Dynamic mechanical properties of styrene‐butadiene composites reinforced by defatted soy flour and carbon black co‐filler

Carboxylated styrene‐butadiene (SB) composites reinforced by a mixture of defatted soy flour (DSF) and carbon black (CB) were investigated in terms of their dynamic mechanical properties. DSF is an abundant renewable commodity and has a lower cost than CB. DSF contains soy protein, carbohydrate, and whey. Aqueous dispersions of DSF and CB were first mixed and then blended with SB latex to form rubber composites using freeze‐drying and compression molding methods. At 140°C, a single filler composite reinforced by 30% DSF exhibited roughly a 230‐fold increase in the shear elastic modulus compared to the unfilled SB rubber, indicating a significant reinforcement effect by DSF. Mixtures of DSF and CB at three different ratios were investigated as co‐fillers. Temperature sweep experiments indicate the shear elastic moduli of the co‐filler composites are between that of DSF and CB composites. Strain sweep experiments were used to study the fatigue and recovery behaviors of these composites. Compared with the DSF composites, the recovery behaviors of the 30% co‐filler composites after the eight consecutive deformation cycles of dynamic strain were improved and similar to that of 30% CB composite. Strain sweep experiments also indicated that the co‐filler composites have a greater elastic modulus than the CB reinforced composites within the strain range measured. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Natural rubber protein as interfacial enhancement for bio‐based nano‐fillers

Natural rubber was enhanced with soy protein nano‐aggregates and carbon black using a hybrid process. The rubber composites reinforced with an optimum amount of soy protein or soy protein/carbon black showed useful tensile properties. The stress‐strain behaviors were analyzed with a micro‐mechanical model that describes the stress–strain measurements well. The model analysis provides insight into filler network characteristics and entanglement modulus. The composites were also analyzed with both linear and nonlinear viscoelastic properties. Temperature and frequency dependent modulus as well as the model analysis of stress softening effect describe the ability of soy protein to constraint polymer chains in the highly filled composites. For the composites reinforced with soy protein, the good tensile properties are attributed to good filler‐polymer adhesion through the compatibilization effect of natural rubber protein. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2188–2197, 2013     

Viscoelastic properties of natural rubber composites reinforced by defatted soy flour and carbon black co‐filler

Filler mixtures of defatted soy flour (DSF) and carbon black (CB) were used to reinforce natural rubber (NR) composites and their viscoelastic properties were investigated. DSF is an abundant and renewable commodity and has a lower material cost than CB. Aqueous dispersions of DSF and CB were first mixed and then blended with NR latex to form rubber composites using freeze‐drying and compression molding methods. A 40% co‐filler reinforced composite with a 1 : 1 DSF : CB ratio exhibited a 90‐fold increase in the rubber plateau modulus compared with unfilled NR, showing a significant reinforcement effect by the co‐filler. The effect, however, is lower than that observed in the carboxylated styrene–butadiene rubber composites reported earlier, indicating a significant effect from the rubber matrix. The co‐filler composites have elastic moduli between those of DSF and CB reinforced composites. Stress softening and recovery experiments indicated that the co‐filler composites with a higher CB content tend to have a better recovery behavior; however, this can not be simply explained from the recovery behaviors of the single filler (DFS and CB) composites. CB composites prepared by freeze‐drying show a strain‐induced reorganization of fillers. Strain sweep experiment data fit with the Kraus model indicates the co‐filler composites with a higher CB content are more elastic, which is consistent with the recovery experiments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Flax‐fabric‐reinforced arylated soy protein composites: Brittle‐matrix behavior

Biocomposites were successfully prepared by the reinforcement of soy protein isolate (SPI) with different weight fractions of woven flax fabric. The flax‐fabric‐reinforced SPI‐based composites were then arylated with 2,2‐diphenyl‐2‐hydroxyethanoic acid (DPHEAc) for 4 h to obtain arylated biocomposites. A new method was proposed to determine the amount of carbon dioxide evolved during the arylation of the soy protein in the presence of DPHEAc. Characterizations of the arylated and nonarylated biocomposites were done by Fourier transform infrared spectroscopy, thermogravimetric analysis, and dynamic mechanical thermal analysis. The results indicate that the arylated soy‐protein‐based composites exhibited mechanical behavior like brittle‐matrix composites, which differentiated them from nonarylated soy‐protein‐based composites, which showed mechanical behavior similar to polymer–matrix composites. In the arylated composites, there was clear evidence of a stick–slip mechanism, which perhaps dominated and, therefore, prevented easy deformation of the reinforced film. Scanning electron microscopy studies revealed cracks in the arylated soy protein composites when they were subjected to tensile tests. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Characterization of Phytagel® modified soy protein isolate resin and unidirectional flax yarn reinforced “green” composites

The mechanical properties and moisture resistance of the soy protein isolate (SPI) resin and flax yarn reinforced composites were improved significantly by incorporation of a poly‐carboxylic acid based modifier, Phytagel®. SPI and Phytagel® were blended to form an interpenetrating network‐like cross‐linked complex. This complex showed significantly improved tensile and moisture properties as well as higher thermal stability as compared to the unmodified SPI resin. The incorporation of Phytagel® (40% w/w of SPI powder) in SPI resin and subsequent lowering of the amount of glycerol (from 30% to 12.5%) led to an overall 10‐fold increase in the tensile fracture stress and a nine‐fold increase in the Young's moduli of the SPI resin along with a seven‐fold decrease in fracture strain. The dynamic mechanical properties such as storage and loss modulus of the modified resin increased and the glass transition temperature also increased by about 56°C. The unidirectional flax yarn reinforced composites were made using two modified resins with 20% and 40% Phytagel® contents. Both resins contained 12.5% glycerol. The composites fabricated using resin containing 20% Phytagel® showed significantly higher tensile and flexural moduli as well as fracture stress in the axial direction than the composites with resin containing 40% Phytagel®, which was higher than the SPI resin based composites. POLYM. COMPOS., 26:647–659, 2005. © 2005 Society of Plastics Engineers     

Structure and mechanical properties of cellulose derivatives/soy protein isolate blends

Biodegradable and biocompatible composites based on soy protein isolate (SPI) and various cellulose derivatives have been prepared, and the dependence of structures and mechanical properties on the content and species of cellulose derivatives for the composites were investigated by X‐ray diffraction, differential scanning calorimetry, scanning electron microscope, and tensile test. The selected cellulose derivatives, such as methyl cellulose (MC), hydroxyethyl cellulose (HEC), and hydroxypropyl cellulose, were miscible with SPI when the content of cellulose derivatives was low, and then the isolated crystalline domains, shown as the structures of network and great aggregate, formed with an increase of cellulose derivative content. The miscible blends could produce the higher strength, and even result in the simultaneous enhancement of strength and elongation for the HEC/SPI and MC/SPI blends. Meanwhile, the moderate content of great MC domains also reinforced the materials. However, the damage of original ordered structure in SPI gave the decreased modulus. Since all the components, i.e., cellulose derivatives and soy protein, are biocompatible, the resultant composites are not only used as environment‐friendly material, but the biomedical application can be expected, especially for the tissue engineering scaffold. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Elastic moduli of particulate composites with graded filler‐matrix interfaces

The elastic response of plane‐array models of composites reinforced by particles or aligned fibers having graded interfaces with the matrix is analyzed. Such microstructure is representative of a new class of polymer matrix composite materials in which the filler is nanometer‐sized. In such materials, the polymer chains in the matrix are preferentially oriented close to the interface with the relatively rigid fillers, this leading to a graded interfacial layer about each inclusion. The composite elastic moduli are determined based on the properties and geometry of the interfacial graded layer as well as on the moduli of the filler and the matrix, and the volume fraction of filler. Conversion curves are constructed allowing for an equivalence to be established between the present case and that of similar composites without graded interfaces. Based on these conversion curves, standard homogenization algorithms can be applied to determine the overall elastic properties of such composite. The fillers are considered to be stiffer than the matrix, both rigid and of finite stiffness. Results for both sliding and bonded interfaces are presented. The effect of anisotropic material properties in the graded region on the composite moduli is also investigated. The results of the model are compared with published experimental data.     

Role of Star‐Like Hydroxylpropyl Lignin in Soy‐Protein Plastics

Summary: Star‐like hydroxypropyl lignin (HL) was compounded into soy protein isolated (SPI) to develop a potential biodegradable plastic with better mechanical performance than pure sheet‐SPI. The structure and properties of the composite materials were characterized by WAXD, DSC, SEM, TEM and tensile tests. The addition of just 2 wt.‐% HL resulted in tensile strength (σ_b) of 16.8 MPa, 2.3 times that of pure sheet‐SPI, with no accompanying decrease in elongation at break as a result of strong interaction and with good miscibility among components. As the HL content increased, the HL molecules could self‐aggregate as oblate supramolecular domains, while the stronger interactions between HL and glycerol resulted in the detaching of glycerol from the SPI matrix. It can be concluded that the insertion of HL as single molecules into the SPI matrix would provide materials with optimum mechanical properties. Compared with other lignin/SPI composites, the stretching chains on HL play a key role in the improvement of mechanical properties because of a stronger adhesion of HL onto the SPI matrix as well as the interpenetration of SPI into supramolecular HL domains.

Schematic illustration of the supramolecular domain created by the aggregation of hydroxypropyl lignin, which can interpenetrate with soy protein isolate.     

Electrospun soy‐protein‐based nanofibrous membranes for effective antimicrobial air filtration

Soy proteins are gaining more and more attention because of its multifunction and biodegradability. Silver nanoparticles (AgNPs) are introduced into the nanofibers to prevent growth of microorganisms over the filter media. In the present study, the multifunctional and antimicrobial nanofibrous membranes were prepared by electrospinning the soy protein isolate (SPI)/polymide‐6 (PA6)‐silver nitrate system followed by ultraviolet reduction. The morphology of SPI/PA6 nanofibrous membranes was characterized by scanning electron microscopy. Antibacterial property of nanofibrous membranes were investigated against Escherichia coli and Bacillus subtilis. The optimized fiber membrane exhibited over 95% filtration efficiency of PM_0.3 (particulate matter size less than 0.3 μm). The successful synthesis of SPI/PA6‐AgNPs nanofibrous membranes would make it to be the potential candidate for novel antibacterial and high‐performance air filter. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45766.     

Characterization of defatted soy flour and elastomer composites

Defatted soy flour (DSF) is an abundant renewable commodity and is more economically favorable then soy protein isolate or soy protein concentrate. DSF contains soy protein, soy carbohydrate, and soy whey. The aqueous dispersion of DSF was blended with styrene‐butadiene latex to form elastomer composites. The inclusion of soy carbohydrate increased the tensile stress in the small strain region, but reduced the elongation at break. The shear elastic modulus of the composites showed an increase in the small strain region, consistent with its stress‐strain behavior. The inclusion of soy carbohydrate and soy whey also improved the recovery behavior in the nonlinear region. At small strain, the shear elastic modulus of 30% filled composites at 140°C was about 500 times higher than that of the unfilled elastomer, indicating a significant reinforcement effect generated by DSF. Compared with soy protein isolate (SPI), the stress softening effect and recovery behavior under dynamic strain indicate the addition of soy carbohydrate and soy whey may have increased the filler‐rubber interaction. In general, the DSF composites gave better mechanical properties compared with the protein composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 353–361, 2005     

Electrical and mechanical properties of melamine‐formaldehyde–based laminates with shungite filler

Processing issues and the electrical and mechanical properties of a novel combination of a natural carbonaceous filler, Karelian shungite, and a water soluble thermosetting polymer, melamine‐formaldehyde, were investigated. Two types of shungite with different carbon contents were investigated and compared to a commercial carbon black. The larger particle size and chemically more active surface of the shungites compared to carbon black leads to easy handling with little dusting and allows water to be used as dispersant. Laminates of melamine‐formaldehyde reinforced with random cellulose fibers and filler were prepared by film stacking. The layered structure results in anisotropic resistivities for the shungites with fairly low in‐plane percolation thresholds and a dissipative resistivity above the percolation transition. In comparison, carbon black had a lower percolation threshold and a low isotropic resistivity above the percolation transition. The mechanical properties of the composites were slightly deteriorated by all three fillers, indicating poor interfacial adhesion. The results of Fourier transform infrared (FTIR) measurements are interpreted as indicating hydrogen bonding and thus relatively weak adhesion between filler and polymer. Aqueous mixtures of melamine‐formaldehyde and shungite filler had lower viscosities than corresponding melamine‐formaldehyde and carbon black filler mixtures. POLYM. COMPOS., 26:552–562, 2005. © 2005 Society of Plastics Engineers     

改性大豆分离蛋白对顺丁橡胶/丁苯橡胶复合材料性能的影响

将糊化改性的大豆分离蛋白( SPI)等量替代炭黑填充至顺丁橡胶/丁苯橡胶中,研究了改性SPI的粒径和热性能,考察了改性SPI用量对橡胶复合材料物理机械性能、热性能、压缩生热性能的影响,并与白炭黑和轻质碳酸钙填充复合材料进行了对比.结果表明,改性SPI的中位径由原来的115.25 μm减小至37.63 μm,比表面积由原...     

Toughness optimization of glass‐fiber reinforced PA 6/PA 66‐based composites: Effect of matrix composition and colorants

Mixing of polyamide 6 (PA 6) and polyamide 66 (PA 66) is integrated in the trend of development of new and improved materials by combination of different polymers and some reinforcing materials to polymer composites. The specific polymer composite PA 6/PA 66 reinforced with short glass‐fibers combines the good coloring of PA 6, and the small moisture absorption of PA 66. Technical applications of PA 6/PA 66 composites are mainly used in the automotive industry. Specific requirements of this industry lead to the necessity to optimize the material resistance against crack propagation of the PA 6/PA 66 composites, using mechanical and fracture mechanical methods. So, the present investigations focus on fracture mechanics toughness optimization of the PA 6/PA 66 composites, including unstable and stable crack growth. The aim of this toughness optimization is to find out the optimal mixing ratio of PA 6/PA 66. Applications of PA 6/PA 66 in the automotive industry and specific client wishes are the main reasons for black‐coloring of the PA materials. The influence of several black‐colorants (carbon black, nigrosine, spinel, iron oxide) on mechanical and fracture mechanical properties of the PA composites is also investigated using fracture mechanical methods. As experimental fracture mechanical method, preferentially, the instrumented Charpy impact test (ICIT) and the new cut method to determine the stable crack growth of glass‐fiber reinforced materials was used. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Rheological study of dispersions prepared with modified soybean protein isolates

Structural modifications of modified soy protein isolates (SPI) were distinguished by rheological behavior. SPI were prepared by acidic (pH 2.5) and thermal-acidic treatment without (pH 1.6) and with neutralization (pH 8.0). Dynamic properties of dispersions were determined through the variation of storage and loss moduli with frequency, and loss tangent behavior was analyzed. Changes in viscoelastic parameters with protein concentration (10–12% wt/vol) and time of heating (15–60 min) were also determined. Flow properties of dispersions were estimated through apparent viscosity and flow and consistency index measurements. Rheological behavior of dispersions was compared with those found by experiment with commercial mayonnaise, mustard, and salad dressing. The analysis of rheological parameters showed that thermally treated isolates formed dispersions with high elastic modulus and consistency index with a structure mainly stabilized by hydrophobic interactions, although no gelation process after cooling was observed. From the rheological point of view, it was deduced that thermally treated isolates could be used as ingredients in the formulation of salad dressings. The alkaline sample would be more versatile because, depending on protein concentration and thermal treatment, the consistency of its dispersions was like that in salad dressing, or similar to those of mustard and mayonnaise.     

Toughened carbon fiber fabric‐reinforced pCBT composites

Toughened carbon fiber‐fabric reinforced polymerized cyclic butylene terephthalate (pCBT) composites were obtained by chemical modification of cyclic butylene terephthalate (CBT) with small amounts of epoxy resin and isocyanates as chain extenders. Homogeneous CBT/epoxy and CBT/isocyanate blends were prepared by melt blending the components in a lab‐scale batch mixer at low temperatures and high shear rate. Melt blending was stopped before the ring‐opening polymerization of CBT could start. The modified CBT was the starting material for carbon fiber fabric‐reinforced pCBT composites (fiber content at about 65 wt%) which were prepared by ring‐opening polymerization during compression molding using a simple powder prepreg method. Interlaminar shear strength, flexural strength, and failure strain of the chemically modified composites increased up to 60% with respect to unmodified pCBT composites. Nevertheless, the flexural moduli slightly decreased due to the toughening effect of the chain extender on the pCBT matrix. Drop weight impact tests revealed that the energy absorption of the modified composites was relatively higher as compared to unmodified pCBT composites. POLYM. COMPOS., 37:1453–1460, 2016. © 2014 Society of Plastics Engineers     

Thermo‐mechanical and adhesive properties of polymeric films based on ZnAl‐hydrotalcite composites for active wound dressings

Composite films based on sodium carboxymethyl cellulose (Na‐CMC) loaded with a ZnAl(OH)₂CO₃·yH₂O hydrotalcite (ZnAl‐HTlc), were developed and characterized. The composites were mechanically more stable than the matrix alone: the noticeable enhancement of elastic modulus, creep resistance and failure properties, all proportional to the filler content, came at the expenses of a certain embrittlement. The filler tended to aggregate in the composites and the size of the aggregates increased with ZnAl‐HTlc amount. Contact angle measurements highlighted how ZnAl‐HTlc introduction in the polymeric matrix could strongly modify the wettability conditions of the films increasing their hydrophilicity. Bioadhesion tests showed that the adhesion behavior of the composites decreased as ZnAl‐HTlc amount increases, testifying the influence of the filler on the ability of the film to bind skin surface. Therefore, the developed films may find application as active wound dressings since ZnAl‐HTlc can be easily intercalated with an active pharmaceutical ingredient to be progressively released on the wound. POLYM. ENG. SCI., 59:E112–E119, 2019. © 2018 Society of Plastics Engineers     

Antistatic‐reinforced biocomposites of polyamide‐6 and polyaniline‐coated curauá fibers prepared on a pilot plant scale

Curauá fibers were used with success as a reinforcing agent in polyamide‐6, however, for several applications, an antistatic dissipation property is also desirable and the incorporation of an intrinsically conducting polymer is a suitable way to promote this. The novelty of this work is the simultaneous introduction of these two properties, antistatic and reinforcement, using one filler, obtained by depositing polyaniline on the surface of short curauá fibers. Nearly 5–30 wt% of these modified fibers were dispersed by extrusion in polyamide‐6, the composites were injection molded and characterized by electrical, mechanical, morphological, and rheological properties. The tensile strength of the polyamide‐6 composites reinforced with 5 and 30 wt% of polyaniline coated curauá fibers, was 56% higher and 23% lower than the values obtained for pure polyamide‐6, respectively. Also, the composite reinforced with 5 wt% of fibers, when processed with lower shearing rates, showed conductivity in the range of antistatic materials, 4 μS cm⁻¹. Scanning electronic microscopy and infrared spectroscopy showed an improvement in interfacial adhesion in PA‐6/CF‐PAni composites. The composite prepared with 5 wt% of polyaniline coated curauá fibers gave the best balance between the electrical and the mechanical properties. Extrusion and injection molding methods used here are suitable for continuous large scale production. POLYM. COMPOS., 34:1081–1090, 2013. © 2013 Society of Plastics Engineers     

Effect of nanoclay on physical,mechanical, and microbial degradation of jute‐reinforced,soy milk‐based nano‐biocomposites

Jute‐reinforced, soy milk‐based nano‐biocomposites were fabricated using both natural and organically modified nanoclay to study their effect on physical, mechanical, and degradation properties. Different weight percentages of nanoclays were used to modify soy milk by solution casting process. The jute fibers were then impregnated in modified soy resin and compressed to fabricate nano‐biocomposites. About 5 wt% of organically modified nanoclay‐loaded jute composite showed maximum tensile and flexural strength. X‐ray diffraction and transmission electron microscopy (TEM) analysis of fabricated composites confirmed about the formation of nanostructure. Impact, microhardness, dynamic mechanical analysis results of nano‐biocomposites revealed that nanoclay has influenced to improve such physical and mechanical properties. Microbial degradation study of nano‐biocomposites was carried out in cultured fungal bed. Weight loss, tensile loss, and field emission scanning electron microscopy photographs of composites revealed that composites are biodegradable in nature. The prime advantages of these composite are their eco‐compatibility as jute and soy resin, the basic constituents of composites are biodegradable in nature. These composites can be utilized in automobile, packaging, furniture sectors by replacing nondegradable plastic‐based composite. POLYM. ENG. SCI., 54:345–354, 2014. © 2013 Society of Plastics Engineers     

Influence of filler structure on microhardness of carbon black–polymer composites

The microhardness, H, of carbon black–polycarbonate and carbon black–low‐density polyethylene composites was investigated. Two types of microadditives with different average particle sizes were employed. It has been shown that the morphology of the polymeric matrix conspicuously influences the hardness dependence of the composites with volume concentration of filler, ϕ. The microhardness of the carbon black–polycarbonate composites shows a steplike behavior with respect to carbon black content, while the H value of the carbon black–low‐density polyethylene composite linearly increases with increasing ϕ. The influence of filler structure on the microhardness of the carbon black–polymer composites is also discussed. Results favor the concept that a smaller carbon black particle size (smaller aggregate diameters and interaggregate distances) enhances the microhardness of the composites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 90–95, 2001     

Effect of nanostructures of modified clay–carbon black on physico‐mechanical,electrical, and acoustic properties of elastomer‐based composites

Elastomeric composites based on nitrile rubber (NBR), carbon black (CB), and organically modified nanoclay (NC) were prepared using a laboratory two‐roll mixing mill. Influences of the hybrid filler system (CB+NC) on various properties of NBR compound were analyzed. It was found that the addition of hybrid filler (CB+NC) over only carbon black enhances various properties. It was also found that the addition of nanoclay to the rubber matrix effectively improved key properties. Acoustics and electrical properties were modified with reduced water absorption because of layered clay platelets. The lower volume resistivity of NBR composites reflected better electrical conductivity attributed to the presence of nanoclay leading to effective filler connectivity. X‐ray diffraction and transmission electron microscopy measurements revealed that nanoclays were mostly intercalated and were uniformly dispersed. Use of calcium stearate facilitated dispersion of nanoclay in the rubber matrix which was observed through the formation of nanostructures including “nano” and “halo” units. Time temperature superposition in dynamic mechanical analysis test of the composites indicated lower mechanical loss in the frequency range of interest. The advantages accruing due to overall property enhancement, including lower water absorption, and better electrical and excellent acoustic properties of NBR composites make it suitable as underwater acoustic transparent materials for transducer encapsulation application. POLYM. COMPOS., 37:1786–1796, 2016. © 2014 Society of Plastics Engineers