Physicochemical Properties and Adhesion Performance of Canola Protein Modified with Sodium Bisulfite

The objective of this research was to study the adhesion properties of sodium bisulfite (NaHSO₃)-modified canola protein. Protein was extracted from canola meal through alkali solubilization and acid precipitation methods, then modified with different concentrations of NaHSO₃ (0–15 g/L) during the isolation process. As NaHSO₃ concentration increased, canola protein purities decreased. Amino acid profiles showed that the hydrophobic amino acids in canola protein constituted only 27% of total protein, indicating that canola protein is mostly hydrophilic. The reducing effects of NaHSO₃ were exerted on canola protein through the breaking of disulfide bonds in both its cruciferin and napin components, as reflected by the protein electrophoresis profile, DSC data, and morphological images. The wet protein isolates were used as adhesives. The greatest wet shear strength of canola protein adhesive without modification was 3.97 MPa with 100% wood cohesive failure (WCF), observed at a curing temperature of 190 °C. NaHSO₃ had slight weakening effects on the adhesion performance of canola protein. Canola protein modified with 3 g/L NaHSO₃ exhibited wet shear strength similar to the control at 190 °C and higher strength at 150 and 170 °C. The NaHSO₃ modification significantly improved handling and flowability of canola protein adhesives.     

Laccase/TEMPO-modified lignin improved soy-protein-based adhesives: Adhesion performance and properties

The aim of this study was to enhance the water resistance of soy protein (SP) adhesives using laccase/TEMPO-modified lignin. Kraft lignin was depolymerized by laccase enzyme in the presence of TEMPO to expand the oxidation reaction of both phenolic and non-phenolic compounds. This simplified process has the distinct advantage of enhancing lignin-protein interaction. Compared with SP adhesives, lignin-protein adhesives showed a stronger elastic modulus, higher thermal stability, and increased wet adhesion performance. Wet shear strength increased by 106% from 0.693 to 1.429 MPa, and partial wood failure was observed after the test. Better performance was also observed in the three-cycle soaking test. At the same time, the stronger interactions between -COO^- and -NH₂ groups of protein and lignin led to a decrease in flowability and spreadability.     

Development of High-Strength Soy Protein Adhesives Modified with Sodium Montmorillonite Clay

This study investigated the high strength of a soy protein adhesive system with good flowability at high protein concentration. Sodium montmorillonite (Na MMT), the most widely used silicate clay, was incorporated into viscous, cohesive soy protein adhesives at concentrations ranging from 1 to 11 % (dry basis, w/w). Hydroxyethyl cellulose was used as a suspension agent to stabilize the soy protein and nano clay to be the dispersion system. The interaction between soy protein and Na MMT was characterized by XRD, FTIR, Zeta potential and DSC. Results indicated that soy protein molecules were adsorbed on the surface of the interlayer of Na MMT through hydrogen bonding and electrostatic interaction. The soy protein/Na MMT adhesives had the intercalation structure with Na MMT contents ranging from 1 to 11 %. Adhesion strength, specifically wet adhesion strength, of soy protein adhesives at isoelectric point (pI) was significantly improved by the addition of Na MMT. It is believed that the physical cross‐linking reactions between soy protein and Na MMT mainly contribute to the improved adhesion performance of soy protein adhesives. Wet adhesion strength increased from 2.9 MPa of control soy protein adhesive to 4.3 MPa at 8 % Na MMT. An increase of pH beyond pI value resulted in decreased adhesion strength due to increased surface charges of soy protein and slightly reduced affinity of soy protein on the nano clay surface.     

Physicochemical Properties of Soy Protein Adhesives Obtained by In Situ Sodium Bisulfite Modification During Acid Precipitation

Successful industrial applications of soy protein adhesives require high adhesion strength and low viscosity at high solid protein concentration. This study examined the effects of β-conglycinin (7S) and glycinin (11S) ratios on the physicochemical properties of soy protein adhesives. Soy protein adhesives with various 7S/11S ratios were extracted from soy flour slurry modified with sodium bisulfite using the acid precipitation method, which is based on the different solubilities of 7S and 11S globulins. Seven glycinin-rich soy protein fractions and six β-conglycinin-rich soy protein fractions were obtained. The external morphology of the samples changed from the viscous cohesive phase to the clay-like phase without cohesiveness. The viscous cohesive samples had good flowability and good water resistance with a wet adhesion strength of 2.0–2.8 MPa. They were stable for up to several months without phase separation at room temperature. Based on the results, we suggest that proper protein–protein interaction, hydration capacity (glycinin-rich soy protein fractions), and certain ratios of 7S and 11S (β-conglycinin rich soy protein fractions) in the soy protein sample are crucial to continuous protein phase formation. Hydrogen bonding, electrostatic forces, and hydrophobic interactions are involved in maintaining the protein viscous cohesive network, whereas disulfide bonds do not exert significant effects. This study describes a new way to investigate viscous cohesive soy protein systems with high solid protein content, thus alleviating the disadvantages of traditional methods for studying the adhesive properties of soy protein isolates, which tend to have poor water resistance, low solid contents, and short storage life.     

Correlation between Physical Properties and Shear Adhesion Strength of Enzymatically Modified Soy Protein-Based Adhesives

This work was to correlate physical properties with adhesion properties of soy protein‐based adhesives. By building such a correlation, the adhesion properties can be predicted by measuring physical properties of soy protein‐based adhesives. In this context, three important physical properties, viscosity, tacky force, and water resistance, were selected to correlate with adhesion strength of enzymatically modified soy protein‐based adhesives (ESP). Response surface methodology, specifically central composite design, was used with three independent variables to prepare ESP: trypsin concentration (X₁), incubation time (X₂), and glutaraldehyde (GA) concentration (X₃). The three physical properties measured were all greatly affected by our three independent variables with significance at the 95 % confidence level. The responses were then correlated with the adhesion properties of ESP. In conclusion, viscosity can be used to predict the dry adhesion strength of ESP based on the coefficient of determination (R²) of 0.8558. In addition, tacky force and water resistance can be used to represent wet adhesion strength of ESP based on R² of 0.7082 and 0.6930, respectively (P < 0.05). This work preliminarily identified the significant physical properties that can predict the adhesion strength of the ESP system crosslinked with GA, but the results need to be further confirmed by another protein modification system to give a generic conclusion.     

Soy Protein Adhesive Blends with Synthetic Latex on Wood Veneer

Environmental pollution has prompted an interest in and a need for bio-based wood adhesives. Modified soy protein has shown adhesion properties similar to those of formaldehyde based adhesives. The objective of this research was to investigate the compatibility of a modified soy protein (MSP) with six commercial synthetic latex adhesives (SLAs). Four different blending ratios of MSP and SLAs were studied. Adhesion; structural change; and rheological, thermal, and morphological properties of the MSP/SLAs blends were characterized. Dry adhesion strength of MSP, SLAs and their blends were all similar with 100% wood cohesive failure. Water resistance of all six SLAs was improved by blending with MSP in terms of the wet adhesion strength. The wet adhesion strength of MSP/PBG (40/60) blends was 6.416 MPa, as compared to 4.66 MPa of pure PBG (press bond glue, urea formaldehyde based resin). Viscosity of MSP/SLAs blends was reduced significantly and reached the lowest value at 40–60% MSP. Infrared spectra, thermal properties, and morphological images indicated that chemical reactions occurred between soy protein and PBG molecules. The MSP provided some functional groups, such as carboxylic (–COOH), hydroxyl (–OH) and amino groups (–NH₂), that cross-linked with hydroxymethyl groups (–CH₂–OH) of PBG, and also acted as an acidic catalyst for the self-polymerization of urea formaldehyde based resin.     

The effect of hydrolyzed soy protein isolate on the structure and biodegradability of urea–formaldehyde adhesives

The hydrolyzed soy protein isolate (HSPI) was used to partially substitute urea to synthesis modified urea–formaldehyde (UF) adhesives via copolymerization process, in order to reduce the dependency on petroleum-based chemicals and mitigate possible environmental pollution. The soy protein isolate (SPI), HSPI, and modified UF adhesives were characterized by attenuated total reflection Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), and thermo-gravimetric analysis (TGA). The bonding strength, adhesive properties, biodegradability, and micrographs of the UF and HSPI-modified UF after degradation were also measured. The results show that the SPI native structure is unfolded during the treatment with sodium hydroxide. The thermal stability of HSPI is better than SPI. HSPI can incorporate into the structure of cured UF adhesives with three different feeding methods. And the best bonding strength of modified UF adhesives is 1.31?MPa when HSPI is added at the first step. The formaldehyde emission of modified UF adhesives is lower compared with UF. The earlier the HSPI is added, the better the properties for modified UF adhesives can be obtained. The degradation rate of modified UF adhesives improved nearly two times compared to the UF after six months of degradation in biologically active soil. There are microorganisms adhering to the surface of modified UF from the SEM micrographs.     

Characterization of Fractionated Soy Proteins Produced by a New Simplified Procedure

It was possible to fractionate soy protein into two soy protein isolate fractions (>90% protein) enriched in either glycinin or β-conglycinin by using a new simplified procedure (referred to as the Deak procedure) employing CaCl₂ and NaHSO₃. The Deak procedure produced fractions with higher yields of solids, protein, and isoflavones, and similar protein purities as well as improved functional properties compared to fractions recovered by established, more complex soy protein fractionation procedures. The Deak glycinin-rich fraction comprised 15.5% of the solids, 24.4% of the protein, and 20.5% of the isoflavones in the starting soy flour, whereas the glycinin-rich fraction of the established procedure (Wu procedure) comprised only 11.6% of the solids, 22.3% of the protein, and 9.6% of the isoflavones. The Deak β-conglycinin-rich fraction comprised 23.1% of the solids, 37.1% of the protein, and 37.5% of the isoflavones in the starting soy flour, whereas the Wu β-conglycinin-rich fraction comprised only 11.5% of the solids, 18.5% of the protein, and 3.3% of the isoflavones. Protein purities were >80% for both fractions when using both procedures. The Wu procedure produced protein fractions with slightly higher solubilities and similar surface hydrophobicities; whereas, the fractions produced by the Deak procedure had superior emulsification and foaming properties and similar dynamic viscosity behaviors.     

Adhesion properties of soy protein adhesives enhanced by biomass lignin

Soy protein adhesives have great potential as sustainable eco-friendly adhesives. However, low adhesion under wet conditions hinders its applications. The objective of this research was to enhance the water resistance of soy protein adhesives. The focus of this research was to understand the effect of protein to lignin ratio and lignin particle size i.e. large (35.66 μm), medium (19.13 μm), and small (10.26 μm) on the adhesion performance of soy protein adhesives as well as to characterize its rheological and thermal properties. Results showed that the lignin particle size and the protein to lignin ratio greatly affected the adhesion performance of soy protein adhesives. The addition of lignin slightly increased the viscosity, spreadability, and thermostability of soy protein adhesives. The wet strength of soy protein adhesives increased as lignin particle size decreased. Soy protein mixed with small size lignin at a protein to lignin ratio of 10:2 (w/w) at 12% concentration presented the lowest contact angle and the highest wet adhesion strength of 4.66 MPa., which is 53.3% higher than that of 10% pure soy protein adhesive. The improvements in adhesion performance and physicochemical properties of soy protein adhesives by lignin were ascribed to the interactions between protein and lignin. Lignin with smaller particle size increased the wet shear strength of soy protein adhesives because a larger surface area of lignin was available to interact with the protein.     

Isoelectric pH of polyamide–epichlorohydrin modified soy protein improved water resistance and adhesion properties

Protein macromolecules derived from plants have been considered as alternative resources for various applications, including adhesives, films, rubbers, and biocomposites. Plant protein polymers are pH sensitive and need to be modified to meet application performance. This study demonstrated interactions between polyamide–epichlorohydrin (PAE) and soy protein as affected by pH and temperature. PAE and soy protein molecules formed reversible ionic complexes at room temperature at a pH range of 4–9. The complexation interactions acted as physical crosslinking, which stabilized the soy protein structure and increased its denaturation temperature and enthalpy. The viscosity of adhesives derived from the interaction of PAE and soy protein was affected significantly by the complexation formation, denaturation, and pH. The complexation interactions improved the adhesion properties of the PAE/modified soy protein. pH also played an important role in the adhesion performance, which was attributed to the pH dependence of the protein conformation and PAE/soy protein complexation interactions. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 103: 2261–2270, 2007     

Thermal properties and adhesiveness of soy protein modified with cationic detergent

This research studied the effects of cationic detergents on the adhesiveness and thermal properties of soy protein isolate (SPI). Three cationic detergents, hexadecyltrimethyl ammonium bromide, ethylhexadecyldimethyl ammonium bromide (EDAB), and benzyldimethylhexadecyl ammonium chloride, each at concentrations of 1.3, 2.6, 5.2, and 7.8 mM, were used to modify SPI. The effect of pH at selected EDAB concentrations was also studied. Results showed that both detergent concentration and pH had significant effects on the adhesiveness of modified SPI. SPI modified with detergent at a concentration of 2.6 mM yielded the greatest dry tensile strength and water resistance, which indicated that a moderate protein denaturation might be favorable to the adhesion of SPI. Both modified and unmodified SPI showed greater adhesive strength at their optimal pH values. Modified SPI showed greatest adhesive strength at pH 7, whereas unmodified SPI showed greatest adhesive strength at pH 4.5; the tensile strength of modified SPI was greater than that of unmodified SPI. The protein-denaturation temperature and the enthalpy of modified SPI adhesives were also analyzed by using DSC. Denaturation of the native structure of SPI increased as detergent concentration increased.     

Jet cooking dramatically improves the wet strength of soy adhesives

The impact of jet cooking on shear strength of soy-and-water adhesives was investigated to understand the higher shear strength of commercial soy protein isolates compared to soy flours. Soy flour-based wood adhesives are appealing because of their bio-based content, low formaldehyde emission, and low cost, but their commercial application is limited by low wet cohesive strength. Previous researchers proposed that the process of jet cooking (steam injection with high turbulence followed by rapid cooling) was responsible for the high (~3 MPa) wet shear strength of adhesives made with commercially produced soy protein isolate, using the ASTM D 7998 test. In this work, we show that jet cooking did dramatically increase the wet strength of laboratory-produced, native-state soy protein isolate from 0.6 to 3 MPa, a strength similar to many commercial isolates. Jet cooking was far less effective at developing wet strength of soy flours, but greatly increased the viscosity of virtually all our soy materials. We hypothesize that the benefits of jet cooking are primarily a result of nonequilibrium protein aggregation states because subsequent wet autoclaving of jet cooked soy proteins dramatically decreased wet strength. The dramatic differences in adhesive properties between commercial soy protein isolates and soy flours suggests that the common practice of using results obtained with commercial isolates to predict the performance of soy flour adhesives is inappropriate.     

Effects of the molecular weight on the properties of thermoplastics prepared from soy protein isolate

Commercial soy protein isolate (SPI) was fractionated into four fractions by an acidifying method from pH 5.7 to 4.5 with 2M HCl. A mixture of SPI with glycerin (50 g/100 g of dry SPI) was compression‐molded to obtain thermoplastic sheets. The weight‐average molecular weight (M_w) of the fractions, the structure, and the mechanical properties of the thermoplastic SPI sheets were investigated with light scattering, IR spectroscopy, wide X‐ray diffraction patterns, differential scanning calorimetry, ultraviolet spectroscopy, scanning electron microscopy, and tensile testing. After heating compression, the SPI sheets were transparent and exhibited a smooth and homogeneous structure. Moreover, the crystallinity degree of the thermoplastic SPI was obviously higher than that of the premix before compression because of the formation of intermolecular hydrogen bonding. The M_w's of the fractions were 1.17 × 10⁵ to 3.21 × 10⁵, and they increased with increasing pH value in fractionation. The mechanical properties and water resistance (R) of the SPI sheets increased with increasing M_w of the SPI fractions. The tensile strength and breaking elongation of the SPI sheets with an M_w value of 3.21 ×10⁵ were 5.7 MPa and 135%, respectively, and the R value was 0.54 after immersion in water for 15 days. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3373–3380, 2001     

Soy proteins as plywood adhesives: formulation and characterization

Soybean proteins have great potential as bio-based adhesives. The objectives of our study were to develop and characterize formaldehyde-free soybean wood adhesives with improved water resistance. Second-order response surface regression models were used to determine the effects of soy protein isolate concentration, sodium chloride, and pH on adhesive performance. All three variables affected both dry and wet strengths of bonded wood specimens. The optimum operation zone for preparing adhesives with improved water resistance is at a protein concentration of 28% and pH 5.5. Sodium chloride had negative effects on adhesive performance. Soy adhesives modified with 0.5% sodium chloride had dry strength, wet strength, and boiling strength of bonded specimens comparable to nonmodified soy adhesives. Rheological study indicated that soy adhesives exhibited shear thinning behavior. Adhesives modified with sodium chloride showed significantly lower viscosity and yield stress. Sodium chloride-modified soy adhesives formed small aggregates and had low storage moduli, suggesting reduced protein–protein interactions. These formaldehyde-free soy adhesives showed strong potential as alternatives to commercial formaldehyde-based wood adhesives.     

Urea-Modified Soy Globulin Proteins (7S and 11S): Effect of Wettability and Secondary Structure on Adhesion

This investigation characterized wettability and adhesive properties of the major soy protein components conglycinin (7S) and glycinin (11S) after urea modification. Modified 7S and 11S soy proteins were evaluated for gluing strength with pine, walnut, and cherry plywood and for wettability using a bubble shape analyzer. The results showed that different adhesives had varying degrees of wettability on the wood specimens. The 7S soy protein modified with urea had better wettability on cherry and walnut. The 11S soy protein modified with 1M urea had better wettability on pine. The 1M urea modification gave 11S soy protein the greatest bonding strength in all the wood specimens. The 3M urea modification gave 7S soy protein stronger adhesion on cherry and walnut than did 11S protein; but with pine, 11S soy protein had greater adhesion strength than 7S soy protein. Measurement of protein secondary structures indicated that the β-sheet played an important role in the adhesion strength of 3M urea-modified soy protein in cherry and walnut, while random coil was the major factor reducing adhesion strength of 7S soy protein modified with 1M urea.     

Processing and characterization of biodegradable soy plastics: Effects of crosslinking with glyoxal and thermal treatment

Processing and modification routes to produce and to improve properties of biodegradable plastics from soy isolate were studied. Soy isolate, acid‐treated and crosslinked soy were subsequently compounded, extruded, and injection molded. Acetic acid and glyoxal were examined concerning their suitability for acid treating and crosslinking of soy, and their effect on the final properties of the obtained materials. Heat treatment was also used as a possible methodology to crosslink the protein structure. The molded specimens were tested in terms of their tensile properties and solubility at different pHs, and were also evaluated for the degree of crosslinking and molecular weight distributions. The obtained plastics were rigid and brittle with stiffness ranging from 1436 MPa for soy, to 1229 MPa for glyoxal crosslinked soy, up to 2698 MPa for heat‐treated soy. The differences in stiffness were discussed in terms of the crosslinking efficiency and spatial distribution. The solubility profiles were studied as a function of the pH of the immersion solutions and the crosslinking degree of each material. A reduction in protein solubility with decreasing pH was observed, with a minimum between pH 4 and 5 and a resolubilization of the protein at pHs lower than pH 4 and greater than 8. Higher levels of crosslinking resulted in a decrease of the solubility and an aggregation of the protein molecules. The soy plastics proved to be very versatile materials with potential to be used in applications where quite demanding performances are expected, such as in the biomedical field. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 604–610, 2005     

Adhesion properties of soy protein crosslinked with organic calcium silicate hydrate hybrids

The objective of this work was to investigate if inorganic calcium silicate hydrate (CSH) hybrids would improve soy protein wet adhesion properties. 3‐aminopropyltriethoxysilane (APTES) was used as a crosslinking agent to make covalent linkage between organic soy protein and inorganic CSH phases. Soy protein–calcium silicate hydrate (MSP‐CSH) composites with different mole ratio of APTES were prepared and the effect of crosslinking reaction on physicochemical properties such as thermal, rheological, FTIR spectroscopic, and morphological and adhesion properties were studied with physical aging effect. Covalent linkage was observed between CSH and soy protein using the FTIR technique. With aging effect, the denaturation temperature (T_d) and enthalpies (ΔH_d) of each fraction of soy protein increased in DSC thermograms, representing higher thermal stability, and the viscoelasticity of the composites also increased. The roughly coated surface of the MSP‐CSH composite was observed in SEM images. All these changes further confirmed the interaction between CSH and soy protein molecules. Dry and wet adhesion strength of the MSP‐CSH composites was higher than the control MSP alone. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40693.     

Alkali-modified soy proteins: Effect of salts and disulfide bond cleavage on adhesion and viscosity

Soy protein isolates were treated with NaCl, Na₂SO₄, or Na₂SO₃ (disulfide bond-cleaving agent) at a pH of 10.0 and 50°C, and the effects of these salts on viscosity, adhesive strength on woods, and water resistance of the treated isolates were investigated. Viscosity and adhesive strength decreased with increasing concentrations of these salts. At a concentration of 0.1 M, these three salts reduced the viscosity of soy proteins with no significant adverse effects on adhesive strength and water resistance. Addition of 0.1 M NaCl, Na₂SO₄, or Na₂SO₃ reduced adhesive strength insignificantly from 1230 N to 1120, 1060, or 1013 N, respectively. The viscosity of protein isolate modified at pH 10.0 and 50°C in the absence of salts was >30,000 cP. Treatment with NaCl or Na₂SO₄ resulted in viscosity reductions to 6000 or 1050 cP, respectively. The Na₂SO₃ treatment yielded an isolate with the lowest viscosity of 110 cP and which retained adhesive and water-resistive properties. The water resistance of modified soy proteins with and without 0.1 M Na₂SO₃ treatment was not significantly different with 3.3 and 6.6% cumulative delaminations occurring after four water soaking cycles. Treatment with 0.1 M Na₂SO₃ resulted in an isolate with a 28% decrease in disulfide linkages.     

Role of Star‐Like Hydroxylpropyl Lignin in Soy‐Protein Plastics

Summary: Star‐like hydroxypropyl lignin (HL) was compounded into soy protein isolated (SPI) to develop a potential biodegradable plastic with better mechanical performance than pure sheet‐SPI. The structure and properties of the composite materials were characterized by WAXD, DSC, SEM, TEM and tensile tests. The addition of just 2 wt.‐% HL resulted in tensile strength (σ_b) of 16.8 MPa, 2.3 times that of pure sheet‐SPI, with no accompanying decrease in elongation at break as a result of strong interaction and with good miscibility among components. As the HL content increased, the HL molecules could self‐aggregate as oblate supramolecular domains, while the stronger interactions between HL and glycerol resulted in the detaching of glycerol from the SPI matrix. It can be concluded that the insertion of HL as single molecules into the SPI matrix would provide materials with optimum mechanical properties. Compared with other lignin/SPI composites, the stretching chains on HL play a key role in the improvement of mechanical properties because of a stronger adhesion of HL onto the SPI matrix as well as the interpenetration of SPI into supramolecular HL domains.

Schematic illustration of the supramolecular domain created by the aggregation of hydroxypropyl lignin, which can interpenetrate with soy protein isolate.     

Soy-based,tannin-modified plywood adhesives

In this research, two different types of commercial tannins, namely a hydrolysable tannin (chestnut) and a condensed flavonoid tannin (mimosa), were used to prepare two types of soy-based (soy flour (SF) and soy protein isolate) adhesives for making plywood. Thermogravimetric properties (TGA) and its derivative as function of temperature (DTG) of different soy-based adhesive were measured in the range 40°C–300°C. Thermomechanical analysis (TMA) from 25°C to 250°C was done for the different resin formulations. Duplicate three-ply laboratory plywood panels were prepared by adding 300 g/m² of the adhesives’ total resin solid content composed of SF or isolated soy protein (ISP), urea, chestnut, and mimosa tannin extracts with hexamine as hardener. Based on the results obtained, tannins can improve SF adhesion properties. The TMA showed that chestnut tannin extract appeared to react well with SF, while mimosa tannin extract appeared to react well with ISP. Matrix-assisted laser desorption ionization time of flight (MALDI-TOF) mass spectrometry also showed that among other reactions, the soy protein amino acids reacted with the tannins. Furthermore, delamination and shear strength test results showed the good water resistance of plywood bonded with soy-based tannin modified adhesive.