Interfacial adhesion in sisal fiber/SBR composites: an investigation by the restricted equilibrium swelling technique

Short sisal fiber-reinforced styrene butadiene rubber (SBR) composites were prepared and characterized by the restricted solvent swelling technique. The solvent swelling characteristics of SBR composites containing untreated and bonding agent-added mixes were investigated in a series of aromatic solvents, such as benzene, toluene, and xylene. The diffusion experiments were conducted by the sorption gravimetric method. The adhesion between the rubber and short sisal fibers was evaluated from the restricted equilibrium swelling measurements. The anisotropy of swelling of the composite was confirmed by this study. The effect of fiber orientation in controlling the anisotropy of restricted swelling was also demonstrated. As the fiber content increased, the solvent uptake decreased, due to the increased hindrance and good fiber-rubber interactions. Bonding agent-added mixes showed enhanced restriction to swelling, due to the strong interfacial adhesion. The bonding system containing hexa-resorcinol in the mix produces an in-situ resin, which binds the fiber and the rubber matrix firmly. In addition, as the penetrant size increases from benzene to xylene, the uptake decreases. The swelling index values of the composites support this observation. Due to the improved adhesion between the short sisal fiber and SBR, the ratio of the volume fraction of rubber in the dry composite sample to the swollen sample (V _T) decreases. The extent of fiber orientation of the composites was also analysed from the restricted swelling method. SEM studies of the composite revealed the orientation of short fibers. The sorption data support the Fickian diffusion trend, which is typical in the case of cross-linked rubbers.     

Uptake of aromatic solvents by polyethylene films

The sorption properties of the solvents benzene, toluene, and xylene in polyethylene films at 40, 60, and 80°C were investigated. The diffusion coefficient increased with an increase in the sorption temperature for the solvents and was highest for xylene and least for benzene. The inability of xylene to show a definite order of the diffusion coefficients at the investigated temperatures was attributed to the presence of two methyl side groups in the molecule. The solubilities of the solvents in polyethylene increased with an increase in the sorption temperature, and the following order of the solubilities could be observed: xylene > toluene > benzene. The permeabilities of the solvents in polyethylene depended on the sorption temperature, and the following order of the permeabilities was observed: xylene > toluene > benzene. The calculated activation energies of sorption in polyethylene films were all positive; benzene had the highest energy of sorption, and xylene had the lowest. The calculated enthalpies of sorption (ΔH_S) were also positive for the three solvents and were in the following order: xylene > toluene > benzene. The calculated entropies of sorption (ΔS) were negative for the solvents and showed trends similar to the variation of ΔH_S among the solvents. The change in the Gibbs free energies of sorption (ΔG_S), evaluated with the expression ΔG_S = ΔH_S ? TΔS (where T is the Kelvin temperature), were all positive, and this was an indication of the nonspontaneity of the solubility of polyethylene in the aromatic solvents at 313 K. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3849–3854, 2007     

Cellulose nanofibres and cellulose nanowhiskers based natural rubber composites: Diffusion,sorption, and permeation of aromatic organic solvents

This article investigates the transport behavior of three aromatic organic solvents, viz. benzene, toluene, and p‐xylene in natural rubber nanocomposite membranes containing cellulose nanofibres (CNFs) and cellulose nanowhiskers (CNWs) isolated from bamboo pulp. The solvent molecules act as molecular probes to study the diffusion, sorption, and permeation through the nanocomposites, and provide information on the nanocomposite structure and matrix–filler interactions. Both the nanocelluloses were found to decrease the uptake of aromatic solvents in nanocomposite membranes, but the effect was more significant in the case on nanofibers compared to nanowhiskers. Furthermore, the uptake decreased with increased penetrant size; being the highest for benzene and the lowest for p‐xylene. Transport parameters such as diffusion coefficient, sorption coefficient, and permeation coefficient have been calculated. Comparison of the experimental values of equilibrium solvent uptake with the predicted values indicated that both the nanocelluloses have restricted the molecular mobility at the interphase and thereby decreased the transport of solvents through the materials; being more significant for nanofibers. The results showed that both the used cellulosic nanomaterials act as functional additives capable of manipulating and tailoring the transport of organic solvents through elastomeric membranes, even at concentrations as low as 2.5 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on the diffusion characteristics of some aromatic solvents into polypropylene film

The sorption properties of the solvents benzene, toluene, and xylene into polypropylene films at 40, 60, and 80°C have been investigated. The diffusivity and permeability of the solvents into polypropylene films were found to increase in the order of solvent, benzene, toluene, and xylene at the different temperatures studied. The properties were also found to be temperature dependent. The zsolubility of the solvents into polypropylene films was found to be highest in toluene, followed by xylene, and least in benzene. However, a general increase in solubility with temperature was observed for all the solvents studied. The calculated values of activation energy of diffusion did not show any relationship with solvent properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1985–1989, 2006     

Castor oil‐based polyurethane–polyester nonwoven fabric composites: Mechanical properties,chemical resistance,and water sorption behavior at different temperatures

Castor oil‐based polyurethane (PU)–polyester nonwoven fabric composites were fabricated by impregnating the polyester nonwoven fabric in a composition containing castor oil and diisocyanate. The effects of different diisocyanates such as toluene‐2,4‐diisocyanate (TDI) and hexamethylene diisocyanate (HMDI) on the mechanical properties have been studied for neat PU sheets and their composites with polyester nonwoven fabric. Chemical resistance of the PU composites has been assessed by exposing the specimens to different chemical environments. Percentage water absorption of composites and neat PU sheets has been determined both at room temperature and in boiling water. Both TDI‐ and HMDI‐based PU composites showed a marginal improvement in tensile strength retention at 100°C heat ageing. Water sorption studies were carried out at different temperatures, viz, 30, 50, and 70°C, based on immersion weight gain method. From the sorption results, the diffusion (D) and permeation (P) coefficients of water penetrant have been calculated. Attempts were made to estimate the empirical parameters such as n, which suggests the mode of transport (non‐Fickian), and K, a constant which depends on the structural characteristics of the polymer in addition to its interaction in boiling water. The temperature dependence of the transport coefficients has been used to estimate the activation energy parameters for diffusion (E_D) and permeation (E_p) processes from Arrhenius plots. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Molecular transport of n‐alkanes into PU/PBMA interpenetrating polymer network systems

The methylene diisocyanate (MDI) and toluene diisocyanate (TDI) based polyurethane/polybutyl methacrylate (PU/PBMA‐50/50) interpenetrating polymer network (IPN) membranes have been prepared. The molecular migration of n‐alkane penetrants such as hexane, heptane, octane, nonane, and decane through PU/PBMA (50/50) membranes has been studied at 25, 40, and 60°C using a weight gain method. From the sorption results, diffusion (D) and permeation (P) coefficients of n‐alkane penetrants have been calculated. Molecular migration depends on membrane‐solvent interactions, size of the penetrants, temperature, and availability of free volume within the membrane matrix. Attempts have been made to estimate the parameters of an empirical equation and these data suggest that molecular transport follows Fickian mode. From a study of temperature dependence of transport parameters, activation energy for diffusion (E_D) and permeation (E_P) have been estimated from the Arrhenius relation. Furthermore, sorption results have been interpreted in terms of enthalpy (ΔH) and entropy (ΔS) of sorption. The liquid concentration profiles have been computed using Fick's equation with appropriate initial and boundary conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 739–746, 2003     

Evaluation of kinetics and transport mechanism of solvents through natural rubber composites containing organically modified gadolinium oxide

The solvent transport properties of the prepared composites were analysed using solvents of varying cohesive energy density and the effect of both modified as well as unmodified filler on the sorption and diffusion behaviour of NR vulcanisates has been investigated. It is found that the equilibrium uptake decreases with increase in filler content, as anticipated owing to the restrictions offered by the filler for solvents to diffuse into the polymer matrix. The mechanism of transport in natural rubber composites was carefully tracked and it was found to exhibit an anomalous mode of solvent transport where the polymer relaxation is in par with the rate of diffusion. Theoretical modelling of the swelling parameters was done and the results were found to be in agreement with existing models. The excellent swelling resistance coupled with the simultaneous improvement in mechanical properties would definitely pave way for the utilisation of these composites as barrier membranes.     

Sorption and diffusion of aldehydes and ketones into natural rubber blends

Sorption and diffusion of aldehydes and ketones through different NR blends of bromobutyl (BIIR), chlorobutyl (CIIR), neoprene, EPDM, polybutadine, and SBR were studied at 25, 40, and 60°C. From the data, the Arrhenius activation parameter for diffusion, E_D, was determined. From the temperature dependence of the sorption constant, the enthalpy of sorption, ΔH, and entropy of sorption, ΔS, were also determined. The activation parameters are found to follow the conventional trend. Transport properties are affected by the nature of the interaction of solvent molecule, by its size, and also by the structural variation of the elastomers. For all the solvents, the polymer blends remained intact but the blends in the presence of benzaldehyde showed degradative reactions at higher temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 101–112, 1998     

Sorption and diffusion of water into melamine–formaldehyde‐incorporated poly(vinyl acetate)–polyester nonwoven fabric composites

A series of composites were fabricated by impregnating a polyester nonwoven fabric with melamine–formol (MF)‐incorporated poly(vinyl acetate) (PVAc) latex. The effect of different weight ratios of MF/PVAc, i.e. 0/100, 5/100, 10, 100, 15/100 and 20/100 (dry, wt/wt), on the water sorption and diffusion into the composites was evaluated. Water sorption studies were carried out at different temperatures, i.e. 30, 50 and 70 °C, based on the immersion weight gain method. From the sorption results, the diffusion (D) and permeation (P) coefficients of water penetrant were calculated. A significant increase in the diffusion and permeation coefficients was observed with an increase in the temperature of sorption. Drastic reductions in diffusion and permeation coefficients were noticed with increasing MF content in the composites. Attempts were made to estimate the empirical parameters like n, which suggests the mode of transport, and K, a constant which depends on the structural characteristics of the composite in addition to its interaction with water. The temperature dependence of the transport coefficients was used to estimate the activation energy parameters for diffusion (E_D) and permeation (E_p) processes from Arrhenius plots. Copyright © 2006 Society of Chemical Industry     

Benzene,Toluene and p‐xylene Interactions and the Role of Microbial Communities in Remediation Using Bioventing

Aromatic hydrocarbons, particularly benzene, toluene and xylene (BTX), are major contaminants at many hazardous waste sites. We studied volatilization and biodegradation of BTX from unsaturated soil through bioventing. Following inoculation with indigenous soil microorganisms obtained from the Dagang Oil Field in Tianjin, China, varying amounts of BTX were added to soil in a stainless steel column provided with a constant flow of CO₂‐ free air and pure N₂. Volatilization‐to‐biodegradation ratios of benzene, toluene and p‐xylene were 6:1, 2:1 and 2:1 respectively. Final concentrations recorded in soil gas after three weeks were 0.128 mg/L benzene, 0.377 mg/L toluene and 0.143 mg/L p‐xylene. Interactions between the contaminants occurred: benzene and p‐xylene degradation were accelerated while toluene was being degraded, and the presence of p‐xylene increased the lag period for benzene degradation.     

Effect of adhesion on the equilibrium swelling of natural rubber-aluminium powder composites

Equilibrium swelling of natural rubber composites containing aluminium powder has been investigated in a series of aromatic hydrocarbon solvents, such as benzene, toluene, xylene, and mesitylene. These composites were vulcanized by four vulcanizing systems, viz. conventional, efficient, dicumyl peroxide, and a mixture, consisting of sulfur and dicumyl peroxide. In each system, the effect of aluminium powder with and without bonding agent was studied. The results showed that addition of bonding agent reduced the swelling considerably, and its effect is more pronounced in the conventional system due to increased adhesion. The dependence of the diffusion coefficient on the crosslinking system and the solvent–polymer interaction parameter were calculated from diffusion data. These results are also indicative of the improved adhesion with hexa-resorcinol–silica bonding system in these composites. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2427–2438, 1998     

Diffusion of benzene vapor in blends of poly(vinyl acetate) and poly(methyl acrylate)

Sorption and diffusion of benzene in miscible blends of poly(vinyl-acetate), PVAc, and poly(methyl acrylate), PMA, have been studied. The polymer-polymer interaction parameter values calculated from equilibrium vapor sorption data were all negative, indicating favorable interaction between the two polymers. The sorption of benzene vapor into these blends was measured at a temperature above the T_g's of the pure polymers and found to obey Fickian kinetics. The mutual diffusion coefficients were estimated from the initial slopes of the sorption curves. The concentration dependent diffusion coefficients were fitted to the empirical relation D = D_o exp(αC) which satisfactorily correlated the data. Values of the constant D_o were found to vary continuously with blend composition, while the α values did not. These experimental data were analyzed employing Fujita's free volume theory. It was found that the data was consistent with this theory. If the f_o values for the blends are assumed to be the weighted average of the component polymers, then the β parameter values for the blends also obey the additivity rule.     

Interaction of silica and carbon black fillers with natural rubber/poly(ethylene‐co‐vinyl acetate) matrix by swelling studies

The interaction of a black filler and a white filler, which are extensively used in the rubber industry, with natural rubber/poly (ethylene‐co‐vinyl acetate) (NR/EVA) blends vulcanized by DCP has been examined by equilibrium swelling technique. Blends loaded with intermediate super abrasion furnace black (ISAF) and those with silica (SiO₂), of same loading, have been used. The silica incorporated blends sorbed a higher amount of aromatic solvents, compared with the ISAF filled blends, when NR was the continuous phase. However, the silica filled systems showed lower sorption characteristics when EVA became the continuous phase. This has been explained in terms of the differences in the interaction between the filler particles and the blend components. The swelling coefficient, diffusion coefficient, and molar mass between crosslinks have been computed to complement the experimental observations. POLYM. COMPOS., 28:705–712, 2007. © 2007 Society of Plastics Engineers     

Characterization and transport properties of ceramic filler incorporated natural rubber composites

Crystalline glass–ceramic fillers were prepared from calcium carbonate, silica, alumina, and calcium fluoride by heating and subsequent quenching in cold water. The fillers were incorporated into natural rubber (1,4-cis-polyisoprene) and the filled rubber composites were crosslinked with sulfur in the presence of different rubber additives. The unfilled and filled rubber composites were characterized. The transport properties of benzene, toluene, and p-xylene (BTX) through the rubber composites were studied in terms of sorption, diffusion, permeation, and mass transfer coefficients. The effect of the ceramic fillers on the mechanical, thermal and transport properties were studied. The sorption data at different temperatures were used for calculating activation energy of diffusion, permeation, free energy, and enthalpy of sorption. The BTX remained in the liquid state within the composite matrix as evident from negative ΔS. The diffusion coefficient (D) and mass transfer coefficient (k_mtc) of BTX decreased with the increase in filler loading. Accordingly, for the transport of BTX the unfilled rubber showed a D (D × 10⁷ cm²/s) and mass transfer coefficient (k_mtc × 10⁴ cm/s) of 5.67/3.97/2.96 and 7.71/7.08/7.04, respectively which decreased to 5.06/2.95/2.57 and 7.53/6.95/6.90, respectively for the composite containing 50 wt.% ceramic filler.     

Surface resistance and diffusion characteristics of toluene into calcium carbonate‐ and polymer‐coated calcium carbonate‐filled natural rubber composites

Solvent absorption has been followed in compression‐molded rubber vulcanizates for toluene in natural rubber (gum), calcium carbonate (CC)‐filled natural rubber composites, and polymer‐encapsulated calcium carbonate (PCC)‐filled natural rubber composites. The surface resistance is found to affect the absorption process of the composites. Diffusion from the sample sides is considered for thickness and the diffusion coefficients corrected accordingly. Aspects of the effect of PMMA on the equilibrium toluene take up, Fickian mode of transport; transport coefficients; activation parameters; and crosslink density are studied. The sorption results have been interpreted in terms of first‐order kinetic model. The crosslink densities calculated from equilibrium sorption successfully to explain the transport coefficient values of the composites. POLYM. ENG. SCI., 53:2487–2497, 2013. © 2013 Society of Plastics Engineers     

Interfacial properties and initial step of the water sorption in unidirectional unsaturated polyester/vegetable fiber composites

In this work the interfacial properties of polyester/vegetable fiber composites were analyzed by flexural testing. The compressive/tensile (σ) and shear (τ) stresses were determined for each composite in function of the span-to-depth ratio (λ). The general behavior of the composites was similar to that of composites reinforced with DuPont Kevlar fiber, i.e., a maximum σ stress value is obtained. Flexural test validity for determining the Young's and shear moduli, E₁₁ and G₁₂, was ascertained. The Young's modulus agreed with that expected from the rule of mixtures for the composites with lowest fiber content. Short beam tests were performed on the composites. The shear stress value was improved by means of the matrix modification. Moisture sorption experiments and dynamic mechanical analysis were also performed on the natural fiber composites in the first Fickian step. Water sorption at 50% RH and 90% RH can be satisfactorily described by using a diffusional model. Water diffusion on parallelepiped samples shows a positive deviation from the Fickian behavior. Fiber capillary flow occurs through the fiber and the debonded matrix/fiber interphase during the initial Fickian step.     

Diffusion and sorption of nitroplasticizers in vinyl copolymer elastomer and its composites

To study the aging behavior of cured vinyl copolymer elastomer (VCE) under thermal and nitroplasticizer (NP) environment, we investigated the sorption and diffusion of NP in VCE and its composites. The sorption kinetics of NP into VCE and its composites with respect to filler concentration (0–80%) and temperature (18–70°C) were investigated by conventional gravimetric method. The NP sorption process is endothermic. Kinetic studies show that Fickian diffusion can describe the NP sorption in the VCE polymer. The samples with a high filler concentration show more complicated behavior at low temperature than that at high temperature. The present article discusses the dependences of diffusion coefficient and other related parameters on the polymer concentration and morphological structures of the samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40729.     

Moisture sorption of a three‐dimensional braided carbon fiber–epoxy composite under different media

A three‐dimensional braided carbon fiber–epoxy (C_3D/EP) composite was prepared by the vacuum‐assisted resin transfer molding (VARTM) technique. Its moisture absorption behavior under different media was characterized and compared with a unidirectional composite. Similar to the unidirectional composite, diffusion in the 3D composite obeys Fick's second law of diffusion when immersed in distilled water and phosphate‐buffered saline. In HCl and NaOH solutions, no Fickian behavior was observed. The similarity between the unidirectional and 3D composites suggests that fiber structure does not change diffusion pattern. However, the two composites showed different diffusion parameters (k, D, and M_e) in each medium studied. The 3D composite showed lower k, D, and M_e values because of its stronger hindrance effect to transport of moisture molecules. Diffusion in PBS is slower than that in distilled water because of the presence of heavy ions, but the diffusion pattern remains unchanged. In HCl, the diffusion behavior of the two composites cannot be described by Fick's law. In addition, the k value calculated from the initial linear part of the moisture sorption curve is much lower than that in distilled water. Diffusion in NaOH is unusual; the uptake initially increases rather rapidly but quickly drops, which is likely caused by the extensive solubility of the polymer matrix. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 507–512, 2005     

Experimental and simulation studies on molecular transport of substituted monocyclic aromatic liquids into fluoropolymer sheet membranes: Liquid structure–diffusion, –sorption,and –permeation relationships

The present study reports an investigation on the molecular transport of 10 monocyclic aromatic liquids (benzene, chlorobenzene, 1,2‐dichlorobenzene, bromobenzene, toluene, p‐xylene, trimethylbenzene, ethylbenzene, methoxybenzene, and ethoxybenzene) at 40 and 50°C through sheet polymeric membranes (FLS‐2650) using a sorption gravimetric technique. Diffusion and permeation coefficients of these liquids were calculated from the sorption data using Fick's diffusion equation. Sorption results were analyzed typically in the case of benzene and chlorobenzene to compute the concentration profiles at different depths along the thickness direction of the sheet membranes and at different time intervals by solving the Fick's equation under appropriate boundary conditions, based on the numerical simulation method developed in “C” language using a finite‐difference method. Transport results were analyzed to establish the relationships between the penetrating liquid structures with diffusion, permeation, and sorption data. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 991–996, 2004     

Transport of organic solvents through coir-fiber-reinforced natural rubber composites: a method for evaluating interfacial interaction

Use is made of the transport of organic solvents such as benzene, toluene and xylene to understand the interfacial interaction in cross-linked coir-fiber-reinforced natural rubber composites. Attempts were made to analyze the interfacial bonding in the composites containing coir fibers subjected to different chemical treatments. Based on experiments, a probable mechanism of transport is suggested. The diffusion coefficient and solubility in the rubber compound–solvent system have been evaluated. The swelling of composites containing untreated and NaOH-treated coir increased initially with fiber loading, but decreased at higher levels of fiber loading. But the swelling of composites which contained coir fiber treated with solutions of NaOH, toluene diisocyanate and natural rubber decreased gradually with fiber loading. It was also found that the swelling of this composite was the least. This is due to the high interfacial interaction between the fiber and the matrix which resists the uptake of organic solvents. It was seen that silica was not a necessary constituent of the bonding system for coir fiber reinforced natural rubber composites.