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{WC-3328 LIBRARY
2,, Michigan State
200w f University

 

This is to certify that the
thesis entitled

MICROWAVE POST TREATMENT TO REDUCE LEACHING
OF COPPER FROM ACQ TYPE C TREATED SOUTHERN
YELLOW PINE

presented by

SEDRIC PANKRAS M

has been accepted towards fulfillment
of the requirements for the

MS degree in Forestry

 

 

Major Professor’s Signature

4/n/oe

Date

 

MSU is an Affirmative Action/Equal Opportunity Institution

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MICROWAVE POST TREATMENT TO REDUCE LEACHIN G OF
COPPER FROM ACQ TYPE C TREATED SOUTHERN YELLOW PINE

By

Sedric Pankras M

A THESIS

Submitted to
Michigan State University
In partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE
Department of Forestry

2006

ABSTRACT

MICROWAVE POST TREATMENT TO REDUCE LEACHING OF
COPPER FROM ACQ TYPE C TREATED SOUTHERN YELLOW PINE

By
Sedric Pankras M

Microwave and air dry post treatments were explored as a method to reduce the
amount of copper leaching from ACQ type C preservatives treated southern pine.
Southern yellow pine was pressure treated with ACQ type C, having copper elemental
concentration of 0.5% and 0.8%, at an average copper retention of 3.2 kg/m3 and 4.9 kg/3
respectively. After post treatments treated cube samples were subject to laboratory
leaching following AWPA — E1 1- 97 (AWPA, 2005). Samples were subjected to three
point static bending test to evaluate the effect of post treatments on bending strength in
terms of modulus of elasticity (MOE) and modulus of rupture (MOR) according to
modified ASTM D-l43-94 (ASTM, 2005). Color change of samples before and after
ACQ type C and post treatments was also measured. Microwave post treatment
significantly reduced the amount of copper leaching from ACQ treated wood compared
to air dry post treated samples, with 30minutes being the optimum condition for 3%: inch
cubes. MOE and MOR of microwave and air dry post treated samples are not
significantly different from untreated samples. Color change, AE, of microwave post
treated samples are not significantly different from air dry post treated samples. In
conclusion microwave post treatment is effective at reducing leaching of copper from

ACQ type C treated southern yellow pine without reduction in bending strength and no

significant color change compared to air dry post treated samples.

Dedicated to my parents, sisters and loving friends

iii

ACKNOWLEDGEMENT

I would like express my sincere thanks to my major advisor Dr. D. Pascal
Kamdem for his guidance, support and patience throughout my masters program. I
express my sincere thanks to committee members, Dr. Stanley L Flegler and Dr. Pascal
Nzokou for their valuable suggestions and support.

I am obliged to my research group including Haihong J iang, Cui Weining, Joshua
Rawson, Kyle Wehner, Joseph Pennock and Smith Sundar for their support in my
research activities in the lab.

I express my sincere thanks to Ashok Raghavendra for his help in statistic
analysis of data.

The continued financial support from USDA-CSREES Eastern Hardwood
Utilization program in Department of Forestry, Michigan State University throughout

my research program is gratefully acknowledged.

iv

TABLE OF CONTENTS

LIST OF TABLE .................................................................................. viii
LIST OF FIGURES ................................................................................. ix

LITERATURE REVIEW ............................................................................ 6

2.1 Alkaline copper quat (ACQ) .............................................................. 6
2.2 Copper loss from alkali / amine copper based preservative
treated wood ............................................................................. 7

2.3 Interaction of alkali/amine based copper preservatives with wood
components .................................................................................... 8

2.4 Factors affecting fixation and leaching of preservative chemical from treated

wood .......................................................................................... 11
2.4.1 Species ....................................................................... 11
2.4.2 Source of active ingredients ............................................... 11
2.4.3 Retention of the treated wood ............................................. 13
2.4.4 Post conditioning temperature and relative humidity .................. 14
2.5 Microwave- Dielectric heating effect ............................................... 16
2.6 Post treatment methods to achieve fixation ........................................ 20
2.6.1 Kiln drying .................................................................. 20
2.6.2 Steaming ..................................................................... 21
2.6.3 Hot water fixation .......................................................... 21
2.6.4 Microwave heating ......................................................... 22
2.6.5 Radiofrequency (RF) heating ............................................. 23

2.7 Mechanical property of wood ........................................................ 23

2.7.1 Stress — strain relations ..................................................... 23
2.7.2 Strength and elastic properties of wood ................................. 25
2.7.3 Factors affecting mechanical property of wood ........................ 26
2.7.3.1 Specific gravity ..................................................... 26
2.7.3.2 Moisture content ................................................... 26
2.7.3.3 Temperature ......................................................... 27
2.7.3.4 Exposure to chemicals ............................................. 27
2.7.3.5 Fatigue ............................................................... 27

2.7.3.6 Treatment with preservatives and fire retardant chemicals..28

2.7.3.9 Conditioning and post treatment methods ..................... 29
MATERIALS AND METHODS .................................................................. 30
3.1 Summary of the experimental procedure ................................... 30
3.2 Specimen preparation ......................................................... 30
3.3 Preparation of ACQ type C treating solution ............................... 31
3.4 pH of the treating solution ................................................... 31
3.5 Pressure treatment of samples using ACQ type C ........................ 31
3.6 Retention (kg/m3) .............................................................. 32
3.7 Initial copper content in leaching blocks .................................. 32
3.8 Microwave post treatment ................................................... 33
3.9 Air drying post treatment .................................................... 33
3.10 Leaching of post treated samples .......................................... 33
3.11 Static bending strength ..................................................... 34

vi

3.11.1 Non destructive method to calculate MOE ...................... 34

3.11.2 Destructive method for MOE and MOR ......................... 35

3.12 Color change ................................................................. 35

3.11 Data analysis ................................................................. 37

RESULTS AND DISCUSSION .................................................................. 38
4.1 Retention ....................................................................... 38

4.2 Microwave and air dry post treatments .................................... 38

4.3 Leaching — Effect of microwave and air dry post treatments ........... 39

4.4 Mechanical properties — MOE and MOR ................................. 52

4.4.1 Non destructive MOE ............................................. 52

4.4.2 Destructive MOE .................................................. 52

4.4.3 Correlation of non- destructive and destructive MOE ........ 54

4.4.4 Destructive MOR .................................................. 54

4.3 Color change - AE ............................................................ 66
CONCLUSIONS .................................................................................... 70
APPENDIX ........................................................................................... 73
REFERENCE ....................................................................................... 113

vii

Table 2.1

Table 4.1

Table 4.2

Table 4.3

Table 4.4

Table 4.5

Table 4.6

Table 4.7

Table 4.8

Table 4.9

LIST OF TABLES

ACQ formulations ........................................................................ 6
Temperature and moisture content of the post treated samples... . . . . .......42
Initial copper content in six blocks used for leaching .............................. 43
Average cumulative copper leached from post treated

southern yellow pine, treated with ACQ type C, having 0.5% Cu elemental,
for a copper retention of 3.2 kg/m3 .................................................. 44

Percentage of copper leached from post treated southern yellow pine

treated with ACQ type C, having Cu elemental 0.5%,

for a copper retention of 3.2 kg/m3 .................................................... 46
Average cumulative copper leached from post treated southern yellow pine,
treated with ACQ type C, having 0.8% Cu elemental,

for a copper retention of 4.9 kg/m3 ................................................... 48
Percentage of copper leached from post treated southern yellow pine

treated with ACQ type C, having Cu elemental 0.8%,

for a copper retention of 4.9 kg/m3 ................................................... 50
Non- destructive MOE before and after ACQ type C and post treatments. . ...56
Destructive MOE after ACQ type C and post treatments ......................... 59

MOR of ACQ type C and post treated southern yellow pine ..................... 64

Table 4.10 Lightness ‘L’and chromaticity co-ordinates ‘a’ and ‘b’ of samples

after ACQ type C and post treatment ................................................ 68

viii

LIST OF FIGURES

Figure 2.1 Microwave heating of dielectric material .......................................... 19
Figure 2.2 Stress- strain relations .................................................................. 24
Figure 4.1 Average cumulative copper leached from post treated southern

yellow pine, treated with ACQ type C, having 0.5 % Cu elemental,

for a copper retention of 3. 2 kg/m3 .................................................. 45
Figure 4.2 Percentage of copper leached from southern yellow pine

treated with ACQ type C, having Cu elemental 0. 5%,

for a copper retention of 3. 2 kg/m3 ................................................. 47
Figure 4.3 Average cumulative copper leached from post treated southern yellow pine,

treated with ACQ type C, having 0. 8% Cu elemental,

for a copper retention of 4. 9 kg/m3 ................................................... 49
Figure 4.4 Percentage copper leached from southern yellow pine

treated with ACQ type C, having 03. 8% copper elemental,

for a copper retention of 4. 9 kg/m3 ................................................ 51
Figure 4.5 Non Destructive MOE of southern yellow pine

before and after ACQ type3 C (0. 5% Cu elemental) treatment

for a retention of 3. 2 kg/m3 and post treatment .................................. 57
Figure 4.6 Non Destructive MOE of southern yellow pine

before and after ACQ type3 C (0. 8% Cu elemental) treatment

for a retention of 4. 9 kg/m3 and post treatment ................................... 58
Figure 4.7 Destructive MOE after ACQ type C and post treatments ........................ 60
Figure 4.8 Non- Destructive MOE after post treatment and specific gravity relation. ....61
Figure 4.9 Destructive MOE and specific gravity relation .................................... 62
Figure 4.10 Relation of destructive and non- destructive MOE after post treatment. . ....63
Figure 4.11 MOR after ACQ type C and post treatments ..................................... 65

Figure 4.12 Color change, AE after ACQ type C and post treatments ...................... 69

ix

INTRODUCTION

Wood is used for many indoor and outdoor applications such as poles, fencing,
decking, siding and walls, furniture, flooring etc. Southern yellow pine (Pinus spp) is
widely used for decking through out the United States because of its treatability with
preservative chemicals. Several species such as long leaf pine (Pinus palustris), short leaf pine

(Pinus echinata), loblolly pine (Pinus taeda), slash pine (Pinus elliorti) are grouped as southern
pine (Wood Hand book, 1999).

Wood is prone to decay in conditions that favor the growth of micro organisms
like fungi. Wood can be made more durable by treatment with preservative chemicals.
‘Preservation’ is defined as treatment of wood to make it more durable (Corkhil, 1989).
However some of the preservative chemicals will migrate from timber to the
surroundings during outdoor exposure, known as ‘leaching’ (Corkhil, 1989). This
includes gaseous form of chemicals emitted from treated wood, disintegration of solid
form of chemical from the treated wood or the water soluble chemicals removed due to
the action of water. ‘Fixation’ is the insolubilization mechanism that converts water
soluble substances originally present in the treating solution to less soluble materials
within the wood (Nicholas 1973).

Preservative treated woods are economical and durable. However, we need to
ensure that chemicals used in treated wood do not harm the environment or other non
target organisms. For the last three decades wood treated with chromated copper arsenate
(CCA) has performed well in resisting decay and termite attack. Today there is growing

public sensitivity to leaching of chemicals from treated wood and disposal of chemical

treated wood. Because of these issues CCA registrants submitted a voluntary label
change to environmental protection agency (EPA). Effective since December 31, 2003
EPA label change limited the use of CCA treated wood products only for non- residential
applications (Lebow, 2004). Several waterborne copper based preservatives, with no
arsenic and chromium, have been formulated. Alkaline Copper Quat (ACQ), copper azole
(CA), borates are listed in the book of standards of AWPA (American wood preservers
association) as potential replacements for CCA. Most of the alternative preservatives use
copper as active ingredient because it is a very good fungicide with low mammalian
toxicity.

One of the limiting factors of amine based copper wood preservatives is the
leachability of copper to the surrounding area. Studies show that up to 35% of copper in
copper amine based preservative treated southern pine can be leached out (Waldron et a1
2003). Stabilization of copper in the treated wood is essential to reduce the depletion of
copper from treated wood to the environment.

Fixation occurs during the interaction of the ingredients of a formulation of wood
preservatives and components of wood. The interaction varies with the wood species, the
preservative formulation and post treatment temperature and relative humidity.

Copper undergo cation exchange reactions with wood components (Dahlgreen
and Hartford, 1972; Staccioli et al, 2000). Carboxylic group in hemicellulose and the
phenolic hydroxyl and ester group in lignin are the major ion exchange sites for copper
during copper amine wood reaction (J iang and Ruddick, 1999; Zhang and Kamdem
,1999; Kamdem and Zhang, 2000). Reaction between lignin guaiacyl group and copper

ethanolamine to form lignin- copper- ethanolamine complexes also have been reported

(Ruddick et al 2001). Copper can complexes with cellulose matrix to form Cu (H)
diamagnetic polynuclear clusters (Druz et a1, 2001). Carboxylic, phenolic and hydroxylic
ion exchange functionalities have different pKa values (Negative logarithm of
dissociation constant). Carboxylic acid groups of hemicellulose have a pKa value of 4,
phenolic groups of lignin have a pKa value of 10-12 and hydroxyl groups of cellulose
have a pKa value of 13-15 (Sjostrom, 1989). The different pKa value of the functional
groups may suggest a certain role of pH of treating solution in influencing the ion
exchange reactions between copper amine treating solution and wood. At lower pH or
neutral conditions, carboxylic acid groups in wood are dissociated. Increase in pH results
availability of phenolic groups for ion exchange. At very high pH, hydroxile groups
provide additional ion exchange sites (Rennie et al., 1987).

Copper sources, type of amine and amine to copper molar ratio of copper amine
solution have been reported to affect stabilization of copper in treated wood (Zhang and
Kmadem, 1999; Jiang and Ruddick, 2000; Lucas and Ruddick, 2002).

Since the number of reactive sites in wood is limited the retention of the treated
wood has a major role in the stabilization and leaching of copper in copper amine treated
wood. The preservative components will compete for the available reactive site in the
wood. It have been reported that the amount of preservative component leaching from
ACQ treated wood increases with increase in retention (Pasek, 2003; Tascioglu et al,
2005; Ung and Cooper, 2005).

Post conditioning temperature is also reported to favors fixation of copper amine
based preservatives, CA and ACQ (Pasek, 2003; Tascioglu et a1, 2005 ; Ung and Cooper,

2005). It is reported that lack of moisture in the treated sample as result of rapid drying

inhibits the ionic mobility necessary for fixation reaction (Chen et a1, 1994). Higher rate
and fixation extent have been reported for ACQ treated samples post treated at 500C
compared to samples post treated at 220C (Ung and Cooper, 2005).

Fixation can be achieved by air drying treated wood at ambient temperature.
Anderson (1990) provides an extensive review of accelerated fixation of CCA. Hot air
(Kiln drying), hot water, steam, and hot oil are some accelerated fixation methods. Each
method has limitations generally include longer processing time, waste water generation
and potential strength reduction. Accelerated fixation methods capable of minimizing
waste water generation in the case of steam or hot water and minimum strength
alterations are desirable.

Electromagnetic radiations, radio waves and microwaves, were used to season and
accelerate the fixation of CCA waterborne preservative and copper amine formulation in
southern yellow pine (Torgovnikov and Vinden 2000, Vinden et a1 2000, Smith et a1
1996, Avramidis and Ruddick, 1996, Fang et a1 2001, Cao and Kamdem 2004). Cao and
Kamdem (2004) reported 40-45% reduction in percentage of copper leached by 20
minute microwave.

Microwave wavelength ranges from 1 cm to 1 m in the electromagnetic spectrum
between radio waves and infrared waves. Microwaves can penetrate up to 2 inch
thickness of wood (Smith et a1, 1996). Microwave wavelength will allow energy to
penetrate into wood and heat the core faster to facilitate fixation with very little drying
(Smith et a1 1996).

Wood with high moisture content under high temperature heating will result in

discoloration as result of the formation of colored substances from the oxidation of

phenolic compound of the wood and the formation of dark material from the hydrolysis
of hemicellulose and lignin (Hon and Minemura, 2000). During microwave post
treatment temperature is not expected to rise more than 650C. So the discoloration occurs
as a result of high temperature heating may not occur after microwave post treatment.
Hydrolysis of hemicellulose and lignin during high temperature heating of wood can
result in strength reduction. As strength reduction occu as a cumulative thermal process
over time (Winandy, 1988), short time microwave may not results in strength reduction.
Even though microwave has been used as an alternative method to season and
accelerate fixation of wood preservatives in the recent past, the technology is not widely
used in the wood industry. No published studies have been done regarding the use of
microwave to reduce the migration of copper from ACQ type C treated southern yellow
pine. The aim of this project is to study the efficacy of microwave post treatment as a
method to reduce leaching of copper from ACQ type C treated southern yellow pine. The
impact or the effect of microwave on some properties of ACQ treated wood such as

bending strength and color change will also be evaluated.
Hypothesis was formulated as follows;

During microwave energy will be generated with potential side effects; reduction
in moisture content, increase in temperature, increase in rate of chemical reaction of
copper with hemicellulose, lignin and cellulose of wood, chemical degradation of

hemicellulose and lignin.

REVIEW OF LITERATURE

2.] Alkaline copper quat (ACQ)

ACQ consists of copper in the form of copper oxide (CuO) and quatemarium

compounds also known as quat mainly didecyldimethylammonium chloride (DDAC) or

alkylbenzyldimethyl ammonium compound (BAC). AWPA standardized several ACQ

formulations, ACQ type A, ACQ type B, ACQ type C and ACQ type D. The ACQ

formulations are summarized in table 2.1 (AWPA, 2005).

Table 2.1 ACQ formulations

 

ACQ type

Active ingredients

 

Copper
as CuO

Quat

Note

 

ACQ-A

50%

DDAC-50%

Copper content dissolved in ethanolamine
and! or ammonia to give solution having pH
range of 8-11. With ethanolamine the weight
of ethanolamine to copper oxide shall be
2.75 i: 0.25: 1, and with ammonia weight of
ammonia to cooper oxide shall be 1:1

 

ACQ-B

66.7%

DDAC-33.3%

Ingredients dissolved in aques ammonia
solution. The weight of ammonia to copper
oxide in the treating solution should be 1:1.

 

ACQ-C

66.7%

BAC-33.3%

Copper components dissolved in
ethanolamine and/or ammonia to give
solution having pH 8-11. With ethanolamine
the weight of ethanolamine to copper oxide
shall be 2.75 :t 0.25: 1, and with ammonia
weight of ammonia to copper oxide shall be
1:1.

 

ACQ-D

 

 

66.7 %

 

DDAC-33.3%

 

Copper content dissolved in ethanolamine
and/or ammonia to give solution having pH
range of 8-11. With ethanolamine the weight
of ammonia to copper oxide shall be 2.75i
0.25:1, and with ammonia weight of ammonia
to copper oxide shall be 1:1

 

 

2.2 Copper loss from alkali / amine copper based preservative treated wood

One of the limiting factor of new generation alkali/ amine copper based
preservatives is the migration of preservative components, specifically copper, from
treated wood. Leached out copper will either accumulate in soil or will percolate along
with rain water to ground water system or get washed in rivers and streams.
Accumulation of copper or for that matter any other heavy metals in water bodies at
higher level is toxic to many aquatic organisms.

The amount of copper leached from alkali/ amine copper based preservatives, in
laboratory and field conditions, have been studied by many researchers (Jin and Preston,
1993., Yamomota et al., 1999., Esser, 2000., Kennedy and Collins, 2001., Chung and
Ruddick, 2003., Lucas and Ruddick, 2002., Waldron et al, 2003., Pasek, 2003).

J in and Preston (1993) studied depletion of copper from ACQ treated southern
yellow pine following laboratory leaching, soil depletion and ground contact exposure
methods. They reported a 14.69% copper loss for samples treated with 6.4kg/m3 retention
from laboratory leaching test, 17.38%-17.60% copper loss for samples placed in soil bed
for 3-6 months, 19% copper loss for samples exposed in Hilo, Hawaii, for 44 months as
part of field stake study.

In a laboratory leaching test Lucas and Ruddick (2002) reported that copper
leaching from copper monoethanolamine, having solution concentration of 0.5% and 1%
(expressed as CuO), treated Scots pine is close to 15% and 25% respectively. In a similar
study Cao and Kamdem (2004) reported 15% copper leaching from southern yellow pine
treated with copper ethanolamine for 3.2 kg/m3 c0pper retention. Later Cui at al (2005)

reported a copper leaching of 5.7-18.8% from southern yellow pine cubes treated with

copper monothanolamine at copper retention varying from 2.12-5.70 kg/m3. Waldron et
a1 (2003) reported that almost 35% of copper available for leaching in ACQ treated
southern yellow pine.

Yamamota et a1 (1999) studied copper leaching from ACQ treated Japanese cedar
(Chriptomera Japonica). They reported a copper loss of 18711 g and 400 u g per cm3 for
ACQ retention of 2.7 kg/m3 and 5.7 kg/m3 respectively from accelerated laboratory
leaching method compared to copper loss of 50 ug and 97 pg per cm3 from outdoor
leaching test for 6 months. His study shows that more preservative components are
leached in accelerated laboratory leaching compared to the actual field exposure studies.

Shower test and submersion test were done by Esser et a1 (2000) to study the
amount of copper leached from ACQ treated wood. They reported 112 mg/m2 cumulative
copper leaching after 64 days submersion test and 67 mg/m3 after shower test.

Chung and Ruddick (2000) studied copper leaching from ACQ type C treated
hem-fir used as decking by exposing 1% ACQ treated hem- fir in natural conditions for
16 months. They reported a copper leaching of 4.96% in natural conditions.

2.3 Interaction of alkali/amine based copper preservatives with wood components

Copper amine is a primary ingredient in arsenic free, copper based, new
generation preservative such as ACQ and CA. Fixation chemistry of these preservatives
are not well understood. Several studies were done to understand the possible interaction
of active ingredients in the new generation preservatives with wood. Some of the
important literature is summarized below.

Studies show that copper undergo cation exchange reaction with wood

components during treatment (Dahlgreen and Hartford, 1972., Staccioli et a1, 2000).

Dahlgreen and Hartford (1972) reported copper cation and chromium cation exchange
reactions occur during CCA fixation. Staccioli et a1 (2000) did cation exchange capacity
tests of copper on saponified wood and holocellulose and reported that copper behaves as
bivalent cation with saponified wood and holocelloulose. They reported carboxyl group
of polyoses as the major group responsible for cation exchange reactions.

The pH of the treating solution has a major role in controlling the ion exchange
reactions. Carboxylic acid groups (pKa value 4) of hemicellulose are ionized in neutral
or weakly acidic conditions. Phenolic groups (pKa value 10-12) of lignin are ionized at
relatively higher pH. Same time hydroxyl groups (pKa value 13-15) of cellulose are
ionized only in very strong base (Sjbstrbm, 1989). Study by Pizzi (1983) shows that the
amount of adsorbed copper during CCA treatment increases as the pH increases. At lower
pH or neutral conditions, carboxylic acid groups in wood are dissociated. Increase in pH
results availability of phenolic groups for ion exchange. At very high pH, hydroxile
groups provide additional ion exchange sites (Rennie et al., 1987).

Ruddick (1992) and Hughes et a1 (1994) did electron spin resonance (ESR)
spectroscopic studies on fixation of copper amine. They suggested that copper amine
complexes bound with wood through oxygen in the wood. Interaction of copper
ethylenediamine solution with wood has been studied by J iang and Ruddick (1999) using
Fourier Transformed Infrared Spectroscoy (FT IR) and X-ray photoelectron spectroscopy
(XPS). Their study concluded that copper react with amine and wood components during
treatment, interaction of copper with wood primarily happening through carboxylic and

phenolic group of wood components in agreement with Zhang and Kamdem (1999).

Solid deposits formed in copper ethanolamine treated wood was studied by Zhang
and Kamdem (2000) using X-ray diffraction (XRD) technique. They concluded that
copper present in its cupric form in copper amine treated wood. Later Zhang and
Kamdem (2000) used Electron Paramagnetic Resonance Spectroscopy (EPR) to study the
possible stereochemistry of copper complexes formed during copper amine treatment,
and concluded that copper complexes in both treating solution and treated wood are in the
form of CuN202, where copper is legated with two nitrogen and two oxygen.

Ruddick et a1 (2001) studied reactions of vanillin, a lignin model compound with
monoethonolamine to better understand the role of guaiacyl functionality in lignin on the
formation of copper amine complexes in wood using Fl" IR, ESR and X ray
crystallographic studies and suggested that when wood is treated with ethanolamine
copper solution, reaction between the lignin guaiacyl group and ethanolamine copper
solution take place to form lignin- copper- ethanolamine complexes.

Druz et al (2001) studied interaction of copper with cellulose using Electron spin
resonance (ESR), X-ray diffraction (XRD) and concluded that pH value of solution and
light can influence the formation of copper complexes in cellulose matrix. They
suggested the formation of Cu (11) diamagnetic polynuclear clusters in cellulose treated
with copper solutions.

Recently Cao and Kamdem (2005) studied microdistribution of copper in copper
ethanolamine treated southern yellow pine using scanning electron microscopy coupled
with energy dispersive X-ray analysis in relation with the distribution of lignin, cellulose
and hemicellulose in the cell wall region. They found more copper in middle lamella and

cell comers compared to secondary wall of copper ethanolamine treated wood.

10

2.4 Factors affecting fixation and leaching of preservative chemical from treated
wood

Waterbome preservatives interact with wood components during treatment.
Stabilization and leaching of preservative component in wood there for varies with
species, preservative formulation, post treatment conditions and the conditions during
outdoor exposure. Better knowledge about the factors which determine the stabilization
of preservative in the wood is pertinent to device strategies to reduce the migration of
preservative components to the environment.

2.4.1 Species

Anatomical and chemical composition of wood varies from species to species. For
instance softwood and hardwood differ in anatomical and chemical make up, hardwood
contain less amount of lignin than softwood and their hemicellulose consists of primarily
xylan pentose sugar while softwood hemicellulose contains hexose sugar (Koch, 1985).
As water born wood preservatives react with wood components the stabilization reaction
may vary among species.

Ung and Cooper (2005) studied stabilization of ACQ type D in different species
white spruce (Picea glauca), balsam fir (Abies balsamea), redpine (Pinus resinosa) and
Jack pine (P. banksiana). The effect of species on stabilization and leaching of
preservative component was minor among the species group they evaluated.

2.4.2 Source of active ingredients

Copper source, type of amine and amine to copper molar ratio and pH of treating
solution will affect copper stabilization in copper amine based preservative treated wood,
which in turn will affect leaching of copper from the treated wood. Effect of copper

source, type of amine and amine to copper molar ratio of copper amine solution on

11

stabilization of copper in treated wood has been reported (Zhang and Kmadem, 1999;
Jiang and Ruddick, 2000; Lucas and Ruddick, 2002).

J iang and Ruddick (2000) compared leaching of copper 2- ethanolamine and
copper ethylnediamine treated Scots pine to study the influence of different amines, 2-
ethanolamine and ethylenediamine, on the fixation of copper in wood. They suggested
that if the copper to amine bonding is too strong, the preservative will remain unreacted
in wood and will tend to leach easily. Their study reported that copper ethylenediamine
treated samples retained lower amount of copper after leaching, showing that copper
insolubilisation/fixation reaction for copper ethylenediamine is less compared to copper
2-ethanolamine. They attributed this to the formation of very stable
[bis(ethelenediarnine)copper]2+ cation with a very polar interaction to wood and highly
basic nature of ethelynediamine. They attributed the low amount of copper leaching from
copper ethanolamine on its inability to produce stable cationic species and its ability to
form covalently bonded copper-amine complexes. Lucas and Ruddick (2002) also
studied the effect of type of the amine on copper stabilization in treated wood. They
reported a copper leaching close to 15% for Scots pine sapwood treated with 0.5% copper
monoethanolamine compared to a copper leaching close to 62% for 0.5 % copper
ethylenediamine treated wood.

Zhang and Kamdem (1999) studied the effect of copper source, type of amine and
amine to copper molar ratio of copper amine solutions on copper stabilization in treated
southern yellow pine. They reported 12% copper loss from copper hydroxide systems,
10% copper carbonate, 7% from copper sulphate and 6% from copper nitrate from wood

treated with 0.5% copper amine. In the same study they reported that higher molecular

12

weight of amine can increase copper stabilization. They reported a copper loss of 5% for
tertiary amine systems compared to 12% for monethanolarnine. In the same study they
emphasized that increase in amine to copper molar ratio reduce the ability of copper
fixation in wood and there for increase the leachability of copper in treated samples in
agreement with Lucas and Ruddick (2002). An increase in copper leaching from 15 % to
38% was reported by Lucas and Ruddick (2002) when amine to copper molar ratio
increased from 6:1 to 8:1 in case of 0.5% copper monoethanolarnine treated Scots pine.

Druze et al (2001) studied the amount of copper stabilization in cellulose treated
with copper sulphate and copper carbonate at different pH. Their study shows an increase
in copper adsorption in cellulose with increase in pH. They reported a copper absorption
of 1-2 mg/g of cellulose at pH <2.5 compared to a copper absorption of 8-9 mg/g of
cellulose at pH >8.5.
2.4.3 Retention of the treated wood

Copper amine — wood reactions are explained by ionic exchange reactions with
carboxylic and phenolic groups of wood componets (J in and Preston, 1993; Staccioli et
a1, 2000). Loubinoux and Malek (1992) and Loubinoux et a1 (1992) concluded that
fixation of quaternary ammonium salts related to the number of anionic sites in wood and
involve cation exchange reactions. Since the number of these reaction sites are limited
copper and quaternary ammonium compounds will compete for the same reaction sites in
the wood. At higher retention more preservative components are in the wood competing
for the limited reactive sites. In that case some of the preservative components react with
the available reactive sites and the remaining chemical remain in wood unreacted. The

effect of ACQ retention on fixation and leaching has been reported. Leaching of chemical

13

components will be more for high retention samples when compared to low retention
samples (Pasek, 2003, Tascioglu et a1, 2005; Ung and Cooper, 2005).

Tasciouglu et a1 (2005) reported 91% and 95% adsorption of CuO in red pine
treated with ACQ solution having concentration of 0.75% and post treated at 22°C and
50°C respectively compared to 33% and 43% for samples treated with 3% ACQ
solution. It can be concluded from this study that increase in concentration of treating
solution may result in higher retention at the same time will result in low amount of
preservative component stabilized in the wood.

Ung and Cooper (2005) studied the copper stabilization in ACQ-D treated white
spruce (Picea glauca), balsam fir (Abies balsamia L), redpine (Pinus resinosa Ait), Jack
pine (Pinus banksiana Lamb), Douglas fir (Pseudotsuga menzeissi) and aspen (Populous
tremuloides). Their study reported that copper stabilized much faster when lower ACQ
retentions samples conditioned at 50°C compared to high retention samples conditioned
at 22°C. They reported that high retention treatments held without drying at 22°C took
five weeks or more for copper to stabilize in wood.

2.4.4 Post conditioning temperature and relative humidity

Effect of temperature and moisture on fixation of CCA has been extensively
studied by many researchers. The rate of CCA fixation is highly temperature dependent,
higher the temperature, faster the fixation reaction (McNamara, 1989; Cooper and Ung,
1992; Smith et al, 1996; Cooper and Ung 1989; Cooper et al, 1997). CCA fixation time
will be less for high humidity fixation compared to the fixation under drying conditions
(Alexander and Cooper, 1993; Chen et a1 1994). This can be explained by the fact that

moisture content decreases rapidly during drying conditions. Decrease in moisture

l4

content below fiber saturation point interfere the mobility of CCA component in the
wood and decreases fixation (Kaldas, 1996., Dahlgreen and Hartford, 1972).

The effect of temperature on copper amine based preservative has been reported.
It is reported that higher temperature favors fixation of copper amine based wood
preservatives (Pasek, 2003; Ung and Cooper, 2005; Tascioglu et a1, 2005). Tascioglu et al
(2005) reported higher rate and amount of preservative fixation for ACQ treated red pine
post treated at 500C for 7 days compared to samples post treated at 22°C for 7 weeks.
They reported CuO adsorption of 91%, 66%, 49% and 33% for redpine cubes treated
with ACQ solution concentration of 0.75 %, 1.5%, 2.25% and 3.00% respectively and
post treated at 50°C compared to adsorption of 95 %, 88%, 64% and 43% for samples post
treated at 220C.

Ung and Cooper (2005) studied copper stabilization in ACQ treated wood at
different retentions and post conditioned at 220 and 50°C. Their study reported that
samples post conditioned at 500C took 1-5 day for copper stabilization, same time
samples post conditioned at 22°C took 4-55 days, depending on species and retention.
They reported a copper leaching of 6.1-16.4% for samples stabilized at 50°C compared to
4.8- 10.7% for samples stabilized at 220.

These studies show that high temperature and high moisture content is essential
to achieve fixation. High temperature accelerate fixation reaction and high moisture
content acts as a medium to facilitate the movement of unreacted chemical from one part

of wood to other to have maximum fixation.

15

2.5 Microwaves - Dielectric heating effect

Microwave radiations are electromagnetic radiations with wavelength of 1 cm to
1m, and frequencies of 30 GHz to 300 MHz respectively. In electromagnetic spectrum
microwaves lies in between infrared radiation and radio frequencies. Wavelength ranges
of 1cm to 250m of microwaves used for RADAR transmission and remaining range of
wavelength is used for telecommunication. To avoid the conflicts with communication
purposes microwave heaters are operated either at 12.2 cm (2.45GHz) or at 33.3 cm (900
MHz) unless the heater is covered to avoid radiation losses (Mingos and Baghurst, 1997).

A material capable of being heated with microwave energy is said to be polar.
Polar refers to molecules have both positive and negative opposing charges (dipolar).
When microwave energy field alternates from negative to positive at particular frequency
results in the rotation of molecules of the material with positive and negative. The friction

generated by the molecules rubbing together as they rotate generates heat (Fig 2.1).

In liquids and solids molecules are not free to rotate independently. Materials can
be heated up by applying high frequency electromagnetic waves. High frequency
electromagnetic waves behave like an electric field and apply force on charged particles.
A current will be induced if the particles in the substances can move. If the charge
carriers are restricted to certain regions they will move until an opposite force balances
the movement, the result is dielectric polarization. Conduction and dielectric
polarizations are source of microwave heating and the microwave heating mainly

depends on frequency and power applied (Mingos and Baghurst, 1997).

16

Total polarization can be occurred for a dielectric material,

a, =ae +aa +ad +ai

Where ae = Electronic polarization, aa = Atomic polarization, ad = Dipolar
polarization, a,- = Interfacial polarization.

The electronic polarization is a result of the alignment of electrons around
particular nuclei. Atomic polarization is due to the relative displacement of nuclei due to
unequal distribution of charge within the molecule. Dipolar polarization arises from the
orientation of permanent dipoles in the electric field. Interfacial polarization or Maxwell-
Wagner effect occurs when there is build up of charges at interfaces. Time scale for of

ac and era are faster than the microwave frequencies and therefore will not contribute to
the dielectric heating. At the same time scale of ad and possibly of al- are comparable

with microwave frequencies and add to dielectric heating of microwave. Importance of

al- in microwave region is not well documented (Mingos and Baghurst, 1997).

Dipolar polarization of water is as an effect of momentum formed from the
differing electro negativities of the oxygen and hydrogen. Temperature of the water
hardly rises at low frequencies because the time taken by electric field to change the
direction is more than the response time of the dipoles. In microwave frequency time of
field change is same as the time change of dipoles. Because of the torque they experience
they rotates and results in polarization lags behind the changes of electric field. The lag
indicates that the water absorbs energy from the field and gets heated up (Mingos an

Baghurst, 1997).

17

Dielectric constant, e. and dielectric loss, 6" mainly governs dielectric properties
of materials. Dielectric constant is the ability of molecule to be polarized by the electric
field. Dielectric loss indicates the efficiency of electromagnetic radiation can be
converted to heat. The ratio of dielectric loss and dielectric constant is loss tangent, tan 6 ,
defines the ability of a material to convert electromagnetic energy to heat energy at given
temperature and frequency (Mingos an Baghurst, 1997).

Even though maximum heating is for high frequency microwaves around 20 GHz,
domestic microwave oven operates at low frequency microwave at 2.4SGHz to ensure
heating of materials through the interior. If we are keeping the frequency for maximum
heating rate (high frequency) it penetrates only the outer region.

The rate of increase of temperature due to the electric field created by microwave

can be determined by the following equation.

it 2
.§_T- : Constant X ibis.—
51 pCp

Where E ,zms is the field intensity, pis the density, Cp specific heat capacity,

£"is dielectric loss, f is frequency (Mingos an Baghurst, 1997).

18

 

Figure 2.1 Microwave heating of dielectric material

2.6 Post treatment methods to achieve fixation

Anderson (1990) in his review paper describes kiln drying, hot water fixation and
steam injection as post treatment methods to accelerate fixation of CCA in treated
lumber. Feasibility of using microwaves and radio waves to accelerate fixation of CCA
have been reported (Smith et al, 1996). Recently Cao and Kamdem (2004) used
microwave post treatment to accelerate fixation of copper amine in southern yellow pine.
These accelerated post treatment methods are discussed below.

2.6.1 Kiln drying

In kiln drying temperature and relative humidity inside the kiln is adjusted using
dry bulb and wet bulb temperature. Drying schedule varies with species, the idea is to dry
the lumber with less defects. Temperature limit suggested for kiln drying CCA treated
southern yellow pine is 70°C (Anderson, 1990). One of the disadvantages of kiln dried
CCA treated sample is leaching of high amount of CCA components compared to air
dried samples (Conardie and Pizzi, 1989; Lee et a1, 1993; Chen et al, 1994).

Chen et a1 (1994) studied heat transfer and wood moisture effect on CCA fixation
in red pine poles in different drying conditions. They observed slower fixation under
drying condition. They hypothesized several possible reasons for slower fixation under
drying conditions. (1) Low rate of heating of wood in a low humidity environment:
Under low humidity conditions heat capacity of kiln air is lower and the heat transferred
to wood surface is lower. And also under drying conditions the thermal energy reaching
wood surface is used for the evaporation of water at the wood surface and is not available
to get transferred in to the wood to accelerate fixation. (2) Evaporation of moisture during

drying will cool the wood surface and slower fixation rate: Under dying conditions

20

evaporation from the surface will cool the wood in proportion to the rate of drying. Thus
drier the kiln atmosphere lower the wood temperature. Since rate of fixation is depend on
wood temperature not on ambient temperature (Christensen, 1990) the fixation rate will
be reduced. (3) Lower moisture content of wood resulting from the drying environment
may reduce fixation rate: If the wood moisture content drops the mobility of CCA
reaction products in the wood may be reduced resulting in retarded fixation reactions.
2.6.2 Steaming

In this method treated samples are exposed to steam at high temperature. Steam at
110-1200C for one hour is sufficient to induce complete fixation of CCA (Anderson,
1990). Steaming offers the benefits of high thermal capacity, low recycled water and low
sludge formation. Higher operating temperature can degrade wood components and cause
resin mobilization (Anderson, 1990). For instance in southern yellow pine resine

exudation occurs above 80°C causing unsightly green flecks (Anderson, 1990).
2.6.3 Hot water fixation

In this process after treatment the temperature of the lumber is raised by
application of hot water either under pressure or at atmospheric pressure (Anderosn,
1990). Hot water fixation is of two types, one is MSU fixation process and the other is
atmospheric pressure hot water fixation. In MSU fixation process lumber is treated by an
empty cell process and the temperature of the lumber is raised by application of hot water
under pressure prior to draining the excess treatment solution. In atmospheric pressure
hot water fixation process hot water at atmospheric pressure in an open bath is used as the

heat transfer medium.

21

2.6.4 Microwave heating

Dielectric heating effect of microwave to heats up polar material has been widely
used in the food industry. Microwave for conditioning the wood and to achieve fixation
of preservative chemicals is not a current practice in wood industry. However studies
show that high temperature and high moisture content is essential to achieve fixation of
waterborne preservative in wood. Moisture content of treated wood coming out of the
treating cylinder is high. As microwave can heats up materials across its cross section to a
high temperature very quick before substantial moisture reduction from treated wood, it
can be utilized to accelerate fixation of wood preservative in wood.

Smith et a1 (1996) studied the feasibility of using microwaves and radio waves to
accelerate the fixation of CCA components in southern yellow pine. They treated
southern yellow pine with CCA for ground contact and marine use. Immediately after
treatment samples were post treated using electromagnetic waves for 0, 10, 20 and 30
minutes with both RF (radio frequency) at 75MHz and microwaves at 2.4SGHz. They
monitored ambient fixation for 0, 0.5, 1, and 6 days. They reported that 99% of the
chromium was fixed in 30 minutes of microwave. They suggested that microwaves were
able to fix CCA preservative in southern yellow pine in minutes rather than hours or
days.

Cao and Kamdem (2004) used microwave post treatment to reduce the amount of
copper leaching from copper-ethanolamine (Cu-EA) pressure treated southern yellow
pine cubes measuring 0.75 by 0.75 by 0.75 inch. In their experiment they used a
microwave of 2.4SGHz at a low power level of 100 watt to avoid over heating, and to

lower the impact of treatment on mechanical, physical and chemical pr0perties of treated

22

specimen. Their results showed that microwave post treatment reduced the amount of
copper leached in samples having 6.4kg/m3 and 3.2 kg/m3 copper retention from 47 to
20% and 15% to 8.4% respectively after 20 minute microwave.
2.6.5 Radiofrequency (RF) heating

Radio frequency has been used to accelerate fixation of CCA in wood (Smith et
a1, 1996; Fang et al, 2001). Fang et al (2001) investigated the use of radio-frequency at
atmospheric pressure to accelerate the fixation of CCA in Douglas —fir (Pseudotsuga
menziesi), western red cedar (T huja plicata) and red pine poles. RF heating of these
species resulted in complete conversion of hexavalent chromium to the trivalent form.
The fixation time was reduced to less than 5 hours with RF at 13.56 MHz.
2.7 Mechanical property of wood

Wood is an orthotropic material; that has unique and independent mechanical
properties in the three mutually perpendicular axis, longitudinal radial and tangential.
2.7.1 Stress - strain relation

‘Stress’ is the applied force per unit area of a material. It is usually expressed in
psi (lb/inz) or in pascal (N/mz). External force applied to a body will create internal stress
resulting in deformation of the body. The deformation can be expressed as ‘strain’. Strain
is defined as the change in length per unit of length in the direction of the stress and is
unit less. Stress — strain relation is shown in the following figure (Fig 2.4). Strain will
increase proportionally with the stress applied up to the ‘proportional limit’ or ‘elastic
lirrrit’. The region of curve below the proportional limit is called ‘elastic region’. In the
elastic region when the stress is removed the body can regain its original shape. Below

the proportional limit the ratio of stress and strain is a constant called the

23

,(S

Plastic region

    

Fracture point

Stress

Elastic region

 

 

Strain

Figure 2.2 Stress- strain relations

24

‘modulus of elasticity’ (MOE). After elastic limit strain is not proportional to stress
applied, each unit of stress will result in more strain than that of the strain produced
below the proportion limit for a unit stress. This will continue till the ‘fracture point’.
Fracture point is the point where the particular material can withstand maximum stress
without failure of the material. Stress after the fracture point will result in the failure of
the specimen. The region of the curve from elastic limit to fracture point is called ‘plastic
region’ (Bowyer et a1, 2003).
2.7.2 Strength and elastic properties of wood

There are so many elastic and strength properties of wood discussed in the
literature. Modulus of elasticity (MOE) and Modulus of elasticity parallel to grain
(Young’s modulus) are used to describe the elastic property of wood. Strength property
of wood is described by bending strength (modulus of rupture, MOR), compression
strength parallel to grain, compression perpendicular to grain, tension strength parallel to
grain, shear strength parallel to grain, toughness and hardness. Wood that is strong with
respect one strength property may not be strong when measuring a different property. The
type of mechanical property has to be measured for a wood product is therefore
determined by the type of loading to which that product will be exposed.

Modulus of elasticity (MOE): It is generally determined by use of a bending test.
It reflects the stiffness and strength of long beams. MOE can be calculated by the

following equation. MOE is generally expressed in psi or pascal.

3
_ PL
MOE ' X810

25

Where P is the concentrated centre load, D is deflection at mid span resulting from P ,
L is the span of the sample, I is moment of inertia a function of the beams section for

beam with rectangular cross section (Bowyer et al, 2003).

_wxd3
12

I

 

Where w is width, (1 is depth (Bowyer et a1, 2003).
Bending strength: Modulus of rupture (MOR): It reflects the maximum load
carrying capacity of wood in bending. Bending strength can be calculated by the

following equation. MOR is generally expressed in psi or pascal.

MOR =1.5PL
bd2

Where P is the breaking load, L span of the specimen, b width of specimen, d depth of
specimen ((Bowyer et a1, 2003).
2.7.3 Factors affecting mechanical property of wood:
2.7.3.1 Specific gravity

It is an excellent index of mechanical property of a species. Mechanical property
within a species has a linear relationship with specific gravity (Wood Handbook, 1999).
2.7.3.2 Moisture content

Strength and elastic properties of wood increases as wood dries below fiber
saturation point. This increase in mechanical property is due to the removal of water from
the cell wall, which results in the pulling of long chain molecules closer and become
more tightly bonded (Bowyer et a1, 2003). Watkinson and Gosliga (1990) studied
moisture content induced by different relative humilities on mechanical properties of

hardboard, particleboard and medium density fiberboard. Their result show that 95%

26

relative humidity increased the moisture content to 22% and reduced MOE to 47-63%. At
high relative humidity moisture content of wood will be high. Similar results were
obtained by McNatt (1974).
2.7.3.3 Temperature

Mechanical properties of wood have an inverse relationship with temperature. It
decreases with increasing temperature when it is heated and will decrease when it is
cooled. The reduction of strength is minimum at temperature equal or less than 100°C.
Strength reduction at high temperature is cumulative thermal process over time, occurring
as result of degradation of wood components at elevated temperature (W inandy, 1988). In
a review paper Winandy (1988) reported 8-35% reduction in MOR in CCA treated wood
exposed to elevated temperature ranging from 870 to 138°C. Strength reduction occurring
during high temperature heating will be more sensitive if the moisture content of wood is
high (Bowyer et al, 2003).
2.7.3.4 Exposure to chemicals

Exposure of wood to severe acidic or alkaline environments can result in loss of
strength from hydrolysis of cellulose, oxidation by oxidizing agents and delignification.
Soft wood are more resistant to strength loss resulting from chemical exposure compared
to hard wood. In general wood which are less permeable to moisture movement are
resistant to chemical degradation (Bowyer et a], 2003).
2.7.3.5 Fatigue

It is the ability of material to retain its strength when subject to repeated severe
loading. Strength property of wood will decrease when it is exposed to repeated loading.

Repeated stress has more effect when defects such as knots are present.

27

2.7.3.6 Treatment with preservatives and fire retardant chemicals

Oilbome preservatives generally will not result in appreciable strength loss
because they are not reacting with cell wall components. Same time most of the water
based wood preservatives have some heavy metal oxides as their active ingredient and
they can undergo hydrolytic reduction with sugar components of cell wall. This oxidation
of cell wall components may result in strength reduction (Winandy, 1988).

However studies by Winandy et al (1985) on strength properties of CCA treated
air dried southern pine showed that reduction in MOR, MOE, work to maximum load
(WML) and maximum crushing strength (MCS) is not significant for samples treated
with CCA retention of 0.25 — l pcf. They reported significant reduction in WML for
southern yellow pine treated with CCA retention of 2.5 pcf.

Winandy (1988) suggested that the effect of water based preservatives on strength
can be magnified if the treated wood is kiln dried at extreme conditions. Winandy
(1988) reported 8-35% reduction in MOR of CCA treated wood dried at temperature
range of 87-1380C.

Effect of ACQ and kiln dry post treatment on MOE and MOR of southern yellow
pine is reported (Barnes et a1, 1993). They reported no significant difference in MOE and
MOR between untreated and southern yellow pine treated with ACQ for retention of
9.6kg/m3.

LaVan et a1 (1996) studied the mechanical property of fire retardant treated
plywood, made of southern yellow pine, after cyclic temperature exposure. They pressure
treated southern pine plywood with guanylurea/boric acid (GUP/B) and mono ammonium

phosphate. They kiln dried the treated samples at 43°C. After 9 days the temperature was

28

changed to 490C for another 7 days. Their result show that cyclic temperature exposure
ranging from ambient to 650C have minimal effect on strength properties.
2.7.3.7 Conditioning and post treatment methods

Reduction in strength properties associated with the use of steaming and kin
drying, to condition wood, and to post treat waterborne CCA and ACQ treated wood
have been reported. (Anderson, 1990; 1987, Bendsten et al, 1983; Barnes et a1, 1993).
Reduction in strength properties

Collins and Vinden (1987) studied strength reduction in radiate pine after
conventional steaming. They steam conditioned radiate pine in an autoclave, MOE and
MOR of the steam conditioned samples were compared with control samples. Their
results show losses in both MOE and MOR at fairly low steam temperature and steam
times. They observed 11% loss in MOE after steaming at 115°C for 1-3 hr. The loss was
increased to 16% when the steaming temperature and duration was increased to 130°C for
5 hr. They observed more loss in MOR after steaming. One hour steaming at 115°C
resulted in 21% loss in MOR and 35% when steamed at 130°C for 5 hr.

Bendsten et a1 (1983) evaluated bending properties of longleaf pine treated with
water borne ammonical copper arsenate (ACA), CCA type A, CCA type B at retentions
ranging from 0.25 pcf to 2.5 pcf. After treatment they let the samples either to be air dried
at 80°F or kiln dried at 1400F. Their results show that for all materials kiln dried after
treatment MOR decreased with increasing retentions for all preservatives.

Barnes et a1 (1993) reported reduction in MOR of southern yellow pine treated
with ACQ for retention of 9.6kg/m3 and kiln dried at 71°C compared to the untreated

samples.

29

MATERIALS AND METHODS

3.1 Summary of the experimental procedure

Defect free southern yellow pine was selected to prepare required sample size for
leaching, strength and color property studies. Samples were conditioned at 21°C and 65%
relative humidity to an equilibrium moisture content of 10i 2%. Conditioned samples
were treated with ACQ type C and subjected to two post treatments air drying and micro
waving at different durations. After post treatments samples for leaching study were
subjected to leaching to study the amount of copper leaching from different post treated
southern yellow pine according to AWPA-E11-97 standard (AWPA, 2005). Samples
were subjected three point static bending test to evaluate the effect of post treatments on
bending strength in terms of MOE (Modulus of elasticity) and MOR (Modulus of
rupture) according to ASTM-143-94 standard (ASTM D, 2004). Color change of samples
before and after ACQ type C and post treatments were also measured. Data obtained for
leaching, strength change, and color change after post treatments were analyzed.
3.2 Specimen preparation
3.2.1 Specimen preparation for leaching study

Specimens measuring 19 by 19 by 19 :1: 0.2 mm were prepared according to the
sample preparation described for laboratory leaching in AWPA-E1 1-97 standard
(AWPA, 2005). Samples were taken from one board of southern yellow pine having a
specific gravity of 0.5 to reduce the board to board density variation. Samples with

similar density were selected for the study.

30

3.2.2 Specimen preparation for static bending test: For non-destructive MOE and
Destructive MOE and M 0R

Samples were prepared southern yellow pine sap wood board having a specific
gravity of 0.54 according to specimen preparation described for three point static bending
of clear specimen in the ASTM D-143-94 standard (ASTM, 2005) with a modification in
sample size. Flat sawn samples measuring 1.27 by 1.27 by 22.86 cm (.5 by .5 by 9 inch)
were prepared, keeping a span to depth ratio of 14, specified in the standard. Sample size
was reduced to facilitate easy rotation during microwave post treatment to achieve even
heating of the samples.
3.2.3 Specimen preparation to study color change

The specimen size measuring 0.5 by 7 by 10 cm was prepared to study color change.
3.3 Preparation of ACQ type C treating solution

NW 100 with a copper elemental concentration of 7.4% was received from
OSMOSE. Stock solution received was diluted for ACQ type C formulation having
copper elemental concentration of 0.5% and 0.8%.
3.4 pH of the treating solution

pH of the treating solution was measured using pH meter Consort-P601.
3.5 Pressure treatment of samples using ACQ type C

Samples conditioned for equilibrium moisture content were pressure treated with
ACQ type C in a cylindrical tank having a radius of 15.2 cm (6 inch) and a length of 47
cm (18.5 inch) using an initial vacuum of 84.6 KPa (25 inch mercury) for duration of 20

minutes and a pressure of 1034 KPa (150 Psi) for 60 minutes following a final vacuum

31

for 20 minutes. Samples were weighed before and after treatment to determine solution
pick up.
3.6 Retention (kg/m3)

Copper retention of the ACQ type C treated sample was calculated using
following equation

WGxCxlO
V

Copper (Cu) retention (kg/m3) =
Where (WG ), weight gain of the sample in grams after treatment: W2 - W1, W1 is
weight of the sample in grams before the treatment, W2 is weight of the sample in

grams after treatment, C is weight of copper grams in 100g treating solution, V is

volume of the sample in cm3 or ml.

 

1.25

Copper oxide (CuO) retention (kg/m3) = WG XVC x 10 x

WGxCx10X1.25

AC t c t t' k 3:
Q ype re en ron( g/m) Vx.667

 

Note: Molecular weight of Cu: CuO 2 l: 1.25

Weight CuO: ACQ type C = 0.667: 1
3.7 Initial copper content in leaching blocks

Initial copper content in each block was calculated using the solution pick up
(weight gain after treatment) and concentration of treating solution using the following
equation.
Initial copper content (mg) =WG x C x 1000
Where W0 is weight gain after treatment (solution pick up) in grams, C is concentration

of treating solution in %.

32

3.8 Microwave post treatment

Samples were subjected to microwave post treatment in a Gold star multiwave
microwave oven with a frequency of 2.45 G Hz and a power level of 100W for duration
of 0, 10, 20 and 30 minutes (Smith et a1, 1996; Cao and Kamdem 2004) Microwave was
done at low power (100W) to avoid over heating. Weight of the samples before and after
post treatment and dry weight of the corresponding samples were used to calculate the
moisture content after post treatment.

High performance non contact thermometer model MX4 from Raynger (Raytek,
Sata Cruz, CA, USA) was used to monitor surface temperature of samples during
microwave post treatments.
3.9 Air drying post treatment

After ACQ type C treatment samples were kept in a room set at 21°C (70°F) and
65% relative humidity. Air drying was continued for 21 days.
3.10 Leaching of post treated samples

One hundred and sixty samples were prepared for this study. Samples were
weighed and grouped in to 2 groups of 80 samples and pressure treated with ACQ type C
having copper concentration of 0.5% and 0.8%. After ACQ treatment group of 80
samples were divided into 5 small groups of 15 samples each and subjected to post
treatments. The remaining 5 samples were used for acid digestion.

Three out of 15 samples from each post treatment group was randomly selected
for further chemical analysis if needed. The remaining 12 samples of each post treatments

were subjected to leaching according to the method described for laboratory leaching in

33

AWPA-E11-97 (AWPA, 2005). Copper content in the leachate collected during 0, 6, 24,
48 hours then after every 48 hours of the leaching study was measured using Perkin
Elmer 3110 Atomic absorption spectrometer. The amount of copper leached to the 300
ml water was calculated using the following equation.

Copper content in 300 ml leachate (mg) = AA x DF x 0.3

Where AA is atomic Absorption reading (mg/1), DF , dilution factor, which is the ratio
of final volume to initial volume during dilution.

Cumulative copper leached in % (compared to the initial copper content) was
further calculated. Percentage of copper leached from different post treatment groups,
after 14 days of leaching were compared.

3.11 Static bending strength
3.11.1 Non destructive method to calculate MOE

For this particular study load required making a displacement of 0.19 cm (.075
inch) (Below the proportional limit) on each of the samples were measured before
treatment using Universal testing machine, Instron model No -4206, following the
procedure described in the ASTM D-143-94 (2004) for three point static bending. MOE
of each sample was further calculated, from the load and displacement measurement,

using the following equation.

3
_ PL
MOE ’ 4310

Where P is the concentrated centre load, D is deflection at mid span resulting from P ,
L is the span of the sample, I is moment of inertia a function of the beams section for

beam with rectangular cross section (Bowyer et a1, 2003).

34

_wxd3
12

 

I

Where w is width, d is depth (Bowyer et al, 2003).

Load required making the same displacement after post treatments were measured
on the same position of the sample to study any change in MOE after post treatment.

One hundred and twenty samples were prepared and conditioned. Load required
to make a displacement of 0.19 cm (.075 inch) was measured on each sample to calculate
MOE. Samples were grouped into 2 groups of 60 samples and treated with ACQ type C
having elemental copper of 0.5% and 0.8%. After ACQ type C treatment each treatment
group of 60 samples were divided in to 4 small groups of 15 samples each and subjected
to post treatments. After the post treatment samples were conditioned. Load required to
have the same of 0.19 cm (.075 inch) was measured using Universal testing machine,
Instron (Model No: 4206).
3.11.2 Destructive method for MOE and MOR

The samples used for non destructive method to calculate MOE were further used
to measure MOE and MOR using Universal testing machine, Instron (Model-4206)
following the procedure described in the ASTM D-143-94 (2004) for the three point
bending of clear samples with the specimen size modification described in the earlier
section. Load was applied upto failure to measure MOE and MOR. MOE and MOR
obtained for the post treated samples were compared with 15 control samples (without
ACQ type C treatment and post treatments).
3.12 Color change

Twenty samples each were treated with ACQ type C having copper elemental of

0.5% and 0.8%. Samples were divided in to 5 groups of 4 after ACQ treatment and

35

subjected to post treatment. Color change of the wood surface before and after post
treatment was determined according to ISO 2470 standard (Anonymous 1999) using a
Micro flash Elrepho model 200 Reflectrometer from Data Color International, Charlotte,
NC with CIELAB system. The CIELAB system is characterized by three color
parameters ‘L’, ‘a’ and ‘b. The ‘L’ axis represent the lightness, ’a’ and ‘b’ are the
chromaticity co-ordinates. In the CIELAB co- ordinate ‘+a’ is for red, ‘-a’ is for green,
‘+b’ for yellow, ‘-b’ for blue. ‘L’ varies from 100 (white) to 0 (black). These values were

used to calculate color change (AE), using the following equations.

 

AE= \/AL2 +Aa2 +Ab2

AL=Lf-Li
Aa=af —a,-
Ab=bf-bi

Where Lf, af, bf are final values of lightness L and chroma ‘a’ and ‘b’
L,, a,-, b,- are initial lightness L and chroma ‘a’ and ‘b’
Average of 5 readings per sample was taken for this study.

Color change after post treatments were compared to study the effect of post treatment in

color change.

36

3.13 Data analysis

A factorial experimental design with post treatment, at different levels, and ACQ
retention at two levels as factors was used for this study. Data was analyzed using
factorial analysis of variance (ANOVA). Residual diagnostics was performed to check
for the fulfillment of the AN OVA assumptions and eventually to select appropriate data
transformations. Interaction between post treatment and ACQ type C retention were
studied as a primary step. Post treatments were compared either grouping the post
treatment results for different retentions (if the interaction is insignificant) or keeping
them separate (if the interaction is significant). Multiple comparisons were done where it

was relevant.

37

RESULTS AND DISCUSSION

4.1 Retention

ACQ type C treating solutions having copper elemental concentration 0.5% and
0.8% had a pH of 9.3 i 0.1. Samples pressure treated with both the treating solutions
were observed to have good solution pick up close to 100%. Average copper retention
calculated for samples treated with 0.5% copper elemental ACQ type C was 3.2 kg/m3.
This corresponds to an average CuO retention of 4 kg/m3 and ACQ retention of 6 kg/m3.
Samples treated with 0.8% copper elemental ACQ type C had an average copper
retention of 4.9 kg/m3, which corresponds for an average CuO retention of 6.1 kg/m3 and
ACQ retention of 9.2 kg/m3.
4.2 Microwave and air dry post treatments

Temperature and moisture content change during microwave and air dry post
treatments were summarized in table 4.1. Surface temperature of the samples before post
treatment was about 19°C. A rapid increase in surface temperature of the samples was
observed during microwave post treatment. Surface temperature of the post treated
samples increased to a maximum of 64- 700C, even with 10 minutes of microwave. Not
much change in surface temperature was observed with 20 and 30 minutes microwave
post treatment. Treated samples had an average moisture content of 115% immediately
after treatment, but this moisture content observed to decrease during microwave post
treatment. Moisture content of the samples reduced to 72%, 30% and 13% respectively

after 10, 20 and 30 minutes of microwave. The moisture content of air dried samples

38

reduced to 9.5 % after 21 days. Surface temperature of the samples after 21 days of air
drying post treatment was the same as before the post treatment.
4.3 Leaching - Effect of microwave and air dry post treatment

Initial copper content in the blocks used for leaching calculated based on solution
pick up and concentration of copper in the treating solutions were summarized in table
4.2 and detailed in appendix table 1-2. Total initial copper content in the leaching blocks
(6 blocks) observed to vary from 126-143 mg and 195-219 mg respectively for 0.5% (3.2
kg/m3 copper retention) and 0.8% (4.9 kg/m3 copper retention) copper elemental ACQ
type D treated samples.

Cumulative copper leached over different leaching durations up to 336 hours of
leaching is summarized in table 4.3, 4.5 and figure 4.1, 4.3. Results shows that copper is
leached to surrounding water medium over time by the action of water, indicating the
amount of un-reacted c0pper in the post treated samples. Irrespective of the retention and
post treatment maximum amount of copper is observed to leach out during initial 48
hours of leaching.

Percentage of copper leached during different intervals of leaching experiment,
calculated based on initial copper content and the cumulative copper leached during the
corresponding leaching duration, is summarized in table 4.4, 4.6 and figure 4.2, 4.4 and
detailed in appendix table 3-12. Results show that irrespective of the retention and post
treatment major share of the total percentage of copper leached after 336 hours of
leaching is occurred within 48 hours (Table 4.4, 4.6, Figure 4.2, 4.4).

Percentage of copper leached out from the samples treated with 0.8% copper

ACQ, having a copper retention of 4.9 kg/m3 was higher than that of the samples treated

39

with 0.5% copper ACQ having a copper retention of 3.2 kg/m3 in all the post treatment
groups. The percentage of copper leached out, from the samples treated with 0.5% copper
ACQ for a copper retention of 3.2 kg/m3, after 336 hr leaching were 33, 27, 17, 13 and
17 respectively for 0 minutes microwave, 10 minutes microwave, 20 minutes microwave,
30 minutes microwave and 21 days air dry post treatments, compared to 42, 32, 30, 19
and 22 for the samples treated with 0.8% copper ACQ for a copper retention of 4.9 kg/m3
copper. Results show that retention of the treated samples has a significant effect
(P<0.001) in the percentage of copper leaching from southern yellow pine treated with
ACQ type D in agreement with the studies of Pasek (2003), Tascioglu et al (2005) and
Ung and Cooper (2005).

Copper amine based preservatives and wood interactions, mainly ion exchange
reactions between copper complexes and quaternary ammonium salts in the preservative
solution and wood depends on the number of anionic sites in wood (Jin and Preston,
1991; Staccioli et a1, 2000., Loubinoux and Malek, 1992 and Loubinoux et a1, 1992).
Since the number of these reaction sites in the wood is limited copper complexes and
quaternary ammonium compounds will compete for the same reaction sites in the wood.
In case of samples treated with ACQ type C for a copper retention of 4.9 kg/m3 the
competition of preservative components for the available reaction sites will be much
higher compared to the samples treated for a copper retention of 3.2 kg/m3. Some of the
preservative components in the wood will react with the reaction sites close to it; some
other may migrate to other part of the wood, if there is enough moisture to facilitate ionic
mobility (Chen et al, 1994), and the remaining unreacted preservative components may

get physically deposited in the wood as the treated wood get dried. Unreacted

40

preservative components will get leached out when treated wood come in contact with
water. The amount of unreacted preservative components will be higher in samples
treated for higher retention. This can be the reason for the higher percentage of copper
leaching from samples treated for a copper retention of 4.9 kg/m3 compared to samples
treated for a copper retention of 3.2 kg/m3.

For samples treated with ACQ solution having an elemental copper of 0.5% thirty
minutes microwave reduced leaching to 13% compared to 17% for air dry post treated
samples. At the same time for samples treated with ACQ having an elemental copper
0.8% thirty minutes microwave reduced leaching up to 19% compared to 22% for air
dries samples (Table 4.4, 4.6, figure 4.2, 4.4). In both the case the difference was
statistically significant. Result shows a significant decrease (P<0.001) in the percentage
of copper leached with an increase in microwave duration for both retention levels (Table
4.4, 4.6, fig 4.2, 4.4), indicating the effect of microwave to reduce the depletion of copper
within 30 rrrinutes of microwave. Same trend was reported by Jinzhen and Cao (2004).
There was an overall significant difference in percentage of copper leached from
microwave and air dry post treated samples (P<0.001). Lower percentage of copper
leaching observed for thirty minute microwave post treated samples compared to air dried
samples shows that the amount of copper stabilized in thirty minute microwave post
treated sample is higher than that of air dried samples. This can be due to rapid increase
in temperature (up to 64-700C) during microwave post treatment before the moisture
content drops down to 13% after 30 minute microwave (Table 4.1). Increase in
temperature will accelerate the ion exchange reaction of preservative components with

wood; in that case stabilization of copper in the wood will be higher.

41

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Table 4.2 Initial copper content in six blocks used for leaching

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Treating Average retention Initial copper content
solution (kg/m3) treitcirsiten t Rep in 6 leaching blocks
concentration Cu CuO ACQ (mg)

MO 1 137.45

M0 2 126.65

M10 1 137.70

M10 2 126.50

0.5% Cu 3.2 4 6 M20 1 13390

M20 2 142.80

M30 1 138.15

M30 2 133.55

A 1 134.60

A 2 131.30

M0 1 200.72

MO 2 206.16

M 10 l 21 1.04

M10 2 212.80

0.8% Cu 4.9 6.1 9.2 M20 1 ”2'16

M20 2 215.52

M30 1 218.80

M30 2 217.36

A 1 196.72

A 2 195.12

 

 

 

 

 

 

 

 

 

Where M0, M10, M20 and M30 represent microwaving post treatment for different

duration of 0 minute, 10 minutes, 20 rrrinutes and 30 minutes. A is air dry post treatment.

43

Table 4.3 Average cumulative copper leached from post treated southern yellow pine,

treated with ACQ type C, having 0.5% Cu elemental, for a copper retention of 3.2 kg/m3

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duaration (h) Cumulative copper leached (mg)
M0 M10 M20 M30 A

6 37.52 22.53 11.73 8.11 11.86
24 41.74 30.48 19.43 13.25 16.62
48 42.88 33.55 21.16 14.25 19.17
96 43.18 34.19 21.96 15.58 20.65
144 43.38 34.77 22.79 16.73 21.21
192 43.50 34.99 22.96 16.93 21.74
240 43.57 35.09 23.17 17.06 21.88
288 43.67 35.26 23.35 17.25 22.07
336 43.74 35.42 23.61 17.46 22.18

 

 

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45

Table 4.4 Percentage of copper leached from post treated southern yellow pine treated

with ACQ type C, having Cu elemental 0.5%, for a copper retention of 3.2 kg/m3

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duration (h) % Cu leached

M 0 M 10 M 20 M 30 A

6 28 17 8 6 9
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48 32 25 15 10 14
96 33 26 16 ll 16
144 33 26 16 12 16
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47

Table 4.5 Average cumulative copper leached from post treated southern yellow pine,

treated with ACQ type C, having 0.8% Cu elemental, for a copper retention of 4.9 kg/m3

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

. Cumulative copper leached (mg)
Duran“ 0” M0 M10 M20 M30 A

6 51.60 42.27 41.56 22.67 21.95
24 74.46 57.60 53.59 32.47 33.39
48 80.68 63.73 59.58 37.29 37.13
96 83.56 66.60 62.87 40.17 39.98
144 84.31 67.44 63.94 41.23 41.38
192 84.64 67.78 64.36 41.75 42.17
240 84.89 68.00 64.65 42.08 42.80
288 85.09 68.21 64.88 42.34 43.45
336 85.26 68.38 65.07 42.53 43.94

 

48

 

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49

Table 4.6 Percentage of copper leached from post treated southern yellow pine treated

with ACQ type C, having Cu elemental 0.8%, for a copper retention of 4.9 kg/m3

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duration °/o Copper leached

(h) M0 M10 M20 M30 A
6 25 20 1 9 1O 1 1
24 37 27 25 1 5 1 7
48 40 30 28 17 1 9
96 41 31 29 1 8 20
1 44 41 32 3O 1 9 21
1 92 42 32 30 1 9 22
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51

4.4 Mechanical properties - MOE and MOR
4.4.1 Non destructive MOE

MOE calculation before and after are detailed in appendix table 13 and
summarized in table 4.7 and figure 4.5, 4.6. Results shows an increase of 5-8% in MOE
for all microwave post treatment for different durations of 10, 20 and 30 minutes and air
drying post treatment for 21 days. MOE of 0.5% ACQ treated 30 minute post microwave
treated samples increased from 7663 MPa to 8064 MPa compared to an increase from
7456 MPa to 7833 MPa for 0.8% ACQ treated 30 minute microwave post treated
samples. Same time MOE of 0.5% ACQ treated air dried samples showed an increase
from 7878 MPa to 8303 M Pa compared to an increase from 7456 MPa to 7833 MPa for
0.8% ACQ treated air dried samples. But the observed increase in MOE cannot be
attributed as a result of post treatment as the errors to measure the load required to make
the displacement of 0.19 cm from the sample after post treatment, from exactly the same
position, are highly probable while using Instron. No decrease in MOE was observed
either for samples microwave post treated at different durations or for air dried samples.
These results suggests that short term micro waving up to 30 minuets at 100W is not
resulting in any thermal degradation of wood components such as cellulose and lignin to
cause any reduction in elasticity of southern yellow pine in agreement with the fact that

strength reduction is cumulative thermal process over time (Winandy, 1988).

52

4.4.2 Destructive MOE

Destructive MOE of southern yellow pine samples subjected to different post
treatments and control samples are summarized in table 4.8 and figure. 4.7and detailed in
appendix table 14.

Southern yellow pine samples, neither treated with ACQ type C nor any post
treatments, shows an average MOE of 10040 M Pa in Universal Testing machine. ACQ
type C, having copper elemental concentration of 0.5% and 0.8%, treated air dried
samples was observed with MOE of 10100 M Pa and 10150 M Pa respectively. No
significant difference in MOE was observed for air dry post treated samples when
compared to control samples (Pr>.3485) in agreement with the studies of Barnes et a1
(1993). This shows that ACQ type C treatment is not resulting in strength reduction,
resulting from the hydrolysis and delignification of wood components, in southern yellow
pine.

MOE of 30 minute microwave post treated southern yellow pine were 10398 M
Pa and 10152 M Pa respectively for samples treated with ACQ type C having 0.5% and
0.8% Cu elemental. Results shows that MOE of 30 minute microwave post treated
samples are not significantly different from air drying post treated and control samples
(Pr>O.3485).

No significant difference in MOE was observed between samples treated with
ACQ type C, having 0.5% copper elemental, for a copper retention of 3.2 kg/m3 and
samples treated with ACQ type C, having 0.8% copper elemental, for a copper retention

of 4.9 kg/m3 (Pr>0.4910), irrespective of the post treatments.

53

4.4.3 Correlation of non-destructive and destructive MOE

MOE of post treated samples, measured non - destructively and destructively, are
plotted against specific gravity in figure 4.8 and figure 4.9 respectively. Increase in MOE
was observed for an increase in specific gravity for destructive and non- destructive
MOE. Correlation coefficient was observed to less in both the cases. It is due to the fact
that the MOE is forming a clusture across the specific gravity range (0.5- 0.58) (Figure
4.8 and Figure 4.9). Comparatively good trend was observed for destructive MOE, in
agreement with the fact that mechanical strength increase as specific gravity increases.
This result shows that MOE measured using destructive method is more reliable. MOE of
the each sample measured after post a treatment using destructive method is plotted
against MOE measured non-destructively in figure 4.10. Good correlation was observed
between destructive and non-destructive MOE. This result suggests that non- destructive
MOE can be effectively used for the initial sample selection, to reduce the variability in
MOE, for studying the effect of treatments on mechanical property.
4.4.4 Destructive MOR

MOR of post treated and control samples were detailed in appendix table 14 and
summarized in table 4.9 and figure 4.11. For control samples MOR varied from 102-104
M Pa. At the same time for post treated samples, samples treated with 0.5% (3.2 kg/m3
copper retention) and 0.8% (4.9 kg/m3 copper retention) copper elemental ACQ type C
solution MOR varied from 102-110 M Pa.

No reduction in MOR was observed for air dry post treated samples compared to

the control at both the retention levels in agreement with the Barnes et a1 (1993). MOR of

54

control sample was 102 M Pa while samples treated at a copper retention of 3.2 kg/m3
had MOR of 104 M Pa compared to 109 M Pa for samples treated at 4.9 kg/m3 retention.

MOR of samples treated at a copper retention of 3.2 kg/m3 and microwave post
treated for 30 minutes was 103 M Pa compared to 109 M Pa obtained for 4.9 kg/m3
copper retention samples.

Statistical analysis shows that there is no significant difference in MOR between
control and post treated samples (Pr>0.9556). This result shows that 30 minute
microwave post treatment at a power level of 100W or air drying post treatment, not
resulting in strength reduction in southern yellow pine. This again supports the argument

that strength reduction is a cumulative thermal process over time (Winandy, 1988).

55

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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4.5 Color change - AE

Color change of southern yellow pine samples from green condition after ACQ
type C and post treatment were detailed in appendix table 15 and summarized in table
4.10 and figure 4.12. Light yellow color of southern yellow pine was changed to light
bluish green after ACQ and post treatment.

Li ghtness ‘L’ value of southern yellow pine observed to decrease after ACQ type
D and post treatments. Average percentage decrease in ‘L’was -31% to ~32% for samples
treated with 0.5% copper elemental ACQ (3.2 kg/m3 Cu) compared to -37% to -39% for
samples treated with 0.8% (4.9 kg/m3 Cu) (Table 4.10). This result shows that lightness
of southern yellow pine decreasing after ACQ type C. The decrease in lightness was
higher for samples treated at higher retention.

Chromaticity ‘a’ of the same samples also observed to decrease after ACQ type C
and post treatment. An average decrease of -79% to -84% was observed for samples
treated at 3.2 kg/m3 copper retention compared to ~99 to -111% for samples treated at 4.9
kg/m3, showing that chromaticity ‘a’ value is shifting from red to green, and the shift is
higher for samples treated with higher copper retention (Table 4.10). Same trend was
observed with chromaticity ‘b’. An average decrease of -32 to -41% was observed for
samples treated at 3.2 kg/m3 copper retention compared to -36 to -38% for samples
treated at 4.9 kg/m3, showing the shift towards blue from yellow (Table 4.10). Statistical
analysis of the color change data shows that concentration of treating solution has a
significant effect on color change of the sample from green condition after ACQ and post

treatment (Pr<0.001).

66

Southern yellow pine treated at 3.2 kg/m3 copper retention showed a color
change, AE value of 27.94 and 27.69 for air dried and 30 minute microwave post treated
samples. At the same time samples treated at 4.9 kg/m3 showed a color change of 32.31
and 34.49 respectively for air dried and 30 minute microwave post treated samples (Table
4.10). No significant difference in color change was observed among air dried and
microwave post treated sample within retention level (Pr>0.5559). These results shows
that 30 minute microwave post treated samples retain the same color as air dried samples.
Heating wood at high temperature will result in the formation of colored substances from
oxidation of the phenolic compound of the wood and the formation of dark material from
the hydrolysis of hemicellulose and lignin (Hon and Minemura, 2000) to cause a
discoloration. This implies that increase in temperature up to 64-700C during microwave
post treatment not resulting in the formation of colored substances in the wood to have a

discoloration.

67

M0000 0.0 00 000088 8008 a 08 00 000.0 00300 OU<

003 0880 8903 8088008 mm .mex Nm .3 000088 8008 a .80 :0 000.0 00300 OU< 003 0880 80003 308808 20 88:5

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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00.N0 00- 00.0 T 0N.0_. 0N.0N w P T 00.0- 00.0- 500 #0. 00.00- 00.N0 0N.N0 0 ZZNE
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8020880 3.00 000 U 899 OU< 800 83008 00 b. 000 .0. 802008-00 0600.00.50 000.4. 385005 02 .0 .8000.

68

AE

E 0.5% Cu ACQ (3.2 kg/m3 Cu retention)
. 0.5% Cu ACQ (3.2 kg/m3 Cu retention)

 

A M10 M20 M3)

Post treatments

Figure 4.12 Color change, AE after ACQ type C and post treatments

69

CONCLUSIONS

Percentage of copper leached from thirty minute microwave post treated samples,
treated with ACQ type C at a copper retention of 3.2 kg/m3 was 13% while 17% copper
leaching was observed for air dry post treated samples. At the same time percentage of
copper leached from thirty minutes microwave post treated samples, treated at a copper
retention of 4.9 kg/ m3 was 19% compared to 22% observed for air dry post treated
samples. These results concludes that microwave post treatment can be used to reduce
the leaching of copper from ACQ type C treated southern yellow pine. Decrease in
copper leaching observed for thirty minute microwave post treated samples can be
attributed to rapid increase in temperature (up to 64-7OOC) during microwave post
treatment. Copper stabilization in the treated wood will increase at higher temperature
(Pasek, 2003; Ung and Cooper, 2005; Tascioglu, 2005). Similar result regarding the
effect of microwave to reduce leaching of copper was reported by Cao and Kamdem
(2004) in copper amine treated southern yellow pine. They reported 15% copper leaching
for air dried samples treated with copper amine for a copper retention of 3.2 kg/m3
compared to 8.4% for twenty minute microwave post treated samples.

Increase in microwave duration from zero minutes to thirty minute reduced
copper leaching from 33% to 13% in case of samples treated with ACQ for a copper
retention of 3.2 kg/m3 compared to 42% to 19% in case of samples treated at copper
retention of 4.9 kg/m3. Same trend of decreasing copper leaching with increasing

microwave duration was observed by Cao and Kamdem (2004).

70

Percentage of copper leached from air dry post treated sample treated at a copper
retention of 3.2 kg/m3 and 4.9 lvtg/m3 was 17% and 22% respectively. Percentage of
copper leached from thirty minute microwave post treated sample treated at a copper
retention of 3.2 kg/m3 and 4.9 kg/m3 was 13% and 19% respectively. These results
conclude that copper leaching will be higher for samples treated at higher copper
retention invariably of the post treatments. Similar results have been reported by Pasek
(2003), Tascioglu et a1 (2005), and Ung and Cooper (2005). Increase in copper leaching
with increase in copper retention can be explained by the fact that in case of samples
treated at higher retention more copper complex is competing to undergo cation exchange
reaction with wood components. As the number of anionic sites is limited in wood, the
amount of unreacted preservative components in the treated wood will be higher for
samples at higher retention, which will result in higher copper loss.

Average destructive MOE of the control sample was 10040 MPa. MOE of air dry
and 30 minute microwave post treated samples, treated at 3.2 kg/m3 was 10100 MPa and
10398 MPa respectively compared to 10150 MPa and 10152 MPa for samples treated at
4.9 kg/m3. MOE of the air dry and microwave post treated samples are not significantly
different from the control samples. It can be concluded from the results that ACQ
treatment not resulting in the reduction of MOE of southern yellow pine in agreement
with Barnes et al (1993). No published research is available in the literature regarding the
effect of microwave post treatment on strength properties of treated wood. Present study
shows that increase in temperature up to 64-700C after thirty minute microwave not

resulting in degradation of wood components to cause any reduction in MOE.

71

Average MOR of control sample was 102 MPa. MOR of air dry and 30 minute
microwave post treated samples, treated at 3.2 kg/m3was 104 MPa and 103 MPa
respectively compared to 109 MPa and 109 MPa for samples treated at 4.9 kg/m3. There
was no significant difference in MOR of air dry and microwave post treated samples
compared to the control samples. This implies that ACQ treatment not reducing the MOR
of southern yellow pine in agreement with Barnes et al (1993). It can be concluded from
the result that thirty minute microwave not resulting in degradation of wood components
to cause reduction in MOR.

Color change, AE of air dry and microwave post treated southern yellow pine
treated at 3.2 kg/m3 copper retention was 27.94 and 27.69 respectively compared to 32.31
and 34.49 for samples treated at 4.9 kg/m3. Color changes of thirty 30 minute microwave
post treated samples are not significantly different from air dry post treated samples
irrespective of the retention. It is reported that at higher temperature colored substances
may formed in wood by the oxidation of phenolic compounds of the wood and hydrolysis
of hemicellulose and lignin (Hon and Minemura, 2000). Results suggest that increase in
temperature during 30 minute microwave not resulting in the formation of colored
substances in the wood.

In conclusion microwave post treatment is effective to reduce migration of copper
from ACQ type C treated southern yellow pine without reduction in bending strength and

no significant color change compared to air dry post treated samples.

72

APPENDIX

73

Table 1. Copper content in southern yellow pine treated with ACQ type C having 0.5%

copper

Where W1 is weight before treatment, W2 is weight after treatment

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

W2-W1 Copper content (mg)
Treatment Sample W1 (g) W2 (g) (g) (W 2-W l) * 0.5 % It 1000
1 4.5 9.31 4.81 24.05
2 3.81 8.94 5.13 25.65
MO-l 3 4.27 7.87 3.6 18.00
4 3.95 8.23 4.28 21.40
5 4.24 8.99 4.75 23.75
6 3.78 8.7 4.92 24.60
Copper content in 6 blocks - 137.58
7 4.14 8.51 4.37 21.85
8 4.46 9.11 4.65 23.25
MO-2 9 4.24 8.87 4.63 23.15
10 4.08 8.84 4.76 23.80
11 3.84 7.45 3.61 18.05
12 4.51 7.82 3.31 16.55
Copper content in 6 blocks - 126.65
13 4.04 9.08 5.04 25.20
14 4.56 9.31 4.75 23.75
15 4.22 9.1 1 4.89 24.45
MM“ 16 4.52 9.11 4.59 22.95
17 4.02 8.76 4.74 23.70
18 4.42 7.95 3.53 17.65
Copper content in 6 blocks - 137.70
19 3.75 8.03 4.28 21.40
20 4.59 8.63 4.04 20.20
21 4.35 9.01 4.66 23.30
MIO'Z 22 4.19 8.26 4.07 20.35
23 4.47 8.14 3.67 18.35
24 4.46 9.04 4.58 22.90
Copper content in 6 blocks - 126.50
25 3.78 8.01 4.23 21.15
26 4.58 9.02 4.44 22.20
27 4.56 9.1 4.54 22.70
M20" 28 4.5 9.08 4.58 22.90
29 4.42 8.91 4.49 22.45
30 4.49 8.99 4.5 22.50

 

 

Copper content in 6 blocks - 133.90

 

74

 

Table 1 continued

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

31 4.53 9.21 4.68 23.40

32 4.66 9.41 4.75 23.75

33 4.44 9.26 4.82 24.10

M204 34 4.27 9.17 4.9 24.50
35 4.35 8.95 4.6 23.00

36 4.64 9.45 4.81 24.05

Copper content in 6 blocks - 142.80

37 4.47 9.07 4.6 23.00

38 4.6 9.22 4.62 23.10

39 4.49 9.08 4.59 22.95

M30" 40 3.95 8.48 4.53 22.65
41 4.37 9.06 4.69 23.45

42 4.51 9.11 4.6 23.00

Copper content in 6 blocks - 138.15

43 4.41 9.09 4.68 23.40

44 4.46 9.09 4.63 23.15

45 4.58 8.74 4.16 20.80

mm 46 4.48 8.92 4.44 22.20
47 4.31 8.87 4.56 22.80

48 4.44 8.68 4.24 21.20

Copper content in 6 blocks - 133.55

61 4.55 8.88 4.33 21.65

62 4.03 8.67 4.64 23.20

A- 1 63 4.63 8.86 4.23 21.15
64 4.45 9.02 4.57 22.85

65 4.54 9.19 4.65 23.25

66 4.48 8.98 4.5 22.50

Copper content in 6 blocks - 134.60

67 4.58 9.08 4.5 22.50

68 4.58 9.69 5.11 25.55

A-2 69 4.41 7.79 3.38 16.90
70 4.43 8.46 4.03 20.15

71 4.54 9.14 4.6 23.00

72 4.36 9.00 4.64 23.20

Copper content in 6 blocks - 131.30

 

75

 

Table 2. Copper content in southern yellow pine treated with ACQ type C having 0.8%

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

copper
Treatment Sample M (g) w2 (g) W2-W1 (g) 0’9"“ “mm“ (mg)
(WZ-Wl) * 0.8% *1000
173 4.85 8.73 3.88 31.04
174 4.39 8.96 4.57 36.56
MO-l 175 4.43 8.58 4.15 33.20
176 4.54 8.09 3.55 28.40
177 4.13 8.60 4.47 35.76
178 4.70 9.17 4.47 35.76
Copper content in 6 blocks - 200.72
179 4.48 8.55 4.07 32.56
180 4.32 8.76 4.44 35.52
M0-2 181 4.36 9.39 5.03 40.24
182 4.42 7.96 3.54 28.32
183 4.00 8.99 4.99 39.92
184 4.86 8.56 3.70 29.60
Copper content in 6 blocks - 206.16
188 4.76 9.21 4.45 35.60
189 4.81 8.93 4.12 32.96
M10-1 190 4.21 9.15 4.94 39.52
191 4.84 8.80 3.96 31.68
192 4.10 8.76 4.66 37.28
193 4.70 8.95 4.25 34.00
Copper content in 6 blocks - 211.04
194 4.17 9.04 4.87 38.96
195 4.88 9.08 4.20 33.60
196 4.61 9.06 4.45 35.60
M 10'2 197 4.67 8.76 4.09 32.72
198 4.55 9.14 4.59 36.72
199 4.61 9.01 4.40 35.20
Copper content in 6 blocks - 212.8
200 4.88 9.00 4.12 32.96
201 4.57 8.32 3.75 30.00
M20-1 202 4.54 9.02 4.48 35.84
203 4.24 8.94 4.70 37.60
204 4.47 9.09 4.62 36.96
205 4.16 9.01 4.85 38.80
Copper content in 6 blocks - 212.16
206 4.12 8.87 4.75 38.00
207 4.11 8.65 4.54 36.32
208 4.83 9.20 4.37 34.96
M20“? 209 4.18 9.08 4.90 39.20
210 4.52 8.77 4.25 34.00
211 4.33 8.46 4.13 33.04
Copper content in 6 blocks - 215.52

 

 

76

 

Table 2 continued

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

215 4.90 9.46 4.56 36.48

216 4.69 9.04 4.35 34.80

217 4.16 9.32 5.16 41.28

M30“ 218 4.89 9.03 4.14 33.12
219 4.28 9.11 4.83 38.64

220 4.53 8.84 4.31 34.48

Cop aer content in 6 blocks - 218.8

401 4.48 9.21 4.73 37.84

402 4.45 9.34 4.89 39.12

403 4.13 8.37 4.24 33.92

mm 404 4.31 8.49 4.18 33.44
405 4.79 9.32 4.53 36.24

406 4.86 9.46 4.60 36.80

Copper content in 6 blocks - 217.36

410 4.41 8.51 4.10 32.80

41 1 4.45 9.11 4.66 37.28

A-l 412 4.91 9.12 4.21 33.68
413 4.42 8.68 4.26 34.08

414 4.91 8.24 3.33 26.64

415 4.86 8.89 4.03 32.24

Copper content in 6 blocks - 196.72

416 4.91 9.32 4.41 35.28

417 4.15 8.58 4.43 35.44

A-2 418 4.62 9.16 4.54 36.32
419 4.92 8.54 3.62 28.96

420 4.93 8.54 3.61 28.88

421 4.24 8.02 3.78 30.24

Copper content in 6 blocks - 195.12

 

77

 

Table 3. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.5% c0pper, for a copper retention of 3.2 kg/m3 with no post
treatment

Where ‘AA’ is atomic absorption reading of leachate for copper,‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative c0pper leached in
mg, ‘% Cu’ is percentage copper leached.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duratlon R e p M0 °/
(hr) AA (mg 11) DF Cu 300 ml (mg) c Cu (mg) c;
6 1 12.80 10 38.40 38.40 28
2 12.22 10 36.65 36.65 29

Average 12.51 10 37.52 37.52 28
24 1 14.49 1 4.35 42.75 31
2 13.59 1 4.08 40.72 32

Average 14.04 1 4.21 41.74 32
48 1 4.03 1 1.21 43.96 32
3.63 1 1.09 41.81 33

Average 3.83 1 1 .15 42.88 32

96 1 0.68 1 0.20 44.16 32
2 1.27 1 0.38 42.19 33

Avera e 0.97 1 0.29 43.18 33
144 1 0.67 1 0.20 44.36 32
2 0.71 1 0.21 42.40 33

Average 0.69 1 0.21 43.38 33
192 1 0.48 1 0.14 44.51 32
2 0.31 1 0.09 42.49 34

Average 0.40 1 0.1 2 43.50 33

2 40 1 0.26 1 0.08 44.58 32
2 0.22 1 0.06 42.56 34

Avera e 0.24 1 0.07 43.57 33
288 1 0.38 1 0.12 44.70 33
2 0.30 1 0.09 42.65 34

Average_ 0.34 1 0.10 43.67 33
336 1 0.27 1 0.08 44.78 33
0.20 1 0.06 42.71 34
Avergge 0.24 1 0.07 43.74 33

 

 

 

 

 

 

78

Table 4. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.5% copper, for a copper retention of 3.2 kg/m3 and post
treated for 10 minutes microwave

Where ‘AA’ is atomic absorption reading of leachate for copper, ‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative copper leached in
mg, ‘% Cu’ is percentage copper leached.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duration R e p M10 0/
(hr) AA (mg II) DF Cu 300 ml (mg) c Cu (mg) c;
6 1 7.89 10 23.67 23.67 17
2 7.13 10 21.39 21.39 17

Average 7.51 10 22.53 22.53 17
24 1 2.41 10 7.23 30.90 22
2 2.89 10 8.67 30.06 24

Avera e 2.65 1 7.95 30.48 23
48 1 1 1.87 1 3.56 34.46 25
2 8.60 1 2.58 32.64 26

Average 10.24 1 3.07 33.55 25
96 1 2.07 1 0.62 35.08 25
2 2.21 1 0.66 33.30 26

Average 2.14 1 0.64 34.19 26
144 1 2.26 1 0.68 35.76 26
2 1 .59 1 0.48 33.78 27

Average 1 .92 1 0.58 34.77 26

1 92 1 0.86 1 0.26 36.02 26
2 0.57 1 0.17 33.95 27

Avera e 0.72 1 0.21 34.99 26
240 1 0.39 1 0.12 36.13 26
2 0.34 1 0.10 34.05 27

Average 0.36 1 0.1 1 35.09 27
288 1 0.46 1 0.14 36.27 26
2 0.68 1 0.20 34.26 27

Avera e 0.57 1 0.17 35.26 27
336 1 0.43 1 0.13 36.40 26
2 0.63 1 0.19 34.45 27

Average 0.53 1 0.16 35.42 27

 

 

 

 

 

 

 

79

Table 5. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.5% copper, for a copper retention of 3.2 kg/m3 and post
treated for 20 minutes microwave

Where ‘AA’ is atomic absorption reading of leachate for copper, ‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative copper leached in
mg, ‘% Cu’ is percentage copper leached.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duration Rep M20 %
(hr) AA (mg II) DF Cu 300 ml (mg) c Cu (mg) Cu
6 1 3.76 10 11.28 11.28 8

2 4.06 10 12.18 12.18 9

Avera e 3.91 10 11.73 11.73 8
24 1 2.58 10 7.73 19.01 14
2 2.56 10 7.67 19.85 14

Avera e 2.57 1 7.70 19.43 14
48 1 6.22 1 1.87 20.87 16
2 5.36 1 1.61 21.46 15

Avera e 5.79 1 1.74 21.16 15
96 1 3.27 1 0.98 21.85 16
2 2.07 1 0.62 22.08 15

Avera e 2.67 1 0.80 21.96 16
144 1 3.10 1 0.93 22.78 17
2 2.42 1 0.72 22.80 16

Avera e 2.76 1 0.83 22.79 16
192 1 0.58 1 0.17 22.96 17
2 0.56 1 0.17 22.97 16

Avera e 0.57 1 0.17 22.96 17
240 1 0.73 1 0.22 23.17 17
2 0.66 1 0.20 23.16 16

Average 0.69 1 0.21 23.17 17
288 1 0.62 1 0.19 23.36 17
2 0.59 1 0.18 23.34 16

Avera e 0.60 1 0.18 23.35 17
336 1 0.84 1 0.25 23.61 18
2 0.89 1 0.27 23.61 17

Average 0.86 1 0.26 23.61 17

 

 

 

 

 

80

Table 6. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.5% copper, for a copper retention of 3.2 kg/m3 and post
treated for 30 minutes microwave

Where ‘AA’ is atomic absorption reading of leachate for copper, ‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative copper leached in
mg, ‘% Cu’ is percentage copper leached.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duration Rep M30

(hr) AA (:39 II) DF Cu 300 ml (mg) 0 Cu (m % Cu

6 1 2.60 10 7.81 7.81 6

2.80 10 8.41 8.41 6

Avergge 2.70 10 8.11 8.11 6

24 1 17.10 1 5.13 12.93 9

17.22 1 5.16 13.57 10

Average 17.16 1 5.15 13.25 10

48 1 3.35 1 1.01 13.94 10

3.32 1 1.00 14.57 1 1

Averggg 3.34 1 1 .00 14.25 10

96 1 4.42 1 1.32 15.26 1 1

4.44 1 1.33 15.90 12

Average 4.43 1 1.33 1 5.58 11

144 1 4.16 1 1.25 16.51 12

3.53 1 1.06 16.96 13

Avefle 3.84 1 1.15 16.73 12

192 1 0.83 1 0.25 16.76 12

0.50 1 0.15 17.11 13

Average 0.66 1 0.20 16.93 12

240 1 0.43 1 0.13 16.89 12

0.42 1 0.13 17.23 13

Average 0.43 1 0.13 17.06 13

288 1 0.73 1 0.22 17.11 12

0.52 1 0.16 17.39 13

Averagg 0.63 1 0.19 17.25 13

1 0.62 1 0.19 17.30 13

336 0.81 1 0.24 17.63 13

Average 0.71 1 0.21 17.46 13

 

 

 

 

 

 

81

Table 7. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.5% copper, for a copper retention of 3.2 kg/m3 and post
treated for 21 days air drying

Where ‘AA’ is atomic absorption reading of leachate for copper, ‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative copper leached in
mg, ‘% Cu’ is percentage copper leached.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duration R A o
9P» /o
(hr) AA (mg/I) DF Cu 300 ml (mg) c Cu (mg) Cu
6 1 3.91 10 11.73 11.73 9
2 4.00 10 11.99 11.99 9

Average 3.95 1 0 1 1 .86 1 1 .86 9
24 1 16.69 1 5.01 16.74 12
15.04 1 4.51 16.50 13
Average 15.87 1 4.76 16.62 12
48 1 8.20 1 2.46 19.20 14
2 8.82 1 2.65 19.14 15
Avera e 8.51 1 2.55 19.17 14
96 1 5.15 1 1.54 20.74 15
2 4.70 1 1.41 20.55 16
Avera e 4.92 1 1.48 20.65 16
144 1 1.81 1 0.54 21.28 16
2 1.92 1 0.58 21.13 16
Average 1 .86 1 0.56 21 .21 1 6
192 1 1.82 1 0.55 21.83 16
2 1.77 1 0.53 21.66 16
Avera e 1.79 1 0.54 21.74 16
240 1 0.34 1 0.10 21.93 16
2 0.55 1 0.16 21.82 17
Avera e 0.44 1 0.13 21.88 16
288 1 0.54 1 0.16 22.09 16
2 0.74 1 0.22 22.04 17
Average 0.64 1 0.19 22.07 17
336 1 0.32 1 0.10 22.19 16
2 0.42 1 0.13 22.17 17
Average 0.37 1 0.1 1 22.18 1 7

 

82

 

Table 8. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.8% copper, for a copper retention of 4.9 kg/m3 with no post
treatment

Where ‘AA’ is atomic absorption reading of leachate for copper,‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative copper leached in
mg, ‘% Cu’ is percentage copper leached.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M0
Duaggon Rep AA (mg DF Cu 300 ml C Cu %
(1) (mg) (mm Cu
6 1 17.88 10 53.64 53.64 27
2 16.52 10 49.56 49.56 24
Avera e 17.20 10 51.60 51 .60 25
24 1 7.09 10 21.26 74.90 37
8.15 10 24.46 74.02 36
Average 7.62 10 22.86 74.46 37
48 1 1.83 10 5.50 80.40 40
2 2.31 10 6.94 80.96 39
Average 2.07 10 6.22 80.68 40
96 1 9.19 1 2.76 83.16 41
2 10.01 1 3.00 83.96 41
Average 9.60 1 2.88 83.56 41
144 1 2.35 1 0.71 83.87 42
2 2.62 1 0.79 84.75 41
Average 2.49 1 0.75 84.31 41
192 1 1.06 1 0.32 84.18 42
2 1.16 1 0.35 85.10 41
Averagg 1 .1 1 1 0.33 84.64 42
240 1 0.76 1 0.23 84.41 42
2 0.92 1 0.28 85.37 41
Avera e 0.84 1 0.25 84.89 42
288 1 0.64 1 0.19 84.60 42
2 0.70 1 0.21 85.58 42
Avera e 0.67 1 0.20 85.09 42
336 1 0.53 1 0.16 84.76 42
2 0.62 1 0.19 85.77 42
Averagg 0.57 1 0.17 85.26 42

 

83

 

Table 9. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.8% copper, a copper retention of 4.9 kg/m3and post treated
for 10 minutes microwave

Where ‘AA’ is atomic absorption reading of leachate for copper, ‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative copper leached in
mg, ‘% Cu’ is percentage copper leached.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duration Rep M10 0/
(hr) AA (mg ll) DF Cu 300 ml (mg) c Cu (mg) C;
6 1 14.85 10 44.54 44.54 21
13.33 10 40.00 40.00 19

Average 14.09 10 42.27 42.27 20
24 1 5.07 10 15.21 59.75 28
2 5.15 10 15.46 55.46 26

Average 5.11 10 15.34 57.60 27
48 1 19.66 1 5.90 65.65 31
2 21 .21 1 6.36 61.82 29

Avera e 20.43 1 6.13 63.73 30
96 1 8.40 1 2.52 68.17 32
2 10.70 1 3.21 65.03 31

Average 9.55 1 2.86 66.60 31

1 44 1 2.58 1 0.77 68.94 33
2 3.04 1 0.91 65.94 31

Average 2.81 1 0.84 67.44 32
192 1 0.97 1 0.29 69.23 33
2 1.26 1 0.38 66.32 31

Average 1.11 1 0.33 67.78 32
240 1 0.76 1 0.23 69.46 33
2 0.73 1 0.22 66.54 31

Avera e 0.74 1 0.22 68.00 32
288 1 0.71 1 0.21 69.67 33
2 0.69 1 0.21 66.74 31

Avera e 0.70 1 0.21 68.21 32
336 1 0.62 1 0.19 69.86 33
2 0.55 1 0.17 66.91 31

Avegge 0.59 1 0.1 8 68.38 32

 

 

 

 

 

 

84

Table 10. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.8% copper, a copper retention of 4.9 kg/m3 and post treated
for 20 minutes microwave

Where ‘AA’ is atomic absorption reading of leachate for copper, ‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative copper leached in
mg, ‘% Cu’ is percentage c0pper leached

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M20
Du(r::;on Rep AA (mg DF Cu 300 ml C Cu %
ll) (mg) (mg) Cu
6 1 13.80 10 41.41 41.41 20
13.90 10 41.71 41.71 19
Average 13.85 10 41.56 41 .56 19
24 1 3.86 10 11.58 52.99 25
2 4.17 10 12.50 54.20 25
Avera e 4.01 10 12.04 53.59 25
48 1 19.43 1 5.83 58.82 28
2 20.49 1 6.15 60.35 28
Averagg 19.96 1 5.99 59.58 28
96 1 10.75 1 3.23 62.04 29
2 1 1.20 1 3.36 63.71 30
Average 10.98 1 3.29 62.87 29
1 44 1 3.39 1 1.02 63.06 30
2 3.70 1 1.11 64.82 30
Average 3.55 1 1 .06 63.94 30
192 1 1.48 1 0.44 63.50 30
2 1.31 1 0.39 65.21 30
Average 1 .39 1 0.42 64.36 30
240 1 0.96 1 0.29 63.79 30
2 0.98 1 0.29 65.51 30
Avera e 0.97 1 0.29 64.65 30
288 1 0.75 1 0.23 64.01 30
2 0.78 1 0.23 65.74 31
Average 0.77 1 0.23 64.88 30
336 1 0.63 1 0.19 64.20 30
2 0.65 1 0.20 65.94 31
Average 0.64 1 0.19 65.07 30

 

85

 

Table 11. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.8% copper, a copper retention of 4.9 kg/m3 and post treated
for 30 minutes microwave

Where ‘AA’ is atomic absorption reading of leachate for copper, ‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative copper leached in
mg, ‘% Cu’ is percentage copper leached

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duration R e p M30 %
(hf) AA (mg ll) DF Cu 300 ml (mg) C Cu (mg) Cu
6 1 7.38 10 22.13 22.13 10
7.73 10 23.20 23.20 11

Average 7.56 1 0 22.67 22.67 10
24 1 2.94 10 8.81 30.94 14
2 3.58 10 10.73 33.93 16

Average 3.26 1 0 9.77 32.43 1 5
48 1 14.70 1 4.41 35.35 16
2 17.42 1 5.23 39.15 18

Average 16.06 1 4.82 37.25 17
96 1 9.19 1 2.76 38.11 17
2 10.00 1 3.00 42.15 19

Average 9.59 1 2.88 40.13 18
144 1 3.31 1 0.99 39.10 18
2 3.76 1 1.13 43.28 20

Averagg 3.54 1 . 1.06 41.19 19
192 1 1.74 1 0.52 39.62 18
2 1.70 1 0.51 43.79 20

Average 1.72 1 0.52 41.71 19
240 1 1.11 1 0.33 39.95 18
2 1 .1 1 1 0.33 44.12 20

Average 1.11 1 0.33 42.04 1 9
288 1 0.88 1 0.26 40.22 18
2 0.83 1 0.25 44.37 20

Avera e 0.86 1 0.26 42.30 19
336 1 0.66 1 0.20 40.42 18
2 0.61 1 0.18 44.56 20

Avegge 0.63 1 0.19 42.49 19

 

 

 

 

 

 

 

86

Table 12. Cumulative and percentage copper leached from southern yellow pine treated
with ACQ type C, having 0.8% copper, a copper retention of 4.9 kg/m3and post treated
for 21 days air drying (A)

Where ‘AA’ is atomic absorption reading of leachate for copper, ‘Rep’ is replication, ‘Cu
300 ml’ is copper leached in 300 ml water in mg, ‘C Cu’ is cumulative copper leached in
mg, ‘% Cu’ is percentage copper leached.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duration R e p A %
('1') AA (mg II) DF Cu 300 ml (mg) C Cu (mg) Cu
6 1 7.21 10 21.63 21.63 11
2 7.42 10 22.26 22.26 1 1

Average 7.32 10 21.95 21 .95 11
24 1 3.90 10 11.70 33.33 17
2 3.73 10 11.19 33.45 17

Average 3.81 10 11.44 33.39 17
48 1 12.44 1 3.73 37.06 19
2 12.49 1 3.75 37.19 19

Average 12.47 1 3.74 37.13 19
96 1 9.48 1 2.84 39.91 20
2 9.54 1 2.86 40.05 21

Average 9.51 1 2.85 39.98 20
144 1 4.65 1 1.39 41.30 21
2 4.69 1 1.41 41.46 21

Average 4.67 1 1 .40 41 .38 21
192 1 2.77 1 0.83 42.13 21
2 2.46 1 0.74 42.20 22

Averag: 2.61 1 0.78 42.1 7 22
240 1 2.12 1 0.64 42.77 22
2 2.13 1 0.64 42.84 22

Average 2.12 1 0.64 42.80 22
288 1 2.11 1 0.63 43.40 22
2.18 1 0.65 43.49 22

Average 2.15 1 0.64 43.45 22
336 1 1.77 1 0.53 43.93 22
1.51 1 0.45 43.94 23

Average 1 .64 1 0.49 43.94 22

 

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1. Copper leaching

Independent variables:

Statistical analysis

a) ACQ treating solution at two concentration R1=O.5% and R2=0.8%

b) Post treatments:

Microwavaing at different durations, 0 min, 10 min, 20 min and 30 min

Air drying for 21 days

Dependendent variable: Amount of c0pper leached in mg

 

 

 

 

 

 

 

 

 

Mean
Source DF Type 3 88 square F value Pr > F
ACQ solution 1.00 318.79 318.79 890.17 <.0001
Post treatments 4.00 1145.14 286.28 799.40 <.0001
ACQ solution * Post treatments 4.00 42.64 10.66 29.77 <.0001

 

 

Multiple comparisons of treatments

 

 

 

 

 

 

 

 

 

 

 

ACQ solution Post treatments Copper leached LS mean number
LS means
R1 0 min microwave 33.15 1
R1 10 min microwave 26.83 2
R1 20 min microwave 17.08 3
R1 30 min microwave 12.86 4
R1 21 days air dry 16.69 5
R2 0 min microwave 41.92 6
R2 10 min microwave 32.27 7
R2 20 min microwave 30.43 8
R2 30 min microwave 19.5 9
R2 21 days air dry 22.43 10

 

 

 

 

 

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2. Non destructive MOE

Independent variables:

a) ACQ treating solution at two concentration R1=0.5% and R2=0.8%

b) Post treatments:

Microwavaing at different durations 10 min, 20 min and 30 min

Air drying for 21 days

Dependendent variable: Non destructive MOE.

* Square root transformation of the non- destructive MOE difference (before and after

ACQ and post treatments) was used for the analysis.

 

 

 

 

 

 

Type 3 Test of fixed effect
Numerator Denominator
Effect DF DF Pr > F
ACQ solution 1 112 0.7531
Post treatment 3 1 12 0.0733
ACQ solution 1 Post treatment 3 112 0.825

 

 

 

 

 

109

3. Destructive MOE

Independent variables:

a) ACQ treating solution at two concentration R1=0.5% and R2=0.8%

b) Post treatments:

Microwaving at different durations 10 min, 20 min and 30 min

Air drying for 21 days

Dependendent variable: Destructive MOE.

* MOE of the control samples which is neither ACQ treated nor post treated also

taken in account for the analysis.

 

 

 

 

 

Source DF Type 3 SS Mean square F value Pr > F
ACQ solution 2 1293401529 646700.764 0.72 0.491
Post treatments 3 3005046804 1001682268 1.1 1 0.3485
ACQ solution * Post treatments 3 3156345263 1052115.088 1.16 0.3263

 

 

 

 

 

 

110

 

4. Destructive MOR

Independent variables:

a) ACQ treating solution at two concentration R1=0.5% and R2=0.8%

b) Post treatments:

Microwaving at different durations 10 min, 20 min and 30 min

Air drying for 21 days

Dependendent variable: Destructive MOE.

* MOR of the control samples which is neither ACQ treated nor post treated also

taken in account for the analysis.

 

 

 

 

 

 

 

 

 

 

Source DF Type 3 88 Mean square F value Pr > F

ACQ solution 2 1329.451373 664.725686 10.68 <.0001

Post treatments 3 20.052592 6.684197 0.1 1 0.9556

ACQ solution * Post treatments 3 22.766076 7.588692 0.12 0.947

 

111

 

4. Color change, AE

Independent variables:

a) ACQ treating solution at two concentration R1=0.5% and R2=0.8%
b) Post treatments:

Microwaving at different durations 10 min, 20 min and 30 min

Air drying for 21 days

Dependendent variable: Color change, AE

 

 

 

 

 

 

 

 

 

 

Mean
Source DF Type 3 SS square F value Pr > F
ACQ solution 1 202.7539 202.7539 51.43 <.0001
Post treatments 3 8.388654 2.796218 0.71 0.5559
ACQ solution " Post treatments 3 9.911051 3.303684 0.84 0.4863

 

112

 

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Dahlgren, SE. and W.H. Hartford. 1972. Kinetics and mechanism of fixation of Cu-Cr-
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J iang, X. and Ruddick, J. N. R. 1999. A spectroscopic investigation of copper
ethelenediamine fixation in wood.. Do No. IRG/WP/99-20160. Inter. Res. Group
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