Mechanical properties and microstructure of poly(ethylene terephthalate) microfiber prepared by carbon dioxide laser heating

We determined that a poly(ethylene terephthalate) microfiber was easily obtained by irradiating a carbon dioxide laser to an annealed fiber. The annealed fiber was prepared by zone drawing and zone annealing. First, an original fiber was zone drawn at a drawing temperature of 90°C under an applied tension of 4.9 MPa, and the zone‐drawn fiber was subsequently zone annealed at 150°C under 50.9 MPa. The zone‐annealed fiber had a degree of crystallinity of 48%, a birefringence of 218.9 × 10^?3, tensile modulus of 18.8 GPa, and tensile strength of 0.88 GPa. The microfiber prepared by laser heating the zone‐annealed fiber had a diameter of 1.5 μm, birefringence of 172.8 × 10^?3, tensile modulus of 17.6 GPa, and tensile strength of 1.01 GPa. The draw ratio estimated from the diameter was 9165 times; such a high draw ratio has thus far not been achievable by any conventional drawing method. Microfibers may be made more easily by laser heating than by conventional technologies such as conjugate spinning. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1955–1958, 2003     

Biodegradable polymers for use in surgery — poly(glycolic)/poly(Iactic acid) homo and copolymers: 2. In vitro degradation

The degradation mechanism of a series of polyglycolic/polylactic acid, (PGA/PLA), homo and copolymers synthesized as in Part 1¹, has been studied _vitro. An in vitro test model similar to that described in a previous study⁹, was used. The effects of time, temperature and pH on the rate and mechanism of degradation were elucidated. The degree of degradation was monitored molecularly by gel permeation chromatography (g.p.c.), tensile strength determination and mass loss measurements. The mechanism of degradation is shown to be by hydrolysis. The copolymers of PGA and PLA are shown to have a wide range of degradation rates governed by the hydrophilic/hydrophobic balance and crystallinity of the respective copolymer. The effect of the glass transition temperature (T_g) of PGA on its sensitivity to degradation is also demonstrated.     

Hydrolytic degradation of nonoriented poly(β-propiolactone)

The hydrolytic degradation of poly(β-propiolactone) with a molecular weight M_w of 32,000 has been studied in a buffered salt solution (pH 7.2) at 37°C. Within 42 days, the embrittlement of the samples made tensile strength measurement impossible, which is due to the rapid reduction of molecular weight, 50% reduction after 49 days. The maximum weight due to water absorption was measured to 1.2 wt %, reached after 2 days. The absorbed water acts as a plasticizer in poly(β-propiolactone) observed by the displacement in the maxima of the tan δ_α peak. A fast increase of crystallinity in the samples has been observed during the first 50 days of degradation, with the increase continued up until 190 days, after which a decline of the crystallinity can be observed, indicating hydrolityc degradation of the crystalline part of the samples. The mass loss of the samples becomes prominent after 150 days of immersion and reached a value of 14.6% after 260 days.     

Characterisation of vulcanised natural rubber behaviour by monotonic and in situ cyclic X-ray scattering tests

Abstract

The effect of curing and loading conditions on the mechanical response of natural rubber are investigated by monotonic and in situ X-ray cyclic tensile tests. Tests are conducted on four samples, which differ by vulcanisation conditions. Samples are subject to two strain rates (2.7?×?10^??3 s^??1 and 16.66?×?10^??3 s^??1), and numerous imposed elongation levels range from 450 to 900%. The coupling between the strain rates and the elongation levels on the stress softening evolution resulting from strain induced crystallisation is investigated. In situ thermomechanical tensile cyclic test is performed in order to withdraw the effect of the strain induced crystallisation on the maximum stress decrease. The experimental results analysis shows that an optimum vulcanisation condition (150°C, 30?min) enhances the hardening process in the monotonic loading due to the strain induced crystallisation. However, under optimum curing conditions, cyclic loading induces a large hysteresis loss, a high stress softening and a high degree of strain induced crystallinity. The material softening sensitivity is controlled by coupled effect of strain ranges and elongation levels. This panoply of experimental measurements present a key information for material parameters identification that are useful to predict the lifetime of engineering components made of natural rubber such as racks, laminated rubber bearings and tires.     

Dynamic tensile strength of polyurea-bonded steel/E-glass composite joints

The dynamic tensile strengths of E-glass composite/polyurea and polyurea/steel interfaces within the E-glass composite/polyurea/AL-6XN stainless steel joint were measured using a laser spallation technique. Values of 370?±?20?MPa were obtained for the polyurea/composite interface while a much higher value of 486?±?20?MPa was obtained for the steel/polyurea interface. Because of the transient nature of the stress pulse, the strain rate changes continuously as the interface stress builds up. A peak strain rate of 5?×?10⁵?s^?1 was estimated. The effect of moisture on the tensile strength of the E-glass/polyurea interface was also examined. The effect was found to be minimal, with the tensile strength stabilizing at 320?±?25?MPa after 30?days of exposure to a 90%RH, 50?°C environment. When comparing the strengths of corresponding interfaces in an epoxy-bonded joint from a previous study, it was concluded that polyurea results in a much stronger and durable joint.     

Strain‐rate‐dependent mechanical properties of polypropylene separator for lithium‐ion batteries

The mechanical integrity of battery separators is critical for battery safety and durability. A comprehensive study of strain‐rate‐dependent tensile and puncture properties of a polypropylene lithium‐ion battery separator is presented here with a new model. Due to anisotropy of the polymeric membrane, tensile testing was conducted for different directions. Results showed that tensile strength and elastic modulus were increased 1000% and 500%, respectively, for different directions. It was also demonstrated that tensile strength changed 10 to 25% with strain rate (1.67 × 10^?4 to 1.67 × 10^?1 s^?1) for different directions. An equation was obtained for the first time for flow stress versus strain rate at varied tensile directions with respect to machine direction. Moreover, puncture testing was performed and it was shown that puncture strength was increased 140% with increasing strain rate from 0.25 to 250 mm min^?1. Two failure modes were also observed in puncture samples. Finally, Eyring's model was used to calculate activation enthalpy of the porous polypropylene separator. © 2020 Society of Chemical Industry     

Effect of gamma irradiation and irradiation temperature on hydrolytic degradation of synthetic absorbable sutures

The purpose of this study is to examine the effects of γ irradiation and the relative magnitude of T_irr to T_g on the physical, mechanical, thermal, morphological, and hydrolytic properties of two types of synthetic absorbable polymers. Polyglycolic acid (PGA) and glycolide-trimethylene carbonate block copolymer fibers in the form of 2/0 size Dexon and Maxon sutures from Davis/Geck were used in this study. In addition, injection-molded PGA disks were also used for determining how different polymer morphology affected the outcomes of γ irradiation and irradiation temperature. These two types of biomaterials were ⁶⁰Co γ irradiated at two irradiation temperatures (55 and ?78°C in dry ice). Both γ-irradiated and control speciments were immersed in a phosphate buffer solution of pH 7.44 at 37°C for various durations of hydrolysis. After each predetermined duration, the specimens were removed for subsequent testing which included determinations of tensile strength, weight loss, level of crystallinity, melting temperature, intrinsic viscosity, surface morphology, and infrared spectroscopic characteristics. γ irradiation at both irradiation temperature resulted in a faster hydrolytic degradation of these two biodegradable polymers. There was no apparent irradiation temperature effect in terms of mass loss, intrinsic viscosity, level of crystallinity, and melting temperature. However, irradiation temperature effect was evident in those properties that depended on the tie-chain segments located in the noncrystalline domains, such as tensile strength. The observed seffect of irradiation temperature was attributed to chain mobility which could facilitate cage recombination of macromolecular radical pairs at the irradiation temperature lower than the glass transition temperature of the irradiated polymers. © 1995 John Wiley & Sons, Inc.     

Control of structure, morphology and property in electrospun poly(glycolide-co-lactide) non-woven membranes via post-draw treatments

Non-woven biodegradable membranes fabricated by electrospinning have recently attracted a great deal of attention for biomedical applications. In this study, microstructure, morphology and texture of electrospun poly(glycolide-co-lactide) (GA/LA: 90:10, PLA10GA90) non-woven membranes were investigated after post-draw and thermal treatments to tailor the degradation and mechanical properties. As-prepared electrospun PLA10GA90 membranes exhibited a low degree of crystallinity. When annealed at elevated temperatures without drawing, the membrane showed a higher degree of crystallinity with distinct lamellar structure but no overall orientation. The crystal orientation improved significantly when the membrane was drawn and annealed. As the elongation ratio increased, the degree of orientation and the tensile strength were increased. The corresponding tensile retention time was also increased from 2 to 12 days during in vitro degradation. Post-drawn and annealed membranes exhibited a slower degradation rate in the beginning of incubation, but a faster rate after two weeks of degradation when compared to as-spun membranes.     

Flexural fatigue behavior and residual strength evolution of SiCnws-C/C composites

The flexural fatigue behavior and residual flexural strength evolution of SiC nanowires reinforced carbon/carbon (SiCnws-C/C) composites were investigated. Specimens were loaded at a stress level of 65% of their static flexural strength for 10⁵, 5?×?10⁵ and 10?×?10⁵ cycles, and their residual flexural strength was increased by 4.87%, 13.73% and 62.45% respectively after cyclic loading. Results indicate that the residual strength after cyclic load is affected by the formation and propagation of cracks, interfacial degradation, as well as the relief of residual thermal stress. An appropriate interfacial debonding and releasing of residual thermal stress are responsible for the large improvement of residual strength of SiCnws-C/C composites after 10?×?10⁵ fatigue cycles. Compared with carbon/carbon composites, SiCnws-C/C composites demonstrate higher mechanical strength and stronger resistance to crack propagation, which are ascribed to the strengthening effect brought by the SiC nanowires, including their pull-out, breaking and bridging.     

A chemical means to study the in vitro hydrolytic degradation of poly(glycolic acid)

A chemical means was developed to examine the in vitro hydrolytic degradation of both γ-irradiated and nonirradiated poly(glycolic acid) (PGA)-absorbable polymers for the purpose of obtaining information how irradiation affected PGA degradation and how the results related to the previously observed mechanical and morphological data. The method was based on the chemical reaction between the degradation product of the polymer, glycolic acid, and chromotropic acid, and the subsequent measurement of the absorbance of the reaction products by a UV/visible spectrophotometer. It was found that the unirradiated PGA specimens exhibited a two-stage hydrolytic degradation mechanism. This observation supported the previously hypothesized hydrolytic degradation mechanism on the basis of the level of crystallinity data. As the dosage of irradiation increases, the characteristic two-stage degradation mechanism becomes less profound and eventually disappears at 20 Mrads. A monotonic degradation profile was then observed at this dosage level. As reported in the literature, the widespread use of mechanical properties to evaluate the degradation phenomena of this class of polymer does not, however, provide the details of the degradation mechanism as revealed by the present study. The interrelationship between tensile strength, level of crystallinity, glycolic acid concentration, and pH levels of the medium, and their changes as hydrolytic degradation proceeds, are discussed for the purpose of elucidating the mechanism in more detail.     

The temperature and strain-rate dependence of mechanical properties in polyoxymethylene

The computer aided design approach used in current applications of semicrystalline polyoxymethylene (POM) requires high strain-rate mechanical data. The primary aim of this work has been to measure the room temperature modulus and tensile strength of injection molded samples of POM of different molecular weights at cross-head speeds of between 10^?5 ms^?1. We observe no major transition in bulk mechanical behavior in this range of test speeds, the Young's modulus E, in particular, showing little strain rate dependence. This is rationalized on the basis of tensile tests over a range of temperatures, these indicating room temperature to correspond to the plateau in the E(T) curves (T_g for these materials is taken to be ?70°C, and the DSC melting onset occurs at ～ 170°C). The tensile strength increases as ～log(d?/dt) and the behavior is found to be highly nonlinear, strains to fail of the order of 1 being observed even at the highest strain rates, depending on the molecular weight. It is believed that the yield stress of th crystalline regions determines the tensile strength above T_g, the higher degree of crystallinity associated with lower molecular weights resulting in a slightly higher tensile strength. Nevertheless, failure is qualitatively brittle, with no necking and relatively little permanent deformation. This behavior is discussed in terms of morphological investigations of the fractured samples by optical and scanning electron microscopy (SEM). In attempting to relate ultimate failure to the molecular/crystalline structure of the samples, measurements of the critical stress intensity for crack initiation in mode I opening, K_IC, as a function of crystallization temperature T_c have been carried out using compact tension specimens machined from injection molded and compression molded plaques. K_IC increases with molecular weight and decreases with T_c at low test speeds (in spite of an increase in crystallinity with T_c). This is accounted for in terms of a crack shielding model for crack initiation and of molecular rearrangements occurring during crystallization which lead to a decrease in the effective entanglement density with T_c. The implications of this model are then compared with K_IC results over a range of cross-head speeds and temperatures.     

Highly deacetylated chitosan and its properties

A preparative method has been established for obtaining chitosan products which have a desired degree of deacetylation of up to virtually 100%. Effective deacetylation was attained by intermitently washing the intermediate product in water two or more times during the alkali treatment. The weight average molecular weight (M?_w) of the product, which was measured by gel permeation liquid chromatography, was about 5 × 10⁵ at the highest deacetylation of nearly 100%, and the degradation of the molecular chain was not so significant. Tensile strength of the wet film increased markedly with increasing degree of deacetylation, while the dry film did not show a corresponding significant increase of the tensile strength. In the infrared spectra of chitosan film new sharp bands appeared especially at the high degree of deacetylation. This was attributed to increased “crystallization” brought about by high deacetylation.     

Molecular Orientation and Mechanical Properties of Poly(Vinyl Alcohol) Fibers

Abstract

A number of poly(vinyl alcohol) fibers with different draw ratios was characterized by measuring the birefringence, crystalline orientational order, crystallinity, tensile strength, and modulus. The birefringence, tensile strength and modulus increased with increasing draw ratio whereas the crystallinity and crystalline order parameters remained constant within narrow limits. The increase in birefringence has to be attributed solely to an increase in chain orientation in the amorphous phase of the semicrystalline fiber. The tensile strength and modulus are therefore directly related to the chain orientation in the amorphous phase. With the aid of a simple two-phase model it was found that the modulus of the amorphous phase in its disordered conformation was 4.8 GPa. The intrinsic birefringence of the amorphous phase was found to be 79 × 10^?3, i.e. much higher than the value obtained for the crystalline phase (52 × 10^?3). When this value was used in calculations, it was found that the order parameter of the amorphous phase increased from around 0.1 for a draw ratio of 1 to approximately 0.6 for a draw ratio of 5, whereas the order parameter of the crystalline phase was close to 1 for all draw ratios.     

Facile fabrication of polyethylene/silver nanoparticle nanocomposites with silver nanoparticles traps and holds early antibacterial effect

Antibacterial polyethylene (PE)/silver nanoparticle (AgNP) nanocomposites containing AgNPs at concentrations of 5 × 10^?5, 5 × 10^?4, and 5 × 10^?3 wt % were fabricated and tested. Transmission electron microscopy revealed an even dispersion of surface AgNPs in the PE/AgNP nanocomposites. No AgNP agglomeration was observed. The tensile strength, elongation at break, and Young's modulus of these PE/AgNP nanocomposites were similar to those of neat PE. Differential scanning calorimetry demonstrated that the PE/AgNP nanocomposites and neat PE had similar melting and crystallization temperatures of 126 ± 0.5 and 109 ± 0.6°C, respectively. The heats of fusion of the PE/AgNP nanocomposites containing AgNPs at concentrations of 5 × 10^?5 and 5 × 10^?4 and of 5 × 10^?3 wt % were lower than those of neat PE by 5 and 7%, respectively. These PE/AgNP nanocomposites were immersed in shaking liquid cultures of the potential pathogenic bacteria Escherichia coli, Bacillus subtilis, and Salmonella typhimurium in the lag phase. The results show that the growth rates of all of the tested bacteria were restricted effectively after 1.5, 3, and 6 h of cultivation, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43331.     

Influence of polycaprolactone/polyglycolide blended electrospun fibers on the morphology and mechanical properties of polycaprolactone

Polycaprolactone (PCL) and polyglycolide (PGA) are two biopolymers that have been used as in situ biomedical devices for various applications. The obstacle of creating a composite that captures the benefit of PCL's long degradation time, while acquiring the strength from PGA is overcoming the lack of surface adhesion between the two biopolymers for stress transfer to occur. This study investigates the use of miscible PCL‐PGA blended fibers, created by electrospinning, to increase the interfacial bonding of fibers to the PCL matrix of the polymer–polymer composite. The use of the blended fibers will thereby create the ability of load transfer from the long‐term PCL matrix to the stronger PCL‐PGA fiber reinforcement. The incorporation of the PCL‐PGA fibers was able to increase the tensile yield strength and Young's modulus over that of the bulk PCL, while decreasing the percent elongation at break. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40224.     

Properties and structure of never-dried cotton fibers. III. Cotton fibers from bolls in early stages of growth

Like other kinds of cotton fibers already studied, American cotton fibers taken from cotton bolls immediately before and after opening show high angles of torsional rotation during ambient humidity changes. Cotton fibers taken from cotton bolls at 19 and 24 days postanthesis show remarkably higher angles of rotation and much lower dry and wet tensile strengths than the fibers taken from cotton bolls immediately before and after opening. The wet tensile strength of cotton fibers at 24 days postanthesis is higher than the dry strength like the fibers taken from bolls immediately before and after opening, but fibers at 19 days postanthesis show almost the same tensile strength in the never-dried, dried, and rewetted states. CP/MAS ¹³C NMR spectroscopy reveals that the never-dried cotton fibers at 19 days or longer postanthesis have high crystallinities. It seems that the degree of crystallinity is somewhat decreased in the dry state and restored by rewetting. The crystallinity increases with the age of growth.     

Preparation and characterization of chitosan/PEG/gelatin composites for tissue engineering

Chitosan scaffolds have gained much attention in tissue engineering. However, brittleness and low biodegradability limit scaffolds application, especially in use as guided tissue regeneration membranes (GTRm) in surgical operations. The first objective of this work is to improve the brittleness of the chitosan membrane, which is not desired for use via adding polyethylene glycol (PEG) to chitosan, and the second objective is to accelerate the degradation rate by blending gelatin with the binary chitosan‐PEG mixture. The addition of PEG softened the blend membrane in vision and in touch. The tensile compliant increased from 7.87 × 10^?3 (MPa^?1) for chitosan membrane to 3.63 × 10^?1 (MPa^?1) for chitosan‐PEG‐gelatin (CPG) membrane. Degradation results in vitro indicated that CPG membrane degraded faster and weight loss increased more significantly than chitosan membrane and the lowest tensile strength of CPG membrane could meet the requirement of the application. CPG membrane showed significant improvement in degradation and flexibility in comparison with the chitosan membrane. Cell adhesion, viability, and proliferation onto the external surface of CPG membrane with C2C12 cell had been evaluated in vitro and quantified by a methyl thiazolyl tetrazolium (MTT) reduction assay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of tensile strain rate on the mechanical properties of constrained-uniaxially and simultaneous-biaxially drawn poly(ethylene terephthalate) sheets

The dependency of the mechanical properties (Young's modulus, yield strength, breaking strain, and breaking energy) of preoriented poly(ethylene terephthalate) (PET) sheets on the tensile deformation speeds was examined and discussed in relation to changes of density and birefringence. The procedures for preorientation were constrained-uniaxially (CU) and simultaneous-biaxially (SB) drawings at 65°C. The performance characteristics of the present tensile testing at room temperature were obtained over a wide range of extension rates (1.7 × 10^?4?13.1 m/s = 0.29–2.3 × 10⁴%/s) without changing the mode of deformation and the shape of the test pieces. The CU drawn PET is strain-rate-independent and mechanically superior in structure in the preextended direction with draw ratio λ > 2.5. In the SB drawn PET such a structure comes into existence at λ > 3, which has, furthermore, no dependency on draw direction (mechanically isotropic). The draw ratio of the latter case corresponded to the birefringence (?Δn/d) of about 5 × 10^?2. These results imply a possibility of producing the strain rate (from low to impact speeds) independent, anisotropy-free, and mechanically superior molded products of PET if adequate extrusion or blow molding methods which induce multiaxial orientation with ?Δn/d > 5 × 10^?2 are developed.     

Preparation and characterization of poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) blends for proton exchange membrane

Poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) (PVdF/SPPESK) blend membranes are successfully prepared by solution blending method for novel proton exchange membrane (PEM). PVdF crystallinity, FTIR‐ATR spectroscopy, thermal stability, morphology, water uptake, dimension stability, and proton conductivity are investigated on PVdF/SPPESK blends with different PVdF contents. XRD and DSC analysis reveal that the PVdF crystallinity in the blends depends on PVdF content. The FTIR‐ATR spectra indicate that SPPESK remains proton‐conducting function in the blends due to the intactness of ? SO₃H group. Thermal analysis results show a very high thermal stability (T_d1 = 246–261°C) of the blends. PVdF crystallinity and morphology study demonstrate that with lower PVdF content, PVdF are very compatible with SPPESK. Also, with lower PVdF content, PVdF/SPPESK blends possess high water uptake, e.g., P/S 10/90 and P/S 15/85 have water uptake of 135 and 99% at 95°C, respectively. The blend membranes also have good dimension stability because the swelling ratios are at a fairly low level (e.g., 8–22%, 80°C). PVdF/SPPESK blends with low PVdF content exhibit very high proton conductivity, e.g., at 80°C, P/S 15/85 and P/S 10/90 reach 2.6 × 10^?2 and 3.6 × 10^?2 S cm^?1, respectively, which are close to or even higher than that (3.4 × 10^?2 S cm^?1) of Nafion115 under the same test condition. All above properties indicate that the PVdF/SPPESK blend membranes (particularly, with 10–20% of PVdF content) are very promising for use in PEM field. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermally induced crystallization and enzymatic degradation studies of poly (L‐lactic acid) films

Poly(L ‐lactic acid) (PLLA) films with different crystallinities were prepared by solvent casting and subsequently annealed at various temperatures (T_a) (80–110°C). The effects of crystallinity on enzymatic degradation of PLLA films were examined in the presence of proteinase K at 37°C by means of weight loss, DSC, FTIR spectroscopy, and optical microscopy. DSC and the absorbance ratio of 921 and 956 cm^?1 (A₉₂₁/A₉₅₆) were used to evaluate crystallinity changes during thermally induced crystallization and enzymatic hydrolysis. The highest percentage of weight loss was observed for the film with the lowest initial crystallinity and the lowest percentage of weight loss was observed for the film with highest crystallinity. FTIR investigation of degraded films showed a band at 922 cm^?1 and no band at 908 cm^?1 suggested that all degraded samples form α crystals. The rate of degradation was found to depend on the initial crystallinity of PLLA film and shown that enzymatic degradation kinetics followed first‐order kinetics for a given enzyme concentration. DSC crystallinity and IR absorbance ratio, A₉₂₁/A₉₅₆ ratio, showed no significant changes with degradation time for annealed PLLA films whereas as‐cast PLLA film showed an increase in crystallinity with degradation; this revealed that degradation takes place predominantly in the free amorphous region of annealed PLLA films without changing long range and short range order © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013