混炼方式对螺旋纳米碳纤维增强天然橡胶复合材料力学性能的影响

采用干法和湿法两种混炼工艺制备了螺旋纳米碳纤维(HCNFs)/炭黑(CB)/天然橡胶(NR)复合材料,通过扫描电镜、拉伸试验机和应变扫描仪分别对所制备复合材料的界面形貌、力学性能和Payne效应进行了测试分析,考察了混炼方式对复合材料宏观力学性能及Payne效应的影响。结果表明,与纯CB填料相比,在干湿两种混炼方式下,添加适量的HCNFs(1～6份)能提高HCNFs/CB/NR复合材料的300%定伸应力、扯断伸长率、拉伸强度和硬度。与干法混炼相比,湿法混炼能明显增强HCNFs/CB/NR复合材料的Payne效应,并提升在HCNFs高添加量(2～6份)条件下的拉伸强度和扯断伸长率,这主要源于湿法混炼能够有效改善HCNFs在橡胶基质中的分散性。     

Preparation and performance of oleylamine modified silica-reinforced natural rubber composites

Oleylamine (OA) modified silica (SiO₂-g-OA) was prepared using γ-(2,3-epoxypropoxy) propytrimethoxysilane (KH560) and OA, silica/natural rubber (NR) and SiO₂-g-OA/NR composites were prepared by mechanical blending in an internal mixer, and SiO₂-g-OA was characterized by Fourier transform infrared spectroscopy, thermal gravimetric analyzer, and contact angle analyzer. The mechanical properties, abrasion resistance, curing characteristics, Payne effect, and morphology of silica/NR and SiO₂-g-OA /NR composites were investigated using universal testing machine, Akron abrasion tester, rubber processing analyzer, and scanning electron microscope, respectively. The results showed that SiO₂-g-OA became more hydrophobic and had better compatibility with NR. Moreover, SiO₂-g-OA/NR had weaker Payne effect, better vulcanization performance, and more excellent mechanical properties. As the content of filler was more than 30 phr, SiO₂-g-OA/NR had lower rolling resistance and higher wet skid resistance. Compared with silica modified by other coupling agents, SiO₂-g-OA had the best reinforcement effect on NR.     

Interfacial interactions and properties of natural rubber–silica composites with liquid natural rubber as a compatibilizer and prepared by a wet‐compounding method

Natural rubber–silica [W(NR–SiO₂)] composites were prepared by wet‐compounding technology with liquid natural rubber (LNR) as a compatibilizer. The effects of the LNR content and wet‐compounding technology on the filler dispersion, Payne effect, curing characteristics, mechanical properties, and interfacial interactions were investigated. The results show that the incorporation of LNR promoted vulcanization and decreased the Payne effect of the W(NR–SiO₂) composites. With the addition of 5 phr LNR, the remarkable improvements in the mechanical properties of the W(NR–SiO₂) vulcanizates were correlated with the improved silica dispersion and strengthened interfacial bonding. Furthermore, the W(NR–SiO₂) vulcanizates containing LNR exhibited improvements in both the wet‐skid resistance and rolling‐resistance performance. The interfacial interactions, quantitatively evaluated by the Mooney–Rivlin equation and Lorenz–Park equation on the basis of the rubber elasticity and reinforcement theory, were strengthened in the presence of LNR. Accordingly, an interfacial structural model was proposed to illustrate the improvements in the mechanical properties of the W(NR–SiO₂) composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46457.     

Studies on the effect of 4A zeolite on the properties of intumescent flame-retardant agent filled natural rubber composites

This investigation focused on the research of 4A zeolite on the properties of intumescent flame retardant (IFR) agent filled natural rubber (NR) systems. The first part focused on the evaluation of such characteristics as cure characteristics, tensile property, abrasion loss, and cross-linking density of NR composites. Experimental results demonstrated that the addition of 4A zeolite could increase the cross-linking density of the NR systems. The incorporation of 0.3 phr of 4A zeolite with 50 phr of IF Ragent could improve the elongation value from 480 to 610%, probably 27% increase. Also, the abrasion loss was decreased from 0.95 to 0.70 cm³, nearly 26%. The second part focused on the study of flame-retardant (FR) properties of 4A zeolite filled NR systems. The properties and structure of these composites were characterized by limited oxygen index (LOI), thermogravimetric analysis (TGA), and cone calorimeter. It was proved that the addition of 0.3 phr of 4A zeolite into the IFR filled NR systems could lead to an increase of LOI value and thermal stability, together with a decrease of mass loss ration, rate of heat release (RHR), carbon monoxide (CO) evolution and carbon dioxide (CO₂) evolution, and so on, in a word, an improvement of FR properties.     

Preparation of nano‐reinforced thermal conductive natural rubber composites

Natural rubber (NR) composites highly filled with nano‐α‐alumina (nano‐α‐Al₂O₃) modified in situ by the silane coupling agent bis‐(3‐triethoxysilylpropyl)‐tetrasulfide (Si69) were prepared. The effects of various modification conditions and filler loading on the properties of the nano‐α‐Al₂O₃/NR composites were investigated. The results indicated that the preparation conditions for optimum mechanical (both static and dynamic) properties and thermal conductivity were as follows: 100 phr of nano‐α‐Al₂O₃, 6 phr of Si69, heat‐treatment time of 5 min at 150°C. Furthermore, two other types of fillers were also investigated as thermally conductive reinforcing fillers for the NR systems: (1) hybrid fillers composed of 100 phr of nano‐α‐Al₂O₃ and various amounts of the carbon black (CB) N330 and (2) nano‐γ‐Al₂O₃, the particles of which are smaller than those of nano‐α‐Al₂O₃. The hybrid fillers had better mechanical properties and dynamic performance with higher thermal conductivity, which means that it can be expected to endow the rubber products serving under dynamic conditions with much longer service life. The smaller sized nano‐γ‐Al₂O₃ particles performed better than the larger‐sized nano‐α‐Al₂O₃ particles in reinforcing NR. However, the composites filled with nano‐γ‐Al₂O₃ had lower thermal conductivity than those filled with nano‐α‐Al₂O₃ and badly deteriorated dynamic properties at loadings higher than 50 phr, both indicating that nano‐γ‐Al₂O₃ is not a good candidate for novel thermally conductive reinforcing filler. POLYM. COMPOS., 37:771–781, 2016. © 2014 Society of Plastics Engineers     

黏土/天然橡胶纳米复合材料的制备及性能

利用乳液插层法制备了黏土／天然橡胶纳米复合材料,研究了该复合材料的力学性能、应力应变行为、耐磨性、气体阻隔性和耐老化性能。结果表明,黏土／天然橡胶纳米复合材料与高耐磨炭黑(N330)、白炭黑增强橡胶相比,邵尔A型硬度、定伸应力和撕裂强度较高,拉伸强度相当。黏土、N330以及白炭黑对天然橡胶的拉伸结晶有影响,填料用量对材料拉伸强度的影响存在最佳值。黏土／天然橡胶纳米复合材料具有良好的耐磨性、气体阻隔性和耐老化性能。     

Properties of nanoparticles filled soft poly(vinyl chloride) composites including antistatic plasticizer

Nanoparticles (NP) filled permanently antistatic poly(vinyl chloride) (PVC) composites, constituted of dibutyl phthalate (DBP) and antistatic plasticizer (AP) which included bis[2‐(2‐methoxyethoxy)ethyl]phthalate doped with sodium perchlorate (NaClO₄), were prepared in a Haaka torque rheometer. Surface resistivity measurement, mechanical test, scanning electron microscopy (SEM) investigation, and thermal gravimetric analysis (TGA)‐differential scanning calorimetry (DSC) analysis were used to investigate the comprehensive properties of PVC/AP/NP (100/40/x) (A40/NP) and PVC/AP/DBP/NP (100/40/40/x) (A80/NP) composites. The results demonstrated that the surface resistivity of A40/NP composites was lower than that of pure A40 composites at a humidity of 60% and 0.1% as the nano SiO₂ or TiO₂ content is 2 phr, respectively. Moreover, the surface resistivity of A40 composites was decreased by about half an order of magnitude even at the humidity of 0.1% when 2 phr of NP was added. The surface resistivity of A80/NP composites achieved the optimum value as the SiO₂ and TiO₂ content were 1 phr and 2 phr, respectively. Because the DBP functioned as small molecule plasticizer which endowed PVC composites with comparatively large free volume, the surface resistivity of A80/NP composites is much lower than that of A40/NP composites. The tensile strength and elongation at break of A40/NP (100/2) and A80/NP (100/2) were increased to some extent with respect to pure PVC/AP composites. DSC‐TGA analysis and rheological properties demonstrated that NP filled PVC composites processed good thermostability and thermoprocessability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Flexible,lead-free,gamma-shielding materials based on natural rubber/metal oxide composites

Properties such as gamma shielding, cure characteristics, and mechanical properties of natural rubber (NR) system with addition of oxides such as: iron (II, III) oxide (Fe₃O₄), tungsten (III) oxide (W₂O₃), or bismuth (III) oxide (Bi₂O₃) were studied for potential replacement of flexible lead (Pb), and introduced as gamma-shielding materials, to minimize risks caused by Pb. The results showed that increase in the content of oxides such as Fe₃O₄, W₂O₃, or Bi₂O₃ from 0 to 100, 300, and 500 parts/100 parts of rubber by weight (phr) increased the gamma attenuation coefficients, tensile modulus at 100% elongation, and hardness (Shore A), though they reduced the tensile strength and elongation-at-break. The composites also underwent thermal aging tests at 70 °C for 96 h. The results indicated slight reduction in the overall tensile properties. Specifically, for NR composites with 300 or 500 phr of Bi₂O₃, the mass attenuation coefficients (μ _m) of these composites were the highest among other composites and even higher than lead sheets that were measured using the same set-up. The outcome of the results imply great possibilities of replacing hazardous lead-containing gamma-shielding materials with the investigated composites, while still providing safe and efficient gamma-shielding properties for the users.     

Properties of Ferrite-Filled Natural Rubber Composites

Nickel zinc ferrite (Ni-ZnFe₂O₄)-filled natural rubber (NR) composite was prepared at various loading of ferrite. The tensile properties included in this study were tensile strength, tensile modulus and elongation at break. The tensile strength and elongation at break of the composites increased up to 40 parts per hundred rubber (phr) of ferrite and then decreased at higher loading whereas the tensile modulus was increased gradually with increasing of ferrite loading. Scanning electron microscopy (SEM) was used to determine the wettability of filler in rubber matrix. From the observation, the increase of filler loading reduced the wettability of the filler. Thermal stability of the composites was conducted by using a thermogravimetry analyser (TGA). The incorporation of ferrite in NR composites enhanced the thermal stability of NR composites. The swelling test results indicate that the swelling percentage of the composites decreased by increasing of ferrite loading. The initial permeability, μ_i and quality factor, Q of magnetic properties of NR composites achieved maximum value at 60 phr of ferrite loading for frequency range between 5000–40,000 kHz. The maximum impedance, Z _max of the NR composites was at the highest value at 80 phr ferrite loading for frequency range between 200–800 MHz.     

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     

Structure and property of polyurethane/SiO2 composite elastomer prepared via in situ polymerization

A series of polyurethane (PU)/SiO₂ composites were prepared via in situ polymerization through a prepolymer process. The effect of SiO₂ content on mechanical and solvent‐resistant properties of PU/SiO₂ composites was investigated. It was found that with increasing SiO₂ content, the tensile strength and toughness, hardness, and modulus of PU composites increased. PU/SiO₂ composites exhibited only one loss peak corresponding to the glass transition temperature of the soft‐segment of PU, which shifted insignificantly with increasing SiO₂ content. The equilibrium swelling ratio and swelling rate constant in cyclohexanone and xylene were reduced by increasing SiO₂ content, indicating the enhancement of the solvent resistance of the PU elastomer. Morphology observation of PU/SiO₂ composites showed that the acicular SiO₂ dispersed uniformly in PU matrix, and there was no obvious aggregation even at 9 wt % loading of SiO₂. The reinforcing and toughening effects depended largely on the dispersion of SiO₂ in PU matrix and the interfacial layer formed between the two phases. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Densification, microstructure and mechanical properties of SiO2-cBN composites by spark plasma sintering

SiO₂-cBN composites were consolidated by spark plasma sintering at 1473-1973 K. The effects of cBN content and sintering temperature on the relative density, phase transformation, microstructure and mechanical properties of the SiO₂-cBN composites were investigated. The relative density of the SiO₂-cBN composites increased with increasing SiO₂ content. The phase transformation of cBN to hBN in SiO₂-cBN composites was identified at 1973 K, showing the highest transformation temperature in cBN-containing composites. The SiO₂-20 vol% cBN composites sintered at 1673 K showed the highest hardness and fracture toughness of 12.5 GPa and 1.5 MPa m^1/2, respectively.     

Effect of conductive carbon black on electrical conductivity and performance of tire tread compounds filled with carbon black/silica hybrid filler

For green tires, carbon black (CB) is partially replaced by silica (SiO₂) in the tread formula in order to improve wet grip (WG) and fuel saving efficiency (FSE). However, such replacement inversely affects electrical conductivity of a tire resulting a greater potential for static shock or electrostatic ignition. This work aimed to improve electrical conductivity of the tread compound by partially replacing either CB or SiO₂ by 0–12 phr of conductive carbon black (CCB) (with replacing ratio of 2:1) and investigating the effect of such replacement on the tire performance. Although the partial replacement of CB or SiO₂ by CCB increased the magnitude of transient filler network resulting in the negative effects on heat build-up, WG and FSE of the tread vulcanizates, it significantly improved electrical conductivity. Surface resistivity decreased sharply when CB or SiO₂ was replaced by 3 phr of CCB, revealing the point of percolation threshold. In addition, the partial replacement of CB or SiO₂ by CCB did not cause significantly change of both hardness and tensile properties. At any given CCB loading, the SiO₂ replacement provided greater surface conductivity and higher abrasion resistance with lower WG and FSE than the CB replacement.     

Magnetic and dielectric properties of natural rubber and polyurethane composites filled with cobalt ferrite

Abstract

Cobalt ferrite (CoFe₂O₄) powders synthesised by sol–gel techniques were incorporated into natural rubber (NR) and polyurethane (PU) by two-roll milling at different loadings from 0 to 45 phr. In either NR or PU composites, the magnetisations were proportional to the CoFe₂O₄ loading, but the coercive field remained rather insensitive to the loading. The frequency response from 1 MHz to 1 GHz revealed that the real part of the magnetic permeability increased significantly only in the case of 45 phr CoFe₂O₄, while the imaginary part was modest in both NR and PU composites. In contrast, the electrical permittivity of CoFe₂O₄–PU was larger than that of CoFe₂O₄–NR composites, and both parts at 100 MHz had linear variations with the loading, in agreement with Wagner’s equation.     

高耐磨炭黑填充型粉末NR研究(Ⅲ)硫化胶的物理机械性能

研究了高耐磨炭黑(N330)填充型粉末天然橡胶[P(NR/N330)]硫化胶的物理机械性能.结果发现炭黑乳化剂、炭黑、操作油和包覆剂的用量及玻璃化转变温度对P(NR/N330)硫化胶的物理机械性能的影响比较明显.在适宜的粉末化条件下制备的P(NR/N330),其硫化胶的物理机械性能优于天然胶乳与炭黑的简单共沉胶(ENR/N330),而300%定伸应力则低于块状NR/N330机械混炼胶(MNR/N330).P(NR/N330)硫化胶拉伸断面形貌的SEM分析表明,包覆剂在用量为15份时,与NR基体形成互锁结构;DSC分析表明,二者部分相容,因此硫化胶具有较好的物理机械性能.     

Densification and mechanical properties of cBN–TiN–TiB2 composites prepared by spark plasma sintering of SiO2-coated cBN powder

cBN–TiN–TiB₂ composites were fabricated by spark plasma sintering at 1773–1973 K using cubic boron nitride (cBN) and SiO₂-coated cBN (cBN(SiO₂)) powders. The effect of SiO₂ coating, cBN content and sintering temperature on the phase composition, densification and mechanical properties of the composites was investigated. SiO₂ coating on cBN powder retarded the phase transformation of cBN in the composites up to 1873 K and facilitated viscous sintering that promoted the densification of the composites. Sintering at 1873 K, without the SiO₂ coating, caused the relative density and Vickers hardness of the composite to linearly decrease from 96.2% to 79.8% and from 25.3 to 4.4 GPa, respectively, whereas the cBN(SiO₂)–TiN–TiB₂ composites maintained high relative density (91.0–96.2%) and Vickers hardness (17.9–21.0 GPa) up to 50 vol% cBN. The cBN(SiO₂)–TiN–TiB₂ composites had high thermal conductivity (60 W m⁻¹ K⁻¹ at room temperature) comparable to the TiN–TiB₂ binary composite.     

High-temperature mechanical properties of NextelTM 610 fiber reinforced silica matrix composites

Novel Nextel? 610 fiber reinforced silica (N610f/SiO₂) composites were fabricated via sol-gel process at a sintering temperature range of 800–1200?°C. The sintering-temperature dependent microstructures and mechanical properties of the N610f/SiO₂ composites were investigated comprehensively by X-ray diffraction, nanoindentation, three-point bending etc. The results suggested a thermally stable Nextel? 610 fiber whose properties were barely degraded after the harsh sol-gel process. A phase transition in the silica matrix was observed at a critical sintering temperature of 1200?°C, which led to a significant increase in the Young's modulus and hardness. Due to the weak fiber/matrix interfacial interaction, the 800?°C and 1000?°C fabricated N610f/SiO₂ composites exhibited quasi-ductile fracture behaviors. Specially, the latter possessed the highest flexural strength of ≈ 164.5?MPa among current SiO₂-matrix composites reinforced by fibers. The higher sintering-temperature at 1200?°C intensified the SiO₂ matrix, but strengthened the interface, thus resulting in a brittle fracture behavior of the N610f/SiO₂ composite. Finally, the mechanical properties of this novel composite presented good thermal stability at high temperatures up to 1000?°C.     

Preparation,morphology and properties of natural rubber composites filled with untreated short jute fibres

Green composites were obtained by incorporation of short jute fibres in natural rubber matrix using a laboratory two-roll mill. The influence of untreated fibre content (1, 2.5, 5, 7.5 and 10 phr) on the mechanical properties, dynamic mechanical properties, swelling properties was examined. The behaviour of prepared green composites under cyclic compression was also investigated. Fibre dispersion in rubber matrix was studied by scanning electron microscopy. The highest tensile strength (21.1 MPa) and highest tear strength (39.9 N/mm) were found for composites containing 2.5 and 5 phr of short jute fibres, respectively. The results also suggested that increasing fibrous filler content resulted in increasing of tensile moduli 100, 200 and 300 % of elongation and hardness, and decreasing of rebound resilience and abrasion resistance of prepared jute/natural rubber composites. The cyclic compression test showed that increasing the amount of short jute fibres in the rubber matrix is related to increase of the energy dissipated in the composite. The incorporation of short jute fibres into the rubber matrix improves the stiffness of the composites, and it is related to the interaction between fibre surface and rubber matrix. The application of short fibres in higher amounts leads to formation of fibre agglomerates reducing the mobility of the rubber polymer chains. The mentioned agglomerates act as defects in rubber matrix, which caused decreasing of some properties, e.g. relative elongation at break.     

Thermal stability and abrasion resistance of polyacrylate/nano-silica hybrid coatings

Polyacrylate (PAE)/nano-silica (SiO₂) hybrids were prepared by an in situ sol–gel process of tetraethyl orthosilicate in the presence of PAE toluene solution. The hybrid coatings were fabricated using a PAE/SiO₂ suspension by the traditional casting. Their intermolecular interaction and morphology, as well as thermal, mechanical, and optical properties, were investigated using Fourier transform infrared spectroscopy, field-emission scanning electron microscope, differential scanning calorimetry and TG/DTA thermogravimetric analysis, coating impact testing, and UV–Vis spectroscopy, respectively. At the same time, their abrasive properties were carried out by abrasion resistance and nanoindentation tests. The results indicate that silica nanoparticles, with diameter about 30 nm, can disperse homogeneously in the PAE matrix, where hydrogen bonds between the PAE and nano-silica are formed. Therefore, homogeneous dispersion of nano-silica particles provides high transparency for the PAE/SiO₂ hybrid coating as the size of nano-silica phase is much smaller than the wavelength (390–770 nm) of visible light. PAE/nano-silica hybrid coatings have increased T _g and thermal stability including the onset decomposition temperature, 10 % weight loss temperature, and char at 700 °C. Additionally, the incorporation of nano-silica particles improves the glossiness of the PAE/nano-silica hybrid coatings and enhances their abrasion resistance and surface hardness. The nano-silica content has obvious effect on the thermal, mechanical, optical, and anti-abrasion properties of PAE/SiO₂ hybrid coatings. With the consideration of all the properties of hybrid coatings, the PAE/SiO₂ hybrid containing 10 phr of nano-silica has the optimal composition. These PAE/nano-silica hybrid coatings have potential applications in high-performance hologram image recording.     

Improving ablation properties of liquid silicone rubber composites by in situ construction of rich-porous char layer

In this article, ammonium polyphosphate (APP) and ammonium pentaborate (APB) were introduced to liquid silicone rubber with an aim of building rich-porous char structure in situ, thereby improving thermal insulation properties. Thermogravimetric analyses indicated that the incorporation of APP greatly increased the char residue of the composites. Oxy-acetylene torch tests showed that the addition of either APP or APB powders effectively enhanced the ablation resistance of the composites, whereas Shore A hardness tests revealed that the APP-containing composites exhibited a higher hardness than APB-filled counterparts. The linear ablation rates of composites with 40 phr APP or APB were reduced by 34.16% and 36.19%, respectively, when compared with the control sample. The maximum back-face temperatures of composites with 40 phr APP or APB was reduced to as low as 73°C. The APP-containing composites exhibited superior ablation resistance, considering both the linear ablation rate and the mechanical properties of char layer. In addition to SiO₂, SiC, and C, B₂O₃ was produced in the APB composites, as characterized by XRD and Raman analysis. Combined with SEM, it was proven that the formation of a firm, continuous, rich-porous and thermal insulation char layer was advantageous to improve the ablation and insulation properties.