Development and characterization of graphitic carbon nitride as nonblack filler in natural rubber composites

A new type of elastomeric composite containing natural rubber (NR) and graphitic carbon nitride (g-C₃N₄) has been successfully prepared with the reinforced property. The reinforcing effect of g-C₃N₄ in NR composites was examined by cure, mechanical, morphological, and swelling studies. Besides, epoxidized NR with 50-mol % epoxy level (ENR-50) was used as a compatibilizer to enhance the hydrophilic g-C₃N₄ filler capacity for hydrophobic NR composites. At the same filler load level, the mechanical properties of NR/g-C₃N₄ composites, such as tensile strength and tensile modulus, were consistently increased with increased ENR-50 content. To note, the ENR compatibilized composites have shown better-reinforced performance, which has been attributed to the hydrogen bonding interactions between the uncondensed amine groups in g-C₃N₄ and the polar groups in ENR. We believe that these newly prepared NR composites based on g-C₃N₄ as nonblack filler and ENR-50 as compatibilizer can find potential applications in modern day rubber research. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48136.     

Mechanical and dynamic mechanical properties of natural rubber blended with waste rubber powder modified by both microwave and sol–gel method

Waste rubber powder (WRP) was modified by microwave, sol–gel method, and both microwave and sol–gel method, respectively. The mechanical and dynamic mechanical properties of natural rubber (NR)/modified WRP composite were investigated. The influence of bis‐(3‐(triethoxysilyl)‐propyl)‐tetrasulfide (TESPT) content on curing characteristics and mechanical properties of vulcanizate was also studied. The results showed that NR/WRP modified by both microwave and sol–gel method composite owned the best mechanical properties. Rubber processing analyzer was used to characterize the interaction between silica and rubber chains and the dispersion of silica. With increase of TESPT content, the Payne effect decreased. Scanning electron microscopy indicated the coherency and homogeneity of in situ generated silica filled vulcanizate. Dynamic mechanical analyzer showed that NR/WRP modified by both microwave and sol–gel method composite with 5 phr TESPT exhibited the lower tan δ at temperature range of 50–80°C, compared with composite without TESPT and the higher tan δ at temperature of 0°C, compared with the conventional modification of WRP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of bis(3‐triethoxysilylpropyl) tetrasulfide on the crosslink structure,interfacial adhesion,and mechanical properties of natural rubber/cotton fiber composites

Bis(3‐triethoxysilylpropyl) tetrasulfide (TESPT) was used to improve the interfacial adhesion between cotton fiber and natural rubber (NR). The crosslink density, interfacial adhesion, mechanical properties, dynamic mechanical properties, and morphology of NR/cotton fiber composites were investigated. The composites with TESPT had higher crosslink density, better mechanical properties, higher initial modulus, and higher yield strength than the composites without TESPT because of the difference in interfacial adhesion. The results of an interfacial adhesion evaluation, the high storage modulus and low damping values of the composites with TESPT, and the coarse surfaces of the pullout fibers implied the enhancement of interfacial adhesion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on Tensile,Electrical, and Thermal Properties of Aluminium Particle Filled Natural Rubber (NR) and Ethylene-Propylene-Diene Terpolymer (EPDM) Composites

Comparative studies on the effect of aluminium particles in natural rubber (NR) and ethylene-propylene-diene terpolymer (EPDM) were conducted. The incorporation of aluminium particles in NR or EPDM composites increased the cure time, t ₉₀, and scorch time, t _S2 . At a fixed filler loading, EPDM composites exhibited longer t ₉₀ and t _S2 than NR composites. The results also indicate that the maximum torque, M _H of aluminium filled NR and EPDM composites increase with increasing filler loading. For tensile properties, EPDM composites show lower tensile properties than NR composites. Thermogravimetric analysis (TGA) results show that aluminium filled EPDM composites have better thermal stability than aluminium filled NR composites.

The results for electrical properties indicate that the electrical properties of aluminium filled NR and EPDM composites increase with increase in filler loading.     

Natural rubber-graft-poly(2-hydroxyethyl acrylate) on cure characteristics and mechanical properties of silica-filled natural rubber composites

The grafting of poly(2-hydroxyethyl acrylate) onto natural rubber (NR-g-PHEA) was used to compatibilize NR composites with silica filler. The NR/silica compounds were prepared with various grafting percentages of NR-g-PHEA (0, 6.5, 10.5, and 14.5%) and fixed amounts of 3 parts per hundred of rubber (phr) NR-g-PHEA and 20 phr silica. The cure characteristics were examined using a moving die rheometer. The physicomechanical properties of NR/silica composites were determined in terms of tensile strength, bound rubber content, and dynamic mechanical analysis. Thermal properties were assessed with thermogravimetric analysis. The results showed that scorch time and cure time tend to decrease with the level of grafting in NR-g-PHEA. The NR-g-PHEA decreased tan δ, whereas bound rubber content in NR/silica compounds increased, which indicates improved silica dispersion in the NR matrix. The mechanical properties improved with level of grafting in NR-g-PHEA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48738.     

Properties of natural rubber filled with untreated and treated spent coffee grounds

This work studied the properties of spent coffee ground (SCG) filled natural rubber (NR). The SCG was initially characterized by various techniques, prior to being added into rubber. Results revealed that SCG had relatively large particle size with very low specific surface area. It is mainly composed of organic compounds (such as protein, fatty acid, cellulose, hemicellulose, and lignin) with small quantity of inorganic substances (oxides of potassium, silicon, magnesium, calcium, and phosphorous). The incorporation of SCG in NR gave relatively low reinforcement and tended to retard vulcanization due to the presence of hydroxyl groups on the SCG surface. In addition to untreated SCG, reinforcement of SCG treated by liquid epoxidized natural rubber (LENR) and bis ‐ ( 3‐ triethoxysilylpropyl) tetrasulfide (TESPT) was investigated. Improvement of rubber properties was observed when SCG surface was treated. Overall, TESPT‐treated SCG gave the rubber with the highest mechanical properties, followed by LENR‐treated SCG and untreated SCG, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46060.     

Cure characteristics,mechanical, thermal,and coloring properties of natural rubber/dye‐loaded shell powder composites

To explore the application of shell powder (SP) in rubber, a dye‐loaded SP (DSP) bio‐filler based on SP and Congo red was incorporated into natural rubber (NR). The adsorption experiments demonstrated that the maximum monolayer adsorption capacity of Congo red onto SP was 69.3 mg/g. The effect of aluminate coupling agent and DSP was investigated by evaluating the cure characteristics, mechanical, thermal, and coloring properties of NR/DSP composites. It was suggested that the optimum amount of aluminate coupling agent was 2 wt %, and the best tensile strength (24.80 MPa) of vulcanizates was achieved at the DSP content of 20 phr, while other mechanical properties such as tear strength kept increasing with the addition of DSP. Furthermore, the improved thermal stability and uniform color distribution of the NR composites was obtained. The results indicate that DSP is promising to become a low‐cost filler and pigment for rubber materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45750.     

On the potential of organoclay with respect to conventional fillers (carbon black,silica) for epoxidized natural rubber compatibilized natural rubber vulcanizates

Onium modified montmorillonite (organoclay) was compounded with natural rubber (NR) in an internal mixer and cured by using a conventional sulfuric system. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) in 10 parts per hundred rubber (phr) was used as a compatibilizer in this study. For comparison purposes, two commercial fillers: carbon black (grade N330) and silica (grade vulcasil‐S) were used. Cure characteristics were carried out on a Monsanto MDR2000 Rheometer. Organoclay filled vulcanizate showed the lowest values of torque maximum, torque minimum, scorch, and cure times. The kinetics of cure reaction showed organoclay could behave as a cocuring agent. The mechanical testing of the vulcanizates involved the determination of tensile and tear properties. The improvement of tensile strength, elongation at break, and tear properties in organoclay filled vulcanizate were significantly higher compared to silica and carbon black filled vulcanizates. In terms of reinforcing efficiency (RE), organoclay exhibited the highest stiffness followed by silica and carbon black filled vulcanizates. Scanning electron microscopy revealed that incorporation of various types of fillers has transformed the failure mechanism of the resulting NR vulcanizates compared to the gum vulcanizates. Dynamic mechanical thermal analysis (DMTA) revealed that the stiffness and molecular relaxation of NR vulcanizates are strongly affected by the filler–rubber interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2438–2445, 2004     

Effect of carbon nanotubes decorated with silver nanoparticles as hybrid filler on properties of natural rubber nanocomposites

Decoration of carbon nanotube (CNT) surfaces with silver nanoparticles (AgNPs) was performed using N,N-dimethylformamide reducing agent. The CNT-decorated with AgNP (CNT-AgNP) was then used to prepare natural rubber (NR) nanocomposites via latex mixing method. Cure characteristics, mechano-thermal relaxation, electrical conductivity, and thermal properties of the composites were investigated. It was found that the CNT-AgNP gave cure properties improved over plain NR compounds in terms of scorch time, degree of vulcanization, and activation energy. In addition, temperature scanning stress relaxation measurement revealed stronger network formation after incorporation of AgNP into the NR matrix due to the interaction among CNT and AgNP particles. This also provided high conductivity and low percolation threshold concentration for the CNT-AgNP filled NR, relative to plain CNT filled NR composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47281.     

Autoclaved aerated concrete waste (AACW): An alternative filler material for the natural rubber industry

Material waste from the production of autoclaved aerated concrete, a porous material, should be considered as a valuable byproduct for use as a filler material for the rubber industry. Natural rubber (NR) composites filled with different loading (over the range of 0–60 phr) of autoclaved aerated concrete waste (AACW) as a new eco‐friendly material were produced using two roll mills and then were studied for their cure characteristics, mechanical and aging properties, and morphology, and also compared with commercial fillers, calcium carbonate (CaCO₃), and silica (SiO₂). In most cases, the cure characteristics and mechanical and aging properties of the SiO₂‐filled NR composites were significantly better than those of the AACW‐ and CaCO₃‐filled NR composites. However, these properties for AACW‐filled composites appeared to be higher than CaCO₃‐filled composites. The reason for this could be due to a larger surface area which is both porous and of an irregular shape of the AACW filler used. Scanning electron microscope images showed that the morphology of the rubber filled with SiO₂ was finer and more homogenous compared with the rubber filled with AACW or CaCO₃. Overall results revealed that the reinforcement ability of AACW‐filled NR composites was generally better when compared with CaCO₃‐filled NR composites; therefore, AACW can be used effectively as a cheaper filler for production of rubber products where end‐use properties of a rubber product is specifically required. POLYM. COMPOS., 36:2030–2041, 2015. © 2014 Society of Plastics Engineer     

Comparison Properties of Natural Rubber (SMR L)/Ethylene Vinyl Acetate (EVA) Copolymer Blends and Epoxidized Natural Rubber (ENR-50)/Ethylene Vinyl Acetate (EVA) Copolymer Blends

Mixing torque, morphology, tensile properties and swelling studies of natural rubber/ethylene vinyl acetate copolymer blends were studied. Two series of unvulcanized blends, natural rubber/ethylene vinyl acetate (SMRL/EVA) copolymer blend and epoxidized natural rubber (50% epoxidation)/ethylene vinyl acetate (ENR-50/EVA) copolymer blend were prepared. Blends were prepared using a laboratory internal mixer, Haake Rheomix polydrive with rotor speed of 50 rpm at 120°C. Results indicated that mixing torque value and stabilization torque value in ENR-50 blends are lower than SMRL blends. The process efficiency of ENR-50/EVA blends is better due to less viscous nature of the blend compared to SMRL/EVA blends as indicated in stabilization torque graph. Tensile properties like tensile strength, M100 (modulus at 100% elongation) and E _b (elongation at break) increase with increasing EVA fraction in the blend. At the similar blend composition, ENR-50 blend shows better tensile properties than SMRL blends. In oil resistance test, swelling percentage increased with immersion time and rubber composition. At a similar immersion time, ENR-50 blends exhibit better oil resistance compared to SMRL blends. Scanning electron microscopy (SEM) of tensile fractured surface indicated that EVA/ENR-50 blends need higher energy to cause catastrophic failure compared to EVA/SMRL blends. In etched cryogenically fractured surface, size and distribution of holes due to extraction of rubber phase by methyl ethyl ketone (MEK) were studied and holes became bigger as rubber composition increased due to coalescence of rubber particle.     

Synergic effect of N‐benzylimine aminothioformamide secondary accelerator during sulfur vulcanization of a styrene‐butadiene‐natural rubber blend

In this study we reported synergic activity of a novel secondary accelerator N‐Benzylimine aminothioformamide (BIAT) along with tetramethylthiuram disulfide (TMTD) in improving cure and mechanical properties of gum and filled mixes of Styrene‐Butadiene Rubber (SBR). The feasibility of application of BIAT in sulfur vulcanization of an ideal blend of SBR and natural rubber (NR) has also been investigated. The mechanical properties like t ensile strength, tear resistance, hardness, compression set, and abrasion loss were measured. Swelling values were also determined as a measure of crosslink densities of the vulcanizates. The binary accelerator system BIAT‐TMTD was found very effective in improving cure properties of the mixes of pure SBR and a 50/50 blend of SBR and NR.There was also found simultaneous improvement in mechanical properties of vulcanizates of both pure and blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Curing characteristics and mechanical properties of rattan‐powder‐filled natural rubber composites as a function of filler loading and silane coupling agent

Curing characteristics, tensile properties, morphological studies of tensile fractured surfaces using scanning electron microscopy (SEM), and the extent of rubber filler interactions of rattan‐powder‐filled natural rubber (NR) composites were investigated as a function of filler loading and silane coupling agent (CA). NR composites were prepared by the incorporation of rattan powder at filler loading range of 0–30 phr into a NR matrix with a laboratory size two roll mill. The results indicate that in the presence of silane CA, scorch time (t_s2), and cure time (t₉₀) of rattan‐powder‐filled NR composites were shorten, while, maximum torque (M_H) increased compared with NR composites without silane CA. Tensile strength and tensile modulus of composites were enhanced whereas elongation at break reduced in the presence of silane CA mainly due to increase in rubber‐filler interaction. It is proven by SEM studies that the bonding between the filler and rubber matrix has improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel ternary blends of natural rubber/linear low-density polyethylene/thermoplastic starch: influence of epoxide level of epoxidized natural rubber on blend properties

Novel degradable materials based on ternary blends of natural rubber (NR)/linear low-density polyethylene (LLDPE)/thermoplastic starch (TPS) were prepared via simple blending technique using three different types of natural rubber (i.e., unmodified natural rubber (RSS#3) and ENR with 25 and 50 mol% epoxide). The evolution of co-continuous phase morphology was first clarified for 50/50: NR/LLDPE blend. Then, 10 wt% of TPS was added to form 50/40/10: NR/LLDPE/TPS ternary blend, where TPS was the particulate dispersed phase in the NR/LLDPE matrix. The smallest TPS particles were observed in the ENR-50/LLDPE blend. This might be attributed to the chemical interactions of polar functional groups in ENR and TPS that enhanced their interfacial adhesion. We found that ternary blend of ENR-50/LLDPE/TPS exhibited higher 100 % modulus, tensile strength, hardness, storage modulus, complex viscosity and thermal properties compared with those of ENR-25/LLDPE/TPS and RSS#3/LLDPE/TPS ternary blends. Furthermore, lower melting temperature (T _m) and heat of crystallization of LLDPE (?H) were observed in ternary blend of ENR-50/LLDPE/TPS compared to the other ternary blends. Also, neat TPS exhibited the fastest biodegradation by weight loss during burial in soil for 2 or 6 months, while the ternary blends of NR/LLDPE/TPS exhibited higher weight loss compared to the neat NR and LLDPE. The lower weight loss of the ternary blends with ENR was likely due to the stronger chemical interfacial interactions. This proved that the blend with ENR had lower biodegradability than the blend with unmodified NR.     

Mechanistic aspects of silane coupling agents with different functionalities on reinforcement of silica‐filled natural rubber compounds

Silane coupling agents containing different specific functionalities are studied to gain understanding of their roles in silica‐filled natural rubber (NR) compounds. Five different silane coupling agents, that is bis‐(triethoxysilylpropyl) tetrasulfide (TESPT), bis‐(triethoxysilylpropyl) disulfide (TESPD), octyltriethoxysilane, vinyltrimethoxysilane, and bis‐(trimethyl‐silylmethyl) tetrasulfide (TMSMT), are comparatively investigated, by taking the most commonly used TESPT as a reference. The results reveal that alkoxy‐based silanes can effectively reduce the filler–filler interaction and lower compound viscosity owing to the effect of silane‐to‐silica hydrophobation which contributes to better compatibility between silica and NR. The alkoxy‐silanes with a sulfur moiety, that is TESPT and TESPD, show more pronounced improvement in overall properties as a result of filler–rubber interactions. The use of TMSMT which has no alkoxy groups but contains only a sulfur moiety elucidates that there are three reaction mechanisms involved in systems with sulfur‐alkoxy‐based silane. These are as follows: (1) the silane‐to‐silica or silanization/hydrophobation reaction; (2) the silane‐to‐rubber or coupling reaction; and (3) rubber–rubber crosslinking originating from active sulfur released by the polysulfide‐based silane TESPT. These simultaneous reactions are temperature dependent, and show an optimum level at a dump temperature of approximately 140–150°C, as depicted by filler–filler and filler–rubber interactions, as well as mechanical properties of such compounds. POLYM. ENG. SCI., 55:836–842, 2015. © 2014 Society of Plastics Engineers     

Influence of Particle Type and Silane Coupling Agent on Properties of Particle-Reinforced Styrene-Butadiene Rubber

Silica- and carbon-filled styrene butadiene rubber (SBR) were prepared. The influence of particle type and silane coupling agent on cure characteristics, physical and dynamic mechanical properties of particle-reinforced SBR were investigated. Minimum torque, maximum torque and tensile strength increased with increase of the filler content. The tensile strength and elongation at break were highest for presence of bis-(3-triethoxysilylpropyl) tetrasulfide (TESPT) in silica-filled vulcanizates. The dynamic mechanical properties show that tan δ at temperatures of ?20–0°C of the SiO₂/TESPT/SBR vulcanizate was highest of all. Tan δ at temperatures of 50–70°C of the SiO₂/TESPT/SBR vulcanizate was lower than carbon-filled SBR.     

Reclaiming of rubber by a renewable resource material (RRM). III. evaluation of properties of NR reclaim

Sulfur‐cured filled natural rubber (NR) is successfully reclaimed by using a renewable resource material (RRM) and diallyl disulfide (DADS), which is the major constituent of RRM. Reclaiming of NR vulcanizate was carried out at 60°C for 35 min in an open two‐roll mixing mill. Evaluation of the properties of NR reclaim was carried out by mixing it with virgin rubber in various proportions. The cure characteristics and mechanical properties of the virgin NR/ reclaim NR blend were studied. With increase in the proportion of reclaim rubber (RR) in virgin NR/ reclaim NR blend scorch time and optimum cure time decrease. To increase scorch time N‐cyclohexylthiophthalimide as prevulcanization inhibitor (PVI) was added in NR/RR (50/50) blend. It was found that use of 40% NR reclaim with virgin rubber resulted 83% retention of tensile strength of that of the virgin NR vulcanizate. Effect of carbon black loading was studied in NR/RR (50/50) blends. Tensile properties and swelling value of different NR/RR blends were evaluated before and after aging. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1493–1502, 2000     

低共熔溶剂与偶联剂协同改性白炭黑对胎面胶性能的影响

研究了硅烷偶联剂(TESPT)与低共熔溶剂(DES)协同改性白炭黑对作为胎面胶的天然橡胶复合材料性能的影响.用傅里叶变换红外光谱分析了 TESPT和DES与白炭黑之间的相互作用,用橡胶加工分析仪和扫描电镜分析了白炭黑之间的相互作用,并测试了复合材料的硫化特性、力学性能和耐磨性,通过动态力学分析仪考察了其滚动阻力和抗湿滑...     

Improved cure characteristics and mechanical properties of an epoxidized natural rubber filled with cerium oxide nanoparticles: Influence of epoxide levels and filler loading

In this study, cerium oxide nanoparticles (nanoceria, CeNP) were used as a nanofiller in epoxidized natural rubber with varying epoxide levels, including 25% epoxidation (ENR-25) and 50% epoxidation (ENR-50). Co-precipitation methods were employed to synthesize a pure phase of CeNP with an average particle size of 11.4 ± 2.0 nm. CeNP was characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy. The effect of CeNP loading with 0–3 parts per hundreds of rubber (phr) on the properties of rubber nanocomposites was explored. ENR-25 nanocomposites with 1 phr of CeNP exhibited higher tensile strength and elongation at break compared to ENR-50 nanocomposites. These findings correspond to a lower Payne effect, improved scorch safety, and better processability. The strongest and most effective CeO₂–ENR interactions via silane linkages are expected to outperform sulfur crosslinking in ENR-25 having 1 phr of CeNP. Microstructural evaluation of an ENR-25 sample containing 1 phr of CeNP indicated well-distributed nanofillers in the ENR-25 matrix, indicating that CeNP and ENR-25 appeared to be well-matched. Hardness of all ENR nanocomposites increased with CeNP loading. The cracking resistance, creep properties, and thermal stability of rubber nanocomposites were unaffected by addition of CeNP in the ENR-25 and ENR-50 samples.     

Preparation of zinc‐oxide‐free natural rubber nanocomposites using nanostructured magnesium oxide as cure activator

The effect of sol–gel synthesized magnesium oxide (MgO) nanoparticles as cure activator is studied for the first time in the vulcanization of natural rubber (NR) and compared with conventional zinc oxide (ZnO) in terms of cure, mechanical, and thermal properties. The NR vulcanizate with 1 phr (Parts per hundred parts of rubber) nano MgO shows an excellent improvement in the curing characteristics and the value of cure rate index is about 400% greater for NR vulcanizate containing 1 phr nano MgO in comparison to the NR vulcanizate with 5 phr conventional ZnO. Both mechanical and thermal properties of NR vulcanizate are found to be satisfactory in the presence of 1 phr nano MgO as cure activator in comparison to conventional NR vulcanizate. This study shows that only 1 phr nano MgO can successfully replace 5 phr conventional ZnO with better resulting properties in the sulfur vulcanization of NR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42705.