Jingjing Li,
Xiaona Li,
Jianzhang Li* and
Qiang Gao*
MOE Key Laboratory of Wooden Material Science and Application, MOE Engineering Research Center of Forestry Biomass Materials and Bioenergy, Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing, 100083, China. E-mail: lijingjing_0325@bjfu.edu.cn; gaoqiang@bjfu.edu.cn; lijianzhang126@126.com; Fax: +86 01062338083, +86 01062336912; Tel: +86 01062336912, +86 01062338083
First published on 16th September 2015
This study was conducted to evaluate the potential of peanut meal (PM) to produce plywood adhesives via sodium dodecyl sulfate (SDS) and ethylene glycol diglycidyl ether (EGDE) modification. Five-ply plywood specimens were fabricated to measure water resistance. The physical properties, cross section, thermal behavior, and functional groups of the resultant adhesives were characterized in detail. The results showed using SDS and EGDE in the adhesive formulation greatly improved the water resistance of the resultant adhesive by 90% and met the interior use plywood requirements. This improvement was attributed to three reasons: (1) SDS broke the structure of the PM protein and exposed inner active groups, which reacted with EGDE and formed a dense network to improve the water resistance of the resultant adhesive; (2) EGDE decreased the adhesive viscosity and led to the adhesive easily penetrating into wood and forming more interlocks; (3) the adhesive with SDS and EGDE created a smooth surface of the cured adhesive to prevent moisture intrusion. Additionally, compared with the peanut meal-based control adhesives, the viscosity of the cured adhesive was reduced by 95.8% to 24
140 mPa s, which further demonstrated that peanut meal has favorable potential as an alternative adhesive material for plywood.
In recent years, soy protein-based adhesive is currently the most commonly researched alternative adhesive.3,4 And the mainly disadvantage of the soy protein-based adhesive was the low water resistance. Within the past few years, researchers successfully used synthesized resin to improve the water resistance of the soy protein-based adhesive, such as phenol formaldehyde resin,5 polyamidoamine epichlorohydrin resins,6 latex,7 epoxy resin,8 and so on. However, all those researches were based on the single resource – soybean meal, which was easily affected by the soy market. And in order to further expand the protein resources, researchers have explored many other plant proteins for wood adhesives, such as wheat gluten and its protein fractions,9 corn germ protein,10 and jatropha seed protein.11 However, the adhesive prepared with the protein was low in these raw materials and the resultant adhesives were not practical for industrial application.
Peanut meal (PM) is a co-product of the extraction of peanut-based edible oil. China has the largest global peanut production industry ever since 1993,12 largely due to the fact that increased use of peanuts as feedstock for the edible oil industry has likewise increased PM production. Generally, peanut meal was used as livestock feed, fertilizer or fuel, which did not make full use of protein resource.
PM is quite rich in plant protein, with protein content 10–15% higher than soybean meal. The storage proteins of soybean meal are mainly composed of 11S globulins (glycinin), 7S globulins (vicilin), which account for approximately 70% of total storage proteins.13 Compared to the soy protein, about 87% of the peanut protein is globulin, consisting of two major fractions: arachin (glycinin) and conarachin (vicilin), which is higher than that in soy protein.14 For soy protein-based adhesive, the 7S and 11S globulins are main mass to produce the bond force in the adhesives, which contain massive active groups burred inside. These active groups can react with the chemical compounds to improve the water resistance of the resultant adhesive. Therefore, PM proteins have many notable features in common with soybean proteins, consequently, it is highly feasible to replace soybean meal with PM to develop wood adhesive – this can broadens the availability of protein sources of raw materials.
In the 1950s, PM as a raw material was firstly used as the wood adhesive, which consisting of hexane-extracted meal, sodium hydroxide, sodium silicate, calcium hydroxide, and carbon disulfide–carbon tetrachloride.15,16 In this formulation, the denatured peanut protein molecular chains formed the mutual entanglement structures and hydrogen bonds and produce mechanical properties during the long curing process. However, the hydrogen bonds were easily broken in the wet state, resulting in the poor water resistance of the adhesive. In the past 10 years, only one article has appeared on wood adhesives with peanut protein. Yang used the peanut, soybean, and blood meal protein hydrolyzates, mixing with phenol-formaldehyde (PF), to develop wood adhesive and found using PM with PF resin have a low water resistance.17 From another perspective of view, in this research, PM was used as a filler to modify PF resin, which was not a protein-based adhesive. With the progress on the soy protein-based adhesive, using PM as a raw material to develop wood adhesive became more feasible.
Considering the property of the PM, SDS used as a denature agent to break the structure of PM protein and expose inner active groups. Then, using EGDE, containing epoxy groups, may react with the exposed hydrophilic groups in protein and form a network to improve the water resistance of the adhesive, which make a feasible way to develop PM-based wood adhesive. In addition, EGDE with low viscosity may reduce the viscosity of the resultant adhesive and make it easily penetrated into wood to produce more interlock, which increase the water resistance and solid content of the adhesive. In this study, peanut meal flour, SDS, and EGDE were used to develop the proposed peanut meal-based adhesive, and five-ply plywood was fabricated to measure the water resistance of the adhesive. The cross section, thermal behavior, and functional groups of the cured adhesives were used to investigate the mechanism of water resistance enhancement and explore the adhesive potential of PM. The primary goals of this study are proving the feasibility of PM as an effective plywood adhesive, adding value to peanut crop production, and promoting the utilization of PM.
| Amino acids | Wt (%) |
|---|---|
| Aspartic acid (Asp) | 5.04 |
| Threonine (Thr) | 1.61 |
| Serine (Ser) | 2.28 |
| Glutamic acid (Glu) | 8.26 |
| Glycine (Gly) | 1.95 |
| Alanine (Ala) | 1.99 |
| Valine (Val) | 2.03 |
| Isoleucine (Ile) | 2.05 |
| Leucine (Leu) | 3.50 |
| Tyrosine (Tyr) | 1.53 |
| Phenylalanine (Phe) | 2.29 |
| Histidine (His) | 1.76 |
| Lysine (Lys) | 2.81 |
| Arginine (Arg) | 3.26 |
| Proline (Pro) | 2.29 |
Once EGDE was introduced, however (adhesive C), all ten specimens didn't delaminate after the third cycle, indicating that the water resistance of the bonded plywood significantly increased, which met the interior plywood requirements described in the American National Standard 2000 (ANSI/HPVA HP-1). The EGDE added during the adhesive preparation process reacted with side-chain functional groups of some of the peanut protein amino acids, such as Ph–OH (Tyr), –NH– (primary chain of the peptide and Arg), –C
C– (tryptophan), and –SH (cysteine) and formed several water-resistant chemical bonds during the curing process, which generated network structures that prevented water intrusion and improved cross-linking density, thus enhancing the bond strength of the resultant plywood.20 Scheme 1 depicts this reaction in detail. For adhesive D, three out of ten specimens bonded by the resultant adhesive delaminated and failed to meet the standard requirements for interior plywood, indicating that the utilization of SDS was necessary in this experiment. Additionally, plywood samples were not able to be prepared by adhesive E, which was attributed to two reasons: one was its low viscosity, which may over-penetrate an adhesive to the wood's internal structure. The other reason was the difficulty to cure, which should add a curing agent. Therefore, adhesive E will no longer be discussed.
000 mPa s, depending on the application and the nature of the materials to be glued.21
The apparent viscosity versus shear rate of different adhesive formulations is shown in Fig. 1. As shear rate increased, the apparent viscosity of all adhesives decreased, until viscosity then grew stable and did not decrease with further increase in shear rate; this demonstrated the shear thinning behavior of the adhesives, defining them as pseudoplastic fluids. For adhesive A, the highest initial viscosity was 338
300 mPa s – too high to flow, to where adhesive A was not able to be applied effectively on the veneer surface, preventing mechanical inter-locking between the wood and adhesive during the curing process and resulting in low shear strength.
![]() | ||
| Fig. 1 Apparent viscosity of different adhesive formulations: (A) the PM adhesive, (B) the PM/SDS adhesive, (C) the PM/SDS/EGDE adhesive, (D) the PM/EGDE adhesive. | ||
The initial viscosity of the adhesive B increased 68.3%, from 338
300 to 569
200 mPa s. SDS use increased viscosity by swelling and unfolding protein molecules, decreasing the distance and increasing the friction between them. Moreover, the axial ratio or axis of rotation of protein molecules increased due to swelling and unfolding, further increasing viscosity.15 Incorporating EGDE dramatically decreased the initial viscosity of the adhesive by 95.8%, from 569
200 to 24
140 mPa s, because the viscosity of EGDE is very low and the material has small molecular substance – these qualities lubricate protein molecules so that EGDE acts as a disperser, distributed throughout the PM to decrease the viscosity of the resultant adhesive.22 Compared to adhesive C, the viscosity of adhesive D was decreased by 41.9% from 24
140 to 14
030 mPa s. The result further proofed that the use of SDS improved the viscosity in this experiment.
![]() | ||
| Fig. 2 The cross sections of cured adhesives in different formulations: (A) the PM adhesive, (B) the PM/SDS adhesive, (C) the PM/SDS/EGDE adhesive, (D) the PM/EGDE adhesive. | ||
![]() | ||
| Fig. 3 TGA/DTG curves of different adhesive formulations: (A) the PM adhesive, (B) the PM/SDS adhesive, (C) the PM/SDS/EGDE adhesive, (D) the PM/EGDE adhesive. | ||
Wood begins to decompose around 220 °C,26 Regions I was important for the application of the modified peanut meal-based adhesive. So the thermal behavior of the adhesive would be discussed in Regions I. Comparing adhesive A with B, the initial temperature of degradation was decreased from 176.9 to 174.5 °C (Table 3), indicating that the use of SDS decreased the thermal stability of the resultant adhesive, as the same result was gated comparing adhesive D (167.2 °C) with C (160.2 °C). Because SDS broke intra-molecular and intermolecular hydrogen bonds, and destroyed the secondary and tertiary structure of protein molecules. For adhesives B and C, the initial temperature of degradation was decreased from 174.5 to 160.2 °C and a new peak (177 °C) appeared in the DTG curves of adhesive C blends at Region I, due to further chemical reaction having occurred between EGDE and peanut protein. This chemical reaction could further increase the cross-linking density of the adhesive and improve the water resistance of the resultant plywood, which was in accordance with the result of Luo's research.20
In Regions III, the TGA curves may show the property of adhesives with EGDE and side reflect the reason about the increase of the water resistance. So the thermal behavior of the adhesive would also be discussed in Regions III. The main decomposition temperature of blends at Region III significantly increased from 314 to 326 °C between adhesives B and C, respectively, suggesting that the thermal stability of adhesive C was better than that of adhesive B, and likely further implying that the cross-linking reaction between peanut protein and EGDE formed a large amount of chemical bonds and increased the cross-linking density. This analysis provided further evidence that EGDE, SDS, and peanut protein successfully formed high quality adhesives.
O in-plane bending.29
![]() | ||
| Fig. 4 FTIR spectrums of different adhesive formulations: (A) the PM adhesive, (B) the PM/SDS adhesive, (C) the PM/SDS/EGDE adhesive, (D) the PM/EGDE adhesive. | ||
| Wavenumber (cm−1) | Description |
|---|---|
| 3600–3000 | Free and bound O–H and N–H groups |
| 2927 | Symmetric –NH2 stretch |
| 2870 | Asymmetric –NH2 stretch |
| 1737 | C O stretch (ester) |
| 1659 | C O stretch, (amide I) |
| 1542 | N–H bend, (amide II) |
| 1450 | –CH2 (deformation) of methylol groups |
| 1394 | COO– bend |
| 1245 | C–N stretch, N–H bend, (amide III) |
| 1034 | –C–NH2 bend |
Compared to adhesive A, there was no new peak in the FTIR spectra of adhesive B, and a same result was observed between adhesive C and D, implying that the interaction was only a protein denaturation process rather than a chemical reaction. This observation is consistent with previous research.23 For adhesive C, the absorption peak areas of COO– (1394 cm−1)30 dropped lower than the peak at 1450 cm−1 of adhesive B,31 likely because the epoxy groups of EGDE resin connected with the COO– groups of peanut protein during the curing process, which suggest that the amount of hydrophilic groups in the adhesive decreased after introducing the EGDE, altogether improving the water resistance of the adhesive. A new peak was observed at 1737 cm−1, attributed to the stretching vibrations of ester C
O. This peak indicates that the epoxy group in the EGDE reacted with the carboxyl group of the peanut protein, forming ester linkage. The decrease of hydrophilic groups (peanut protein) and the formation of cross-linking structures (adhesive C) provide evidence that further proves that PM can, in fact, be utilized successfully to prepare protein adhesives.
Using SDS to formulate adhesive increased the water resistance of the resultant plywood by 10%, attributing to the protein molecules denaturation and inner hydrophobic amino acids exposition.
Using EGDE reacted with the exposed active groups of the peanut protein molecules and formed additional network structures, markedly improving the cross-linking density of the resultant adhesive by 90%. In addition, introducing EGDE created a smooth surface of the cured adhesive to prevent moisture intrusion and reduced adhesive viscosity to form more interlock with wood surface, which further improved the water resistance of the adhesive.
The viscosity of the PM/SDS/EGDE adhesive was reduced by 95.8% to 24
140 mPa s and the water resistance of its resultant plywood met interior use plywood requirements, proving that peanut meal has the potential to be utilized readily and successfully to prepare bio-based adhesives.
| This journal is © The Royal Society of Chemistry 2015 |