Effect of annealing on the structure and properties of polyvinylidene fluoride hollow fiber by melt‐spinning

Polyvinylidene fluoride hollow fibers were prepared by melt‐spinning technique under three spinning temperatures. The effects of annealing treatment on the structure and properties of hollow fiber were studied by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), tensile test, and scanning electron microscopy (SEM) measurements. DSC and WAXD results indicated that the annealing not only produced secondary crystallization but also perfected primary crystallization, and spinning and annealing temperature influenced the crystallinity of hollow fiber: the crystallinity decreased with the increase of spinning temperature; 140°C annealing increased the crystallinity, and hardly influenced the orientation of hollow fiber; above 150°C annealing increased the crystallinity as well, and furthermore had a comparative effect on the orientation. The tensile tests showed that the annealed samples, which did not present the obvious yield point, exhibited characteristics of hard elasticity, and all the hollow fiber had no neck phenomenon. Compared with the annealed sample, the precursor presented a clear yield point. In addition, the annealed samples had a higher break strength and initial modulus by contrast with the precursor, and the 140°C annealed sample showed the smallest break elongation. SEM demonstrated the micro‐fiber structure appeared in surface of drawn sample. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 935–941, 2007     

Enhancement of Mechanical Properties of FDM‐PLA Parts via Thermal Annealing

The objective of this study is to investigate the possibility of enhancing mechanical properties of poly(lactic acid) (PLA) samples processed by a rapid manufacturing (RM) technique by increasing PLA crystallinity degree via thermal annealing. The samples are manufactured by fused deposition modeling (FDM) at different temperatures and subsequently evaluated by three‐point bending flexural and tensile tests. The polymer processed at 215 °C is thermally annealed over its glass transition temperature in order to increase the degree of crystallinity to the maximum attainable level as measured by the differential scanning calorimetry and confirmed by X‐ray diffraction. The increase in the degree of crystallinity of FDM‐PLA enhances flexural stress of the samples by 11–17%. The study also demonstrates applicability of radiation sterilization for FDM‐PLA parts. Therefore, thermal annealing might be introduced into a standard RM technology of PLA, particularly for sterilizable customized implants, to efficiently improve their mechanical properties.     

Effect of crystallinity on enthalpy recovery peaks and cold‐crystallization peaks in PET via TMDSC and DMA studies

Poly(ethylene terephthalate) (PET) sheets of different crystallinity were obtained by annealing the amorphous PET (aPET) sheets at 110°C for various times. The peaks of enthalpy recovery and double cold‐crystallization in the annealed aPET samples with different crystallinity were investigated by a temperature‐modulated differential scanning calorimeter (TMDSC) and a dynamic mechanical analyzer (DMA). The enthalpy recovery peak around the glass transition temperature was pronounced in TMDSC nonreversing heat flow curves and was found to shift to higher temperatures with higher degrees of crystallinity. The magnitudes of the enthalpy recovery peaks were found to increase with annealing times for samples annealed ≤30 min but to decrease with annealing times for samples annealed ≥40 min. The nonreversing curves also found that the samples annealed short times (≤40 min) having low crystallinity exhibited double cold‐crystallization peaks (or a major peak with a shoulder) in the region of 108–130°C. For samples annealed long times (≥50 min), the cold‐crystallization peaks were reduced to one small peak or disappeared because of high crystallinity in these samples. The double cold‐crystallization exotherms in samples of low crystallinity could be attributed to the superposition of the melting of crystals, formed by the annealing pretreatments, and the cold‐crystallizations occurring during TMDSC heating. The ongoing crystallization after the cold crystallization was clearly seen in the TMDSC nonreversing heat flow curves. DMA data agreed with TMDSC data on the origin of the double cold‐crystallization peaks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An optical investigation of high‐tenacity polyester (H‐T PET) fibers annealed at different temperatures

A two‐beam “Interphako” interference microscope was used to study the effect of annealing on the physical properties of high‐tenacity poly(ethylene terephthalate) H‐T PET fibers. The PET fibers were annealed with free ends for 1 h at temperatures ranging from 100 to 200°C. The shrinkage, refractive indices, and orientation angle of the PET fibers were determined for different annealing temperatures. The measured birefringence and orientation function were found to have decreased with increasing temperature, whereas the degree of crystallinity and the onset temperature (DSC) increased. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Influence of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) on miscibility and properties of atactic poly(methyl methacrylate)

Miscibility and properties of two atactic poly(methyl methacrylate)‐based blends [containing 10 and 20% of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)] have been investigated as a function of thermal treatments. Differential scanning calorimetry and dynamic mechanical thermal analysis of blends quenched in liquid nitrogen or ice/water, after annealing at T > 190 °C, showed a single glass transition temperature, indicating miscibility of the components for the time‐temperature history. Two glass transition temperatures, equal to those of the pure components, are instead found for blends after annealing at T < 190 °C. Scanning electron microscopy confirmed the homogeneity for the former quenched blends and phase separation for the latter. These results indicate the presence of an upper critical solution temperature (UCST). Tensile experiments, performed on two series of samples annealed at temperatures above and below the UCST, showed that the copolyester induces a decrease of Young's modulus and stresses at yielding and break points, and a marked increase of elongation at break. Differences in tensile properties between the two series of annealed blends are accounted for by the physical state of the components at room temperature after annealing above or below the UCST. Copyright © 2004 Society of Chemical Industry     

Creating a Protective Shell for Reactive MoSi2 Particles in High‐Temperature Ceramics

Alumina encapsulated molybdenum silicide (MoSi₂) intermetallic particles were synthesized using a simple precipitation method followed by calcining at temperatures of 800°C–1000°C, to prevent the premature oxidation of MoSi₂ at high temperatures. The shell composition and the influence of the calcining temperature on microcapsule integrity were investigated by means of X‐ray photoelectron spectroscopy, X‐ray diffraction, scanning electron microscopy, and thermogravimetric analysis. The results demonstrate that the composition and the mechanical stability of the alumina shell can be tuned by the annealing temperature. After calcining at 800°C and 850°C the alumina shell remains intact. Calcining at higher temperature promotes the formation of mullite, which leads to cracking of the shell. However, when annealed at 1000°C for 24 h these cracks were filled with mullite and preserved the molybdenum silicide particles. Furthermore, the mechanical stability of the shell was improved by applying an intermediate calcining treatment at 450°C prior to the annealing process at 1000°C.     

Effect of high‐temperature annealing on the elastoplastic response of isotactic polypropylene in loading–unloading tests

A series of uniaxial tensile loading–unloading tests is performed on isotactic polypropylene at room temperature. Prior to mechanical testing, injection‐molded specimens are annealed for 24 h at temperatures T = 145, 150, 155, 158, 160, 163, and 165°C, which cover the entire region of high‐temperature annealing temperatures. A constitutive model is developed for the elastoplastic behavior of a semicrystalline polymer at small strains. The stress–strain relations are determined by six adjustable parameters that are found by matching observations in cyclic tests. Fair agreement is demonstrated between the experimental data and the results of numerical simulation. It is shown that all material constants are affected by the annealing temperature, which is explained by changes in the crystalline morphology driven by thermal treatment. Some of the adjustable parameters experience finite jumps in the vicinity of the critical temperature T_c = 159°C. These jumps are attributed to the α₂ → α₂′ phase transformation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 186–196, 2003     

Effects of annealing time and temperature on the crystallinity and heat resistance behavior of injection‐molded poly(lactic acid)

The effects of annealing time and temperature on the crystallinity of injection‐molded poly(lactic acid) (PLA) were investigated using differential scanning calorimetry and wide‐angle x‐ray diffraction. Differential scanning calorimetry, tensile test, and dynamic mechanical analysis showed that an increase in crystallinity in the PLA parts from the annealing treatment offers several benefits such as a higher glass transition temperature, better heat resistance, and greater storage modulus and tensile strength. Based on the experimental data, the degree of crystallinity, annealing time, and annealing temperature were found to closely follow the time–temperature superposition relationship. Namely, a master curve could be constructed based on either the Williams–Landel–Ferry equation or the Arrhenius relationship by shifting the crystallinity isotherms in the logarithmic scale horizontally along the log‐time axis. This relationship provides a quantitative guideline for annealing postinjection‐molded PLA parts to improve the heat resistance and mechanical properties. An increase of over 17% and 26% in tensile strength was achieved at an annealing temperature of 80°C for 30 min and 65°C for 31 h, respectively. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Gasoline permeation resistance of the as‐blow‐molded and annealed polyethylene,polyethylene/polyamide,and polyethylene/modified polyamide bottles

An investigation of the gasoline permeation resistance of the as‐blow‐molded and annealed polyethylene, polyethylene (PE)/polyamide (PA), and polyethylene/modified polyamide (MPA) bottles is reported. The gasoline permeation resistance improves dramatically after blending PA and MPA barrier resins in PE matrices during blow‐molding, and the order of barrier improvement corresponds to the order of barrier improvement of the barrier resins added in PE. Somewhat unexpectedly, the gasoline permeation rates of the annealed PE and/or PE/PA bottles annealed at 90°C or higher temperatures increase significantly with the annealing temperature and time. On the contrary, the gasoline permeation resistance of the annealed PE/MPA bottles increase significantly as the annealing temperature and/or time increase. For instance, the gasoline permeation rate of the PE/MPA bottle annealed at 120°C for 32 h is about 190 times slower than that of the as‐blow‐molded PE bottle. Further investigations found that, after blending the MPA and PA barrier resins in PE matrices, the relatively nonpolar hydrocarbon components present in the gasoline fuels were significantly blocked, without permeation during the permeation tests, in which the as‐blow‐molded PE/MPA bottle inhibited the permeation of hydrocarbon components more successfully than did the as‐blow‐molded PE/PA bottle. In contrast, the amounts of polar components that permeated through the as‐blow‐molded PE/PA and PE/MPA bottles were very small and about the same as the amount that permeated through the as‐blow‐molded PE bottle. Possible mechanisms accounting for these interesting behaviors are proposed in this study. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2827–2837, 2001     

Effect of high‐temperature annealing on the microstructure and mechanical properties of polypropylene with shish kebab or spherulite structure

Various annealing temperatures below, near, or above the melting temperature were used to anneal polypropylene with oriented shish kebab and isolated spherulite structures in this work. The results showed that a high annealing temperature decreases the time needed to achieve the ideal material property. When the annealing temperature is near or above the melting temperature, the impact strength would be 1.6 times improved by partial melting and recrystallization. The crystal structure of the oriented shish kebab or isolated spherulite structures was improved when annealed at 150 °C, whereas annealing at 165 or 170 °C recombined the crystal lamellae of the structure. Moreover, the high crystallinity and thick lamellae improved the impact and yield strength values of the spherulite structure. However, excessively high crystallinity and thick lamellae in the oriented shish kebab structure did not result in good mechanical performance. Therefore, the prediction of mechanical properties for the shish kebab structure based on crystallinity and lamellar thickness is not feasible. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46465.     

Influence of annealing treatment on the structure and properties of poly(4‐methyl‐1‐pentene)‐based films and membranes

The poly(4‐methyl‐1‐pentene) casting films were prepared by melt extrusion and annealed below the melting temperature. The effect of annealing conditions on the structure and properties of casting films and stretched membranes was discussed. In this work, a new peak around annealing temperature, as shown in melting curves, revealed the increase in thickness of lamellar structure. Annealing treatment led to improvements of amorphous thickness and crystal orientation. And the thickness of crystal phase correlated with the logarithm of annealing time. The increase in annealing temperature or time led to the improvements of the hard elasticity of samples. Additionally, the larger porosity of stretched membranes was observed as the annealing time and temperature increased. An optimum annealing condition to prepare microporous membranes was 30 min, 200 °C. This work also discussed the importance of annealing treatment in the preparation of microporous membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46491.     

X‐ray diffraction studies on reverse‐annealed polyethylenes

Linear low and high density polyethylene sheets were compression molded and crystallized at a 5–10°C/min cooling rate. Parts of the sheets were annealed at different temperatures up to 2°C below the melting temperature. The small angle X‐ray scattering (SAXS) and the wide angle X‐ray scattering intensities of the annealed samples were studied. SAXS intensities showed particle scattering with a bimodal size distribution. The estimated radii of gyration were 15–17 nm and 5–7 nm, respectively. The crystallinity and the radius of gyration increased slightly with increasing annealing temperature for some samples; others did not show any change. No peaks characteristic of intercorrelated lamellar crystallinity in the SAXS intensities developed during the annealing. The original broad peak of high density polyethylene disappeared from the SAXS recordings on annealing. The length of the perfect chain versus melting temperature was calculated by the Thomson‐Gibbs formula and Flory's concept of melting temperature depression where methyl groups and tertiary carbon atoms at the branches were regarded as second components (solvent). Linear relationships were found for both cases. Experimental data for a linear low density polyethylene obtained from the literature were in between the two functions. A lamellar model of crystallization corresponding to the data is proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 340–349, 2001     

All‐wood biocomposites by partial dissolution of wood flour in 1‐butyl‐3‐methylimidazolium chloride

After cedar‐derived wood flour (WF) and bark flour (BF) were mixed with 1‐butyl‐3‐methylimidazolium chloride (BMIC) at 100°C, the obtained compounds with BMIC content 40 wt % were compression‐molded at 210°C to give WF/BMIC and BF/BMIC composites, respectively. The BMIC contained in the composites was twice extracted with ethanol at 60°C to afford WF/BMIC‐E and BF/BMIC‐E biocomposites, which were subsequently annealed at 200°C for 24 h to produce WF/BMIC‐A and BF/BMIC‐A biocomposites. The Fourier transform infrared spectroscopic analysis revealed that WF has a higher content of cellulose and a lower content of lignin than BF does, and that the BMIC content diminished by the extraction process. The scanning electron microscopy analysis showed that woody particles joined together by the compression molding of WF/BMIC and BF/BMIC compounds, and that the extraction of BMIC roughened the surface and the annealing again smoothed the surface due to the fusion of the residual BMIC and woody particles. The XRD measurements indicated that the annealing enhanced the crystallinity of cellulose component. The tensile properties and 5% weight loss temperature of the biocomposites were considerably improved by the extraction of BMIC and further by the annealing. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Interferometric determination of the physical properties of annealed isotactic polypropylene fibers

Automated variable wavelength interference microscope was used to study the effect of annealing process on the physical properties of isotactic polypropylene fibers (4:1 draw ratio, 515 tex, Bolton UK). The isotactic polypropylene (iPP) fibers were annealed at temperatures ranging from 60°C to 140°C. The spectral dispersion curves of refractive indices and birefringence of iPP fibers were determined at different annealing temperatures. The resulting data were used to determine the optical orientation function, orientation angle, degree of crystallinity, and dispersion parameters of the annealed samples. The study indicates that, the measured birefringence, orientation function, and the dispersion of crystallinity of iPP fibers have been improved with the increasing of annealing temperature. POLYM. ENG. SCI., 59:35–41, 2019. © 2018 Society of Plastics Engineers     

Effects of Recycling on the Mechanical Behavior of Polypropylene at Room Temperature Through Statistical Analysis Method

This article reports the effects of recycled material percentage, annealing conditions, and glass fiber percentage on the mechanical behavior of injection molded polypropylene samples. Specimens were prepared with different percentages of recycled material ranging from 0 to 100%. Two groups of samples, i.e., non‐annealed and annealed at 150°C, were tested to investigate annealing effects. The effects of adding fiber (0–7.5%) to specimens was also investigated. It was found that increasing the amount of recycled material improves the material properties in a non‐linear trend. Annealing had a significant positive effect on both non‐fiber‐added and fiber‐added samples: it improved the yield stress of non‐reinforced polypropylene samples by more than 10% and their Young's modulus by about 50%. Fiber‐added materials showed more variability, and adding fiber also improved the Young's modulus and the yield stress of the samples by about 50%. The results indicate that the three factors investigated improved toughness of the injected polypropylene samples; however the effects are not significant. The study findings reveal that using recycled polypropylene has no significant effect on the material properties of polypropylene. POLYM. ENG. SCI., 56:1283–1290, 2016 © 2016 Society of Plastics Engineers     

Morphology and mechanical properties of injection molded poly(ethylene terephthalate)

This work reports on the relationships between processing, the morphology and the mechanical properties of an injection molded poly(ethylene terephthalate), PET. Specimens were injection molded with different mold temperatures of 30°C, 50°C, 80°C, 100°C, 120°C, 150°C, while maintaining constant the other operative processing parameters. The thermomechanical environment imposed during processing was estimated by computer simulations of the mold‐filling phase, which allow the calculation of two thermomechanical indices indicative of morphological development (degree of crystallinity and level of molecular orientation). The morphology of the moldings was characterized by differential scanning calorimetry (DSC) and by hot recoverable strain tests. The mechanical behavior was assessed in tensile testing at 5 mm/min and 23°C. A strong thermal and mechanical coupling is evidenced in the injection molding process, significantly influencing morphology development. An increase in the mold temperature induces a decrease of the level of molecular orientation (decrement in the hot recoverable strain) and an increment in the initial crystallinity of the moldings (decrement in the enthalpy of cold crystallization), also reflected in the variations of the computed thermomechanical indices. The initial modulus is mainly dependent upon the level of molecular orientation. The yield stress is influenced by both the degree of crystallinity and the level of molecular orientation of the moldings, but more significantly by the former. The strain at break was not satisfactorily linked directly to the initial morphological state because of the expected morphology changes occurring during deformation. Polym. Eng. Sci. 44:2174–2184, 2004. © 2004 Society of Plastics Engineers.     

Dynamic mechanical analysis of fibers. II. Estimation of fiber orientation and characterization of heat set PET yarns

A drawn PET yarn was heat set (annealed) at temperatures between 110°C and 245°C in an unconstrained mode and the samples characterized by dynamic mechanical analysis (DMA). A method for estimating the fiber orientation factor (α) is proposed using DMA and shown to be more sensitive than the crystalline orientation (x-ray diffraction) or total orientation (birefringence) measurements of the heat set yarns. The extension/shrinkage behavior of the heat set yarns has been discussed in the light of morphological changes, e.g., degree of orientation and the micro-crystallite formation. Unlike in the unconstrained mode, heat setting under constraint does not lead to the formation of micro-crystallites as revealed by differential scanning calorimetry. As a consequence, although the modulus and degree of orientation increase upon constrained annealing, the thermal stability, i.e., loss of orientation (reflected by shrinkage) could not be improved.     

Secondary crystallization and premelting endo‐ and exotherms in oriented polymers

Crystallization in polyamide 6 (nylon 6) fibers during annealing was studied in detail by following the changes that occurred in the neighborhood of crystalline relaxation temperatures, by using wide‐ and small‐angle X‐ray scattering and differential scanning calorimetry (DSC). Two distinct crystallization regimes were observed depending on whether annealing was carried out below or above onset of crystalline relaxation at ～190°C. In fibers annealed below 190°C, minor melting peaks were followed by exothermic transitions. These were attributed to ～1.5% (by weight) of microcrystals formed during annealing that melt and recrystallize during the DSC scan. These microcrystals are nucleated from unoriented amorphous chains between the lamellar stack within a fibril, and are shown to account for the observed increase in the crystalline orientation and decrease in permeability. Fibers annealed above 190°C did not show the exotherm and had significantly fewer microcrystals. The crystallization in this regime was attributed to the growth of existing lamellae, as evidenced by the increase in crystallite size, crystalline density, crystalline orientation, lamellar spacing, and lamellar intensity. The changes at annealing temperatures >190°C are accompanied by increased dyeability, indicative of more open amorphous regions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 447–454, 2006     

Influence of thermal annealing on mechanical properties and in vitro degradation of poly(p‐dioxanone)

Poly(p‐dioxanone) (PDO), a versatile poly(ester‐ether), has been used for a variety of biomedical applications. Functional performance of this semicrystalline polymer heavily relies on its crystallinity and crystalline behavior. Upon extended exposure to heat above the glass transition temperature and below the melting temperature, PDO undergoes thermal annealing. Isothermal studies at elevated temperatures utilizing a differential scanning calorimeter were performed in order to determine the most appropriate conditions to anneal the polymer. Of the investigated mechanical properties, yield strength and elastic modulus were significantly improved with annealing. This improvement over nonannealed samples was also observed with samples subjected to phosphate‐buffered saline (PBS) solution at 37°C for 2 weeks. After 1 month continuous immersion in PBS solution, the PDO became brittle with deteriorated elongation at break but maintained yield strength and modulus. At 2 months, all specimens exhibited cracks on the surface and a complete loss of mechanical strength. The enhanced yield strength by thermal annealing creates more opportunities for PDO in medical device implants particularly in applications involving soft tissue repair and hemostasis. POLYM. ENG. SCI., 59:1701–1709 2019. © 2019 Society of Plastics Engineers     

Influence of annealing treatment on the heat distortion temperature of nylon‐6/montmorillonite nanocomposites

It has been recognized that the incorporation of nanoscale montmorillonite (MMT) layers into polymer matrix enhances significantly the heat resistance of the resultant nanocomposites, especially for nylon‐6 (N6)/clay nanocomposites (NCNs). In the present work, the heat distortion temperature (HDT) of NCNs, including the intercalated N6/Na‐montmorillonite (Na‐MMT) and the exfoliated N6/organo‐montmorillonite (OMMT) ones, have been investigated for both non‐annealed and annealed testing specimens in comparison with the neat N6. As expected, the incorporation of MMT obviously improved HDT of NCNs, with the highest HDT value obtained in the N6/OMMT system due to its exfoliated nano‐structure. After an annealing treatment at 80°C for 6 hr, the HDT revealed noticeable increase for all the samples, particularly for the intercalated N6/Na‐MMT nanocomposite that showed the highest increment of 34°C. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared (FTIR) techniques were employed to clarify the origin of the variation in HDT after annealing, and the results suggest that the increases in the crystallinity, the glass transition temperature, and the order degree of hydrogen bonding may account for the noticeable increases in the HDT of the nanocomposites after annealing. POLYM. ENG. SCI., 45:1247–1253, 2005. © 2005 Society of Plastics Engineers