Mechanical and barrier properties of carbon nanotube reinforced PCL‐based composite films: Effect of gamma radiation

Carbon nanotube (CNT) reinforced (0.05–0.5% by wt) polycaprolactone (PCL)‐based composites were prepared by compression molding. Addition of 0.2% CNT caused a 131% improvement of tensile strength (TS) of PCL films. The tensile modulus (TM) and elongation at break (Eb) of PCL were also significantly improved with the addition of CNT. The water vapor permeability of PCL was 1.51 g·mm/m²·day but 0.2% CNT containing PCL films showed 1.08 g·mm/m²·day. Similarly, the oxygen transmission rate (OTR) of PCL films was found to decrease with the addition of CNT. But, carbon dioxide transmission rate (CO₂TR) of PCL film was improved due to incorporation of CNT. Effect of gamma radiation on PCL films and CNT reinforced PCL‐based composites were also studied. The TS of the irradiated (10 kGy) PCL films gained to 75% higher than control sample. The TS of the 0.2% CNT reinforced composite film was reached to 41 MPa at 15 kGy dose. The barrier properties of non‐irradiated and irradiated (10 kGy) PCL films and composites (0.2% CNT reinforced) were also measured. Both PCL films and composites showed lower values of WVP upon irradiation and indicated better water vapor barrier. The OTR and CO₂TR of the irradiated (10 kGy) PCL films and composites were decreased compared to their counterparts. Surface and interface morphologies of the composites were studied by scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical and barrier properties of nanocrystalline cellulose reinforced poly(caprolactone) composites: Effect of gamma radiation

Nanocrystalline cellulose (NCC) reinforced poly(caprolactone) (PCL) composites were prepared by compression molding. The NCC content varied from 2 to 10% by weight. NCC played a significant role in improving the mechanical properties of PCL. The addition of 5 wt % NCC caused a 62% improvement of the tensile strength (TS) value of PCL films. Similarly, tensile modulus (TM) values were also improved by NCC reinforcement but elongation at break (Eb) values decreased montonically with NCC content. The water vapor permeability (WVP) of PCL was 1.51 g·mm/m²·day·kPa, whereas PCL films containing 5 wt % NCC showed a WVP of 1.22 g·mm/m²·day·kPa. The oxygen transmission rate (OTR) and carbon dioxide transmission rate (CO₂TR) of PCL decreased by 19 and 17%, respectively, with 5 wt % NCC incorporation. It was found that the mechanical and barrier properties of both PCL and PCL‐NCC composites further improved with 10 kGy gamma irradiation treatment. The combination of NCC and radiation significantly increased the TS, TM, and Eb (by 156, 123, and 80%, respectively, compared to untreated PCL). The WVP, OTR, and CO₂TR decreased by 25–35% with respect to untreated PCL. The surface and interface morphologies of the PCL‐NCC composites were studied by scanning electron microscopy and suggested homogeneous distribution of NCC within the PCL matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effectiveness of silane monomer on chitosan films and PCL-based tri-layer films

Chitosan films were prepared by casting from its 1% (w/w) solution. Tensile strength (TS), tensile modulus (TM), and elongation at break (Eb%) of chitosan films were found to be 30 MPa, 450 MPa, and 8%, respectively. Silane monomer (3-aminopropyl tri-methoxy silane) (1–7%, w/w) was added into the chitosan solution (1%, w/w), and films were casted. The highest TS (38 MPa) and TM (620 MPa) values were found at 5% (w/w) silane content films. Polycaprolactone (PCL) films were prepared by compression molding; the values of TS, TM, and Eb of PCL films were found to be 12 MPa, 226 MPa, and 70%, respectively. Using chitosan and silane containing chitosan films, PCL-based tri-layer films were prepared by compression molding. Chitosan (also silane-incorporated chitosan) content in the tri-layer films varied from 10 to 50% by weight. The values of TS and TM of the silane containing composites were found to be 21 and 410 MPa, respectively, which is significantly higher (40% TS and 34% TM) than control composites. Molecular interactions due to silane addition were supported by FT-IR analysis. The surface of the films and the interface of the tri-layer films were investigated by scanning electron microscope (SEM). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on the Mechanical and Thermal Properties of Jute-Reinforced Methyl Acrylate Grafted PET Composites

Polyethylene terephthalate (PET) granules were grafted with methyl acrylate (MA) from the solution containing 10% MA in methanol (86%) solvent and photo initiator (4%) for 10 min and then cured under UV radiation. MA-grafted PET films were prepared at 260°C and 5 ton pressure using heat press. Jute fabric-reinforced, MA-grafted, PET-based composites (25% fiber by weight) were fabricated by compression molding. Mechanical, thermal and soil degradation tests of the composites were performed. It was found that the MA grafted PET composites showed higher mechanical properties over the ungrafted PET/jute composite.     

Structure,mechanical, and electrical properties of high‐density polyethylene/multi‐walled carbon nanotube composites processed by compression molding and blown film extrusion

The structure and properties of melt mixed high‐density polyethylene/multi‐walled carbon nanotube (HDPE/MWCNT) composites processed by compression molding and blown film extrusion were investigated to assess the influence of processing route on properties. The addition of MWCNTs leads to a more elastic response during deformations that result in a more uniform thickness distribution in the blown films. Blown film composites exhibit better mechanical properties due to the enhanced orientation and disentanglement of MWCNTs. At a blow up ratio (BUR) of 3 the breaking strength and elongation in the machine direction of the film with 4 wt % MWCNTs are 239% and 1054% higher than those of compression molded (CM) samples. Resistivity of the composite films increases significantly with increasing BURs due to the destruction of conductive pathways. These pathways can be recovered partially using an appropriate annealing process. At 8 wt % MWCNTs, there is a sufficient density of nanotubes to maintain a robust network even at high BURs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42665.     

Physico-Mechanical and Degradation Properties of Gamma-Irradiated Biocomposites of Jute Fabric-Reinforced Poly(caprolactone)

Jute fabric-reinforced poly(caprolactone) biocomposites (30–70% jute) were fabricated by compression molding. Tensile strength, tensile modulus, bending strength, bending modulus and impact strength of the non-irradiated composites (50% jute) were found to be 65 MPa, 0.75 GPa, 75 MPa, 4.2 GPa and 6.8 kJ/m², respectively. The composites were irradiated with gamma radiation at different doses (50–1000 krad) at a dose rate of 232 krad/hr and mechanical properties were investigated. The irradiated composites containing 50% jute showed improved physico-mechanical properties. The degradation properties of the composites were observed. The morphology was evaluated by scanning electron microscope.     

Composites from biodegradable and biocompatible methylcellulose,poly(d,l-lactide-co-glycolide) and poly(1,4-butylene succinate) with enhanced properties

Polymer materials based on fossil resources have brought great convenience to various industries. However, environmental pollution is becoming increasingly conspicuous due to their difficult degradation in nature. Therefore, biodegradable composites are highly desired. In the present work, a simple and feasible preparation approach was presented to fabricate biodegradable and biocompatible composite films including methylcellulose/poly(d ,l -lactide-co-glycolide) (MC/PLGA) and methylcellulose/poly(1,4-butylene succinate) (MC/PBS). The effects of MC/PLGA and MC/PBS mass ratios on the morphology, crystalline state, mechanical properties and thermal stability of the composite films were systematically investigated. At the same time, the influence of thermal compression treatment on mechanical properties (tensile strength and elongation) and the cyclic utilization of the composite films were also estimated. The composite films displayed enough good mechanical properties, re-usability and thermal stability.     

Thermal,Mechanical and Morphological Characterization of Jute/Gelatin Composites

Jute fabrics/gelatin biocomposites were fabricated using compression molding. The fiber content in the composite varied from 20–60 wt%. Composites were subjected to mechanical, thermal, water uptake and scanning electron microscopic (SEM) analysis. Composite contained 50 wt% jute showed the best mechanical properties. Tensile strength, tensile modulus, bending strength, bending modulus and impact strength of the 50% jute content composites were found to be 85 MPa, 1.25 GPa, 140 MPa and 9 GPa and 9.5 kJ/m², respectively. Water uptake properties at room temperature were evaluated and found that the composites had lower water uptake compared to virgin matrix.     

Tunability of polycaprolactone hydrophilicity by carboxymethyl cellulose loading

Carboxymethyl cellulose (CMC) is herein proposed as additive in polycaprolactone (PCL) matrices to obtain composites with tunable hydrophilicity. This composite material can be obtained by compression molding. The thermogravimetric degradation profile, the FTIR spectra, values of the water contact angle (WCA), water and phosphate‐buffered saline uptake values, and the results of a cytotoxicity assessment are presented herein. The concentrations of CMC in the groups of samples are 0, 2, 5, 10, and 20%. The WCA on the prewetted state decreases proportionally to the concentration of the additive. These results evidence the possibility of obtaining a PCL‐based composite with tunable hydrophilicity. Besides, the biological assessment does not reveal any cytotoxic effects. Therefore, the addition of CMC entails an innovative strategy to control the water affinity of PCL in biomedical applications where such feature is required to improve diffusion of biological medium through, or accelerate degradation by hydrolysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46134.     

Studies of the Physico-Mechanical,Interfacial, and Degradation Properties of Jute Fabrics/Melamine Composites

Jute fabrics/melamine composites (20% fiber) were prepared by compression molding. Mechanical properties of the composites were evaluated. Mechanical properties of starch-treated jute/melamine composites, including tensile strength (31%), bending strength (29%), tensile modulus (23%), bending modulus (25%), impact strength (113%), and hardness (4%), inproved significantly over the untreated composite. Fracture surfaces of untreated and treated composites were studied by scanning electron microscopy (SEM) and supported poorer fiber matrix adhesion for the untreated composite than that of the treated composite. Water uptake and soil degradation tests of untreated and treated composites were also performed.     

Preparation,physicochemical properties and biocompatibility of biodegradable poly(ether-ester-urethane) and chitosan oligosaccharide composites

In the paper, novel composites of biodegradable poly(ether-ester-urethane) (PEEU) and water-soluble chitosan oligosaccharide (CHO) were prepared using a simple physical mixing method and their potential application as biomaterials was assessed. The PEEU and CHO were dissolved in N,N-dimethylformamide to get a homogenous solution, then the composite films were obtained by the solvent evaporation method. The composites were characterized by FT-IR, and the influence of CHO content on the physicochemical properties of the composite films, including thermal properties, surface morphologies, mechanical properties, surface and bulk hydrophilicity, and in vitro biodegradability, were researched. The thermal stability studies indicated that the composite films had lower initial decomposition temperature and higher maximum decomposition temperature than PEEU film. Only one broad endothermic peak found in DSC curves demonstrated the high compatibility of CHO with PEEU. The ultimate stress and elongation at break of composite films decreased with the increment of CHO content, and the CHO content in the composites should be controlled no more than 25 wt% in order to maintain the mechanical properties (ultimate stress: 18.5 MPa; elongation at break: 890%) to meet the requirement of implant materials. The surface morphologies of composite films were observed by cold field emission scanning electron microscope (FE-SEM), and the results indicated that the homogeneous-dispersed composites could be obtained with CHO content being less than 20 wt%. The results of water contact angle and water absorption showed that the surface and bulk hydrophilicity were closely related with the water-solubility of CHO component. In vitro degradation studies showed that the degradation rate increased with the increasing content of CHO in composites, indicating that the degradation rate of composite films could be controlled by adjusting CHO content. The surface blood compatibility of the composite films was examined by bovine serum albumin adsorption and platelet adhesion tests. It was found that composite films had improved resistance to protein adsorption and possessed excellent resistance to platelet adhesion.     

Thermal and mechanical properties of compression‐molded pMDI‐reinforced PCL/gluten composites

Many biopolymers and synthetic polymers composites were developed by different researchers for environmental protection and for cost reduction. One of these composites is polycaprolactone (PCL) and vital wheat gluten or wheat flour composites were prepared and compatibilized with polymeric diphenylmethane diisocyanate (pMDI) by blending and compression‐molding. PCL/pMDI blend exhibited glass transition (T_g) at ?67°C (0.20 J/g/°C) and vital gluten at 63°C (0.45 J/g/°C), whereas no T_g was recorded for wheat flour. Although T_g was unmistakable for either PCL or gluten, all composite exhibited one T_g, which is strong indication of interaction between PCL and the fillers. Several samples amongst the blended or compression‐molded composites exhibited no T_g signifying another confirmation of interaction. The ΔH of the endothermic (melting) and the exothermic (crystallization) for PCL was decreased as the percentage of gluten or flour increased, whereas the overall ΔH was higher for all composites compared to the theoretical value. The presence of pMDI appeared to strengthen the mechanical properties of the composites by mostly interacting with the filler (gluten or flour) and not as much with PCL. The FTIR analysis ruled out covalent interaction between PCL, pMDI, or the fillers but suggested the occurrence of physical interactions. Based on the data presented here and the data published earlier, the presence of pMDI did not change the nature of interaction between PCL and gluten, but it improved the mechanical properties of the composite. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Development and compatibility assessment of new composite film based on sugar beet pulp and polyvinyl alcohol intended for packaging applications

In this study, interaction and compatibility between sugar‐beet pulp (SBP) and polyvinyl alcohol (PVA) in blend films was assessed. Film‐forming dispersions of different ratios of SBP to PVA (100/0, 75/25, 50/50, and 25/75) were cast at room temperature. The effects of adding PVA to SBP on the resulting film's physical, mechanical and barrier properties and thermal stability were investigated. X‐ray diffraction and environmental scanning electron microscopy (ESEM) were used to characterize the structure and morphology of the composites. When PVA was also added to the composite films, the films became softer, less rigid and more stretchable than pure SBP films. The addition of PVA gave significantly greater elongation at break (12.45%) and lower water vapor permeability (1.55 × 10^?10 g s^?1 m^?1 Pa^?1), but tensile strength did not markedly change, remaining around 59.68 MPa. Thermogravimetric analysis also showed that SBP/PVA film had better thermal stability than SBP film. The ESEM results showed that the compatibility of SBP50/PVA50 was better than those of other composite films. These results suggest that when taking all the studied variables into account, composite films formulated with 50% PVA are most suitable for various packaging applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41354.     

Calcium copper titanate/polyurethane composite films with high dielectric constant,low dielectric loss and super flexibility

Calcium copper titanate(CCTO)/polyurethane composite films with high dielectric constant, low dielectric loss and super flexibility were fabricated by incorporating CCTO ceramic powders into millable polyurethane elastomer (MPU) matrix using a rubber milling combined with hot compression molding method. The composite films show uniform microstructures and the dielectric constant is as high as 35.2 while the dielectric loss is only 0.041 when CCTO content reaches 40 vol% at 100 Hz and room temperature (RT). Moreover, it is important to note that this film has stable dielectric constant and dielectric loss in a relatively wide temperature range (from 0 °C to 70 °C), which is significantly import to the practice use of electronic devices based on CCTO composites. In addition, the flexibility of the film could be retained even when the CCTO content is up to 40 vol% and the elongation at break of this composite film is as high as 159.1%. Theoretical analysis indicates that the experimental data are in good conformity to the effective medium theory (EMT) model with a derived n = 0.21, suggesting more close association of the dielectric constant with the CCTO filler size and shape.     

The Preparation and Characterization of Silk/Gelatin Biocomposites

There is a growing interest in the use of composite materials. Silk fiber/gelatin biocomposites were fabricated using compression molding. The fiber content in the composite varied from 10–30 wt%. Composite containing 30 wt% silk showed the best mechanical properties. Tensile strength, tensile modulus, bending strength, bending modulus and impact strength, hardness of the 30% silk content composites were found 54 MPa, 0.95 GPa, 75 MPa and 0.43 GPa and 5.4 kJ/m², 95.5 Shore A, respectively. Water uptake properties at room temperature, accelerated weathering aging, irradiation, thermomechanical analysis, and degradation in soil were carried out in this experiment.     

Films from oat spelt arabinoxylan plasticized with glycerol and sorbitol

The development of packaging films based on renewable materials is an important and active area of research today. This is the first extensive study focusing on film‐forming properties of an agrobiomass byproduct, namely, oat spelt arabinoxylan. A plasticizer was needed for cohesive film formation, and glycerol and sorbitol were compared. The tensile properties of the films varied with the type and amount of the polyol. With a 10% (w/w) plasticizer content, the films containing glycerol had higher tensile strength than the films containing sorbitol, but with a 40% plasticizer content, the result was the opposite. Sorbitol‐plasticized films retained their tensile properties better than films with glycerol during 5 months of storage. The films were semicrystalline with similar crystallinity indices of 0.20–0.26. The largest crystallites (9.5 nm) were observed in the film with 40% glycerol. The softening of films with 40% (w/w) glycerol started at a significantly lower relative humidity (RH) than that of the corresponding sorbitol‐containing films. The films with sorbitol also had lower water vapor permeability (WVP) than the films with glycerol. The films plasticized with 10% (w/w) sorbitol had a WVP value of 1.1 g mm/(m²·d·kPa) at the RH gradient of 0/54%. The oxygen permeability of films containing 10% (w/w) glycerol or sorbitol was similar: 3 cm³·μm/(m²·d·kPa) at 50–75% RH. A higher plasticizer content resulted in more permeable films. Permeation of sunflower oil through the films was not detected. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enzymatic degradation of blends of poly(ε‐caprolactone) and poly(styrene‐co‐acrylonitrile) by Pseudomonas lipase

In polymer blends, the composition and microcrystalline structure of the blend near surfaces can be markedly different from the bulk properties. In this study, the enzymatic degradation of poly(ε‐caprolactone) (PCL) and its blends with poly(styrene‐co‐acrylonitrile) (SAN) was conducted in a phosphate buffer solution containing Pseudomonas lipase, and the degradation behavior was correlated with the surface properties and crystalline microstructure of the blends. The enzymatic degradation preferentially took place at the amorphous part of PCL film. The melt‐quenched PCL film with low crystallinity and small lamellar thickness showed a higher degradation rate compared with isothermally crystallized (at 36, 40, and 44°C) PCL films. Also, there was a vast difference in the enzymatic degradation behavior of pure PCL and PCL/SAN blends. The pure PCL showed 100% weight loss in a very short time (i.e., 72 h), whereas the PCL/SAN blend containing just 1% SAN showed ～50% weight loss and the degradation ceased, and the blend containing 40% SAN showed almost no weight loss. These results suggest that as degradation proceeds, the nondegradable SAN content increases at the surface of PCL/SAN films and prevents the lipase from attacking the biodegradable PCL chains. This phenomenon was observed even for a very high PCL content in the blend samples. In the blend with low PCL content, the inaccessibility of the amorphous interphase with high SAN content prevented the attack of lipase on the lamellae of PCL. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 868–879, 2002     

Multifunctional polyimide/graphene oxide composites via in situ polymerization

In this article, we detail an effective way to improve electrical, thermal, and gas barrier properties using a simple processing method for polymer composites. Graphene oxide (GO) prepared with graphite using a modified Hummers method was used as a nanofiller for r‐GO/PI composites by in situ polymerization. PI composites with different loadings of GO were prepared by the thermal imidization of polyamic acid (PAA)/GO. This method greatly improved the electrical properties of the r‐GO/PI composites compared with pure PI due to the electrical percolation networks of reduced graphene oxide within the films. The conductivity of r‐GO/PI composites (30:70 w/w) equaled 1.1 × 10¹ S m^?1, roughly 10¹⁴ times that of pure PI and the oxygen transmission rate (OTR, 30:70 w/w) was reduced by about 93%. The Young's modulus of the r‐GO/PI composite film containing 30 wt % GO increased to 4.2 GPa, which was an approximate improvement of 282% compared with pure PI film. The corresponding strength and the elongation at break decreased to 70.0 MPa and 2.2%, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40177.     

Poly(lactic acid)/titanium dioxide nanocomposite films: Influence of processing procedure on dispersion of titanium dioxide and photocatalytic activity

Poly(lactic acid)/titanium dioxide (TiO₂) composite films were prepared by direct melt processing using three different procedures (i.e., compression molding, twin‐screw melt extrusion, and melt extrusion and thermoforming). The effect of TiO₂ loading and processing procedures on the phase morphology and on the thermal, mechanical, and barrier properties of the obtained nanocomposites were analyzed respectively by field‐emission scanning electron microscopy‐energy dispersive spectrometry, differential scanning calorimetry, universal testing machine, and water vapor and oxygen permeability measurements. The incorporation of TiO₂ nanoparticles into the poly(lactic acid) matrix increased the crystallinity and improved the barrier properties of the composites. The maximum tensile strength was achieved at the 2% content of TiO₂ for the films produced by compression molding and twin‐screw melt extrusion, whereas the tensile strength for films produced by melt extrusion and thermoforming decreases markedly with an increasing TiO₂ content. The photocatalytic activities of the obtained nanocomposites were investigated by analyzing the degradation of methyl orange. Results confirmed that the processing procedures and the distribution of TiO₂ in the polymer matrix are the key parameters, which rule the photocatalytic behavior of composite films. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Effect of electron beam radiation on the performance of biodegradable Bionolle-jute composite

To study the radiation effect on the physical, thermal, mechanical and degradable properties of biodegradable polymer Bionolle (chemosynthetic polyester poly(1,4-butylene succinate)), Bionolle films prepared by compression molding process and were irradiated with electron beam (EB) radiation of different doses. Gel content was found to increase with increase of radiation dose. Tensile strength of Bionolle was enhanced when Bionolle film was exposed under 20 kGy radiation. The loss of tensile strength of both unirradiated and irradiated Bionolle is 70% and 8% due to thermal aging at 70°C for 30 days. Both irradiated and unirradiated films of Bionolle were subjected to different degradation test in compost (soil burial), enzyme and storage degradation both in outdoor and indoors conditions. The loss of weight due to soil (compost) degradation test decreased with increase of radiation dose. The loss of weights of irradiated samples were found to be very less within the first three months of compost degradation. After 120 days, tensile strength of the Bionolle films irradiated at 20 kGy and 100 kGy were 68 MPa and 40 MPa, respectively, compared to the value (30 MPa) of the unirradiated Bionolle samples. Loss of tensile strength of irradiated Bionolle due to storage degradation like in roof, ground and indoors was minimum compared to unirradiated Bionolle. The weight loss due to enzymatic degradation was found to be decreased with increase of radiation dose. The tensile strength of jute reinforced Bionolle composites (23 wt.-% jute content) irradiated at 20 kGy was found to be higher (22%) than that of an unirradiated composite.