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1. Introduction
Chemical preservatives are widely used to prolong the service life of wood. Unfortunately,
some of the preservative substances can be gradually leached from treated wood into the
environment during exterior applications and can be toxic to plants, animals and human
health. Most studies on the depletion of preservatives from treated wood were performed with
small samples on a laboratory scale. Although these studies provide repeatable conditions and
are useful for shorter test durations, they have little applicability to real conditions. These
issues raised the consideration of a larger sample that is more closely associated with
commercialized material for possible improvement of the laboratory tests.
In my study I did a series of laboratory tests with smaller samples (i.e., 8 mango wood
samples and also checked the day by day changes in percentage of chemical preservative i.e.,
chromium, copper and boron which is present in the treated wood. The distribution of
chromium, copper and boron in the treated wood were also assessed. Laboratory leaching
tests were conducted in accordance to a continuous water supply procedure. In addition,
wood samples were analyzed after leaching to determine remaining metals and their
distribution in the wood specimens.
Wood is one of the most commonly used raw material in a wide variety of applications such
as poles, fences, decks, masts, constructional timber, children playgrounds etc. Wood is
susceptible to decay in conditions that are suitable for the growth of fungi. Chemicals are
used to treat the wood to prolong the service life against fungal and insect attacks. For
example, untreated railway ties that are used in North America would have an average life of
five years (Konasewich andHenning, 1998) whereas treated ties with creosote under service
conditions are estimated to serve 30 years (Webb, 1990).
Chromated copper arsenate (CCA) was the main water-based preservative formulation for
residential and industrial applications for decades. CCA is no longer permitted to be used in
India due to the concern of the arsenic exposure that could potentially be a health hazard.
Europe, Germany was the first country where the use of arsenic in preservatives was
forbidden and formulations such as chromated copper borate (CCB) and chromium copper
(CC) were introduced. The waterborne preservative containing Cr, Cu and B in its
formulation is considered to be less toxic than CCA, because of the absence of arsenic, but it
is more susceptible to leaching (Fox et al., 1994).
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Despite the fact that copper-based solutions have been widely used as fungicides for many
biocidal products, their main disadvantage is insufficient fixation. It is important that copper
present in the treating solution is fixed within the wood cells to reduce its depletion from
treated wood. It has been documented that the copper leaching from treated wood with the
new generation of copper based preservatives like copper-HDO and copper-ethanolamine is
still higher than that of the chromium-copper-based wood preservative (Habicht et al., 2003,
Temizetal., 2006).
Chromium compounds have been applied as fixing agents for decades and they are still the
most important commercial fixing agent to reduce copper leaching from the treated wood.
After the implementation of ''European Commission concerning the placing of biocidal
products on the market in 1998 (BPD 98/8/EC) '', the application of chrome-containing
preservative formulations was accepted based on the following requirements:-
(I) Products containing chromic acid, the active substance must be a copper compound, such
as copper.
(II) oxide or copper hydroxide.- The mass ratio of chromic acid to copper (II) oxide in all
products must be no more than 3:1.
Also, there are requirements regarding the use of the chrome-containing products:
- Treated wood should not be used in Use Class 1 or Class 2 applications as there are other
chromium-free alternative products available presenting a lesser risk for these uses and
should not be used in Use Class 5 (marine) applications as no data on efficacy against marine
organisms is available.
- To be applied only via vacuum pressure processes.
- Treated wood must undergo appropriate procedures to ensure fixation has been fully
completed and that full reduction of hexavalent chromium to the safer chromium trivalent
form has been achieved.
- There should be no hexavalent chromium in leachates or on the surface of treated wood
when it is placed on the market. It was demonstrated that some of the biocide substances can
gradually migrated from treatedwood into the environment during outdoor exposure and
could be toxic to plants and animals (Lebow, 1996).
In order to determine the leaching of wood preservative components from treated wood, there
are two major approaches: laboratory and field tests but dueto insufficient time and material
3
the experiment is performed in laboratory. A considerable amount of literature has been
published on laboratory evaluations of the factors that can influence the depletion of
preservative chemicals from treated wood (e.g., Smith and Williams, 1973a,b; Cooper,
1994; Haloui and Vergnaud, 1997; Schoknecht et al., 2004).
Laboratory leaching tests are reproducible. A challenge of laboratory tests is their inability to
compare to the situations found in real conditions and also their results are hardly
transformable to real conditions. Laboratory tests are usually conducted with small samples
to magnify the leaching conditions and accelerate the acquisition of results. Small sized
samples should not be used to estimate the depletion of wood preservative in service
conditions (Lebow, 1996); since larger samples are comparable to commercial-size material
in development and evaluation of laboratory methods rather than lab scale tests.
Besides the type of preservative, retention and wood species (Hingston et al., 2001), the
effectiveness of a preservative treatment is influenced by the distribution and penetration of
the preservative in the wood (Ibach, 1999).
Therefore, information on distribution of preservative chemicals within wood is important in
developing and understanding of all phases of preservatives from impregnation to outdoor
performance.1996; Schultz et al., 2002) thereby causing changes in metal contents and their
distribution within the wood These changes may affect the effectiveness of the treated wood
against biodegradation. Knowing the residual chemical content and its distribution can
provide useful information on the preservative performance in real conditions, environmental
issues, and future reuse of wood.
2. Aim of the study
The objectives of this study were to determine:
- The changes in the percentage of chromium, copper and boron in treated wood before and
after leaching
- The comparison of chromium, copper and boron leaching potential in laboratory protocol
tests.
4
3. Literature review
3.1 Composition and structure of wood
Wood is made up of cells which contain many different polymer molecules. The wood cell
wall is composed of three major components; cellulose, lignin, and hemicelluloses. In
addition, wood contains small amounts (5% to 10%) of extractives (Miller, 1999). General
description of the wood components is described below:
- Cellulose, the major component, is a linear polymer of 10.000 to 15.000 ß-D-linked
glucose anhydride units and constitutes approximately 50% of wood’s dry weight. In
“native cellulose”, hydrogen bonds exist between the OH-groups of neighboring glucose
units and neighboring cellulose molecules. Regions of crystalline cellulose and areas of lower
order (amorphous, paracrystalline cellulose) alternate (Schmidt, 2006).
- Lignin constitutes 26 to 39% of the wood substance in softwoods and 18 to 39% in
hardwoods. Lignin is a complex, three-dimensional macromolecule in the range of 10kDa
and is highly hydrophobic reducing the hygroscopicity of wood and improving itsresistance
to microorganisms. It functions as a binding and encrusting material in the cellwall
distributed with hemicelluloses in the spaces of inter-cellulose microfibrils. Most softwood
lignins are as guaiacyllignins (G-lignins) polymers predominantly made of coniferyl alcohol
(C). Hardwood lignins are guaiacyl-syringyllignins (GS-lignins) and consist predominantly of
C and sinapyl alcohol (S). Guaiacyl-syringyl-p-hydroxyphenyllignins occur in grasses
(monocotyledons). In the lignin molecule, the basic modules are linked with a variety of
chemical bonds, ether and carbon-carbon linkages. The ß-O-4-linkage is the most frequent
interunit linkage. Lignin quantity and composition vary as with the tree age, xylem and bark,
between rot and stem wood, heartwood and sapwoodearlywood and latewood, and in
different wood cells and cell wall layers. Although lignin occurs in wood throughout the cell
wall, its concentration is high in the tertiary wall and middle lamella primary wall region.
Lignin is also the primary site for bonding of chromium in wood preservatives (Pizzi, 1990).
- Hemicelluloses of wood (15 to 35%) are a complex combination of relatively shortpolymers
made of xylose (pentose), arabinose, galactose, mannose, and glucose withacetyl and uronic
side-groups. The major hemicellulose of hardwoods is the O-acetyl-(4-O-methylglucurono)-
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xylan or briefly xylan. Hemicelluloses of conifers (glucomannans,galactoglucomannans)
consist mainly of the hexose mannan.
- Extractives are deposited in wood without strongly bonding with other wood substancesand
are soluble in organic solvents.
3.2 Protection and preservation of wood
Wood has been a major construction material throughout history. Wood can be damaged by
fungi, bacteria, insects and termites (e.g. Schmidt, 2006). Manifold protection and
preservation measures have been experienced or are still in use. Wood protection in the
broader sense comprises non-chemical methods like organizational measures and measures
by design, use of naturally durable woods, application of antagonists, wood modifications,
thermal modifications and wood hydrophobizations that do not affect the environment
(Willeitner and Schwab, 1981;Militz and Krause, 2003; Rapp and Müller, 2005). Wood
preservation has been associated predominantly with chemical modifications.
Simple, however, often less effective application methods of chemical preservatives to the
woodare brushing, spraying and dipping. Pressure treatment of wood with biocidal products
is the primary industrial method utilized for developing treatment chemicals into wood and
has been proven to protect the wood effectively from biological attacks. The degree of
protection depends on the preservative chemical used and its proper penetration. To preserve
the wood, it is necessary for biocide substances to penetrate into the wood adequately.
Several factors influence the degree of protection that can be achieved with biocides such as
(Morris, 1996):
- Method of wood treatment,
- Quantitative ratio of heartwood to sapwood,
- Permeability of wood,
- Wood moisture content.
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3.3 Chromium ,copper and boron
For decades chromated copper arsenate (CCA) was the major preservative for residential and
industrial construction with soil contact because it is very effective, inexpensive and can be
fixed very well after treatment. Three different types of CCA-formulations for treatment of
wood have been developed over time. Type A contained more chromium, while Type B had
more arsenic. Type C of CCA is comprised of 47.5% chromium trioxide, 18.5% copper oxide
and 34.0%arsenic pentoxide. Type C has been the most common formulation because of its
resistance to leaching and excellent field efficacy.
Water-borne preservative treatments must be applied by a vacuum-pressure treating process.
Fixation is generally referred to as the conversion of water-soluble inorganic components into
stabilized components, which resist depletion and provide longer service life of the treated
wood.Lebow (1996) pointed out that the essence of CCA fixation is the reduction reaction of
chromium from the hexavalent to the trivalent state, and the subsequent precipitation or
adsorption of copper. Factors including temperature, relative humidity and treating solution
pH-value are the main parameters affecting fixation reactions (Pizzi, 1983a,b; Peek and
Willeitner, 1981, 1988).A study by Guo et al. (2002) on the fixation of early wood,
latewood, sapwood and heartwood of CCA-treated Douglas fir, southern pine and eastern
larch indicated that wood density, extractives and species affected the fixation of CCA.
Chromium is the least mobile of CCA components and its mobility depends on its
valencystate.Trivalent chromium is very reactive with organics and fixes to soil and
sediments quickly.Hexavalent chromium is more soluble but less absorbed and the rate of its
movement through soil and groundwater is the same (Rouse and Pyrih, 1990). The valence
state of chromium is a function of the oxygen content and redox potential, pH-value,
suspended inorganic, and the presence of dissolved or particulate organic matter (Lebow,
1996). When there are no organic compounds in the media, hexavalent chromium is the most
stable form in equilibrium with atmospheric oxygen (McGrath and Smith, 1990).
Copper has been known for having wood protection qualities since the eighteenth
century(Freeman and McIntyre, 2008). Copper is a primary fungicide and because of its
excellent fungicidal properties and low mammalian toxicity has been used in many wood
preservative formulations. The production of wood treated with copper based preservatives
has advantages: it is easy to create waterborne formulations; it is easy to analyze and
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determine penetration in wood; and copper slows photo degradation by UV radiation
(Freeman and McIntyre, 2008). Adsorption of copper is a very important factor in
determining its mobility and is influenced by pH-value, amount and type of adsorbents
(Lebow, 1996).
Boron is a chemical element with symbol B and atomic number 5. Because boron is
produced entirely by cosmic ray spallation and not by stellar nucleo synthesis it is a low-
abundance element in both the Solar system and the Earth's crust. Boron is concentrated on
Earth by the water-solubility of its more common naturally occurring compounds, the borate
minerals. These are mined industrially as evaporates, such as borax and kernite. The largest
proven boron deposits are in Turkey, which is also the largest producer of boron minerals.
Chemically un combined boron, which is classed as a metalloid, is found in small amounts
in meteoroids, but is not found naturally on Earth. Industrially, very pure boron is produced
with difficulty, as boron tends to form refractory materials containing small amounts of
carbon or other elements. Several allotropes exist: amorphous boron is a brown powder, and
crystalline boron is black, extremely hard (about 9.5 on the Mohs scale), and a poor
conductor at room temperature. The primary use of elemental boron is to make boron
filaments, which are used in a similar way to carbon fibers in some high-strength materials.
Almost all boron use is as chemical compounds. About half of global consumption of boron
compounds is as additives for glass fibers in boron-containing fiberglass used for insulation
or as structural materials. The next leading use is to make boron polymers and ceramics that
play specialized roles as high-strength lightweight structural and refractory
materials. Borosilicate glass glassware is used for its greater strength and breakage resistance
(thermal shock resistance) than ordinary soda lime glass. Boron compounds are also used
as fertilizers in agriculture, and in sodium perborate bleaches. In minor uses, boron is an
important dopant for semiconductors, and boron-containing reagents are used as
intermediates in the synthesis of organic fine chemicals. A few boron-containing organic
pharmaceuticals are used, or are in study. Natural boron is composed of two stable isotopes,
one of which (boron-10) has a number of uses as a neutron-capturing agent.
In biology, borates have low toxicity in mammals (similar to table salt), but are more toxic
to arthropods and are used as insecticides. Boric acid is mildly antimicrobial, and a natural
boron-containing organic antibiotic is known. Boron is essential to life. Small amounts of
8
boron compounds play a strengthening role in the cell walls of all plants, making boron
necessary in soils. Experiments indicate a role for boron as an ultra trace element in animals,
but its role in animal physiology is unknown. (www.wikipedia.com)
3.4 Laboratory studies on preservative leaching.
Over the past years, attention considerable has been focused on the depletion of biocidal
products from treated wood due to public and scientific awareness. The performance of
preservative chemicals can be achieved either under service conditions or under laboratory
tests. Until recently, most studies were conducted in the laboratory scale. The procedures are
either based on constant immersion or short immersion cycles. Constant immersion tests are
usually used to describe leaching of preservative-treated wood in contact with the ground or
in contact with fresh or salt water. Short time immersions are intended to simulate
intermittent wetting and drying events for wood held in storage after treatment and for
wooden commodities that are not in ground or water contact.
Laboratory leaching tests are a fundamental approach to generate data from treated wood
under controlled conditions. Their great advantage is their repeatability. Laboratory tests are
rapid and inexpensive. However, according to the international standards for laboratory
leaching pointed out that result from these method tests cannot be applied to determine the
depletion of preservative chemicals in real conditions since the results cannot be related to
outdoor exposure of wood in service. There are a number of possible explanations for this.
Wood exposed in laboratory leaching test is subjected to different conditions from those
affecting wood under real service conditions. These include actual environmental conditions,
physical stresses and metabolizing organisms. In addition, chemical retention, penetration
and scale and size of the commercial treated wood are different than the treated wood in
comparison to laboratory samples.
Environmental parameters are important for the preservative performance. The following
section covers some important factors that impact on the chemical depletion from the treated
wood during outdoor exposure. Exposure time of the treated wood can determine the amount
preservative leached from treated wood. Lebow (1996) stated that most of metal leaching
from treated wood occurs during the first exposure to the leaching medium. This time-
9
dependent depletion pattern is a function of the sample size, the amount and type of surface
exposed and the amount of chemicals fixed to wood.
The climatic conditions also play an important role in the leaching process, particularly
rainfall, temperature, and sunshine. Water is the key factor for depletion and mobility of
preservatives in treated wood, regardless of exposure type. It has been demonstrated that
leaching of CCA components is significantly increased due to a low pH-value of the leaching
water (Murphy and Dickinson, 1990; Kim and Kim, 1993).
Temperature contributes on the drying and wetting of wood, solubility of the unfixed or
poorly fixed preservative components and brings components to the wood surface (Choi et
al., 2004).Increasing temperature increases the amount of leached CCA compounds (Van
Eetvelde et al.,1994, 1995a,b). The amount of time directly exposed to sunlight can have an
effect on the exposed surface of the wood and UV radiation leads to an attack on lignin (Choi
et al., 2004)which is the primary bonding site of chromium (Pizzi, 1990).
The wood properties of the species are other factors affecting the amount of leaching. Low
permeable species like spruce tend to be more resistance to leaching (Wilson, 1971). Wood
species also affect the distribution of preservative within the wood (Lebow, 1996). CCA
components fixation in latewood is much more than in earlywood due to more reacting
substances and greater density.
An important factor in depletion of preservatives is the size and dimension of the wood
sample (Lebow, 1996). Large surface area/volume ratios of small samples permits more
surface are available for leaching and more rapid water penetration (Cooper, 1994). It may
destroy a considerable amount of treated wood due to erosion and attack by organisms
causing difficulty in interpretation of long-term leaching experiments (Lebow et al., 2008).
Development of laboratory tests to quickly provide comparable data to outdoor exposure is
an important part of any laboratory standard protocol.
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4. Material and methodology
4.1 Sample preparation
The type of wood used for the preparation of the samples in this study was Mangifera
indica(Mango Wood), obtained from the Wood Preservation Laboratory, FRI stored under
shelter. The samples were prepared from the heartwood/sapwood parts of the randomly
chosen planks; it was chosen to be regular-fibre, knotless, crack-free and free from other
defects. The plank was surface planed with a planer and then ripped by a circular saw with
rough dimensions of15×3.5×3.5 (length × width × thickness)into 8 samples.
Treated wood Dimensions (cm) Sapwood/heart-wood
( 7Mangifera Indica.) 15×3.5×3.5 Sapwood
Control wood Dimensions (cm) Sapwood/heart-wood
( 1Mangifera Indica.) 15×3.5×3.5 Sapwood
Table 1.1
The performance of wood preservative chemicals was evaluated using laboratory
experiments. During the laboratory experiment 8 wood stakes are first treated with CCB
by full cell process and then leave it for 10 days for fixation. In 8 wood stakes 1 wood
stakes is taken as control. The laboratory tests were accelerated by placing treated woods
(which is further converted into powder form by grinding the wood samples and then place
it in the separation with continuous water supply tap followed by the determination of metal
concentrations in wood stakes on First ,Third, Seventh and Tenth day.
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4.2 Solution preparation
Figure: CCB Solution
For all experiments, treating the wood stakes with solution of 4%commercial chromium-and
copper and boron (CCB) containing preservatives The treating solution were made by
diluting the chromium-and copper- and boron containing preservatives with tap water in
4:3:1.5 ratio.
4.3 Sample treatment and fixation
The wood stakes were treated in according to full cell process. Prior to impregnation, the
wood stakes were dried for 24 hours at 60°C to minimize cracking. Samples then were dried
at 103°C for 24h and the dry weight was recorded. The stakes were treated by vacuum-
pressure (full cell process).The duration of vacuum and pressure was held constant for all
samples. The samples were placed in a pilot plant subjected to a vacuum of 56 cm of
mercury is created for 30 min followed by pressur3.5kg/cm2
to 12.5kg/cm2
for one and half
hour in a treating cylinder .The samples were taken out after the pressure was released and
then stored for 10 days for fixation of CCB in open air.
Figure: Pilot treating cylinder used for impregnation of wood samples.
12
4.4 Determination of metal retention
(Calculation of chromium and copper and boron retention based on technical data
sheet)
The retention level of metals in the wood samples was calculated by the amount of solution
absorbed(retention value in( gm/cm3)
Retention R=
𝐺𝐶
100
g/cm3
OR
Retention R=(
𝐺𝐶
𝑉
× 10) kg/cm3
Where-
G=the weight of treating solution absorbed by block (W2-W1) in grams.
C= the weight in g of the preservative present in 100 g of the solution.
V=the volume of the test block in cm3
Volume=(3.5𝑐𝑚 × 3.5𝑐𝑚 × 15𝑐𝑚)
=183.75cm3
(Table showing weights before treatment with CCB and after treatment with CCB)
Initial weight ( in g) Final weight(in g) Difference in weight Wet weight retention
107.0g Control Control Control
108.4g 226.2g 117.8g (0.02564)g/cm3
104.8g 215.8g 111g (0.02416)g/cm3
111.8g 224.6g 112.8g (0.02455)g/cm3
107.4g 220.6g 113.2g (0.02464)g/cm3
117.8g 226.8g 109g (0.02372)g/cm3
112.2g 224.2g 112g (0.02438)g/cm3
106.4g 219.2g 112.8g (0.02455)g/cm3
Note: Wet weight retention=Retention R=
𝐺𝐶
100
g/cm3
After getting wet weight retention, keep the samples in open air flow condition for
fixation of CCB for 10 days.
13
Treated wood with CCB after 10 days of fixation
5. Stages of sample preparation for leaching of treated wood in laboratory
 After 10 days of fixation take the weights of treated wood.
 Cut the wood stakes into smaller pieces so that it can easily grind.
 Grind Second number stake for dry salt retention.
 Grind third to eight number sample for final leaching.
 Use separation flask for final leaching by continious water method.
 The grind wood (3-8) powder(100g) is subjected in separation flask for leaching
of CCB from wood powder.
 Collect the Elute of 1,3,7,10 day(kinectics)
 Condense the Elute s of different days into 100 ml liquid in measuring flask.
 Measure CCB concentration in each elute by anaylitical method.
 Take 10 gm of dried residual saw dust from separation flask and calculate CCB .
 Finally compare all CCB concentration to check how much CCB is leaced out.
 Draw graph.
f
14
(((
Picture showing steps in leaching of CCB from Magnifera Indica
15
16
`
17
5.1 Calculation of copper, chrome .boron by analytical method in FRI laboratory
(Wood preservation in India by Satish Kumar and Inderdev)
AIM:1
Determination of hexavalent chromium as potassium dichromate (k2cr207)hexavalent
.chromium is determined by reduction with an excess ferrous ammonim sulphate
solution(Fe((NH4)2(SO4)2.6H20)
solution and subsequent titration of the excess ferrous salt with 1 percent potassium
dichromate solution using barium diphenyl amine sulphonate as an internal indicator.
REAGENTS
1. Phosphoric acid
2. Ferrous ammonium sulphate
3. Potassium dichromate solution
4. Barium diphenyl amine sulphonate solution
PROCEDURE
Pipette 10ml of filtering treating solution (CCB) into 250ml of conical flask and add 3-5ml
phosphoric acid and 20ml ferrous ammonium sulphate solution into a conical flask.This will
cause a colour change from orange to clear green. no trace of yellow should remain. rinse
while distilled water and add 10 drops of the indicator barium diphenyl amine sulphonate and
titrate the solution with 1 percent [potassium dichromate. The end point is reached when the
colour change from clear bright green to purple colour.At the time of carrying g out for
going titration another 20ml portion of same ferrous ammonium sulphate solution into 250ml
conical flask and add 3-5ml phosphoric acid and add 10 rops of barium diphenyl amine
sulphonate indicator and rinse the flask with distilled water and carryout the titration with 1
percent potassium dichromate solution to the same end point as above
CALCULATION
Percent concentration of𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚𝑎𝑠Fe2cr2o7
=
𝑊𝑖𝑡ℎ𝑜𝑢𝑡𝐶𝐶𝐵 − 𝑊𝑖𝑡ℎ𝐶𝐶𝐵
10
18
AIM:2
Determination of copper as CuSo4.5H2O (Copper-sulphate).Copper is determined
hydrometrically (use of iodine).After first destroying the chromate with hydrogen peroxide
(H2O2) excess of hydrogen peroxide is removed by boiling. After adjusting the acid
concentration potassium iodide is added and the solution is titrated immediately with sodium
thiosulphate solution of known strength reagent.
REAGENTS
1. Concentrated hydrochloric acid
2. Hydrogen peroxide
3. Sodium hydroxide solution
4. Potassium iodide(KI)
5. Starch indicater function
PROCEDURE
Pipette 10ml filtered treating solution into a 250ml conical flask and add 10ml concentrated
HCL and 10ml hydrogen peroxide carefully ground the side of flask while gently stirring the
content and rinse the flask with minimum amount of distilled water and heat solution gently
until all oxygen evaluation stops and then boil for approximate 5minutes.When the volume of
solution has been reduced to about 5ml for yellowish green solution and adjust the acidity of
the solution by adding 20 percent sodium hydroxide solution slowly with constant stirring
until a permanent precipitate just forms. Then add concentrated HCL drop by drop until the
precipitate just dissolve. After which add 1or 2 drop of acid HCL more. Cool the solution at
approximate 5 to 10 ml 20 percent potassium iodide (KI) and add 5-10ml starch solution. The
solution turns in blue color and titrate the solution immediately with 0.955 percent solution of
sodium thiosulphate.Continue the titration until the blue color fades.
CALCULATION
Consumption of sodium thiosulphate solution divide by 10 is equal to percent of copper as
copper sulphate.
19
AIM; 3
Quantitative determination of Boron.
REAGENTS:
1. Dilute sodium hydroxide solution=10 %(w/v).
2. Phenolphthalein indicator.
3. Concentrated hydrochloric acid.
4. Methyl orange.
5. Glycerol
DIGESTION OF WOOD FLOUR:
A mixture of about 2.5 to 5.0 gm of finely ground wood to a paste with saturated barium
hydroxide in platinum crucible. Dry on a water bath, ash slowly in muffle furnance first at
low temp and then gradually raise the temperature to dull red heat(500o-600o) ashing should
be completed in about 1.5 hours when no trace of carbon remains. Half fill the crucible with
distilled water and dilute HCL to discolor the ash. Keep the crucible covered during this
operation, make the solution to a known volume in a graduate flask, the solution should be
used for determination of boron.
PROCEDURE:
Take 10ml solution of about 1-1.25%boric acid in a nickel or platinum crucible and add 2-
3ml of 10%NaoH Solution and evaporate to nearly dryness over a water bath charring the
residue for about 5min at a dull red heat. Dissolve the residue in about 10-15ml warm
distilled water into a conical flask and add 2 drops of phenolphthalein indicator resulting a
red color .Then add concentrated HCL drop s till color fades and add 2 drops of methyl
orange indicator resulting yellow color and add few drops of concentrated HCL till the
solution is acidic to this indicator is red by means of dilute NaoH,Adjust the solution to
methyl orange and point yellow and boil gently for 15 min under air reflex condenser making
sure that steam doesn’t issue from the top of the condenser (This step is to remove co2 from
the solution).Cool the solution and readjust the methyl orange end point yellow ,add a
measured amount (approx0 equal to 1.5 times the volume of the solution of glycerol into the
solution and add 0.5 ml of phenolphthalein indicator and titrate with N/10standard carbonate
free sodium hydroxide solution to the phenolphthalein end point pink.
20
6.Result and Discussion:
1. CCB is formed by dissolving copper, chrome, boron preservative in 10L water at 4%
concentration with 4:3:1.5 ratios.
 For copper
4
8.5
× 4=1.882 %
 For chrome
3
8.5
× 4=1.441%
 For boron
1.5
8.5
× 4=0.705%
Therefore, for 10L Copper is 188g, Chrome is 144g and for Boron is 70g
2. Dry Salt Retention
=
𝑇𝑜𝑡𝑎𝑙𝑠𝑎𝑙𝑡
𝑣𝑜𝑙𝑢𝑚𝑒
× 1000 𝑘𝑔/𝑚3
For finding DSR we cut all samples from its both end so that we can get to know
about penetration of CCB in wood samples by spot test.
After cutting second number sample from both ends length, breath and thickness of wood
sample is 9.133cm, 3.5cm, 3.5cm
Therefore,
Volume is 9.1𝑐𝑚 × 3.5𝑐𝑚 × 3.5𝑐𝑚
=111.8 cm3
Density=Mass/volume
=71.7g/111.8cm3
=0.64g/cm3
2.1 Laboratory analysis for finding Cu,Cr,Br from 2nd
number wood sample (powder form)
a. Percent concentration of𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚𝑎𝑠K2cr2o7
Without CCB=12.5
With CCB=12.0
21
=Without CCB-With CCB /10
=0.05% of chromiumas potassium dichromate.
b.Consumption of sodium thiosulphate solution divide by 10 is equal to percent of copper as
copper sulphate.
Percent concentration of copper after consumption of sodium thiosulphate is 10.5/10=1.05%
c. Percent concentration of boron is 0.50%
Total salt =1.05% of 188g+0.05%of 144g+0.50% of 70g
=1.974+0.072+0.35
=2.046g
Weight of 2nd number sample is 47.4g (powder form)
Weight of 3rd to 8th
number sample is 293.2g (powder form)
Since, we are considering 2nd
number sample for Dry salt retention
Therefore,
Mass of wood sample is 47.4g
Density of wood sample is 0.64gm/cm3
Volume in powder form is mass/density=47.4g/0.64g/cm3
=74cm3
Dry salt retention is
=
𝑇𝑜𝑡𝑎𝑙𝑠𝑎𝑙𝑡
𝑣𝑜𝑙𝑢𝑚𝑒
× 1000𝑘𝑔/𝑚3
=
2.046
74
× 1000
27.64kg/m3
or 0.02764g/cm3
22
3.Laboratory analysis of CCB Leaching on 1,3,7,10 day
DAYS Copper leached (%)
Chromium leached
(%)
Boron leached (%)
1 0.10 0.05 0.15
3 0.15 0.05 0.20
7 0.20 0.05 0.25
10 0.25 0.05 0.30
Fig: Graph showing leaching of copper, chrome, boron
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
1 3 7 10
CCB(%)
NO. OF DAYS
GRAPH SHOWING LEACHING OF CCB(%)
COPPER(%)
CHROMIUM(%)
BORON(%)
23
7.CONCLUSION:
 The cumulative amount of leached metals from all specimens showed that boron
leached higher than copper and copper leaching was higher than that of chromium .
 𝑙𝑒𝑎𝑐ℎ𝑖𝑛𝑔 𝑜𝑓 𝑏𝑜𝑟𝑜𝑛 > 𝑙𝑒𝑎𝑐ℎ𝑖𝑛𝑔 𝑜𝑓 𝑐𝑜𝑝𝑝𝑒𝑟 > 𝑙𝑒𝑎𝑐ℎ𝑖𝑛𝑔 𝑜𝑓 𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚
 The resistance of chromium to leaching should be due to fixation properties of
chromium in wood.
 It is known that during fixation reactions with wood, chromium reacts strongly with
lignin while copper binds with cellulose materials.
 The low amount of chromium depletion was observed in numerous laboratory.
 Boron compounds in current use as wood preservatives are susceptible to loss via
leaching,under certain conditions.This is because they are not chemically fixed after
treatment and remain mobile within the treated wood.
 The quantity ofpreservative leached is a function of specimen size, type of leaching
exposure and the leach resistance of the preservative component in question. For the
more leachable preservative components, constant immersion of lumber specimens or
simulated rainfall oil specimens resulted in the greater losses.
 The change in color of liquid from dark color to light which is collected in the
form of elute shows the percentage change in elute visually.
 Mangifera Indica (Mango wood) is not susceptible for constructional purpose even
though it is treated with CCB because after a prolong rainfall CCB can be easily
leached ot from wood.
 Fixation of CCB on Mangifera Indica is good.
24
REFERENCES:
Cooper, P.A. 1994. Leaching of CCA: is it a problem? In: Environmental considerations in
the manufacture, use and disposal of pressure-treated Wood. Forest Products
Society.Madison, WI, USA.
Choi, S., Ruddick, J.R. and Morris, P. 2004. Chemical redistribution in CCA treated decking.
Forest Products Journal 54:33-37.
Freeman, M.H. and McIntyre, C. R. 2008. A comprehensive review of copper-based wood
preservatives with a focus on a new micronized or dispersed copper system. Forest
Product Journal 58: 6-27.
Fox, R.F., Pasek, E.A., Deshan, P.N. [and others]. 1994. Copper azole wood preservatives.
Proposal to the American Wood Preservers’ Association Committees to include
CopperAzole Type A in AWPA Standard P-5. Conley, GA: Hickson Corporation.
Guo, A.L., Cooper, P.A., Ung, Y.T. and Ruddick, J.R. 2002. Comparison of fixation rates of
early wood, latewood, sapwood, and heartwood of CCA-treated Douglas-fir, southern
pine, and eastern larch. Forest Products Journal 52:77-80.
Habicht, J., Hantzschel, D. and Wittenzellner, J. 2003. Influence of different fixation and
ageing procedure on the leaching behavior of copper from selected wood
preservatives in laboratory trials. The International Research Group on Wood
Preservation, Stockholm.IRG/WP 03-20264
Haloui. A. and Vergnaud, J.M. 1997. Study of the release in water of chemicals used for
wood preservation. Effect of wood dimensions. Wood Science and Technology 31:51-
62.
25
Hingston, J.A., Collins, C.D., Murphy, R.J. and Lester, J.N. 2001. Leaching of chromated
copper arsenate wood preservatives: a review. Environmental Pollution 111:53-66.
Ibach, R.E. 1999. Wood preservation. Wood handbook: Wood as an engineering material.
Forest Products Laboratory, USDA Forest Service. Madison, WI. 21p.
Kim, J.J. and Kim, G.H. 1993. Leaching of CCA components from treated wood under acidic
conditions. The International Research Group on Wood Preservation,
Stockholm.IRG/WP 93-50004.
Konasewich, D.E. and Henning, F.A. April 1998. Chromated Copper Arsenate Wood
Preservation facilities, Environment Canada, Report EPS 2 /WP/3.
Lebow, S. 1996. Leaching of wood preservative components and their mobility in the
environment. General Technical Report FPL-GTR-93, US Department of Agriculture,
Forest Products Laboratory, Madison.
Lebow, S., Lebow, P., Woodward, B., Halverson, S., Abott, W. and West, M. 2009. Efficacy
of a borax-copper preservative in exposed applications. Research paper, FPL-RP-655,
US Department of Agriculture, Forest Products Laboratory, Madison.
McGrath, S.P. and Smith, S. 1990. Chromium and nickel. In: Alloway, B.J., ed. Heavy metals
in soils. New York: John Wiley and Sons:125-150
Miller, R.B. 1999. Structure of wood. Wood handbook: Wood as an engineering material.
Forest Products Laboratory, USDA Forest Service. Madison, WI. 33p
Morris, P.I. 1996. Towards a unified international hazard class system. The International
Research Group on Wood Preservation, Stockholm. IRG/ WP 96-20081.
Militz, H. and Krause, A. 2003. Verfahren der Holzmodifizierungfür den Fenster- und
Fassadenbau. RosenheimerFenstertage 6:101-106.
26
Murphy, R. and Dickinson, D. 1990. The Effect of acid rain on CCA treated timber. The
International Research Group on Wood Preservation, Stockholm. IRG/WP 99-3579.
Peek, R.D. and Willeitner, H. 1981. Accelerated fixation of chromate-containing wood
preservatives by superheated steam. Effect of different heat-treatment on the leaching
of preservatives. HolzAlsRoh-Und Werkstoff 39:495-502.
Peek, R.D. and Willeitner, H. 1988. Fundamentals of steam fixation of chromated wood
preservatives. The International Research Group on Wood Preservation,
Stockholm.IRG/WP 3483.
Pizzi, A. 1990. Chromium interactions in CCA/CCB wood preservatives. Part I. Interactions
with wood carbohydrates. Holzforschung 44:373-380.
Rapp, A.O. and Müller, J. 2005. NeueVerfahren und Tendenzen. In: HolzschutzimHochbau.
Müller,J. (Hrsg.). Stuttgart: Fraunhofer IRB-Verlag .S. 331-347.
Rouse, J.V. and Pyrih, R.Z. 1990. In place clean up of heavy metal contamination of soil and
ground water at wood preservation sites. In: Proceedings, American Wood Preservers
‘Association 86:215-220
Schmidt, O. 2006. Wood and tree fungi. Biology, damage, protection, and use. Springer-
Verlag,Berlin-Heidelberg, Germany. 334 S.
Schoknecht, U., Wegner, R., Melcher, E., Seidel, B., Kussatz, C. and Maletzki, D. 2004. The
influence of test parameters on the emission of biocides from preservative-treated
wood in leaching tests. Umweltforschungsplan des Bundesministeriumsfür Umwelt,
Naturschutz und Reaktorsicherheit. Förderkennzeichen (UFOPLAN) 20367441.
Berlin: BundesanstaltfürMaterialprüfung und -forschung, Abschlussbericht. 161 S.
Smith, D.N.R. and Williams, A.I. 1973a. The effect of composition on the effectiveness and
fixation of copper-chrome-arsenic and copper-chrome preservatives. Part II: selective
absorption and fixation. Wood Science and Technology 7:142-150.
27
Smith, D.N.R. and Williams, A.I. 1973b. The effect of composition on the effectiveness and
fixation of copper-chrome-arsenic and Copper-chrome preservatives: Part I:
effectiveness. Wood Science and Technology 7:60-76.
Temiz, A., Yildiz, U.C. and Nilsson, T. 2006. Comparison of copper emission rates from
wood treated with different preservatives to the environment. Build Environ 41:910-
914.
Van Eetvelde, G., Waldemar, J.H., Militz, H. and Stevens, M. 1995b. Effect of
leachingtemperature and water acidity on the loss of metal elements from CCA
treated timber inaquatic applications: Part 2: Semi-industrial investigation. The
International Research Group on Wood Preservation, Stockholm. IRG/WP 95-50046.
Webb, D.A. 1990. Wood preservative treatments for crossties and potential future treatments.
The Railway Tie Association Annual Meeting, Birmingham, Alabama, October 10-
12.
Willeitner, H. and Schwab, E. 1981. Holz-AussenanwendungimHochbau. Verlagsanstalt
Alexander Koch, Stuttgart.
Williams, R., Lebow, S. and Lebow, P. 2003. Effect of weathering on chromated copper
arsenate (CCA) treated wood: leaching of metal salts and change in water repellency.
In: Proceedings, American Wood-Preservers’ Association 99:125-141.
Wood preservation in India by Satish Kumar and Inderdev

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paras dissertation pdf

  • 1. 1 1. Introduction Chemical preservatives are widely used to prolong the service life of wood. Unfortunately, some of the preservative substances can be gradually leached from treated wood into the environment during exterior applications and can be toxic to plants, animals and human health. Most studies on the depletion of preservatives from treated wood were performed with small samples on a laboratory scale. Although these studies provide repeatable conditions and are useful for shorter test durations, they have little applicability to real conditions. These issues raised the consideration of a larger sample that is more closely associated with commercialized material for possible improvement of the laboratory tests. In my study I did a series of laboratory tests with smaller samples (i.e., 8 mango wood samples and also checked the day by day changes in percentage of chemical preservative i.e., chromium, copper and boron which is present in the treated wood. The distribution of chromium, copper and boron in the treated wood were also assessed. Laboratory leaching tests were conducted in accordance to a continuous water supply procedure. In addition, wood samples were analyzed after leaching to determine remaining metals and their distribution in the wood specimens. Wood is one of the most commonly used raw material in a wide variety of applications such as poles, fences, decks, masts, constructional timber, children playgrounds etc. Wood is susceptible to decay in conditions that are suitable for the growth of fungi. Chemicals are used to treat the wood to prolong the service life against fungal and insect attacks. For example, untreated railway ties that are used in North America would have an average life of five years (Konasewich andHenning, 1998) whereas treated ties with creosote under service conditions are estimated to serve 30 years (Webb, 1990). Chromated copper arsenate (CCA) was the main water-based preservative formulation for residential and industrial applications for decades. CCA is no longer permitted to be used in India due to the concern of the arsenic exposure that could potentially be a health hazard. Europe, Germany was the first country where the use of arsenic in preservatives was forbidden and formulations such as chromated copper borate (CCB) and chromium copper (CC) were introduced. The waterborne preservative containing Cr, Cu and B in its formulation is considered to be less toxic than CCA, because of the absence of arsenic, but it is more susceptible to leaching (Fox et al., 1994).
  • 2. 2 Despite the fact that copper-based solutions have been widely used as fungicides for many biocidal products, their main disadvantage is insufficient fixation. It is important that copper present in the treating solution is fixed within the wood cells to reduce its depletion from treated wood. It has been documented that the copper leaching from treated wood with the new generation of copper based preservatives like copper-HDO and copper-ethanolamine is still higher than that of the chromium-copper-based wood preservative (Habicht et al., 2003, Temizetal., 2006). Chromium compounds have been applied as fixing agents for decades and they are still the most important commercial fixing agent to reduce copper leaching from the treated wood. After the implementation of ''European Commission concerning the placing of biocidal products on the market in 1998 (BPD 98/8/EC) '', the application of chrome-containing preservative formulations was accepted based on the following requirements:- (I) Products containing chromic acid, the active substance must be a copper compound, such as copper. (II) oxide or copper hydroxide.- The mass ratio of chromic acid to copper (II) oxide in all products must be no more than 3:1. Also, there are requirements regarding the use of the chrome-containing products: - Treated wood should not be used in Use Class 1 or Class 2 applications as there are other chromium-free alternative products available presenting a lesser risk for these uses and should not be used in Use Class 5 (marine) applications as no data on efficacy against marine organisms is available. - To be applied only via vacuum pressure processes. - Treated wood must undergo appropriate procedures to ensure fixation has been fully completed and that full reduction of hexavalent chromium to the safer chromium trivalent form has been achieved. - There should be no hexavalent chromium in leachates or on the surface of treated wood when it is placed on the market. It was demonstrated that some of the biocide substances can gradually migrated from treatedwood into the environment during outdoor exposure and could be toxic to plants and animals (Lebow, 1996). In order to determine the leaching of wood preservative components from treated wood, there are two major approaches: laboratory and field tests but dueto insufficient time and material
  • 3. 3 the experiment is performed in laboratory. A considerable amount of literature has been published on laboratory evaluations of the factors that can influence the depletion of preservative chemicals from treated wood (e.g., Smith and Williams, 1973a,b; Cooper, 1994; Haloui and Vergnaud, 1997; Schoknecht et al., 2004). Laboratory leaching tests are reproducible. A challenge of laboratory tests is their inability to compare to the situations found in real conditions and also their results are hardly transformable to real conditions. Laboratory tests are usually conducted with small samples to magnify the leaching conditions and accelerate the acquisition of results. Small sized samples should not be used to estimate the depletion of wood preservative in service conditions (Lebow, 1996); since larger samples are comparable to commercial-size material in development and evaluation of laboratory methods rather than lab scale tests. Besides the type of preservative, retention and wood species (Hingston et al., 2001), the effectiveness of a preservative treatment is influenced by the distribution and penetration of the preservative in the wood (Ibach, 1999). Therefore, information on distribution of preservative chemicals within wood is important in developing and understanding of all phases of preservatives from impregnation to outdoor performance.1996; Schultz et al., 2002) thereby causing changes in metal contents and their distribution within the wood These changes may affect the effectiveness of the treated wood against biodegradation. Knowing the residual chemical content and its distribution can provide useful information on the preservative performance in real conditions, environmental issues, and future reuse of wood. 2. Aim of the study The objectives of this study were to determine: - The changes in the percentage of chromium, copper and boron in treated wood before and after leaching - The comparison of chromium, copper and boron leaching potential in laboratory protocol tests.
  • 4. 4 3. Literature review 3.1 Composition and structure of wood Wood is made up of cells which contain many different polymer molecules. The wood cell wall is composed of three major components; cellulose, lignin, and hemicelluloses. In addition, wood contains small amounts (5% to 10%) of extractives (Miller, 1999). General description of the wood components is described below: - Cellulose, the major component, is a linear polymer of 10.000 to 15.000 ß-D-linked glucose anhydride units and constitutes approximately 50% of wood’s dry weight. In “native cellulose”, hydrogen bonds exist between the OH-groups of neighboring glucose units and neighboring cellulose molecules. Regions of crystalline cellulose and areas of lower order (amorphous, paracrystalline cellulose) alternate (Schmidt, 2006). - Lignin constitutes 26 to 39% of the wood substance in softwoods and 18 to 39% in hardwoods. Lignin is a complex, three-dimensional macromolecule in the range of 10kDa and is highly hydrophobic reducing the hygroscopicity of wood and improving itsresistance to microorganisms. It functions as a binding and encrusting material in the cellwall distributed with hemicelluloses in the spaces of inter-cellulose microfibrils. Most softwood lignins are as guaiacyllignins (G-lignins) polymers predominantly made of coniferyl alcohol (C). Hardwood lignins are guaiacyl-syringyllignins (GS-lignins) and consist predominantly of C and sinapyl alcohol (S). Guaiacyl-syringyl-p-hydroxyphenyllignins occur in grasses (monocotyledons). In the lignin molecule, the basic modules are linked with a variety of chemical bonds, ether and carbon-carbon linkages. The ß-O-4-linkage is the most frequent interunit linkage. Lignin quantity and composition vary as with the tree age, xylem and bark, between rot and stem wood, heartwood and sapwoodearlywood and latewood, and in different wood cells and cell wall layers. Although lignin occurs in wood throughout the cell wall, its concentration is high in the tertiary wall and middle lamella primary wall region. Lignin is also the primary site for bonding of chromium in wood preservatives (Pizzi, 1990). - Hemicelluloses of wood (15 to 35%) are a complex combination of relatively shortpolymers made of xylose (pentose), arabinose, galactose, mannose, and glucose withacetyl and uronic side-groups. The major hemicellulose of hardwoods is the O-acetyl-(4-O-methylglucurono)-
  • 5. 5 xylan or briefly xylan. Hemicelluloses of conifers (glucomannans,galactoglucomannans) consist mainly of the hexose mannan. - Extractives are deposited in wood without strongly bonding with other wood substancesand are soluble in organic solvents. 3.2 Protection and preservation of wood Wood has been a major construction material throughout history. Wood can be damaged by fungi, bacteria, insects and termites (e.g. Schmidt, 2006). Manifold protection and preservation measures have been experienced or are still in use. Wood protection in the broader sense comprises non-chemical methods like organizational measures and measures by design, use of naturally durable woods, application of antagonists, wood modifications, thermal modifications and wood hydrophobizations that do not affect the environment (Willeitner and Schwab, 1981;Militz and Krause, 2003; Rapp and Müller, 2005). Wood preservation has been associated predominantly with chemical modifications. Simple, however, often less effective application methods of chemical preservatives to the woodare brushing, spraying and dipping. Pressure treatment of wood with biocidal products is the primary industrial method utilized for developing treatment chemicals into wood and has been proven to protect the wood effectively from biological attacks. The degree of protection depends on the preservative chemical used and its proper penetration. To preserve the wood, it is necessary for biocide substances to penetrate into the wood adequately. Several factors influence the degree of protection that can be achieved with biocides such as (Morris, 1996): - Method of wood treatment, - Quantitative ratio of heartwood to sapwood, - Permeability of wood, - Wood moisture content.
  • 6. 6 3.3 Chromium ,copper and boron For decades chromated copper arsenate (CCA) was the major preservative for residential and industrial construction with soil contact because it is very effective, inexpensive and can be fixed very well after treatment. Three different types of CCA-formulations for treatment of wood have been developed over time. Type A contained more chromium, while Type B had more arsenic. Type C of CCA is comprised of 47.5% chromium trioxide, 18.5% copper oxide and 34.0%arsenic pentoxide. Type C has been the most common formulation because of its resistance to leaching and excellent field efficacy. Water-borne preservative treatments must be applied by a vacuum-pressure treating process. Fixation is generally referred to as the conversion of water-soluble inorganic components into stabilized components, which resist depletion and provide longer service life of the treated wood.Lebow (1996) pointed out that the essence of CCA fixation is the reduction reaction of chromium from the hexavalent to the trivalent state, and the subsequent precipitation or adsorption of copper. Factors including temperature, relative humidity and treating solution pH-value are the main parameters affecting fixation reactions (Pizzi, 1983a,b; Peek and Willeitner, 1981, 1988).A study by Guo et al. (2002) on the fixation of early wood, latewood, sapwood and heartwood of CCA-treated Douglas fir, southern pine and eastern larch indicated that wood density, extractives and species affected the fixation of CCA. Chromium is the least mobile of CCA components and its mobility depends on its valencystate.Trivalent chromium is very reactive with organics and fixes to soil and sediments quickly.Hexavalent chromium is more soluble but less absorbed and the rate of its movement through soil and groundwater is the same (Rouse and Pyrih, 1990). The valence state of chromium is a function of the oxygen content and redox potential, pH-value, suspended inorganic, and the presence of dissolved or particulate organic matter (Lebow, 1996). When there are no organic compounds in the media, hexavalent chromium is the most stable form in equilibrium with atmospheric oxygen (McGrath and Smith, 1990). Copper has been known for having wood protection qualities since the eighteenth century(Freeman and McIntyre, 2008). Copper is a primary fungicide and because of its excellent fungicidal properties and low mammalian toxicity has been used in many wood preservative formulations. The production of wood treated with copper based preservatives has advantages: it is easy to create waterborne formulations; it is easy to analyze and
  • 7. 7 determine penetration in wood; and copper slows photo degradation by UV radiation (Freeman and McIntyre, 2008). Adsorption of copper is a very important factor in determining its mobility and is influenced by pH-value, amount and type of adsorbents (Lebow, 1996). Boron is a chemical element with symbol B and atomic number 5. Because boron is produced entirely by cosmic ray spallation and not by stellar nucleo synthesis it is a low- abundance element in both the Solar system and the Earth's crust. Boron is concentrated on Earth by the water-solubility of its more common naturally occurring compounds, the borate minerals. These are mined industrially as evaporates, such as borax and kernite. The largest proven boron deposits are in Turkey, which is also the largest producer of boron minerals. Chemically un combined boron, which is classed as a metalloid, is found in small amounts in meteoroids, but is not found naturally on Earth. Industrially, very pure boron is produced with difficulty, as boron tends to form refractory materials containing small amounts of carbon or other elements. Several allotropes exist: amorphous boron is a brown powder, and crystalline boron is black, extremely hard (about 9.5 on the Mohs scale), and a poor conductor at room temperature. The primary use of elemental boron is to make boron filaments, which are used in a similar way to carbon fibers in some high-strength materials. Almost all boron use is as chemical compounds. About half of global consumption of boron compounds is as additives for glass fibers in boron-containing fiberglass used for insulation or as structural materials. The next leading use is to make boron polymers and ceramics that play specialized roles as high-strength lightweight structural and refractory materials. Borosilicate glass glassware is used for its greater strength and breakage resistance (thermal shock resistance) than ordinary soda lime glass. Boron compounds are also used as fertilizers in agriculture, and in sodium perborate bleaches. In minor uses, boron is an important dopant for semiconductors, and boron-containing reagents are used as intermediates in the synthesis of organic fine chemicals. A few boron-containing organic pharmaceuticals are used, or are in study. Natural boron is composed of two stable isotopes, one of which (boron-10) has a number of uses as a neutron-capturing agent. In biology, borates have low toxicity in mammals (similar to table salt), but are more toxic to arthropods and are used as insecticides. Boric acid is mildly antimicrobial, and a natural boron-containing organic antibiotic is known. Boron is essential to life. Small amounts of
  • 8. 8 boron compounds play a strengthening role in the cell walls of all plants, making boron necessary in soils. Experiments indicate a role for boron as an ultra trace element in animals, but its role in animal physiology is unknown. (www.wikipedia.com) 3.4 Laboratory studies on preservative leaching. Over the past years, attention considerable has been focused on the depletion of biocidal products from treated wood due to public and scientific awareness. The performance of preservative chemicals can be achieved either under service conditions or under laboratory tests. Until recently, most studies were conducted in the laboratory scale. The procedures are either based on constant immersion or short immersion cycles. Constant immersion tests are usually used to describe leaching of preservative-treated wood in contact with the ground or in contact with fresh or salt water. Short time immersions are intended to simulate intermittent wetting and drying events for wood held in storage after treatment and for wooden commodities that are not in ground or water contact. Laboratory leaching tests are a fundamental approach to generate data from treated wood under controlled conditions. Their great advantage is their repeatability. Laboratory tests are rapid and inexpensive. However, according to the international standards for laboratory leaching pointed out that result from these method tests cannot be applied to determine the depletion of preservative chemicals in real conditions since the results cannot be related to outdoor exposure of wood in service. There are a number of possible explanations for this. Wood exposed in laboratory leaching test is subjected to different conditions from those affecting wood under real service conditions. These include actual environmental conditions, physical stresses and metabolizing organisms. In addition, chemical retention, penetration and scale and size of the commercial treated wood are different than the treated wood in comparison to laboratory samples. Environmental parameters are important for the preservative performance. The following section covers some important factors that impact on the chemical depletion from the treated wood during outdoor exposure. Exposure time of the treated wood can determine the amount preservative leached from treated wood. Lebow (1996) stated that most of metal leaching from treated wood occurs during the first exposure to the leaching medium. This time-
  • 9. 9 dependent depletion pattern is a function of the sample size, the amount and type of surface exposed and the amount of chemicals fixed to wood. The climatic conditions also play an important role in the leaching process, particularly rainfall, temperature, and sunshine. Water is the key factor for depletion and mobility of preservatives in treated wood, regardless of exposure type. It has been demonstrated that leaching of CCA components is significantly increased due to a low pH-value of the leaching water (Murphy and Dickinson, 1990; Kim and Kim, 1993). Temperature contributes on the drying and wetting of wood, solubility of the unfixed or poorly fixed preservative components and brings components to the wood surface (Choi et al., 2004).Increasing temperature increases the amount of leached CCA compounds (Van Eetvelde et al.,1994, 1995a,b). The amount of time directly exposed to sunlight can have an effect on the exposed surface of the wood and UV radiation leads to an attack on lignin (Choi et al., 2004)which is the primary bonding site of chromium (Pizzi, 1990). The wood properties of the species are other factors affecting the amount of leaching. Low permeable species like spruce tend to be more resistance to leaching (Wilson, 1971). Wood species also affect the distribution of preservative within the wood (Lebow, 1996). CCA components fixation in latewood is much more than in earlywood due to more reacting substances and greater density. An important factor in depletion of preservatives is the size and dimension of the wood sample (Lebow, 1996). Large surface area/volume ratios of small samples permits more surface are available for leaching and more rapid water penetration (Cooper, 1994). It may destroy a considerable amount of treated wood due to erosion and attack by organisms causing difficulty in interpretation of long-term leaching experiments (Lebow et al., 2008). Development of laboratory tests to quickly provide comparable data to outdoor exposure is an important part of any laboratory standard protocol.
  • 10. 10 4. Material and methodology 4.1 Sample preparation The type of wood used for the preparation of the samples in this study was Mangifera indica(Mango Wood), obtained from the Wood Preservation Laboratory, FRI stored under shelter. The samples were prepared from the heartwood/sapwood parts of the randomly chosen planks; it was chosen to be regular-fibre, knotless, crack-free and free from other defects. The plank was surface planed with a planer and then ripped by a circular saw with rough dimensions of15×3.5×3.5 (length × width × thickness)into 8 samples. Treated wood Dimensions (cm) Sapwood/heart-wood ( 7Mangifera Indica.) 15×3.5×3.5 Sapwood Control wood Dimensions (cm) Sapwood/heart-wood ( 1Mangifera Indica.) 15×3.5×3.5 Sapwood Table 1.1 The performance of wood preservative chemicals was evaluated using laboratory experiments. During the laboratory experiment 8 wood stakes are first treated with CCB by full cell process and then leave it for 10 days for fixation. In 8 wood stakes 1 wood stakes is taken as control. The laboratory tests were accelerated by placing treated woods (which is further converted into powder form by grinding the wood samples and then place it in the separation with continuous water supply tap followed by the determination of metal concentrations in wood stakes on First ,Third, Seventh and Tenth day.
  • 11. 11 4.2 Solution preparation Figure: CCB Solution For all experiments, treating the wood stakes with solution of 4%commercial chromium-and copper and boron (CCB) containing preservatives The treating solution were made by diluting the chromium-and copper- and boron containing preservatives with tap water in 4:3:1.5 ratio. 4.3 Sample treatment and fixation The wood stakes were treated in according to full cell process. Prior to impregnation, the wood stakes were dried for 24 hours at 60°C to minimize cracking. Samples then were dried at 103°C for 24h and the dry weight was recorded. The stakes were treated by vacuum- pressure (full cell process).The duration of vacuum and pressure was held constant for all samples. The samples were placed in a pilot plant subjected to a vacuum of 56 cm of mercury is created for 30 min followed by pressur3.5kg/cm2 to 12.5kg/cm2 for one and half hour in a treating cylinder .The samples were taken out after the pressure was released and then stored for 10 days for fixation of CCB in open air. Figure: Pilot treating cylinder used for impregnation of wood samples.
  • 12. 12 4.4 Determination of metal retention (Calculation of chromium and copper and boron retention based on technical data sheet) The retention level of metals in the wood samples was calculated by the amount of solution absorbed(retention value in( gm/cm3) Retention R= 𝐺𝐶 100 g/cm3 OR Retention R=( 𝐺𝐶 𝑉 × 10) kg/cm3 Where- G=the weight of treating solution absorbed by block (W2-W1) in grams. C= the weight in g of the preservative present in 100 g of the solution. V=the volume of the test block in cm3 Volume=(3.5𝑐𝑚 × 3.5𝑐𝑚 × 15𝑐𝑚) =183.75cm3 (Table showing weights before treatment with CCB and after treatment with CCB) Initial weight ( in g) Final weight(in g) Difference in weight Wet weight retention 107.0g Control Control Control 108.4g 226.2g 117.8g (0.02564)g/cm3 104.8g 215.8g 111g (0.02416)g/cm3 111.8g 224.6g 112.8g (0.02455)g/cm3 107.4g 220.6g 113.2g (0.02464)g/cm3 117.8g 226.8g 109g (0.02372)g/cm3 112.2g 224.2g 112g (0.02438)g/cm3 106.4g 219.2g 112.8g (0.02455)g/cm3 Note: Wet weight retention=Retention R= 𝐺𝐶 100 g/cm3 After getting wet weight retention, keep the samples in open air flow condition for fixation of CCB for 10 days.
  • 13. 13 Treated wood with CCB after 10 days of fixation 5. Stages of sample preparation for leaching of treated wood in laboratory  After 10 days of fixation take the weights of treated wood.  Cut the wood stakes into smaller pieces so that it can easily grind.  Grind Second number stake for dry salt retention.  Grind third to eight number sample for final leaching.  Use separation flask for final leaching by continious water method.  The grind wood (3-8) powder(100g) is subjected in separation flask for leaching of CCB from wood powder.  Collect the Elute of 1,3,7,10 day(kinectics)  Condense the Elute s of different days into 100 ml liquid in measuring flask.  Measure CCB concentration in each elute by anaylitical method.  Take 10 gm of dried residual saw dust from separation flask and calculate CCB .  Finally compare all CCB concentration to check how much CCB is leaced out.  Draw graph. f
  • 14. 14 ((( Picture showing steps in leaching of CCB from Magnifera Indica
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  • 17. 17 5.1 Calculation of copper, chrome .boron by analytical method in FRI laboratory (Wood preservation in India by Satish Kumar and Inderdev) AIM:1 Determination of hexavalent chromium as potassium dichromate (k2cr207)hexavalent .chromium is determined by reduction with an excess ferrous ammonim sulphate solution(Fe((NH4)2(SO4)2.6H20) solution and subsequent titration of the excess ferrous salt with 1 percent potassium dichromate solution using barium diphenyl amine sulphonate as an internal indicator. REAGENTS 1. Phosphoric acid 2. Ferrous ammonium sulphate 3. Potassium dichromate solution 4. Barium diphenyl amine sulphonate solution PROCEDURE Pipette 10ml of filtering treating solution (CCB) into 250ml of conical flask and add 3-5ml phosphoric acid and 20ml ferrous ammonium sulphate solution into a conical flask.This will cause a colour change from orange to clear green. no trace of yellow should remain. rinse while distilled water and add 10 drops of the indicator barium diphenyl amine sulphonate and titrate the solution with 1 percent [potassium dichromate. The end point is reached when the colour change from clear bright green to purple colour.At the time of carrying g out for going titration another 20ml portion of same ferrous ammonium sulphate solution into 250ml conical flask and add 3-5ml phosphoric acid and add 10 rops of barium diphenyl amine sulphonate indicator and rinse the flask with distilled water and carryout the titration with 1 percent potassium dichromate solution to the same end point as above CALCULATION Percent concentration of𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚𝑎𝑠Fe2cr2o7 = 𝑊𝑖𝑡ℎ𝑜𝑢𝑡𝐶𝐶𝐵 − 𝑊𝑖𝑡ℎ𝐶𝐶𝐵 10
  • 18. 18 AIM:2 Determination of copper as CuSo4.5H2O (Copper-sulphate).Copper is determined hydrometrically (use of iodine).After first destroying the chromate with hydrogen peroxide (H2O2) excess of hydrogen peroxide is removed by boiling. After adjusting the acid concentration potassium iodide is added and the solution is titrated immediately with sodium thiosulphate solution of known strength reagent. REAGENTS 1. Concentrated hydrochloric acid 2. Hydrogen peroxide 3. Sodium hydroxide solution 4. Potassium iodide(KI) 5. Starch indicater function PROCEDURE Pipette 10ml filtered treating solution into a 250ml conical flask and add 10ml concentrated HCL and 10ml hydrogen peroxide carefully ground the side of flask while gently stirring the content and rinse the flask with minimum amount of distilled water and heat solution gently until all oxygen evaluation stops and then boil for approximate 5minutes.When the volume of solution has been reduced to about 5ml for yellowish green solution and adjust the acidity of the solution by adding 20 percent sodium hydroxide solution slowly with constant stirring until a permanent precipitate just forms. Then add concentrated HCL drop by drop until the precipitate just dissolve. After which add 1or 2 drop of acid HCL more. Cool the solution at approximate 5 to 10 ml 20 percent potassium iodide (KI) and add 5-10ml starch solution. The solution turns in blue color and titrate the solution immediately with 0.955 percent solution of sodium thiosulphate.Continue the titration until the blue color fades. CALCULATION Consumption of sodium thiosulphate solution divide by 10 is equal to percent of copper as copper sulphate.
  • 19. 19 AIM; 3 Quantitative determination of Boron. REAGENTS: 1. Dilute sodium hydroxide solution=10 %(w/v). 2. Phenolphthalein indicator. 3. Concentrated hydrochloric acid. 4. Methyl orange. 5. Glycerol DIGESTION OF WOOD FLOUR: A mixture of about 2.5 to 5.0 gm of finely ground wood to a paste with saturated barium hydroxide in platinum crucible. Dry on a water bath, ash slowly in muffle furnance first at low temp and then gradually raise the temperature to dull red heat(500o-600o) ashing should be completed in about 1.5 hours when no trace of carbon remains. Half fill the crucible with distilled water and dilute HCL to discolor the ash. Keep the crucible covered during this operation, make the solution to a known volume in a graduate flask, the solution should be used for determination of boron. PROCEDURE: Take 10ml solution of about 1-1.25%boric acid in a nickel or platinum crucible and add 2- 3ml of 10%NaoH Solution and evaporate to nearly dryness over a water bath charring the residue for about 5min at a dull red heat. Dissolve the residue in about 10-15ml warm distilled water into a conical flask and add 2 drops of phenolphthalein indicator resulting a red color .Then add concentrated HCL drop s till color fades and add 2 drops of methyl orange indicator resulting yellow color and add few drops of concentrated HCL till the solution is acidic to this indicator is red by means of dilute NaoH,Adjust the solution to methyl orange and point yellow and boil gently for 15 min under air reflex condenser making sure that steam doesn’t issue from the top of the condenser (This step is to remove co2 from the solution).Cool the solution and readjust the methyl orange end point yellow ,add a measured amount (approx0 equal to 1.5 times the volume of the solution of glycerol into the solution and add 0.5 ml of phenolphthalein indicator and titrate with N/10standard carbonate free sodium hydroxide solution to the phenolphthalein end point pink.
  • 20. 20 6.Result and Discussion: 1. CCB is formed by dissolving copper, chrome, boron preservative in 10L water at 4% concentration with 4:3:1.5 ratios.  For copper 4 8.5 × 4=1.882 %  For chrome 3 8.5 × 4=1.441%  For boron 1.5 8.5 × 4=0.705% Therefore, for 10L Copper is 188g, Chrome is 144g and for Boron is 70g 2. Dry Salt Retention = 𝑇𝑜𝑡𝑎𝑙𝑠𝑎𝑙𝑡 𝑣𝑜𝑙𝑢𝑚𝑒 × 1000 𝑘𝑔/𝑚3 For finding DSR we cut all samples from its both end so that we can get to know about penetration of CCB in wood samples by spot test. After cutting second number sample from both ends length, breath and thickness of wood sample is 9.133cm, 3.5cm, 3.5cm Therefore, Volume is 9.1𝑐𝑚 × 3.5𝑐𝑚 × 3.5𝑐𝑚 =111.8 cm3 Density=Mass/volume =71.7g/111.8cm3 =0.64g/cm3 2.1 Laboratory analysis for finding Cu,Cr,Br from 2nd number wood sample (powder form) a. Percent concentration of𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚𝑎𝑠K2cr2o7 Without CCB=12.5 With CCB=12.0
  • 21. 21 =Without CCB-With CCB /10 =0.05% of chromiumas potassium dichromate. b.Consumption of sodium thiosulphate solution divide by 10 is equal to percent of copper as copper sulphate. Percent concentration of copper after consumption of sodium thiosulphate is 10.5/10=1.05% c. Percent concentration of boron is 0.50% Total salt =1.05% of 188g+0.05%of 144g+0.50% of 70g =1.974+0.072+0.35 =2.046g Weight of 2nd number sample is 47.4g (powder form) Weight of 3rd to 8th number sample is 293.2g (powder form) Since, we are considering 2nd number sample for Dry salt retention Therefore, Mass of wood sample is 47.4g Density of wood sample is 0.64gm/cm3 Volume in powder form is mass/density=47.4g/0.64g/cm3 =74cm3 Dry salt retention is = 𝑇𝑜𝑡𝑎𝑙𝑠𝑎𝑙𝑡 𝑣𝑜𝑙𝑢𝑚𝑒 × 1000𝑘𝑔/𝑚3 = 2.046 74 × 1000 27.64kg/m3 or 0.02764g/cm3
  • 22. 22 3.Laboratory analysis of CCB Leaching on 1,3,7,10 day DAYS Copper leached (%) Chromium leached (%) Boron leached (%) 1 0.10 0.05 0.15 3 0.15 0.05 0.20 7 0.20 0.05 0.25 10 0.25 0.05 0.30 Fig: Graph showing leaching of copper, chrome, boron 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 1 3 7 10 CCB(%) NO. OF DAYS GRAPH SHOWING LEACHING OF CCB(%) COPPER(%) CHROMIUM(%) BORON(%)
  • 23. 23 7.CONCLUSION:  The cumulative amount of leached metals from all specimens showed that boron leached higher than copper and copper leaching was higher than that of chromium .  𝑙𝑒𝑎𝑐ℎ𝑖𝑛𝑔 𝑜𝑓 𝑏𝑜𝑟𝑜𝑛 > 𝑙𝑒𝑎𝑐ℎ𝑖𝑛𝑔 𝑜𝑓 𝑐𝑜𝑝𝑝𝑒𝑟 > 𝑙𝑒𝑎𝑐ℎ𝑖𝑛𝑔 𝑜𝑓 𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚  The resistance of chromium to leaching should be due to fixation properties of chromium in wood.  It is known that during fixation reactions with wood, chromium reacts strongly with lignin while copper binds with cellulose materials.  The low amount of chromium depletion was observed in numerous laboratory.  Boron compounds in current use as wood preservatives are susceptible to loss via leaching,under certain conditions.This is because they are not chemically fixed after treatment and remain mobile within the treated wood.  The quantity ofpreservative leached is a function of specimen size, type of leaching exposure and the leach resistance of the preservative component in question. For the more leachable preservative components, constant immersion of lumber specimens or simulated rainfall oil specimens resulted in the greater losses.  The change in color of liquid from dark color to light which is collected in the form of elute shows the percentage change in elute visually.  Mangifera Indica (Mango wood) is not susceptible for constructional purpose even though it is treated with CCB because after a prolong rainfall CCB can be easily leached ot from wood.  Fixation of CCB on Mangifera Indica is good.
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