Epoxidized natural rubber toughened poly(lactic acid)/halloysite nanocomposites with high activation energy of water diffusion

Poly(lactic acid)/halloysite nanotube (PLA/HNT) nanocomposites were prepared using melt compounding followed by compression molding. Epoxidized natural rubber (ENR) was used to toughen the PLA nanocomposites. The properties of PLA/HNT nanocomposites were characterized by impact tests, thermal analysis (DSC), morphological analysis (FESEM, TEM), and Fourier transform infrared spectroscopy (FTIR). Water absorption tests were performed at three immersion temperature (30, 40, 50°C). The maximum water absorption (M_m), diffusion coefficient (D), and the activation energy of water diffusion (E_a) were determined. The impact strength of PLA/HNT6 nanocomposites was increased significantly to ～296% by the addition of 15 wt % ENR. The incorporation of HNT and ENR increase its nucleation effect and assist in the crystallization process of PLA. The HNT has good affinity with PLA and ENR, which was revealed by TEM and FTIR. The M_m of PLA was increased in the presence of HNT and ENR. Nevertheless, the D value and the E_a of the PLA nanocomposites were found to be affected by the HNT and ENR contents. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42850.     

Influence of heat treatment on the heat distortion temperature of poly(lactic acid)/bamboo fiber/talc hybrid biocomposites

Influence of heat treatment and fillers on the heat distortion temperature (HDT) of poly(lactic acid) hybrid biocomposites was intensively studied through HDT testing, polarizing microscope (POM), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). With loading 20 wt % BF or 20 wt % talc, improvement of HDT in PLA composite was about 10°C comparing with neat PLA after heat treatment. Moreover, there was a great improvement (above 45°C) of HDT in PLA composites with loading 20 wt % BF and 20 wt % talc simultaneously after heat treatment. Transcrystallization was observed during heat treatment and isothermal crystallization of PLA composites with loading BF and talc simultaneously. There was no similar phenomenon in other PLA composite with loading only one filler. The possible mechanism of forming transcrystallization was proposed. DSC and DMA were also used to clarify the variation in HDT before and after heat treatment, and the results suggest that the crystallinity, modulus and glass transition changed, especially formation of transcrystallization played a key role in improvement of HDT in PLA composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of halloysite nanotubes on the performance of plasticized poly(lactic acid)‐based composites

The objective of this study is processing and characterization of Halloysite nanotube (HNT)/poly(lactic acid) (PLA) nanocomposites. As HNT filler, a domestic source was used (ESAN HNT). The results obtained from this HNT were compared with a well‐known reference HNT (Nanoclay HNT). To achieve the desired physical properties and clay dispersion, composites were compounded via direct melt mixing in a laboratory twin‐screw compounder. However, the constituents were observed to be incompatible without a compatibilizer. To improve the flexibility of nanocomposites and provide compatibilization between PLA and HNT, two types of blends were prepared: PLA plasticized with poly(ethylene glycol) (PEG) denoted as P‐PLA and PLA toughened with a thermoplastic polyurethane (TPU) denoted as T‐PLA. Despite the limited improvement in the P‐PLA blends, TPU addition improved the flexibility of PLA/HNT without deteriorating the tensile strength in a great manner. This was attributed to the relatively better compatibilization effect of TPU and the role of nanotubes acting as bridges between the TPU and PLA phases. POLYM. COMPOS., 37:3134–3148, 2016. © 2015 Society of Plastics Engineers     

Halloysite nanotube reinforced polylactic acid composite

Polylactic acid (PLA) has a long history in medical applications. Reinforced PLA has the potential to be used in the medical applications that require high mechanical strength such as coronary stents and bone fixation devices. Halloysite nanotube (HNT) has received considerable attention recently due to its tubular structure, high aspect ratio, high mechanical strength, thermal stability, biocompatibility and sustained drug releasing properties. Halloysite has been investigated in compounding with many polymers. However, the research in compounding halloysite with biodegradable materials for use in biological applications is sparse. In this study various weight fractions of HNT was compounded with the biodegradable polymer PLA using a melt compounding method. Tensile test, Fourier infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), contact angle test, scanning electron microscopy (SEM), void content and thermogravimetric analysis (TGA) were carried out to study the PLA/HNT composite. Tensile test results indicated that Young's modulus and stiffness of PLA were enhanced with the addition of HNT; FTIR spectra showed the interaction between the PLA and HNT; whereas contact angle measurements indicated that the wettability of the PLA/HNT composite was not affected by the addition of HNT. However, the thermal stability of PLA was adversely effected by the addition of HNT which may be related to the presence of voids between the polymer and matrix. Nevertheless, the reinforced PLA/HNT composite, which maintains the surface characteristics, may prove beneficial for use in biological applications. POLYM. COMPOS., 38:2166–2173, 2017. © 2015 Society of Plastics Engineers     

Morphologies,crystallization, and mechanical properties of PLA-based nanocomposites: Synergistic effects of PEG/HNTs

In this study, the compounding modifier poly(ethylene glycol)/halloysite nanotubes (PEG/HNTs) was prepared by supersonic vibration and dynamic vacuuming. A series of poly(lactic acid) (PLA)/PEG and PLA/PEG/HNT composites were fabricated using a twin-screw extruder. Fourier transform infrared spectroscopy indicated that the hybrid between PEG and HNTs had no evident chemical interaction via supersonic vibration and dynamic vacuuming. The dispersed morphology of the compounding modifier in the PLA matrix was tested by high-resolution scanning electronic microscopy and transmission electron microscopy. The results showed that the low content of PEG/HNTs presented a good dispersion morphology. The binding energy of the PLA-based composites was studied through contact angle measurements. The results showed that PEG and PEG/HNTs can decrease the water contact angle of PLA, and that the binding energy between PEG and HNTs is higher than that of PLA/HNTs, which leads to more location of HNTs in the PEG phase. The crystallization behavior of PLA-based composites was examined by wide-angle X-ray diffraction and differential scanning calorimetry. The results suggested that the addition of PEG and PEG/HNTs effectively enhanced the crystallization of PLA and that the diffraction peak intensity of the PLA-based composites reached a maximum when the content of PEG/HNTs was 1.2 wt %. The spherulite morphology indicated that the addition of PEG resulted in perfect spherulites. The mechanical properties of PLA-based composites were analyzed with a universal testing machine and impact tester, which confirmed that the tensile strength and impact strength of the PLA-based composites increased slightly when the content of the PEG/HNT modifier was 1.2 wt %, while the tensile modulus of the PLA-based composites increased distinctly. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47385.     

Kinetics and crystal structure of poly(lactic acid) crystallized nonisothermally: Effect of plasticizer and nucleating agent

The kinetics of neat poly(lactic acid) (PLA) and its composites with triphenyl phosphate (TPP) and/or talc crystallized nonisothermally at different cooling rates of 1, 2.5, 5, 7.5, and 10°C/min was analyzed by differential scanning calorimetry and described by Avrami equation and combined Avrami‐Ozawa equation. The results showed that talc acted as PLA nucleating agent accelerated crystallization rate by decreasing the crystallization half‐time t_1/2 or rate parameter F(T), whereas TPP acted as PLA plasticizer decreased crystallization rate. For neat PLA and plasticized PLA, the average values of Avrami exponent n were almost close to each other, but added TPP decreased crystallization rate constant k. As for PLA composites with talc, the crystallization process was relatively complex, and was divided into three regimes. At a given cooling rate, the value of n₂ was almost larger than that that of n₁ or n₃, whereas the value of k₂ was less than that of k₁ or k₃. The effective activation energy ΔE_x calculated from Friedman formula increased with the increase of relative crystallinity and TPP content, whereas decreased with the presence of talc. Wide angle X‐ray diffraction verified that all samples crystallized nonisothermally in cooling rate range of 1–10°C/min form α‐form. POLYM. COMPOS., 31:2057–2068, 2010. © 2010 Society of Plastics Engineers     

阻燃型玻纤增强PA10T复合材料的热氧老化性能

采用溴化环氧树脂对聚对苯二甲酰葵二胺(PA10T)进行改性,并通过熔融共混法制备阻燃型玻璃纤维(GF)增强PA10T复合材料,采用人工加速热氧老化手段,研究了热氧老化对其力学性能的影响,并用扫描电子显微镜(SEM)对复合材料的冲击断面形貌进行观察。结果表明,随热氧老化时间增加,复合材料的拉伸强度、弯曲强度和缺口冲击强度均下降明显,分子链松弛过程减弱;老化10 d后,复合材料的弯曲弹性模量仅略有下降而储能模量达到最大值,表明在热氧老化初期PA10T分子链之间发生了微交联,但随老化时间继续增加,两者均下降明显。SEM结果表明GF与树脂基体之间界面粘接作用的强弱是影响材料热氧老化性能变化的主要因素。     

Unique isothermal crystallization phenomenon in the ternary blends of biopolymers polylactide and poly[(butylene succinate)-co-adipate] and nano-clay

Melt and cold isothermal crystallization studies were carried out on polylactide (PLA)/poly[butylene succinate)-co-adipate] (PBSA) neat blend and blend-clay composites. The neat blend and blend-clay composites were prepared by melt-blending in a batch mixer. The weight ratio of PLA to PBSA was fixed at 70:30, while the content of the organoclay was varied from 0 to 9 wt%. The spherulitic growth rates and morphologies of PLA and PBSA in the samples were examined through polarized optical microscopy, while the rate of crystallization and the extent of crystallinity were studied through differential scanning calorimetry. The kinetics of melt and cold crystallization of PLA were adequately described by the Avrami model. There was a strong dependence of the rate of crystallization and extent of crystallinity of PLA on the extent of clay loading and flow induced morphology. For composites with 2 and 6 wt% clay loading, uniquely slower crystallization occurred. A qualitative relationship between phase morphology and crystallization, as affected by clay loading, is therefore described.     

Non-isothermal crystallization kinetics of poly (lactic acid)/modified carbon black composite

A novel method was employed to modify the surface of carbon black (CB) by an organic small molecule in a Haake Rheomix mixer. Jeziorny equation, the Ozawa model and Mo equation were employed to describe the non-isothermal crystallization process of poly (lactic acid) (PLA), PLA/CB and PLA/modified carbon black (MCB) composites. It is found that the Ozawa model fail to describe the non-isothermal crystallization process for PLA and its composites, while Jeziorny equation and Mo’s theory provide a good fitting. The comparison of crystallization kinetics between PLA/MCB and PLA through Lauritzen–Hoffman model indicates that there appears a transition from regimes II to III in PLA and PLA/MCB. The fold surface free energy σ _e of PLA/MCB composite is higher than that of neat PLA, implying that the existence of nucleating agent is unfavorable for the regular folding of the molecule chain.     

Effect of flax fiber content on polylactic acid (PLA) crystallization in PLA/flax fiber composites

Crystallization of polylactic acid (PLA) has a profound effect on its thermal stability and mechanical properties. However, almost no crystallization occurs in actual injection molding process due to rapid cooling program. In this paper, flax fiber was employed as nucleator to enhance the crystallization capability of PLA. Effects of flax fiber content on cold crystallization, melt crystallization, crystallinity, crystal form, morphologies, and size of spherulites of PLA/flax fiber composites were investigated. Dynamic mechanical analysis was innovatively employed to study cold crystallization temperature of PLA/flax fiber composites under dynamic force, and the relationship between cold crystallization temperature (y) and flax fiber content (x) data was fitted by the function y = 34.1 × exp (?x/5.7) + 78.0. The differential scanning calorimetry results showed that the cold crystallization temperature of composites dropped, the melt crystallization temperature of composites increased, and the crystallinity of composites improved with increasing of flax fiber content. Using polarized optical microscopy, it has been found that the spherocrystal size of composites was much smaller than that of neat PLA, and flax fiber induced transcrystallization on the flax fiber surfaces. Wide-angle X-ray diffraction was applied to reveal that flax fiber significantly enhanced the formation of α-form PLA crystals.     

Crystallization behavior of α‐cellulose short‐fiber reinforced poly(lactic acid) composites

The isothermal crystallization behavior of α‐cellulose short‐fiber reinforced poly(lactic acid) composites (PLA/α‐cellulose) was examined using a differential scanning calorimeter and a petrographic microscope. Incorporating a natural micro‐sized cellulose filler increased the spherulite growth rate of the PLA from 3.35 μm/min for neat PLA at 105°C to a maximum of 5.52 μm/min for the 4 wt % PLA/α‐cellulose composite at 105°C. In addition, the inclusion of α‐cellulose significantly increased the crystallinities of the PLA/α‐cellulose composites. The crystallinities for the PLA/α‐cellulose composites that crystallized at 125°C were 48–58%, higher than that of the neat PLA for ～13.5–37.2%. The Avrami exponent n values for the neat and PLA/α‐cellulose composites ranged from 2.50 to 2.81 and from 2.45 to 3.44, respectively, and the crystallization rates K of the PLA/α‐cellulose composites were higher than those of the neat PLA. The activation energies of crystallization for the PLA/α‐cellulose composites were higher than that of the neat PLA. The inclusion of α‐cellulose imparted more nucleating sites to the PLA polymer. Therefore, it was necessary to release additional energy and initiate molecular deposition. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improving the flame retardance and melt dripping of poly(lactic acid) with a novel polymeric flame retardant of high thermal stability

A polymeric flame retardant containing phosphorus and nitrogen (PCNFR) was synthesized and characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance and gel permeation chromatography. The thermal decomposition temperatures at 10% weight loss (T_{10 wt%}) of PCNFR were around 358 °C, and the char yield at 600 °C reached about 60 wt% both in nitrogen and air by thermogravimetric analysis. The flame retarded poly(lactic acid) (PLA) composites with PCNFR were prepared. The thermogravimetric analysis results showed that PCNFR could improve the thermal stability of the flame retarded PLA composites with low loading (≤10 wt%) and at high temperature zone (≥390 °C). The condensed products from the decomposition of the flame retarded composites at 380 °C and 450 °C for different intervals were analyzed by Raman spectroscopy, and the results showed that time and temperature influenced the structure of the char residue evidently. When incorporating 30 wt% PCNFR into PLA, the limited oxygen index of the flame retarded composites reached 25.0%, and V‐0 rating was achieved. The char residues were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy in detail. Copyright © 2016 John Wiley & Sons, Ltd.     

Halloysite nanotubes immobilized by chitosan/tannic acid complex as a green flame retardant for bamboo fiber/poly(lactic acid) composites

In order to develop an environmentally benign flame retardant for bamboo/PLA composites (BPC), chitosan (CS) and tannic acid (TA) were used as cationic and anionic polyelectrolyte respectively to stabilize halloysite nanotubes (HNT) on the surface of bamboo fiber (BF) and poly(lactic acid) (PLA). Mechanical performance tests showed that the flexural properties of BPC were moderately enhanced with the addition of HNT, while the incorporation of CS/TA complex (FR) exhibited a slight increase. The results of thermogravimetric analysis demonstrated that CS/TA complex and HNT improved the thermal stability of the BPC synergistically, which increased the char residue. Limiting oxygen index and cone calorimetry tests were used to study the flammability of BPC and the results showed that the addition of CS/TA complex and HNT had a synergistic effect on the flame retardant performance of BPC materials. The macroscopic and microscopic morphological studies confirmed the formation of HNT layer in the matrix of BPC/5FR@5HNT samples, which facilitated more stabile char residue with the best flame retardant performance.     

Thermal properties and aging characteristics of chemically modified oil palm ash-filled natural rubber composites

The chemically modified oil palm ash (OPA) with the cetyltrimethylammonium bromide (CTAB) solution was prepared prior to compounding with the natural rubber and other curing ingredients. The aging resistance and thermal stability of CTAB-modified OPA-filled natural rubber composites were evaluated in the same manner as non-modified OPA samples. The retention tensile properties after thermal aging was measured and based on the result shown, the CTAB-modified OPA-filled natural rubber composites imparted insignificant effect to aging resistance as compared to the non-modified OPA-filled natural rubber composites at very low OPA loading; however, the effect became apparent beyond 3 phr OPA loading where the CTAB-modified OPA-filled natural rubber composites provided better aging resistance than the corresponding non-modified OPA-filled natural rubber composites. The thermogravimetric analysis indicated that the CTAB-modified OPA-filled natural rubber composites exhibited lower thermal stability which showed lower temperature at their respective weight loss and lesser char residue than that of non-modified OPA-filled natural rubber composites. This was attributed to the CTAB which started to decompose at the temperature of 210 °C. However, for the range from ambient temperature to 210 °C, the CTAB-modified OPA-filled natural rubber composites produce better thermal stability than those of non-modified OPA-filled natural rubber composites.     

剑麻纤维/聚丙烯木塑复合材料的热氧老化性能研究

以剑麻纤维(SF)、聚丙烯(PP)为原料,经熔融共混、模压成型工艺制备木塑复合材料。探讨了SF/PP复合材料的力学性能、热性能随老化时间和SF含量的变化规律,借助扫描电镜对复合材料老化前后的冲击断面进行微观结构分析。结果表明:老化后复合材料的冲击强度、弯曲强度和弯曲模量随剑麻含量的增加而降低;同时,复合材料中PP相的结晶速率、结晶度也有所降低,但复合材料的热稳定性基本没有变化。     

Crystallization of poly(lactic acid) enhanced by phthalhydrazide as nucleating agent

The effect of phthalhydrazide compound on the nonisothermal and isothermal crystallization behavior of bio-based and biodegradable poly(lactic acid) (PLA) was investigated by differential scanning calorimetry and polarized optical microscopy. The nonisothermal melt crystallization of PLA started much earlier in the presence of phthalhydrazide even at a phthalhydrazide content as low as 0.1 wt%. The isothermal crystallization kinetics was analyzed by the Avrami model. It was found that the Avrami exponent of the PLA crystallization was not significantly influenced by the addition of phthalhydrazide, indicating that the crystallization mechanism almost did not change in the composites. The crystallization half-time of PLA/phthalhydrazide composites decreased significantly with increase in phthalhydrazide loading. The observation from optical microscopy showed that the presence of phthalhydrazide increased the number of nucleation sites. The above observations indicate that phthalhydrazide is an efficient nucleating agent of PLA.     

Isothermal crystallization behavior of hybrid biocomposite consisting of regenerated cellulose fiber,clay, and poly(lactic acid)

Quantitative analysis of isothermal crystallization kinetics of PLA/clay nanocomposite and PLA/clay/regenerated cellulose fiber (RCF) hybrid composite has been conducted. The crystallization rate constant (k) according to Avrami equation was higher in PLA/clay nanocomposite than in PLA/clay/RCF hybrid composite at the same crystallization temperature. The equilibrium melting temperature obtained by Hoffman–Weeks equation was almost same in both composites, whereas stability parameter was greater in hybrid composite than in nanocomposite. Activation energy of hybrid composite for crystallization was larger than that of nanocomposite. The value of nucleation parameter (K_g) and surface free energy (s_e) of hybrid composite were larger than nanocomposite, indicating that hybrid composite has a less folding regularity than nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Basalt fiber reinforced and elastomer toughened polylactide composites: Mechanical properties,rheology, crystallization,and morphology

A series of the reinforced and toughened polylactide (PLA) composites with different content of basalt fibers (BF) were prepared by twin screw extruder. The toughness of BF/PLA composite s was improved further by the addition of polyoxyethylene grafted with maleic anhydride (POE-g-MAH), ethylene–propylene–diene rubber grafted with maleic anhydride (EPDM-g-MAH), and ethylene-acrylate-glycidyl methacrylate copolymer (EAGMA), relatively. The mechanical properties, rheology, crystallization, and morphology of BF/PLA composites were studied. The results showed that basalt fiber had significant reinforcing and toughening effect in comparsion with glass fiber. EAGMA was more effective in toughening BF/PLA composites than POE-g-MAH and EPDM-g-MAH. When the content of EAGMA achieved to 20 wt %, the impact strength of BF/PLA/EAGMA composite increased to 33.7 KJ/m², meanwhile the value was improved by 71.1% compared with pure PLA. According to dynamic rheometer testing, the use of the three kinds of elastomers increased the melt dynamic viscosity. Differential scanning calorimetry analysis showed that POE-g-MAH and EPDM-g-MAH can decrease the cold crystallization temperature (T_cc) to approximately 20°C and dramatically improve crystallinity (χ_c) of BF/PLA composites. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal and biodegradation properties of poly(lactic acid)/fertilizer/oil palm fibers blends biocomposites

Poly(lactic acid) (PLA) and NPK fertilizer with empty fruit bunch (EFB) fibers were blends to produced bioplastic fertlizer (BpF) composites for slow release fertilizer. Thermal properties of BpF composites were investigated by thermogavimteric analysis (TGA), differential scanning calorimetry (DSC), and morphological and degradation properties were anlayzed by scanning electron microscopy (SEM), soil burial test, respectively. TGA themogram display that neat PLA, PLA/NPK, and BpF composites degradate at different temperatures. DSC curves of PLA and other composites exhibited same glass transition temperature (T_g) value indicating that both major blend components are miscible. The T_g, crystallization temperature (T_c), melting temperature (T_m) values also decreased with increased amount of fertilizer and fibers. The T_m of BpF composites did not change with an increase in fertilizer content because thermal stability of PLA and PLA/NPK composites was not affected. Soil burial and fungal degradation test of PLA, PLA/NPK, and BpF composites were also carried out. Soil burial studies indicated that BpF composites display better biodegradation as compared with neat NPK. Fungal degradation study indicated that fungi exposure times of BpF composites show higher value of degradation as compared with PLA/NPK. We attribute that developed BpF composites will help oil palm plantation industry to use it as slow release fertilizer. POLYM. COMPOS. 36:576–583, 2015. © 2014 Society of Plastics Engineers     

Thermal properties and crystallization behaviors of polylactide/redwood flour or bamboo fiber composites

A series of polylactide/redwood flour (PLA/RWF) and polylactide/bamboo fiber (PLA/BF) composites were successfully prepared using a solution mixing procedure. Fourier transform infrared spectroscopy (FTIR) and wide-angle X-ray diffraction (XRD) were employed to characterize these composites. Thermal properties and crystallization behaviors of PLA composites were determined by their respective techniques of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). With the increasing content of fibers, the glass transition temperature (T _g ), crystallization temperature (T _c ), and melting temperature (T _m ) of PLA/RWF composites decreased first and then increased, but T _g and T _m of PLA/BF composites increased first and decreased afterwards. It is suggested that fibers could improve the segmental mobility of PLA; meanwhile, the different morphologies, sizes, and densities of RWF and BF have different effects on thermal properties of composites. Under the increasing content of RWF, the crystallization rate of the composite increased first and decreased afterwards. When the content of RWF was 5%, the crystallization rate was at its maximum. It could be possible that the addition of fibers was able to nucleate PLA and increase the degree of crystallinity, but the excess content of fibers easily led to heterogeneous composites and subsequent poor crystallization behaviors. In a word, thermal properties and crystallization behaviors of PLA composites were regularly changing by increasing content of fibers.