Crystallisation behaviour and transparency of poly(lactic acid) nucleated with dimethylbenzylidene sorbitol

In this paper, dimethylbenzylidene sorbitol (DMBS) was applied to poly(lactic acid) (PLA) as a nucleating and clarifying agents. Eight level concentrations, from 0.25 to 10?wt-%, were added and measured some changes in the thermal, mechanical, physical and morphological properties. Experimental results revealed that the nucleated PLA crystallised earlier together with the reductions of the crystallisation temperature (T_c) at all DMBS concentrations, while the glass transition temperature (T_g) reduced by around 10°C. The degree of crystallinity (X_c) increased from 1.48 to 16.6% corresponding to the decreased crystallisation time (t_c) from more than 40 to less than 5?min at 100°C. The nucleated PLA maintained its clarity at all DMBS concentrations, with reductions of the haze value from around 36–29%. The tensile modulus and tensile strength increased slightly with the content of DMBS up to 1.5?wt-%. Beyond this content, they dropped slightly.     

Properties of coconut shell powder‐filled polylactic acid ecocomposites: Effect of maleic acid

Ecocomposites were produced by incorporating coconut shell powder (CSP) into polylactic acid (PLA) resin. The effect of filler content and chemical modification on the mechanical properties, thermal properties, and morphology of PLA/CSP ecocomposites were investigated. The addition of filler has decreased the tensile strength and elongation at break of PLA/CSP ecocomposites. However, tensile strength and modulus of elasticity of PLA/CSP ecocomposites were enhanced by maleic acid treatment. Meanwhile, glass transition temperature (T_g) and crystallinity (X_c) of PLA/CSP ecocomposites increased at 30 php of filler content and increased the presence of maleic acid (MA). However, the melting temperature (T_m) and crystallization temperature (T_c) were not significantly changed with the filler content and MA modification The thermal stability of PLA/CSP ecocomposites increased with the CSP content. The MA modification improved the thermal stability of PLA/CSP ecocomposites through better filler–matrix interaction. The improvement was confirmed by scanning electron microscope study. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Mechanical and thermal properties of coconut shell powder filled polylactic acid biocomposites: effects of the filler content and silane coupling agent

The effects of the filler content and the coupling agent 3-aminopropyltriethoxysilane (3-APE) on the mechanical properties, thermal properties, and morphologies of polylactic acid (PLA)/coconut shell powder (CSP) biocomposites were investigated. It was found that increasing the CSP content decreased the tensile strengths and elongations at break of the PLA/CSP biocomposites. However, incorporating CSP increased their modulus of elasticity. The tensile strengths and modulus of elasticity of the PLA/CSP biocomposites were enhanced by the presence of 3-APE, which can be attributed to a stronger filler–matrix interaction. The thermal stabilities of the biocomposites increased with the filler content, and they were enhanced by 3-APE treatment. Meanwhile, the presence of CSP increased the glass transition temperatures (T _g) and crystallinities (X _c) of the PLA/CSP biocomposites at a filler content of 30 php. After 3-APE treatment, T _g and X _c of the PLA/CSP biocomposites increased due to enhanced interfacial bonding. The presence of a peak crystallization temperature (T _c) for the PLA/CSP biocomposites indicated that the CSP has a nucleating effect. The melting temperatures (T _m) and the T _c values of the biocomposites were not significantly affected by the filler content and 3-APE. PLA/CSP biocomposites that had been treated with 3-APE presented the strongest filler–matrix interaction, as confirmed by SEM.     

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     

The crystallization behavior and mechanical properties of polylactic acid in the presence of a crystal nucleating agent

The crystallization behavior of polylactic acid (PLA) was studied in the presence of a crystal nucleating agent, ethylenebishydroxystearamide (EBH). The crystallization rate and crystallinity were significantly increased with addition of EBH. The isothermal crystallization half-time at 105°C was decreased from 18.8 minutes for neat PLA to 2.8 minutes for PLA with 1.0 wt % of EBH. The crystallinity of PLA with 1.0 wt % EBH was about 35% after 5-minute annealing at 105°C. Like neat PLA, the double melting peaks were also observed for nucleated PLA. The changes of the double melt peaks were investigated with various crystallization temperatures, heating rates, and annealing times. The heat deflection temperature (HDT) of nucleated PLA was up to 93°C after annealing. The correlation between crystallinity and HDT was demonstrated. A percolation threshold of crystallinity was found corresponding to HDT. The crystal size of nucleated PLA was significantly decreased with addition of EBH. The mechanical properties of annealed PLA blends simultaneously; showed improved modulus and impact strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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

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

The influence of cobaltous chloride modification on physical properties and microstructure of modified PAN fiber during carbonization

Modification of polyacrylonitrile (PAN) fibers with cobaltous chloride has increased crystal size, crystallinity, and density, and also improved tensile strength and modulus of the resulting carbon fibers. In this study, the effect of cobaltous chloride modification on the physical properties, microstructure, and elemental composition of PAN fibers during the carbonization process was examined. The resultant carbon fibers developed from modified PAN fibers had a lower formation temperature of carbon basal planes than those fibers that developed from the original one. The modification process not only improved the tensile strength but also increased the tensile modulus by about 15% of the resulting carbon fibers at carbonization temperature of 1300°C. A higher stacking size (L_c), or a greater carbon basal plane in crystalline, is one of the reasons to improve the modulus and conductivity of the final carbon fibers. The modification process also increased the electrical conductivity by about 15% at 1300°C and by about 150% at 2500°C. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2409–2415, 1998     

Annealing effect on the shape memory properties of polylactic acid (PLA)/thermoplastic polyurethane (TPU) bio-based blends

PLA and TPU were melt-blended to form shape memory bio-based blends with or without post-annealing effect. To the authors’ best knowledge, this is the first work to discuss the annealing effect on the PLA-based SMP blends. Annealed TPU showed regularly fractured surfaces unlike the macro-phase segregated domains for non-annealed TPU. After 3 h-annealing treatment, spherulites were observed for PLA, but not for TPU. The crystallinity of PLA increased, close to 3-fold increment, for annealed blends in comparison with non-annealed blends. The shape memory behaviors of PLA/TPU blends predeformed under three different predeformation temperatures (25, 80, 120 °C) were investigated. The annealing effect was helpful in enhancing the shape fixing ratio of the PLA/TPU (60/40) blend at high predeformation temperature of 120 °C in comparison with 25 °C. However, the suitable selection of the optimum predeformation temperature at 80 °C outweighed the annealing effect to attain the high shape fixing ratio, even in the case of non-annealed blends. The annealing effect often increased the perfection of crystal domains/interfaces and the larger crystal sizes, which would be detrimental to the molecular extensibility. The overall annealing effect on the shape recovery ratios were quite effective for both PLA/TPU blends of 80/20 and 60/40 without sacrificing the shape fixing ratios at the optimum predeformation temperature of 80 °C, attributing to the increased crystallinity of PLA and homogenized phase domains of TPU. Particularly, the annealing treatment did significantly increase the recovery ratio of the blends, more than 2-fold increment, especially for PLA/TPU (60/40) blend. At both lower or higher predeformation temperatures, the stress concentration between the increased crystalline domains and amorphous regions tended to dominate the annealing effect, leading to a negative contribution to the shape recovery processes.     

Annealing and crystallization kinetics of poly(lactic acid) pieces obtained by additive manufacturing

In this study, we investigated the influence of isothermal treatment of poly(lactic acid) (PLA) 3D printed samples at different crystallization temperatures. In this case, we analyzed the effect of each crystallization temperature on spherulites formation in printed PLA, affecting the final mechanical properties of pieces. For such, the thermomechanical properties, morphological structure, and crystallization kinetics were analyzed before and after thermal treatment. The 3D printed samples were heat treated at 80°C, 90°C, 100°C, 110°C, and 119°C. With annealing, we observed an improvement in the mechanical PLA properties; however, the exothermic crystallization peak was different for the samples. Pieces before annealing were found to have a low crystallinity index (Ic) of 2%–7%, and the pieces after annealing presented a considerable Ic (27%–34%). Annealing temperatures of 100°C, 110°C, and 119°C produced the fastest crystallization kinetics, while annealing temperatures of 80°C and 90°C resulted in the lowest crystallization kinetics for complete crystallization. After annealing, improvement in the flexural strength (34%–47%) and Young's modulus (26%–51%) for all annealed pieces occurred. The appropriate condition was observed at 100°C, which was the onset temperature of crystallization, owing to the combination of the shorter time of crystallization with the increased mechanical properties.     

Effect of thermal annealing on the mechanical and thermal properties of polylactic acid–cellulosic fiber biocomposites

Polylactic acid (PLA) biocomposites were produced by a combination of extrusion and injection molding with three cellulosic reinforcements (agave, coir, and pine) and contents (10, 20, and 30%). In particular, some samples were subjected to thermal annealing (105 °C for 1 h) to modify the crystallinity of the materials. In all cases, morphological (scanning electron microscopy) and thermal (differential scanning calorimetry, dynamical mechanical thermal analysis) characterizations were related to the mechanical properties (Charpy impact, tensile and flexural tests). The results showed that annealing increased the crystallinity for all the materials produced, but different mechanical behaviors were observed depending on fiber type and content. For example, annealing increased the impact strength and flexural modulus of PLA and PLA biocomposites (agave, coir, and pine), while decreasing their flexural strength. But the main conclusion is that fiber addition combined with thermal annealing can substantially increase the thermal stability of the studied materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43750.     

Regulation of trans‐1,4‐polyisoprene crystallinity and mechanical properties of styrene‐butadiene rubber/trans‐1,4‐polyisoprene vulcanizate

The effects of processing temperature and bis‐[γ‐(triethoxysilyl)‐propyl]‐tetrasulfide (Si69) on crystallization, morphology, and mechanical properties of styrene‐butadiene rubber (SBR)/trans‐1,4‐polyisoprene (TPI) vulcanizate are investigated. The crystallinity and crystalline melting temperature (T_m) of TPI in the vulcanizates with TPI/silica/(Si69) pre‐mixed at 150 °C are much lower than that pre‐mixed at 80 °C. At the same pre‐mixing temperature, the presence of 1 phr Si69 leads to a decreased crystallinity and T_m. The TPI domains with phase size of about 1 μm and silica are well dispersed in the vulcanizate, and TPI crystals get smaller in size and less in amount by pre‐mixing TPI, silica and Si69 at 150 °C. The vulcanizates with TPI/silica/(Si69) pre‐mixed at 150 °C have decreased tensile strength and modulus at a given extension than that pre‐mixed at 80 °C. At the same pre‐mixing temperature, the tensile strength and modulus of the vulcanizate increase with the addition of 1 phr Si69. The crystallinity of TPI component in SBR/TPI vulcanizate is effectively controlled by changing processing temperature and adding Si69, which is important for theoretical research and practical application of TPI. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44395.     

Effect of annealing and orientation on microstructures and mechanical properties of polylactic acid

Two types of polylactic acid (PLA) films (one amorphous and one semi‐crystalline) were produced by sheet extrusion. Talc was used as a nucleation agent for the semi‐crystalline PLA. The films were annealed above their T_g or were uniaxially orientated in two ways: (1) via a drawing system in front of the extruder and die or (2) via a three‐roller stretching system. The slower crystallization rate and lower melting stress of the PLA resulted in amorphous film using the drawing system. Annealing above T_g increased crystallinity and polymer chain relaxation, which resulted in increases in both strength and toughness. Stretching above T_g also produced simultaneous crystallization and chain relaxation, which resulted in increases in both modulus and toughness. Both modulus and tensile strength in the stretching direction were higher than in the crosswise direction. Talc acted not only as a rigid filler to reinforce the PLA, but also as a nucleation agent for the PLA, especially during annealing. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Water vapor permeability of poly(lactide)s: Effects of molecular characteristics and crystallinity

Amorphous‐made poly(L ‐lactide) [i.e., poly(L ‐lactic acid) (PLLA)], poly(L ‐lactide‐co‐D ‐lactide)[P(LLA‐DLA)](77/23), and P(LLA‐DLA)(50/50) films and PLLA films with different crystallinity (X_c) values were prepared, and the effects of molecular weight, D ‐lactide unit content (tacticity and optical purity), and crystallinity of poly(lactide) [i.e., poly(lactic acid) (PLA)] on the water vapor permeability was investigated. The changes in number‐average molecular weight (M_n) of PLLA films in the range of 9 × 10⁴–5 × 10⁵ g mol^?1 and D ‐lactide unit content of PLA films in the range of 0–50% have insignificant effects on their water vapor transmission rate (WVTR). In contrast, the WVTR of PLLA films decreased monotonically with increasing X_c from 0 to 20%, while leveled off for X_c exceeding 30%. This is probably due to the higher resistance of “restricted” amorphous regions to water vapor permeation compared with that of the “free” amorphous regions. The free and restricted amorphous regions are major amorphous components of PLLA films for X_c ranges of 0–20% and exceeding 30%, respectively, resulting in the aforementioned dependence of WVTR on X_c. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Experimental investigation and optimization of printing parameters of 3D printed polyphenylene sulfide through response surface methodology

Today fused filament fabrication is one of the most widely used additive manufacturing techniques to manufacture high performance materials. This method entails a complexity associated with the selection of their appropriate manufacturing parameters. Due to the potential to replace poly-ether-ether-ketone in many engineering components, polyphenylene sulfide (PPS) was selected in this study as a base material for 3D printing. Using central composite design and response surface methodology (RSM), nozzle temperature (T), printing speed (S), and layer thickness (L) were systematically studied to optimize the output responses namely Young's modulus, tensile strength, and degree of crystallinity. The results showed that the layer thickness was the most influential printing parameter on Young's modulus and degree of crystallinity. According to RSM, the optimum factor levels were achieved at 338°C nozzle temperature, 30 mm/s printing speed, and 0.17 mm layer thickness. The optimized post printed PPS parts were then annealed at various temperatures to erase thermal residual stress generated during the printing process and to improve the degree of crystallinity of printed PPS's parts. Results showed that annealing parts at 200°C for 1 hr improved significantly the thermal, structural, and tensile properties of printed PPS's parts.     

Thermal and mechanical properties of injection moulded heat-treated oil palm empty fruit bunch fibre-reinforced high-density polyethylene composites

ABSTRACT

Oil palm empty fruit bunch (OPEFB) was heat treated at 180°C using a vacuum oven for one hour, extruded and compounded with high-density polyethylene at 10%, 20% and 30% weight fraction. The composites then were injection moulded into dumb-bell shaped specimens. The effect of composition and heat treatment on the thermal properties of composites were investigated using Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). The tensile and flexural properties were also tested using an Instron Universal Testing Machine. TGA shows an increase in the degradation peak temperature of the heat-treated composites. DSC revealed an increasing trend in the degree of crystallinity (X_c) of the matrix as the heat-treated empty fruit bunch was used as a filler. An increment in the tensile modulus and tensile strain were observed for the treated fibre composites. In addition, the tensile strength value was increased for treated fibre composites with lower fibre loading.     

Motion mode of poly(lactic acid) chains in film during strain‐induced crystallization

How stress and temperature impact the movement of poly(lactic acid) (PLA) chains in the process of tensile film stretching was studied. The motion mode of chains was investigated through the study of the strain‐induced crystallization and orientation through changes in the draw temperature (T_d), draw ratio, and draw rate. The crystallinity and orientation degrees of the PLA films were measured by differential scanning calorimetry, Fourier transform infrared spectroscopy, and polarized optical microscopy. According to the competition between the orientation caused by the stretching and relaxation of chains under the temperature field, the motion modes of PLA chains during strain were divided into four types, modes I–IV. When T_d was 100°C, the PLA chains acted in mode I, in which the relaxation rate of chains was so fast that no crystallinity or orientation could be obtained. Beyond a draw rate of 20 mm/min at a T_d of 90°C, the type of chain movement changed from mode I to II. In mode II, only crystallites could be reserved after unloading. Chains in the PLA film moved in mode III at a T_d of 80°C; then, both the crystallization and orientation were enhanced monophonically with increasing draw rate. Beyond the draw rate of 10 mm/min at a T_d of 70°C, the orientation rate of chains was much faster than the relaxation one, and the motion mode transformed from mode III to IV. Then, obvious decreases in the crystallinity and orientation were observed with further increases in the draw rate; this resulted from the destruction of the crystallites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42969.     

Miscibility and phase structure of binary blends of polylactide and poly(vinylpyrrolidone)

The miscibility, crystallization behavior, and component interactions of two binary blends, poly(L ‐lactide) (L ‐PLA)/poly(vinylpyrrolidone) (PVP) and poly(D ,L ‐lactide) (DL ‐PLA)/PVP, were studied with differential scanning calorimetry and Fourier transform infrared (FTIR) spectroscopy. The composition‐dependent changes of the glass‐transition temperature (T_g) and degree of crystallinity (X_c) of the L ‐PLA phase indicated that L ‐PLA and PVP were immiscible over the composition range investigated. However, the sharp decrease of X_c with increasing PVP content in the second heating run demonstrated that the cold crystallization process of L ‐PLA was remarkably restricted by PVP. In DL ‐PLA/PVP blends, the existence of two series of isolated T_g's indicated that DL ‐PLA and PVP were phase‐separated, but evidence showed that there was some degree of interaction at the interface of the two phase, especially for the blends with low DL ‐PLA contents. FTIR measurements showed that there was no appreciable change in the spectra of L ‐PLA/PVP with respect to the coaddition of each component spectrum, implying the immiscibility of the two polymers. In contrast to L ‐PLA, the intermolecular interaction between DL ‐PLA and PVP was detected by FTIR; this was evidenced by the observation of a high‐frequency shift of the C?O stretching vibration band of PVP with increasing DL ‐PLA content, which suggested some degree of miscibility. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 973–979, 2003     

Influence of talc particle size and content on crystallization behavior,mechanical properties and morphology of poly(lactic acid)

This research aimed to employ inorganic filler such as talc to promote crystallization in poly(lactic acid) (PLA). Three different talc particle sizes, namely 1, 5 and 30 µm, were used as nucleating agents; each was compounded with PLA at various contents from 0 to 10 wt%. The crystallization temperature (T _c) reduced most rapidly from 128 to 107 °C with the presence of 1 wt% talc. Beyond this concentration, the T _c still decreased but only minutely. Compared to other sizes, finer talc particles were found to promote a slightly higher degree of crystallinity. X-ray diffraction peaks indicated that the α-crystal was formed in all PLA/talc compositions. The heat distortion temperature values suggested that the modified PLA could resist the thermal deformation from 58 °C to a maximum value of 139 °C when 1 µm talc was added at 10 wt%. With the presence of talc, the composites were more brittle and both tensile elongation at break and impact strength were decreased.     

Blends of polylactide and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) with low content of hydroxyvalerate unit: Morphology,structure, and property

The Polylactide (PLA)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) blends with four different weight ratios were prepared by melt mixing. PLA and PHBV in PLA/PHBV blends were immiscible while the weak interaction between PLA and PHBV existed. The PHBV domains below 2 μm were dispersed in PLA matrix uniformly. The addition of PHBV made the crystallization of PLA easier due to PHBV acting as nucleating agent. PLA spherulites in PLA/PHBV blends presented various banded structures. In addition, the crystallinity of neat PLA was lower than those of PLA/PHBV blends. With the increase of PHBV content in PLA/PHBV blends, the crystallinity of PLA/PHBV blends increased. PHBV could enhance significantly the toughness of PLA. However, with the increase of PHBV content, the yield stress (σ_y), tensile modulus (E), and the yield strain (ε_y) of PLA/PHBV blends decreased gradually. In addition, incorporation of PHBV to PLA caused a transformation from an optical transparent to an opaque system. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42689.     

Dual glassy relaxations in physically aged semi‐crystalline poly(L‐lactic acid)

Semi‐crystalline poly(L ‐lactic acid) (PLLA) was physically aged below the glass transition temperature for various times to investigate its amorphous phase behavior. During a differential scanning calorimetry heating scan, dual enthalpy recovery endotherms were found to appear in the glass transition region of PLLA, aged at 52 °C, of a particular degree of crystallinity (X_c) within a definite range. Below the lower X_c limit, only the low endotherm corresponding to the free amorphous phase was observed; above the upper X_c limit, only the high endotherm corresponding to the constrained amorphous phase was observed. Dual tan δ peaks in dynamic mechanical analysis confirmed the coexistence of the dual amorphous phases. Both lower and upper limits of the X_c range increased with an increase in isothermal crystallization temperature from the melt. Long‐term physical aging at 52 °C, which did not affect X_c, allowed the evolution of the free amorphous phase to the constrained amorphous phase in PLLA with X_c within the definite range. The effects of physical aging at various temperatures on the enthalpy recovery endotherms were also investigated. Copyright © 2011 Society of Chemical Industry