Scaling of the viscoelasticity of highly filled carbon black polyethylene composites above the melting point

Different types of linear low-density polyethylene and ethylene butylacrylate copolymers were mixed with various types of carbon black in amounts between 25 and 40% by weight. Viscoelastic properties were measured using dynamic mechanical analysis applying a frequency sweep. Typically, the complex modulus approaches asymptotically a constant value at small frequencies, which is referred to as ‘yield modulus’. These results were analysed using a scaling approach according to which the complex modulus and the frequency are normalised by the yield modulus and the quotient of the yield modulus and the polymer viscosity, respectively. Thus a master curve is achieved for nearly all samples independent of the polymer and carbon black type and loading. A similar scaling behaviour has been observed earlier for differently concentrated suspensions of carbon black in Newtonian liquids, but not for filled polymers and different carbon blacks. Thus, contributions from polymer and carbon black to the compounds' viscoelastic properties are discussed.     

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     

炭黑／橡胶导电复合材料的电阻率—温度特性的研究

本文研究了几种橡胶与不同用量的ISAF,CF组成的导电复合材料的电阻率——温度(p——T)特性。结果发现:极性不饱和度大的橡胶(CR、NBR)导电复合材料电阻率受温度影响大,特别是60份CF的CR复合材料具有明显的电阻(率)(PTC)特性,电阻事变化达四个数量级。非极性不饱和度小的橡胶(EPDM、IIR)导电复合材料,其电阻率不受温度影响。本文还研究了温度对导电复合材料电流——电压(I——V)特性的影响,进一步证明其p——T特性。文中还对几种橡胶导电复合材料的P——T特性的机理进行探讨。     

高结构导电炭黑填充硅橡胶复合材料的性能

研究了导电炭黑（ＨＧ－ＣＢ）的高结构对乙烯基甲基硅橡胶（ＶＭＱ－１１０）复合材料电性能和机构性能的影响。由ＴＥＭ观察看出,随ＨＧ－ＣＢ用量增加,其在硫化胶中形成的导电网络逐渐完善,用量达１９份（质量份,下同）时已形成完整的导电网络,导电机理可用电子隧道效应来解释,同时随ＨＧ－ＣＢ填充量增加,复合材料的拉伸强度、硬度增大,但对ＶＭＱ－１１０的硫化有影响。欠硫现象严重,ＨＧ－ＣＢ的用量一般控制在１０～１５份,所得硅橡胶复合材料具有较佳的电性能和机械性能。     

Temperature dependence of electrical resistivity for carbon black filled ultra-high molecular weight polyethylene composites prepared by hot compaction

In this article, the temperature dependence of electrical resistivity is studied for carbon black (CB)/ultra-high molecular weight polyethylene (UHMWPE) composites. A new positive temperature coefficient (PTC) material with a very low percolation threshold is produced by the hot compaction method. The very low percolation threshold can be attributed to the segregation of CB in the interfacial regions of UHMWPE particles. The percolation threshold decreases with the increase of the molecular weight of UHMWPE, and with the decrease of the particle size of CB. For CB filled lower molecular weight UHMWPE (145M) composites, the PTC temperature, at which a sharp increase in the resistivity of the composite occurs, decreases with the increase of CB size. However, for a higher molecular weight UHMWPE (630M) filled with CB, the second PTC effect is observed and the negative temperature coefficient (NTC) effect is eliminated. A mechanism is proposed to explain these phenomena based on the optical microscopy and TEM observations. It can be concluded that the degree of the intermixing between CB and UHMWPE particles plays an important role in determining the electrical properties of the composites.     

炭黑橡胶体系热物性影响因素研究

用激光导热分析仪测试3种炭黑填充橡胶复合材料的热物性,探索其影响规律,包括热扩散系数、导热系数和定压比热容随温度、炭黑用量以及炭黑种类的变化规律。结果表明,温度对于3种胶料的热物性影响不大;炭黑用量对热物性有较明显的影响,热扩散系数和导热系数均随填充量的增加而增大,而定压比热容则随填充用量的增加而减小;炭黑的品种对于复合材料的热物性有一定的影响。乙炔炭黑橡胶体系呈现优良的热物性。     

2种导电炭黑复合橡胶体系的导热性能研究

研究了2种导电炭黑复合天然橡胶材料的导热性能随着温度和填料用量的变化规律。结果表明,温度对于导电炭黑复合体系导热性能的影响不大。乙炔黑复合体系具有极高的导热性能,随着炭黑用量的增加,其导热性能优势越加明显。据透射电镜观察填料的微观形态,乙炔黑链枝状结构丰富,聚集体之间以面接触为主,这是其复合橡胶导热性能优异的原因,乙炔黑复合材料的热导率与炭黑体积分数呈线性关系。40B2复合体系的热导率与炭黑体积分数呈现逾渗规律,逾渗阈值在炭黑体积分数8.30%至13.63%之间。据扫描电镜观察复合材料的微观结构,逾渗现象与炭黑在基体内的分布密切相关。为更精确地描述填料用量与复合体系热导率的关系,对2种复合体系的热导率与炭黑的体积分数进行了回归。     

Hybrid electro-conductive composites with improved toughness, filled by carbon black

The influence of both carbon black (CB), and an ethylene-propylene copolymer grafted by maleic anhydride (EP-g-MA), on the static mechanical properties, impact strength, peel and shear strengths as well as on the electrical conductivity of composites based on high-density polyethylene (HDPE) matrix, was investigated in this paper. It was found that CB improves the stress at yield, the stress at break, and Young’s modulus, as well as the shear strength and peel strength, of the HDPE/CB composites. The percolation threshold was found at 4.5 vol.% of CB. The addition of EP-g-MA to the HDPE/CB composites improves their impact strength, the peel and shear strengths, and the electrical conductivity.     

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     

Reversible electrical behavior with strain for a carbon black‐filled rubber

Most unfilled elastomers exhibit a high electrical resistance. Fillers are usually added to elastomers to enhance their mechanical properties. Frequently the filler type used is an electrically conductive carbon black and the inclusion of such fillers reduces the resistivity of the elastomer compound. Previous work has shown that for elastomers containing high abrasion furnace, carbon black fillers such as N330 (or N300 series) at a volume fraction above the percolation threshold the resistivity changes with strain, the precise resistivity versus strain behavior being nonlinear and irreversible for conventional carbon black fillers. A strain‐measuring device, deriving strain directly from a measure of the resistivity, requires that the behavior be reversible and reproducible from cycle to cycle. This work presents the electrical resistivity behavior of a natural rubber (NR) compound filled with Printex XE2 carbon black. This type of filler has a significantly different morphology to the N300 series blacks examined previously. The Printex was incorporated into the rubber at a volume fraction above its percolation threshold and its behavior is contrasted to that observed with N300 series carbon black‐filled NR. Here, and for the first time, reversible electrical resistivity dependence with strain is reported for an elastomer filled with Printex XE2. This reversible behavior under strain opens up the possibility of applications, such as a flexible load sensor, pressure sensor, or switch. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Selection of dispersants for the dispersion of carbon black in organic medium

The dispersion of the carbon black pigment in non-aqueous medium requires the use of dispersant additives. Two carboxylic dispersants of different chemical nature and molar masses have been investigated regarding this purpose. Their adsorption behavior has been evaluated by means of adsorption isotherms. The molecular interactions taking place at the surface have been inferred from IR and ¹³C RMN spectroscopies. The rheological behavior of the dispersions has considerably been improved by the presence of the copolymer dispersant of higher molar mass. It might adsorb at the surface by hydrogen bindings while taking a flat conformation with tails and possibly few loops that contributed to the steric stabilization of particles. The consequences of the deflocculation of the suspension on the colorimetric properties are an enhanced tinting strength and improved color stability.     

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     

Alternating electric field induced agglomeration of carbon black filled resins

This letter reports on our observation that an alternating electric field is able to induce the formation of an electrically conducting network in carbon black (CB) filled resins well below the zero-field percolation threshold. Compared with the recently presented dc method, the ac agglomeration is more efficient in two respects: it proceeds significantly faster under equivalent conditions and is still effective at higher ionic concentration. In contrast to the ramified form of dc-induced CB networks, ac agglomeration favors the formation of parallel CB chains. The experimental results can be explained taking into account ionic conductivities of the matrices as well as charges and field induced dipoles on the CB particles.     

Electrical and mechanical properties of conducting carbon black filled composites based on rubber and rubber blends

The electrical and mechanical properties of new conductive rubber composites based on ethylene–propylene–diene rubber, acrylonitrile butadiene rubber (NBR), and their 50/50 (weight ratio) blend filled with conductive black were investigated. The threshold concentrations for achieving high conductivity are explained on the basis of the viscosity of the rubber. The electrical conductivity increases with the increase in temperature whereas the activation energy of conduction decreases with an increase in filler loading and NBR concentration in the composites. The electrical hysteresis and electrical set are observed during the heating–cooling cycle, which is mainly due to some kind of irreversible change occurring in the conductive networks during heating. The mechanisms of conduction in these systems are discussed in the light of different theories. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 887–895, 1999     

Localization of carbon nanotubes in polyamide 6 blends with non-reactive and reactive rubber

Blending of two immiscible polymer matrices can be an effective way to combine favourable properties of both blend partners. The additional incorporation of multiwalled carbon nanotubes (MWCNTs) in such thermoplastic blends may further enhance the blend properties and especially generate electrical conductivity.     

Co-compatibilising effect of carbon nanotubes and liquid isoprene rubber on carbon black filled natural rubber/polybutadiene rubber blend

Abstract

Bis-(triethoxysilylpropyl)-tetrasulfane functionalised carbon nanotubes (t-CNTs) were used as compatibiliser along with liquid isoprene rubber (LIR) in the natural rubber (NR)/polybutadiene rubber (BR) blend. Their reinforcing and compatibilising effects were evaluated by mechanical, fatigue crack growth resistance properties and blend homogeneity. Scanning electron microscope and transmission electron microscope showed enhanced interfacial adhesion between the binary rubber phases and improved dispersion of the minor phase in the rubber blend respectively with the co-existence of LIR and carbon nanotubes. The tensile strength of the carbon black (CB) filled NR/BR blend reached its optimum when 3 phr CB was replaced with an equal amount of t-CNTs in the presence of 7 phr LIR, while the fatigue crack growth resistance property achieved its maximum in the presence of 3 phr LIR. This interesting co-compatibilisation behaviour of t-CNTs and LIR suggests that t-CNTs have a better effect than CB with the assistance of LIR, which is an effective plasticiser in the NR/BR blend.     

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.     

Structure and properties of hollow carbon black and filled rubber nanocomposites

Abstract

Hollow carbon black (HCB) is introduced in this work. It has a special hollow structure, high specific surface area, high structure and high electric conductivity. Hollow carbon black is used to fill styrene–butadiene rubber (SBR). The bound rubber test results show that the bound rubber of SBR/HCB can be measured when the HCB content reaches 25 phr because a strong filler network is formed, which indicates good electric conductivity of SBR/HCB. In comparison, the bound rubber of SBR/N330 can not be measured even when the N330 content is 40 phr. The mechanical measurements show that HCB has very good reinforcing effect on SBR especially when the filler content is low. The electric conductivity and thermal conductivity increase with the increase in filler content. At the same filler content, the properties of SBR/HCB nanocomposites are better than those of SBR/N330 nanocomposites, which suggests that HCB has good application potential.     

Structure and electrical properties of carbon black

The incorporation of conductive particles into a polymer matrix modifies fundamentally the electrical conductivity of the composite. The importance of carbon black structure on other mechanical and rheological properties is also well documented. Besides common techniques, like DBP-absorption and CDBP-absorption, void-volume, determined by the measurement of the volume of a given quantity of carbon black under a given pressure, has been considered as a more absolute technique. The present work considers the void-volume technique under a broader angle. The evolution of the volume of a given carbon black weight under increasing pressure as well as the evolution of the electrical resistivity is recorded and analysed.     

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