Effect of Protein Surface Hydrophobicity and Surface Amines on Soy Adhesive Strength.

Soy is considered one of the most promising natural materials for manufacturing wood adhesives due to its low cost, high protein content, and ready availability. However, more cost-effective ways of improving its wet shear strength are needed to achieve wider market acceptance. Protein adhesive wet strength depends on the use of (typically expensive) crosslinking additives as well as the processing/denaturation of the protein. It has been commonly stated in the literature that protein denaturation leads to higher bond strength by activating the surface and exposing the reactive groups. Therefore, we investigated how differences in surface reactive groups (surface hydrophobicity and reactive amine groups) brought on with different denaturation treatments relate to bonding performance. Fourteen soy protein isolates (SPIs) with different denaturation histories were investigated. Characterization of the SPIs included surface hydrophobicity, surface amine content, extent of protein hydrolysis, and bond strength (wet and dry, with and without polyamidoamine epichlorohydrin (PAE) crosslinking agent) by ASTM D7998. The molecular weight patterns showed that proteins denatured by extensive hydrolysis had very low bond strengths. Adding the crosslinker, PAE, improved all the shear strength values. We found that the number of water-accessible reactive amine groups on protein surfaces had no impact on the adhesive strength, even with the amine-reactive crosslinker, PAE. Conversely, increased surface hydrophobicity was beneficial to adhesive strength in all cases, though this correlation was only statistically significant for wet strength without PAE. While, in general, denatured proteins are typically thought to form better bonds than native state proteins, this work suggests that it matters how proteins are denatured, and what surfaces become exposed. Denaturation by hydrolysis did not improve bond strength, and extensive hydrolysis seemed highly detrimental. Moreover, exposing hydrophobic surface groups was beneficial, but exposing covalent bond-forming reactive amine groups was not.

Preparation of Thermoplastic Cellulose Esters in [mTBNH][OAC] Ionic Liquid by Transesterification Reaction.

The transesterification of cellulose with vinyl esters in ionic liquid media is suggested as a prospective environmentally friendly alternative to conventional esterification. In this study, various long-chain cellulose esters (laurate, myristate, palmitate, and stearate) with a degree of substitution (DS) up to 1.8 have been synthesized in novel distillable ionic liquid, [mTBNH][OAC]. This IL has high dissolving power towards cellulose, which can improve homogeneous transesterification. Additionally, [mTBNH][OAC] has durability towards recycling and can be regenerated and re-used again for the next cycles of esterification. DMSO is used as a co-solvent because of its ability to speed up mass transport due to lower solvent viscosity. The optimization of the reaction parameters, such as co-solvent content, temperature (20-80 °C), reaction time (1-5 h), and a molar ratio of reactants (1-5 eq. AGU) is reported. It was found that within studied reaction conditions, DS increases with increasing reaction time, temperature, and added vinyl esters. Structure analysis using FTIR, 1H, and 13C NMR after acylation revealed the introduction of the alkyl chains into cellulose for all studied samples. The results also suggested that the substitution order of the OH group is C7-O6 > C7-O2 > C7-O3. Unique, complex thermal and rheological investigation of the cellulose esters shows the growth of an amorphous phase upon the degree of substitution. At the same time, the homogeneous substitution of cellulose with acyl chains increases the melt viscosity of a material. Internal plasticization in cellulose esters was found to be the mechanism for the melt processing of the material. Long-chain cellulose esters show the potential to replace commonly used externally plasticized cellulose derivatives.

Tensile and Surface Wettability Properties of the Solvent Cast Cellulose Fatty Acid Ester Films.

Thermoplastic cellulose esters are promising materials for bioplastic packaging. For that usage, it is important to understand their mechanical and surface wettability properties. In this study, a series of cellulose esters are prepared, such as laurate, myristate, palmitate, and stearate. The aim of the study is to investigate the tensile and surface wettability properties of the synthesized cellulose fatty acid esters to understand their suitability as a bioplastic packaging material. Cellulose fatty acid esters are first synthesized from microcrystalline cellulose (MCC), then dissolved in pyridine solution, and after the solvent cast into thin films. The cellulose fatty acid ester acylation process is characterized by the FTIR method. Cellulose esters hydrophobicity is evaluated with contact angle measurements. The mechanical properties of the films are tested with the tensile test. For all the synthesized films, FTIR provides clear evidence of acylation by showing the presence of characteristic peaks. Films' mechanical properties are comparable to those of generally used plastics such as LDPE and HDPE. Furthermore, it appears that with an increase in the side-chain length, the water barrier properties showed improvement. These results show that they could potentially be suitable materials for films and packaging materials.

Investigation of Efficient Alkali Treatment and the Effect of Flame Retardant on the Mechanical and Fire Performance of Frost-Retted Hemp Fiber Reinforced PLA.

This research investigates an effective alkali (NaOH) treatment and fire-retardant coating to produce biocomposites from frost-retted hemp fiber and PLA. The fiber surface treatment with various NaOH concentrations was investigated throughout a range of soaking times. The results show that the extracted non-cellulosic fiber content increases with treatment duration and NaOH concentration, while the fraction of targeted components removed remains nearly unchanged after soaking for 1, 2, and 4 h with a 5 wt.% NaOH solution. At the composite level, the treatment with 5 wt.% NaOH solution for 1 h emerged as the most efficient, with tensile strength, Young's modulus, flexural strength, and flexural modulus of 89.6 MPa, 9.1 GPa, 121.6 MPa, and 9.6 GPa, respectively, using 30 wt.% fibrous reinforcement. The fire performance of the examined batches of biocomposites improved significantly with the novel fire-retardant (Palonot F1) coating. However, the tensile strength notably decreased, while the flexural properties showed only a slight reduction. In most cases, the biocomposites with the alkali-treated hemp fiber had delayed ignition during the 5 min exposure to the cone heater. The findings in this work contribute to studies that will be required to give design guidelines for sustainable building options.

Effect of Hemp Fiber Surface Treatment on the Moisture/Water Resistance and Reaction to Fire of Reinforced PLA Composites.

The effects of surface pretreatment (water and alkali) and modification with silane on moisture sorption, water resistance, and reaction to fire of hemp fiber reinforced polylactic acid (PLA) composites at two fiber loading contents (30 and 50 wt.%) are investigated in this work. Moisture adsorption was evaluated at 30, 50, 75 and 95% relative humidity, and water resistance was determined after a 28-day immersion period. The cone calorimetry technique was used to investigate response to fire. The fiber surface treatment resulted in the removal of cell wall components, which increased fiber individualization and homogeneity as shown in scanning microscopic pictures of the composite cross-section. Although the improved fiber/matrix bonding increased the composite's water resistance, the different fiber treatments generated equal moisture adsorption results for the 30 wt.% reinforced composites. Overall, increasing the fiber amount from 30 to 50 wt.% increased the composite sensitivity to moisture/water, mainly due to the availability of more hydroxyl groups and to the development of a higher pore volume, but fire protection improved due to a reduction in the rate of thermal degradation induced by the reduced PLA content. The new Oswin's model predicted the composite adsorption isotherm well. The 30 wt.% alkali and silane treated hemp fiber composite had the lowest overall adsorption (9%) while the 50 wt.% variant produced the highest ignition temperature (181 ± 18 °C).

The Effect of Prestressing and Temperature on Tensile Strength of Basalt Fiber-Reinforced Plywood.

The reinforcement of plywood is demonstrated by laminating pretensioned basalt fibers between veneer sheets, to fabricate so-called prestressed plywood. Belt type basalt fibers bearing a specific adhesion promoting silane sizing were aligned between veneer sheets with 20 mm spacing and were pretensioned at 150 N. Three-layer plywood samples were prepared and tested for tensile strength at room temperature and at 150 °C. The room temperature tensile tests revealed a 35% increase in tensile strength for prestressed plywood compared to that of the conventional specimen. The reinforcement effect deteriorated at 150 °C but was restored upon cooling to room temperature. The deterioration is attributed to the weakening of bonding between the basalt fibers and phenolic resin matrix at elevated temperatures due to the softening of the resin.