Grafting of Triphenylmethyl Group onto Polyurethane and the Impact on the Shape Recovery and Flexibility at Extremely Low Temperature

The bulky and rigid triphenylmethyl group was grafted onto polyurethane (PU) to reduce the molecular attractions between hard segments and to improve the mobility of the PU chain under freezing conditions. The triphenylmethyl-grafted PU exhibited improvement in the cross-link density, solution viscosity, maximum tensile stress, shape recovery at 10 °C, and low temperature flexibility compared with the plain PU. The soft segment melting was not affected by the grafted triphenylmethyl group, whereas the soft segment crystallization disappeared with the increase of the triphenylmethyl group content. The glass transition temperature (T_g) increased with the increase of the triphenylmethyl group content. The rapid increase of the tensile strength and shape recovery at 10 °C resulted from the cross-linking effect, whereas the strain at break and shape retention at -25 °C slightly decreased with the increase of the triphenylmethyl group content. The triphenylmethylgrafted PU displayed an excellent low temperature flexibility even at -50 °C due to the improved mobility of the PU chain compared to ordinary PU.     

Characterization and mechanical properties of prepolymer and polyurethane block copolymer with a shape memory effect

The prepolymer and the final polyurethane (PU) block copolymer were synthesized by reacting 4,4-methylene bis(phenylisocyanate) with poly(tetramethylene glycol) and the prepolymer with 1,4-butanediol as a chain extender, respectively, to investigate the relation between phase separation and it’s resulting properties. According to FT-IR data, the phase separation of hard and soft segments in the prepolymer and the PU block copolymer grew bigger by increasing the hard segment content, and the PU showed more dominant phase separation than the prepolymer. The heat of fusion due to soft segments decreased in both the prepolymer and the PU by increasing the hard segment content, whereas the heat of fusion due to hard segments increased in the PU did not appear in the prepolymers. The breaking stress and modulus of the prepolymer increased by increasing the hard segment content, and the elongation at break decreased gradually, and the PU showed the highest breaking stress and modulus at 58 % hard segment content. However, the best shape recovery of the PU was obtained at 47 % hard segment content due to the existence of proper interaction among the hard segments for shape memory effect. Consequently, the mechanical properties and shape memory effect of the PU were influenced by the degree of phase separation, depending on the incorporation of chain extender as well as the hard segment content.     

Preparation of starch-based polyurethane films and their mechanical properties

In this study, polyurethane films were prepared using starch as the main polyol component, and the mechanical properties of these films were investigated. The starch content of the polyols was 30–50 wt%. To confirm the formation of a urethane linkage between the −OH of starch and −NCO of toluene 2,4-diisocyanate, Fourier transform infrared (FT-IR) spectroscopic analysis was performed. Differential scanning calorimetry (DSC) thermograms of the polyurethanes resulted in two endothermic peaks, which shifted to higher temperatures with increasing starch content and −NCO/−OH molar ratio. Due to the melting behavior of polyurethane, films could be prepared by hot pressing at an appropriate temperature. Polyurethane films were prepared with various polyol starch content and −NCO/−OH molar ratios. Tensile testing indicated that the breaking stress and elastic modulus increased significantly with starch content and −NCO/−OH molar ratio. In addition, bending tests indicated an increase in breaking stress and bending modulus with starch content and −NCO/−OH molar ratio and decreased breaking strain. The strain rate in both tensile and bending tests had a significant effect on the mechanical properties.     

Use of acetylated softwood kraft lignin as filler in synthetic polymers

Partially acetylated softwood kraft lignin (ASKL) is used as filler in synthetic polymers such as LDPE, PP, PS and PET. ASKL/synthetic polymer composites are prepared by melt-blending and compression molding with ASKL content up to 50.0 wt%. The chemical and physical properties of ASKL/synthetic polymer composites are also investigated. TGA results show that ASKL is more thermally stable than SKL up to 200 °C. FTIR spectra demonstrate a formation of free volume by crystallization of LDPE in ASKL/LDPE composite. DSC results show that the glass transition temperature of ASKL decreased by acetylation, and ASKL/synthetic polymer composites (50/50 w/w) have a single glass transition. The AFM images of ASKL/synthetic polymer composites show no significant phase separation. Young’s moduli of ASKL/synthetic polymer composites increased with ASKL content in some extents. Tensile strength and breaking strain of ASKL/PET composite are almost retained in spite of the addition of ASKL as a result of a contraction in free volume or densification.     

The grafting of recycled polyol from waste polyurethane foam onto new polyurethane and its impact on shape recovery and water vapor permeation

Recycled polyols from waste polyurethane (PU) foams were grafted onto PU to improve the properties such as tensile strength, shape recovery, low-temperature flexibility, and water compatibility. The recycled polyol was either purified by column chromatography before grafting or was used directly for grafting. The soft segment melting temperature of PU did not notably increase with the addition of polyol, whereas the glass transition temperature increased with increased polyol content. The tensile strength sharply increased at low polyol content and decreased at high polyol content, while the strain at break did not significantly change with an increase in polyol content. The shape recovery at 10 oC notably improved compared with unmodified PU and remained high after four cyclic tests. Polyol-grafted PU demonstrated better lowtemperature flexibility and reduced the water vapor permeability of PU membranes. Overall, grafting recycled polyol onto PU significantly improved the tensile stress, shape recovery, and low-temperature flexibility of PU.     

Structures and mechanical properties of plied and twisted polyacrylonitrile nanofiber yarns fabricated by a multi-needle electrospinning device

Polyacrylonitrile (PAN) nanofiber filaments were manufactured continuously for several hours by a homemade multi-needle electrospinning device. The yarns were continuously obtained by plying and twisting nanofiber filaments using a self-made twisting device. The structures and mechanical properties of yarns were investigated. The influences of twist setting temperatures and periods of time on morphology and mechanical properties were discussed. The results showed that the alignment degree of nanofibers along the filament axis could reach 70.9 %. The twist angle increased with increasing twists and the number of filaments. With increasing twists, the breaking stress and strain increased initially and then decreased; the maximum breaking stress and strain were 34.7 MPa and 26.1 %, respectively; the initial modulus decreased with increasing twists and plies, the maximum modulus was 391.3 MPa. Both the breaking stress and strain increased with the increase of twist setting temperatures and times. The optimal setting temperature and time were 90 °C and 30 min, respectively, the maximum breaking stress and strain were 32.8 MPa and 20.8 %, meanwhile, the crystallinity improved from 34.5 % to 39.9 %. This study demonstrates the possibility of continuously and stably manufacturing PAN nanofiber yarns.     

Compressive viscoelastic properties of softwood kraft lignin-based flexible polyurethane foams

Softwood kraft lignin (SKL)-based water-blown flexible polyurethane foams were prepared using SKL as a crosslinking agent and a hard segment polyol. Polyethylene glycol (PEG) as a soft segment diol and 2,4-toluene diisocyanate (TDI) were used. While increasing hard segment content caused the increase in crosslink density in foams, the foams became more and more viscous with increasing hard segment content due to the distinctive phase heterogeneity in foams. In this case, the contributiveness of the filler-like behaviors of separated hard segments always overtook the crosslinking effects derived from SKL in terms of overall viscoelasticity, thus the resultant viscometric properties such as tanδ _max and hysteresis loss increased as hard segment content increased. Furthermore, increasing M _n,PEG caused the severer microphase separation and intensified the filler effects in foams, thus the foams became more viscous with increasing M _n,PEG. The 25 % and 65 % CFD values and Young’s moduli of foams increased with increasing hard segment content due to the increase in crosslink density for foams, and the properties also increased with increasing foam density. Most of foams showed the support factors in the range of 2–3, which are suitable values for cushioning use. Even though the microscopic deformation behaviors in foams are irrelevant to foam density, the cyclic compressive tests showed that the higher foam density possess the better shape recovery performances.     

Influence of Drawing and Annealing on the Crystallization,Viscoelasticity, and Mechanical Properties for Middle-molecular-weight Polyethylene Fishing Monofilaments

The influence of drawing and annealing on the crystallization, viscoelasticity and mechanical properties for middle-molecular-weight polyethylene (MMWPE) fishing monofilaments was investigated. It was found that the drawing procedure had a positive effect on the crystallization of the MMWPE fishing monofilaments. Meanwhile, the glass transition temperature of the MMWPE monofilaments shifted to higher temperature, and the α-relaxation associated with crystalline phases became higher and broader with the increase in the drawing ratio. Moreover, the breaking strength of MMWPE fishing monofilaments can be effectively improved by increasing the drawing ratio. Meanwhile, the knot strength increased first and then decreased. However, the increase in annealing temperature improved the knot strength. With increasing annealing temperature, the orientation factor decreased and induced the γ-relaxation peak at high magnitude. This indicated that the amorphous structure could become disordered during annealing treatment. In addition, the annealing temperature can clearly influence the working temperature dependence of the stress-strain behavior. When the working temperature rose from 20 °C to 30 °C, the MMWPE monofilaments after annealing at 120 °C exhibited low modulus loss due to their high α- transition temperature. Thus, an important method for improving the mechanical properties by controlling the drawing and annealing conditions was established.     

Mechanical anisotropy in unidirectional glass fabric reinforced oligomeric siloxane modified polyester composites

In this study, the effect of incorporation of oligomeric siloxane into unsaturated polyester on mechanical behavior of unidirectional glass fiber/polyester composites has been investigated by means of tensile, flexural and short beam shear tests. The amount of oligomeric siloxane added into unsaturated polyester was in the range 1?C3 % by weight of the glass fabrics. Mechanical tests were conducted at different angles (0 °, 45 °, and 90 °) with respect to fiber direction. The higher siloxane content exhibited a tendency to have greater tensile, flexural and interlaminar shear strength values in machine direction, bias direction and cross direction. From Scanning electron microscopy images, the presence of polyester particles on the unidirectional glass fiber surface confirmed better adhesion.     

Studies on the ternary blends of liquid crystalline polymer and polyesters

Thermotropic liquid crystalline polymer made up of poly(p-hydroxybenzoate) (PHB)-poly(ethylene terephthalate) (PET) 8/2 copolyester, poly(ethylene 2,6-naphthalate) (PEN) and PET were mechanically blended to pursue the liquid crystalline phase of ternary blends. Complex viscosities of blends decreased with increasing temperature and PHB content. DSC thermal analysis indicated that glass transition temperature (Tg) and melting temperature (Tm) of blends increased with increasing PHB content. Both tensile strength and initial modulus increased with raising PHB content and take-up speed of monofilaments. In the WAXS diagram, only PEN crystal reflection at 2Θ=15.5^o appeared but PET crystal reflection was not shown in all compositions. The degree of transesterification and randomness of blends increased with blending time but sequential length of both PEN and PET segment decreased.     

Synthesis of thermotropic polyurethanes containing imide units and their mesophase behavior

Thermotropic polyurethanes were synthesized from 1,6-hexane diisocyanate (HDI) as a diisocyanate, 1,6-hexane diol (HD), and rigid diols containing imide unit such as N,N′-bis(4-hydroxyphenyl)-3,4,3′,4′-biphenyl-dicarboxyimide (BPDI) or bis-N-(4-hydroxyphenyl)-4,4′-oxydiphthalimide (ODPI). The effects of structure difference between BPDI and ODPI and composition of HD/BPDI (ODPI) on the thermal and liquid crystalline behavior were studied. Thermotropic polyurethanes with an inherent viscosity of 0.59–0.70 were obtained. The melting temperature of BPDI-based polyurethanes were in the range of 150–290°C, however, those of ODPI-based polyurethanes were in the range of 150–190°C. All the polyurethanes based on ODPI (25–100 mole %) clearly exhibited a stable liquid crystalline phase, and BPDI-based polyurethane having 5–25% of BPDI showed a mesophase. The melting and isotropization temperatures (T _m , T _i ) andΔT(T _i −T _m ) increased with increasing BPDI and ODPI content. The polyurethanes based on BPDI has higher melting points and thermal stability compared to ODPI-based polyurethanes.     

Physical and mechanical properties of jute, bamboo and coir natural fiber

A systematic study has been carried out to investigate the mechanical and physical properties of jute, bamboo and coir (brown and white) single fibers. The tensile properties (tensile strength, Young’s modulus and strain to failure) were determined by varying span length. Scanning electron microscopic analysis was also carried out to determine the physical properties of fibers in order to correlate with its strength, Young’s modulus and strain to failure. The Young’s modulus and strain to failure were corrected using newly developed equations. The study revealed that with increasing test span length the Young’s modulus increased and tensile strength as well as strain to failure decreased. This is because no extensometer could be used in this test set-up and machine displacement (denoted by α) was used for the modulus determination. It is also attributed that larger span length helps to minimize the machine displacement compared to smaller ones due to the reduced relative effect of slippage in the clamps. Among all fibers, the Young’s modulus of bamboo fiber was the highest. Jute fiber had smoother surface compared to other three examined fibers.     

The effect of gelation and curing temperatures on mechanical properties of pultruded kenaf fibre reinforced vinyl ester composites

Process parameters such as gelation and curing temperatures are parameters that influence the pultruded kenaf reinforced vinyl ester composites profile quality and performance. The effect of gelation and curing temperatures on mechanical (tensile, flexural and compression properties) and morphological properties of pultruded kenaf reinforced vinyl ester composites were analyzed. Obtained results indicated that increase of gelation and curing temperatures during the pultrusion process of kenaf reinforced vinyl ester composites influenced the mechanical properties of the composites. When the gelation and curing temperatures were increased, tensile strength, tensile modulus, flexural strength, flexural modulus and compressive strength were affected and they were either increased or decreased. The factors that influenced these results include improper curing, excessive curing, water diffusion, and the problems associated with interfacial bonding between fibre and matrices. The optimum values of the tensile strength for gelation and curing temperatures of kenaf pultruded composites were at 100 °C and 140 °C, tensile modulus at 80 °C and 180 °C, flexural strength at 100 ° and 140 °, flexural modulus at 120 ° and 180 °, and compressive strength at 120 °C and 180 °C, respectively. The scanning electron micrographs of tensile fractured samples clearly show that with the increase in gelation temperature, it creates the lumens between matrix and kenaf fibre thus reducing tensile properties whereas increasing the curing temperature caused less fibre pull out and enhanced fibre/matrix interfacial bonding.     

Green composites. I. physical properties of ramie fibers for environment-friendly green composites

The surface topography, tensile properties, and thermal properties of ramie fibers were investigated as reinforcement for fully biodegradable and environmental-friendly ‘green’ composites. SEM micrographs of a longitudinal and cross-sectional view of a single ramie fiber showed a fibrillar structure and rough surface with irregular cross-section, which is considered to provide good interfacial adhesion with polymer resin in composites. An average tensile strength, Young’s modulus, and fracture strain of ramie fibers were measured to be 627 MPa, 31.8 GPa, and 2.7 %, respectively. The specific tensile properties of the ramie fiber calculated per unit density were found to be comparable to those of E-glass fibers. Ramie fibers exhibited good thermal stability after aging up to 160°C with no decrease in tensile strength or Young’s modulus. However, at temperatures higher than 160°C the tensile strength decreased significantly and its fracture behavior was also affected. The moisture content of the ramie fiber was 9.9%. These properties make ramie fibers suitable as reinforcement for ‘green’ composites. Also, the green composites can be fabricated at temperatures up to 160°C without reducing the fiber properties.     

Influence of reducing agents on properties of thermo-molded wheat gluten bioplastics

The present work aims to study the influence of reducing agents of sodium bisulfite, sodium sulfite and thioglycolic acid on the equibiaxial extensional deformation of glycerol plasticized wheat gluten and the properties of gluten bioplastics thermo-molded at 125 °C. Moisture absorption, weight loss and water uptake, uniaxial tensile properties (Young's modulus, tensile strength, elongation at break and tensile set), and morphology observations were performed to characterize the physical properties of the thermo-molded gluten bioplastics. The results showed that reducing agents facilitated the viscous flow and restrained the elastic recovery of the plasticized gluten while not hindering the crosslinking reaction of gluten proteins during thermo-molding. On the contrary, reducing agents do not significantly influence moisture absorption, Young's modulus, tensile strength and the morphology of the gluten bioplastics thermo-molded at 125 °C. It is shown that reducing agents are highly effective for tailoring the flow viscosity of the plasticized gluten dough and the mechanical properties of thermo-molded gluten bioplastics.     

Electrospinning of <Emphasis Type="Italic">Bombyx mori</Emphasis> silk fibroin nanofiber mats reinforced by cellulose nanowhiskers

Cellulose nanowhisker (CNW) reinforced electrospun Bombyx mori silk fibroin (SF) nanofibers were fabricated. The morphology, structure, and mechanical properties of nanofibers were investigated by FE-SEM, TEM, FTIR, and tensile testing. It was found that the nanofiber size decreased obviously from 250 nm in the unreinforced mat to 77–160 nm in the CNW reinforced mats depending on the CNW content due to the increased conductivity of spinning dope. In the reinforced mats, the CNWs were embedded in the SF matrix separated from each other, and aligned along the fiber axis. There was a positive correlation between the CNW content and the tensile strength and Young’s modulus of reinforced mats. However the strain at break dropped gradually with the increase of CNW. When the CNW content was 2 w/w%, the tensile strength and Young’s modulus of reinforced SF nanofiber mats were about 2 times higher than those of unreinforced mat.     

Properties of Frozen Wheat Doughs at Subzero Temperatures

The subzero properties of wheat doughs were measured by dynamic mechanical thermal analysis (DMTA) and dielectric thermal analysis (DETA) over the temperature range −90 to +40 °C and by¹H-nuclear magnetic resonance (NMR) T₂relaxation over the range −45 to 0 °C. The experiments revealed two transitions in the dough: one independent of frequency at −10 °C (attributed to ice melting) and one dependent on frequency at −30 °C (attributed to a glass transition). The glass transition temperatures measured by DMTA moved to higher temperatures during frozen storage when the optimal water content of dough was used. A reduction in the water content eliminated this phenomenon. A similar effect of water reduction was observed by NMR studies, in which amplitude ratios and decay times were used to calculate the phase transitions. However, the glass transition recorded by NMR was independent of frozen storage with optimal water content. The changes of water state in frozen doughs were studied by ultracentrifugation (the amount of liquid phase) and NMR (freezable water based on liquid amplitude ratios). Frozen storage increased the liquid phase in dough with optimal water content. Thus, ice crystals are growing during frozen storage resulting in the concentration of polymers and a higher glass transition observed by DMTA. The increase of liquid phase during storage was substantially lower when the water content of dough was decreased. Ice crystals» growth can be minimised by reducing water content. The experiments were carried out with four different flours. The measurement of glass transition temperature by DMTA, DETA or NMR did not reveal great differences in doughs made from different flours. The amount of liquid phase was strongly flour dependent.     

Modeling and differential evolution optimization of PAN carbon fiber production process

In this research, results of an experimental and artificial neural network fuzzy interface system (ANFIS) modeling of operating parameters on tensile strength of the carbon fibers are investigated. To do these experiments, the commercial polyacrylonitrile (PAN) fiber of Polyacryl Iran Corporation (PIC) was used as the precursors. The results show that increasing all of parameters improves tensile strength performance. ANFIS was applied to predict tensile strength of carbon fibers as a function of stabilization temperature at first stage (STFIS), stabilization temperature at second stage (STSS), stabilization temperature at third stage (STTS), stabilization temperature at fourth stage (STFOS), and carbonization temperature (CT). The optimum levels of influential factors, determined for tensile strength are STFIS 200 °C, STSS 225 °C, STTS 240 °C, STFOS 260 °C, CT, and 1400 °C. The modeling results showed that there is an excellent agreement between the experimental data and the predicted values. Furthermore, the fiber process is optimized applying differential evolution (DE) algorithm as an effective and robust optimization method.     

Mechanical properties of denim fabric reinforced poly(lactic acid)

Denim, a twilled cotton fabric, was used to enhance the mechanical and thermal properties of poly(lactic acid) (PLA). The denim fabric reinforced composites with different numbers of denim layers were fabricated by using a hand layup method. The impact, tensile, and dynamic mechanical properties of the composites were observed with increasing denim layers to examine the reinforcing effect of denim fabrics. Numerical analysis was carried out to model the elastic modulus of the composite by using a commercial software. Three-dimensional geometry of the denim fabric reinforced PLA composite was generated through a CAD program, and the elastic modulus was calculated by applying uniform deformation on one surface. The impact strength, tensile strength, and thermal properties of the composites were improved by piling denim fabrics. The denim fabric reinforced composites exhibited outstanding impact strength due to the retarded crack propagation as well as large energy dissipation. The 3 layer denim reinforced composite showed best results among all specimens, and its impact strength, tensile strength, and tensile modulus were measured to be 82 J/m, 75.76 MPa, and 4.65 GPa, respectively. The PLA/denim composites have good mechanical properties and can substitute traditional composites such as glass fiber or carbon fiber reinforced composites.     

Moisture absorption effect on thermal, dynamic mechanical and mechanical properties of injection-molded short glass-fiber/polyamide 6,6 composites

Polymer composites of polyamide 6,6 reinforced with short glass fiber were prepared by injection molding, conditioned under dry, 50 % relative humidity and wet. Investigations by DSC, DMA and tensile tests were conducted. FLD study showed that more fiber degradation occurred during processing of the composites with higher fiber loading. DSC analysis revealed that the incorporation of glass fiber and moisture into the PA 6,6 matrix resulted in a remarkable decrease in the degree of crystallinity. DMA results revealed the glass transition temperatures were sensitive to moisture absorption and their values moved to a lower temperature upon exposure to moisture. Incorporation of glass fiber into the polyamide 6,6 gave rise to a significant improvement in tensile modulus and tensile strength, while tensile strain was reduced. Exposure to different environments from dry to wet conditions resulted in a decrease in the strength and modulus, while tensile strains decreased.