Modification of tetraethylorthosilicate crosslinked poly(vinyl alcohol) membrane using chitosan and its application to the pervaporation separation of water–isopropanol mixtures

Tetraethylorthosilicate crosslinked poly(vinyl alcohol) membrane was modified by varying the amounts of chitosan. The resulting membranes were characterized by Fourier transform infrared spectroscopy and differential scanning calorimetry. The effects of chitosan content and feed composition on the pervaporation performance of the membranes were analyzed. The modified membranes exhibit simultaneous increase of both flux and selectivity. The membrane containing 15 mass % of chitosan shows the highest separation selectivity of 2991, with a flux of 2.39 × 10^?2 kg/(m² h) at 30°C for 10 mass % of water in the feed. The total flux and flux of water are almost overlapping each other, manifesting that the membranes could be used effectively to break the azeotropic point of water–isopropanol mixture, so as to remove water from the isopropanol. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The activation energy values obtained for water permeation (E_pw) are significantly lower than those of isopropanol permeation (E_pIPA), suggesting that the membranes developed here have higher separation ability for water–isopropanol system. In addition, difference was negligibly small between the activation energy values of total permeation (E_p) and water permeation (E_pw), indicating that coupled transport is minimal because of a higher selective nature of membranes. The E_p and E_D values ranged between 40.92 and 52.60, and 39.58 and 52.47 kJ/mol, respectively. The positive heat of sorption (ΔH_s) values observed in all the membranes suggests that Henry's mode of sorption is predominant. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1380–1389, 2006     

Preparation and characterization of Silicalite‐1/PDMS surface sieving pervaporation membrane for separation of ethanol/water mixture

To improve the pervaporation performance of Silicalite‐1/PDMS composite membrane by adding a small amount of Silicalite‐1 zeolite, novel Silicalite‐1/PDMS surface sieving membranes (SSMs) were prepared by attaching Silicalite‐1 particles on the PDMS membrane surface. The obtained membranes and traditional mixed‐matrix membranes (MMMs) were characterized by SEM, XRD, TGA, FT‐IR, and pervaporation separation of ethanol–water mixture. Effects of Silicalite‐1 particles content, feed temperatures, and feed compositions on the separation performance were discussed. From the cross‐section view SEM images of SSMs, a two‐layer structure was observed. The thickness of the Silicalite‐1 layer was about 300 nm to 2 μm. The TGA analysis indicates that the zeolite concentration in 3 wt % SSM is lower than 10 wt % MMMs. In the ethanol/water pervaporation experiment, the separation factor of Silicalite‐1/PDMS SSMs increased considerably compared with pure PDMS membrane. When the suspensions concentrations of Silicalite‐1 particles reached 3 wt %, the separation factor was about 217% increase over pure PDMS membrane and 52.9% increase over 10 wt % Silicalite‐1/PDMS MMMs. As the ethanol concentration in the feed increases, the separation factor of SSMs increases, whereas permeation flux decreases. At the same time, with increasing operating temperature, the permeation flux of SSMs increased. The stability of SSMs at high temperature is better than the traditional MMMs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42460.     

Genipin‐cross‐linked chitosan‐based hydrogels: Reaction kinetics and structure‐related characteristics

The main aim of this work is the synthesis and characterization of cross‐linked chitosan systems. Chitosan hydrogels can be prepared by physical or chemical cross‐linking of polymer chains. Chemical cross‐linking, leading to the creation of hydrogel networks possessing improved mechanical properties and chemical stability, can be achieved using either synthetic agents or natural‐based agents. In this work, the cross‐linker Genipin, a naturally derived compound, was selected because of the lower acute toxicity compared to many other commonly used synthetic cross‐linking reagents. In particular, the chemical stabilization of chitosan through genipin cross‐linking molecules was performed and characterized by calorimetric analyses (differential scanning calorimetry), swelling measurements in different pHs, and ionic strength. The reaction kinetics was carried out by means of rheological measurements, and both the activation energy (E_a) and the reaction order (m) were calculated. The hydrogel analyses were carried out at different concentrations of genipin (GN1 and GN2). The results were used to evaluate the possibility to use the chemical cross‐linked chitosan–genipin hydrogel for biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42256.     

Peroxide induced cross‐linking by reactive melt processing of two biopolyesters: Poly(3‐hydroxybutyrate) and poly(l‐lactic acid) to improve their melting processability

Poly(3‐hydroxybutyrate) (PHB) and poly(l ‐lactic acid) (PLLA) were individually cross‐linked with dicumyl peroxide (DCP) (0.25–1 wt %) by reactive melt processing. The cross‐linked structures of the polymer gel were investigated by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopies. The size of the polymer crystal spherulites, glass transition temperature (T_g), melting transition temperature (T_m), and crystallinity were all decreased as a result of cross‐linking. Cross‐linking density (ν_e) was shown to increase with DCP concentration. Based on parallel plate rheological study (dynamic and steady shear), elastic and viscous modulus (G″ and G′), complex viscosity (η^*) and steady shear viscosity (η) were all shown to increase with cross‐linking. Cross‐linked PHB and PLLA showed broader molar mass distribution and formation of long chain branching (LCB) as estimated by RheoMWD. Improvements in melt strength offer bioplastic processors improved material properties and processing options, such as foaming and thermoforming, for new applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41724.     

Modification of highly brittle polystyrene sulfonic acid-co-maleic acid crosslinked sodium alginate membrane into flexible membranes by the incorporation of dibutyl phthalate as a plasticizer for pervaporation separation

To convert highly brittle into flexible membrane, the polystyrene sulfonic acid-co-maleic acid crosslinked sodium alginate (PSSAMA/NaAlg) membrane was modified by incorporating the different weight% of dibutyl phthalate (DBP) as a plasticizer. The effect of DBP content on the physico-chemical properties of the membranes was thoroughly examined. The membranes exhibited lower glass transition temperatures with increasing the plasticizer content in the matrix of PSSAMA/NaAlg. The separation performance of the membranes for water/isopropanol and water/1,4-dioxane was studied at different temperatures. Among the modified membranes, the membrane containing 6 wt% of DBP exhibited the highest separation factors of 24,129 with a flux of 13.57 × 10⁻² kg/m² hr and 23,353 with a flux of 12.99 × 10⁻² kg/m² hr for water/isopropanol and water/1,4-dioxane at 30°C, respectively. From the temperature-dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The estimated activation energy values for permeation of water (E_pw) and isopropanol (E_pIPA) were, respectively, ranged between 12.09 and 8.79, and 42.52 and 32.79 kJ/mol. A negative heat of sorption (ΔH_s) values was obtained for all the membranes, suggesting that Langmuir's mode of sorption was predominant. Based on the results, it is concluded that the modified membranes demonstrated excellent pervaporation performance for the separation of water/isopropanol and water/1,4-dioxane.     

Development of novel grafted hybrid PVA membranes using glycidyltrimethylammonium chloride for pervaporation separation of water–isopropanol mixtures

Tetraethylorthosilicate incorporated hybrid poly(vinyl alcohol) membranes were grafted with glycidyltrimethylammonium chloride (GTMAC) in different mass%. The resulting membranes were subjected to physico-chemical investigations using Fourier transform infrared (FTIR) spectroscopy, wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA) and scanning electron microscopy (SEM). The effects of grafting and feed composition on pervaporation performance of the membranes were systematically investigated. The membrane containing 30 mass% of GTMAC exhibited the highest separation selectivity of 1570 with a flux of 1.92 × 10^?2 kg/m² h at 30 °C for 10 mass% of water in the feed. The total flux and flux of water are almost overlapping each other, manifesting that these membranes could be used effectively to break the azeotropic point of water–isopropanol mixtures. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The activation energy values obtained for water permeation (E_pw) are two to three times lower than those of isopropanol permeation (E_pIPA), suggesting that the developed membranes have higher separation ability for water–isopropanol system. The E_p and E_D values ranged between 63.73 and 33.07, and 62.78 and 32.75 kJ/mol, respectively. The positive heat of sorption (ΔH_s) values was obtained for all the membranes, suggesting that Henry's mode of sorption is predominant in the process.     

The influence of cross‐linking reaction on the mechanical and thermal properties of polyarylene ether nitrile

The processing of cross‐linked polyarylene ether nitrile (PEN), which has a triazine rings structure, has been investigated under different reaction times and temperatures. In this study, the PEN films prepared by the tape‐casting formed the thermally stable triazine rings by catalytic cross‐linking reaction gradually, which was characterized by Fourier transform infrared spectroscopy. The chemical cross‐linking reaction occurred as the CN group absorption of PEN at 2221 cm⁻¹ decreased and a new absorption peak, at 1682 cm⁻¹, was observed, and the absorption peak intensity would be progressively larger, with the extension of the processing time. After the formation of cross‐linking networks, the cross‐linking degree and thermal and mechanical properties of the processed films were improved substantially, compared with the untreated films. The film with added ZnCl₂ as the catalyst was more rapidly cross‐linked, and its properties were better than that without catalyst at the same treatment conditions. The glass‐transition temperature (T_g) of PEN films processed at 350°C for 4 h (213.65°C) was higher than that of PEN films before the treatment (161°C), and the tensile strength was also improved significantly. The PEN was processed at 350°C for 2 h, whose initial decomposition temperature increases by about 10°C, compared with that of untreated film, at one time. The rheology behavior of the cross‐linked films was processed on dynamic rheometer to monitor and track the process of polymer cross‐linking reaction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Pervaporation of tertiary butanol/water mixtures through chitosan membranes cross‐linked with toluylene diisocyanate

Membranes made from 84% deacetylated chitosan biopolymer were cross‐linked by a novel method using 2,4‐toluylene diisocyanate (TDI) and tested for the separation of t‐butanol/water mixtures by pervaporation. The unmodified and cross‐linked membranes were characterized by Fourier transform infra red (FTIR) spectroscopy, X‐ray diffraction (XRD) studies and sorption studies in order to understand the polymer–liquid interactions and separation mechanisms. Thermal stability was analyzed by differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA) while tensile strength measurement was carried out to assess mechanical strength. The membrane appears to have good potential for breaking the aqueous azeotrope of 88.2 wt% t‐butanol by giving a high selectivity of 620 and substantial water flux (0.38 kg m^?2 hr^?1). The effects of operating parameters such as feed composition, membrane thickness and permeate pressure on membrane performance were evaluated. Copyright © 2005 Society of Chemical Industry     

Dehydration of THF‐water mixtures using zeolite‐incorporated polymeric membranes

Using a solution technique, polymeric composite membranes were prepared by the incorporation of NaY zeolite into chitosan. The resulting membranes were tested for pervaporation separation of water–tetrahydrofuran mixtures in a temperature range of 30–50°C. The effect of membrane swelling on the separation performance was studied by varying the water composition in the feed from 5 to 30 mass %. Pervaporation data demonstrated that both flux and selectivity increased simultaneously with increasing zeolite content in the membrane. This was explained on the basis of enhancement of hydrophilicity, selective adsorption, and establishment of molecular sieving action. It was found that both total flux and flux of water are close to each other, suggesting that the developed membranes are highly selective toward water. The membrane containing the highest loading of zeolite exhibited the highest separation selectivity of 2140 with a substantial water flux of 16.88 × 10^?2 kg/(m² h) at 30°C for 5 mass % of water in the feed. From the temperature dependency of diffusion and permeation data, the Arrhenius activation parameters were estimated. A significant difference was noticed between E_pw and E_pTHF, E_Dw and E_DTHF values, signifying that membranes developed with higher loading of zeolite exhibited remarkable separation selectivity toward water. The E_p and E_D values ranged between 11.69 and 21.23, and 11.21 and 20.72 kJ/mol, respectively. All the membranes exhibited positive ΔH_s values, suggesting that the heat of sorption is still dominated by Henry's mode of sorption. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Multi‐point monitoring of cross‐linking reactions

The feasibility of deploying optical fiber sensors to obtain qualitative and quantitative information on the cross‐linking characteristics of thermosetting resin systems has been demonstrated by a number of researchers. This article is concerned with the demonstration of a low‐cost fiber‐optic Fresnel sensor system for monitoring the cross‐linking reactions at multiple locations. Cross‐linking reactions can be influenced by a number of parameters including the stoichiometry of the resin and hardener, and the heat‐transfer rates in and out of the preform as a function of the cross‐section of the preform. In situations where there is a variation in the thickness of the preform or when large components are processed, a facility to monitor the cross‐linking reactions at multiple locations will be valuable because the rate and extent of the cross‐linking can be inferred. In this article, six Fresnel sensors were immersed in individual vials containing an epoxy/amine resin system and processed (cross‐linked) in an air‐circulating oven. One additional vial with a Fresnel sensor immersed in the neat epoxy resin (no hardener) was co‐located in the oven to enable the effect of temperature to be monitored. The feasibility of using the multiplexed Fresnel sensors for cure monitoring was demonstrated successfully. The sensors in the post‐cross‐linked samples were used to study the effects of heating and cooling cycles. The feasibility of detecting the glass transition temperature using the Fresnel sensor is discussed along with the factors that give rise to variability in the output Fresnel signals. © 2014 The Authors. Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41088.     

Preparation and high oxygen‐enriching properties of cross‐linking polydimethylsiloxane/SiO2 nanocomposite membranes for air purification

Nanocomposite membrane based on polydimethylsiloxane (PDMS) and nanoscale SiO₂ particles were prepared by a convenient and mild sol–gel copolymerization of tetraethoxysilane as well as cross‐linking reaction. The oxygen‐enriching properties of cross‐linking PDMS/SiO₂ nanocomposite membranes containing different silica conversion and SiO₂ contents were investigated. The results showed that the nanocomposite membranes exhibited good membrane‐forming ability, superior mechanical properties, and high solvent resistance as well as excellent oxygen‐enriching properties for air purification. The oxygen‐enriching performance was regulated by the organic/inorganic ratio and silica conversion in the sol–gel synthesis process. Permeability and selectivity could increase simultaneously with the addition of nanoscale SiO₂. The oxygen permeation coefficient of the nanocomposite membrane increased to 680 Barrer and oxygen/nitrogen separation factor kept 3.0 or so, both higher than those of the corresponding pure PDMS membrane. The high oxygen‐enriching properties of the nanocomposite membranes arose from the introduction of SiO₂ particles, the sol–gel copolymerization, and cross‐linking method. © 2012 American Institute of Chemical Engineers AIChE J, 59: 650–655, 2013     

Preparation and properties of novel boric acid modified poly(aryl ether sulfone) membranes

In this article, boric acid‐modified poly(aryl ether sulfone) (PES‐B) membranes were prepared by solution blending, solution casting, evaporation, and programmed temperature curing method for the first time. The chemical modification of poly(aryl ether sulfone) was accomplished by the curing of poly(aryl ether sulfone) with pendent phenyl hydroxide (PES‐OH) under the function of boric acid. The reaction mechanisms and the effects of boric acid content were thoroughly investigated. Processing conditions and structures of PES‐B were determined by FT‐IR spectra. It has been found that the B(OH)₃/PES composite membranes were completely cured after treatment at 300°C for 4 h. When boric acid content was over 4.7%, PES‐B membranes presented phase separation and full cross‐linking structures. DSC measurements demonstrated that the addition of boric acid had influenced the glass transition temperature of PES‐B, which provided the proof of the appearance of cross‐linking network structure. TGA results confirmed that the thermal stability of the prepared PES‐B composites was improved. Furthermore, the cross‐linked composite membranes exhibited excellent mechanical property and solvent resistance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40860.     

A comparison of triazole cross‐linked polymers based on poly‐AMMO and GAP: Mechanical properties and curing kinetics

Triazole cross‐linked polymers based on poly(3‐azidomethyl‐3‐methyl oxetane) (poly‐AMMO) and glycidyl azide polymer (GAP) were prepared using bis‐propargyl‐1,4‐cyclohexyl‐dicarboxylate (BPHA) as curing agent, respectively. Swelling tests demonstrated that cross‐linking densities of the resulted polymers both increased with the increase of BPHA. Triazole cross‐linked polymers based on poly‐AMMO showed superior tensile strength and elongation at break than those of GAP at comparable stoichiometry. The curing kinetics was also investigated by FTIR, and GAP exhibited faster reaction rate when reacted with BPHA than that of poly‐AMMO. In addition, with the increase of cross‐linking density, the glass transition temperature (T_g) of as‐prepared polymers significantly increased, and poly‐AMMO‐based polymers showed stronger T_g‐raising effect than GAP‐based polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43341.     

Preparation of zeolite‐incorporated poly(dimethyl siloxane) membranes for the pervaporation separation of isopropyl alcohol/water mixtures

ZSM‐5 zeolite‐incorporated poly(dimethyl siloxane) membranes were prepared, and the molecular dispersion of the zeolite in the membrane matrix was confirmed with scanning electron microscopy. After the swelling of the membranes was studied at 30°C, the membranes were subjected to the pervaporation separation of isopropyl alcohol/water mixtures at 30, 40, and 50°C. The effects of the zeolite loading and feed composition on the pervaporation performances of the membranes were analyzed. Both the permeation flux and selectivity increased simultaneously with increasing zeolite content in the membrane matrix. This was examined on the basis of the enhancement of hydrophobicity, selective adsorption, and the establishment of molecular sieving action. The membrane containing the highest zeolite loading (30 mass %) had the highest separation selectivity (80.84) and flux (6.78 × 10^?2 kg m^?2 h^?1) at 30°C with 5 mass % isopropyl alcohol in the feed. From the temperature dependence of the diffusion and permeation values, the Arrhenius activation parameters were estimated. A pure membrane exhibited higher activation energy values for permeability (E_p) and diffusivity (E_D) than zeolite‐incorporated membranes, and signified that permeation and diffusion required more energy for transport through the pure membrane because of its dense nature. Obviously, the zeolite‐incorporated membranes required less energy because of their molecular sieving action, which was attributed to the presence of straight and sinusoidal channels in the framework of the zeolite. For the zeolite‐incorporated membranes, the activation energy values obtained for isopropyl alcohol permeation were significantly lower than the water permeation values, and this suggested that the zeolite‐incorporated membranes had higher selectivity toward isopropyl alcohol. The E_p and E_D values ranged between 21.81 and 31.12 kJ/mol and between 15.27 and 41.49 kJ/mol, respectively. All the zeolite‐incorporated membranes exhibited positive values of the heat of sorption, and this suggested that the heat of sorption was dominated by Henry's mode of sorption. sorption. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1377–1387, 2005     

Divinyl benzene cross‐linked HTPB‐based polyurethaneurea membranes for separation of p‐/o‐xylene mixtures by pervaporation

Cross‐linked hydroxy terminated polybutadiene (HTPB)‐based polyurethaneurea (PU), HTPB‐divinyl benzene (DVB)‐PU, was synthesized by a three‐step polymerization process. It was first used as membrane material to separate p‐/o‐xylene mixtures by pervaporation (PV). The effects of the content of cross‐linker DVB, feed concentration, and operating temperature on the PV performance of HTPB‐DVB‐PU membranes were investigated. The membranes demonstrated p‐xylene permselectivity as well as high total flux. The introduction of DVB significantly enhanced the temperature resistance ability of the HTPB‐DVB‐PU membranes. With increasing DVB content, the separation factor increased while the total flux decreased a little. The highest separation factor reaches 2.01 and the total flux is 33 g/m²h with feed concentration of 10 wt % p‐xylene at 30°C. These PV performances with increasing DVB content were explained in terms of the view point of chemical compositions and physical structures of the HTPB‐DVB‐PU membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and pervaporation performance of chitosan‐poly(methacrylic acid) polyelectrolyte complex membranes for dehydration of 1,4‐dioxane

Polyelectrolyte complex (PEC) membranes composed of chitosan (CS) and poly(methacrylic acid) (PMAA) were prepared by mixing the polymer solutions in different ratios. The chemical interaction and crystallinity of the resulting PEC membranes were respectively analyzed by Fourier transform infrared spectroscopy (FTIR) and wide‐angle X‐ray diffraction (WAXD). Differential scanning calorimetry (DSC) was used to characterize the thermal properties of the membranes. The membranes thus obtained were subjected to pervaporation (PV) separation of water‐dioxane mixtures. Among the PEC membranes, membrane containing 30 wt% ratio of PMAA (M‐3) exhibited the highest separation selectivity of 840 with a flux of 12.07 × 10^?2 kg/m²h at 30°C at 15 wt% of water in the feed. By the incorporation of NaY zeolite into PEC up to 5 wt%, we have been able to overcome the trade‐off phenomenon existing between flux and selectivity in PV process. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The resulting activation energy values obtained for water permeation (E_pw) are much lower than those of dioxane permeation (E_po), suggesting that the developed membranes have higher separation efficiency for water‐dioxane system. Based on the heat of sorption (ΔH_s) values, the mode of sorption was discussed. POLYM. ENG. SCI., 56:715–724, 2016. © 2016 Society of Plastics Engineers     

Chemically amplified,positive tone,cross‐linkable thick‐film polymer

A new class of positive tone, permanent materials has been demonstrated, which are chemically amplified (CA), aqueous‐developable, and cross‐linkable. The intended purpose is a patterning and cross‐linking method to create high sensitivity permanent dielectrics for microelectronic devices and packages. The photochemistry is based on traditional CA, acid‐catalyzed deprotection of a protected organic functionality to yield an aqueous base soluble group such as a carboxylic acid or alcohol. This CA chemistry produces high contrast and high photo‐speed patterning, which is especially valuable for thick‐film applications where high UV exposure doses are required for non‐CA materials. The photospeed is about an order of magnitude faster than commercial materials at a similar thickness. Subsequent to patterning, the remaining films or features can be cross‐linked by a variety of chemical mechanisms. The working photo‐patterning and cross‐linking mechanisms are demonstrated on a random copolymer of tert‐butyl methacrylate (TBMA) and 2‐hydroxyethyl methacrylate (HEMA). The optical contrast (at 248 nm) was found to be 12.7 and the sensitivity, D₁₀₀, was calculated to be 50.2 mJ/cm² in a 9.07‐μm‐thick film. Undeveloped regions were cross‐linked after patterning. The esterification reaction is much slower than the TBMA deprotection, so that the cross‐linking reaction does not interfere with the photopatterning. Cross‐linking was also evident by the change in thin film stress 6.2 to 17.9 MPa during a thermal cure. Other polymers for Fischer esterification are discussed with their advantages and disadvantages along with other cross‐linking chemistries. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 759‐765, 2013     

Pervaporation separation of water–acetic acid mixtures through NaY zeolite‐incorporated sodium alginate membranes

The pervaporation (PV) separation and swelling behavior of water–acetic acid mixtures were investigated at 30, 40, and 50°C using pure sodium alginate and its zeolite‐incorporated membranes. The effects of zeolite loading and feed composition on the pervaporation performance of the membranes were analyzed. Both the permeation flux and selectivity increased simultaneously with increasing zeolite content in the polymer matrix. This was discussed on the basis of a significant enhancement of hydrophilicity, selective adsorption, and molecular sieving action, including a reduction of pore size of the membrane matrix. The membrane containing 30 mass % of zeolite showed the highest separation selectivity of 42.29 with a flux of 3.80 × 10^?2 kg m^?2 h^?1 at 30°C for 5 mass % of water in the feed. From the temperature dependency of diffusion and permeation data, the Arrhenius activation parameters were estimated. The E_p and E_D values ranged between 72.28 and 78.16, and 70.95 and 77.38 kJ/mol, respectively. The almost equal magnitude obtained in E_p and E_D values signified that both permeation and diffusion contribute equally to the PV process. All the membranes exhibited positive ΔH_s values, suggesting that the heat of sorption is dominated by Henry's mode of sorption. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2101–2109, 2004     

Plasticizer migration from cross‐linked flexible PVC: Effects on tribology and hardness

Uses of flexible poly(vinyl chloride) (PVC) are restricted by plasticizer migration affecting material properties. Moreover, the use of phthalate‐based plasticizers is being questioned worldwide because of their potential toxicity to humans and environment. Chemical modification of PVC structure is one of the most effective tools for reduction of plasticizer diffusion. In this work, a flexible dry blend based on cross‐linked PVC was obtained using a difunctional amine, namely isophoron diamine (IPDA) as the cross‐linking agent. The gel fraction was evaluated from insoluble portions obtained by means of solvent extraction; the efficiency of cross‐linking in reducing the plasticizer leaching was evaluated by migration tests. Effects of addition of IPDA on PVC thermal stability were determined by thermogravimetric analysis (TGA). The cross‐linking reaction turned out to be responsible for accelerating thermal degradation. Tribological properties of flexible uncross‐linked, cross‐linked and rigid PVC were determined. Flexible formulations were held in contact for 32 days with rigid PVC sheets. Plasticizer migration towards the interface caused an increase of dynamic friction compared to that of the reference rigid PVC.Vickers microhardness h_Vickers values of rigid PVC sheets decreased due to plasticizer surface absorption. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Effects of polyisocyanate on properties and pot life of epoxy resin cross‐linked soybean meal‐based bioadhesive

In this study, polyisocyanate (pMDI) was introduced into epoxy resin modified soybean meal‐based bioadhesive to address the issue of low dry bond strength. Specifically, we investigated the effects of adding pMDI in terms of amount and storage time on dry bond strength, water resistance, and pot life of adhesive. Factors examined included shear strength, apparent viscosity, chemical reaction, crystallinity, and morphology of modified adhesives. Results indicated that the dry bond strength and water resistance of the resultant plywood was respectively improved 29.5% and 39.7% by adding 2% pMDI. In addition, the pot life of modified adhesive reached in 4 h. Results also shown that the cross‐linking reactions between epoxy group and carbonyl as well as isocyano and amino increased the cross‐linking density and formed a denser cross‐linking network structure of cured adhesive. The composite cross‐linked soybean meal‐based adhesive is environmental‐friendly and high‐performance, which will promote the industrial application of the soy protein‐based adhesives. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43362.