Volume 1
Current Research on Fatigue Cracks
T. TANAKA, M. JONO and K. KOMAI
Volume 2
Statistical Research on Fatigue and Fracture
T. TANAKA, S. NISHIJIMA and M. ICHIKAWA
Volume 3
High Temperature Creep-Fatigue
R. OHTANI, M. OHNAMI and T. INOUE
Volume 4
Localized Corrosion
F. HINE, K. KOMAI and K. YAMAKAWA
Volume 5
Recent Studies on Structural Safety
T. NAKAGAWA, H. ISHIKAWA and A. TSURUI
Volume 6
Fractography
Volume 7
Computational Plasticity
T. INOUE, H. KITAGAWA and S. SHIMA
Volume 8
Fracture Mechanics
H. OKAMURA and K. OGURA
Volume 9
Soil Improvement
Volume 10
X-Ray Diffraction Studies on the Deformation and Fracture of Solids
K. TANAKA, S. KODAMA and T. GOTO
RECENT RESEARCH ON WOOD
AND
WOOD-BASED MATERIALS
Edited by
N O B U O SHIRAISHI
Kyoto University, Japan
HIROMU KAJITA
Kyoto Prefectural University, Japan
MISATO NORIMOTO
Kyoto University, Japan
L O N D O N and N E W YORK
ELSEVIER SCIENCE PUBLISHERS L T D
Crown House, Linton Road, Barking, Essex IG11 8JU, England
ISBN 1-85861-004-4
N o responsibility is assumed by the Publisher for any injury and/or damage to persons or
property as a matter of products liability, negligence or otherwise, or from any use or
operation of any methods, products, instructions or ideas contained in the material herein
All rights reserved. N o part of this publication may be reproduced, stored in a retrieval
system, or transmitted in any form or by any means, electronic, mechanical, photocopying,
recording, or otherwise, without the prior written permission of the publisher.
HIROSHI JINNO
President, Society of Materials Science, Japan
V
Preface
N O B U O SHIRAISHI
HIROMU KAJITA
MISATO NORIMOTO
vii
List of Contributors
TAKANORI ARIMA
Department of Forest Products, Faculty of Agriculture, The Tokyo
University, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113, Japan
JUN-ICHI AZUMA
Department of Wood Science and Technology, Faculty of Agriculture,
Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto 606-
01, Japan
JOSEPH GRIL
Laboratoire de Mecanique Generate des Milieux Continus, Universite
de Montpellier II, USTL, Place E. Bataillon, 34000 Montpellier Cdx
2, France
TOSHIMITSU HATA
Wood Reasearch Institute, Kyoto University, Uji, Kyoto 611, Japan
YUJI IMAMURA
Wood Research Institute, Kyoto University, Uji, Kyoto 611, Japan
HIROMU KAJITA
Department of Forestry, Faculty of Agriculture, Kyoto Prefectural
University, Shimogamo, Sakyo-ku, Kyoto 606, Japan
xi
xii LIST OF CONTRIBUTORS
FUMIO KAMIYA
Forestry and Forest Products Research Institute, P.O. Box 16,
Tsukuba Norin Kenkyu Danchi-nai, Ibaraki 305, Japan
SHUICHI KAWAI
Wood Research Institute, Kyoto University, Uji, Kyoto 611, Japan
KOHEI KOMATSU
Forestry and Forest Products Research Institute, P.O. Box 16,
Tsukuba Norin Kenkyu Danchi-nai, Ibaraki 305, Japan
JUNSUKE MUKUDAI
Department of Forestry, Faculty of Agriculture, Kyoto Prefectural
University, Shimogamo, Sakyo-ku, Kyoto 606, Japan
TAKASHI NAKAI
Forestry and Forest Products Research Institute, P.O. Box 16,
Tsukuba Norin Kenkyu Danchi-nai, Ibaraki 305, Japan
MISATO NORIMOTO
Wood Research Institute, Kyoto University, Uji, Kyoto 611, Japan
KEIZO OKAMURA
Department of Wood Science and Technology, Faculty of Agriculture,
Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto 606-
01, Japan
SHIRO SAKA
Department of Wood Science and Technology, Faculty of Agriculture,
Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto 606-
01, Japan
HIKARU SASAKI
MIKIO SHIMADA
Wood Research Institute, Kyoto University, Uji, Kyoto 611, Japan
LIST OF CONTRIBUTORS xiii
NOBUO SHIRAISHI
Department of Wood Science and Technology, Faculty of Agriculture,
Kyoto University, Kitashirakawa, Oiwake-cho, Sakyo-ku, Kyoto 606-
01, Japan
BAMBANG SUBIYANTO
Division of Material Science, R&D Center for Applied Physics, In-
donesian Institute of Sciences, Kompleks Puspiptek, Serpong, Tanger-
ang 13510, Indonesia
MASAHARU SUZUKI
Department of Applied Biological Science and Technology, Tokyo
Noko University, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183, Japan
MUNEZOH TAKAHASHI
Wood Research Institute, Kyoto University, Uji, Kyoto 611, Japan
NAOHIKO TSUJIMOTO
Central Research Laboratory, Oji Paper Company Ltd, 1-10-6
Shinonome, Koto-ku, Tokyo 135, Japan
QIAN W A N G
M I N G ZHANG
Department of Wood Science and Technology, Faculty of Agriculture,
Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto 606-
01, Japan
Structure and Chemical Composition of
Wood as a Natural Composite Material
SHIRO SAKA
ABSTRACT
The architecture of the molecular arrangement and ultrastructure of wood cell walls is
described in relation to the physical and mechanical properties of wood as a natural
composite material. The chemical composition of wood is also summarized to illustrate the
heterogeneity in distribution of the cell wall constituents.
INTRODUCTION
1
2 SHIRO SAKA
WOOD CELLS
V
FIG. 1. Schematic diagram of the major wood cells [ 1 ] . wf, wood fiber; tr,
tracheid; ve, vessel element; ap, axial parenchyma cell; rtr, ray tracheid; rp, ray
parenchyma cell.
TABLE 1
Cells in softwoods
Longitudinal Transverse
woods, the principal types of cell are vessel, tracheid, fiber and paren-
chyma, which are more complex than those in softwoods, as shown in
Table 2. Since softwood tracheids and hardwood fibers constitute the
majority of wood cells, they contribute in a major way to the physical and
chemical properties of wood.
TABLE 2
Cells in hardwoods
Longitudinal Transverse
transversely on the inner surface (P^. The S layer inside the P wall
is composed of three sublayers termed S S and S , based on dif-
1 ? 2 3
FIG. 3. Schematic diagram of the microfibrillar orientation in the wood cell wall
from softwood tracheids and hardwood fibers: P and Pi are the external and
0
internal surfaces of the primary wall: S and S 3 are the intermediate layers
1 2 2
than in S [ 7 ] .
1 2
In addition to these wall layers, a layer called the middle lamella (ML)
or intercellular layer (I) is located between the P walls of adjacent cells.
Since it is difficult to distinguish ML from the two P walls on either side,
the term compound middle lamella (CML) is generally used to designate
the combination of ML with the two adjacent P walls (Fig. 4).
TABLE 3
Comparison between the chemical composition of hard-
woods and softwoods [2]
Softwoods Hardwoods
layer are oriented nearly parallel to the fiber axis [6, 7 ] . However, some
variations in the fibrillar orientation exist. The closest parallelism to the
cell axis has been reported for the gelatinous (G) layer in tension wood
[8], which is made up of the abnormal hardwood xylem tissues formed in
a leaning stem or branch. Saiki [ 9 ] has reported for several softwood
species that the microfibrillar angles in the latewood tracheid S layer are
2
has a lower lignin content than that in earlywood [13, 15-18], except for
juvenile wood [16]. Furthermore, Nanko et al. [19] have found in the
reaction phloem fiber that the unlignified layer had microfibrils oriented
parallel to the fiber axis, while the microfibrils in the lignified layer were
oriented at an angle to the fiber axis.
STRUCTURE AND CHEMICAL COMPOSITION OF WOOD 7
of the tracheid secondary wall, the whole lignin content of wood could be
expected to be closely correlated to the lignin concentration in the S 2
layer of the tracheid. Thus, Fig. 5 indicates that the lignin concentration
in the S layer increases with increasing microfibrillar angle of the
2
| 30
25
20
0 10 20 30 40 50
Microfibrillar angle (e)
FIG. 5. Relationship between the microfibrillar angle (9) in the tracheid S layer
2
Mf
also been measured by electron and optical diffraction patterns. Since one
microfibril can be seen as a single crystal, the existence of 3-5 nm
elementary fibrils has been ruled out [33]. Furthermore, from obser-
vations of the lattice lines along the microfibrils, it has been concluded that
there is no periodicity in the longitudinal direction [32]. Unfortunately,
the lattice image of cellulose microfibrils in wood has not yet been taken
successfully due to the low crystallinity and small size of the crystallite.
Lignin
To investigate the distribution of lignin in wood, a number of reliable
methods can be used. As representative techniques, potassium permanga-
nate staining has been qualitatively used with electron microscopy [35],
while studies have also been reported by electron microscopy of the lignin
skeleton left after removing the constituent polysaccharides with hydro-
fluoric acid [36] or brown rot fungus [37].
In a quantitative assay of the lignin distribution, ultraviolet (UV) micro-
scopy by Goring and co-workers [39-41] has provided good results with
thin sections of wood. Saka et al [42-44] have developed a new method
based on specific bromination for lignin in a nonaqueous system, the
bromine concentration in each morphological region of wood then being
determined by transmission electron microscopy (TEM) or scanning
electron microscopy (SEM) coupled with energy-dispersive X-ray analysis
(EDXA). When the lignin reactivity toward bromination is known, the
distribution of lignin can be determined in various morphological regions
of wood. Figure 8 shows a direct comparison made between the two
1.00
Latewood Earlywood
i
Lignin concentration (g/g)
0.80
v -----
MIDDLE
LAMELLA (cc)
0.60 oo o
Q
O uv
0.40 EDXA
BOUNDARY
0.20
SECONDARY
WALL
I I
15 10 5 5 10
Cell number
FIG. 8. Variation of lignin concentration across the earlywood/latewood
boundary by UV microscopy ( O ) and TEM-EDXA ().
STRUCTURE AND CHEMICAL COMPOSITION OF WOOD 11
than that in either the S or S layer. The line profile of the bromine
x 3
TABLE 4
Distribution of lignin in loblolly pine tracheids as determined by bromination
with SEM-EDXA
Early wood S
t 13 12 025
5
2 60 44 0-20
5
3 9 9 028
ML 12 21 0-49
a
ML cc 6 14 064
Latewood Sj 6 6 0-23
5
2 80 63 018
5
3 5 6 025
ML 6 14 051
a
ML cc 3 11 078
a
Middle lamella at the cell corner
[46] have also reported the similar finding of high U V absorbance near
the lumen/wall interface for juvenile wood tracheids of Japanese fir (Abies
sachalinensis Fr. Schm.).
Hardwood lignins consist mainly of guaiacyl and syringyl residues, and
their ratio seems to change from one morphological region to another.
Although Fergus and Goring [47, 48] have attempted to determine the
distribution of lignin in white birch (Betula papyrifera Marsh.) by U V
spectral analysis, the syringyl and guaiacyl residues have markedly
different UV absorptivity. Therefore, it is essential to know the exact ratio
before the lignin concentration in a particular morphological region can
be computed from the U V absorption.
12 SHIRO SAKA
Saka et al [49, 50] have developed a new method for computing the ratio
of guaiacyl and syringyl residues in various morphological regions by
combining UV microscopy with bromination-EDXA (UV-EDXA), which
can be used to determine the lignin distribution in hardwoods. Shown in
Table 5 is the ratio of guaiacyl to syringyl residues in various morphological
regions of white birch wood as determined by the UV-EDXA technique
[49]. The results indicate that the fiber secondary wall (S ) contains pre-
2
sists mostly of guaiacyl residues. For the ray parenchyma cell, about equal
proportions of guaiacyl and syringyl residues were contained in lignin. For
the cell corner middle lamella (ML ), 80 to 100% of the lignin was found to
CC
Fiber/fiber.
b
Fiber/vessel.
c
Fiber/ray.
d
Ray/ray.
13
14 SHIRO SAKA
with fibers and vessels has the highest lignin concentration. In spite of
sufficient spatial resolution for analysis by the EDXA system, the
middle lamella between the cell corner areas (ML) was 10 to 30% lower
in concentration than the cell corner middle lamella (ML ). It is of
CC
100*
80
Sugar composition
60
40
20-
P ST S2 S3<W)
Gl ucuronoa rabi noxyl an
Galactoglucomannan
Cellulose
FIG. 10. Distribution of polysaccharides across the cell wall in tracheids from
Cryptomeria japonica [57].
16 SHIRO SAKA
the wood cell wall in tracheids from Cryptomeria japonica (Fig. 10).
Interestingly, cellulose is rich in the middle of the S layer, whereas the
2
Inorganic Constituents
As a general rule, elements other than carbon, hydrogen, oxygen and
nitrogen make up between 0 1 and 0-5% of the weight of wood [58, 59].
This proportion, although small, contains a wide variety of elements,
numbering over thirty [60]. Some of the inorganic elements present in
wood are essential for wood growth, whereas others are not necessarily
required.
Although a fair amount of information is available on the inorganic
constituents of wood [60-62], little has been published on their mor-
phological distribution in the cell wall. Saka and Goring [63] have
studied the distribution of inorganic constituents from the pith to the
outer ring of black spruce by the TEM-EDXA technique. This technique
provides a simple and powerful tool for determining any element above
neon in the periodic table.
Figure 11 shows the seven morphological regions in tracheids, ray
tracheids and ray parenchyma cells that have been investigated. Fifteen
different elements above neon in the periodic table were detected,
including Na, Mg, Al, S, CI, K, Ca, Cr, Fe, Ni, Cu, Zn and Pb.
Although the secondary walls usually contain detectable amounts of
only four elements (sulfur, chlorine, potassium and calcium), almost
all the elements are localized and concentrated in the torus and half-
bordered pit membrane regions (Fig. 12). This result may be related to a
high concentration of pectic materials in the pit membrane regions.
The total content of inorganic constituents decreases in the order of
torus (2%) > half-bordered pit membrane (1%)> middle lamella
(0-4%) > ray parenchyma cell wall (0*3%)> tracheid secondary wall (01
to 015%).
In addition, the total content of inorganic constituents is higher in
earlywood than latewood for all the morphological regions studied. This
finding supports the concept [64] that earlywood tracheids having large
lumens and abundant pits play an important role in water conduction,
while thick-walled latewood tracheids with far fewer pits may act as
physical or mechanical support for the wood.
STRUCTURE AND CHEMICAL COMPOSITION OF WOOD 17
FIG. 12. X-ray spectra from the tracheid secondary wall and tracheid torus.
CONCLUDING REMARKS
REFERENCES
[39] J.A.N. Scott, A.R. Procter, B.J. Fergus and D.A.I. Goring, Wood Sci.
TechnoU 3, 73 (1969).
[40] J.A.N. Scott, A.R. Procter, B.J. Fergus and D.A.I. Goring, Wood Sci.
TechnoU 4, 237 (1970).
[41] J.R. Wood and D.A.I. Goring, J. Microscopy, 100, 105 (1974).
[42] S. Saka, R.J. Thomas and J.S. Gratzl, Tappi, 6 1 , 73 (1978).
[43] S. Saka and R J . Thomas, Wood Sci. TechnoU 16, 1 (1982).
[44] S. Saka, P. Whiting, K. Fukazawa and D.A.I. Goring, Wood Sci. TechnoU
16, 269 (1982).
[45] S. Saka and R.J. Thomas, Wood Sci. TechnoU 16, 167 (1982).
[46] K. Fukazawa and H. Imagawa, Wood Sci. TechnoU 15, 45 (1981).
[47] BJ. Fergus and D.A.I. Goring, Holzforsch., 24, 118 (1970).
[48] B.J. Fergus and D.A.I. Goring, Holzforsch., 24, 113 (1970).
[49] S. Saka and D.A.I. Goring, Holzforsch., 42, 149 (1988).
[50] S. Saka, S. Hosoya, F.GT. St-Germain and D.A.I. Goring, Holzforsch., 42,
79 (1988).
[51] N. Terashima, K. Fukushima and K. Takabe, Holzforsch., 40, 101 (1986).
[52] P. Whiting, B.D. Favis, F.G.T. St-Germain and D.A.I. Goring, J. Wood
Chem. TechnoU 1, 29 (1981).
[53] W.A. Cote, Jr., N.P. Kutscha, B.W. Simson and T.E. Timell, Tappi, 5 1 , 33
(1968).
[54] T. Fujii, H. Harada and H. Saiki, Mokuzai Gakkaishi, 27, 149 (1981).
[55] H. Meier, J. Pol. Sci., 5 1 , 11 (1961).
[56] H. Meier and K.C.B. Wilkie, Holzforsch., 13, 177 (1959).
[57] K. Takabe, Ph.D. Thesis, Dept. Wood Sci. Technol., Kyoto Univ. (1984).
[58] A.J. Panshin and C. de Zeeuw, Textbook of Wood Technology, Vol. 1, 3rd
ed. (1970) McGraw-Hill, New York.
[59] B.L. Browning, The Chemistry of Wood (1963) John Wiley & Sons, New
York, Interscience Publishers.
[60] E.L. Ellis, Cellular Ultrastructure of Woody Plants (1965) ed. by W.A. Cote,
Jr., Syracuse Univ. Press, New York.
[61] E.L. Ellis, For. Prod. J., 12, 271 (1962).
[62] W.L. Galligan, H. Stern and P. Hohenschuh, For. Prod. J., 15, 185 (1965).
[63] S. Saka and D.A.I. Goring, Mokuzai Gakkaishi, 29, 648 (1983).
[64] H.P. Brownt, Wood Chemistry, Vol. 1, 2nd ed. (1952) ed. by L.E. Wise and
E.C. John, Reinhold Publishing Corp., New York.
Oriented Strand and Fiber Boards
HIROMU KAJITA and JUNSUKE MUKUDAI
ABSTRACT
Oriented mat-forming methods that employ mechanical and electrostatic orientation
were studied. The effects of some variables on the degree of particle alignment and on the
physical and mechanical properties of oriented boards were investigated. A production
system applying the electrostatic method, in which electrodes are located only on the reverse
side of the forming belt, is proposed.
Keywords: oriented strand board, oriented fiber board, mechanical orientation, electrostatic
orientation, alignment angle
INTRODUCTION
1. Mechanical method
The particles were aligned by a laboratory-size mechanical orienter, in
which many reciprocating plates were set parallel to each other at regular
intervals [1, 2]. The stroke and the frequency of the reciprocating plates
were 13 cm and 80 times per minute, respectively. Wood particles were
21
22 HIROMU KAJITA AND JUNSUKE MUKUDAI
dropped onto the reciprocating plates and passed through the spaces
between them (10 mm), forming a mat on a caul. The degree of particle
alignment could be controlled by changing the free-fall distance between
the bottom of the reciprocating plates and the top of the particle mat.
This mechanical orienter could align some particles, especially those that
were long or in slender flakes [ 1 ] , but small particles and fines were more
difficult to align mechanically, the electrostatic method being the most
suitable for these. Figure 1 shows typical examples of the distribution of
alignment angle (the angle between the cardinal direction of alignment
and the longer axis of the particle). With increasing free-fall distance, the
distribution curve gradually flattens and approaches the random dis-
tribution curve. These results show the same trends as those reported by
Suzuki and Sekino [3] and by Kawei et al. [4]. Figure 2 shows the effect
of free-fall distance on the degree of alignment with flake- and strand-type
particles. The average alignment angle (AAA) of the strand-type particles
increased with increasing free-fall distance, and the value is larger than
that for the flake-type particles. It seems that the spacing distance
72.5 %
O 52.9 %
s
Free-fall
40 :
distance
2 cm
o 4 cm
6 cm
30
8 cm
* Random
(
Frequency
Plate spacing: 10 mm
20
10
30 60 90
Alignment angle (degrees)
FIG. 1. Distribution of alignment angles for flakes of 0-5 x 10 x 50 mm.
ORIENTED STRAND AND FIBER BOARDS 23
40
lauan, sliver^
Cl.8-2.3-19.2mnn,,
30
"^sugi , semi-strand
( 0 . 5 * 2 . 3 "26.4mm) C
20'
* ^ s u g i , long tlakc
( 0 . 5 - 1 0 5 0 mm )
10<
2 4 6 8 10
Free-fall distance (cm)
FIG. 2. Relationship between the average alignment angle and free-fall distance
for strand- and flake-type particles of sugi (Cryptomeria japonica D. Don) and
lauan (Shorea spp.).
between the plates was too wide for the strand-type particles. Therefore,
one way of improving the alignment of these particles is to adjust the
spacing distance to a value closer to the particle width [1, 5]. A free-fall
distance of less than 3 cm did not affect AAA of the flakes, the value being
about 10 degrees. On the other hand, with a free-fall distance of over
3 cm, AAA increased with increasing free-fall distance. This is because
particles which had been oriented while between the plates became
disordered during free falling between the bottom of the plates and the
top of the particle mat.
Figures 3 and 4 show the relationships between the bending properties
(modulus of rupture (MOR) and modulus of elasticity (MOE)) and board
density and particle alignment. These figures show parabolic curves for
the bending properties against board density, both MOR and M O E
increasing with increasing board density [ 2 ] .
By increasing the board density from 0-50 to 0-70 g/cm , MOR of the 3
8
Single-layer board
Modulus of elasticity (GPa)
0
0.6 0.7 0.8
Board d e n s i t y (gem )
- 3
80
L Three-layer board
60
(MPa)
Modulus of rupture
40
3
O
= 20
J- J- J-
0.5 0.6 0.7
Board density (gem )
- 3
with AAA of 18 degrees. This means that about 30% of the raw material
weight of manufactured boards can be saved.
Figure 5 shows how a decrease in AAA affects the ratio of parallelism to
orthogonality (||/) for bending properties. Board density had no signifi-
cant effect on the ratio, but a marked increase in the value of the
| | / l ratio for bending properties with decreasing AAA is clearly depicted.
Especially, the tendency for an increase in the ||/J_ ratio of the three-layer
boards is much greater than that of the single-layer boards. The pattern of
response for MOE of the single-layer boards is similar to that for MOR. On
the other hand, it seems that the ||/_L ratio for MOR of the three-layer
boards aligned to less than 20 degrees is greater than that for M O E ,
although there are not enough data to explain the results at this stage.
The internal bond-strength (IB) and thickness swelling (TS) measured
after 24 hours of soaking were not significantly different between the
random and oriented particleboard [ 2 ] , the effect of board density on IB
26 HIROMU KAJITA AND JUNSUKE MUKUDAI
4
Single-layer board
2
!
i
MOE///MOE^
LE-L/LE//
0 10 20 30 40
Average alignment angle (degrees)
2. Electrostatic method
With this method, the fibers or particles fall freely through an electro-
static field, become polarized and are aligned in the direction of the
electrical lines of force within the field. There are three types of electrode
arrangement in the high-voltage electrostatic orientation system (Fig. 6)
[8].
Particle Particle
^ 0 0
Particle
^ Teflon-coated 1 ^ I I
glass fiber mesh 0
Kawai et al. [4] have investigated the effects of species, particle shape,
particle moisture content and electrostatic field intensity on the degree of
alignment in aligned particle mats using the configuration shown in Fig.
6(a) (method A). The field intensity and particle moisture content are
significant factors for particle alignment, whereas none of the other
factors showed a statistically significant effect. With an increase in the
28 HIROMU KAJITA AND JUNSUKE MUKUDAI
Orientation
direction
50
Average alignment angle (degrees)
40 Random ^ 1
30-
20 -
*
Electrode method B
A
4 L Electrode method C
O akamatsu , strand (m.c. 13 %, U M F )
A lauan, strand (m.c.13%, U M F )
softwood , fiber (m.c. 11 %)
J-
5 10 15 20
M a t height (mm)
FIG. 7. Relationship between the mat height and average alignment angle for
akamatsu (Pinus densiflora S. et Z.) and lauan (Shorea spp.) particleboards. (1)
Average orientation in a random-formed mat; (2) average orientation in an
oriented mat using the top-bottom electrode combination (method B); (3) average
orientation in an oriented mat using bottom electrodes only (method C).
TABLE 1
3
Properties of semi-strand board adjusted to board density 0-7 g/cm
akamatsu
lauan (Shorea spp.) (Pinus densiflora S. et Z.)
Board property Oriented Random Ratio Oriented Random Ratio
I 1 R HA ll/R I 1 R HA ll/R
MOE, dry (GPa) 5-8 2-1 3-6 2-8 1-6 4-7 1-7 2-9 2-7 1-6
MOE, wet (GPa) 2-5 10 1-5 2-3 1-7 1-7 0-6 11 2-9 1-6
MOR, dry (MPa) 36-3 17-1 26-4 20 1-4 29-6 14-7 21-2 2-0 1-4
MOR, wet (MPa) 110 6-3 9-3 1-7 1-2 10-5 5-7 6-7 1-8 1-6
IB (MPa) 0-6 0-6 n.s. 0-5 0-5 n.s.
TS (%) 14-5 17-9 n.s. 37.6 36.2 n.s.
LE (%) 0-27 0-76 0-50 0-36 0-48 0-18 0-93 0-52 019 0-35
HIROMU KAJITA AND JUNSUKE MUKUDAI
Notes: Parallel to orientation; 1: perpendicular to orientation; wet: 70 C, 2 h then 20 C, 1 h immersion; IB: internal
bond strength; TS: thickness swelling after 24 h immersion at 20 C; LE: linear expansion measured on wet bending
specimens; n.s.: not significant.
ORIENTED STRAND AND FIBER BOARDS 31
using method C [8]. Oriented boards from lauan (Shorea spp.) and
akamatsu (Pinus densiflora Sieb. et Zucc.) are fairly orthotropic, with the
ratio for M O E in the range 2-3-2-9. M O E in the oriented direction
is 60 to 70% greater than that of random boards, while the ratios of
MOR are somewhat less than those of MOE. LE of oriented strand
board (OSB) in the oriented direction is 1/3 to 1/5 of that in the
perpendicular direction. Bending-creep deflection in the oriented direc-
tion is as low as that of plywood.
The proposed configuration for industrial application of this system is
shown in Fig. 8. One set each of electrostatic orienters for top and bottom
mats is used, the less-oriented top portion of each mat being removed by
shaving to make an evenly oriented mat. The upper mat is turned over
by a flexible reversing-belt and a rigid drum without disturbing the
orientation of the particles, the turned-over mat then being deposited on
top of the lower mat by using a sliding plate with a low coefficient of
friction. A continuous particle mat with well oriented surfaces results.
Coupled with a continuous press, this method is ideal for continuously
oriented thin-board production [8].
REFERENCES
[1] H. Kajita and J. Mukudai, J. Soc. Mater. Sci. Jpn., 30, 736 (1981).
[2] H. Kajita, Mokuzai Gakkaishi, 33, 865 (1987).
32 HIROMU KAJITA AND JUNSUKE MUKUDAI
ABSTRACT
Dimensionally stable low-density (0-4-0-6 g / c m ) particleboard is required as a substitute
3
for plywood panels. This paper discusses the limit for lowering the density of particleboards
by using isocyanate resins and the effects of various factors such as the species (density) and
configuration of the particles, the resin content and resin components on the properties of
low-density particleboard.
The mechanical properties of boards from different species had linear relationships with
the compaction ratio (the board density divided by raw material density), and the practical
lower limit of the compaction ratio was found to be 0-7-0-8 for isocyanate resin. The
thickness swelling of the boards was independent of the species of raw material, and
increased with increasing compaction ratio, i.e., low-density (low-compaction) particle-
boards were more dimensionally stable. Linear relationships between the mechanical
properties and shape factors based on the particle configuration and derived from fracture
mechanics theory were observed. Both the mechanical and dimensional properties of the
boards improved with increasing resin content, but were generally independent of the
formulation of isocyanate compound adhesives such as the free-isocyanate group content
and functionality of crude methylene diphenyl diisocyanate (MDI). Crude M D I alone,
compound resin, and unreacted mixed resin did not make much difference in the board
properties either.
INTRODUCTION
33
34 SHUICHI KAWAI AND HIKARU SASAKI
80
Modulus of rupture, MOR (MPa)
60 I
Light red meranti
PT = 0A0
Apitong p = 0.70/
T
I/
40 Balsa-apitong
,,-0.29.
20
O Balsa
100 Light red meranti
Apitong
50
higher density species at the same level of compaction ratio, and increases
exponentially with increasing compaction ratio. This explanation fits
Fig. 3 well. When the bonding strength of the adhesive is sufficient,
however, the internal bond strength will be limited by the tensile or
bending failure of the particles, which results in a saturation curve in the
36 SHUICHI KAWAI AND HIKARU SASAKI
O Balsa p = 0.21
r
I
2 Light red
<aw) 8/ *M^uaj;s puoq
meranti p = 0.4C
r
I Apitong p = 0.7C
r
4
I Balsa-apitong |~
P r = 0.29J
|BUJ9ju|
FIG. 3. Relationship between the internal bond strength and compaction ratio.
The configuration of particles is given in Fig. 1; p is the density of the raw
r
material.
o Balsa P r = 0.21
40
! Apitong = 0.70 P r
& Balsa-apitong / M
20 p =0.29 X
r / ^
i 1 1 i i i
0 1.0 2.0
Compaction ratio, CR
FIG. 4. Relationship between the thickness swelling and compaction ratio after
31 days of water immersion. M represents the master line for different boards of
each species, CW is the theoretical thickness swelling of a balsa-apitong board,
and p is the density of the raw material. The configuration of the particles is
r
given in Fig. 1.
particles with different dimensions that were strictly controlled for length
(A), width (a>), and thickness (d) were each used to produce low-density
particleboards with a density of 0-40 g/cm , using an isocyanate com- 3
pound adhesive [ 4 ] .
The bending strength increased with increasing X and with decreasing
d. N o clear effect of co on the bending strength was observed, but the
bending strength seems to have decreased with increasing co. The inter-
nal bond strength increased with increasing d, and with decreasing X
and co.
Such an effect of particle configuration on the mechanical strength of a
board can be explained by fracture mechanics theory. In the layered
structure of a particle mat, voids formed along with the particles are
assumed to be cracks. The dominant crack which affects the bending
38 SHUICHI KAWAI AND HIKARU SASAKI
strength.
In the same manner, the crack dimensions are considered to be
proportional to the product of X and co for tensile stress in the direction of
the board thickness, so the effect on internal bond strength is inversely
proportional to the square root of their product. The internal bond
strength is also proportional to the mass of adhesive per unit area, i.e.,
roughly to the thickness of the particles. Therefore, internal bond strength
is proportional to d(Xoj)~ , which is called the shape factor in internal
05
bond strength.
Figures 5 and 6 show the relationships between these shape factors,
and the bending strength and internal bond strength, respectively. A
linear relationship between the internal bond strength and the shape
factor can be seen in Fig. 6, showing that the effect of particle configur-
ation on the internal bond strength can be well explained by the shape
factor derived from fracture mechanics theory.
On the other hand, the data taken all together in Fig. 5 are not
linear. However, excluding the data from X = 1 0 mm and also for the
particles with the largest cross-sectional area (w = 7mm, <5 = 0-7 mm)
with X = 20 and 30 mm (those within the broken line), a linear rela-
tionship was also found between the bending strength and the shape
factor. This can be interpreted as follows: as the particles become
smaller, in this case at 10 mm in length, the number of cracks markedly
increases and thus the cracks along the board thickness are com-
pounded. This explains why fracture was initiated at a much lower
stress level than the theoretically predicted value based on simple crack
dimensions. In the case of an extremely large cross-sectional area, this
compounded effect on bending strength is extended to the boards with
X = 30 mm.
LOW-DENSITY PARTICLEBOARD 39
30 r-
25 h
20 h-
CL
3
Modulus
10 h-
5
2 4 6 8 10 12
M - (mm 05)
FIG. 5. Relationship between the modulus of rupture and (nX/2Sco) , the shape
05
factor in bending strength. The board density is 0-4 g/cm , and an isocyanate resin
3
flaker were pressed into particleboards with densities of 0-4 and 0-6 g/cm , 3
12
Internal bond strength (MPa)
1J0
3.8
0.6
D.4
t
FIG. 6. Relationship between the internal bond strength and S(X(o)~ ' , the 0 s
shape factor in internal bond strength. The board density and adhesive used are
given in Fig. 5.
N C O functional numbers from 2-3 to 3-2, and by using these resins (an
N C O group content of 18%) with polyether polyol and their unreacted
mixtures at a resin content level from 2 to 20%.
Figure 7 shows the effect of the isocyanate resin content on the internal
bond strength of the particleboards. An increase in the resin content
improved both the mechanical and dimensional properties of the particle-
boards. Crude MDI alone, the compound resin, and unreacted mixed
resin did not make any great difference in the board properties.
The effects of factors taken in this paper such as the species (density) and
configuraton of particles, the resin content, and the board density on the
mechanical and dimensional properties of particleboards were determined
by a multiple regression analysis [3, 4, 5]. Both the moduli of rupture and
elasticity could be predicted adequately with the board density and bulk
density of the particle mat as predictor variables (R = 0-90). The particle 2
mat bulk density correlated inversely with the shape factor in bending,
(nX/2d(o) divided by the density of the raw material (r= 0.85). This
05
9
LOW-DENSITY PARTICLEBOARD 41
1 J
0 5 10 15 20
Resin content (%)
FIG. 7. Relationship between the internal bond strength and resin content for a
board density of 0 6 and 0 4 g/cm . 3
Board density
06 0 4 (g/cm ) 3
suggests that the bulk density of a particle mat might be a useful index to
represent the factors of particle density and configuration in relation to the
bending strength of a board. The internal bond strength can be well
predicted by the board density to the second power and the particle density
(.R = 0-93). Resin content is definitely another important factor, although
2
REFERENCES
[1] S. Kawai, Wood Research and Technical Notes, No. 24, 31 (1988).
[2] S. Kawai, H. Sasaki, S. Ishihara, A. Takahashi and M. Nakaji, Mokuzai
Gakkaishi (J. Japan Wood Res. Soc), 3 4 , 973 (1988).
[3] S. Kawai, H. Suda and H. Sasaki, Mokuzai Gakkaishi, 32, 385 (1987).
[4] H. Suda, S. Kawai and H. Sasaki, Mokuzai Gakkaishi, 32, 376 (1987).
[5] S. Kawai, H. Suda, M Nakaji and H. Sasaki, Mokuzai Gakkaishi, 32, 876,
(1986).
Steam-Injection Pressing Technology
HIKARU SASAKI, SHUICHI KAWAI, TOSHIMITSU HATA
ABSTRACT
In order to establish the optimum steam-injection pressing technology, the characteristics
of curing adhesives under high steam pressure, the temperature behavior in the particle mat
core during steam-injection pressing, and the length of pressing time were investigated. A
semi-continuous steam-injection press of test-plant scale was then developed and applied to
the production of thick, low-density particleboard.
The duration and pressure of steam injection with urea formaldehyde (UF) and
urea-melamine formaldehyde ( U M F ) adhesives needed to be carefully determined for
particleboard production by high-temperature steam-injection pressing, too-high steam
temperatures resulting in a poor internal bond strength. On the other hand, the internal
bond strength of those boards bonded with other resins was not perceptibly influenced by
the steam temperature.
The temperature in the middle layer of a particle mat with a thickness of 20 or 40 mm
reached more than 100 C at the moment of steam injection, whereas it takes 4 and 11
minutes, respectively, in the case of hot pressing. The computer simulation predicts that
only a few seconds of steam injection is required for a mat thickness within 100 mm to reach
100C in the mat core.
Isocyanate bonded particleboards with a thickness of 20 mm could be produced with
a press time of around one minute. This corresponds to only about one-fifth of the
press time of a conventional hot-platen press, and this effect of steam-injection pressing
on shortening the press time would be greater for thicker board production.
The newly developed semi-continuous, steam-injection press worked satisfactorily, and
100 mm thick low-density particleboards bonded with an isocyanate resin could be
manufactured with a 90-second press cycle.
43
44 HIKARU SASAKI ET AL.
Keywords: pressing technology, steam-injection press, adhesive curing, press time, particle-
board, continuous press.
INTRODUCTION
of the resins cured by this process was then compared with the figure for
resins (control) cured in an oil bath under atmospheric pressure.
Figure 1 shows the hardness ratios of the U F and U M F adhesives in
relation to the steam injection conditions. At higher temperatures and
consequently greater steam pressures, the maximum value (peak) for the
hardness of the cured U F adhesive occurred with a short steam-injection
time. At a lower temperature, the peak occurred with a longer steam-
STEAM-INJECTION PRESSING TECHNOLOGY 45
100
eo
40
20
FIG. 1. Relationship between the hardness ratio and steam-injection time for
U F and U M F resins.
injection time. After this peak, the hardness decreased with increasing
steam-injection time at all temperature levels, and finally the resin
decomposed to a liquid. The time range in which the preferred hardness
of the resin for bonding exists was wider at lower temperatures than at
higher temperatures. Therefore, the duration and pressure for steam
injection with a U F adhesive needs to be determined carefully for particle-
board production by high-temperature steam-injection pressing.
The reason for this hardness change with the U F resin may have been
that the condensation and decomposition reactions occurred simulta-
neously in the resin during steam injection at high temperatures. The
former reaction is dominant until the hardness reaches its peak, whereas
the latter is dominant after the peak. In this case, decomposition may
have been caused by the presence of excessive water, which could not be
easily extracted from the reaction system under high pressure and would
have accelerated hydrolysis.
The trends in this relationship for the U M F and P M F resins were
similar to those for UF. However, the hardness peak of these two
resins occurred after a longer steam-injection time than that for the U F
resin, which suggests that these resins required more heat energy for
curing than did the U F resin. The hardness of the P F adhesive cured
with steam injection was quite low compared with that of the PF resin
cured under atmospheric pressure. The isocyanate resins could be
46 HIKARU SASAKI ET AL.
cured under all steam pressure conditions, and foamed after reacting
with water.
The foregoing observations indicate that curing adhesives under high
pressure (temperature) is different from that under atmospheric condi-
tions. The concept that both higher temperature and longer heating time
always results in better curing does not hold true under high-pressure
conditions. Polymerization and decomposition may occur one after the
other under such conditions.
Particleboards with a density of 0-6 g/cm were manufactured under
3
(C) 1501
100
Temperature
50
I Steam on
I I I I I
0 2 4 6 8 10
Pressing time (min)
FIG. 2. Temperature behavior in the middle layer of the mat during steam-
injection and conventional hot-platen pressing. A: Steam injection (steam pressure,
0 6 3 MPa; time, 3 0 sec; initial moisture content, 11%; board thickness, 2 0 mm); B:
steam injection (0-63 MPa, 30 sec, 0%, 20 mm); C: steam injection (0-63 MPa, 30 sec,
11%, 20 mm); D: steam injection (0-63 MPa, 30 sec, 11%, 4 0 mm); E: conventional
hot platen (initial moisture content, 11%; board thickness, 20 mm); F: conventional
hot platen (initial moisture content, 11%; board thickness, 4 0 mm). Board
parameters: particles, semi-flake; board density, 0-4 g/cm (only A, 0-6 g/cm );
3 3
200
(sec)
150
Steam-injection time
100
50
tion also predicts that about 180 sec of steam injection is required for the
core of 500 mm thick mat to reach 100 C, the temperature necessary for
an isocyanate resin to cure in about one minute [1]. Thus, such a thick
board could be produced with 4-5 min of press time by steam-injection
pressing.
(MPa)
2.5
2.0
Internal bond strength
1.5
1.0
0.5
0 1 2 3 4 5
Total pre8sing time (min)
FIG. 4. Relationship between the total pressing time and internal bond strength
of a particleboard.
Board density
0-4 0-6 (g/cm ) 3
upper and lower flat hot platens with steam injection from each surface
were used. The press moves with the forming belt and mat during
pressing, and after moving a certain distance, opens and returns to the
initial position. This operation is repeated, and boards can be continu-
ously produced. A teflon-coated glass net was used for the forming belt to
allow steam to be injected from the hot platens into the mat through the
belt.
Figure 5 illustrates this press. Perforated steam-injection plates with a
thickness of 32 mm are attached to upper and lower hot platens with
dimensions of 1200 (L) x 850 (W) x 35 (T) mm. The upper platen can move
up and down with a maximum pressure of 1-5 MPa. At the surface of the
steam-injection plates, holes of 2-0 mm in diameter for injecting steam are
drilled in a 25 x 25 mm spacing pattern. These holes are grouped into four
sections with an area of 300 x 8 5 0 mm each. Steam injection in each
section can be opened or closed separately by control valves. The inlet to
the press is provided with a tapered cold press 200 mm in length to
Lifting jack Upper platen jack Unit: mm
^1
Oil t a n k |
Hot platens
200^"
Conveyor >
STEAM-INJECTION PRESSING TECHNOLOGY
reduce any discontinuity in pressure and mat thickness. The angle of the
taper can be changed within the range 1/4-1/10 by changing the attach-
ment plate.
This press moves in the direction of the mat conveyor in a reciprocat-
ing motion. For this purpose, the press is supported by four wheels
running on two rails. The press is small size and operates at a low speed
because it was only designed for experimental purposes. However, the
equipment is suitable to study the fundamental problems of semi-
continuous steam-injection pressing.
Steam injected from the hot platens diffuses not only in the thick-
ness direction but also in the horizontal direction of the mat. There-
fore, the selection of position, time and duration for steam injection
are very important to prevent the adhesive from pre-curing in a
mat which is waiting its turn for hot pressing in the tapered cold
press.
Experiments were conducted to press 100 mm thick lauan low-density
particleboard with a density 0-4 g/cm with this semi-continuous steam-
3
REFERENCES
ABSTRACT
The mechancial properties of laminated veneer lumber (LVL) made from plantation
thinnings (9-year old) grown in Sabah, Malaysia were investigated. The species used were
Acacia mangium (AM), Gmelina arborea (GA), Albizia falcata (AF) and Eucalyptus deglupta
(ED). Laminated veneer lumber (LVL) was made up of 9-ply veneers of 2-5 mm thickness
from each species, using staggered scarf joints for the veneers. Composite beams were
constructed with LVL flanges and a low-density semi-strand board (LDB) web, and the
mechanical properties were tested.
The average standard deviation in modulus of elasticity (MOE) of LVL was \/y/n (where
n is the ply number) of that of solid sawn lumber of the same species.
The modulus of rupture (MOR) of LVL was almost the same as that of solid sawn
lumber, and the reduction in the variation of M O R was not as great as that found with
MOE.
M O E and M O R for the composite beam were lower than the figures for LVL, but much
higher than those for LDB. The variation in these properties was a little less than that of
LVL, so that the composite beam tested is potentially useful as a structural member.
With the short-span bending test specimens, shearing failure occurred near the glue layer
between the flange and web. The criteria derived for the onset of bending or shear failure
were useful for predicting the failure pattern.
55
56 HIKARU SASAKI ET AL.
INTRODUCTION
EXPERIMENTAL P R O C E D U R E
Raw Materials
Nine-year old logs from thinning operations at a plantation in Sabah,
Malaysia were used. The logs were selected, cut into 2 m lengths and
shipped to Japan with the cooperation of the Sabah Foundation. The
species, volume and diameter of each type of log are shown in Table 1.
Each 2 m long log was cut in half, and one half was sawn into JAS
(Japanese Agricultural Standards) sized lumber including knotty and
clear specimens. The other half was peeled into veneers 2-5 mm thick by
using a lathe (Tanouchi type) with a powered back-up roll which was
developed by the authors' group.
LVL
Scarf joints slope) were used to join the ends of the veneers, this
being done with the Hashimoto automatic scarf joint method, automatic
assembly, and final semi-continuous (intermittent) hot-pressing.
Nine-ply LVL with well-staggered end scarf joints was made, using a
urea melamine formaldehyde resin adhesive, by hot-pressing at 105 C
and 0-8 MPa pressure for four minutes. The dimensions of each LVL
material were 4 m long, 920 mm wide and 21 mm thick.
Composite Beam
Composite beams were constructed from LVL flanges and a low-
density particleboard (LDB) web. This board, 60 mm thick with a specific
gravity of 0-4, was made from semi-strand particles of Shorea species, and
TABLE 1
Logs from the Sabah Foundation [1]
line. Cold pressing for 24 h at a pressure of 0-34 MPa was applied for
curing.
Before this composite process, block shear tests were carried out
on the glue bond made between the LVL material and the edge of the
low-density particleboards with varying application rates of the glue.
The results are shown in Fig. 2, which includes the results with the iso-
cyanate resin. The isocyanate resin had better bonding strength than
the phenol resorcinol resin under dry conditions. In other tests under
wet conditions (4h boiling, 2 h drying (105 C), cooling in water), both
resins showed equal bonding strength with high glue applications.
From this preliminary experiment, it was concluded that the optimum
amount of glue application in the liquid condition was 180 g / m 2
for the isocyanate resin and 300 g / m for the phenol resorcinol resin
2
adhesive.
[mm]
LVL
7 100
80
B
5
60
iia8uaaas Surpuog
3 40 -G
2
H 20
V
0
0 50 100 150 200 250 300 350
Glue application, solid base (g/m ) 2
RESULTS A N D DISCUSSION
18r
16-
14-
12-
10-
8-
6-
Normalized frequency
HIKARU SASAKI ET AL.
4 -
2-
0 -
FIG. 3. Comparison of MOE distribution for dimension lumber and LVL (2-5 mm x 9 ply) from plantation thinnings from Sabah,
Malaysia [2]. Refer to Table 1 for definitions of AF, GA, ED and AM.
Sized lumber
T TTT
LAMINATED VENEER LUMBER AND COMPOSITE BEAMS
FIG. 4. Comparison of MOR distribution for dimension lumber and LVL (2-5 mm x 9 ply) from plantation thinnings from Sabah,
Malaysia [2]. Refer to Table 1 for definitions of AF, GA, ED and AM.
61
62 HIKARU SASAKI ET AL.
8
moe
4 h A ED-LVL O PB ( Edgewise b e n d i n g )
AF-LVL PB ( H o r i z o n t a l b e n d i n g )
C
2 h
0
0.3 0.35 0.4 0.45 0.5 0.55
Specific gravity
FIG. 5. MOE as a function of specific gravity in a composite beam, LVL and
low-density particleboard (web) [4]. Refer to Table 1 for definitions of ED and A F .
LAMINATED VENEER LUMBER AND COMPOSITE BEAMS 63
60
*oh
40
20
CD
40
JL _L
20 40 60 80 100 120 140
MOE (GPa)
FIG. 7. Relationship between MOE and MOR for sized lumber, L V L , and a
composite beam [4]. Refer to Table 1 for definitions of ED and A F .
64 HIKARU SASAKI ET AL.
2LR//*[l-f (l-e)]<l
2
(1)
Bending failure occurred when
2LRIh[\-t {\-e)\>\
2
(2)
Si 5
i 4
u
" 3
I2
U
A : Horizontal shear in bending
B : Horizontal shear along the
glue line in bending
1 C : ASTM edgewise shear
_L -L
0.3 0.35 0.4 0.45 0.5 0.55
Specific gravity
FIG. 8. Shearing strength as a function of specific gravity in a composite beam,
LVL, and low-density particleboard (web) [ 4 ] . Refer to Table 1 for definitions of
ED and A F .
LAMINATED VENEER LUMBER AND COMPOSITE BEAMS 65
A: ED Y= -0.02X+33.6, r =-0.76
B: AF Y= -0.02X+31.5, r*=-0.91
2 A
Critical span
^ C r i t i c a l span
length for AFv
length for E D
(from eq. 1 )
(from eq. 1 )
Li L_
200 400 600 800 1000 1200
Span length (mm)
FIG. 9. Shearing strength of a composite beam as a function of span length [4].
Refer to Table 1 for definitions of E D and AF.
The predicted values from these equations agree qualitatively with the
experimental results shown in Fig. 9.
Although the test results from the compressive indentation strength
perpendicular to the lamination of the beam are abridged, the compres-
sive strength of the composite beams was found to be similar to that of
the solid lumber and of LVL, and the deformation was very much
influenced by the species of the LVL flanges.
CONCLUSION
proportion to the square root of the ply number. The application of LVL
to the flanges of a composite beam provided high stiffness with little
variation. However, the strength level is still not high enough, and further
technological development is necessary to increase the strength.
REFERENCES
[1] Q. Wang, H. Sasaki and R. A. Kader, Mokuzai Kenkyu Shiryo (Wood Res.
and Tech. Notes), No. 25, 45 (1989).
[2] Q. Wang, T. Hayashi, H. Sasaki and Y. Nagaya, Mokuzai Gakkaishi, (J.
Japan Wood Res. Soc), 36, 624 (1990).
[3] M. R. Spiegel, Theory and Problems of Statistics, McGraw-Hill, New York
(1972).
[4] H. Sasaki, Q. Wang, S. Kawai and R. A. Kader, Proc. 1990 Joint Int'l. Conf.
on Processing and Utilization of Low-Grade Hardwoods, Taipei, 173 (1990).
Chemically Modified Particleboards
HIROMU KAJITA
YUJI IMAMURA
ABSTRACT
Studies were carried out on chemically modified particle- and/or fiber-boards to improve
their mechanical properties, dimensional stability, and biological properties. The technology
developed from chemical modification of solid wood was applied to these reconstituted
wood products. This report describes the production and properties of the chemically
modified boards.
Keywords: dimensional stability, chemical modification, phenol resin impregnation, acetyla-
tion, formalization
INTRODUCTION
67
68 HIROMU KAJITA AND YUJI IMAMURA
IPR co
0 * 10
I 1 1 I I I I
0 1 2 3 4 5 6
Number of c y c l e s
Because of the molecular size of phenolic resin, the resin solids cannot
occupy all the sites of potentially accessible regions. A low-molecular
weight resin in an aqueous solution can easily penetrate into the cell wall,
whereas a resin of larger molecular size would be trapped at the lumen
surfaces of the cell walls [1]. As a result, dimensional stability and
biological resistance can be more easily achieved with low-molecular
weight resin.
Acetylation
A number of studies on wood acetylation have been reported in the
past, and acetylated wood is said to have excellent physical and biological
properties related to dimensional stability, and resistance to decay and
termite attack. Acetylation occurs in the reaction with acetic anhydride,
in which acetic acid is split out as a by-product. The hydroxyl groups on
cellulose, hemicellulose, and lignin are converted into hydrophobic acetyl
groups.
Kiguchi and Suzuki [3] have made particleboards from acetylated sugi
particles without a binder, the particles being acetylated by acetic
anhydride with a catalyst of sulfuric acid. The particle surfaces with
acetylated wood components were melted by applied heat, and the
particles were bonded. However, under the optimum conditions for
acetylation, the particle surfaces were darkened, and the wood compo-
nent deteriorated by the hydrolytic reaction of the sulfuric acid. TS of the
acetylated particleboards was reduced considerably, but the IB strength
was one-fifth that of phenol-formaldehyde resin-bonded particleboard.
70 HIROMU KAJITA AND YUJI IMAMURA
maintained their strength for longer than the control boards. The boards
made only from acetylated particles showed little strength reduction after
100 days, and any additional deflection after longer exposure was
minimal. Although the weight loss from termite attack was not as large as
Acetylated particle
c o n t e n t (%]
40
5
30
c/>20
10
I I I i I I I
0 1 2 3 4 5 6
N u m b e r of c y c l e s
REFERENCES
[1] H. Kajita, Mokuzai Gakkaishi (J. Japan Wood Res. Soc), 35, 406 (1989).
[2] H. Kajita and Y. Imamura, Wood Sci. Techn., 26, 63 (1992).
[3] M. Kiguchi and M. Suzuki, Mokuzai Gakkaishi, 3 1 , 200 (1985).
[4] B. Subiyanto, S. Yusuf, S. Kawai and Y. Imamura, Mokuzai Gakkaishi, 35,
412 (1989).
[5] S. Takino, M. Norimoto, S. Kawai and H. Sasaki, Mokuzai Gakkaishi, 35,
625 (1989).
[6] S. Yusuf, M. Takahashi, and Y. Imamura, Mokuzai Gakkaishi, 35, 633
(1989).
[7] K. Nishimoto and Y. Imamura, Mokuzai Kogyo (J. Wood Technol. Assoc.,
Japan), 40, 414 (1985).
[8] Y. Yoshida, S. Kawai, Y. Imamura, K. Nishimoto, T. Sato and M. Nakaji,
Mokuzai Gakkaishi, 32, 965 (1986).
[9] Y. Imamura, K. Nishimoto, Y. Yoshida, S. Kawai, T. Sato and M. Nakaji,
Wood Res., No. 73, 35 (1986).
[10] R.M. Rowell, For. Prod. Abstr., 6, 363 (1983).
[11] Y. Imamura and K. Nishimoto, Wood Res., No. 72, 37 (1986).
[12] H. Fujimoto, T. Anazawa and K. Yamagishi, Mokuzai Gakkaishi, 33, 610
(1987).
[13] H. Fujimoto, T. Anazawa and K. Yamagishi, Proceedings of 23rd Interna-
tional Particleboards/Composite Materials Symposium, ed. by T.M. Mal-
oney, Washington State University, Pullman WS, 95 (1989).
[14] V.C. Mallari, Jr., K. Fukuda, N. Morohoshi and T. Haraguchi, Mokuzai
Gakkaishi, 36, 139 (1990).
[15] M. Kiguchi, Mokuzai Gakkaishi, 36, 867 (1990).
74 HIROMU KAJITA AND YUJI IMAMURA
ABSTRACT
Fungal decay considerably reduces the strength of wood composite materials such as
particleboards and flakeboards with only slight weight loss, so that it is not proper to
estimate their fungal resistance by only using the value of weight loss as an index. A
testing method that combined bending deformation and decay hazard was applied to
wood-based boards to evaluate their mechanical performance under fungal attack. The
rapid reduction of mechanical strength during the early stages of decay is assumed to have
been due to active fungal invasion of the surface of wood elements and consequent glue
failure. The structural performance of boards under biological attack is assessed in
relation to the manufacturing conditions and type of treatment used as well as to the
species of fungi applied. Scanning electron-microscopic observations of the fractured
surfaces were conducted to present visible evidence of glue-line failures due to fungal
invasion and their prevention by introducing a more adequate bonding or glue-additive
treatment.
Keywords: Particleboard, fungal attack, glue-line, bending-creep, fracture, SEM
INTRODUCTION
75
76 YUJI IMAMURA
size and shape of the particles, and the composition and physical
properties of the board [ 1 ] .
Much of the laboratory test data published on the decay of wood uses
a method based on the weight loss after a certain period of time in the
presence of single or mixed organisms. It is known, however, that the
brown-rot fungal attack on solid wood results in a large strength loss
with very low wood weight loss [ 2 ] . Consequently, the strength reduction
in a particleboard due to decay cannot be assumed to be always
associated with weight loss in the specimen.
A test method has been developed to determine the strength loss in
wood while under attack by brown- and white-rot fungi. This test method
determines the deflection under load by bending creep apparatus when
coupled with fungal attack [3, 4 ] .
To evaluate the mechanical performance of particleboards when ex-
posed to wood-decaying fungi, commercial particleboards and two kinds
of treated ones, which were made from acetylated chips and treated with
a fungicide incorporated in the glue, were subjected to bending-creep tests
under progressive fungal attack.
A scanning electron microscope (SEM) was employed to observe the
fractured surfaces, and morphological characteristics of the decayed
particleboards were presented in relation to the board quality and the
species of fungi inoculated into the specimens.
20r~
6.7
E
E M2 t
88
3.3
c
M . !
g
o
a>iO|
*-
Q
20 40 60 80 100
Loading time (days)
FIG. 2. Deflection-time curves for commercial particleboards bonded with
UMF resin (Ml and M2) and PF resin in a creep test under fungal attack by T.
palustris. Arrows indicate fracture of the test boards, and the number above each
arrow shows the value of the weight loss at the time of fracture.
reached more than 10% and the wood particles were substantially
destroyed.
The adhesives used in manufacture are of greater importance for the
fungal growth, as urea-melamine and isocyanate (IS) resins can have a
promoting, and phenolic resins an impeding effect. It has been reported
that unleached phenol-formaldehyde boards showed some toxicity to a
brown-rot fungus in sand-block tests. The presence of some soluble toxic
materials in PF resins may inhibit or slow the attack by T. palustris. This
may account for the longer time to failure of the PF boards compared
with the U M F and IS boards. However, these results do not necessarily
FUNGAL RESISTANCE OF WOOD COMPOSITES FOR STRUCTURAL USE 81
6.6
A 17.8
8.8
I !!
E
20
Deflection
0)
Q 10
J I I I I 111 J I I I I I 111
1 10 100
Loading time (days)
FIG. 4. Deflection-time curves for U M F ( A , A)-, P F ( , ) - , and IS ( O ,
)-bonded particleboards made from untreated ( A , , O ) and acetylated (A, ,
) particles in bending-creep tests under attack by T. palustris.
PERFORMANCE OF GLUE-ADDITIVE-TREATED
PARTICLEBOARDS UNDER FUNGAL ATTACK
20r 8.4
E 3.5
E
I
C
o>
0)
Q
0 I I I l I M i l l I I I I I I I I I I
1 5 10 50 100
Loading time (days)
FIG. 5. Deflection-time curves of untreated low-density particleboards () and
those treated by incorporating azaconazole in IS resin at retention levels of 0 6
(A) and l-0kg/m (). 3
REFERENCES
[1] Y. Imamura, Mokuzai Kogyo (J. Wood Technol Assoc., Japan), 42, 306
(1987).
[2] Y. Imamura and K. Nishimoto, Mokuzai Gakkaishi (J. Japan Wood Res.
Soc), 30, 1027 (1984).
[3] M. Takahashi, Int. Res. Group on Wood Preserv., Document No. IRG/WP/
2163 (1981).
[4] Y. Imamura and K. Nishimoto, J. Soc. Mater. Sci., Japan, 34, 985 (1985).
[5] Y. Imamura and K. Nishimoto, Proceedings of Pacific Regional Wood
Anatomy Conference, 37 (1984).
[6] Y. Imamura and K. Nishimoto, Mokuzai Gakkaishi, 33, 25 (1987).
[7] R.M. Rowell, J.A. Youngquist and Y. Imamura, Wood and Fiber Sci., 20,
266 (1988).
[8] Y. Imamura et al, Paperi ja Puu, 7, 816 (1989).
[9] H. Motoki, M. Sagioka and M. Sakai, Mokuzai Gakkaishi, 31, 193 (1985).
[10] K. Fukuda, Y. Tominaga and T. Haraguchi, Mokuzai Hozon (Wood
Preservation), 15, 10 (1989).
Full-Scale Tests on Wooden Houses During
Progressive Stages of Construction
TAKANORI ARIMA
ABSTRACT
Full-scale tests on houses during progressive stages of construction were conducted with
a vibration generator to determine the influence of components, and the relationships
between the natural frequency and the racking resistance of a house is discussed. The
changes in natural frequency during construction are significant and related to the stiffness
of the load-bearing walls and the damping ratio of the structure. Since the relative stiffness
depends on the amount of lining and cladding materials, as well as on the load-bearing
walls, the non-load-bearing materials play an important role in providing additional
resistive elements. This result was confirmed by the fact that gypsum cracking at the corner
of a wall was initially observed in the full-scale tests and from actual earthquake damage.
The effects of the number of stories, unbalanced walls and floor openings on the
frequency-response curve and the natural frequency are also discussed.
Keywords: Full-scale tests, wooden house, natural frequency, racking resistance, shear wall,
non-destructive testing
INTRODUCTION
85
86 TAKANORI ARIMA
[10, 11]. As static tests of full-scale structures are difficult and expensive
to conduct, it is necessary to develop a non-destructive testing method
that is easy to apply on site, and to measure the dynamic behavior and
stiffness of full-scale houses during progressive stages of construction, and
during the stages of demolition.
The primary purpose of this report is to investigate the relationship
between the stiffness of a full-scale structure and its dynamic natural
frequency, and to evaluate the effects of the construction building stages
and components in providing racking resistance to lateral loads. Based
on the results observed with actual houses, the effects of the number of
stories, unbalanced walls and floor openings on the frequency-response
curve and the natural frequency will also be discussed.
.25
Conventional 2-story structure
.2
I
.15
-P
C
.i I
U
(0
a
w .05
a
"0 5 10 15
FREQUENCY (HZ)
FIG. 1. Frequency-response curves and natural frequency during progressive
stages of construction. (I: diagonal bracings; II and III: + gypsum board cladding;
IV: + siding).
TESTS ON WOODEN HOUSES DURING STAGES OF CONSTRUCTION 87
The main bearing walls for the conventional Japanese structure are
diagonal-braced frames. Increasing the diagonal bracing provided in-
creased racking resistance and natural frequency in the test house.
Gypsum board shear walls of a light-frame construction as internal
bearing walls also provided a significant bracing effect proportional to
the number of walls as shown in Fig. 2. These results show that increasing
the number of bearing walls provided increased natural frequency in the
full-scale house, as was reported for wood structure models in previous
papers.
8
Natural frequency (Hz)
~0 30 60 90 120
10
(Hz)
9
Natural frequency
8
.
0 1.0 1.2 1.4 1.6
Racking load (x 1 0 3
kgf)
FIG. 3. Change in natural frequency of a one-story house during demolition by
reducing the length of gypsum-plaster cladding walls.
K= (2n-f) -W/g
2
Light-frame structure
8 ,, EW-direction
SN-direction
6 a-
'ft.
4
i
r
1 1
N
o
2
0
i
I 1p
V/,
f
c I II III
0)
D
CD 3-story structure
I
8 EW-direction
CO* SN-direction
6
-P
CO
2 4
2
0
i ii III
Stage of construction
FIG. 4. Effect on the natural frequency of lining and cladding materials during
progressive stages of construction. Light-frame structure: I: plywood shear wall;
II: + gypsum board shear wall; III: + siding. 3-stories conventional structure: I:
diagonal bracing: II: + gypsum board cladding; III: + siding).
earlier report. When actual values for K are estimated from X, the
s
10
X J 3/
8
4,
0 2 4 6 8 10 12 14 16
15 r
3
Spring constant, K (x 10
10 -
O
FIG. 6. Relationship between K ob-
tained from vibration tests and the
0 10 20 30 ultimate strength estimated from
Ultimate strength (x 1 0 3
kgf) racking resistance test on a wall.
10
Natural frequency (Hz)
4 Stage II
2
8 1
^ 6 Stage I
1 2 '3 4
Number of stories
100
COLLAPSE OF EXTERNAL WALLS
50 L\ \ \ N CRACKING OF EXTERNAL WALLS
CRACKING OF FOUNDATION
I n IV
<1.2 <1.5 <2.0 2.0<
Ratio of damage {%)
100
CRACKING OF INTERNAL WALLS
50 ILL-FITTING FRAMES
DELAMINATED TILES
i n id iv
100
50 DAMAGED SHOJI (SLIDING PAPER DOORS)
1\ \ \ \| GAPS BETWEEN POSTS AND WALLS
I n ID IV
R e l a t i v e amount of l o a d - b e a r i n g walls
FIG. 8. Damage to houses in the 1978 earthquake expressed as a function of the
relative amount of load-bearing walls (actual amount of bearing walls/required
amount of bearing walls). The ratio of damage is denned as actual number of
damaged houses to the total number of houses investigated. The extent of damage
was slight, needing only minor repairs.
CONCLUSIONS
ACKNOWLEDGEMENT
Thanks are given to the many researchers and scientists whose work
contributed to this report.
REFERENCES
[1] T. Arima, M. Okabe and N. Maruyama, Mokuzai Gakkaishi (J. Japan Wood
Res. Soc), 34, 813 (1988).
[2] T. Murota, T. Arima, H. Okada, M. Sato, K. Saito and K. Mashita,
Kenchiku Kenkyu Shiryo No. 28 (1981).
[3] Ministry of Construction, Development of a New Wood Construction System
for Small Houses, Technology Center for National Land Development of
Japan (1975).
[4] S. Nakajima and T. Arima, Mokuzai Gakkaishi, 36, 291 (1990).
[5] H. Sugiyama, T. Uchisako, N. Ando, H. Hirano and N. Nakamura, ICTE
Seattle Proceedings, 55 (1988).
[6] H. Sugiyama, T. Uchisako, N. Ando, T. Arima, H. Hirano and N.
Nakamura, ICTE Seattle Proceedings, 804 (1988).
[7] G.F. Reardon, PTEC. Auckland Proceedings, 276 (1989).
[8] Japan Housing and Wood Technology Center, Full-scale Test of Conven-
tional Timber Structure House (1986, 1987).
[9] Japan Wood Frame Housing Association, Full-scale Test of Three-storey
2x4 Construction (1979),
[10] T. Arima, Full-scale Test of Timber Construction Using a Vibration Gener-
tor, The Building Center of Japan (1989).
[11] T. Arima, M. Okabe, N. Maruyama and S. Hayamura, IT EC. Tokyo
Proceedings, 778 (1990).
[12] S. Nakajima, T. Arima, N. Nakamura and J. Ichikawa, Mokuzai Gakkaishi,
37, 128 (1991).
Structural Properties of Full-Size
Sawn Timber
TAKASHI NAKAI
ABSTRACT
For developing more reliable stress-grading methods, full-size bending tests were con-
ducted on square sawn timber. It was found that the concept of 'strength ratio', which is
used in ASTM D 245, could not always be applied to all species, but that the modulus of
elasticity could be used as the most suitable practical parameter for grading regardless of
species.
Various methods were studied for measuring the modulus of elasticity, both static and
dynamic, including the methods of stress-wave propagation time measurement and of
fundamental vibration frequency measurement.
A series of destructive tests was conducted in bending, compression and tension of
full-size sawn timber after measuring the static and dynamic moduli of elasticity. The
moduli of elasticity obtained from the deflection at mid-span in the third point loading
condition and from the fundamental vibration frequency and density are regarded as the
most suitable parameters for grading for the Japanese saw-mill industry. A new grading
system should be developed that applies these parameters for large cross-sections such as
flat square sawn timber.
INTRODUCTION
95
96 TAKASHI NAKAI
Many full-size strength test results have revealed that these two
hypotheses are not always valid. North America and some countries in
Europe have finished what they called an 'in-grade test' project for
dimension lumber, which is from 38 mm to 89 mm in thickness and
89 mm or more in width. There is a growing trend to change from the
allowable unit stress design method to the limit state design method, for
which it is essential to determine the characteristic values for graded sawn
timber.
Unlike other countries, Japanese structural sawn timbers that are used
for construction have a relatively large cross section, and are known as
squares (e.g., 10-5 cm by 10-5 cm in cross section) and flat squares (e.g.,
1 2 0 c m by 2 7 0 c m ) , which resemble North America's 'post and timbers'
and 'beam and stringers' respectively. Very little research work has been
carried out on the structural performance of these sections.
Forestry and Forest Products Research Institute has conducted a
series of full-size bending tests on timber cross sections, in the square and
flat square series. As there was a high correlation coefficient regardless of
species between the modulus of elasticity and various strengths such as
modulus of rupture, compressive and tensile strength, several non-
destructive tests to measure the modulus of elasticity were conducted to
seek a practical application of this parameter at saw-mills or lumber
yards for large cross-section timber, which cannot be evaluated by
commercial grading machines which have been developed mainly for
dimension lumber.
MATERIALS A N D TEST M E T H O D S
(1) Squares bending test. This research was carried out with the
co-operation of nine prefectural research organizations under the supervi-
sion of FFPRI [ 2 ] . The species tested in this project were akamatsu
(Pinus densiflora), Douglas fir (Pseudotsuga menziesii), karamatsu (Larix
STRUCTURAL PROPERTIES OF FULL-SIZE SAWN TIMBER 97
f= (V2L)(Efg/py'2
(GPa).
(3) Squares compression and tension tests. This research was conduc-
ted at FFPRI [5, 6 ] . Species tested were akamatsu., Douglas fir, Hem
fir, ezomatsu (Picea jezoensis) and sugi. The size of each specimen was
5 cm x 10 cm x 350 cm, except for sugi, which was 10 cm x 10 cm x
350 cm, and each sample size was about 100, except 200 sugi samples.
A 980 000 N-capacity testing machine was used with 50 cm long tapered
wedge grips, the elongation being measured by digital dial gauges
with 1/100 mm graduations for a 1000 mm gauge length at the center.
Compressive strength was measured for a short column specimen with a
slenderness ratio of 10, which was end-matched to the tensile speci-
men.
(4) Flat squares bending tests. Seven prefectural research organiza-
tions took part in this project under the supervision of FFPRI [ 7 ] . The
species tested were akamatsu, Douglas fir, karamatsu, ezomatsu,
todomatsu (Abies sachalinensis) and sugi. The total number of specimens
tested was 1057 with a typical size of 1 2 0 c m in width and from 2 1 0 c m
to 3 0 0 c m in height. After recording the knot size and location and
measuring Ef the third point loading was applied edgewise with a total
span from 360 cm to 390 cm depending on the length and height of the
specimen.
98 TAKASHI NAKAI
RESULTS A N D DISCUSSION
1. The most important result obtained in this series of tests was that
the value for correlation coefficient r between the knot size and modulus
of rupture (MOR) was high enough for grading, being in the order of 0 6 5
for akamatsu, Dahurian larch and Hem fir. In the case of hinoki and sugi,
the values for r were in the oder of 0 1 5 to 0-25, and although statistically
significant, this is not considered to be a practical value for grading.
From these results, it is obvious that the 'strength ratio' concept cannot
be applied to all species. Only MOE showed a high correlation coefficient
in the order of 0-6 to 0-8 regardless of species.
(2) According to the results obtained in this study, all methods for
measuring the modulus of elasticity gave similar values for the correlation
coefficient between the modulus of elasticity and modulus of rupture. For
practical applications, however, a non-contact measuring method, i.e., Ef
obtained by measuring the fundamental vibration frequency and density,
is regarded as the most suitable. It is also pointed out that EF can be
used quite effectively for grading or sorting logs before sawing. Contact
methods such as measuring the stress wave and ultrasonic wave propaga-
tion time required close contact between the sensor and surface of the
timber cross section, which is not easy to maintain. When using ultra-
sonic waves, a large volume of timber may cause too much decay of wave
for its arrival to be detected.
3. When comparing the fifth percentile value for bending, compressive
and tensile strengths, the ratio obtained for sugi was 1 00:0-84:0-64,
respectively. The results of this test indicate that the allowable tensile unit
stress should be reduced to 60% of the allowable bending unit stress.
4. The relationship between Ef and MOR for flat square sawn timber
was established as shown in Fig. 1, from which it appears that sugi and
the other species should be graded separately. These relationships could
be used for allocating new allowable unit stresses in bending when Ef is
measured for flat square sawn timber.
Other valuable research work [8, 9] for simultaneously measuring
modulus of elasticity E and shear modulus G for full-size timber should
be mentioned for the case of long span beams with a very high ratio of
height to width for large-scale timber construction, because estimating G
for full-size timber is very important to prevent lateral buckling of the
beam. Although the ratio of E/G is assumed to be 15 or 16 worldwide, the
cutting pattern and quality of timber may affect this relationship. Further
research needs to be done to clarify this point.
STRUCTURAL PROPERTIES OF FULL-SIZE SAWN TIMBER 99
100
80
MOR (MPa)
60
40
20
0 5 10 15 20
Ef(GPa)
FIG. 1. Relationship between Ef and MOR for flat square sawn timber.
REFERENCES
[1] T. Nakai and R. Yamai, Bulletin of the Forestry and Forest Products R.I., No.
319, 13 (1982).
[2] Forestry Agency, Rep. No. 25, 196 (1985).
[3] T. Nakai and T. Tanaka, The Journal ofCIB, 27(1), 23 (1989).
[4] T. Nakai, T. Tanaka and H. Nagao, Proceedings of 1990 International
Timber Engineering Conference, Vol. II, 593 (1990).
[5] T. Nakai, T. Ebihara and T. Tanaka, Wood Utilization Division Note, 62-1
(1987).
[6] Strength of Timber and Wood-based Structures Group, Structural Timber: A
Collection and Analysis of Strength Data, Japan Wood Research Society,
Tokyo (1988).
[7] T. Nakai, H. Nagao and T. Tanaka, Summaries of technical papers of annual
meeting, Architectural Institute of Japan, Structures II, 5 (1991).
[8] N. Sobue, Mokuzai Gakkaishi (J. Japan Wood Res. Soc), 32, 274 (1986).
[9] N. Sobue, Mokuzai Gakkaishi, 34, 652 (1988).
Structural Analysis of Subassemblies Using
Plywood Panels
FUMIO KAMIYA
ABSTRACT
Plywood panels are used for the construction of all types of wooden residential buildings
in Japan. It is recognized that such buildings are safe from seismic loads, due to the
contribution of plywood for shear strength. The analytical work carried out in Japan for
predicting the behavior of plywood-sheathed walls and floors is summarized.
INTRODUCTION
101
102 FUMIO KAMIYA
PLYWOOD-SHEATHED WALLS
3500
3000
2500
2000
CO
5 1500
1000
500
0 I 1 1 1 1 1
0 10 20 30 40 50 G0
Shear strain (1CT rad)
3
Step 1. Calculate the shear under the assumption that the stiffness of
each brace is the same. The equivalent stiffness of braces can then
be determined.
Step 2. Determine the number of nails in each diaphragm element
according to the magnitude of the calculated shear.
Step 3. Recalculate the shear for the new stiffness value.
Step 4. Check if the nail stress is less than the allowable figure. Go back
to Step 2 if the answer is 'No', or end if 'Yes'.
14
Total load (tonf)
motion.
106 FUMIO KAMIYA
D/A Actuator
MX+ C X + P = - MXe converter controller
Assumed values|
of M a n d C LVDT
z 1
Earthquake data|
Xe
Test wall
/ Actuator
M a s s s t o r a g e unit ^ - L o a d cell
the test. This model consists of multiple straight lines passing through
several points such as the residual deflections and loads. The computer
program for this analysis is written in the BASIC language, and about
500 lines are required for the program. The calculated and observed
responses are shown in Fig. 6, indicating that the maximum load and
deflection responses could be predicted with an error of less than 5%,
indicating that this analytical method would be suitable for improving a
design.
Def1.(mm)
20
-2
5 10 15
Time (sec)
FIG. 6. Seismic response of plywood-sheathed walls obtained by the pseudo-
dynamic test and by the usual response analysis using the load-deflection model
developed. Earthquake data is from El Centro, NS, 1940.
FURTHER STUDIES
REFERENCES
[1] R.L. Tuomi and W.J. McCucheon, J. ofStruc. Div., ASCE, 104 (ST7), 1131
(1978).
[2] I. Sakamoto, Abstracts of Annual Meeting Papers, Arch. Tech. Inst, of
Japan, 2003 (1980).
[3] F. Kamiya, Trans, of Arc. Inst, of Japan, 309, 86 (1981).
[4] Y. Hirashima, Mokuzai Gakkaishi (J. Japan Wood Res. Soc), 27(2), 141
(1981).
[5] M. Yasumura and H. Sugiyama, Abstracts of Annual Meeting Papers, Arch.
Tech. Inst, of Japan, 2253 (1981).
[6] H. Noguchi, Abstracts of Annual Meeting Papers, Arch. Tech. Inst, of Japan,
1793 (1979).
[7] K. Miyazawa and S. Hirano, Abstracts of Annual Meeting Papers, Arch.
Tech. Inst, of Japan, 25 (1988).
[8] M. Hata, S. Takino and H. Sasaki, Mokuzai Gakkaishi, 34(9), 718 (1988).
[9] S. Nishimori and S. Kuromasa, Abstracts of Annual Meeting Papers, Arch.
Tech. Inst, of Japan, 47 (1989).
[10] H. Nasu and H. Noguchi, Abstracts of Annual Meeting Papers, Arch. Tech.
Inst, of Japan, 43 (1989).
[11] Applied Technology Council, Guidelines for the Design of Horizontal Wood
Diaphragms, USA (1981).
[12] F. Kamiya, Proc. 1990 Intl. Timber Eng. Conf, 502 (1990).
[13] F. Kamiya, Proc. 1989 Intl. Conf. on Timber Eng., 838 (1988).
Mechanical Timber Joints and their
Application to Glulam Portal Frames
KOHEI KOMATSU
ABSTRACT
The nail, drift-pin and bolt are representative fasteners to produce moment-resisting
timber joints, and the characteristics of these fasteners are briefly outlined. A method for
non-linear analysis for glulam frame structures is then introduced. Finally, the analytical
approach is verified by full-size experiments on three kinds of two-storey glulam portal
frames utilizing nailed joints, drift-pinned joints and bolted joints, respectively.
INTRODUCTION
Nails
In New Zealand, where the glulam portal frame was first developed
[1], nailed timber joints with steel gusset plates or plywood gusset plates
109
110 KOHEI KOMATSU
for a slip of 0-5 mm and JP0.25 is the load for a slip of 0-25 mm.
3. For both initial slip modulus K and ultimate strength P of the
s u
Drift-pins
In Japan, drift-pins are used for the moment-resisting joints in glulam
portal frames in preference to nails because of the good joint appear-
ance and its excellent fire-resisting performance. The performance of
individual drift-pin joints with inserted steel plate(s) has been in-
vestigated first by Hata et al. [ 5 ] , then by Maeda [6] and recently by
Kawamoto et al. [7, 8, 9 ] . Unlike the case of nailed joints, initial slip
modulus K and ultimate strength P of drift-pin joint are strongly
s u
metral between the pin and the pin-hole in the steel plate.
2. In the case of loading parallel to the grain, the yield strength of a
drift-pin joint can be well predicted by the so-called 'European yield
theory' [10]. The ultimate strength of a drift-pin joint is slightly
(kgf)
MECHANICAL TIMBER JOINTS APPLIED TO GLULAM PORTAL FRAMES Ill
800 800
(kgf)
Timber: Sugi Timber: Sugi
P
P
Load per n a i 1 ,
Load per n a i 1 ,
400 400
o 200 200
2 4 6 8 10 0 2 4 6
Slip deflection, S (mm) Slip deflection, S (mm)
800
800
(kgf)
(kgf)
Timber: Douglas-fir
600
600 Nail: CN-90 (d=0.41cm)
P
P
Load per n a i 1 ,
Load per n a i l ,
400
400
200
200
Timber: Douglas-fir
Nail: CN-90 (d=0.41cm)
2 4 6 8 10 0 2 4 6 8
Slip deflection, S (mm) Slip deflection, S (mm)
///////AMM///
Load cell
lOOOkgf
or 2000kgf
Nai I Nai I
\
Mr
Del I e c t I on
measurIng
device Output
Output^ 1= Output
I
Steel plate
Timber C l e a r ance
0. 20. 3mm
FIG. 1. Examples of the load (P)-slip (S) relationship for nailed timber joints
with steel side plates.
112 KOHEI KOMATSU
higher than the yield strength, so that the European yield theory
can also be used for estimating ultimate strength P . u
Bolts
According to the experiments by Kanaya et al. [11], the behavior of a
single-bolted timber joint is similar to that of a drift-pin joint up to yield
strength P as shown in Fig. 3. After exceeding the yield point, however,
y
the bolted joint can deform much more and is stronger than the drift-pin
joint, because the presence of washers can generate additional resistance
to deformation as the bending deformation of the bolt shank increases.
By this effect, a moment-resisting joint composed of bolts with steel side
plates is much more ductile and stronger than a drift-pin joint [12].
Generally speaking, however, bolts are not used widely for moment-
resisting joints, because the presence of bolt heads makes the appearance
and fire resistance worse.
G L U L A M PORTAL FRAME
Nonlinear analysis
The deformation of a glulam portal frame strongly depends on the
characteristics of the fastener used in the moment-resisting joints. To
analyze this effect precisely, a non-linear finite element method (FEM)
was developed by Komatsu [13]. As the first step in the analysis, the
load (P)-slip (S) relationship of individual fastener was theoretically
determined by extending the concept of a beam on an elastic foundation
into a non-linear problem in accordance with the previous study by
Tsujino and Hirai [14]. Then, the stiffness matrices of the joint element
were ostensively derived by estimating the total strain energy of the
joint element as the summation of the strain energy from individual
p
Steel plate
ate 1(9BB)
I (91) II G lu lam
rji 3 0 0 0
e
e : Ehd distanoe : Edge distance
Deflection measuring
device
Slip (mm)
v 0 40 70 100
Edge distance ( mm )
MECHANICAL TIMBER JOINTS APPLIED TO GLULAM PORTAL FRAMES
Fig. 2. Dependence of the load (P)-slip (5) characteristics of drift-pin joints on the edge distance and the end distance when
loaded perpendicular to the grain. Main members, sugi (Japanese cedar) glulam of 150 mm width (/); gusset plates: 9 mm
SS41 insert-type steel plate; drift-pin, 16 mm diameter (d) SS41 steel pin.
113
114
6000
5000
4000
(kgf)
3000
2000
Load, P
Drift-pip
1000
KOHEI KOMATSU
0' . . . .
0 5 10 15 20 25
sup , s ( mm)
FIG. 3. Comparison of load (P)-slip (S) characteristics between drift-pin and bolted joints with the same joint geometry.
Main members, sugi (Japanese cedar) glulam of 150 mm width (/); gusset plate, 9 mm thick SS41 insert-type steel plate;
drift-pin, 16mm diameter (d) SS41 steel pin. Each plot corresponds to the individual test results.
MECHANICAL TIMBER JOINTS APPLIED TO GLULAM PORTAL FRAMES 115
fasteners in the joint region. Once the stiffness matrices of the joint
element have been determined, any two-dimensional glulam frame
structure involving various moment-resisting joints can be solved
nearly up to the ultimate stage by employing an FEM program in-
corporating the Newton-Raphson method as a non-linear solu-
tion.
CONCLUSION
o
, o
0
KOHEI KOMATSU
FIG. 4. Schematic diagram of the two-story glulam portal frame specimen and loading system. Glulam members; Ezo-Todo
(Picea-Abies) 150 mm x 600 mm.
MECHANICAL TIMBER JOINTS APPLIED TO GLULAM PORTAL FRAMES 117
c 25000
~ 20000
] 15000
10000
5000
-200-150-100-50
50 100 150 200250300350400450500
-5000 Displacement, S (u)
10000
25000
20000 b) Drift-pinned
| 15000
10000
5000
-200-150-100-50
50 100 150 200250300350400450500
Displacement, 8 ()
25000]
(kgf)
20000
Load. P
150001 c) Bolted
10000
50001
-200-150-100-50
50 100 150 200 250 300 350 400 450 500
Displacement, 8 (MM)
Observed
Computed
REFERENCES
[1] G.B. Walford, Timber Use Manual, Section B2, NZTIF (undated).
[2] K. Komatsu, Mokuzai Gakkaishi (J. Japan Wood Res. Soc), 36(12), 1035-
1041 (1990).
[3] K. Komatsu, Mokuzai Gakkaishi, 36(12), 1042-1049 (1990).
[4] Architectural Institute of Japan: Standard for Structural Calculation of
Timber Structures, 155, Gihoudou (1988).
[5] S. Hata, K. Mori and M. Satou, Summaries of Technical Papers at the
Annual Meeting, Architectural Institute of Japan, 1253-1254 (1986).
[6] M. Maeda, Journal of The Hokkaido Forest Products Research Institute,
4(2), 11-18 (1990).
[7] N. Kawamoto and N. Kanaya, Summaries of Technical Papers at the
Annual Meeting, Architectural Institute of Japan, 99-100 (1988).
[8] N. Kawamoto, N. Kanaya and K. Komatsu, Summaries of Technical
Papers at the Annual Meeting, Architectural Institute of Japan, 101-102
(1989).
[9] N. Kawamoto, K. Komatsu and N. Kanaya, Summaries of Technical
Papers at the Annual Meeting, Architectural Institute of Japan, 117-118
(1990).
[10] H.J. Larsen, Proceedings of the IUFRO-5 Conference, Pretoria, 646-654
(1973).
[11] N. Kanaya, N. Kawamoto and K. Komatsu, Summaries of Technical
Papers at the Annual Meeting, Architectural Institute of Japan, 103-104
(1989).
[12] K. Komatsu, F. Kamiya and Y. Hirashima, Proceedings of The 31st Japan
Congress on Materials Research, 185-191 (1988).
[13] K. Komatsu, Mokuzai Gakkaishi, 34(7), 581-589 (1988).
[14] T. Tsujino and T. Hirai, Mokuzai Gakkaishi, 29(12), 833-838 (1983).
Wood as a Livable Interior Material
MASAHARU SUZUKI
ABSTRACT
It is desirable for new dwelling houses to use renewable plant materials, wood having
many advantages in this respect. It was proved from measurements of the heat flow from
human fingers and by rubbing the finger tips that some wood surfaces were warm and
smooth to the touch in comparison with other materials. The abrasive wear properties of
wood and other interior materials were also assessed, the surface of wood-plastic compos-
ites showing a high level of abrasion resistance.
The hygroscopic behavior of wood and its related materials was determined, and it is
suggested that controlling indoor air humidity is influenced by the water vapor affinity of the
surrounding wall materials. The moisture permeability of face-finished materials and hollow
core panels was obtained, and diagrams to predict moisture condensation were constructed.
The sound transmission loss of wood-based materials was also measured and compared
with the calculated value by using London's modified formula.
INTRODUCTION
119
120 MASAHARU SUZUKI
X10 6
r
3
( /m K)
3
J
2 B
Specific heat
x dens i ty
2
1 2 3 4 x10
Thermal t r a n s m i s s i o n ( / s i . 2 x 10 m )
J 4 2
FIG. 1. Relationship between the thermal transmission from the forefinger and
the heat capacity (specific heat x density) of the material touched. 1, wool; 2, soft
vinyl leather; 3, clothes; 4, foamed polystyrene; 5, insulation board; 6, tatami mat;
7, Chamaecyparis obtusa Endl.; 8, painted wood; 9, plaster board; 10, particle-
board; 11, polyester resin-overlaid plywood; 12, hardboard; 13, phenolic resin; 14,
glass; 15, ceramics; 16, Portland cement; 17, aluminium (1-2 x 1 0 " m ): Contact
4 2
Frictional coefficient
" 0.4 J 2
o 1 0
13 14
15
17
16
2 0.3
2 -1 1 2
Slightly Smooth
rough
FIG. 2. Relationship between the sensory value of the smoothness of a ma-
terial surface and the frictional coefficient in a sliding human skin model. The
sensory value indicates the ease of smooth sliding. 1. Urea resin sheet; 2, paper
for a name card; 3, glass; 4, Paulownia tomentosa Steud.; 5, Fagus crenata Blume;
6, amino alkyd-resin-painted teak; 7, stainless steel; 8, ceramics; 9, melamine-
resin-overlaid sheet; 10, colored amino alkyd-resin-painted plywood; 11, poly-
vinyl chloride sheet; 12, Cercidiphyllum japonicum Sieb.; 13, Betula maximowic-
ziana Regel; 14, Zelkowa serrata Makino; 15, Chamaecyparis obtusa Endl.; 16,
Acer mono Maxim.; 17, Quercus mongolica Fisch. var.
(1)
Frictional coefficient
0.7 o o
o o n o
o o
o o
o o
0.5 o
I I I I I I I 1 I I I I I I I I I 1 I I I 1 I I
A 6 8 10 12 14 16 18 20 22 24 26
kEa r l y wood *Late
wood^
Sample number
FIG. 3. Frictional coefficient by sliding a paraffin wax replica of the skin of the
forefinger on the surface of wood. This is plotted along the annual ring growth of
Cryptomeria japonica D. Don for a vertical load of 1*55 g.
(2)
TABLE 1
Abrasive-wear property of interior materials by the Taber abrader expressed as
the loss in thickness per 100 cycles under load P = 500g
c x1 0 '
6
g\ 10 i
3
Abrasion resistance u (kg
A* 5
8 2A
4
A
6h
A
8ooo 1
A A
D Q
O D m
D
A A a *
q
2hD fiO D
A
AA
^A D6 ^ A
0 0.4 0.8
Annual ring
on proportion ofgrowth process
(3)
where P is the internal pressure induced by contact with the abrasive, <5 is
the frictional force (shear force) and L is the length of friction area.
Abrasion resistance, U, is defined as the amount of the work needed to
remove a unit volume of wood.
In an experiment, a small strip of a specimen would around an
attachment was slid on abrasive paper (no. 180) with 80 jam grit size and
104 degree edge angle.
Figure 4 shows the abrasion resistance of various wood samples
according to annual ring growth. The abrasion resistance of late wood
was higher than that of early wood.
TABLE 2
Hygroscopic property of interior material. Moisture content under 75% relative
humidity at 20 C
Material MC(%) Material MC(%)
Chamaecyparis obtusa Endl. 11 Paper (LBKP) 9
Hydrogen chloride treated 7 Nitrocellulose film 2
Formaldehyde treated 5 Polyurethane resin film 1-2
Acetylated 5 Porous calcium silicate 5
(acetyl content: 16%)
Fagus crenata Blume 13 Polyvinyl chloride film 0-2
170 C heat treated 55 Polyvinyl chloride powder 0-7
126 MASAHARU SUZUKI
(4)
63%, and that by Portland cement is 48%. The absolute value of HCE
can be used and the values for some interior materials are tabulated in
Table 3 [9]. If walling is made from several kinds of finished materials
and their area percentages are a a , a ,..., then
l 5 2 3
HCE = c a +c a
l l 2 2 + c a -\
3 3 (5)
TABLE 3
Humidity control efficiency in a space of 176 cm 3
seems optimum for a dwelling that HCE should be about 55% for a
comfortable range of indoor humidity.
The capacity for absorbing or giving out moisture has been inves-
tigated from two points of view. One is the hygrothermic capacity that is
related to the relative humidity change which follows a temperature
WOOD AS A LIVABLE INTERIOR MATERIAL 127
TABLE 4
|B| value in a house lined with various internal wall materials and relative
humidity increment Ah in a test chamber lined with these same materials (Maki et
al. [10]). Ah was measured by injecting water vapor into the test chamber in a
vacuum at 20 C. The water vapor was injected for 15 min, and Ah was measured
after 60 min.
20r
Moisture content (%)
16 L
8
I
e
12
that in the core, the moisture transmitted through the surface increases
the relative humidity in the inner core. The amount of moisture transmit-
ted may depend on the moisture resistance of the intervening materials
and the difference in water vapor pressure on both sides.
From the increment of relative humidity dh in time dt, the moisture
transmission coefficient, J , is given by the following equation:
t
(6)
where h (t) is the relative humidity at time t in a hollow core (air space),
c
hollow core, a is the amount of water vapor per unit volume for 100%
relative humidity, and p is the saturated water vapor pressure. Figure 6
s
x1
20
2
9
10
10 20 30
T i m e ( h r)
resistance meter was attached to the board, the meter indicating the
changing resistance with increasing moisture content.
Figure 8 shows time plots of log p (electrical resistance) u (moisture
content) and h (relative humidity). When the B-chamber was cooled (see
'cool' in [A]), there was a marked increase in u and finally surface x
moisture condensation.
In order to predict the internal moisture condensation, the following
equations can be derived:
(7)
130 MASAHARU SUZUKI
S7 6 5 4 3 2 S1
O O D O 0 fc> O
U
A -h
P P
B A FIG. 7. Cross-section of a plywood
PI Ar PI Bn
sheathing panel. S, lateral position; T,
temperature; p, water vapor pressure;
h, relative humidity; w, moisture con-
tent; p, electrical resistances; Ar, air
H6h-60-H6h- n
space; PI, plywood; Bn, boundary
layer.
(8)
and R (x) are the resistance of thermal conduction and that of mois-
m
ture permeance up to the x point, and R and R are the total resist-
t m
point of the panel section and compare them with P . If P >P this x X S9
ably well onto a straight line, that at S (the lower portion of the inside
5
surface of the panel) was a little lower than predicted. Heat convec-
tion in the hollow core may have influenced the temperature distribu-
tion. In the case of a multilayer wall with an insulation layer and
underlayer, the temperature distribution could be well predicted by
using Eqn. 7.
WOOD AS A LIVABLE INTERIOR MATERIAL 131
[A]
0 ^ 2 0
- C 6 0
0 ^ 2 0
^ 10
^ 7 0
^ 60
o^ 2C
^110
1
2
60
- 1
4< - cool t
i i i i
8 1 6
xl(
0
Time (min)
FIG. 8. Time plots of p, u and h in the panel shown in Fig. 7. The initial states of
T and h were 25 C and 65%, respectively. Following the change of temperature,
T was reduced to 0C. Dashed lines show the moisture content at the internal
7
LIMITING S O U N D TRANSMISSION
(kPa)
o
ii 11
BnPI Ar PIBr? BnPI
i i
Ar
1i
PI Bn
Thermal resistance
(ratio)
FIG. 9. Prediction diagram for moisture condensation. Refer to Fig. 7 for the
definition of each symbol.
correlation coefficient.
WOOD AS A LIVABLE INTERIOR MATERIAL 133
3f (A)
(B)
0.8
o <& o
0.4 8 ^
1 2 3 4 0 2 ~4
Thickness (cm)
FIG. 10. Relationship between the thickness and R/M ratio for plywood (A) and
particleboard (B). R is the resistive term, and M is the area density.
(9)
coM
where co is the angular frequency, M is the area density, p' is the density
of air, and C is the velocity of sound in air.
It has been found from the vibration properties of a flat plate that the
resistive term had a close relationship with the two dimensional loss
moduli and its vibration amplitude [14].
The sound transmission loss of a double-panel wall is influenced by
the thickness of the wall and the material used for the facing board. A
double-panel wall incorporating a hollow core resonates in the low
frequency range and transmits sound. When the hollow core is filled
with a glass wool mat, the sound transmission loss is increased by
2-3 dB.
Another problem is foot-step noise generated on the second floor being
transmitted to the first floor. There has been some research on the
sound-proofing of wooden structures to achieve lower sound transmit-
tance [15]. Experiments have also been conducted on a floating floor and
on the application of sound-insulating material to reduce floor-impact
noise [16].
134 MASAHARU SUZUKI
CONCLUSION
Wood material has the advantages of high specific strength and good
workability compared with other building materials. In particular, a
wood surface is characterized by warmth to the touch and by some
degree of smoothness. This was clearly proved by measurements on heat
flow and rubbing with a finger tip. The abrasion properties of wood and
other interior materials were measured, and their performance in use was
estimated. The effect of the inhomogeneity in wood tissue on the abrasion
property was shown to be due to its major structural factors.
It is apparent that wood, a hygroscopic material, has a high level of
humidity control efficiency which is important for a dwelling-house. The
transmitted moisture through the face material of a double-panel wall
increased the relative humidity in the intervening air space. These
experimental data confirmed the prediction of water vapour pressure and
the formation of moisture condensation outside or inside the wall.
The sound transmission loss of wood-based materials could be cal-
culated precisely by using London's modified formula. The resistive term
has a close relationship to the two dimensional loss moduli and vibration
amplitude of each wood-based material.
REFERENCES
and
JOSEPH GRIL
ABSTRACT
Chemically treated woods are classified by using a model of the structural change in the
cell wall and the lumen of a cell resulting from the treatment. The dimensional stabilization
of wood by chemical treatment is discussed, based on a generalized concept of the
dimensional stability that allows for the deformation due to the simultaneous action of
moisture changes and external forces applied to the material. Typical cases of chemical
treatment are used to outline the relationship between the structural changes involved and
the resulting properties.
INTRODUCTION
135
136 MISATO NORIMOTO AND JOSEPH GRIL
P:::3
ttt
1 2 3
B 4 5 6
H
d
rrl rr
FIG. 1. Model for the chemical treatment of wood. A, Cellular level: 1-3,
untreated cell wall; 4-6, treated cell wall; 1, untreated; 4, no chemical deposits in
lumen, 2 and 5, deposits on cell wall surface; 3 and 6, filling of lumen. B,
Modification of ligno-cellulosic material at the molecular level. O , hydroxyl
group available for hydrogen bonding; , substitution of hydroxyl group;
# , bulking agent.
138 MISATO NORIMOTO AND JOSEPH GRIL
than in the dry state. Second, the sorption process itself (either adsorption
or desorption) contributes further to the viscosity of the matrix, because
the arrival of water molecules at a sorption site, or their departure from
it, causes a rearrangement of the surrounding molecules, and during the
time needed for that rearrangement (longer than the time needed for
sorption because it involves the movement of longer molecular segments),
they can shift more easily to the more stable configurations implied by
the forces acting on them. This transient effect of sorption explains the
hygromechanical coupling in wood (the 'mechanosorptive effect'), or a
sorption-induced viscosity that cannot be predicted by the direct effect of
moisture or viscosity. The amount of viscosity (compared to elasticity) in
the mechanical response of wood to external forces depends on the level
of the local stresses supported by the matrix at the molecular level. In the
case of longitudinal loading, for example, the proportion of matrix
involvement in the deformation process is determined by the average
inclination of the microfibrillar framework relative to the fiber axis in the
axial-circumferential plane. The greater this inclination, the more the
matrix is involved, and the more the material is subjected to time-
dependent phenomena such as hygrothermal softening, hygromechanical
coupling and mechanical damping. The molecular model of B-l in Fig. 1
does not contain this information. However, it is implicit by the stress-
induced strain being shown as a shear deformation in direction e, which
thus stands for the direction of local stresses supported by the matrix.
The direction of the 'chains' may not be, strictly speaking, that of the
microfibrillar framework. Moreover, the water-reactive zones of the
matrix responsible for the activation of viscosity c acting on e may not be
exactly the same as those involved in moisture-induced expansion c
acting on d. These aspects do not detract from the validity of the
model as a synthetic representation of an extremely complex actual
system.
lumen (A-3). In A-4, -5 and -6, the cell wall is modified. Again three cases
are distinguished: no deposit in the lumen (A-4), deposit on the internal
face of the lumen (A-5) and partial or total filling of the lumen (A-6).
Figure IB analyzes several cases of cell wall modification according to
the molecular model just detailed. The hydroxyl group represented by
the open circles is available for hydrogen bonding with water; the small
closed circles indicate that the hydroxyl group has been substituted with
chemical bonding and is not available any more. The large closed circles
indicate the bulking effect caused by the introduction of large molecules
between the constituents, which replace water molecules. Weak connec-
tions such as hydrogen bonding are represented by two hydroxyl
groups (open circles) facing each other; strong molecular bonding is
shown by a line. The crosslinking effect is thus pictured by an unbroken
sequence of lines and closed circles, either small or large, linking the two
chains. The initial model (B-l) can be modified according to the eight
patterns (2 to 9) of Fig. IB. In patterns 2 and 3, crosslinking occurs
without the bulking effect by using molecules of low molecular weight
that link the two reaction sites with hydroxyl groups. In 2, the reaction
is done in a dry state with a short linkage, preventing both lateral
expansion d and molecular movement e. In 3, the reaction is done in a
swollen state, so that after drying, the structure develops considerable
looseness. Both a crosslinking and a bulking effect occur in patterns 4
and 5. In 4, the reactant is hydrophobic, and in 5 it is hydrophilic
(as shown by the small open circles attached to the big closed circle).
In the remaining four patterns there is a bulking effect but no crosslink-
ing. In 6 and 7, the reactant establishes a stable bond on one side.
Again, it is hydrophobic in 6 and hydrophilic in 7; in pattern 7, the
reactant suppresses hydrogen bonding on one side but simultaneously
creates a new sorption site at the other. In the last two patterns, no
stable bond is established between the reactant and the constituents. In
pattern 8, the bulking agent is extremely hydrophilic and establishes
extensive hydrogen bondings with the constituents, and in pattern 9, it
is hydrophobic and does not interact with the constituents nor with
water.
Any type of chemical modification can be characterized by a combina-
tion of the two criteria A and B of Fig. 1. Several combinations of these
criteria may occur at the same time. In some cases, it is not possible to
determine which combinations are involved in the treatment because of a
lack of knowledge on the mechanism for action that underlies the
treatment.
STRUCTURE AND PROPERTIES OF CHEMICALLY TREATED WOODS 141
CHARACTERIZATION O F W O O D STABILITY
experimental conditions.
where V is the dry volume (low humidity) and V is the wet volume (high
x h
criteria: (1) the mechanosorptive effect, (2) the acoustic properties, and (3)
the static mechanical properties.
Mechanosorptive Creep
Dimensional stability with respect to such stress-induced deformation
as creep or vibrational damping requires a reduction of matrix viscosity
due to moisture sorption. Crosslinking of type B-2, -4 and -5 may
efficiently prevent viscous deformation in the matrix. Bulking along,
however, does not necessarily provide this effect. Only 'hydrophobic
bulking' types B-5 and -9 have a good chance of reducing hygroscopicity.
'Hygrophilic bulking' in types B-7 and -8, however, favors matrix hygro-
scopicity and may thus enhance the plasticizing action of water on the
matrix, resulting in instability.
Mechanosorptive creep was measured in three-point bending tests at
30 C under humidity cycling between 29 and 86% RH. The initial load
was adjusted to obtain a stress level of 10 MPa in the dry state. The creep
test lasted two days for each specimen, which was loaded first at 29%
RH, kept for lOmin., moved to 86% RH for 24 h, and then returned to
29% RH for the remaining 24 h. Specimens of sitka spruce (Picea
sitchensis; 100 mm [ L ] x 15 mm [R] x 2 mm [T]) were modified by vari-
ous treatments and tested according to this procedure.
To characterize the ability of a treatment to reduce mechanosorptive
creep, an 'anti-creep efficiency' (ACE) factor is defined by an expression
similar in format to that for ASE:
where w is the width of the specimen and t is its thickness (in the dry
state), / is the span (80 mm), F is the applied load, / is the deflection after
x
potential for stress-induced strain along the grain under changing humid-
ity conditions. It is the formal equivalent of swelling ratio S, which
STRUCTURE AND PROPERTIES OF CHEMICALLY TREATED WOODS 143
100
Acoustic Properties
Another way to evaluate wood viscoelasticity is to measure the
specific Young's modulus (E/y) and internal friction (tan <5). E/y is related
to the sound velocity, and tan 5 to sound absorption, and both are thus
important parameters of acoustic properties. Pattern A-4 + B-2 should
be effective for increasing E/y, because the small molecular bridges made
while chains a were closed to each other improve the molecular cohe-
sion with a very small weight increase. In all other types (except for
A-4 + B-3), a decrease of E/y would be expected, because bulking either
reduces the molecular cohesion, or improves it, not enough to compen-
sate for the increase in density. The dependency of tan d on the type of
treatment, however, should be close to that of mechanosorptive creep (a
decrease with B-2, -4, -5, -6 and -9 and an increase with B-7 and -8)
because both measurements are related to viscous movement in the
matrix.
144 MISATO NORIMOTO AND JOSEPH GRIL
6_
PEG 3
o-
-150
^ -100
PEGAO^T
WPC2O g 1
-50
< -F 5
PO3-O
B03-O . FIG. 3. Relationship between the
wiC2-W>
- 5 0 ^ >0
A 3
50 increase of specific Young's modulus
(A(/y) ) and increase of internal fric-
P T A(^) C/.) T
3
6 t
tion (Atandj) after chemical treat-
-50 ment. Refer to Fig. 2 for definition of
symbols.
STRUCTURE AND PROPERTIES OF CHEMICALLY TREATED WOODS 145
-1.7
-1-8
o -1-9
c
o
"o -2.0
cn
o
-2.1
-2.2
dotted line is the regression line for untreated wood. Refer to Fig. 2 for definitions
of the other symbols.
strength. With a combination A-4 + B-4, -5, -6 and -9, this may or may
not be the case, depending on the amount of degradation provoked by
the treatment.
The following factors serve to evaluate the improvement of elastic
modulus E and strength a resulting from the treatment:
plane the values obtained from static bending tests in the longitudinal
direction on sitka spruce [2] at 20 C and at either 65% RH (solid circles) or
30% RH (open circles). In practice, it is important to know by how much
the rigidity or strength are reduced in high humidity conditions.
The following factors have been used to evaluate the change in
sensitivity to humidity conditions resulting from the treatment:
9
-50 i 2
i
v S"
-so jsfca
AETCM
V POi
WIC1
P -50
PEGt
FIG. 5. Relationship between the increase of MOR (Aa ) and increase of MOE
T
where SE and da
RH are the relative increase of E and cr, respectively,
RH
between the low humidity condition (30% RH) and high humidity
condition (98% RH), and 5E and <5<x are the corresponding values
RHxi RHu
where 1 and h refer to the low and high humidity conditions, respective-
ly. Figure 6 shows in the RH A-A<7
H plane the results obtained from
R
longitudinal bending of sitka spruce. We have called A the modulus R H
stability.
0-F4
-60 6
-AO Q
D A 2
<
-20
1 0 , | ,
-80 -60 -AO 1
Q 20 40 60
-20
Q
PO2 B02
6
Heat Treatment
Heating wood in a confined atmosphere induces the formation of
cohesive structures between the cell wall components, but at the same
time causes chemical changes as well as degradation. Wood treated with
heat belongs to type A-4 + B-2 of Fig. 1. Degradation of water-reactive
polysaccharides accompanies an increase of dimensional stability, so that
high levels of stability are obtained at the expense of strength properties,
hardness and abrasion resistance are reduced, permeability to water
vapor is reduced, liquid water repellency is increased, wood color
becomes darker, but density is almost unchanged [5]. However, if the
effect of degradation remains small and the formation of cohesive
structures dominates, the strength and specific elastic modulus will
increase, and the internal friction decrease [6]. Figure 5 shows two
examples of heat treatment yielding a reduction in the strength proper-
ties, H (3 hours at 180C and atmospheric pressure, weight percent gain
x
shows that ASE and ACE increase, but only very slightly. Figure 6 shows,
in the case of H , no change in M O E stability and a slight increase in
3
MOR stability.
Formalization
Formalization is a reaction involving the formation of oxymethylene
bridges between the hydroxyl groups of the constituents by formalde-
hyde. Reaction in the vapor phase yields pattern A-4 + B-2, and in the
liquid phase, pattern A-4 + B-3. In Fig. 2, F (vapor phase, HC1 as a
2
increased while E/y has decreased. In Fig. 4, the vapor phase data ( F , 6
F ) lie under the standard line, and those for the liquid phase ( F ) above.
7 5
Esterification
Esterification examples can be mentioned of acetylated wood,
phthalyated wood, wood oligoesterified with maleic anhydride, or
phthalic anhydride, and epichlorohydrin, wood esterified with maleic acid
and glycerol, wood treated with isocyanates, and wood esterified with
alkylketendimer. Among them, acetylation has been most thoroughly
studied [10]. Acetylation of wood is performed with acetic anhydride in
the liquid or vapor phase, and sometimes with ketene gas. Acetylation
leads to the formation of an A-4 + B-6 type of structure, hydrophilic
hydroxyl groups being substituted with hydrophobic and bulky acetyl
groups. Consequently, hygroscopicity decreases and water repellency
increases, density increases depending on the W P G value, a slight color
change occurs and stability to sunlight is improved. ASE increases with
increasing W P G up to 20%, but becomes sluggish for higher WPG; ASE
can reach 65-75%. The creep during humidity changes is much reduced
by acetylation; both ASE and ACE are improved as shown by A x
Etherification
Etherification of wood has been performed with epoxides, alkyl halide
or acrylonitrile. The addition of epoxides provides wood with the
structure of type A-4 + B-7. Under high humidity conditions, the treated
material becomes more hygroscopic than untreated wood, and permea-
bility to water vapor is somewhat increased. Propylene oxide ( P O , x
was previously explained, the B-7 pattern may provide wood with high
ASE but, at the same time, it reduces ACE considerably, thus contrasting
STRUCTURE AND PROPERTIES OF CHEMICALLY TREATED WOODS 151
with acetylation which belongs to the B-6 type. Figure 3 shows for both
P 0 (WPG = 21-9%) and B 0 (WPG = 18-7%) some decrease in E/y and
3 3
a large increase in tan <5, so that, in Fig. 4, both lie above the standard
line. Figure 5 shows for P O , P 0 (WPG = 25-28%), BO and B 0
t 2 i 2
MOE and MOR, and especially for the higher WPG. Figure 6 shows that
both M O E and MOR stability are increased. Compressive strength is
improved in the fiber direction as well as transversely to the fiber.
Regarding the tensile properties, the longitudinal elastic modulus in-
creases, but the longitudinal strength decreases while the transverse
152 MISATO NORIMOTO AND JOSEPH GRIL
[16]. This treatment yields the pattern A-5 + B-8, and provides a material
with fireproof qualities that can be used for fire prevention. It increases
the density but causes almost no color change. The penetration of salts
( B a P 0 and B a H P 0 ) into the cells may result in some ASE increase,
4 4
but ACE should be reduced. Figure 2 shows for WIC (WPG = 42-5%)
X
E/y and an increase of tan S. Protection from decay and fungal attack are
improved.
(MMA) yields an increase of 50% for M O E and 60% for MOR. Tensile
strength, compressive strength, bending strength, impact bending
strength and hardness all are increased by 100-200% [ 5 ] . Pattern A-5
and -6 may improve ASE, but not pattern A-2 and -3, as shown by
W P C ! in Fig. 2, where both the ASE and ACE factors are close to 0%.
MMA induces a large increase in elastic modulus but, at the same time,
a higher relative increase of density, so that for W P C (WPG =121%)
2
in Fig. 3, the net result is a decrease of E/y. The large increase in tan d
STRUCTURE AND PROPERTIES OF CHEMICALLY TREATED WOODS 153
the regression line and on the left side. In addition to its effect on
mechanical properties, WPC improves the surface quality. It is widely
used in architectural features, furniture, sporting goods, crafted objects,
etc.
Wood impregnated with expoxy resins is another case of pattern A-2
and -3 + B-l [5]. Epoxy resin that is partially polymerized is intro-
duced into the cell lumens and cured afterwards. There is almost no
ASE as there is no penetration into the cell wall. Permeability to water
vapor is much reduced and water repellency is increased. Strength,
hardness and abrasion resistance increase drastically. It is used for
wooden boat hulls or the outer ply of plywood, and also for strengthen-
ing decayed wood.
REFERENCES
ABSTRACT
W o o d has been found to be convertible to a thermally flowable material by chemical
modifications, in which thermoplastic properties can be conferred by internal plasticization.
In some cases, the thermoplastic properties must be supplemented by externally blending
the modified wood with plasticizers. Chemically modified wood and untreated wood have
both been found to dissolve or liquefy in various solvents and solutions. The applications
of liquefied wood solutions and plasticized wood are described for preparing films, sheets
and other moldings from the chemically modified wood, for three-dimensionally cured
plastic-like wooden boards, for deep-drawable hard boards, and for hot-melt adhesives.
Also described is the surface-layer plasticization of wood for surface-densification and
embossing, and the preparation of wood-based reactive adhesives.
INTRODUCTION
The methods for processing wood are very limited. While metals,
plastics and glass can be processed in the liquid phase at high tempera-
tures, natural wood cannot. This difference is due to the lack of plasticity
of wood, so that it cannot be melted, dissolved or softened sufficiently for
molding. Consequently, the scope for utilizing wood is restricted, which
sometimes makes wood less valuable as a material. If plastic properties
could be imparted to wood, it would become a more useful material.
This need, and the desirability of using wood waste and renewable
forest product resources better have resulted in extensive new studies on
155
156 NOBUO SHIRAISHI
THERMOPLASTICIZATION OF W O O D
FIG. 1. Lauroylated wood meal (a), a film prepared from the lauroylated wood
meal by compression molding (b), a piece of acetyl-propionylated wood (c), and
compression moldings from acetyl-propionylated wood (d and e).
APPLICATION OF THERMOPLASTICIZED W O O D
C O M M E N T S O N THE LIQUEFACTION O F W O O D
LIQUEFACTION O F CHEMICALLY M O D I F I E D W O O D
There are many potential applications for the liquefaction and dissol-
ution of chemically modified wood. Examples include the fractionation of
modified wood components [31, 32], the preparation of solvent-sensitive
and/or reaction-sensitive wood-based adhesives [1, 3, 27, 30, 33], the
preparation of resinified wood-based moldings such as the foam type [27],
and the preparation of wood-based fibers and their conversion to carbon
fibers [34].
To fractionate modified wood components, the dissolution-precipita-
tion technique has been successfully used [31, 32].
In the preparation of adhesives from chemically modified wood, phenols,
bisphenols and polyhydric alcohols have been used as solvents, and the
resins contained a significant amount of modified wood [1, 3, 27, 30, 33].
The combined use of these reactive solvents with reactive agents, e.g., a
cross-linking agent and/or hardener, has given rise to phenol-formalde-
hyde resins (such as resol resin), polyurethane resins, epoxy resins, etc., all
of which contained a significant amount of chemically modified wood
and possessed outstanding gluability [1, 3, 30, 33].
Molded materials such as foams or pressed shapes can also be obtained
from chemically modified wood solutions. Foams, for example, can be
prepared by adding an adequate amount of water as a foaming agent and a
polyisocyanate compound as a hardener to a 1,6-hexanediol solution of
allylated wood, which is then mixed well and heated. When heated at
100 C, foaming and resinification are initiated within two minutes and
completed within several minutes. If promotors such as triethylamine are
added, rapid reactions occur even at room temperature, and foams can be
obtained within several minutes. The foam has a low apparent density of
0 0 4 g / c m , substantial strength, and significant restoring force to compres-
3
LIQUEFACTION O F U N T R E A T E D W O O D
to liquefy in several organic solvents [2, 36]. For example, after treating
at around 250 C for 15-180 min, wood chips and wood meal were
liquefied in phenols, bisphenols, alcohols (benzyl alcohol), polyhydric
alcohols (1,6-hexanediol and 1,4-butanediol), oxyethers (methyl cello-
solve, ethyl cellosolve, diethylene glycol, triethylene glycol, and poly-
ethylene glycol), 1,4-dioxane, cyclohexanone, diethyl ketone, and ethyl
n-propyl ketone.
The liquefaction of untreated wood can also be achieved at a lower
temperature of 150C and at atmospheric pressure in the presence of an
acid catalyst, phenolsulfonic acid and sulfuric acid having been used [37].
It is possible to obtain paste-like solutions with a high concentration of
wood solute of up to 70% (Fig. 5). After liquefaction, the wood compo-
nents were found to have been degraded and became reactive. The
obtained wooden solute can be used to prepare adhesives and other
moldings, opening a practical new field for utilizing wood materials.
tained from the adhesives after glueing wood veneers at 120-130 C with
a hot-pressing time of 0-5 min to 1 mm thick plywood. This adhesion
temperature of 120 C is at least 15 C lower than that ordinarily used
for resol resin adhesives.
As a second example, foams can be prepared from untreated w o o d -
polyethylene glycol solutions [5]. Both soft and hard types of foams can be
produced according to the preparation conditions. The prepared foams
had a density of around 0 0 4 g/cm , substantial strength, and strong restor-
3
ing force against deformation. These results imply that the wood compo-
nents were not merely blended within the foam bubbles, but also played an
important role in maintaining the dimensional stability of the foams.
The third application example is Novolak-resin type of moldings
prepared from untreated wood-phenol solutions [38]. After one part of
wood meal had been liquefied in two parts of phenol, the unreacted phenols
were distilled under reduced pressure. The resulting liquefied and reacted
wood-phenol powder can be cured directly after wood meal filler and
hexamethylene tetramine have been added and hot-pressed at 170-200 C.
The flexural strength of the moldings was comparable to those made from
commercial Novolak, and an example is shown in Fig. 6.
REFERENCES
[1] N. Shiraishi, Mokuzai Gakkaishi (J. Japan Wood Res. Soc), 32, 755 (1986).
[2] N. Shiraishi, Mokuzai Kogyo (J. Wood Technol. Assoc., Japan), 42, 42 (1986).
[3] N. Shiraishi, Y. Tamura and N. Tsujimoto, Mokuzai Kogyo, 42, 492 (1987;
43, 2 (1988).
[4] N. Shiraishi, Wood and Cellulose Chemistry, Marcel Dekker Inc., New York,
861 (1990).
[5] N. Shiraishi, Cellusosics Utilization; Research and Rewards in Cellulosics,
Elsevier Applied Science, London, 97 (1989).
[6] D.A.I. Goring, Pulp and Paper Mag. Can., 64, T-517 (1963).
[7] S.-Z. Chow, Wood and Fiber, 3, 166 (1972).
[8] S.H. Baldwin and D.A.I. Goring, Svensk Paperstid., 71, 641 (1968).
[9] N. Shiraishi, T. Matsunaga and T. Yokota, J. Appl. Polymer Sci., 24, 2361
(1979).
[10] N. Shiraishi, T. Aoki, M. Norimoto and M. Okumura, Graft Copolymeriz-
ation of Lignocellulosic Fibers, A. C. S. Symp. Series, 187, Amer. Chem. Soc,
Washington D.C., 321 (1982).
[11] N. Shiraishi, T. Aoki, M. Norimoto and M. Okumura, Chemtech, (June)
366, 1983.
[12] N. Shiraishi and M. Yoshioka, Sen-i Gakkaishi, 42(6), T-346 (1986).
[13] M. Morita and I. Sakata, J. Appl. Polymer Sci., 31, 831 (1986).
[14] N. Shiraishi, Chemistry of Wood Utilization, Kyoritsu Publ. Co., Tokyo, 294
(1983).
[15] N. Shiraishi, Advanced Technique and Future Approach in Wood Chemicals,
CMC Inc., Tokyo, 271 (1983).
[16] N. Shiraishi, Mokuzai Kogyo, 37, 194 (1982).
[17] N. Shiraishi, Kobunshi Kako, 31, 500 (1982).
[18] N. Shiraishi, Sen-i to Kogyo, 39, 95 (1983).
[19] N. Shiraishi and K. Goda, Mokuzai Kogyo, 39, 329 (1984).
[20] H. Matsuda and M. Ueda, Mokuzai Gakkaishi, 31, 903 (1985).
[21] H. Matsuda, Mokuzai Kogyo, 44, 637 (1989).
[22] T. Aoki, Proceedings of 11th Symposium on Chemical Processing of Wood,
Tsukuba, 7 (1981).
PLASTICIZATION OF WOOD AND ITS APPLICATION 167
[23] C. Vanasse, E. Chornet and R.P. Overend, Can. J. Chem. Eng., 6 6 , 112
(1988).
[24] H.R. Appel, I. Wender and R.D. Miller, U.S. Bureau of Mines, Technical
Progress Report 25, 1969, 5.
[25] H.R. Appel, Y.C. Fu, E.G. Illig, F.W. Steffgen and R.D. Miller, U.S. Bureau
of Mines, RI 8013, 1975, 27.
[26] N. Shiraishi, Japan Patent Publication Examined, 1988-1992 (appl. June 6,
1986).
[27] N. Shiraishi, S. Onodera, M. Ohtani and T. Masumoto, Mokuzai Gakkaishi,
31, 418 (1985).
[28] N. Shiraishi, N. Tsujimoto and S. Pu, Japan Patent Publication Unex-
amined, 1986-261358 (appl. May 14, 1985).
[29] N. Shiraishi, Japan Patent Publication Unexamined, 1982-2301; 1982-2360.
[30] N. Shiraishi and H. Kishi, J. Appl. Polymer Sci., 32, 3189 (1986).
[31] M. Morita and I. Sakata, Cellulose Chem. Technol, 2 1 , 255 (1987).
[32] R.A. Young, S. Achmadi and D. Barkalow, Preprints of CELLUCON' 84,
Cartrefle-Wrexham, Wales, 64 (1984).
[33] H. Kishi and N. Shiraishi, Mokuzai Gakkaishi, 32, 520 (1986).
[34] N. Tsujimoto, Proceedings of Nth Symposium on Chemical Processing of
Wood, Kyoto, 17 (1984).
[35] M. Morita, Y. Yamawaki, M. Shigematsu and I. Sakata, Mokuzai Gak-
kaishi, 36, 659 (1990).
[36] N. Shiraishi, N. Tsujimoto and S. Pu, Japan Patent Publication Unex-
amined, 1986-261358 (appl. May 14, 1985).
[37] Y. Tanihara, K. Kato, S. Pu, S. Saka and N. Shiraishi, Abstracts of Papers
Presented at 39th National Meeting, Japan Wood Res. Soc, Okinawa, 321
(1989).
[38] K. Kato, M. Yoshioka and N. Shiraishi, Abstracts of Papers Presented at
40th National Meeting, Japan Wood Res. Soc, Tsukuba, 26 (1990).
Wood-Phenol Resin Fiber
NAOHIKO TSUJIMOTO
ABSTRACT
Completely new fields for wood utilization have been opened by the finding that
chemically modified and non-modified wood can both be dissolved or liquefied in several
organic solvents. As an application of this phenomenon, wood-based filaments were formed
by spinning from a wood-phenol solution with hexamethylenetetramine. Successful carbon-
ization of the filaments was carried out at 900 C, and the tensile strength of the resulting
carbon fiber was 11 GPa.
INTRODUCTION
New fields for wood utilization of high added value have been
developed by the plasticization of wood through relatively simple chemi-
cal modifications such as esterification and etherification [1]. There are
two application categories for wood plasticization: the first is related to
products involving thermal fluidity such as hardboard, surface-plasticized
wood and wood-based films, and the second is related to products of
solubilization in solvents, like adhesives [1]. In addition to the dissol-
ution or liquefaction of plasticized wood, new techniques for achieving
the same with non-plasticized wood have been developed [2].
In this paper, three fiber-forming techniques involving different starting
materials and spinning methods are studied: (1) swelling or dissolving
plasticized wood in an organic solvent, before spinning and evaporating
the solvent; (2) similar to the first method, but including a solvent as one
of the fiber-forming components; (3) using a phenol resin solution of
non-modified wood to spin from.
169
170 NAOHIKO TSUJIMOTO
FILAMENTS F R O M PLASTICIZED W O O D
Experimental Procedure
The wood samples were radiata pine wood meal (48 mesh pass-60
mesh on, 170 mesh pass-300 mesh on, and 300 mesh pass) and refiner
mechanical pulp (RMP) was made from radiata pine. The chemical
composition of RMP was the same as that of the original wood, except
for the hot-water extractives. Chemical modification was carried out by
acetylating with trifluoro acetic anhydride [ 3 ] . The yield of acetylated
wood in both the meal and RMP was 145% based on weight, and its
converted substitution degree of acetylation was more than 2-5. The
acetylated wood was swollen or half-dissolved in chloroform at 25 C,
130C or 150C. These swollen or half-dissolved materials were put into
a syringe-shaped spinning device, and then spun through a nozzle of
0-5 mm or 1 0 mm in diameter. The filaments were fixed in shape by
evaporating the chloroform with heated air. These fixed filaments were
elongated in a range from 20% to 60% at 160-200 C, and the tensile
strength of the elongated filaments was measured according to the
procedure of Japan Industrial Standard (JIS) L 1069.
1001 1 1 1 1 1 1 1 r
90 h
(MPa)
80-
70 "
Tensile strength
60-
50-
40-
30-
201 i i I i I l i I
0.5 1.0 1-5
Density (g/cm ) 3
FIG. 1. Relationship between tensile strength and fiber density for differing
diameter of spinning nozzle.
48P: 48 mesh pass-60 mesh on; 170P: 170 mesh pass-300 mesh on; 300P: 300 mesh
pass.
Elongation Treatment
The relationship between the elongation rate and the tensile strength of
filaments was investigated.
As shown in Fig. 2, the filaments made from acetylated RMP swollen
in chloroform at 130C and 150C had a tensile strength increasing in
proportion to increasing elongation rate. The determining factor for
tensile strength seems to have been not only the density already de-
scribed, but also the orientation of fibrils in a filament after the elonga-
tion treatment. In comparison with an acetate fiber (the tensile strength is
around 150 MPa), a dry spun filament obtained from the half-dissolved
solution of plasticized wood had about half the tensile strength.
100 r
90 -
. 1 . , , , , 1
Tensile strength (MPa)
80
70-
60 -
50 -
40
30 >
C
20 -
10 20 30 40 50 60 70 80
Elongation (%)
FIG. 2. Relationship between the tensile strength and elongation rate for
acetylated RMP filaments.
130 C O 150 C
WOOD-PHENOL RESIN FIBER 173
W O O D - P H E N O L RESIN FIBER
Experimental Procedure
Radiata pine RMP was used as the starting material. Chemical
modification of the pulp was carried out by acetylating with trifluoro acetic
anhydride (TFAA method), and also by using perchloric acid as a catalyst
(PCA method) [3]. The dissolution (liquefaction) of the acetylated wood in
the presence of phenol was performed within a stainless steel pressure-
resisting tube at 260 C for a certain period of time without stirring.
Hexamine was added to the solution, and an initial condensation reaction
proceeded with heating until spinning became possible.
Two spinning methods were applied. With the first, a filament was
spun out or picked up from the surface of the spinning solution contained
in a crucible located in an oil bath and was wound by a machine
174 NAOHIKO TSUJIMOTO
positioned above the crucible. The second method used an extruding type
of spinning machine equipped with a monohole spinning nozzle, from
which a filament was spun under nitrogen pressure, and wound by a
machine positioned below the nozzle. The would filament was heated to
250 C at various heating rates until the curing reaction was complete.
The cured filament was then carbonized under increasing temperature up
to 900 C in a nitrogen-filled electric furnace. The cured filament strength
was measured according to JIS L 1069, and the carbon fiber strength
according to JIS R 7601.
Acetylation Yield
The yields of acetylated wood prepared by the TFAA and PCA
methods were 145*3 and 143-4%, respectively, based on the weight of the
starting material. These figures indicate a similar level of acetylation with
each method.
Solubility in Phenol
The solubility of the acetylated wood in phenol was then investigated.
The time to completely liquefy was measured for acetylated wood-phenol
solutions of different concentration, the results being shown in Table 1.
The solubility of the acetylated wood prepared by the TFAA method was
superior to that prepared by the PCA method. This solubility difference
can be explained by the different decomposition of lignin: during acetyla-
tion by the TFAA method, selective dissociation of the a-0-4 bond in
lignin by trifluoroacetic acid occurs, which promotes the solubility of
lignin; this is not the case with acetylation by the PCA method.
TABLE 1
Dissolution times by the TFAA and PCA methods
Acetylated wood content 25 35 40 50
(%)
Dissolution TFAA method 30 30 30
time (min.) 120 120 150
PCA method
WOOD-PHENOL RESIN FIBER 175
x10
VISCOSITY (Pa-s)
50
40
30
20
10
1 2 3 4 5 6 7
FIG. 3. Relationship between the viscosity of the spinning solution and the
added amount of hexamine.
The period for liquefying acetylated wood also influenced the conden-
sation rate, which is shown in Fig. 4. During the liquefaction of acetylated
wood by phenol, some of the acetic acid was eliminated, the amount of
this elimination increasing with increasing liquefaction period. This
observation and the results will be discussed in more detail in the last
section of this paper. As shown in Fig. 4, the condensation reaction was
influenced by the amount of eliminated acetic acid, a small eliminated
amount contributing to a rapid viscosity increase. In order to stabilize the
176 NAOHIKO TSUJIMOTO
10
50
VISCOSITY (Pa-s)
40
30
20
10
o i - I 1 1 1 1 1 1
0 1 2 3 4 5 6 7
LIQUEFACTION T I M E ( n r . )
FIG. 4. Relationship between the viscosity of the spinning solution and the
amount of eliminated acetic acid. No. 1: 60 wt%; No. 2: 6-4 wt%; No. 3: 151 wt%
of eliminated acetic acid.
Spinning
The most suitable liquefaction period was assessed, based on the
spinnability of the fiber and the facility to pick up a filament from the
surface of the spinning solution.
This method for fiber forming is illustrated in Fig. 5. The spinnability is
governed by the ease of elongating a filament at point A and that of
supplying the solution at point B. The characteristics required are
Curing
One of the advantages of wood-phenol resin fiber is that a heating
process is enough to completely cure the filaments.
In a previous report, it was shown that the existence of acetylated wood
in the two-component system of phenol and hexamine, which allows even
chemical bonding to develop, made it possible to cure a filament while
maintaining its shape. On the other hand, a filament spun from a solution
composed only of phenol and hexamine could not maintain its shape
when exposed to an elevated temperature. It was shown that a filament
containing a larger quantity of acetylated wood exhibited greater ability
to maintain its shape during the curing process. Both atmospheres of air
and nitrogen had the same effect on the cured strength of a filament, and
a synergistic effect between acetylated wood and phenol on the filament
strength was also found [ 4 ] .
The reaction mechanism between phenol and hexamine has been
reported [ 5 ] , benzylamine derivatives being formed through amino-
methylation of hexamine, before dimethyleneamine bonds and methylene
bonds are formed with the elimination of ammonia.
In order to clarify that a chemical reaction occurs between wood
substances and hexamine, the interaction between acetylated wood and
hexamine was thermally analyzed. Figure 6 shows the results of a
differential scanning calorimetry (DSC) analysis of the related compounds.
At temperatures above 195 C, a reaction between hexamine and
acetylated wood occurred and resulted in an exothermal peak at 225 C.
On the other hand, acetylated wood alone did not show any peak, and
hexamine by itself showed the exothermal peaks beyond 250 C. The
exothermal peak which started at 195 C, therefore, seems to have been
caused by the aminomethylation between hexamine and wood com-
ponents such as lignin, carbohydrates and their acetyl derivatives.
The reaction mechanism between hexamine, phenol and the solutes
was investigated by identifying and quantifying the gases generated from
a spinning solution at various spinning temperatures.
Gas chromatograms of the generated gases under conditions of dif-
ferent heating temperature and heating period are shown in Fig. 7.
178 NAOHIKO TSUJIMOTO
Acetylated wood
Hexamine .
EXO-
Hexar^f
A c e t y l * ^
FIG. 6. Differential scanning calori-
D 100 200 300 metric thermograms of acetylated
Temperature (C ) wood and hexamine.
H20
NH3
A
V j v
\ 200C,1hr
^^NH3 _J^^ 150C.2hr"
130C,2hr
I 1 11 1
1 1u
0.6
A
0.5 [
A
TENSILE STRENGTH (Gpa)
0.4
Because the tensile strength of the carbon fiber increased with decreasing
diameter, extrusion spinning was used to obtain finer filaments. Figure 9
shows the strength of carbon fibers from extrusion spinning, by which a
tensile strength of more than IT GPa could be obtained. This strength is
higher than that of the pitch carbon fiber of general-purpose grade.
1.3i . . 1 1 1
1.2-
1.1 -
(GPa)
1.0-
TENSILE STRENGTH
0.9-
0.8-
0.71 . . . i i 1 1
3 4 5 6 7 8 9 10
W O O D - P H E N O L RESIN FIBER F R O M U N M O D I F I E D W O O D
20
40% acetylated wood
G E N E R A T E D CHjCOOH (9
P 260*C .
10
0
0 5 10
LIQUEFACTION TIME ( nr. )
FIG. 10. Regenerated acetic acid fraction and dissolution time.
Phenol CH3COOH
WOOD
CONCLUSION
ACKNOWLEDGEMENT
REFERENCES
[1] N. Shiraishi, Mokuzai Gakkaishi (J. Japan Wood Res. Soc), 32, 755 (1986).
[2] N. Shiraishi, H. Tamura and N. Tsujimoto, Mokuzai Kogyo (J. Wood
Technol. Assoc., Japan), 42, 492 (1987); 43, 2 (1988).
[3] N. Shiraishi, K. Tsubouchi, T. Matsunaga and T. Yokota, Proceedings of
30th Annual Meeting of the Japan Wood Research Society, 34 (1980).
[4] N. Tsujimoto, Proceedings of the Nth Symvosium on Chemical Processing of
Wood, Jpn. Wood Res. Soc., 17 (1984).
[5] E.W. Orrell and R. Burns, Plastics and Polymers, 469 (1968).
Carbohydrate Conversion by Irradiation
with a Carbon Dioxide Laser
JUN-ICHI AZUMA, MING ZHANG and KEIZO OKAMURA
Department of Wood Science and Technology, Faculty of Agriculture,
Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku,
Kyoto 606-01, Japan
ABSTRACT
Four polysaccharides, cellulose, glucomannan, /M,3-glucan and starch, were irradiated
with a C O laser beam under a stream of nitrogen, and the chemical properties of the
2
degraded products were characterized. In all cases, melted materials were formed by
blasting with vaporized materials. The amounts of melted materials and vaporized materials
varied greatly depending upon the energy density and duration of irradiation. Scanning
electron microscopic observations indicated that the pyrolytic action of C 0 laser irradi-
2
ation was strictly limited to the surface of the melted layer. The melted materials were
mainly composed of a series of anhydro-oligosaccharides corresponding to the original
polysaccharides, together with monomeric 1,6-anhydrosugars. The vaporized materials
from cellulose were composed of volatile gases and an oily material rich in levoglucosan,
and also contained anhydro-cello-oligosaccharides identical to those observed in the melted
materials. The results of this study demonstrate that C 0 laser irradiation can be used as
2
INTRODUCTION
185
186 JUN-ICHI AZUMA ET AL.
the medium infrared region at 106 /mi, which is suitable for cutting and
drilling a wide variety of non-metallic materials including textiles, leather,
confectionery, plastics, rubber, wood and paper [ 1 - 5 ] . However, prob-
lems concerning the chemical properties of the melted and vaporized
products, and characterization of the reactions caused by laser irradiation
remain to be solved. In order to elucidate these aspects, we have
previously cut filter papers by irradiating with a C 0 laser and partially
2
EXPERIMENTAL P R O C E D U R E
The output power of the laser beam emitted at a wavelength of 10-6 jjm
was determined by a Nihon Kagaku Engineering Model PM-315 power
meter, and the spot size of the laser beam was determined by a Toshiba
beam profile meter. A schematic illustration of the laser irradiation
equipment is shown in Fig. 1. The sample holder for irradiation was made
up with two methylmethacrylate ring plates, 1-5 cm in height and 7-7 cm
and 10-2 cm in respective internal diameter, the bottoms of which were
bonded to the surface of a ceramic plate (95% aluminum oxide) with an
adhesive to make an annulus between the two methylmethacrylate plates.
The diameter of the annulus at the center was 8-9 cm, corresponding to
2 8 0 c m in length per revolution. Polysaccharide powder was inserted
into the annulus and compressed by hand with a methylmethacrylate ring
that fitted in the annulus. The sample holder was then laid on a rotating
plate, and the C 0 laser irradiated for one revolution at various combi-
2
Mirror
Oscillator
Lens
- N i t r o g e n gas
Focus
Defocus
Sample holder
Ceramic p l a t e
Melted material
Rotating plate
M e t h y l m e t h a c r y l a t e ring p l a t e
RESULTS A N D DISCUSSION
density dependence in Fig. 3. The values of energy density which gave the
maximal amount of water-soluble materials below 100 J/cm diminished 2
1 .<4 i i i l i 1 i i 1 I 11 ! | 1 1 1 1 111 1
cz 1.2
\
cn
Speed
in 1.0 - /a
(m/min) -
DIJ9.
/ 0.92
D
E 0.8 -
A m o u n t o"f v a p o rized
0.6
* ' * 1.62
0.4 a 2.49
3.51
JS O o
0.2 ^o~-^ 4.40
n i i iJ I i i i i i i i i I i i l l i iiil i i i ii i I I I
10 10 2
10 3
10 4
350 :
Amount of water-soluble materials (mg/m)
Speed
300 - (m/min)
0.92
250 -
200 -
150 -
100 -
50 -
10 10 2
10 3
10 4
40 -
Proportion of water-soluble materials {%)
35 -
30 -
25 -
20 -
1 5-
10 -
5-
10 10 2
10
5
104
was also present, but its content was as low as 0 1 % of the original
water-soluble materials. Regarding the preparation of the anhydro-
cello-oligosaccharides, only cellobiosan [10] and cellotriosan [11] have
been synthesized, but the anhydro-cello-oligosaccharides having D . P . ^ 4
are newly isolated components which could not be easily separated by
conventional synthetic methods. The reducing sugars were composed of
glucose, cellobiose and cellotriose. All their contents increased with
CARBOHYDRATE CONVERSION BY CARBON DIOXIDE LASER IRRADIATION 191
TABLE 1
!
H-NMR data for the representative anhydrosugars produced by C 0 2 laser
irradiation of cellulose (S in p.p.m.)
Levoglucosan 1 5-44(s)
461(d) 5-45(s)
Cellobiosan 2 (7-8)
[10] [10]
452(d) 4-62(d) 5-45(s)
Cellotriosan 3 (7-8) (7-8)
[1-2] [1-2] [10]
452(d) 454(d) 463(d) 5-46(s)
Cellotetraosan 4 (7-8) (7-8) (7-8)
[1-2] [1-3] [10] [10]
4-52(d) 4-55(d) 463(d) 5-45(s)
Cello-octaosan 8 (7-7) (7-8) (7-8)
[1-4] [5-3] [1-3] [10]
Chemical shifts for anomeric protons in D 0 are given with sodium 2,2,3,3-
2
H l : anhydroglucose residue
a
s, d: multiplicity of signals
( ) coupling constants (J in Hz)
l 2
[ ] molar ratio
* degree of polymerization
TABLE 3
Methylation analysis of the representative anhydrosugars produced by C 0 laser2
irradiation of cellulose
Levoglucosan 1 2,3,4-Glc**
2,3,4,6-Glc 10
Cellobiosan 2 2,3,6-Glc
2,3-Glc 10
2,3,4,6-Glc 10
Cellotriosan 3 2,3,6-Glc 1-2
2,3-Glc 1-2
2,3,4,6-Glc 10
Cellotetraosan 4 2,3,6-Glc 1-8
2,3-Glc 10
2,3,4,6-Glc 10
Cello-octaosan 8 2,3,6-Glc 5-7
2,3-Glc 10
* degree of polymerization
** 2,3,4-Glc = 2,3,4-tri-0-methyl-D-glucopyranose, etc.
may be the transition area from the melted layer to the native cellulose.
The crystallinity indices and molecular weights of the irradiated celluloses
decreased with increasing amounts of water-soluble materials, but re-
covered to the initial level after washing with water. The present results
show that the structural change produced by heating with the C 0 laser 2
under the same conditions as those applied to the cellulose, and the
melted materials were extracted with 80% aqueous ethanol instead of
water, because glucomannan itself is partially soluble in water. The
energy density dependence of the amounts of vaporized materials and
80% aqueous ethanol-soluble materials were similar to those for the case
of cellulose. Because glucomannan has a linear main chain composed of
194 JUN-ICHI AZUMA ET AL.
Levoglucosan
CH OH
2 CH OH
2
OH OH OH
n = 0 - 6
Anhydro-celtooligosaccharides
CH OH
2 CH OH
2
OH OH OH
n = 0 - 8
Anhydro-lamlnarioligosaccharides
FIG. 5. Structures of the anhydro-gluco-oligosaccharides and levoglucosan
formed by C 0 laser irradiation of cellulose, /M,3-glucan and starch.
2
CARBOHYDRATE CONVERSION BY CARBON DIOXIDE LASER IRRADIATION 195
Laser Irradiation
Based on the results just presented, the water-insoluble homologous
polysaccharides were concluded to be easier to handle than the water-
soluble ones with respect to an exact estimation of the amount of
melted materials and the characterization of their structures. We there-
fore applied the present laser-induced conversion method to the two
196 JUN-ICHI AZUMA ET AL.
TABLE 4
X
H-NMR data for the representative anhydrosugars produced by C 0 2 laser
irradiation of glucomannan (S in p.p.m.)
H l : anhydromannose residue
a
s, d: multiplicity of signals
( ) coupling constants ( J in Hz)
1>2
[ ] molar ratio
* degree of polymerization
TABLE 5
Methylation analysis of the representative anhydrosugars produced by C 0 laser
2
irradiation of glucomannan
4-0-Glucosyl-l,6- 2,3,4,6-Glc 10
anhydromannose (G-AM) 2 2,3-Man 10
4-0-Glucosyl-4-j8- 2,3,4,6-Glc 11
mannosyl-1,6-anhydro- 3 2,3,6-Man 0-9
mannose (G-M-AM) 2,3-Man 1-3
4-0-Cellobiosyl- 2,3,4,6-Glc 10
mannosyl-1,6-anhydro- 4 2,3,6-Glc 11
mannose (G-G-M-AM) 2,3,6-Man 1-3
2,3-Man 10
* degree of polymerization
** 2,3,4-Man = 2,3,4-tri-O-methyl-D-mannopyranose, etc.
and high irradiation speed (5*3-51 m/min), a clear maximum was detec-
ted. However, under the other conditions, the amount of the water-
soluble materials monotonously decreased with increasing energy den-
sity. Figure 5 shows the structures of the homologous series of 9
anhydro-laminarioligosaccharides isolated from the water-soluble ma-
terials. The representative results of N M R spectroscopic and methyla-
tion analyses are shown in Tables 9, 10 and 11. The distribution of
these anhydrosugars and levoglucosan was 4-3% (levoglucosan),
6-6% (laminaribiosan), 9-4% (laminaritriosan), 11-4% (laminaritetraosan),
12-9% (laminaripentaosan), 11-7% (laminarihexaosan), 6*5% (lamin-
ariheptaosan), 2-7% (laminarioctaosan), 2-2% (laminarinonaosan) and
2-2% (laminaridecaosan) of the 80% ethanol-soluble materials produced
by irradiating at 2-9 x 1 0 J/cm .
3 2
198 JUN-ICHI AZUMA ET AL.
l 6-Anhydro-0-
f (G-AM)
D-mannopyranose
Ori OH
(G-G-M-AM)
Anhydro-glucomannooligosaccharides
TABLE 6
^ - N M R data for the representative anhydro-oligosaccharides produced by C 0 2
* degree of polymerization
s, d: multiplicity of signals
( ) coupling constants (J l 2H) m z
[ ] molar ratio
C-l n
98-82 98-71 98-75 98-70
C-2 n 72-34 72-72 72-73 72-71
Non-reducing C-3 n 73-87 73-89 73-89 73-88
end residue C-4 n 71-08 70-44 70-43 70-42
C-5 n 73-33 73-77 73-65 73-62
C-6 n 61-67 61-59 61-59 61-57
C-lj 100-50 100-54(s)
C-2; 72-52 72-49(s)
Intermediate C-3i 74-15 74-1 l(s)
residue(s) C-4j 78-28 78-23(s)
C-5i 72-25 72-23(s)
C-6i 61-59 61-57(s)
Intermediate c-i i a
100-64 100-75 100-72
JUN-ICHI AZUMA ET AL.
residue C-2 i a
72-14 72-14 72-14
adjacent to C-3 i a
74-14 74-15 74-11
anhydroglucose C-4 i a 78-40 78-56 78-37
residue C-5 i a 71-91 71-89 71-90
C-6 i a
61-59 61-59 61-57
C-l. 102-18 10218 102-20 10218
C-2 a 70-96 7101 71-02 7103
Anhydroglucose C-3 a 70-69 70-66 70-64 70-59
residue C-4 a 77-34 77-53 77-57 77-54
C-5 a 76-21 76-15 7616 76-13
C-6 a 6613 6610 6610 6609
2
Chemical shifts in D 0 are given with dioxane (67-40 p.p.m.) as an internal standard, s: strong
CARBOHYDRATE CONVERSION BY CARBON DIOXIDE LASER IRRADIATION 201
TABLE 8
Methylation analysis of the representative anhydro-oligosaccharides produced by
CO laser irradiation of corn starch2
2,3,4,6-Glc** 10
Maltosan 2 2,3,6-Glc
2,3-Glc 11
2,3,4,6-Glc 10
Maltotriosan 3 2,3,6-Glc 0-9
2,3-Glc 11
2,3,4,6-Glc 10
Maltotetraosan 4 2,3,6-Glc 1-9
2,3-Glc 1-2
2,3,4,6-Glc 10
Maltoheptaosan 7 2,3,6-Glc 4-7
2,3-Glc 0-9
* degree of polymerization
*2,3,4,6-Glc = 2,3,4,6-tetra-O-methyl-D-glucopyranose, etc.
(mg/m)
300
250
Amount of water-soluble materials
200
150
100
50
n
10 10 2
10 3
10 4
TABLE 9
^ - N M R data for the representative anhydro-oligosaccharides produced by C 0 2
H-K H-l a
456(d) 5-48(s)
Laminaribiose 2 (7-8)
[0-8] [10]
460(d) 4-74(d) 5-48(s)
Laminaritriose 3 (7-9) (7-8)
[0-8] [0-9] [10]
459(d) 479(d) 474(d) 5-48(s)
Laminaritetraose 4 (7-9) (7-9) (7-8)
[09] [11] [0-8] [10]
456(d) 4-79(d) 474(d) 5-48(s)
Laminaridecaose 10 (7-8) (7-8) (7-9)
[1-2] [6-7] [08] [10]
Chemical shifts for anomeric protons in D 0 are given with sodium 2,2,3,3-
2
H l : anhydroglucose residue
a
s, d: multiplicity of signals
( ) coupling constants ( J in Hz)
1>2
[ ] molar ratio
*degree of polymerization
CONCLUSION
2
Chemical shifts in D O are given with dioxane (67-40 p.p.m.) as an internal standard, s: strong
204 JUN-ICHI AZUMA ET AL.
TABLE 11
Methylation analysis of the representative anhydro-oligosaccharides produced by
C 0 laser irradiation of curdlan
2
2,3,4,6-Glc** 10
Laminaribiosan 2 2,4,6-Glc
2,4-Glc 1-2
2,3,4,6-Glc 10
Laminaritriosan 3 2,4,6-Glc 10
2,4-Glc 0-9
2,3,4,6-Glc 10
Laminaritetraosan 4 2,4,6-Glc 1-7
2,4-Glc 1-2
2,3,4,6-Glc 10
Laminaridecaosan 10 2,4,6-Glc 7-8
2,4-Glc 1-3
* degree of polymerization
*2,3,4,6-Glc = 2,3,4,6-tetra-O-methyl-D-glucopyranose, etc.
REFERENCES
York (1976).
[2] C.H. Miller, T.A. Osial and A. Van der Jagt, Pulp Paper Mag. Can., 71, 63
(1973).
[3] C.W. McMillin and J.E. Harry, Forest Prod. J., 21(10), 34 (1971).
[4] S.B. Nordin, J.O. Nyren and E.L. Back, Textile Res. J., 44, 152 (1974).
[5] C.C. Peters and C M . Banas, Forest Prod. J., 27(11), 41 (1977).
CARBOHYDRATE CONVERSION BY CARBON DIOXIDE LASER IRRADIATION 205
ABSTRACT
The biochemical mechanisms for the biodegradation of wood by white-rot and brown-rot
fungi are discussed on the basis of recently reported findings. The white-rot wood decay
process comprises the enzymatic hydrolysis of cellulose and oxidative breakdown of lignin;
the one-electron oxidation mechanism involved in the initial oxidation of lignin is described.
In the enzymatic breakdown of lignin, a cation radical intermediate plays a key role. In the
brown-rot wood decay process, cellulose degradation is more critical than that of lignin,
and the possible role of Fenton's system, which has been receiving keen attention recently,
is discussed in relation to the oxidative breakdown of cellulose. As an alternative hypothesis,
however, the possible role of oxalic acid in the hydrolytic cleavage of the cellulose chain is
proposed, because oxalic acid is one of the strongest physiological organic acids, and is
commonly known as a peculiar secondary metabolite produced by brown-rot fungi.
Keywords: white rot, brown rot, wood decay, biochemical mechanism, one-electron oxida-
tion, ligninase, cellulase, oxalic acid
INTRODUCTION
207
208 MIKIO SHIMADA
DECAY OF W O O D C O M P O N E N T S
L I G N I N D E G R A D A T I O N BY WHITE-ROT F U N G I
FIG. 1. Chemical model of the spruce lignin structure proposed by Freudenberg [4].
BIOCHEMICAL MECHANISMS FOR THE BIODEGRADATION OF WOOD 211
Although the name 'ligninase' has not been rigorously defined, it may
be used as a general term for enzymes that catalyze the breakdown of the
intermonomeric linkages in lignin. The ligninase' isolated from
Phanerochaete chrysosporium was shown to catalyze predominantly CC
bond cleavage, yielding aromatic aldehydes as the major products as
depicted in Fig. 2 [6]. This 'ligninase' is now called lignin peroxidase
(LiP), due to the enzymic requirement of hydrogen peroxide as an
oxidant like other classical peroxidases. LiP contains iron-protopor-
phyrin IX complex at the active site (Fig. 3). The synthetic iron-
tetraphenylporphyrin complex has been demonstrated to exhibit the
same reaction as that of ligninase, and has been a biomimetic model
catalyst for LiP due to its enzyme-mimicking.
OMe
CH OH
2
FIG. 4. A p
One-electron oxidation mechanism for the enzymatic C C bond cleavage of a / M lignin model substrate [10].
214 MIKIO SHIMADA
CELLULOSE D E G R A D A T I O N BY BROWN-ROT F U N G I
FIG. 5. One-electron oxidation mechanism for the aromatic ring cleavage of a monometric lignin model substrate [11].
215
216 MIKIO SHIMADA
1600
o
H
4->
cd
M
H 1200
6
it
o
O 800
<D
<D
W>
<D
'd
<D 400
W>
CD
>
<
0 20 40 60
Crystalline Amorphous
regions regions
Cellulose substrate
A | Endo-cellulase (Cx)
cellulases
D
p-biucosidase
T\
Glucose
80
3soinTiao jo
70
60
Cotton
50
Angiosperm
'd'G.
40
SATIETY
30
20
0 10 20 30 40 50
FIG. 8. Relationship between the D.P. decrease in cellulose in cotton and wood
samples and the weight loss of cellulosic samples by oxidation with Fenton's
system [22].
cellulose
I Brown-roc
cellulose
cdlulos'
ceilulosi .cellulose
Table 1 shows that the incubation of pine kraft pulp with 1% oxalic acid at
35 C for four weeks decreased the viscosity of cellulose to 60% of the
original value. An increase in the concentration of oxalic acid to 5% caused
a more drastic decrease in viscosity to about 30% of the original value.
Although the physiological concentration of the acid in rotten wood has
not been measured, in view of the optimum moisture content for wood
decay, the oxalic acid concentration might be considerably higher than is
thought; cellulose as well as hemicellulose is easily depolymerized by oxalic
acid during the considerably longer period involved in the natural wood
decay process. Recently, Bech-Anderson [27] has reported that hemicel-
lulose (xylan) was hydrolyzed by treating wood meal with a 10% oxalic acid
solution. Therefore, it is proposed that oxalic acid plays a key role in the
degradation of carbohydrates during the brown-rot wood decay process.
TABLE 1
Effects of oxalic acid on the viscosity of cellulose [26]
Treatment method Viscosity (cP) Relative value
COOH
COOH Oxaloacetase ^ COOH
6=0
6H 2
COOH H
* X
CH 3
COOH
CONCLUSION
REFERENCES
[8] H.E. Schoemaker, P J . Harvey, R.M. Bowen and J.M. Palmer, FEBS Lett,
183, 7 (1985).
[9] P.J. Kersten, M. Tien, B. Kalyanaraman and T.K. Kirk, J. Biol. Chem., 260,
2609 (1985).
[10] M. Shimada, T. Habe, T. Higuchi, T. Okamoto and B. Panijpan, Holzfor-
schung, 41, 277 (1987).
[11] M. Shimada, T. Hattori, T. Umezawa and T. Higuchi, FEBS Lett, 221, 327
(1987).
[12] T. Umezawa and T. Higuchi, FEBS Lett., 218, 255 (1987).
[13] M. Shimada and M. Takahashi, in Wood and Cellulosic Chemistry (ed.
D.N.S. Hon and N. Shiraishi), Marcel Dekker, 621 (1991).
[14] H. Wariishi, K. Valli, V. Renganathan and M.H. Gold, J. Biol. Chem., 264,
1418 (1989).
[15] D.A. Kaarik, in Biology of Plant Litter Decomposition, Vol. 1 (ed. by C.H.
Dikkerson and G.J.F. Pugh), Academic Press, New York, 129 (1974).
[16] J.G. Savory, in Biodeterioration of Materials, Elsevier Publishing Co., New
York (1968).
[17] T.C. Scheffer, in Wood Preservation and Its Prevention by Preservative
Treatments (ed. N.S. Cote), Syracuse University Press, Syracuse, New York,
31 (1973).
[18] S. Doi, Mokuzai Gakkaishi (J. Japan Wood Res. Soc), 31, 843 (1985).
[19] E.B. Cowling and W. Brown, Adv. Chem. Ser., 95, 152 (1969).
[20] T.L. Highley, Wood and Fiber, 5, 50 (1973).
[21] M. Ishihara and K. Shimizu, Mokuzai Gakkaishi, 30, 79 (1984).
[22] J.W. Koenig, Wood and Fiber, 6, 66 (1974).
[23] A. Enoki, H. Tanaka and G. Fuse, Wood Sci. Technol, 23, 1 (1989).
[24] T.K. Kirk, T.L. Highley, R. Ibach and M.D. Mozuch, Intern. Res. Group on
Wood Preserv., Document No. 1389 (1989).
[25] C.J. Schmidt, B.K. Whitten and D.D. Nicholas, Proc. Am. Wood Preserv.
Assoc, 11, 157 (1981).
[26] M. Shimada, Y. Akamatsu and M. Takahashi, Proc. Intern. Symposium of
Wood and Pulping Chemistry, Melbourne, Australia, April 29-May 3 (1991).
[27] J. Bech-Anderson, Intern. Res. Group on Wood Preserv., Document No.
1130 (1987).
[28] H. Simazono and O. Hayaishi, J. Am. Chem. Soc, 18, 5126 (1956).
[29] H. Shimazono and O. Hayaishi, J. Biol Chem., 227, 151 (1957).
[30] Y. Akamatsu, D.B. Ma, T. Higuchi and M. Shimada, FEBS Lett., 269, 261
(1990).
[31] N.G. Lewis and M.G. Paice, Plant Cell Wall Polymer: Biogenesis and
Biodegradation, Am. Chem. Soc. Symp. Ser., 399 (1989).
[32] T.K. Kirk and H.-M. Chang, Biotechnology in Pulp and Paper Manufacture,
Butterworth-Heinemann, Boston (1990).
Wood-Preserving Techniques to Prevent
Biodeterioration
MUNEZOH TAKAHASHI
ABSTRACT
Current wood-preserving techniques for preventing biodeterioration are described. Al-
though both toxic and non-toxie chemical treatments for protecting wood have been
extensively studied, the former is still the only practical method for preserving wood.
However, toxic preservatives in wide commercial use have been subjected to public
criticism, so that there is a demand for the development of low-toxicity alternatives and
safer treatment techniques. Several promising examples are described. Among the various
non-toxic treatments, acetylation, phenolic resin impregnation and wood-inorganic material
composite are worthy of consideration for their potential practical use. These treatments
are more applicable to reconstituted wood products than to thick solid timber since the
chemicals penetrate easily into the wood cell wall and voids in small-size elements.
However, a more economical processing system needs to be developed to improve the
cost-effectiveness. Safe disposal of wood products that have been treated with toxic or
non-toxic chemicals should be further considered to avoid an excessive accumulation of
non-degradable wood waste in the environment.
INTRODUCTION
Wood is composed essentially of only cell walls and voids. The cell wall
is a composite material constructed from a variety of organic polymers,
and the voids are filled alternately with air and water. While this basic
feature provides various advantages for their utilization, it quite often
causes undesirable biodeterioration such as microbial and insect attack
on wood in service. The organic polymers of wood cell walls, which are
not necessarily easily degradable, are abundant nutrient sources for the
223
224 MUNEZOH TAKAHASHI
D E V E L O P M E N T OF ALTERNATIVES TO C O N V E N T I O N A L
W O O D PRESERVATIVES
Background
Until the 1960s, creosote, copper-chrome-arsenate (CCA), chlorinated
hydrocarbons {insecticidal D D T , y-BHC, drin chemicals, heptachlor and
chlordane and fungicidal pentachlorophenol (PCP)}, and organotin com-
pounds were the predominant wood preservatives.
Among these, most insecticidal chlorinated carbons were prohibited for
use in many countries, because of the detrimental side effects which were
demonstrated by environmental surveys and toxicological studies. How-
ever, chlordane was allowed for use in Japan until 1986. PCP and
water-soluble Na-PCP have been used world-wide, but they were banned
in Japan for the same reason about ten years ago.
Public criticism about the toxicity and detrimental environmental
effect is also strong against the other major historical preservatives. Bis
(tri-n-butyltin) oxide (TnBTO) also disappeared recently from the market,
this being triggered by the detection of TnBTO in sea-water bred fish
which were enclosed by a preservative-treated breeding net.
The preserving performance of creosoted wood products has been well
evaluated, but a few disadvantages have also been pointed out. These
include the poor paintability of treated products, unfavorable odor,
dermato-inflammation and the carcinogenetic substances in creosote.
WOOD-PRESERVING TECHNIQUES TO PREVENT BIODETERIORATION 225
Oil-borne Preservatives
Several oil-borne chemicals were recently evaluated as wood preserv-
atives and commercialized.
Two organoiodine compounds, 4-chlorophenyl-3-iodopropargyl for-
mal (IF-1000) [ 7 - 1 2 ] and 3-bromo-2,3-diiodo-2-propenyl carbonate
(EBIP) [12-14], were developed in Japan to protect wood from fungal
attack. Two other organoiodine chemicals, 3-iodo-2-propynyl butyl car-
bonate (IPBC) [15-24] and 2,3,3-triiodoallyl alcohol (TIAA) [25], also
became available for the same purpose. Comprehensive studies have been
conducted by Lee et al. to evaluate these compounds as wood preserv-
atives [14, 24-28].
The order of their anti-decay effect after a single-brushing treatment
was TIAA ( 0 5 % ) > I P B C ( 0 - 7 5 % ) > I F - 1000 ( 1 0 % ) > E B I P (10%). The
effect of TnBTO was equal to IF1000. Mixing each compound with
termiticidal chlorpyrifos and a surface active agent gave a synergistic
fungicidal effect against white-rot fungus, Coriolus versicolor. However,
an effect was not always found against two brown-rot fungi, Tyromyces
palustris and Serpula lacrymans. Only IPBC gave a desirable synergistic
effect against all the fungi tested by mixing with a surface active agent.
IF1000 and T N B T O caused an undesirable antagonistic effect against
T palustris when mixed with chlorpyrifos. EBIP showed a synergistic
and/or additive effect against T. palustris and S. lacrymans only when
they were mixed with commercial synergistic and stabilizing agents.
The crossed-paper technique [29, 30] has been extensively used in
biochemical and medical research to determine the effectiveness of
226 MUNEZOH TAKAHASHI
TABLE 1
Effects of mixing organoiodine fungicides with chlorpyrifos (CP) and/or a surface
active agent (S, polyoxyethylene sorbitan fatty acid ester) as evaluated by
crossed-paper tests [26]
CP S CP +S CP S CP +S CP s CP +S
IF-1000 _ + ++ + +++ + + + + +
IPBC ++ ++ +++ ++ ++ +++ ++ ++ + + +
EBIP + + + + + + + + + +
TIAA + ++ + + ++ ++ - + + +
TnBTO - ++ + +++ +++ + + +
TYP, Tyromyces palustris; SEL, Serpula lacrymans; COV, Coriolus versicolor.
+ independent action, + + additive action, + + + synergistic action,
antagonistic action.
TABLE 2
Effects of mixing EBIP with chlorpyrifos (CP), a synergistic agent (S, octa-
chlorodipropylether), and a stabilizer (N, sodium-dioctylsulphosuccinate) as
evaluated by crossed-paper tests [26]
Fungus CP S N CP + S CP + N CP + S + N
TYP ++ + + ++ + +++
SEL ++ ++ ++
COV ++ + ++ ++ +++ +++
Symbols are the same as those in Table 1.
Water-borne Preservatives
Alkylammonium compounds (AAC), which were developed as in-
dustrial biocides, produced promising results in the laboratory as an
alternative to CCA [52-58]. However, fungus-cellar and field trials
did not allow their use in soil-contract situations [59, 60]. The low
toxicity and high anti-termite performance of AAC were well appreciated,
and combination with copper and other agents enhanced their biological
resistance [58, 59, 61, 62]. Although no kind of AAC is currently
used in above-ground situations in New Zealand where it was originally
228 MUNEZOH TAKAHASHI
I M P R O V E M E N T OF PRESERVATION TREATMENT
Pressure Treatment
The Bethell process is still the principal technique in Japan for pressure
impregnating conventional water-borne preservatives. The Ruping and
Lowry processes are employed for treating with oily and oil-borne
preservatives. These treatments were introduced into Japan early in this
century, and several undesirable features have long been recognized.
Seasoning or kiln drying before and after treatment, pre-incising for
treating refractory wood species, low recovery of expensive organic
solvent, and low quality control of treated timber as an industrial
material might inhibit the Japanese wood preserving industry from
expanding the potential market even after the successful development of
treated wood foundation sills during the past two decades, instead of the
decline of wooden poles and sleepers [64].
Improvements to the pressure treatment process have been made by
several workers and have been highly evaluated. O P M (the oscillating
pressure method) and APM (the alternative pressure method) were
developed to treat green timber and to obtain even and deep penetration
of the wood preservatives [66, 67]. Treatment with light organic solvent
preservative (LOSP) is aimed primarily at protecting finished joinery
against accidental wetting during the interval between leaving the factory
WOOD-PRESERVING TECHNIQUES TO PREVENT BIODETERIORATION 229
Dipping is better than brushing and spraying because all surfaces can
absorb liquid freely, and the time for dipping can be suited to the
standard of treatment required. In Japan, dipping is applied exclusively
to control sap-staining fungi and surface mold in fresh-sawn timber.
Timber is loaded on pallets and submerged in a preservative-containing
tank for a short time. Although the treatment is targeted for short-term
protection until leaving the factory or until the next process, undesirable
failures have often occurred during the interval. In most cases, this has
been due to the degeneration of the working solution in a dipping tank.
The concentration of a freshly-prepared solution is checked as a matter
of routine, but periodic re-checking of the solution is poorly conducted
in many treatment plants. Preservative suppliers have to offer a frequent
analysis service to maintain the preservative performance.
E N H A N C E M E N T O F BIOLOGICAL RESISTANCE BY
CHEMICAL TREATMENT
Chemical Modification
Chemical modification of wood generally involves any chemical reac-
tion between the hydroxyl groups of principal wood components and a
single chemical reagent. Hydroxyl groups are the most abundant reactive
sites in the wood cell wall polymers and, therefore, provide the biological
enzymatic reaction sites. Chemical modification has been studied to
enhance such end-product properties as dimensional stability, fire retar-
dancy and biological resistance. There are often some problems with the
chemical treatment of wood that may restrict commercialization. How-
ever, the improvement of biological resistance will be more important for
wood preservation in the near future because it yields no risk of hazard
to health and the environment in the use of end-products.
The reagents used for chemical modification can be divided into the
three classes by the type of bond formed between them and the hydroxyl
group in the wood cell wall: esters, acetals and ethers [71]. An increase in
the resistance to biological attack has been recognized in all classes of
chemical modification with esters: acetic anhydride [72-81], 2,4-tolylene
diisocyanate [82, 83], methyl isocyanate [83]; with acetals; formaldehyde
[84, 85]; and with ethers: jS-propiolactone [86], acrylonitrile [86, 87],
epichlorohydrin or dichlorohydrin [88], propylene oxide and butylene
oxide [79, 89-91]. Some examples of the results are shown in Tables 3-7.
Wood-rotting fungi and termites each have a very specific enzyme
WOOD-PRESERVING TECHNIQUES TO PREVENT BIODETERIORATION 231
TABLE 3
Percentage weight loss in chemically-modified southern
yellow pine blocks after a 12-week exposure to the
brown-rot fungus, Gloeophyllum trabeum [71]
Control 0 62-9
Propylene 200 38-6
oxide 26-7 32-8
Butylene 7-0 18-8
oxide 230 20
Methyl 11-6 12-8
isocyanate 24-3 2-3
Acetic 15-6 2-3
anhydride 24-6 0-8
TABLE 4
Percentage weight loss in chemically-modified southern
yellow pine blocks after a 12-week exposure to the
brown-rot fungus, Lentinus lepideus [71]
Control 0 44-2
Propylene 51 17-5
oxide 24-0 4-8
Butylene 26-3 1-8
oxide
Methyl 21-6 10
isocyanate
Acetic 15-4 3-9
anhydride 18-6 0-7
TABLE 5
Percentage weight loss in chemically-modified southern yellow pine
blocks after a 2-week exposure to the subterranean termite. Re-
ticulitermes flavipes [71]
Control 0 31
Propylene 9 Interior 24
oxide Surface 19
17 Interior 15
Surface 13
34 Interior 5
Surface 8
Butylene 27 Interior 4
oxide Surface 4
34 Interior 3
Surface 3
TABLE 6
Percentage weight loss in acetylated southern pine and aspen flake-
boards after a 12-week exposure to the brown-rot fungus, Gloeophyl-
lum traheum (6% phenolic adhesive) [71]
TABLE 7
Percentage weight loss in acetylated albizzia particleboards after
an 8-week exposure to brown-, white-, and soft-rot fungi [81].
0 PF 21-7 100
5 PF 18-4 7-7
12 PF 11 0-7
20 PF 0 0
0 IC 26-8 24-3 150
5 IC 24-1 21-6 0-7
12 IC 4-3 0 0
20 IC 0 0 0
PF, phenol-formaldehyde resin; IC, isocyanate resin. TYP,
Tyromyces palustris (brown-rot); COV, Coriolus versicolor (white-
rot); CHG, Chaetomium globosum (soft-rot).
tion than white-rot Coriolus versicolor. A 20% weight gain (WPG) was
required to suppress decay by T. palustris in any wood species. On the
other hand, C. versicolor failed to attack acetylated Japanese cedar even
at 6 WPG, although 20 W P G was necessary to suppress its decay of
beech and albizzia (Indonesian fast-growing hardwood).
In spite of the numerous works on the chemical modification of wood,
commercial applications have not yet been attempted in any country
except for acetylation in Japan [92]. Wood modification is effective for
thin or small wood sizes because of its good chemical penetration. A
Japanese commercialized acetylated product is a laminated veneer lum-
ber (LVL) in which 3 mm-thick veneer is treated with an acetic anhydride,
using sodium acetate as a catalyst, prior to hot-pressing. Acetylated LVL
is applied to end-products that are exposed to continued dampness or
outdoor weathering conditions such as bathroom elements, external sign
boards, and roof shingles on traditional wooden shrine buildings.
Property enhancement of reconstituted wood products by acetylation
is also considered promising since the required chemicals react easily with
wood constituents in small-size elements. The biological resistance and
dimensional stability of flakeboard and particleboard were greatly im-
proved by acetylating the wood elements before board production [71,
78-81, 93-95]. Reconstituted wood products are becoming more import-
ant throughout the world as an effective solution to decreasing forest
resources. However, a more economical processing system needs to be
234 MUNEZOH TAKAHASHI
100
$ 60
o
80
1 1 1LI11 >1 1
40
0o) 20
i SX' i1 1 1 Dl
* 0 1 1
I
20
\ *s
V1
\
5 40 \
\
\
tt
60
I
\
80 \-
\
\
20 16 12 8 4 0 4 8 12 16 20
10 0.
Percentage resin loading
\
FIG. 1. Effect of a phenol-formaldehyde resin treatment of western hemlock on
i> i i
the resistance to fungal attack for 12 weeks [96]. Relative weight
loss = W2/Wl x 100. Wl is the % weight loss of untreated wood, W2 is the %
weight loss of phenol-formaldehyde resin-treated wood. 170 molecular weight,
300 molecular weight. Solid line: Tyromyces palustris (brown-rot); broken line:
Coriolus versicolor (white-rot).
WOOD-PRESERVING TECHNIQUES TO PREVENT BIODETERIORATION 235
TABLE 8
Percentage weight loss in wood-inorganic materials (WIC; 9 mm thick
LVLs, 25% weight gain) after an 8-week exposure to Tyromyces palustris
(brown-rot) and Coriolus versicolor (white-rot) [98]
Wood T. palustris C. versicolor
TABLE 9
Percentage weight loss in wood-inorganic materials (WIC: 9 mm thick
LVLs, 25% weight gain) caused by subterranean termite Coptotermes
formosanus, and the mortality of the termites after a 3-week test [98]
F U T U R E CONSIDERATIONS
As already pointed out throughout the world, some widely used wood
preservatives have been publicly criticized because of their relatively high
mammalian toxicity and environmental impact. This fact supports the
strong social demand for low-toxicity alternatives to these unsafe chemi-
cals that are on the list of commercial wood preservatives. Investigations
need to be conducted to develop new wood preservatives based on
screening tests of various chemicals in the laboratory and field. In
addition, the practical application of potentially useful chemicals for
treating and improving wood should be tested, and the quality of the
treated products should be fully evaluated. Various chemical treatments
of wood have been categorized as a non-toxic preservation process, and
some have been evaluated as suitable for wider utilization with recon-
stituted wood products. However, such non-toxic treatments cannot
replace preservative treatments, even if the current low cost-effectiveness
could be improved. Non-toxic chemical treatments are principally for
prevention, and not for remedial and extermination treatments. In
addition, chemical treatments are far more applicable to the production
of reconstituted wood products than to thicker solid timber.
The ecological and physiological approaches to prevent damage by
wood-attacking termites need to be investigated so that the use of
conventional termiticides can be reduced. It would be worth searching for
WOOD-PRESERVING TECHNIQUES TO PREVENT BIODETERIORATION 237
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238 MUNEZOH TAKAHASHI
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240 MUNEZOH TAKAHASHI
241
242 INDEX
Galactoglucomannan, 16
Giant ipil-ipil (Leucaena leucocephala IF-1000, 225
Lam, de Wit), 72 IMF, 46
j9-l,3-Glucan, 194, 196, 201 Inorganic constituents of wood, 16
Glucomannan, 196-8 Intercellular layer, 5
degradation by C 0 laser
2 Internal friction, 143-5
irradiation, 193-5 IPBC, 225
4-/?-Glucosyl-1,6-anhydromannose Iron porphyrin complex, 211
(G-AM), 195 Isocyanates, 39, 44, 46, 80-3
4-/?-Glucosyl-4-/?-mannosyl-1,6-
anhydromannose (G-M-AM),
195 Japanese fir (Abies sachalinensis Fr.
Glucuronoarabinoxylan, 16 Schm.), 11
Glue-additive-treated particleboards,
83
Glue-line failures, 83 Karamatsu (Larix \epto\epis\ 96-97
Glulam portal frames, 109-18
deformation, 112
full-scale experiments, 115 Laminaribiosan, 197
nonlinear analysis, 112-15 Laminaridecaosan, 197
244 INDEX
Refiner mechanical pulp (RMP), 170, Sugi (Cryptomeria japonica), 15, 16,
173 97
Relative humidity, 126, 128 Sugi (Cryptomeria japonica D. Don),
Resin components in low-density 68, 123, 124
particleboard, 39 Surface characteristics
abrasion resistance, 122-5
smoothness to the touch, 120-1
Sawn timber warmth to the touch, 120
correlation coefficient between knot Syringyl residues, 12, 14
size and modulus of rupture
(MOR), 98
modulus of elasticity (MOE), 97 TCMTB, 226
structural properties, 95-9 Termites
Seismic response analysis, 104-7 (Coptotermes formosanus), 68, 72,
Semi-strand board, 30 235, 236
Shorea negrosensis Foxw., 126 (Reticulitermes flavipes), 232
Softwoods (Reticulitermes speratus), 12
cell types, 2 Termiticides, 226-7
cell wall organization, 4-8 Tetrachlorovinphos, 227
chemical composition, 6 Tetraoxane, 73
surface characteristics, 121 Tetraphenyl porphyrin (TPP), 212
Sound absorption, 143 Thermal gradient, 127-30
Sound-insulating material, 133 Thermal properties, 125
Sound transmission, 131-3 Thermoplasticity, 136, 156-60
in wooden houses, 120 TIAA, 225
Sound tansmission loss (STL), 133 Timber joints, 109
Sound velocity, 143 TnBTO, 224
Spinning methods, 173, 176-7 Todomatsu (Abies sachalinensis), 97
unmodified wood solution, 181-2 Touhi (Picea sp.), 97
Spinning nozzle, 171, 174 TPIC, 227
Spinning solutions, 170, 173-6, 181 Triazole compounds, 226
Spinning temperature, 179 Trifluoroacetic acid (TFA), 158
Spruce (Picea jezoencis Carr.), 81 Trifluoroacetic anhydride (TFAA),
Squares bending test, 96 170, 173, 174, 179
Squares compression test, 97 Trioxane, 73
Squares tension test, 97
Starch, 194, 196 Urea formaldehyde (UF), 44-6
Steam-injection pressing, 43-53 Urea-melamine-formaldehyde (UMF)
continuous press development, resin, 44, 45, 78-83
49-52
optimizing press time, 49
temperature behavior of particle Valonia macrophysa, 8-9
mat, 46-9 Vapor-phase treatment, 149
Strength ratio concept, 96 Vibration equation, 104
Stress-induced deformation, 142 Vibration generator, 104
Structural timber. See Sawn timber frequency-response curves from, 86
Styrene-maleic anhydride copolymer Vibration tests on wooden buildings,
(SMA), 159 104
INDEX 247