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.     

Graphene/carbon black/natural rubber composites prepared by a wet compounding and latex mixing process

The extensively used latex mixing approach to prepare graphene can improve the graphene dispersion but meets some challenges in the preparation of high content carbon black filled rubber system like a rubber tire. Owing to the high melt viscosity of the rubber/graphene masterbatch, the dispersion of carbon black is not perfect during twin-roll mixing and some aggregates will be formed. Here we proposed a wet compounding process, combined with ultrasonically assisted latex mixing, named as the WCL method to prepare reduced graphene oxide/carbon black/natural rubber (rGO/CB/NR) composites. The morphological observations confirmed that both graphene and carbon black can be evenly dispersed in the rubber composites. The incorporation of rGO also improves the hardness, thermal conductivity and anti-aging properties of the composites. The rGO/CB/NR composites prepared by the WCL method possess better mechanical properties compared to conventional latex mixing. The entanglement-bound rubber tube model was utilised to understand the reinforcing mechanism.     

天然橡胶湿法混炼的研究进展

根据补强填充体系种类,分别介绍炭黑、白炭黑和石墨烯等与天然橡胶的湿法混炼工艺技术,并对天然橡胶湿法混炼所面临的问题及发展趋势进行了分析和展望。湿法混炼研究包括不同补强填充体系水乳液的配制方式和配方优化及湿法混炼胶的后处理工艺。今后应对湿法混炼多组分复杂反应的特征和混炼胶结构与性能的关系开展深入研究,并加强自动化与连续化生产工艺的研发。     

Preparation and mechanical properties of natural rubber powder modified by carbon nanotubes

A suspension of carbon nanotubes in natural latex was obtained by liquid mixing and then was used to prepare powder natural rubber composites modified with carbon nanotubes by means of spray drying process. The composite powders were round‐like and fine, with an average diameter of less than about 5 μm. The dispersion of carbon nanotubes in the rubber matrix was improved remarkably compared with that obtained by the mechanical mixing method. By means of vulcanization tests, it was found that the addition of vulcanizing agent necessary for the powder rubber containing carbon nanotubes should be evidently greater than that in rubber prepared by mechanical mixing, there evidently existed vulcanization reversions for the natural rubber prepared by mechanical mixing, which disappeared in the powder rubber containing carbon nanotubes prepared by the spray drying process. The mechanical properties of the powder natural rubber containing carbon nanotubes were much improved because of the modification effect of carbon nanotubes in rubber. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4697–4702, 2006     

Viscoelastic properties of natural rubber composites reinforced by defatted soy flour and carbon black co‐filler

Filler mixtures of defatted soy flour (DSF) and carbon black (CB) were used to reinforce natural rubber (NR) composites and their viscoelastic properties were investigated. DSF is an abundant and renewable commodity and has a lower material cost than CB. Aqueous dispersions of DSF and CB were first mixed and then blended with NR latex to form rubber composites using freeze‐drying and compression molding methods. A 40% co‐filler reinforced composite with a 1 : 1 DSF : CB ratio exhibited a 90‐fold increase in the rubber plateau modulus compared with unfilled NR, showing a significant reinforcement effect by the co‐filler. The effect, however, is lower than that observed in the carboxylated styrene–butadiene rubber composites reported earlier, indicating a significant effect from the rubber matrix. The co‐filler composites have elastic moduli between those of DSF and CB reinforced composites. Stress softening and recovery experiments indicated that the co‐filler composites with a higher CB content tend to have a better recovery behavior; however, this can not be simply explained from the recovery behaviors of the single filler (DFS and CB) composites. CB composites prepared by freeze‐drying show a strain‐induced reorganization of fillers. Strain sweep experiment data fit with the Kraus model indicates the co‐filler composites with a higher CB content are more elastic, which is consistent with the recovery experiments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

用作载重子午线轮胎胎面胶的炭黑填充粉末NR结构与性能研究

以天然胶乳和炭黑N234为原料,采用凝聚共沉法制备炭黑填充型粉末NR[P(NR/CB)],研究炭黑用量和不同配方对胶料硫化特性、物理性能、交联密度、微观结构、Payne效应及动态力学性能的影响,并与采用传统机械混炼法制备的炭黑/NR(CB/NR)进行对比.结果表明,与CB/NR硫化胶相比,P(NR/CB)硫化胶具有较高的拉伸强度、撕裂强度、回弹值和抗湿滑性能以及较低的滚动阻力,耐屈挠性能和耐磨性能大致相当,而动态压缩生热和压缩永久变形则降低了近50%.     

An investigation on the reinforcing potential of red earth as filler for natural rubber compounds

Locally sourced red earth (RE) was air‐dried, pulverized, and screened with a sieve of mesh size 75 nm. It was characterized in terms of its moisture content, loss on ignition, silica content, iodine adsorption number, oil absorption, pH, and metal oxide compositions. Natural rubber, standard Nigerian rubber used for this work was first characterized in terms of its dirt, ash and nitrogen contents, volatile matter, plasticity retention index, and Mooney viscosity. The RE was applied as filler wholly and in blends with standard carbon black, CB (N330) filler in the natural rubber compounding using efficient vulcanization system. The cure and the physicomechanical properties of the compounds and vulcanizates were, respectively, measured as function of filler loading. The results were compared with those of the standard carbon black (N330)‐filled natural rubber. It was found, that the RE‐filled natural rubber showed substantial reinforcement of the rubber, though inferior to carbon black (N330) filled vulcanizates, the tensile strength of the carbon black‐filled vulcanizates is about one half times that of the RE‐filled vulcanizates. The tensile properties of the RE‐filled vulcanizates improved markedly by blending the RE‐filler with the carbon black (N330). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of starch on the properties of carbon‐black‐filled styrene–butadiene rubber composites

The influence of starch on the properties of carbon‐black‐filled styrene–butadiene rubber (SBR) composites was investigated. When the starch particles were directly melt‐mixed into rubber, the stress at 300% elongation and abrasion resistance decreased evidently with increasing starch amount from 5 to 20 phr. Scanning electron microscopy observations of the abrasion surface showed that some apparent craters of starch particles were left on the surface of the composite, which strongly suggested that the starch particles were large and that interfacial adhesion between the starch and rubber was relatively weak. To improve the dispersion of the starch in the rubber matrix, starch/SBR master batches were prepared by a latex compounding method. Compared with the direct mixing of the starch particles into rubber, the incorporation of starch/SBR master batches improved the abrasion resistance of the starch/carbon black/SBR composites. With starch/SBR master batches, no holes of starch particles were left on the surface; this suggested that the interfacial strength was improved because of the fine dispersion of starch. Dynamic mechanical thermal analysis showed that the loss factor at both 0 and 60°C increased with increasing amount of starch at a small tensile deformation of 0.1%, whereas at a large tensile strain of 5%, the loss factor at 60°C decreased when the starch amount was varied from 5 to 20 phr. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

过硫酸铵改性炭黑／天然胶乳复合材料的制备与性能研究

摘要：用过硫酸铵水溶液改性炭黑,制备亲水性炭黑悬浮液。采用乳液共混法,将制备的改性炭黑水溶液直接加入天然胶乳。结果表明：改性后炭黑表面亲水性含氧基团增多,粒径减小;与传统干法混炼炭黑,天然橡胶胶料相比,乳液共混改性炭黑／天然胶乳复合材料炭黑分散粒径小且分散均匀,复合材料拉伸强度和撕裂强度显著提高。     

Rare earth compounds modified carbon black filled powdered natural rubber: Preparation,morphology and properties

Ten types of rare earth (RE) compounds modified carbon black (HAF‐RE) were prepared using chemical‐deposit method, then HAF‐RE were mixed with natural rubber latex to prepare HAF‐RE filled powdered natural rubber [P(NR/HAF‐RE)] by a carbon black/rubber latex coagulation method. It is found that most of the P(NR/HAF‐RE) vulcanizates showed better mechanical properties, especially higher tensile modulus, and tensile strength, compared with none‐rare earth modified carbon black filled powdered natural rubber [P(NR/HAF)]. Dysprosium (Dy) modified carbon black (HAF‐Dy) filled powdered natural rubber [P(NR/HAF‐Dy)] was chosen for intensive investigation because of its better comprehensive mechanical properties. It is found that the adding of Dy compounds could help to get smaller particles with narrower particle size distribution, and results from the SEM analysis show that carbon black has been dispersed in rubber matrix uniformly with diameter of 50–150 nm. The TEM analysis showed that Dy compounds could obviously reduce the aggregation of primary particles of carbon black, and promote the dispersion of carbon black in P(NR/HAF‐Dy) particles. © 2008 Wiley Periodicals, Inc. JAppl Polym Sci 2008     

Surface modification of commercial carbon black by silane coupling agents for improving dispersibility in rubber compounds

The dispersion of a filler in a rubber matrix is a crucial parameter affecting the mechanical and dynamical properties of a rubber compound. It is the current issue of the rubber compounding industry because, most fillers are categorized as a mineral, while the rubber is an organic material. The surface modification of the filler has been accepted as an effective technique for the improvement of the abovementioned parameter. First, the surface premodification of commercial carbon black with a grade of N660 (CB) was implemented by four different oxidation methods. After that, among of used methods, the oxidation method using citric acid was selected to produce modified carbon black (CB-Oxi) for further treatment. Subsequently, the coupling agent, Bis[3-(triethoxysilyl)propyl] tetrasulfide (TESPT) was functionalized on the surface of CB-Oxi to produce modified-CB-Oxi. Also, for comparison purposes, the TESPT functionalization was accomplished on untreated CB to form modified-CB. The FTIR spectra of CB-Oxi showed using the premodification method introduced the hydroxyl and carboxyl groups on the surface of CB. The correspondent spectra for modified-CB-Oxi confirmed the existence of silane groups on the surface of the carbon black. However, the mentioned silane groups were not observed on the surface of modified-CB. The findings were strengthened by several characteristic techniques including, FESEM, XRD, EDS, CHNS elemental analysis, and RAMAN spectra. The FESEM graphs and elemental mapping showed homogeneous dispersion and uniform distribution of sulfur and silicon elements on the modified-CB-Oxi surface. According to RAMAN spectra, the disturbance in the structure of carbon black graphite was reduced after surface modification. modified-CB-Oxi is proposed as a potential substitute filler for current commercial carbon black in rubber compounding.     

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 of carbon black/natural rubber latex masterbatch in bead form

Carbon black/natural rubber latex masterbatch in the form of spherical beads was prepared according to the acid-precipitation method. High-loading carbon black (40 phr) was incorporated in natural rubber with the aid of a nonionic surfactant (Nonidet P40). Shearing the beads in an internal mixer provided good integration of carbon black in the rubber matrix and hence the high bound rubber content. Results confirmed the contribution of chemical interaction to the bound rubber content. By an oxidation process, the size of modified carbon black was reduced, whereas the large agglomeration took place in the case of partially graphitized carbon black. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 489–498, 2001     

1,3,5‐trihydroxy benzene as a surface modifier of carbon black and its effect on the filler–rubber interaction

A surface‐modified rubber‐grade carbon black has been prepared by treating it with 1,3,5‐trihydroxy benzene (phluroglucinol) in aqueous solution at different molar concentrations. This modified carbon black has been used as one of the compounding ingredients with natural rubber. An attempt has been made to establish a concentration optimum for the modifier. Improved physicomechanical properties like hardness, heat buildup, hysteresis loss, and improved dynamic mechanical properties are observed for the compounded rubber. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2272–2278, 2003     

Effect of carbon‐based nanoparticles on the cure characteristics and network structure of styrene–butadiene rubber vulcanizate

The network structure of styrene–butadiene rubber (SBR) in the presence of carbon black (CB) with two different structures and multi‐walled carbon nanotubes (MWCNTs) was investigated. Swelling behaviour, tensile properties at various strain rates and cure kinetics were characterized. Experimental data were analysed using the Flory–Rehner model as well as the tube model theory. It is found that the network structure of CB‐filled SBR follows a three‐phase composite model including rigid particles, semi‐rigid bound rubber and matrix rubber. This bound rubber is postulated to be critical for the mechanical and deformational properties, development of crosslinking density in matrix rubber and polymer–filler interaction. For MWCNT‐filled SBR, the bound rubber does not show a substantial contribution to the network structure and mechanical performance, and these properties are greatly dominated by the higher aspect ratio and polymer–filler interaction. Additionally it is deduced that the crosslinking density of matrix rubber increases on incorporation of the fillers compared to unfilled matrix rubber. Copyright © 2012 Society of Chemical Industry     

Influence of nanoclay‐carbon black hybrid fillers on cure and properties of natural rubber compounds

The influence of organically modified nanoclay‐carbon black (CB) hybrid filler on the curing behavior of natural rubber (NR) was explored in this investigation. Here an effort was paid to understand the curing kinetics of organomodified nanoclay filled rubber compounds. On the basis of two different types of modified clay, NR nanocomposites were prepared and cured by a conventional vulcanization system. A faster curing rate and lower torque values were found when the modification was done by quaternary ammonium compounds. The activation energy of the rubber curing process decreased with the incorporation of nanoclay. In addition, it was revealed that the quaternary ammonium compounds used as modifier in the clay show a plasticization effect. Additionally, X‐ray diffraction studies indicated, that the basal spacing of the clay minerals was increased in both cases after incorporation in the rubber matrix. The dynamic mechanical analysis using a strain sweep mode showed that the Payne effect decreases because of an improved dispersion of CB induced by the presence of nanoclay. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

白炭黑粒径对天然橡胶/白炭黑湿法混炼胶性能的影响

通过使用球磨机在液相状态下对白炭黑进行研磨,可得到4种不同粒径白炭黑。采用湿法混炼工艺,将4种不同粒径的白炭黑与天然乳胶进行混合,制备出天然橡胶/白炭黑复合材料。对此种类型复合材料性能测定结果表明:用4种不同粒径的白炭黑制备的复合材料性能呈现出较大差异,当白炭黑粒径为9.4um,复合材料表现出最佳的综合性能。     

Carbon black filled powdered natural rubber: Preparation,particle size distribution,mechanical properties,and structures

Carbon black (HAF) filled powdered natural rubber (P(NR/HAF)) was prepared and the particle size distribution, mechanical properties, and micromorphology of P(NR/HAF) were studied. A carbon black–rubber latex coagulation method was developed for preparing carbon black filled free‐flowing, noncontact staining NR powders with particle diameter less than 0.9 mm. A powdering mechanism model was put forward to describe the powdering process, which shows that the key technical points consist in the surfactant with good emulsification properties and the polymer coating resin with good film forming properties. SEM analysis shows that carbon black and rubber matrix have formed a macroscopic homogenization in the P(NR/HAF) particles without contact staining, and carbon black particles are well dispersed in rubber matrix with diameter of about 50–150 nm. P(NR/HAF) vulcanizate showed better mechanical properties than bale natural rubber/carbon black blends (NR/HAF) and simple NR latex/carbon black blends (NRL/HAF), which depends primarily upon the absence of free carbon black, the fine dispersion of filler on the rubber matrix, and the better interaction between carbon black and rubber matrix due to the proper preparation condition of noncontact staining carbon black filled powdered NR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1763–1774, 2006     

Effect of carbon black on self‐crosslinking network structure of polychloroprene rubber and epoxidized natural rubber blends

The goal of this research is to improve poor network structure of polychloroprene rubber (CR)/epoxidized natural rubber (ENR) self‐crosslinking blends, which could substitute traditional vulcanizates in some application area. Carbon black (CB)–CR/ENR blends were prepared by reacting CR with ENR in the presence of CB. The structure of CR/ENR blends was characterized by attenuated total‐reflectance Fourier transform infrared spectroscopy (FTIR‐ATR). The effect of CB loading on curing characterization and mechanical properties of CR/ENR blends was investigated, and the interaction among CR, ENR, and CB was studied using differential scanning calorimetry. The effect of CB loading on the Payne effect of CR/ENR was investigated using rubber process analyzer. Scanning electron microscope was used to characterize the morphology of CB–CR/ENR blends. The results showed that CR/ENR blends were obtained by the ring‐opening reaction of epoxy groups in ENR and chlorine groups in CR. Mechanical properties of CR/ENR blends increased with the increase of CB loading. The Payne effect of CR/ENR became more remarkable with increasing CB loading. Morphology study indicated that interfacial compatibility between CR and ENR increased with the increase of CB loading because CB could strengthen the self‐crosslinking network structure of CR/ENR blends. The promoting effect of CB on self‐crosslinking reaction was verified by the assessment of crosslink density. POLYM. COMPOS., 38:463–471, 2017. © 2015 Society of Plastics Engineers     

炭黑在橡胶中分散技术研究进展

对于炭黑补强橡胶复合材料,平衡生热、补强以及磨耗之间的关系是炭黑应用的瓶颈问题。炭黑在橡胶基体中的分散性是影响其补强的关键因素之一,从增强炭黑与橡胶之间的相互作用角度出发,炭黑在橡胶中分散技术的研究进展主要体现在炭黑改性、橡胶改性以及液相复合技术方面。重点阐述炭黑的表面改性、聚合物基体的功能化改性以及炭黑与橡胶湿法混炼制备母胶,旨在促进炭黑在橡胶中均匀纳米分散,提高炭黑对橡胶的补强作用,获得性能优异的炭黑/橡胶复合材料。