Processing and thermal properties of composites based on recycled PET,sisal fibers,and renewable plasticizers

This investigation focuses on the preparation of bio‐based composites from recycled poly (ethylene terephthalate) (PET) and sisal fibers (3 cm, 15 wt %), via thermopressing process. Plasticizers derived from renewable raw materials are used, namely, glycerol, tributyl citrate (TBC) and castor oil (CO), to decrease the melting point of the recycled PET (T_m ∼ 265°C), which is sufficiently high to initiate the thermal decomposition of the lignocellulosic fiber. All used materials are characterized by thermogravimetric analysis and differential scanning calorimetry, and the composites are also characterized via dynamic mechanical thermal analysis. The storage modulus (30°C) and the tan δ peak values of CT [PET/sisal/TBC] indicate that TBC also acts as a compatibilizing agent at the interface fiber/PET, as well as a plasticizer. To compare different processing methods, rheometry/thermopressing and compression molding are used to prepare the recycled PET/sisal/glycerol/CO composites. These two different methods of processing show no significant influence on the thermal properties of these composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40386.     

剑麻基抗菌纤维的制备及其结构与性能

在 0 .2 m ol/L 的硝酸溶液中 ,以 0 .0 5 mol/L 高锰酸钾为引发剂先合成剑麻接枝聚丙烯腈纤维。然后用水合肼进行功能化改性 ,合成了一种新型的天然剑麻基抗菌纤维 ,并测定了它的抗菌消臭性能。结果表明 :剑麻纤维经接枝聚丙烯腈改性功能化后 ,其表面含有多种含氮、含氧、杂环等官能团 ,对不同菌类具备优异的杀菌活性 ,并且具有广谱抗菌 ,作用时间持久和效率高等特点。     

Preparation and characterization of benzylated sisal fibers

Sisal fibers were benzylated under different conditions and were characterized with infrared spectroscopy, X‐ray diffraction, thermal analysis, and scanning electron microscopy. The benzylation reaction was monitored by the mass gain as a function of the reaction time. In the first stage, there was a mass loss associated with the loss of lignin and polyoses from the raw fiber, which was accompanied by an increase in mass due to benzyl incorporation. When fiber delignification was carried out before benzylation, the mass gain curves of the benzylation reaction presented no initial mass loss and a much higher mass gain. Benzylation promoted several morphological changes: (1) the loss of the parenchyma cells, (2) the defibrillation of the technical fibers into ultimate fibers, (3) the microdefibrillation of the ultimate fibers, and (4) benzyl incorporation. The crystallinity of the fibers decreased with benzylation, as observed by X‐ray diffraction. The thermal stability of the fibers varied according to the treatment used. Other changes promoted in the fibers by chemical modification were examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2957–2965, 2003     

Preparation and characterization of poly(vinyl chloride)/virgin and treated sisal fiber composites

Mechanical property changes, thermal stability, and water absorption capacity of poly(vinyl chloride) (PVC)/sisal fiber composites were assessed with respect to the effect of maleic anhydride chemical treatments of the sisal fiber, for five different sisal fiber contents, varying from 0 to 30% by weight in the composite. The composites prepared with the untreated sisal exhibited higher tensile modulus and hardness than the unloaded resin, while elongation and tensile strength were reduced. The deterioration in the mechanical properties of PVC blended with sisal fiber is attributed to the presence of moisture, interfacial defects at the fiber and polymer interface, and fiber dispersion in the PVC matrix. The amount of absorbed water is a function of the amount of fiber in the composite (F0 = 0 phr, F5 = 0.77 phr, and F20 = 4.83 phr). The comparison of the results of characterization of F5, F20, and F30 formulations prepared with the untreated fibers and the treated ones showed a reduction in absorbed water after the chemical treatment of fiber with maleic anhydride (F0 = 0 phr, F5 = 0.28 phr, and F20 = 2.99 phr), thus improving the mechanical properties of composites prepared with the treated sisal. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3630–3636, 2007     

Tire rubber–sisal composites: Effect of mercerization and acetylation on reinforcement

Tire rubber particles were mixed randomly with short sisal fibers and hot pressed. Sisal fibers were used as received, mercerized, and mercerized/acetylated. The fibers were characterized by scanning electron microscopy (SEM), thermal gravimetry analysis (TGA), infrared spectroscopy (FTIR), water sorption, and mechanical properties. Thermal stability of the mercerized/acetylated fibers improves (from 200 to 300°C) with respect to the raw fibers, and water sorption is ～ 20% smaller than for the raw and the mercerized fibers. Tensile strength is unchanged after the chemical treatments. Water sorption, mechanical properties, and SEM evaluated the performance of the tire rubber composites. All composites showed enhanced elastic modulus; increase is dependent on fiber load. Smallest water sorption was obtained in composites with the mercerized/acetylated fibers. With these fibers at 10% load, the best results were obtained with the smaller tire rubber particles (320 μm) and at 5% load with the bigger (740 μm) tire rubber particles. Both composites showed ～ 50% increase in tensile strength when compared to similar composites with raw fibers. SEM of the surface of fracture showed that the adhesion between fiber and rubber was enhanced after both chemical treatments. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2507–2515, 2003     

Effect of processing conditions on dimensions of sisal fibers in thermoplastic biodegradable composites

Biodegradable composites based on treated and untreated sisal fiber and mater Bi‐Z were processed using an internal batch mixer. The effect of processing conditions (temperature, speed of rotation, and time of mixing) and alkaline treatment on the dimensions of sisal fiber was studied. The length and diameter of the initial fibers were reduced during mixing and this effect was correlated to the magnitude of the shear stress developed in the mixer. An increase of the speed of rotation and/or a reduction of temperature produced fibers of smaller dimensions but with a higher aspect ratio l/d. Alkaline treatment increased the kinetics associated to the reduction of the fiber's dimensions. A semiempirical model was employed to predict the size of the fibers versus the time of mixing. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1084–1091, 2001     

Preparation and characterization of EVA–sisal fiber composites

In this work, composites of an EVA polymer matrix and short sisal fiber were characterized. The physical‐morphological as well as chemical interactions between EVA and sisal were investigated. When the samples were prepared in the presence of dicumyl peroxide, the results suggest that crosslinking of EVA as well as grafting between EVA and the sisal fibers took place. Morphological changes were studied by scanning electron microscopy (SEM). Results from Hg‐porosimetry, SEM, Fourier transform infrared spectroscopy, surface free energy, and gel content strongly indicate grafting of EVA onto sisal under the composite preparation conditions, even in the absence of peroxide. The grafting mechanism could not be confirmed from solid‐state ¹³C NMR analysis. The grafting had an impact on the thermal and mechanical properties of the composites, as determined by differential scanning calorimetry and tensile testing. Thermogravimetric analysis results show that the composites are more stable than both EVA and sisal fiber alone. The composite stability, however, decreases with increasing fiber content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1607–1617, 2006     

Preparation of biodegradable polyesters/high‐amylose‐starch composites by reactive blending and their characterization

Two different biodegradable polyesters [polycaprolactone (PCL) and poly(3‐hydroxybutyrate‐co‐valerate) (PHBV)] were blended with a maize starch that had high amylose content through the use different reactive approaches. The compatibilization of both systems was obtained. PCL/starch composites were obtained by the addition of a third reactive component that was able to act as a coupling agent, and the reactive interface of PHBV/starch composites was improved during blending with an organic peroxide. Thermal, morphological, and mechanical characterization showed that the compatibilized composite materials had better final proprieties than neat materials or composites prepared without compatibilization. Finally, the degradation of all prepared materials by a compost simulation test was investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1432–1442, 2002     

Short sisal fiber‐reinforced tire rubber composites: Dynamic and mechanical properties

The world tendency toward using recycled materials demands new products from vegetable resources and waste polymers. In this work, composites made from powdered tire rubber (average particle size: 320 μm) and sisal fiber were prepared by hot‐press molding and investigated by means of dynamic mechanical thermal analysis and tensile properties. The effects of fiber length and content, chemical treatments, and temperature on dynamic mechanical and tensile properties of such composites were studied. The results showed that mercerization/acetylation treatment of the fibers improves composite performance. Under the conditions investigated the optimum fiber length obtained for the tire rubber matrix was 10 mm. Storage and loss moduli both increased with increasing fiber content. The results of this study are encouraging, demonstrating that the use of tire rubber and sisal fiber in composites offers promising potential for nonstructural applications. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 670–677, 2004     

Influence of surface treatment of carbon fibers on interfacial adhesion strength and mechanical properties of PLA‐based composites

In the present study C/PLA composites with different fiber surface conditions (untreated and with nitric acid oxidation for 4 h and 8 h) were prepared to determine the influence of surface treatment on the interfacial adhesion strength and mechanical properties of the composites. A chemical reaction at the fiber–matrix interfaces was confirmed by XPS studies. Nitric acid treatment was found to improve the amount of oxygen‐containing functional groups (particularly the carboxylic group, —COOH) on carbon fiber surfaces and to increase the surface roughness because of the formation of longitudinal crevices. The treated composites exhibited stronger interface adhesion and better mechanical properties in comparison to their untreated counterparts. There was a greater percentage of improvement in interfacial adhesion strength than in the mechanical properties. The strengthened interfaces and improved mechanical performance have been mainly attributed to the greater extent of the chemical reaction between the PLA matrix and the carbon fibers. The increased surface roughness also has had a slight contribution. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 367–376, 2001     

Plant oil‐based biofoam composites with balanced performance

BACKGROUND: Biofoam composites were prepared using short sisal fibers as reinforcement and acrylated epoxidized soybean oil as matrix, aiming at replacing traditional unsaturated polyester foams in structural applications. The compressive properties of the composites were examined as a function of fiber loading, fiber length and foam density. RESULTS: The foam composite with 10 phr (parts per hundred of base resin by weight) sisal fiber possessed properties similar to those of commercial unsaturated polyester foams. A study of the failure mechanism revealed that debonding between fiber and matrix was a key issue responsible for catastrophic damage of the composites. According to this finding, surface pre‐treatment of the sisal using an alkali or silane coupling agent was carried out. This brought about positive effects on interfacial interaction and compressive strength of the composites, as desired. Also, soil burial tests proved that the foam composites could be biodegraded, and the incorporated sisal fibers accelerated the biodegradation of the composites. CONCLUSION: This work shows the feasibility of making rigid biofoams from natural resources, which could be potential candidates for structural foams. Copyright © 2009 Society of Chemical Industry     

聚乳酸/羟基磷灰石复合材料的制备及其性能研究

采用溶液共混、超声振荡的方法制备了聚乳酸/羟基磷灰石(PLA/HA)复合材料,采用扫描电镜、红外光谱对PLA/HA复合材料进行了表征,研究了PLA/HA复合材料的力学性能、亲水性能、热稳定性以及降解性能。结果表明,HA颗粒均匀分散在PLA基体中,没有团聚现象发生;与纯PLA比较,PLA/HA复合材料的弯曲强度提高了7.9 MPa,拉伸强度下降不明显;由于HA的加入,提高了PLA/HA复合材料热稳定性,亲水性能也有所改善;降解过程中,PLA/HA复合材料中的HA颗粒能够中和PLA部分酸性代谢产物,降低了材料自催化效应及产生速度,减缓了材料重量损失速度,前6周的重量损失小于1%,在第12周的最终重量损失为5.8%,降解后期的重量损失比纯PLA材料低3%~4%。     

Thermal and mechanical properties of LDPE/sisal fiber composites compatibilized with functionalized paraffin waxes

The effect of maleic anhydride‐grafted hard paraffin wax (MA‐g‐wax) and oxidized hard paraffin wax (OxWax), as possible compatibilizers, on the morphology, thermal and mechanical properties of LDPE/sisal fiber composites were examined. The differential scanning calorimetry (DSC) results show that sisal alone did not change the crystallization behavior of LDPE, while the two waxes influenced the crystallization behavior of LDPE in different ways, whether mixed with LDPE alone or in the presence of sisal. The thermal properties seem to be influenced by the fact that the waxes preferably crystallize around the short sisal fibers, and by the fact that the two waxes have different compatibilities with LDPE. The TGA results show an increase in the thermal stability of the blends in the presence of the two waxes, with LDPE/OxWax showing a more significant improvement. The presence of wax, however, reduced the thermal stability of the LDPE/sisal/wax composites. The presence of OxWax and MA‐g‐wax similarly influenced the tensile properties of the composites. Both waxes similarly improved the modulus of the compatibilized composites, but in both cases the tensile strengths were worse, probably because of a fairly weak interaction between LDPE and the respective waxes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polylactide‐recycled wood fiber composites

Polylactide (PLA)‐recycled wood fiber (RWF) composites with a small amount of silane were compounded using a kinetic‐mixer and molded using an injection molding machine. The molded PLA‐RWF composites were characterized using gel permeation chromatography, scanning electron microscope, X‐ray diffraction, differential scanning calorimeter, tensile testing machine, and a dynamic mechanical analyzer. As observed in the stress–strain plots, the amount of necking before fracture decreased with an increasing RWF content. Similarly, the strain‐at‐break also decreased with the RWF content. The tensile strength remained the same irrespective of the RWF content. Both the tensile modulus and the storage modulus of the PLA‐RWF composites increased with the RWF content. The degree of crystallinity of the PLA increased with the addition of RWF. No reduction in the number–average molecular weight (M_n) was observed for pure PLA and PLA‐10%RWF‐0.5%Silane composites after injection molding; however, substantial reduction in M_n was found in PLA‐20%RWF‐0.5%Silane composites. Finally, a theoretical model based on Halpin–Tsai empirical relations is presented to compare the theoretical results with that of the experimental results. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polyester biocomposites from recycled natural fibers: Characterization and biodegradability

The structure, biodegradability, and morphological properties of composite materials composed of poly(butylene succinate adipate) (PBSA) and bamboo fiber (BF) were evaluated. Composites containing acrylic acid‐grafted PBSA (PBSA‐g‐AA/BF) exhibited noticeably enhanced compatibility between the two components. The dispersion of BF in the PBSA‐g‐AA matrix was highly homogeneous as a result of ester formation and the consequent creation of branched and crosslinked macromolecules between the carboxyl groups of PBSA‐g‐AA and hydroxyl groups in BF. In addition, the PBSA‐g‐AA/BF composite was more easily processed due to a lower melt viscosity. Each composite was subjected to biodegradation tests in an Acinetobacter baumannii compost. Morphological observations indicated severe disruption of film structure after 10–20 days of incubation, and both the PBSA and the PBSA‐g‐AA/BF composite films were eventually completely degraded. The PBSA‐g‐AA/BF films were more biodegradable than those made of PBSA and exhibited a lower molecular weight and intrinsic viscosity, implying a strong connection between these characteristics and biodegradability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Toughening of wood particle composites—Effects of sisal fibers

Sisal fibers were added to wood particle composites to enhance their toughness. The selected matrix was a commercial styrene diluted unsaturated polyester thermoset resin. Fracture tests were carried out using single‐edge notched beam geometries. Stiffness, strength, critical stress intensity factor K_IQ, and work of fracture W_f of notched specimens were determined. The incorporation of sisal fibers into wood particle composites significantly changed the fracture mode of the resulting hybrid composite. For the neat matrix and the wood particle composites, once the maximum load was reached, the crack propagated in a catastrophic way. For hybrid composites, fiber bridging and pull‐out were the mechanisms causing increased crack growth resistance. Addition of a 7% wt of sisal fibers almost doubled the K_IQ value of a composite containing 12% wt of woodflour. Moreover, the W_f increased almost 10‐fold, for the same sample. In general, the two composite toughness parameters K_IQ and W_f increased when the fraction of sisal fibers was increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1982–1987, 2006     

Comparative SAXS study of heated and alkali-treated sisal fibers

The present investigation deals with the fine structural characteristics of heated and alkali-treated sisal fiber using small-angle X-ray scattering (SAXS) technique for nonideal two-phase systems. The SAXS intensities of heated and alkali-treated sisal fibers deviate from Porod's law, indicating that the samples belong to nonideal two-phase systems characterized by continuous variation of electron density at the phase boundary. The macromolecular parameters such as the average periodicity transverse to layers, specific inner surface, volume fractions of void and matter phases, and so on of the samples were evaluated by using one- and three-dimensional correlation functions, which reveal all the information concealed in the slit smeared SAXS patterns. As all the samples under our purview of study have two-phase structure with diffuse phase boundaries, the average thickness of the transition region have been determined. This analysis throws some light on the structural changes that occurred in the dewaxed sisal fiber treated by NaOH solutions and subject to heat treatments. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Water resistance,mechanical properties,and biodegradability of poly(3‐hydroxybutyrate)/starch composites

Composites of poly(3‐hydroxybutyrate), P(3HB), and starch were prepared by solution casting technique. To improve adhesion of starch to P(3HB), stearic acid was added as a compatibilizer and glycerol as a plasticizer. The water resistance, mechanical, and biodegradable properties of the P(3HB)/starch composites were studied. Diffusion and penetration coefficients of water increased with increasing starch content in the composites. The results showed that the elastic modulus and strain at rupture of the P(3HB)/starch composites were enhanced by increasing starch content upto 10 wt % and the tensile strength increased from 21.2 to 93.9 MPa. The presence of starch content higher than 10 wt % had an adverse effect on the mechanical properties of the investigated composites. The biodegradation rate using Actinomycetes increased proportionally to the starch content in the composite and accelerated in a culture medium of pH ≈ 7.0 at 30°C. Enzymatic degradation experiments showed that lipase produced by Streptomyces albidoflavus didnot degrade P(3HB)/starch composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and cytocompatibility of chitosan‐modified polylactide

Chitosan‐modified PLA (CMPLA) was fabricated to improve cytocompatibility of polylactide (PLA). PMAA‐grafted PLA (PMAA‐PLA) was obtained through α‐methacrylic acid (MAA) grafted polymerization on PLA surface with photooxidization and UV irradiation. Steady PMAA‐PLA microparticle suspension with an average size as 172.8 ± 3.6 nm and zeta potential as ?95.0 ± 0.6 mV was prepared through solvent volatilization. By static electricity interaction and other interactions between PMAA‐PLA microsparticles and chitosan molecules, CMPLA was obtained. FTIR, XPS, SEM, and zeta potential analyses indicated that CMPLA was modified with chitosan molecules uniformly. Compared with the PLA control, CMPLA adapted to supporting the attachment and proliferation of L929 cells better. The obtained CMPLA was expected to be used as perfect biomaterial for tissue regeneration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Phenol–furfural resins to elaborate composites reinforced with sisal fibers—Molecular analysis of resin and properties of composites

Resol type resins were prepared in alkaline conditions (potassium hydroxide or potassium carbonate) using furfural obtained by acid hydrolysis of abundant renewable resources from agricultural and forestry waste residues. The structures of the resins were fully determined by ¹H, ¹³C, and 2D NMR spectrometries with the help of four models compounds synthesized specially for this study. MALDI‐Tof mass spectrometry experiments indicated that a majority of linear oligomers and a minority of cyclic ones constituted them. Composites were prepared with furfural–phenol resins and sisal fibers. These fibers were chosen mainly because they came from natural lignocellulosic material and they presented excellent mechanical properties. Thermal analyses (dTG and DSC) and electron microscopy images indicated that the composites displayed excellent adhesion between resin and fibers. Impact strength measurement showed that mild conditions were more suitable to prepare thermosets. Nevertheless, mild conditions induced a high‐diffusion coefficient for water absorption by composites. Composites with good properties could be prepared using high proportion of materials obtained from biomass without formaldehyde. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008