Synthesis and characterization of corn starch based green composites reinforced with Saccharum spontaneum L graft copolymers prepared under micro-wave and their effect on thermal, physio-chemical and mechanical properties

In this paper, green composites of the corn starch were developed by using resorcinol-formaldehyde (Rf) as the cross-linking agent and reinforced with graft copolymers Saccharaum spontaneum L(Ss) and methyl methacrylates (MMA) as principal monomer and its binary mixture with acrylamide (AAm), acrylonitrile(AN), acrylic acid (AA) prepared under micro-wave. The matrix and composites were found to be thermally more stable than the natural corn starch backbone. There was improvement in physico-chemical and mechanical properties of composite were found to exhibit better than matrix. Ss-g-poly(MMA)-MW reinforced composites were found to exhibit better tensile strength, on the other hand Ss-g-poly(MMA + AA)-MW reinforced composites showed maximum compressive strength and wear resistance than other graft copolymers reinforced composite and the basic matrix. Further the matrix and composites were subjected for biodegradation studies through soil composting method. Different stages of biodegradation were evaluated through FT-IR studies and scanning electron microscopic (SEM) techniques.     

Continuous cellulose fiber-reinforced cellulose ester composites. I. Manufacturing options

Thermoplastic fiber composites were prepared using high modulus lyocell (regenerated cellulose) fibers for reinforcement and cellulose acetate butyrate (CAB) as matrix. Choices were made with regard to fiber options (fabric versus continuous tow) and method of matrix deposition (prepregging by powder coating, film stacking, or solution impregnating). The results suggest that solution-prepregged fiber tow consolidated at circa 200°C produced unidirectional consolidated panels with tensile strength, modulus, and strain at failure values of approximately 250MPa,>20GPa and 3–4%, respectively, at fiber volume contents of approximately 60%. Modulus and ultimate tensile strength increased with fiber content, and modulus followed rule-of-mixture behavior. Adequate surface wetting and matrix-fiber adhesion were found with solution-prepregged composites. The unexpectedly low strain at failure (2 to <4%) was attributed to brittle matrix failure, and failure surfaces revealed that the fibers, for the most part, remained intact after the matrix had failed.     

Foamed articles based on potato starch, corn fibers and poly(vinyl alcohol)

Single-use packaging materials made of expanded polystyrene (EPS) have been identified as suitable items to be replaced by biodegradable materials. Plates made with EPS represent a source of non-degradable waste that is difficult to collect and to recycle. Potato starch based foamed plates have been prepared by a baking process. Presently, foam plates have been prepared by baking aqueous mixtures of potato starch, corn fibers, and poly(vinyl alcohol) (PVA) inside a hot mold. The effects of the addition of corn fibers, a co-product of bio-ethanol production, on mechanical properties and moisture resistance of potato starch based foamed plates were investigated. The addition of corn fiber to potato starch batter increased baking time and an increased batter volume is needed to form a complete tray. The mechanical properties of the trays decreased with added corn fiber. In previous studies PVA has been added as aqueous solution to improve strength, flexibility, and water resistance of baked starch trays. In this study, 88% hydrolyzed PVA was added as a powder in the mixture, avoiding the time consuming and costly step of pre-dissolving the PVA. The addition of PVA to potato starch batters containing corn fiber mitigated the reduction in tensile properties seen in trays with added corn fiber. Starch-based trays produced with a high fiber ratio and PVA, showed improved water resistance.     

Studies on the properties and characteristics of starch-LDPE blend films using cross-linked, glycerol modified, cross-linked and glycerol modified starch

Corn starch was modified by cross-linking with epichlorohydrin and plasticizer glycerol. X-ray diffraction studies showed that relative crystallinity of the native and cross-linked starch were similar and were not affected by cross-linking. Different films were prepared by blending corn starch, cross-linked starch or glycerol modified starch in LDPE. The mechanical properties of the films were studied for tensile strength, elongation, melt flow index, and burst strength. The properties of the blend films were compared with LDPE films. It was observed that with the blending of 7.5% native starch, there was a decrease in tensile strength, elongation and melt flow index but burst strength increased. The tensile strength, elongation and melt flow index of the films containing cross-linked starch was considerably higher than those containing native starch but the burst strength showed a reverse trend. For native starch and cross-linked starch modified with glycerol, the elongation and melt flow index of the films increased but burst strength decreased. Surface scanning of the blend films were done by scanning electron microscope. Film containing cross-linked starch/glycerol modified starch in the blend was observed to be smoother than the native starch blend films.     

Effect of fiber length and composition on mechanical properties of carbon fiber‐reinforced polybenzoxazine

The mechanical strength and modulus of chopped carbon fiber (CF)‐reinforced polybenzoxazine composites were investigated by changing the length of CFs. Tensile, compressive, and flexural properties were investigated. The void content was found to be higher for the short fiber composites. With increase in fiber length, tensile strength increased and optimized at around 17 mm fiber length whereas compressive strength exhibited a continuous diminution. The flexural strength too increased with fiber length and optimized at around 17 mm fiber length. The increase in strength of composites with fiber length is attributed to the enhancement in effective contact area of fibers with the matrix. The experimental results showed that there was about 350% increase in flexural strength and 470% increase in tensile strength of the composites with respect to the neat polybenzoxazine, while, compressive properties were adversely affected. The composites exhibited an optimum increase of about 800% in flexural modulus and 200% in tensile modulus. Enhancing the fiber length, leads to fiber entanglement in the composites, resulted in increased plastic deformation at higher strain. Multiple branch matrix shear, debonded fibers and voids were the failures visualized in the microscopic analyses. Defibrillation has been exhibited by all composites irrespective of fiber length. Fiber debonding and breaking were associated with short fibers whereas clustering and defibrillation were the major failure modes in long fiber composites. Increasing fiber loading improved the tensile and flexural properties until 50–60 wt% of fiber whereas the compressive property consistently decreased on fiber loading. Copyright © 2008 John Wiley & Sons, Ltd.     

Short Twaron aramid fiber reinforced thermoplastic polyurethane

Mechanical, dynamic mechanical, and rheological behaviors of a short p‐aramid fiber reinforced thermoplastic polyurethane (TPU) have been studied in the range of 0–30 wt% of fibers. The tensile strength of the composite is improved slightly at higher fiber content with a minimum at around 10 wt% of fibers. The addition of fibers markedly reduces elongation at break and entails a steady increase in the elastic modulus, but decreases the wear resistance of the matrix. Storage modulus (E′) is increased and the shapes of loss tangent (tan δ) peaks point to a possible fiber–matrix interaction. Rheological studies show a power law behavior for all composites and increased viscosity with fiber loading. Study of the tensile and cryogenic fracture surfaces by scanning electron microscopy (SEM) indicates good correlation between the modes of failure and strength of the composites. The micrographs reveal good interfacial adhesion and extensive peeling and fibrillation of the fibers in the compounded and fractured composites. Theoretical models have been used to fit the experimental modulus data. Copyright © 2008 John Wiley & Sons, Ltd.     

Completely biodegradable composites of poly(propylene carbonate) and short,lignocellulose fiber Hildegardia populifolia

The composites of biodegradable poly(propylene carbonate) (PPC) reinforced with short Hildegardia populifolia natural fiber were prepared by melt mixing followed by compression molding. The mechanical properties, thermal properties, and morphologies of the composites were studied via static and dynamic mechanical measurements, thermogravimetric analysis, and scanning electron microscopy (SEM) techniques, respectively. Static tensile tests showed that the stiffness and tensile strength of the composites increased with an increasing fiber content. However, the elongation at break and the energy to break decreased dramatically with the addition of short fiber. The relationship between the experimental results and the compatibility or interaction between the PPC matrix and fiber was correlated. SEM observations indicated good interfacial contact between the short fiber and PPC matrix. Thermogravimetric analysis revealed that the introduction of short Hildegardia populifolia fiber led to a slightly improved thermooxidative stability of PPC. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 666–675, 2004     

Effect of Silane Coupling Agent and Compatibilizer on Properties of Short Rossells Fiber/Poly(propylene) Composites

Rossells fiber reinforced polypropylene composites were prepared by melt mixing. The fiber content was 20 wt%. Octadecyltrimethoxysilane (OTMS) and maleic anhydride grafted polypropylene (MAPP) were used to improve the adhesion between poly(propylene) (PP) and the fiber. The mechanical, rheological, and morphological properties, and heat distortion temperature (HDT) of the composites were investigated. Tensile strength, impact strength, flexural strength and HDT of MAPP modified PP composites increased with an increase in MAPP content. However, no remarkable effect of MAPP content on the Young's modulus of the composites was found. OTMS resulted in small decreases of tensile strength and Young's modulus, and increase in impact strength. Scanning electron micrographs revealed that MAPP enhanced surface adhesion between the fiber surface and PP matrix.     

Effect of Chemical Treatment and Fiber Loading on Mechanical Properties of Borassus (Toddy Palm) Fiber/Epoxy Composites

The aim of the present study was to investigate and compare the mechanical properties of untreated and chemically modified Borassus fiber–reinforced epoxy composites. Composites were prepared by the hand lay-up process by reinforcing Borassus fibers with epoxy matrix. To improve the fiber-matrix adhesion properties, alkali (NaOH) and alkali combined with silane (3-aminopropyltriethoxysilane) treatment of the fiber surface was carried out. Examinations through Fourier transform-infrared spectroscopy and scanning electron microscopy (SEM) were conducted to investigate the structural and physical properties of the Borassus fibers. Tensile properties such as modulus and strength of the composites made with chemically modified and untreated Borassus fibers were studied using a universal testing machine. Based on the experimental results, it was found that the tensile properties of the Borassus-reinforced epoxy composites were significantly improved as compared with the neat epoxy. It was also found that the fiber treated with a combination of alkali and silane exhibited superior mechanical properties to alkali-treated and untreated fiber composites. The nature of the fiber/matrix interface was examined through SEM of cryo-fractured samples. Chemical resistance of composites was also found to be improved with chemically modified fiber composites.     

Profile of enzyme production by trichoderma reesei grown on corn fiber fractions

Corn fiber is the fibrous by-product of wet-mill corn processing. It typically consists of about 20% starch, 14% cellulose, and 30% hemicellulose in the form of arabinoxylan. Crude corn fiber (CCF) was fractionated into de-starched corn fiber (DSCF), corn fiber with cellulose (CFC) enriched, and corn fiber arabinoxylan (CFAX), and these fractions were evaluated as substrates for enzyme production by Trichoderma reesei. T. reesei QM9414 and Rut C-30 grew on CCF, DSCF, CFC, or CFAX and secreted a number of hydrolytic enzymes. The enzymes displayed synergism with commercial cellulases for corn fiber hydrolysis. Mention of trade names or commercial products in this article is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture.     

Microscopic appearance of fractured surfaces and mechanical properties of starch–extended poly(vinyl alcohol)

Mixtures of Mowiol [an industrial plasticized poly(vinyl alcohol)] and corn starch have been examined by scanning electron microscopy (SEM); their impact and crossbreaking strengths, as well as their flexural moduli, measured. The results show fracturing as well as pitting with increased corn starch in Mowiol. The starch granular sizes (determined randomly for a number of samples) fluctuated between 10 and 22 μm, without some definite trend in the distribution. However, a certain degree of uniformity of granular size distribution appears to be achieved with an increase in the starch content of Mowiol. Both the impact and crossbreaking strength decreased with increase in starch, while the flexural modulus increased as the starch content increased. The impact of these observations on the resultant Mowiol/starch composites has been discussed. That transformed poly(vinyl alcohol) is likely to be an invaluable engineering material is not in doubt.     

Continuous cellulose fiber-reinforced cellulose ester composites. II. Fiber surface modification and consolidation conditions

We prepared thermoplastic composite panels using solution impregnation of continuous lyocell (regenerated cellulose) fibers with a cellulose mixed-ester (cellulose acetate butyrate) matrix. We examined both fiber-matrix adhesion and melt consolidation in an effort to produce uniform panels having low void content and high mechanical strength. We characterized the effect of surface modification by acetylation on interfacial adhesion between the cellulose fiber and cellulose ester. Whereas wood fiber acetylation had previously been observed to result in significant strength gains in (discontinuous) wood fiber- reinforced composites (with the same matrix material), we did not observe a similar increase in strength in the continuous lyocell cellulose fiber system. This suggests that interfacial stress transfer is not a limitation in this system. This was confirmed by microscopic examination of the fracture surfaces, which indicated that fiber-matrix adhesion was considerable in the absence of fiber surface modification. We then systematically varied melt consolidation conditions (temperature, pressure and time) in an attempt to define optimum consolidation parameters by using design of experiments (DOE) methodology. We measured both interlaminar shear strength (ILSS) and composite void volume. We found that a minimal void content (ca. 2.83 vol. %) occurred at moderate temperatures (200°C), low consolidation pressures (81.4kPa) and long press times (13min). This was also where we maximized the interlaminar shear strength (ILSS) at a value of 16.3MPa. This agrees with the regression model predictions. We observed the highest tensile properties at the ILSS and void-volume optimal-consolidation condition: a tensile modulus of 22GPa and tensile strength of 246MPa were obtained.     

Mechanical properties of phenol/formaldehyde resin composites reinforced by cellulose microcrystal with different aspect ratio extracted from sisal fiber

Sisal cellulose fiber (SCF) and sisal fiber cellulose microcrystal (SFCM), produced with sulfate pulping method and ball‐milling approach separately, were in‐situ polymerized and dispersed into phenol/formaldehyde (PF) resin, to manufacture SCF/PF and SFCM/PF composites via rolling and molding method and investigate the effect of SCF and SFCM on the impact, flexural, and dynamic mechanical properties of the SCF/PF and SFCM/PF composites. As a result, under the condition of same content, SFCM could preferably enhance these properties maybe resulting from the better dispersion in resin matrix than SCF. In particular, when SFCM content was 7%, the impact strength and equilibrium relaxation modulus of the SFCM/PF composite were increased by 26.5% and 37.7%, while the creep deformation was decreased by 26.5%. In addition, when SFCM content was 5%, the flexural strength, initial storage modulus and glass transition temperature of SFCM/PF composite were increased by 8.5%, 22.6%, and 13°C. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal Analysis of Micro- and Nano-Lignocellulosic Reinforced Styrene Maleic Anhydride Composite Foams

The aim of this study was to measure the thermal properties of foamed nano/macro filler–reinforced styrene maleic anhydride (SMA) composites. SMA (66%) as a polymer matrix (10% maleic anhydride content) and various fillers including wood flour, starch, α-cellulose, microcrystalline cellulose and cellulose nanofibrils as reinforcing agents (30%) and lubricant (4%) were used to manufacture the composites in a twin-screw extruder. According to the thermogravimetric analysis (TGA) results, thermal degradation of all the foamed composites was found to be lower than that of SMA composites. The storage modulus values were negatively affected with a second time foaming (reprocessing [recycling] the initially processed composites a second time), as were loss modulus and T_g. As a result, second-time-foamed composite modulus values were lower than those of the foamed composites. According to the melt flow index (MFI) results, viscosity of the SMA was found to increase with the addition of fillers.     

Wear behavior of straw fiber-reinforced polyvinyl chloride composites under simulated acid rain conditions

In order to investigate the effect of simulated acid rain (SAR) corrosion on the wear-resistance properties of straw fiber/polyvinyl chloride (SPVC) composites, four types of straw fibers (wheat straw (WS), rice straw (RS), corn straw (CS), and sorghum straw (SS) fibers) were utilized and incorporated into poly(vinyl chloride) (PVC). The results show that the SS fibers have high levels of cellulose, lignin and crystallinity, and it also exhibited high adhesion strength with PVC matrix, which endow the SS/PVC with high wear-resistance compared with other three SPVC composites. After SAR corrosion, SPVC composites exhibited severe degradation of the physical, mechanical, and thermal properties, and the fibers were easily pulled out from the matrix to form abrasive particles. The high-speed fiber debris in high-temperature and high-loading environments can be deemed a kind of “incompressible lumps” that will form a certain abrasive wear.     

Enzymatic hydrolysis of high-moisture corn fiber pretreated by afex and recovery and recycling of the enzyme complex

Corn fiber is a grain-processing residue containing significant amounts of cellulose, hemicellulose, and starch, which is collected in facilities where fuel ethanol is currently manufactured. Preliminary research has shown that corn fiber (30% moisture dry weight basis [dwb]) responds well to ammonia-fiber explosion (AFEX) pretreatment. However, an important AFEX pretreatment variable that has not been adequately explored for corn fiber is sample moisture. In the present investigation, we determined the best AFEX operating conditions for pretreatment of corn fiber at high moisture content (150% moisture dwb). The optimized AFEX treatment conditions are defined in terms of the moisture content, particle size, ammonia to biomass ratio, temperature, and residence time using the response of the pretreated biomass to enzymatic hydrolysis as an indicator. Approximate optimal-pretreatment conditions for unground corn fiber containing 150% (dwb) moisture were found to be: temperature, 90?C; ammonia: dry corn fiber mass ratio, 1:1; and residence time 30 min (average reactor pressure under these conditions was 200 pounds per square inch [psig]). Enzymatic hydrolysis of the treated corn fiber was performed with three different enzyme combinations. More than 80% of the theoretical sugar yield was obtained during enzymatic hydrolysis using the best enzyme combination after pretreatment of corn fiber under the optimized conditions previously described. A simple process for enzyme recovery and reuse to hydrolyze multiple portions of AFEX-treated corn fiber by one portion of enzyme preparation is demonstrated. Using this process, five batches of fresh substrate (at a concentration of 5% w/v) were successfully hydrolyzed by repeated recovery and reuse of one portion of enzyme preparation, with the addition of a small portion of fresh enzyme in each subsequent recycling step.     

A comparative study of the characteristics of cross-linked, oxidized and dual-modified rice starches

Rice starch was cross-linked with epichlorohydrin (0.3%, w/w, on a dry starch basis) and oxidized with sodium hypochlorite (2.5% w/w), respectively. Two dual-modified rice starch samples (oxidized cross-linked rice starch and cross-linked oxidized rice starch) were obtained by the oxidation of cross-linked rice starch and the cross-linking of oxidized rice starch at the same level of reagents. The physicochemical properties of native rice starch, cross-linked rice starch and oxidized rice starch were also studied parallel with those of the two dual-modified rice starch samples using rapid visco analysis (RVA), differential scanning calorimetry (DSC), dynamic rheometry and scanning electron microscopy (SEM). It was found that the levels of cross-linking and oxidation used in this study did not cause any significant changes in the morphology of rice starch granules. Cross-linked oxidized starch showed lower swelling power (SP) and solubility, and higher paste clarity in comparison with native starch. Cross-linked oxidized rice starch also had the lowest tendency of retrogradation and highest ability to resistant to shear compared with native, cross-linked, oxidized and oxidized cross-linked rice starches. These results suggest that the undesirable properties in native, cross-linked and oxidized rice starch samples could be overcome through dual-modification.     

Mechanical characterization of polymethyl methacrylate composites reinforced with surface-coated carbon fibers

Using trihydroxy polyether polyol (PPG), diphenylmethane diisocyanate (MDI) as soft segment and hard segment, carbon fiber (CF) as reinforcement, and self-crosslinking CF/polymethyl methacrylate (PMMA) composite was prepared by prepolymer method. In this study, starch and octanoyl chloride were esterified to obtain esterified starch (SE). The fiber is then melt blended with PMMA matrix to prepare PMMA composite. Fourier-transform infrared spectroscopy (FTIR) and SEM were used to analyze and characterize the composites produced. The results show that the composite material was prepared by separately modifying the fiber with NaOH and SE, respectively. The mechanical properties of the composite materials prepared by the modified fiber are improved, and the fiber and the PMMA matrix showed better compatibility. The mechanism of comodified fiber enhanced the mechanical properties of its composites.     

Effect of germ and fiber removal on production of ethanol from corn

Ethanol fermentations were conducted using both whole corn, and corn with 100% of the germ, and a portion (∼74%) of the fiber removed. Ethanol production increased 11% in the germ and fiber-removed corn vs the whole corn. The protein content of distiller's dried grains and solubles increased from 30 to 36%, and phosphate levels were 60% lower in corn with germ and fiber removed vs whole corn. Removal of germ and fiber prior to fermentation allows higher starch loading and results in increased ethanol production. The integration of germ and fiber removal in the dry-grind ethanol industry could increase capacity and add valuable coproducts, resulting in increased productivity and profits.     

Effects of chemical modification on the structure and mechanical properties of starch-based biofilms

Abstract  

In this work, chemically modified corn starch and plasticized corn starch biofilms were obtained and characterized in four steps: (1) preparation of corn starch microparticles, (2) preparation of malic acid-modified corn starch microparticles (MA–SM), (3) preparation of corn starch biofilms and MA–SM-plasticized corn starch biofilms, and (4) characterization of the biofilms. The effects of MA–SM concentration (4, 8, and 12% based on the amount of corn starch) on the structural characteristics and mechanical properties of the biofilms were investigated. Changes in the starch granules after chemical modification were studied by X-ray diffraction, FT-IR spectroscopy, and scanning electron microscopy. The presence of ester carbonyl group stretching vibration at 1,720 cm⁻¹ in FT-IR spectra was evidence of reaction of the starch microparticles with malic acid. The tensile yield strength and Young’s modulus of the films increased with increasing MA–SM content. Water uptake decreased from 69.8% for biofilm without MA–SM to 52.7% for biofilm with MA–SM. The improvement of these properties in the plasticized product could be attributed to the good interaction between the MA–SM filler and the corn starch.