Nylon 11/silica nanocomposite coatings applied by the HVOF process. II. Mechanical and barrier properties

Nylon 11 coatings filled with nominal 0–15 vol % of nanosized silica or carbon black were produced using the high velocity oxy‐fuel combustion spray process. The scratch and sliding wear resistance, mechanical, and barrier properties of nanocomposite coatings were measured. The effect of powder initial size, filler content, filler chemistry, coating microstructure, and morphology were evaluated. Improvements of up to 35% in scratch and 67% in wear resistance were obtained for coatings with nominal 15 vol % contents of hydrophobic silica or carbon black, respectively, relative to unfilled coatings. This increase appeared to be primarily attributable to filler addition and increased matrix crystallinity. Particle surface chemistry, distribution, and dispersion also contributed to the differences in coating scratch and wear performance. Reinforcement of the polymer matrix resulted in increases of up to 205% in the glass storage modulus of nanocomposite coatings. This increase was shown to be a function of both the surface chemistry and amount of reinforcement. The storage modulus of nanocomposite coatings at temperatures above the glass transition temperature was higher than that of unfilled coatings by up to 195%, depending primarily on the particle size of the starting polymer powder. Results also showed that the water vapor transmission rate through nanoreinforced coatings decreased by up to 50% compared with pure polymer coatings. The aqueous permeability of coatings produced from smaller particle size polymers (D‐30) was lower than the permeability of coatings produced from larger particles because of the lower porosities and higher densities achieved in D‐30 coatings. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2272–2289, 2000     

Melting and degradation of nylon‐11 particles during HVOF combustion spraying

Numerical predictions and experimental observations have been correlated to improve the qualitative understanding of the degree of thermal degradation occurring during the HVOF spray deposition of nylon‐11. Particle residence time (～ 1 ms) in the HVOF jet was insufficient for significant decomposition of the nylon‐11, but was sufficient for noticeable discoloration (yellowing) of the particles of a powder with a mean particle size of 30 μm. Experimental observation showed this to be the case even though numerical predictions indicated that the temperature of a 30 μm diameter particle should be considerably higher than the upper degradation limit of nylon‐11. Initial thermal oxidation of nylon‐11 promotes the formation of carbon–carbon double bonds that strongly absorb in the visible spectrum even at concentrations of parts per million causing discoloration of the nylon. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thermally conductive nylon 6,6 and polycarbonate based resins. I. Synergistic effects of carbon fillers

Increasing the thermal conductivity of typically insulating polymers, such as nylon 6,6, opens new markets. A thermally conductive resin can be used for heat‐sink applications. This research focused on performing compounding runs followed by injection molding and thermal conductivity testing of carbon filled nylon 6,6 and polycarbonate based resins. The three carbon fillers investigated included an electrically conductive carbon black, synthetic graphite particles, and a milled pitch‐based carbon fiber. For each polymer, conductive resins were produced and tested that contained varying amounts of these single carbon fillers. In addition, combinations of fillers were investigated by conducting a full 2³ factorial design and a complete replicate in each polymer. The objective of this article was to determine the effects and interactions of each filler on the thermal conductivity properties of the conductive resins. From the through‐plane thermal conductivity results, it was determined that for both nylon 6,6 and polycarbonate based resins, synthetic graphite particles caused the largest increase in composite thermal conductivity, followed by carbon fibers. The combination of synthetic graphite particles and carbon fiber had the third most important effect on composite thermal conductivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 112–122, 2003     

Relative viscosity models and their application to capillary flow data of highly filled hard‐metal carbide powder compounds

The rheological behavior of highly filled polymer systems used in powder injection molding (PIM) technology strongly influences the final properties of the products. In this study, the capillary flow data of multi‐component polymer binders—based on polyethylene, paraffin, ethylene‐based copolymers, and polyethylene glycol—compounded with three various hard‐metal carbide powders were employed. The rheology of such highly filled (up to 50 vol%) multiphase systems is necessarily a complex phenomenon characterized by strain dependent, non‐Newtonian properties complicated by flow instabilities and yield. Over 15 mathematical models proposed for highly filled systems were tested, some of them calculating the maximum filler loading. Due to the complex structure of the filler (irregular shape, particle size distribution) and a multi‐component character of the binder, the applicability of these models varied with the powder‐binder systems studied. However, the particular values of maximum loadings are in good accordance with the predictions based on powder characteristics. Simple modification of Frankel‐Acrivos model to the systems containing unimodal hard‐metal carbide powders with particles of an irregular shape and broad particle size distribution gave precise agreement between experimental data and model prediction. POLYM. COMPOS., 26:29–36, 2005. © 2004 Society of Plastics Engineers.     

Carbon black filled powdered natural rubber: Preparation,particle size distribution,mechanical properties,and structures

Carbon black (HAF) filled powdered natural rubber (P(NR/HAF)) was prepared and the particle size distribution, mechanical properties, and micromorphology of P(NR/HAF) were studied. A carbon black–rubber latex coagulation method was developed for preparing carbon black filled free‐flowing, noncontact staining NR powders with particle diameter less than 0.9 mm. A powdering mechanism model was put forward to describe the powdering process, which shows that the key technical points consist in the surfactant with good emulsification properties and the polymer coating resin with good film forming properties. SEM analysis shows that carbon black and rubber matrix have formed a macroscopic homogenization in the P(NR/HAF) particles without contact staining, and carbon black particles are well dispersed in rubber matrix with diameter of about 50–150 nm. P(NR/HAF) vulcanizate showed better mechanical properties than bale natural rubber/carbon black blends (NR/HAF) and simple NR latex/carbon black blends (NRL/HAF), which depends primarily upon the absence of free carbon black, the fine dispersion of filler on the rubber matrix, and the better interaction between carbon black and rubber matrix due to the proper preparation condition of noncontact staining carbon black filled powdered NR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1763–1774, 2006     

Dynamic percolation phenomenon of poly(methyl methacrylate)/surface fluorinated carbon black composite

The electrical resistivity of polymer filled with conductive filler, such as carbon black (CB) particles, is greatly decreased by incorporating the conductive filler. This is called the percolation phenomenon and the critical CB concentration is called the percolation threshold concentration (Φ*). For CB particle–filled insulating polymer composite at lower than Φ*, the conductive CB network is constructed in the polymer matrix when the composite is maintained at a temperature higher than the glass‐transition temperature or the melting temperature of the polymer matrix. This phenomenon is called dynamic percolation and the time to reach the substantial decrease in resistivity is called percolation time (t_p). To investigate the relationship between the dynamic percolation process and the surface state of CB particles, we used three kinds of carbon black particles such as original carbon black (CB0) and fluorinated carbon black (FCB010 and FCB025)–filled poly(methyl methacrylate) (PMMA). It was observed that the dynamic percolation curves for CB0‐filled PMMA and FCB‐filled PMMA composites shifted to a shorter percolation time with increases in both the annealing temperature and the filler concentration. However, the dynamic percolation curves of FCB‐filled PMMA showed a gradually decreasing trend compared to that of CB0‐filled PMMA composites. The activation energy calculated from an Arrhenius plot of the t_p against the inverse of the annealing temperature was decreased by surface fluorine treatment. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1151–1155, 2003     

Model filled polymers: The effect of particle size on the rheology of filled poly(methyl methacrylate) composites

The effect of size of crosslinked monodisperse spherical polymer particles on the steady shear and dynamic rheology of filled poly(methyl methacrylate) (PMMA) composites was studied for PMMA and polystyrene (PS) particles in the range from 0.1 to 1.3 micron particle size. For PMMA matrices filled with crosslinked PS particles, reduction in filler size increases non‐Newtonian behavior. Particle size effects on the rheology of filled PMMA were much less pronounced for PMMA filler. The rate of growth of steady shear viscosity with aging time was much larger for PMMA filled with PS particles than with PMMA particles. The apparent yield stress of filled PMMA composites was estimated from Casson plots. The yield stress was negligible for PMMA filler but increased with decreasing particle size for PS filler. We suggest that PS particles are rejected by the PMMA matrix and form clusters, causing large enhancements in viscosity and moduli. Polym. Eng. Sci. 44:452–462, 2004. © 2004 Society of Plastics Engineers.     

Mechanical properties of talc-filled polypropylene. Influence of filler content,filler particle size and quality of dispersion

Mechanical properties of polypropylene-talc composites are measured as a function of talc concentration up to 40 wt.-%, Young's modulus of filled polypropylene shows linear increase with talc concentration up to double the value of unfilled polymer. Yield stress and Charpy notch toughness decrease with increasing talc content below matrix level at the highest filler content. Composite ultimate tensile elongation and tensile impact strength decrease sharply beginning at the lowest filler concentration. The influence of the talc particle size on the mechanical properties, especially composite toughness, mentioned above, is investigated. Four type of talc were used. Notch toughness decreases according to a linear dependence with mean size of talc particles. Evaluating impact strength possible content of agglomerates of filler and other additions is necessary to be included: tensile impact strength gives slow linear dependence with increasing content of filler particles and/or agglomerates above about 10 μm. The influence of talc particle size on the toughness of filled polypropylene becomes strong if the rubber particles are present.     

Production of filled hydrogels by mechanochemically induced polymerization

Silica nanoparticles functionalized with polyvinylpyrrolidone (PVP) were obtained by the grinding/mechanical activation of quartz or nonfunctionalized silica nanoparticles in a stirred media mill in the presence of 1‐vinyl‐2‐pyrrolidone, as proven by Fourier transform infrared spectroscopy. The polymer layer thickness formed on the silica nanoparticles after 8 h of mechanical activation in the absence of polymerization initiators amounted to about 10 nm, as derived from shear rheology. The silica nanoparticles functionalized with the hydrophilic PVP by mechanochemical polymerization reaction were used as fillers for hydrogels based on poly(hydroxyethyl methacrylate) (polyHEMA). The water absorption, release properties, and mechanical properties of the polyHEMA–silica composites were measured as functions of the filler content and particle size of the filler. PolyHEMA samples containing 20 wt % of the functionalized silica particles exhibited a higher maximum water absorption than the unfilled polymer; this showed that the hydrophilic interface between the filler and the matrix improved the water absorption. The release of methylene blue from the polyHEMA–silica composites was governed by diffusion and was almost unaffected by the silica particles. The values for the storage modulus and loss modulus of the polyHEMA–silica composites increased with growing filler content. For constant filler content, the storage modulus increased with decreasing particle diameter of the filler; this showed that the reinforcing effect increased with the interface between the filler particles and the matrix polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reuse of cured epoxy as a reinforcement in an epoxy composite

This article discusses the reuse of a thermoset‐based epoxy polymer. In this method, cured epoxy polymer is ground to powder of particle size ranging from 1 to 30 μm. The ground epoxy is then filled in an epoxy polymer to form an epoxy–epoxy composite system using both room and high temperature processing. The amount of filler material was varied from 1 to 10 wt% in the epoxy matrix. Rheology and tensile properties test were then performed. The result shows that the room temperature‐processed epoxy composites (above 5 wt% of powders) resulted in the formation of voids, agglomeration of particles, and reduced degree of cure leading to a decrease in tensile properties. These drawbacks (voids, agglomeration, and low degree of cure) were correspondingly absent in composites processed at high temperature. Results from this work suggest that the thermoset polymer can be reused effectively with minimal changes to the unfilled resin properties. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Hybrid Polyamide/Silica Nanocomposites: Synthesis and Mechanical Testing

A hybrid inorganic‐polymer composite was formed through nanosize silica filler particles (< 30 nm) that were incorporated inside a nylon‐6 matrix. The composite was microtomed and examined with TEM which revealed that the silica particles were well dispersed and non‐aggregated. Optimization of the synthesis conditions relied on appropriate choice of organic solvent and pH control. Crystallinity of the composite was examined with XRD and showed the silica phase remains amorphous while the polyamide phase was semi‐crystalline. Compared to pure nylon‐6, mechanical tests on the hybrid composite showed an increase in impact toughness, an increase in E‐modulus as a function of filler percentage, and a strain‐at‐break of > 0.5.     

Influence of 1,2‐unit contents on retraction behaviors of SBR vulcanizates

Styrene‐butadiene rubber (SBR) has four different repeat units of styrene, cis‐1,4‐, trans‐1,4‐, and 1,2‐uints. Influence of the 1,2‐unit content on the retraction behaviors of SBR vulcanizates reinforced with silica or carbon black was studied. The retraction behaviors were compared in terms of the filler systems and the microstructures of SBR. The silica‐filled vulcanizates containing a coupling agent showed nearly the same retraction behaviors as the carbon black‐filled ones, but the silica‐filled vulcanizates without a coupling agent were recovered slower than the carbon black‐filled ones. The vulcanizates with lower 1,2‐unit content started to recover at lower temperature than that with higher 1,2‐unit content. The recovery rate increased with increase of the 1,2‐unit content of SBR. The experimental results were explained with the polymer‐filler interactions, filler dispersion, glass transition temperature, and modulus. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4707–4711, 2006     

Linear‐nonlinear dichotomy of the rheological response of particle‐filled polymers

Novel nanoparticles, polymer‐particle coupling agents, and functionalized polymers are being developed to enhance the performance of particle‐reinforced polymer systems such as advanced rubber compounds for automobile tires. Understanding the complex rheological behavior of rubber is critical to providing insights into both processability and end‐use properties. One unique aspect of the rheology of filled elastomers is that the incorporation of particles introduces a hysteretic softening (Payne effect) at small dynamic strains. This study demonstrates that this nonlinear viscoelastic behavior needs to be considered when attempting to correlate steady shear response (Mooney viscosity) to oscillatory shear measurements from test equipment such as the Rubber Process Analyzer (RPA). While a wide array of unfilled gum elastomers show good correlation between Mooney viscosity and dynamic torque from the RPA at all of the strain amplitudes used, rubber compounds containing silica and carbon black particles only exhibit good agreement between the two measures of processability when the oscillatory strain amplitude is high enough to sufficiently break up the filler network. Other features of the filler network and its influence on nonlinear rheology are considered in this investigation, including the effects of polymer–filler interactions on filler flocculation and the use of Fourier transform rheometry to illustrate the “linear‐nonlinear dichotomy” of the Payne effect. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40818.     

Fly ash particles and precipitated silica as fillers in rubbers. I. Untreated fillers in natural rubber and styrene–butadiene rubber compounds

In this study, we investigated the effects of untreated precipitated silica (PSi) and fly ash silica (FASi) as fillers on the properties of natural rubber (NR) and styrene–butadiene rubber (SBR) compounds. The cure characteristics and the final properties of the NR and SBR compounds were considered separately and comparatively with regard to the effect of the loading of the fillers, which ranged from 0 to 80 phr. In the NR system, the cure time and minimum and maximum torques of the NR compounds progressively increased at PSi loadings of 30–75 phr. A relatively low cure time and low viscosity of the NR compounds were achieved throughout the FASi loadings used. The vulcanizate properties of the FASi‐filled vulcanizates appeared to be very similar to those of the PSi‐filled vulcanizates at silica contents of 0–30 phr. Above these concentrations, the properties of the PSi‐filled vulcanizates improved, whereas those of the FASi‐filled compounds remained the same. In the SBR system, the changing trends of all of the properties of the filled SBR vulcanizates were very similar to those of the filled NR vulcanizates, except for the tensile and tear strengths. For a given rubber matrix and silica content, the discrepancies in the results between PSi and FASi were associated with filler–filler interactions, filler particle size, and the amount of nonrubber in the vulcanizates. With the effect of the FASi particles on the mechanical properties of the NR and SBR vulcanizates considered, we recommend fly ash particles as a filler in NR at silica concentrations of 0–30 phr but not in SBR systems, except when improvement in the tensile and tear properties is required. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2119–2130, 2004     

Influence of the size of spraying powders on the microstructure and corrosion resistance of Fe-based amorphous coating

The Fe-based amorphous coatings with the composition of Fe₄₈Cr₁₅Mo₁₄C₁₅B₆Y₂ were successfully sprayed on mild steel substrate by the high velocity oxygen fuel (HVOF) spraying process with different feedstock powder sizes (i.e., powder A: −33 + 20 μm, powder B: −45 + 33 μm, powder C: −55 + 45 μm). The coatings were characterized for its morphology, microstructure and thermal stability by using X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The corrosion behavior of the coatings in 3.5 wt% NaCl solution was studied with potentiodynamic and potentiostatic polarization test. It was found that the particle size of the feedstock powders had a significant influence on microstructure and corrosion resistance of the resultant coatings. The coatings sprayed with the finest powders show the most compact structure; while the coating with the coarser powders exhibits a better corrosion resistance. It is found that the corrosion resistance of the coatings is closely related to the wetting behavior which is affected by the oxygen content and the roughness of coatings. The coatings with hydrophobicity exhibit a better corrosion. The present result demonstrates that the amorphous coatings with hydrophobicity and excellent corrosion resistant are promising for industrial application in marine environment.     

Evaluation of interfacial layer properties in the polystyrene/silica nanocomposite

Processing conditions and final mechanical properties of polymer nanocomposites are affected by their interfacial layers behavior. However, it is impossible to determine directly the properties of these layers by dynamic rheometry tests. In this work, the interfacial layers properties are evaluated for polystyrene containing silica nanoparticles by the concept of glass‐transition temperature shift. The samples were prepared via solution‐mixing method and dynamic rheometry was used to determine the viscoelastic behavior of filled polymers in the melt state. This initial step showed that addition of silica particles increased the glass‐transition temperature. By preference, decrease in the filler particle size lead to a drastic increase in the glass‐transition temperature and interfacial layer volume fraction due to relatively high surface area of the small filler particles. Then, in the next step, the viscoelastic properties of interfacial layer have been evaluated on the basis of the properties of neat polystyrene using temperature‐frequency superposition law. For this purpose, the shift factor was calculated from the glass‐transition temperature of the sample with maximum filler content. Finally, the effect of immobilized interfacial layer on the viscoelastic properties of the polymer nanocomposite samples has been estimated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Jamming rheology of model cementitious suspensions composed of comb‐polymer stabilized magnesium oxide particles

The colloidal microstructure of concentrated suspensions containing anionic comb‐polymer‐stabilized magnesium oxide (MgO) particles in water was analyzed by shear rheometry for indications of changes in particle microstructure based on particle size and comb‐polymer usage. As the suspensions were sheared at different rates, jamming in the sheared MgO suspensions was observed as shear stress overshoots. The shear‐induced evolution of the suspension's microstructure was strongly related to the perceived interactions between neighboring MgO particles in the suspension. In the jammed state, interactions are believed to be enhanced by the formation of entanglements between opposing comb‐polymer side‐chains. Steric repulsion between side‐chains was lessened for large particles on account of their diameters, which further enabled side‐chain entanglement during close particle contact under shear. Suspensions with relatively wide particle size distributions (0.5–400 μm) were theorized to form hydrocluster aggregates, while suspensions with narrower particle size distributions (0.5–40 μm) most likely resulted in networked microstructures under the influence of the chain entanglements from the adsorbed comb‐polymer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40429.     

Volume strain measurements on CACO3/polypropylene particulate composites: The effect of particle size

The use of rigid fillers to toughen polymers has received considerable attention in recent years. The role of the rigid particle here is that of debonding, at some stage, from the matrix, thus triggering dilatational processes similar to those observed in rubber‐toughened polymers. The role of particle size in these rigid filled composites has not been studied in great detail. In this work, volume strain measurements were carried out on a series of particulate composites based on polypropylene filled with calcium carbonate (CC) particles with average diameters of 0.07, 0.7, and 3.5 μm and filler volume fractions ranging from 0.05 to 0.30. The experimental results have shown a strong particle size effect. A model is proposed to take this effect into account, based upon the formation of an immobilized layer of polymer on the surface of the filler particles. The experimental results are consistent with a surface layer of 15–25 nm. The results are discussed in relation to the fracture behavior of these composites reported earlier. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 925–935, 2004     

Properties of natural rubber composites reinforced with silica or carbon black: influence of cure accelerator content and filler dispersion

Filler dispersion is a critical factor in determining the properties of filled rubber composites. Silica has a high density of silanol groups on the surface, which lead to strong filler–filler interactions and a poor filler dispersions. A cure accelerator, N‐tert‐butyl‐2‐benzothiazole sulfenamide (TBBS), was found to improve filler dispersion in silica‐filled natural rubber (NR) compounds. For the silica‐filled NR compounds without the silane coupling agent, the reversion ratio generally increased with increase in TBBS content, whereas those of the silica‐filled NR compounds containing the silane coupling agent and carbon black‐filled NR compounds decreased linearly. The tensile strength of the silica‐filled NR vulcanizate without the silane coupling agent increased as the TBBS content increased, whereas carbon black‐filled samples did not show a specific trend. The experimental results were explained by TBBS adsorption on the silica surface and the improvement of silica dispersion with the aid of TBBS. Copyright © 2003 Society of Chemical Industry     

Effect of filler size distribution on the mechanical and physical properties of alumina‐filled silicone rubber

The properties of silicone rubber filled with three kinds of binary mixtures of alumina particles with different size distribution (i.e., 30 μm + 0.5 μm, 10 μm + 0.5 μm, and 5 μm + 0.5 μm) were investigated as a function of relative volume fraction of the 0.5 μm particles in the hybrid alumina (V_s) at a fixed total filler content of 55 vol%. The results indicate that each binary mixture of alumina‐filled silicone rubber exhibited improved thermal conductivity and tensile strength, and decreased dielectric constant, compared to a single particle size filler‐reinforced one, and the maximum improvements were obtained at the V_s ranging from 0.2 to 0.35; the coefficient of thermal expansion (CTE) of filled silicone rubber obviously reduced with increase in the V_s, whereas the elongation at break slightly decreased. At V_s = 0, the larger particles‐filled silicone rubber showed higher thermal conductivity, CTE, dielectric constant, and elongation at break, and lower tensile strength compared with the those of the smaller particles‐filled one. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers