Soy flour adhesive modified with urea, citric

acid and boric acid

Abstract
Purpose
The purpose of this paper is to investigate an adhesive prepared from soy flour (SF) modified with
urea, citric acid and boric acid as an environmentally friendly product for the wood industry.

Design/methodology/approach
Urea solution was prepared at 30°C and then SF was added and stirred at 30°C for 2 hours. Citric
acid solution was added and stirred for another 0.5 hours and then boric acid solution was added
and heated at 30°C for a further 0.5 hours. The resulting adhesive was used to bond poplar veneers.
Shear strength was measured to evaluate the bonding property of the adhesive. Viscometry and FT‐
IR spectrometry were used to test the viscosity and chemical changes, respectively.

Findings
Soy protein has potential value in the preparation of adhesives because of its unique functional
characteristics. The optimum formulation was 100 g of soy powder treated with 9 g of citric acid at
30°C for 0.5 hours in the presence of sodium dihydrogen phosphate (NaH2PO4). After addition of 6 
g of boric acid the resulting adhesive exhibited a shear strength of 0.82 MPa when bonded samples
were treated with water, indicating that boric acid improved the water resistance via the formation
of a chelating polymer.

Research limitations/implications
Compared to synthetic resin such as urea formaldehyde, the SF adhesive exhibited lower water
resistance. Further modification methods and optimum chemical reagents still need to be
investigated.

Originality/value
A new formulation for an environmentally friendly adhesive prepared from SF is identified for the
panel industry. The bonding potential of soy protein was developed without any synthetic resin,
which will promote industrial utilisation of an agricultural by‐product.
Potential Applications of Isinglass Adhesive for
Paper Conservation
Tatyana Petukhova
Paper Conservator, Conservation Lab, 701 Olin Library, Cornell University, Ithaca, NY, 14850.

With new developments in science conservators are exposed to various new materials that help
improve the quality of their work and simplify the conservation process. Nevertheless old
traditional materials and techniques also may offer something "new" to learn from the past.
Some natural adhesives have been used for conservation in different countries for centuries but have
not been introduced widely enough to the international arena. In Russia fish gelatin and isinglass
have been traditionally used as adhesives in painting and icon restoration. The application of fish
glue as an adhesive and consolidant for the restoration of Russian icons is documented as early as
the seventeenth century, in the Siiskii chronicle.
In nineteenth-century Europe domestic isinglass and isinglass imported from Russia were broadly
available and were used for sizing paper in book and paper restoration, for gilding of glass and
wood, and as a fixative for pastel drawings. In historic documents of Western Europe the use of
isinglass has been traced to medieval times in connection with illumination of books, where
isinglass was used as a size on which pigments or gold leaf were laid and occasionally as a medium.
Fish glue is an adhesive prepared from the waste products of fish such as the head, skin, and bones.
Isinglass is defined as a superior fish gelatin product, produced from the swim bladders of certain
species of fish; the quality of the isinglass depends on the chosen species of fish, the manufacturing
process, and additives. Because isinglass has been used in Russia for centuries, methods of its
manufacture were developed to produce an extremely pure product suitable for conservation. The
best grade of isinglass produced today is Russian isinglass, which is prepared from sevrüga and
assëtr (English "sturgeon").
This isinglass fulfills the most -important conservation requirements: it is readily reversible with
moisture and heat; it is non-toxic; and it is easy to prepare and apply. It makes a highly viscous
adhesive that can be prepared in dilute solutions; a thin film produces a strong bond even if there is
very little moisture present when contact is made. In Russian paper conservation isinglass is used as
an adhesive for pre-made hinges that can be easily stored and used when needed, and for lining
pastel drawings executed on board or heavy paper with canvas. But outside of the Soviet Union the
use of isinglass as an adhesive and its advantages when applied to conservation are generally
unknown.
In collaboration with specialists in Food Science and Chemistry at Cornell University the author is
working on a project to develop a pure fish gelatin adhesive suitable for conservation with qualities
similar to Russian isinglass. The author has been familiar with the uses of isinglass since 1973,
when she worked in the Painting Conservation Department at the State Hermitage Museum in
Leningrad, where isinglass is regularly used for consolidation and lining. Compared to other kinds
of isinglass the Russian product is tackier, produces a clear aqueous solution, and behaves quite
differently from other grades during lining. Unfortunately Russian isinglass was impossible to
obtain and the product used for the experiments described here was obtained from a West German
company, Kremer Pigments, in Aichstetten.
The pH of this dry isinglass is around 6 to 6.5. To prepare a solution of isinglass in water, the thin
transparent sheets of dry isinglass were broken into small pieces and soaked in distilled water for an
hour or more. Isinglass, like all collagen, is insoluble in cold water but can be gradually dissolved
by introducing heat. Once the pieces of isinglass had swelled, they were melted in a double boiler
over moderate heat. The temperature of the solution should not exceed 60° C; above this level the
glue begins to degrade rapidly and loses its adhesive properties. The hot solution then was strained
several times through cheesecloth. The West German isinglass has a milky cast and quite a strong
odor that a purer grade does not have. Several solutions of isinglass in water were used (2.5%, 5%,
7%) so the consistency could be varied depending on the purpose of the conservation procedure. A
light-weight Japanese tissue such as tengujo was placed on a sheet of Plexiglas and a hot solution of
isinglass in water, plasticized with glycerin, was applied evenly with a brush. After this procedure
the Japanese tissue was dried for several days and then peeled off the Plexiglas.
This pre-made isinglass film was found most practical for the repairing of archival material that
cannot be washed prior to repairing. Over 70 oversized 19th-century engineering prints by Cooper
from the History of Science Department collection were repaired and hinged with pre-made
isinglass film by the technician and interns under the paper conservator's supervision at the Cornell
University Library conservation lab. A sheet of pre-made isinglass film was cut into appropriate
strips. A strip was placed on the verso of the area to be repaired, shiny side towards the paper object,
and a slight amount of moisture was applied by brushing through the verso of the isinglass film. A
bone folder was used to fix the strip into place and the area was dried with a tacking iron through
silicon release paper.
The technique described above is simple and efficient, and might be used by non-conservators such
as librarians, archivists, or curators with a little training. Hinges made of isinglass film can be used
where it is difficult to cook a starch paste.
The author also experimented with isinglass and fish gelatin adhesives for lining tracing papers.
Transparent papers are usually quite thin and brittle by nature: they are impregnated with oils,
resins, etc., which effect physical and chemical changes of the paper over time. Most tracing papers
are extremely sensitive to light and temperature. Tracing papers with water-soluble media are
particularly unpredictable during conservation. Often they do not accept starch paste, which may
not be strong enough or may be too moist for this kind of paper. Synthetic adhesives are not readily
reversible or present problems of toxicity.
For experimental purposes a poor-quality, machine-made transparent paper was used as a primary
support and Japanese machine-made tengujo tissue was chosen as a secondary support paper.
The first technique: the experimental tracing paper was relaxed between Gore-tex and moistened
blotters. The hot solution of isinglass in water was applied to the Japanese tissue. Once the adhesive
was slightly moist and developed its greatest tack, the lining was performed. After lining, the
experimental paper object was dried between polyester web and dry blotters in a press.
The second technique: a pre-made dry isinglass film made with tengujo tissue was activated with
moisture during pressing. The experimental tracing paper was placed dry on the dry isinglass film
and then pressed between Gore-tex and slightly moistened blotters for less than three minutes.
The third technique: the tracing paper sample was slightly moistened and relaxed before being set
on the pre-made dry isinglass film and pressed.
In each of these trials the experimental sheets of tracing paper were successfully attached to the
isinglass film and a strong adhesion was obtained even when very low levels of moisture were used.
However, all these lining variations need some further development and an appropriate
investigation of the adhesive before they are applied to actual conservation treatments.
The author is continuing her investigations of fish gelatins and isinglass in the hope that a suitable
high-grade product may be found and made available to conservators in this country. The
experiments described above show that for paper conservators isinglass has potentials as a useful
alternative adhesive to paste for certain applications, including: lining and repairing of archival
paper material that can not be repaired with starch paste; conservation of tracing papers or other
papers that require a strong, low-moisture adhesive; or as pre-made isinglass or fish gelatin film for
hinging various paper objects.

Select Bibliography
Becher, C. "Isinglass and fish glue." Scifen-Ö1c-Fette-Wachse, 76 (1950), 391-92.
Brooks, A. "Manufacture and uses of fish glue." Transactions of the American Society of
Mechanical Engineering (Wood Industries), 54 (1932), 20.
Gorin, I. and Cherkasova, Z. Restavratsiîia proizvedeniâ stankovoâ zhivopisi. Moskva: Iskusstvo,
1977.
Grenberg, I. Osnovy muzeinoi konservatsii. Moskva: Iskusstvo, 1976.
Hurd, J. Adhesives guide. London: British Scientific Instrument Research Association, 1959.
Josef, J. "Selected properties of gelatin and glue." Sbornik vysoke iskoly chemocko-technologiscke
v,. Praze teckhnologischeskogo..., 513 (1985) 5-15.
Kernot, J. and N. Speer. "Production of glue and gelatin from fish." Department of Scientific and
Industrial Research, 2nd Report of Adhesives Research Committee (1962), 23-33.
McGuire, P. American Adhesive Index. Padric Publishing, 1962.
Mayer, R. The Artist's handbook of materials and techniques. New York: Viking Press, 1985.
Mills, J. and White, R. The Organic Chemistry of Museum Objects. London: Butterworths, 1987.
Reed, R. Ancient skins, parchments, and leathers. London: Seminar Press, 1972.
Skeist, I. Handbook of adhesives. London: Van Nostrand Reinhold, 1962.
Shields, J. Adhesives handbook. London: Butterworths, 1979.
Slanskii, B. Tekhnica zhivopisi. Moskva: Akademiia Khudozhestv SSSR, 1976. Thompson, D. The
materials and techniques of medieval painting. New York: Dover.

Publication History
Received: Fall 1989

Paper delivered at the Book and Paper specialty group session, AIC 17th Annual Meeting, May 31-
June 4, 1989, Cincinnati, Ohio.
Papers for the specialty group session are selected by committee, based on abstracts and there has
been no further peer review. Papers are received by the compiler in the Fall following the meeting
and the author is welcome to make revisions, minor or major
Improve Performance of Soy Flour-Based
Adhesive with a Lignin-Based Resin
Xiaochun Zhang,1,* Yuding Zhu,1 Youming Yu,1 and Jiangang Song2
Antonio Pizzi, Academic Editor
Author information Article notes Copyright and License information Disclaimer
Go to:

Abstract
A lignin-based resin (LB) was used to improve the performance of soy flour-based adhesives. Soy
flour (SF), polyamidoamine-epichlorohydrin (PAE), and LB were used to develop a plywood
adhesive. The solid content and viscosity of the adhesive, the functional groups, the thermo-
stability, and the crystallinity of the cured adhesives were characterized, and the performance of the
resultant adhesive was evaluated by fabricating three-ply plywood. Results showed that the LB and
PAE mixture used to modify the SF adhesive improved both dry and wet bond strength by 66.3%
and 184.2%, respectively. Therefore, the PAE improved the wet bond strength, and the LB
improved the dry bond strength. The improvement was attributed to: (1) the reaction of LB/PAE
with the functions of the soy protein to form a cross-linking network; (2) a polycondensation
reaction between the LB molecules improved the crosslinking density of the adhesive to form an
interpenetration structure with cross-linked proteins; and (3) the easy penetration of the LB into the
wood surface that enhanced interlocking between the wood and adhesive. Furthermore, the denser
structure created by the LB and the PAE mixture improved thermal stability and decreased the
crystallinity of the cured adhesive. The use of the LB and the PAE mixture increased the solid
content by 35.5%, while still making its viscosity acceptable for industrial applications.
Keywords: soy flour, lignin, adhesive, plywood, bond strength
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1. Introduction
Formaldehyde-based resins—particularly melamine-urea-formaldehyde resin—are widely used to
fabricate plywood panels [1]; however, they are non-biodegradable and petroleum-derived,
resulting in environmental concerns regarding their preparation and use [2,3]. Thus, the
development of adhesives based on ecological and renewable natural resources is crucial. Soy flour
has been used as a wood adhesive for decades, as it is a renewable, abundant, readily available, and
inexpensive raw material [4]. Nevertheless, its poor water resistance has limited the application of
soy flour-based adhesives. Many attempts have been made to improve the water resistance of soy
flour-based adhesives, including protein denaturing agent modification and crosslinker
modification. Denaturing agents such as alkalis [5], urea [6], and sodium dodecyl sulfate (SDS) [7]
can unfold protein molecules to expose their internal hydrophobic groups that improve the water
resistance of the adhesive. However, the water resistance of the resultant plywood does not meet the
requirements for interior use. Crosslinker modifications such as polyamidoamine-epichlorohydrin
(PAE) resin [8], glycidyl methacrylate [9], and polyethylene glycol diacrylate [10] can cross-link
the protein molecules by reacting with the functions to form a network that improves the water
resistance of the adhesive. PAE has been shown to be the most effective crosslinker in improving
the water resistance of the adhesive; however, soy flour-based adhesives with those crosslinkers
have a low dry bonded strength, which limits their application—particularly in the secondary
operation process of its resultant plywood. This is due to large protein molecules that make it
difficult to penetrate the wood surface to form an interlock. Thus, it is important to improve the
performance of soy flour-based adhesives in both dry and wet states.
The use of synthetic resins such as melamine-urea-formaldehyde (MUF) [11], phenol formaldehyde
(PF) [12], or latex-based resins [13,14] can improve the water resistance of the adhesive.
Nevertheless, these adhesives have issues; for example, MUF resins result in formaldehyde
emissions, and latex resins have a low water resistance. PF resin effectively improves both the bond
strength and water resistance of the adhesive, but it has disadvantages such as a high pH value,
which causes a degradation of the soy protein and leads to a decrease in bond strength. The weight
ratio of protein/PF in the adhesive is more than 1:1, therefore making the soy flour more like a filler
in the PF resin, and not a soy protein-based adhesive. The curing temperature of PF resin is also
high (≥150 °C), and the raw material of PF resins is derived from fossil fuels and non-renewable
resources.
In this study, a soy flour (SF)-based adhesive was synthesized using soy flour and PAE. Lignin was
treated with phenol and formaldehyde to develop a lignin resin (LB) with phenolic hydroxyl
methylation, which acted as a modifier to improve the bond performance of the adhesive. Different
additions of LB resin were used to develop different adhesives. The performance of the resultant
adhesives, including the solid content and viscosity of the adhesive, as well as the functional
groups, thermostability, and fracture surface of the cured adhesive were characterized. Three-ply
plywood was fabricated with the resultant adhesives, and their wet bond strength was tested.
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2. Experimental Methods
2.1. Materials
Soy flour (200 mesh) is the meal after removing the oil from soybeans, and was obtained and milled
to flour (SF) from Fuda Protein Biotech Company in Hang Zhou, China. Components of the soy
flour were: 52.2% soy protein, 38.2% saccharides, 7.5% moisture, 2.6% ash, and 0.5% fat. AR-
grade reagents of phenol, formaldehyde solution (37–0 wt %) and sodium hydroxide were obtained
from Zhejiang Chemical Reagent Co., Hang Zhou, China. The lignin (from soft wood) was
produced by the Yongtai Paper Co., Ltd. (Hang Zhou, China), and contained 82.5% klason lignin,
6.2% acid-soluble lignin, 2.5% ash, 5.1% sugar, and 3.7% others. PAE was obtained from Kaiyuan
Chemical Ltd. (Hang Zhou, China), where the solid content was 12.5%, with a viscosity ranging
from 25–45 mPa·s. Eucalyptus veneer (60 × 60 × 1.7 cm, 5% of moisture content) was provided by
Jiashan, China.

2.2. Lignin-Based Resin (LB) Preparation

The LB resin was synthesized by batch copolymerization using lignin, phenol, and formaldehyde.
In the first step, lignin (260 g) and phenol (260 g) with formaldehyde (400 g, 37 wt %) and NaOH
(100 g, 50 wt %) were mixed and stirred in a flask. The mixture was heated to 80 °C and maintained
for 1 h. Next, the second portion of formaldehyde (300 g, 37 wt %) and NaOH (80 g, 50 wt %) was
added to the flask and stirred for 1 h at 80 °C. The mixture was cooled to 40 °C and the free
formaldehyde was removed through a vacuum distillation process to obtain the LB resin. The solid
content of the resultant resin was 62.2%, and the viscosity was 1080 mPa·s at 20 °C.

2.3. Adhesive Preparation and Measurement

Soy flour was mixed with water and stirred for 15 min at 30 °C for each adhesive sample. LB and
PAE were then added and stirred for an addition 15 min at 30 °C. The different adhesive
formulations are shown in Table 1.

Table 1
Adhesive formulations. PAE: polyamidoamine-epichlorohydrin; LB: lignin-based resin; SF: soy
flour.

Adhesive Sample Formulation

a SF adhesive Soy flour (30 g); Water (70 g)
b SF/LB adhesive Soy flour (30 g); Water (70 g); LB (10 g)
c SF/PAE adhesive Soy flour (30 g); Water (40 g); PAE (30 g)
d SF/PAE/LB adhesive Soy flour (30 g); Water (40 g); PAE (30 g); LB (10 g)
2.3.1. Solid Content Measurement
The adhesive solid content was measured by placing approximately 3 g (α) of the adhesive in the
oven and drying at 102 °C for 2 h to obtain a weight (β). The value of the solid content was
calculated using the following equation. The average value of the solid content was calculated over
six parallel samples.

Solid Content (%)=β (g)α (g)×100%

(1)
2.3.2. Dynamic Viscoelastic Measurement
The apparent viscosity of different adhesives was determined by a Brookfield viscometer with a
spinning rate of 1 rpm, where the averages were determined over 10 measurements taken in 3 min
increments at 30 °C.

2.3.3. Fourier Transform Infrared (FTIR) Spectroscopy

The adhesive was cured in an oven at 130 °C for 1 h then ground into a 150-mesh powder by
grinding pellets in an agate mortar. The Fourier transform infrared (FTIR)spectra of the cured
adhesive were tested using a Nicolet 7600 spectrometer (Nicolet Instrument Corporation, Madison,
WI, USA) with an attenuated total reflectance (ATR) accessory (a single reflection diamond crystal)
from 500–4000 cm−1 with a 4 cm−1 resolution over 16 scans.

2.3.4. Thermogravimetric (TG) Measurement

The adhesive was cured in an oven at 130 °C for 1 h then ground into a 150-mesh powder. The
thermal stability of the cured adhesive samples was tested using a thermal gravimetric analyzer
(TGA) instrument (TA Q50, WATERS Company, New Castle, DE, USA). The 3 mg powdered
samples were weighed in a platinum cup and scanned from 30–600 °C at a heating rate of 10
°C/min in a nitrogen environment. The weight change was recorded throughout.
2.3.5. X-ray Diffraction (XRD) Measurement
The adhesive was cured in an oven at 120 ± 2 °C until the weight remained constant. It was then
ground into a powder. X-ray diffraction (XRD) patterns were recorded on a D8 advance
diffractometer (Bruker, Madison, WI, USA) using a cobalt source and 0.02 theta scan ranging from
5° to 60° at 45 kV and 30 mA. The index of the sample determination was carried out using a Jade
5.0 program, Bruker, Madison, WI, USA.

2.4. Plywood Preparation and Testing

The three-ply plywood was fabricated using the following conditions: 130 °C hot pressing
temperature, 90 s/mm hot pressing time, 200 g/m2 glue spreading, and 0.8 MPa hot pressing
pressure.
The wet bond strength was measured via wet bond strength test in accordance with the description
in the China National Standards (GB/T 17657-2013). Twenty plywood specimens (2.5 cm × 10 cm)
were cut from two parallel plywood panels and submerged into water at 63 ± 2 °C for 3 h before a
tension test. The wet bond strength was calculated by the following equation:
Bondingstrength(MPa)=TensionForce(N)Gluingarea(m2),
(2)
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3. Results and Discussion

3.1. Solid Content Measurement
The solid content of the adhesive was calculated from three parallel samples as seen in Table 2.
When the wood adhesive was used, the adhesive with a high solid content had superior performance
[15]. As soy protein-based adhesives are water-based with a low solid content (meaning that more
water is used in the adhesive formulation), this led not only to a low adhesive spread, but the water
also needed to be removed during the hot press process, which costs energy and increases the
interior force of the resultant plywood. Adhesive a exhibited a solid content of 28.2%, where at this
level of solid content, the adhesive had flow issues, indicating that the additives determined the
increase in the solid content. When mixed with LB resin, the solid content of Adhesive b reached
32.9%, which was an increase of 16.7% when compared to Adhesive a. After the addition of PAE,
the solid content of Adhesive d increased to 35.5%, which was an increase of 25.9% when
compared to Adhesive a. However, when only PAE and the SF adhesive were mixed together, the
solid content of Adhesive c was 31.2%, which was a decrease of 12.1% when compared to
Adhesive d. According to the literature, the solid content of soy protein-based adhesives has ranged
from 32–36% [16,17]. Based on those results, the solid content of Adhesive d met the requirements
for the plywood adhesive application.

Table 2
The solid content of the adhesives: (a) SF adhesive; (b) SF/LB adhesive; (c) SF/PAE adhesive; and
(d) SF/LB/PAE adhesive.
 Adhesive a b c d
solid content (%) 28.2 32.9 31.2 35.5

3.2. Dynamic Viscoelastic Measurement

The viscosity of the adhesives is shown in Table 3. The viscosity of the adhesive increased from
28,510 to 687,500 mPa·s after the addition of LB (Adhesive b). This was thought to have occurred
as the LB contained free sodium hydroxide (NaOH), which is effective at denaturing proteins, so it
unfolded the soy protein molecules and exposed the inner functional groups [18]. This increased the
friction between the protein molecules, resulting in an increase in adhesive viscosity. After the
addition of PAE, the viscosity of the resultant adhesive decreased from 28,510 to 19,840 mPa·s,
which may be due to the low viscosity of PAE itself. In addition, the PAE contains smaller
molecules than the soy protein which act as a molecular lubricant that reduces friction between the
molecules, resulting in decreases to adhesive viscosity. This was consistent with results obtained by
Yuan [19]. The viscosity of Adhesive d was 40% lower than that of Adhesive b, further
substantiating that PAE had a viscosity reduction effect.

Table 3
The viscosity of the adhesives: (a) SF adhesive; (b) SF/LB adhesive; (c) SF/PAE adhesive; and (d)
SF/LB/PAE adhesive.

Adhesive a b c d
Initial viscosity (mPa·s) 28,510 687,500 19,840 541,200

3.3. FTIR Spectroscopic Analysis

The FTIR spectra of the various adhesives are shown in Figure 1. Peaks of Adhesive a—observed at
1640, 1513, and 1234 cm−1—were attributed to the characteristic peaks of peptide, amide I (C=O
stretching), amide II (N–H bending), and amide III (C–N and N–H stretching), respectively [20].
The peaks at 1390 and 1028 cm−1 were attributed to COO– and C–O bending, respectively [21],
which was considered constant across all adhesive formulations. After the addition of LB, the amide
II (1513 cm−1) of Adhesive b decreased when compared with Adhesive a (referring to the peak at
1390 cm−1), indicating that N–H decreased in Adhesive b, which was due to LB reacting with the
N–H groups on the soy protein. This reaction formed a cross-linked network in the adhesive to
enhance the water resistance of the adhesive. In the spectra of Adhesive b, the absorption peak of
C=O stretching (amide I) and C–O bending moved from 1640 to 1648 cm−1 and 1028 to 1043 cm−1
(blue shift), respectively, when compared to Adhesive a, suggesting a denser structure was formed
in the adhesive, which further improved the water resistance. When soy protein molecules are cross-
linked to form a network, the structure becomes dense and ordered, resulting in the vibration of
functional groups needing more energy, which presents a blue shift [22].The same change was
observed in the spectra of Adhesive c, indicating that PAE also reacted with the –NH groups on the
soy protein molecule and formed a denser crosslinking structure. When mixing LB and PAE as the
modifier, the absorption peak of –NH2 further decreased, suggesting a much denser structure
formed in the adhesive, thus further increasing the water resistance of the adhesive. The specific
reaction is discussed in Scheme 1.
Figure 1
Fourier transform infrared (FTIR) spectra of the different adhesives: (a) SF adhesive; (b) SF/LB
adhesive; (c) SF/PAE adhesive; and (d) SF/LB/PAE adhesive.

3.4. TGA Analysis

The derivative thermogravimetric (DTG) curves of the different adhesives are shown in Figure 2.
According to Liu [22], the thermal degradation process of a soy protein-based adhesive can be
divided into three main stages: the first stage(weight loss of 0–100 °C) was attributed to the
evaporation of residual moisture; the second stage (weight loss of 100–270 °C) was due to unstable
chemical bond decomposition; and in the third stage (from 270–500 °C), the main structure of the
adhesive degrades and the covalent bonding in the structure decomposes. For Adhesive a, two peaks
were observed in the second stage, indicating the existence of unstable bonds in the cured adhesive.
After mixing PAE with Adhesive a, the peak at the second and third stage decreased, indicating that
PAE reacted with the protein molecule to form stable chemical bonds. This was a different structure
compared with Adhesive a, and increased thermo-stability in the resulting adhesive. Theoretically
speaking, LB had a similar reaction with protein based on the FTIR analysis, which presented a
similar thermal behavior. However, the addition of LB in the adhesive formulation (Adhesives a and
d) presented obvious peaks at 220–260 °C, indicating an increase in unstable bonds in Adhesive c
when compared to the adhesive without LB. This was attributed to the unstable ether bond
formation by a self-condensation reaction of LB. This linked LB penetrated with the cross-linked
soy protein to form an interpenetration network, further increasing the water resistance of the
resulting adhesive (Scheme 2).

Figure 2
The derivative thermogravimetric (DTG) curves of the different adhesives: (a) SF adhesive; (b)
SF/LB adhesive; (c) SF/PAE adhesive; and (d) SF/LB/PAE adhesive.

3.5. XRD Analysis

The crystallinity of the different adhesive formulations is presented in Table 4. The crystallinity of
Adhesive a was 15.5%, as a cross-linked structure formation in an adhesive reduces its crystallinity
within the wood adhesive. Crystallinity decreased to 14.6% after adding LB, most likely due to the
reaction between the LB and soy protein. This also increased the cross-linking density of the cured
adhesive. Furthermore, crystallinity decreased to 13.1% after adding PAE, which was 10.3% lower
than Adhesive b, indicating that a denser structure was formed in Adhesive c that led to an increase
in water resistance. This was in agreement with the results of the wet bond strength measurements.
Crystallinity further decreased to 11.6% after the addition of LB and PAE, indicating a more
compact structure formation in the cured Adhesive d. This was attributed to the reaction between
the protein and LB/PAE that created a cross-linking structure. In addition, the compact structure
also reached the interpenetration network formation by LB condensation, which further increased
the density degree of the adhesive. The results of the adhesive crystallinity analysis were in
accordance with the results found in the FTIR and TGA analyses.

Table 4
The crystallinity of different cured adhesives: (a) SF adhesive; (b) SF/LB adhesive; (c) SF/PAE
adhesive; and (d) SF/LB/PAE adhesive.

Adhesive a b c d
The crystallinity (%) 15.5 14.6 13.1 11.6

3.6. Dry Bond Strength

The dry bond strength of the plywood bonded with different adhesives is shown in Figure 3. The
dry bond strength of the plywood bonded with Adhesive a was 0.98 MPa, as the large protein
molecules made it difficult for the adhesive to penetrate into the wood surface to form a
mechanically interlocked structure, resulting in a low dry bond strength [14]. The interaction
between the soy protein molecules and wood was low, further reducing the bond performance of the
adhesive. The dry bond strength of the resultant plywood increased to 1.32 MPa after adding LB, as
the LB molecules are smaller and can more easily form mechanical interlocking, thus improving the
dry bond strength. In addition, the LB reacted with the protein molecules and themselves to form a
crosslinking structure that increased cohesive strength and improved bond strength. Analogous
results were found with Adhesive c. With the addition of PAE to the adhesive formulation, the PAE
cross-linked the protein molecules to form denser structures that improved bond strength. However,
PAE contributed less in forming mechanically interlocked structures, so improvement of the
plywood with Adhesive c was lower than that of Adhesive b. When mixing PAE and LB, the dry
bond strength of plywood increased to 1.63 MPa, which was 66.3% higher than Adhesive a. This
improvement was attributed to the small molecules increasing interlocking between the wood and
adhesive. The strength of the adhesive itself was enhanced as chemical reactions occurred between
the phenolic hydroxyl methyl (adhesive) and hydroxyl (wood), thus increasing the interaction forces
between the wood and adhesive [23].
Figure 3
The dry bond strength of the plywood with the different adhesives: (a) SF adhesive; (b) SF/LB
adhesive; (c) SF/PAE adhesive; and (d) SF/LB/PAE adhesive.

3.7. Water Shear Strength

The wet bond strengths of the plywood bonded by the various adhesives are shown in Figure 4. The
wet bond strength of the plywood bonded with Adhesive a was 0.38 MPa, as its curing process
involved the loss of water and molecules twined with each other. During this curing process, the
main forces inside Adhesive a were hydrogen bonds, which were easily broken from moisture
intrusion [24]. When using LB, the wet bond strength of plywood with Adhesive b reached 0.69
MPa. This improvement was caused by many reasons. As NaOH in LB is an effective denaturing
agent that unfolds the protein molecules to expose the hydrophobic groups, this resulted in an
improvement in adhesive water resistance [25]. The phenolic hydroxyl group on LB reacted with
the functions of protein (such as, –NH2, –COOH), and formed a cross-linked network, further
increasing the water resistance of the adhesive. The PAE-modified SF adhesive also increased the
wet bond strength of plywood with Adhesive c by 115.8% to 0.82 MPa. In effect, PAE reacted with
the functions of the protein to form a denser structure to enhance the water resistance of the
adhesive, thus demonstrating its efficacy as a curing agent of soy protein. After mixing PAE and
LB, the wet bond strength of the plywood was 1.08 MPa, an increase of 184.2% when compared
with Adhesive a. The NaOH in LB unfolded the soy protein molecule and exposed the active
groups, which facilitated the reaction between the protein molecules and PAE. In addition, the LB
reacted with itself through a polycondensation reaction to form a network (TGA analysis) that
penetrated the PAE cross-linked soy protein network to form an interpenetrating network, therefore
improving the water resistance of the resultant plywood.

Figure 4
The wet bond strength of the plywood with different adhesives: (a) SF adhesive; (b) SF/LB
adhesive; (c) SF/PAE adhesive; and (d) SF/LB/PAE adhesive.
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4. Conclusions
Using LB and PAE to modify SF adhesives improved both the dry and wet bond strength by 66.3%
and 184.2%, respectively. The PAE enhanced the wet bond strength, and the LB enhanced the dry
bond strength. The improvement of the wet bond strength was attributed to: (1) the reaction of LB
and PAE with the functions of the soy proteins to form a cross-linking network; and (2) the
polycondensation reactions between the LB molecules further improved the crosslinking density of
the adhesive and formed an interpenetration structure with cross-linked proteins. The improvement
in dry bond strength was attributed to LB easily penetrating the wood surface to form more
interlocks with the wood. Furthermore, the cross-linked and interpenetration structure created by
LB and PAE also improved thermal stability and decreased the crystallinity of cured adhesives. The
addition of the LB and the PAE mixture increased the solid content by 35.5%, resulting in the
adhesive obtaining an acceptable viscosity for industrial applications. Thus, this appears to be an
effective way to promote soy protein adhesive applications.

Scheme 1
The reaction of the adhesive components. (PAE: polyamidoamine-epichlorohydrin, TR: Tannin
based resin).
Scheme 2
The formation of the interpenetrated network.
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Acknowledgments
The authors are grateful for the financial support from Zhejiang Provincial Natural Science
Foundation of China under Grant No. LY17C160007.
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Author Contributions
Xiaochun Zhang conceived and designed the experiments; Xiaochun Zhang and Yuding Zhu
performed the experiments; Xiaochun Zhang and Youming Yu analyzed the data; Jiangang Song
contributed materials; Xiaochun Zhang wrote the paper.
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Conflicts of Interest
The authors declare no conflict of interest.
Soybean Dry Glue Adhesive
Adhesives Formulation
Applicable Type
Waterborne Adhesives , Natural-based Adhesives
Applicable Base Polymer
Soybeans
Applicable Industrial Sectors
Buildings & constructions , Industrial Assembly , Papers & Packagings , Wood & Related
Industries

Applicable Base Polymer Properties

Soybean flour is formulated into adhesive systems as either the main polymeric component,
incorporated as extenders for other resins. Their primary application is in the manufacture of
plywood, softboard laminating, paper overlaying, and other less stringent applications. These
adhesives are inexpensive and can be used for making semi-water resistant plywood and for coating
some types of paper. They set at room temperatures. One-package soybean glue formulations are
dry powders.

Typical Formulation Ingredients

Ingredient
Parts by weight
Soybean flour
57
Lactic acid casein
15
Hydrated lime
12
Wood flour
5
Sodium carbonate
5
Sodium fluoride
3
Pine oil or equivalent defoamer
3
Processing
The following mixing directions are used for the adhesive formulation described above.

Water at room temperature 20 parts by weight

Dry soybean glue 10 parts by weight

Mix until smooth Let stand for 15 minutes

Then mix briefly and add room temperature water (5 pbw) and mix until smooth. This water
addition may be reduced if a heavier adhesive is desired.
The adhesive can be applied and cured either hot or cold.

Resulting Properties
Soybean glues generally are considered to have limited water resistance but recover their strength
on drying. Soybean glues are susceptible to mold growth. However, a variety of efficient
preservatives are available. A typical dry glue soybean flour composition is listed above.

Tips and Tricks

The flour is generally dispersed in aqueous sodium hydroxide and other alkaline bivalent metallic
ions (e.g., calcium hydroxide) are incorporated to lengthen the working time and to improve water
resistance.
It is generally required to maintain the highest level of soybean content as possible in order to
achieve maximum adhesive properties. Fillers such as wood flour, walnut-shell flour, and clay result
in lower cost, but they also lower the performance properties of the adhesive.

Phosphorylation improves moisture resistance

of soy flour based adhesive
Thursday, 10 April 2014
A green-chemistry approach to improve the moisture resistance of soy flour (SF)-based wood
adhesive is described by American researchers.
Soy-flour increases the wet bond of adhesives Source: Pefkos Victor Burnside-Fotolia.com
Chemical phosphorylation of SF (PSF), using POCl3 as the phosphorylating agent, dramatically
increased its wet bond strength. The optimum POCl3:SF ratio that produced maximum wet bond
strength was about 0.15 (g g−1). The increase in wet bond strength of PSF (PSF0.15) was mostly
due to the phosphate groups incorporated into the proteins and carbohydrates, and to a lesser degree
to phosphorylation-induced protein denaturation.
Phosphate groups acted as cross-linking agents
The attached phosphate groups acted as cross-linking agents, either via covalent esterification with
hydroxyl groups on wood chips or via ionic and hydrogen-bonding interactions with functional
groups in wood chips. At hot-press temperatures above 160°C the wet bond strength of PSF0.15
was >2.6MPa, a level that might be acceptable for interior-used hardwood plywood and
particleboard. POCl3 is a low cost, general-purpose reagent and therefore PSF-based adhesive is
expected to be environmentally friendly.
The study is published in: Journal of Applied Polymer Science, Volume 131, Issue 13, 5 July 2014.