Cardanol grafted natural rubber: A green substitute to natural rubber for enhancing silica filler dispersion

Natural rubber (NR) usage is wide‐spread from pencil erasers to aero tyres. Carbon black and silica are the most common reinforcing fillers in the rubber industries. Carbon black enhances the mechanical properties, while silica reduces the rolling resistance and enhances the wet grip characteristics. However, the dispersion of polar silica fillers in the nonpolar hydrocarbon rubbers like natural rubber is a serious issue to be resolved. In recent years, cardanol, an agricultural by‐product of the cashew industry is already established as a multifunctional additive in the rubber. The present study focuses on dispersion of silica filler in natural rubber grafted with cardanol (CGNR) and determination of its technical properties. The optimum cure time reduces and the cure rate increases for the CGNR vulcanizates as compared to that of the NR vulcanizates at all loadings of silica varying from 30 to 60 phr. The interaction between the phenolic moiety of cardanol and the siloxane as well as silanol functional groups present on the silica surface enhances the rubber–filler interaction which leads to better reinforcement. The crosslink density and bound rubber content are found to be higher for the silica reinforced CGNR vulcanizates. The physico‐mechanical properties of the silica reinforced CGNR vulcanizates are superior to those of the NR vulcanizates. The CGNR vulcanizates show lower compression set and lower abrasion loss. The dynamic‐mechanical properties exhibit less Payne effect for silica reinforced CGNR vulcanizates as compared to the NR vulcanizates. The transmission electron photomicrographs show uniform dispersion of silica filler in the CGNR matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43057.     

Enhancement of hydrophobicity of natural rubber latex films using diatomaceous earth

Enhancement of the hydrophobic nature of natural rubber latex (NRL) films will open up a wide range of applications for them. Incorporating hexadecyltrimethoxysilane treated superhydrophobic diatomaceous earth (DE) in NRL, resulted in films with increased hydrophobicity. The nano-scale surface roughness for the superhydrophobic surface was provided by DE and low surface energy was achieved by treating DE with hexadecyltrimethoxysilane (treated DE). Surface wettability and morphology were analyzed by water contact angle (WCA) measurements and scanning electron microscopic analysis, respectively. About 38% wt/wt hexadecyltrimethoxysilane to DE ratio could make superhydrophobic DE with WCAs larger than 150°. A dispersion of treated DE was incorporated into NRL resulting in hydrophobic NRL films possessing WCAs greater than 110° with 41% treated DE particle loading. The resulting NRL films were harder and had smaller tensile strength compared to normal NRL film.     

Energy dissipation in natural rubber latex films: The effect of stabilizers,leaching and acetone-treatment

Natural rubber (NR) is a versatile material possessing outstanding mechanical properties, which can be used in multiple applications including the rapidly developing dielectric elastomer generators (DEGs). One of the drawbacks of the existing DEGs is their low efficiency, which can be improved by lowering the dielectric and mechanical losses originating from the material. Therefore, the present research was focusing on assessing the ways to minimize the dielectric and mechanical losses of NR films rather than developing a DEG. In this article, the effect of natural proteins and the rubber stabilizers on energy dissipation of NR films was evaluated. Moreover, the effect of sample posttreatment (with water and acetone), curing and time after cure was discussed. As a result, deproteinized NR stabilized by ammonium caseinate outperformed unmodified NR due to reduced dielectric losses, mechanical hysteresis and stress relaxation. Moreover, the posttreatment methods were found to moderately reduce the material-relates losses.     

Preparation of low‐allergen natural rubber latex by transglutaminase catalysis

The technique of enzyme treatment on the water‐soluble proteins and mechanical properties of natural rubber latex (NRL) films was studied. The main aim was to introduce an enzymic catalysis method to tackle the protein allergy problem in NRL product. The suitable pH value, the temperature, and the best proportion of transglutaminase to deal with NRL were found. The protein spillage of modified NRL films was greatly lower than that of unmodified NRL, and the tensile strength and the elongation at break of the modified NRL films almost had been scarcely changed. The compactness of the NRL films was improved simultaneously. These suggest that the modified NRL can be used as a kind of latex with low‐allergy personal barrier products such as surgical gloves. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

天然胶乳橡胶手套硫化问题的探讨

<正>一、引言胶乳硫化能充分改变或改善胶乳胶料性能,通常在胶乳配料时提高温度的情况下进行,硫化后的胶乳称为预硫化胶乳。胶乳硫化一般只适用于天然胶乳,是部分或完     

Length scale dependent deformation in natural rubber

Strong length scale dependent deformation has been previously observed in the elastomer polydimethylsiloxane by indentation type experiments at micro‐ to nanometer length scales with a sharp conical tip. To examine if other nonsilicone based elastomers exhibit similar length scale dependent deformation behavior, natural rubber has been chosen in this study. Performing indentation type tests with a nanoindentation system, the universal hardness and the elastic modulus are determined at different probing depths ranging from about 90 to 5 μm to characterize length scale dependent deformation behavior in natural rubber. The testing with a Berkovich tip resulted in an amazing increase in the universal hardness with decreasing probing depth indicating that the deformation mechanisms at the micrometer length scales are significantly different as compared to those at the macroscopic length scales. The observed length scale dependent deformation is associated with an increase in rotation gradients with decreasing probing depth. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42683.     

Semi-rigid foams of calcium silicate (CaSiO3) embedded in natural rubber latex

Semi-rigid foams were prepared by NR latex with 0, 2, 5, 10, 20 and 30?phr CaSiO₃ added in a sulphur-curing system. The main composition of eggshell is made of 96.23%wt of CaCO₃ and 3.77%wt of other oxide compounds. The CaSiO₃ induced a spontaneous polarisation and reinforced the NR matrix due to ionic charge contents of Ca²⁺, Si⁴⁺ and O^2? in its structure. Furthermore, the CaSiO₃ was found to enhance the mechanical, thermal and physical properties of the composite foams. The suitable condition to prepare the semi-rigid composite foams was by adding 30?phr CaSiO₃ in the NR latex with the sulphur-curing system. The obtained bulk density, the relative composite foam density, the compressive strength, the contact angle with water, and acetone at the water to acetone ratio of 1:1 were found to be 1.2230?g?cm^?3, 0.3611, 588.10?kPa, 103.3°, 26.5° and 85.3°, respectively.     

Effect of atmosphere on the thermal decomposition of chlorinated natural rubber from latex

The kinetics of the thermal decompositions of chlorinated natural rubber (CNR) from latex under both air and nitrogen atmospheres were studied with thermogravimetric analysis (TGA). The thermooxidative decomposition of CNR had two weight-loss step changes in the TGA curves, which occurred at the two distinct temperature ranges of about 160–390 and 390–850°C, respectively. The gaseous products of the first step change were mainly HCl with a little CO₂, and the apparent reaction order (n) was 1.1. The reaction activation energy (E) increased linearly with the increment of heating rate (B), and the apparent activation energy (E₀), calculated by extrapolation back to zero B, was 101.7 kJ/mol. Bs ranging from 5 to 30°C/min were used. The initial temperature of weight loss (T₀) was 1.31B + 252°C, where B is in degrees Celsius per minute. The final temperature of weight loss (T_f) was 0.93B + 310°C, and the temperature of maximum weight-loss rate (T_p) was 1.03B + 287°C. The decomposition weight-loss percentage at T_p (C_p) and that at T_f (C_f) were not affected by B, and the average values were 38 and 60%, respectively. The second weight-loss step change was an oxidative decomposition of the molecular main chain. The value of n was 1.1. E increased linearly with the increment of B, and E₀ was 125.0 kJ/mol. C_f after the second step approached 100%, which indicated complete decomposition. The thermal decomposition of CNR in a N₂ atmosphere had only one weight-loss step change with an n of 1.1. E increased linearly with the increment of B, and E₀ was 98.6 kJ/mol. T₀ was 1.25B + 251°C, T_f was 0.91B + 315°C, and T_p was 1.09B + 286°C. C_p and C_f were not affected by B, and the average values were 37 and 68%, respectively. The weight percentage of more stable, nonthermal decomposed residue was about 30%. The thermal decompositions of CNR in both atmospheres were similar, mainly by dehydrochlorination, at the low temperature range (160–390°C) but were different at the high temperature range (390–850°C). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2590–2598, 2001     

Novel self‐crosslinking film from hydrogenated carboxylated nitrile rubber latex

A new type of self‐crosslinking latex film was prepared from hydrogenated carboxylated nitrile‐butadiene rubber (HXNBR) latex by diimide reduction. The properties of the HXNBR rubber, including film surface morphology, physical properties, thermal stability and ageing properties, were investigated. FTIR spectroscopy was used to confirm the HXNBR structure, from which the degree of hydrogenation can be obtained. The morphology of the film surface was monitored by atomic force microscopy, which confirmed that HXNBR latex can form a continuous film with good cohesive properties from self‐crosslinking latex particles. The self‐crosslinking provided the latex film with excellent tensile strength. The thermal stability was improved after hydrogenation, as indicated by thermogravimetric methods. The activation energy for degradation was determined by Coats‐Redfern plots. Hot air oven thermal ageing confirmed that the oxidation resistance increased as the degree of hydrogenation increased. All these results showed that HXNBR latex can form a self‐crosslinking film with better mechanical properties, and heat and oxidation resistance than those of XNBR latex film in a wide range of film applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39865.     

热裂解气相色谱法测定天然胶乳中的干胶含量

研究热裂解气相色谱法测定天然胶乳中的干胶含量。试验结果表明,干胶含量与裂解主要产物峰面积呈现良好的线性关系,采用标准曲线法测定天然胶乳中的干胶含量,重复测定的相对标准偏差为0.14%,与国标法的平均相对误差为1.51%,定量分析结果准确,操作简便。     

Surface functionalization of rubber latex nanoparticles with sulfidosilane moieties

Polybutadiene latex particles were functionalized with bis[3‐(triethoxysilyl) propyl] tetrasulfide (TESPT) in the presence of zinc oxide as an activator and ethanol as a co‐solvent. The success of this reaction was confirmed both by the peaks attributed to Si‐O groups at 1085 and 1110 cm^?1 and C‐S bond at 630 cm^?1 which appeared after reaction in Attenuated Fourier Transform Infrared (ATR‐FTIR) Spectra and also by increasing in the particle size diameter of latex particles (from 95 to 127 nm) in Dynamic Light Scattering analysis. X‐ray Diffraction results also showed changes in crystalline structure of the modified particles (as a strong decrease in the intensity of peak at 2θ=19.54). The effect of reactant concentration in a constant amount of TESPT (by varying the water and ethanol content), reaction time, activator size (micro and nanoparticles), and pH (≈7, 8.5) were investigated on degree of grafting (obtained from thermogravimetric analysis and ATR‐FTIR spectra), particle size diameter, cross‐link density, and swelling ratio of the samples. The amounts of silane grafting and cross‐link density of polymer particles were increased by an increase in the reaction time. The highest grafting degree was observed at low concentration of TESPT. Silane functionalization was also improved in a slight basic condition (pH=8.5) rather than neutral pH. The grafting reaction took place such as sulfur pre‐vulcanization and the possible mechanism of this reaction was discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43268.     

Effect of magnesium and phosphate ions on the stability of concentrated natural rubber latex and the properties of natural rubber latex–dipped products

The presence of Mg²⁺ ions was found to be a major cause of destabilization of natural rubber (NR) latex. On the other hand, the addition of excess PO ions to remove Mg²⁺ ions could adversely affect the physical properties of dipped products made of NR latex. A series of concentrated latex samples were treated with varying amounts of Mg²⁺ and PO ions. Changes with time in the characteristics of the treated latex samples such as mechanical stability time, volatile fatty acid number, and chemical stability time and in the physical properties of the dipped products such as aged and unaged tensile properties were monitored. The latex batch with a PO ion concentration of 30 ppm was found to produce the best‐quality latex and dipped products. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3120–3124, 2006     

In situ epoxidized natural rubber: Improved oil resistance of natural rubber

This study sought to synthesize an in situ epoxidized natural rubber (NR) from 20% dry rubber content latex stabilized by nonionic surfactant, 5 phr of Terric 16A16, in the presence of hydrogen peroxide and formic acid at the temperature of 50°C. The molar ratios of H₂O₂ and HCOOH to isoprene unit were equal, 0.75 : 0.75. Reaction was carried out for 3 to 8 h. This reaction yielded products of various epoxide contents depending on reaction time. Based on DSC characterization, epoxide contents of the in situ epoxidized natural rubbers (ENRs) were about 22–39 mol %. Tensile properties and tear resistance of the in situ ENRs were equal to, or better than, those of NR and commercial ENRs. The in situ epoxidation improved resistance to petroleum ether, but not to toluene. Changes in volume and weight of specimens immersed in ASTM no. 3 oil and automobile oils (various trade names: Shell engine oil, Shell gear oil, and Toyota motor oil) exhibited significant decrease after epoxidation, except in Shell brake fluid. Similar results were obtained from tensile testing of the oil‐immersed specimens. Tensile strength and elongation at break of the in situ ENRs were much higher than those of NR after immersion in those oils at room temperature for 7 days, except the immersion in brake fluid. Improved oil resistance of the in situ ENRs under severe condition was obtained in gear oil. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 261–269, 2003     

Study on properties of natural rubber reinforced by poly(sodium‐4‐styrenesulfonate)‐decorated carbon black with a latex compounding technique

Natural rubber filled with poly(sodium‐4‐styrenesulfonate) (PSS)‐decorated carbon black (CB) by employing a latex compounding technique was prepared. The result of scanning electron microscope demonstrated that CB was uniformly dispersed in the matrix. Comparing to traditional dry compounding, an improvement in physical and mechanical properties was observed in the composites attributed to the homogeneous distribution of CB in matrix and an augment of bound rubber. Owing to the changes of the physical properties of CB surface, vulcanizate filled with oxidized CB via latex way exhibited higher mechanical properties. The resulting vulcanizates displayed a diminished interaction between fillers based on the consequence of strain dependence of storage modulus. Furthermore, a splendid wet‐skid resistance was obtained in vulcanizates fabricated by latex compounding technique in comparison with vulcanizates prepared by traditional dry compounding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42346.     

Noncatalytic hydrogenation of natural rubber latex

Hydrogenation is an important method of chemical modification, which improves the physical, chemical, and thermal properties of diene‐based elastomers. Natural rubber latex (NRL) could be hydrogenated to a strictly alternating ethylene–propylene copolymer using diimide generated in an in situ system. The diimide generated using the in situ technique for hydrogenation of NRL was accomplished by thermolysis of p‐toluenesulfonyl hydrazide (TSH). A molar ratio of TSH to double bonds equal to 2 : 1 was found to be the optimum ratio to provide a high percentage of hydrogenation. 95% Degree of saturation of NRL was achieved in o‐xylene. Hydrogenated products are characterized by FTIR and NMR spectroscopy. The thermal stability of hydrogenated rubber was improved as shown from the results of thermogravimetric analysis. From the differential scanning calorimetry measurement, the glass transition temperature of the hydrogenated product did not appear to change. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2885–2895, 2007     

Fatigue crack growth dynamics in filled natural rubber

Abstract

We present fatigue experiments performed on filled natural rubber and study the correlations between crack growth dynamics and fracture morphologies imprinted by an irregular crack path. Slow crack growth dynamics is obtained by cyclic fatigue in a pure shear test. We will show that an unstable crack growth regime exists for high loads. We will also discuss the appearance of sawtooth striations which follow a scenario that significantly differs from previous results reported in the literature.     

Diimide hydrogenation of natural rubber latex

Hydrogenation is one important method of chemical modification, which improves the physical, chemical and thermal properties of diene‐based elastomers. Natural rubber latex (NRL) could be hydrogenated to a strictly alternating ethylene‐propylene copolymer using a diimide reduction system. The diimide reduction technique of NRL was accomplished by using hydrazine hydrate/hydrogen peroxide and Cu²⁺ as catalyst. The hydrogenated products are characterized by FTIR and NMR spectroscopy. It has been found that cupric acetate is a highly active catalyst for the reaction and the addition of a controlled amount of gelatin demonstrated a beneficial effect on the degree of hydrogenation, whereas, sodium dodecyl sulfate (SDS) acted as a stabilizer of the latex particle in the reaction system and reduced the degree of hydrogenation. In the presence of SDS, a longer reaction time and a higher amount of hydrazine hydrate was required for hydrogenation of NRL. Gel formation during hydrogenation does not significantly affect the degree of hydrogenation. Gel inhibitors such as hydroquinone also decrease the degree of hydrogenation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Reinforcement of natural rubber

In this article, we report on recent investigations on filled natural rubber. These investigations include a mechanical characterization as well as a molecular analysis based on measurements of chain orientation. It is demonstrated that at intermediate strains, the increase in the moduli can be explained by the inclusion of rigid particles in the soft matrix and from molecular interactions between the rubber and the filler. These interactions can be evaluated by equilibrium swelling and by orientational measurements. With regard to the unfilled formulation, carbon black– and silanized‐filled natural rubber exhibit increases in the cross‐linking density ascribed to filler‐polymer links, whereas a large decrease in the orientational level, evidenced by birefringence and by infrared dichroism, is observed when silica is added without any coupling agent. Finally, two specific effects—the Payne and Mullins effects, both related to energy dissipation phenomena—are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2301–2316, 2002     

Enhancement of the antibacterial activity of natural rubber latex foam by the incorporation of zinc oxide nanoparticles

The synthesis and characterization of ZnO‐nanoparticle‐incorporated natural rubber latex foam (NRLF) are described in this article. ZnO nanoparticles were added as the primary gelling agent by the replacement of the microsized ZnO particles, whereas the control sample of the NRLF was made without the addition of any ZnO particles. ZnO nanopowder was evaluated by X‐ray diffraction (XRD), whereas the aqueous dispersion of nano‐ZnO was evaluated by transmission electron microscopy (TEM) micrograph analysis. The modified NRLF materials were evaluated by scanning electron microscopy (SEM)–energy‐dispersive X‐ray (EDX) analysis and XRD analysis. The antibacterial activities of the modified NRLF samples were evaluated quantitatively and qualitatively by antibacterial susceptibility tests against Gram‐positive Staphylococcus aureus and Gram‐negative Escherichia coli bacteria. We found that the XRD peaks matched perfectly with reference code 98‐002‐6593, which was the hexagonal phase. The particle sizes given by TEM image analysis were less than 60 nm. Most of the XRD peaks obtained for the modified NRLF matched with that of the ZnO nanopowder; this proved the presence of nano‐ZnO in the modified NRLF. Further, it was proven by SEM and EDX analysis. The NRLF modified by nanosized ZnO inhibited the growth of the so‐called bacteria in a very strong manner. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39601.     

Preparation and thermal stability of brominated natural rubber from latex

The effects of pH value of reaction system, reaction time, reaction temperature, bromine concentration, and amount of potassium persulfate on the bromination reaction in the preparation of brominated natural rubber (BNR) from natural rubber latex were discussed. It has been found from the thermal analysis, that is, the thermal degradation of BNR in nitrogen is a two‐step reaction, and 16% carbonide with a stable structure remained at 470–650°C. The thermo‐oxidative degradation of BNR in air is also a two‐step reaction, and the percentage of degraded BNR reaches to nearly 100% at 600°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010