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.     

Tailoring the thermal and mechanical properties of injection-molded poly (lactic acid) parts through annealing

The effect of cold-crystallization on poly (lactic acid) (PLA) injection-molded parts was systemically investigated at different annealing temperatures (80/100/120°C) and annealing times (0.5/1/1.5/2 hr). The relative crystallinity (X_c) and crystal form (α' and α) of samples was investigated by differential scanning calorimetry (DSC) and wide X-ray angle diffraction (WAXD). The dependence of the thermal and mechanical performance on relative crystallinity and crystal form/morphology was discussed in detail. A linear relationship between the increment of heat distortion temperature (HDT) and that of X_c was found. The tensile strength, tensile modulus and storage modulus all increased with annealing time and annealing temperature, while the tensile toughness presented a different behavior. The elongation at break for specimens reached a maximum value of 16.9% after annealing at 80°C for 2 hr, which is a threefold improvement compared to PLA samples prepared without annealing. This work suggests that annealing is an effective method for tailoring the physical properties of PLA products.     

Effects of annealing on the hierarchical crystalline structures and mechanical properties of injection‐molded bars of high‐density polyethylene

The effect of annealing on the microstructural evolution and mechanical properties of high‐density polyethylene parts molded via gas‐assisted injection molding was investigated using scanning electron microscopy, differential scanning calorimetry, two‐dimensional wide‐angle X‐ray diffraction and tensile testing. The results indicated that a variety of annealing temperatures could induce considerable variations in the hierarchical structures, crystallinity, lamellar thickness and yield stress of the molded bars. According to these results, the annealing temperatures could be divided into three regions. In the low‐temperature region of annealing at 80 °C, the spatial variation of the superstructure developed along the thickness direction and mechanical properties of the annealed sample were mainly unchanged and similar to those of the original specimen. At 100 and 120 °C, the intermediate temperature region of annealing, the thickness of the crystals, degree of orientation and yield stress of annealed samples were greatly improved. Finally, at 127 °C, the degree of orientation decreased and yield stress slightly improved, an indication of the high‐temperature annealing region being characterized by increasing melting/recrystallization and causing relaxation of oriented molecular chains. A model is proposed to interpret the mechanism of the annealing treatment of the samples at various temperatures. © 2013 Society of Chemical Industry     

Physical and mechanical properties of poly(L‐lactic acid) nucleated by dibenzoylhydrazide compound

Benzoylhydrazide compounds were evaluated as a nucleating agent for poly(L ‐lactic acid) (PLA). From the results of the differential scanning calorimetry, octamethylenedicarboxylic dibenzoylhydrazide (OMBH) was found to be most effective for acceleration of PLA crystallization under higher cooling rate of ?50°C min^?1. PLA with OMBH of 1 wt % exhibited very short crystallization half‐time with wide range of isothermal temperature from 90 to 130°C. The molding cycle time of PLA with OMBH in injection molding was less than 3 min, and the cooling time was one‐third of ethylenebis(12‐hydroxystearylamide)/talc system as a nucleating agent. Physical and mechanical properties improved extremely, and the heat distortion temperature of 124°C, flexural modulus of 4.1 GPa, and Izod impact strength of 7.9 kJ m^?2 were achieved. This indicates that the utilization of OMBH makes it possible to extend the application range of PLA as automotive parts and electric appliances, which require higher heat resistance and stiffness. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 244–250, 2007     

Crystallization and thermomechanical properties of PLA composites: Effects of additive types and heat treatment

This research work has concerned a study on thermomechanical and crystallization properties of poly(lactic acid) (PLA) composites containing three different types of additives; namely: kenaf fiber (20 pph), Cloisite30B nanoclay (5 pph), and hexagonal boron nitrile (h‐BN; 5 pph). The composites were prepared using a twin screw extruder before molding. Crystallization behaviors of the various composites were also examined using a differential scanning calorimetry. By adding the additives, tensile modulus of the polymer composites increased, whereas their tensile strength and elongation values decreased as compared to those of the neat PLA. Heat distortion temperature (HDT) values of the materials slightly increased, for about 3–5°C. However, after annealing at 100°C, HDT values of the fabricated PLA composites rapidly increased with annealing time before reaching a plateau after 10 min. The HDT values of above 120°C were achieved when 20 pph kenaf fiber was used as an additive. The above results were in a good agreement with DSC thermograms of the composites, indicating that percentage crystallinity of the materials increased on annealing and crystallization rate of the PLA/kenaf system was the highest. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Annealing effects in poly(phenylene sulfide) as observed by dynamic mechanical analysis

Poly(phenylene sulfide) (PPS) is a semicrystalline engineering resin with exceptional solvent resistance and thermal performance. Properties such as these are directly related to the high crystallinity of PPS. In order to exploit its crystalline nature, PPS should be molded at a high tool temperature (hot oil tool) to allow for the highest crystallization rate, and therefore the highest percent crystallinity. Alternately, if a low mold temperature is used, the molded parts should be annealed. This latter process has been studied for injection molded neat PPS resin for various annealing temperatures. Two different grades of PPS were studied that represent cured and linear types. Samples were studied as-molded, and annealed at 160, 180, 200 and 220°C. Increases in glass transition temperature were noted upon annealing. An increase in storage modulus was also noted for annealed samples. This increase persisted up to approximately the annealing temperature. Differential scanning calorimetry has been used to show that annealing PPS allows for a secondary crystallization to occur whereby an endotherm appears that corresponds to the secondary crystalline phase melting near the annealing temperature. As the annealing temperature is increased, the area of the endotherm increases. The secondary crystallization explains the higher storage modulus that persists up to the annealing temperature. These results are discussed in terms of crystallinity and overall effect on heat distortion temperature.     

注射成型立构复合聚乳酸的热变形性能分析

采用左旋聚乳酸（PLLA）和右旋聚乳酸（PDLA）为原料,采用熔融共混法制备了立构复合聚乳酸（SC?PLA）粉末,再通过注射成型制备了SC?PLA样条,并通过差示量热扫描仪（DSC）和热变形温度测定仪对SC?PLA粉末和样条的熔融、结晶情况和热变形性能进行了表征分析。结果表明,SC?PLA粉末的结晶能力与初始熔融状态直接相关;当熔融温度为220~230 ℃时,SC?PLA粉末的熔融稳定时间增加,有助于SC?PLA体系结晶,该温度适合SC?PLA的注射成型加工;SC?PLA样条中SC?PLA结晶度越高,均聚物PLA结晶度越低,越有助于样条热变形性能的提高;低注射温度和以SC?PLA粉末、PLLA、PDLA为原料成型有助于SC?PLA样条在220 ℃下加热再退火后获得较高的SC?PLA结晶度,其热变形温度最高可达到150 ℃以上;注射成型过程中,有利于保留更多SC?PLA晶体和提高SC?PLA结晶度的方式,有助于提高样条在退火后的热变形性能。     

Characterization of two precursor polyblends: Polyhydroxyamide and poly(amic acid)

Blends of two precursor polymers, polyhydroxy amide (PHA) and poly(amic acid) (PAA), were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The presence of PHA enhanced thermal and mechanical properties of the polyblends. All of the polyblended films showed large endothermic peaks that decreased monotonically with increasing heat treatment temperature. The cyclization onset temperature (T₁), initial decomposition temperature (T₂), and weight residue at 900°C of the polyblends were shown to be in the ranges of 144–146°C, 532–540°C, and 44–45%, respectively. Also, the thermal stabilities were enhanced consistently with increasing annealing temperature from 25 to 250°C. The ultimate strength and initial modulus of the polyblends increased from 84 to 136 MPa and from 2.93 to 5.34 GPa, respectively, with increasing PHA content. Similar to the trend of thermal stability, increasing the annealing temperature of the polyblends increased the tensile properties of the films. The observed tensile properties are discussed in terms of the morphology of the fractured films as studied by scanning electron microscopy (SEM). The degree of crystallinity of the polyblends was characterized as a function of heat treatment temperatures by wide angle X‐ray diffractometry (WAXD).     

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     

Flax fiber‐reinforced polylactide stereocomplex composites with enhanced heat resistance and mechanical properties

Polylactide stereocomplex (sc‐PLA) prepared by blending equivalent proportion of poly(l ‐lactic acid)/poly(d ‐lactic acid) (PLLA/PDLA) and its composites reinforced with 10, 20, and 30% flax fibers were fabricated by melt compounding and followed by injection molding. The mechanical properties, crystallinity, cross‐section morphology, and heat resistance of sc‐PLA and flax/sc‐PLA composites were compared. The results showed that homocrystallites (hc) and stereocomplex crystallites (sc) were formed simultaneously in sc‐PLA and its composites, with a melting temperature at ∼170 and ∼210°C, respectively. The crystallinity and sc content of composite increased with the increasing content of the flax fibers. The sc content of 30% flax/sc‐PLA composite could reach 98.4%, 32% higher than that of sc‐PLA (66.4%). When compared with nonblended PLLA, heat resistance of sc‐PLA increased slightly, but at the expense of mechanical properties. By the addition of flax fibers, the mechanical properties of flax/sc‐PLA composite improved significantly. The highest tensile strength, Young's modulus, and notched Izod impact strength of flax/sc‐PLA composite were 52.90 MPa, 6.42 GPa, and 5.27 kJ/m², respectively, improved by 54, 132, and 343% when compared with sc‐PLA. Moreover, the heat resistance of composite was also improved greatly by reinforcing with flax fibers. The Vicat softening temperature of 30% flax/sc‐PLA composite could achieve 162.5°C, nearly 100°C higher than that of PLLA. POLYM. COMPOS., 38:472–478, 2017. © 2015 Society of Plastics Engineers     

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.     

Biorenewable blends of polyamide‐11 and polylactide

Polyamide‐11(PA11) is melt blended with polylactide (PLA) using 0.00 to 0.10 wt% titanium isopropoxide catalyst to investigate potential compatibilizing reactions. Blend properties are characterized by differential scanning calorimetry (DSC), thermogravimetric analysis, dynamic mechanical thermal analysis, and tensile and impact testing. DSC shows two separate glass transition temperatures indicating only partial miscibility. Base etching to remove PLA domains followed by field emission scanning electron microscopy confirms the two phase nature of the blends. Storage and tensile moduli of the blends increase monotonically with increasing PLA content. Interchange reactions during reactive mixing were investigated by ¹³C‐NMR spectroscopy but the analysis shows little evidence of interchange reactions. This is true irrespective of catalyst level and mixing time over the temperature range from 185°C to 225°C. At the upper end of the temperature range investigated, significant degradation is observed. The combined results indicate that degradation reactions dominate over compatibilizing interchain transreactions. POLYM. ENG. SCI., 54:1523–1532, 2014. © 2013 Society of Plastics Engineers     

Influence of alkali treatment on flax fiber for use as reinforcements in polylactide stereocomplex composites

The flax and equivalent proportion of poly(l ‐lactic acid)/poly(d ‐lactic acid) (PLLA/PDLA) were melt compounded and injection molded to prepare flax‐reinforced polylactide stereocomplex (sc‐PLA) bio‐composite, and the effect of alkali treatment on the structure and properties of flax as well as the flax/sc‐PLA composite was investigated. SEM and FTIR results showed hemicellulose in flax was almost completely removed after alkali treatment and the treated flax (ALK‐flax) bundles were more separated with a cleaner surface than untreated flax (UN‐flax). DSC results showed homo‐crystallites (hc, T_m = 160–170°C) and stereocomplex crystallites (sc, T_m ～210°C) coexisted in sc‐PLA and flax/sc‐PLA composites. Compared with sc‐PLA, the total crystallinity and sc‐crystallinity of flax/sc‐PLA composite increased regardless of whether the flax were treated with alkali, whereas ALK‐flax/sc‐PLA composite showed a little higher crystallinity than UN‐flax/sc‐PLA composite. TGA results confirmed ALK‐flax/sc‐PLA composite had a higher thermal degradation temperature than UN‐flax/sc‐PLA composite. The mechanical tests indicated although the mechanical properties of sc‐PLA increased significantly by reinforcing with flax, the ALK‐flax/sc‐PLA composite showed little lower mechanical properties than UN‐flax/sc‐PLA composite. The alkali treatment of flax had no obvious influence on the Vicat softening temperature (VST) of flax/sc‐PLA composites, a higher heat resistance with VST at ～155°C could be obtained for flax/sc‐PLA composite. POLYM. ENG. SCI., 55:2553–2558, 2015. © 2015 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.     

Crystallization behavior and morphology of polylactic acid (PLA) with aromatic sulfonate derivative

This article provides a detailed investigation of crystallization behavior and morphology of polylactic acid (PLA) in the presence of a nucleating agent: potassium salt of 5‐dimethyl sulfoisothalate, an aromatic sulfonate derivative (Lak‐301). Isothermal crystallization kinetics of PLA melt mixed with Lak at concentrations of 0.25–1 wt % was investigated at a range of crystallization temperature, 140–150 °C. To gain further insight on the effect of Lak, nonisothermal differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized optical microscope (POM), heat deflection temperature (HDT), and rheology were also performed. At 0.25 wt % Lak, crystallinity of PLA increased from 10% to 45%, and in 1 wt % Lak, maximum crystallinity of 50% was achieved. With 1 wt % Lak, crystallization half time reduced to 1.8 min from 61 min for neat PLA at 140 °C. The isothermal crystallization kinetics was analyzed using Avrami model. Values of the Avrami exponent for PLA with Lak were mainly in the range of 3 indicating a three dimensional crystal growth is favored. Crystallization rate was found to increase with increase in Lak content. Observation from POM confirmed that the presence of Lak in the PLA matrix significantly increased the nucleation density. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43673.     

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.     

Super‐ductile PBT alloy with excellent heat resistance

A super‐ductile PBT alloy with excellent heat resistance was successfully fabricated by reactive blending of poly(butylene terephthalate) (PBT) with poly(ethylene‐co‐glycidyl methacrylate) together with linear low density polyethylene (LLDPE) and hydrogenated styrene‐butadiene‐styrene block copolymer (SEBS). It possesses a unique tensile stress–strain curve with no yielding point and large elongation at break, moreover, the alloy did not show serious deterioration of the mechanical properties by high temperature annealing at 150°C for 96 h. The structure‐properties relationship is discussed on the basis of transmission electron microscopy, differential scanning calorimetry, dynamic mechanical analysis, and wide‐angle X‐ray diffraction analysis. The outstanding ductile nature seems to come from the negative pressure effect of LLDPE (or LLDPE/SEBS) particles that dilates the PBT ligament matrix to enhance the local segment motions. POLYM. ENG. SCI., 2008. © 2008 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     

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     

Improving mechanical performance of injection molded PLA by controlling crystallinity

Currently, use of poly(lactic acid) (PLA) for injection molded articles is limited for commercial applications because PLA has a slow crystallization rate when compared with many other thermoplastics as well as standard injection molding cycle times. The overall crystallization rate and final crystallinity of PLA were controlled by the addition of physical nucleating agents as well as optimization of injection molding processing conditions. Talc and ethylene bis‐stearamide (EBS) nucleating agents both showed dramatic increases in crystallization rate and final crystalline content as indicated by isothermal and nonisothermal crystallization measurements. Isothermal crystallization half‐times were found to decrease nearly 65‐fold by the addition of only 2% talc. Process changes also had a significant effect on the final crystallinity of molded neat PLA, which was shown to increase from 5 to 42%. The combination of nucleating agents and process optimization not only resulted in an increase in final injection molded crystallinity level, but also allowed for a decreased processing time. An increase of over 30°C in the heat distortion temperature and improved strength and modulus by upwards of 25% were achieved through these material and process changes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008