CA2417670A1 - Preserving compositions - Google Patents
Preserving compositions Download PDFInfo
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- CA2417670A1 CA2417670A1 CA002417670A CA2417670A CA2417670A1 CA 2417670 A1 CA2417670 A1 CA 2417670A1 CA 002417670 A CA002417670 A CA 002417670A CA 2417670 A CA2417670 A CA 2417670A CA 2417670 A1 CA2417670 A1 CA 2417670A1
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- Prior art keywords
- zinc
- boron
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- vacuum
- wood
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-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/14—Boron; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/163—Compounds of boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/22—Compounds of zinc or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/32—Mixtures of different inorganic impregnating agents
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The specification describes wood preserving compositions comprising basic aqueous solutions of zinc and boron compounds. In particular the specificati on describes wood preserving compositions comprising zinc borate dissolved in aqueous ammonia. Other preservatives such as copper and quaternary ammonium compounds may also be included. Wood impregnated with the preservative composition is resistant to leaching.
Description
2 cA 02417670 2003-01-28 pCT/AU01/00325 _ g _ PRESERVING COMPOSITIONS
The present invention relates to preserving compositions for porous products, especially wood.
Compounds of boron have been used in the preservation of wood for a number of years. However, one of the difficulties experienced in use of these compounds is their propensity to leach from the substrate into which they have been impregnated.. Consequently, compounds of boron have not been particularly useful in preserving timber exposed to water, for example, pylons embedded in a sea bed.
Basic zinc compounds also have toxic efficacy with respect to wood destroying organisms, both in the marine and land environments. However, despite this efficacy having been known, basic zinc compounds have not been used commercially.
The present invention is based on the discovery that a composition comprising a basic zinc compound and a 2C compound of boron has a toxic efficacy to wood destroying organisms, both in the marine and land environments with the added benefit of a reduction in the rate at which the boron compound leaches from the impregnated substrate.
Accordingly, the present invention provides a preserving composition which includes a basic zinc compound and a compound of boron.
A preferred composition comprises zinc ions and borate ions in an aqueous solution of ammonia. The zinc ions may be derived from any soluble zinc compound and the borate ions may be derived from any soluble borate but zinc borate is preferred. Examples of soluble zinc compounds include zinc sulfate and zinc chloride and examples of soluble borates include sodium borate and potassium borate. A solution of zinc ions and borate ions 3J in aqueous ammonia may be prepared by dissolving zinc borate in an aqueous solution of ammonia at a temperature of about 66°C. Alternatively, a soluble zinc salt may be WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 _ 2 _ combined with a soluble borate salt in an aqueous ammonia solution at a temperature of about 66°C.
The preserving composition of the present invention may be combined with other additives having efficacy as preservatives. These include copper sulfate, fluorides such as potassium fluoride and quaternary ammonium compounds.
Porous compoundsE especially porous cellulosic compounds, may be impregnated with the preserving composition of the present invention by flooding the porous compound at reduced pressure. Preferably, the pressure is reduced to a level in the range between 0.5 kPa and 0.9 kPa.
In a further aspect, the present invention ~5 provides a means of impregnating a substrate with a preserving composition by means of coacervation.
Coacervation occurs when a liquid compound separates into two phases below a particular temperature. One phase is rich in one compound and the other is leaner. Coacervation 2C is similar to crystallisation from a mother liquor.
The following examples illustrate the invention.
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25 Preparation of Impregnant ~ 1000 grams of ammonia solution (28°0) was added to 1000 grams of water.
~ With constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia 30 solution.
~ The solution was heated gently at 66°C to form a clear solution.
Preparation of Wood Blocks 35 ~ Pinus radiata clear sapwood was used for the impregnation, and all the wood blocks were conditioned to less than 15°o moisture level.
~ The numbered blocks prepared for the impregnation were:
028, 107, 147, 282 and 307.
~ The volume of the blocks was measured and the results are given below. Although the volume of each block varies slightly, the volume of every individual block was measured to ensure the accuracy of retention calculated.
Block No. 028 107 147 282 307 Volume (m3x10-6) 12.675 12.521 12.649 12.684 12.848 ~ The weight of the blocks was determined Impregnation ~ Once a vacuum of 0.9 kPa was reached, the vacuum pump ~5 was kept runraing for 30 minutes, and the lowest vacuum achieved before flooding was 0.65 kPa.
~ Flooding was commenced under vacuum.
~ Vacuum was released to atmospheric pressure.
~ Atmospheric pressure was employed for 60 minutes.
~ The solution was s~xcked back to the work vessel under vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
~ After a vacuum of 2.5 kPa was reached, the vacuum was run for 30 minutes.
~ The lowest vacuum reached was 2.1 kPa before the vacuum was released.
~ The weight of blocks was determined, and the uptake and retention of chemicals calculated. The results are as follows.
Block No. 107 307 028 282 147 Uptake (g) 7.7165 9.0291 8.3166 8.084 7.8495 Retention 67~_~R ~n~ ~~ ~~~ ~d ~z~ zn can ec WO 01/70472 cA 02417670 2003-O1-28 pCT/AU01/00325 -a-( kg/m3 ) ~ Blocks were dried naturally in the open air.
Leaching ~ The leaching was conducted as detailed in the American Wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in exactly the same way as in the impregnation with preservatives.
~ ~nce a vacuum of 1.5 kPa was reached, the vacuum pump was kept running for 30 minutes, and the lowest vacuum achieved before flooding was 1.3 kPa.
~ Distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure.
~ The amounts of water used was 50 ml per block, and the total amount of water used was 300 ml. The loss of water to the uptake was re-added.
~ ~nce the leaching was commenced, the leachant was changed at intervals of 6 hours, 2a hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnantt Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron and zinc are 12.07g/L and 27.89g/L respectively.
~ The determined concentration of the impregnant was used WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 to calculate the mass balance.
2. Analysis of leachates ~ The leachates were analysed directly without any further sample preparation.
The concentrations of boron and zinc in the leachates are as follows.
Sample L1 L2 L3 L4 L5 L6 L7 L8 L9 B (pgn) 204 192 202 107 62.5 48.3 37.429.7 26.6 Zn (pgn) 113 90.7 93.916.5 16.9 14.0 13.49.80 9.35 .3. Analysis of digested wood blocks ~ Four out of five blocks were used for the digestion and analysis, and the other one was used for penetration test.
~ The four blocks were quantitatively powdered, homogenised and dried at 100°C for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the 2G digestion.
~ The digestion was carried out based on the American Wood Preserver's Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ The solutions obtained from the digestion were analysed for boron and zinc and the results are as follows.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 Block No. 028 107 147 307 B in digestion 197 153 147 219 solution (ppm) Total B in each 55.23 44.66 43.74 57.13 block (mg) Zn in digestion 770 729 744 858 solution (ppm) Total Zn in each 215.7 212.7 217.2 224.1 block (mg) Summary of Results jB Total boron uptake 397.2 mg I
I Total boron in wood 200.8 mg Boron mass fraction in wood 0.479 i Total boron in leachate 218.1 mg Boron mass fraction in leachate 0.521 Mass balance 105.5 Boron retention after leaching 3.96 kg/m3 Zn Total zinc uptake 918.0 mg Total zinc in wood 869.7 mg Zinc mass fraction in wood 0.906 Total zinc in leachate 90.61 mg Zinc mass fraction in leachate 0.094 Mass balance 104.6%
Zinc retention after leaching 17.16 kg/m3 Comment ~verloading could have been committed resulting in a relatively high mass fraction of boron being leached out. The impregnation procedure followed the Bethell full-cell schedule. The severe overloading occurred and some boron leached as a consequence of excess preservative compound being present within the vessels.
The boron retention after leaching, however, is still very high, 3.66 kg/m3, compared with 1 kg/m3 required WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 -a-by an American company.
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Preparation of Impregnant The impregnant used in Example 2 was prepared in the same way as in Example 1.
1000 grams of ammonia solution (28%) was added to 1000 grams of water.
~ With constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia solution.
~ The solution was heated gently at 66°C to form a clear solution.
Preparation of Wood Blocks ~ Very similar procedure to that in Example 1 was used to prepare the blocks.
~ The numbered blocks prepared for the impregnation were:
062, 100, 206, 223 and 239.
~ The volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation While the impregnation was conducted in a similar way to that in Example 1, different vacuums were used.
Once a vacuum of 2.1 kPa was reached, the vacuum pump was kept running for 30 minutes, and the lowest vacuum achieved before flooding was 1.9 kPa.
~ Flooding was commenced under vacuum.
~ Vacuum was released to atmospheric pressure after flooding completed.
~ Atmospheric pressure was employed for 60 minutes.
~ The solution was sucked back to the work vessel under vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 g _ ~ After a vacuum of 2.5 kPa was reached, the vacuum was run for 30 minutes.
~ The lowest vacuum reached was 2.3 kPa before the vacuum was released.
~ The weight of blocks was determined, and the uptake and retention of chemicals calculated. The results are as follows.
Block No. 062 100 206 223 239 Uptake (g) 8.8483 5.4833 8.0169 6.9345 8.2680 Retention 702.86 433.94 629.96 553.03 663.35 ( kg % m3 ) ~ Blocks were dried naturally in the open air.
beaching The leaching was carried out in a similar way to that in Example 1 except different vacuums were used.
~ The leaching was conducted as detailed in the American Wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in exactly the same way as in the impregnation with preservatives.
~ Once a vacuum of 1.6 kPa was reached, the vacuum pump was kept running for 30 minutes, and the lowest vacuum achieved before flooding was 1.4 kPa.
Distilled water was used for the flooding.
~ Vacuum was released t~ atmospheric pressure.
~ The amount of water used was 50 ml per block, and the total amount of water used was 300 ml. The loss of water to the uptake was re-added.
~ Once the leaching was commenced, the leachant was changed at intervals of 6 hours, 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 _ g _ Analysis of Impregnant, Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron and zinc are 11.30g/L and 28.28g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of leac&ates ~ The leachates were analysed directly without any further sample preparation.
~ The boron concentrations in the leachates are as follows.
Sale L1 L2 L3 L4 L5 L6 L7 L8 L9 B (pFcn) 236 170 68.1 40.4 29.4 25.3 21.9 20.6 17.3 3. Analysis of digested Wood blocks ~ Four out of five blocks were used for the digestion and analysis, and the other one was used for penetration test.
~ The four blocks were quantitatively powdered, homogenised and dried at 100°C for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the digestion.
~ The digestion was carried out based on the American Wood Preserver's Association Standard A7-93 using nitric WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 acid, sulfuric acid and perchloric acid.
The solutions obtained from the digestion were analysed for boron and zinc and the results are as follows.
Block No. 100 206 223 239 B in digestion 85.3 166 118 165 solution (ppm) Total B in each 24.14 47.42 34.16 47.31 block (mg) Zn in digestion 556 724 672 741 solution (ppm) Total Zn in each 157.5 206.3 193.9 212.9 block (mg) Summary of Results B Total boron uptake X324.2mg Total boron in wood 153.0mg Boron mass fraction in wood 0.504 Total boron in leachate 150.9mg I Boron mass fraction in leachate 0.496 Mass balance 93.74 I
I Boron retention after leaching 3.04 kg/m3 Zn Total zinc uptake X 811.7mg i Total zinc in wood 770.6mg Zinc mass fraction in wood 0.949 Total zinc in leachate Zinc mass fraction in leachate Mass balance Zinc retention after leaching 15.30kg/m3 Comment 1G Overloading could have been committed resulting in a relatively high mass fraction of boron being leached out. The impregnation procedure followed the Bethell full-cell schedule. The severe overloading occurred and some boron leached as a consea_uence of excess preservative _ 11 _ compound being present within the vessels.
The boron retention after leaching, however, is still very highA 3.04 kg/m', compared with 1 kg/m3 required by an American companyo Preparation of Impregnant While the formulation used in this example is different from that used in Examples 1 and 2, the preparation of the impregnant was commenced in the similar way to that in Examples 1 and 2.
~ 1000 grams of ammonia solution (28%~ was added to 1000 grams of water.
~ With constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia solution.
~ The solution was heated gently at 66°C to form a clear solution.
~ 200 grams of copper sulfate were added gradually and then the solution was cooled to room temperature.
Preparation of Wood Flocks Same procedures were used to prepare blocks as that used in Examples 1 and 2.
~ The numbered blocks prepared for the impregnation were:
043, 044, 190, 211 and 245.
~ The volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation While the impregnation was conducted in a similar way to that in Examples 1 and 2, different vacuums were used.
~ Once a vacuum of 1.9 kPa was reached, the vacuum was maintained for 30 minutes, and the vacuum before flooding was also 1.7 kPa.
~ Flooding was commenced under vacuum.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 ~ Vacuum was released to atmospheric pressure after flooding completed.
~ Atmospheric pressure was employed for 60 minutes.
~ The solution was sucked back to the work vessel under vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
After a vacuum of 2.4 kPa was reached, the vacuum was run for 30 minutes.
~ The lowest vacuum reached was 2.3 kPa before the vacuum was released.
The mass of blocks was determined straight after the pressure treatment, and the uptake and retention of chemicals calculated. The results are as follows.
Block No. 043 044 190 211 245 Uptake (g~ 7.8235 8.2008 8.3631 7.2498 7.3124 Retention 617.58 638.19 659.65 576.98 579.43 ( kg/m3 ~
Blocks were dried naturally in the open air and conditioned for two weeks.
i~lOTEo The vacuum utilised in this modified Bethell schedule is very important and we have discovered this to be a 2C significant part of this process, ultimately aimed at reduced boron leaching.
Leaching The leaching was carried out in a similar way to that in Examples 1 and 2 although different vacuums were used.
~ The leaching was conducted as detailed in the American Wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in exactly the same way as in the impregnation with preservatives.
~ Once a vacuum of 1.5 kPa was reached, the vacuum pump was kept running for 30 minutes.
~ Distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure.
~ The amount of water used was 50 ml per block, and the total amount of water used was 300 ml. The loss of water to the uptake was re-added.
~ Once the leaching was commenced, the leachant was changed at intervals of 6 hours, 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnant, Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron( zinc and copper were 10.80g/L, 26.94g/L and 36.52g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of leachates ~ The leachates were analysed directly without any further sample preparation.
~ The concentrations of boron and copper in the leachates were as follows.
Sample L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 B (ppm) 377 221 92.0 53.0 37.3 5.37 13.1 9.66 8.50 5.25 C~ (txml '~~ _ 9 1 d J ~, ~,1 r, 11 ~ 17 1 GG ~ ~c 1 oc 1 cn , n., WO 01/70472 cA 02417670 2003-01-28 PCT/AU01/00325 3. Analysis of digested wood blocks ~ Four out of five blocks were used for the digestion and analysis, and the other one was used for a penetration test.
~ The four blocks were quantitatively powdered, homogenised and dried at 100°C for 2 hours before analysis.
3.0000 grams of wood powder were taken for the digestion.
1G ~ The digestion was carried out based on the American Wood preserver's Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ fihe solutions obtained from the digestion were analysed for boron, zinc and copper and the results are as 25 follows.
Block No. 043 044 190 211 B in digestion 63.9 52.5 50.2 43.7 solution (ppm) Total B in each 18.22 16.89 16.00 14.28 block (mg) Zn in digestion 475 542 540 414 solution (ppm) fiotal Zn in each 135.4 174.3 172.2 135.3 block (mg) Cu in digestion ? 1092 1144 920 solution (ppm) fiotal ~u in each 108.6 351.3 364.9 300.5 block (mg) _ 15 _ Summary of Results B Total boron uptake 341.7 mg Total boron in wood 65.38 mg Boron mass fraction in wood 0.249 Total boron in leachate 197.2 mg Boron mass fraction in leachate 0.751 Mass balance 76.84 o Boron retention after leaching 1.29 kg/m3 Zn Total zinc uptake X852.4mg Total zinc in wood 617.2 mg Zinc mass fraction in wood 0.724 Total zinc in leachate ?
Zinc mass fraction in leachate ?
Mass balance ?
Zinc retention after leaching 12.16 kg/m3 Cu Total copper uptake mg Total copper in wood 1125 mg Copper mass fraction in wood 0.985 Total copper in leachate 17.61 mg Copper mass fraction in leachate 0.015 i Mass balance 98.93 ~I Copper retention after leaching 22.17 kg/m3 ravTUrnT ze w Preparation of Impregnant While the formulation used in this example is different from that used in Examples 1, 2 and 3, the impregnant was first prepared as that in Example 3 and then 8.9 grams of potassium fluoride were added.
~ 1000 grams of ammonia solution (28°0) was added to 1000 grams of water.
~ i~Vith constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia solution.
~ The solution was heated gently at 66°C to form a clear WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 solution.
200 grams of copper sulfate were added gradually and then the solution was cooled to room temperature.
~ 8.9 grams of potassium fluoride were added.
Preparation of Wood Blocks The procedure used to prepare blocks is very similar to that in Examples 1 and 2.
~ The numbered blocks prepared for the impregnation wereo 066, 143, 200, 205 and 26~L.
~ The volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation 1~ While tine impregnation was conducted in a similar way to that in Examples 1 and 2, different vacuums were used.
~ Once a vacuum of 3.9 kPa was reached, the vacuum pump was kept running for 30 minutes, and the vacuum before flooding was also 1.9 kPa.
2C ~ Flooding was commenced under vacuum.
~ Vacuum was released to atmospheric pressure after flooding was completed.
~ Atmospheric pressure was employed for 60 minutes.
~ The solution was sucked back to the work vessel under 25 vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
~ After a vacuum of 2.5 kPa was reached, the vacuum was run fox 30 minutes.
30 ~ The lowest vacuum reached was 2.3 kPa before the vacuum was released.
~ The weight of blocks was determined straight after the pressure treatment, and the uptake and retention of chemicals calculated. The results are as follows.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 Block No~ 066 143 200 205 261 Uptake (g) 7.2259 7.4066 7.2929 7.1257 7.6352 Retention 573.03 593.29 580.64 567.38 612.88 ( kg/m3 ) ~ Blocks were dried naturally in the open air.
Leaching The leaching was carried out in a similar way to that used in Example 1 although different vacuums were used.
~ The leaching was conducted as detailed in the American Wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in exactly the same way as in the impregnation with 1G preservatives.
~ Once a vacuum of 0.5 kPa was reached, the vacuum pump was kept running for 30 minutes.
~ Distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure.
~ The amount of water used was 50 ml per block, and the total amount of water used was 300 ml. The loss of water to the uptake was re-added.
~ ~nce the leaching was commenced, the leachant was changed at intervals of 6 hours. 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnant, Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 analytical instrument ~ The diluted impregnant was determined and the concentrations of boron, zinc and copper were 10.63g/L, 2~.llg/L and 36.55g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of leachates The leachates were analysed directly without any further sample preparation.
~ The concentrations of boron and copper in the leachates were as follows.
Sample Li L2 L3 L4 L5 L6 L7 L8 L9 S (pl~~ 469 501 48.4 20.020.7 13.7 7.45 5.826.13 Cu (ppzn) 57.Q~ 46.2 4.32 2.783.61 2.87 1.99 2.201.69 3. Analysis of digested wood blocks ~ Four out of five blocks were used for the digestion and analysis, and the other one was used for a penetration test.
~ The four blocks were quantitatively powdered, homogenised and dried at 100°C for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the digestion.
~ The digestion was carried out based on the American Wood Preserver's Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ The solutions obtained from the digestion were analysed for boron, zinc and copper and the results are as follows.
WO 01/70472 cA 02417670 PCT/AU01/00325 Block No. 143 200 205 261 B in digestion 61.0 40.0 47.6 53.4 solution (ppm) Total B in each 19.39 13.60 15.51 17.59 block (mg) Zn in digestion 410 333 370 467 solution (ppm) Total Zn in each 130.2 113.3 120.6 153.8 block (mg) Cu in digestion 45.0 29.7 646 1048 solution (ppm) Total Cu in each 134.0 86.80 252.7 345.3 block (mg) Summary of Results B Total boron uptake 313.3mg Total boron in wood 66.09mg Boron mass fraction in wood 0.201 Total boron in leachate 262.1mg Boron mass fraction in leachate 0.799 Mass balance 104.7 i Boron retention after leaching 1_.32kg/m3 ~Zn Total zinc uptake 798.8mg Total zinc in wood 517.9mg Zinc mass fraction in wood 0.648 Total zinc in leachate ?
Zinc mass fraction in leachate ?
Mass balance ?
i Zinc retention after leaching 10.35kg/m3 Cu Total copper uptake 1077 mg Total copper in wood 818.7mg Copper mass fraction in wood 0.963 Total copper in leachate 31.12mg Copper mass fraction in leachate 0.037 Mass balance 78.92 Copper retention after leaching 16.35kg/m3 WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 ExAMPLE 5 Preparation of Impregnant The formulation used in this example is the same as that in Example 3.
~ 1000 grams of ammonia solution (28%~ was added to 1000 grams of water.
~ With constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia 1G solution.
~ The solution was heated gently at 66°C to form a clear solution.
~ 200 grams of copper sulfate were added gradually and then the solution was cooled to room temperature.
Preparation of Wood Flocks The procedure used to prepare blocks is very similar to that in the other examples. Ten blocks were used in this example rather than five blocks as in the previous 20 examples.
~ The numbered blocks prepared for the impregnation were:
168, 039, 212, 125, 313, 080, 238, 299, 195 and 051.
~ The volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation While the impregnation was conducted in a similar way to that used in the other examples, different vacuums were used.
3G ~ Once a vacuum of 1.0 kPa was reached, the vacuum pump was kept running for 30 minutes, and the vacuum before flooding was 0.6 kPa.
~ Flooding Was commenced under vacuum.
~ Vacuum was released to atmospheric pressure after flooding completed.
~ Atmospheric pressure was employed for 90 minutes.
~ The solution was sucked back to the work vessel under WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
~ After a vacuum of 1.3 kPa was reached, the vacuum was run for 30 minutes..
The lowest vacuum reached was 1.2 kPa before the vacuum was released.
~ The weight of blocks was determined straight after the pressure treatmento and the uptake and retention of chemicals calculated, The results are as follows.
Block No. 168 039 212 125 313 TJptake (g) 7.8782 8.6661 8.1115 9.0619 7.8899 Retention 631.92 701.65 644.38 720.57 622.53 ( kg/m3 ) Block No. 080 238 299 195 051 Uptake (g) 7.9759 9.4277 8.8812 9.3488 8.9464 Retention 639.15 739.31 696.62 738.04 695.30 (kg/m3 ) ~ Blocks were dried naturally in the open air.
beaching The leaching was carried out in a similar way to that in the other examples although different vacuums were used.
~ The leaching was conducted as detailed in the American Tnlood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in 2C exactly the same way as ir. the impregnation with preservatives.
~ Once a vacuum of 0.9 kPa was reached, the vacuum pump was kept running for 30 minutes. A vacuum of 0.6 kPa was achieved before flooding.
2~ ~ Distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure.
~ The amount of water used was 50 ml per block, and the WO 01/70472 CA 02417670 2003-O1-28 pCT/AU01/00325 total amount of water used was 500 ml. The loss of water to the uptake was re-added.
~ Once the leaching was commenced, the leachant was changed at intervals of 6 hours, 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnant~ Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1~ 1~ ~naTysis of impregnant The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron, zinc and copper are 5.61g/L, 21.25g/L and 48.07g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of .leac&ates ~ The leachates were analysed directly without any further sample preparation.
~ The concentrations of boron, zinc and copper in the leachates are as follows.
Sample L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 L11 B (ppm)174 186 157 80.1 48.5 32.0 22.4 15.611.9 9.62 7.59 Zn (pgn)86.5 47.428.2 10.9 4.07 4.49 1.26 1.381.04 1.51 1.14 Cu (ppm)131 113 110 59.3 26.8 18.9 5.14 2.881.75 2.17 1.52 3. Analysis of digested wood blocks ~ After the penetration test, all the ten blocks were quantitatively powdered, homogenised and dried at 100°C
for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the digestion.
~ The digestion was carried out based on the American Wood Breserver~s Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ The solutions obtained from the digestion were analysed for boron, zinc and copper and the results are as follows.
Block No. 168 039 212 125 313 B in digestion 38.9 40.5 39.7 50.0 35.1 solution (ppm) Total B in eacr~ 9.733 9.866 9.387 11.91 8.326 block (mg) Zn in digestion 539 593 595 632 579 solution (ppm) Total Zn in each 134.8 144.5 140.6 150.5 137.1 block (mg) Cu in digestion 1644 1813 1898 1997 1794 solution (ppm) Total Cu in each 411.3 441.5 448.3 475.8 425.0 block (mg) Block No. 080 238 299 195 051 B in digestion 40.5 43.4 41.4 52.5 49.0 solution (ppm) Total B in each 9.402 10.68 10.62 12.80 12.26 block (mg) Zn in digestion 588 626 590 635 611 solution. (ppm) Total Zn in each 136.5 154.1 151.5 154.8 152.6 block (mg) Cu in digestion 1728 1807 1647 1770 1757 solution (ppm) Total Cu in each 401.1 444.5 422.6 431.7 439.2 WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 - 24 _ Summary of Results B Total boron uptake 483.3 mg Total boron in wood 105.0 mg Boron mass fraction in wood 0.220 i Total boron in leachate 372.2 mg ! Boron mass fraction in leachate 0.780 Mass balance 98.75 I Boron retention after leaching 1 0.832 kg/m3 ;Zn Total zinc uptake 1831 mg j i i Total zinc in wood 1457 mg Zinc mass fraction in. wood 0.939 Total zinc in leachate 93.97 mg Zinc mass fraction in leachate 0.061 Mass balance 84.68 o i Zinc retention after leaching 11.55 kg/m3 Cu Total copper uptake 4143 mg Total copper in wood 4341 mg Copper mass fraction in wood 0.948 Total copper in leachate 236.5 mg Copper mass fraction in leachate 0.052 ! Mass balance 110.5 o i j Copper retention after leaching 34.41 kg/m3 Comment ~ The foramulation prepared and utilised as detailed in Examples 3P 4 and 5 all contain copper. Each formulation detailed in every example to date contains zinc. Of great importance is the fact that basic (alkaline) zinc containing compounds have been found to exhibit a high degree of toxic efficacy to wood destroying organisms both in the marine and land environments. We have discovered a way of combining the efficacy of boron within a complex basic polyborate-zinc system which reduces the leaching of boron from commodities treated with this preservative composition.
The efficacy of basic zinc containing compositions was WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 never researched beyond its initial discovery We have discovered a successful way of complementing the efficacy of boron with that of basic zinc compounds with the unexpected, unique reduction of the leaching of boron, resulting from the interaction of the preservative composition and its impregnated, soaked, brushed, sprayed or diffusion treated substrate.
~ Fluorine is an important component of Example 4 in which it contributes additional synergistic efficacy.
~ The formulation utilised in Example 5 was prepared with a lower boron concentration. This constitutes one of several preservative compositions purposely formulated to result in a lower boron retention in timber and other treated commodities which are to be used above ground and especially in building, walkway, bush tracks and numerous other constructions. Especially useful in indoor environments, such compositions will constitute economic protection without any less or reduction in efficacy.
Preparation of Impregnant The preservative composition was first prepared 2~ as detailed in Example 1. 1551 grams of this solution were slowly combined with 30 grams of N-alkyl tallow N dimethyl amino propyl N trimethyl ammonium dichloride in isopropanol water solution. This composition was agitated for several hours until a clear solution was produced. The solution was made up to 2000 grams, by addition of double distilled water. The pH of this composition was determined as 12.6.
Quaternary ammonium salts have long been known to exhibit high surface activity coupled with biological and fungicidal efficacy. Such complex compositions have usually been used to formulate emulsions of cationic nature at low pH. These unique properties have been retained in this complex wood preservative composition. Penetration WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 26 _ and distribution in treated timber have been enhanced and complemented by additional efficacy and boron fixation.
Iioweverp boron diffusion and movement within the treated commodity has not been hindered, nor fixation rendered so efficient as to hinder efficacy. More surprising and wholly unexpected is the enhanced biocidal efficacy and composition stability in an alkaline environment.
A further very important development, relevant to this composition and previous surface activated compositions such as detailed in Example 7, is their inherent property of self-emulsification with a wide variety of oils which includeP but are not limited to, petroleum derived oil s mineral oils, vegetable oils and more especially creosote oils, the latter having great wood 1~ preservation significance and limited potential for diversity of formulation and application.
Preparation of Wood Blocks The procedure used to prepare blocks is very similar to that in the other examples. Totally ten blocks were used in this example.
The numbered blocks prepared for the impregnation were:
218, 144, 250, 217, 258, 001, 3.32, 303, 274 and 226.
~ the volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation While the impregnation was conducted in a similar way to that used in the other examples, different vacuums were used.
~ Once a vacuum of 0.9 kPa was reached, the vacuum pump was kept running for 30 minutes, and the vacuum before flooding was also 0.9 kPa.
~ Flooding was commenced under vacuum.
~ ~Jacuum was released to atmospheric pressure after flooding completed.
~ Atmospheric pressure was employed for 90 minutes.
m 27 -~ The solutiora was sucked back to the work vessel under vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks for 30 minutes, and a vacuum of 1.9 kPa was reached before the vacuum was released.
The weight of blocks was determined straight after the pressure treatment, and the uptake and retention of chemicals calculated The results are as follows.
Block No. 218 144 250 217 258 Uptake (g) 9.6596 9.4843 9.6391 10.1950 8.7983 Retention 757.97 755.66 758.86 799.99 699.50 ( kg/m3 ?
Block No. 001 132 303 274 226 Uptake (g~ 9.6670 9.9522 9.2082 9.6967 10.0360 Retention 774.17 785.43 725.00 764.24 785.34 (kg/m'2 ~ Blocks were dried naturally in the open air.
Leaching All blocks were dried at 108°C for 24 hours before leaching, and the leaching was carried out in a similar way to that in the other examples although different vacuums were used.
~ The leaching was conducted as detailed in the American wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in the 2C exactly same way as in the impregnation with preservatives.
~ Once a vacuum of 1.5 mmHg was reached, the vacuum pump was kept running for 35 minutes. The final vacuum achieved before flooding was also 1.5 mmHg.
~ The flooding was conducted under vacuum, and distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure after the WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 flooding was completed.
~ The amount of water used was 50 ml per block, and the total amount of water used was 500 ml. The loss of water to the uptake was re-added.
~ Once the leaching was commenced, the leachant was changed at the intervals of 6 hours, 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnant, Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
2. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron, zinc and copper are 4.43g/L, 17.07g/L and 42.32g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of leachates ~ The leachates were analysed directly without any further sample preparation.
~ The concentrations of boron, zinc and copper in the leachates are as follows.
Sample L1 L2 L3 L4 L5 L6 L7 L8 L9 B (pgn)208 195 134 80.342.0 27.3 20.5 16.2 11.4 Zrn 85.3 62.1 38.9 18.27.09 5.10 2.51 2.47 (p~m; 2.43 C_'m 97_9 91n &S ~n ~o S ,~ ~ , o, ~ n~
(nrm) a ~ , co WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 3~ Analysis of digested wood blocks ~ After the penetration test, all the ten blocks were quantitatively powdered, homogenised and dried at 100°C
for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the digestion.
~ The digestion was carried out based on the American Wood Preserver's Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ The solutions obtained from the digestion were analysed for boron, zinc and copper and the results are as follows.
Block No. 218 144 250 217 258 B in digestion 31.4 19.5 23.0 29.3 15.9 solution (ppm) Total B in each 7.487 4.789 5.683 6.942 4.266 block (mg) Zn in digestion 623 584 593 636 488 solution (ppm) Total Zn in each 149.7 143.8 146.2 156.3 131.1 block (mg) Cu in digestion 1647 1726 1692 1740 1465 solution. (ppm) Total Cu in each 392.1 424.8 417.6 427.4 393.6 block (mg) Block No. 001 132 303 274 226 B in digestion 25.5 26.2 19.0 22.7 24.1 solution (ppm) Total B in each 6.059 6.588 5.121 5.799 6.074 block (mg) Zn in digestion 607 601 535 593 625 solution (ppm) Total Zn in each 144.5 151.4 144.2 151.7 157.4 block (mg) WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 Cu in digestion 1664 1598 1455 1503 1606 solution (ppm) Total Cu in each 395.9 402.3 392.2 384.6 404.4 block (mg) Summary of Results B Total boron uptake 1426.8 mg c Total boron in wood 58.81 mg Boron mass fraction in wood 0.138 I Total boron in leachate 367.5 mg Boron mass fraction in leachate 0.862 Mass balance I 99.88o I
Boron retention after leaching 0.464 kg/m3 iZn Total zinc uptake 1645 mg Total zinc in wood 1476 mg Zinc mass fraction in wood 0.929 I Total zinc in leachate 112.0 mg Zinc mass fraction in leachate 0.071 Mass balance 96.57 Zinc retention after leaching 11.66 kg/m3 Cu Total copper uptake 4076 mg Total copper in wood 4035 I mg ' Copper mass fraction in wood 0.955 Total copper in leachate 189.9 mg Copper mass fraction in leachate 0.045 i Mass balance 103.6 Copper retention after leaching 31.86 kg/m3
The present invention relates to preserving compositions for porous products, especially wood.
Compounds of boron have been used in the preservation of wood for a number of years. However, one of the difficulties experienced in use of these compounds is their propensity to leach from the substrate into which they have been impregnated.. Consequently, compounds of boron have not been particularly useful in preserving timber exposed to water, for example, pylons embedded in a sea bed.
Basic zinc compounds also have toxic efficacy with respect to wood destroying organisms, both in the marine and land environments. However, despite this efficacy having been known, basic zinc compounds have not been used commercially.
The present invention is based on the discovery that a composition comprising a basic zinc compound and a 2C compound of boron has a toxic efficacy to wood destroying organisms, both in the marine and land environments with the added benefit of a reduction in the rate at which the boron compound leaches from the impregnated substrate.
Accordingly, the present invention provides a preserving composition which includes a basic zinc compound and a compound of boron.
A preferred composition comprises zinc ions and borate ions in an aqueous solution of ammonia. The zinc ions may be derived from any soluble zinc compound and the borate ions may be derived from any soluble borate but zinc borate is preferred. Examples of soluble zinc compounds include zinc sulfate and zinc chloride and examples of soluble borates include sodium borate and potassium borate. A solution of zinc ions and borate ions 3J in aqueous ammonia may be prepared by dissolving zinc borate in an aqueous solution of ammonia at a temperature of about 66°C. Alternatively, a soluble zinc salt may be WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 _ 2 _ combined with a soluble borate salt in an aqueous ammonia solution at a temperature of about 66°C.
The preserving composition of the present invention may be combined with other additives having efficacy as preservatives. These include copper sulfate, fluorides such as potassium fluoride and quaternary ammonium compounds.
Porous compoundsE especially porous cellulosic compounds, may be impregnated with the preserving composition of the present invention by flooding the porous compound at reduced pressure. Preferably, the pressure is reduced to a level in the range between 0.5 kPa and 0.9 kPa.
In a further aspect, the present invention ~5 provides a means of impregnating a substrate with a preserving composition by means of coacervation.
Coacervation occurs when a liquid compound separates into two phases below a particular temperature. One phase is rich in one compound and the other is leaner. Coacervation 2C is similar to crystallisation from a mother liquor.
The following examples illustrate the invention.
pvrt~rnr~
25 Preparation of Impregnant ~ 1000 grams of ammonia solution (28°0) was added to 1000 grams of water.
~ With constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia 30 solution.
~ The solution was heated gently at 66°C to form a clear solution.
Preparation of Wood Blocks 35 ~ Pinus radiata clear sapwood was used for the impregnation, and all the wood blocks were conditioned to less than 15°o moisture level.
~ The numbered blocks prepared for the impregnation were:
028, 107, 147, 282 and 307.
~ The volume of the blocks was measured and the results are given below. Although the volume of each block varies slightly, the volume of every individual block was measured to ensure the accuracy of retention calculated.
Block No. 028 107 147 282 307 Volume (m3x10-6) 12.675 12.521 12.649 12.684 12.848 ~ The weight of the blocks was determined Impregnation ~ Once a vacuum of 0.9 kPa was reached, the vacuum pump ~5 was kept runraing for 30 minutes, and the lowest vacuum achieved before flooding was 0.65 kPa.
~ Flooding was commenced under vacuum.
~ Vacuum was released to atmospheric pressure.
~ Atmospheric pressure was employed for 60 minutes.
~ The solution was s~xcked back to the work vessel under vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
~ After a vacuum of 2.5 kPa was reached, the vacuum was run for 30 minutes.
~ The lowest vacuum reached was 2.1 kPa before the vacuum was released.
~ The weight of blocks was determined, and the uptake and retention of chemicals calculated. The results are as follows.
Block No. 107 307 028 282 147 Uptake (g) 7.7165 9.0291 8.3166 8.084 7.8495 Retention 67~_~R ~n~ ~~ ~~~ ~d ~z~ zn can ec WO 01/70472 cA 02417670 2003-O1-28 pCT/AU01/00325 -a-( kg/m3 ) ~ Blocks were dried naturally in the open air.
Leaching ~ The leaching was conducted as detailed in the American Wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in exactly the same way as in the impregnation with preservatives.
~ ~nce a vacuum of 1.5 kPa was reached, the vacuum pump was kept running for 30 minutes, and the lowest vacuum achieved before flooding was 1.3 kPa.
~ Distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure.
~ The amounts of water used was 50 ml per block, and the total amount of water used was 300 ml. The loss of water to the uptake was re-added.
~ ~nce the leaching was commenced, the leachant was changed at intervals of 6 hours, 2a hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnantt Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron and zinc are 12.07g/L and 27.89g/L respectively.
~ The determined concentration of the impregnant was used WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 to calculate the mass balance.
2. Analysis of leachates ~ The leachates were analysed directly without any further sample preparation.
The concentrations of boron and zinc in the leachates are as follows.
Sample L1 L2 L3 L4 L5 L6 L7 L8 L9 B (pgn) 204 192 202 107 62.5 48.3 37.429.7 26.6 Zn (pgn) 113 90.7 93.916.5 16.9 14.0 13.49.80 9.35 .3. Analysis of digested wood blocks ~ Four out of five blocks were used for the digestion and analysis, and the other one was used for penetration test.
~ The four blocks were quantitatively powdered, homogenised and dried at 100°C for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the 2G digestion.
~ The digestion was carried out based on the American Wood Preserver's Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ The solutions obtained from the digestion were analysed for boron and zinc and the results are as follows.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 Block No. 028 107 147 307 B in digestion 197 153 147 219 solution (ppm) Total B in each 55.23 44.66 43.74 57.13 block (mg) Zn in digestion 770 729 744 858 solution (ppm) Total Zn in each 215.7 212.7 217.2 224.1 block (mg) Summary of Results jB Total boron uptake 397.2 mg I
I Total boron in wood 200.8 mg Boron mass fraction in wood 0.479 i Total boron in leachate 218.1 mg Boron mass fraction in leachate 0.521 Mass balance 105.5 Boron retention after leaching 3.96 kg/m3 Zn Total zinc uptake 918.0 mg Total zinc in wood 869.7 mg Zinc mass fraction in wood 0.906 Total zinc in leachate 90.61 mg Zinc mass fraction in leachate 0.094 Mass balance 104.6%
Zinc retention after leaching 17.16 kg/m3 Comment ~verloading could have been committed resulting in a relatively high mass fraction of boron being leached out. The impregnation procedure followed the Bethell full-cell schedule. The severe overloading occurred and some boron leached as a consequence of excess preservative compound being present within the vessels.
The boron retention after leaching, however, is still very high, 3.66 kg/m3, compared with 1 kg/m3 required WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 -a-by an American company.
pvawecr_~ °>
Preparation of Impregnant The impregnant used in Example 2 was prepared in the same way as in Example 1.
1000 grams of ammonia solution (28%) was added to 1000 grams of water.
~ With constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia solution.
~ The solution was heated gently at 66°C to form a clear solution.
Preparation of Wood Blocks ~ Very similar procedure to that in Example 1 was used to prepare the blocks.
~ The numbered blocks prepared for the impregnation were:
062, 100, 206, 223 and 239.
~ The volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation While the impregnation was conducted in a similar way to that in Example 1, different vacuums were used.
Once a vacuum of 2.1 kPa was reached, the vacuum pump was kept running for 30 minutes, and the lowest vacuum achieved before flooding was 1.9 kPa.
~ Flooding was commenced under vacuum.
~ Vacuum was released to atmospheric pressure after flooding completed.
~ Atmospheric pressure was employed for 60 minutes.
~ The solution was sucked back to the work vessel under vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 g _ ~ After a vacuum of 2.5 kPa was reached, the vacuum was run for 30 minutes.
~ The lowest vacuum reached was 2.3 kPa before the vacuum was released.
~ The weight of blocks was determined, and the uptake and retention of chemicals calculated. The results are as follows.
Block No. 062 100 206 223 239 Uptake (g) 8.8483 5.4833 8.0169 6.9345 8.2680 Retention 702.86 433.94 629.96 553.03 663.35 ( kg % m3 ) ~ Blocks were dried naturally in the open air.
beaching The leaching was carried out in a similar way to that in Example 1 except different vacuums were used.
~ The leaching was conducted as detailed in the American Wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in exactly the same way as in the impregnation with preservatives.
~ Once a vacuum of 1.6 kPa was reached, the vacuum pump was kept running for 30 minutes, and the lowest vacuum achieved before flooding was 1.4 kPa.
Distilled water was used for the flooding.
~ Vacuum was released t~ atmospheric pressure.
~ The amount of water used was 50 ml per block, and the total amount of water used was 300 ml. The loss of water to the uptake was re-added.
~ Once the leaching was commenced, the leachant was changed at intervals of 6 hours, 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 _ g _ Analysis of Impregnant, Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron and zinc are 11.30g/L and 28.28g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of leac&ates ~ The leachates were analysed directly without any further sample preparation.
~ The boron concentrations in the leachates are as follows.
Sale L1 L2 L3 L4 L5 L6 L7 L8 L9 B (pFcn) 236 170 68.1 40.4 29.4 25.3 21.9 20.6 17.3 3. Analysis of digested Wood blocks ~ Four out of five blocks were used for the digestion and analysis, and the other one was used for penetration test.
~ The four blocks were quantitatively powdered, homogenised and dried at 100°C for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the digestion.
~ The digestion was carried out based on the American Wood Preserver's Association Standard A7-93 using nitric WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 acid, sulfuric acid and perchloric acid.
The solutions obtained from the digestion were analysed for boron and zinc and the results are as follows.
Block No. 100 206 223 239 B in digestion 85.3 166 118 165 solution (ppm) Total B in each 24.14 47.42 34.16 47.31 block (mg) Zn in digestion 556 724 672 741 solution (ppm) Total Zn in each 157.5 206.3 193.9 212.9 block (mg) Summary of Results B Total boron uptake X324.2mg Total boron in wood 153.0mg Boron mass fraction in wood 0.504 Total boron in leachate 150.9mg I Boron mass fraction in leachate 0.496 Mass balance 93.74 I
I Boron retention after leaching 3.04 kg/m3 Zn Total zinc uptake X 811.7mg i Total zinc in wood 770.6mg Zinc mass fraction in wood 0.949 Total zinc in leachate Zinc mass fraction in leachate Mass balance Zinc retention after leaching 15.30kg/m3 Comment 1G Overloading could have been committed resulting in a relatively high mass fraction of boron being leached out. The impregnation procedure followed the Bethell full-cell schedule. The severe overloading occurred and some boron leached as a consea_uence of excess preservative _ 11 _ compound being present within the vessels.
The boron retention after leaching, however, is still very highA 3.04 kg/m', compared with 1 kg/m3 required by an American companyo Preparation of Impregnant While the formulation used in this example is different from that used in Examples 1 and 2, the preparation of the impregnant was commenced in the similar way to that in Examples 1 and 2.
~ 1000 grams of ammonia solution (28%~ was added to 1000 grams of water.
~ With constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia solution.
~ The solution was heated gently at 66°C to form a clear solution.
~ 200 grams of copper sulfate were added gradually and then the solution was cooled to room temperature.
Preparation of Wood Flocks Same procedures were used to prepare blocks as that used in Examples 1 and 2.
~ The numbered blocks prepared for the impregnation were:
043, 044, 190, 211 and 245.
~ The volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation While the impregnation was conducted in a similar way to that in Examples 1 and 2, different vacuums were used.
~ Once a vacuum of 1.9 kPa was reached, the vacuum was maintained for 30 minutes, and the vacuum before flooding was also 1.7 kPa.
~ Flooding was commenced under vacuum.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 ~ Vacuum was released to atmospheric pressure after flooding completed.
~ Atmospheric pressure was employed for 60 minutes.
~ The solution was sucked back to the work vessel under vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
After a vacuum of 2.4 kPa was reached, the vacuum was run for 30 minutes.
~ The lowest vacuum reached was 2.3 kPa before the vacuum was released.
The mass of blocks was determined straight after the pressure treatment, and the uptake and retention of chemicals calculated. The results are as follows.
Block No. 043 044 190 211 245 Uptake (g~ 7.8235 8.2008 8.3631 7.2498 7.3124 Retention 617.58 638.19 659.65 576.98 579.43 ( kg/m3 ~
Blocks were dried naturally in the open air and conditioned for two weeks.
i~lOTEo The vacuum utilised in this modified Bethell schedule is very important and we have discovered this to be a 2C significant part of this process, ultimately aimed at reduced boron leaching.
Leaching The leaching was carried out in a similar way to that in Examples 1 and 2 although different vacuums were used.
~ The leaching was conducted as detailed in the American Wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in exactly the same way as in the impregnation with preservatives.
~ Once a vacuum of 1.5 kPa was reached, the vacuum pump was kept running for 30 minutes.
~ Distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure.
~ The amount of water used was 50 ml per block, and the total amount of water used was 300 ml. The loss of water to the uptake was re-added.
~ Once the leaching was commenced, the leachant was changed at intervals of 6 hours, 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnant, Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron( zinc and copper were 10.80g/L, 26.94g/L and 36.52g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of leachates ~ The leachates were analysed directly without any further sample preparation.
~ The concentrations of boron and copper in the leachates were as follows.
Sample L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 B (ppm) 377 221 92.0 53.0 37.3 5.37 13.1 9.66 8.50 5.25 C~ (txml '~~ _ 9 1 d J ~, ~,1 r, 11 ~ 17 1 GG ~ ~c 1 oc 1 cn , n., WO 01/70472 cA 02417670 2003-01-28 PCT/AU01/00325 3. Analysis of digested wood blocks ~ Four out of five blocks were used for the digestion and analysis, and the other one was used for a penetration test.
~ The four blocks were quantitatively powdered, homogenised and dried at 100°C for 2 hours before analysis.
3.0000 grams of wood powder were taken for the digestion.
1G ~ The digestion was carried out based on the American Wood preserver's Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ fihe solutions obtained from the digestion were analysed for boron, zinc and copper and the results are as 25 follows.
Block No. 043 044 190 211 B in digestion 63.9 52.5 50.2 43.7 solution (ppm) Total B in each 18.22 16.89 16.00 14.28 block (mg) Zn in digestion 475 542 540 414 solution (ppm) fiotal Zn in each 135.4 174.3 172.2 135.3 block (mg) Cu in digestion ? 1092 1144 920 solution (ppm) fiotal ~u in each 108.6 351.3 364.9 300.5 block (mg) _ 15 _ Summary of Results B Total boron uptake 341.7 mg Total boron in wood 65.38 mg Boron mass fraction in wood 0.249 Total boron in leachate 197.2 mg Boron mass fraction in leachate 0.751 Mass balance 76.84 o Boron retention after leaching 1.29 kg/m3 Zn Total zinc uptake X852.4mg Total zinc in wood 617.2 mg Zinc mass fraction in wood 0.724 Total zinc in leachate ?
Zinc mass fraction in leachate ?
Mass balance ?
Zinc retention after leaching 12.16 kg/m3 Cu Total copper uptake mg Total copper in wood 1125 mg Copper mass fraction in wood 0.985 Total copper in leachate 17.61 mg Copper mass fraction in leachate 0.015 i Mass balance 98.93 ~I Copper retention after leaching 22.17 kg/m3 ravTUrnT ze w Preparation of Impregnant While the formulation used in this example is different from that used in Examples 1, 2 and 3, the impregnant was first prepared as that in Example 3 and then 8.9 grams of potassium fluoride were added.
~ 1000 grams of ammonia solution (28°0) was added to 1000 grams of water.
~ i~Vith constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia solution.
~ The solution was heated gently at 66°C to form a clear WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 solution.
200 grams of copper sulfate were added gradually and then the solution was cooled to room temperature.
~ 8.9 grams of potassium fluoride were added.
Preparation of Wood Blocks The procedure used to prepare blocks is very similar to that in Examples 1 and 2.
~ The numbered blocks prepared for the impregnation wereo 066, 143, 200, 205 and 26~L.
~ The volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation 1~ While tine impregnation was conducted in a similar way to that in Examples 1 and 2, different vacuums were used.
~ Once a vacuum of 3.9 kPa was reached, the vacuum pump was kept running for 30 minutes, and the vacuum before flooding was also 1.9 kPa.
2C ~ Flooding was commenced under vacuum.
~ Vacuum was released to atmospheric pressure after flooding was completed.
~ Atmospheric pressure was employed for 60 minutes.
~ The solution was sucked back to the work vessel under 25 vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
~ After a vacuum of 2.5 kPa was reached, the vacuum was run fox 30 minutes.
30 ~ The lowest vacuum reached was 2.3 kPa before the vacuum was released.
~ The weight of blocks was determined straight after the pressure treatment, and the uptake and retention of chemicals calculated. The results are as follows.
WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 Block No~ 066 143 200 205 261 Uptake (g) 7.2259 7.4066 7.2929 7.1257 7.6352 Retention 573.03 593.29 580.64 567.38 612.88 ( kg/m3 ) ~ Blocks were dried naturally in the open air.
Leaching The leaching was carried out in a similar way to that used in Example 1 although different vacuums were used.
~ The leaching was conducted as detailed in the American Wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in exactly the same way as in the impregnation with 1G preservatives.
~ Once a vacuum of 0.5 kPa was reached, the vacuum pump was kept running for 30 minutes.
~ Distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure.
~ The amount of water used was 50 ml per block, and the total amount of water used was 300 ml. The loss of water to the uptake was re-added.
~ ~nce the leaching was commenced, the leachant was changed at intervals of 6 hours. 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnant, Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 analytical instrument ~ The diluted impregnant was determined and the concentrations of boron, zinc and copper were 10.63g/L, 2~.llg/L and 36.55g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of leachates The leachates were analysed directly without any further sample preparation.
~ The concentrations of boron and copper in the leachates were as follows.
Sample Li L2 L3 L4 L5 L6 L7 L8 L9 S (pl~~ 469 501 48.4 20.020.7 13.7 7.45 5.826.13 Cu (ppzn) 57.Q~ 46.2 4.32 2.783.61 2.87 1.99 2.201.69 3. Analysis of digested wood blocks ~ Four out of five blocks were used for the digestion and analysis, and the other one was used for a penetration test.
~ The four blocks were quantitatively powdered, homogenised and dried at 100°C for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the digestion.
~ The digestion was carried out based on the American Wood Preserver's Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ The solutions obtained from the digestion were analysed for boron, zinc and copper and the results are as follows.
WO 01/70472 cA 02417670 PCT/AU01/00325 Block No. 143 200 205 261 B in digestion 61.0 40.0 47.6 53.4 solution (ppm) Total B in each 19.39 13.60 15.51 17.59 block (mg) Zn in digestion 410 333 370 467 solution (ppm) Total Zn in each 130.2 113.3 120.6 153.8 block (mg) Cu in digestion 45.0 29.7 646 1048 solution (ppm) Total Cu in each 134.0 86.80 252.7 345.3 block (mg) Summary of Results B Total boron uptake 313.3mg Total boron in wood 66.09mg Boron mass fraction in wood 0.201 Total boron in leachate 262.1mg Boron mass fraction in leachate 0.799 Mass balance 104.7 i Boron retention after leaching 1_.32kg/m3 ~Zn Total zinc uptake 798.8mg Total zinc in wood 517.9mg Zinc mass fraction in wood 0.648 Total zinc in leachate ?
Zinc mass fraction in leachate ?
Mass balance ?
i Zinc retention after leaching 10.35kg/m3 Cu Total copper uptake 1077 mg Total copper in wood 818.7mg Copper mass fraction in wood 0.963 Total copper in leachate 31.12mg Copper mass fraction in leachate 0.037 Mass balance 78.92 Copper retention after leaching 16.35kg/m3 WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 ExAMPLE 5 Preparation of Impregnant The formulation used in this example is the same as that in Example 3.
~ 1000 grams of ammonia solution (28%~ was added to 1000 grams of water.
~ With constant agitation using a magnetic stirrer, 222.5 grams of zinc borate were added to the diluted ammonia 1G solution.
~ The solution was heated gently at 66°C to form a clear solution.
~ 200 grams of copper sulfate were added gradually and then the solution was cooled to room temperature.
Preparation of Wood Flocks The procedure used to prepare blocks is very similar to that in the other examples. Ten blocks were used in this example rather than five blocks as in the previous 20 examples.
~ The numbered blocks prepared for the impregnation were:
168, 039, 212, 125, 313, 080, 238, 299, 195 and 051.
~ The volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation While the impregnation was conducted in a similar way to that used in the other examples, different vacuums were used.
3G ~ Once a vacuum of 1.0 kPa was reached, the vacuum pump was kept running for 30 minutes, and the vacuum before flooding was 0.6 kPa.
~ Flooding Was commenced under vacuum.
~ Vacuum was released to atmospheric pressure after flooding completed.
~ Atmospheric pressure was employed for 90 minutes.
~ The solution was sucked back to the work vessel under WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks.
~ After a vacuum of 1.3 kPa was reached, the vacuum was run for 30 minutes..
The lowest vacuum reached was 1.2 kPa before the vacuum was released.
~ The weight of blocks was determined straight after the pressure treatmento and the uptake and retention of chemicals calculated, The results are as follows.
Block No. 168 039 212 125 313 TJptake (g) 7.8782 8.6661 8.1115 9.0619 7.8899 Retention 631.92 701.65 644.38 720.57 622.53 ( kg/m3 ) Block No. 080 238 299 195 051 Uptake (g) 7.9759 9.4277 8.8812 9.3488 8.9464 Retention 639.15 739.31 696.62 738.04 695.30 (kg/m3 ) ~ Blocks were dried naturally in the open air.
beaching The leaching was carried out in a similar way to that in the other examples although different vacuums were used.
~ The leaching was conducted as detailed in the American Tnlood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in 2C exactly the same way as ir. the impregnation with preservatives.
~ Once a vacuum of 0.9 kPa was reached, the vacuum pump was kept running for 30 minutes. A vacuum of 0.6 kPa was achieved before flooding.
2~ ~ Distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure.
~ The amount of water used was 50 ml per block, and the WO 01/70472 CA 02417670 2003-O1-28 pCT/AU01/00325 total amount of water used was 500 ml. The loss of water to the uptake was re-added.
~ Once the leaching was commenced, the leachant was changed at intervals of 6 hours, 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnant~ Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
1~ 1~ ~naTysis of impregnant The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron, zinc and copper are 5.61g/L, 21.25g/L and 48.07g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of .leac&ates ~ The leachates were analysed directly without any further sample preparation.
~ The concentrations of boron, zinc and copper in the leachates are as follows.
Sample L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 L11 B (ppm)174 186 157 80.1 48.5 32.0 22.4 15.611.9 9.62 7.59 Zn (pgn)86.5 47.428.2 10.9 4.07 4.49 1.26 1.381.04 1.51 1.14 Cu (ppm)131 113 110 59.3 26.8 18.9 5.14 2.881.75 2.17 1.52 3. Analysis of digested wood blocks ~ After the penetration test, all the ten blocks were quantitatively powdered, homogenised and dried at 100°C
for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the digestion.
~ The digestion was carried out based on the American Wood Breserver~s Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ The solutions obtained from the digestion were analysed for boron, zinc and copper and the results are as follows.
Block No. 168 039 212 125 313 B in digestion 38.9 40.5 39.7 50.0 35.1 solution (ppm) Total B in eacr~ 9.733 9.866 9.387 11.91 8.326 block (mg) Zn in digestion 539 593 595 632 579 solution (ppm) Total Zn in each 134.8 144.5 140.6 150.5 137.1 block (mg) Cu in digestion 1644 1813 1898 1997 1794 solution (ppm) Total Cu in each 411.3 441.5 448.3 475.8 425.0 block (mg) Block No. 080 238 299 195 051 B in digestion 40.5 43.4 41.4 52.5 49.0 solution (ppm) Total B in each 9.402 10.68 10.62 12.80 12.26 block (mg) Zn in digestion 588 626 590 635 611 solution. (ppm) Total Zn in each 136.5 154.1 151.5 154.8 152.6 block (mg) Cu in digestion 1728 1807 1647 1770 1757 solution (ppm) Total Cu in each 401.1 444.5 422.6 431.7 439.2 WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 - 24 _ Summary of Results B Total boron uptake 483.3 mg Total boron in wood 105.0 mg Boron mass fraction in wood 0.220 i Total boron in leachate 372.2 mg ! Boron mass fraction in leachate 0.780 Mass balance 98.75 I Boron retention after leaching 1 0.832 kg/m3 ;Zn Total zinc uptake 1831 mg j i i Total zinc in wood 1457 mg Zinc mass fraction in. wood 0.939 Total zinc in leachate 93.97 mg Zinc mass fraction in leachate 0.061 Mass balance 84.68 o i Zinc retention after leaching 11.55 kg/m3 Cu Total copper uptake 4143 mg Total copper in wood 4341 mg Copper mass fraction in wood 0.948 Total copper in leachate 236.5 mg Copper mass fraction in leachate 0.052 ! Mass balance 110.5 o i j Copper retention after leaching 34.41 kg/m3 Comment ~ The foramulation prepared and utilised as detailed in Examples 3P 4 and 5 all contain copper. Each formulation detailed in every example to date contains zinc. Of great importance is the fact that basic (alkaline) zinc containing compounds have been found to exhibit a high degree of toxic efficacy to wood destroying organisms both in the marine and land environments. We have discovered a way of combining the efficacy of boron within a complex basic polyborate-zinc system which reduces the leaching of boron from commodities treated with this preservative composition.
The efficacy of basic zinc containing compositions was WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 never researched beyond its initial discovery We have discovered a successful way of complementing the efficacy of boron with that of basic zinc compounds with the unexpected, unique reduction of the leaching of boron, resulting from the interaction of the preservative composition and its impregnated, soaked, brushed, sprayed or diffusion treated substrate.
~ Fluorine is an important component of Example 4 in which it contributes additional synergistic efficacy.
~ The formulation utilised in Example 5 was prepared with a lower boron concentration. This constitutes one of several preservative compositions purposely formulated to result in a lower boron retention in timber and other treated commodities which are to be used above ground and especially in building, walkway, bush tracks and numerous other constructions. Especially useful in indoor environments, such compositions will constitute economic protection without any less or reduction in efficacy.
Preparation of Impregnant The preservative composition was first prepared 2~ as detailed in Example 1. 1551 grams of this solution were slowly combined with 30 grams of N-alkyl tallow N dimethyl amino propyl N trimethyl ammonium dichloride in isopropanol water solution. This composition was agitated for several hours until a clear solution was produced. The solution was made up to 2000 grams, by addition of double distilled water. The pH of this composition was determined as 12.6.
Quaternary ammonium salts have long been known to exhibit high surface activity coupled with biological and fungicidal efficacy. Such complex compositions have usually been used to formulate emulsions of cationic nature at low pH. These unique properties have been retained in this complex wood preservative composition. Penetration WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 26 _ and distribution in treated timber have been enhanced and complemented by additional efficacy and boron fixation.
Iioweverp boron diffusion and movement within the treated commodity has not been hindered, nor fixation rendered so efficient as to hinder efficacy. More surprising and wholly unexpected is the enhanced biocidal efficacy and composition stability in an alkaline environment.
A further very important development, relevant to this composition and previous surface activated compositions such as detailed in Example 7, is their inherent property of self-emulsification with a wide variety of oils which includeP but are not limited to, petroleum derived oil s mineral oils, vegetable oils and more especially creosote oils, the latter having great wood 1~ preservation significance and limited potential for diversity of formulation and application.
Preparation of Wood Blocks The procedure used to prepare blocks is very similar to that in the other examples. Totally ten blocks were used in this example.
The numbered blocks prepared for the impregnation were:
218, 144, 250, 217, 258, 001, 3.32, 303, 274 and 226.
~ the volume and the moisture of the blocks were measured.
~ The weight of the blocks was determined.
Impregnation While the impregnation was conducted in a similar way to that used in the other examples, different vacuums were used.
~ Once a vacuum of 0.9 kPa was reached, the vacuum pump was kept running for 30 minutes, and the vacuum before flooding was also 0.9 kPa.
~ Flooding was commenced under vacuum.
~ ~Jacuum was released to atmospheric pressure after flooding completed.
~ Atmospheric pressure was employed for 90 minutes.
m 27 -~ The solutiora was sucked back to the work vessel under vacuum at the end of the pressure period.
~ Vacuum was applied to the pressure vessel containing the treated blocks for 30 minutes, and a vacuum of 1.9 kPa was reached before the vacuum was released.
The weight of blocks was determined straight after the pressure treatment, and the uptake and retention of chemicals calculated The results are as follows.
Block No. 218 144 250 217 258 Uptake (g) 9.6596 9.4843 9.6391 10.1950 8.7983 Retention 757.97 755.66 758.86 799.99 699.50 ( kg/m3 ?
Block No. 001 132 303 274 226 Uptake (g~ 9.6670 9.9522 9.2082 9.6967 10.0360 Retention 774.17 785.43 725.00 764.24 785.34 (kg/m'2 ~ Blocks were dried naturally in the open air.
Leaching All blocks were dried at 108°C for 24 hours before leaching, and the leaching was carried out in a similar way to that in the other examples although different vacuums were used.
~ The leaching was conducted as detailed in the American wood Preserver's Association Standard E11-8.
~ The blocks were impregnated with distilled water in the 2C exactly same way as in the impregnation with preservatives.
~ Once a vacuum of 1.5 mmHg was reached, the vacuum pump was kept running for 35 minutes. The final vacuum achieved before flooding was also 1.5 mmHg.
~ The flooding was conducted under vacuum, and distilled water was used for the flooding.
~ Vacuum was released to atmospheric pressure after the WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 flooding was completed.
~ The amount of water used was 50 ml per block, and the total amount of water used was 500 ml. The loss of water to the uptake was re-added.
~ Once the leaching was commenced, the leachant was changed at the intervals of 6 hours, 24 hours and every 48 hours afterwards, and the leachates were collected for analysis.
Analysis of Impregnant, Leachates and Digested Blocks after Leaching All the analyses were carried out using techniques of AAS (Atomic Absorption Spectrometry) and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) with the final results based on ICP analysis.
2. Analysis of impregnant ~ The impregnant was diluted to an appropriate concentration that is within the working range of the analytical instrument.
~ The diluted impregnant was determined and the concentrations of boron, zinc and copper are 4.43g/L, 17.07g/L and 42.32g/L respectively.
~ The determined concentration of the impregnant was used to calculate the mass balance.
2. Analysis of leachates ~ The leachates were analysed directly without any further sample preparation.
~ The concentrations of boron, zinc and copper in the leachates are as follows.
Sample L1 L2 L3 L4 L5 L6 L7 L8 L9 B (pgn)208 195 134 80.342.0 27.3 20.5 16.2 11.4 Zrn 85.3 62.1 38.9 18.27.09 5.10 2.51 2.47 (p~m; 2.43 C_'m 97_9 91n &S ~n ~o S ,~ ~ , o, ~ n~
(nrm) a ~ , co WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 3~ Analysis of digested wood blocks ~ After the penetration test, all the ten blocks were quantitatively powdered, homogenised and dried at 100°C
for 2 hours before analysis.
~ 3.0000 grams of wood powder were taken for the digestion.
~ The digestion was carried out based on the American Wood Preserver's Association Standard A7-93 using nitric acid, sulfuric acid and perchloric acid.
~ The solutions obtained from the digestion were analysed for boron, zinc and copper and the results are as follows.
Block No. 218 144 250 217 258 B in digestion 31.4 19.5 23.0 29.3 15.9 solution (ppm) Total B in each 7.487 4.789 5.683 6.942 4.266 block (mg) Zn in digestion 623 584 593 636 488 solution (ppm) Total Zn in each 149.7 143.8 146.2 156.3 131.1 block (mg) Cu in digestion 1647 1726 1692 1740 1465 solution. (ppm) Total Cu in each 392.1 424.8 417.6 427.4 393.6 block (mg) Block No. 001 132 303 274 226 B in digestion 25.5 26.2 19.0 22.7 24.1 solution (ppm) Total B in each 6.059 6.588 5.121 5.799 6.074 block (mg) Zn in digestion 607 601 535 593 625 solution (ppm) Total Zn in each 144.5 151.4 144.2 151.7 157.4 block (mg) WO 01/70472 cA 02417670 2003-01-28 pCT/AU01/00325 Cu in digestion 1664 1598 1455 1503 1606 solution (ppm) Total Cu in each 395.9 402.3 392.2 384.6 404.4 block (mg) Summary of Results B Total boron uptake 1426.8 mg c Total boron in wood 58.81 mg Boron mass fraction in wood 0.138 I Total boron in leachate 367.5 mg Boron mass fraction in leachate 0.862 Mass balance I 99.88o I
Boron retention after leaching 0.464 kg/m3 iZn Total zinc uptake 1645 mg Total zinc in wood 1476 mg Zinc mass fraction in wood 0.929 I Total zinc in leachate 112.0 mg Zinc mass fraction in leachate 0.071 Mass balance 96.57 Zinc retention after leaching 11.66 kg/m3 Cu Total copper uptake 4076 mg Total copper in wood 4035 I mg ' Copper mass fraction in wood 0.955 Total copper in leachate 189.9 mg Copper mass fraction in leachate 0.045 i Mass balance 103.6 Copper retention after leaching 31.86 kg/m3
Claims (11)
1. A preserving composition which includes a basic zinc compound and a compound of boron.
2. A preserving composition according to claim 1 wherein the composition includes zinc ions and borate ions in an aqueous solution of ammonia.
3. A preserving composition according to claim 1 or claim 2 wherein the composition includes ions of copper.
4. A preserving composition according to claim 3 wherein the ions of copper are cupric ions.
5. A preserving composition according to claim 4 wherein the cupric ions are derived from copper sulfate.
6. A preserving composition according to any one of the preceding claims wherein the composition includes fluoride ions.
7. A preserving composition according to claim 6 wherein the fluoride ions are derived from potassium fluoride.
8. A preserving composition according to any one of the preceding claims wherein the composition includes a quaternary ammonium compound.
9. A preserving composition according to any one of the preceding claims wherein the composition comprises an aqueous solution containing from 5gms per litre to saturation of borate ions and from 10gms per litre to saturation of zinc ions.
10. A method of preserving a cellulosic compound by impregnating the cellulosic compound with a preserving composition according to any one of claims 1 to 9.
11. A method according to claim 10 wherein the cellulosic compound is flooded with the preserving composition under vacuum.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPQ6449 | 2000-03-24 | ||
| AUPQ6449A AUPQ644900A0 (en) | 2000-03-24 | 2000-03-24 | Preserving compositions |
| PCT/AU2001/000325 WO2001070472A1 (en) | 2000-03-24 | 2001-03-23 | Preserving compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2417670A1 true CA2417670A1 (en) | 2001-09-27 |
Family
ID=3820546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002417670A Abandoned CA2417670A1 (en) | 2000-03-24 | 2001-03-23 | Preserving compositions |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1282491A4 (en) |
| AU (2) | AUPQ644900A0 (en) |
| CA (1) | CA2417670A1 (en) |
| NZ (1) | NZ522185A (en) |
| WO (1) | WO2001070472A1 (en) |
| ZA (1) | ZA200208584B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6896908B2 (en) | 2001-01-30 | 2005-05-24 | U.S. Borax Inc. | Wood preservative concentrate |
| US7470313B2 (en) | 2004-04-03 | 2008-12-30 | Pq Corporation | Amino acid-solubilized borate, silicate and zinc compositions and methods for treating wood products |
| US7547354B2 (en) | 2004-04-03 | 2009-06-16 | Pq Corporation | Ammoniacal borate and zinc compositions, and methods for treating wood products |
| US7497900B2 (en) | 2004-04-03 | 2009-03-03 | Pq Corporation | Two-part borate, silicate and zinc compositions, and methods for treating wood products |
| CN105196381A (en) * | 2015-08-27 | 2015-12-30 | 福建省漳平木村林产有限公司 | Zinc borate corrosion preventing and flame retarding agent |
| JP2024511720A (en) * | 2021-03-19 | 2024-03-15 | アークサーダ・リミテッド・ライアビリティ・カンパニー | Reinforced wood preservative containing zinc and boron |
| CN114474267A (en) * | 2022-02-26 | 2022-05-13 | 漳州市桥头木业有限公司 | Corrosion-resistant plywood and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB139974A (en) * | 1919-06-11 | 1920-03-18 | Alphonse Lambert | Process for hardening and preserving permeable soft woods |
| US2194827A (en) * | 1936-06-29 | 1940-03-26 | Gordon Aaron | Impregnating material for preserving wood |
| DE3742834A1 (en) * | 1987-12-17 | 1989-07-13 | Wolman Gmbh Dr | WOOD PRESERVATIVES |
| US5207823A (en) * | 1990-04-03 | 1993-05-04 | Kabushiki Kaisha Koshii Preserving | Wood preservative composition and process for treating wood with the same |
| WO1992018007A1 (en) * | 1991-04-12 | 1992-10-29 | Saneish Pty. Ltd. | Production of shaped bodies which have fungicidal and insecticidal properties |
| NZ264079A (en) * | 1993-07-28 | 1996-05-28 | Koshi Preserving Kk | Aqueous wood preservative containing copper, zinc and/or boron compound(s), and a volatile basic compound |
-
2000
- 2000-03-24 AU AUPQ6449A patent/AUPQ644900A0/en not_active Abandoned
-
2001
- 2001-03-23 AU AU4209401A patent/AU4209401A/en active Pending
- 2001-03-23 CA CA002417670A patent/CA2417670A1/en not_active Abandoned
- 2001-03-23 EP EP01914823A patent/EP1282491A4/en not_active Withdrawn
- 2001-03-23 WO PCT/AU2001/000325 patent/WO2001070472A1/en not_active Application Discontinuation
- 2001-03-23 NZ NZ522185A patent/NZ522185A/en unknown
-
2002
- 2002-10-23 ZA ZA200208584A patent/ZA200208584B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP1282491A4 (en) | 2004-12-29 |
| AUPQ644900A0 (en) | 2000-04-20 |
| EP1282491A1 (en) | 2003-02-12 |
| AU4209401A (en) | 2001-10-03 |
| NZ522185A (en) | 2004-07-30 |
| WO2001070472A1 (en) | 2001-09-27 |
| ZA200208584B (en) | 2003-10-23 |
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