Kenaf fiber/poly(ε‐caprolactone) biocomposite with enhanced crystallization rate and mechanical properties

Plant‐derived kenaf fiber (KF)‐reinforced poly(ε‐caprolactone) (PCL) biocomposites were successfully fabricated by the melt mixing technique. The crystallization behavior, morphology, and mechanical and dynamic mechanical properties of PCL/KF composites with various KF weight contents were investigated. The crystallization rate, tensile and storage moduli significantly improved as compared to the virgin polymer. The half times of PCL/KF composite (20 wt % fiber content) in isothermal crystallization at 40°C and 45°C reduced to 31.6% and 42.0% of the neat PCL, respectively. Moreover, the tensile and storage modulus of the composite are improved by 146% and 223%, respectively, by the reinforcement with 30% KF. The morphology evaluated by SEM indicates good dispersion and adhesion between KF and PCL. Overall, these findings reveal that KF can be a potential reinforcement for the biodegradable polymer composites owing to its good ability to improve the mechanical properties as well as crystallization rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Isothermal crystallization kinetics of silk fibroin fiber‐reinforced poly(ε‐caprolactone) biocomposites

BACKGROUND: Poly(ε‐caprolactone) (PCL) has attracted great attention due to its wide applications for pharmaceutical controlled released systems and implanted polymer devices. In this study, silk fibroin fiber (SF) obtained from degumming treatment of silk was used to prepare novel reinforced PCL biocomposites. The isothermal crystallization behavior of these composites was investigated using differential scanning calorimetry measurements. RESULTS: With a decrease of isothermal crystallization temperature (T_c) and an increase of fiber filler, the crystallization time of the SF/PCL composites becomes shorter, the crystallization rate constant (K) increases and the Avrami exponent (n) gradually decreases (being between 1 and 2). The crystallization of PCL and SF/PCL composites occurs in the same regime. With the gradual addition of fiber, lateral surface free energy (σ) is nearly unchanged, but fold surface free energy (σ_e) decreases. CONCLUSION: Heterogeneous nucleation is dominant and different growth morphologies coexist during the isothermal crystallization process of the SF/PCL hybrid systems. Although the introduction of SF obviously increases the overall crystallization rate of PCL, the growth rate constant and nucleation constant of PCL are reduced because of the confinement effect of fiber network structures on the molecular mobility of polymer molecular chains. Copyright © 2009 Society of Chemical Industry     

Effect of electron beam irradiation on the crystallization of silk fibroin fiber‐reinforced poly(ε‐caprolactone) biocomposites

In the medical industry, ionizing radiation has attracted increasing interest in recent years for the sterilization of biomedical materials due to its high effectiveness at relatively low cost and simple operation. In the study reported here, silk fibroin (SF) fiber was used to prepare novel reinforced poly(ε‐caprolactone) (PCL) biocomposites, and the effect of electron beam irradiation on both non‐isothermal and isothermal crystallization kinetics of the SF/PCL biocomposites was investigated. The models of Ozawa treatment, Avrami analysis and regime theory of crystal growth are applicable for describing the non‐isothermal and isothermal crystallization kinetics of the irradiated PCL and SF/PCL composites. Compared with non‐irradiated PCL and SF/PCL composites, the irradiated specimens exhibit the same crystallization regime (regime II) and similar lateral surface free energy (σ), except for smaller fold surface free energy (σ_e) and work of chain folding (q). The crosslinked PCL network formed in the irradiation process can act as a nucleation agent and accelerate the primary crystallization of PCL. However, the restriction effect of the crosslinked PCL network on the molecular chain mobility will reduce the overall crystallization rate of PCL, and this restriction effect appears stronger in the non‐isothermal crystallization process than in the isothermal crystallization process. Copyright © 2009 Society of Chemical Industry     

剑麻预处理对热塑性淀粉复合材料力学性能及降解性能的影响

采用碱、蒸汽爆破等对剑麻纤维进行预处理,考察了不同预处理方法对剑麻纤维增强热塑性淀粉力学性能及降解性能的影响。结果表明:碱处理能够提高复合材料的力学性能,延长材料降解周期,是制备剑麻纤维增强热塑性淀粉复合材料有效的预处理方法;剑麻纤维增强热塑性淀粉的机理是甘油在淀粉及剑麻纤维之间起到桥梁作用,提高了热塑性淀粉与剑麻纤维的界面结合力,从而提高了复合材料的力学性能。     

剑麻纤维增强热塑性淀粉复合材料的制备及性能研究

为研究剑麻纤维增强的热塑性淀粉复合材料的制备工艺及热稳定性,以玉米淀粉为原料,先制得热塑性淀粉,再以剑麻纤维为骨架增强体制备剑麻纤维增强热塑性淀粉复合材料,通过正交试验优化制备工艺,DSC、TG/DTG、SEM分析其热稳定性及结构。正交试验表明,各因素对材料抗拉强度影响的主次顺序为纤维长度 >纤维用量 >模压成型温度 >填料用量;最佳工艺条件为纤维长度15mm、纤维用量35g、模压成型温度200℃、填料用量5g,此时材料的抗拉强度可达到4.45MPa。利用差示扫描量热分析和热重分析分别对热塑性淀粉及剑麻纤维复合材料的热稳定性进行了分析,结果表明,热塑处理提高了淀粉的熔融温度,有利于淀粉与纤维素羟基间的氢键结合,且热塑过程在一定程度上降低了淀粉的热稳定性;剑麻纤维复合材料的热降解过程主要发生在200~400℃温度区间。SEM分析显示最佳工艺条件下得到的复合材料具有较好的泡孔结构。     

高含量碳纤维增强尼龙6等温结晶动力学的研究

采用差示扫描量热仪（DSC）研究了高含量碳纤维（CF）增强尼龙6的等温结晶行为，并应用Avrami方程分析了尼龙6的等温结晶动力学过程。结果表明，CF在尼龙6基体中起到了异相成核作用，提高了结晶速率；尼龙6的等温结晶过程主要为成核过程控制。     

Relationship between processing and properties of biodegradable composites based on PCL/starch matrix and sisal fibers

Biocomposites were produced using polycaprolactone and starch as matrix, and sisal fibers as reinforcement. The matrix is a biodegradable commercial product called MaterBi‐Z, which is based on a polycaprolactone and starch system. The relationship between processing conditions and properties is reported. An alkaline treatment was performed in order to improve the adhesion and the compatibility of the fiber with the matrix. The effect of the treatment on the tensile properties and morphology was determined. Fiber content enhances the tensile properties of the biodegradable composite. The experimentally observed tensile properties (modulus and tensile strength) of short sisal fiber reinforced MaterBi‐Z matrix composites with different fiber loading are compared with the existing theories of reinforcement. SEM photomicrographs of the fractured composite surfaces are also analyzed.     

Poly(ε-caprolactone)/poly(ethylene oxide) diblock copolymer. I. Isothermal crystallization and melting behavior

The isothermal crystallization and melting behavior of the poly(ε-caprolactone)(PCL)/poly(ethylene oxide)(PEO) diblock copolymer has been studied by WAXD, SAXS, and DSC methods. Only the PCL block is crystallizable; the PEO block of weight fraction 20% cannot crystallize, although its corresponding homopolymer has strong crystallizability. The long period, amorphous layer, and crystalline lamella of the PCL/PEO block copolymer all increase with the rise in the crystallization temperature, and the thickness of the amorphous layer is much larger than that of crystalline lamella due to the existence of the PEO block in the amorphous region. The isothermal crystallization of the PCL/PEO block copolymer is investigated by using the theory of Turnbull and Fischer. It is found that the amorphous PEO block has a great influence on the nucleation of PCL block crystallization, and the extent of this influence depends on crystallization conditions, especially temperature. The outstanding characteristics are the phenomenon of the double melting peaks in the melting process of the PCL/PEO block copolymer after isothermal crystallization at different temperatures and the transformation of melting peaks from double peaks to a single peak with variations in the crystallization condition. They are related mainly to the existence of the PEO block bonding chemically with the PCL block. In summing up results of investigations into the crystallization and melting behavior of the PCL/PEO block copolymer, it is interesting to notice that when the PCL/PEO block copolymer crystallizes at three different crystallization temperatures, i.e., below 0°C, between 0 and 35°C, and above 35°C, the variation of peak melting temperature is similar to that of overall crystallization rates in the process of isothermal crystallization. The results can be elucidated by the effect of the PEO block on the crystallization of the PCL block, especially its nucleation. © 1996 John Wiley & Sons, Inc.     

Preparation and characterization of biodegradable poly(ϵ‐caprolactone) self‐reinforced composites and their crystallization behavior

Self‐reinforced poly(?‐caprolactone) (PCL) composites were prepared by dispersing a homologous nucleating agent within the PCL matrix through melt mixing. Coalesced PCL, featuring more orderly chain arrangements, acted as the nucleating agent leading to improvement of crystallization for the melt PCL matrix. Non‐isothermal melt crystallization behavior, isothermal melt crystallization kinetics, spherulitic morphology and the crystal structure of neat PCL and the PCL self‐reinforced composites were studied in detail. The results indicated that both non‐isothermal and isothermal melt crystallization of PCL composites were enhanced significantly by the homologous nucleating agent, while the crystallization mechanism and crystal structures remained unchanged. The results of tensile mechanical tests showed that the Young's modulus of the composites was improved by up to 77% with the incorporation of 20 wt% nucleating agent. Biocompatibility tests demonstrated that the cells could adhere to and proliferate well on the surface of the self‐reinforced PCL composites. © 2017 Society of Chemical Industry     

Isothermal and nonisothermal crystallization kinetics of poly(ϵ‐caprolactone)

With increasing environmental awareness, evaluating the potential of biopolymers as a substitute for traditional materials has been of great interest. Crystallization kinetics provides fundamental knowledge required for evaluation, playing vital role in determining the final properties of the product. In this study, the isothermal and nonisothermal crystallization kinetics of poly(?‐caprolactone) (PCL) were investigated with the help of various models. The Avrami model best described the isothermal crystallization kinetics, suggesting three‐dimensional spherulitic growth, which was in agreement with the morphology studies; whereas the Liu model fit well under nonisothermal crystallization conditions. The failure of the Kissinger model to determine the activation energy was overcome with the Friedman model. The kinetic crystallizability determined by the Ziabacki model indicated a higher crystallization ability of PCL at lower cooling rates. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Performance of an acrylic acid grafted polycaprolactone/starch composite: Characterization and mechanical properties

In this article, the properties of a polycaprolactone and starch composite (PCL/starch) and an acrylic acid grafted polycaprolactone and starch composite (PCL‐g‐AA/starch) were examined by Fourier transform infrared spectroscopy, nuclear magnetic resonance, differential scanning calorimetry, Instron mechanical testing, and scanning electron microscopy. Mechanical properties of PCL became significantly worse when it was blended with starch, due to the poor compatibility between the two phases. Much better dispersion and homogeneity of starch in the polymer matrix was obtained when PCL‐g‐AA was used in place of PCL in the composite. Improved mechanical and thermal properties of the PCL‐g‐AA/starch composite, notably an increase in tensile strength at breakpoint, evidenced its superiority to the PCL/starch one. Furthermore, PCL‐g‐AA/starch was more easily processed than PCL/starch because the former had lower melt viscosity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2888–2895, 2003     

Isothermal and nonisothermal crystallization kinetics of poly(ε‐caprolactone)/multi‐walled carbon nanotube composites

Differential scanning calorimeter (DSC) and polarized optical microscopy (POM) have been used to investigate the isothermal and nonisothermal crystallization behavior of poly(ε‐caprolactone) (PCL)/multi‐walled carbon nanotube (MWNT) composites. PCL/MWNT composites have been prepared by mixing the PCL polymer with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) in tetrahydrofuran solution. Raman spectrum of c‐MWNT indicated the possible presence of carboxylic acid groups at both ends and on the sidewalls of the MWNTs. The TEM micrograph showed that the c‐MWNT is well separated and uniformly dispersed in the PCL matrix. DSC isothermal results showed that the introduction of c‐MWNT into the PCL initiates strongly heterogeneous nucleation, which induced a change of the crystal growth process. The activation energy of PCL significantly decreases by adding 0.25 wt% c‐MWNT into PCL/c‐MWNT composites and then increases as c‐MWNT content increases. The result demonstrates that the addition of c‐MWNT into PCL induces the heterogeneous nucleation at lower c‐MWNT content and then inhibits the polymer chain transportation ability during crystallization at higher c‐MWNT content. In this study, we have also studied the nonisothermal crystallization kinetics and melting behavior of PCL/c‐MWNT composites at various cooling rates. The correlation among isothermal and nonisothermal crystallization kinetics and melting behavior of PCL/c‐MWNT composites can be also discussed. POLYM. ENG. SCI., 46:1309–1317, 2006. © 2006 Society of Plastics Engineers     

Effect of layering pattern on dynamic mechanical properties of randomly oriented short banana/sisal hybrid fiber–reinforced polyester composites

Dynamic mechanical test methods have been widely employed for investigating the structures and viscoelastic behavior of polymeric materials to determine their relevant stiffness and damping characteristics for various applications. Randomly oriented short banana/sisal hybrid fiber–reinforced polyester composites were prepared by keeping the volume ratio of banana and sisal 1 : 1 and the total fiber loading 0.40 volume fraction. Bilayer (banana/sisal), trilayer (banana/sisal/banana and sisal/banana/sisal), and intimate mix composites were prepared. The effect of layering pattern on storage modulus (E′), damping behavior (tan δ), and loss modulus (E″) was studied as a function of temperature and frequency. Bilayer composite showed high damping property while intimately mixed and banana/sisal/banana composites showed increased stiffness compared to the other pattern. The Arrhenius relationship has been used to calculate the activation energy of the glass transition of the composites. The activation energy of the intimately mixed composite was found to be the highest. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2168–2174, 2005     

Non‐isothermal crystallization kinetics of poly(ε‐caprolactone) in hydrogen‐bond‐coupled polymeric‐inorganic hybrid materials

Some hydrogen‐bonding‐interactions‐mediated poly(ε‐caprolactone) (PCL)/silica (SiO₂) polymeric‐inorganic hybrids were prepared by the sol–gel process. The non‐isothermal crystallization kinetics of PCL in the hybrids was investigated by means of differential scanning calorimetry. The results show that the Jeziorny method, together with the combination of the Avrami and Ozawa equations, is applicable to describe the non‐isothermal crystallization kinetics of the PCL in the hybrid system, while the Ozawa theoretical method can be used just for the pure PCL and the 70/30 TEOS/PCL hybrids. Depending on the composition of the PCL/silica, the hybrids displayed microphase separation at various scales, which in turn affect the crystallization behavior and mechanism of PCL in the hybrids. On the one hand, the inorganic component (viz SiO₂) could act as the nucleating agent to facilitate the crystallization of PCL in the hybrids. On the other hand, the SiO₂ networks also confine the crystallization of PCL. Copyright © 2004 Society of Chemical Industry     

聚苯硫醚/碳纳米管复合材料等温结晶性能研究

利用双螺杆挤出机制备了聚苯硫醚(PPS)/多壁碳纳米管(MWCNTs)复合材料,然后通过差示扫描量热法(DSC)研究了纯PPS以及PPS/MWCNTs复合材料的等温结晶过程,并运用Avrami模型对纯PPS以及PPS/MWCNTs复合材料的等温结晶动力学进行分析。研究结果表明,MWCNTs的加入明显缩短了PPS的半结晶期,提高了结晶速率;Avrami模型能够较好地描述PPS及PPS/MWCNTs复合材料的等温结晶动力学。     

A Comparative Study on the Mechanical Properties of Jute and Sisal Fiber Reinforced Polymer Composites

The aim of the present study is to investigate and compare the mechanical properties of raw jute and sisal fiber reinforced epoxy composites with sodium hydroxide treated jute and sisal fiber reinforced epoxy composites. This is followed by comparisons of the sodium hydroxide treated jute and sisal fiber reinforced composites. The jute and sisal fibers were treated with 20% sodium hydroxide for 2 h and then incorporated into the epoxy matrix by a molding technique to form the composites. Similar techniques have been adopted for the fabrication of raw jute and sisal fiber reinforced epoxy composites. The raw jute and sisal fiber reinforced epoxy composites and the sodium hydroxide treated jute and sisal fiber reinforced epoxy composites were characterized by FTIR. The mechanical properties (tensile and flexural strength), water absorption and morphological changes were investigated for the composite samples. It was found that the sodium hydroxide treated jute and sisal fiber reinforced epoxy composites exhibited better mechanical properties than the raw jute and raw sisal fiber reinforced composites. When comparing the sodium hydroxide treated jute and sisal fiber reinforced epoxy composites, the sodium hydroxide treated jute fiber reinforced composites exhibited better mechanical properties than the latter.     

Miscibility and crystallization behavior of biodegradable poly(ε‐caprolactone)/tannic acid blends

Miscibility, isothermal melt crystallization kinetics, spherulitic morphology and growth rates, and crystal structure of completely biodegradable poly(ε‐caprolactone) (PCL)/tannic acid (TA) blends were studied by differential scanning calorimetry, polarized optical microscopy, and wide angle X‐ray diffraction in detail in this work. PCL and TA are miscible as evidenced by the single composition dependent glass transition temperature over the whole compositions range and the depression of equilibrium melting point of PCL in the PCL/TA blends. Isothermal melt crystallization kinetics of neat PCL and an 80/20 PCL/TA blend was investigated and analyzed by the Avrami equation. The overall crystallization rates of PCL decrease with increasing crystallization temperature for both neat PCL and the PCL/TA blend; moreover, the overall crystallization rate of PCL is slower in the PCL/TA blend than in neat PCL at a given crystallization temperature. However, the crystallization mechanism of PCL does not change despite crystallization temperature and the addition of TA. The spherulitic growth rates of PCL also decrease with increasing crystallization temperature for both neat PCL and the PCL/TA blend; moreover, blending with TA reduces the spherulitic growth rate of PCL in the PCL/TA blend. It is also found that the crystal structure of PCL is not modified in the PCL/TA blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization kinetics of thermosetting polymer blends of poly(ε‐caprolactone) and unsaturated polyester resin

A study has been made of the isothermal crystallization kinetics of poly(ε‐caprolactone) (PCL) in partially miscible crosslinked polyester resin (PER)/PCL blends by using differential scanning calorimetry (DSC). For comparison, miscible blends of PCL with uncured polyester resin, i.e., oligoester resin (OER), were also investigated. The overall crystallization rate of PCL remarkably decreased with the addition of amorphous component, OER or PER. The kinetic rate constant K_n decreased sharply for both the OER/PCL blends and the crosslinked PER/PCL blends with decreasing PCL concentration. The mechanism of nucleation and geometry of the growing PCL crystals was not remarkably affected by the incorporation of OER, but changed considerably with the addition of PER. However, the overall crystallization rate of PCL in the crosslinked PER/PCL blends was much higher compared with the corresponding uncured OER/PCL blends, which is attributable to the phase‐separated structure and the reduced miscibility in the crosslinked blends. According to the nucleation and growth theories, the nucleation process was considered to be the rate controlling step in the crystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 322–327, 1999     

Effect of isothermal crystallization on the amorphous phase mobility of polycarbonate/poly(ε-caprolactone) blends

Polycarbonate/poly(ε-caprolatone), PC/PCL, amorphous miscible blends with 90/10 and 80/20 composition in weight, have been studied by X-ray diffraction and broad-band dielectric spectroscopy. The molecular dynamics for the high T_g component segmental mobility have been followed by analyzing the isothermal dielectric losses as a function of frequency with Havriliak-Negami distributions. The PCL plasticization effect is observed as a lowering of the Vogel-Tammann-Fulcher terminal temperature without any significant change in the other relaxation parameters. The isothermal crystallization process of the 90/10 PC/PCL blend has been studied in real time both by following the decrease of mobile amorphous material from the variation of the dielectric losses, and by wide angle X-ray scattering to follow the crystal growth. Quantitative comparisons show the disappearance of much higher amounts of mobile amorphous chains than those that are transferred to the crystallites. The existence of a rigid amorphous phase in the blend is established in non-negligible amounts as the isothermal crystallization of PC develops. The remaining mobile amorphous phase has unchanged dynamics.     

Crystallization and morphology studies of biodegradable poly(ε‐caprolactone)/silica nanocomposites

Biodegradable poly(ε‐caprolactone) (PCL)/silica nanocomposites at various silica loadings were prepared via direct melt compounding method in this work. Scanning electron microscopy observation indicated that when the silica content was < 3 wt%, the nanoparticles dispersed evenly in the PCL matrix and exhibited only aggregates with particle size of less than 100 nm. The results of nonisothermal melt crystallization showed that the crystallization peak temperature was higher in the nanocomposites than in neat PCL; moreover, the overall crystallization rate was faster in the nanocomposites than in neat PCL during isothermal melt crystallization. Both nonisothermal and isothermal melt crystallization studies suggested that the crystallization of PCL was enhanced by the presence of silica and influenced by the silica loading. The effect of silica on the crystallization behavior was twofold: the presence of silica may provide heterogeneous nucleation sites for the PCL crystallization while the aggregates of silica may restrict crystal growth of PCL. However, the crystal structure of PCL remained almost unchanged despite the presence of silica in the nanocomposites. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers