Microstructural characterization of corn starch‐based porous thermoplastic composites filled with multiwalled carbon nanotubes

Microstructural characterization of corn starch‐based porous thermoplastic (TPS) composites containing various contents (0.1, 0.5, and 1 wt %) of multiwalled carbon nanotubes (MWCNTs) was performed. Corn starch was plasticized with a proper combination of glycerol and stearic acid. TPS composites with MWCNT were prepared conducting melt extrusion followed by injection molding. TPS containing 1 wt % of MWCNTs exhibited higher tensile strength and elastic modulus values than neat TPS. Moreover, TPS electrical conductivity was determined to increase with increasing content of MWCNTs. X‐ray diffraction measurements revealed that incorporation of MWCNTs increased the degree of TPS crsystallinity to some extent. Scanning electron microscopy examination revealed that MWCNT altered TPS surface morphology and tensile failure modes, significantly. Transmission electron microscopy investigation showed that dispersion characteristics of MWCNTs within TPS were in the form of tiny clusters around micro pores of TPS, which is considered influential on electrical conductivity of the resulting composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

New electromagnetic shielding materials based on viscose‐carbon nanotubes composites

A convenient approach for the preparation of cellulose ‐ carbon nanotubes (CNT) hybrid materials owning electromagnetic shielding properties, based on viscose (V) and TEMPO‐oxidized viscose fibers (VO) is proposed. Viscose ‐ carbon nanotubes (V‐CNT) and TEMPO‐oxidized viscose ‐ carbon nanotubes (VO‐CNT) composites were prepared by embedding carbon nanotubes on the surface of two types of cellulose fibers, that is, viscose and its C₆‐oxidized derivative. The chemical composition, morphology, and thermal stability of the prepared hybrid materials were thoroughly investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analyses. Moreover, electrical properties of the original and composite fibers were assessed. POLYM. ENG. SCI., 59:1499–1506 2019. © 2019 Society of Plastics Engineers     

Mechanical and thermal properties of wood fibers reinforced poly(lactic acid)/thermoplasticized starch composites

Thermoplasticized starch (TPS) filled poly(lactic acid) (PLA) blends are usually found to have low mechanical properties due to poor properties of TPS and inadequate adhesion between the TPS and PLA. The purpose of this study was to investigate the reinforcing effect of wood fibers (WF) on the mechanical properties of TPS/PLA blends. In order to improve the compatibility of wood with TPS/PLA blends, maleic anhydride grafted PLA (MA‐g‐PLA) copolymer was synthesized and used. TPS, TPS/PLA blends, and WF reinforced TPS/PLA composites were prepared by twin‐screw extrusion and injection molded. Scanning electron microscope and crystallinity studies indicated thermoplasticity in starch. WF at two different weight proportions, that is, 20% and 40% with respect to TPS content were taken and MA‐g‐PLA at 10% to the total weight was chosen to study the effect on mechanical properties. At 20% WF and 10% MA‐g‐PLA, the tensile strength exhibited 86% improvement and flexural strength exhibited about 106% improvement over TPS/PLA blends. Increasing WF content to 40% further enhanced tensile strength by 128% and flexural strength by 180% with respect to TPS/PLA blends. Thermal behavior of blends and composites was analyzed using dynamic mechanical analysis and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46118.     

Influence of Hybrid Cellulose/Bentonite Fillers on Structure,Ambient, and Low Temperature Tensile Properties of Thermoplastic Starch Composites

Thermoplastic starch (TPS) composites incorporating bentonite/cellulose (Bent/Cellulose) hybrid fillers in different ratios were prepared by film casting. Ultra-sonication was done to promote good dispersion of filler in the host TPS and enhance the filler-matrix interactions. Ultra-sonicated fillers resulted in superior improvement in the tensile properties when the samples preconditioned at both ambient and 2°C. Upon preconditioning at 2°C, the TPS composite containing the ultra-sonicated hybrid bent/cellulose in 80:20 ratio displayed the greatest tensile properties achievement among all the tested materials. These could be due to the effect of low temperature interactions between the starch, plasticizers, and the hybrid fillers. Differential scanning calorimetry analysis proved the changes in the crystallinity and dynamic characteristic of the TPS molecular chains which benefit in enhancing the biopolymer elongation at break and toughness, even when stored at refrigerated condition. In summary, the TPS/bent/cellulose composite has potential to be further developed for refrigerated food packaging application. POLYM. ENG. SCI., 60:810–822, 2020. © 2020 Society of Plastics Engineers     

Development and material properties of poly(lactic acid)/poly(3‐hydroxybutyrate‐co−3‐hydroxyvalerate)‐based nanocrystalline cellulose nanocomposites

This study is focused on the development and analysis of the thermal and structural behavior of nanocrystalline cellulose (NCC)‐based bionanocomposites (BCs). Nanocrystalline cellulose was prepared by controlled acid hydrolysis of oil palm empty fruit bunch fibers. The resulting NCC was surface modified using TEMPO‐mediated oxidation and solvent exchange methods for surface functionalization and also to improve dispersion of fillers. Solvent exchange NCC reinforced polymer blend containing poly(lactic acid)/poly‐(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) was prepared by using solution casting technique at various NCC loading percentages. The addition of NCC resulted in the improvement of structural, thermal, and mechanical properties of BCs as compared to that of the polymer blend. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44328.     

Electrospun polyvinyl alcohol/waterborne polyurethane composite nanofibers involving cellulose nanofibers

TEMPO‐oxidized cellulose nanofibers (TOCNs) were used as nanofillers in this work. Composite nanofibers of polyvinyl alcohol (PVA)/waterborne polyurethane (WPU) reinforced with TOCNs were produced by electrospinning. The reinforcing capability of TOCNs was investigated by tensile tests. Scanning electron microscopy (SEM), X‐ray diffraction, and thermogravimetry analyses were also carried out in order to characterize the appearance, crystallinity, and reinforcing effect of the cellulose nanofibers. SEM results showed that PVA/WPU/TOCNs composite nanofibers presented a highly homogeneous dispersion of TOCNs. The reinforced composites had about 44% increase in their mechanical properties with addition of only 5 wt % of TOCNs while about 42% decrease in elongation at break. The TOCNs reinforced composite nanofibers were more thermally stable than pure PVA/WPU nanofibers. The development of crystalline structure in the composite fibers was observed by XRD. Since PVA, WPU, and TOCNs are hydrophilic, non‐toxic, and biocompatible, and therefore, these nanocomposite nanofibers could be used for tissue scaffolding, filtration materials, and medical industries as wound dressing materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41051.     

High performance modified thermoplastic starch/linear low‐density polyethylene blends in one‐step extrusion

In this study, the morphology and the mechanical properties of thermoplastic starch (TPS)/linear low‐density polyethylene (LLDPE) blends prepared by one‐step and two‐step extrusion processing conditions were contrasted. In the presence of citric acid (CA), the compatibility of TPS/PE blends were proved to transfer to a high continuous dispersion in one‐step extrusion process by scanning electron microscopy analysis. By increasing the interaction between two phases, the mechanical properties of the blends were markedly improved, even reached the levels of the conventional plastics. The rheological study proved that the viscosity (η) of TPS and TPS/PE blends were both decreasing with increase in the content of CA at the same temperature, which ascribed to the acidity of CA was propitious to fragmentation and dissolution of cornstarch granules, deteriorated the chain entanglement in starch, and weakened the interaction of starch molecules. Both FTIR spectroscopy and thermal properties analysis of TPSs and TPS/PE blends showed that the interactions between starch and plasticizer became stronger in the presence of CA. POLYM. COMPOS. 28:89–97, 2007. © 2007 Society of Plastics Engineers     

Surface treatment of cellulose fibers with methylmethacrylate for enhanced properties of in situ polymerized PMMA/cellulose composites

Cellulose micro/nanofibers (CNF), prepared from jute fibers were surface treated with methyl methacrylate (MMA) for better dispersion into poly methyl methacrylate (PMMA) matrix. PMMA/cellulose composites were prepared by in situ suspension polymerization technique. The surface treatment of CNF was confirmed by Fourier transform infrared spectroscopy (FTIR) and Nuclear magnetic resonance (NMR) analysis. MMA‐treated cellulose micro/nanofibers (MCNF) demonstrated improved affinity and dispersion in MMA monomer as well as in the PMMA/cellulose composites. Thermal properties of the cellulose composites were analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The glass transition temperature (T_g) of PMMA increased by nearly 19°C in the in situ cellulose composites compared to that of unreinforced PMMA as indicated by DSC. TGA showed increased thermal stability of the cellulose composites. Enhanced tensile properties as well as significantly lower moisture uptake were observed in the in situ prepared PMMA/cellulose composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39808.     

Compatibility improvement of poly(lactic acid)/thermoplastic starch blown films using acetylated starch

The present research aims to improve the compatibility between relatively hydrophobic poly(lactic acid) (PLA) and hydrophilic thermoplastic starch (TPS) and the properties of the PLA/TPS blends by replacing TPS from native cassava starch (TPSN) with TPS from acetylated starch (TPSA). The effects of the degree of acetylation (DA) of acetylated starch, that is, 0.021, 0.031, and 0.074, on the morphological characteristics and properties of PLA/TPS blend are investigated. The melt blends of PLA and TPS with a weight proportion of PLA:TPS of 50:50 are fabricated and then blown into films. Scanning electron microscopy confirms the dispersion of TPS phase in the PLA matrix. Better dispersion and smaller size of the TPS phase are observed for the PLA/TPSA blend films with low DA of acetylated starch, resulting in improved tensile and barrier properties and increased storage modulus, thermal stability, and T_g, T_cc, and T_m of PLA. Elongation at break of the PLA/TPSA blend increases up to 57%, whereas its water vapor permeability and oxygen permeability decrease about 15%. The obtained PLA/TPSA blend films have the potential to be applied as biodegradable flexible packaging.     

Effects of silica on the morphology,structure, and properties of thermoplastic cassava starch/poly(vinyl alcohol) blends

Thermoplastic cassava starch (TPS)/poly(vinyl alcohol) (PVA)/silica (SiO₂) composites were prepared by a melt‐mixing method. The effects of the content and surface properties of SiO₂ on the processing, mechanical properties, thermal stability, morphology, and structure of the TPS/PVA/SiO₂ composites were investigated. With increasing SiO₂ content, the plasticizing times of the TPS/PVA/SiO₂ composites were shortened. After the SiO₂ surface was treated with a silane coupling agent (KH550), the plasticizing times of the TPS/PVA/SiO₂ composites decreased significantly. The tensile strength, elongation at break, and Young's modulus of the TPS/PVA/SiO₂ composites increased. The mechanical properties of the TPS/PVA/SiO₂ composites containing treated SiO₂ were higher than those with untreated SiO_2. The thermal decomposition temperatures of the TPS/PVA/SiO₂ composites were improved with the addition of SiO₂. The presence of inorganic fillers was beneficial to the improvement of the thermal stability of the polymers. The reaction between the treated SiO₂ and the starch molecules was beneficial to the formation of more stable structures. The treated SiO₂ indicated good interfacial adhesion and uniform dispersion in the matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44020.     

Biodegradable polypropylene/thermoplastic starch nanocomposites incorporating halloysite nanotubes

In this work, polypropylene/thermoplastic starch (PP/TPS) with and without halloysite nanotubes (HNTs) was prepared via melt mixing in order to obtain environmentally friendly plastics. PP‐grafted maleic anhydride (PP‐g‐MA) was used to improve the compatibility among the highly incompatible polymers. The mechanical characterization showed a reduction in the tensile properties of the polymer when TPS increased; however, HNT successfully compensated for some of the observed losses. The results from the thermogravimetric analysis (TGA) indicated that HNT is an efficient reinforcement for the thermal stability improvement. TPS caused an increase in the storage modulus (G′) and the complex viscosity (η*) which marks a change in the viscoelastic properties of the system. The scanning electron microscope (SEM) images showed the effective plasticization of starch and better dispersion of TPS in the presence of HNT. Some samples were also buried in the soil to measure their sustainability after their lifetime lapse. The results indicated that TPS improves the biodegradability of the PP/TPS system. PP considerably lowered the moisture uptake of TPS; nevertheless, HNT caused a slight increase in the moisture absorption. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45740.     

Rheological,mechanical, thermal,and morphological properties of blends poly(butylene adipate-co-terephthalate), thermoplastic starch,and cellulose nanoparticles

The objective of the present study was the preparation and characterization of poly(butylene adipate-co-terephthalate) (PBAT) and thermoplastic starch (TPS) blends reinforced with cellulose nanoparticles (CNCs) by extrusion. The work was conducted in four steps. Initially, the CNCs were prepared from eucalyptus cellulose pulp by acid hydrolysis. The second step was the preparation of the nanocomposite (TPS-CNC), composed of cassava starch, CNC, glycerol, and citric and stearic acids, by double screw extrusion. The third step was the preparation of PBAT/TPS-CNC blends in twin-screw extruders. In the fourth step, the films were produced by flat extrusion. Blends exhibited similar rheological behavior, increasing the CNC concentration in blends increased the viscosity as a function of the shear rate, and altered the behavior of the shear storage (G′) and shear loss (G″) curves as a function of the oscillation frequency (ω). The presence of CNC in blend provided improvements significant in mechanical properties, with 120% increase in Young's modulus, and 46% increase in maximum tensile. Thermal behavior (thermogravimetric analysis and differential scanning calorimetry) was altered with the incorporation of the CNC, showing a single melt peak (T_m) and a slight increase in T_g, indicating good dispersion between the phases of the blends, corroborating with the fracture surface microscopy of films.     

Morphological investigation of cellulose acetate/cellulose nanocrystal composites obtained by melt extrusion

Composites were prepared from cellulose acetate (CA) and cellulose nanocrystals (CNC) by melt extrusion using two methods for the introduction of CNC: direct mixing and predispersion in CA solution. CNC were isolated using hydrochloric acid to increase thermal stability allowing the composites to be processed above 150 °C. The effect of CNC dispersion on the composites morphology, thermal, and mechanical properties was investigated. Field emission scanning electron microscopy and transmission electron microscopy results indicated that the predispersion method allows better CNC dispersion and distribution when compared to the direct mixture method. In addition, predispersion promotes preferential CNC orientation in relation to the injection flow. The predispersion method also showed a 14% Young's modulus increase in composites containing 15 wt % CNC while no significant change was observed when using the direct mixing. The results obtained in this work show that, to achieve the percolation threshold, nanoparticle distribution is as important as their content. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44201.     

聚碳酸亚丙酯/热塑性氧化淀粉的流变、形态和性能

采用熔融共混的方法制备了马来酸酐接枝聚碳酸亚丙酯(PPCMA)/热塑性淀粉(TPS)、PPCMA/热塑性氧化淀粉(TPOS)和PPCMA/ DL-TPOS(铝酸酯预处理的TPOS)复合材料,研究淀粉的氧化以及偶联剂的加入对PPC复合材料流变、形态和性能的影响。加入淀粉后的PPC复合材料拉伸强度有较大提高,红外光谱结果显示淀粉和PPCMA之间形成了氢键作用,这可能是力学性能提高的主要原因;热塑性氧化淀粉与PPCMA基材的界面相容性提高,PPCMA/TPOS复合材料的力学性能、储能模量、损耗模量和复数黏度均高于PPCMA/TPS复合材料;铝酸酯对TPOS的预处理促进了TPOS在PPCMA中的分散,提高了复合材料的拉伸强度,在PPCMA/DL-TPOS体系中,当DL-TPOS含量为40%(质量分数)时拉伸强度达到最大值,与PPCMA相比,提高了4.6倍。     

Effect of graphene loading on thermomechanical properties of poly(vinyl alcohol)/starch blend

Polymer nanocomposites based on poly(vinyl alcohol) (PVA)/starch blend and graphene were prepared by solution mixing and casting. Glycerol was used as a plasticizer and added in the starch dispersion. The uniform dispersion of graphene in water was achieved by using an Ultrasonicator Probe. The composites were characterized by FTIR, tensile properties, X‐ray diffraction (XRD), thermal analysis, and FE‐SEM studies. FTIR studies indicated probable hydrogen bonding interaction between the oxygen containing groups on graphene surface and the –OH groups in PVA and starch. Mechanical properties results showed that the optimum loading of graphene was 0.5 wt % in the blend. XRD studies indicated uniform dispersion of graphene in PVA/starch matrix upto 0.5 wt % loadings and further increase caused agglomeration. Thermal studies showed that the thermal stability of PVA increased and the crystallinity decreased in the presence of starch and graphene. FE‐SEM studies showed that incorporation of graphene increased the ductility of the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41827.     

Transparent low‐density polyethylene/starch nanocomposite films

Low‐density polyethylene (LDPE)/starch nanocomposite films were prepared by melt extrusion process. The first step includes the preparation of starch–clay nanocomposite by solution intercalation method. The resultant product was then melt mixed with the main matrix, which is LDPE. Maleic anhydride‐grafted polyethylene (MAgPE), produced by reactive extrusion, was used as a compatibilizer between starch and LDPE phases. The effects of using compatibilizer, clay, and plasticizers on physico‐mechanical properties were investigated. The results indicated that the initial intercalation reaction of clay layers with starch molecules, the conversion of starch into thermoplastic starch (TPS) by plasticizers, and using MAgPE as a compatibilizer provided uniform distribution of both starch particles and clay layers, without any need of alkyl ammonium treatment, in LDPE matrix. The nanocomposite films exhibited better tensile properties compared to clay‐free ones. In addition, the transparency of LDPE film did not significantly change in the presence of TPS and clay particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Silver‐loaded lyocell fibers modified by tempo‐mediated oxidation

The purpose of this research was to accomplish antimicrobial properties in lyocell fibers by Ag⁺ ions sorption from aqueous silver nitrate solution. Sorption properties of lyocell fibers were improved by the selective TEMPO‐mediated oxidation, i.e. oxidation with sodium hypochlorite and catalytic amount of sodium bromide and 2,2,6,6‐tetramethylpiperidine‐1‐oxy radical (TEMPO). The most suitable experimental conditions for the selective TEMPO‐mediated oxidation were determined by changing oxidation conditions: concentration of sodium hypochlorite, as well as duration of sorption. The obtained results showed that the maximum sorption capacity (0.809 mmol of Ag⁺ ions per gram of fibers) of modified lyocell fibers was obtained for the sample modified with 4.84 mmol NaClO per gram of cellulose, during 1 h. The antifungal activity of the TEMPO‐oxidized lyocell fibers with silver ions against fungi from the Candida family, Candida albicans (ATCC 24433), and antibacterial activity against two strains: Staphylococcus aureus (ATCC 25923) and Escherichia coli (ATCC 25922) were confirmed in vitro. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of nanosilica on retrogradation properties and structures of thermoplastic cassava starch

Composites of thermoplastic cassava starch (TPS) and nanosilica (SiO₂) were prepared by the melting method. The effect of nano‐SiO₂ on the retrogradation properties and structures of cassava starch was investigated. The retrogradation degree of TPS/nano‐SiO₂ composites increased with increasing retrogradation time. The retrogradation rate of TPS significantly increased after the addition of nano‐SiO₂, but excessive nano‐SiO₂ content leads to a decrease in the retrogradation rate of TPS. According to the Fourier transform infrared spectroscopy results, the retrogradation degree of TPS/nano‐SiO₂ composites increased with the increase of retrogradation time and addition of nano‐SiO₂. Scanning electron microscopy analysis indicated that nano‐SiO₂ particles were uniformly and finely dispersed in the starch materials, but the nano‐SiO₂ particles aggregated in the cassava starch with a further increase in nano‐SiO₂ content. X‐ray diffraction revealed that the crystalline structure of the starch was gradually altered from A‐type to V‐type with the increase of retrogradation time. TPS/SiO₂ composites indicated a mixture of A+V types, and the intensity of the V‐type strengthened with the increase of retrogradation time and SiO₂ content. Polarized light microscopy analysis revealed clear Maltese cross patterns, and the number of spherulites in TPS/nano‐SiO₂ composites increased with increasing retrogradation time and nano‐SiO₂ content, but the retrogradation of starch was inhibited with further increases of nano‐SiO₂ content. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45687.     

Polyolefins–biofibre composites: A new way for an industrial production

Low density polyethylene (LDPE) composites based on cellulose fibres have been processed by high shear extrusion with water injection to help dispersion of fibres and release nanofibres from cellulose. Influence of extrusion parameters as shear, residence time, storage conditions of the matrix, and effect of water injection on the morphological properties of the composites have been studied using microscopy. Optimization of the extrusion parameters is necessary to reach a dispersion of the fibres. Increasing shearing forces and residence time allows limiting the presence of large aggregates of cellulose fibres. Use of powdered LDPE, even for short residence time and low shear, is efficient to produce well‐dispersed composites. Injection of water during the extrusion also improves the quality of the dispersion. However, no nanofibres are observed. The main effect is a spectacular decrease of the discoloration (yellowing) due to cellulose degradation. Mechanical properties of the composites have been investigated. Young modulus increases with cellulose content and reinforcing effect is more important above 10% by weight. For well‐dispersed composites, the extrusion parameters have no significant influence on the stiffness of the composites. However, due to the weakness of the interface, the ductility of composites is reduced compared with LDPE. POLYM. ENG. SCI., 47:467–476, 2007. © 2007 Society of Plastics Engineers.     

Study of nanoreinforced shape memory polymers processed by casting and extrusion

Multi‐walled carbon nanotubes (CNTs) and cellulose nanofibers (CNFs) reinforced shape memory polyurethane (PU) composite fibers and films have been fabricated via extrusion and casting methods. Cellulose nanofibers were obtained through acid hydrolysis of microcrystalline cellulose. This treatment aided in achieving stable suspensions of cellulose crystals in dimethylformamide (DMF), for subsequent incorporation into the shape memory matrix. CNTs were covalent functionalized with carboxyl groups (CNT‐COOH) and 4,4′‐methylenebis (phenylisocyanate) (MDI) (CNT‐MDI) to improve the dispersion efficiency between the CNT and the polyurethane. Significant improvement in tensile modulus and strength were achieved by incorporating both fillers up to 1 wt% without sacrificing the elongation at break. Electron microscopy was used to investigate the degree of dispersion and fracture surfaces of the composite fibers and films. The effects of the filler (type and concentration) on the degree of crystallinity and thermal properties of the hard and soft segments that form the PU sample were studied by calorimetry. Overall, results indicated that the homogeneous dispersion of nanotubes and cellulose throughout the PU matrix and the strong interfacial adhesion between nanotubes and/or cellulose and the matrix are responsible for the enhancement of mechanical and shape memory properties of the composites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers