Rheology of copolymers containing carbon black

The rheological response of random copolymers of styrene and butyl methacrylate containing carbon black simulates the behavior of toner in the electrophotographic process. Both the relative viscosity and the dependence of viscosity on shear rate were increased by raising the temperature and raising the concentration and surface area of carbon black. For high concentrations and surface areas of carbon black and at elevated temperatures, a well-defined yield stress varied from 2.5 × 10² to 1.6 × 10⁴ Pa, depending on the concentration and nature of the carbon black but independent of the type of polymer and temperature, implying the formation of a carbon black network. Plasticization by carbon black was favored at low surface area and concentration of carbon black and at elevated temperatures.     

Dynamic mechanical behavior of copolymers containing carbon black

The storage and loss moduli of random copolymers of styrene and butyl methacrylate containing carbon black of varied surface area were determined by dynamic mechanical analysis at several temperatures about 100°C above the glass-transition temperature, T_g. At low frequencies, the pure polymers exhibit linear double log plots of moduli against frequency, with slopes of unity and approaching two for G″ and G′, respectively. With the addition of carbon black filler, both G′ and G″ become independent of frequency and temperature at low frequencies, consistent with yield behavior arid the formation of a carbon black network. The limiting dynamic complex modulus exceeds the yield stress from steady shear rheology, perhaps indicating the extent of the carbon black network, which was highest for low-molecular-weight copolymer and polystyrene. The filled random copolymers behaved Theologically like similarly filled polystyrenes of comparable molecular weights. Plasticization effects observed in the steady shear rheology of filled copolymers containing small concentrations of carbon black were not observed in dynamic mechanical analysis, although dynamic moduli converge at high frequency.     

Rheology of polymers containing carbon black

In order to elucidate the flow behavior of electrophotographic toner systems, shear stress was measured as a function of shear rate in a cone and plate rheometer for polymer melts containing carbon blacks of surface area 24 and 625 m²/g at several concentrations and temperatures. Polymers included high and low molecular weight polystyrene and poly(butyl methacrylate). The addition of carbon black to the polymers caused a large increase in viscosity, especially at low shear rates and shear stresses. As the concentration of carbon black was increased, the viscosity at low shear rates became unbounded below a value of the shear stress designated the yield stress. The absolute magnitude of the yield stress depended primarily on the concentration and surface area of the carbon black and was independent of the polymer and temperature. Apparently, carbon black forms an independent network within the polymer at low shear rates which precludes flow. In some cases, the viscosity of polymers filled with carbon black was lower than that of the pure polymer. This effect was favored for polystyrene compared to poly(butyl methacrylate) and was facilitated by increasing the molecular weight of polystyrene, reducing the surface area and concentration of carbon black, and by increasing the temperature and shear rate.     

Electrical conductivity of polymers containing carbon black

Changes in volume resistivity with temperature of carbon-black-filled polymers and a random copolymer of styrene and butyl methacrylate were measured. For polystyrene containing 20 wt % carbon black, of surface area 24 m²/g, the resistivity changes abruptly from 10¹³ to 10⁶ ohm-cm above 150°C. Poly(butyl methacrylate) did not show well-defined changes in resistivity on heating. The random copolymer containing 16.7 or 28.6 wt % carbon black, of surface area 24 m²/g, showed a resistivity exceeding 10¹³ ohm-cm, that decreased to about 10⁷ ohm-cm on heating above 120°C. This Copolymer containing 16.7 wt % carbon black, of surface area 625 m²/g, shows a resistivity of about 108 ohm-cm that decreases sharply to 10³ ohm-cm by 150°C. Decreases in resistivity on increasing the temperature in the quiescent state are correlated with the observation of a yield stress at low shear rates in rheological studies. It is suggested that carbon black agglomerates at elevated temperature and forms an independent conductive network that prevents flow.     

Dynamic mechanical behavior of polymers containing carbon black

The dynamic mechanical behavior of carbon black filled polymers of styrene and butyl methacrylate was examined at low strain amplitude and frequency in order to minimize destruction of the composite structure and elucidate the basis of yield and plasticization observed in steady shear. For specific filled systems, both G′ and G″ became independent of frequency and temperature at low frequencies, consistent with a yield phenomenon and the formation of a carbon black network. On the other hand, although the high molecular weight polystyrene showed plasticization effects at higher shear rates in steady shear rheology, such, plasticization effects were never observed in dynamic mechanical analysts. Yield behavior was observed most readily for the low molecular weight polystyrene. Limiting moduli for filled polystyrenes were independent of temperature, whereas, for polybutyl methacrylate, were sensitive to temperature. It is suggested that an independent network of carbon black is strongest in the low molecular weight polystyrene and weakest in poly (butyl methacrylate).     

Cationic photopolymerization of epoxides containing carbon black nanoparticles

The active centers responsible for cationic photopolymerizations are essentially non-terminating, and continue to propagate after the illumination is ceased. In this contribution, the mobility of the long-lived cationic active centers is investigated for the cure of epoxides containing carbon black nanoparticles. Concentration profiles for the cationic active centers produced during illumination were coupled with an analysis of the active center reactive diffusion during the post-illumination period, revealing that migration of the active centers leads to cure beyond the illuminated depth. A kinetic analysis yielded predicted cure times for coatings of varying thickness and carbon black loading, showing good agreement with experimental results obtained for photopolymerizations of cycloaliphatic diepoxide coatings containing a monodisperse carbon black with mean hydrodynamic radius of 29.2 nm. These results indicate that the long lifetimes and reactive diffusion of cationic active centers may be used for effective curing of coatings containing carbon black nanoparticles. This comprehensive approach could be applied to other opaque nanocomposite systems.     

Electrically conductive thermosetting resins containing low concentrations of carbon black

A cured vinyl ester resin containing electrically conductive carbon black (CB) particles shows electrical percolation at very low CB concentration (<0.5 phr). CB particles have a strong tendency to agglomerate in a low‐viscosity resin, such as vinyl ester, unsaturated polyester resin, and epoxy resins. The agglomeration process in the low‐viscosity vinyl ester resin generates electrically conductive paths already in the resin's liquid state, which undergo partial fixation by room temperature curing and full fixation by hot postcuring. The fully cured castings containing CB concentrations above percolation are characterized by a constant, temperature‐independent conductivity, over a wide temperature range. The current–voltage relationships of the cured vinyl ester/CB castings obey a power‐law dependency. The presence of the continuous CB paths in the vinyl ester casting is clearly observed in fracture surfaces formed at 100°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1165–1170, 2000     

Microwave absorbing rubber composites containing carbon black and aluminum powder

Natural rubber (NR), epoxidized natural rubber (ENR), and chlorosulfonated polyethylene (CSM) composites filled with conductive carbon black and aluminum powder have been prepared by using a two‐roll mill. An electromagnetic interference shielding effectiveness of those rubber composites was carried out in the frequency range of 8–12GHz (X‐band microwave). The increase of filler loading enhanced shielding effectiveness of the rubber composites. Conductive carbon black was more effective in shielding than aluminum powder. Binary filler‐filled rubber composites showed higher shielding effectiveness than that of single filler‐filled rubber composites. It has been observed that the shielding effectiveness of these rubber composites could be ranked in the following order: ENR ≥ CSM > NR, whereas the mechanical properties of the rubber composites were in the order of CSM > ENR > NR. The correlation between shielding effectiveness and electrical conductivity as well as mechanical properties of the rubber composites are also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Nonlinear viscoelastic behavior of butadiene–acrylonitrile copolymers filled with carbon black

Various viscoelastic measurements including dynamic mechanical measurements in tension at 110 Hz from ?60° to 160°C, tensile stress relaxation measurements with 100% elongation at 25°, 54°, and 98°C, capillary flow measurements at 70°, 100°, and 125°C, and high-speed tensile stress–strain measurements carried to break at 25°, 56°, and 98°C were performed on four samples of carbon black-filled butadiene–acrylonitrile copolymers. All the data were treated with the same equation for time–temperature conversion. The capillary viscosity–shear rate curves were significantly lower than the complex viscosity–angular frequency curves, indicating “strain softening” with extrusion. The viscosity was estimated from the stress–strain relationship at the yield point. The viscosity as a function of the strain rate is significantly higher than the complex viscosity as a function of angular frequency, indicating “strain hardening” with extension. The strain softening and strain hardening are attributable to the structural changes upon deformation of the carbon black-filled elastomers. With the unfilled elastomers, neither strain softening nor strain hardening were observed in similar measurements.     

Electrical conductivity of polystyrene/styrene-butadiene block copolymer blends containing carbon black

The electrical resistivity and mechanical properties of carbon black (CB)-filled polystyrene (PS)/styrene-butadiene block copolymer (SB) blends have been studied. Good electrical performance was achieved with pure SB and PS/SB blends indicating an inhomogeneity of these materials and the heterogeneous micro-dispersion of the CB particles. The percolation threshold of the filler inside SB or PS/SB blends is around 3.6 wt%, which is lower than that expected for incompatible PS/PBD blend. The addition of small amount CB decreases the elongation at break of PS/SB blends indicating some disturbance at the interface of these compatible material. Received: 28 July 1996/Revised version: 1 October 1996/Accepted: 3 October 1996     

Electrical conductivity of polymer blends containing liquid crystalline polymer and carbon black

This paper presents results of a study of melt‐processed immiscible polymer blends of high impact polystyrene (HIPS), liquid crystalline polymer (LCP) and carbon black (CB). Relationships between composition, electrical resistivity and morphology of the blends produced by Brabender mixing followed by compression molding, extrusion through a capillary rheometer, extrusion through a single‐screw extruder and injection molding were investigated. The LCP phase morphology in the blends was found sensitive to the processing conditions. A blend composition of at least 20 wt% LCP and 2 phr CB is necessary to preserve the conductivity of filaments produced over a wide range of shear rates. Enhancement of conductivity of blends containing CB and 30 wt% or more LCP was observed, under processing at 270°C and increasing levels of shear rate. An important role of the skin region in determining the resisitivy of injection molded samples was found. A good agreement between resistivity values of extruded or injection molded blends with resistivity values of filaments produced at similar conditions by a capillary rheometer was shown. Hence, the study of shear rate effect on resistivity of capillary rheometer filaments may serve as a predictor of resistivity behavior in real processing procedures. Polym. Eng. Sci. 44:528–540, 2004. © 2004 Society of Plastics Engineers.     

Cellulose containing block copolymers

Summary Solution properties of trimethylcellulose-poly(oxytetramethylene two and star block copolymers with defined molecular weights are reported. The solubility behavior of the concerned block copolymers is mainly governed by the solubility of the trimethylcellulose blocks. The solubility parameters for TMC and POTM indicate that both polymers are incompatible with each other. This is confirmed by the appearance of phase separation in concentrated solutions of corresponding blends even in nonselective solvents. Intrinsic viscosities of the block copolymers are reported and compared to corresponding polymer blend solutions.     

Cellulose containing block copolymers

Summary The preparation steps leading to trimethylcellulose — (b-poly(oxytetramethylene)) — block copolymers of the star type are described. This includes the synthesis of fully substituted cellulose derivative blocks each with one reactive endgroup by partial cleavage of trimethylcellulose, the activation of those endgroups to initiate the living cationic polymerization of poly(oxytetramethylene) — blocks and coupling of the resulting twoblocks by poly(4 — vinylpyridine) to form starshaped block copolymers.Herrn Prof. Dr. G. Manecke zu seinem 65. Geburtstag gewidmet     

Electrical conductivity and rheological behavior of multiphase polymer composites containing conducting carbon black

Multiphase polymer composites of carbon black (CB), polypropylene (PP) and low density polyethylene (LDPE) were prepared by melt‐mixing method to reduce the amount of CB in the conductive composites. SEM images showed that CB preferably located in LDPE phase and formed electrically conductive path. The measurement of conductive properties showed that the ternary materials possessed lower percolation than binary composites of CB/PP or CB/LDPE, the former was ～6 wt% and the latter was 9–10 wt%. Positive temperature coefficient (PTC) effects of the binary and ternary composites were investigated, indicating that the latter exhibited a relatively high PTC intensity. A rheological percolation estimated by a power law function is 2.66 wt% of CB loading, suggesting an onset of solid‐like behavior at low frequencies. This difference between the electrical and rheological percolation thresholds may be understood in terms of the smaller CB–CB distance required for electrical conductivity as compared with that required to impede polymer mobility. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Viscosity of quartz-like glass containing cesium cations

The results of the measurements of the viscosity of quartz-like glass formed based on the high-silica alkali-borosilicate porous glass are presented in this work. The porous glass is impregnated by aqueous solutions containing cesium ions and then thermally treated until the pores collapse and a quartz-like glass is formed.