不同硫化体系对天然橡胶的动静态性能的影响研究

分别制备了以炭黑和白炭黑为补强填料的不同硫化体系天然橡胶(NR)复合材料,研究硫化体系对NR胶料静态和动态性能的影响。结果表明:普通硫化体系硫化胶具有较高的交联密度、较好的物理性能和优异的耐磨性能;对于白炭黑补强体系,普通硫化体系硫化胶具有最低的滚动阻力;而对于炭黑补强体系,平衡硫化体系硫化胶具有最低的滚动阻力;胶料拉伸强度的增大有利于耐磨性的提高。     

炭黑和白炭黑补强NR动态性能的研究

研究了炭黑和白炭黑用量对天然橡胶动态性能的影响。结果表明,炭黑和白炭黑分别填充NR的弹性模量G′对动态应变振幅的响应不同,两者与NR间的相互作用强度和机理也不同;填料用量多于30份时才会形成明显的填料网络结构,硫化时交联网络的形成能够促进填料网络的形成;硅烷偶联剂改变了白炭黑与天然橡胶的作用方式,硫化胶动态损耗降低;电镜扫描结果表明,在硅烷偶联剂作用下,白炭黑与橡胶间产生的化学结合使白炭黑粒子在动态变形条件下的团聚程度显著低于炭黑。     

补强体系对NR硫化胶疲劳破坏特性的影响

用断裂力学方法研究炭黑N330、炭黑N330/白炭黑和白炭黑补强NR硫化胶的疲劳破坏特性.结果表明,与炭黑N330和炭黑N330/白炭黑补强的NR硫化胶相比,白炭黑补强的NR硫化胶疲劳寿命较长,内部潜在缺陷较少,抗裂纹扩展性能较好;随着疲劳时间的延长,NR硫化胶拉断时的应变能密度减小;疲劳寿命方程能够快速、准确地预测NR硫化胶的疲劳寿命.     

炭黑和白炭黑增强NR的微观网络结构及动态性能

采用"填料粒子相互作用距离"的新观点,研究了炭黑和白炭黑增强的NR的填料网络结构和动态性能。结果表明,当白炭黑和炭黑填充份数相同时,由于白炭黑尺寸较小,在NR基体中相互作用距离小,易形成相互作用较强的填料网络。动态测试发现,白炭黑填充混炼胶比炭黑填充混炼胶具有更明显的Payne效应;白炭黑填充硫化胶具有更低的滞后损失和更小的生热。     

不同填料对丁苯橡胶硫化胶应力软化效应的影响

研究炭黑、白炭黑和白炭黑/硅烷偶联剂TESPT填充丁苯橡胶硫化胶的应力软化效应,并通过扫描电子显微镜表征填料在胶料中的分散程度,探讨填料-填料相互作用、橡胶-填料相互作用、循环加载拉伸及恢复条件等因素对硫化胶应力软化效应的影响。结果表明:炭黑填充硫化胶的应力软化效应最强,白炭黑填充硫化胶的应力软化效应最弱,加入硅烷偶联剂TESPT后白炭黑填充硫化胶的应力软化效应增强;白炭黑填充硫化胶的应变能恢复程度最高,炭黑填充硫化胶次之,白炭黑/硅烷偶联剂TESPT填充硫化胶最低。     

干燥方式对天然橡胶性能的影响

探讨直接烘干、絮胶烘干、微波烘干和烟熏烘干4种干燥方式对天然橡胶(NR)性能的影响。结果表明:微波烘干时间远远短于其他3种干燥方式,且几乎不存在夹生胶现象;微波烘干NR纯胶、炭黑和白炭黑填充NR硫化胶物理性能均较优,絮胶烘干NR次之;絮胶烘干炭黑填充NR硫化胶的损耗因子(tanδ)最小,微波烘干NR白炭黑填充配方硫化胶的tanδ最小。     

炭黑/白炭黑双相填料的配比对溶聚丁苯橡胶性能的影响

考察了用白炭黑取代部分炭黑作为填充剂对溶聚丁苯橡胶(SSBR)硫化胶物理机械性能和动态力学性能的影响。结果表明,采用炭黑/白炭黑双相填料可以提高SSBR硫化胶的物理机械性能和动态力学性能,原因在于双相填料增强了填料与橡胶大分子之间的相互作用,提高了填料在橡胶基质中的分散性。当用20份白炭黑与30份炭黑组成双相填料时,SSBR硫化胶的各项性能达到最佳。     

白炭黑/炭黑并用对NR/BR硫化胶磨耗性能及形态的影响

采用电子显微镜（SEM）研究了白炭黑与炭黑并用对天然橡胶／顺丁橡胶（NR／BR）硫化胶磨耗性能及形态的影响。结果表明：白炭黑和炭黑并用能显著提高硫化胶的耐磨性，当白炭黑／炭黑质量比为45／10时，硫化胶耐磨性最高，其磨耗表面磨纹最细密。     

偶联剂Si 69对NR/BR/NBR共混硫化胶性能的影响

研究了偶联剂Si 69对NR／BR／NBR共混胶体系的硫化特性、交联密度和硫化胶的物理机械性能及动态力学性能的影响。结果表明，偶联剂Si 69在共混硫化胶中可以起到提高聚合物与填料间的相互作用和交联密度的作用，它在白炭黑增强硫化胶中对性能的改善比在炭黑增强硫化胶中的改善更显著。     

白炭黑/炭黑配比对天然橡胶基复合材料性能的影响

以硅烷偶联剂作为白炭黑(SiO_2)的表面改性剂,以改性SiO_2/炭黑作为天然橡胶(NR)的混合填料,采用半有效硫化体系制备了NR基复合材料。研究结果表明:当m(SiO_2)∶m(炭黑)=20∶40时,硫化胶中混合填料分散均匀,并且硫化胶的撕裂强度(62 k N/m)相对最高、交联密度相对最大且佩恩效应相对较弱。     

Synergistic effect of carbon black and carbon–silica dual phase filler in natural rubber matrix

In this article, the synergistic effects of carbon black (CB) and modified carbon–silica dual phase filler (MCSDPF) on the properties of natural rubber (NR) were investigated. MCSDPF was prepared by modifying carbon–silica dual phase filler (CSDPF) with bis(3‐triethoxysilylpropyl)tetrasulphane (Si‐69). Fourier transform infrared spectroscopy and thermogravimetric analyzer analyses revealed that Si‐69 was successfully grafted to CSDPF. NR‐based compounds containing various combinations of MCSDPF and CB were prepared through a mechanical mixing. Investigations of mechanical properties, ageing resistance, abrasion resistance, dynamic mechanical properties, and morphology of tear fractured surface of MCSDPF/CB/NR vulcanizates were conducted. Our study shows that adding MCSDPF led to significant improvement in the tear resistance, fatigue life, and elongation at break of MCSDPF/CB/NR vulcanizates. Optimum stoichiometric combination of MCSDPF and CB inside the NR matrix was derived (ratio of MCSDPF and CB in wt% = 15/50), which showed synergistic effects of MCSDPF upon CB that was ultimately reflected in their tensile strength, wet skid resistance, and rolling resistance. POLYM. COMPOS., 35:1466–1472, 2014. © 2013 Society of Plastics Engineers     

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.     

Norbornylized soybean oil as a sustainable new plasticizer for rubbers with hybrid fillers

Carbon black (CB) and precipitated silica are two major reinforcing fillers in rubbers. CB/silica hybrid filler is also widely used in rubbers to provide balanced properties. CB/silica‐hybrid‐filler‐filled styrene‐butadiene rubber (SBR) containing naphthenic oil (NO), soybean oil (SO) and norbornylized SO (NSO) was investigated. The swelling and curing behavior and rheological, mechanical, thermal, aging and dynamic properties were studied and compared with earlier reported data on CB‐ or silica‐filled SBR. NSO provides better scorch safety and faster cure than SO. Compared with NO, the addition of SO and NSO enhances the thermal stability and aging resistance of SBR vulcanizates. SBR/NSO vulcanizates with hybrid filler exhibit a higher tensile and tear strength than SBR/NO and SBR/SO vulcanizates. A synergistic effect in the abrasion resistance of vulcanizates containing the hybrid filler is observed. An increase of sulfur content in the hybrid‐filler‐filled SBR/NSO vulcanizates provides further improvement in abrasion resistance, wet traction and rolling resistance. © 2017 Society of Chemical Industry     

Fly ash particles and precipitated silica as fillers in rubbers. I. Untreated fillers in natural rubber and styrene–butadiene rubber compounds

In this study, we investigated the effects of untreated precipitated silica (PSi) and fly ash silica (FASi) as fillers on the properties of natural rubber (NR) and styrene–butadiene rubber (SBR) compounds. The cure characteristics and the final properties of the NR and SBR compounds were considered separately and comparatively with regard to the effect of the loading of the fillers, which ranged from 0 to 80 phr. In the NR system, the cure time and minimum and maximum torques of the NR compounds progressively increased at PSi loadings of 30–75 phr. A relatively low cure time and low viscosity of the NR compounds were achieved throughout the FASi loadings used. The vulcanizate properties of the FASi‐filled vulcanizates appeared to be very similar to those of the PSi‐filled vulcanizates at silica contents of 0–30 phr. Above these concentrations, the properties of the PSi‐filled vulcanizates improved, whereas those of the FASi‐filled compounds remained the same. In the SBR system, the changing trends of all of the properties of the filled SBR vulcanizates were very similar to those of the filled NR vulcanizates, except for the tensile and tear strengths. For a given rubber matrix and silica content, the discrepancies in the results between PSi and FASi were associated with filler–filler interactions, filler particle size, and the amount of nonrubber in the vulcanizates. With the effect of the FASi particles on the mechanical properties of the NR and SBR vulcanizates considered, we recommend fly ash particles as a filler in NR at silica concentrations of 0–30 phr but not in SBR systems, except when improvement in the tensile and tear properties is required. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2119–2130, 2004     

Interfacial Interactions of Silica and Natural Rubber Enhanced by Hydroxyl Telechelic Natural Rubber as Interfacial Modifier

The incompatibility between hydrophilic silica and hydrophobic rubber is an important problem on using silica in nonpolar rubber. In this study, hydroxyl telechelic natural rubber (HTNR) that contains hydroxyl‐terminated groups was introduced into silica‐reinforced natural rubber (NR) in order to improve the bonding strength between rubber and silica. The properties of silica‐reinforced NR compounds and vulcanizates as a function of varying silica contents were evaluated at a fixed HTNR concentration at 8% wt/wt of silica content. The results show that the improvement of silica dispersion and decreasing of filler–filler interactions (Payne effect) were obtained in the NR compounds and vulcanizates with HTNR addition. The enhancements in tensile properties, crosslink density, abrasion resistance, heat build‐up, and thermal properties of the silica‐reinforced NR vulcanizates with added HTNR confirmed that HTNR performed good as interfacial modifier of silica. In the study, the optimum properties of silica‐reinforced NR vulcanizate were achieved at 30 phr silica with 2.4 phr HTNR. However, HTNR still showed poorer efficiency than the synergy between commercial silane coupling agent, bis [3‐(triethoxysilyl) propyl] tetrasulphide (TESPT) and diphenylguanidine (DPG) when used in silica‐reinforced NR vulcanizate. J. VINYL ADDIT. TECHNOL., 26:291–303, 2020. © 2019 Society of Plastics Engineers     

Fatigue resistance of silica‐filled natural rubber vulcanizates: comparative study of the effect of phosphorylated cardanol prepolymer and a silane coupling agent

The fatigue resistance of silica‐filled natural rubber (NR) mixes modified with phosphorylated cardanol prepolymer (PCP) was studied in comparison with similar compositions without PCP and with those containing the same dosage of a silane coupling agent (Si‐69). Considerable improvement in the fatigue resistance was observed for the PCP‐modified NR vulcanizate containing 20 phr of silica compared with the unmodified and Si‐69 modified vulcanizates. In addition, the tear strength of the PCP‐modified NR vulcanizate was higher than that of the others. Atomic force microscopy and the scanning electron microscopy of the vulcanizates showed better dispersion of silica particles in the NR matrix in the presence of PCP than in the unmodified and Si‐69‐modified NR vulcanizates. It is assumed that, at a dosage of 5 phr, PCP functions as a coupling agent between NR and the silica particles thereby improving the filler dispersion and consequently the mechanical properties of the vulcanizate. Copyright © 2005 Society of Chemical Industry     

Ultrasonic Extrusion of NR Gum and Its Effect on the Structure and Properties of Unfilled and Silica-Filled NR

Natural rubber (NR) has been extruded without and with ultrasonic treatment at various ultrasonic amplitudes. The effect of ultrasonic treatment on structure of NR, its compounds with silica and silica/silane and their vulcanizates have been studied. Processing-structure-properties relationship of untreated and treated materials has been established. With the increase of ultrasonic amplitude power consumption is increased and die pressure is reduced. Size exclusion chromatography measurements show that the NR molecular weight is reduced with the ultrasonic treatment. The storage modulus and loss modulus, complex viscosity and loss tangent results also confirmed the degradation of NR chains by imposition of ultrasound, especially after treatment at high amplitude. After mixing with silica and silica/silane, it was found that degradation of NR caused a reduction in the rubber–filler interaction, an increase in the filler–filler interaction and flocculation upon heating. Physical properties of vulcanizates including M100, ultimate elongation, and stress at break are also deteriorated. POLYM. ENG. SCI., 60:925–934, 2020. © 2020 Society of Plastics Engineers     

A comparative study of aging characteristics and thermal stability of oil palm ash,silica, and carbon black filled natural rubber vulcanizates

Filler‐filled natural rubber (NR) vulcanizates were prepared by conventional laboratory‐sized two roll mills and cured using sulfuric system. The effect of thermal aging on physical properties and thermogravimetric analysis (TGA) of oil palm ash (OPA) and commercial fillers (i.e., silica vulkasil C and carbon black N330)‐filled NR vulcanizates at respective optimum loading and equal loading were studied. Before aging, the OPA‐filled vulcanizates showed comparable optimum strength as carbon black‐filled vulcanizates. The hardening of aged filler‐filled NR vulcanizates happened after aging, thereby tensile strength and elongation at break reduced while the modulus increased. Fifty phr carbon black‐filled vulcanizates showed better retention in tensile properties as compared to silica (10 phr) and OPA (1 phr). This was attributed to the addition of different filler loading and this finding was further explained when equal loading of filler‐filled vulcanizates was studied. Fourier transform infra‐red analysis showed chemical structure had changed and tensile fractured surface exhibited smooth appearance due to the deterioration in tensile properties after aging. TGA also denoted the thermal stability was depending on the amount of filler loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4474–4481, 2013     

Effect of carbon black/nanoclay hybrid filler on the dynamic properties of natural rubber vulcanizates

In this study, natural rubber (NR) nanocomposites based on carbon black (CB) and two poly(ethylene glycol) (PEG)‐modified clay hybrid filler were fabricated. The morphology and mechanical properties were studied. The dynamic properties of NR vulcanizates were investigated over a range of strain amplitude at two temperatures. It was found that NR with hybrid filler exhibits superior mechanical properties over that with CB as single phase filler. The hybrid filler causes a significant alteration in the dynamic properties of rubber. The Payne effect becomes more pronounced in rubber with modified clay. A decrease in loss factor (tanδ) was observed for rubber with hybrid filler also. The results revealed that the inclusion of nanoclay (NC) could induce a stronger and more developed filler network. Because of the anisotropy of the nanolayers, NC would depress the reconstruction of filler network, or lower the reformation rates when broken down under deformation, giving rise to lower tanδ value at broad temperature range as well as strain amplitude. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.