Enhancement of basic properties of polysaccharide-based composites with organic and inorganic fillers: A review

The global shift towards biodegradable composite has made polysaccharides a green alternative to synthetic polymers owing to their biocompatibility, sustainability, and ecofriendly biomaterials. Despite the limitations in their applications, many studies have validated the effectiveness of using organic or inorganic fillers to ameliorate their mechanical and barrier properties. However, the understanding of how polysaccharides matrix is enhanced by fillers is still inexplicit. Hence, it is imperative to review the effects of using inorganic and organic fillers in some prominent polysaccharides in terms of mechanical and water barrier properties while taking into account the function of filler morphology, size and loading. Although it is intricate to indicate the best filler used for each of the polysaccharides matrices, this review served as a “food for thought” on the established works of enhanced-matrix filler combinations aimed at improving the mechanical and barrier properties of biodegradable films based on neutral or negatively charged polysaccharides-based composite films for potential application in food packaging, agriculture, biomedicine and constructions sector. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47251.     

Mechanical properties of natural rubber filled with flyash

The mechanical properties of flyash‐filled natural rubber were investigated and compared with those filled with calcium carbonate. A number of composites with varying percentage of the fillers were prepared using a two‐roll mill and molded on compression molding press. Specimens were subjected to mechanical testing. The properties studied were tensile strength, modulus at various elongations, hardness, density, etc. From the results it was observed that flyash‐filled composites were better in mechanical properties compared to those filled with calcium carbonate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 995–1001, 2002     

Mechanical and aging properties of cross‐linked ethylene propylene diene rubber / styrene butadiene rubber blends

The mechanical properties and aging characteristics of blends of ethylene propylene diene monomer (EPDM) rubber and styrene butadiene rubber (SBR) were investigated with special reference to the effect of blend ratio and cross‐linking systems. Among the blends, the one with 80/20 EPDM/SBR has been found to exhibit the highest tensile, tear, and abrasion properties at ambient temperature. The observed changes in the mechanical properties of the blends have been correlated with the phase morphology, as attested by scanning electron micrographs (SEMs). The effects of three different cure systems, namely, sulfur (S), dicumyl peroxide (DCP), and a mixed system consisting of sulfur and peroxide (mixed) on the blend properties also were studied. The stress‐strain behavior, tensile strength, elongation at break, and tear strength of the blends were found to be better for the mixed system. The influence of fillers such as high‐abrasion furnace (HAF) black, general‐purpose furnace (GPF) black, silica, and clay on the mechanical properties of 90/10 EPDM/SBR blend was examined. The ozone and water aging studies also were conducted on the sulfur cured blends, to supplement the results from the mechanical properties investigation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2606–2621, 2004     

Effect of fillers on thermal and mechanical properties of polyurethane elastomer

The effects of five different types of fillers on the thermal and mechanical properties of hydroxyl-terminated polybutadiene-based polyurethane elastomers were explored to develop a filled polyurethane elastomeric liner for rocket motors with hydroxyl-terminated polybutadiene-based composite propellants. Two type of carbon black, silica, aluminum oxide, and zirconium(III) oxide were used as filler. Based on the improvement in the tensile properties and the erosion resistance achieved in the first part of the study, an ISAF-type carbon black was selected to be used as the main filler in combination with an additional filler. The second part involves the investigation of polyurethane elastomers containing a second filler in various amounts in addition to the ISAF-type carbon black used as the main filler. In addition to the thermal and mechanical properties, the processability of the uncured polyurethane mixtures were also explored by measuring the viscosity in this second part of the study. The studied fillers do not considerbly change the thermal degradation temperatures and the thermal conductivity of the polyurethane elastomers with a filler content up to 16 wt %. The best improvement in the erosion resistance and tensile strength of the polyurethane elastomers with additional fillers is also achieved when filled with the ISAF-type carbon black, whereas the use of zirconium(III) oxide as additional filler provides almost no improvement in these properties. Viscosity of the uncured polyurethane mixtures increases with the increasing filler content and with the decreasing particle size of the filler. Aluminum oxide-filled elastomers seem to be the most suitable compositions having sufficiently high thermal and mechanical properties, together with the processability of uncured mixtures. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1057–1065, 1998     

Effect of modified carbon black on the filler–elastomer interaction and dynamic mechanical properties of SBR vulcanizates

A new modified carbon black (GCB) was prepared by adding special RFL latex into N220. Dynamic properties were obtained over a wide range of temperatures and strains on vulcanizates filled with GCB and unmodified carbon black, respectively. The results show that the GCB can effectively decrease the tan δ value at 60 and 90°C of SBR vulcanizates compared with that of the common unmodified carbon blacks, which responds to the fact that GCB is beneficial to lower rolling resistance and heat generation of the vulcanizates in comparison to that of the unmodified carbon black. Among the factors responsible for this, filler networking and filler–elastomer interaction play a dominant role. The effects of filler loading on mechanical properties of vulcanizates were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3707–3712, 2006     

Effect of temperature on dynamic rheological properties of uncured rubber materials in both the linear and the nonlinear viscoelastic domains

Investigating how rubber materials are affected by strain and strain rate (or frequency) in the room‐to‐curing temperature range allows to fully characterize them not only with respect to their processing behavior but also in view of their likely performances after vulcanization. Using a closed cavity dynamic rheometer, the adequate test protocols and data treatment, three gum elastomers, and three carbon black filled compounds were investigated in the 60–180°C range. The article describes the test protocol and the associated data treatment that were developed to document the effects of strain and temperature in both the linear and the nonlinear domains. Complex modulus G* and third relative torque harmonic variations with strain amplitude and temperature are reported and discussed in details. A set of relatively simple mathematical equations are demonstrated to offer the possibility to summarize large quantities of experimental data through a limited number of parameters whose physical meaning can be explained with respect to known aspects of polymer and rubber sciences. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Natural rubber vulcanizate reinforced by modified coal‐shale‐based fillers

Coal shale is considered a waste material in coal mining and washing processes. It comprises both inorganic and organic components. In this study, two kinds of coal shale were microcracked, burned, modified by enoxidation natural rubber (ENR), and then used as reinforcing fillers for natural rubber (NR). The NR vulcanizates reinforced with this modified filler were characterized by bounded rubber content, apparent crosslink density, and various mechanical property tests. The results show that the ultramicro coal‐shale powder was a good filler for NR. It could be mixed quickly, and it dispersed well in NR, which resulted in a significant enhancement. After modification by ENR, the reinforcement properties were improved further. The results suggest that this new type of filler could be used as a semireinforcing filler to replace or partially replace carbon black. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1397–1400, 2004     

Elaboration and properties of renewable polyurethanes based on natural rubber and biodegradable poly(butylene succinate) soft segments

Natural rubber (NR) is a renewable bio‐based polymer, while poly(butylene succinate) (PBS) belongs to the family of biodegradable renewable polymers. In this article, novel polyurethanes (PUs) were prepared using hydroxyl telechelic natural rubber (HTNR) and hydroxyl telechelic poly(butylene succinate) (HTPBS) as soft segments, and using toluene‐2,4‐diisocyanate (TDI) and 1,4‐butanediol (BDO) as hard segment. HTPBS oligomers of = 2000 and 3500 g mol^?1 were synthesized by bulk polycondensation of succinic acid (SA) with BDO. The polyurethane materials were obtained by casting process after solvent evaporation. The influence of the hard segment content and the molecular weight of HTPBS on the materials’ thermo‐mechanical properties were investigated by means of tensile testing, DSC, TGA, and DMTA. The obtained polyurethanes were amorphous with phase separations between hard and soft segments as well as between HTNR and HTPBS segments, and they exhibited good physical properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42943.     

Optimizing mechanical and morphological properties of biodegradable thermoplastic elastomer based on epoxidized natural rubber and poly(butylene succinate) blends

Biodegradable thermoplastic elastomer (BTPE) blends of epoxidized natural rubber (ENR) and poly(butylene succinate) (PBS) were prepared by the melt mixing process. Influences of the processing parameters mixing temperature, rotor speed, and mixing time on mechanical and morphological properties of BTPE were investigated. Taguchi method was applied to improve the mechanical and morphological properties by optimizing the processing parameters. That is, the experimental design adopted the L9 Taguchi orthogonal array with three manipulated factors (i.e., mixing temperature, rotor speed, and mixing time). Analysis of mean and analysis of variance were also exploited and the mixing temperature was found to be the most significant processing parameter regarding mechanical properties. The mixing temperature showed large contributions to Young's modulus, 100% modulus, tensile strength, and elongation at break, namely 45.33, 40.38, 49.31, and 36.04%, respectively. Furthermore, the optimum conditions found for mixing temperature, rotor speed, and mixing time were 140 °C, 100 rpm and 10 min, respectively. The result was confirmed by atomic force microscopy and scanning electron microscopy micrographs showing fine‐grained co‐continuous phase morphology of the ENR/PBS blends. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46541.     

Effect of the diisocyanate structure and the molecular weight of diols on bio‐based polyurethanes

Bio‐based polyurethanes (PU) containing poly(ε‐caprolactone) diol (PCL) and hydroxyl telechelic natural rubber (HTNR) were synthesized. The effect of the diisocyanate structure and the molecular weights of diols on the mechanical properties of PU were investigated. Three different molecular structures of diisocyanate were employed: an aliphatic diisocyanate (hexamethylene diisocyanate, HDI), an aromatic diisocyanate (toluene‐2,4‐diisocyanate, TDI) and a cycloalkane diisocyanate (isophorone diisocyanate, IPDI). Two molecular weights of each diol were selected. When HDI was employed, a crystalline PU was generated while asymmetrical structures of TDI and IPDI provided an amorphous PU. The presence of crystalline domains was responsible of a change in tensile behavior and physical properties. PU containing TDI and IPDI showed a rubber‐like behavior: low Young's modulus and high elongation at break. The crystalline domains in PU containing HDI acted as physical crosslinks, enhancing the Young's modulus and reducing the elongation at break, and they are responsible of the plastic yielding. The crystallinity increased the tear strength, the hardness and the thermal stability of PU. There was no significant difference between the TDI and IPDI on the mechanical properties and the physical characteristics. Higher molecular weight of PCL diol changed tensile behavior from the rubber‐like materials to the plastic yielding. Thermal and dynamic mechanical properties were determined by using DSC, TGA and DMTA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of fillers and additives on the properties of SBR vulcanizates

Methacrylic acid (MAA) and methyl methacrylate (MMA) were used as additives for peroxide‐cured styrene–butadiene rubber (SBR) filled with three inorganic fillers with different particle sizes and surface activity, for example, MgO, Mg(OH)₂, and BaSO₄. The experimental results show that the introduction of MAA can improve the mechanical properties of SBR vulcanizates filled with MgO, Mg(OH)₂, or BaSO₄. A small amount of MAA leads to significant increases in the modulus, tensile strength, and tear strength. MMA has little effect on the mechanical properties of the SBR vulcanizates. The SEM micrographs show that MAA can improve the interfacial bonding between SBR and the three kinds of fillers. The SBR–filler interaction was studied by Kraus plots. The relationship between the SBR–filler interaction and the mechanical properties was explored. m, a characteristic constant of a filler–SBR matrix, represents the interfacial bonding between fillers and SBR and the accumulated structure of the fillers. At a given ?, a high value of m means a strong interaction between SBR and the filler and, therefore, strong mechanical properties. The Payne effect of the SBR vulcanizates was observed, and the vulcanizates have low storage moduli at high strains and high storage moduli at low strains, and the moduli are nonlinear and increase the nonlinearity as the filler content increases. The loss moduli and loss factor reach their maximums at moderate and high strain amplitudes, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 775–782, 2003     

Influences of porous reduction graphene oxide/molybdenum disulfide as filler on dielectric properties,thermal stability,and mechanical properties of natural rubber

A ternary composite system consisting of natural rubber (NR), porous reduced graphene oxide (rPGO), and molybdenum disulfide (MoS₂) was introduced for applying in the dielectric field, of which rPGO and MoS₂ hybrid conductive filler (rPGM) was prepared by an effective and environmentally friendly method-microwave reduction. And the well-dispersed NR composites (NGM) were made by the latex co-precipitation method. Due to the large specific surface area of rPGM itself and the synergistic dispersion of rPGO and MoS₂, it formed many stable interface structures with the NR matrix, which not only made the blend exhibit high elasticity and withstood large deformation as NR but also greatly improved the dielectric, mechanical and thermal stability of the NR matrix. Compared with neat NR, the dielectric constant of nanocomposite increased by 11 times in the presence of rPGM conductive filler, and the leakage current generated by direct contact of fillers was reduced due to the attachment of MoS₂ to the surface of rPGO; when 2% rPGM was added, the NR exhibited the highest tensile strength (21.3 MPa), elongation at break (495%), and abrasion resistance (0.165 cm⁻³); in addition, the thermal stability of the nanocomposite was also improved. These phenomena indicate that rPGM had great potential in conductive fillers and provided a reliable way for NR applications in the field of dielectric elastomers.     

Effect of natural rubber on wood‐reinforced tannin composites

Natural rubber latex was added to composite materials formulated from a quebracho tannin adhesive crosslinked with hexamethylenetetramine and wood flour as a reinforcing filler. The final microstructure of the thermoset modified by the addition of different concentrations of latex was observed by scanning electron microscopy. The flexural and impact behavior of the modified materials was analyzed and related to the final microstructure of the composites. The effect of exposing the materials to humid environments was also evaluated. The measurements indicated that the addition of latex did not significantly reduce water absorption. However, it facilitated the preparation process of samples with low filler contents because of the increased viscosity of the mixture, which inhibited particle settling. On the other hand, the flexural properties increased with the addition of latex‐containing proteins through a reaction similar to tanning in leathers. The impact properties presented a similar trend, with the largest change occurring between 0 and 5% natural rubber in the matrix formulation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of polymeric curing agent modified with silazanes on the mechanical properties of silicone rubber

Polymeric curing agent modified with hexamethyldisilazane (PCA‐D), or with hexamethylcyclotrisilazane (PCA‐T), was used to improve the mechanical properties of hydroxyl‐teminated polydimethylsiloxane (PDMS) rubber. The structure and the gel time of PCA were characterized by ²⁹Si NMR and shear viscosity measurement, respectively. The PCA modified with silazanes was more stable in storage than that without treatment (PCA‐0). Chemical bonds were formed during the reaction of silazanes and PCA according to ²⁹Si NMR results. The crosslink density (γ_e) and the mechanical properties of PCA/PDMS rubber were determined by swelling equilibrium and stress–strain tests. It was found that PCA treated with both silazanes could better enhance the mechanical properties of PCA/PDMS rubber compared with PCA‐0. PCA‐T/PDMS rubber, with additional crosslinks, was the best among the three types of PCA/PDMS rubber on the mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Processing and properties of phthalic anhydride modified soy protein/glycerol plasticized soy protein composite films

Phthalic anhydride modified soy protein (PAS)/glycerol plasticized soy protein (GPS) composite films were fabricated by using extrusion and compression‐molding. Modified with phthalic anhydride, the soy protein lost its thermoplastic ability and was used as a filler to reinforce the GPS matrix. Fourier transform infrared spectra, optical transmittance, scanning electron microscope, mechanical tests, water resistance tests, as well as thermo‐gravimetric analysis were carried out to investigate the structure and properties of PAS and the plastic composites. The similar chemical structure of PAS and GPS led to compatibility of the two components resulting in high transparency and enhanced tensile properties of the composites. The water resistance of GPS was also improved by the incorporation of PAS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42221.     

Hybrid composite based on poly(vinyl alcohol) and fillers from renewable resources

Hybrid composite laminates consisting of polyvinyl alcohol (PVA) as continuous phase (33% by weight) and lignocellulosic fillers, derived from sugarcane bagasse, apple and orange waste (22% by weight) were molded in a carver press in the presence of water and glycerol such as platicizers agents. Corn starch was introduced as a biodegradation promoter and gluing component of the natural filler and synthetic polymeric matrix in the composite (22% by weight). The prepared laminates were characterized for their mechanical properties and degradative behavior in simulated soil burial experiments. The fibers type and content in composite impacted mechanical properties. Materials based on PVA and starch with apple wastes and sugarcane bagasse fillers were much harder (Young's Modulus respectively, 57, 171 MPa) than materials prepared with orange wastes (17 Mpa). Respirometric test revealed that soil microbes preferentially used natural polymers and low molecular weight additive as a carbon source compared to biodegradable synthetic polymer. The presence of PVA in formulations had no negative effect on the degradation of lignocellulosic fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Enhanced soft dielectric composite generators: the role of ceramic fillers

A notable issue in the field of dielectric elastomers is the characterization of composite materials with improved electromechanical coupling destined for mechanical-to-electrostatic energy converters. To this aim, random composites, where ceramic fillers with high dielectric constant are dispersed in a silicone matrix, represent an interesting option. Currently, the most promising reinforcing materials to be immersed in a silicone matrix, already tested for soft dielectric actuators, are lead magnesium niobate–lead titanate (PMN–PT) and lead zirconate-titanate (PZT). To estimate the performance improvement entailed by the composite device with respect to the homogeneous matrix, a typical four-phase cycle is considered in the model, where nominal load and electric charge are alternately held constant. Different materials are being studied: a composite consisting of a matrix in poly-dimethyl-siloxane (PDMS) reinforced with PMN–PT, assuming a filler concentration of 10% in volume and a PDMS–PZT composite with a 1% volume fraction of the ceramic component. In comparison with pure PDMS, the PDMS–10%PMN–PT allows an increase of more than 60% in the harvested energy per unit volume, while the PDMS–1%PZT composite, entailing a minor improvement, here in the range 23.5–37.4%, exhibits a better performance in terms of generated energy per unit weight. These results provide a guide for the choice and design of materials suitable for the realization of enhanced energy harvesters.     

Effect of fillers on morphological properties and wear characteristics of XNBR/NR blends

The blends of carboxylated acrylonitrile butadiene rubber (XNBR) and natural rubber (NR) were prepared using a blending technique in the presence of different types of carbon black. The effect of filler on morphological and wear characteristics was studied. ISAF N234 carbon black showed a significant effect on curing, mechanical, and thermal studies. The DIN abrader results showed high abrasion resistant properties of 80 wt % NR and 20 wt % XNBR with ISAF N234. The rubber compound containing 40 wt % of NR and 60 wt % of XNBR with ISAF N234 is found to be the toughest rubber against all types of rock. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120:710–718, 2011     

Reinforcement of natural rubber

In this article, we report on recent investigations on filled natural rubber. These investigations include a mechanical characterization as well as a molecular analysis based on measurements of chain orientation. It is demonstrated that at intermediate strains, the increase in the moduli can be explained by the inclusion of rigid particles in the soft matrix and from molecular interactions between the rubber and the filler. These interactions can be evaluated by equilibrium swelling and by orientational measurements. With regard to the unfilled formulation, carbon black– and silanized‐filled natural rubber exhibit increases in the cross‐linking density ascribed to filler‐polymer links, whereas a large decrease in the orientational level, evidenced by birefringence and by infrared dichroism, is observed when silica is added without any coupling agent. Finally, two specific effects—the Payne and Mullins effects, both related to energy dissipation phenomena—are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2301–2316, 2002