Content uploaded by Pascal Kamdem
Author content
All content in this area was uploaded by Pascal Kamdem on Feb 18, 2015
Content may be subject to copyright.
Water-Borne Copper Naphthenate:
A Chromium and Arsenic Free Preservative for Wood and Composites
By
Mike Freeman1, Pascal Kamdem2, and James A. Brient3
1- Wood Scientist, 7421 Hunters Tree Cove, Memphis, TN, 38125
2-Professor - Michigan State University, Dept. of Forestry, East Lansing, MI, 38824
3- Chemical Products Technology Manager, Merichem, Houston, TX 77012
ABSTRACT
Copper naphthenate is a well-known commercial wood preservative used for
preservative treatment of wood poles, fence posts, lumber, glulam beams, timbers, and
wooden shakes/shingles. In recent years, researchers have begun to investigate
alternative formulations that transform the typically oil-borne preservative into new,
environmentally friendly water borne systems. Included in the research reported here
are seven-year stake test efficacy data comparing water borne copper naphthenate in
Southern Pine (SYP) at multiple exposure sites in the USA with oil borne copper
naphthenate, ACQ and CCA -Type C. This paper will also compare some other
alternate formulations of water borne copper naphthenate using alternative coupling
systems to make the oil-borne preservative water borne in nature. Additional work
indicates that water borne copper naphthenate may be a good biocide candidate for
the protection of wood composites. This emerging preservation technology offers a
potential new lumber and wood composite treatment offering benefits to treaters and
consumers over conventional wood preservatives in performance and environmental
matters. Future reports will evaluate the performance of water borne copper
naphthenate (i.e., efficacy) in the lesser-studied softwood species of Red Pine and
Ponderosa Pine and in Maple, Oak, Beech, and Y. Poplar.
Waterborne copper naphthenate (WB Cu-N) was used to treat southern yellow pine
(Pinus spp) stakes. The treated stakes were exposed in test sites located in
Gainesville, Florida, Augusta and East Lansing, Michigan and Aberdeen, Mississippi.
CCA, ACQ and oil-borne copper naphthenate (CuNap) were used for comparison.
Decay fungi and termites destroyed untreated samples within 2 years on all sites. After
3 years exposure in Florida, the rating of stakes with 2.0 kg/m3 copper retention from
WB Cu-N is still equivalent to CCA at 5kg/m3 retention, ACQ at 6.4 kg/m3 retention
and oil borne copper naphthenate at 1.6 kg/m3 copper (as metal) retention. After 7
2
years exposure in Mississippi or Florida, and 6 years in Michigan, 0.76±0.07 kg/m3 Cu
metal from WB Cu-N offered a good protection comparable to CCA and ACQ
treatments. This study clearly suggests that WB Cu-N can be used as a wood
preservative for both above ground and ground contact applications.
Keywords: Copper Naphthenate, Hardwoods, Softwoods, efficacy, performance,
composites, Water Borne Preservatives, ACN, retention, field exposure
Introduction
Wood is used in many outdoor applications as major structural material, where it is
susceptible to biological and environmental degradation. Various chemical
preservatives have been used to protect wood against biodegradation. This usually
involves impregnation or pressure treatment with toxic chemicals such as copper
chromium arsenate (CCA), pentachlorophenol (PCP) and creosote (Winandy et al.,
1993; Smith et al, 1996; Goodell and Pendlebury, 1991; De Groot et al., 1992;
Kamdem et al., 1996). However, in recent years many wood preservatives have been
under increased scrutiny due to their impact on the environment. For example, concern
about the leaching of arsenic from CCA treated wood into ground water sources and
streams (Lebow and Tippie, 2001; Stevanovic-Janezic et al. 2001) and in human
exposure in playground equipment and on decking materials has led to its phase –out
in consumer uses.
Both field and administrative personnel are often asked to justify the choice of treated
wood in constructions structures, and there is sometimes pressure to reduce or
eliminate the use of treated wood in favor of products that are perceived as more
environmentally friendly (Lebow and Tippie, 2001). That increased social pressure is
mainly directed against a large range of wood preservatives such as creosote,
3
pentachlorophenol, and arsenic based formulations (Kamdem et al., 1996). For those
reasons combined with the VOC compliance issues, the wood preservative industry is
looking for alternative, more environmentally friendly wood preservatives. A great deal
of research is focused on the development of new chemicals with low toxicity and less
harmful impact on the environment (Freeman, 1992; Grace et al. 1993; Kamdem et al.
1996).
Several copper amine based formulations are under development. Oil-borne copper
naphthenate (Cu-N) is a well known commercially used wood preservative for
treatment of wood poles, fence posts, lumber, glulam beams, timbers, and wooden
shakes/shingles. Recently, researchers have begun to investigate alternative
waterborne formulations as new, environmentally friendly products. Water borne
formulation of copper naphthenate (WB Cu-N) could be more extensively used
because of its low volatile organic compounds emissions and its relatively low cost
compared to the oil-borne formulations (Kamdem et al. 1996, Kamdem and Freeman
2001). However, before a new preservative is fully accepted, it must undergo a series
of tests including a standard field stake test to demonstrate its suitability for the
intended purpose. In North America, the appropriate test is the AWPA E7-93 (AWPA,
1999), which provides guidance on methods to present data from field tests as decay
rating over time for a range of preservative retention. The method has been qualified
as practical and simple as a tool for deriving conclusions from results of stakes tests on
water borne preservatives (Cook and Morris, 1995).
Other Background Information
Shaw (1994) presented an extensive discussion of efficacy and performance data on
decade old wood stakes in a high hazard decay site in Florida using amine-solubilized
water borne Cu-N. In this study, WB Cu-N performed well as compared to CCA-C and
Oil Borne Cu-N. In comparison, performance was equivalent between CCA-C at
4
retentions of 0.40-0.60 pcf oxides to WB Cu-N at retentions of 0.15 pcf (Cu as metal) to
oil-borne Cu-N at 0.13 pcf (Cu as metal).
Other methods of solubilizing oil-borne Cu-N have been used in the past with varying
results. The most common solubilizing agents for Cu-N have historically been either
ammonia or amines. In two different independent studies, where ammonia was the
primary solubilizing agent for Cu-N, results in test plots in both Central Florida and in
Dorman Lake, MS (Hazard zones 5, and 4, respectively) indicate in SYP (Pinus spp.)
in 19 mm x 19 mm sapwood stakes in plots where both termites and decay fungi
destroyed untreated controls in less than 2 years, stakes continued to perform well
after 10 + years with retentions of 0.21 pcf in FL or retentions of 0 pcf (Cu as metal) in
MS. In MS, retentions of 0.045 pcf Cu (WB Cu-N) compared favorably with CCA-C
retentions of 0.274 pcf total oxides after 8 + years. This data can be seen graphically in
Figure 1. The performance of another ammoniacal Cu-N system against decay fungi
and termites is presented in Figures 2 and 3. These data indicate that even the slightly
lesser performing ammoniacally solubilized WB Cu-N could be a very functional
replacement product for the arsenic and chromium-containing product CCA-Type C.
Additionally, the amine WB Cu-N formulation being studied in this report has been
used extensively for over the counter brush on and cold soak application for a number
of years. Trade names that are readily and commercially available include Behr
Products #1, Zinsser No. 1 and No.2, Fields Copper Nap, Henry Green Wood
Preservative, and Jasco # 1. End-cut solutions containing WB Cu-N referenced in
AWPA Standard M-4 are also manufactured by Arch and CSI. . Furthermore, mine
timbers of red oak and other mixed hardwoods have performed well after either a 24 or
a 72 hour cold soak in a 2% Cu (as metal) formulation of WB Cu-N for over 15 years in
moist, high humidity, and decay prone environments in coal and mineral mines when
used as support timbers. One mine timber user reported that he had better
performance with WB Cu-N that he had with Penta in mineral spirits when comparing
the life span of hardwood mine timbers in KY and WV.
5
When WB CuNap was applied to Western Red Cedar (WRC) machine or hand split
shakes and machine grade shingles, either with or without water-repellent dye added,
shingles and shakes in Palm Beach, FL and Seattle, WA performed well with no moss,
algae, or lichens growing on them after two years. Samples were removed with a
standard 1-sq.inch wood surface (sapstain) sampling punch at time intervals of 0
months (initial treatment), 6 months, 12 months, and 24 months after treatment. Initial
treatment had retention levels of 270 ug/cm2 of Cu (as metal), and samples taken at 1
year and at 2 years showed Cu losses of 17% and 24% respectively. The trend for Cu
loss from the wood surface was slightly greater in the Seattle, WA test roof structures,
but not significantly different. Wood samples from these same test roves were also
sent to Michigan Technological University in Houghton, MI. for isolation and
characterization of any fungal infestation at 6 months, 12 months, and 24 months after
treatment. No basidiomycete (decay) fungi were found on any of the test samples
during any of the sampling intervals. In fact, only zygomycete fungi were isolated from
the three Seattle test roof structures at the 24-month sampling interval. This test
indicates that WB Cu-N is an excellent protectant for wood roofing materials, and
superior to many other pesticidal and non-biocidal, water repellant only treatments.
WB Cu-N has also been used to successfully treat Aspen composites bound with
Phenol-Formaldehyde (PF) resin systems. (Schmidt; 1991). In the study with WB Cu-N
incorporated into the PF resin system and then sprayed and tumbled onto the Aspen
flakes, OSB produced from those same flakes had significant resistance to decay from
basidiomycete attack and no reduction in any mechanical properties such as IB, MOR,
MOE, and WPL. The treated composite was light brown in color, and the color
darkened with increasing loadings of WB Cu-N. Interestingly, no mold or surface fungi
attacked these boards when exposed to mold room conditions of >90°F and > 90% RH
for 90 days. This preliminary study demands further investigation as WB Cu-N may be
an excellent candidate for the protection of wood and wood-plastic composites for the
6
future and may even protect these composites for in ground exposure or extended
wetting conditions.
Objective of this Study
The objective of this study is to evaluate the biological performance of WB Cu-N
treated wood by using a series of field tests in different hazard and geographical
zones. Soft maple and yellow pine stakes were pressure treated with various
concentrations of copper in WB Cu-N and installed for decay testing in Michigan,
Mississippi and Florida. Alternate formulations using ammonia as the coupling agent
rather than amine were also pressure treated and installed in locations in Mississippi
and Florida to compare performance in SYP using alternate formulation technologies.
Material and Methods
Soft maple (Acer rubrum) and southern yellow pine (Pinus spp) stakes were selected
for this project. Stakes were cut from air-dried defect-free boards and surfaced to 0.75”
(19 mm) X 0.75” (19 mm) X 20” (400 mm).
Stakes were treated with waterborne copper naphthenate (WB Cu-N), oilborne copper
naphthenate (OB Cu-N), ammoniacal copper quat (ACQ-C) and chromated copper
arsenate (CCA) to the target retentions presented in table 1 using a Bethell (full cell)
process.
A full cell laboratory process including an initial vacuum of 25 inches of mercury for 30
minutes, one-hour pressure at 180-200 psi at room temperature and a final vacuum of
25 inches of mercury for 30 minutes was used for WB Cu-N. Commercial treaters
using ACQ-C, CCA and OB Cu-N were employed to treat the samples at large
commercial treatment facilities (Kamdem et al. 1996).
7
An average of 10 stakes for each species and chemical were exposed in test sites in
Augusta and East Lansing, Michigan, Gainesville, Florida and Aberdeen, Mississippi.
They were randomly installed vertically to half their length in rows of holes made with
an iron bar (Divot stick).
Augusta is located in southwest Michigan about 50 km east of Lake Michigan (42° 24'
N, 85° 24' W, elevation 288 m). Annual rainfall averages 890 mm y-1 and mean annual
temperature is 9.7 °C. Most regional soils are sandy loam and silky clay loam of
moderate fertility. The East Lansing test site is located at the Tree Research Center
south of the Michigan State University campus. The site receives an average rainfall of
750 mm y-1, and the mean annual temperature is 7.9 °C. The Aberdeen site is located
in “Hardwood” forest in Aberdeen, MS. The average annual rainfall is 1416 mm and
mean temperatures are above 17°C. The site is located on a poorly drained silty clay
soil, occasionally subject to floods. The Gainesville site is located at the Austin Cary
Memorial Forest of the University of Florida in Gainesville. The climate can be
characterized as warm subtropical, and the site receives an average of 1310 mm of
rainfall each year with temperature averages above 15°C during most of the year. The
site soils are well-drained sandy soils and are infested with termites.
2.2 Decay rating:
Each stake was rated annually for decay on a 0 to 10 rating scheme according AWPA
standard E7-93 (AWPA, 1999). The stakes were removed from the ground, cleaned
from the adhering soil, and their cross section around the ground contact examined for
signs of decay and termite damage. AWPA standard E7-93 (AWPA, 1999)
recommends evaluating wood preservatives by field test with stakes as described in
table 1.
Data for each group were averaged and presented as a log score on a 100 to 0 scale
for all retentions, and plotted over time for analysis. The average rating was also
8
plotted over the concentrations used to determine the minimum successful
concentration.
Results and Discussion
The average ratings of WB Cu-N treated stakes over the exposure time in all sites are
presented in Figures 4-8.
Soft maple and yellow pine performed well in East Lansing when treated with WB Cu-N
at retentions as low as 0.71kg/m3 after 5 years. Control stakes were critically decayed
after only 3 years, and were completely destroyed by the fifth year (Figure 4).
In Augusta where site conditions were very close to East Lansing conditions, the decay
trend was very similar to that obtained in East Lansing. After 5 years exposure, yellow
pine treated with WB Cu-N at 0.71 kg/m3 showed some decrease in its decay rating but
was still in acceptable conditions. All the retentions above 0.71 kg/m3 performed well
for yellow pine. For soft maple, all the treated stakes were performing well after 5 years
exposure. Control for both species were significantly decayed by the second year and
completely destroyed by the fifth year (Figure 5).
In Aberdeen, all soft maple treated stakes with WB Cu-N at 0.56kg/m3 showed
significant change in their decay rating after 6 years exposure. Maple stakes treated
above 0.56kg/m3 performed well. Yellow pine stakes treated at 0.71kg/m3 and above
also performed very well, showing no significant decay after 6 years exposure. Control
stakes for both species were completely destroyed between 3 to 5 years (Figure 6).
Figure 7 shows that in Florida, the control stakes were all destroyed within the first
year. Yellow pine stakes were adequately protected after 3 years exposure with WB
Cu-N treatment at 0.71kg/m3 retention and above. For soft maple however, stakes
treated with the lowest retention of 0.56kg/m3 were considerably decayed by the third
9
year of exposure. Results obtained in Florida confirm the fact that the site is very active
and able to reveal some trends after only 3 years of exposure.
The lowest concentration of WB Cu-N (0.56-0.71 kg/m3) also performed well, generally
rating above 70% in Michigan and Mississippi after 5 years and Florida after 3 years
field exposure for yellow pine. Soft maple WB Cu-N treated stakes performed well in
Michigan after 5 years, but showed low rating (57%) in Mississippi after 6 years, and
they were completely destroyed in Florida after only three years. Control stakes were
completely destroyed by decay fungi and termites in all sites.
Illustrative data concerning the dose- response of the WB Cu- can be plainly
seen in Figure 8. WB Cu-N seems to follow the same type of curves for dose-
response as seen for other types of water borne systems, and very similar to that
of earlier tested creosote type preservatives.
Conclusion
The results obtained from Michigan, Mississippi and Florida revealed that WB Cu-N
can be an effective, environmentally friendly wood preservative for outdoor wood
structures made from yellow pine and maple used in ground contact. The ratings of
stakes treated with WB Cu-N at 4-5 kg/m3 (as Cu) retention is comparable to ratings
obtained for stakes treated with CCA at 4-5 kg/m3 retention, oil borne Cu-N at 3-4
kg/m3 retention and ACQ-C at 6-8 kg/m3 retention.
The study proposes that retentions of 0.71±0.07 kg/m3 Cu metal for yellow pine and
0.56kg/m3 for soft maple using this waterborne Cu-N formulation offers moderate
ground contact protection for 7 years exposure in Mississippi, 7 years in Michigan and
5 years in Florida. At this copper retention, the performance of waterborne Cu-N
treated yellow pine is comparable to treatment with ACQ-C at 8.44 kg/m3, CCA at 5.63
kg/m3 and oil borne Cu-N at 3.94 kg/m3. The proposed retention for soft maple has a
10
performance comparable to that of ACQ at 6.86 kg/m3, CCA at 4.37 kg/m3 and OB Cu-
N at 3.12 kg/m3. Previously reported efficacy data on this system in long term stake
tests in hazard zone 5 (Florida) indicate that 0.15 pcf (Cu as metal) in WB Cu-N is
roughly equivalent to 0.13 pcf (Cu as metal) oil-borne CuNap and 0.60 pcf (as oxides)
CCA-C.
11
Table 1: Average retention of WB Cu-N treated samples
Water-Borne Cu-N (as elemental Cu)
Treatment
Solution → 2% 1.5% 1% 0.5% 0.25% 0.13%
Species kg/m3/(pcf) kg/m3/(pcf) kg/m3/(pcf) kg/m3/(pcf) kg/m3/(pcf) kg/m3/(pcf)
YP
10.904*
(0.68)**
8.004
(0.50)
5.278
(0.33)
2.581
(0.16)
1.3195
(0.08)
0.70876
(0.04)
SM
8.528
(0.53)
6.708
(0.42)
4.108
(0.26)
1.95
(0.12)
1.092
(0.07)
0.56108
(0.04)
Table 2: Average retention of CCA, OB-Cu-N and ACQ type C treated
samples
CCA (total oxide)
Oil Borne Cu-N (as
elemental copper) ACQ type C
Treatment
Solution → 2% 1% 1% 0.5% 0.25% 2% 1% 0.55
Species kg/m3/(pcf) kg/m3/(pcf) kg/m3/(pcf) kg/m^3/(pcf) kg/m3/(pcf) kg/m3/(pcf) kg/m3/(pcf) kg/m3/(pcf)
YP
11.37*
(0.710)**
5.626
(0.35)
3.944
(0.25)
1.856
(0.12)
0.9715
(0.06)
11.716
(0.73)
8.439
(0.53)
5.51
(0.34)
SM
9.048
(0.565)
4.368
(0.27)
3.12
(0.20)
1.534
(0.10)
0.819
(0.05)
9.256
(0.58)
6.864
(0.43)
4.784
(0.30)
Table 3: Decay rating scheme according to AWPA E 93
Rating Description of Condition
10 Sound, suspicion of decay permitted
9 Trace decay to 3% of cross section
8 Decay from 3 to 10% of cross section
7 Decay from 10 to 30% of cross section
6 Decay from 30 to 50% of cross section
4 Decay from 50 to 75% of cross section
0 Failure
Table 4: Condition of stakes treated with WB Cu-N after 7 years exposure in Michigan, 6 years in Mississippi and 4 years
in Florida
2% 1.50% 1.00% 0.50% 0.25% 0.13% Control
Location Species Logscore % failure Logscore % failure Logscore % failure Logscore % failure Logscore % failure Logscore % failure Logscore % failure
East Lansing, MI YP 98 0 96 0 83 12 80 14 80 14 78 16 0 100
RM 90 0 84 0 83 12 72 22 60 33 53 50 0 100
Augusta, MI YP 86 0 100 0 92 10 95 0 84 18 49 54 0 100
RM 100 0 97 0 95 0 80 33 80 11 56 60 0 100
Aberdeen, MS YP 96 0 96 0 94 9 92 10 81 20 81 30 23 90
RM 99 0 95 0 84 10 82 27 81 20 57 36 0 100
Gainesville, FL YP 100 0 100 0 100 0 100 0 95 0 95 0 0 100
RM 100 0 100 0 100 0 97 0 67 33 40 42 0 100
Table 5: Condition of stakes treated with CCA, OB Cu-N and ACQ type C after 7 years exposure in Michigan, 6 years in
Mississippi and 4 years in Florida
CCA total oxide OB Cu-N elemental Cu % ACQ type C %
2%
1%
1%
0.50%
0.25%
1%
0.50% 0.25%
logscore % failure logscore % failure logscore % failure logscore % failure logscore % failure logscore % failure logscore % failure logscore % failure
East Lansing, MI YP 87 12 77 50 83 33 90 28 55 66 100 0 75 20 - NA
RM 100 0 81 12 100 0 82 20 68 20 100 0 96 0 88 20
Augusta, MI YP 95 12 87 25 90 0 69 40 NA NA NA NA NA NA NA NA
RM 100 0 74 30 100 0 72 18 56 76 NA NA NA NA NA NA
Aberdeen, MS YP 100 0 97 0 97 0 89 0 86 25 95 0 95 0 80 25
RM 100 0 98 0 97 0 83 9 82 9 81 11 66 42 NA NA
Gainesville, FL YP 100 0 91 22 87 13 NA NA 40 100 84 30 74 45 58 72
RM 100 0 95 0 93 0 93 0 60 100 96 0 87 15 62 62
13
Figure 1. % Values based on AWPA C-4 minimal loading for OB CuNap in
SYP Poles
COPPER NAPHTHENATE
AMMONIACAL CN STAKE TEST
0
10
20
30
40
50
60
70
80
90
100
02468101214
EXPOSURE, years
RATING
0.21Cu (350%) CN 0.61Cu (1000%) CN 0.85Cu (1400%) CN 0.8 (267 %) PCP/T
1.4 (467%) PCP/T 3.96 (1300%) PCP/T 0.15 (50%) PCP/O1 0.32 (107%) PCP/O1
0.15 (50%) PCP/O2 0. 33 (110%) PCP/O2 0.15 (50%) PCP/O3 0.34 (113%) PCP/O3
14
Figure 2. Ammoniacal Formulation. Note: Retentions are as CuNap, not as
Cu metal.
Figure 3. Ammoniacal Formulation. Note: Retentions are as CuNap, not as
Cu metal.
JS-1 Decay Ratings - Dorman
0
2
4
6
8
10
0 24 48 72 96 120 144 168 192
Months Exposur
e
CONTROL
CCA-C 0.112 pcf
CCA-C 0.274 pcf
CUNAP 0.113 pc
f
CUNAP 0.277 pc
f
CUNAP 0.449 pc
f
JS-1 Termite Ratings - Dorman
0
2
4
6
8
10
0 24 48 72 96 120 144 168 192
Months Exposure
CONTROL
CCA-C 0.112 pcf
CCA-C 0.274 pcf
CUNAP 0.113 pc
f
CUNAP 0.277 pc
f
CUNAP 0.449 pc
f
15
Figure 4.
Decay curves of WB Cu-N treated yellow pine stakes exposed in East
Lansing, MI
0
20
40
60
80
100
120
1234567
Years of exposure
Average rating (log scale)
10.9 kg/m3 of Cu
8.0 kg/m3 of Cu
5.28 kg/m3 of Cu
0.71 kg/m3 of Cu
Control
2.58 kg/m3
CCA (5.63kg/m3 of Cu)
Decay curves of WB Cu-N treated soft maple stakes exposed in East
Lansing, MI
0
20
40
60
80
100
120
1234567
Years of exposure
Average rating (log scale)
8.53 kg/m3 of Cu
6.71 kg/m3 of Cu
4.11 kg/m3 of Cu
1.95 kg/m3 of Cu
0.56 kg/m3 of Cu
Control
1.09kg/m3
CCA (4.37kg/m3 of Cu)
16
Figure 5.
Decay curves of WB Cu-N treated yellow pine stakes exposed in
Augusta, MI
0
20
40
60
80
100
120
1234567
Years of exposure
Average rating (log scale)
10.9 kg/m3 of Cu
8.0 kg/m3 of Cu
5.28 kg/m3 of Cu
2.58 kg/m3 of Cu
1.32 kg/m3 of Cu
0.71 kg/m3 of Cu
Control
CCA (5.63kg/m3 of Cu)
Decay curves of WB Cu-N treated soft maple exposed in Augusta, MI
0
20
40
60
80
100
120
1234567
Years of exposure
Average rating (log scale)
6.71 kg/m3 of Cu
4.11 kg/m3 of Cu
1.95 kg/m3 of Cu
1.09 kg/m3 of Cu
0.56 kg/m3 of Cu
Control
CCA (4.37kg/m3 of Cu)
17
Figure 6
Decay curves of WB Cu-N treated yellow pine stakes exposed in
Aberdeen, MS
0
20
40
60
80
100
120
01234567
Years of exposure
Average rating (log scale)
10.9 kg/m3 of Cu
8.0 kg/m3 of Cu
5.28 kg/m3 of Cu
2.58 kg/m3 of Cu
1.32 kg/m3 of Cu
0.71 kg/m3 of Cu
Control
Decay curves of WB Cu-N treated soft maple stakes exposed in
Aberdeen, MS
0
20
40
60
80
100
120
01234567
Y
ears of exposure
Average rating
8.53 kg/m3 of Cu
6.71 kg/m3 of Cu
4.11 kg/m3 of Cu
1.95 kg/m3 of Cu
1.09kg/m3 of Cu
0.56 kg/m3 of Cu
Control
18
Figure 7.
Decay curves of WB Cu-N treated yellow pine stakes exposed in
Gainesville, FL
0
20
40
60
80
100
120
1234
Years of exposure
Average rating (log scale)
10.9 kg/m3 of Cu
8.0 kg/m3 of Cu
5.28 kg/m3 of Cu
2.58 kg/m3 of Cu
1.32 kg/m3 of Cu
0.71 kg/m3 of Cu
Control
CCA (5.63 kg/m3 of Cu)
Decay curves of WB Cu-N treated soft maple stakes exposed in
Gainesville, FL
0
20
40
60
80
100
120
1234
Years of exposure
Average rating (log scale)
8.53 kg/m3 of Cu
6.71 kg/m3 of Cu
4.11 kg/m3 of Cu
1.95 kg/m3 of Cu
1.09 kg/m3 of Cu
0.56 kg/m3 of Cu
Control
CCA (4.37kg/m3 of Cu)
19
Figure 8.
Dosage response curves for WB CuN treated yellow pine exposed at various
locations for up to 7 years
0
20
40
60
80
100
120
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75
Cu concentration (pcf)
Average rating (log score)
East Lansing, MI
Augusta, MI
Aberdeen, MS
Gainesville, Fl
Dosage response curves for WB CuN treated red maple exposed at various
locations for up to 7 years
0
20
40
60
80
100
120
0 0.1 0.2 0.3 0.4 0.5 0.6
Cu concentration (pcf)
Average rating (log score)
East Lansing, MI
Augusta, MI
Aberdeen, MS
Gainesville, Fl
20
References
Anon.____. 2000. American Wood-Preservers’ Association Book of Standards. AWPA,
Granbury, TX.
Anon.____. 1993. American Wood Preservers Association. Standard method of evaluating
wood preservatives by field-tests with stakes. AWPA Standard E7-93. AWPA Book of
standards. Granbury, Texas.
Amburgey, T.L. and M.H. West. 1989 Field Tests with a Groundline Pole Treatment.
Paper presented at the First International Conference on Wood Poles and Piles
sponsored by. EDM and Col. State Univ., Ft. Collins, CO, publishers. Mississippi State
Forest Prod. Lab., Mississippi State, MS.
Amburgey, T.L., and M.H. Freeman. 1997. Groundline treatments with a water-borne
copper naphthenate-boron paste. In: Proc., 2nd Southeastern Pole Conference, MS
State, MS. Jan 22-25, 1996. p. 157.
Amburgey, T.L., and M.H. Freeman. 1993. Groundline treatments with a water-borne
copper naphthenate-boron paste. Proc Amer Wood-Pres Assoc., 89:105.
Amburgey, T.L. and M.H. Freeman. 2000. Copper-Boron Groundline Treatment for
Poles: An Update on the Efficacy and Performance of a Copper Naphthenate-Borax
Preservative Paste. Paper presented at the International Conference on Utility Line
Structures in Fort Collins, CO, held March 20-22, 2000. Col. State Univ. and EDM Inc.
Ft. Collins, CO.
Angerhofer, R. A. and Metker, L. W. 1988. Preliminary Assessment of the Relative
Toxicity of Copper Naphthenate, (Mooney Chemicals), Acute Studies. Phase 3. May
1984 – October 1987. U.S. Army Environmental Hygiene Agency, Report AD-A201272
on Study No. 75-51-0497-88
Angerhofer, R. A. and Taylor, L. M. 1988. Preliminary Assessment of the Relative
Toxicity of Copper Naphthenate Acute Studies. Phase 2. May 1984 – June 1986. U.S.
Army Environmental Hygiene Agency, Report AD-A190851 on Study No. 75-51-0497-88
Arsenault, R.D. 1992. Personal Communication.
Barnes, H.M., M.G. Sanders, and T.L. Amburgey. 2003. Field Testing of Copper
Carboxylate Preservatives. Paper submitted to the International Research Group on
Wood Preservation. Conf. held in Brisbane, AU. IRG, Stockholm, Sweden (In Press)
Brient, J.A, Wessner, P.J., and Doyle, M.N. 1995. Naphthenic Acids, In: Kirk-Othmer
Encyclopedia of Chemical Technology, 4th Ed., John Wiley & Sons, Inc., New York, NY,
Vol. 16, pp. 1017-1029.
Brient, J.A., R. E. Moyer, M.H. Freeman, H. Jiang, and M.J. Kennedy. 2000. Copper
Naphthenate: An Analysis of the Materials Found in the Worldwide Marketplace Using A
New Analytical Technique. Inter Res Group on Wood Pres, IRG 00-
21
Cook J. A. and P. I. Morris 1995. Modeling data from stake tests of waterborne wood
preservatives. Forest Prod. J. 45 (11/12) 61-65.
Craciun R. and D.P. Kamdem 1997. X-ray Photoelectron Spectroscopy and FTIR
Spectroscopy Applied to the study of waterborne copper naphthenate wood
preservatives. Holzforschung 51: 207-213.
Davidson, H.L. 1977. Comparison of wood preservatives in Mississippi post study (1977
Progress Rept.) Res. Note FPL-01. USDA Forest Serv., Forest Prod. Lab., Madison,
Wis. 16 pp.
DeGroot, R. C.; Stroukoff, M. 1986. Efficacy of alternative preservatives used in dip
treatments for wood boxes. Research Paper, Forest Products Laboratory, USDA Forest
Service, No. FPL-RP-481.
De Groot R. C., B. M. Woodward and S. LeVan 1992. Alternative species and
preservatives for wood roofing: laboratory decay studies. Forest Prod. J. 42 (11/12) 57-
60.
DeGroot, R.C., C.L. Link, and J.B. Huffman, 1988. Field trials of copper naphthenate
treated wood. Proc. Amer Wood Pres Assoc. 86:. 131-145
Forsyth, Paul G., Morrell, Jeffrey J. 1992. Diffusion of copper and boron from a
groundline wrap formulation through Douglas-fir heartwood. For. Prod. J., 42(11-12):,
27-29
Freeman, M.H, D.P. Kamdem, E.L. Schmidt, and Pascal Nzokou. 2002. Water-Borne
Copper Naphthenate:
A Potential New Preservative for Softwoods, Hardwoods, and Composites. Proceeding
of FPS meeting entitled: Enhancing the Durability of Lumber and Engineered Wood
Products. Forest Products Society, Madison, WI.
Freeman, M.H. and J. A., Brient. 2001. Copper Naphthenate: An Update and Status
Report on an Effective Wood Pole Preservative. In Proceedings of NWPPA and WEI
Utility Pole Structures Conference and Trade Show. Proceedings published by Oregon
State Univ. Press, Corvallis, OR.
Freeman, M.H., and D.P. Kamdem. 2001. Water-Borne Copper Naphthenate: An
Emerging New Technology. A Technical Forum presented at the 2001 Annual Meeting
of the American Wood Preservers Assoc. in Minneapolis, MN. AWPA, Granbury, TX.
Freeman, M.H. and T.L. Amburgey. 1994. A Copper Naphthenate-Boron Wood
Preservative Remedial Treatment Paste. As above, then IRG 94-
Freeman, M.H. 1992. Copper Naphthenate: An Effective Wood Pole and Crossarm
Preservative. In Proceedings of the First Southeastern Pole Conference, Starkville, MS.
FPS Proceedings 7314. Forest Products Society, Madison, WI.
Freeman M.H. and T.J. Leech, 1993. A Copper Naphthenate Treated Wood Consumer
Information Sheet(CIS) and Hazardous Goods Shipping Label Prototype. Submitted to
22
the American Wood Preservers Institute, Vienna, VA. ISK Biosciences, Inc. Memphis,
TN.
Freeman, M.H. 1992. Copper Naphthenate- Technical Specification and Use Manual: A
Compilation of Data and Technical References into the Use of Copper Naphthenate as a
Wood Preservative. ISK BIOTECH, Corp. - Industrial Biocides Division, Memphis, TN.
240 pp.
Freeman, M. H. and M.H. West. 1989. Treatment of Green Fence Posts and
Unseasoned Timbers with diffusible water borne copper naphthenate solution. Chapman
Chemical Company Technical Bulletin. Chapman Chemical Co., Inc., Memphis, TN
38109. 4 pp.
Grace, J. K., Yamamoto, R. T., Laks, P. E. 1993. Evaluation of the termite resistance of
wood pressure treated with copper naphthenate. For. Prod. J., 43 (11-12):,.72-76.
Greenberger, M.; Spring, R. v.; Kaplan, D. L. 1990. Efficacy of solvent and water-based
preservatives for wood. Phase 2. Report (1990), NATICK/TR-90/021; Order No. AD-
A219704, Gov. Rep. Announce. Index (U. S.), Vol. 90(14), Abstr. No. 036,884
Gooddell B. and A. J. Pendlebury 1991. Preservative treatment and field test monitoring
of spruce pole stock: pressure and diffusible chemical treatments. Forest Prod. J. 41 (4)
39-44.
Hartford, W.H. 1973. Chemical and physical properties of wood preservatives. In: Wood
Deterioration and its Prevention by Preservative Treatment. D.D. Nicholas, ed. Syracuse
Univ. Press, N.Y.
Hilditch, E. A.; Sparks, C. R.; Worringham, J. H. M. 1983. Further developments in
metallic soap based wood preservatives. Record of the Annual Convention of the British
Wood Preserving Association, pp. 61-72.
Kamdem D.P., R. Fair and M. Freeman 1996. Efficacy of waterborne emulsion of copper
naphthenate for northern red oak (Quercus rubra) and soft maple (Acer rubrum). Holz
als roh-und Wersktoff 54 :183-187.
Kamdem, D. Pascal, Mike H. Freeman, Elmer L. Schmidt and Justin Zyskowski. 2001.
Waterborne Copper Naphthenate: A New Preservative for Hardwoods, Softwoods, and
Composites. A Technical Forum presented at the 33rd Annual Meeting of the Forest
Products Society in Baltimore, MD. FPS, Madison, WI.
Kamdem, D.P., Freeman, M.H. and T.L. Woods.1996. The Bioefficacy of CuNapSol
Treated Western Red Cedar and Southern Yellow Pine. As above IRG 96-
McIntyre, C. R. 2000. Copper Naphthenate Performance: A New Way to Look at Old
Data. Paper presented at the 2000 IRG Annual Meeting, Kona, HI. IRG, Stockholm,
Sweden.
Kamdem D. P., L. Murdoch, M. Freeman and P. Chow .1992. Preservative treatment of
hardwoods. FPRS Proc. “Preservative treatment for the 90’s and Beyond. Conf. In
Savannah, GA. For. Prod. Society, Madison, WI.
23
Lebow S. T. and M. Tippie 2001. Guide for minimizing the effect of preservative treated
wood on sensitive environments. General technical report FPL-FTR-122. USDA.
McIntyre, C.R. 2001. Letter and soil block data on water-borne and oil-borne Copper
Naphthenate to AWPA Sub-Committee T-7 (Quality Control and Inspection). McIntyre
And Assoc., Walls, MS. 2 pp.
McIntyre, C.R. 2000. The Performance of Copper Naphthenate. Paper presented at the
International Conference on Utility Line Structures in Fort Collins, CO, held March 20-22,
2000. Col. State Univ. and EDM Inc. Ft. Collins, CO.
McIntyre, C.R. The Tabular and Graphical Performance of Copper Naphthenate Wood
Preservative Systems: An Internal Report to Merichem Chemical and Refinery Services,
Houston, TX. 18 pp.
Minich, A. and Goll, M. 1948. The Technical Aspects of Copper Naphthenate as a Wood
Preserving Chemical. Proc. Amer. Wood-Preserv. Assoc., 44:265-270
Morrell, J.J. 1997. The Performance of Water Borne Copper Naphthenate Formulations
in Soil Block and Fungus Cellar Trials. Oregon Sate Univ. Report, OSU, Corvallis, OR.
Nicholas, D.D. and M.H. Freeman. 2000. Comparative Performance of
Pentachlorophenol and Copper Naphthenate in a Long Term Field Stake Test. Paper
presented at the International Conference on Utility Line Structures in Fort Collins, CO,
held March 20-22, 2000. Col. State Univ. and EDM Inc. Ft. Collins, CO.
Nicholas, D.D. 1996. Performance of Water Borne Copper Naphthenate in Soil Block
Tests using a new and novel compressive Strength Loss Evaluation Method. Internal
Report from Mississippi State University, Forest Products Lab, College of Forestry and
Forest Products, Miss. State, MS.
Pohleven, F., Petric, M. 1995. The biological properties of copper and zinc carboxylates
in wood preservation. Conf. Coord. Chem., 15th(Current Trends in Coordination
Chemistry), pp. 379-82.
Richter, D.L. 1996. The performance of Water Borne Wood Preservative Coatings on
Fungal Growth on Southern Pine and Western Red Cedar Substrates. Internal Memo
and Report. Michigan Tech, Univ., Houghton, MI.
Schmidt, E. L. 1991. A Resin Compatible Copper Naphthenate to Preserve Aspen
Composites. For Prod J. 41(5): 31-32.
Shaw, J.L. 1994. Results of test activity on a water-borne copper naphthenate wood
preservation system. Proc Amer Wood-Pres Assoc,. 90 :385-394.
Smith, W. B., Abdullah, N., Herdman, D., DeGroot, R. C. 1996. Preservative treatment
of red maple. For. Prod. J., 46(3):35-41 35-41.
Sparks, C. S. 1978. A new brand of metallic chemicals for use in wood preservation.
Record of the Annual Convention of the British Wood Preserving Assocaition, pp. 48-51.
24
Stevanovic-Janezic T., P.A. Cooper and Y. Tony Ung 2001. Chromated Arsenate
Preservative treatment of North American Hardwoods. Holzforschung 55 (1) 7-12.
Talerek, W.G., at: http://www. Merichem.com/copper/newsrel_frame.html
Tang, Yijun.2001. Copper Migration in Preservative Treated Wood Stakes. Internal
report to D. P. Kamdem and The Wood Science Group, Mich. State Univ., East Lansing,
MI. 18 pp.
Tomashiro, M.1988. Personal Communication on protection of wood substrate with
Water Borne Copper Naphthenate. Univ. of Hawaii, Honolulu, HI.
U.S. Army: Environmental Hygiene Agency - AHEA. 1987. Preliminary Assessment of
the Relative Toxicity of Copper Naphthenate. Study No. 75-51-0497088
Winandy E. J. and K. A. McDonald 1993. Material and preservative treatments for
outdoor wood structures. Wood Design Focus 4 (3) 8-13.
