Processing and Physical Properties of Plastics Made from Soy Protein Polyester Blends

Blending soy protein with polyesters using a polyvinyllactam as a compatibilizer successfully made soy protein-based plastics. The polyesters used to produce blends included polycaprolactone (PCL) and Biomax (a commercial biodegradable polyester). The blends were processed by compounding extrusion and injection molding. Blends containing soy protein/Biomax-poly(vinyl alcohol) had tensile strengths ranging from 16–22 MPa, with samples containing larger percentages of the synthetic polymer exhibiting greater strengths. Blends made from soy protein, Biomax, and PCL had tensile strengths ranging from 27–33 MPa. All the blends had high Young's moduli but demonstrated brittle characteristics as evident from their low elongations at break, ranging from 1.8–3.1%. Plastics made from soy protein/polyester blends exhibited low water absorption and had good stability under ambient conditions relative to the plastics made from soy protein alone. Blends made from soy protein flour produced plastics with the lowest water absorption.     

Adhesive Performance of Sorghum Protein Extracted from Sorghum DDGS and Flour

Distillers dried grains with solubles (DDGS) is the main co-product from grain-based ethanol production. The objective of this research was to compare the adhesive performance of three types of sorghum proteins: acetic acid-extracted sorghum protein from DDGS (PI), aqueous ethanol-extracted sorghum protein from DDGS (PII) and acetic acid-extracted sorghum protein from sorghum flour (PF). Physicochemical properties including amino acid composition, and rheological, thermal and morphological properties also were characterized. Results showed that PI had the best adhesion performance in terms of dry, wet and soak adhesion strength, followed by PF and PII. The wet strength of PI at a concentration of 12% protein assembled at 150 °C was 3.15 MPa, compared to 2.17 MPa and 2.59 MPa for PII and PF, respectively. DSC thermograms indicated that the PF protein isolates contained higher levels of carbohydrates than PI and PII; such non-protein contaminants in the PF isolate could be the reason for its lower adhesion strength than PI. In addition, PI might have more hydrophobic amino acids aligned at the protein-wood interface than PII, which could explain the better water resistance of PI. The optimum sorghum protein concentration and pressing temperature for maximum adhesion strength was 12% and 150 °C. PI had a significantly higher wet strength (3.15 MPa) than unmodified soy protein (1.63 MPa for soy protein). The high percentage of hydrophobic amino acids in PI (57%) was likely a key factor in the increased water resistance of PI compared with soy protein (36% hydrophobic amino acids). These results indicated that sorghum protein has huge potential as an alternative to petroleum-based adhesives.     

Canola straw as a bio-waste resource for medium density fiberboard (MDF) manufacture

Canola straw as an agricultural residue has been investigated for MDF production. The variables were steaming time (2, 5 and 8 min), the resin content (9% and 11%), and press time (4 and 6 min). Common physical and mechanical properties of experimental boards including modulus of rupture (MOR), modulus of elasticity (MOE), internal bond strength (IB) and thickness swelling (TS) were measured. Fiber properties of canola straw including length, diameter and cell wall thickness were determined. The results showed that all the tested mechanical properties improved with the increase of steaming time level. The results were close to the minimum requirements of MDF specified in the ANSI A208.2 standard. Dimensional stability of the MDFs improved as adhesive content increased. The IB values are positively affected by the increase of press time. MDF properties made from canola straw possess acceptable qualities as compared to those made from other non-wood plants. Furthermore, the fiber dimensions of canola straw were also in the range of reported values in hardwoods.     

A Processing,Characterization and Marine Biodegradation Study of Melt-Extruded Polyhydroxyalkanoate (PHA) Films

A series of polyhydroxyalkanoates (PHA), all containing 1% nucleating agent but varying in structure, were melt-processed into films through single screw extrusion techniques. This series consisted of three polyhydroxybutyrate (PHB) and three polyhydroxybutyrate-valerate (PHBV) resins with varying valerate content. Processing parameters of temperature in the barrel (165–173 °C) and chill rolls (60 °C) were optimized to obtain cast films. The gel-permeation chromatography (GPC) results showed a loss of 8–19% of the polymer’s initial molecular weight due to extrusion processing. Modulated differential scanning calorimetry (MDSC) displayed glass transition temperatures of the films ranging from −4.6 to 6.7 °C depending on the amount of crystallinity in the film. DSC data were also used to calculate the percent crystallinity of each sample and slightly higher crystallinity was observed in the PHBV series of samples. X-ray diffraction patterns did not vary significantly for any of the samples and crystallinity was confirmed with X-ray data. Dynamic mechanical analysis (DMA) verified the glass transition trends for the films from DSC while loss modulus (E′) reported at 20 °C showed that the PHBV (3,950–3,600 MPa) had the higher E′ values than the PHB (3,500–2,698 MPa) samples. The Young’s modulus values of the PHB and PHBV samples ranged from 700 to 900 MPa and 900 to 1,500 MPa, respectively. Polarized light microscopy images revealed gel particles in the films processed through single-screw extrusion, which may have caused diminished Young’s modulus and tensile strength of these films. The PHBV film samples exhibited the greatest barrier properties to oxygen and water vapor when compared to the PHB film samples. The average oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) for the PHBV samples was 247 (cc-mil/m²-day) and 118 (g-mil/m²-day), respectively; while the average OTR and WVTR for the PHB samples was 350 (cc-mil/m²-day) and 178 (g-mil/m²-day), respectively. Biodegradation data of the films in the marine environment demonstrated that all PHA film samples achieved a minimum of 70% mineralization in 40 days when run in accordance with ASTM 6691. For static and dynamic incubation experiments in seawater, microbial action resulting in weight loss as a function of time showed all samples to be highly biodegradable and correlated with the ASTM 6691 biodegradation data.     

Properties of Distillers Grains Composites: A Preliminary Investigation

Interest in renewable biofuel sources has intensified in recent years, leading to greatly increased production of ethanol and its primary coproduct, Distillers Dried Grain with Solubles (DDGS). Consequently, the development of new outlets for DDGS has become crucial to maintaining the economic viability of the industry. In light of these developments, this preliminary study aimed to determine the suitability of DDGS for use as a biofiller in low-cost composites that could be produced by rapid prototyping applications. The effects of DDGS content, particle size, curing temperature, and compression on resulting properties, such as flexural strength, modulus of elasticity, water activity, and color were evaluated for two adhesive bases. The composites formed with phenolic resin glue were found to be greatly superior to glue in terms of mechanical strength and durability: resin-based composites had maximum fiber stresses of 150–380 kPa, while glue composites had values between 6 kPa and 35 kPa; additionally, glue composites experienced relatively rapid microbial growth. In the resin composites, both decreased particle size and increased compression resulted in increased mechanical strength, while a moderate DDGS content was found to increase flexural strength but decrease Young’s modulus. These results indicate that DDGS has the potential to be used in resin glue-based composites to both improve flexural strength and improve potential biodegradability.     

Management of agricultural biomass wastes: Preliminary study on characterization and valorisation in clay matrix bricks

In this work the feasibility of using woody agricultural biomass wastes as grapes and cherries seeds, sawdust, as pore forming agent, and sugar cane ash, as silica precursor, in bricks, were reported.Sawdust and grapes and cherries seeds, thanks to their organic substances content, during their combustion, bring an energetic support in the bricks firing phase and act as pore forming agent. Usually the addition of this kind of waste is limited to 10 wt.% in order to reach an equilibrium between positive (weight and shrinkage decrease and porosity increase) and negative (increase of water absorption and mechanical resistance decrease) effects. The results show that grapes and cherries seeds, added in a percentage of 5 wt.% to a brick formulation, have better influence with respect to the sawdust, maintaining the mechanical properties of the fired brick (950 °C), showing modulus of rupture around 21–23 MPa with a weight reduction of 3–10% (respect to the standard one). Regarding the sugar cane ash, the addition of 5 wt.% improves the mechanical properties (modulus of rupture around 27 MPa) and no weight decrease is observed. These results confirmed the role played by this kind of agricultural waste, which thanks to its high silica content (61 wt.%) is capable to demonstrate a filler and plasticity reducing effect on the brick bodies. Tests carried out highlighted that the addition of these by-products (5 wt.%) do not change negatively the main technological properties measured (water absorption, linear shrinkage, flexural resistance, etc.) and permit to hypothesize their use to obtain bricks with both insulating and higher mechanical properties using a pore agent forming or silica carrier alternative raw materials, respectively.     

Technical assessment of three layered cement-bonded boards produced from wastepaper and sawdust

The technical properties of three layered cement-bonded boards (CBBs) made from wastepaper and sawdust were investigated. The CBBs were produced at three density levels of 1000, 1200 and 1300 kg/m3 and at four cement/particle ratios of 2.0:1, 2.5:1, 3.0:1 and 3.5:1 on a weight to weight basis. The technical properties evaluated were modulus of rupture (MOR), modulus of elasticity (MOE), water absorption (WA) and thickness swelling (TS). The MOR values ranged from 4.85 to 11.69 MPa and MOE values ranged from 2.80 to 5.57 GPa. The mean values of WA and TS after 24 h of water soaking of the CBBs ranged from 18.18% to 40.49% and 3.55% to 12.13%, respectively. MOR and MOE of the CBBs increased with increase in board density, but MOR decreased with the increase in cement/particle ratio. On the other hand, WA and TS decreased with increase in board density and cement/particle ratio. CBBs produced from wastepaper and sawdust at cement/particle ratios of 3.0:1 and 3.5:1 are suitable for building construction such as paneling, ceiling and partitioning.     

Comparison of Polylactic Acid/Kenaf and Polylactic Acid/Rise Husk Composites: The Influence of the Natural Fibers on the Mechanical, Thermal and Biodegradability Properties

This paper investigates and compares the performances of polylactic acid (PLA)/kenaf (PLA-K) and PLA/rice husk (PLA-RH) composites in terms of biodegradability, mechanical and thermal properties. Composites with natural fiber weight content of 20% with fiber sizes of less than 100 μm were produced for testing and characterization. A twin-screw extrusion was used to compound PLA and natural fibers, and extruded composites were injection molded to test samples. Flexural and Izod impact test, TGA, soil burial test and SEM were used to investigate properties. All results were compared to a pure PLA matrix sample. The flexural modulus of the PLA increased with the addition of natural fibers, while the flexural strength decreased. The highest impact strength (34 J m⁻¹), flexural modulus (4.5 GPa) and flexural strength (90 MPa) were obtained for the composite made of PLA/kenaf (PLA-K), which means kenaf natural fibers are potential to be used as an alternative filler to enhance mechanical properties. On the other hand PLA-RH composite exhibits lower mechanical properties. The impact strength of PLA has decreased when filled with natural fibers; this decrease is more pronounced in the PLA-RH composite. In terms of thermal stability it has been found that the addition of natural fibers decreased the thermal stability of virgin PLA and the decrement was more prominent in the PLA-RH composite. Biodegradability of the composites slightly increased and reached 1.2 and 0.8% for PLA-K and PLA-RH respectively for a period of 90 days. SEM micrographs showed poor interfacial between the polymer matrix and natural fibers.     

Study on Biodegradable Starch/OMMT Nanocomposites for Packaging Applications

The thermoplastic starch (TPS) and nanocomposite(TPS/OMMT) was prepared with 15% carbamide, 15% ethanolamine and different contents of organic activated montmorillonite (OMMT) by twin-screw extruder with a 130 °C barrel temperature. Fourier transforms infrared spectroscopy and wide angle X-ray diffraction shown that the alkylamine in dodecyl benzyl dimethyl ammonium bromide could react with MMT via cation exchange reaction. After treated, the d(001)space distance of MMT increased from 1.5 to 1.7 nm. Scanning electron microscope revealed that the lower contents of OMMT could disperse well in the matrixes of TPS. The carbamide, ethanolamine and the OMMT could destroy the crystallization behavior of starch, but only the OMMT restrained this behavior for long-term storing. Mechanical properties investigation indicated that the tensile strength and modulus of TPS/OMMT nanocomposites were better than those of TPS, while the elongation at break was descended with the increasing of OMMT contents. When the content of OMMT was 4%, the tensile strength and modulus of TPS was improved from 4.2 and 42 MPa to 6.0 and 76 MPa, respectively.     

Biodegradable plastic made from soybean products. II. Effects of cross-linking and cellulose incorporation on mechanical properties and water absorption

Soy isolate was treated with formaldehyde and glyoxal at 1.0, 2.5, and 5.0% (w/w isolate) and with adipic and acetic anhydrides. The materials were then compression-molded into plastic tensile bars and tested for tensile and yield strength, percentage elongation, Young's modulus, and water absorption. Treatment with 5% formaldehyde increased the tensile strength significantly, to 4.9 kg/mm², compared with the untreated sample (3.7 kg/mm²). The yield strength increased slightly, to 0.68 kg/mm². Elongation was significantly less after treatment with formaldehyde. Young's modulus increased after treatment and leveled off at 174 kg/mm². Water absorption decreased as the formaldehyde concentration increased. Treatment with either glyoxal or adipic/acetic anhydride had a detrimental effect on the mechanical properties of the plastic specimens. Water absorption was decreased by glyoxal treatment but was not affected by adipic/acetic anhydride treatment. Long-fiber (lf), short-fiber (sf), and microcrystalline (mc) cellulose were incorporated into soy isolate at various levels. Cellulose addition decreased the percentage elongation and increased the rigidity of the plastic. All three cellulose additions increased Young's modulus. The tensile strength increased with the addition of sf-cellulose to soy isolate; lf-cellulose decreased the tensile strength, whereas the incorporation of mc-cellulose did not have a significant effect. The yield strength increased slightly with the addition of sf-cellulose and was less affected by the addition of lf- or mc-cellulose. All three types of cellulose slightly decreased water absorption at ca. 15% content.Journal Paper No. J-15563 of the Iowa Agriculture and Home Economics Experiment Station, Ames; Project No. 2863.     

Potential utilization of burned wood in manufacture of medium density fiberboard

The potential utilization of burned wood in the manufacture of medium density fiberboard (MDF) was investigated. For this aim, the MDF panels were made of various mixtures of burned pine wood (Pinus sylvestris L.), unburned beech (Fagus orientalis L.) and oak (Ouercus robur L.) woods under commercial conditions in an MDF company. The mixture ratio of the unburned beech and oak woods to the burned pine wood were 50/50 wt%. The mixing ratios of burned wood chips with unburned wood chips were 0:100, 25:75, 50:50, 75:25 and 100:0, %, respectively. A commercial urea–formaldehyde resin was used as a binder. The physical properties measured in the investigation included density and thickness swelling, while the mechanical properties examined were bending strength, modulus elasticity, internal bond, screw holding ability perpendicular to the plane of panel, and janka hardness perpendicular to the plane of the panel. Surface roughness and color of the panels were also measured. The results indicated that all the panels met the mechanical properties of general-purpose MDF requirements of EN 622-5. The surface roughness of the MDF panels containing burned wood decreased with increasing burned wood content but remained higher than the control panels. The dimensional stability of the MDF panels decreased with the incorporation of burned wood fibers as compared with the control MDF panels.     

Effects of using arsenic–iron sludge wastes in brick making

The arsenic–iron sludge generated in most of the treatment systems around the world is discharged into the nearest watercourse, which leads to accumulative rise of arsenic and iron concentrations in water. In this study, attempts were made to use the arsenic–iron sludge in making bricks and to analyze the corresponding effects on brick properties. The water treatment plant sludge is extremely close to brick clay in chemical composition. So, the sludge could be a potential substitute for brick clay. This study involved the addition of sludge with ratios 3%, 6%, 9% and 12% of the total weight of sludge–clay mixture. The physical and chemical properties of the produced bricks were then determined and evaluated and compared to control brick made entirely from clay. Results of different tests indicated that the sludge proportion and firing temperature were the two key factors in determining the quality of bricks. The compressive strength of 3%, 6%, 9% and 12% sludge containing brick samples were found to be 14.1 MPa, 15.1 MPa, 9.4 MPa and 7.1 MPa, respectively. These results indicate that the compressive strength of prepared bricks initially increased and then decreased with the increase of sludge proportion. Leaching characteristics of burnt bricks were determined with the variation of pH at a constant temperature. The optimum amount of sludge that could be mixed with clay to produce good bonding of clay–sludge bricks was found to be 6% (safely maximum) by weight.     

Effects of Storage Time on Properties of Soybean Protein-Based Plastics

Soybean protein has been considered as a potential biodegradable polymer in the manufacture of plastics. The purpose of this investigation was to characterize the effect of storage time on thermal and mechanical properties of soybean protein isolate (SPI) plastics. SPI was separated from defatted soy flour, modified with 1M or 2M urea, or plasticized with glycerol, and compression molded into plastics. Plastic made from SPI alone was used as a control. For all SPI plastics, glass transition temperatures and dynamic storage modulus increased and loss tangent decreased during storage. Excess enthalpy of relaxation of all SPI plastics had an exponential relationship with storage time, indicating a fast aging rate at the beginning of storage. All SPI plastics tended to be stiff and brittle during storage. The plastics with glycerol had the slowest aging rate and were fairly stable after 60 days, with about 8.8 MPa tensile strength and 168% strain at break. Plastics with the 2M urea-modification SPI also had a slow aging rate and became relative stable after 60 days, with about 10 MPa tensile strength and 72% elongation.     

Effects of recycled glass substitution on the physical and mechanical properties of clay bricks

In this study, wasted glasses from structural glass walls up to 45 wt.% were added into clay mixtures in brick manufacturing process. Physical and mechanical properties of clay bricks were investigated as functions of the wasted glass content and the firing temperature. The results indicated that with proper amount of wasted glasses and firing temperature, clay bricks with suitable physical and mechanical properties could be obtained. The compressive strength as high as 26–41 MPa and water absorption as low as 2–3% were achieved for bricks containing 15–30 wt.% of glass content and fired at 1100 °C. When the glass waste content was 45 wt.%, apparent porosity and water absorption was rapidly increased.     

Fabrication and Characterization of Biodegradable Composite Films Made of Using Poly(caprolactone) Reinforced with Chitosan

Chitosan was dissolved in 2?% aqueous acetic acid solution and the films were prepared by solution casting. Values of tensile strength (TS), tensile modulus (TM), elongation at break (Eb?%) and water vapor permeability (WVP) of the chitosan films were found to be 30?MPa, 450?MPa, 8?% and 4.7?g?mm/m²?day?kPa, respectively. Poly(caprolactone) (PCL) films were prepared from its granules by compression molding and the values of TS, TM, Eb and WVP were 14?MPa, 220?MPa, 70?% and 1.54?g?mm/m²?day?kPa, respectively. PCL was reinforced with chitosan films, and composite films were prepared by compression molding. Amount of chitosan in the composite films varied from 10 to 50?% (w/w). It was found that with the incorporation of chitosan films in PCL, both the values of TS and TM of composite films increased significantly. The highest mechanical properties were found at 50?% (w/w) of chitosan content. The Oxygen transmission rate (OTR) of composite film was found to decrease significantly than PCL films. Thermal properties of the composite were also improved as compared to PCL. The water uptake test of the composite also showed promising results with a good stability of composite films. The interface of the composite was investigated by scanning electron microscopy and showed good interfacial adhesion between PCL and chitosan films.     

Effect of carbon dioxide injection on production of wood cement composites from waste medium density fiberboard (MDF)

The possibility of recycling waste medium density fiberboard (MDF) into wood-cement composites was evaluated. Both new fibers and recycled steam exploded MDF fibers had poor compatibility with cement if no treatment was applied, due to interference of the hydration process by the water soluble components of the fiber. However, this issue was resolved when a rapid hardening process with carbon dioxide injection was adopted. It appears that the rapid carbonation allowed the board to develop considerable strength before the adverse effects of the wood extractives could take effect. After 3-5 min of carbon dioxide injection, the composites reached 22-27% of total carbonation and developed 50-70% of their final (28-day) strength. Composites containing recycled MDF fibers had slightly lower splitting tensile strength and lower tensile toughness properties than those containing new fibers especially at a high fiber/cement ratio. Composites containing recycled MDF fibers also showed lower values of water absorption. Unlike composites cured conventionally, composites cured under CO(2) injection developed higher strength and toughness with increased fiber content. Incorporation of recycled MDF fibers into wood cement composites with CO(2) injection during the production stage presents a viable option for recycling of this difficult to manage waste material.     

Assessment of the recycling potential of fresh concrete waste using a factorial design of experiments

Recycling of industrial wastes and by-products can help reduce the cost of waste treatment prior to disposal and eventually preserve natural resources and energy. To assess the recycling potential of a given waste, it is important to select a tool capable of giving clear indications either way, with the least time and work consumption, as is the case of modelling the system properties using the results obtained from statistical design of experiments. In this work, the aggregate reclaimed from the mud that results from washout and cleaning operations of fresh concrete mixer trucks (fresh concrete waste, FCW) was recycled into new concrete with various water/cement ratios, as replacement of natural fine aggregates. A 3² factorial design of experiments was used to model fresh concrete consistency index and hardened concrete water absorption and 7- and 28-day compressive strength, as functions of FCW content and water/cement ratio, and the resulting regression equations and contour plots were validated with confirmation experiments. The results showed that the fresh concrete workability worsened with the increase in FCW content but the water absorption (5–10 wt.%), 7-day compressive strength (26–36 MPa) and 28-day compressive strength (32–44 MPa) remained within the specified ranges, thus demonstrating that the aggregate reclaimed from FCW can be recycled into new concrete mixtures with lower natural aggregate content.     

Improving Water Resistance of Soy-Based Adhesive by Vegetable Tannin

In this research tannic acid was used to prepare soy-based adhesives for making plywood and fiber board. The different resin formulations were analyzed by Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and its derivative as a function of temperature (DTG) and Fourier Transform Infra-red (FTIR) spectroscopy. The results showed that the addition of tannic acid to soy-based adhesive decreased soy-based adhesive viscosity and its pH. The DSC analysis showed that the denaturation temperature of soy-based adhesives decrease by adding tannic acid. The TGA and DTG curves showed that the thermal degradation of soy flour starts above 146 °C. The FTIR spectroscopy results also showed that the soy flour amino acids appeared to react well with tannic acid. Furthermore, delamination and shear strength test results showed the good water resistance of plywood bonded with soy-based tannic acid-modified adhesive. The mechanical and physical properties such as MOR, MOE, IB, and water resistance of fiberboard were improved, by adding tannic acid to the soy-based adhesive.     

Sorting efficiency and combustion properties of municipal solid waste during bio-drying

One aerobic and two combined bio-drying processes were set up to investigate the quantitative relationships of sorting efficiency and combustion properties with organics degradation and water removal during bio-drying. Results showed that the bio-drying could enhance the sorting efficiency of municipal solid waste (MSW) up to 71% from the initial of 34%. The sorting efficiency was correlated with water content negatively (correlation coefficient, r = −0.89) and organics degradation rate positively (r = 0.92). The higher heating values (HHVs) were correlated with organics degradation negatively for FP (i.e. the sum of only food and paper) (r = −0.93) but positively for the mixing waste (MW) (r = 0.90), whereas the lower heating values (LHVs) were negatively correlated with water content for both FP (r = −0.71) and MW (r = −0.96). Other combustion properties depended on organics degradation performance, except for ignition performance and combustion rate. The LHVs could be greatly enhanced by the combined process with insufficient aeration during the hydrolytic stage. Compared with FP, MW had higher LHVs and ratios of volatile matter to fixed carbon. Nevertheless, FP had higher final burnout values than MW.     

Development of Proteinous Bioplastics Using Bloodmeal

The aim of this work was to investigate the use of bloodmeal as a thermoplastic biopolymer. Processing required water and chemical additives to perform three main functions: breaking covalent cross-links using sodium sulfite (SS), sodium dodecyl sulfate and urea as processing aids, and evaporating some processing water to allow formation of new interactions to stabilize the final structure. Extrusion was only possible in the presence of SS and strongly influenced by water and urea content. It was found that once water had been removed, mechanical properties increased significantly, indicating the formation of new intermolecular forces. SDS was required for processing and consolidation, but, it may restrict formation of new intermolecular forces, if used in excessive quantities. Materials based on optimal additive levels had a tensile strength of 8 MPa, Young’s modulus of 320 MPa and toughness 1.6 MPa m^½.