Effect of silanized silica nanofiller on tack and green strength of selected filled rubbers

BACKGROUND: Tack and green strength of filled and gum (unfilled) natural rubber (NR), poly(styrene‐co‐butadiene) rubber (SBR), polybutadiene rubber (BR) and (SBR‐BR) blend with different loadings of reinforcement agent, silanized silica nanofiller (Coupsil 8113), were studied and the results compared and discussed. RESULTS: It was found that silica was fully dispersed in rubber matrix after 13 min of mixing. In addition, with some exceptions for NR and (SBR‐BR) blend, filler loading decreased the tack strength of the studied filled rubbers. Green strength and Mooney viscosity increased with filler loading for all studied filled rubbers but with different rates and amounts. The optimum filler loadings for NR and (SBR‐BR) filled blend were 30 and 10 phr, respectively. Tacks of NR filled rubbers were much higher than those of synthetic filled rubbers. CONCLUSION: It was concluded that filler loading alters substantially the tack and green strength of the rubbers under investigation. Copyright © 2009 Society of Chemical Industry     

Study of jute fiber reinforced polyester composites by dynamic mechanical analysis

Cyanoethylation of jute fibers in the form of nonwoven fabric was studied, and these chemically modified fibers were used to make jute–polyester composites. The dynamic mechanical thermal properties of unsaturated polyester resin (cured) and composites of unmodified and chemically modified jute–polyester were studied by using a dynamic mechanical analyzer over a wide temperature range. The data suggest that the storage modulus and thermal transition temperature of the composites increased enormously due to cyanoethylation of fiber. An increase of the storage modulus of composites, prepared from chemically modified fiber, indicates its higher stiffness as compared to a composite prepared from unmodified fiber. It is also observed that incorporation of jute fiber (both unmodified and modified) with the unsaturated resin reduced the tan δ peak height remarkably. Composites prepared from cyanoethylated jute show better creep resistance at comparatively lower temperatures. On the contrary, a reversed phenomenon is observed at higher temperatures (120°C and above). Scanning electron micrographs of tensile fracture surfaces of unmodified and modified jute–polyester composites clearly demonstrate better fiber–matrix bonding in the case of the latter. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1505–1513, 1999     

Using modulated‐temperature differential scanning calorimetry to study interphases in blends of styrene–butadiene and polybutadiene rubbers filled with a silanized silica nanofiller

Polybutadiene and styrene–butadiene rubber compounds containing a high loading of a precipitated silica nanofiller were prepared. The silica surfaces were pretreated with bis(3‐triethoxysilylpropyl) tetrasulfide to prevent the silica from interfering with the reaction mechanism of sulfur cure in the rubber. The rubber compounds were mixed together for different times and at different temperatures to produce styrene–butadiene rubber/polybutadiene rubber blends. The mass fraction and composition of the interphase in the blends were subsequently determined with modulated‐temperature differential scanning calorimetry. At 60–65°C, the mass fraction of the interphase in the blend increased after the rubbers were mixed together for 10 min, and then it decreased significantly when the mixing time was increased to 20 min. When the two rubbers were mixed together for 7 min at 60–105°C, the mass fraction of the interphase in the blend increased slightly because of a higher mixing temperature. The composition of the interphase in the blend also changed with the mixing time and mixing temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Assessment degradation of natural rubber by moving die processability test and FTIR spectroscopy

Thermal and mechanical degradation of natural rubber (NR) mixed with N‐(1,3‐dimethylbutyl)‐N′‐phenyl‐p‐phenylenediamine (6PPD), polymerized 1,2‐dihydro‐2,2,4‐trimethyl‐quinoline (TMQ), and 50/50 weight basis mixture under high temperature and shearing conditions were investigated using a moving die processability test and FTIR spectroscopy. Relationship between dynamic properties in terms of tan δ value and chemical changes of NR molecules during degradation were correlated. The results indicated that the NR mixed with antioxidants caused decreased level of chain scission and oxidative degradation. The 6PPD provided better protection of NR against degradation at elevated temperature than TMQ. Furthermore, it was found that a prolonged mixing time caused more pronounced oxidative degradation on NR molecules than increased mixing temperature. The antioxidative capability of those antioxidants on NR was ordered based on their effectiveness as follows: 6PPD > 6PPD mixed with TMQ > TMQ. It was also found that the moving die processability test and FTIR spectroscopy are efficient routes to estimate the oxidative degradation of NR molecules. Therefore, the techniques could be applied to assess or compare antioxidative capability of various types and amounts of antioxidants used in the rubber formulation within a reasonable testing time. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigation on gradient dielectric characteristics of bamboo (Dentroclamus strictus)

Dependence of dielectric constant (ε′) and dielectric dissipation factor (tan δ) on distance from outermost skin to the center of bamboo has been determined. Dielectric measurements have been done in the temperature range of 24–120°C and in the frequency range, 4–100 kHz. Gradient behavior in ε′ and tan δ has been found in bamboo. It has also been observed that ε′ and tan δ increase with increasing temperature and decrease with increasing frequency. Relaxation times have been calculated for the four samples at 80, 90, and 100°C temperatures, which show that relaxation time decreases with the increase of temperature because of the increased molecular mobility. A continuous increase in the hardness from center (48) to outer surface (70) and density from 0.45 to 0.80 g/cc has been observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 380–386, 2006     

Investigation on gradient dielectric characteristics of bamboo (Dendrocalamus strictus)

Dielectric constant (ε′) and tan δ dependence on distance from the outer most skin to the center of bamboo has been determined. Dielectric measurements have been done in the temperature range from 24 to 120°C and in the frequency range from 4 to 100 kHz. Gradient behavior in dielectric constant (ε′) and tan δ has been found in bamboo. It has also been observed that the dielectric constant (ε′) and tan δ increase with the increasing temperature and decrease with the increasing frequency. Relaxation times have been calculated for the four samples at 80, 90, and 100°C temperatures, which show that relaxation time decreases with the increase of temperature due to the increased molecular mobility. A continuous increase in the hardness from the center 48 to the outer surface 70 and density from 0.45 to 0.80 g/cc has been observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3489–3494, 2006     

Dynamic mechanical analysis of fiber-reinforced phenolics

Dynamic mechanical analysis (DMA) was used to investigate the thermomechanical behavior and the effects of postcuring on a range of glass-reinforced phenolics. The materials examined were a pure resol (reinforced with S- and E-glass), a pure novolac (reinforced with S-glass), and three derivatives of the resol and/or novolac: a resol/novolac blend, a phenolic–furan graft copolymer, and a rubber-modified resol (all reinforced with S-glass). The blend and copolymer were prepared to obtain phenolic resins with improved impact strength, without degeneration of their high-temperature performance. They have a more loosely crosslinked structure compared to the pure resol or novolac. The rubber-modified resol was prepared with the intention of reducing the brittleness of the resin structure by incorporating an elastomeric phase within the resol resin matrix. It was found that the stiffness and glass transition temperature (T_g) of the materials could be increased by postcuring, which also produced a decrease in their damping capacity. Knowing that the postcure process is a function of time and temperature, a master curve was constructed that allowed prediction of the T_g of the resol/novolac blend over a broad range of postcure times and temperatures. The effect of frequency on the storage modulus of the pure resol (S-glass), copolymer, and blend was also studied from 0.01 to 100 Hz. Master curves were constructed by time–temperature superpositioning that allowed prediction of the storage modulus at times and temperatures that are not experimentally accessible. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 649–658, 1999     

Dynamic mechanical properties of particle‐reinforced EPDM composites

The dynamic mechanical property of particle‐reinforced ethylene–propylene–diene monomer (EPDM) matrix composites has been studied by using a dynamic mechanical thermal analyzer (DMTA). The individual composite has been reinforced with the various reinforcing particles as follows: silicon carbide particles (SiCps) of 60 μm in average diameter with various volume fractions (i.e., 10–40%); copper (Cu) and aluminum (Al) particles with 20 vol %; and SiCps with 6 and 36 μm in different average diameters with 20 vol % over the total composite volume. It is shown from the experimental results that the dynamic elastic modulus values increase and the composites with 40 vol % SiCps exhibit higher tan δ values through the entire rubbery phase after the glass transition region compared with the composites with lower particle volume percentages. This shows that the composites with 20 vol % Cu particles have the higher dynamic elastic modulus but the lower peak tan δ value than the composites with other particles of 20 vol % do. Scanning electron microscopy results show that the effective particle volume in the composite with Cu particles is higher than the other composites, although the same particle volume fraction of 20% has been used. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1595–1601, 2003     

Dynamic thermomechanical and tensile properties of chain-extended poly(ethylene terephthalate)

A series of chemically modified poly(ethylene terephthalate) (PET) samples was received after chain extension of a virgin sample at different reaction times with a new diepoxide as chain extender. These samples showed different intrinsic viscosity and degrees of branching or crosslinking. The effect of this differentiation on thermal properties was studied by dynamic mechanical thermal analysis and the determined T_g values were found to be in good agreement with those obtained by differential scanning calorimetry and thermomechanical analysis. Also, the branching or crosslinking exhibited significant improvement in tensile mechanical properties, which were studied, and the results are discussed. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 797–803, 1998     

Synergistic effect on flame retardancy and thermal behavior of polycarbonate filled with α‐zirconium phosphate@gel‐silica

A new kind of flame retardant (ZS) with layered α‐zirconium phosphate disks (α‐ZrP) as the core and inorganic flame retardant (gel‐silica, GS) to shield solid acid sites on the surface of α‐ZrP as the shell, was synthesized via a facile method. The incorporation effects of ZS with silicone resin on the thermal properties and flame retardance of PC composites were investigated. The presence of ZS could improve the thermal stability of PC matrix. With the addition of ZS contents increased to 3 wt %, the limiting oxygen index (LOI) of the composite was 32.3% and the vertical burning (UL‐94) test reached a V‐0 rating. However, with more contents of ZS, the LOI value decreased, and without the GS layer, the LOI value was decreased significantly as well. The synergism between the α‐ZrP core and gel‐silica shell, also with the silicone resin were found. Based on these results, the flame‐retardant mechanism was proposed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44829.     

Some considerations concerning the dynamic mechanical properties of cured styrene–butadiene rubber/polybutadiene blends

The dynamic mechanical response of several binary mixtures of a styrene–butadiene copolymer and high cis‐polybutadiene has been studied. The loss tangent and shear modulus were measured with a free damping torsion pendulum at temperatures between 143 and 343 K in argon atmosphere. From the loss tangent data the glass transition temperature of each sample was evaluated. The results can be represented by the Fox equation that relates the glass transition temperature of the blend with that of constituent polymers. The influence in the loss tangent data of the crystallization of the high cis BR used in the blend is discussed. A study of the separation of the crystalline and amorphous parts in the polybutadiene using the storage modulus data is presented. Finally, the loss of crystallinity at different contents of SBR in the blend is analysed using the dynamic mechanical data. © 2000 Society of Chemical Industry     

Effective biosynthesis of poly(3‐hydoxy‐ butyrate‐co‐4‐hydroxybutyrate) with high 4‐hydroxybutyrate fractions by Wautersia eutropha in the presence of α‐amino acids

BACKGROUND: Biopolymers produced by microbes are in demand as their biodegradable and biocompatible properties make them suitable for disposable products and for potential use as biomaterials for medical applications. The effective microbial production of copolyesters of 3‐hydroxybutyrate (3HB) and 4‐hydroxybutyrate(4HB) with high molar fractions of 4HB unit by a wild‐type Wautersia eutropha H16 was investigated in culture media containing 4‐hydroxybutyric acid (4HBA) and different carbon substrates in the presence of various α‐amino acids. RESULTS: The addition of carbon sources such as glucose, fructose and acetic acid to the culture medium containing 4HBA in the presence of α‐amino acids resulted in the production of random poly(3HB‐co‐4HB) with compositions of up to 77 mol% 4HB unit, but the yields of copolyesters with 60–77 mol% 4HB units were less than 15 wt% of dried cell weights. In contrast, when carbon sources such as propionic acid and butyric acid were used as the co‐substrates of 4HBA in the presence of α‐amino acids, poly(3HB‐co‐4HB) copolyesters with compositions of 72–86 mol% 4HB were produced at maximally 47.2 wt% of dried cell weight (11.3 g L^?1) and the molar conversion yield of 4HBA to 4HB fraction in copolyesters was as high as 31.4 mol%. Further, poly(3HB‐co‐4HB) copolyesters with compositions of 93–96 mol% 4HB were isolated at up to 35.2 wt% of dried cell weights by fractionation of the above copolymers with chloroform/n‐hexane. CONCLUSION: The productivity of copolyesters with over 80 mol% 4HB fractions was as high as 0.146 g L^?1 h^?1 (3.51 g L^?1 for 24 h) by flask batch cultivation. Copyright © 2007 Society of Chemical Industry     

Segmented copolymers with monodisperse crystallizable hard segments: Novel semi-crystalline materials

Segmented block copolymers with short monodisperse crystallizable hard segments have interesting structures and properties. In the melt, such short monodisperse segments are miscible with the matrix segments. Moreover, upon cooling, they crystallize fast, demonstrating a very high crystallinity, and only a small crystallization window is needed. The melting temperature of the short segments is high, provided that they can H-bond and/or contain aromatic groups. The melting temperature was found to decrease with increasing matrix segment concentration, due to the solvent effect of the matrix segments. At concentrations of crystallizable segment of 4-35 wt%, good dimensional and solvent stabilities were obtained.The monodisperse segments crystallized into nano-ribbons with uniform thickness and high aspect ratio, and these dispersed nano-ribbon crystallites constituted physical crosslinks, while acting also as reinforcing fillers. At concentrations of the monodisperse segments below 20 wt% no spherulitic ordering took place, and the semi-crystalline polymers were transparent. The monodisperse crystallizable segments can be used in combination with matrix segments of either low or high glass transition temperature, and may even contain (bio)functional units.     

Modifications of carbon for polymer composites and nanocomposites

The various forms of carbon used in composite preparation include mainly carbon-black, carbon nanotubes and nanofibers, graphite and fullerenes. This review presents a detailed literature survey on the various modifications of the carbon nanostructures for nanocomposite preparation focusing upon the works published in the last decade. The modifications of each form of carbon are considered, with a compilation of structure-property relationships of carbon-based polymer nanocomposites. Modifications in both bulk and surface modifications have been reviewed, with comparison of their mechanical, thermal, electrical and barrier properties. A synopsis of the applications of these advanced materials is presented, pointing out gaps to motivate potential research in this field.