Phase study of nylon 6/poly (acrylic acid) blends cast from solutions in aqueous formic acid

Blends of nylon 6 (Ny6) with poly(acrylic acid) (PAA) were prepared in film form from solutions in a mixture of formic acid and water by evaporating the solvent. The miscibility and phase constitution of the binary blends obtained over a wide composition range (5/95–95/5) were examined by wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and dynamic mechanical measurements. A Ny6 homopolymer film and Ny6/PAA blends with PAA concentrations ≥ 50 wt% exhibited a WAXD profile stemmed from the coexistence of two different crystalline modifications of Ny6, i.e. the α and γ forms. Above 50 wt% PAA content, the solution-cast blends showed no definite crystallinity. It was found by DSC thermal analysis that the polymer pair is substantially miscible in the non-crystalline state, since a single glass transition temperature (T_g) was situated between the T_gs of the two homopolymers at every composition; however, the T_g versus composition plots did not follow a monotonic function but yielded a peak maximum at a PAA concentration of c. 25 wt%. In order to interpret this phenomenon, attention was given to the following point revealed by dynamic mechanical measurements: at the compositions of Ny6/PAA = 100/0–50/50, a phase of low regularity such as a nematic structure is formed in the cast films.     

Investigation on the interpenetrating polymer networks (ipns) of polyvinyl alcohol and poly(N-vinyl pyrrolidone) hydrogel and its in vitro bioassessment

Poly(vinyl alcohol) (PVA) and poly(N-vinyl pyrrolidone) (PVP) composite hydrogel with interpenetrating polymer networks (IPNs) was prepared by in situ polymerization and compared with pure PVA hydrogel. The prepared IPN hydrogel was characterized by infrared spectroscopy (IR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. The mechanical property and cell culture were also tested. The results show that PVP can chemically bond with PVA and form uniform blend hydrogel. The content of PVP can affect the structure, crystallinity, glass transition temperature (T_g), and mechanical property of the hydrogel. The T_g of the PVA hydrogel is 2.7°C while the T_g of the IPN hydrogel is −37°C. The IPN hydrogel has lower glass transition temperature, corresponding to better elastic properties, and has better mechanical performance on stretch and compression than PVA hydrogel. The crystallinity (X_c) of PVA hydrogel and IPN hydrogel is 65.3 and 26.3%, respectively. The DMA curves and XPS analysis suggest that PVA and PVP are well miscible on a molecular level in the IPN hydrogel. The cell proliferation trend demonstrates that the addition of PVP has a positive influence on the cell growth and the IPN hydrogel may be used as a promising biomaterial for artificial cartilage substitute. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Physico-chemical,thermal, and mechanical properties of PLA-nHA nanocomposites: Effect of glass fiber reinforcement

In this study, tri-layered composites were prepared by reinforcing poly-lactic acid (PLA) nano-hydroxyapatite (n-HA) (1 and 5 wt%) and 20 mol% continuous phosphate glass fibers (PGF). Initially, the effect of addition of 1 and 5% n-HA on the structural, thermal, mechanical, and thermo-mechanical properties of 100% PLA was investigated. With 5 wt% n-HA addition the tensile modulus (TM), flexural modulus (FM), tensile strength (TS), and flexural strength (FS) of 100% PLA was improve by 14.9, 47.4, 6, and 32.9%, respectively. Whereas, the un-notched impact strength of the nanocomposites suffer 2% deterioration. However, T _g decreased by 0.3°C and T _c increased by 10°C as 5 wt% n-HA was added to 100% PLA. Afterwards, the 5% n-HA/PLA composite were reinforced with 20 mol% continuous PGF and the TM, FM, TS, and FS of the tri-layered composites were 162.6, 412.5, 28.4, and 157.4% higher as compared to 100%PLA. Furthermore, the storage modulus of the 1% n-HA-filled composites was 500 MPa lower than 100%PLA, while 5 wt% n-HA-filled composites showed similar storage modulus as 100% PLA. 5 wt% n-HA-filled composite showed the highest peak of loss modulus which may be attribute to the chain segment of PLA matrix after the incorporation of HA. Thus, n-HA and PGF reinforcement resulted in improved mechanical properties of the composites and have great potential as biodegradable bone fixation device with enhanced load-bearing ability.     

Basalt fiber reinforced and elastomer toughened polylactide composites: Mechanical properties,rheology, crystallization,and morphology

A series of the reinforced and toughened polylactide (PLA) composites with different content of basalt fibers (BF) were prepared by twin screw extruder. The toughness of BF/PLA composite s was improved further by the addition of polyoxyethylene grafted with maleic anhydride (POE-g-MAH), ethylene–propylene–diene rubber grafted with maleic anhydride (EPDM-g-MAH), and ethylene-acrylate-glycidyl methacrylate copolymer (EAGMA), relatively. The mechanical properties, rheology, crystallization, and morphology of BF/PLA composites were studied. The results showed that basalt fiber had significant reinforcing and toughening effect in comparsion with glass fiber. EAGMA was more effective in toughening BF/PLA composites than POE-g-MAH and EPDM-g-MAH. When the content of EAGMA achieved to 20 wt %, the impact strength of BF/PLA/EAGMA composite increased to 33.7 KJ/m², meanwhile the value was improved by 71.1% compared with pure PLA. According to dynamic rheometer testing, the use of the three kinds of elastomers increased the melt dynamic viscosity. Differential scanning calorimetry analysis showed that POE-g-MAH and EPDM-g-MAH can decrease the cold crystallization temperature (T_cc) to approximately 20°C and dramatically improve crystallinity (χ_c) of BF/PLA composites. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of citrate ester plasticizers on the thermal and mechanical properties of poly(DL‐lactide)

Citrate esters triethyl citrate, tributyl citrate, and acetyl tributyl citrate were used as plasticizers for amorphous poly(D,L ‐lactide) (PDLLA). The resultant compositions were analyzed by means of differential scanning calorimetry (DSC), dynamic mechanical thermal analysis, and tensile testing to investigate the properties of the blends. Glass transition temperatures (T_gs) obtained by DSC were also compared to theoretically calculated T_gs. Increasing plasticizer content decreased the resultant T_g of the blend with plasticizer efficiency enhanced as the molecular weight of the citrate ester increased. However, in blends with high plasticizer content, a lack of miscibility also occurred with increased molecular weight. Theoretical results were comparable with those obtained experimentally at compositions, which were miscible. Increasing plasticizer content increased the ductility and decreased the strength of the polymer. The addition of 10 wt % plasticizer to PDLLA decreased tensile strength by over 50% with the deterioration larger at higher concentrations of plasticizer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Development of high Tg epoxy resin and mechanical properties of its fiber‐reinforced composites

A new epoxy resin with high glass transition temperature (T_g) (～ 180°C) and a viscosity low enough for infiltration into dry reinforcements at 40°C was developed for the vacuum‐assisted resin transfer molding process. To study the curing behavior and viscosity, several blends were formulated using multifunctional resin, aromatic hardener, and reactive diluents. Effects of these components on the viscosity and T_g were investigated by thermomechanical analysis, dynamic scanning calorimetry, and rheometer. Experimental results showed that a liquid aromatic hardener and multifunctional epoxy resin should be used to decrease the viscosity to <1 Pa·s at 40°C. Moreover, the addition of a proper reactive diluent decreased the viscosity and simultaneously minimized the deterioration of T_g. Mechanical properties of the composite produced with the optimized blend were evaluated at both room‐temperature and high‐temperature conditions. According to the results, the composite showed comparable mechanical properties with that of the current commercial resin. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Amphiphilic networks. XI. Mechanical properties and morphology

The bulk properties of two types of amphiphilic networks, poly(2-hydroxyethyl methacrylate)-l-polyisobutylene (PHEMA-l-PIB, H-network) and poly(N,N-dimethylacrylamide)-l-polyisobutylene (PDMAAm-l-PIB, A-network), have been investigated. Tensile strengths decreased considerably by swelling, and the decrease was more severe by swelling in water than in n-heptane. Elongations increased by swelling in water; however, the change was not consistent upon swelling in n-heptane. The hardness of dry networks decreased with increasing PIB content, while for wet networks it was similar to dry networks containing 85 wt % PIB. Small-angle X-ray scattering showed that average interdomain spacings decreased with increasing PIB content. According to dynamic mechanical thermal analysis (DMTA) the glass transition temperatures (T_g) of the respective hydrophobic and hydrophilic components shift toward each other with increasing PIB content. A “liquid-liquid transition” (T_ll) above the T_g of the hydrophilic component was apparent by DMTA, but could not be found by differential scanning calorimetry (DSC). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 901–910, 1997     

Electrical and mechanical characteristics of composites consisting of fractionated poly(3‐hexylthiophene) and conducting particles

The dynamic viscoelasticity of fractionated poly(3‐ hexylthiophene)titanium carbide (P3HT/TiC) composites was examined with regard to their electrical characteristics. The elastic modulus (E′) at 0°C [i.e., near the glass‐transition temperature (T_g) of P3HT] increased with increasing TiC content of the composite. In particular, composites whose TiC content exceeded the threshold concentration showed a high E′. This was caused by the high E′ of TiC and the strong interaction between TiC and P3HT. When the sample was heated above the T_g, E′ decreased rapidly and an increase in the loss tangent appeared near the T_g of P3HT. Mechanical loss was caused by friction between TiC and P3HT. The change in mechanical characteristics affected the electrical conductivity. When the TiC content of the composite approximated to the threshold concentration, a significant change in mechanical characteristics took place, so that a large positive temperature coefficient (PTC) effect was observed near the T_g. To explain the PTC phenomenon, we propose a model of conductive pathway for P3HT/TiC. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1429– 1433, 2002     

Effects of mesoporous SBA-15 contents on the properties of polystyrene composites via in-situ emulsion polymerization

Different loading of mesoporous molecular sieve SBA-15 was used to prepare polystyrene (PS)/SBA-15 composite materials via in-situ emulsion polymerization. The influence of SBA-15 silica on the styrene emulsion polymerization was studied regarding to the monomer conversion, particle size and particle size distribution, stability and viscosity of the resulting emulsion. The structure and properties of the composites were investigated by infrared spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and gel permeation chromatography (GPC). In addition, the glass transition temperature (T_g), thermal mechanical property and thermal stability of the composite film were measured by differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA), respectively. The results indicated that the composite emulsion showed high monomer conversion, thick viscosity, low coagulum, uniform particle size and broad size distribution. Molecular weight of the polymer decreased with the increase of mesoporous silica. SBA-15 silica was dispersed evenly in PS matrix at a loading of 5 %. The PS/SBA-15 composite material containing 10 % silica maintained a certain ordered structure. DMA results demonstrated that PS/SBA-15 composite exhibited greater storage modulus and high T_g compared to pure PS. The improved thermal stability and T_g of the composite were also confirmed by the TGA and DSC.     

Pultruded fiber reinforced blocked polyurethane (PU) composites. II. Processing variables and dynamic mechanical properties

Unidirectional fiber reinforced blocked polyurethane (PU) composites have been prepared by the pultrusion process. The effects of processing variables on the mechanical properties and dynamic mechanical properties of fiber reinforced PU composites by pultrusion have been studied. The processing variables investigated included pulling rate (in-line speed), die temperature, postcure time and temperature, and filler type and content. The dynamic mechanical properties of the composites produced by the process were studied utilizing dynamic mechanical spectrometer. Results show that the composites possessed various optimum pulling rates at different die temperatures. From the DSC data analysis, swelling ratio, and mechanical properties, the optimum die temperature was determined. It was found that the mechanical properties increase with filler content for various types of filler. The increasing of mechanical properties depends on the optimum postcure temperature and time. However, the properties decreased for longer postcure times since the composite materials were degraded. The glass-transition temperature (T_g) increased slightly and the damping peak (tan δ) was broadened due to fiber reinforcement. The dynamic mechanical moduli (G′, G″) of pultruded PU composites are apparently higher than those of the matrices. The moduli (G′, G″) increase with increasing fiber and filler content, and the damping peak becomes broad. Effect of postcuring on the degree of crosslinking, T_g, and dynamic modulus will be discussed.     

Study on morphology control and how to affect mechanical properties of polyimide/silica hybrid films

A series of polyimide (PI)/silica hybrid films were prepared by sol–gel method, using hydrolyzed tetraethoxysilane and poly amic acid‐imides (PAA‐Is), which were different imidization degree controlled by chemical imidization method. The imidization degree was characterized by Fourier transform infrared spectra and their corresponding morphology was characterized by scanning electron microscopy. The results show that there are two kinds of silica particles and their formative morphology obeys the double phase separation mechanism. According to the increase of PAA‐I imidization degree, amount of nano silica particles decreased and the diameter of macro silica particles increased in the hybrid films. Tensile testing, dynamic mechanical analysis, and thermal mechanical analysis results show that, according to the amount of nano silica particles increasing, the hybrids have the higher the mechanical properties, glass transition temperature (T_g), and thermal expansion coefficient. Through controlling PI/silica hybrid films microstructure, its mechanical properties can be controlled. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhancement in the thermal and dynamic mechanical properties of high performance liquid crystalline epoxy composites through uniaxial orientation of mesogenic on carbon fiber

In this work, a high performance liquid crystalline epoxy composite was prepared and the effect of the alignment of LCE with long lateral substituent on the carbon fiber surface curing at low temperature on fracture toughness, dynamic mechanical, and thermal properties of liquid crystalline epoxy with lateral substituent (LCE6) was investigated by polarized optical microscopy (POM), wide angle X‐ray diffraction measurements (WAXS), dynamic mechanical analysis (DMA), thermogravimetric (TGA), and scanning electron microscopy (SEM). Curing degree of the composite was observed by FTIR. The experimental results indicate that the fracture toughness, glass transition temperature (T_g), thermal stability, degradation kinetics are associated with the alignment of LCE6 along long axis of carbon fiber. The alignment of LCE6 on carbon fiber surface can increase mesogen network density, which leads to higher fracture toughness, higher thermal stability, increase of the activation energies and higher T_g of the composite. The dynamic mechanical analysis shows that the compoaite possesses extremely higher dynamic storage moduli, which indicates that this LCE6/DDM/CF composite can be a high performance composite. Thus, the compoaite can be a potential candidate for advanced composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40363.     

The glass transition temperature of nitrated polystyrene/poly(acrylic acid) blends

Low-molecular-weight polystyrene was nitrated to different levels. The nitrated polystyrene was blended with different molecular weights of poly(acrylic acid), PAA. The glass transition temperatures (T_g) for the mixtures were investigated by differential scanning calorimetry. A single T_g was observed for all blends, indicating single-phase blends. In general, it was found that the T_g increases with molecular weight of PAA. The T_g values of the blends showed a positive deviation from the linear average T_g as a result of strong hydrogen bonding between the segments of the component polymers. The observed T_g values were not adequately represented by simple predictive equations or by single-parameter fitting equations. However, two-parameter fitting equations gave a reasonable representation of the data.     

Surface‐grafting of ground rubber tire by poly acrylic acid via self‐initiated free radical polymerization and composites with epoxy thereof

Commercially available recycled ground rubber tire (GRT) particles, found to contain persistent mechano‐free radicals confirmed by electron paramagnetic spectroscopy for the first time self‐initiates free radical polymerization of acrylic acid (AA). The poly acrylic acid (PAA) grafted GRT (PAA‐g‐GRT) was confirmed by Attenuated Total Reflection Fourier Transform Infrared spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis (TGA). Epoxy composites using the PAA‐g‐GRT as filler were prepared and their mechanical properties were studied. The PAA‐g‐GRT/epoxy composite showed higher mechanical properties with an increase of modulus up to 180% as compared with the neat GRT/epoxy composite. Surface morphology of GRT, neat GRT/epoxy, and PAA‐g‐GRT/epoxy composites were analyzed by scanning electron microscopy. This technology introduces a new concept to functional and reactive recycling and the cost effective utilization of renewable resource green materials. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Preparation and properties of multiwalled carbon nanotube/epoxy‐amine composites

Different amounts of multiwalled carbon tubes (MWCNTs) were incorporated into an epoxy resin based on diglycidyl ether of bisphenol A and both epoxy precursor and composite were cured with 4,4′‐diamino diphenyl sulfone. Transmission and scanning electron microscopy demonstrated that the carbon nanotubes are dispersed well in the epoxy matrix. Differential scanning calorimetry measurements confirmed the decrease in overall cure by the addition of MWCNTs. A decrease in volume shrinkage of the epoxy matrix caused by the addition of MWCNTs was observed by pressure–volume–temperature measurements. Thermomechanical and dynamic mechanical analysis were performed for the MWCNT/epoxy composites, showing that the T_g was slightly affected, whereas the dimensional stability and stiffness are improved by the addition of MWCNTs. Electrical conductivity measurements of the composite samples showed that an insulator to conductor transition takes place between 0.019 and 0.037 wt % MWCNTs. The addition of MWCNTs induces an increase in both impact strength (18%) and fracture toughness (38%) of the epoxy matrix with very low filler content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

In situ polymerization of titanium isopropoxide in polycaprolactone: Properties and characterization of the hybrid nanocomposites

In this study, tetra isopropyl ortho titanate (TTIP) and polycaprolactone (PCL) were chosen as the ceramic precursor and the continuous phase, respectively, for the preparation of novel nanocomposites by using an in situ sol‐gel process. In addition, acrylic acid grafted polycaprolactone (PCL‐g‐AA) was investigated as an alternative to PCL. The hybrids (PCL/TiO₂ and PCL‐g‐AA/TiO₂) were characterized via Fourier transform infrared (FTIR) spectroscopy, dynamic mechanical thermal analysis (DMA), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and Instron mechanical testing. It was found that the carboxylic acid groups of acrylic acid acted as coordination sites for the titania phase to form chemical bonds, thus improving the properties of the acrylic acid grafted composite compared with its acrylic‐acid‐free counterpart. The TiO₂ content also determined the strength of interfacial bonding between the polymer chains and the ceramic phase, as shown by changes in glass transition temperature (T_g) with TiO₂ content. The maximum values of tensile strength and T_g were obtained with the PCL‐g‐AA/TiO₂ composite at 10 wt % TiO₂. At TiO₂ contents above this, excess particles led to segregation between the organic and inorganic phases. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1749–1757, 2004     

Morphology and properties of poly(benzoxazine‐co‐urethane)s based on bisphenol‐S/aniline benzoxazine

Poly(benzoxazine‐co‐urethane) was prepared by melt‐blending bisphenol‐S/aniline‐type benzoxazine (BS‐a) with isocyanate‐terminated polyurethane (PU) prepolymer based on 2,4‐toluene diisocyanate and poly(ethylene glycol), followed by thermally activated polymerization of the blend. The copolymerization reaction between BS‐a and PU prepolymer was monitored using Fourier transform infrared spectroscopy. The morphology, dynamic mechanical properties, and thermal stability of the poly(benzoxazine‐co‐urethane) were studied using scanning electron microscopy, dynamic mechanical analysis, and thermogravimetry. Homogeneous morphology is shown in scanning electron micrographs of the fracture surfaces of poly(benzoxazine‐co‐urethane)s with different urethane weight fractions, and the roughness of the surface increases with urethane content increasing. Correspondingly, a single glass transition temperature (T_g) is shown on the dynamic mechanical analysis curves of the poly(benzoxazine‐co‐urethane)s, and the T_g is higher than that of the polybenzoxazine. With increase in the urethane content, the T_g and water absorption of poly(benzoxazine‐co‐urethane) increase, whereas the storage modulus and thermal stability decrease. POLYM. ENG. SCI., 53:2633–2639, 2013. © 2013 Society of Plastics Engineers     

Studies on the glass transition of blends of nylon-6 and polyacrylic acid

The glass transition temperatures (T_g) of blends of polyacrylic acid (PAA)–Nylon 6 in various proportions used as membrane material in pervaporation separation of acetic acid–water and ethanol–water mixtures were determined using differential scanning calorimetry (DSC). All the samples examined showed a single T_g which lay between the T_g of Nylon 6 and PAA, indicating that complete miscibility was achieved in these polymer blends. Further evidence of complete miscibility was obtained by scanning electron microscopy (SEM) of cross sections of the blended films which showed a uniform structure. An interesting phenomenon was observed during the DSC measurements which showed a shift in T_g of the blended samples with scanning time. Infrared and thermogravimetric measurements were conducted to further investigate this phenomenon and the results were explained as the change in T_g being caused by the elimination of water molecules and the formation of anhydrides in the polyacrylic acid portion of the polymer blends.     

Microstructure,crystallization and dynamic mechanical properties of polyamide/clay nanocomposites after melt‐state annealing

Polyamide 6/clay (PA/clay) nanocomposites produced by melt‐compounding were treated under various melt‐state annealing processes. The effect of melt‐state annealing on the microstructure, crystallization, and dynamic mechanical properties was characterized by transmission electron microscope (TEM), modulated differential scanning calorimetry (MDSC), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and dynamic mechanical analysis (DMA). Clay layers were exfoliated in PA matrix. The crystalline transformation between α and γ‐crystalline phase was virtually dependent on the annealing process and clay loading. After melt‐state annealing between 230 and 250°C, clay induced the appearance of a new endothermic peak in PA/clay. PA/clay after melt‐state annealing exhibited a higher elastic modulus above T_g and a lower β relaxation below T_g as compared with the non‐annealed sample. FTIR analysis demonstrated that the melt‐state annealing caused strong hydrogen bonding interaction of amide groups with clay layers. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Gelatin/montmorillonite hybrid nanocomposite. I. Preparation and properties

Gelatin/montmorillonite (MMT) hybrid nanocomposite was directly prepared with unmodified MMT and gelatin aqueous solution. Thermal and mechanical properties of the composite were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and tensile tests. The results indicated that an intercalated or partially exfoliated nanocomposite could be achieved, and the properties of the composite were significantly improved. A T_g peak of high temperature disappeared in the DSC curve of the composite, and the thermogravity and thermally decomposed rate decreased obviously. The tensile strength and Young's modulus were also improved notably, which varied with MMT content, as well as the pH of gelatin matrix. Meanwhile, SEM photographs showed a plasticizing trend of gelatin fracture surface due to intercalation with MMT. Furthermore, the wet mechanical behavior was initially studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1189–1194, 2002