Weak boundary layers on vulcanized styrene–butadiene rubber treated with sulfuric acid

A synthetic vulcanized styrene-butadiene rubber (R2) was used in this study. The presence of paraffin wax and zinc stearate in the rubber composition prevented the adhesion of R2 rubber to solvent-based polyester-urethane adhesive. To increase the adhesion properties of R2 rubber, a surface treatment with sulfuric acid (cyclization) was applied, and the length of the immersion in sulfuric acid and the time between the immersion time and the neutralization were varied. The treated R2 rubber surfaces were characterized using ATR-IR spectroscopy, contact angle measurements (water, ethanediol), and scanning electron microscopy (SEM). The mechanical properties of the treated rubber were obtained from stress-strain experiments. The joint strength was obtained from the T-peel test on treated R2 rubber/polyurethane adhesive joints. Due to the penetration of the sulfuric acid into the R2 rubber bulk, the mechanical properties decreased. The treatment with sulfuric acid produced several chemical modifications on the rubber surface: sulfonation of the butadiene and the creation of C C and C O bonds. Furthermore, the surface treatment of the R2 rubber with sulfuric acid removes paraffin wax from the rubber surface, which had a beneficial effect on adhesion to the polyurethane adhesive. To remove the wax layer, the surface was wiped with petroleum ether solvent after treating the R2 rubber with sulfuric acid. However, in some experiments a progressive migration of wax from the R2 rubber bulk to the surface with time happened. The migration of wax was prevented by increasing the immersion time in H₂SO₄ by more than 5 min.     

The effect of styrene–butadiene latex carboxylation on adhesion

Styrene–butadiene latices are widely used as binders in pigmented coatings for the paper and board industry. White pitch deposition, which is one type of surface fouling, is a well-known problem at paper machines using coated broke as a raw material. The main component of white pitch is latex, such as styrene–butadiene. The viscoelastic properties of styrene–butadiene latex have been found to affect on white pitch formation, but the effect of carboxylation has not been studied extensively. Carboxylation has traditionally performed to latices in order to increase colloidal stability, but it has also effect on mechanical properties of the latices.In this paper, we studied the adhesion potential of three styrene–butadiene latices by using a cylindrical probe tack method under dry and aqueous conditions while varying the carboxylation degree of the latex. Adhesion potential was measured using low and high energy surfaces as adherents. The results show that carboxylation influences adhesion potential of latices in both dry and aqueous environments.     

Effects of modified silica on the co-vulcanization kinetics and mechanical performances of natural rubber/styrene–butadiene rubber blends

Rubber blends are widely used for combining the advantages of each rubber component. However, to date, how to determine and distinguish the vulcanization kinetics for each single rubber phase in rubber blends during the co-vulcanization process is still a challenge. Herein, high-resolution pyrolysis gas chromatography–mass spectrometry (HR PyGC-MS) was employed for the first time to investigate the vulcanization kinetics of natural rubber (NR) and styrene–butadiene rubber (SBR) in NR/SBR blends filled with modified silica (SiO₂). The reaction rates of crosslinking of each rubber phase in NR/SBR were calculated, which showed that the crosslinking rates of NR were much lower than those of SBR phase in the unfilled blends and blends filled with unmodified and silane modified silica. Interestingly, the vulcanization rates of NR and SBR phase were approximately same in the vulcanization accelerator modified silica filled blends, showing better co-vulcanization. In addition, the vulcanization accelerator modified silica was uniformly dispersed and endowed rubber blends with higher mechanical strength compared to the untreated silica. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48838.     

Preparation and characterization of natural rubber/ultrafine full-vulcanized powdered styrene–butadiene rubber blends

In this paper, natural rubber (NR)/ultrafine full-vulcanized styrene–butadiene powdered rubber (UFPSBR) blends were prepared and studied for the first time. Scanning electron microscopy and thermogravimetric analysis were employed to characterize UFPSBR. Equilibrium swelling method was used to determine the crosslink density of NR/UFPSBR vulcanizates. The results on mechanical properties showed that when NR/UFPSBR ratio was 100/5, the formulation exhibited favorable performances compared to pure NR vulcanizates. The heat build-up temperature also decreased after adding UFPSBR into the NR formulation. In dynamic mechanical analysis, in the temperature range of ?10 to ?5 °C, loss factor (tanδ) values of NR/UFPSBR vulcanizates showed an increasing trend over the given temperature range and exhibited a peak value at approximate ?5 °C. This indicates that wet traction and rolling resistance of samples were improved after UFPSBR was added in NR. This research demonstrates that UFPSBR can be incorporated into a conventional NR formula to successfully improve the comprehensive performances and dynamic mechanical properties of NR formula.     

Synthesis of emulsion styrene butadiene rubber by reversible addition–fragmentation chain transfer polymerization and its properties

Emulsion polymerization is generally used to synthesize styrene butadiene rubber (SBR), and the molecular weight of this rubber can be easily increased. However, the broad molecular weight distribution (MWD) of SBR increases energy loss and adversely affects the dynamic viscoelastic properties. To overcome this disadvantage, reversible addition–fragmentation chain transfer (RAFT) polymerization, which is a type of living polymerization, is applied to emulsion polymerization for preparing RAFT emulsion SBR (ESBR). The molecular weight and microstructure of RAFT ESBR are compared to those of commercially available ESBR 1502 by gel permeation chromatography and proton nuclear magnetic resonance spectroscopy. The aforementioned two polymers are used to prepare unfilled ESBR compounds, which are compared in terms of key physical properties (abrasion resistance, mechanical properties, and dynamic viscoelastic properties). It is confirmed that various physical properties of RAFT ESBR are improved due to its narrow MWD. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47069.     

Thermal decomposition kinetics of dynamically vulcanized polyamide 6–acrylonitrile butadiene rubber–halloysite nanotube nanocomposites

Thermally stable thermoplastic elastomer nanocomposites based on polyamide 6 (PA6), acrylonitrile butadiene rubber (NBR), and halloysite nanotubes (HNTs) were dynamically vulcanized, and their nonisothermal decomposition kinetics were examined. The Friedman, Kissinger–Akahira–Sunose (KAS), Ozawa–Wall–Flynn (FWO), and modified Coats–Redfern (m-CR) isoconversional models were used to obtain information about the kinetics of the thermal decomposition of PA6–NBR–HNTs in terms of the activation energy per partial mass loss monitored through thermogravimetric analyses performed at different heating rates. An erratic trend was due to the Friedman model, especially for systems having higher HNT loadings, whereas the KAS, FWO, and m-CR models revealed very similar meaningful thermal decomposition kinetics. A relatively high activation energy corroborating a reliable thermal stability was obtained by the addition of HNTs to PA6–NBR, and the resistance against decomposition was higher for systems containing more HNT. This signified the role of the HNTs as thermal stability modifiers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47483.     

Structure–property relationships of silica/silane formulations in natural rubber,isoprene rubber and styrene–butadiene rubber composites

The mechanical performance of natural rubber (NR), synthetic poly-isoprene rubber (IR), and styrene–butadiene rubber (SBR) composites filled with various silica/silane systems is investigated. The results are analyzed by referring to micro-mechanical material parameters, which quantify the morphological and structural properties of the polymer and filler network. These are obtained from fits with the dynamic flocculation model (DFM) describing the strongly nonlinear quasi-static stress–strain response of filler-reinforced elastomers as found from multihysteresis measurements of the investigated compounds. We focus on the reinforcement mechanisms of silica compounds with coupling and covering silane, respectively. The fitted material parameters give hints that the coupling silane provides a strong chemical polymer–filler coupling, which is accompanied by improved strength of filler–filler bonds for all three rubbers types. This may result also from the chemical coupling of short chains bridging adjacent silica particles. It implies larger stress values for the coupling silane and, in the case of NR and IR, a more pronounced “Payne effect” compared to the covering silane. In contrast, for SBR, the coupling silane delivers a lower Payne effect, which is explained by differences in the compatibility between rubber type and silane-grafted silica surface. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48435.     

Chemical modification of styrene–butadiene–styrene (SBS) rubber by reactive grafting with maleic anhydride

A procedure to increase the adhesion of block styrene-butadiene-styrene (SBS) rubber consisting of the reactive grafting with maleic anhydride (MA) in the presence of an organic peroxide radical initiator is proposed. The influence of the reactive grafting on the surface properties of SBS has been studied with special emphasis on the improvement of the adhesion to polyurethane adhesive. The grafting of MA onto SBS was carried out in the presence of different concentrations of 2,5-dimethyl-2,5-di(tertbutyl peroxy) hexane (DBPH) as initiator to generate oxygen radicals by thermal decomposition, which induce the grafting reaction. The modification process was performed in the molten state using a Brabender mixer to premix the reactants and a hot press to initiate the functionalizing reaction. ATR-IR and XPS spectroscopies were employed to verify the grafting of MA on SBS. The changes in wettability on the modified SBS rubber were determined by contact angle measurements. Adhesion properties were evaluated from T-peel tests of SBS rubber/polyurethane adhesive joints. Reasonable extents of MA grafting on SBS were obtained (evidenced by the presence of a weak carbonyl vibration at 1700 cm^-1 in the ATR-IR spectra and by the carbon- oxygen band at a binding energy of 287.0 eV in the XPS spectra). The higher the DBPH amount, the higher the MA amount grafted onto the SBS surface. The maximum grafting level was obtained using 2 wt% MA. Grafted species seemed to be mainly concentrated on the surface of the SBS-molded sheets. The wettability of the modified rubber increased with respect to the original polymer, new carbon-oxygen moieties were created and the C/O ratio increased. A noticeable enhancement in peel strength values was observed, which was ascribed to the creation of interfacial interactions between the polyurethane and the SBS rubber surfaces.     

Soybean oil induced efficient thermal–oxidative degradation of covalently crosslinked styrene butadiene rubber

It has been a technical challenge of recycling tire rubbers due to the covalently crosslinked polymer network structure. Unlike conventional recombination of crosslinked SBR under thermal oxidation, SBR vulcanizate was efficiently degraded by thermal oxidation at 150 °C in presence of soybean oil, resulting in 47.3% sol fraction by weight. The structural evolution of SBR vulcanizates during thermal oxidation was characterized by sol–gel ratio, chemical structure, molecular weight, and oxidative erosion on the rubber surface. It was found that the continuous oxidation process facilitated main chain scission of SBR vulcanizates, resulting in a decrease of molecular weight of the sol fraction. The concentration of carbonyl groups, sol fraction, and surface erosion continually increased with reaction time. The large amounts of soybean oil significantly affect the thermal stability of SBR vulcanizates. Moreover, soybean oil is more efficient in decomposition of the SBR vulcanizates and results in more homogeneous and efficient oxidation reactions than paraffin oil. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48935.     

Preparation of dispersible nanosilica surface-capped by hexamethyl disilazane via an in situ surface-modification method and investigation of its effects on the mechanical properties of styrene–butadiene/butadiene rubber

Silica has been established as one of the most promising materials in green tires. The filler–rubber interactions can increase the comprehensive performance of rubber composites. In this study, sodium silicate was used as the silicon source and hexamethyl disilazane (HMDS; molecular formula: C₆H₁₉NSi₂) was used as a modifier to synthesize dispersible silica (DNS) via an in situ surface-modification method. The effects of the HMDS-capped silica on the properties of rubber–matrix composites made of styrene–butadiene rubber (SBR) and high-cis-polybutadiene rubber (BR9000 or BR) were investigated with Zeosil 1165MP (Z1165-MP; a commercial highly dispersible silica produced by Rhodia for the production of green tires in the rubber industry) as a reference. The results show that the SBR–BR–DNS composite was before the SBR–BR–Z1165-MP composite in increasing the tear strength and elongation at break and reducing the compression heat buildup. On the basis of the resulting properties, the reinforcing behaviors in the rubber–matrix composites were analyzed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47763.     

Thermal and mechanical enhancement of styrene–butadiene rubber by filling with modified anthracite coal

Anthracite is the highest rank of coal with a layered structure similar to that of graphite. Here, styrene–butadiene rubber/modified anthracite (MA) composites were prepared and analyzed. The microstructure and dispersion of the anthracite were improved by ball milling with the modifier bis-(γ-triethoxysilylpropyl)-tetrasulfide (KH-Si69). The particle size of the modified coal was decreased significantly to ~3 μm, while surface interactions with the modifier yielded enhanced lamellar morphology and hydrophobic surfaces. The anthracite lamellae were well dispersed in the rubber matrix, providing good reinforcement; the tensile strength of the composite exceeded that of a composite with carbon black (CB) N660 filler (16.65 vs. 14.68 MPa). Moreover, low-level CB or silica compositing further promoted the dispersion of coal particles in the rubber, effectively enhancing the mechanical reinforcement behavior of the coal particles as well as the thermal stability of the rubber composite. Notably, it led to a 10.63% improvement in tensile strength and a 9.96 °C increase in the 5% mass loss temperature compared to the composite with a single MA filler. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48203.     

Carbon black reinforced thermoplastic vulcanisates based on ethylene–vinyl acetate copolymer/styrene–butadiene rubber blends

Thermoplastic vulcanisates (TPVs) based on ethylene–vinyl acetate copolymer (EVA)/styrene–butadiene rubber (SBR) blends were prepared by dynamic vulcanisation, with the TPVs being reinforced by carbon black (CB). Experimental results indicated that the mechanical properties of dynamically vulcanised EVA/SBR blends were enhanced remarkably by the incorporation of CB. Morphology study showed that the SBR particles with average diameter of 20?μm were dispersed evenly on the etched surface of EVA/SBR/CB TPVs. The Mullins effect could be observed in the stress–strain curves of EVA/SBR TPVs and EVA/SBR/CB TPVs during the uniaxial loading–unloading cycles. Compared with EVA/SBR TPVs, CB reinforced EVA/SBR TPVs had the relatively higher stress, residual deformation and internal friction loss.     

Supercapacitive properties of electrodeposited polypyrrole on acrylonitrile–butadiene rubber as a flexible current collector

Flexible sheets consisting of acrylonitrile–butadiene rubber (NBR) and vapor-grown carbon fiber (VGCF) are newly prepared varying the composition (VGCF 10–30 wt%) for use as a current collector of supercapacitor electrodes. The electrical conductivity of as-prepared VGCF/NBR current collector can be enhanced as the content of VGCF increases. The VGCF/NBR current collector is then electrodeposited with pyrrole using a potentiodynamic cyclic voltammetry to yield a polypyrrole (PPy)/VGCF/NBR composite electrode. Cyclic voltammetry result for the PPy/VGCF/NBR composites shows that the sample with 30 wt% VGCF achieves a maximum specific capacitance (125.8 F g^?1) at 5?mV?s^?1 and reaches a lower specific capacitance at higher scan rates. In addition, the flexibility of supercapacitor electrode of PPy can also be established with a comparable capacitance value by using the NBR-based current collector.     

Effect of silica reinforcement on natural rubber and butadiene rubber vulcanizates by a sol–gel reaction with tetraethoxysilane

The effect of silica reinforcement was studied for natural rubber (NR) and butadiene rubber (BR) vulcanizates by a sol–gel reaction with tetraethoxysilane at different temperatures. The formation of silica in the rubber vulcanizates was investigated analytically with Fourier transform infrared spectroscopy and energy-dispersive X-ray analysis. The variations of the mechanical and dynamic properties were measured in the NR and BR vulcanizates with silica filling. The hardness of the rubber vulcanizates increased with silica filling in the rubber matrix. The tensile strength and elongation at break decreased with silica filling in the NR vulcanizates. The moduli at 50, 100, and 300% elongation increased with silica filling in the rubber matrix. The storage modulus of silica-filled rubber vulcanizates became higher than that of pure rubber vulcanizates. The temperature dependence of the loss modulus also increased with silica filling. The temperature dependence of the loss tangent was maintained, regardless of silica filling in the BR vulcanizates. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Treatment with Ar–O2 low-pressure plasma of vulcanized rubber sole containing noticeable amount of processing oils for improving adhesion to upper in shoe industry

Vulcanized rubber (L3 rubber) containing intentionally noticeable excess of processing oils in its formulation was treated with Argon–Oxygen (Ar–O₂) (2:1, vol/vol) low-pressure (LP) plasma for achieving a satisfactory level of adhesion to waterborne polyurethane adhesive. The effectiveness of the Ar–O₂ LP plasma treatment of L3 rubber depended on both the configuration of the plasma chamber shelves and the treatment time. Surface modifications were assessed by attenuated total reflectance-IR and X-ray photoelectron spectroscopy, contact angle measurements, and scanning electron microscopy. Ar–O₂ LP plasma treatment in direct configuration provided the most effective surface modification of the L3 rubber, and the increase in the treatment time improved the extent of the surface modifications. However, even important surface modifications were produced by Ar–O₂ LP plasma treatment, adhesion of treated L3 rubber was not improved due to the creation of weak boundary layer at the polyurethane–rubber interface after joint formation. Heating at 80 °C for 12 h of the as-received L3 rubber prior to Ar–O₂ LP plasma treatment enhanced the extent of the surface modifications, and improved adhesion was obtained for Ar–O₂ LP plasma treatment times higher than 600 s.     

Application of hygrothermally decomposed polyurethane in rubber recipes Part 2–Influence of hygrothermally decomposed polyester–urethane on cure characteristics and viscoelastic behaviour of styrene/butadiene rubber

Abstract

Hygrothermally decomposed polyester–urethane (HD PUR) was mixed at concentrations up to 20 pphr with a styrene/butadiene rubber (SBR), using an efficient vulcanisation system. Changes in the cure behaviour were followed by vulcametry, plate–plate rheometry, and differential scanning calorimetry. It was found that the degree of crosslinking was increased by the incorporation of HD PUR, which acts as an accelerator in SBR stocks. Increasing crosslinking resulted in higher stiffness and strength and was accompanied by a reduction in elongation at break and swelling index.     

Chemical modification of styrene–butadiene–styrene co-polymer by grafting of N-carbamyl maleamic acid

A styrene–butadiene–styrene (SBS) block co-polymer was functionalized using different amounts of N-carbamyl maleamic acid (NCMA) and benzoyl peroxide as initiator. NCMA, which is a bifunctional monomer, was synthesized in our laboratories. The concentration of NCMA used in the functionalization of SBS ranged from 0.5 to 3% (w/w) based on the co-polymer mass. Benzoyloxy radicals generated from the thermal decomposition of benzoyl peroxide initiated the grafting reaction. The concentration of the initiator was kept constant at 0.076% (w/w). FT-IR spectroscopy was used to determine the amount of NCMA effectively grafted onto the SBS. The maximum amount of monomer grafted was about 0.3% (w/w) when the SBS was modified with 1% (w/w) NCMA. The effect of grafting on the surface properties and the adhesion to polyurethane adhesive of the modified SBS were evaluated. Contact angle values were obtained using liquid droplets. When the concentration of the NCMA used in the grafting reaction was 1% (w/w), the contact angles with water on original and modified SBS were 95° and 77°, respectively. Adhesion properties were evaluated by standard peel tests employing a commercial polyurethane adhesive. The modified SBS having the largest amount of NCMA displayed a T-peel strength value 5-times higher than the corresponding value measured with the original SBS.     

Surface modification of magnesium hydroxide and its application in flame-retardant oil-extended styrene–ethylene–butadiene–styrene/polypropylene composites

Magnesium hydroxide (MH) was modified with triethoxysilane and polymethyl–vinyl silicone rubber and used to prepare flame-retardant oil-extended styrene–ethylene–butadiene–styrene (O-SEBS)–polypropylene (PP) composites. The water contact angle of modified magnesium hydroxide (MMH) reached 141°; this indicated that MMH possessed excellent hydrophobic properties. The samples (1.6 mm) passed the UL-94 V-0 rating during vertical burning tests when the loading amount of MH or MMH was 70 wt %. This indicated the modification did not decrease the flame-retardant properties of MH. The tensile strength and elongation at break values of the MMH–O-SEBS–PP composites increased by 20.4 and 88.9%, respectively, compared with those of the MH–O-SEBS–PP composites. The modification of MH enhanced the interfacial compatibility between the flame retardant and the matrix; thus, the mechanical performance was enhanced. Moreover, MMH was scarcely extracted after water treatment for 168 h at 70 °C. As a result, the mechanical properties and flame retardancy of the MMH–O-SEBS–PP composites were well maintained after the water treatment. The modification of the MH endowed the O-SEBS–PP composites with an excellent compatibility and water-resistant performance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47129.     

Effect of nanoclay on mechanical and thermal properties of triblock SBS (styrene–butadiene–styrene) and its binary blend nanocomposites: comparison between polyethylene and polystyrene

ABSTRACT

In this study, the effect of organo-modified nanoclay (OMMT) on the mechanical and thermal properties of SBS and its blend with low-density polyethylene (LDPE) and polystyrene was investigated. The effect of nanoclay content in the presence of LDPE or PS on the final properties of SBS was studied by tensile tester, dynamic mechanical thermal analysis (DMTA), thermal gravimetric analysis (TGA), X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). Addition of nanoclay affected the mechanical and rheological properties. From X-ray and DMTA results, it was found that due to more affinity between the nanoparticles and the SBS/PE blend, the 2 theta characteristic peak of nanoclay shifted to lower angles. SEM studies showed better dispersion and lower inter-particle distance of nanoparticles in SBS/PE composites in comparison with SBS/PS and SBS composites, confirming the XRD and DMTA results. It can be concluded that nanoclay acts as a compatibilizer in the SBS/LLDPE blend. TGA studies showed higher stability of SBS/PS composites compared to SBS and SBS/PE ones.     

Phosphorylated cardanol prepolymer-grafted carboxylated styrene–butadiene rubber for better processing with enhancing silica filler dispersion

Cardanol is a byproduct of cashew industry of semiforest origin. It is cheap and available in humongous amount and acts as a multifunctional additive in rubber compounds. It can be oligomerized with orthophosphoric acid to make phosphorylated cardanol prepolymer (PCP). Hence, cardanol has been chemically grafted on to the backbone chain of carboxylated styrene–butadiene rubber (XSBR) by employing melt grafting technique in presence of peroxide initiator to include multifunctional properties. The PCP-grafted XSBR (PCP-g-XSBR) was characterized by using Fourier transform infrared spectroscopy and ¹H-NMR techniques and optimize the grafting conditions such as percent of grafting and grafting efficiency by using Taguchi methodology. PCP-g-XSBR was compounded with silica filler for a comparative study in terms of processing behavior with XSBR. The cure characteristics such as the cure rate and the optimum cure time of the unfilled PCP-g-XSBR compounds were determined by oscillating disc rheometer. The thermal analysis of PCP-g-XSBR vulcanizate exhibits slightly better thermal stability as well as plasticization effect. Morphological behaviors also display the less cracked and filled fracture surfaces with better filler dispersion in PCP-g-XSBR vulcanizate. The mechanical properties of the compounded PCP-g-XSBR vulcanizates also improve compare to XSBR vulcanizates. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47528.