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     

稀土掺杂炭黑填充型非硫调节型粉末氯丁橡胶的性能与结构

利用镧系稀土（Ln）对炭黑表面有特殊的活化作用,采用化学沉积法制备了稀土掺杂炭黑（HAF—Ln）,并将HAF—Ln与非硫调节型氯丁胶乳（CR232胶乳）进行共混,采用凝聚共沉法制备了稀土掺杂炭黑填充型非硫调节型粉末氟丁橡胶[P（CR232／HAF—Ln）]。研究了稀土类型及用量对P（CR232／HAF—Ln）硫化胶力学性能的影响,发现采用稀土La、Sm和Tm掺杂的P（CR232／HAF—Ln）具有较好的力学性能。通过P（CR232／HAF—Ln）硫化胶拉伸断面的SEM分析,发现稀土La、Sm和Tm可有效改善炭黑在橡胶基体中的分散。     

炭黑填充型粉末天然橡胶的密炼机塑炼特性研究

采用实验室微型密炼机（Brabender转矩流变仪）研究了炭黑填充型粉末天然橡胶[P（NR/HAF）]的密炼机塑炼/混炼性能,即塑炼时间、塑炼温度和转速等基本工艺参数对胶料门尼粘度的影响。与传统的块状天然橡胶/炭黑（NR/HAF）的密炼机混炼相比,P（NR/HAF）在密炼机混炼时具有较高的混炼温升和较快的升温速率,使得胶料在较高的温度下被塑炼,从而表现出与传统的NR/HAF不同的密炼机混炼特性,其最佳塑炼温度有所降低。通过逐步回归分析建立的“门尼粘度-塑炼条件”模型可以较好地拟合和预测不同塑炼条件下P（NR/HAF）密炼机塑炼后胶料的门尼粘度。     

Dispersion of carbon black in high‐abrasion furnace black filled nonsulfur modified powdered polychloroprene rubber

High‐abrasion furnace black (HAF, grade N330) filled nonsulfur modified powdered polychloroprene rubber [P(CR231/HAF)] was prepared with the method of carbon black–rubber latex coagulation using CR231 latex as raw rubber material, HAF as reinforcing filler, and polymeric resin as coating resin. The influence of the content of dispersing agent and coating resin on contact staining and dispersion properties of carbon black in P(CR231/HAF) were investigated. The results show that the addition of dispersing agent and coating resins can decrease the contact staining level of carbon black effectively. When the dispersing agent/HAF (w/w) ratio was 0.12 or 0.1, 10 phr coating resin was added, and P(CR231/HAF) without contact staining can be prepared. The analysis on scanning electron microscopy and surface energy spectrum showed that free carbon black crumb on the surface and inner of P(CR231/HAF) particles causes its contact staining. The well dispersion of carbon black in the P(CR231/HAF) can eliminate contact staining effectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 192–196, 2006     

Determination of the modes of action of a cationic surfactant for property development in carbon black filled natural rubber compounds

Work to separate the contributions of fatty diamine surfactant (termed a multifunctional additive [MFA]) to property development, from mastication, elastomer–filler interface and crosslink density effects has been carried out. Improvement in mechanical properties resulting from the MFA is dominated by its effect on carbon black dispersion, compared with its effect on crosslink density. Results show that there is a slight improvement in resistance to crack initiation (tensile test) and a substantial improvement in resistance to crack growth (tear strength) as MFA level increases compared with the results for control compounds (extended mixing time compounds). This improvement is attributed to the influence of the MFA on energy dissipation at the rubber–carbon black interface.     

Experimental analysis of viscoelastic properties in carbon black‐filled natural rubber compounds

Processability and viscoelastic properties of natural rubber (NR) compounds filled with different carbon black loadings and types were investigated with the use of a steady shear rheometer, namely, the Mooney viscometer, and an oscillatory rheometer, namely, the Rubber Process Analyser (RPA2000). It was found that the type and amount of carbon black strongly influence the viscoelastic properties of rubber compounds. Both the dilution effect and filler transient network are responsible for the viscoelastic properties, depending on the vulcanization state. In the case of uncured compounds, the damping factor of the uncured NR decreases with increasing black loading. This is attributed to the reduction of mobilized rubber content in the compound (or the dilution effect). However, in the case of the cured NR vulcanizates, the filler transient network is the dominant factor governing the damping factor of the vulcanizate. With increasing black loading, the damping factor of the vulcanizate clearly increases. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2197–2203, 2005     

紫炭黑／天然橡胶共混胶性能的研究

采用机械共混法,探讨了紫炭黑（PCB）用量以及紫炭黑经偶联剂Si69改性后对紫炭黑／天然橡胶共混胶力学性能和热稳定性的影响,通过扫描电子显微镜（SEM）观察紫炭黑／天然橡胶共混胶的分散情况和断面形貌。结果表明,紫炭黑能提高橡胶的力学性能和热稳定性,经硅烷偶联剂Si69改性处理的紫炭黑可提高共混胶的力学性能,当Si69的用量为紫炭黑质量的8％时,胶料的力学性能最佳,其拉伸强度达到29．48MPa。     

Hysteresis and strain-dependent dynamic mechanical properties of epoxidized natural rubber filled with surface-oxidized carbon black

High-temperature molding of a mixture of epoxidized natural rubber (ENR) and intermediate super abrasion furnace (ISAF) carbon black results in strong rubber–filler interaction, the extent of which is greater in the case of the oxidized grade of the carbon black. It has been observed that ENR is bonded to the filler surface through the formation of primary bonds, such as ester and phenolic ether. An extensive filler–filler network formation takes place through the hydrogen bonding between the active groups of the rubber and filler surface. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 723–730, 1998     

Particle size distribution,mixing behavior,and mechanical properties of carbon black (high‐abrasion furnace)–filled powdered styrene butadiene rubber

High‐abrasion furnace black (HAF, grade N330)–filled powdered styrene butadiene rubber [P(SBR/HAF)] was prepared and the particle size distribution, mixing behavior in a laboratory mixer, and mechanical properties of P(SBR/HAF) were studied. A carbon black–rubber latex coagulation method was developed for preparing carbon black–filled free‐flowing, noncontact staining SBR powders, with particle diameter less than 0.9 mm, under the following conditions: carbon black content > 40 phr, emulsifier/carbon black ratio > 0.02, and coating resin content > 2.5 phr. Over the experimental range, the mixing torque τ_α of P(SBR/HAF) was not as sensitive to carbon black content and mixing temperature as that of HAF‐filled bale SBR (SBR/HAF), whereas the temperature build‐up ΔT showed little dependency on carbon black content. Compared with SBR/HAF, P(SBR/HAF) showed a 20–30% mixing energy reduction with high carbon black content (>30 phr), which confers to powdered SBR good prospects for internal mixing. Carbon black and the rubber matrix formed a macroscopic homogenization in P(SBR/HAF), and the incorporation step is not obvious in the internal mixing processing results in these special mixing behaviors of P(SBR/HAF). A novel mixing model of carbon black–filled powdered rubber, during the mixing process in an internal mixer, was proposed based on the special mixing behaviors. P(SBR/HAF) vulcanizate showed better mechanical properties than those of SBR/HAF, dependent primarily on the absence of free carbon black and a fine dispersion of filler on the rubber matrix attributed to the proper preparation conditions of noncontact staining carbon black–filled powdered SBR. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2494–2508, 2004     

掺杂氧化钐的炭黑用量对粉末天然橡胶性能的影响

高耐磨炉黑(HAF)填充型粉末天然橡胶(NR)[P(NR/HAF)]硫化胶的缺点是300%定伸应力低,因此,采用Sm2O3掺杂HAF(HAF-Sm),用凝聚共沉法制备了掺杂Sm2O3的HAF填充型粉末天然橡胶(NR)[P(NR/HAF-Sm)],研究了其硫化胶的力学性能与Sm2O3及HAF用量之间的关系。结果表明:在炭黑用量为10~100份,当炭黑用量相同、Sm2O3的质量分数为HAF的3%时,其P(NR/HAF-Sm)硫化胶的300%定伸应力显著高于P(NR/HAF)硫化胶,而与块状NR(MNR)/HAF机械混炼胶料硫化胶的相近;其拉伸强度、100%定伸应力和撕裂强度明显高于P(NR/HAF)及MNR/HAF硫化胶。这说明适量的Sm2O3掺杂HAF可显著提高炭黑填充型粉末NR硫化胶的300%定伸应力及其他力学性能。     

Effect of carbon black loading on curing characteristics and mechanical properties of waste tyre dust/carbon black hybrid filler filled natural rubber compounds

Curing characteristics, tensile properties, fatigue life, swelling behavior, and morphology of waste tire dust (WTD)/carbon black (CB) hybrid filler filled natural rubber (NR) compounds were studied. The WTD/CB hybrid filler filled NR compounds were compounded at 30 phr hybrid filler loading with increasing partial replacement of CB at 0, 10, 15, 20, and 30 phr. The curing characteristics such as scorch time, t₂ and cure time, t₉₀ decreased and increased with increment of CB loading in hybrid filler (30 phr content), respectively. Whereas maximum torque (M_HR) and minimum torque (M_L) increased with increasing CB loading. The tensile properties such as tensile strength, elongation at break, and tensile modulus of WTD/CB hybrid filler filled NR compounds showed steady increment as CB loading increased. The fatigue test showed that fatigue life increased with increment of CB loading. Rubber–filler interaction, Q_f/Q_g indicated that the NR compounds with the highest CB loading exhibited the highest rubber–filler interactions. Scanning electron microscopy (SEM) micrographs of tensile and fatigue fractured surfaces and rubber–filler interaction study supported the observed result on tensile properties and fatigue life. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

改性炭黑对天然橡胶/顺丁橡胶并用胶性能的影响

采用3种方法对传统炭黑进行表面改性,考察了改性前后炭黑表面形貌及结构的变化,并采用改性炭黑填充天然橡胶（NR）/顺丁橡胶（BR）并用胶,考察了改性炭黑对并用胶力学性能、硫化特性及动态力学性能等的影响。结果表明,与未改性炭黑相比,细化粒径、调高pH值及木质素改性处理后,炭黑表面的粗糙程度增加;且细化改性炭黑具有更高的比表面积,调高pH值改性炭黑具有更多疏松的二次结构,木质素改性炭黑粒径略有增加。对于炭黑填充NR/BR,用细化粒径及调高pH值方法处理的炭黑进行填充,NR/BR硫化胶的力学性能、耐磨性能及抗湿滑性均得到明显改善,但硫化延迟效应明显;木质素改性后,炭黑填充胶的力学性能、耐磨性能均出现不同程度的降低。     

甲基丙烯酸固态原位接枝改性炭黑对天然橡胶和顺丁橡胶性能的影响

考察了固态原位接枝改性制备的甲基丙烯酸接枝改性炭黑对天然橡胶(NR)和顺丁橡胶。(BR)静态力学性能、动态力学性能的影响。结果表明。甲基丙烯酸改性炭黑比普通商品炭黑填充的NR硫化胶具有更好的静态力学性能;甲基丙烯酸改性炭黑曼有利于降低NR和BR硫化胶的滚动阻力。同时,有利于提高NR硫化胶的抗湿滑性。     

半补强炭黑填充型粉末氯丁橡胶(Ⅰ)粒径分布

采用均匀试验设计的方法研究了三个主要因子(炭黑、炭黑分散剂、包覆剂)对半补强炭黑(SRF，N765)填充型硫调节型粉末氯丁橡胶[P(CR／SRF)]产物粒径分布和产物的接触污染性的影响，建立了这些性能与上述变量之间的函数关系模型，并进行了验证。研究表明，增加炭黑用量和炭黑分散剂用量有利于减小产物粒子的平均粒径；而产物的接触污染性随炭黑分散剂用量和包覆剂用量的增加而降低。验证结果表明，所提出的模型可以很好地表征产物特性与三个变量之间的关系。SEM分析表明，P(CR／SRF)粒子表面和内部尚存在部分未被包覆的游离炭黑粒子是造成接触污染性的主要原因。     

改性炭黑增强三元乙丙橡胶的力学性能与加工性能

研究了用甲基丙烯酸缩水甘油酯(GMA)、甲基丙烯酸-2-羟乙酯(HEMA)和N-羟甲基丙烯酰胺(NMA)3种单体改性炭黑增强三元乙丙橡胶(EPDM)的力学性能,并用橡胶加工分析仪分析了GMA、HEMA和NMA改性炭黑对EPDM未硫化胶的加工性能。结果表明,GMA、HEMA和NMA改性炭黑均改善了EPDM硫化胶的力学性能,当其用量分别为3.75,3,3份时,EPDM硫化胶的定伸应力、拉伸强度和撕裂强度达到最佳值;降低频率、提高应变或温度有利于改善改性炭黑增强EPDM的加工性能。     

炭黑在天然橡胶/溶聚丁苯橡胶硫化胶中的分散及其对性能的影响

考察了溶聚丁苯橡胶(SSBR)用量、炭黑的种类及用量对天然橡胶(NR)/SSBR硫化胶动态力学性能和力学性能的影响.结果表明,炭黑与SSBR的结合作用比与NR弱;随SSBR用量的增加,炭黑在NR/SSBR共混硫化胶中的分散性提高,Payne效应减弱,频率敏感性增强;随SSBR用量的增加,NR/SSBR共混硫化胶的拉伸强度和撕裂强度减小,扯断伸长率变化不大;而定伸应力则呈先减小后增大的趋势;随不同种类的炭黑在NR/SSBR硫化胶中分散性的提高,定伸应力呈上升趋势,损耗因子和压缩生热呈减小趋势.     

Mechanical properties and crosslink density of rare earth‐modified high‐abrasion furnace‐filled powdered natural rubber

High‐abrasion furnace‐filled powdered natural rubber [P(NR/HAF)] has more advantages than traditional HAF‐filled bale NR (NR/HAF) because of its better environmental performance and easier processing quality, but its lower mechanical properties are disadvantageous. To improve the mechanical properties, rare earth‐modified HAF‐filled powdered NR [P(NR/HAF‐Ln)] (Ln = Sm,La,Pr) was prepared by means of coacervation–coprecipitation, using rare earth‐modified HAF as separant and filler. The effect on mechanical properties of P(NR/HAF‐Ln) vulcanizate exerted by the emulsifier/HAF ratio, powdering temperature, Ln/HAF ratio and type of Ln, and HAF content were studied. The results indicated that when optimum formulation, the mechanical properties of P(NR/HAF‐Ln) vulcanizate were better than P(NR/HAF) vulcanizate. In addition, the relationship of the apparent crosslink density and HAF content of P(NR/HAF‐Ln), P(NR/HAF), NR/HAF vulcanizates was also investigated, along with their SEM microphotographs of tensile fracture surface, which indicated that the excellent mechanical properties of P(NR/HAF‐Ln) vulcanizate was attributed to correct amount of Ln that could increase crosslink density and reinforce the interface structure of NR matrix/HAF‐Ln particle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1755–1762, 2006     

半补强炭黑填充型粉末氯丁橡胶(Ⅱ)物理机械性能

采用均匀试验设计的方法研究了三个主要因子(炭黑、炭黑分散剂、包覆剂)对半补强炭黑(SRF)填充型硫调节型粉末氯丁橡胶[P(CR／SRF)]混炼胶的硫化特性、硫化胶老化前与老化后物理机械性能的影响。建立了这些性能与上述变量之间的函数关系模型，并进行了验证。验证结果表明，本章所提出的模型可以很好地表征产物性能与三个变量之间的关系。扫描电镜(SEM)分析表明，炭黑在P(CR／SRF)中的分散程度优于CR／SRF，采用粉末化技术有利于提高填料在橡胶基体中的分散效果。     

废轮胎热解炭黑在天然橡胶中的应用研究

研究废轮胎热解炭黑(CB_P)对天然橡胶(NR)胶料各项性能的影响,并与炭黑N220,N330,N660和N774进行对比。结果表明:CB_P聚集体粒径分布宽,灰分含量远高于普通炭黑;添加CB_P的NR胶料的拉伸强度和撕裂强度很高,100%和300%定伸应力很低,耐磨性能和耐屈挠疲劳性能较差。     

加工助剂对炭黑填充丁腈橡胶性能的影响

在填充50份(质量,下同)高耐磨炭黑(HAF)且用过氧化物硫化的丁腈橡胶(NBR)中使用一种新型加工助剂M(一种具有特定相对分子质量的含醚键和羟基等多种官能团的氟硅化合物),测定了炭黑填充NBR胶料的门尼黏度、硫化特性和硫化胶的物理机械性能,用橡胶加工分析仪和扫描电子显微镜对其进行了分析,并与加入硅烷偶联剂Si69及常用的以脂肪酸酯和不饱和脂肪酸锌皂为主要成分的2种分散剂进行了比较。结果表明,使用上述加工助剂均有利于炭黑在NBR胶料中的分散,胶料的加工性能和硫化胶的物理机械性能均得到不同程度的改善;以脂肪酸酯和不饱和脂肪酸锌皂为主要成分的分散剂能延缓炭黑填充NBR胶料的过氧化物硫化和降低硫化胶的交联密度;随着Si69的用量在2.0～6.0份范围内增加,胶料的正硫化时间减小,硫化胶的交联密度和定伸应力增加,而硫化胶的撕裂强度、耐热空气老化性、耐热油性、耐压缩永久变形性能和溶胀指数有下降的趋势;在Si69用量2.0～6.0份内及用量相同时,与无加工助剂和使用其他加工助剂相比,加工助剂M对胶料的硫化无明显影响,能够改善其加工性能,硫化胶的综合性能较好,其中耐热和压缩永久变形性能的改善最为明显。