Rubber Particle Size Research Articles

Development of an empirical model for determining G*/sin δ in crumb rubber modified binders

This paper describes the development of an empirical model which may be used for predicting the G*/sin δ for neat and crumb rubber modified (CRM) binders. The model was developed using 36 unique CRM binder combinations, crumb rubber concentrations were varied at 5% intervals between 5% and 20%. The effects of crumb rubber particle size on model accuracy were also studied, ultimately a model was produced with the capability of predicting G*/sin δ values over a range of temperatures and crumb rubber concentrations. By definition, the upper limit of the performance grade is dependent on the G*/sin δ value; therefore, the relationship was also considered in terms of high end failure temperature. The rubber coefficient for G*/sin δ ( R cg) was identified as an important parameter in the estimation of G*/sin δ in addition to the CRM. This term is a quantitative representation of the increase typically witnessed in G*/sin δ values with the addition of CRM. Ambient ground CRM exhibited higher R cg values than cryogenically ground particles. Additionally, 95% confidence intervals were generated for the predictive model, thus providing a range of accuracy for the model. The resulting confidence intervals were approximately ±1300 Pa, these confidence intervals were seen to capture 92.6% of the 462 data points used. Findings from this research suggest that the differences between cryogenic and ambient CRM binder are accurately described using the R cg, furthermore binder properties may be predicted using an empirical equation.

Sand–rubber mixtures (large rubber chips)

Mixtures of small rigid sand particles Dsand large soft rubber particles Drare prepared at different volume fractions and tested to investigate their small-strain and zero-lateral strain responses (Dr /Ds≈ 10). Both data sets are simultaneously gathered in an oedometer cell instrumented with bender elements. Data are analyzed in the context of mixture theory and with the aid of numerical simulations. Results show that the sand skeleton controls the mixture response when the volume fraction of rubber particles is Vrubber ≤ 0.3, while the rubber skeleton prevails at Vrubber ≥ 0.6. The large size and incompressibility of rubber particles provides high stress-induced stiffness in the sand skeleton near the equatorial plane of rubber particles. The corresponding increase in local small-strain shear modulus Gmaxresults in earlier wave arrivals in mixtures with Vrubber ≤ 0.3 than in pure sand, while the quasi-static constrained modulus is highest in pure sand. The constrained modulus and shear wave velocity are power functions of the applied effective stress in all mixtures. Results from this study (Dr /Ds≈ 10) and from a previous complementary study with small rubber particles (Dr /Ds= 0.25) show that the development of internal fabric, particle level processes, and the associated macroscale response of sand–rubber mixtures depend on the relative size between the soft rubber chips and the stiff sand particles Dr /Dsand their volume fractions.

Borracha de pneus como modificador de cimentos asfálticos para uso em obras de pavimentação

This work presents the results of a research on the technical feasibility of the use of asphalt-rubber binder by the asphalt paving industry. In Brazil more than 30 million tires a year are disposed of, mostly in inadequate sites, causing serious health and environmental problems. The effects of the main factors (rubber content, rubber particle size, temperature of mixture, reaction time) on the behavior of asphalt-rubber binders are evaluated by traditional and Superpave Method tests, the latter based on certain fundamental properties directly related to field performance. Results of the statistical analysis of the factorial design of laboratory experiments show the most significant effect of rubber contents, or rather, that asphalt-rubber binder may increase the resistance against permanent deformation and fatigue cracking

Novel methods for synthesis of high‐impact polystyrene with bimodal distribution of rubber particle size

AbstractBy using in situ prepolymerization and radiation curing, high‐impact polystyrene (HIPS) with a bimodal distribution of the size of the rubber particles (bimodal HIPS) was synthesized in the presence of ultrafine full‐vulcanized powdered styrene–butadiene rubber (UFPSBR) and polybutadiene rubber (BR). TEM photographs indicated that UFPSBR was dispersed uniformly as a single particle with a diameter of about 100 nm. On the other hand, bimodal HIPS with different rubber particle size distributions could also be obtained by blending HIPS and UFPSBR grafting styrene (UFPSBR‐g‐St) with different grafting yields. The bimodal HIPS with the smallest rubber particle size, at about 100 nm, could be prepared by blending the monomodal HIPS containing big rubber particles with polystyrene/UFPSBR. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

TENSILE STRESS STRAIN BEHAVIOR OF POLYPROPYLENE TOUGHENED WITH BI-MODAL SEBS

The objective is to characterize the effect of the bimodal distribution of rubber particles and its blend ratio on the mechanical properties of the thermoplastic polypropylene blended with two different styrene-ethylene-butadiene-styrene tri-block copolymer (SEBS) at the intermediate and high strain rates. Tensile tests are conducted at the nominal strain rates from 10−1 to 102 (1/sec). Phase morphology is investigated to estimate the bi-modal rubber particle size distribution. In addition, the in-situ observation is conducted during uniaxially stretching within transmission electron microscopy (TEM) step by step to investigate the deformation events depending on the elongation of samples. The elastic modulus increased gradually as the blend ratio of large rubber particle increased. An increase in the rupture strain was found for the bimodal rubber-particle distributed blend system where the blend ratios of small rubber particle and large rubber particle were the same. This is because the smaller particles dominant blend systems show the band-like craze deformation while the localized plastic deformation is taken place in the larger particles dominated blend systems. The synergistic effect of these rubber particles gives rise to a strong increase in the ductility of these bimodal rubber-particle distributed polypropylene systems.

The influence of matrix viscosity and composition on the morphology, rheology, and mechanical properties of thermoplastic elastomer nanocomposites based on EPDM/PP

AbstractThe morphological and rheological properties of thermoplastic elastomer nanocomposites (TPE nanocomposites) were studied using different viscosities of polypropylene (PP) and ethylene‐propylene‐diene monomer (EPDM) rubber content (20, 40, 60 wt%). The components, namely EPDM, PP, Cloisite 15A, and maleic anhydride‐modified PP as compatibilizer, were compounded by a one‐step melt mixing process in a laboratory internal mixer. The structure of the nanocomposites was characterized with X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and rheometry in small amplitude oscillatory shear. The distribution state of the clay between the two phases (PP and EPDM) was found to be dependent on the viscosity ratio of PP to EPDM. In the nanocomposites prepared based on low viscosity PP (LVP) and EPDM, the clay was mostly dispersed into the PP phase and the size of the dispersed rubber particles decreased in comparison with unfilled but otherwise similar blends. However, the dispersed elastomer droplet size in the high viscosity PP (HVP) blends containing 40 and 60% EPDM increased with the introduction of the clay. For TPE nanocomposites, the dependence of the storage modulus (G′) on angular frequency (ω) followed a clear nonterminal behavior. The increase in the storage modulus and the decrease in the terminal zone slope of the elastic modulus curve were found to be larger in the LVP nanocomposite in comparison with the HVP sample. The yield stress of nanoclay‐filled blends prepared with LVP increased more than that of HVP samples. The tensile modulus improved for all nanocomposites but a higher percentage of increase was observed in the case of LVP samples. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers

Phase Morphology and Mechanical Properties of Rubber-Toughened Polypropylene Nanocomposites: Effect of Elastomer Polarity

The objective of this work was to investigate the effect of elastomer polarity on phase structure and mechanical properties of PP nanocomposites. The nonpolar and polar elastomers studied were polyethylene octene (POE) and polyethylene octene grafted maleic anhydride (POEgMAH), respectively. The results from mechanical studies showed that the POEgMAH-toughened polypropylene nanocomposites have higher Izod impact strength but lower tensile and flexural properties than the unmaleated ones. X-ray diffraction (XRD) was used to characterize the formation of nanocomposites. XRD studies revealed that intercalated rubber-toughened PP nanocomposites (RTPPNC) had been successfully prepared where the macromolecule segments PP were intercalated into the interlayer space of organoclay. XRD also indicated that the incorporation of polar POEgMAH elastomers into PP nanocomposites contribute to a better intercalation effect and formed a more exfoliated combinations structure compared to POE. Scanning electron microscope (SEM) was used for the investigation of the phase morphology and rubber particle size and particle-size distribution. SEM study revealed a two-phase morphology where POE as droplets dispersed finely and uniformly in the PP matrix. The POEgMAH-toughened PP nanocomposites shows a much finer dispersion of elastomer particles than POE-toughened PP nanocomposites.

Thermoplastic vulcanizates obtained by reaction-induced phase separation: Interplay between phase separation dynamics, final morphology and mechanical properties

Reaction-induced phase separation (RIPS) of miscible blends of poly(ɛ-caprolactone) (PCL) and an epoxy resin based on poly(propylene oxide) (PPO) was used to prepare thermoplastic vulcanizates (TPVs) with fine rubber dispersions. Scanning electron microscopy (SEM) confirmed the formation of cross-linked rubber particles dispersed in the thermoplastic matrix at PCL contents ≥20wt%. The morphology development during phase separation was studied by optical microscopy (OM) and time-resolved small-angle light scattering (SALS). It was shown that higher curing temperatures lead to a decrease in rubber particle size, but at the same time lead to an increase in the extent of particle connectivity. In some cases, gelation of the PPO-rich phase limits full structure development, which leads to extensive connectivity between the dispersed rubber particles and a strong deterioration in tensile properties.

Particle Size Effect of Crumb Rubber on Rheology and Morphology of Asphalt Binders with Long-term Aging

ABSTRACT Two different particle sizes of crumb rubber at three different concentrations were mixed with two asphalts to investigate the effect of rubber particles on the fundamental internal microstructure of asphalt binders with respect to their long-term aging performance. The rheological, morphological, and chemical properties of unaged and aged unmodified and rubber modified asphalt binders were studied as a function of long-term oxidative aging. Based on the limited study, the results indicate that the amounts of rubber particles added into asphalt binder are asphalt dependent. For highly incompatible asphalt, rubber concentration has substantial effect on the long-term flow properties of asphalt binders. For compatible asphalt, addition of rubber increased the elasticity of asphalts and also reduced viscosity buildup with aging. In addition, particle size of rubber does not show significant differences in terms of its effect on the long-term aging characteristics of asphalt binder. Furthermore, results from atomic force microscopy (AFM) showed that some fractions of the rubber particles may be dissolved in the asphalt due to devulcanization of the rubber, and hence, could explain the appearance of “new” material in the AFM image of the recovered asphalt samples.

Effect of Total Rubber Content on Ductility of Polypropylene Blended with Bimodal Distribution of Styrene-Ethylene-Butadiene-Styrene Particle Size

The objective is to characterize the effects of total rubber amount on the mechanical properties of the thermoplastic polypropylene blended with two different styrene-ethylene-butadiene-styrene tri-block copolymer (SEBS) at the intermediate and high strain rates. PP and two types of SEBS were blended so that the total rubber amounts were 10 and 20 wt% against PP by the two-step blending procedure. Tensile tests are conducted at the nominal strain rates from 3 × 10-1 to 102s-1. Phase morphology is investigated to estimate the bi-modal rubber particle size distribution. In addition, the fracture surfaces were observed by scanning electron microscopy (SEM) in order to understand the difference of the toughening mechanism for PP toughened with the bimodal rubber particle size distribution in PP and SEBS blends at various total rubber contents. The large material ductility is obtained in the fracture mechanism of craze bands. The craze bands are obtained in the blend whose total SEBS content is larger than 20 wt%. In addition, the weight ratio of small SEBS particles against total SEBS particles is larger than 20% and the inter-particle distance of large SEBS particles ranging between 100 and 300nm are additional condition for crazes bands. The synergistic effect of these rubber particles gives rise to a strong increase in the ductility of these bimodal rubber-particle distributed polypropylene systems.

Tensile behavior of polypropylene blended with bimodal distribution of styrene‐ethylene‐butadiene‐styrene particle size

AbstractThe objective is to characterize the effects of the bimodal distribution of rubber particles and its blend ratio on the mechanical properties of the thermoplastic polypropylene blended with two different styrene‐ethylene‐butadiene‐styrene triblock copolymer at the intermediate and high strain rates. Tensile tests are conducted at the nominal strain rates from 3 × 10−1 to 102 (1/s). Phase morphology is investigated to estimate the bimodal rubber particle size distribution. In addition, the in situ observation is conducted during uniaxially stretching within transmission electron microscopy step by step to investigate the deformation events depending on the elongation of samples. The elastic modulus increased gradually as the blend ratio of large rubber particle increased. An increase in the rupture strain and the strain energy up to failure was found for the bimodal rubber particle distributed blend system where the blend ratios of small rubber particle and large rubber particle were same. This is because the smaller particles dominant blend systems show the bandlike craze deformation while the localized plastic deformation is taken place in the larger particles dominated blend systems. The synergistic effect of these rubber particles gives rise to a strong increase in the ductility of these bimodal rubber particle distributed polypropylene systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Effect of rubber particle size on the impact tensile fracture behavior of MBS resin with a bimodal particle size distribution

We performed impact tensile fracture experiments on methylmethacrylate–butadiene–styrene (MBS) resin with small and large particles in a bimodal size distribution, and examined the effects of particle size on fracture behavior by fixing the total rubber content (28 wt%) and the small particle size (about 140 nm), and varying the size of large particles (about 490 nm or 670 nm). Dynamic load P′ and displacement δ′ of single-edge-cracked specimens were measured using a Piezo sensor and a high-speed extensometer, respectively. A P′−δ′ diagram was used to determine external work Uex applied to the specimen, elastic energy Ee stored in the specimen, and fracture energy Ef for creating a new fracture surface As. Energy release rate was then estimated using Gf = Ef/As. Values of Gf were correlated with fracture loads and mean crack velocity vm determined from load and time relationships. We then examined the effect of particle size on Gf and vm, and results indicated that particle size plays an important role in changing the values of Gf and vm.

Thermoplastic Vulcanizates by Reaction-Induced Phase Separation of a Miscible Poly(ε-Caprolactone)/Epoxy System

Abstract A new method for the preparation of thermoplastic vulcanizates (TPVs) was successfully applied. Starting with a miscible system of a semi-crystalline thermoplastic polymer and an elastomer precursor, phase separation was induced by the increase in molecular weight during selective crosslinking of the elastomer precursor. As a model system, the semi-crystalline thermoplastic poly(Ε-caprolactone) (PCL) was used in combination with a rubbery epoxy resin based on poly(propylene oxide) (PPOn-epoxy). This approach enables the dispersion of up to 80 wt% of crosslinked rubber in a thermoplastic matrix, providing morphologies that are typical for TPVs. A range in rubber particle size of 0.5 to 3 μm was obtained by this new method, without the need of blend compatibilization or dynamic processing. The materials exhibit mechanical and rheological properties typical for TPVs and the rubber particles feature a high crosslink density. At high curing temperatures and high PPOn-epoxy contents, connectivity of the rubber particles is observed, which is attributed to the phase separation mechanism. Connectivity of the rubber particles has a negative influence on both the mechanical properties and the rheological behavior.

Preparation and characterization of rubber‐toughened poly(trimethylene terephthalate)/organoclay nanocomposite

AbstractRubber‐toughened poly(trimethylene terephthalate) (PTT)–organoclay nanocomposite (RTPTTCN) was prepared by a melt mixing technique. The rubber‐toughened PTT (RTPTT) was made by blending it with ethylene propylene diene terpolymer (EPDM) and with a small amount of maleated EPDM as a compatibilizer. XRD and TEM analysis indicated that the RTPTTCN forms a partially exfoliated nanocomposite. It was observed from SEM analysis that the clay nanoparticles induced a reduction of rubber particle size in the PTT matrix. Tensile and dynamic mechanical analysis indicated that the clay nanoparticles enhance the stiffness of the RTPTT without adversely affecting its toughness. Melt rheological studies revealed that the nanocomposites exhibited strong shear thinning behavior, and a percolated network of the clay particles was formed. It was also observed from DSC that the clay nanoparticles caused an increase in the nonisothermal crystallization temperature of the PTT. POLYM. ENG. SCI., 47:863–870, 2007. © 2007 Society of Plastics Engineers

Compatibilization of PP/SEBS-MAH blends by grafting Glycidyl Methacrylate onto Polypropylene

In this paper, the glycidyl methacrylate(GMA) was grafted to Polypropylene(PP) macromolecular backbone by melt radical grafting. The grafted PP-g-GMA was used to compatibilize PP/SEBS-g-MAH blend in a Haake apparatus. The result of Fourier Transform Infrared(FTIR) spectrum showed that the GMA had been grafted to PP. And the reaction between epoxy groups in the GMA and MAH groups in SEBS-g-MAH had taken place. The result of torque test showed that the torque values of the compatibilized blends were higher than that of the uncompatibilized blends. The observation of Scanning Electron Microscopy (SEM) showed that the dispersed phase domain size of compatibilized blends decreased evidently than uncompatibilized blends. When the content of SEBS-g-MAH was 16 wt % and the PP-g-GMA was 2 wt % in the blend, the rubber particle size had a minimum value. Those indicated that the PP-g-GMA could compatibilize PP/ SEBS-g-MAH blends effectively. Notched Izod impact tests showed the addition of PP-g-GMA in the PP/SEBS-g-MAH blends induced a remarkable improvement of toughness and yielded a tougher PP blends.

Modeling of asphalt-rubber rotational viscosity by statistical analysis and neural networks

It is of a great importance to know binders' viscosity in order to perform handling, mixing, application processes and asphalt mixes compaction in highway surfacing. This paper presents the results of viscosity measurement in asphalt-rubber binders prepared in laboratory. The binders were prepared varying the rubber content, rubber particle size, duration and temperature of mixture, all following a statistical design plan. The statistical analysis and artificial neural networks were used to create mathematical models for prediction of the binders viscosity. The comparison between experimental data and simulated results with the generated models showed best performance of the neural networks analysis in contrast to the statistic models. The results indicated that the rubber content and duration of mixture have major influence on the observed viscosity for the considered interval of parameters variation.

Effects of clay on phase morphology and mechanical properties in polyamide 6/EPDM-g-MA/organoclay ternary nanocomposites

In this study, both organoclay and EPDM-g-MA rubber were used to simultaneously improve the toughness and stiffness of polyamide 6 (PA6). We first prepared PA6/EPDM-g-MA/organoclay ternary nanocomposites using melt blending. Then the composites were subjected to traditional injection molding and so-called dynamic packing injection molding. The dispersion of clay, phase morphology, crystallinity and orientation of PA6 as well the mechanical properties were characterized by WAXD, SEM, DSC, 2D-WAXS and mechanical testing, respectively. The effects of clay on phase morphology and mechanical properties of PA6/EPDM-g-MA blends could be summarized as follows: (1) weakening interphase adhesion between PA6 and EPDM-g-MA rubber particles, resulted in increasing of rubber particle size, as the clay and rubber contents are low; (2) preventing coalescence of rubber domains, arisen in decreasing of rubber particle size, as the clay and rubber contents are high; (3) the blocking effect on the overlap of stress volume around rubber particles caused broadening of the brittle–ductile transition region and decrease of toughness, and (4) the effective stress transfer leading a better reinforcement when the interparticle distance is smaller than the critical value.

Effect of Rubber Particle Size on Impact Tensile Fracture Behavior of MBS Resin

The single-edge-cracked specimens of MBS resin with two different sizes of rubber particles were fractured under impact tensile loading. The dynamic load and displacement were measured using a piezo sensor and a high-speed extensometer, respectively. The load and displacement diagram, i.e. the external work Uex applied to the specimen was used to determine the elastic energy Ee and the fracture energy Ef for creating a new fracture surface As. Energy release rate was then estimated using Gf = Ef/As. The values of Gf were correlated with the fracture loads and the mean crack velocities determined from the load and time relationships. The effect of the particle size on the impact tensile fracture behavior was then examined. The results showed that the particle size plays an important role in changing the impact fracture behavior of MBS resin.

Multiscale Modeling of Deforation Behavior of Rubber Blended Semi-Crystalline Polymer

To elucidate the toughening mechanism in rubber particle modified semi-crystalline polymers in which the average matrix ligament thickness plays important roles, the micro-to mesoscopic deformation behavior of rubber/semi-crystalline polymer blends was modeled by using large-deformation finite element homogenization method. In this paper, the deformation behavior of three kinds of models which have different size of rubber particles was investigated. A series of computational simulation clarified that highly localized deformation is induced by the initial orientation of lamellae at interface region for the case of smaller size of rubber particles, and it produces larger strain in the matrix due to localization and propagation of the deformation zone. Furthemore, the microscopic deformation is mainly absorbed by not only a slip along chain direction in the crystalline phase, but also interlamellar shear in the amorphous phase, which must be closely related to the toughening mechanism of the rubber/semi-crystalline polymer blends.

Effect of octene content in poly(ethylene‐co‐1‐octene) on the properties of poly(propylene)/poly(ethylene‐co‐1‐octene) blends

AbstractEthylene‐octene random copolymer (EOC) is one of the most commonly employed elastomers for PP, and as such its rubber toughening efficiency has been extensively studied. However, most existing studies employ EOC containing an octene comonomer of about 8 mol %. Therefore, in this study, we investigated the effect of EOC octene comonomer content on the morphology and thermal and mechanical properties of PP‐ethylene random copolymer (PP‐CP)/EOC (80/20 wt %/wt %) blends. It was clearly shown that the properties of the blends are significantly affected by the octene content. The rubber particle size of the blends decreased as the octene content in the EOC was increased, which was a consequence of the reduced interfacial tension between PP‐CP and EOC. Impact strength of the blends as a function of octene content displayed a brittle‐ductile transition. The tensile yield strength and modulus of the PP‐CP/EOC blends were decreased by addition of EOC, owing to incorporation of the soft EOC into the hard PP‐CP. The tensile yield strength and modulus of PP‐CP/EOC blends decreased monotonically with the octene content in the EOC. The melting temperature as well as the crystallinity of the PP‐CP phase were not affected significantly by the addition of EOC whereas a notable shift in melting and crystallization temperatures was observed for the EOC phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1133–1139, 2007