Utilization of linseed cake as a postagricultural functional filler for poly(lactic acid) green composites

Linseed cake (LC), a byproduct of linseed oil extraction, is used as a functional filler for production of biodegradable composites. To determine the influence of residual linseed crude oil contained in lignocellulosic filler on the properties of the poly(lactic acid) (PLA)-based composites with 5–30% filler content, two types of LC were analyzed: a defatted and an unmodified one. Complex analysis of the composites' properties change was conducted in relation to their structure modification caused by the addition of a waste filler. It was found that the addition of LC resulted in simultaneous plasticization and improved crystallization of PLA. Lignocellulosic particles and crude linseed oil contained in the LC powder provided a modifying effect, influencing the level of crystallinity and mechanical and thermomechanical properties. Using LC may thus overcome one of the main drawbacks of PLA, which is brittleness and low crystallinity. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47152.     

Poly(lactic acid) stereocomplex formation: Application to PLA rheological property modification

Poly(lactic acid) (PLA) stereocomplex formation in isothermal conditions in the absence and presence of a nucleating agent was studied from a rheological point of view due to sensitivity of viscoelastic properties to structural changes during this process. PDLA was melt blended in low concentrations with PLLA to produce a stereocomplex. Amorphous samples were prepared and crystallization was carried out in a rheometer at high temperatures to simulate melt processing conditions. Stereocomplexation was explored over time by measuring rheological parameters in small deformation oscillatory shear mode at a low frequency using parallel plate geometry. Kinetic data obtained by this means was compared to data from calorimetric studies, showing a different trend depending on the characterization method. Moreover, after the completion of crystallization, final crystalline structure was probed over a wide range of frequencies to investigate the rheological modification role of PDLA on PLLA major component. Differences in rheological characteristics of asymmetric PLLA/PDLA blends as compared to neat PLLA were associated to the structural changes happening because of the formation of the stereocomplex. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41073.     

Poly(lactic acid) biocomposites with mango waste and organo-montmorillonite for packaging

Poly(lactic acid) (PLA) is a biodegradable polymer used in packaging, but its properties can be improved by manufacturing composite matrixes. The combination of PLA, starch, and nano-montmorillonite leads to materials with superior mechanical properties. Mango lump is rich in cellulose and starch. The goal of this study is to develop and characterize biocomposites based on PLA, mango waste, and nano-organo-montmorillonite for packaging. The samples were microstructurally, morphologically, and mechanically characterized. Physical interaction between the phases was observed. The mango components displaced the PLA X-ray diffraction peaks and the clays altered their intensity, by interfering with chain packing. The addition of single components to PLA increased the samples’ transition temperatures, but the addition of multiple components diminished them. PLA showed adhesiveness to cellulose fibers and nonadhesiveness to starch granules. Thicker samples presented better mechanical properties. PLA–mango–“chocolate clay” samples are relatively stable materials, while PLA–mango–“bofe clay” samples could represent promising highly biodegradable materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47512.     

Effect of compatibilization on the performance of biodegradable composites using cotton fiber waste as filler

The usefulness of cotton waste as a source of reinforcing fibers for the preparation of cost‐effective and biodegradable composites has been investigated. Biodegradable polyester (bionolle 3020) is melt‐compounded together with cotton fibers. Maleic anhydride‐grafted bionolle (bionolle‐g‐MA) is used as a compatibilizer. The grafting reaction is carried out in an intensive mixer in the presence of dicumyl peroxide as initiator. The effects of fiber and compatibilizer content as well as graft content are evaluated by mechanical property measurements and scanning electron microscopy. The compatibilizer improved all mechanical properties significantly. Moreover, the water absorption and swelling of composites decreased, while the thermal stability increased slightly. Also, the biodegradation of the polyester bionolle 3020, as well as that of its composites with cotton fibers, were studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1825–1835, 2003     

Bio‐based polymeric resin from agricultural waste,neem (Azadirachta indica) seed cake,for green composites

Protein‐based polymeric resin has been developed from nonconventional and nonedible “neem seed cake (NSC)” that has very limited low‐value applications. Neem protein (NP), after extraction from defatted NSC, was used to prepare resin with two common plasticizers (glycerol and sorbitol). Properties of the NP resin sheets were evaluated as a function of plasticizer content. Increase of plasticizer content in NP sheets from 15 to 30% (w/w) enhanced fracture strain with a reduction in tensile strength, modulus, and thermal properties. Sorbitol‐plasticized NP sheets showed better mechanical and thermal properties in comparison to glycerol‐plasticized sheets. Effect of cross‐linking with glyoxal on the mechanical and thermal properties of sorbitol‐plasticized NP sheets was also investigated. Properties improved significantly at 10% (w/w) glyoxal content. Overall, with the enhanced properties of NP sheets, NP can be a viable alternative for edible protein‐based resin for making green composites. NP resin can also be used to replace some synthetic resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 10.1002/app.41291.     

Effect of ultrasonic oscillations on the rheological behavior and morphology of Illite‐filled high‐density polyethylene composites

The effects of ultrasonic oscillations on the rheological and viscoelastic properties and morphology of high‐density polyethylene (HDPE)/Illite (70/30) composites were studied. The experimental results showed that the die pressure and apparent viscosity of the HDPE/Illite (70/30) composites were reduced greatly, and so the mass‐flow rate significantly increased in the presence of ultrasonic oscillations during the extrusion. Scanning electron microscopy and linear viscoelasticity tests showed that ultrasonic oscillations improved the dispersion of the Illite particles into the HDPE matrix. The aggregation of the Illite particles disappeared on the fractured surfaces of HDPE/Illite (70/30) composites extruded in the presence of ultrasonic oscillations, and this indicated that ultrasonic oscillations promoted the homogeneous dispersion of Illite particles into the HDPE matrix. Ultrasonic oscillations caused the permanent reduction of the dynamic viscosity and zero‐shear viscosity of HDPE/Illite (70/30) composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 379–384, 2005     

马来酸酐/二乙烯基苯接枝聚乳酸对微晶纤维素/聚乳酸复合材料性能的影响

研究了马来酸酐(MAH)/二乙烯基苯(DVB)接枝聚乳酸(PLA-g-DVB/MAH)对微晶纤维素(MCC)/聚乳酸(PLA)复合材料性能的影响。首先采用熔融接枝法,将DVB作为MAH的共聚单体接枝到PLA分子链上制备PLA-g-DVB/MAH接枝聚合物,然后以PLA-g-DVB/MAH为相容剂,采用注射成型法制备MCC/PLA复合材料。利用FTIR对PLA-g-DVB/MAH进行表征,探究了PLA-g-DVB/MAH对MCC/PLA复合材料流变及力学性能的影响。结果表明,MAH成功接枝到PLA上,并得到接枝聚合物PLA-g-DVB/MAH;添加PLA-g-DVB/MAH后,MCC/PLA复合材料的储能模量、复数黏度、平衡扭矩以及剪切热都有明显升高;PLA-g-DVB/MAH的添加有利于改善MCC和PLA的界面相容性,进而提高了MCC/PLA复合材料的力学性能。     

Poly(vinyl chloride)–green coconut fiber composites and their nonlinear viscoelastic behavior as examined with fourier transform rheometry

Using a purposely modified torsional dynamic rheometer with a closed cavity, I investigated composites of poly(vinyl chloride) (PVC) and green coconut fibers (GCFs) with Fourier transform (FT) rheometry, a new dynamic test technique that resolves the complex dynamic response of materials submitted to harmonic strain into their main and harmonic components. Because of instrument limitations in the low‐strain region, torque signal harmonic components had to be corrected to yield results that suited established theoretical considerations. The preparation method of the composites had major effects on their linear and nonlinear viscoelastic responses; essentially, no homogeneous material could be prepared by dry blending plus extrusion, in contrast to dry blending plus mixing, which is the recommended technique; this was likely because PVC plasticization was then achieved. One of the most important rheological characteristics of the PVC–GCF composites was the quasidisappearance of the linear viscoelastic behavior. Nevertheless, an easy extrapolation technique was used to extract linear modulus data from the FT results, which led me to the conclusion that the reinforcing effect of the GCFs was essentially hydrodynamic with little, if any, interfacial interaction between the polymer matrix and the fibers. The results gathered from nonlinear viscoelastic properties, as obtained through FT rheometry, supplement this conclusion. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3638–3651, 2006     

Effects of filler type on the nonisothermal crystallization kinetics of poly(butylene terephthalate) (PBT) composites

In this study, melt‐crystallization behaviors of poly(butylene terephthalate) (PBT) composites including different types of inorganic fillers were investigated. Composite samples having 5 wt % of fillers were prepared by melt processing in a twin screw extruder using commercial grades of calcite (CA), halloysite (HL), and organo‐montmorillonite (OM) as filler. Depending on the filler type and geometry, crystallization kinetics of the samples was studied by differential scanning calorimetry (DSC) methods. Effect of filler type on the nonisothermal melt‐crystallization kinetics of the PBT was analyzed with various kinetic models, namely, the Ozawa, Avrami modified by Jeziorny and Liu‐Mo. Crystallization activation energies of the samples were also determined by the Kissinger, Takhor, and Augis–Bennett models. From the kinetics study, it was found that the melt‐crystallization rates of the samples including CA and HL‐nanotube were higher than PBT at a given cooling rate. On the other hand, it was also found that organo‐montmorillonite reduced the melt‐crystallization rate of PBT. It can be concluded that organic ammonium groups in the OM decelerate the crystallization rate of PBT chains possibly due to affecting the chain diffusion through growing crystal face and folding. This study shows that introducing organically modified alumina‐silicate layers into the PBT‐based composites could significantly reduce the production rate of the injection molded parts during the processing operations. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Additive manufacturing of green composites: Poly (lactic acid) reinforced with keratin materials obtained from Angora rabbit hair

In this research, additive manufacturing of polylactic acid (PLA) reinforced with keratin was studied. Keratin was obtained from Angora rabbit hair and modified with NaOH. Scanning electron microscopy (SEM) images showed that the modified surfaces were rougher than untreated surfaces. Furthermore, SEM images in the composites' fracture regions showed surface changes, associated with the nature of the reinforcement. Likewise, thermomechanical properties of the composites were attributed to the nature of the reinforcement and the type of keratin. Besides, the 3D printed composites showed higher thermal conductivity values than PLA with the addition of keratin. Cytotoxicity tests revealed an improvement in cell growth compared to the control and PLA. These results are meaningful toward the development of high thermal conductors and biocompatible composites with applications in different fields, where the use of only natural polymers is necessary.     

Agricultural residue-derived lignin as the filler of polylactic acid composites and the effect of lignin purity on the composite performance

In this study, corn stover lignin with different purities was used as filler in polylactic acid (PLA) matrix. It was found that the impurity metals present in unpurified lignin can significantly affect the performance of the composites in terms of their thermal stability, rheological behavior, mechanical properties, and hydrophobicity. Among the PLA composites, the ones fabricated with the lignin containing 4% of impurities overall had the best thermal stability and tensile strength. From melt rheology analysis, it was also found that the presence of the impurity metals decreases the complex viscosity of the composites. It is suggested that the impurity metals acted as catalysts to promote the interaction between lignin and PLA, resulting in an improved compatibility between PLA and the filler. In the present study, mechanical properties and hydrophobicity of the composites were further improved by acetylating the lignin with the optimum content of impurities. Tensile strength of the composite with the acetylated lignin was comparable to that of pure PLA, whereas the modulus increased to as high as 2.75 GPa. Overall, the study showed that unpurified lignin could be used as filler to achieve similar or better performance than the composites made with highly purified lignin fillers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47915.     

Mechanical Behavior and Fracture Toughness of Poly(L‐lactic acid)‐Natural Fiber Composites Modified with Hyperbranched Polymers

Summary: The use of hyperbranched polymers (HBP) with hydroxy functionality as modifiers for poly(L ‐lactic acid) (PLLA)‐flax fiber composites is presented. HBP concentrations were varied from 0 to 50% v/v and the static and dynamic tensile properties were investigated along with interlaminar fracture toughness. Upon addition of HBP, the tensile modulus and dynamic storage modulus (E′) both diminished, although a greater decline was noticed in the static modulus. The elongation of the composites with HBP showed a pronounced increase as large as 314% at 50% v/v HBP. The loss factor (tan δ) indicated a lowering of the glass transition temperature (T_g) due to a change in crystal morphology from large, mixed perfection spherulites to finer, smaller spherulites. The change in T_g could have also resulted from some of the HBP being miscible in the amorphous phase, which caused a plasticizing effect of the PLLA. The interlaminar fracture toughness measured as the critical strain energy release rate (G_IC) was significantly influenced by HBP. At 10% v/v HBP, G_IC was at least double that of the unmodified composite and a rise as great as 250% was achieved with 50% v/v. The main factor contributing to high fracture toughness in this study was better wetting of the fibers by the matrix when the HBP was present. With improved ductility of the matrix, it caused ductile tearing along the fiber‐matrix interface during crack propagation.

ESEM photograph of propagation region of the interlaminar fracture toughness specimens with 30% v/v of HBP.     

Effect of bismaleimide reactive extrusion on the crystallinity and mechanical performance of poly(lactic acid) green composites

Poly(D ‐,L ‐lactic acid) (PDLA) and PDLA‐wood pulp fiber injection molded composites were modified with very small amounts (< 1 wt %) of N′‐(o‐phenylene)dimalemide and 2,2′‐dithiobis(benzothiazole) by reactive extrusion and their resulting mechanical and thermal properties characterized. The modification produced an increase in the percent crystallinity (X_c), heat deflection temperature (HDT), impact energy, tensile strength, and modulus in PDLA. A significant reduction in the melting temperature (T_m) and an increase in the thermal resistance (T_max) were also found. Fourier‐Transform infrared spectroscopy (FTIR) suggests the creation of hydrogen bonds, a thiol ester and/or ester bond during the modification. Reactive extrusion of commercially available poly(lactic acid) (PLA) by means of N′‐(o‐phenylene)dimalemide and 2,2′‐dithiobis(benzothiazole) provides a low cost and simple processing method for the enhancement of the properties of this biopolymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The role of conductive pathways in the conductivity and rheological behavior of poly(methyl methacrylate)–graphite composites

Up to now, research on the dynamic process of conductive network formation has tended to focus on composite particles with one‐dimensional geometry, such as carbon black and carbon nanotubes. However, studies on this subject based on fillers with two‐dimensional structure, such as graphite, are rare in the literature. In this work, the dynamic percolation and rheological properties of poly(methyl methacrylate) (PMMA)–graphite composites under an electric field were investigated. The activation energies of conductive network formation and polymer matrix mobility were calculated from the temperature dependence of the percolation time and the zero‐shear viscosity. It was found that the activation energy calculated from the zero‐shear viscosity was not influenced by the electric field in the concentration range investigated, but the electric field had an effect on the activation energy calculated from the percolation time. This finding emphasizes that the electrical and rheological properties have different physical origins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43810.     

Surface modification of halloysite nanotubes with l‐lactic acid: An effective route to high‐performance poly(l‐lactide) composites

To improve the interfacial bonding between halloysite nanotubes (HNTs) and poly(l ‐lactide) (PLLA), a simple surface modification of HNTs with l ‐lactic acid via direct condensation polymerization has been developed. Two modified HNTs were obtained: HNTs grafting with l ‐lactic acid (l‐HNTs) and HNTs grafting with poly(l ‐lactide) (p‐HNTs). The structures and properties of l‐HNTs and p‐HNTs were investigated. Then, a series of HNTs/PLLA, l‐HNTs/PLLA and p‐HNTs/PLLA composites were prepared using a solution casting method and were characterized by polarized optical microscopy (POM), field scanning electron microscopy, and tensile testing. Results showed that l ‐lactic acid and PLLA could be easily grafted onto the surface of HNTs by forming an Al carboxylate bond and following with condensation polymerization, and the amounts of the l ‐lactic acid and PLLA grafted on the surface of the HNTs were 5.08 and 14.47%, respectively. The surface‐grafted l ‐lactic acid and PLLA played the important role in improving the interfacial bonding between the nanotubes and matrix. The l‐HNTs and p‐HNTs can disperse more uniformly in and show better compatibility with the PLLA matrix than untreated HNTs. As a result, the l‐HNTs/PLLA and p‐HNTs/PLLA composites had better tensile properties than that of the HNTs/PLLA composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41451.     

Study on the mechanical and thermal properties of poly(lactic acid)/office waste paper fiber composites

Environment friendly composites with favorable mechanical properties and low water absorption performance were successfully produced from poly(lactic acid) (PLA), office waste paper fiber (OWF), and coupling agents. The perfect sample was easily manufactured by melting–blending and injection molding. The PLA/OWF composites were comparable with other PLA/plant fiber composites, and the results indicated that the PLA/OWF composites show better performance than PLA/wheat straw fiber composites and PLA/bamboo fiber composites. On this basis, influence of modification of OWF on the properties of composites was investigated. The infrared results show that the OWF modification by different coupling agents was successful, and the scanning electron microscopy indicates that prepared composites exhibit good interfacial compatibility due to preferable binding force between fiber and matrix. With addition of 2 wt% γ-(2,3-propylene oxides)propyl trimethylsilane, the composite exhibits high tensile strength of 58.96 MPa, reflecting increase of 14% than the pure PLA. According to the crystallization and melting performance table, OWF can act as nucleating agent to promote the crystallization properties on composites, while the coupling agents have little effect on thermal stability. This article confirmed that the OWF has appropriate properties and is suitable for preparing composite materials and this work provides a novel idea for the utilization of office waste paper.     

Effect of structural relaxation at physiological temperature on the mechanical property of poly(L‐lactic acid) studied by microhardness measurements

Besides hydrolysis, the physical properties of poly(L ‐lactic acid), PLLA, may change, at a shorter time‐scale, at physiological temperature, because of structural relaxation. This process may be relevant as it may contribute for the time‐dependent modifications of the mechanical performance of PLLA‐based implants, or in other properties such as specific volume or permeability. In this work, microhardness was measured at room temperature after ageing poly(L ‐lactic acid) samples at 37°C during different periods, ranging from 15 min to 15 days. For the PLLA analyzed, the initial Vickers microhardness was around 140 MPa and an increase higher than 55% was observed in a time span of 15 days. The relaxation of enthalpy at 37°C was also monitored by differential scanning calorimetry, and both results were successfully described by a simple model that considers a nonexponential evolution of the quantities sensitive to physical ageing. The time‐scales of the structural relaxation probed by microhardness or by enthalpy were different, and the results suggested that the evolution of the mechanical property was slower than the later. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2628–2633, 2006     

Influence of electron beam treatment of jute on the thermal properties of random and two-directional jute/poly(lactic acid) green composites

In the present study, randomly aligned jute fiber/poly(lactic acid) (PLA) and two-directionally aligned jute fabric/PLA green composites with jute (50% by weight) treated with electron beam at different dosages (0, 5, 10, 30, 50, and 100?kGy) were fabricated by compression molding technique and the effect of electron beam treatment on their thermal properties was investigated in terms of thermal expansion, thermal stability, dynamic mechanical thermal property, and heat deflection temperature (HDT). The dynamic storage modulus and HDT of neat PLA were significantly increased by incorporating jute fibers or fabrics into PLA, whereas the coefficient of thermal expansion (CTE) and the damping property were decreased, reflecting the enhancement in the interfacial adhesion between the jute and the PLA by electron beam treatment with an optimal dosage of 10?kGy and the reinforcing effect by jute. The result exhibited that the thermal stability, storage modulus, and HDT of jute/PLA green composites were highest with the electron beam irradiation of jute at 10?kGy and lowest at 100?kGy, whereas the CTE and tan δ were lowest at 10?kGy and highest at 100?kGy. The thermal behavior of random jute/PLA green composites shows a similar tendency to that of 2D jute/PLA counterparts and the influence of electron beam irradiation on the thermal properties studied was consistent with each other. The thermomechanical analysis, dynamic mechanical thermal analysis, thermogravimetric analysis, and HDT results were in agreement with each other, showing a comparable effect of electron beam irradiation on composites thermal characteristics.     

Mechanical properties and biomass carbon ratios of poly(butylene succinate) composites filled with starch and cellulose filler using furfural as plasticizer

Polymer composites consisting of poly(butylene succinate) (PBS) as matrix and corn starch (CS) or cellulose filler (CF) with a small amount of furfural (FR) from biomass were prepared by a hot‐pressing method at 120°C from a powder mixture. Mechanical properties of the composites' films were investigated using tensile test methods. The strain of these films was found to be developed by adding CS or CF and further improved by adding FR. The strain at break PBS with 15 wt % FR was improved by more than 16 times of that of PBS without FR. The biomass carbon ratios of polymer composites with oil‐based PBS (major component) and with biobased CS, CF, and FR were evaluated by ¹⁴C concentration ratio measured by accelerator mass spectrometry (AMS) based on ASTM D6866. PBS with 40 wt % CS or CF had a biomass carbon ratio of 31 and 36%, respectively. PBS with 15 wt % FR had a biomass carbon ratio of 3.4%. This deviation was confirmed by FR content calculated from the peak area of the ¹H‐NMR spectrum of PBS with FR which was 3.4%, almost the same as the biomass carbon ratio measured by AMS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of ultrasonic vibration on the rheological behavior of high‐density polyethylene composites filled with flash aluminum flake pigments

The metallic effect of polymer composites was produced through the loading of flash aluminum flake pigments (FAFPs) into polymers. This production method could eliminate postprocessing techniques, such as spray coating, painting, or metallization. We used a self‐improved, ultrasound‐assisted capillary rheometer to explore the rheological behavior of high‐density polyethylene composites filled with FAFPs in the absence and presence of ultrasound treatment. The effects of the ultrasound intensity, experimental temperature, filler content, and particle size on the composite viscosity were studied. The results show that the composite viscosity not only decreased as the ultrasound intensity, experimental temperature, and particle size increased but also decreased as the filler content decreased. A viscosity model of the polymer melts was proposed to illustrate the relationship between the viscosity and ultrasonic intensity. The viscosity obeyed the equations under ultrasonic vibration. The predicted results for the composite viscosity complied greatly with the experimental values. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44906.