properties of CB, such as specific surface area, content of carboxylic acid group, and size of primary particle, on the particle size of CB in dispersion were also discussed. Finally, the photosensitivity of P(SEH)‐b‐P(SEHD)C?C/CB composite was monitored by a photodifferential scanning calorimeter. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6185–6197, 2008  相似文献   

16.
The effect of nanoclay on the fatigue crack growth behavior was investigated. Fatigue tests were carried out on edge notched specimens under cyclic tension loadings. A power–law dependency between crack growth rate and tearing energy was obtained. Natural rubber (NR) filled with 5 phr organically modified montmorillonite (OMMT) possessed the lowest value of the exponent, b, and the smallest crack growth rate at a given tearing energy, denoting the strongest resistance to crack growth. Strain‐induced crystallization was probed by synchrotron WAXD experiments, showing earliest occurrence and strongest ability of crystallization in NR with 5 phr OMMT due to the better exfoliation and orientation of clay layers. The study on the viscoelastic property by dynamic mechanical analysis indicated that NR filled with 10 phr OMMT had the largest contribution to tearing energy attributed to the viscoelastic dissipation in the viscoelastic region in front of the crack tip. This revealed that the strain‐induced crystallization played a more important role in the crack growth resistance than the viscoelastic dissipation for clay filled rubber. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

17.
In the present work, rubber/clay nanocomposites were prepared by a solution mixing process using fluoroelastomers and different nanoclays (namely, Cloisite NA+, Cloisite 10A, Cloisite 20A, and Cloisite 30B). Fluoroelastomers having different microstructure and viscosity (Viton B‐50, Viton B‐600, Viton A‐200, and VTR‐8550) were used. Characterization of the nanocomposites was done by using X‐ray diffraction and atomic force microscopy. The mechanical and dynamic mechanical properties were studied. The surface energy of the clays and the elastomer was also measured. Even with the addition of only 4 phr of clay in Viton B‐50, tensile strength and modulus improved by 30–96% and 80–134%, respectively, depending on the nature of the nanoclays. Exfoliation was observed with both the unmodified and the modified clays at low loading in all the fluoroelastomers. Best properties were observed with the unmodified clay. All the grades of fluororubber followed the same trend. The increment (19%) in storage modulus was also higher in the case of the unmodified clay filled Viton B‐50 system. The results were explained with the help of thermodynamics, surface energies, and swelling studies. The difference in surface energy, Δγ, between the rubber and the unmodified clay was lower. The work of adhesion (67.63 mJ/m2) between Viton B‐50 and Cloisite NA+ was also higher than that (51.42 mJ/m2) between Viton B‐50 and Cloisite 20A. Negative ΔHS value for the unmodified clay‐filled system thermodynamically favored the formation of the nanocomposite as compared to the modified clay filled samples where ΔHS is positive or zero. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 162‐176, 2006  相似文献   

18.
Acrylonitrile butadiene rubber (NBR)/poly(vinyl chloride) (PVC) alloy, filled with anhydrous copper sulfate (CuSO4) particles, was investigated for the first time. The material could be crosslinked in the existence of CuSO4 by heat pressing, without any other crosslink agents. The crosslinking in the material was induced by in situ coordination between nitrile groups of NBR and solid CuSO4 particles, which is thoroughly different from the traditional vulcanization of rubber materials. The coordination crosslinking is formed during heat pressing, other than in solutions, which is valuable for practical applications. The resulting material showed excellent tensile properties, and the maximum strength was close to 90 MPa. The CuSO4 particles act not only as crosslink agents, but also as reinforcing fillers in the polymer matrix. In this work, dynamic mechanical analysis, differential scanning calorimetry, Fourier transform infrared spectrum, X‐ray photoelectron spectroscopy, scanning electron microscope, energy‐dispersive X‐ray spectrum, equilibrium swelling method, and tensile test were performed for the characterization of the material. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 378–386, 2006  相似文献   

19.
The objectives of this paper are to study the crystallization behavior and fracture characteristics of spherical alumina (Al2O3) nanoparticle‐filled polypropylene (PP) composites. Nanocomposites containing 1.5–5.0 wt % of the Al2O3 nanoparticles (pretreated with silane coupling agent) were prepared for this investigation. Wide angle X‐ray diffraction (WAXD) results show that a small amount of β‐crystal of PP forms after adding the Al2O3 nanoparticles. According to differential scanning calorimetric (DSC) and optical microscopy (OM) measurements, the Al2O3 nanoparticles make PP spherulite size reduced and crystallization temperature of PP enhanced, by acting as effective nucleating agents. However, there are no obvious differences in the crystallinity for the virgin PP and the Al2O3/PP nanocomposites. Tensile test shows that both the Young's modulus and the yield strength of the Al2O3/PP nanocomposites increase with the particle content increasing, suggesting that the interfacial interaction between the nanoparticles and PP matrix is relatively strong. Under quasi‐static loading rate, the fracture toughness (KIC) of the Al2O3/PP nanocomposites was found to be insensitive to nanoparticle content. Under impact loading rate, the Izod impact strength and the impact fracture toughness (Gc) indicate that the impact fracture toughness increases initially with the addition of 1.5 wt % of the Al2O3 nanofillers into the PP matrix. However, with the further addition of up to 3.0 and 5.0 wt % nanoparticles, both the Izod impact strength and impact Gc change very little. By observing the single‐edge‐double‐notch (SEDN) specimens with optical microscopy after four point bending (4PB) tests, it was found that numerous crazes and microcracks form around the subcritical crack tip, indicating that crazing and microcracking are the dominant fracture mechanisms. Scanning electron microscopy (SEM) observation confirms this result. In addition, when the strain rate of 4PB tests was increased, some wave‐like branches were formed along the fractured edge for the Al2O3/PP nanocomposites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3652–3664, 2005  相似文献   

20.
A small‐angle X‐ray scattering (SAXS) and swelling study of natural rubber and styrene–butadiene rubber blends (NR/SBR) is presented. To this aim, specimens of NR and SBR and blends with 75/25, 50/50, and 25/75 NR/SBR ratios (in phr) were prepared at a cure temperature of 433 K and the optimum cure time (t100). This time was obtained from rheometer torque curves. The system of cure used in the samples was sulfur/nt‐butyl‐2‐benzothiazole sulfenamide. From swelling tests of the cured samples, information about the molecular weight of the network chain between chemical crosslinks was obtained. For all cured compounds, in the Lorentz plots built from SAXS scattering curves, a maximum of the scattering vector q around 0.14 Å?1 was observed. However, the q position shows a linear‐like shift toward lower values when the SBR content in the SBR/NR blend increases. In pure NR or SBR the q values show a different tendency. The results obtained are discussed in terms of the existence of different levels of vulcanization for each single phase forming the blend and the existence of a third level of vulcanization located in the interfacial NR/SBR layer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2320–2327, 2009  相似文献   

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