Preparation, properties and cytotoxicity evaluation of a biodegradable polyester elastomer composite

Multi-walled carbon nanotube (MWCNT)/poly(glycerol–sebacate–citrate) (PGSC) elastomer composite were prepared and their morphologies, compositions, glass transition temperatures, mechanical properties, water absorption, biodegradation and cytotoxicity were investigated. Results showed that the chemical structures of PGSC elastomers were hardly influenced by the MWCNT loadings, and physical adsorption was thought as the main interaction between the MWCNTs and PGSC matrixes. When the MWCNT loading was 3 wt%, MWCNTs displayed a homogenous dispersion in the matrixes, and the composite's strength and modulus respectively reached 4.4 MPa and 9.2 MPa, increasing by 62.96% and 33.33% than that of pure PGSC matrixes. The degradation rates of the composites tended to decrease with the increase of MWCNT loadings in simulated body fluid (SBF) solution. The composites presented no cytotoxicity especially when the MWCNT loadings were above 1 wt%. We expect the composites can be used as degradable bio-coatings and tissue engineering scaffolds in future.     

Industrial cutting waste granite dust reinforced cardanol benzoxazine/epoxy resin hybrid composites for high-voltage electrical insulation applications

An attempt has been made to develop hybrid composites from benzoxazine monomer (C-ddm) hybridized with DGEBA epoxy resin (EP) and reinforced with varying weight percentages (20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt%) of glycidoxypropyltrimethoxy- silane (GPTMS) functionalized granite dust (GD) obtained from industrial granite cutting and polishing process in order to utilize them for electrical insulation applications. The thermal stability of granite dust reinforced poly(EP-co-C-ddm) composites was studied by TGA analysis. Among the composites samples studied, 100 wt% GD reinforced poly(EP-co-C-ddm) composites possess better thermal stability than that of other neat matrices and composites. Among the composites prepared using varying weight percentages of functionalized GD reinforcement, it was observed that 80 wt% GD reinforced poly(EP-co-C-ddm) composites possesses better hydrophobic character than that of other neat matrices and composites. The value of LOI calculated for neat matrix (poly[EP-co-C-ddm]) and 20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt% GD reinforced composites was found to be 22, 28, 34, 40, 43 and 45 respectively. The 80 wt% GD reinforced poly(EP-co-C-ddm) composites possess the higher values of tensile strength and flexural strength of 47 MPa and 140 MPa, respectively than those of their samples. The values of electrical surface resistivity and electrical volume resistivity of all the neat matrices and GD reinforced polybenzoxazine composites were found to be in the order of 10¹² and 10¹³ respectively. The values of dielectric strength obtained from break down voltage (BDV) for neat matrix [poly(EP-co-C-ddm)] and 20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt% of GD reinforced poly(EP-co-C-ddm) composites are 15.0, 15.5, 16.5, 17.0, 17.0 and 17.0 kV/mm, respectively. Data obtained from thermal stability, hydrophobic behavior and dielectric studies it was inferred that the hybrid polymer composites developed in the present work can be conveniently used in the form insulators, sealants, adhesives and matrices where application demands at high-performance industrial and engineering applications.     

Thermal and electrical conduction behavior of alumina and multiwalled carbon nanotube incorporated poly(dimethyl siloxane)

Alumina particles were incorporated in poly(dimethyl siloxane) (PDMS) matrix in company with multiwalled carbon nanotube (MWCNT) for improving the thermal and electrical conductivities. The concentration of MWCNT was increased from 0 to 10 wt% to PDMS at fixed amounts of alumina (200 and 300 wt% to PDMS). Thermal conductivity of PDMS composites was increased with the increasing amount of MWCNT and the excellent dispersibility of the incorporated pristine MWCNT was achieved. Thermal and electrical conductivities of the composites were increased with the increasing concentration of the alumina because the alumina particles help disperse MWCNT within the PDMS matrix due to the ball milling effect during compounding. The properties of the alumina and MWCNT incorporated PDMS composites were investigated in terms of the curing characteristics, electrical conductivity, and thermal conductivity. The MWCNT/alumina incorporated composite showed the high electrical conductivity to the level of the semiconductor.     

Effects of flower-like ZnO nanowhiskers on the mechanical, thermal and antibacterial properties of waterborne polyurethane

A novel waterborne polyurethane/flower-like ZnO nanowhiskers (WPU/f-ZnO) composite with different f-ZnO content (0-4.0 wt%) was synthesized by an in-situ copolymerization process. The f-ZnO consisting of uniform nanorods was prepared via a simple hydrothermal method. In order to disperse and incorporate f-ZnO into WPU matrix, f-ZnO was modified with γ-aminopropyltriethoxysilane. Morphology of f-ZnO in WPU matrix was characterized by scanning electron microscope. The properties of WPU/f-ZnO composites such as mechanical strength, thermal stability as well as water swelling were strongly influenced by the f-ZnO contents. It was demonstrated that appropriate amount of f-ZnO with good dispersion in the WPU matrix significantly improved the performance of the composites. The mechanical property was enhanced with an increase of f-ZnO content up to the optimum content (1 wt%) and then declined. Incorporation of f-ZnO enhanced the water resistance of the composites remarkably. It was amazing to observe that the thermal degradation temperatures of the composites initially decreased significantly and then leveled off with content increase of f-ZnO, which was different from the results of other WPU composite systems reported. Antibacterial activity of WPU/f-ZnO composite films against Escherichia coli and Staphylococcus aureus was also tested. The results revealed that the antibacterial activity enhanced with the increasing f-ZnO content, and the best antibacterial activity was obtained at the loading level of 4.0 wt% f-ZnO.     

A new bio-based nanocomposite: fibrillated TEMPO-oxidized celluloses in hydroxypropylcellulose matrix

Utilization of TEMPO-oxidized celluloses in bio-based nanocomposites is reported for the first time. TEMPO-oxidized wood pulps (net carboxylate content 1.1 mmol/g cellulose) were fibrillated to varying degrees using a high intensity ultrasonic processor. The degree of fibrillation was controlled by varying sonication time from 1 to 20 min. The sonication products were then characterized independently and as fillers (5 wt% loading) in hydroxypropyl cellulose nanocomposite films. Nanofibril yields ranging from 11 to 98 wt% (on fiber weight basis) were obtained over the range of sonication times used. Suspension viscosities increased initially with sonication time, peaked with gel-like behavior at 10 min of sonication and then decreased with further sonication. The thermal degradation temperature of unfibrillated oxidized pulps was only minimally affected (6 °C decrease) by the fibrillation process. Dynamic mechanical analysis of the nanocomposites revealed strong fibril-matrix interactions as evidenced by remarkable storage modulus retention at high temperatures and a suppression of matrix glass transition at “high” (~5 wt%) nanofibril loadings. Creep properties likewise exhibited significant (order of magnitude) suppression of matrix flow at high temperatures. It was also believed, based on morphologies of freeze-fracture surfaces that the nanocomposites may be characterized by high fracture toughness. Direct fracture testing will however be necessary to verify this suspicion.     

Effect of surface treatment with potassium permanganate on ultra-high molecular weight polyethylene fiber reinforced natural rubber composites

The effects of surface treatment using potassium permanganate on ultra-high molecular weight polyethylene (UHMWPE) fibers reinforced natural rubber (NR) composites were investigated. The results showed the surface roughness and the oxygen-containing groups on the surface of the modified fibers were effectively increased. The NR matrix composites were prepared with as-received and modified UHMWPE fibers added 0–6 wt%. The treated fibers increased the modulus and tensile stress at a given elongation. The tear strength increased with increasing fiber mass fraction, attained maximum values at 4 wt%. The hardness of composites exhibited continuous increase with increasing the fiber content. The dynamic mechanical tests showed that the storage modulus and the tangent of the loss angle were decreased in the modified UHMWPE fibers/NR composites. Several micro-fibrillations between the treated fiber and NR matrix were observed, which meant the interfacial adhesion strength was improved.     

Comparison of the effect of mica and talc and chemical coupling on the rheology,morphology, and mechanical properties of polypropylene composites

The effect of filler types of mica and talc on the oscillatory shear rheological properties, mechanical performance, and morphology of the chemically coupled polypropylene composites is studied in this work. The Maleic Anhydride grafted Polypropylene (MAPP) was used as an adhesion promoter for coupling mineral particles with the polypropylene matrix. The samples were prepared by a co‐rotating, L/D = 40, 25 mm twin screw extruder. The tensile tests carried out on the injection molded samples showed a reinforcing effect of talc up to 20 wt% on the Polypropylene (PP). The tensile strength of PP‐mica composites showed a slight decrease at all percentages of mica. The effect of chemical coupling by using MAPP on the tensile strength was more pronounced in increasing the tensile strength for PP‐mica than PP‐talc composites. The complex viscosity curve of pure PP and the composites, showed a Newtonian plateau (η₀) up to 30 wt% at low frequency terminal zone. By increasing the filler content to 40 and 50 wt%, the complex viscosity at very low shear rates sharply increased and showed yield behavior that can be due to the formation of filler particles networks in the melt. At the optimum amount of coupling agent, a minimum in cross over frequency curve against MAPP content is observed. The optimum amount of coupling agent for PP‐talc composites is about 1.5%, and about 3% for PP‐mica formulations. The analysis of viscosity behavior at power‐law high region, revealed the more shear thinning effect of mica than talc on the PP matrix resin. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis, characterization and in vitro degradation of a novel degradable poly((1,2-propanediol-sebacate)-citrate) bioelastomer

Degradable bioelastomers represent a useful class of biomaterials. In this paper, a novel biodegradable network of elastomeric polyesters, poly((1,2-propanediol-sebacate)-citrate) (PPSC), was synthesized by condensation of 1,2-propanediol, sebacic acid and citric acid without any catalyst. An oligomeric diol of 1,2-propanediol-sebacate was first synthesized by carrying out a controlled condensation reaction between 1,2-propanediol and sebacic acid, and then a pre-polymer was synthesized by condensation of the diol and citric acid, whereat the pre-polymer was post-polymerized and simultaneously crosslinked in mold at 120 °C. A series of PPSC polymers were prepared at different post-polymerization times and different monomers' ratio. T_g confirms that PPSC is totally amorphous at 37 °C. The mechanical properties of PPSC testified that the new polymers are typical elastomers with low hardness and large elongation. The different post-polymerization times and monomers' ratio had strong influence on the degradation rates and mechanical performances. The material was expected to be useful for drug controlled delivery, tissue engineering scaffold and other biomedical applications.     

Electrically conductive composites of polyethylene filled with polyamide particles coated with silver

New types of electrically conductive polymeric composites were prepared on a base of high-density polyethylene (HDPE) matrix filled with silver-coated polyamide (PA) particles. The electrical, mechanical and adhesive properties of those composites are reported in this paper. The percolation concentration of the filler within a matrix was found to be 4 vol.%. Composites filled with high filler content were highly electrically conductive; their electrical conductivity reached the value of 6.8 × 10² S cm⁻¹. Mechanical properties and rheology of these composites were discussed. The adhesive properties of the composites to metal sharply increased with an increase in the filler content.     

Anti-trade-off in dehydration of ethanol by novel PVA/APTEOS hybrid membranes

Novel organic–inorganic hybrid membranes were prepared through sol–gel reaction of poly(vinyl alcohol) (PVA) with γ-aminopropyl-triethoxysilane (APTEOS) for pervaporation (PV) separation of ethanol/water mixtures. The membranes were characterized by FTIR, EDX, WXRD and PALS. The amorphous region of the hybrid membranes increased with increasing APTEOS content, and both the free volume and the hydrophilicity of the hybrid membranes increased when APTEOS content was less than 5 wt%. The swelling degree of the hybrid membranes has been restrained in an aqueous solution owing to the formation of hydrogen and covalent bonds in the membrane matrix. Permeation flux increased remarkably with APTEOS content increasing, and water permselectivity increased at the same time, the trade-off between the permeation flux and water permselectivity of the hybrid membranes was broken. The sorption selectivity increased with increasing temperature, and decreased with increasing water content. In addition, the diffusion selectivity and diffusion coefficient of the permeants through the hybrid membranes were investigated. The hybrid membrane containing 5 wt% APTEOS has highest separation factor of 536.7 at 50 °C and permeation flux of 0.0355 kg m⁻² h⁻¹ in PV separation of 5 wt% water in the feed.     

An efficient and convenient strategy toward fire safety and water resistance of polypropylene composites through design and synthesis of a novel mono‐component intumescent flame retardant

A novel mono‐component flame‐retardant additive poly (dimethylol melamine piperazine pyrophosphate) defined as PDMPP was synthesized from formaldehyde, melamine, and piperazine pyrophosphate. Its chemical structure was well characterized by Fourier transform infrared spectroscopy, ¹³C and ³¹P solid‐state nuclear magnetic resonance, and elemental analysis tests. PDMPP was incorporated into polypropylene (PP) matrix, and the fire‐retardant performance, thermal properties, and water resistance of PP composites were investigated in detail. PP/23 wt% PDMPP composites before and after water resistance tests both achieved UL‐94V‐0 grade during vertical burning tests, and the limiting oxygen index was slightly declined from 26.7% to 26.3%. Small amount of PDMPP was extracted by hot water, and the weight loss percentage was 0.67% during water resistance tests. The piperazine and triazine rings in PDMPP contributed to a much better char‐forming capability, and then a greatly expanded and coherent char residue was generated during combustion and exhibited excellent isolation effect. The heat release rate, carbon monoxide production, and smoke production rate of the flame‐retarded PP composites before and after water resistance tests were effectively suppressed to a low level. Consequently, the introduction of PDMPP apparently improved the fire safety of PP composites as well as excellent water‐resistant performance.     

The tensile properties of HNO3‐treated carbon fiber reinforced ABS/PA6 composites

In this study, acrylonitrile‐butadiene‐styrene (ABS) terpolymer was reinforced with HNO₃‐treated short carbon fibers (SCFs) [(hollow carbon fibers (HCFs)]. The effects of HCF concentration on the tensile properties of the composites were examined. Increasing the HCF concentration in the ABS matrix from 10 to 30 wt% resulted in improved tensile strength and tensile modulus. To obtain a strong interaction at the interface, polyamide 6 (PA6) at varying concentrations was introduced into the ABS/10 wt% SCF composite. The incorporation and increasing amount of PA6 in the composites increased tensile properties of the ABS/PA6/HCF systems due to the improved adhesion at the interface, which was confirmed by the ratio of tensile strength as an adhesion parameter. These results were also supported by scanning electron micrographs of the ABS/PA6/HCF composites, which exhibited an improved adhesion between the SCFs and the ABS/PA6 matrix. Copyright © 2009 John Wiley & Sons, Ltd.     

Study on superabsorbent composite. III. Swelling behaviors of polyacrylamide/attapulgite composite based on acidified attapulgite and organo-attapulgite

A novel kind of salt-resistant superabsorbent composite, polyacrylamide/attapulgite, from acrylamide (AM) and attapulgite (APT) was prepared by free-radical aqueous polymerization, using N,N′-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The organification of APT with hexadecyltrimethyl ammonium bromide (HDTMABr) was proved by FTIR and XRD. The effects of acidified APT (H⁺-APT), organo-APT (HDTMABr-APT) and the content of APT in the superabsorbent composite on the water absorbency and the initial swelling rate for the superabsorbent composite in distilled water and in various saline solutions were studied. The effects of incorporated HDTMABr-APT and H⁺-APT on the reswelling ability of the superabsorbent composites were investigated. The results indicate that the incorporation of APT had remarkable influence on the improvement of water absorbency and swelling rate of the composites. Comparing with the composite doped with H⁺-APT, the water absorbency for the composite doped with 10 wt% HDTMABr-APT was enhanced from 2140 g g⁻¹ to 2800 g g⁻¹ in distilled water and from 100 g g⁻¹ to 121 g g⁻¹ in 0.9 wt% NaCl solution, respectively. The water absorbency of the composites in various saline solutions decreased with the increasing concentration, especially for the multivalent cations. In addition, the reswelling ability of the superabsorbent composites is also improved evidently by adding a small amount of HDTMABr-APT into the composite, comparing with that of incorporated with H⁺-APT.     

Electrical, mechanical and adhesive properties of ethylene-vinylacetate copolymer (EVA) filled with wollastonite fibers coated by silver

New type of electrically conductive polymeric composites was prepared using ethylene-vinylacetate (EVA) matrix filled with silver-coated wollastonite (W-Ag) fibers. The electrical, mechanical and adhesive properties of the composites are reported in this paper. The electrical percolation threshold was found about 8 vol.% and the highly electrical conductivity value (1.8 × 10⁵ S m⁻¹) is reached for 29 vol.% of filler fraction. The mechanical and adhesive properties of these composites were also discussed and correlated with some models.     

Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant

An intumescent flame retardant spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine (SPDPM) has been synthesized and its structure was characterized by Fourier transformed infrared spectrometry (FTIR), ¹H and ³¹P nuclear magnetic resonances (NMR). A series of polylactide (PLA)-based flame retardant composites containing SPDPM were prepared by melt blending method. The combustion properties of PLA/SPDPM composites were evaluated through UL-94, limiting oxygen index (LOI) tests and microscale combustion calorimetry (MCC) experiments. It is found that SPDPM integrating acid, char and gas sources significantly improved the flame retardancy and anti-dripping performance of PLA. When 25 wt% flame retardant was added, the composites achieved UL-94 V0, and the LOI value was increased to 38. Thermogravimetric analysis (TGA) showed that the weight loss rate of PLA was decreased by introduction of SPDPM. In addition, the thermal degradation process and possible flame retardant mechanism of PLA composites with SPDPM were analyzed by in situ FTIR.     

Modification of proton conductive polymer membranes with phosphonated polysilsesquioxanes

New hybrid membranes for fuel cell applications based on sulfonated poly(ether ether ketone) (SPEEK) and phosphonated polysilsesquioxanes were synthesized. The impedance spectroscopy measurements show an increase of the proton conductivity for all studied composites, in comparison to plain SPEEK. For hybrid membranes containing 20 wt% of polysilsesquioxane with 80 mol% of phosphonated units the conductivities can reach values that are similar to Nafion 117^® at 100% RH. The best results of proton conductivity (142 mS/cm) were obtained for composites with 40 wt% of the same polysilsesquioxane at 120 °C also at 100% RH.     

“One‐pot” synthesis of crosslinked silicone‐containing macromolecular charring agent and its synergistic flame retardant poly(l‐lactic acid) with ammonium polyphosphate

A crosslinked silicone‐containing macromolecular charring agent (CSi‐MCA) was synthesized via “one‐pot” process, and it was combined with ammonium polyphosphate (APP) to synergistically improve the flame retardancy of poly(l ‐lactic acid) (PLA). The chemical structure of synthesized CSi‐MCA was characterized by Fourier transform infrared spectroscopy and solid‐state ¹³C nuclear magnetic resonance. The thermal gravimetric analyzer indicated that the CSi‐MCA displayed good thermal stability and high residue via the catalytic crosslinking. Furthermore, the flame retardant effect of CSi‐MCA and APP as intumescent flame retardants in PLA system was investigated by limited oxygen index, UL94, and cone calorimeter test. When the content of CSi‐MCA was 5 wt% and APP was 10 wt% (CSi‐MCA/APP = 1/2), the limited oxygen index value of composites was 33.6 and UL94 classed a V‐0 rating. The peak heat release rate and total heat release of PLA composites containing both APP and CSi‐MCA decreased significantly in comparison with those with APP or CSi‐MCA alone. The flame retardancy mechanism was investigated via analyzing residual chars by scanning electron microscopy and X‐ray photoelectron spectroscopy as well as the possible chemical reaction between APP and CSi‐MCA by thermal gravimetric analyzer and Fourier transform infrared spectroscopy. The results showed that the enhanced flame retardancy was attributed mainly to synergistic effect of CSi‐MCA and APP, which could form a compact, continuous, and protective layer during combustion. Copyright © 2017 John Wiley & Sons, Ltd.     

Waste marble dust-filled sustainable polymer composite selection using a multi-criteria decision-making technique

This research works with the optimal design of marble dust-filled polymer composites using a multi-criteria decision-making (MCDM) technique. Polylactic acid (PLA) and recycled polyethylene terephthalate (rPET)-based composites containing 0, 5, 10, and 20 wt% of marble dust were developed and evaluated for various physicomechanical and wear properties. The results showed that the incorporation of marble dust improved the modulus and hardness of both PLA and rPET. Moreover, a marginal improvement in flexural strength was noted while the tensile and impact strength of the matrices were deteriorating due to marble dust addition. The outcomes of wear analysis demonstrated an improvement in wear resistance up until 10 wt% filler reinforcement, after which the incidence of dust particles peeling off from the matrix was observed, thereby reducing its efficiency. The best tensile modulus of 3.23 GPa, flexural modulus of 4.39 GPa, and hardness of 83.95 Shore D were obtained for 20 wt% marble dust-filled PLA composites. The lowest density of 1.24 g/cc and the highest tensile strength of 57.94 MPa were recorded for neat PLA, while the highest impact strength of 30.94 kJ/m² was recorded for neat rPET. The lowest wear of 0.01 g was obtained for the rPET containing 5 wt% marble dust content. The experimental results revealed that for the examined criteria, the order of composite preference is not the same. Therefore, the optimal composite was identified by adopting a preference selection index-based MCDM technique. The findings demonstrated that the 10 wt% marble dust-filled PLA composite appears to be the best solution with favorable physical, mechanical, and wear properties.     

Thermal,structural and morphological assessment of PVP/HA composites

Composites of poly(vinyl pyrrolidone)/hydroxyapatite (PVP/HA), at variable proportions (100/0; 80/20; 50/50; 20/80 wt%) were prepared and characterized by Fourier transformer-infrared spectroscopy (FT-IR), wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermogravimetry/differential thermogravimetry (TG/DTG). PVP carbonyl stretching was slightly shifted to lower frequency in composites indicating the formation of hydrogen bonding with HA hydroxyl groups. At the first cycle of heating, the calorimetric curves revealed a broad peak the intensity of which was reduced insofar as the amount of PVP decreased in the composites. This peak was attributed to the PVP enthalpy relaxation. According to the TG/DTG curves, PVP degraded into two steps sharply perceivable in the composites. The first decay was ascribed to the release of the pyrrolidone pendant groups and the following one concerned the burning of the hydrocarbon chains. The HA molecules seem to exert a catalytic action on the PVP degradation.     

Kinetics of the dehydrochlorination of poly(vinyl chloride) in the presence of NaOH and various diols as solvents

The dehydrochlorination of PVC in the presence of NaOH was investigated in different diols. Diethylene glycol (DEG), triethylene glycol (TEG), and propylene glycol (PG) were found to be effective in accelerating the dechlorination of PVC. The dehydrochlorination was promoted in the order TEG > DEG > PG, which was in agreement with the compatibility between PET and the diol. Compatibility resulted in an improved penetration of the PVC particle by the solvent, leading to the acceleration of the dehydrochlorination. The dehydrochlorination of PVC in NaOH/diol followed first-order kinetics, confirming the progress of the reaction under chemical reaction control. The apparent activation energies were 82 kJ mol⁻¹, 109 kJ mol⁻¹, and 151 kJ mol⁻¹ for TEG, DEG, and PG, respectively. The lower the activation energy became the faster the dehydrochlorination of PVC proceeded.