The Nucleation Effect of Grafted Carbon Black on Crystallization of Poly(Ethylene Terephthalate)/Grafted Carbon Black Composite

Poly(ethylene terephthalate)/grafted carbon black (PET/GCB) and poly(ethylene terephthalate)/carbon black (PET/CB) composites were prepared by melt blending. The nucleating effect of CB and GCB were investigated using differential scanning calorimetry (DSC) analysis. The morphologies of the spherulites in PET, PET/CB and PET/GCB composites were observed by means of scanning electron microscopy (SEM). All results showed that GCB had higher nucleating activity than CB in PET and PET/GCB composite had higher rate of nucleation and crystallization. The melting behaviors of neat PET, PET/CB and PET/GCB composites after non‐isothermal crystallization were investigated as well. It was evident that the melting behavior of PET is greatly influenced by addition of CB and GCB.     

Crystallization Behavior of Poly(Lactic Acid) Filled with Modified Carbon Black

A novel method was employed to modify the surface of carbon black (CB) by an organic small molecule in a Haake Rheomix mixer. The modified carbon black (MCB) was dispersed uniformly in poly(lactic acid; PLA). The crystallization behaviors of PLA, PLA/CB and PLA/MCB composites were investigated by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS) and polarizing optical microscopy. It is found that the addition of CB or MCB can influence the crystallization behavior of PLA. PLA/MCB has a faster crystallization rate and higher crystallization peak temperature than PLA/CB. For non-isothermal studies, Jeziorny and Mo equations were employed. The Mo equation can well describe the non-isothermal crystallization of the three samples. For PLA/CB and PLA/MCB composites containing 3wt% fillers, the nucleating activity for CB is about 0.32, and about 0.16 for MCB. All these results show that MCB is an effective nucleating agent. PLA/MCB has a higher nucleation rate than PLA/CB because of the finer dispersed particles size and improved interaction between MCB and PLA.     

Isothermal-Treatment-Induced Network Formation of Carbon Black in Isotactic Polypropylene/Carbon Black Composites

The effect of isothermal treatment on network formation of nanoscale dispersed carbon black (CB) particles in mild-compounded isotactic polypropylene (iPP)/CB composite is investigated. Network formation of CB took place in a quiescent melt without any flow and expansion since the isothermal treatment of the composite was carried out under high pressure conditions. TEM was used to inspect the network formation of the well-dispersed CB. Resistivity temperature and dynamic rheological behaviors of samples before and after isothermal treatment were examined to investigate the relationship between fillers’ network formation and electrical conductivity enhancement.     

Influence of In-situ Grafting on the Dispersion of Carbon Black in Solvents and Natural Rubber

In-situ grafting of natural rubber (NR) onto the carbon black (CB) surface by a solid-state method was used to obtain grafted carbon black (GCB). The morphology of the original CB and GCB particles was observed by AFM and TEM. The original CB particles fused together and occurred as large dendritic agglomerates while the GCB particles occurred as small aggregates about 150 nm in diameter. The dispersion and dispersion stability of CB and GCB in toluene and cyclohexene were studied by zeta potential and a spectrophotometer. The results showed that the grafting procedure can improve both dispersion and dispersion stability of CB particles. The dispersion in NR was studied by DMA and observed by SEM. It was shown that GCB has better dispersion than CB in a NR matrix. As expected a weakened filler-filler interaction and enhanced filler-polymer interaction occurred after grafting modification.     

Polyamide 6/modified Carbon Black Nanocomposites Prepared via In Situ Polymerization

Polyamide 6/modified carbon black (PA6/MCB) composites were prepared via in-situ ring opening polymerization of caprolactam in the presence of dispersed carboxyl group modified carbon black (MCB). The dispersion of MCB in the PA6 matrix, nonisothermal crystallization and melting behaviors, and volume resistivity of the composites were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and a resistivity meter, respectively. The results indicated that MCB dispersed well in the PA6 matrix. When the MCB content was 5 wt%, the MCB particles were of a nanoscale. The conductivity percolation threshold of the PA6/MCB composites was 8 wt% due to the good dispersion of MCB in the PA6 matrix. The addition of MCB elevated the cold crystallization temperature of PA6, reflecting the effectiveness of MCB as nucleating agents. However, the MCB decreased the crystallization enthalpy of PA6 during both heating and cooling processes.     

Preparation and Characterization of Acrylic Resin/Hindered Phenolic Antioxidant (AO80)-modified Carbon Black Nanocomposite

To improve the dispersion stability of carbon black (CB) in an acrylic resin coating, a hindered phenolic antioxidant (AO80) was chosen to modify the CB by a solid state method based on the blending of CB and AO80 in an internal mixer. The modified CB (m-CB) was directly introduced into the acrylic resin with 50% solid content in butyl acetate by ball milling without any other treatment. That the majority of the m-CB particles were nanosized in ethanol was proven by a particle size analyzer. Transmission electron microscopy (TEM) and field emission scanning electron microscope (FESEM) micrographs indicated that the m-CB particles were also dispersed in the acrylic resin as nanoscale particles. Compared with the unmodified CB, the modification of CB can decrease the viscosity of the acrylic resin/m-CB nanocomposite and improve its flow property. The adhesion and gloss of the acrylic resin/m-CB nanocomposite were also improved. More importantly, the UV shielding and stability of the acrylic resin/m-CB nanocomposite were enhanced.     

Simulation of Carbon Black Network in Filled Rubber

Carbon black (CB) is one of the most important fillers for rubber and plastics materials. How to describe the CB network is a fundamental problem for establishing relationships between the CB network and the mechanical properties of filled rubber. In view of the electrical conductivity of CB, an infinite circuit consisting of numerous contact resistors, interconnected with each other, is proposed to simulate the CB network in filled rubber; the resistances were determined by considering the tunneling conduction mechanism and a Gaussian distribution for the CB aggregate junction width. As an example, the electrical resistivity of CB (N330) filled natural rubber during uniaxial deformation was studied. It was found that the logarithm of resistivity was an approximately linear function of the extension ratio, and the resistivity increased with the increase of average number of primary particles per aggregates. Additionally, some published experimental points lie between the curves calculated for five primary particles and for seven primary particles per aggregate at extension ratios below 1.2. The calculations suggested that the average number of primary particles per aggregate for CB type N330 might be between five and seven.     

Variation of the Payne Effect in Natural Rubber Reinforced by Graft-Modified Carbon Black

Carbon black (CB) was modified by liquid grafting and used for natural rubber (NR) reinforcement. Payne effects during NR reinforcement by the graft-modified carbon black (GCB) were analyzed in this paper. The results showed a proportional relationship between filler content and the Payne effect. Rubber compounds with GCB presented weaker Payne effects than their non-modified counterparts. Qualitative analysis of the correlation between filler network structure and filler content was conducted according to the relationship between bound rubber of a rubber compound and shear modulus. The impact of the storage period on the Payne effect was further studied, and the results demonstrated that the longer the storage period of the rubber compound, the stronger the Payne effect tended to be. The mechanisms by which the Payne effects were manifested differed according to the content of the filler in the rubber.     

Improvement of Mechanical Properties and Ultraviolet Resistance of Polyethylene Pipe Materials Using High Density Polyethylene Matrix Grafted Carbon Black

In recent years, high grade high density polyethylene (HDPE) pipe materials are being more and more widely used for water and gas supply. Carbon black (CB) is usually used as an anti-UV-light reagent for pipe materials. However, homogeneous dispersion of CB in the HDPE matrix and modification of the interface has always been a great challenge. In this work, HDPE matrix grafted CB (HDPE-g-CB) was successfully prepared through HDPE radicals formation by a thermo-mechanical method and subsequent radical capture by the CB surface. The weight percentage of grafted HDPE approached 10 wt% and the modification sharply reduced the surface free energy of the CB. The SEM (scanning electron micrographs) and TEM (transmission electron microscopy) results showed that HDPE-g-CB was uniformly dispersed in the HDPE pipe materials and the domain size of the dispersed phase was remarkably decreased from that in HDPE/CB. Therefore, compared with the HDPE/CB, the mechanical properties and ultraviolet (UV) resistance of HDPE/HDPE-g-CB were significantly improved, positively influencing the expected life span of pipelines.     

Characteristic Frequency of Carbon Black Filled Rubber

Due to the high electrical conductivity of carbon black (CB) particles, the presence of CB improves the conductivity of filled rubbers. The impedance spectra of CB filled rubber were simulated using an infinite resistor‐capacitor (RC) circuit by considering the tunneling conduction mechanism for the CB contact regions. The calculated results had a similar appearance to the experimental results, i.e., the Cole‐Cole plot was a semi‐circle and a peak appeared in a plot of the imaginary component of complex impedance with respect to the frequency from which the characteristic frequency was obtained. For a simple RC circuit in parallel connection, the logarithm of the characteristic frequency should be a linear function of the 1/3 power of the average number of primary particles per aggregate. A slight deviation from the line found in the simulations was attributed to the network contribution. Additionally, low CB loading had little effect on the characteristic frequency, in accordance with the experimental data, while high loading had a marked effect. Furthermore, the calculations showed that the characteristic frequency was affected not only by the distribution of individual CB aggregates, but also by the percentage of agglomerates at high CB loading.     

Studies on the Nonisothermal Crystallization Behavior of Polypropylene/Multiwalled Carbon Nanotubes Nanocomposites

Polypropylene/multiwalled carbon nanotubes (PP/MWNTs) nanocomposites were prepared by a melt compounding process. The morphology and nonisothermal crystallization of these nanocomposites were investigated by means of optical microscopy, scanning electron microscopy, and differential scanning calorimetry. Scanning electron microscope micrographs of PP/MWNTs composite showed that the MWNTs were well dispersed in the PP matrix and displayed a clear nucleating effect on PP crystallization. Avrami theory, modified by Jeziorny and Mo's method, was used to analyze the kinetics of the nonisothermal crystallization process. It was found that the addition of MWNTs improved the crystallization rate and increased the peak crystallization temperature of the PP/MWNTs nanocomposites as compared with PP. The results show that the Jeziorny theory and Mo's method successfully describe the nonisothermal crystallization process of PP and PP/MWNTs nanocomposites.     

Effect of Compression Pressure on the Ethylene Propylene Diene Terpolymer (EPDM)/Acrylonitrile Butadiene Copolymer (NBR) Rubber Blends Filled with Different Types of Carbon Black

Blends of ethylene-propylene diene terpolymer/acrylonitrile butadiene copolymer (EPDM/NBR) loaded with different types [(N326-HAF) and (N774-SRF)] and ratios of carbon black (CB) fillers were prepared. The mechanical properties of the EPDM/NBR rubber blends unloaded and loaded with different ratios of CB were investigated. Among the blends, the one with 75% EPDM and 25% NBR, both loaded and unloaded with CB, were found to exhibit the highest tensile strength and elongation at break. The observed changes in the mechanical properties of the blends were correlated to the morphology as observed by scanning electron microscopy. The changes of the electrical resistivity of the rubber blend composites during compression were investigated. The experimental results were explained from the position that an external pressure induces either an increase or decrease of the resistivity of the blend composites according to whether annihilation or creation of effective conductive paths occurs, respectively.     

Comparative Properties of Styrene-Butadiene Rubbers (SBR) Containing Pyrolytic Carbon Black,Conventional Carbon Black,and Organoclay

To evaluate the reinforcing potential of pyrolytic carbon black, styrene-butadiene rubber (SBR) was filled with pelletized pyrolytic carbon black (pCB_p), N660 industrial CB, their blend in a 1/1 ratio, and the latter also in the absence and presence of additional organoclay (OC). The Shore A hardness of the filled SBR gums was 65 ± 2°. Effects of the compositions on the filler dispersion, cure behavior, dynamic mechanical thermal parameters (including the Payne effect), tensile mechanical (including the Mullins effect), and fracture mechanical (making use of the J-integral concept) properties were studied and discussed. Though pCB_p had a higher specific surface weight than CB, the latter proved to be a more active filler with respect to the tensile strength. The opposite tendency was found for the tear strength and fracture mechanics characteristics (J-integral at crack tip opening, tearing modulus, and trouser tear strength). This was traced to an enlargement in the crack tip damage zone supported by the dispersion characteristics of the pCB_p. The performance of pCB_p was similar to that of CB with respect to some other properties. OC supported the filler networking which positively affected the resistance to crack initiation.     

Carbon Black Filled Powdered Natural Rubber

Carbon black (CB) filled powdered natural rubber [P(NR/N234)] was prepared using a patented method of latex/CB coagulation technology. The influence of curing recipes and CB contents on the curing, mechanical, and dynamic properties were studied in depth, and the results were compared with that of NR/N234 compounds based on traditional dry mixing of bale NR and CB. The results showed that, compared with NR/N234, P(NR/N234) showed higher tensile strength, tear strength, rebound elasticity and flexibilities, and the antiabrasion properties were similar, while the dynamic temperature-build-up and dynamic compression permanent set were about 50% of that of NR/N234. The analysis based on scanning electron micrographs (SEM) and the Payne effect showed that the fine dispersion of CB in the rubber and the enhanced interaction between CB and rubber contributed to the excellent properties of P(NR/N234), sufficient that they make P(NR/N234) a potential material for the tread compounds of heavy-duty all-steel cord radial tires.     

BLENDS OF THERMOTROPIC LIQUID CRYSTALLINE POLYESTER AND POLY(ETHYLENE TEREPHTHALATE)

Two kinds of blends of thermotropic liquid crystalline polymers (LCPs) and poly(ethylene terephthalate) (PET) were prepared by solution and melt blending, respectively. Crystallization behavior of the blends was observed by differential scanning calorimetry (DSC). The LCP in both blends considerably decreased the cold crystallization temperature of PET and increased the crystallization rate in the low-temperature region, but did not show any significant effect on crystallization in the high-temperature region. Phase behavior of samples prepared by melt blending was investigated with the scanning electronic microscope (SEM). It was found that LCP/PET blends display a biphasic structure with an aromatic unit-rich phase as a dispersed domain, and a highly oriented fibrous structure was formed on the fracture surface of the blends. During the melt blending process, PET reacted with LCP through transesterification, as indicated by both DSC and SEM measurements.     

Dynamic Fatigue Behavior of Natural Rubber Reinforced with Nanoclay and Carbon Black

The dynamic fatigue behaviors of natural rubber (NR) filled with carbon black (CB) and both nanoclay (NC) and CB at same hardness was evaluated using the stepwise increasing strain test (SIST) and long-term testing. Compared with NR/CB composites, NR/CB/NC nanocomposites exhibited higher fatigue-limited strain, stronger dynamic stress relaxation, and longer compression fatigue life. By examining the fracture morphologies, nonlinear viscoelastic behavior, and hysteresis loss of filled NR, it was found that NR, synergisticly reinforced by NC and CB, exhibited improved anti-fatigue ability than NR filled with CB due to stronger filler–filler interactions between NC and CB (a local filler network) and the high aspect ratio and typical lamellar structure of NC.     

Preparation of a Novel Oriented Structure in Carbon Black Filled Isotactic Polypropylene Composites by Microwave Selective Heating

Microwave heating technology has numerous advantages compared with the traditional heating methods and has been widely used to process materials. However, most thermoplastics do not possess a sufficiently high dielectric property to be heated by microwaves. In this study, carbon black (CB) was utilized as the microwave absorber to improve the microwave heatability of isotactic polypropylene (iPP). Effects of CB contents on the microwave heatability of iPP/CB composites were studied. The temperature of iPP/CB composites with relatively low CB content (5% and 10%) increased slowly and tended to remain unchanged after 120 s of microwave exposure. In contrast, iPP/CB composites with relatively high CB content (15% and 20%) presented a much faster heating rate and the temperature of the sample kept increasing with the prolongation of exposure time. On the basis of the fact that iPP/CB composites with different CB contents have different microwave heatability, a novel oriented structure, in which the core layer has relatively high orientation and the surface layer has relatively low orientation, was prepared by selective microwave heating. Two-dimensional wide angle X-ray diffraction (2D-WAXD) analysis indicates that the orientation parameter calculated by the (040) plane of the surface layer (0.45) was lower than that of the core layer (0.83). The novel oriented structure is different from the common skin-core structure formed in the samples of semicrystalline polymers by traditional polymer processing methods, in which orientation of the skin layer is higher than that of the core layer. The novel oriented structure has not been reported before to our knowledge and its formation mechanism is also discussed in this paper.     

炭黑橡胶复合材料导热逾渗行为

研究了导电炭黑40b2填充天然橡胶复合材料的导热性能和力学性能随炭黑体积分数的变化规律,并采用扫描电子显微镜观察了炭黑橡胶体系内部的炭黑分布状况.结果表明,导热性能随炭黑体积分数的变化规律存在类似于导电逾渗现象的导热逾渗现象,逾渗阈值在8.3%～13.63%之间.在逾渗阈值之后,复合材料的拉伸强度下降.炭黑橡胶复合材料...     

Molecular dynamics simulation on surface modification of carbon black with polyvinyl alcohol

A novel and reasonable model of carbon black (CB) was built to investigate the surface encapsulation modification of CB particles with polyvinyl alcohol (PVA) by molecular dynamic simulation. The modification process of PVA on CB surface was intuitively exhibited, which indicated that the encapsulation films were formed by stacking PVA molecules layer by layer on the surface of CB. The dispersion stability of unmodified and modified CB particles was compared both by simulation and by scanning electron microscope graphs. The simulation results indicated that surface modification had great effect on reducing the interaction energy of CB/water interface so as to alleviate agglomeration phenomenon significantly. Moreover, the influences of PVA amount on the morphology and the compatibility of PVA/CB interface were also investigated. The amount of PVA would neither influence the arrangement of single PVA molecule nor change the orientation of the single PVA layer but only decide the thickness of the modification film. Besides, the energy analysis results indicated that a suitable thickness of PVA coating could improve the dispersion stability of CB particles.     

Influence of Carbon Black on Crosslink Density of Natural Rubber

Vulcanization and reinforcement are two important factors contributing to the properties of vulcanized rubber. In order to investigate the influence of carbon black (CB) on chemical crosslinking, three groups of samples with different crosslink densities were prepared. In each group with the same crosslink density, different amounts of CB were introduced. Data fitting showed that delta torque (ΔM = M _H–M _L, the difference between the highest and lowest torques during curing) in the cure curves of each group had a good linear relationship with CB load and extrapolation of the fitting lines almost intercepted the x coordinate at the same value, which indicated that CB had no influence on the chemical crosslinking of the rubber. To verify the above result, a series of nonfilled natural rubber (NR) vulcanizates with different crosslink densities were studied using equilibrium swelling and the swelling ratios were compared with those of corresponding CB filled rubbers with the same sulfur and accelerator amount. The results of both the equilibrium swelling and NMR relaxation parameter measurements showed that CB filled vulcanizates had higher apparent crosslink densities than those of unfilled ones due to the strong interaction between rubber molecules and the surface of the CB particles. The swelling ratios of filled rubbers had a parallel relationship with those of the unfilled ones which indicated that CB had little influence on chemical crosslink density introduced by chemical vulcanization.