扫描探针DFM模式下的炭黑表面微观结构研究

采用扫描探针显微镜（SPM）的技术，用动态非接触扫描模式DFM扫描炭黑微观的表面结构，通过加入适当的分散剂来观察单个炭黑粒子的表面形貌，得出了炭黑粒径及表面粗糙度等数值，发现表面粗糙度是炭黑补强的重要参数，丰富了炭黑补强在微观方面的内容。     

溶剂法制备碳纳米管结合胶及其微观结构的研究

利用溶剂法制备碳纳米管结合胶,确定了制备高质量碳纳米管结合胶的实验参数：橡胶／甲苯溶液的质量浓度为0．020g／mL,橡胶与碳纳米管的质量比为4：1,反应时间为7h。用扫描探针显微镜对天然橡胶、碳纳米管及其结合胶的微观形貌进行研究,得到了碳纳米管结合胶的清晰结构。碳纳米管结合胶的结构为天然橡胶分子在定向紧密排列的碳纳米管的两侧沿着纳米管的表面与碳纳米管结合形成环状的闭合结构,随着纳米管管径的增大,结合胶的结构趋向于炭黑结合胶的结构。     

扫描探针显微镜在炭黑/苯乙烯-丁二烯-苯乙烯嵌段共聚物结合橡胶微观结构研究中的应用

利用扫描探针显微镜(SPM)的DFM模式观察苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)和炭黑/SBS混合物的微观形貌。结果表明:不同浓度的SBS溶液的微观形貌差异较大;炭黑/SBS混合物的分离物成"手镯"环状结构,尺寸为100nm左右,与炭黑相连物质的长度为200～300nm,横向直径约为100nm,与SBS单体的尺寸吻合,可初步判定该结构为炭黑/SBS结合橡胶。     

炭黑对硫化胶基本性能定伸应力的影响

炭黑聚集体的形状与结构直接影响硫化胶的重要物理性质—定伸应力,就从炭黑对橡胶的补强理论出发,结合炭黑生产实践,从炭黑的生产过程控制,原料的选择以及工艺的调整对炭黑聚集体的形状与结构的影响进行了讨论,并提出了解决办法。     

橡胶复合材料中炭黑微观结构图像的拟合算法

将炭黑聚集体视为由多个圆形原生粒子构成,对橡胶复合材料中炭黑聚集体形态进行图像拟合分析。基于炭黑补强橡胶复合材料的微观结构图像,在采用图像分割和阈值迭代等方法处理图像背景缺陷的基础上,研究了轮廓骨架算法、最大内切圆算法和K-means聚类算法3种拟合算法处理炭黑聚集体图像,并用峰值信噪比和结构相似度2个指标对图像拟合效果进行评价。结果表明,轮廓骨架算法拟合炭黑聚集体形态效果最优,更适用于炭黑补强橡胶复合材料微观结构重构时对炭黑聚集体形态的描述。     

微观结构对丁腈橡胶硫化胶物理性能的影响

研究橡胶基体及填料微观结构对丁腈橡胶(NBR)硫化胶物理性能的影响。结果表明:随着丙烯腈质量分数的增大,炭黑补强NBR硫化胶的拉伸强度先增大后减小,拉断伸长率减小,邵尔A型硬度和撕裂强度增大;随着生胶门尼粘度的增大,炭黑补强NBR硫化胶的邵尔A型硬度基本不变,定伸应力增大,拉伸强度和拉断伸长率减小;随着炭黑粒径的减小,硫化胶的定伸应力呈增大趋势,拉伸强度和撕裂强度增大,高定伸下炭黑粒径对应力的贡献较大;随着炭黑结构度的提高,硫化胶定伸应力增大,拉伸强度和撕裂强度减小。     

扫描探针显微镜在高分子材料中的应用

本文简单介绍扫描探针显微镜的工作原理及其在高分子领域中的应用。     

高性能SBR／BR／炭黑共混胶的研究

利用炭黑上结合胶一旦形成就很难脱离的特性,通过控制结合胶成分的方法制备丁苯橡胶（SBR）／顺丁橡胶（BR）／炭黑共混胶。通过改变SBR／BR并用比和用不同橡胶控制结合胶成分的试验对比发现,用物理性能好且为富相的橡胶组分来控制结合胶的形成,硫化胶的物理性能较好。此外,结合胶的成分直接影响硫化胶的动态力学性能。     

高结构炭黑在不同并用胶内的性能评估

炭黑是橡胶工业的常用补强剂,该文评估了三种高结构炭黑（N339、N347、N375）分别在四种胶料（天然橡胶、溶聚丁苯橡胶、聚丁二烯橡胶、丁苯橡胶）中的补强性能及其对胶料性能的影响。     

A molecular explanation for the origin of bound rubber in carbon black filled rubber compounds

Some of the theories that have been developed to explain the origin of bound rubber are critically reviewed and discussed with respect to published data. Theories for carbon black filled compounds and for silica–silicone rubber mixtures are considered; the phenomena involved are likely to be very different, with clear chemical aspects for the latter systems. A common feature emerges, however, from these theories: the area of the polymer–filler interaction site, which is generally considered as a fitting parameter in most approaches. This article concentrates on this aspect and suggests that, with respect to recent findings about the very surface of carbon black particles, an explanation for bound rubber can be offered that considers strong topological constraints exerted by the filler surface on rubber segments. Calculations of interaction site area made with experimental data give values close to a fraction of the half-lateral surface of the structural unit representative of the rubber considered. It follows that the bound rubber variation during storage can now be understood by considering a slow replacement of short rubber chains initially adsorbed on filler particles by larger ones, as demonstrated by calculated data. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2257–2268, 1997     

高分子材料微观形态结构的扫描电镜研究

利用扫描电镜对聚乙烯(PE)、丙烯腈-丁二烯-苯乙烯共聚物(ABS)等高分子材料填料的分散性及表面与断裂界面进行了研究。结果表明,扫描电镜能够详细观察研究高分子材料的表面结构、微观相分离等,便于表征高分子材料微观结构形态,是分析高分子材料微观结构形态的有效手段。     

Effect of bound rubber on characteristics of highly filled styrene–butadiene rubber compounds with different types of carbon black

Viscosity and cure time of a filled rubber compound having an accelerated sulfur cure system are affected by types and contents of the rubber and the filler as well as of the curatives. Bound rubber content is used as level of the reinforcement. Influence of bound rubber on viscosity and cure time of a rubber compound was studied using highly filled styrene–butadiene rubber compounds with carbon black having different structures. The bound rubber content increases with increase of the carbon black content and also increases as the carbon black structure is developed. The Mooney viscosity increases linearly with increase of the bound rubber content irrespective of the carbon black structure when the primary particle size of carbon black is nearly the same. The Mooney scorch time decreases linearly with increase of the bound rubber content irrespective of the carbon black structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1001–1006, 2004     

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     

一种环氧基小分子多功能添加剂对炭黑在天然橡胶基体中分散性的影响

在天然橡胶与填充炭黑不同阶段的混炼加工过程中,不同份数的环氧基多功能添加剂（E-MFA）被加入到混炼体系中.笔者从混炼胶的键合橡胶含量和混炼流变曲线两个方面对不同E-MFA含量和添加模式对炭黑在橡胶基体中的分散程度的影响进行了研究.结果表明：随着E-MFA含量的增加,炭黑在橡胶基体中的分散程度逐渐提高.当添加量增加到2.5份时,分散程度达到最大.另外从扭矩（τα）-时间（t）的拟合指数式所得参数可知,E-MFA的加入减小了混炼扭矩对混炼时间的依赖性.     

Thermal destruction of carbon black network structure in natural rubber vulcanizate

To investigate thermal destruction and rearrangement of the carbon black (CB) network consisting of CB aggregates in rubbery matrix, the proper heat‐treatment temperature without thermal decomposition of rubber matrix were examined by using differential scanning calorimetry, dynamic mechanical measurements, and thermal expansion measurements. 383 K was chosen as the heat‐treatment temperature under vacuum. The volume resistivity (ρ_v) of 50 phr CB‐filled natural rubber vulcanizate (CB‐50) increased rapidly up to a heat‐treatment time of 24 h and it decreased by further heat‐treatment time, whereas the ρ_v of CB‐80 remained almost constant without depending on heating time. Three‐dimensional electron microscope (3D‐TEM) observations revealed that after the heat‐treatment for 75 h, the average lengths of the crosslinked and the branched chains and the crosslinked points density (D_cross) of the CB network decreased, whereas the branched points density (D_branch) increased with decrease of D_cross. After the heat‐treatment, their fractions (F_cross′s) of crosslinked chains decreased, whereas their fractions (F_branch′s) of the branched ones increased. Especially, F_branch of CB‐50 became larger than that of CB‐80, while the decrease of F_cross of CB‐50 was almost the same as that of CB‐80 by the heat‐treatment. And, F_cross and F_branch of the heat‐treated CB‐50 were the same compositions (F_cross and F_branch = ca. 0.7 and ca. 0.3, respectively) as those of the heat‐treated CB‐80. It is suggested that the CB network of CB‐80 is more thermal stable than that of CB‐50. These results directly indicate that CB network is broken and is rearranged by a heat‐treatment. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of bound polymer on cure characteristics of natural rubber compounds reinforced with different types of carbon blacks

Rubber compounds are reinforced with fillers such as carbon black and silica. The cure characteristics of a filled rubber compound vary with the filler type and content. The influence of the type of carbon black on the cure characteristics of carbon black filled natural rubber compounds is investigated using two types of carbon black (N220 and N550), which are different in primary size and structure. The cure time and cure rate become faster as the carbon black content increases. The crosslink density also increases and reversion resistance is improved with the increase of carbon black content. The cure time and cure rate of the compound filled with N550 are faster than those of the compound filled with N220 at the same level of bound rubber content. In addition, higher crosslink density is also observed in the compound filled with N550 compared to that of the compound filled with N220 at the same level of bound rubber content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2282–2289, 2005     

炭黑对橡胶增强机理的研究现状

介绍了目前炭黑增强橡胶的一些理论,如分子链滑动理论、结合胶理论、填料网络理论、炭黑表面结构理论和范德华网络理论,分析了这些理论存在的合理性与局限性,指出了橡胶增强理论新的研究方向。