The Quality of PinuspinasterArBinenn Particleboards Using Natural Adhesive Made of Corn Starch, Tannin and Chitosan
THE QUALITY OF
PinuspinasterArBinennPARTICLEBOARDS USING
NATURAL ADHESIVE MADE OF CORN STARCH,
TANNIN AND CHITOSAN
SONIA SOMADONA
THE GRADUATE SCHOOL
BOGOR AGRICULTURAL UNIVERSITY
BOGOR
2012
DECLARATION
I
declare
that
this
thesisentitled
The
Quality
of
PinuspinasterArBinennParticleboards Using Natural Adhesive Made of Corn
Starch, Tannin and Chitosan is my own work with the direction of the supervising
committee and has not been submitted in any form for any college except in
ENGREF, France (require by Double Degree Program). Information and quotes
from journals and books have been acknowledge and mentioned in the thesis
where they appear. All complete references are given at the end of the paper.
I understand that my thesis will become part of the collection of Bogor
Agricultural University. My signature below give, the copyright of my thesis to
Bogor Agricultural University.
Bogor, October 2012
Sonia Somadona
E251100151
ABSTRACT
SONIA SOMADONA.The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and Chitosan.Under the
supervision of SURDIDING RUHENDI and BERTRAND CHARRIER.
The development and optimization of a new, environment-friendly
adhesive made from abundant and renewable cornstarch, tannin and chitosan is
described in this study. At present, the production of wood composites mainly
relies on petrochemical and formaldehyde-based adhesives such as phenolformaldehyde (PF) resins and urea-formaldehyde (UF) resins. Natural adhesive is
not only environmentally friendly but also less expensive as compared to other
exterior binders used in wood composite industry. The objective of this study is to
evaluate the quality of adhesive and particleboard produced. This research
describes performances of natural adhesive obtained from cornstarch, tannin and
chitosan (solid content, viscosity, gel time, pH and bond strength). Results
describe physical properties of all particleboard production according to standard
EN 323, 2004. Mechanical properties of particleboard did not fulfilled standard
EN 312 for IB, MOR and MOE.
Keywords: corn starch, tannin, chitosan, particleboard, quality of adhesive and
particleboard.
SUMMARY
SONIA SOMADONA.The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and Chitosan.Under the
supervision of SURDIDING RUHENDI and BERTRAND CHARRIER.
Currently, the majority of wood based panels for furniture or construction
(particle board, OSB, plywood, LVL, etc.) has used synthetic adhesives such as
urea-formaldehyde, melamine formaldehyde, phenol-formaldehyde and
resorcinol-formaldehyde are derived from petroleum andnon renewable fossil
resource.They contain formaldehyde which is volatile and harmful for human
health
Renewable raw materials have several own advantages such as
availability, and regeneration. The use of adhesives from renewable raw materials
will replace the petroleum based adhesives as they are more environmentally
friendly and are able to reduce formaldehyde emissions. These renewable raw
materials are corn, tannin and chitosan. These three materials represent an
alternative to natural adhesivesin place of synthetic adhesives.
The study was conducted testing the quality of natural adhesives from
these three resources and the quality of particleboard using the natural adhesives.
Tested the quality of adhesive such as solid content, gel time, pH and viscosity
with reference to JIS K 6833-1980) was conducted and for tested quality of
particleboard according to standard methods of European Standard EN 310, 317,
319, and 323 for particleboard and fiberboard.
The qualities of natural adhesive are as follows : solid content has value
between 30.79% - 31.37 %, viscosity between 30800 cP - 37083.33cP, gel time
value about 671.67 second - 980.92 second, pH between 10.66 - 11.91 and bond
strength between 2. 29 N/mm2 - 2.98 N/mm2.Based on the results, the solid
content value of natural adhesive made of three reneweble raw materials (corn
starch, tannin, and chitosan) under the standards set.While the viscosity, gel time
and pH do not have the standard. The bond strength of natural adhesive has a
value above the standards (≥ 1 N/mm2)
The qualities of particleboard produced in this research are as follows :
density has value between 0.39 g/cm3 - 0.43 g/cm3, moisture content between 9.64
% -12.29 %, thickness swelling in 2 h between 21.82 % - 23.22 %, thickness
swelling in 24 h between 25.44 % - 28.28 %, internal bond between 0.03 N/mm2 0.12 N/mm2, MOR value between 0.93 N/mm2 - 1.73 N/mm2 and MOE between
91.27 N/mm2 - 182.19 N/mm2.The quality of particleboard produced only
moisture content and density has a value above the European Standard.
Whileinternal bond, thickness swelling, MOE and MOE were lower than
beEuropean Standard.
Keywords: synthetic adhesives, renewable raw materials, corn, tannin, chitosan,
particleboard, quality of adhesive and particleboard.
© CopyrightIPB, 2012
Copyright Reserved by Law
Prohibited quoting part or all of this paper without mentioning or citing
the sources. Quotation is only for educational purposes, research, writing papers,
preparing reports, writing criticism, or review of an issue, and the citations will
not harm the interests of IPB
Prohibited topublish andreproducepart or all ofthis paperin any
formwithoutpermissionIPB
THE QUALITY OF PinuspinasterArBinenn
PARTICLEBOARDS USING NATURAL ADHESIVE MADE
OF CORN STARCH, TANNIN AND CHITOSAN
SONIA SOMADONA
Thesis
In partial fulfillment of the requirements for the degree
of Master of Science at Department of Forest Product
THE GRADUATE SCHOOL
BOGOR AGRICULTURAL UNIVERSITY
BOGOR
2012
Thesis External Examiner: Dr. Ir. JajangSuryana, M. Sc
Title
: The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and
Chitosan
Name
: Sonia Somadona
NIM
: E 251100151
Approvedby :
Advisory Committee
Prof. Dr. Ir. SurdidingRuhendi
Prof. Dr. Bertrand Charrier
Chairman
Member
Accepted by:
Chairman of The Department of
Dean of The Graduate School
Forest Product
Prof. Dr. Ir. WayanDarmawan, M.Sc.
Dr. Ir. DahrulSyah, M.Sc.Agr
Date of Examination :
Date of Graduation :
ACKNOWLEDGEMENTS
Gratitude to Allah SWT, because of the abundance of his gifts are given
the opportunity and health writer so I can complete thesis on the theme
"The
Quality of PinuspinasterArBinenn Particleboards Using Natural adhesive Made of
Corn Starch, Tannin and Chitosan"
First of all, I am very grateful to Prof. Dr. Ir. SurdidingRuhendi and
Prof. Dr. BertrandCharrier for his skillful and patient guidance throughout my
master study. I also appreciate his work on review and revision of this thesis. His
scientific and earnest attitude in research will definitely be beneficial to my future
work and life.
I also thanks full to Ministry of National Education and Department of
Forest Product Bogor Agricultural University for Double Degree IndonesiaFranceScholarship
Last but not the least, I would like to thank my parents (Alm) Iskandar As
and Hj. Husdaliza, SE and my sister Gita Suliska, (Alm) EziRahmadhani for their
unselfish love and continuous support for motivation. I would like tothank Raya
Syah Putra for love and fidelity to me.
Bogor, October 2012
Sonia Somadona
TABLE OF CONTENTS
Page
LIST OF FIGURE
xii
LIST OF APPENDIX
xiv
INTRODUCTION
1
Background
1
Objectives of Research
2
LITERATURE REVIEW
3
Particleboard
3
Tannin
4
CornStarch
5
Chitosan
5
MATERIAL AND METHOD
7
Time and Place of Research
7
Materials and Research Equipment
7
Experimental Design
7
Adhesive Preparation
7
ParticleboardPreparation
Testing of Adhesive
8
9
Solid Content
9
Viscosity
9
Gel Time
10
pH
10
Bond Strength of Adhesive
10
Testing of Particleboard
11
Density
11
Moisture Content
11
Thickness Swelling
12
Internal Bond
12
MOR and MOE
13
RESULTS AND DISCUSSION
15
Quality of Adhesive
15
Solid Content
15
Viscosity
15
Gel time and pH
16
Bond Strength
17
Quality of Particleboard
18
Density
18
Moisture Content
19
Thickness Swelling
20
Internal Bond
21
MOR and MOE
21
CONCLUSIONS
23
REFERENCES
25
APPENDIX
29
LIST OF FIGURES
No
Page
1.
Particleboard
3
2.
Condensed tannin and Hydrolyzable tannin
4
3.
Glucose molecule
5
4.
Chitosan
6
5.
Process of the particleboardpreparation
8
6.
Cutting diagram particleboard
9
7.
Test of adhesion of adhesive
11
8.
Testing Internal Bond
12
9.
Way of testing the MOR and MOE
13
10. The Average Value of the Solid Content of Natural Adhesive
15
for Different Concentration of Chitosan
11. The Average Value of the Viscosity of Natural Adhesive
16
for Different Concentration of Chitosan
12. The Average Value of the Gel Time of Natural Adhesive
17
for Different Concentration of Chitosan
13. The Average Value of the pH of Natural Adhesive
17
for Different Concentration of Chitosan
14. The Average Value of the Bond Strength of Natural Adhesive
18
for Different Concentration of Chitosan
15. The Average Value of theDensityof Particleboard
18
for Different Concentration of Chitosan
16. The Average Value of theMoisture Contentof Particleboard
19
for Different Concentration of Chitosan
17. The Average Value of theThickness Swelling2h and 24h
20
of Particleboard for Different Concentration of Chitosan
18. The Average Value of theInternal Bondof Particleboard
21
for Different Concentration of Chitosan
19. The Average Value of theMORof Particleboard
for Different Concentration of Chitosan
22
20. The Average Value of theMOEof Particleboard
for Different Concentration of Chitosan
22
LIST OF APPENDIX
1.
The Average Value of Qualityof Natural Adhesive
27
for Different Concentration of Chitosan
2.
The Average Value of Qualityof Particleboard
for Different Concentration of Chitosan
28
INTRODUCTION
Background
Currently, the majority of wood based panels for furniture or construction
(particle board, OSB, plywood, LVL, etc.) has used synthetic adhesives such as
urea-formaldehyde,
melamine
formaldehyde,
phenol-formaldehyde
and
resorcinol-formaldehyde .These adhesive are derived from petroleum, which is
non renewablefossil resource. They contain formaldehyde which is volatile
product during both the manufacturing process and after the implementation. The
emission of formaldehyde is harmful for human health(Vick, 1999). Moreover, oil
prices are not stable, affected the price of products that use petroleum-based
adhesives (urea-formaldehyde, melamine formaldehyde, phenol-formaldehyde
and resorcinol-formaldehyde, etc).
Renewable raw materials have several own advantages such as
availability, and regeneration. The use of adhesives from renewable raw materials
will replace the petroleum based adhesives as they are more environmentally
friendly and are able to reduce formaldehyde emissions.
Corn (Zea mays L.) is a commodity of global agriculture. It is an important
source of carbohydrates and protein. Starch is used as an adhesive in a range of
products such as binders, materials, glues and pastes (Imam et al. 1999, Yazaki
and Collins 1997).
Tannins are formed of glycosides or organic polymers which contained in
various plants. Tannins are divided into two groups: condensed tannins and
hydrolyzable tannins. Hydrolyzable tannins are polyphenolic compounds based
complexes of digallic acid and D-gluchilose. While condensed tannins are
composed of units from flavonoids and are used to replace the phenolic
compounds as well as the UF and MUF synthesis in wood-based panels. They do
not emission formaldehyde when used as an adhesive (Pizzi 2006).
Shrimp is one of the most seafood marketed worldwide. The shrimp is
usually exported as frozen without head or skin, so that the waste accounts for 50
to 60% by weight of whole shrimp. Peshkova and Li (2003) indicate that chitosan
can be used as an adhesive.
These three materials represent an alternative to natural adhesivesin place
of synthetic adhesives. Therefore, it is important to conduct studies on the
performance of natural adhesivesfrom these three resources and the quality of
particleboard using the natural adhesives.
Objectives of Research
The objectives of this research are:
1.
To use renewable raw materials to replace synthetic products (especially if
they are hazardous products).
2.
Essential that these glues have physical and mechanical properties at least
similar to synthetic materials (in this case Urea formaldehyde).
3.
These adhesives can be used by industrial processing systems.
LITERATURE REVIEW
Particleboard
According to Bowyer et al. (2003) and Tsoumis (1991), particleboard is a
panel product manufactured by embedding the particles together (such as small
pieces of wood or other lignocellulosic material), with wood as a primary
resource. Dumanauw (1990) states that the advantages of particle boards
compared with solid wood are free from knots and checks, size and density can be
adjusted, thickness and density are uniform, more isotropic, quality or surface
appearance can be adjusted according to market or costumer desire. Particleboard
typically has two face layers made from fine wood furnish (external layer) and
one core layer made from coarse wood furnish. Generally particleboard is less
expensive than solid wood. However, compared to solid wood, particleboard has a
lower dimensional stability, lower in screw holding and strength. Particleboard is
mainly used for furniture and kitchen cabinets products.
Approximately 95 %
of the lignocellulosic material
used for
particleboardproduction is wood, but other agro-based residues have not been
frequently utilized. Annual plant wastes, such as flax and hemp shives, bagasse,
cotton stalks, small grain straw (including rice straw), peanut husks, rice husks,
grape stalks, and palm stalks are inexpensive and valuable raw materials for
lignocellulosic board production (Kozlowski et al. 1994).
Figure 1. Particleboard (ShouguangZhongjia Industry and Trade Compay)
Tannins
Tannin is a general term for a widely occurring group of substances that
comes from the plants with varying proportions. Tannins are polyphenolic
compounds which are able to interact with other macromolecules such as proteins
and carbohydrates. Moreover tannin are an excellent renewable resource which
can be used for replacing petroleum-derived phenolic compounds.
Different types of tannins have been used for a long time in the production
of adhesives (Godwin and Mercier. 1983). Hydrolyzable tannin are derivatives of
gallic acid (3,4-5 trihydroxyl benzoic acid). Gallic acid which is esterifies to a
core polyol, and the galloylgroups may be further esterifies or oxidativelycross
linked to yield more complex hydrolyzable tannins. Hydrolyzable tannin can be
decomposed in water, which can react to form other useful substances such as
gallic acid, pyrotocatechic acid and sugar. While condensed tannins, constituting
more than 90% of the total world production of commercial tannins, are both
chemically and economically more interesting for the preparation of resin
adhesive (Pizzi and Mittal. 2003). Condensed tannins have a complex chemistry.
It is a group of phenolic polymers which are widely distributed in the plant
kingdom particularly with woody growth habit. These compounds consist of
flavan-3-ol units linked together through C4-C6 or C4-C8 bonds (Rahim and
Kassim.2008).
(a)
(b)
Figure 2.(a) Condensed tannin, (b) Hydrolyzable tannin
(staff.science.uva.nl)
Corn Starch
Starch is a renewable resource available in abundant quantities at a very
low cost. Starch is a carbohydrate food reserve in plants and the major energy
resource for non-photosynthetic organisms. Starch granules are composed
primarily from different chemically biopolymers (amylase and amylopectine). The
proportions of amylase and amylopectin depend on the variety of corn. Amylase is
essentially a linear molecule which consists of α-glucopyranosyl residues linked
via (1-4) glycosides bonds. While amylopectin molecules, on the other hand, are
highly branched, with α-glucopyranosyl residues linked by (1-4) glycosides
linkages and by α-(1-6) bonds at branch points. Ratio and proportion of amylase
ranged from 20% to 25%, and 75% to 80% for amylopectin respectively
The size of a starch granule also depends on the source, and the potato
starch granules are the largest granules from all sources. When heated, in the
presence of excess water, starch granules lose their crystalline, absorb large
amounts of water, and leach amylase out, which impart viscosity to the
starch/water system (Imam et al. 1999).
Figure 3. Glucose molecule(erzagenatrika.blogspot.com)
Chitosan
Chitosan is N-deacetylatedpolysaccharide that comes from chitin. Chitin
was extracted from crustacean shells, such as shrimp, crab, lobster, squid, and
even beetles. Chitosan is obtained after eliminating 70% of acetyl groups
(CH3C0-) present in chitin. Chitosan does not dissolve in water solvent, alcohol,
and acetone. It is also insoluble in a solution with pH greater than 6.5, but soluble
in dilute organic acids such as acetic acid (Sugita et al. 2009). Chitosan is not
toxic so that it can be utilized in the food industry as food preservatives,
antioxidants, and drinks purified. Currently, chitosan has been exploited by
industries for high quality adhesive, purification of drinking water (having a
coagulation power), increasing the dye industry in paper, textile and pulp
(Alamsyah. 2001). Suptijah P (2006) found that chitosan has a specific shape,
containing amine groups in the carbon chain and positively charged as opposed to
other polysaccharides.
Chitosan is a naturally occurring biopolymer thin sheet-shaped, has no
odor, white in color and the most abundant biomaterial. Chitosan is considered to
be a random copolymer comprised primarily of repeat sugar units with the
structure of a (1-4)-linked 2-amino-2- deoxy-b-D-glucopyranose and comprised
also of some units of (1-4)-linked 2-acetamido-2-deoxy-b- D-glucopyranose
(Wong et al. 2006).
Figure 4. Chitosan(sigmaaldrich.com)
MATERIAL AND METHOD
Time and Place of Research
This researchwas conducted in Laboratory of Physical Chemistry,
University of Pau and Pays de l’Adour, France. This research was carried out
from January 2012 to July 2012.
Materials and Research Equipment
The material used in this research was particle Pinuspinaster from
particleboard industry in Mont de Marsan with moisture content ≤ 5 %. Fine
particles with a size of 10 mesh and coarse particles with a thickness of 5 mm,
length 50 mm and width 4-5 mm were used.Corn starch was obtained from Fisher
scientific while quebracho tannin was obtained from Silva team, chitosan with
molecular weight 600.000-800.000, hexamine, NaOH and aquadest.
Several equipments are used in this study such as: water bath, oven, rotary
mixer,rotary blender, pressing machine, universal testing machine, pH meter,
caliper, viscometer and precision balance.
Experimental Design
The experiments in completely randomized design with three replicates
with different solution concentration of chitosan are (0, 10, 15, and 20 %).The
results obtained were subjected to an analysis of variance (ANOVA) used
software Minitab 15 to identify the effect of the chitosan concentration of chitosan
for quality a of adhesive and properties particle board. Duncan test was applied to
compare treatment means.
AdhesivePreparation
To prepare ± 600 g of adhesive, a corn starch water solution was prepared
at 65% (w/v)concentration, by dissolving 162.5 g of corn starch in 250 ml of
aquadest and stirring at roomtemperature, to which 16.25 g of wattle
quebrachotanninare added and 83 ml of chitosan solution with concentration of 0,
10, 15, to 20% was added. The amount of hexamine, used as a hardener, was 32.5
ml. The hexamine was dissolved in aquadest to give a solution of concentration
equal to 30% before being added to the solution of corn starch-tannin-chitosan.
The solution was mixed and then 125 ml of sodium hydroxide (33%) were added.
Particleboard Preparation
Particleboard was made by three layers, face, core, and back. Ratio
between face/back and core is 30:70 based on weight strands. Target of density is
set to 0.6 g/cm3and the size of panel is 22 cm x 22 cm x 2 cm. The particleboard
preparation showed in Figure 5.
Particle
Blending
ρ= 0,6 g/cm³
Dimension:
22 cm x 22 cm
The natural
adhesive as much
as 10%
Mat forming
Pressing (195 oC,
d i 8 i )
Conditioning during 2
The quality tesrting based on European Standart EN 310, 317,
319 and 323
Figure 5.Process of the particleboard preparation
All boards were cut and tested according to standard methods of European
Standard EN 310, 317, 319, and 323 for particleboard and fiberboard. The
specimenstests were obtained from each board according to the cutting diagram
showed in Figure 6.
22 cm
22 cm
Figure 6. Cutting diagram of particleboard
Notes :
1. MOE and MOR (20 cm x 5 cm)
2. Density and Moisture content (15 cm x 5 cm)
3. Internal bond (5 cm x 5 cm)
4. Thickness swelling (5 cm x 5 cm)
Testing of Adhesive
Test the quality of adhesive, the studysolid content, gel time, pH and
viscosity with reference to JIS K 6833-1980) was conducted.
Solid Content
Solid Content is ratio between the weight of sample before and after
heating at a given temperature until weight constant. Method of determination the
solids content :
1. Sample of adhesive (1.5 gram was placed in to petridish (W1)
2. The adhesive in the petridish was dried in an oven at 105 ± 2 oC for 1 hour
3. Petridish was put in a desiccator for 10 minutes, then weighed
4. Drying and measuremass were performed until constant weight (W2).
Solid content is determined by the formula:
Viscosity
The principle of measuring the viscosity is a measure of internal friction
induced by the cohesion of the molecules in the adhesive. The viscosities of the
natural adhesive were determined using a Brookfield Viscometer at 20 rpm using
spindle number S07 and expressed in cP. The viscosity was measured in triplicate
at 25 ± 1 °C.
Gel Time
Gelation is defined as the point where the resin ceases to be a viscous
liquid and becomes soft, elastic, solid rubber (Pizzi and Stephanou. 1993). Five
gram of adhesive was placed in a test tube and heated in boiling water or in water
bath at temperatures above 100 °C under continuous mixing. The reactivity of a
mixture is defined as the time measured from the beginning of heating until
gelation occurred.
pH
The pH measurement is a measure of the concentration of H + ions in a
solution. The method for determining the pH of the adhesive using a pH meter is
as follows:
1. The samples of adhesive are poured into a 200 ml beaker and the acidity
was measured at 25 °C using a pH meter.
2. Before pH measurement, a calibration of the pH meter is first performed
with buffer solutions of pH equal to 4 and 7 at a temperature of 25 oC.
Bond Strength of Adhesive
Maritime pine veneer with a thickness of 3 mm was cut to rectangular
specimen 2.5 x 11. 5 cm (according to British Standard 1204, 1965, part 2, for
synthetics resin adhesives). The adhesive was applied to one side of piece of
veneer. The application area was 2.5 x 2.5 cm for each veneer. The spread rate of
adhesive was 120-150 g/m2 on a dry weight basis (Ihat and Nilgul. 2002, Pizzi.
1977). The press temperature and press time were set at 195 oCduring 8 min. After
that, the veneer was conditioned in a room temperature (25 oC and 65 % relative
humidity) for 24hour.
Bonding quality was evaluated from the percentage of wood failure at the
bonding area and bond strength of each specimen. The description of the
procedure in Figure 7 is below:
Figure 7. Test of adhesion of adhesive
Testing of Particleboard
Density
Density of a particleboard were determined according were determined
according to the European Standard method (EN 323) on specimens with
dimensions 200 mm x 50 mm x 20 mm. The density is the average of the
measured densities on the test specimens of each panel. This density is the ratio of
the mass of each specimen and volume.
Where :
Ρ
: density
M
: mass of the sample
V
: volume of the sample
Moisture Content
European Standard (EN 323) was using to determine moisture content. It
corresponds to the mass loss from the sample after drying in an oven at 103 ± 2
°C to constant weight. Denoted by H, the water content is expressed as a
percentage by weight and is equal to:
Where :
H
: moisture content (%)
M1
: mass of the sample before drying in an oven (g).
M2
: mass of the sample after drying in an oven until constant weight (g).
Thickness Swelling
Thickness swelling was determined according to the European Standard
method (EN 317). To determine thickness swelling properties, particleboards were
cut into 50 mm × 50 mm and soaked in water at room temperature (20 ± 2 °C) for
both 2 hour (h) and 24 hour (h). The thickness and weight of the particleboard
samples were measured before and immediately after soaking. Thickness swelling
were calculated as ratios of absorbed water and increased thickness to the values
before soaking, respectively, and expressed as percentages.
Where :
t1
: thickness of sample before immersion (mm)
t2
: thickness of sample after immersion (mm)
Internal Bond
Size of sample 50 mm x 50 mm x 20 mm were attached to two aluminum
blocks with polypropylene adhesive and left to dry. Two blocks drawn
perpendicular to the surface of the specimen until the maximum load. Internal
bond values calculated using the formula:
where:
IB
: internal bond (N/mm2)
Pmax
: maximum compressive load (N)
A
: surface area the sample (mm2)
Direction of the load
Aluminum block
Sample
Direction of the load
Figure 8. Testing Internal Bond
Modulus of elasticity (MOE) and Modulus of Rupture (MOR)
According to European Standard EN 310, twelve specimens of dimensions
200 mm x 50 mm x 20 mm on each panel particles were used to determine the
strength in three-point bending. The flexural modulus of elasticity (MOE) and
bending strength (MOR) were calculated using the following formulas:
Where :
Fi
: load at proportional limit (N/mm2)
L
: length of span (mm)
e
: thickness of specimen (mm)
: the bending load (N/mm2)
ai
b
: width of specimen (mm)
Where :
Frupture
: maximum compressive load (N/mm2)
L
: length of span (mm)
b
: width of specimen (mm)
e
: thickness of specimen (mm)
Sample used measuring 20 mm x 50 mm x 20 mm in air dry conditions
with the loading pattern shown in Figure 9 :
L
Sample
L
Figure 9.Way of testing the MOR and MOE
a
RESULTS AND DISCUSSION
Quality of Adhesive
Solid Content
Figure 10shows that addition of chitosan induces small decrease of solid
content of the adhesive. The value of solids content in adhesive without added of
chitosan solution is 30.79% which is not significantly different from that after the
addition of chitosan with a concentration at 20% (31.27%).
65,00
70,00
Solid content (%)
60,00
50,00
40,00
30.79
30.86
31.27
31.37
30,00
20,00
10,00
0,00
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 10. The Average Value of the Solid Content of Natural
Adhesive for Different Concentration of Chitosan
The solid content of the samples increased with increased concentration of
chitosan, although not significant.Higher solid content of adhesives may increase
the number of adhesive molecules that will react with wood during adhesion
process. Increase of solid content will improve the quality of adhesive. Vick
(1999) state that solid content in a certain limit, the higher resulting bond strength
of board because many molecules of the adhesive that react with the wood in the
gluing process. Also, solid content has more effect on both IB, MOR and MOE.
ANOVA results showed that the treatment factor had no significant effect
on solid content values.
Viscosity
The viscosity values of resins made from different additions of chitosan
solution;
65:10:0,
65:10:10,
65:10:15
and
65:10:20
(corn
starch:quebrachotannin:chitosan solution, weight ratios) were tested. The results
of viscosity test are shown in Figure 11.
50000,00
37083.33 (b)
Viscosity (cP)
40000,00
30800 (a)
31333.33 (a)
33200 (a)
30000,00
20000,00
10000,00
2726,67
0,00
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 11. The Average Value of the Viscosity of Natural Adhesive
for Different Concentration of Chitosan
The viscosity of the samples increased with increased concentration of
chitosan. The increase in viscosity may be due to protein unfolding in accordance
with Angleimer and Montgomery (1976) who stated that an increase in intrinsic
viscosity is one of the effects of protein denaturation. The higher viscosity of
adhesive, the more difficult the adhesive flows on the wood surface because
penetrating the medium and glue line very slowly then caused difficulty to
applying adhesive (Corn Products International. 2006).
ANOVA results showed that treatment factor had significant effect on
viscosity. The advanced test, Duncan test, showed that the concentration of
chitosan 20% were significantly different with concentration of chitosan 0%,
10%, and 15%.
Gel Time and pH
Gel time is defined as the point at which polycondensates formed by the
reaction of a cornstarch-quebrachotannin-chitosan solution become an elastic,
rubbery solid. Gel time is highly dependent on the pH of the adhesive: the gel
time generally decreases when the pH of the adhesive is increases, but does not in
this study, where the gel time increases when pH increases. This is because the
properties of corn starch when first heated melted, and then thickens. The results
of tested gel time and pH can be seen in Figure 12 and 13. At lower pH and
highconcentration of chitosan solution, the gel time is shorter.
1200
980.92 (b)
Gel time (s)
1000
877.35 (b)
800
671.67 (a)
733.36 (a)
600
400
125,68
200
0
A65T10Ch0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 12. The Average Value of Gel Time of Natural Adhesive
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had significant effect on
gel time values. The advanced test, Duncan test, showed that concentration of
chitosan 20% were significantly different with concentration of chitosan 0% and
10%, but were not significantly different with concentration of chitosan 15%.
14,00
12,00
10.66 (a)
10.83 (b)
11.02 (c)
11.91 (d)
pH
10,00
8,00
6,76
6,00
4,00
2,00
0,00
A65T10Ch0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 13. The Average Value of the pH of Natural Adhesive
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had significant effect on
bond strength values. The advanced test, Duncan test, showed that the
concentration of chitosan 20% were significantly different with concentration of
chitosan 0%, 10%, and 15%.
Bond Strength
The bond strength values of resins made with different additions of
chitosan
solution
65:10:0,
65:10:10,
65:10:15,
and
65:10:20
(corn
starch:quebrachotannin:chitosan solution, weight ratios) were tested. The results
of the effect of substitution level of chitosan solution on the bond strength are
shown in Figure 14. The increase of chitosan solution substitution level, bond
strength is relatively affected by the presence of chitosan solution up to 15%
(65:10:15). The bond then decrease due to the presence of chitosan solution of
20% (65:10:20). It is interesting to observe, when the substitution level is higher
than 15%, resin showed small tendency reductions in bond strength values. Thus
it can be concluded that substitution level of 15% is optimal for the preparation of
Bond Strength (N/mm2)
(corn starch-quebracho tannin-chitosan solution, weight ratios) wood adhesives.
4
3,5
3
2,5
2
1,5
1
0,5
0
3.17
2.98
2.74
2.29
A65T10CH0
2.79
A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 14. The Average Value of the Bond Strength of Natural Adhesive
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had no significant effect
on bond strength values.
Quality of Particleboard
Density
Figure 15 shows the density of the particleboard by the using of corn
starch-quebrachotanin-chitosan solution adhesives. The average values of density
are 0.39-0.46 g/cm3.
Density (g/cm3)
0,6
0,5
0,4
0.46
0.39
0.41
0.42
0.43
0,3
0,2
0,1
0
A65T10CH0
A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 15.The Average Value of the Density of Particleboard for
Different Concentration of Chitosan
These results pointed out that the density of particleboard produced is
categorized as medium density. This category is adopted from the classification
according to Maloney (1993) that divides the particleboard into a low density
particleboard that is less than 0.40 g/cm3, medium density that is between 0.400.80 g/cm3, and a high density for more than 0.80 g/cm3. For overall, not all of the
particle boards achieved the density target of 0.6 g/cm3. Can be caused by
moisture content on particleboard that adapted the ambient temperature while
conditioning process. In addition, other factor that may affect the density of board
were evaporation of water when pressing process, the lost of particle during
pressing process and the end of pressing process and measurement process of
dimensions which is not in all parts of particleboard thus there is a possibility of
non compact side of particleboard was not measured.
ANOVA results showed that the treatment factor had no significant effect
on density.
Moisture Content
The result of moisture content of particleboard made of natural adhesive
(corn starch-quebrachotannin-chitosan solution) and UF are between 7.44%12.29%. The moisture content of the particleboards is based on European
Standard EN 323 which suggests 5% to 13%. High moisture content may affect
the quality of the particle board. According to Kollmanet al. (1975),moisture
content is one of the factors that affect the quality of adhesion.The moisture
content of particleboards are shown in Figure 16.
Moisture content (%)
14
12.29 (b)
12
10.38 (a)
10
9.71 (a)
9.64 (a)
7,44
8
6
4
2
0
A65T10CH0
A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 16. The Average Value of the Moisture Content of Particleboard
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had significant effect on
moisture content. The advanced test, Duncan test, showed that the concentration
of chitosan 0% were significantly different with concentration of chitosan 10%,
15%, and 20%.
Thickness Swelling
Based on EN Standards, particleboard should have a maximum thickness
swelling (TS) value of 8% for 2h immersion. In addition, the maximum TS for 24
h requirement EN312 (2004) is 15%. Average TS of the specimens ranged from
10.24% to 23.22% and 11.41% to 28.28% for 2 h and 24h immersion,
respectively. Panel which used natural adhesive (corn starch 65% and tannin 10%)
gave the highest TS of 23.22 and 28.28% after soaking for 2 h and 24h,
respectively. Springback of the panels as they are soaked in water is transferred in
less-dimensional stability which is a common behavior of any wood composite
(Kalaycıogluand Nemli. 2006). In general, panels did not satisfy the thickness
swelling requirement for general uses. This is probably because of no utilization
wax (hydrophobic substance) in particleboard manufacturing.
Bond quality and adhesive properties affected the thickness swelling
(Sauter, 1996). The high thickness swelling of particleboard because using natural
adhesive made of corn starch, tannin and chitosan so water was able to penetrate
easily into the weakly bonded particleboard. Also,raw materials natural adhesive
had the carbohydrate content, making it rich in hydroxy groups.
Figure 17 shows the thickness swelling of particleboard samples for 2 h
25.44
2 Hour
20
15
11,41
24 Hour
10,24
25
21.82
26.59
22.34
27.33
22.25
30
28.28
Thickness swelling (%)
35
23.22
and 24h.
10
5
0
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 17. The Average Value of the Thickness Swelling 2 h and 24 h
of Particleboard for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had no significant effect
on thickness swelling 2h and 24h.
Internal Bond
Internal bond (IB) data ranged from 0.03 to 0.33 N/mm2. The minimum
requirement of internal bond strength for general purpose (EN 312, 2004) and
interior fitments (EN 312, 2004) are 0.24 and 0.35 N/mm2, respectively.
According to the test results, internal bond values of all the particle boards
produced were lower than the European Standard EN 312, just particleboard used
UF average value as 0.33 N/mm2. Figure 18 shows the average value of internal
IB (N/mm2)
bond.
0,4
0,35
0,3
0,25
0,2
0,15
0,1
0,05
0
0,33
0.12 (d)
0.07 (c)
0.062 (b)
0.03 (a)
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 18. The Average Value of the IB of Particleboard for
Different Concentration of Chitosan
The low value of IB may be caused by during the blending process of the
adhesive. Wood particles were not uniformly mixed with glue. According to
Cavdaret al.(2008) internal bond strength is very sensitive to resin distribution on
the strands and vertical density profiles of the panels.
ANOVA results showed that the treatment factor had significant effect on
internal bond. The advanced test, Duncan test, showed that the treatment is
significantly different on each treatment.
MOR and MOE
Based on EN Standards 11.5 and 1500 N/mm2 are the minimum
requirements for respectively MOR and MOE of particleboard panels for interior
fitments including furniture manufacturing application (EN 312, 2004). Average
MOR and MOE of the specimens ranged from 0.93 to 2.97 N/mm2 for MOR and
91.27 to 474.44 N/mm2 for MOE.
All panels made with natural adhesive and UF had the lower values
compared to other types of specimens and exceed the EN Standards for MOR and
MOE for interior fitments including furniture manufacturing application. This
may be caused by during the blending process of the adhesive and the wood
particles which are not well mixed so that the particleboard does not coherent
enough with the glue. The high level of viscosity is probably at the origin of
theses low performances. Figure 19 and 20 shows the average value MOR and
MOR (N/mm2)
MOE.
4
3,5
3
2,5
2
1,5
1
0,5
0
2.96
1.48
1.73
1
0.93
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 19. The Average Value of the MOR of Particleboard
for Different Concentration of Chitosan
600
474,44
MOE (N/mm2)
500
400
300
182.19
147.79
200
164.55
91.27
100
0
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 20. The Average Value of the MOE of Particleboard
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had no significant effect
on MOR and MOE.
CONCLUSIONS
1. The resulting natural adhesive qualities are as follows: solid content has value
between 30.79% - 31.37 %, viscosity between 30800 cP - 37083.33cP, gel time
value about 671.67 second - 980.92 second, pH between 10.66 - 11.91 and
bond strength between 2. 29 N/mm2- 2.98 N/mm2.
2. The qualities of particleboard produced in this research are as follows: density
has value between 0.39 g/cm3- 0.43 g/cm3, moisture content between 9.64 % 12.29 %, thickness swelling in 2 h between 21.82 % - 23.22 %, thickness
swelling in 24 h between 25.44 % - 28.28 %, internal bond between 0.03
N/mm2- 0.12 N/mm2, MOR value between 0.93 N/mm2- 1.73 N/mm2 and
MOE between 91.27 N/mm2- 182.19 N/mm2.
3. The factors that affect the quality of adhesive such as: quality of raw materials,
characteristics of the raw materials. While The factors that affect the quality of
particleboard are adhesive viscosity and solid content of adhesive, and process
preparation of particleboard.
4. If compared to the adhesive quality of UF and particle board using UF,the
natural adhesive is far below the standard, thus affecting the quality of the
particleboard.
REFERENCES
Angleimer, A.F., Montgomery, M.W. 1976. Amino Acids, Peptides and
Proteins.In: Fenema, O.R. (Ed.), Food Chem. Marcel Dekker. New York,
NY. 205-284.
Alamsyah
R.
2001.
KarakteristikdanPenerapanKhitindanKhitosan.JurnalTeknologiIndustri. II
(2).61-68.
Bowyer, J.L. Shmulsky, R. Haygreen, J.G. 2003. Forest Product and Wood
Science An Introdution 4th Ed. USA : Iowa State Press A Blackwell Publ.
Corn Products International, Inc. 2006.Corrugating Starch Adhesives Manual.
USA. 9-10.
DepartemenKehutanandan
Perkebunan.1999.PanduanKehutanan
Indonesia.DepartemenKehutanandan
Perkebunan
Republik
Indonesia.Jakarta.
Dumanauw, J. F. 1990.
Atas.Semarang.
Mengenal
Kayu.
Pendidikan
Industri
Kayu
European Standard EN 310. 1993. Wood-based PanelsDetermination of
Modulusof Elasticity in Bending and of Bending Strength. European
Committee for Standardization. Brussels. Belgium.
European Standard EN 312. 2003. Particleboards - Specifications.
EuropeanCommittee for Standardization. Brussels. Belgium.
European Standard EN 317. 1993. Particleboards and Fiberboards
Determinationof Swelling in Thickness After Immersion in Water.
European Committee for Standardization. Brussels. Belgium.
European Standard EN 319. 1993. Particleboards and FiberboardsDeterminationof
Tensile Strength Perpendicular to the Plane of the Board. European
Committee for Standardization. Brussels. Belgium.
European Standard EN 323. 1993. Wood-based Panels Determination of
Density.European Committee for Standardization. Brussels. Belgium.
Foley,W. J.,Iason, G. R. and Mcarthur, C. 1999. Role of Secondary Metabolites In
the Nutritional Ecology of Mammalian Herbivores: How Far Have We
Come In 25 Years In: Nutritional Ecology of Herbivores, H.-J.G. Jung and
G. C. Fahey Jr, (Eds) American Society of Animal Science, Illinois. 130–
209.
Godwin, T.W.; and Mercier, E.I. 1983. Introduction to Plant Biochemistry, 2nd
ed. Pergamon Press. Oxford, UK.
Imam, S.H., Mao, L., Chen, L., Greene, R.V. 1999. Wood Adhesive
FromCrosslinkedpoly(Vinyl Alcohol) And Partially Gelatinized Starch:
Preparation and Properties. Starch/Stärke.51 (6).225–229.
Japanese Industrial Standard. 1980. General Testing Methods for Adhesive. JIS K
6833-1980. Japanese Standard Associations. Japan.
Kalaycioglu H., Nemli, G. 2006. Producing Composite Particleboard FromKenaf
(Hibiscus Cannabinus L.) Stalks, Industrial Crops And Products.24. 177–
180.
Kollmann, F.F.P., E.W. Kuenzi and A.J. Stamn. 1975. Principle of Wood Science
and Technology. Vol. 11. Springer–Verlag, Berlin. Heildelberg. New
York.
Lopez, C. dan P. Shanley. 2004. Kekayaan Hutan Asia. PT Gramedia
PustakaUtama, Anggota IKAPI. Jakarta.
Nemli, G., Gezer, E.D., Yildiz, S., Temiz, A., Aydın, A. 2006. Evaluation of
theMechanical, Physical Properties and Decay Resistance of Particleboard
MadeFrom Particles Impregnated With Pinus Brutia Bark Extractives.
Bioresour.Technol. 97 (16). 2059–2064.
Maloney T M. 1993. Modern Particleboard and Dry Process Fiberboard
Manufacturing. San Francisco : Miller Freeman Inc.
Peshkova, S., K. Li. 2003. Investigation Of Chitosan-Phenolics Systems As
Wood Adhesives. Journal of Biotechnology. 102. 199-207.
Pizzi, A., K. L. Mittal. 2003. Handbook Of Adhesive Technology Second
Edition, Revised And Expanded. Marcel Dekker Inc . New York. 568-582
Pizzi, A. 2006. Recent Developments In Eco-Efficient Bio-Based Adhesives for
Wood Bonding: Opportunities and Issues. J. Adhesion Science
Technology. 20 (8).829–846.
Rahim, A and Kassim, J. 2008.Recent Development of Vegetal Tannins in
Corresion Protection of Iron and Steel.Recent Patent on Materials
Sciences. 1. 223-231.
Sauter, S.L. 1996. Developing Composites From Wheat Straw. In: Proceedings of
The 30th International Symposium of Washington State University on
Particleboard/Composite Materials. 197-214.
Singh, N., K. S. Sandhu, and M. Kaur. 2005. Physicochemical Properties
Including Granular Morphology, Amylase Content, Swelling and
Solubility, Thermal and Pasting Properties of Starches From Normal,
Waxy, High Amylase and Sugary Corn. Progress InFood Biopolymer
Research. 1. 43-55.
Sugita P, T Wukirsari, ASjahriza, D Wahyono. 2009. KitosanSebagaiSumber
Biomaterial MasaDepan. IPB Press. Bogor.
SuptijahP.
2006.DeskripsiKarakteristikFungsionaldanAplikasiKitindanKitosan.Dala
m:Prosiding Seminar NasionalKitin-Kitosan2006 ; Bogor, 16 Maret 2006.
DepartemenTeknologiHasilPerairan, FakultasPerikanandanIlmuKelautan
IPB. Bogor. 14-24.
Sutigno.2004. MutuPapanpartikel.http:// mofrinet.cbn.ne.id/ informasi/setjen/
pustan/info-v.htm.[13April 2010].
Tsoumis G. 1991. Science and Technology of Wood. Van Nostrand Reinhold.
New York.
Vick, C.B. 1999. Wood Handbook: Wood as an Engineering Material. Southern
Forest Products Association. Wisconsin.
Wong, K., Sun, G., Zhang, X., Dai, H., Liu, Y., He, C., Leong, K.W. 2006. PEIChitosan,A Novel Gene Delivery System With Transfection Efficiency
Comparableto Polyethylenimine In Vitro and After Liver Administration
In Vivo. Bioconjug.Chem. 17. 152–158.
Yamada, K., T. Chen., G. Kumar., O. Vesnovsky., L. D. Timmie., and G. F.
Payne. 2000. Chitosan Based Water-Resistant Adhesive. Analogy to
Mussel Glue. Journal: Biomacromolecules. 1. 252-258.
Yazaki Y, Collins PJ. 1997. Uses of Wattle Extract: Tannin Based Adhesives.
Rural Industries Research and Development Corporation.RIRDC
Publication No. 97/72.Chapter 15.127-143.
APPENDIX
APPENDIX
Appendix 1.The Average Value of Qualityof Natural Adhesive for Different Concentration of Chitosan
Quality of
Tipe of Adhesive
Adhesive
Natural
Synth
etic
0%
10%
15%
20%
Solid Content (%)
30.79
30.86
32.27
31.37
65
Viscosity (cP)
30800
31333
33200
37083.
2680
Gel Time (second)
671.67 .33
pH
10.66
Bond
(N/mm2)
Strength
2.29
877.3
733.3
6
10.83
5
UF
33
125.6
980.92
8
11.02
11.91
6.76
2.98
2.79
3.17
2.74
29
Appendix 2.The Average Value of Qualityof Particleboard for Different Concentration of Chitosan
Quality of ParticleBoard
Tipe of Adhesive
Natural
Synthet
ic
0%
10%
15%
20%
UF
Density (g/cm3)
0.39
0.41
0.42
0.43
0.46
Moisture Content (%)
12.29
10.38
9.71
9.64
7.44
Thickness Swelling 2 h (%)
23.22
22.34
21.82
10.24
Thickness Swelling 2 h (%)
28.28
22.25
26.59
25.44
11.41
Internal Bond (N/mm )
0.03
27.33
0.062
0.12
0.33
MOR (N/mm2)
0.93
0.07
1.48
1.73
2.96
MOE (N/mm2)
91.27
1.00
164.55
182.19
474.44
2
147.79
ABSTRACT
SONIA SOMADONA.The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and Chitosan.Under the
supervision of SURDIDING RUHENDI and BERTRAND CHARRIER.
The development and optimization of a new, environment-friendly
adhesive made from abundant and renewable cornstarch, tannin and chitosan is
described in this study. At present, the production of wood composites mainly
relies on petrochemical and formaldehyde-based adhesives such as phenolformaldehyde (PF) resins and urea-formaldehyde (UF) resins. Natural adhesive is
not only environmentally friendly but also less expensive as compared to other
exterior binders used in wood composite industry. The objective of this study is to
evaluate the quality of adhesive and particleboard produced. This research
describes performances of natural adhesive obtained from cornstarch, tannin and
chitosan (solid content, viscosity, gel time, pH and bond strength). Results
describe physical properties of all particleboard production according to standard
EN 323, 2004. Mechanical properties of particleboard did not fulfilled standard
EN 312 for IB, MOR and MOE.
Keywords: corn starch, tannin, chitosan, particleboard, quality of adhesive and
particleboard.
SUMMARY
SONIA SOMADONA.The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and Chitosan.Under the
supervision of SURDIDING RUHENDI and BERTRAND CHARRIER.
Currently, the majority of wood based panels for furniture or construction
(particle board, OSB, plywood, LVL, etc.) has used synthetic adhesives such as
urea-formaldehyde, melamine formaldehyde, phenol-formaldehyde and
resorcinol-formaldehyde are derived from petroleum andnon renewable fossil
resource.They contain formaldehyde which is volatile and harmful for human
health
Renewable raw materials have several own advantages such as
availability, and regeneration. The use of adhesives from renewable raw materials
will replace the petroleum based adhesives as they are more environmentally
friendly and are able to reduce formaldehyde emissions. These renewable raw
materials are corn, tannin and chitosan. These three materials represent an
alternative to natural adhesivesin place of synthetic adhesives.
The study was conducted testing the quality of natural adhesives from
these three resources and the quality of particleboard using the natural adhesives.
Tested the quality of adhesive such as solid content, gel time, pH and viscosity
with reference to JIS K 6833-1980) was conducted and for tested quality of
particleboard according to standard methods of European Standard EN 310, 317,
319, and 323 for particleboard and fiberboard.
The qualities of natural adhesive are as follows : solid content has value
between 30.79% - 31.37 %, viscosity between 30800 cP - 37083.33cP, gel time
value about 671.67 second - 980.92 second, pH between 10.66 - 11.91 and bond
strength between 2. 29 N/mm2 - 2.98 N/mm2.Based on the results, the solid
content value of natural adhesive made of three reneweble raw materials (corn
starch, tannin, and chitosan) under the standards set.While the viscosity, gel time
and pH do not have the standard. The bond strength of natural adhesive has a
value above the standards (≥ 1 N/mm2)
The qualities of particleboard produced in this research are as follows :
density has value between 0.39 g/cm3 - 0.43 g/cm3, moisture content between 9.64
% -12.29 %,
PinuspinasterArBinennPARTICLEBOARDS USING
NATURAL ADHESIVE MADE OF CORN STARCH,
TANNIN AND CHITOSAN
SONIA SOMADONA
THE GRADUATE SCHOOL
BOGOR AGRICULTURAL UNIVERSITY
BOGOR
2012
DECLARATION
I
declare
that
this
thesisentitled
The
Quality
of
PinuspinasterArBinennParticleboards Using Natural Adhesive Made of Corn
Starch, Tannin and Chitosan is my own work with the direction of the supervising
committee and has not been submitted in any form for any college except in
ENGREF, France (require by Double Degree Program). Information and quotes
from journals and books have been acknowledge and mentioned in the thesis
where they appear. All complete references are given at the end of the paper.
I understand that my thesis will become part of the collection of Bogor
Agricultural University. My signature below give, the copyright of my thesis to
Bogor Agricultural University.
Bogor, October 2012
Sonia Somadona
E251100151
ABSTRACT
SONIA SOMADONA.The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and Chitosan.Under the
supervision of SURDIDING RUHENDI and BERTRAND CHARRIER.
The development and optimization of a new, environment-friendly
adhesive made from abundant and renewable cornstarch, tannin and chitosan is
described in this study. At present, the production of wood composites mainly
relies on petrochemical and formaldehyde-based adhesives such as phenolformaldehyde (PF) resins and urea-formaldehyde (UF) resins. Natural adhesive is
not only environmentally friendly but also less expensive as compared to other
exterior binders used in wood composite industry. The objective of this study is to
evaluate the quality of adhesive and particleboard produced. This research
describes performances of natural adhesive obtained from cornstarch, tannin and
chitosan (solid content, viscosity, gel time, pH and bond strength). Results
describe physical properties of all particleboard production according to standard
EN 323, 2004. Mechanical properties of particleboard did not fulfilled standard
EN 312 for IB, MOR and MOE.
Keywords: corn starch, tannin, chitosan, particleboard, quality of adhesive and
particleboard.
SUMMARY
SONIA SOMADONA.The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and Chitosan.Under the
supervision of SURDIDING RUHENDI and BERTRAND CHARRIER.
Currently, the majority of wood based panels for furniture or construction
(particle board, OSB, plywood, LVL, etc.) has used synthetic adhesives such as
urea-formaldehyde, melamine formaldehyde, phenol-formaldehyde and
resorcinol-formaldehyde are derived from petroleum andnon renewable fossil
resource.They contain formaldehyde which is volatile and harmful for human
health
Renewable raw materials have several own advantages such as
availability, and regeneration. The use of adhesives from renewable raw materials
will replace the petroleum based adhesives as they are more environmentally
friendly and are able to reduce formaldehyde emissions. These renewable raw
materials are corn, tannin and chitosan. These three materials represent an
alternative to natural adhesivesin place of synthetic adhesives.
The study was conducted testing the quality of natural adhesives from
these three resources and the quality of particleboard using the natural adhesives.
Tested the quality of adhesive such as solid content, gel time, pH and viscosity
with reference to JIS K 6833-1980) was conducted and for tested quality of
particleboard according to standard methods of European Standard EN 310, 317,
319, and 323 for particleboard and fiberboard.
The qualities of natural adhesive are as follows : solid content has value
between 30.79% - 31.37 %, viscosity between 30800 cP - 37083.33cP, gel time
value about 671.67 second - 980.92 second, pH between 10.66 - 11.91 and bond
strength between 2. 29 N/mm2 - 2.98 N/mm2.Based on the results, the solid
content value of natural adhesive made of three reneweble raw materials (corn
starch, tannin, and chitosan) under the standards set.While the viscosity, gel time
and pH do not have the standard. The bond strength of natural adhesive has a
value above the standards (≥ 1 N/mm2)
The qualities of particleboard produced in this research are as follows :
density has value between 0.39 g/cm3 - 0.43 g/cm3, moisture content between 9.64
% -12.29 %, thickness swelling in 2 h between 21.82 % - 23.22 %, thickness
swelling in 24 h between 25.44 % - 28.28 %, internal bond between 0.03 N/mm2 0.12 N/mm2, MOR value between 0.93 N/mm2 - 1.73 N/mm2 and MOE between
91.27 N/mm2 - 182.19 N/mm2.The quality of particleboard produced only
moisture content and density has a value above the European Standard.
Whileinternal bond, thickness swelling, MOE and MOE were lower than
beEuropean Standard.
Keywords: synthetic adhesives, renewable raw materials, corn, tannin, chitosan,
particleboard, quality of adhesive and particleboard.
© CopyrightIPB, 2012
Copyright Reserved by Law
Prohibited quoting part or all of this paper without mentioning or citing
the sources. Quotation is only for educational purposes, research, writing papers,
preparing reports, writing criticism, or review of an issue, and the citations will
not harm the interests of IPB
Prohibited topublish andreproducepart or all ofthis paperin any
formwithoutpermissionIPB
THE QUALITY OF PinuspinasterArBinenn
PARTICLEBOARDS USING NATURAL ADHESIVE MADE
OF CORN STARCH, TANNIN AND CHITOSAN
SONIA SOMADONA
Thesis
In partial fulfillment of the requirements for the degree
of Master of Science at Department of Forest Product
THE GRADUATE SCHOOL
BOGOR AGRICULTURAL UNIVERSITY
BOGOR
2012
Thesis External Examiner: Dr. Ir. JajangSuryana, M. Sc
Title
: The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and
Chitosan
Name
: Sonia Somadona
NIM
: E 251100151
Approvedby :
Advisory Committee
Prof. Dr. Ir. SurdidingRuhendi
Prof. Dr. Bertrand Charrier
Chairman
Member
Accepted by:
Chairman of The Department of
Dean of The Graduate School
Forest Product
Prof. Dr. Ir. WayanDarmawan, M.Sc.
Dr. Ir. DahrulSyah, M.Sc.Agr
Date of Examination :
Date of Graduation :
ACKNOWLEDGEMENTS
Gratitude to Allah SWT, because of the abundance of his gifts are given
the opportunity and health writer so I can complete thesis on the theme
"The
Quality of PinuspinasterArBinenn Particleboards Using Natural adhesive Made of
Corn Starch, Tannin and Chitosan"
First of all, I am very grateful to Prof. Dr. Ir. SurdidingRuhendi and
Prof. Dr. BertrandCharrier for his skillful and patient guidance throughout my
master study. I also appreciate his work on review and revision of this thesis. His
scientific and earnest attitude in research will definitely be beneficial to my future
work and life.
I also thanks full to Ministry of National Education and Department of
Forest Product Bogor Agricultural University for Double Degree IndonesiaFranceScholarship
Last but not the least, I would like to thank my parents (Alm) Iskandar As
and Hj. Husdaliza, SE and my sister Gita Suliska, (Alm) EziRahmadhani for their
unselfish love and continuous support for motivation. I would like tothank Raya
Syah Putra for love and fidelity to me.
Bogor, October 2012
Sonia Somadona
TABLE OF CONTENTS
Page
LIST OF FIGURE
xii
LIST OF APPENDIX
xiv
INTRODUCTION
1
Background
1
Objectives of Research
2
LITERATURE REVIEW
3
Particleboard
3
Tannin
4
CornStarch
5
Chitosan
5
MATERIAL AND METHOD
7
Time and Place of Research
7
Materials and Research Equipment
7
Experimental Design
7
Adhesive Preparation
7
ParticleboardPreparation
Testing of Adhesive
8
9
Solid Content
9
Viscosity
9
Gel Time
10
pH
10
Bond Strength of Adhesive
10
Testing of Particleboard
11
Density
11
Moisture Content
11
Thickness Swelling
12
Internal Bond
12
MOR and MOE
13
RESULTS AND DISCUSSION
15
Quality of Adhesive
15
Solid Content
15
Viscosity
15
Gel time and pH
16
Bond Strength
17
Quality of Particleboard
18
Density
18
Moisture Content
19
Thickness Swelling
20
Internal Bond
21
MOR and MOE
21
CONCLUSIONS
23
REFERENCES
25
APPENDIX
29
LIST OF FIGURES
No
Page
1.
Particleboard
3
2.
Condensed tannin and Hydrolyzable tannin
4
3.
Glucose molecule
5
4.
Chitosan
6
5.
Process of the particleboardpreparation
8
6.
Cutting diagram particleboard
9
7.
Test of adhesion of adhesive
11
8.
Testing Internal Bond
12
9.
Way of testing the MOR and MOE
13
10. The Average Value of the Solid Content of Natural Adhesive
15
for Different Concentration of Chitosan
11. The Average Value of the Viscosity of Natural Adhesive
16
for Different Concentration of Chitosan
12. The Average Value of the Gel Time of Natural Adhesive
17
for Different Concentration of Chitosan
13. The Average Value of the pH of Natural Adhesive
17
for Different Concentration of Chitosan
14. The Average Value of the Bond Strength of Natural Adhesive
18
for Different Concentration of Chitosan
15. The Average Value of theDensityof Particleboard
18
for Different Concentration of Chitosan
16. The Average Value of theMoisture Contentof Particleboard
19
for Different Concentration of Chitosan
17. The Average Value of theThickness Swelling2h and 24h
20
of Particleboard for Different Concentration of Chitosan
18. The Average Value of theInternal Bondof Particleboard
21
for Different Concentration of Chitosan
19. The Average Value of theMORof Particleboard
for Different Concentration of Chitosan
22
20. The Average Value of theMOEof Particleboard
for Different Concentration of Chitosan
22
LIST OF APPENDIX
1.
The Average Value of Qualityof Natural Adhesive
27
for Different Concentration of Chitosan
2.
The Average Value of Qualityof Particleboard
for Different Concentration of Chitosan
28
INTRODUCTION
Background
Currently, the majority of wood based panels for furniture or construction
(particle board, OSB, plywood, LVL, etc.) has used synthetic adhesives such as
urea-formaldehyde,
melamine
formaldehyde,
phenol-formaldehyde
and
resorcinol-formaldehyde .These adhesive are derived from petroleum, which is
non renewablefossil resource. They contain formaldehyde which is volatile
product during both the manufacturing process and after the implementation. The
emission of formaldehyde is harmful for human health(Vick, 1999). Moreover, oil
prices are not stable, affected the price of products that use petroleum-based
adhesives (urea-formaldehyde, melamine formaldehyde, phenol-formaldehyde
and resorcinol-formaldehyde, etc).
Renewable raw materials have several own advantages such as
availability, and regeneration. The use of adhesives from renewable raw materials
will replace the petroleum based adhesives as they are more environmentally
friendly and are able to reduce formaldehyde emissions.
Corn (Zea mays L.) is a commodity of global agriculture. It is an important
source of carbohydrates and protein. Starch is used as an adhesive in a range of
products such as binders, materials, glues and pastes (Imam et al. 1999, Yazaki
and Collins 1997).
Tannins are formed of glycosides or organic polymers which contained in
various plants. Tannins are divided into two groups: condensed tannins and
hydrolyzable tannins. Hydrolyzable tannins are polyphenolic compounds based
complexes of digallic acid and D-gluchilose. While condensed tannins are
composed of units from flavonoids and are used to replace the phenolic
compounds as well as the UF and MUF synthesis in wood-based panels. They do
not emission formaldehyde when used as an adhesive (Pizzi 2006).
Shrimp is one of the most seafood marketed worldwide. The shrimp is
usually exported as frozen without head or skin, so that the waste accounts for 50
to 60% by weight of whole shrimp. Peshkova and Li (2003) indicate that chitosan
can be used as an adhesive.
These three materials represent an alternative to natural adhesivesin place
of synthetic adhesives. Therefore, it is important to conduct studies on the
performance of natural adhesivesfrom these three resources and the quality of
particleboard using the natural adhesives.
Objectives of Research
The objectives of this research are:
1.
To use renewable raw materials to replace synthetic products (especially if
they are hazardous products).
2.
Essential that these glues have physical and mechanical properties at least
similar to synthetic materials (in this case Urea formaldehyde).
3.
These adhesives can be used by industrial processing systems.
LITERATURE REVIEW
Particleboard
According to Bowyer et al. (2003) and Tsoumis (1991), particleboard is a
panel product manufactured by embedding the particles together (such as small
pieces of wood or other lignocellulosic material), with wood as a primary
resource. Dumanauw (1990) states that the advantages of particle boards
compared with solid wood are free from knots and checks, size and density can be
adjusted, thickness and density are uniform, more isotropic, quality or surface
appearance can be adjusted according to market or costumer desire. Particleboard
typically has two face layers made from fine wood furnish (external layer) and
one core layer made from coarse wood furnish. Generally particleboard is less
expensive than solid wood. However, compared to solid wood, particleboard has a
lower dimensional stability, lower in screw holding and strength. Particleboard is
mainly used for furniture and kitchen cabinets products.
Approximately 95 %
of the lignocellulosic material
used for
particleboardproduction is wood, but other agro-based residues have not been
frequently utilized. Annual plant wastes, such as flax and hemp shives, bagasse,
cotton stalks, small grain straw (including rice straw), peanut husks, rice husks,
grape stalks, and palm stalks are inexpensive and valuable raw materials for
lignocellulosic board production (Kozlowski et al. 1994).
Figure 1. Particleboard (ShouguangZhongjia Industry and Trade Compay)
Tannins
Tannin is a general term for a widely occurring group of substances that
comes from the plants with varying proportions. Tannins are polyphenolic
compounds which are able to interact with other macromolecules such as proteins
and carbohydrates. Moreover tannin are an excellent renewable resource which
can be used for replacing petroleum-derived phenolic compounds.
Different types of tannins have been used for a long time in the production
of adhesives (Godwin and Mercier. 1983). Hydrolyzable tannin are derivatives of
gallic acid (3,4-5 trihydroxyl benzoic acid). Gallic acid which is esterifies to a
core polyol, and the galloylgroups may be further esterifies or oxidativelycross
linked to yield more complex hydrolyzable tannins. Hydrolyzable tannin can be
decomposed in water, which can react to form other useful substances such as
gallic acid, pyrotocatechic acid and sugar. While condensed tannins, constituting
more than 90% of the total world production of commercial tannins, are both
chemically and economically more interesting for the preparation of resin
adhesive (Pizzi and Mittal. 2003). Condensed tannins have a complex chemistry.
It is a group of phenolic polymers which are widely distributed in the plant
kingdom particularly with woody growth habit. These compounds consist of
flavan-3-ol units linked together through C4-C6 or C4-C8 bonds (Rahim and
Kassim.2008).
(a)
(b)
Figure 2.(a) Condensed tannin, (b) Hydrolyzable tannin
(staff.science.uva.nl)
Corn Starch
Starch is a renewable resource available in abundant quantities at a very
low cost. Starch is a carbohydrate food reserve in plants and the major energy
resource for non-photosynthetic organisms. Starch granules are composed
primarily from different chemically biopolymers (amylase and amylopectine). The
proportions of amylase and amylopectin depend on the variety of corn. Amylase is
essentially a linear molecule which consists of α-glucopyranosyl residues linked
via (1-4) glycosides bonds. While amylopectin molecules, on the other hand, are
highly branched, with α-glucopyranosyl residues linked by (1-4) glycosides
linkages and by α-(1-6) bonds at branch points. Ratio and proportion of amylase
ranged from 20% to 25%, and 75% to 80% for amylopectin respectively
The size of a starch granule also depends on the source, and the potato
starch granules are the largest granules from all sources. When heated, in the
presence of excess water, starch granules lose their crystalline, absorb large
amounts of water, and leach amylase out, which impart viscosity to the
starch/water system (Imam et al. 1999).
Figure 3. Glucose molecule(erzagenatrika.blogspot.com)
Chitosan
Chitosan is N-deacetylatedpolysaccharide that comes from chitin. Chitin
was extracted from crustacean shells, such as shrimp, crab, lobster, squid, and
even beetles. Chitosan is obtained after eliminating 70% of acetyl groups
(CH3C0-) present in chitin. Chitosan does not dissolve in water solvent, alcohol,
and acetone. It is also insoluble in a solution with pH greater than 6.5, but soluble
in dilute organic acids such as acetic acid (Sugita et al. 2009). Chitosan is not
toxic so that it can be utilized in the food industry as food preservatives,
antioxidants, and drinks purified. Currently, chitosan has been exploited by
industries for high quality adhesive, purification of drinking water (having a
coagulation power), increasing the dye industry in paper, textile and pulp
(Alamsyah. 2001). Suptijah P (2006) found that chitosan has a specific shape,
containing amine groups in the carbon chain and positively charged as opposed to
other polysaccharides.
Chitosan is a naturally occurring biopolymer thin sheet-shaped, has no
odor, white in color and the most abundant biomaterial. Chitosan is considered to
be a random copolymer comprised primarily of repeat sugar units with the
structure of a (1-4)-linked 2-amino-2- deoxy-b-D-glucopyranose and comprised
also of some units of (1-4)-linked 2-acetamido-2-deoxy-b- D-glucopyranose
(Wong et al. 2006).
Figure 4. Chitosan(sigmaaldrich.com)
MATERIAL AND METHOD
Time and Place of Research
This researchwas conducted in Laboratory of Physical Chemistry,
University of Pau and Pays de l’Adour, France. This research was carried out
from January 2012 to July 2012.
Materials and Research Equipment
The material used in this research was particle Pinuspinaster from
particleboard industry in Mont de Marsan with moisture content ≤ 5 %. Fine
particles with a size of 10 mesh and coarse particles with a thickness of 5 mm,
length 50 mm and width 4-5 mm were used.Corn starch was obtained from Fisher
scientific while quebracho tannin was obtained from Silva team, chitosan with
molecular weight 600.000-800.000, hexamine, NaOH and aquadest.
Several equipments are used in this study such as: water bath, oven, rotary
mixer,rotary blender, pressing machine, universal testing machine, pH meter,
caliper, viscometer and precision balance.
Experimental Design
The experiments in completely randomized design with three replicates
with different solution concentration of chitosan are (0, 10, 15, and 20 %).The
results obtained were subjected to an analysis of variance (ANOVA) used
software Minitab 15 to identify the effect of the chitosan concentration of chitosan
for quality a of adhesive and properties particle board. Duncan test was applied to
compare treatment means.
AdhesivePreparation
To prepare ± 600 g of adhesive, a corn starch water solution was prepared
at 65% (w/v)concentration, by dissolving 162.5 g of corn starch in 250 ml of
aquadest and stirring at roomtemperature, to which 16.25 g of wattle
quebrachotanninare added and 83 ml of chitosan solution with concentration of 0,
10, 15, to 20% was added. The amount of hexamine, used as a hardener, was 32.5
ml. The hexamine was dissolved in aquadest to give a solution of concentration
equal to 30% before being added to the solution of corn starch-tannin-chitosan.
The solution was mixed and then 125 ml of sodium hydroxide (33%) were added.
Particleboard Preparation
Particleboard was made by three layers, face, core, and back. Ratio
between face/back and core is 30:70 based on weight strands. Target of density is
set to 0.6 g/cm3and the size of panel is 22 cm x 22 cm x 2 cm. The particleboard
preparation showed in Figure 5.
Particle
Blending
ρ= 0,6 g/cm³
Dimension:
22 cm x 22 cm
The natural
adhesive as much
as 10%
Mat forming
Pressing (195 oC,
d i 8 i )
Conditioning during 2
The quality tesrting based on European Standart EN 310, 317,
319 and 323
Figure 5.Process of the particleboard preparation
All boards were cut and tested according to standard methods of European
Standard EN 310, 317, 319, and 323 for particleboard and fiberboard. The
specimenstests were obtained from each board according to the cutting diagram
showed in Figure 6.
22 cm
22 cm
Figure 6. Cutting diagram of particleboard
Notes :
1. MOE and MOR (20 cm x 5 cm)
2. Density and Moisture content (15 cm x 5 cm)
3. Internal bond (5 cm x 5 cm)
4. Thickness swelling (5 cm x 5 cm)
Testing of Adhesive
Test the quality of adhesive, the studysolid content, gel time, pH and
viscosity with reference to JIS K 6833-1980) was conducted.
Solid Content
Solid Content is ratio between the weight of sample before and after
heating at a given temperature until weight constant. Method of determination the
solids content :
1. Sample of adhesive (1.5 gram was placed in to petridish (W1)
2. The adhesive in the petridish was dried in an oven at 105 ± 2 oC for 1 hour
3. Petridish was put in a desiccator for 10 minutes, then weighed
4. Drying and measuremass were performed until constant weight (W2).
Solid content is determined by the formula:
Viscosity
The principle of measuring the viscosity is a measure of internal friction
induced by the cohesion of the molecules in the adhesive. The viscosities of the
natural adhesive were determined using a Brookfield Viscometer at 20 rpm using
spindle number S07 and expressed in cP. The viscosity was measured in triplicate
at 25 ± 1 °C.
Gel Time
Gelation is defined as the point where the resin ceases to be a viscous
liquid and becomes soft, elastic, solid rubber (Pizzi and Stephanou. 1993). Five
gram of adhesive was placed in a test tube and heated in boiling water or in water
bath at temperatures above 100 °C under continuous mixing. The reactivity of a
mixture is defined as the time measured from the beginning of heating until
gelation occurred.
pH
The pH measurement is a measure of the concentration of H + ions in a
solution. The method for determining the pH of the adhesive using a pH meter is
as follows:
1. The samples of adhesive are poured into a 200 ml beaker and the acidity
was measured at 25 °C using a pH meter.
2. Before pH measurement, a calibration of the pH meter is first performed
with buffer solutions of pH equal to 4 and 7 at a temperature of 25 oC.
Bond Strength of Adhesive
Maritime pine veneer with a thickness of 3 mm was cut to rectangular
specimen 2.5 x 11. 5 cm (according to British Standard 1204, 1965, part 2, for
synthetics resin adhesives). The adhesive was applied to one side of piece of
veneer. The application area was 2.5 x 2.5 cm for each veneer. The spread rate of
adhesive was 120-150 g/m2 on a dry weight basis (Ihat and Nilgul. 2002, Pizzi.
1977). The press temperature and press time were set at 195 oCduring 8 min. After
that, the veneer was conditioned in a room temperature (25 oC and 65 % relative
humidity) for 24hour.
Bonding quality was evaluated from the percentage of wood failure at the
bonding area and bond strength of each specimen. The description of the
procedure in Figure 7 is below:
Figure 7. Test of adhesion of adhesive
Testing of Particleboard
Density
Density of a particleboard were determined according were determined
according to the European Standard method (EN 323) on specimens with
dimensions 200 mm x 50 mm x 20 mm. The density is the average of the
measured densities on the test specimens of each panel. This density is the ratio of
the mass of each specimen and volume.
Where :
Ρ
: density
M
: mass of the sample
V
: volume of the sample
Moisture Content
European Standard (EN 323) was using to determine moisture content. It
corresponds to the mass loss from the sample after drying in an oven at 103 ± 2
°C to constant weight. Denoted by H, the water content is expressed as a
percentage by weight and is equal to:
Where :
H
: moisture content (%)
M1
: mass of the sample before drying in an oven (g).
M2
: mass of the sample after drying in an oven until constant weight (g).
Thickness Swelling
Thickness swelling was determined according to the European Standard
method (EN 317). To determine thickness swelling properties, particleboards were
cut into 50 mm × 50 mm and soaked in water at room temperature (20 ± 2 °C) for
both 2 hour (h) and 24 hour (h). The thickness and weight of the particleboard
samples were measured before and immediately after soaking. Thickness swelling
were calculated as ratios of absorbed water and increased thickness to the values
before soaking, respectively, and expressed as percentages.
Where :
t1
: thickness of sample before immersion (mm)
t2
: thickness of sample after immersion (mm)
Internal Bond
Size of sample 50 mm x 50 mm x 20 mm were attached to two aluminum
blocks with polypropylene adhesive and left to dry. Two blocks drawn
perpendicular to the surface of the specimen until the maximum load. Internal
bond values calculated using the formula:
where:
IB
: internal bond (N/mm2)
Pmax
: maximum compressive load (N)
A
: surface area the sample (mm2)
Direction of the load
Aluminum block
Sample
Direction of the load
Figure 8. Testing Internal Bond
Modulus of elasticity (MOE) and Modulus of Rupture (MOR)
According to European Standard EN 310, twelve specimens of dimensions
200 mm x 50 mm x 20 mm on each panel particles were used to determine the
strength in three-point bending. The flexural modulus of elasticity (MOE) and
bending strength (MOR) were calculated using the following formulas:
Where :
Fi
: load at proportional limit (N/mm2)
L
: length of span (mm)
e
: thickness of specimen (mm)
: the bending load (N/mm2)
ai
b
: width of specimen (mm)
Where :
Frupture
: maximum compressive load (N/mm2)
L
: length of span (mm)
b
: width of specimen (mm)
e
: thickness of specimen (mm)
Sample used measuring 20 mm x 50 mm x 20 mm in air dry conditions
with the loading pattern shown in Figure 9 :
L
Sample
L
Figure 9.Way of testing the MOR and MOE
a
RESULTS AND DISCUSSION
Quality of Adhesive
Solid Content
Figure 10shows that addition of chitosan induces small decrease of solid
content of the adhesive. The value of solids content in adhesive without added of
chitosan solution is 30.79% which is not significantly different from that after the
addition of chitosan with a concentration at 20% (31.27%).
65,00
70,00
Solid content (%)
60,00
50,00
40,00
30.79
30.86
31.27
31.37
30,00
20,00
10,00
0,00
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 10. The Average Value of the Solid Content of Natural
Adhesive for Different Concentration of Chitosan
The solid content of the samples increased with increased concentration of
chitosan, although not significant.Higher solid content of adhesives may increase
the number of adhesive molecules that will react with wood during adhesion
process. Increase of solid content will improve the quality of adhesive. Vick
(1999) state that solid content in a certain limit, the higher resulting bond strength
of board because many molecules of the adhesive that react with the wood in the
gluing process. Also, solid content has more effect on both IB, MOR and MOE.
ANOVA results showed that the treatment factor had no significant effect
on solid content values.
Viscosity
The viscosity values of resins made from different additions of chitosan
solution;
65:10:0,
65:10:10,
65:10:15
and
65:10:20
(corn
starch:quebrachotannin:chitosan solution, weight ratios) were tested. The results
of viscosity test are shown in Figure 11.
50000,00
37083.33 (b)
Viscosity (cP)
40000,00
30800 (a)
31333.33 (a)
33200 (a)
30000,00
20000,00
10000,00
2726,67
0,00
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 11. The Average Value of the Viscosity of Natural Adhesive
for Different Concentration of Chitosan
The viscosity of the samples increased with increased concentration of
chitosan. The increase in viscosity may be due to protein unfolding in accordance
with Angleimer and Montgomery (1976) who stated that an increase in intrinsic
viscosity is one of the effects of protein denaturation. The higher viscosity of
adhesive, the more difficult the adhesive flows on the wood surface because
penetrating the medium and glue line very slowly then caused difficulty to
applying adhesive (Corn Products International. 2006).
ANOVA results showed that treatment factor had significant effect on
viscosity. The advanced test, Duncan test, showed that the concentration of
chitosan 20% were significantly different with concentration of chitosan 0%,
10%, and 15%.
Gel Time and pH
Gel time is defined as the point at which polycondensates formed by the
reaction of a cornstarch-quebrachotannin-chitosan solution become an elastic,
rubbery solid. Gel time is highly dependent on the pH of the adhesive: the gel
time generally decreases when the pH of the adhesive is increases, but does not in
this study, where the gel time increases when pH increases. This is because the
properties of corn starch when first heated melted, and then thickens. The results
of tested gel time and pH can be seen in Figure 12 and 13. At lower pH and
highconcentration of chitosan solution, the gel time is shorter.
1200
980.92 (b)
Gel time (s)
1000
877.35 (b)
800
671.67 (a)
733.36 (a)
600
400
125,68
200
0
A65T10Ch0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 12. The Average Value of Gel Time of Natural Adhesive
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had significant effect on
gel time values. The advanced test, Duncan test, showed that concentration of
chitosan 20% were significantly different with concentration of chitosan 0% and
10%, but were not significantly different with concentration of chitosan 15%.
14,00
12,00
10.66 (a)
10.83 (b)
11.02 (c)
11.91 (d)
pH
10,00
8,00
6,76
6,00
4,00
2,00
0,00
A65T10Ch0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 13. The Average Value of the pH of Natural Adhesive
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had significant effect on
bond strength values. The advanced test, Duncan test, showed that the
concentration of chitosan 20% were significantly different with concentration of
chitosan 0%, 10%, and 15%.
Bond Strength
The bond strength values of resins made with different additions of
chitosan
solution
65:10:0,
65:10:10,
65:10:15,
and
65:10:20
(corn
starch:quebrachotannin:chitosan solution, weight ratios) were tested. The results
of the effect of substitution level of chitosan solution on the bond strength are
shown in Figure 14. The increase of chitosan solution substitution level, bond
strength is relatively affected by the presence of chitosan solution up to 15%
(65:10:15). The bond then decrease due to the presence of chitosan solution of
20% (65:10:20). It is interesting to observe, when the substitution level is higher
than 15%, resin showed small tendency reductions in bond strength values. Thus
it can be concluded that substitution level of 15% is optimal for the preparation of
Bond Strength (N/mm2)
(corn starch-quebracho tannin-chitosan solution, weight ratios) wood adhesives.
4
3,5
3
2,5
2
1,5
1
0,5
0
3.17
2.98
2.74
2.29
A65T10CH0
2.79
A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 14. The Average Value of the Bond Strength of Natural Adhesive
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had no significant effect
on bond strength values.
Quality of Particleboard
Density
Figure 15 shows the density of the particleboard by the using of corn
starch-quebrachotanin-chitosan solution adhesives. The average values of density
are 0.39-0.46 g/cm3.
Density (g/cm3)
0,6
0,5
0,4
0.46
0.39
0.41
0.42
0.43
0,3
0,2
0,1
0
A65T10CH0
A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 15.The Average Value of the Density of Particleboard for
Different Concentration of Chitosan
These results pointed out that the density of particleboard produced is
categorized as medium density. This category is adopted from the classification
according to Maloney (1993) that divides the particleboard into a low density
particleboard that is less than 0.40 g/cm3, medium density that is between 0.400.80 g/cm3, and a high density for more than 0.80 g/cm3. For overall, not all of the
particle boards achieved the density target of 0.6 g/cm3. Can be caused by
moisture content on particleboard that adapted the ambient temperature while
conditioning process. In addition, other factor that may affect the density of board
were evaporation of water when pressing process, the lost of particle during
pressing process and the end of pressing process and measurement process of
dimensions which is not in all parts of particleboard thus there is a possibility of
non compact side of particleboard was not measured.
ANOVA results showed that the treatment factor had no significant effect
on density.
Moisture Content
The result of moisture content of particleboard made of natural adhesive
(corn starch-quebrachotannin-chitosan solution) and UF are between 7.44%12.29%. The moisture content of the particleboards is based on European
Standard EN 323 which suggests 5% to 13%. High moisture content may affect
the quality of the particle board. According to Kollmanet al. (1975),moisture
content is one of the factors that affect the quality of adhesion.The moisture
content of particleboards are shown in Figure 16.
Moisture content (%)
14
12.29 (b)
12
10.38 (a)
10
9.71 (a)
9.64 (a)
7,44
8
6
4
2
0
A65T10CH0
A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 16. The Average Value of the Moisture Content of Particleboard
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had significant effect on
moisture content. The advanced test, Duncan test, showed that the concentration
of chitosan 0% were significantly different with concentration of chitosan 10%,
15%, and 20%.
Thickness Swelling
Based on EN Standards, particleboard should have a maximum thickness
swelling (TS) value of 8% for 2h immersion. In addition, the maximum TS for 24
h requirement EN312 (2004) is 15%. Average TS of the specimens ranged from
10.24% to 23.22% and 11.41% to 28.28% for 2 h and 24h immersion,
respectively. Panel which used natural adhesive (corn starch 65% and tannin 10%)
gave the highest TS of 23.22 and 28.28% after soaking for 2 h and 24h,
respectively. Springback of the panels as they are soaked in water is transferred in
less-dimensional stability which is a common behavior of any wood composite
(Kalaycıogluand Nemli. 2006). In general, panels did not satisfy the thickness
swelling requirement for general uses. This is probably because of no utilization
wax (hydrophobic substance) in particleboard manufacturing.
Bond quality and adhesive properties affected the thickness swelling
(Sauter, 1996). The high thickness swelling of particleboard because using natural
adhesive made of corn starch, tannin and chitosan so water was able to penetrate
easily into the weakly bonded particleboard. Also,raw materials natural adhesive
had the carbohydrate content, making it rich in hydroxy groups.
Figure 17 shows the thickness swelling of particleboard samples for 2 h
25.44
2 Hour
20
15
11,41
24 Hour
10,24
25
21.82
26.59
22.34
27.33
22.25
30
28.28
Thickness swelling (%)
35
23.22
and 24h.
10
5
0
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 17. The Average Value of the Thickness Swelling 2 h and 24 h
of Particleboard for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had no significant effect
on thickness swelling 2h and 24h.
Internal Bond
Internal bond (IB) data ranged from 0.03 to 0.33 N/mm2. The minimum
requirement of internal bond strength for general purpose (EN 312, 2004) and
interior fitments (EN 312, 2004) are 0.24 and 0.35 N/mm2, respectively.
According to the test results, internal bond values of all the particle boards
produced were lower than the European Standard EN 312, just particleboard used
UF average value as 0.33 N/mm2. Figure 18 shows the average value of internal
IB (N/mm2)
bond.
0,4
0,35
0,3
0,25
0,2
0,15
0,1
0,05
0
0,33
0.12 (d)
0.07 (c)
0.062 (b)
0.03 (a)
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 18. The Average Value of the IB of Particleboard for
Different Concentration of Chitosan
The low value of IB may be caused by during the blending process of the
adhesive. Wood particles were not uniformly mixed with glue. According to
Cavdaret al.(2008) internal bond strength is very sensitive to resin distribution on
the strands and vertical density profiles of the panels.
ANOVA results showed that the treatment factor had significant effect on
internal bond. The advanced test, Duncan test, showed that the treatment is
significantly different on each treatment.
MOR and MOE
Based on EN Standards 11.5 and 1500 N/mm2 are the minimum
requirements for respectively MOR and MOE of particleboard panels for interior
fitments including furniture manufacturing application (EN 312, 2004). Average
MOR and MOE of the specimens ranged from 0.93 to 2.97 N/mm2 for MOR and
91.27 to 474.44 N/mm2 for MOE.
All panels made with natural adhesive and UF had the lower values
compared to other types of specimens and exceed the EN Standards for MOR and
MOE for interior fitments including furniture manufacturing application. This
may be caused by during the blending process of the adhesive and the wood
particles which are not well mixed so that the particleboard does not coherent
enough with the glue. The high level of viscosity is probably at the origin of
theses low performances. Figure 19 and 20 shows the average value MOR and
MOR (N/mm2)
MOE.
4
3,5
3
2,5
2
1,5
1
0,5
0
2.96
1.48
1.73
1
0.93
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 19. The Average Value of the MOR of Particleboard
for Different Concentration of Chitosan
600
474,44
MOE (N/mm2)
500
400
300
182.19
147.79
200
164.55
91.27
100
0
A65T10CH0 A65T10CH10 A65T10CH15 A65T10CH20
UF
Figure 20. The Average Value of the MOE of Particleboard
for Different Concentration of Chitosan
ANOVA results showed that the treatment factor had no significant effect
on MOR and MOE.
CONCLUSIONS
1. The resulting natural adhesive qualities are as follows: solid content has value
between 30.79% - 31.37 %, viscosity between 30800 cP - 37083.33cP, gel time
value about 671.67 second - 980.92 second, pH between 10.66 - 11.91 and
bond strength between 2. 29 N/mm2- 2.98 N/mm2.
2. The qualities of particleboard produced in this research are as follows: density
has value between 0.39 g/cm3- 0.43 g/cm3, moisture content between 9.64 % 12.29 %, thickness swelling in 2 h between 21.82 % - 23.22 %, thickness
swelling in 24 h between 25.44 % - 28.28 %, internal bond between 0.03
N/mm2- 0.12 N/mm2, MOR value between 0.93 N/mm2- 1.73 N/mm2 and
MOE between 91.27 N/mm2- 182.19 N/mm2.
3. The factors that affect the quality of adhesive such as: quality of raw materials,
characteristics of the raw materials. While The factors that affect the quality of
particleboard are adhesive viscosity and solid content of adhesive, and process
preparation of particleboard.
4. If compared to the adhesive quality of UF and particle board using UF,the
natural adhesive is far below the standard, thus affecting the quality of the
particleboard.
REFERENCES
Angleimer, A.F., Montgomery, M.W. 1976. Amino Acids, Peptides and
Proteins.In: Fenema, O.R. (Ed.), Food Chem. Marcel Dekker. New York,
NY. 205-284.
Alamsyah
R.
2001.
KarakteristikdanPenerapanKhitindanKhitosan.JurnalTeknologiIndustri. II
(2).61-68.
Bowyer, J.L. Shmulsky, R. Haygreen, J.G. 2003. Forest Product and Wood
Science An Introdution 4th Ed. USA : Iowa State Press A Blackwell Publ.
Corn Products International, Inc. 2006.Corrugating Starch Adhesives Manual.
USA. 9-10.
DepartemenKehutanandan
Perkebunan.1999.PanduanKehutanan
Indonesia.DepartemenKehutanandan
Perkebunan
Republik
Indonesia.Jakarta.
Dumanauw, J. F. 1990.
Atas.Semarang.
Mengenal
Kayu.
Pendidikan
Industri
Kayu
European Standard EN 310. 1993. Wood-based PanelsDetermination of
Modulusof Elasticity in Bending and of Bending Strength. European
Committee for Standardization. Brussels. Belgium.
European Standard EN 312. 2003. Particleboards - Specifications.
EuropeanCommittee for Standardization. Brussels. Belgium.
European Standard EN 317. 1993. Particleboards and Fiberboards
Determinationof Swelling in Thickness After Immersion in Water.
European Committee for Standardization. Brussels. Belgium.
European Standard EN 319. 1993. Particleboards and FiberboardsDeterminationof
Tensile Strength Perpendicular to the Plane of the Board. European
Committee for Standardization. Brussels. Belgium.
European Standard EN 323. 1993. Wood-based Panels Determination of
Density.European Committee for Standardization. Brussels. Belgium.
Foley,W. J.,Iason, G. R. and Mcarthur, C. 1999. Role of Secondary Metabolites In
the Nutritional Ecology of Mammalian Herbivores: How Far Have We
Come In 25 Years In: Nutritional Ecology of Herbivores, H.-J.G. Jung and
G. C. Fahey Jr, (Eds) American Society of Animal Science, Illinois. 130–
209.
Godwin, T.W.; and Mercier, E.I. 1983. Introduction to Plant Biochemistry, 2nd
ed. Pergamon Press. Oxford, UK.
Imam, S.H., Mao, L., Chen, L., Greene, R.V. 1999. Wood Adhesive
FromCrosslinkedpoly(Vinyl Alcohol) And Partially Gelatinized Starch:
Preparation and Properties. Starch/Stärke.51 (6).225–229.
Japanese Industrial Standard. 1980. General Testing Methods for Adhesive. JIS K
6833-1980. Japanese Standard Associations. Japan.
Kalaycioglu H., Nemli, G. 2006. Producing Composite Particleboard FromKenaf
(Hibiscus Cannabinus L.) Stalks, Industrial Crops And Products.24. 177–
180.
Kollmann, F.F.P., E.W. Kuenzi and A.J. Stamn. 1975. Principle of Wood Science
and Technology. Vol. 11. Springer–Verlag, Berlin. Heildelberg. New
York.
Lopez, C. dan P. Shanley. 2004. Kekayaan Hutan Asia. PT Gramedia
PustakaUtama, Anggota IKAPI. Jakarta.
Nemli, G., Gezer, E.D., Yildiz, S., Temiz, A., Aydın, A. 2006. Evaluation of
theMechanical, Physical Properties and Decay Resistance of Particleboard
MadeFrom Particles Impregnated With Pinus Brutia Bark Extractives.
Bioresour.Technol. 97 (16). 2059–2064.
Maloney T M. 1993. Modern Particleboard and Dry Process Fiberboard
Manufacturing. San Francisco : Miller Freeman Inc.
Peshkova, S., K. Li. 2003. Investigation Of Chitosan-Phenolics Systems As
Wood Adhesives. Journal of Biotechnology. 102. 199-207.
Pizzi, A., K. L. Mittal. 2003. Handbook Of Adhesive Technology Second
Edition, Revised And Expanded. Marcel Dekker Inc . New York. 568-582
Pizzi, A. 2006. Recent Developments In Eco-Efficient Bio-Based Adhesives for
Wood Bonding: Opportunities and Issues. J. Adhesion Science
Technology. 20 (8).829–846.
Rahim, A and Kassim, J. 2008.Recent Development of Vegetal Tannins in
Corresion Protection of Iron and Steel.Recent Patent on Materials
Sciences. 1. 223-231.
Sauter, S.L. 1996. Developing Composites From Wheat Straw. In: Proceedings of
The 30th International Symposium of Washington State University on
Particleboard/Composite Materials. 197-214.
Singh, N., K. S. Sandhu, and M. Kaur. 2005. Physicochemical Properties
Including Granular Morphology, Amylase Content, Swelling and
Solubility, Thermal and Pasting Properties of Starches From Normal,
Waxy, High Amylase and Sugary Corn. Progress InFood Biopolymer
Research. 1. 43-55.
Sugita P, T Wukirsari, ASjahriza, D Wahyono. 2009. KitosanSebagaiSumber
Biomaterial MasaDepan. IPB Press. Bogor.
SuptijahP.
2006.DeskripsiKarakteristikFungsionaldanAplikasiKitindanKitosan.Dala
m:Prosiding Seminar NasionalKitin-Kitosan2006 ; Bogor, 16 Maret 2006.
DepartemenTeknologiHasilPerairan, FakultasPerikanandanIlmuKelautan
IPB. Bogor. 14-24.
Sutigno.2004. MutuPapanpartikel.http:// mofrinet.cbn.ne.id/ informasi/setjen/
pustan/info-v.htm.[13April 2010].
Tsoumis G. 1991. Science and Technology of Wood. Van Nostrand Reinhold.
New York.
Vick, C.B. 1999. Wood Handbook: Wood as an Engineering Material. Southern
Forest Products Association. Wisconsin.
Wong, K., Sun, G., Zhang, X., Dai, H., Liu, Y., He, C., Leong, K.W. 2006. PEIChitosan,A Novel Gene Delivery System With Transfection Efficiency
Comparableto Polyethylenimine In Vitro and After Liver Administration
In Vivo. Bioconjug.Chem. 17. 152–158.
Yamada, K., T. Chen., G. Kumar., O. Vesnovsky., L. D. Timmie., and G. F.
Payne. 2000. Chitosan Based Water-Resistant Adhesive. Analogy to
Mussel Glue. Journal: Biomacromolecules. 1. 252-258.
Yazaki Y, Collins PJ. 1997. Uses of Wattle Extract: Tannin Based Adhesives.
Rural Industries Research and Development Corporation.RIRDC
Publication No. 97/72.Chapter 15.127-143.
APPENDIX
APPENDIX
Appendix 1.The Average Value of Qualityof Natural Adhesive for Different Concentration of Chitosan
Quality of
Tipe of Adhesive
Adhesive
Natural
Synth
etic
0%
10%
15%
20%
Solid Content (%)
30.79
30.86
32.27
31.37
65
Viscosity (cP)
30800
31333
33200
37083.
2680
Gel Time (second)
671.67 .33
pH
10.66
Bond
(N/mm2)
Strength
2.29
877.3
733.3
6
10.83
5
UF
33
125.6
980.92
8
11.02
11.91
6.76
2.98
2.79
3.17
2.74
29
Appendix 2.The Average Value of Qualityof Particleboard for Different Concentration of Chitosan
Quality of ParticleBoard
Tipe of Adhesive
Natural
Synthet
ic
0%
10%
15%
20%
UF
Density (g/cm3)
0.39
0.41
0.42
0.43
0.46
Moisture Content (%)
12.29
10.38
9.71
9.64
7.44
Thickness Swelling 2 h (%)
23.22
22.34
21.82
10.24
Thickness Swelling 2 h (%)
28.28
22.25
26.59
25.44
11.41
Internal Bond (N/mm )
0.03
27.33
0.062
0.12
0.33
MOR (N/mm2)
0.93
0.07
1.48
1.73
2.96
MOE (N/mm2)
91.27
1.00
164.55
182.19
474.44
2
147.79
ABSTRACT
SONIA SOMADONA.The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and Chitosan.Under the
supervision of SURDIDING RUHENDI and BERTRAND CHARRIER.
The development and optimization of a new, environment-friendly
adhesive made from abundant and renewable cornstarch, tannin and chitosan is
described in this study. At present, the production of wood composites mainly
relies on petrochemical and formaldehyde-based adhesives such as phenolformaldehyde (PF) resins and urea-formaldehyde (UF) resins. Natural adhesive is
not only environmentally friendly but also less expensive as compared to other
exterior binders used in wood composite industry. The objective of this study is to
evaluate the quality of adhesive and particleboard produced. This research
describes performances of natural adhesive obtained from cornstarch, tannin and
chitosan (solid content, viscosity, gel time, pH and bond strength). Results
describe physical properties of all particleboard production according to standard
EN 323, 2004. Mechanical properties of particleboard did not fulfilled standard
EN 312 for IB, MOR and MOE.
Keywords: corn starch, tannin, chitosan, particleboard, quality of adhesive and
particleboard.
SUMMARY
SONIA SOMADONA.The Quality of PinuspinasterArBinenn Particleboards
Using Natural Adhesive Made of Corn Starch, Tannin and Chitosan.Under the
supervision of SURDIDING RUHENDI and BERTRAND CHARRIER.
Currently, the majority of wood based panels for furniture or construction
(particle board, OSB, plywood, LVL, etc.) has used synthetic adhesives such as
urea-formaldehyde, melamine formaldehyde, phenol-formaldehyde and
resorcinol-formaldehyde are derived from petroleum andnon renewable fossil
resource.They contain formaldehyde which is volatile and harmful for human
health
Renewable raw materials have several own advantages such as
availability, and regeneration. The use of adhesives from renewable raw materials
will replace the petroleum based adhesives as they are more environmentally
friendly and are able to reduce formaldehyde emissions. These renewable raw
materials are corn, tannin and chitosan. These three materials represent an
alternative to natural adhesivesin place of synthetic adhesives.
The study was conducted testing the quality of natural adhesives from
these three resources and the quality of particleboard using the natural adhesives.
Tested the quality of adhesive such as solid content, gel time, pH and viscosity
with reference to JIS K 6833-1980) was conducted and for tested quality of
particleboard according to standard methods of European Standard EN 310, 317,
319, and 323 for particleboard and fiberboard.
The qualities of natural adhesive are as follows : solid content has value
between 30.79% - 31.37 %, viscosity between 30800 cP - 37083.33cP, gel time
value about 671.67 second - 980.92 second, pH between 10.66 - 11.91 and bond
strength between 2. 29 N/mm2 - 2.98 N/mm2.Based on the results, the solid
content value of natural adhesive made of three reneweble raw materials (corn
starch, tannin, and chitosan) under the standards set.While the viscosity, gel time
and pH do not have the standard. The bond strength of natural adhesive has a
value above the standards (≥ 1 N/mm2)
The qualities of particleboard produced in this research are as follows :
density has value between 0.39 g/cm3 - 0.43 g/cm3, moisture content between 9.64
% -12.29 %,