Compatibilising effect of carbon black on morphology of NR–NBR blends

Abstract

It is proposed that a non-polar filler can reduce interfacial energies between polar and non-polar polymers. Experiments have been carried out to test this hypothesis using carbon black as the filler in blends of natural rubber (NR) and a nitrile rubber (NBR) with an acrylonitrile content of 45%. Blends of NR–NBR (70/30) were prepared in an internal mixer with varying amounts of carbon black. The dramatic decrease in domain size on addition of carbon black was nonetheless lower than that predicted. Further experiments showed that the amount of carbon black available at the interface for compatibilisation was influenced by preferential incorporation into the lower viscosity elastomer (NBR). Thus, elastomers of similar viscosity should be added to the mixer prior to the carbon black in order to maximise the amount of ‘free’ unwetted carbon black present when the elastomers are blended together. Blending experiments carried out under these conditions resulted in a morphology close to the prediction based on thermodynamic theory.     

Influence of nano–micrometre powder blends on microstructure and mechanical properties of silicon nitride

Abstract

A well known route to making tough silicon nitride compositions is to control the grain size and aspect ratio distributions. This is usually done by choosing the appropriate powder characteristics, sintering conditions, as well as sintering additives. The effect of hot pressing a blend of nano and micrometre scale silicon nitride powder is explored here. Microstructures and mechanical properties are determined for these hot pressed ceramics and are compared with a reference silicon nitride. Hardness and fracture toughness are determined at room temperature using hardness indents produced by a macro Vickers hardness indenter. Grain size and aspect ratio distributions and their impact on mechanical properties are presented. Blending of nano and micrometre scale powder is shown to result in a refined microstructure with an increase in the area/volume fraction of finer grains. Rising R curves are established for these ceramics demonstrating toughening behaviour. Crack bridging and crack path deviation are identified as possible toughening mechanisms.     

Mechanical and thermal properties of copoly(styrene/acrylonitrile) compatibilised Nylon–thermoplastic elastomer blends

Abstract

The effects of blend compositions on the mechanical and thermal properties of polymer blends containing Nylon 66 and a thermoplastic elastomer (TPE), Santoprene^®, have been studied. A 5% styrene/acrylonitrile copolymer was added to neat Nylon, TPE, and their blends. The blends were injection moulded and the tensile and impact properties were investigated. The morphology and thermal properties of the blends were observed using scanning electron microscopy and differential scanning calorimetry.

The presence of double melting temperatures showed that the Nylon 66 and TPE are immiscible. However, blending produced a modification of mechanical and thermal properties. At TPE/Nylon ratios above 50 : 50 the tensile properties of TPE improved. In addition the impact properties of Nylon improved above the 50 : 50 ratio, i.e. in the TPE rich region. Both the melting temperature and crystallinity were depressed in the region of 50 : 50 blend composition. The presence of two phases, which is evidence of immiscibility of the blends, was confirmed by scanning electron microscopy.     

Conductive rubbers made by adding conductive carbon black to EVA,EPDM, and EVA–EPDM blends

Abstract

Electrically conductive rubbers have been prepared by the incorporation of conductive carbon black into ethylene/vinyl acetate (EVA) copolymers, ethylene/propylene/diene monomer (EPDM) terpolymers, and a 50 : 50 EVA–EPDM blend. The electrical and mechanical properties of these composites have been studied. The percolation limit for high conductivity in the filled rubbers depends on their compatibility as well as the viscosity and polarity of the rubbers. The electrical resistivity decreases with increasing temperature and the activation energy for conduction decreases with increasing filler loading. The temperature dependence of resistivity can be correlated with data from DSC, XRD, and DMTA measurements. Electrical set and electrical hysteresis have been observed during heating–cooling cycles. The change in resistivity with applied pressure is also reported.     

Understanding the influence of anti-reversion agent and metal oxide dose on natural rubber–carbon black system

Sulfidic linkages that are formed during the vulcanization process of natural rubber (NR) are unstable at a higher temperature and can be reversed into conjugated diene. To overcome such issue and to build a compound that is hostile to inversion and with increasing service life, anti-reversion agent (ARA), for example, N,N′-4,4′-diphenylmethyene bismaleimide (BMDM), is added into the formulation. This work explains the conjugation reaction mechanism of conjugated diene and BMDM by means of gas chromatography–mass spectrometry and Fourier transform infrared spectroscopy. The first phase of this study is associated with the change in ARA dosage keeping ZnO dosage the same. It is observed that 5 phr of BMDM and 2 phr ZnO combination (ARA4) shows lowest reversion at 160°C. The modulus value at 300% elongation increased 12% by the incorporation of BMDM as compared to the compound of no BMDM (ARA1). The second part is all about keeping BMDM dosage the same at 5 phr level and varying ZnO phr by 3, 4, and 5. From the overall results, it is observed that at a suitable dosage of BMDM and ZnO (5 phr BMDM and 3 phr ZnO combination [ARA5]), least reversion can be achieved and vulcanizates containing optimized BMDM and ZnO show better retention properties after aerobic aging as compared to ARA1.     

Influence of quinone grafting via Friedel–Crafts reaction on carbon porous structure and supercapacitor performance

High specific surface area carbon has been modified with para-benzoquinone (p-BQ) via Friedel–Crafts reaction catalyzed by Iron(III) chloride followed by oxidation, in order to explore alternative strategies for obtaining high energy density supercapacitor materials by the combination of the double layer capacitance of carbons with the redox pseudocapacitance of the organic redox couple added on the carbon surface.Suitable structural and physicochemical characterization proved the formation of covalent bonds between carbon and p-BQ, and the electrochemical characterization showed a significant increase in gravimetric capacitance values after the addition of p-BQ which is maintained even after many cycles.This gravimetric capacitance increase was not only due to the redox reactions of p-BQ, but also to an increased double layer capacitance after p-BQ modification even when the BET surface area decreases after modification. A correlation with the pore structure of carbons showed that the increased double layer capacitance can be attributed to a better matching of carbon pore size with the size of electrolyte ions after p-BQ addition. Thus, this new addition strategy opens the way for the development of carbon-based materials for supercapacitors with higher energy densities coming from both increased pseudocapacitive reactions and increased double layer capacitance.     

Elastomeric composites based on ethylene–propylene–diene monomer rubber and conducting polymer-modified carbon black

Thermally stable elastomeric composites based on ethylene–propylene–diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via “in situ” deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300°C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5–10 phr depending on the formulation and electrical dc conductivity values in the range of 1 × 10⁻³ to 1 × 10⁻² S cm⁻¹ above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Steam reforming of methanol over Pt–Zn alloy catalyst supported on carbon black

Steam reforming of methanol over Zn-promoted Pt catalyst supported on an electrically conductive carbon black has been investigated after H₂ reduction at 873 K. X-ray diffraction measurement showed that Pt–Zn alloy was formed on the carbon black (C). The Zn-promoted Pt/C catalyst showed higher activity and selectivity to CO₂ compared with unpromoted Pt/C catalyst. Methyl formate was formed over the Zn-promoted Pt/C catalyst in decomposition of methanol (without water). This suggests that steam reforming of methanol over the Zn-promoted Pt/C catalyst can proceed via methyl formate, which is different from that of the unpromoted Pt/C catalyst.     

Elastomeric conductive composites based on conducting polymer–modified carbon black

Thermally stable elastomeric composites were prepared via melt processing from poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) and conducting polymer-modified carbon black (CPMCB) additives. CPMCB additives represent a novel thermally stable conductive compound made via “in-situ” deposition of polyaniline or polypyrrole on carbon black particles. Incorporating CPMCB is advantageous to the melt processing of composites, as it reduces the melt viscosity in comparison to the use of pure carbon black. Thermogravimetric analyses (TGA) showed that the composites are thermally stable with no appreciable degradation at temperatures as high as 300°C. In addition, the electrical conductivity of the composites was found to be very stable at high temperatures. Polym. Compos. 25:617–621, 2004. © 2004 Society of Plastics Engineers.     

Impact of graphene oxide nanoparticles and carbon black on the gamma radiation sensitization of acrylonitrile–butadiene rubber seal materials

Seals prepared from acrylonitrile–butadiene rubber (NBR) are primarily used in nuclear services. Nevertheless, at relatively high ionizing radiation doses, NBR seal materials may undergo radiation-induced degradation processes, leading to adverse effects on the sealing ability life. Herein, to strengthen the functional characteristics of NBR seals against radiation, graphene oxide (GO) nanoparticles were prepared and characterized by transmission electron microscopy, X-ray diffraction (XRD), Fourier transform infrared (FTIR), and ultraviolet/visible spectroscopies. Various NBR/GO composites fabricated with different ratios of GO nanoparticles and in the presence or absence of carbon black (CB) were investigated via cross-linking density, scanning electron microscopy, XRD, FTIR, and mechanical and thermal stability analyses. The synergistic effect of the simultaneous presence of GO and CB on the NBR seal sensitization to gamma radiation up to a dose of 1 MGy was studied. The physicomechanical properties were enhanced by adding GO nanosheets up to 3 phr and by incorporating 35 phr of a CB with GO until 5 phr. Further, the application of γ-irradiation resulted in an overall enhancement in the mechanical, physical, and thermal stability of the prepared composites up to 0.5 and 1 MGy with GO nanosheets in the absence or presence of CB particles, respectively. The mechanical measurements indicated significant increments by loading with GO nanosheets in the absence and presence of CB as well as by irradiation. The tensile strength elevated up to about 121%, 336%, and 366% by adding 3 phr GO, 3 GO:35 CB phr, and 5 GO:35 CB phr, respectively.     

Shell–core structured carbon fibers via melt spinning of petroleum- and wood-processing waste blends

In the last decades, carbon fibers with light weight and high strength have experienced the largely increased uses in various industrial applications. However, their expected uses in the automotive industry and building are largely limited because of their high production cost. Herein, we have demonstrated an effective method of making low cost carbon fibers via the melt spinning of petroleum-processing residue (pyrolyzed fuel oil, PFO)/lignin blends. Careful selection of tetrahydrofuran as the solvent to dissolve both PFO and lignin was made to optimize the miscible blend. The melt spinnable blend with a softening point of 260–280 °C exhibited good spinning ability at 280 °C. The plasticizing function of PFO allowed the highly cross linked lignin-based pitch to have high fluidity in the melt spinning process. Based on detailed TEM observations, the thermally treated fiber prepared at 2800 °C exhibited a shell–core structure, consisting of a highly crystalline surface from PFO and an amorphous disordered core from lignin. Such a crystalline surface structure gave rise to a high modulus value (up to 100 GPa) to the prepared carbon fibers.     

Influence of wrapping on some properties of MWCNT–PMMA and MWCNT–PE composites

The melt processing technique was used to elaborate composites made with a polymer matrix [polymethylmethacrylate (PMMA) or polyethylene (PE)] and multiwall carbon nanotubes (MWCNT). Nanotubes were wrapped by amphiphilic block copolymer (PE–co-polyethylene oxide) in aqueous solution to facilitate the dispersion and the handling. Morphology and physical properties (thermal, mechanical, electrical, and rheological) of the resulting composites were investigated. The wrapping of MWCNT allowed a good dispersion of these nanoparticules in the polymer matrices. Physical properties such as thermal degradation, mechanical behavior, and conduction are improved. The use of wrapped MWCNT allows to reduce drastically the melt viscosity of the blends of crystalline PE composites whereas it is almost non efficient for amorphous PMMA ones.     

Influence of the carbon surface on cathode deposits in non-aqueous Li–O2 batteries

Cup-stacked carbon nanotubes (CSCNT) with different surface properties were used for the non-aqueous Li–O₂ battery cathodes, and then examined at high magnification to understand how the discharge products were deposited on the cathode. As-prepared CSCNT based cathode had many reactive edges consisting of truncated conical graphene layers. After discharge, discharge products with average particle size 50 nm covered a nanotube, resulting in a layer-like texture. On the other hand, a heat-treated CSCNT based cathode was composed of edges terminated by graphitization of several graphene layers. After discharge, the size of the products was almost the same but the products were agglomerated, forming a bulky morphology. It was, thus, found that the carbon surface structure was closely related with the morphology of the cathode deposits after discharge. First principles calculations also indicated that no terminated edges acted as preferential active sites in adsorbing and storing the reaction species. It was, therefore, concluded that the active edges of the carbon surface were indispensable for controlling the morphology of cathode deposits and improving the battery performance.     

Investigation of hot pressed ZrB2–SiC–carbon black nanocomposite by scanning and transmission electron microscopy

Hybrid ZrB₂-based composite having 10 vol% nano-sized carbon black and 20 vol% SiC was fabricated by vacuum hot pressing at 1850 °C under 20 MPa for 60 min. The microstructure and sinterability of the as-sintered ceramic was studied by X-ray powder diffraction, scanning electron microscopy, X-ray spectroscopy, scanning transmission electron microscopy and transmission electron microscopy analyses. A fully-dense hybrid composite could be achieved by hot pressing method under the aforementioned conditions. No new in-situ phase formation was detected after sintering process. Although the densification progressed in a non-reactive manner, the addition of carbonaceous material assisted the sinterability acting as the surface oxides cleaner. The precise phase and nanostructural investigations of the prepared ceramic verified the partial graphitization of carbon black and conversion of amorphous nano-additive into crystalline graphite nano-flakes.     

Studies on the adhesive properties of neoprene–phenolic blends

Polychloroprene (neoprene) rubber in combination with phenolic resins is a versatile adhesive formulation. The phenolic resin used in this case was derived from a mixture of cardanol, a meta-substituted naturally-occurring substance, and phenol. Cardanol is the main ingredient of cashew nut shell liquid (CNSL), a renewable resource. This study aims to investigate the adhesive properties of cardanol-based resin when used in combination with two grades of polychloroprene rubber. The effects of varying the solid content and resin content, choice of resin, fillers, crosslinking agents, adhesion promoters, solvents, etc. in the adhesive formulations were also studied. Moreover, relative proportions of rubber and resin that give optimum adhesion performance were identified. The results show that cardanol-phenol-formaldehyde resin is an effective ingredient in adhesives for bonding aluminium to aluminium and SBR to SBR. The addition of 3-aminopropyltriethoxysilane to the formulation improves the bond strength of metal-to-metal specimens.     

Effect of carbon black on corrosion resistance of Al2O3–SiC–C castables to SiO2–MgO slag

Metallurgical solid waste recycling is the shape of things to come in green development of Chinese iron and steel industry. Utilization of ironworks slag for producing mineral wool at high temperature is an important approach. However, refractory lining is seriously corroded by the SiO₂–MgO based slag at 1600 °C during the production process. Different production steps need different atmospheres, the changeable service atmospheres (air and reducing atmosphere) put forward high requirements for slag resistance. The Al₂O₃–SiC–C castables containing carbon black are usually used in iron runner, which faces high-temperature service condition of 1450 °C–1500 °C. Nevertheless, the function of carbon black in the Al₂O₃–SiC–C castables at 1600 °C is till essentially unknown. In the current study, the carbon black was introduced to tabular alumina based Al₂O₃–SiC–C castables to improve corrosion resistance to SiO₂–MgO based slag at 1600 °C. The result showed that 0.4 wt% carbon black was suitable for the castables, which the slag resistance of castables was significantly improved. The carbon black had contributed to block slag by wettability resistance. By comparison with the castables without carbon black, the corrosion index and penetration index had been reduced by 20.2% and 28.0%, respectively, under air atmosphere. And there were little corrosion or penetration under reducing atmosphere for castables with 0.4 wt% carbon black. For the mechanical properties, the Al₂O₃–SiC–C castables with 0.4 wt% carbon black could serve production process although the carbon black impaired the physical properties.     

Influence of internal diffusion barriers on carbon diffusion in pure titanium and Ti–6Al–4V during diamond deposition

Diamond coatings were deposited on pure titanium and Ti–6Al–4V, at a temperature in the range of 600–750 °C, in a microwave plasma from CH₄/H₂ and CO/H₂ mixtures. The influence on carbon diffusion of different intermediate layers, especially tungsten, niobium, titanium nitride and pure titanium previously deposited on titanium alloys by physical vapor deposition (PVD) is reported. These intermediate layers are always composed of at least two sub-layers: (1) an internal diffusion barrier and (2) an external titanium layer that allows some carbon diffusion to be maintained. After diamond deposition, X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) observations coupled with energy-dispersive X-ray (EDX) analysis of the final multilayer systems allow us to determine the diffracting phases, their lattice parameters and the efficiency of the different barriers. The carbon diffusion coefficients in the titanium carbide phase and in the α-titanium solid solution are deduced from an experimental study carried out on pure titanium with or without an underlying diffusion barrier. The results are compared to the carbon diffusion in Ti–6Al–4V alloy. This work permitted us to calculate the carbon concentration profiles in both pure titanium and Ti–6Al–4V substrates.     

Electro-deposition and characterizations of nickel coatings on the carbon–polythene composite

Nickel coating on the carbon–polythene composite plate was prepared by electrodeposition in a nickel sulfate solution in this work. The morphology and cross-sectional microstructure of the nickel coating were examined by scanning electron microscope (SEM) and optical microscope (OM), respectively. The influence of bath temperature on the nickel deposition rate was investigated experimentally. The adhesion between the coating and the substrate was evaluated by the pull-off test. The corrosion behavior of the coating in an aqueous solution of NaCl was studied by electrochemical methods. The results showed that the nickel electrodeposition rate could reach up to 0.68 μm min⁻¹ on average under conditions of cathodic current density of 20 mA cm⁻² and bath temperature of 60 °C. It was confirmed that increasing the bath temperature up to 50 °C had a positive effect on the nickel deposit rate, while an adverse effect was observed beyond 60 °C. The adhesion strength between the nickel coating and the substrate can be more than 2.3 MPa. The corrosion potential of the bright coating in the NaCl solution was more positive than that of the dull coating, and the anodic dissolution rate of the bright coating was also far lower at the same polarization potential compared with the dull coating.     

Influence of additives on microstructure and property of microarc oxidized Mg–Si–O coatings

Ceramic coatings were fabricated on ZK60 magnesium alloy substrate by microarc oxidation (MAO) in Na₂SiO₃–KOH base electrolyte with four kinds of additives (i.e. KF, NH₄HF₂, C₃H₈O₃ and H₂O₂). The effects of these additives on microstructure and property of coatings were investigated. The surface morphology, phase composition and corrosion resistance of the ceramic coatings were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and simulation body fluid (SBF) immersion test respectively. It is found that different additives can change the spark discharge phenomenon during microarc oxidation. It is proved that both potassium fluoride (KF) and ammonium bifluoride (NH₄HF₂) promote discharge and accelerate reaction while the introduce of glycerol (C₃H₈O₃) leads to the refining of sparks and reduction of thermal effects. Results also demonstrate that the introduce of hydrogen peroxide (H₂O₂) contributes to the increase of coating surface roughness and enlargement of surface micropore size. XRD results indicate that the ceramic coatings are mainly composed of Mg₂SiO₄, MgSiO₃ and SiO₂. The introduce of H₂O₂ hinders the reaction between SiO₂ and MgO and creates favorable conditions for the formation of the MgO phase. The ceramic coatings formed in base electrolyte containing 7 g/L NH₄HF₂ and 5 mL/L C₃H₈O₃ exhibit the highest corrosion resistance.