Tensile behavior and structural evolution of poly(lactic acid) monofilaments in glass transition region

A series of amorphous poly(lactic acid) (PLA) monofilaments with various D-isomer contents of 1∼9 mol% have been prepared and then elongated uniaxially at 25∼65 °C in the glass transition region. Both initial modulus and maximum strength of PLA monofilaments are appreciably decreased with increasing the temperature, especially at ∼50 °C, and they were somewhat lower for the monofilament with higher D-isomer content. Structural evolution, chain orientation, and thermal properties of PLA monofilaments drawn uniaxially with various draw ratios at 65 °C were then investigated by using wide-angle X-ray diffraction, polarized Raman spectroscopy, and differential scanning calorimetry, respectively. X-ray diffraction patterns clearly exhibited the development of chain orientation and stain-induced crystallization of the monofilaments as a function of draw ratio (DR). The dichroic ratio, a measure of the chain orientation, was quantitatively evaluated from the polarized Raman spectra. It was revealed that the dichroic ratios increased up to DR=4 and decreased slightly at DR>4 owing to the strain-induced crystallization for PLA monofilaments with D-isomer contents of 1 and 4 mol%. The glass transition and cold-crystallization temperatures of PLA monofilaments increased and decreased, respectively, with the increment of DR. The strain-induced enthalpy relaxation endothermic peak appearing in glass transition region became intense with increasing the DR.     

Effect of conformation on the properties of uniaxially drawn polylacide films upon drawing temperature

Polylactide(PLA) films were drawn at various drawing temperature of 65, 90 and 120 °C. The effects of drawing temperature on structural conformation and properties of PLA films were investigated. It was confirmed that the PLA films at drawing temperature of 65 and 90 °C were composed of α′ phase crystal form. The strain-induced crystallization and molecular orientation increased with increasing the draw ratio, which result in improving the mechanical and thermal properties of α′ phase PLA films. However, at drawing temperature of 120 °C, the strain-induced crystallization and molecular orientation of PLA films were not distinctly detected. It was supposed that the rate of the chain relaxation was faster than chain orientation and strain-induced crystallization during uniaxial drawing process.     

Fine structure and physical properties of poly(buthylene terephthalate) sheets prepared by roller drawing method

Poly(butylene terephthalate) sheets were prepared by roller-drawing method with various draw ratio. The drawing temperature is 100 °C and draw ratios were varied 2, 2.5, 3, 3.5 and 4. The effect of draw ratio on the crystal structure, the molecular orientation, dynamic viscoelastic properties, sonic modulus and tensile properties of the roller-drawn PBT sheets were investigated. In WAXD results, with increasing of the draw ratio, (010) and (100) planes of preferred orientation have the strongest intensity on the equator. In the meridional scans, it was confirmed that α and β crystal co-existed in the roller drawn PBT sheets with various draw ratio. Uniaxially roller-drawn PBT sheets clearly increased orientation along the stretched direction at high draw ratio. And the four-methylene groups of PBT orient along the surface of the sheet. The mechanical properties of PBT sheets were improved by orientation-induced crystallization during roller drawing process at 100 °C.     

Crystal structure and thermal properties of poly(vinylidene fluoride)-carbon fiber composite films with various drawing temperatures and speeds

PVDF-CF composite films were prepared using a melt pressing method. The PVDF-CF composite films were cut into rectangular shapes with a gauge length and width of 10 and 5 mm, respectively. The films were drawn using a universal testing machine equipped with a hot chamber. The drawing temperatures and speeds were 50∼150 °C and 100∼000 %/min, respectively. The crystal structure and physical properties of the resulting PVDF-CF films were investigated by wide angle X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis and scanning electron microscopy. The crystal form of the initial films was the 〈alpha〉 phase (non polarity, lamellar structure) of PVDF. The maximum draw ratio was 4.2. The drawn PVDF-CF films prepared at 100 °C were mainly the 〈beta〉 phase (polarity, fibrillar structure) of PVDF. With increasing drawing speeds, the 〈alpha〉 phase became the dominant phase of PVDF in the PVDF-CF films. The thermal properties of the PVDF-CF films improved with increasing drawing temperature, and the dynamic mechanical properties improved with increasing drawing speed.     

Carbon nanofiber/poly(vinylidene fluoride-hexafluoro propylene) composite films: The crystal structure and thermal properties with various drawing temperatures

Carbon nanofiber (CNF)/polyvinylidene fluoride-hexafluoro propylene (PVDF-HFP) composite film was prepared by solution casting and melt pressing. The resultant 2 % CNF/PVDF-HFP composite films were uniaxially drawn at 50 °C, 75 °C, and 100 °C, respectively. In the SEM images, the morphology of drawn CNF/PVDF-HFP composite film confirmed the orientation of the CNF and the polymer matrix. The WAXD results showed the coexistence crystal phase of PVDF-HFP. The drawn CNF/PVDF-HFP composite film demonstrates improved electrical properties. The DSC thermogram results indicated no change in the melting temperature but slightly increased crystallinity with increasing drawing temperature. Dynamic mechanical analysis and tensile test showed an improvement in the storage modulus and stress at a drawing temperature of 75 °C.     

Hybrid organic-inorganic POSS (polyhedral oligomeric silsesquioxane)/polypropylene nanocomposite filaments

Octamethyl-POSS and Octaphenyl-POSS reinforced polypropylene nanocomposite monofilaments were prepared by melt blending route. It was observed that incorporation of Octamethyl-POSS and Octaphenyl-POSS in polypropylene show improvement in mechanical as well as thermal properties. Octaphenyl POSS/PP nanocomposites show significant increase in thermal stability even at very low concentration as compared to neat polymer matrix. An increase of 100 and 140 °C was observed in thermal degradation temperature at 5 wt% loss and maximum degradation over neat PP filaments respectively at low OP-POSS loadings (<5 wt%). Both Octamethyl-POSS and Octaphenyl-POSS act as lubricating agents facilitating drawing which results in improvement in orientation as well as mechanical properties.     

Study of microstructure of oriented PET fibres exposed to supercritical carbon dioxide

Samples of partially oriented yarn (POY) PET fibers were uniaxially drawn at temperatures below, near, and above the glass transition temperature at a constant draw ratio before exposure to supercritical carbon dioxide (scCO₂) in the presence of tension at a temperature of 80 °C and a pressure of 220 bar. The effects of drawing temperature and scCO₂ exposure on structural changes and on mesomorphic transitions, in particular, were investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and birefringence and density measurements. A good correlation was obtained among the results obtained from various techniques. Results indicated that the development of a transient mesophase structure depended strongly on process temperature. By drawing PET fibers in the samples at temperatures below the glass transition (cold-drawing), a mesophase structure developed in which the highly extended chains played a key role in structural changes incurred. Meanwhile, exposure to scCO₂ led to the plasticization of the samples accompanied by their reduced glass transition and cold crystallization temperatures. This process also gave rise to the appearance of a second melting peak at about 135 °C that is related to the melting of imperfect and thin crystals, thereby inducing structural changes in the treated fibers. In the case of samples subjected to cold drawing and to scCO₂ exposure, the transformation of the mesophase structure into the crystalline phase was found to be strongly affected by scCO₂ exposure, while this same effect was negligible in the case of hot drawn samples.     

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.     

Crystallization and molecular relaxation of poly(ethylene terephthalate) annealed in supercritical carbon dioxide

Poly(ethylene terephthalate) was annealed at different temperature and pressure of supercritical carbon dioxide (CO₂) using samples quenched from the melt. Crystallization and molecular relaxation behavior due to CO₂-annealing of samples were investigated using differential scanning calorimetric and dynamic mechanical measurements. The glass transition and crystallization temperatures significantly decreased with increasing temperature and pressure of CO₂. The dynamic mechanical measurement of samples annealed at 150 °C in supercritical CO₂ showed three relaxation peaks, corresponding to existence of different amorphous regimes such as rigid, intermediate, and mobile domains. As a result, the mobile chains were likely to facilitate crystallization in supercritical state. It also led to the decreased modulus of CO₂-annealed samples with increasing pressure.     

Crystal structure and thermal properties of poly(vinylidene fluoridehexafluoropropylene) films prepared by various processing conditions

Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP) films were prepared using either a melt pressing or solution casting methods. The resulting PVDF-HFP films were drawn uniaxially at various drawing temperatures and speeds. The mp-PVDF-HFP films were more transparent and had more drawability than the sc-PVDF-HFP films. The crystal form of the initial films was the alpha-phase (non polarity) of PVDF. The maximum draw ratio was 7.6. The mp-PVDF-HFP films were prepared at a drawing speed of 2500 %/min at 100 °C. With increasing drawing speed, the beta-phase (polarity) became the dominant phase of PVDF in mp-PVDF-HFP films. The thermal properties of the resulting PVDF-HFP films improved with increasing drawing temperature.     

Effect of thermal annealing on mechanical properties of polyelectrolyte complex nanofiber membranes

Optimization of mechanical properties is required in the applications of tissue-engineered scaffolds. Thermal annealing strategy is proposed to improve the mechanical properties of polyelectrolyte complex nanofiber membranes. The effects of annealing on the structural and mechanical properties of electrospun chitosan-gelatin (CG) nanofiber membranes were investigated using tensile tests, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). Tensile test results showed that annealing processing at 90 °C produced 1.3-fold and 1.1-fold increase on Young’s modulus and tensile strength, respectively. By scanning electron microscopy (SEM) observation, it was found there was a formation of partial interfiber bonding when annealing temperature was elevated over the glass transition temperature (T _g ) of CG nanofibers. FTIR results showed enhanced molecular interactions within fibers, suggesting that annealing treatment promoted the conjunction between chitosan and gelatin. In contrast, no detectable changes in crystallinity for CG nanofiber specimens were exhibited on XRD patterns following annealing treatment. In addition, thermal annealing induced the improvement in thermal stability, aqueous stability and swelling capacity. Therefore, annealing is proved to be an effective strategy for mechanical enhancement of polyelectrolyte complex nanofibrous scaffolds. The enhanced stiffness and strength is mainly attributed to the formation of interfiber bonding and strengthened molecular interactions between chitosan and gelatin.     

Structure development and dynamic properties in high-speed spinning of high molecular weight PEN/PET copolyester fibers

The structure development and dynamic properties of fibers produced by high-speed spinning of P(EN-ET) random copolymers were investigated. The as-spun fibers were found to remain amorphous up to the spinning speed of 1500 m/min, and subsequent increases in speed resulted in the crystalline domains containing primarilyα crystalline modification of PEN. Theβ modification was not found up to spinning speeds of 4500 m/min. On the other hand, annealing of constrained fibers spun at the 2100 m/min at 180, 200, and 240°C exhibitedβ-form crystalline structure, while the annealed fibers spun in 600–1500 m/min range exhibited dominantlyα-form. Howeverβ-form crystals disappeared above the spinning speed of 3000 m/min. With increasing spinning speeds from 600 to 4500 m/min, the storage modulus of as-spun fibers increased continuously and reached a value of about 10.4 Gpa at room temperature. The tanδ curves showed theα-relaxation peak at about 155–165°C, which is considered to correspond to the glass transition. Theα-relaxation peaks became smaller and broader, and shift to higher temperatures as the spinning speed increases, meaning that molecular mobility in the amorphous region is restricted by increased crystalline domain.     

Characteristics of Electrical Heating Elements Coated with Graphene Nanocomposite on Polyester Fabric: Effect of Different Graphene Contents and Annealing Temperatures

This paper reports the fabrication of electrical heating elements based on the graphene/waterborne polyurethane (WPU) composite coated on polyester fabric with toughness like that of artificial leather. Samples were prepared with 0, 4, 8, and 16 wt% of graphene by using the knife edge method, and then, the samples were annealed from 100 oC to 160 °C. The graphene content had a large effect on the electrical and electrical heating properties. The surface resistivity was decreased by approximately 6 orders of magnitude with an increase from 0 wt% to 16 wt% graphene/WPU composite fabric. The electric heating properties were also improved, as indicated by the percolation threshold. Samples with various graphene contents were annealed, and it was found that the electrical and electrical heating properties were improved, and the most enhanced properties were obtained when the samples were annealed at 120 °C. The initial modulus and tensile strength were increased in comparison with those of 0 wt% and 16 wt% graphene/WPU composite coated on fabrics, but the elongation at break value was slightly decreased with an increasing graphene content. When the samples were annealed, initial modulus and tensile strength of samples were improved at 120 °C and 140 °C, and they were slightly decreased at 160 °C. However, the elongation at break showed an opposite tendency to the tensile strength. With the increase in content of graphene and annealing at 120 °C and 140 °C, the samples were more stiff and tough, and at 160 °C, the samples were softer. Therefore, graphene/WPU composite coated on polyester fabric by use of the annealing process may have applications in electrical heating elements due to its excellent heating performance and toughness like that of artificial leather.     

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.     

Preparation and characterization of melt-spun PVC filament yarns

Polyvinyl chloride (PVC) fibers were melt-spun to prepare mono and multifilament yarns. To find optimum spinning and drawing conditions, various parameters such as spinning temperature, spinneret diameter, drawing temperature, and drawing ratio were examined. From the observation of the spinnability under various conditions, we found that the optimum conditions were as following: the extrusion temperature and die temperature were 175–180°C and 185–190°C, and the drawing temperature and drawing ratio were 85–95°C and 3.4, respectively. Under these conditions, the spinneret diameter could be reduced to the minimum value, 0.5 mm. Spun PVC filament yarns were subjected to the different yarn texturing process of stuffing box and pin false-twist method. The PVC yarn fabric was prepared by the knitting of textured yarns. Finally, the anion-emission and antibiotic properties of the knitted PVC fabrics were precisely evaluated.     

Heat resistance,impact strength,and transparency of PET copolymer containing fluorenylidene bis(2-phenoxyethanol)

Poly(ethylene terephthalate) (PET) copolymers containing fluorenylidene bis(2-phenoxyethanol) (FBPE) were prepared. The glass transition temperature of copolymers increased continuously with the composition of FBPE. The glass transition temperature of PET/FBPE copolymer at loading of 15 mol% FBPE was 107 °C, which was 35 °C higher than that of PET. The melting temperature of PET/FBPE copolymers was decreased with the composition of FBPE, and it disappeared above 6 mol% of FBPE. The heat deflection temperature of copolymers increased from 60.7 °C for PET to 89.9 °C for the copolymer containing 15 mol% of FBPE. The values of optical transmittance of copolymers were 89-90 % at 550 nm, and no significant change was observed with the FBPE composition. The impact strength value of copolymer at loading of 10 mol% FBPE was 26 J/m, which was 20 J/m higher than that of PET.     

The evaluation of the thermal and mechanical properties of aramid/semi-carbon fibers hybrid composites

In this research work, aramid and semi-carbon fibers (SCFs) were hybridized in the form of interlayer or layer by layer into epoxy matrix by hand lay-up method. Afterward, the effect of hybridization on the thermal and mechanical properties of epoxy composites was characterized by thermal analysis; horizontal burning; tensile and bending tests. Based on the results of the mechanical tests, increasing SCFs to aramid fibers ratio decreased tensile strength, elastic and flexural modulus. But with increasing this ratio to 53 % failure strain reduced, whereas in the ratios of more than 53 %, the failure strain enhanced. The results of thermal analysis curves indicated that there are three stage mass loss at the temperature ranges of 100-220, 270-470 and 500-620 °C. It was also found that with increasing the SCFs to aramid fibers ratio decreased the third-stage of the mass loss. The results of horizontal burning showed that increasing the SCFs to aramid fibers ratio decreased the rate of burning.     

An effective and simple process for obtaining high strength silkworm (Bombyx mori) silk fiber

This article describes a new process for strengthening natural silk fibers. This process is simple yet effective for mass production of high strength silk fibers, enabled by drawing at a lower temperature and immediately heat setting at a higher temperature. The processing conditions were investigated and optimized to improve the strength. Silk fibers drawn to the maximum ratio at room temperature and then heat set at 200 °C show best tensile properties. Some salient features of the resulting fibers are tensile strength at break reaching 533±10.2 MPa and Young’s modulus attaining 12.9±0.57 GPa. These values are significantly higher than those of natural silk fibers (tensile strength increased by 44 % and Young’s modulus by 135 %). Wide-angle X-ray diffraction and FTIR confirm the transformation of silk I to silk II crystalline structure for the fiber obtained from this process. DSC and TGA data also provide support for the structural change of the silk fiber.     

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.     

Thermal and structure properties of biobased cellulose nanowhiskers/poly (lactic acid) nanocomposites

Cellulose nanowhiskers were used to improve the performance of poly (lactic acid) (PLA). The nanocomposites mixed with three different molecular weight of poly (ethylene glycol) (PEG) were characterized by mechanical testing, thermal gravimetry and differential scanning calorimetry. The tensile test showed an increase in tensile strength and elongation at break with the addition of PEG to PLA/CNW nanocomposites, the thermal analysis results showed an increase of crystallization temperature (T _c) and crystallization compatibility (larger crystallization and melting areas), which indicated that the cellulose nanowhiskers (CNW) and PEG or CNW alone should not be considered as nucleating agents for the PLA matrix; The CNW was homo-dispersed which contributed to decreasing mobility of polymer chain segments. The compatibility between hydrophobic PLA matrix and the hydrophilic CNW was improved by the addition of different molecular weight polymeric-PEG. The thermo gravimetric analysis indicated that the thermal stability of the different composites were reflected well in the region between 25 °C and 245 oC. The structure of the PLA/CNW/PEG composites was characterized by AFM, which showed that the CNW dispersed in the PLA matrix evenly.