ARTICLE IN PRESS

International Journal of Adhesion & Adhesives 24 (2004) 485–493

Development and characterization of a wood adhesive

using bagasse lignin
Mozaffar Alam Khana, Sayed Marghoob Ashrafa,*, Ved Prakash Malhotrab
a
Department of Chemistry, Materials Research Laboratory, Jamia Millia Islamia University, New Delhi110 025, India
b
Micro Industrial Corporation, G-9, Udyog Nagar, Rohtak Road, Delhi-110 041, India
Accepted 20 January 2004

Abstract

Bagasse is spent fiber left after extraction of sugar. It is mainly used as a fuel to concentrate sugarcane juice. In the present work,
the possibility of preparing wood adhesives from bagasse has been explored. The parameters for the preparation of a lignin phenol
formaldehyde (LPF) adhesive, (lignin concentration, formaldehyde to phenol molar ratio, catalyst concentration, reaction time and
reaction temperature) have been optimized. It was found that up to 50% of phenol can be substituted by bagasse lignin to give LPF
wood adhesive having better bonding strength in comparison to a control phenol formaldehyde (CPF) wood adhesive. Prepared
resins were characterized using IR, DSC and TGA. IR spectra of LPF resin showed structural similarity with CPF resin. Thermal
stability of LPF resin was found to be lower as compared to CPF resin. DSC studies reveal a lower curing temperature for LPF
adhesive in comparison to CPF adhesive. A shelf-life study reveals that LPF exhibits consistent behavior as compared to CPF in
respect to adhesive strength.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: A. Adhesive for wood; B. Bagasse lignin; C. Phenol formaldehyde; D. Curing; E. Lignin phenol formaldehyde adhesive

1. Introduction value depends on competing with alternative sources for

Bagasse is a greyish yellow spent fiber left after the
crushing of sugar cane. It is reported that around 8
million tons of dry bagasse was produced in India in
the year 2001 [1]. Bagasse is usually burned to supply the
energy required for evaporation of water during the
crystallization of sugar. Around 70% by weight of
bagasse is used as fuel. A large amount of surplus
bagasse still remains unused and is dumped as landfill or
simply burned as waste. Various alternative uses for this
excess material have been investigated. The initial work
for utilization of bagasse was carried out at Imperial
Institute of Sugar Technology, London, where the
possibility of manufacturing cellulose from bagasse
was investigated [2]. Pulp and paper production from
bagasse was first achieved in 1938, but its economic
*Corresponding author. Tel.: +91-011-26831717; fax: +91-11-
26840229.
E-mail address: smashraf jmi@yahoo.co.in (S.M. Ashraf).
pulp [3,4]. Doss et al. investigated the possibility of
deriving carbon black from bagasse [5]. Composites
derived from bagasse exploit solely the physical char-
acteristic of the cellulose component as reinforcing filler.
In this context, one of the most promising applications
for bagasse is the manufacturing of roofing elements and
boards using phenolic resin as polymeric binder [6–8].
Hassan et al. studied the possibility of converting
bagasse into thermoplastic material [9].
Among all the applications of bagasse, its utilization
as a raw material for the preparation of adhesives is
most promising. The main components of bagasse are
cellulose, hemicellulose and lignin. Among these three,
lignin has some structural similarity with PF resin
condensates [10]. Lignin has been widely used for the
preparation of phenol formaldehyde adhesives [11,12].
Sayyah et al. used bagasse pith for preparation of
phenolic resin [13]. Although different agrowaste are
used for the preparation of lignin based adhesives, but it
has been shown that bagasse lignin has more hydroxy

0143-7496/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijadhadh.2004.01.003
 ARTICLE IN PRESS
486 M.A. Khan et al. / International Journal of Adhesion & Adhesives 24 (2004) 485–493
groups per phenylpropane unit [14,15] and hence,
appears more suitable for the preparation of phenolic
resin.
Adhesives are required in many wood processing
industries such as particleboard, wood panels, fiber
boards and plywood etc. Among the various adhesive
used for the production of these articles, resole phenol
formaldehyde is the most common type of adhesive.
With the increasing use of composite materials such as
strand board, flake board, and composite lumber, the
demand for adhesives is increasing. These adhesives are
in adequate supply today, but scarcity of petroleum
products could affect the future cost and availability of
these petroleum based adhesives. To avoid this scenario,
it is imperative to explore the possibility of replacing
petroleum based raw materials. Throughout the world
intensive efforts are being made to replace various
petroleum based raw materials with these kind of
adhesives.
Numerous reports have been published on the
preparation of adhesives from bagasse and bagasse
lignin [13–18], but any report on the optimization of
reaction conditions for the preparation of these adhe-
sives is not available in the literature. In this work, we
have attempted to study the various parameters for the
preparation of bagasse lignin substituted phenol for-
maldehyde adhesives. Prepared adhesives were charac-
terized in detail and compared with CPF adhesive in
performance.
2. Experimental
2.1. Materials used
Phenol (99%) of M/s Qualigens (India), formalde-
hyde solution (37%) of M/s Merck (India), sulphuric
acid (98%) and methanol (99%) of M/s s.d Fine
Chemicals (India) and sodium hydroxide (97%) of M/s
Rankem (India) were used for experimental work.
Bagasse was collected from Titavi Sugar Mills of
Muzaffarnagar, U.P., India. It was washed with distilled
water, dried in oven at 10075
C for 4 h, ground using
conventional mixer/grinder and subsequently used for
delignification.
2.2. Lignin extraction from bagasse
Delignification was performed in a two neck round
bottom flask equipped with a condenser and a thermo-
meter. 250 g of dried ground bagasse and 2.5 kg of
5 mol/l sodium hydroxide were charged into flask.
Temperature was maintained at 10071
C for 7 h Black
liquor so obtained was filtered to remove suspended
pulp fibers and then neutralized with 50% H2SO4
solution under constant stirring. The precipitated lignin
was filtered under vacuum, washed repeatedly with hot
distilled water till neutral. A 159 g lignin cake was
obtained having 33% solid content.
2.3. Adhesive preparation
Phenol formaldehyde (PF) and lignin phenol formal-
dehyde (LPF) both were prepared in a four neck round
bottom flask equipped with a stirrer, thermometer,
reflux condenser and dropping funnel.
2.3.1. Preparation of phenol formaldehyde (PF) adhesive
11.64 g of molten phenol, 20.27 g formaldehyde
solution and 10 g each of distilled water and methanol
were taken in a flask. The mixture was heated to
8071
C. 1.16 g of sodium hydroxide in distilled water
was then added and the reaction was continued for 4 h
at 8071
C.
2.3.2. Preparation of lignin phenol formaldehyde adhesive
Lignin phenol formaldehyde (LPF) adhesive was
prepared in two steps: the first step consists of
preparation of lignin phenol adduct (LP) and the second
step consists of the preparation of LPF adhesive (i.e.
polymerization step).
In the first step, 85 g of lignin cake having 33% lignin
content was added to a beaker, 28 g phenol equal to the
lignin content in the cake (w/w) was added to it. The
lignin phenol mixture was mixed and stirred for an hour
at 40
C to obtain a homogenous mass. The resulting
adduct was found to contain 50% moisture. In the
second step, 23.28 g of LP adduct (prepared in the first
step), additional phenol (to make the desired lignin:
phenol ratio), 20.27 g of formaldehyde solution, 10 g of
methanol were mixed using mechanical stirrer. The
temperature was raised to 80
C. 1.16 g of NaOH
dissolved in distilled water was added to the mixture
and the reaction was continued for 4 h.
2.4. Testing and analysis of the adhesives
Hydroxyl value was determined as per IS:548: Part–I.
A known amount of the sample is acetylated under
controlled condition and titrated against alcoholic KOH
solution. Hydroxyl value was calculated using the
formula:
56:1  N  Y
Hydroxyl value ¼ ; ð1Þ
W
where N is normality of alcoholic KOH, Y is alcoholic
KOH solution required for sample—blank, and W is
weight of sample taken.
Elemental analysis of lignin was carried out using a
CHN Rapid Elemental Analyzer model Heraeus
5002651. 10–20 mg lignin was put in oxidative combus-
tion chamber at 950
C using cerium oxide as oxidation
 ARTICLE IN PRESS
M.A. Khan et al. / International Journal of Adhesion & Adhesives 24 (2004) 485–493 487

catalyst. During combustion C and H are converted into 3. Results and discussion
CO2 and H2O respectively. The gases so produced are
separated as peak. Integration of peak gives the 3.1. Characterization of extracted lignin
concentration of elements.
The percent non-volatile content (solid content) of the Lignin extracted from bagasse was characterized for
adhesives are determined as per ASTM D 4426–93. hydroxyl value, elemental analysis, glass transition
The gel time of adhesives was determined using a temperature (Tg ), maximum absorbance ðlmax ) and IR
indigenous make gel meter. 1–2 g of adhesive was put spectra. Hydroxyl value, C,H,O values, lmax and Tg
into the grooves on metal plate at 10071
C. The values are given in Table 1.
adhesive was stirred using a glass rod and the time for Fig. 1 shows the IR spectrum of bagasse lignin. The
formation of the fiber was noted. bands observed at 1030, 1086, 1136, 1268, 1462, 1520
Adhesive strength or close contact joint of samples and 1625 cm1 are the characteristic peaks of bagasse
were tested as per IS 851-1978. A teak wood–teak wood lignin (Table 4). The band at 1625 cm1 is assigned to
interface of 7% moisture content was used for specimen aromatic benzene ring vibrations. The band present at
preparation. The adhesive was applied on both sides 1462 cm1 is due to the methoxy CH3 group. The band
of interface. The glued samples were then pressed at 1268 cm1 is attributed to the C–O of the guaiacyl
in clamps under pressure of approximately 50 N. ring. The bands at 1136 and 1030 cm1 are assigned to
The clamp samples were kept in an oven at 12572
C guaiacyl and syringyl C–H. The band at 1086 cm1 is
for 2 h. After conditioning the samples were tested assigned to the C–O stretching in secondary alcohol.
on Instron testing machine at a cross head speed of The bands at 1268 and 1086 cm1 are typical of soft
50 mm/min. wood lignin [19].
The shear properties were measured by tension
loading of adhesives as per ASTM D 2339–94A. Ply 3.2. Optimization of reaction parameters
laminates of moisture content 7.5% was used for
specimen preparation. The adhesive was applied on Various parameters like bagasse lignin concentra-
both side of interface. The glued samples were pressed tion, formaldehyde to phenol molar ratio, catalyst
in compression moulding machine at 120
C at a
pressure of 50 kg cm2 for 6 min and then cooled. After
Table 1
conditioning, the laminates were cut into 82.6  25.4 mm Analysis of extracted bagasse lignin
specimens. Test specimens were tested using Instron
machine at a crosshead speed of 3 mm/min. Properties Unit Value
The IR spectra of lignin, CPF and optimized LPF Hydroxyl value Dimensionless 296
adhesives were taken in KBr pellet. The pellets were Elemental analysis %
dried in oven at 10075
C for an hour and IR spectra Carbon 44.39
Hydrogen 5.46
were taken on FTIR spectrophotometer (NICOLET Oxygen 50.15
Impact 410). Glass transition temp., Tg

C 111
An UV spectrum of lignin was taken on a Schmazdu Maximum absorbance, lmax nm 286
160 A UV spectrometer. Lignin was dissolved in DMSO
(0.005%) and scanned for lmax in the range 200–350 nm.
Thermal transitions were measured using Differential
Scanning Calorimeter, DSC 2910, TA Instrument’s. The
sample was heated at a heating rate of 10
C/min from
ambient to 250
C in a nitrogen atmosphere.
Thermal stability of CPF and optimized LPF
adhesives was measured using thermogravimetric
analyzer TGA-DTA 2960, TA Instruments. The
CPF and LPF samples were heated from ambient to
700
C, at a heating rate of 10
C/min in a nitrogen
atmosphere.
Shelf-life of CPF and LPF adhesives was studied as
per ASTM D 1337-91. Storage life was measured by
determining the viscosity and bond strength of the
freshly prepared and stored adhesives. The adhesives
were stored in sealed PVC bottles at 2572
C. Viscosity
and bond strength were measured weekly for six weeks
to check the shelf-life of the adhesives. Fig. 1. IR spectra of alkali bagasse lignin.
 ARTICLE IN PRESS
488 M.A. Khan et al. / International Journal of Adhesion & Adhesives 24 (2004) 485–493

concentration, reaction time and reaction temperature 3.2.2. Formaldehyde to phenol molar ratio
were studied. These parameters were varied and their Fig. 3 shows the effect of formaldehyde to phenol
effect on non-volatile content, gel time, adhesive molar ratio (F/P) at 50% bagasse lignin substitution on
strength and shear strength was studied. Various physico-mechanical properties. It is observed that non-
prepared adhesives are given in Table 2. volatile content increases up to formaldehyde to phenol
molar ratio of 2.0. Beyond this a sharp decrease in non-
3.2.1. Lignin to phenol ratio volatile content is observed. The behaviour of gel time is
Fig. 2 shows the effect of lignin concentration on found to be the reverse of that of non-volatile content.
physico-mechanical properties. An increase in non- At higher values of F/P, it appears that crosslink
volatile content and decrease in gel time is observed formation is hindered, which reduces the rate of
on incorporation of lignin into the CPF adhesive. Both crosslink formation and increases the gel time. It is
of these effects indicate an increase in crosslink density
on incorporation of the lignin. Pizzi et al. has shown
that gel time is inversely proportional to the rate of
polycondensation and crosslinking of the resin [20].
Adhesive strength and shear strength increases till 50%
lignin concentration and then decreases on further
increasing the lignin concentration to 60%. An increase
in adhesive and shear strength values is attributed to the
increasing crosslink density in the modified adhesive
with increasing amount of lignin. An increase in
adhesive and shear strength also indicates that the
incorporation of lignin in CPF resin provides a better
reinforcement structurally. The decrease in gel time with
increase in the loading of lignin shows that crosslinking
rate has noticeably increased, resulting into higher
crosslinking between lignin and phenol to form LPF
condensates. This causes an increase in adhesive
strength. This increase in crosslink density accompanied
by a decrease in gel time continues till 50% loading of
the lignin. It is observed that beyond 50% lignin loading
in CPF, gel time slightly increases shown that rate of
crosslinking and thereby the crosslink density decreases
bringing the adhesive strength about slight decrease in Fig. 2. Effect of lignin concentration on physico-mechanical proper-
adhesive strength. ties of LPF adhesives.

Table 2
Various prepared adhesives

Sl. no. Adhesive Lignin F to PL adduct Catalyst Reaction Reaction

code substitution (% of P) (molar ratio) concentration (% of P) time (h) temperature (
C)

1. A 0 2.0 10 4 80
2. B 10 2.0 10 4 80
3. C 25 2.0 10 4 80
4. D 35 2.0 10 4 80
5. E 50 2.0 10 4 80
6. F 60 2.0 10 4 80
7. G 50 1.5 10 4 80
8. H 50 2.5 10 4 80
9. I 50 3.0 10 4 80
10. J 50 2.0 5 4 80
11. K 50 2.0 15 4 80
12. L 50 2.0 10 2 80
13. M 50 2.0 10 6 80
14. N 50 2.0 10 4 60
15. O 50 2.0 10 4 90
 ARTICLE IN PRESS
M.A. Khan et al. / International Journal of Adhesion & Adhesives 24 (2004) 485–493
Fig. 3. Effect of F/P molar ratio on physico-mechanical properties of
50% lignin substituted LPF adhesive.
expected that with lower crosslink formation at F/P
>2.0, the non-volatile content in the resin would be
reduced. Our results however, show that the rate of
network formation is higher at lower F/P ratio (1.5–2.0)
and lower at higher F/P ratio (2.0–3.0) causing
respectively the decrease and increase in gel times. It
may be concluded that some factors including excessive
hydrogen bond formation between formaldehyde mole-
cules may hinder the crosslink formation. Values of
adhesive and shear strength further support these
observations. From these observations it is concluded
that formaldehyde to phenol molar ratio of 2.0 is
optimal for preparation LPF adhesive.
3.2.3. Catalyst concentration
Effects of catalyst concentration on the above proper-
ties are given in Fig. 4. It is observed that non-volatile
content, adhesive strength and shear strength are
maximum at 10% catalyst concentration. Gel time
decreases on increasing the catalyst concentration. A
decrease in gel time with increase in catalyst concentra-
tion is attributed to the enhancement of the condensa-
tion reaction due to the effect of catalyst. It has been
shown that the presence of catalyst accelerates the
reaction involving dimethylene ether bridges or hydro-
489
Fig. 4. Effect of catalyst (NaOH) Concentration on physico-mechan-
ical properties of 50% lignin substituted LPF adhesive.
xyl methyl groups due to an increase in pH of the basic
medium [7]. It is concluded that 10% catalyst concen-
tration is optimal for the preparation of LPF adhesive.
3.2.4. Reaction time
Fig. 5 shows the effect of reaction time on various
properties. It is observed that adhesive strength and
shear strength both increase with an increase in reaction
time till 4 h reaction time and then decrease. An increase
in adhesive and shear strength with increase in reaction
time is attributed to better crosslinking. Resin yield
(non-volatile solids) is also maximum at 4 h reaction
time. At 2 h reaction time resin yield, adhesive and shear
strength values are low, which indicates that in this time
reaction failed to reach to completion. On increasing the
reaction time to 6 h, a decrease in shear and adhesive
strength is observed. The resin still sets but the
prolonged reaction time appears to cause the breaking
of a fraction of crosslinks or some other deformation
occurs in the structure, which results in the decreased
adhesive and shear strength. From the above discus-
sions, it is concluded that for the preparation of LPF
adhesive, a reaction time of 4 h is optimal.
3.2.5. Reaction temperature
Effect of reaction temperature on the prepared
adhesives is given in Fig. 6. The adhesive was prepared
 ARTICLE IN PRESS
490 M.A. Khan et al. / International Journal of Adhesion & Adhesives 24 (2004) 485–493
Fig. 5. Effect of reaction time on physico-mechanical properties of
50% lignin substituted LPF adhesive.
at 60
C, 80
C, 90
C and 100
C. The adhesive prepared
at 100
C gels during reaction. As observed from Fig. 6,
adhesive strength and shear strength increase sharply on
increasing the temperature from 60
C to 80
C, and then
decreases slightly. It appears that the crosslink forma-
tion reaction starts at 60oC. However, at this tempera-
ture, the rate and the extent of crosslink formation are
lower. With the increase in temperature, rate and extent
of network formation increases. This causes the increase
in resin yield. At 80
C, shear strength and adhesive
strength both are highest. At 90
C the resin yield
decreases and gel time is also found to decrease slightly
at this temperature. The small decrease in gel time shows
that the rate of network formation is slightly less, which
causes a small decrease in the non-volatile content. Our
earlier observations that shear and adhesive strength of
LPF adhesives are directly proportional to the resin
yield is confirmed by these results also. It can be inferred
that 80
C is the optimal polymerization temperature for
preparation of LPF adhesives.
3.3. Characterization of adhesives
The LPF adhesive prepared at optimized conditions
was compared with CPF adhesive for their detailed
Fig. 6. Effect of reaction temperature on physico-mechanical proper-
ties of 50% lignin substituted LPF adhesives.
property profiles. Table 3 presents the physico-mechan-
ical properties of CPF and optimized bagasse lignin
substituted phenol formaldehyde (LPF) adhesives. As
observed adhesive strength, shear strength, non-volatile
solids and viscosity are higher in the case of LPF. This
indicates higher crosslink density and molecular weight
of LPF adhesive.
Fig. 7 presents the IR spectra of CPF and LPF
adhesives, and assignments of peaks in the spectra are
given in Table 4. It is observed that IR spectra of CPF
and LPF show similar dispositions of peaks, which
indicates structural similarity of the two adhesive
systems. Peaks in the region 850–750 cm1 are due to
trisubstituted ring and confirm the formation of three
dimensional network structures.
Fig. 8 presents the DSC thermogram of PF and LPF
adhesives. In both the cases a sharp endotherm, which is
a consequence of curing in PF adhesive is observed. The
peak temperature (TP ), onset temperature (To ), and DT
ðTp 2To Þ are presented in Table 5. Parameter (TP 2To ) is
a measure of rate of curing. From the table, it is
observed that although in the CPF resin curing starts at
a lower temperature, the peak temperature is high. The
DT value is 35
C for the CPF resin and it decreases to
7
C for the LPF resin. The higher value of DT in the
 ARTICLE IN PRESS
M.A. Khan et al. / International Journal of Adhesion & Adhesives 24 (2004) 485–493 491

Table 3 case of CPF resin shows a lower rate of curing. In the

Physico-mechanical Properties of CPF and LPF Adhesives
Property
Non-volatile content (%)
Gel time at 100
C (s)
Viscosity at 25
C (cP)
Adhesive strength (kg cm2)
Shear strength (kg cm2)
case of LPF resin, curing starts at a higher temperature
Adhesive but peak temperature is low. This gives a lower value of
DT; which shows higher rate of curing in the case of
CPF LPF
LPF resin. The results are further confirmed by gel time
35 38 results, which decrease on incorporation of bagasse
480 225 lignin. Higher rates of curing in the case of LPF
2 10
adhesive indicate that incorporation of lignin accelerates
11 24
15 32 the curing of CPF resin. This shows that LPF condenses
faster as compared to CPF. The higher onset tempera-
ture in the case of lignin substituted adhesive indicates
some incubation time for initiation of the curing. Once
started, curing progresses very fast and is complete in a
temperature range of 7
C.
Fig. 9 shows the TGA thermogram of CPF and LPF
resin. Decomposition temperatures and percentage
weight loss values are given in Table 5. The TGA
thermogram of CPF and LPF resin is divided into three
main regions: the first up to 300
C, the second up to
600
C and the third beyond 600
C. The initial weight

Fig. 7. IR spectrum of CPF (A) and LPF (B). Fig. 8. DSC thermograms of CPF and LPF.

Table 4
Assignment of peaks of lignin, CPF and LPF

Wave numbers (cm1) Peak assignment Remarks

Lignin CPF LPF

3424 3378 3368 n (OH) Alcohol aliphatic & aromatic

2932 2923 2927 nip (CH2) In plane aliphatic
2846 2847 2842 nop (CH2) Out of plane aliphatic
1625 1581 1595 n (CQC) Benzene ring
— 1504 1502 n (CQC) Benzene ring

1462 1408 1457 n (CQC) Benzene ring

— 1378 1378 dip (OH) Phenolic
1268 1208 1260 nip (C–O) Phenolic
1136 1170 1136 dip (CH) Aromatic
1030 1051 1051 n (C–O) Methylol

n: Stretching ; d: deformation ; ip : in plane ; op: out of plane

 ARTICLE IN PRESS
492 M.A. Khan et al. / International Journal of Adhesion & Adhesives 24 (2004) 485–493

Table 5
Thermal Properties of CPF and LPF

Resin code TGA analysis DSC analysis

First thermal event Second thermal event Endothermic event

TI ( C) Tmax ( C) Tf ( C) Wt. loss (%) TI ( C) Tmax ( C) Tf ( C) Wt. loss (%) Tp (
C) To (
C) DT (
C)

A 124 190 242 14 468 503 552 22 125 90 35

E 134 263 324 23 405 494 546 16 119 112 07

40
CPF
35 LPF

Viscosity at 25°C (cP)

30
25
20
15
10
5
0
0 7 14 21 28 35 42
Storage Time (in days)
Fig. 10. Effect of storage time on viscosity.

Fig. 9. TGA thermograms of CPF and LPF.

stability of the lignin substituted phenol formaldehyde

loss in the temperature range of 120–300
C is believed
to arise from post curing reactions of phenolic resin.
This is also confirmed by an endotherm in DSC
thermogram. In this temperature range, weight loss is
observed as a consequence of loss of water and
paraformaldehyde, due to reaction of hydroxymethyl
groups with each other leading to further crosslinking.
Christiansen et al. also reported a DSC transition in the
range of 139–151
C, which they attributed to cross-
linking in phenolic resin [21]. The second event is a
consequence of the breakdown of methylene linkages in
phenolic resin. The aromatic structure is stable till this
temperature and starts degrading above 600
C. In this
region, aromatic skeleton begins to degrade with very
little weight loss. It is observed that as compared to
CPF, LPF is less stable in the initial stages, but at higher
temperatures both are comparable. In the case of LPF
resin the first thermal event starts at higher temperature
but ends early and shows a steep curve in this region.
This shows a higher rate of weight loss in LPF as
compared to CPF. The second thermal event starts
almost at the same temperature in both the cases. In this
thermal event CPF loses 22% weight, whereas, LPF
loses 16% weight. In the case of LPF resin, a higher
weight loss in the initial stages may be attributed to the
breakdown of side chains present in lignin. Improved
resin in the later stages shows a stable three dimensional
network. This further confirms our earlier interpretation
of an increase in crosslink density on lignin substitution.
The shelf-lives of CPF and LPF adhesives were
studied in respect of consistency and adhesive strength
of freshly prepared and stored adhesives. The adhesive
strength and viscosity was measured at 7 days intervals.
Fig. 10 gives the viscosity of CPF and LPF with respect
to storage time. For CPF the initial viscosity was 2 cP.
The value remained same for 7 days, beyond which an
increase in viscosity was observed. The value reached
15 cP after 42 days of storage. In the case of LPF the
initial viscosity value was observed 10 cP. A continuous
increase in viscosity was noticed through out the 42
days. The study reveals that the viscosity of CPF and
LPF adhesives increase continuously throughout the
storage period. Fig. 11 depicts the increase in the value
of adhesive strength with respect to storage time. The
figure shows an increase of adhesive strength during
storage. After 28 days of storage, LPF adhesive shows
adhesive strength of 27 kg cm2. Further increase in
storage time did not improve the adhesive strength even
up to 42 days. The above experiments establish that LPF
has initial adhesive strength values about twice that of
CPF and after 42 days storage the adhesive strength of
LPF still remains about 1.5 times higher than CPF. It
can therefore be concluded that LPF adhesive shows
 ARTICLE IN PRESS
M.A. Khan et al. / International Journal of Adhesion & Adhesives 24 (2004) 485–493 493

Adhesive strength (kg/cm2) 35 6. DSC studies show a lower curing temperature and
30
higher rate of curing for LPF adhesive.
7. Shelf-lives of CPF and LPF adhesives are compar-
25
able. LPF exhibits uniform consistent behaviour
20 during storage in respect of adhesive strength.
15

10 CPF
LPF References
5

0 [1] www.fao.org, 2002.

0 7 14 21 28 35
Storage time (in days)
Fig. 11. Effect of storage time on adhesive strength.
improved performance characteristics including adhe-
sive strength over CPF adhesives.
4. Conclusions
Various conclusions drawn from the present studies
are:
1. Up to 50% of phenol can be substituted with bagasse
alkali lignin.
2. The optimized condition for preparation of bagasse
lignin substituted PF adhesives are a lignin to phenol
ratio 50%, formaldehyde to phenol molar ratio of
2.0, catalyst concentration 10% of phenol, reaction
time 4 h and reaction temperature of 80
C.
3. Incorporation of lignin increases the crosslink density
in PF adhesives.
4. IR spectra of LPF resin show a similar structural
pattern with CPF resin.
5. Thermal stability of CPF and LPF is comparable.
42
[2] Int Sugar J 1932; 482:240.
[3] Atchison JE. 14th Congress of the International Society of
Sugarcane Technology, 1971. p. 1851.
[4] Atchison JE. 14th Congress of the International Society of
Sugarcane Technology, 1971. p. 1189.
[5] Doss KSG, Jain NS. J Sci Ind Res 1945–46, p. 393.
[6] Mobarak F, Fatimy Y, Augustin H, Holzforschung. 1982;36:
131.
[7] Usmani AM, Salyer IO. In: Proceedings of the Polymeric
Applications of Renewable Resources materials, NY; August
89; Polym Sci Technol 1981;17:41.
[8] Guha SRD. Ind Pulp Paper 1959;14:6.
[9] Hassan ML, Wakil NA, Sefain MZ. J Appl Polym Sci
2001;79(11):1965.
[10] Forss KG, Fuhrmann A. Forest Prod J 1979;29(7):39.
[11] Benar P, Adilson RG, Dalmo M, Schuchardt V. Bioresource
Technol 1999;68:11.
[12] Wenlery A, Ala A, Brain T. Polym Int 1989;47:69.
[13] Sayyah SM, Saad SM, Metwally NE, Shaaban SM. Acta
Polymeric 1988;39(10):574–82.
[14] Klashorst GH, Cameroon FA, Pizzi A. Holzals Roh-und
werkstoff, 1985;43:477–81.
[15] Klashorst GH, D.Sc. thesis, University of Pretoria, 1985.
[16] Khan MA, Ph.D. thesis, Jamia Millia Islamia University, India,
2003.
[17] Ysbrandy RE, et al. Cell Chem Tech 1991;25:369.
[18] Sayyah SM, Gawish NM, Morad A, Moustafa AB. Ind J Techn
1985;23:348.
[19] Panday KK. J Appl Polym Sci 1999;71:1969.
[20] Pizzi A, Stephanou A. J Appl Polym Sci 1994;51:1351–2.
[21] Christiansen AW, Gollob L. J Appl Polym Sci 1985;30:2279.