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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
0143-7496/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijadhadh.2004.01.003
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groups per phenylpropane unit [14,15] and hence, was filtered under vacuum, washed repeatedly with hot
appears more suitable for the preparation of phenolic distilled water till neutral. A 159 g lignin cake was
resin. obtained having 33% solid content.
Adhesives are required in many wood processing
industries such as particleboard, wood panels, fiber 2.3. Adhesive preparation
boards and plywood etc. Among the various adhesive
used for the production of these articles, resole phenol Phenol formaldehyde (PF) and lignin phenol formal-
formaldehyde is the most common type of adhesive. dehyde (LPF) both were prepared in a four neck round
With the increasing use of composite materials such as bottom flask equipped with a stirrer, thermometer,
strand board, flake board, and composite lumber, the reflux condenser and dropping funnel.
demand for adhesives is increasing. These adhesives are
in adequate supply today, but scarcity of petroleum 2.3.1. Preparation of phenol formaldehyde (PF) adhesive
products could affect the future cost and availability of 11.64 g of molten phenol, 20.27 g formaldehyde
these petroleum based adhesives. To avoid this scenario, solution and 10 g each of distilled water and methanol
it is imperative to explore the possibility of replacing were taken in a flask. The mixture was heated to
petroleum based raw materials. Throughout the world 8071 C. 1.16 g of sodium hydroxide in distilled water
intensive efforts are being made to replace various was then added and the reaction was continued for 4 h
petroleum based raw materials with these kind of at 8071 C.
adhesives.
Numerous reports have been published on the 2.3.2. Preparation of lignin phenol formaldehyde adhesive
preparation of adhesives from bagasse and bagasse Lignin phenol formaldehyde (LPF) adhesive was
lignin [13–18], but any report on the optimization of prepared in two steps: the first step consists of
reaction conditions for the preparation of these adhe- preparation of lignin phenol adduct (LP) and the second
sives is not available in the literature. In this work, we step consists of the preparation of LPF adhesive (i.e.
have attempted to study the various parameters for the polymerization step).
preparation of bagasse lignin substituted phenol for- In the first step, 85 g of lignin cake having 33% lignin
maldehyde adhesives. Prepared adhesives were charac- content was added to a beaker, 28 g phenol equal to the
terized in detail and compared with CPF adhesive in lignin content in the cake (w/w) was added to it. The
performance. 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
2. Experimental second step, 23.28 g of LP adduct (prepared in the first
step), additional phenol (to make the desired lignin:
2.1. Materials used phenol ratio), 20.27 g of formaldehyde solution, 10 g of
methanol were mixed using mechanical stirrer. The
Phenol (99%) of M/s Qualigens (India), formalde- temperature was raised to 80 C. 1.16 g of NaOH
hyde solution (37%) of M/s Merck (India), sulphuric dissolved in distilled water was added to the mixture
acid (98%) and methanol (99%) of M/s s.d Fine and the reaction was continued for 4 h.
Chemicals (India) and sodium hydroxide (97%) of M/s
Rankem (India) were used for experimental work. 2.4. Testing and analysis of the adhesives
Bagasse was collected from Titavi Sugar Mills of
Muzaffarnagar, U.P., India. It was washed with distilled Hydroxyl value was determined as per IS:548: Part–I.
water, dried in oven at 10075 C for 4 h, ground using A known amount of the sample is acetylated under
conventional mixer/grinder and subsequently used for controlled condition and titrated against alcoholic KOH
delignification. solution. Hydroxyl value was calculated using the
formula:
2.2. Lignin extraction from bagasse
56:1 N Y
Hydroxyl value ¼ ; ð1Þ
Delignification was performed in a two neck round W
bottom flask equipped with a condenser and a thermo- where N is normality of alcoholic KOH, Y is alcoholic
meter. 250 g of dried ground bagasse and 2.5 kg of KOH solution required for sample—blank, and W is
5 mol/l sodium hydroxide were charged into flask. weight of sample taken.
Temperature was maintained at 10071 C for 7 h Black Elemental analysis of lignin was carried out using a
liquor so obtained was filtered to remove suspended CHN Rapid Elemental Analyzer model Heraeus
pulp fibers and then neutralized with 50% H2SO4 5002651. 10–20 mg lignin was put in oxidative combus-
solution under constant stirring. The precipitated lignin tion chamber at 950 C using cerium oxide as oxidation
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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.
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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
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
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at 60 C, 80 C, 90 C and 100 C. The adhesive prepared property profiles. Table 3 presents the physico-mechan-
at 100 C gels during reaction. As observed from Fig. 6, ical properties of CPF and optimized bagasse lignin
adhesive strength and shear strength increase sharply on substituted phenol formaldehyde (LPF) adhesives. As
increasing the temperature from 60 C to 80 C, and then observed adhesive strength, shear strength, non-volatile
decreases slightly. It appears that the crosslink forma- solids and viscosity are higher in the case of LPF. This
tion reaction starts at 60oC. However, at this tempera- indicates higher crosslink density and molecular weight
ture, the rate and the extent of crosslink formation are of LPF adhesive.
lower. With the increase in temperature, rate and extent Fig. 7 presents the IR spectra of CPF and LPF
of network formation increases. This causes the increase adhesives, and assignments of peaks in the spectra are
in resin yield. At 80 C, shear strength and adhesive given in Table 4. It is observed that IR spectra of CPF
strength both are highest. At 90 C the resin yield and LPF show similar dispositions of peaks, which
decreases and gel time is also found to decrease slightly indicates structural similarity of the two adhesive
at this temperature. The small decrease in gel time shows systems. Peaks in the region 850–750 cm1 are due to
that the rate of network formation is slightly less, which trisubstituted ring and confirm the formation of three
causes a small decrease in the non-volatile content. Our dimensional network structures.
earlier observations that shear and adhesive strength of Fig. 8 presents the DSC thermogram of PF and LPF
LPF adhesives are directly proportional to the resin adhesives. In both the cases a sharp endotherm, which is
yield is confirmed by these results also. It can be inferred a consequence of curing in PF adhesive is observed. The
that 80 C is the optimal polymerization temperature for peak temperature (TP ), onset temperature (To ), and DT
preparation of LPF adhesives. ðTp 2To Þ are presented in Table 5. Parameter (TP 2To ) is
a measure of rate of curing. From the table, it is
3.3. Characterization of adhesives observed that although in the CPF resin curing starts at
a lower temperature, the peak temperature is high. The
The LPF adhesive prepared at optimized conditions DT value is 35 C for the CPF resin and it decreases to
was compared with CPF adhesive for their detailed 7 C for the LPF resin. The higher value of DT in the
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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
Table 5
Thermal Properties of CPF and LPF
40
CPF
35 LPF
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