CA1058353A - Thickened ammonia-base wood preservatives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A novel thickened wood treating composition and procedure for application as a covered layer to a wood surface for treating wood are provided herein. The composition includes (A) a preservative component which is either (i) a normally water-insoluble salt which is either zinc arsenate, zinc arsenite, copper arsenate or copper arsenite or mixtures thereof; or (ii) an ammonia-soluble salt which is either copper borate or zinc borate or mixtures thereof, or copper chromate or zinc chromate or mixtures thereof; or (iii) an ammonia dispersible organometallic compound which is either of copper naphthenate, zinc napthenate or mixtures thereof, copper-8-quinolinolate, zinc-8-quinolinolate or mixtures thereof, or tributyltin oxide; and, together with one of the above, (iv) sufficient aqueous ammonia, in a concentration of 1 to 28% by weight NH3 to solubilize the normally water-insoluble salt (i), or the ammonia-soluble salt (ii) or to disperse the organo-metallic compound (iii). It also includes (B) a sufficient amount of a thickener of a particularly recited (v) single phase type, or a particularly recited (vi) the mastic type, to provide a thickened composition having a viscosity of 30-120 poises (Brookfield Viscometer 25°C) for dip application; of 250-800 poises for mechanical deposition; or even thicker and thixotropic for trowel application. This provides a composition which can be used to provide preservative protection to wooden poles whether they be in service, or prior to being used, and whether the poles are wet or dry. The composition is applied to the wooden poles, and an ammonia-impervious atmosphere is created around the pole for a time sufficient to permit penetration of the pole. Such atmosphere may, for example, be provided by an ammonia-impervious sheet, wrap or tape material, e.g., polyethylene film.

Description

```` ~ ~058353 This invention relates to compositions and proceduxes for preserYing wooden poles, thereby prolonging the service life of wooden poles partially buried in the ground by treatment either beEore or after they are so partially buried and whether the poles are wet or dry.
Telephone'communication poles, and wooden power transmission poles will decay in line service (particularly at the ground/air inter-face) unless protected with wood preservatives. Generally, for a long service life (50 years or more), the poles are pressure impregnated with wood preservatives. These preservatives often lose effectiveness over a period of 25 to 35 years, generally in the groundline region (i.e.
the ground/air interface) where conditions for leaching microbial acti-vity and slow movement of preservative to the surrounding soil deplete the preservatives to ine~ffective levels. It is much more economical to apply a remedial form of preservative treatment to replenish the toxicity required at the groundline region than to replace the old poles with new impregnated ones. Poles which are given such remedial treatment with presently available preservatives are expected to last from 5 to 15 years longer than if they had been left untreatedO Hence, the groundline treatment must be repeated at 5 to 15 year intervals.
~20 The need for prolonging the service life of existing poles is most urgent. Because many users of such poles cannot meet the demand for new pole requirements, existing poles must consequently be so improved that they will not require early replacement. This, in turn, means that the need for an improved form of groundline preservative is therefore urgently required.
A number of preservative mastics, or paste-type chemical formu-lations for groundline treatment exist. Most of these formulations con-tain pentachlorophenol in a suitable solvent, and non-leach resistant additives such as, for example, sodium fluoride and borax. Such formula-tions are applied to the groundline areas of utility poles in the form of bandages. However, since pentachlorophenol has been in short supply for the past few years and since this shortage may continue in the future, an - 1- ~ , 1~58353 '. .
alternative preservative is desirable,''0n the other hand, the non-leach ;' resistant chemicals, when used alone,'have a short life, and have been found not to be economically favourable.' While pentachlorophenol is very leach resistant, the rate of '~
penetration of thes~ systems is very Slow9 often requiring more than 5 years for the toxic pentachlorophenol system to penetrate 1-1/2 inch depth. It is also-believed'that the pentachlo~ophenol bandages lose -'' some of their effectiveness after 10 to-15 years following pole treatments, and that re-treatments may be necessary at a maximum of 15 year intervals. ;~
On the other hand, while sodium fluoride penetrates rapidly, the levels of retention are very often too lo~ to be effective. ' Pentachlorophenol', the'main component of the'above-described ~ .
groundline preservatives, is oil soluble and is carried in solvents such as, for example, grease,'thickened oil base, etc. Consequently, the system is not essentially compatible with wet wood, i.e. wood which is considerably above the fibre saturation point. A very high percentage of poles are wet at the butt ends where effective treatment is required. It has also been found that the toxic components in many of the commercial formulations of groundline bandage preservatives do not penetrate the entire sapwood depth in poles. Consequently, it is believed that suit-able groundline treatment of poles may exténd their service life by 2 to 5 years.
A soluble borate such as, for example,'sodium tetraborate in water has been used in "pressure-diffusion" treatments in Australia.
Such process consists of impregnating round material with a high concen-tration of the borate in an abbreviated schedule (in the retort) and then ~' stacking the material to allow deeper penetration by diffusion. However, this technique suffers the disadvantage that an expensive pressure system is necessary. ~-Other prior art compositions suffer further disadvantages.
Thus, United States Patent ~o. 2,875,020 issued February 24, 1959 to R.G. Ring provides a wood preservative method and package including a `~ ~058353 porous fibrous oil and water permeable sheet, e.g~ a porous fibrous material such'as, for example,'fabrics and felted'-mats of vegetable fibres or glass fibre; a layer'on one side only of the sheet of an - inert, oil base carrier'of grease-like consistency containing at least

2% pentachloropheno~, and a synthetic reservoir oil and water impervious film completely enclosing the sheet and layer, e.g. a sleeve of poly-ethylene, polyvinyl compounds, etc. Such procedure is labour intensive ~'~
and undesirable.' United States Patent No. 2,939,704 issued June 7, 1960 to C.E.
Wilkinson provides a composition including a suitable asphalt base, cut back with a volatile diluent, as well as an inorganic filler consisting essentially of fine asbestos fibres, fine mica, fine vermiculate or fine alkali metal tetraborate. This suffers the disadvantage of lack of com-patibility of the organic component (the asphalt), i.e. the most effec-tive preservative constituent, with wet wood. ' United States Patent No. 3,376,144 issued April 2, 1968 to R.E.Strutz provides a wood preservative composition thickened with a combina-tion of a microcrystalline wax, water'soluble non-ionic surfactant, and water, combined with a mixture of an organic wood preservative liquid and an alkaline inorganic alkali metal salt. This composition suffers the disadvantage of a low level of retention.
United States Patent No. 3,390,951 issued July 2, 1968 to J.H.
Finger et'al provides a method of strengthening, preserving and extending the life of wooden poles by applying a metal band ~o the pole surrounding the zone of weakness with a fibrous resin impregnated material, and connecting tension means to the pole above the upper band means and below the lower band means and extending therebetween. This procedure suffers the disadvantage of being too labour intensive and provides a separate heterogenous addition to the pole.
United States Patent No. 3,409,388 issued November 5, 1968 to R.F. Nelson provides a method for preserving wooden poles by applying a . bandage which is an elongated tube of preservative impermeable water 1[)58353 soluble material, to spaced areas of the pole and dissolving the protec-tive ~ilm to permit direct contact'between the preservative and the pole.
This suffers the'disadvantage of low level of retention of of not pro-viding optimum times of contact of the'wrapped preservative with the wood.
Canadian Patent No. 568,393 issued January 6, l9S9 to Bror 0.
H~ger proposed to provide an agent for the preservation of wood including -an aqueous ammoniacal so3ution of an amine-forming metal of the group consisting of copper, zinc, nickel, cobalt, cadmium and silver, and dis-solved carbon dioxide of a content of at least two-thirds of the metal content. This composition is far too dilute to be used for groundline treatment. The same patentee, in Canadian Patent No. 960,959 issued January 14, 1975, provided a~composition consisting essentially of (1) a metal compound selected from the group consisting of the oxides, hydroxides, and carbonates of copper, zinc, nickel, cadmium and cobalt, and (2) a fatty acid having fr~m 6 to 12 carbon atoms per molecule, dis-solved in (3) an ammoniacal water solution. Both these compositions suffer'the disadvantage that they do not have optimum high water repel-lency, optimum low water uptake, optimum fast and high preservative penetration, and optimum resistance to arsenic leaching.
Finally, Canadian Patent No. 978,474 issued November 25, 1975 naming Michael R. Clarke and Jaromir R. Rak as inventors, provides a dilute aqueous composition comprising a normally water-insoluble compound ' selected from zinc arsenate, zinc arsenite, copper arsenate, copper arsenite or mixtures thereof, a water repellent component, including a carbonate or bicarbonate and sufficient ammonia to dissolve the normally water-insoluble compound. This composition, while it is very useful, is too dilute to be used to preserve wooden poles at the groundline in the form of bandages. Also, the composition is not sufficiently compatible with wet poles.
An object of one aspect of this invention is to provide a wood treating composition which may be'used'for treating wet poles.

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`~ An object of another aspect of this invention is to provide a wood treating composition having high levels of retention.
An object of another aspect of thé present invention is to provide a thickened pole preservative including two components, namely, an-aqueous ammoniacal multiple preservative and a thickener carrier system.
An object of another aspect of this invention is to provide ammonia-base compositions including an active preservative and havingathickener to give a paste-like consistency.
An object of yet another aspect of this invention is to provlde a method of preserving wooden poles, e.g., by the use of a bandage-type application to in-service wood or by applying to poles prior to being used, or by applying a:
composition to the wooden poles in such a manner that the composition penetrates into the pole.
By à bro~ad aspect of this invention, a thickened r ammonia-base wood treating composition is provided for application as a covered layer to a wood surface, the composition comprising: (A) a preservative component which is one of (i) a normally water-insoluble salt selected from the group consisting of zinc arsenate, zinc arsenite, copper arsenate, copper arsenite and mixtures thereof; (ii) an ammonia-soluble salt selected from the group consisting of copper borate, zinc borate or mixtures thereof, and copper chromate, zinc chromate or mixtures thereof; or (iii) an ammonia dispersible organometallic compound selected from the group consisting of copper naphthenate, zinc naphthenate or mixtures thereof, copper-8-quinolinolate, zinc-8-quinolinolate or mixtures thereof, or tributyltin oxide; and (iv) sufficient aqueous ammonia, in ~ 1 . 5 . .. . .. . . .. . ... . .

a concentration of 1 to 28% by weight NH3 to solubilize the normally water-insoluble salt (i), or the ammonia-soluble salt (ii), or to disperse the organometallic eompound tiii); ~;
and (B) a suffieient amount of a thiekener eomponent selected from the group consisting of: (v~)(a) a saturated fatty acid of 12 to 22 carbon atoms; (b) an unsaturated fatty acid of 12 to 22 earbon atoms; (c) a eopper, zine, sodium, potash, or amine salt of a saturated fatty aeid of 12 -to 22 carbon atoms; (d) a copper, zinc, sodium, potash, or amine salt of an unsaturated fatty acid of 12 to 22 earbon atoms;
or (e) mixtures there~f; (vi)(a) asbestos screenings; (b) natural serpentine fibrous fragments; (e) miea flakes; (d) adipie acid plus asbestos screenings; (e) adipic acid plus natural serpentine fibrous fragments; or (f) adipic acid plus miea flakes; (vii) a mastie of (a) a petroleum fraction seleeted from oils and greases with one of (b) asbestos sereenings; (e) natural serpentine fibrous fragments; (d) miea r ~ flakes; (e) adipie aeid plus asbestos screenings; (f) adipie aeid plus natural serpentine fibrous fragments; or (g)adipie aeid plus miea flakes; and (viii) a metallie soap seleeted from an insoluble soap of naphthenie aeid, oetoie aeid,.2-ethylhexoie aeid, rosin aeids or tall oil aeids, with ¦ aluminum, ealeium, eadmium, eobalt, eopper, iron, lead, manganese, niekel, tin or zine; to provide a thickened composition having a viscosity of at least 30 poises, and desirably to provide one composition of 30 to 120 po~ses, and another composition of 250 to 800 poises. (As used herein, the viscosity in poises is as measured by a Brookfield Viseometer at 25C.).
In preferred variants of this invention the preservative may be: (A)(i) a normally water-insoluble salt ~ -6-:,` ;, :

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~OS8353 selected from the group consisting of zinc arsenate, zinc arsenite, copper arsenate, copper arsenite and mixtures thereof;
and (iv) sufficient aqueous ammonia, in a concentration o~
1 to 28% by weight-NH3 to solubilize the salt (i); or it may be: (A)(ii) an ammonia-soluble salt selected from the group consisting of copper borate, zinc borate or mixtures thereof, ... .
and copper chromate, zinc chromate or mixtures thereofi and ~,} (iv) sufficient aqueous ammonia, in a concentration of 1 to ~, _ 28% by weight NH3 to solubilize the salt (ii); or it may be:

~3 (A)(iii) an ammonia dispersib]e organometallic compound selected ~ from the group consisting of copper naphthenate, zinc naphthenate '~ or mixtures thereof, copper-8-qu~nolinolate, zinc-8-quinolinolate i or mixtures *hereof, or tributyltin oxide; and (iv) sufficient .~, ~
aqueous ammonia, in a concentration of 1 to 28~ by weight NH3 to disperse the compound (iii).

In another variant, the composition includes an acrylic resin as a water repellency improving agent.

~ In yet another variant, the composition includes r .~, .
zinc thiocyanate, copper thiocyanate or mixtures thereof to ! ~ I
~20 increase toxicity. t In one variation, the thickener comprises a metallic soap.

In a preferred variation, the composition includes 0.1 to 4% by weight copper arsenate, copper arsenite, ~, .
zinc arsenate or zinc arsenite or mixtures thereof (as Zn and/or ~. Cu metal) of the total aqueous solution; 0.15 to 10% by weight ,~t of the total aqueous solution or a carbonate or a bicarbonate; r ~ j and from 15-26% ammonia.

In another variant, the ratio of active ~ 30 preservative ammoniaJwater in the preservative component (A) is ;"~ 20-40/15-25/65-35, while in yet another variant, the ratio of ~ preservative component (A)/thickener component (B) is 31-85/69-15.

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Examples of suitable wood trea-ting compositions within aspects of this invention include: (i) an-ammoniacal solution of copper arsenate as the preservative and zinc stearate as the thickener; (ii) an ammoniacal solution of copper arsenate as the preservative and stearic acid as the ; thickener; (iii) an ammoniacal solution of copper arsenate s ~1' .
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-- as the preservative and lauric acid as the thickener; (iv) an ammoniacal solution of copper arsenate as the preservative : and asbestos screenings as the thickener; (v) an ammoniacal solution of copper arsenate as the preservative and a mastic of adipic acid and asbestos screenings as the thickener; (vi) an ammoniacal solution of copper arsenate as the preservative and a mastic of a petroleum grease and asbestos screenings as the thickener; (vii) an ammoniacal solution of copper arsenate as the preservative and a mastic of a petroleum grease and . natural serpentine fibrous fragments as the thickener; (viii) an ammoniacal solution of copper chromate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener; (ix) an ammoniacal solution of copper metaborate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as thè thickener; (x) an ammoniacal solution of copper arsenite as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener; (xi) an ~.
ammoniacal solution of zinc arsenate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener; (xii) an ammoniacal solution of zinc arsenate and copper arsenate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener; (xiii) an ammoniacal solution of copper borate as the preservative and zinc stearate as the thickener; (xiv) an ammonical solution of copper naphthenate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous ragnlents as the thickener; (xv) an ammoniacal solution of copper naphthenate as the preservative and a mastic of a petroleum grease and asbestos fibers as the thickener; (xvi) an ammoniacal solution of copper borate as the pr ervative and a mastic of natural , . ~
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serpentine fibrous fragments and a petroleum grease as the thickener; L

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- ~_ (xvii) an ammoniacal solution o~` copper ammonium arsenate as the preservative and a mastic of natural serpentine fibrous fragments and a petroleum grease as the thickener; and (xviii) ~"
an ammoniacal solution of zinc ammonium arsenate as the preservative and a mastic of natural serpentine fibrous fragments and a petroleum grease as the thickener.
The wood treating composition within another aspect of the invention contains sufficient thickener (B) to provide a composition for dip treatmen-t and having a viscosity of 30-120 poises.
The wood treating composition within yet another aspect of the invention contains sufficient thickener (B) to ', provide a composition for brush, roller or trowel treatment, and having a viscosity greater than 120 poises.
The wood treating composition of another aspect of this invention contains sufficient thickener (B) to provide a composition for brush, roller or trowel treatment, and having a viscosity of 250-800 poises.
The wood treating composition of still another r aspect of this invention contains sufflcient thickener (B) to provide a composition for trowelling which does not flow spontaneously but lS thixotropic.
By another aspect of the invention, a method is provided for preserving wooden poles by the steps of: (a) applying a coating thereto of any of the compositions described above to give a covered layer which is substantially uniform and to provide a layer which is at least 1/8" thick; (b) providing a substantially ammonia impervious enclosed atmosphere around such coated wooden poles for a time sufficient to permit penetration into the poles; and (c) re~oving the a~
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~~ enclosure providing the ammonia impervious enclosed atmosphere, thereby to permit volatile material to escape and provide a ' ' preservative treated wooden pole.
In one variant of this aspect, the ammonia impervioùs enclosed atmosphere may be provided by a polyethylene sheet enclosure.
By yet-another aspect of this invention, a method is provided for prolonging the service~life of wooden poles including the steps of applying a thickened ammonia composition as described above to a preselected groundline area of a wooden pole to give a covered layer which is substantially uniform and thus to provide a layer of at least 1/8" thick; and applying a substantially ammonia and water impervious bandage including means for sealing such bandage around its edges to the coated r groundline area of the wooden pole, the bandage providing enforced contact between the wooden pole and the coàting. ;' In one variant of this aspect, the bandage is I
formed of polyethylene tape.
` The essence of'~his invention involved the use of 1, an ammoniacal preservative solution as a thickened ~semi-solid) ~' preservative composition which can be ~onveniently applied to utility poles in situ as a coating by e.g., the trowelling, or which can be applied by dipping poles therein, or which can ~'~ be applied by brushing thereon. The thickened ammoniacal wood :
treating compositions of aspects of this invention achieve rapid penetration into permeable as well as refractory species ~, of wooden poles. The use of ammonia as a vehicle for including rapid penetration-of'preservative chemicals in groundline'type treatments according to a preferred aspect of this invention ~ 30 has not, heretofore, bee~'used.
;~ Moreover? the conjoint use of ammonia and a ~L ' ' 1058353 .; ,.~
thickener, either the single phase or the mastic type for the treatment of wooden poles~ either in situ in the ground, or individually, or in bundles, has not been suggested heretofore.
It is believed that a synergistic effect is achieved in that the ammonia carries the otherwise water immiscible thickener components into the wood bein~ treated~ ¦
As noted above 5 there are three classes of preservatives useful in aspects of this invention. One class comprises water-insoluble but ammonia-soluble zinc arsenate, zinc arsenite, copper arsenate or copper arsenite or mixtures thereof.
Another class includes water-soluble, ammonia- 1, soluble salts, namely, copper metaborate or zinc metaborate or mixtures thereof or copper chromate or zinc chromate or mixtures thereof.
A third class includes water-insoluble, ammonia dlspersible organometallics, e.g., copper naphthenate or zinc r naphthenate or mixtures thereQf, copper 8-quinolinolate or zinc r 8 quinolinolate or mixtures thereof, or tributyltin oxide.
An especially preferred preservative is that disclosed and - I .

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claimed in Canadian ~atent ~o. 978~474 issued NoYember 25~ 1975 in the name of Michael R. ~larke'and 3aromir R. ~ak. 'Thus, the following preser-vatives'may be'thickened to provide compositions of aspects of the invention:
The prese~vative is based on copper and/or zinc ammonium com~
plexes containing aresenic anions ~As or As ) and other additives, all components being soluble in one common aqueous ammoniacal solution. In the above-noted'composition, the preservative compounds in the form of water-insoluble salts of zinc or copper'or a mixture of these are . 10 solubilized in admixture with certain specified water'repellent compounds in the ammoniacal solution. ' ;.
The preservative composition comprises an aqueous solution con- '' taining: (a) a normally water-insoluble compound selected'from the group .': .
consisting of zinc arsenate, zinc arsenite, copper arsenate,'and copper ''~
arsenite and mixtures'thereof in an amount of 0.1 to 4% by weight (as Zn '~
or Cu metal~ of the'total aqueous solution; (b) 0.15 to 10% by weight of ' ' the total aqueous solution of a water repellent component comprising one .'..
of (i) a water-insoluble organic acidic compound having a solubility of 0.2% and in concentration a~ueous ammonia, the water-insoluble organic acidic compound being selected'from the group consisting of a substan-tially water-insoluble saturated or unsaturated monocarboxylic acid having f between 8 and 15 carbon atoms in the'carboxylic acid; a substantially water-insoluble saturated or unsaturated'monocarboxylic acid having between'8 and 15 carbon atoms in the carboxylic acid substituted with a hydrocarbon radical; a substantially water-insoluble saturated or unsaturated monocarboxylic acid having between 8 and 15 carbon atoms in the carboxylic acid substituted'with a hydroxyl radical; a substantially water-insoluble saturated or unsaturated monocarboxylic acid having between 8 and ~5 carbon atoms in the'carboxylic acid substituted with a halogen; maleinized'unsaturated fatty acids from animal or vegetable sources, and having an acia value of 200 to 500; maleinized unsaturated fatty acid esters from animal or vegetable sources and having an acid -~ lOS8353 value of 200 to 500, maleinized unsaturated fatty.acids, formed by the reaction of maleic acid with fatty polycarboxylic acids and having an acid value between 200 and 500,' maleinized unsaturated fatty acids . formed by the'reaction of maleic alkyds with fatty:polycarboxylic acids, and having an acidr~alue between'200 and 500; maleinized unsaturated fatty acid resins formed'by the'reaction of maleic acid with fatty poly-carboxylic acids, and having an acid value between 200 and 500; malein-ized unsaturated'fatty:acid resins formed'by the'reaction of maleic alkyds with fatty polycarboxylic acids, and having an acid value between 200 and 500; aromatic carboxylic acids having an acid value between 200 and 500; acid esters of phosphoric acid with monohydric alcohols and having an acid value between'200 and 500; acid esters of phosphoric acid .
with fatty alcohols and having~an acid value between 200 and 500; synth-etic polycarboxylic acids having an acid value between 200 to 500, and ~.
mixtures thereof, in an amount of up to 200% of the'zinc or copper, or (ii) a combination of the'selected'organic acidic compound and a carbon-ate or bicarbonate ion selected from the'group consisting of zinc carbon-ate,'zinc bicarbonate,'copper'carbonate and copper bicarbonate in an '~
amount of up to 150% of'the zinc or copper; and (c) ammonia, in an amount of 1 to 28% by weight of the total aqueous solution; the ammonia being sufficient to solubilize the normaliy water-insoluble salt of zinc or copper and the normally water-insoluble water-repellent compound.
The constituents of the'preservative composition may range in concentration (expressed'as percentage by weight of the total) as follows: -l. Zinc and/or copper arsenic compound, present as the arsenate or the ac arsenite, in an amount of 0.1-4 (as Zn or Cu metal). .
2..Water repellent compound being a water-insoluble organic acidic com-pound having a solubility ~ 0.2,.the'compound being present in proportions ranging between 0% and 200% of the'zinc or copper; or carbonate or bicar-bonate ions present in proportions ranging between'0% and 150% of the zinc or copper; or both the'water-insoluble organic acid compound and the car-bonate or bicarbonate in an amount of 0.15-10, and ' , :::

~058353

3. Ammonia~ in an amount of 1-28.
Whether'copper and/or zinc is used, the organic acidic component ' .
may generally be defined'as an acidic compound which is insoluble in water but wh~ch is capable of forming compounds with the'metal'ammonia complex -which are saluble ~n aqueous ammoniacal solutions. The'organic acidic ;' component has a solubility of _ 0.5%, preferably >3% in concentrated .
aqueous ammonia (28%).-Such'component may be'a substantially water- ; :
insoluble monocarboxylic acid having between 8 and 15 carbon atoms in .
the carboxylic acid and being either unsubstituted or substituted'with hydrocarbon radicals, hydroxyl radicals or halogens.- Examples include capric (decanoic), lauric (dodecanoic), myristic ~tetradecanoic);
unsaturated fatty acids, for example a 9'10-decylenic, ~ 9'10-dode- ' cylenic. The preferred materials are those saturated and unsaturated higher aliphatic acids containing from nine to fifteen carbon atoms.
Other'organic acidic compounds which may be'ysed are maleinized unsatur-ated fatty acids or esters from animal or vegetable sources such as, for example,'sardine and o~her fish oils, lard, coconut oil, sesame oil, .. . . .
soybean oil, tung oil, corn oil, and having an acid value of 200 - 500;
maleinized unsaturated fatty acids, oils and resins formed by the reaction of maleic acid or maleic alkyds with the fatty polycarboxylic acids having an acid value between 200 and 500; aromotic carboxylic acids and deri-vatives thereof having an acid value between 200 and 500; the acid esters of phosphoric acid with monohydric alcohols or fatty alcohols having an acid value between 200 and 500; condensation polymers in which the acid value is between 200 and 500; and any mixtures of the above. Other acids which may be usediinclude synthet;c polycarboxylic acids such as, for example, polyesters and alkyds having an acid value betweén 200 - 500.
The above-identified organic acidic compounds may be used as the sole water repellent agent, or may be used in admixture with a car-boante ion, or a bicarbonate ion. The carbonate ion or bicarbonate ion '' :
can be provided either'by selection of the zinc carbonate,'zinc bicar- ~' bonate, copper carbonate or copper'bicarbonate,'or it can be fonmed by . . - - - , ~ . , lOS83S3 reaction of a suitable zinc or copper salt, e.g~ the oxide with ammonium carbona~e or ammonium bicartoonate ~n the ammonia solution. 'In addition, the'carbonate or the'bicarbonate ma~ be used'as the'sole water'repellent agent or may be used'in admixture with the'above-identified organic acidic compounds.
The organic acidic components used are those which are charac-terized'in that they'form compounds with copper'and/or with æinc which are water-insoluble,'but which'are soluhle to greater'than 0.2%, prefer-ably greater than 3%, in 28% aqueous ammonia solution.
If the'composition is one containing zinc ions, the wood mater-; ial provided is one having high aesthetic considerations, while if the solution is one containing copper'ions, the'wood material provided is one having low aesthetic considera~ions. In either'case, the essential presence of arsenic acids or arsenious acids or mixtures thereof in such composition results in a composition which protects the wood against biological degradation. ~en carboxylic acids and/or carbonic or bicar-bonic acid ions are present in the'composition, the composition imparts high water repellency and weather resistance to the'wood. When'carbonic or bicarbonic acid ions or mixtures'thereof are present in the composi~
tion, the'composition imparts protection to the wood against glowing combustion.
The'level'of'ammonia used'in the'preservative component com- ';
positions described above is generally in excess of that required to form the copper'or zinc salts or coordinating complexes; the pH of the aqueous compositions will generally be pH 9 or higher. The non-volatile solids of the compositions may vary between'1% and 25% (in the case of zinc), or between 1% and 15% (in the'case of copper, or mixtures of copper and zinc~.
In one embodiment of preservative component, the compositions comprise an aqueous solution of a zinc ammonium arsenate or arsenious ~ ' complex'with the'water'repellent additive in the form of carbonate or carboxylic acids, as defined'above,'which is characterized by its ability 1058353 ~
to give rapid penetratlon into wood substance and which on drying leaves wood with its natural appearance and colour, resistant to biological deterioration, resistant to weathering and resistant to glowing combus-tion. The treating solution has excellent stability under processing conditions. ~ ~' One example of such preservative component composition is:
zinc meta arsenite '1.5 parts by weight zinc carbonate 4.5 parts by weight decanoic acid 3 parts by weight aqueous ammonia (5~ ammonia91 parts by weight in water) In another'embodiment of preservative component, the composition comprises an aqueous solution of a copper ammonium arsenic or arsenious complex'with the'water'repellent additive in the form of carbonate or carboxylic acids, as defined above,'which is characterized in that it renders the wood resistant to weathering and resistant to biological deterioration, The treating solution has excellent stability under pro-cessing conditions.
One example of such preservativç component composition is:
copper arsenate 3 parts by weight copper carbonate ' 3 parts by weight organic additive ' 2 parts by weight e.g., as decanoic acid ~ ' aqueous ammonia 92 parts by weight (5% ammonia in water) Another preservative component composition is based on zinc or ' zinc and copper ammonium complexes containing arsenic anions (As or AsV), with the weight ratio of zinc or zinc and copper (as oxides) to arsenic (as oxides) being 1.5 or more,'containing carbonate or bicarbonate ions, and preferably the weight ratio of C02/NH3/Zn/As or C02/NH3/Zn+Cu/As being 1.7-2.3/5.9-6.7/1.9-2.9/.9, all components being soluble in one common aqueous ammoniacal solution. In the above-noted composition, the preservative compounds in the'form of water-insoluble salts of zinc or a .: : :

mixture of zinc and copper are solu~ilized in admixture with certain specified'water repellent compounds in the'ammoniacal solution.
Such p~eservative component c~mposition comprises an aqueous solution containing ~a) a normally water-insoluble compound of zinc or zinc and copper'wi~h arsenic acid or arsenious acid in an amount of 0.1 - i

4~ by weight'(as Zn or Zn + Cu metal) of the total aqueous solution, the weight ratio of zinc or zinc and copper'(as oxides) to arsenic (as oxides) being 1.5 or more;' Cb)'0.15 - 10% by'weight of the total aqueous solu-tion of carbonate and/or bicarbonate ions in an amount of up to 150% of the zinc or the'zinc and copper, and (c) ammonia, in an amount of 1 - 28%
by weight of the total aqueous solution; and the'ratio of CO2/NH3/Zn/As or C02/NH3/Zn + Cu/As being 1.7-2.3/5.9-6.7/1.9-2.9~.9, the ammonia being -sufficient to solubilize the'~ormally water-insoluble salt of zinc or zinc and copper, and the carbonate and/or bicarbonate. ;
Tke constituents of the preservative composition may range in concentration (expressed'as percentage by weight'of the total) as follows: ' 1. Zinc or zinc and copper'arsenic compound, present as the arsenate or ~ ' the arsenite with the'weight'ratio of zinc or zinc and copper (as oxides~
to arsenic ~as oxides) being 1.5'or more,'in an amount of 0.1-4 (as Zn or Zn + Cu metal), 2. Carbonate and/or bicarbonate ions present in propor~
tions ranging up to 150% of the zinc or zinc and copper, in an amount of 0.15 - 10; and 3. Ammonia, in an amount of 1 - 28; and the balance, to ;' ~
100%, water, and preferably with the ratio of C02/NH3/,Zn/As or ' CO2/NH3/Zn + Cu/As being 1.7-2.3/5.g-6-7/1-9-2 9/ 9 One embodiment of such preservative component compositions comprises an aqueous solution of a zinc ammonium arsenate or arsenious complex with the water repellent additive in the form of carbonate which ! iS characterized by its ability to give rapid penetration into wood sub-stance and which, on drying, leaves wood with its natural appearance and colour, resistant to biological deterioration,resistant to weathering and resistant to flowing combustion. 'The treating solution has excellent stability under processing conditions and has been found to have very low --~ lOS8353 arsenic leachability.
One example of such-treating composition is:
arsenic oxide ~III)1.2 parts by weight zinc oxide3.6'parts by weight N~4HCO34.2 parts by weight aqueous ammonia (28% NH , 20 ml in 100 ml water~ 91 parts by weight Another example of such treating composition is:
arsenic oxide (V)1.4 parts by weight zinc oxide3.5 parts by weight NH4HCO34.1 parts by weight aqueous ammonia (28% NH , 20 ml in 100 ml water)3 90 parts by weight A preservative CompoRent composition comprises an aqueous solu-tion of a copper ammonium arsenic or arsenious complex with the water repellent additive in the form of carbonate and/or bicarbonate, which is characterized in that it gives rapid penetration into the wood substance and which, on drying, renaers the wood resistant to weathering and resis-tant to biological deterloration. The'treating solution has excellent stability under processing conditions and has been'found to have medium arsenic leachability.
One example of such composition''is: -arsenic oxide ' !1.4 parts by weight copper oxide '2.4 parts by weight '~
NH4HC031.8 parts by weight aqueous ammonia (28% NH , 25 ml in 100 ml water~ 94.4 parts by weight The above-descri6ed'preservative component is-used with a thickener component to provide the wood treating compos'itions of various aspects of this invention. One example of thickener used in formulating compositions of aspects of this invention is fatty acids of 12 - 22 carbon atoms. This includes the saturated fatty acids: lauric, tridecylic, .. ,, ~ ~
myristic, pentadecylic, palmitic, margaric, stearic, nondecylic, arachidic, .

and achenic, and the unsaturated fatty acids~ _dodecylic, palmi- ~
. .
toleicJ oleic, succinoleic~ pelrosel~nic~ vaccenic~ linoleic, linolenic, eleostearic, licanic, parinaric, tariric, gadoleic, arachidonic, cetoleic, and erucic. The'presence of carboxylic acid group in the thickener appears to be desir~ble in assisting stability and proYiding ease of mixing.
Various salts and soaps of these fatty acids may alsobe used.
More common ones'include copper, zinc, sodium, potash,'amine salts and metallic soaps. '~
As used herein, the term "metallic soap" is intended to mean an ' insoluble soap of stearic acid, naphthenic acid, octoic acid, 2-ethyl-hexoic acid, rosin ta resinate of the resin acids) or tall oil ~a tallate of tall oil acids) with heavy.metals, e.g. aluminium, calcium, cadmium, cobalt, copper, iron, lead, manganese, nickel, tin or zinc.
Another example of a thickener is a fibrous thickener. These include asbestos, natural serpentine or mica flakes. While asbestos fibres'are useful, since asbestos fibres have been indicated as being a ' ., .
health hazard, it is desirable to replace the asbestos content with a ''~
natural serpentine compound, especially that mined in Timmins, Ontario, ~ ' Canada, and known as Hedman Cationic Fibre (HCF). The Hedman Cationic Fibre can be described as follows: ' ' Hedman Cationic Fibre is the trade name of a natural serpentine ~ ' compound. Serpentine is the'geological name for a group of minerals having in common the same chemical formula of hydrous magnesium silicates.
The most common varieties of serpentine are Antigorite, Lizardite and Chrysotile. The Hedman product consists predominantly of Lizardite, the balance (approximately 15 percent by volume or 10 weight percent) being Chrysotile.
Lizardite is a one-layer'orthorhombic polymorph of serpentine.
In its natural state lizardite in the'Hedman ore has a platey or flaky structure. The thin plates'are up to 5 microns in diameter, inflexible and brittle. 'Due to vigorous shearing and other mechanical action in -- lg -- ' ' '' "' '' the Hedman plant circuit~ many of the lizardite plates are broken up into fragments and appear in abundance in the'finished'product as pris-matic laths'of 0.2'to l.O'microns in length. 'The'main characteristics of lizardite are platey'structure,'which can easily be recognized'with the aid of electron di~fraction. 'The'plates are thin and do not generally absorb and/or shatter'the electron beam to the'extent that non-serpentine plates (for instance biotite)'do. 'In the'Hedman product, the'fragmented ' liæardite prismatic laths can be identified on 17,600X electro micro-graphs. Also, lizardite is inflexible and non-fibrous. ~ ', Chrysotile is a fibrous variety of serpentine and it is also called'serpentine fibre. Those ~ibres'which are'longer than 5 microns and have a length-to-diameter'ratio of at least 3:1 are called'"asbestos fibres". .~ ' ' The main characteristics of chrysotile are fibrous, the fibres having a tube running along the'length.' (This tubular structure belongs excluslvely to chrysotile).
The'concentration of fibres'longer'than 5 microns in the fib-rous portion of the Hedman product was determined, Only 0.2% of the fibrous (chrysotile)'portion are longer'than 5 microns, (i.e. an asbestos portion). This was 30'to 40 times less than in those short asbestos fillers which may be'used as a fibrous thickener. Since only 10 - 15 per-cent, with a maximum being 20%, of the Hedman product i9 chrysotile, only 0.02 tO 0.04 percent of the'total product is "asbestos fibres".
A portion of the fibrous thickener may be replaced by a dibasic ~ ;
acid, namely succinic, glutaric, adipic, pimelic, suleric, azelaic, or sebacic acid. However, it is preferred that such replacement acid be adipic acid, As ~oted'before,~ t--is believed that the'presence of carboxylic acid groups assists in stabilizing the'composition as well as enabling greater ,,, ~058353 ease of mixing.
; The thickener may be used as a single phase thickener, or as a mastic type. If used as a mastic type, it may be:' asbestos screenings and a petroleum residue selected from oils, greases, petroleum jelly or ~' petrolatum; natur~l serpentine and a petroleum residue selected from '' oils, greases, petroleum jelly or petrolatum; mica flakes and a petrol- ;
eum residue selected from oils, greases, petroleum jelly or petrolatum;
i; adipic acid, asbestos screen;ngs and a petroleum residue selected from ;~
oils, greases, petroleum jelly and petrolatum; adipic acid, natural serpentine and a petroleum residue selected from oils~ greases, petroleum jelly and petrolatum; and adipic acid, mica flakes'and a petroleum . . .
residue selected from oils, greases, petroleum jelly and petrolatum.
Any thick petroleum residue, be it oil, grease, petroleum jelly or petrolatum may be used. The'thickened'ammonia-base preservatives can ~' have a wide variation in viscosity depending on the mode which is desired to apply it to the wood surface.' In all cases, the thickened preservative should remain aæ an adherent layer'and not run off. For dip application, the viscosity is preferably wlthin the range of 30 to 120 poises'(Brook-" field Viscometer, 25C.). For mechanical deposition ~as by brush, roller, trowel, etc.~, the'viscosity should be higher than 120 poises, preferablywithin 250 to 800 poises. Thicker'materi'als can be used'for trowel application, e.g. the'composition may have a consistency similar to that of a cup grease or of heavy putty. These thickened mixtures do not flow spontaneously and are thixotropic. 'When passed through a colloid mill, the thick grease-like mixtures do not liquefy but remain as a thick paste, i.e. are stable at high shear but are thixotropic.
As used hereinabove,'"petrolatum" may be defined as white mineral oil, liquid paraffin, or white paraffin oil, and being a colourless transparent oily liquid, a mixture of liquid hydrocarbons; almost taste-; 30 less and odorless even when warm; sp. gr. 0.828-0.880 ~25C.) (light?, 0.860-0.905 (26C.?'~eav~?; soluble in ether, chloroform, carbon disul-fide9'benzine,'benzene,'boiling alcohol, and fixed or volatile oils;

_ 20 -- , ..

insoluble in water, cold alcohol, glycerine, and derived by distillation of high boiling C330-390oc-) petroléum fractions. ' It is also desira61e to improve the water'repellency of the treated wood by'including, in the'composition, an acrylic wax or acrylic ' resin.
As used herein, the term ~acrylic resin" is intended to embrace any thermoplastic or thermosetting polymer Qr copolymer of acrylic acid, metha~rylic acid, esters of these acids or acryl~petrile, and polymer- ;
- ized, in most instances'from acrylonitrile and the methyl or ethyl esters of acrylic or methacrylic acid. 'This includes'polyacrylates'and poly-methacrylates. Acrylic resins, having repeating acrylonitrile units [-CH2CH(CN)-] and acrylic rubbers, e.g. nitrile rubber having the repeat-g [ CH2CH CHCH2CH2CH(C~)-] are also included. ~ ' In order'to provide added toxicity, it is desirable to add zinc and/or copper thiocyanate to provide improved compositions of aspects of this invention.
By another variant, a preservative may be prepared'as a semi-solid mass consisting of normally water-insoluble arsenates and/or arsenites which are maintained soluble in the ammoniacal medium. The ; ~' ammonia is believed also to act as a rapid penetrating agent carrying the preservative deeply into the'wood. 'Uet'wood cam be penetrated'remarkably well. It is believed that the ammonia escapes in the gaseous phase and the preservative remains in the wood and becomes essentially permanently fixed. Preservatives deposited in the wood in this process can have a life expectancy of more than 30 years based upon long term outdoor exposure tests of wood treated with similar toxic salts.
The ammoniacal based'preservatives of aspects of this invention have an enhanced capability of penetrating wet wood during the extreme cold winter months. 'Transmission poles, bridge piles, and wharf timbers could be treated in the'late autumn when the water table is low and the preservative would be penetrated before the spring water levels are elevated.

` ` 1058353 ~
j' The ammoniacal based preserYatiYes o~ aspects of this invention thus have wide ut~lity, 'The'arsenic-containing ammoniacal preservatives, as well as the arsenic-free'formulations of aspects of this invention are particularly suitable ~i.e.''are substantially non-leachable) for the ; treatment of wood ~ith high moisture content. This condition frequently occurs in utility poles set in low-lying areas and in bridge piles set ';~
in streams and in wharf piles. It is essential that~the'ammoniacal based preservatives of aspects of this invention, when applied to the'groundline areas of poles in the'form of bandages, be'bandaged'with an ammonia-' 10 impervious wrapper to reduce'loss of volatile ammonia, and also that the ' bandage include means for sealing the bandage around its edges. Any ammonia-impervious sheet, wrap or tape material can be used'to enclose ' the treated wood surface~.' Polyethylene film has been found to work well, but other film or sheet'material, e.g. acetal resins, for example those known by the'Trade Marks of Delrin and Celcon; cellulose acetate film;
polyethylene terephthalate film, for example that known'by'the Trade Mark of Mylar; polyolefins including copolymers of ~thylene, polypropylene, ethylene propylene terpolymer, and polytetrafluoroethylene, for example that known by the'Trade Marks of Halon and Teflon; polyvinyl alcohol;
polyvinyl butyral resins; polyvinyl chloride; polyvinyl chloride- "
acetate,' and polyvinyl fluoride.' ' Since ammonia-based'preservatives penetrate wood more readily than simple water-borne chemical salts (except possibly sodium fluoride) modified preservatives of aspects of this invention have been provided for preserving by dip treatments or by brush treatments. Deposits of ' ' 1/8 to 3/16 inch (3 to 5 mm) thickness are sufficient for both dipping and brushing.
After applying the coating, it is essential to provide an essentially ammonia-impervious environment around the'pole or poles (from material as described above?. Individual poles may be enclosed in a thin . .
film bag, e.g. of the material described above,'and sealed. Alternatively, piles'of treated'poles'may be c~vered'with a sheet of material described ~ 10S83S3 above. In any event, the'enclosed'environment must be maintained for a time sufficient to permit penetration into the wood. A time of three ' ' to four weeks is believed to be sufficient. '~
Dip treatments are useful wherever treated'wood is required - when pressure treat~lng plants are not accessible.
Brush treatments are useful for treatment of timbers in place where decay hazard exists but the'timbers are sound or incipient decay is suspect, for example,'for joists in crawl spaces, beams in wharf and bridge supports, and possibly for treating deep checks in transmission poles.
It has been'found that the'toxic ingredlents penetrate wood more readily than ordinary water-60rne salts and are not leachable as are regular water-borne salts. 'Simple equipment and minimal training of ' ;
operators is required. In general, it is more economical than pressure ' '~
treatments. . .
The treatment is optimum in green ~unseasoned) wood. The treatment provides for a reduction of the loss of ammonia by evaporation or fuming. The treated'material should be:close piled, wrapped to retain 1058353 ~ ~
ammonia, and be stored fo~ 30 days or longer. ' In the bandage wrapping procedure,'the'test poles'were sealed ~ '; by a band of wire tightened'with pliers at the'upper and lower edges.
Pole sections which were set in water'for 30 days were sealed'at the bandage edges'with~a water'resistant adhesive tape.
In a specific variant of this invention, a composition contain-ing zinc and/or copper'stearate-and zinc and/or copper (meta) borate in an ammoniacal solution has been found to be particularly useful. Such zinc and/or copper'stearate-ammoniacal zinc and/or copper borate system ' is different from any other groundline system, in that it involves the use of zinc and/or copper stearate as a thickener vehicle and the use of zinc and/or copper borate as a preservative. ` ' The organometallic~preservative component dispersed in a thickened ammoniacal composition, e.g. copper and/or zinc naphthenate, copper and/or zinc-8-quinolinoleate, and tributyltin oxide, of still other aspects of this invention is particularly suitable for preserving large seasoning ' checks, cracks, and pile cut-offs Utility poles, especially those treated with water-borne salts', frequently split longitudinally and expose the heartwood which i8 then'vulnerable to decay. The organo-metallic preservative can be applied with a grease gun using fine or ' fish tail-nozzles to fill cracks, breaks, checks and seasoning splits.
Copper naphthenate, as shown'by a 22 year old test of above-ground expos-ure conducted by the'laboratory, is very effective for, treatments of ~ ' aerial sections of poles. This formulation is also useful for groundline sections of poles set in dry locations and could incorporate agricultural fungicides such as, for example, that known by the'Trade Mark of Mirex, for combatting termites, carpenter'ants, etc. As discussed above, it is necessary to apply a wrapper to minimize loss of ammonia when the com-position of aspects of this invention is used as a groundline treatment.
Alternatively, a strip seal of some type should be used. 'It is possible, as well, that a plurality or bundle of poles could be wrapped together.
The following examples'are given'to illustrate aspects of the : , . . : : . . .

~OS8353 invention.
.....
- ~xamples 1 - 6 -Thickened'copper arsenate and zinc arsenate preservatives are provided'by first providing copper arsenate and zinc arsenate solutions as follows:

By By Copper Arsenate Weight Parts Copper (as basic copper'carbonate)' 700 g 3.5 Arsenic (as H3As04 - 71%) 400 g 2.0 Ammonium bicarbonate (NH4HC03) 360 g 1.8 Water of solution 200 g 1.0 This solution is dissolved in 26 percent ammonia water to a volume of 2100 ml (10.5 parts). The yield is approximately 30 percent active copper arsenate solids in 23 percent ammonia solution.

! - By By Zinc Arsenate Weight Parts Zinc (as zinc oxides) 123.5 g 2.9 Arsenic (as H3As04 - Jl%) 84.7 g 2.0 Ammonium bicarbonate ~NH4HC03) 142.6 g 3.4 This solution is dissolved in 627 g (14.8 parts) of 26 percent am~onia water, to yield approximately 24 percent active zinc arsenate solids in 16.7 percent ammonia solution.
Two types of thickened'preservatives are provided. The first type is represented by the following four single phase-substrate systems, prepared by thickening either the zinc arsenate or the copper arsenate solutions with suitable single phase substrates, e.g. stearate acid, zinc stearate~ lauric acid, or asbestos screenings. The'examples which follow are those prepared with copper arsenate.

% (by weight?
1. Copper arsenate solution 85 Zinc stearate 15 2. Copper arsenate solution 35 Stearic acid 65 t ' ' , ' , ' : ' ' ;' ~ ~ . . ' , , .
' %-(by weight) .
3. Copper'arsenate solution 40 Lauric acid 60 '~ 4. Copper arsenate solution 70 Asbestos screenings 30 The second type is represented'by the'following two mastic carrier systems, prepared'by thickening either the zinc arsenate~or the copper'arsenate solution with a suitable mastic carrier system, e.g. ' ' Vaseline (Trade ~ark for a petroleum jelly consisting of a semi-solid mixture of carbons, having a m.p. usually ranging between 38 and 60C;
it is colourless, or of a pale yellow colour, translucent, and a semi- ' solid unctuous mass) and asbestos screenings, or the more expensive adipic acid and asbestos screenings. The following are two examples of compositions prepared with copper arsenate:
% ~by weight)

5. Copper arsenate solution 48 Adipic acid 49 Asbestos screenings 3 - -

6. Copper arsenate solution 60 Vaseli~e 20 Asbestos screenings20 It was found that all these compositions were effective in exhibiting good characteristics from the handling properties as ' required for field treatments of in-line poles, and in respect of pene-tration. Composition No. 6 gave the best results.
It is observed that these copper and/or zinc arsenate and/or'~ ' -arsenite solutions can be mixed in any proportions for use in the semi-solid thickened formulations of aspects of this invention. However, for ~ ' heavy-duty treatments this preservative should consist of at least 50 30' percent copper arsenate and/or arsenite and up to 50% zinc arsenate and/or arsenite, and for the most severe hazards the proportion of copper arsenate and/or arsenite is increased'to 100 percent.

` ` 10583S3 ; . ~ .
Example 7 An example using HCF instead of asbestos screenings was pre- -pared as follows:
~ .
Wei~ht (~
Preservative: copper arsenate solution 34.5 '' ,;,.
Carrier: serpentine (HCF~ 34.5 ' Grease lPetrofibe 220, the'Trade Mark for -31.0 ~' industrial grade,'soft, low melting petro-latum. Petrolatum may be described as follows: Properties: Almost colourless to amber-coloured, gelatinous, olly, trans-lucent, semi-sol~d, amorphous mass whose consistency varies'with the'temperature.' I Soluble in chloroform, ether, benzine, car-'~ bon disulfide,'benzene and oils; very slightly soluble in alcohol; insoluble in water. Sp. gr. 0.8I5-0'.'880 ag 60C; m.p.
38-60PC. Chief'constituents: Hydrocarbons of the methane s~ries, (ClGH3 Up to C 2H66) and of the olefin series, ~C 4H , etc~
Derivation: by fractional disl~ ation of still residues from the steam distillation of paraffin-base petroleum, or from steam-reduced amber crude oils (oils from which ' the light'fractions have been removed).l The formulation has very satisfactory physical properties.
-Examples 8 a~d 9 It is also possible to provide, within ambits of this invention, arsenic-free formulations. The following arsenic-free preservatives were made in ammoniacal solutions:
% (by weight) 8. Copper carbonate + sodium chromate 46 equivalent to approximately 37 percent copper chromate ' Hedman cationic fibre rHCF) 31 Petrofibe 220 23 9. Copper meta borate,'Cu(BO2)2 (20%) 46 Petrofibe 220 23 This mastic carrier system is suitable not only for ammoniacal preservatives, but also suitable for certain organic preservatives (copper naphthenate,:etc.)'which'remain stable in am~oniacal carrier system.

Examples 10 - 14 The'following formulations were prepared'and found to be `~ satisfactory and release the'preservative salts for the'bandage-type treatments:
~ % (by weight~
10. Copper arsenate solution or zinc 31 '; ' arsenate, or a mixture of ~inc arsenate and copper'arsenate ''' ~20 to 40% salts, i.e. 15-20%
ammonia solutions of excess ammonia Industrial petrolatum 34.5 -Fibre ~asbestos, or Hedman Cationic ' 34.5 Fibre (HCF)] 100.0 11. Copper metaborate, Cu(~02)2, 20% in 46 ammonia solution Industrial petrolatum 23 Fibre rasbestos or HCF) '- 31 10 0 ! ', .
12. Copper arsenate solution in ammonia 80 (or copper'borate solution~
Zinc stearate '''20 13. Copper carbonate + sodium chromate in 46 ammonia water equivalent to approxi~
mately 35% copper chromate Industrial petrolatum 23 Fibre (asbestos or HCF) 31 100 ::
14. Copper naphthenate ~8% Cu) 25 Industrial petrolatum30 '' Ammonia water'(26% NH3) 20 Fibre (asbestos or HCF) 25 `' It has been found that zinc and/or copper is'an excellent vehicle for ammoniacal zinc and/or copper borate and will hold 5 to 6 times its weight of solution. Water insoluble borates have not been used heretofore as the prime ingredient in groundline bandage treatments because of the'solubility problems.- The preservatives are generally used ~058353 , - in water-soluble form and therefore remain leachable. Copper and/or zinc ', borate in the ammoniacal so~ution according to aspects of this invention penetrate wood as well as the'arsenate and/or arsenite system of the previously described aspects of this in~ention. The copper and/or zinc borate system'of asipects of this invention have very hi'gh leach resis-tance.
The tests were conducted'as follows:
' Sections of logs of red pine,'jack pine, and white spruce were obtained, debarked and treated by spreading the preservative mixture with a spatula. Moisture content (MC~ was determined on the outer'l-inch and inner l-l/2-inch zones'by the oven-drying method.
The treated areas were tightly wrapped in polyethylene film and the specimens were stored~indoors for 30 days. One series of speci-mens was storèd outdoors during the winter months (5 months). One set of ' creosoted'white spruce specimens was included in the'tests.
Results Test results are shown in Table 1. The influence of MC on ' depth of penetration is shown in the Table below.
'' , ' ' 20 .. . .

.~ , . .
, ~ .

. :

- ' 30 ., . ' ', ` . . ' .. , :

_~ 1058353 . .
: ' , 0 o ~ ~
a) ?~1 14 ~D h V t~l ~ ~1 ~ 00 c~l `;t O o~ O t') ~1 ? h O ~/ ~i c~ i ~i C~i O _i ~ ~ ~Y;

o E~ .,1 ? ,~
~ r( O O 0~ ~D O C~ o o o ~ ~ ~o ~ .
,~ oa) _i_ico~oo~ ~i~i ooo h ~J

0 ~ ~ ~ ~ , m o ~ o o~ c~ 0 cl ~ o o 5 oo o u~
8 .~ a) ~ ~ . ~ ~ ~ ~ i c~l ~ Ul 8 ~ ~.~ ~, , , . ~ p~ 0 bO ~ ~ ~h . -C ~ ' C ~ ~ ' ~ o ¦ ~ x ~o I u~ ~ ~ J ~ ~ ~ ~ 1 ~ 0 ~ ~ ~ ~ 0 ~ ~ ' X ~ ~ ~ ooIt~ ~ ~1 ~1 ~1 O~ ) O~ ~ ~O ~ N
~:t ~ a) ~ ~
. ~1 ~1 ~1 o~.0 ~ 0 ~ q 00 ~ ~ ~ O ~D ;
~J : ~ u~ u~ 00 0 a~ a~ o~ ~ o~ c~ ~ 1~ O
. :~ ~3 , 3 V C ~ ,~ C O C ~ C

:~ ~ , 3 3 ~ 3 p ~ ~z ~ ~ , .

~ ` 1058353 - 1. Thickened ammonia base preservatives of aspects of this invention penetrate wet wood rapidl~ to depths approximately equal to pressure preserved wood (red pine, iack pine, and white spruce species).
l One inch or greater penetration at retentions exceeding 1 pound per r,~ cubic foot of active salts can be obtained.
2. The preservatives of aspects of thls invention are stable to temperature changes and can be used for treatments of timbers during winter months where other types of preservatives may not be suitable.
3. The preservatives of aspects of this invention become fixed in the wood and are expected to be equivalent to pressure treated wood i in performance, i.e. to be effectlve for 30 years or more.
~ 4. The preservatives of aspects of this invention penetrate ;~ creosoted wood and should be well suited to retreatment of degraded communication`and power line poles in service.
Tests on the fungidical effectiveness of copper meta boroate -~in treated wood against two test fungi have béen carried out. At` a retention of 0.39 pound per cubic foot, no decay attack (based on weight ; 1088) was noted; in the same test series untreated specimens lost 35 percent and 37 percent of their weight against these two fungi. This retention could be easily obtained by the bandage method.
The system of aspects of this invention shows unexpected rapid diffusion (one inch in 30 days) at unexpected high retentions (1 pcf of salts) (based on calculated weight loss of the applied material).
The reoults of comparative tests between Pol-Nu (the Trade Mark for a widely used pentachlorophenol-grease preservative), and the ammonia composition of aspects of this invention are shown below in Table 2.
The CAA formulation was the model because penetration could be observed :: .
easily.
':
; 30 ~ ~ `" .' ' ' ",': , - 31 - ~
: :

` -~`" 1058353 Table 2 ;Comparison;of ~0~-~U~and CAA system Average depth of penetratîon MC Average reten~ion for l-inch depth Species Pol-Nu CAA % Pol-Nu CAA Solids :, . --- . _ _ :
W. spruce0.244 0.600 93 0.0642 0.189 ,~ :
Jack pine 0.556 0.320 44.5 0.0628 D.171 W. spruce - - 13.8 - -W. spruce - Vl-1.44 138 - 2.35 (ZAA) V2-1.04 138 - 2.04 (CAA, ZAA) . _ , . ------ -- . :
The preservative can be applied to poles or bridge piles during low water periods, a protective sheath applied, to be effective enough for submersion in water at high level or flooding conditions. T~o 30-day immersion tests were carried out. The preservative of aspects of this .
invention may be applied during low water period, or during winter time.
Copper borate, copper arsenate and zinc arsenate have been tested in penetration tests. The copper arsenate preservative was used as the model system because of availability. The arsenic-containing formulations would be used under "restricted" category of the Pest Con-trol Products Act (Department of Agriculture), i.e. only trained per-sonnel in wood preservation, or authorized persons could carry out treat-ments. The non-arsenic containing formulations could be designed "commercial" since they are expected to comply with the defined limita-tions.
A system of thickened ammonia-base wood preservatives was formulated which has advantages over the standard grease-type (known by the Trade Marks of Pol-Nu, Woodtreat AA, etc), and paste-type (known by the Trade Marks of Osmosar, FCAP, etc.) preservatives. The grease-types penetrate dry wood but diffuse very slowly, while the paste-types pene-trate wet wood and remain leachable, usually at fairly low concentrations because the process is limited by the amount of preservative brushed on the wood.
The compositions of certain aspects of this invention may be _ 32 -.

--` 10583S3 :~
applied to the'posts by the'dip treatment or the'brush treatment.
Suitable compositions have been'formulated'by'thickening concentrated'ammoniacal copper'arsenate,'or copper borate preservative solutions by'the addition of thickening agents, compatible gels, etc. to provide composition's having viscosities for dip treatments of 30 tO 120 poises, and for brush,'roller, trowel, etc. treatments of higher than 120 poises,-e.g.' from 250 - 800 poises. Other'thicker, thixotropic con-; sistencles are als'G operative.'' Example 15 .. .. ... .. . . ..
Preservative for dip treatments: % (by'weight) Preservative solution (copper borate;' 51.3 copper'ammonium arsenate; or zinc ammonium arsenate)' HCF (inert)~ ' 33-3 Industrial Vaseline (Petrofibe) lS.4 100.0 E~ample'16 Preservative for brush treatments:

Preservative solut~on (copper borate; 43.
copper ammonium arsenate; or zinc ammonium arsenate) HCF tinert) 28.2 Industrial Vaseline rPetrofibe~ 13.0 Petroleum Oil (S.A.E. 20) 15.4 100. 0 Such modification of the'mastic type preservative was tested for brush application and appeared'to be satisfactory.
The effectiveness of these treatments usi~ng inorganic salts (which remain leachable)'has been demonstrated in tests under Canadian conditions. For example, jack pine rail ties had an average life in track to 18 years compared to 6 to 8 years untreated. Fence posts treated by brushing (jack pine and white spruce)'lasted for 20 years compared to 3 to 6 years untreated. ' ~ ' The'thickened'-ammonia-base preservative has been found to have the'following main advantages.-'~' -- 33 -- .:

- , : ,: . . . .

--'` 105~353 ::
' 1. It may penetrate ~et'~ood rapidly; usually l-inch depth ' -can be obtained'in a month.''Generally poles are wet'at the'groundline and many grease-type preservatives'also-înclude water'solubles'sodium .~ - . . . . .
~ fluoridejor borax, because the grease alone is not compatible to wet wood. -R . 2. The'preservative of aspects of this invention in the treated sections of wood is at high concentrations, equivalent to, or exceeding, '- ~' requirements b~'pressure treatment. 'This, in itself~ is remàrkable for , diffusion treatment. ' `,i 3.'The'preservative saits of aspects of this invention become i 10 fixed in the wood and are expected'to provide adequate fungal protection for 30 years or longer. 'This'is also remarkable for diffusion treatments.
For example,'Pol-Nu is expected'to be effective ~or 12 to 15 years~ while Osmosar and RCAP for a maximum of 8 to lO years.
4. The'preservative of aspects of this invention will penetrate wood durinjg winter exposure and could therefoFe be'used'in locations where grease-type or pasté-type preservatives'may be ruled out. For example, bridge pilings set in streams, ponds, or running water, could be treated in the'fall at iow water'level, or possibly shortly after freeze-up, and the preservative saits would be penetrated and non-leach- j -~.
able (upon loss of ammonia) in the spring when water levels would be restored. Grease-types'penetrate too slowly, and paste-types remain - leachable and not suitable for this difficult requirement.
; 5. The'preservative of aspects of this invention is stable in closed containers and is not affected by freezing, as is ~oodtreat AA
(penta emulsion type).
6. The preservative of aspects of this invention penetrates wet creosoted wood and is therefore particularly well suitable to retreatment : .
of old creosoted poles.

.

Claims (24)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A thickened aqueous ammoniacal wood treating composition, for application as a covered layer to a wood surface, said composition comprising:
(A) a preservative component which is selected from from the group consisting of (i) a normally water-insoluble salt selected from the group consisting of zinc arsenate, zinc arsenite, copper arsenate and copper arsenite and mixtures thereof;
(ii) an ammonia-soluble salt selected from the group consisting of copper borate, zinc borate, or mixtures thereof, and copper chromate, zinc chromate, or mixtures thereof;
(iii) an ammonia-dispersible organometallic compound selected from the group consisting of copper naphthenate, zinc naphthenate or mixtures thereof, copper-8-quinolinolate, zinc-8-quino-linolate or mixtures thereof, or tributyltin oxide;
and (iv) sufficient aqueous ammonia, in a concentration of about 1 to about 28% by weight NH3 to solubilize said salt (i) or to solubilize said salt (ii) or to disperse said compound (iii), and (B) a sufficient amount of a thickener component selected from the group consisting of:
(v) (a) a saturated fatty acid of 12 to 22 carbon atoms, (b) an unsaturated fatty acid of 12 to 22 carbon atoms; (c) a copper, zinc, sodium, potash, or amine salt of a saturated fatty acid of 12 to 22 carbon atoms;
(d) a copper, zinc, sodium, potash, or amine salt of an unsaturated fatty acid of 12 to 22 carbon atoms; or (e) mixtures thereof;
(vi-) (a) asbestos screenings; (b) natural serpentine fibrous fragments; (c) mica flakes;
(d) adipic acid plus asbestos screenings; (e) adipic acid plus natural serpentine fibrous fragments; or (f) adipic acid plus mica flakes;
(vii) a mastic of (a) a petroleum fraction selected from oils and greases with one of (b) asbestos screenings;
(c) natural serpentine fibrous fragments;
(d) mica flakes;
(e) adipic acid plus asbestos screenings;
(f) adipic acid plus natural serpentine fibrous fragments; or (g) adipic acid plus mica flakes;
and (viii) a metallic soap selected from an insoluble soap of naphthenic acid, octoic acid, 2-ethyl-hexoic acid, rosin acids or tall oil acids, with aluminum, calcium, cadmium, cobalt, copper, iron, lead, manganese, nickel, tin or zinc;
to provide a thickened composition having a viscosity of not less than 30 poises.

2. The thickened ammoniacal wood treating composition of claim 1 wherein the preservative component of said composition contains:

(A)(i) a normally water insoluble salt selected from the group consisting of zinc arsenate, zinc arsenite, copper arsenate, copper arsenite and mixtures thereof;
and(ii) sufficient aqueous ammonia, in a concentration of 1 to 28% by weight NH3 to solubilize said salt (i).

3. The thickened ammoniacal wood treating composition of claim 1 wherein the preservative component of said composition contains:
(A)(ii) an ammonia soluble salt selected from the group consisting of copper borate, zinc borate or mixtures thereof, and copper chromate, zinc chromate or mixtures thereof;
and (iv) sufficient aqueous ammonia, in a concentration of 1 to 28% by weight NH3 to solubilize said salt (ii).

4. The thickened ammoniacal wood treating composition of claim 1 wherein the preservative component of said composition contains:
(A)(iii) an ammonia dispersible organometallic compound selected from the group consisting of copper naphthenate, zinc naphthenate or mixtures thereof; copper-8-quinolinolate, zinc-8-quinolinolate or mixtures thereof;
or tributyltin oxide;
and (iv) sufficient aqueous ammonia, in a concentra-tion of 1 to 28% by weight NH3 to disperse said compound (iii).

5. The thickened ammoniacal wood treating composition of claim 1 including therein an acrylic resin as a water repellency improving agent.

6. The thickened ammoniacal wood treating composition of claim l including zinc thiocyanate, copper thiocyanate or mixtures thereof to increase toxicity.

7. The thickened ammoniacal wood treating composition of claims 2, 3 or 4 wherein said thickener comprises a metallic soap.

8. The thickened ammoniacal wood treating composition of claims 2, 3 or 4 wherein said thickener comprises asbestos screenings, natural serpentine fibrous fragment or mica flakes.

9. The thickened ammoniacal wood treating composition of claims 2,3, or 4 wherein said thickener comprises a petroleum fraction selected from oil and greases with one of asbestos screenings; natural serpentine fibrous fragments;
and mica flakes.

10. The thickened ammonical wood treating composition of claims 2, 3 or 4 wherein said thickener comprises adipic acid, a petroleum fraction selected from oils and greases with one of asbestos screenings; natural serpentine fibrous fractions; and mica flakes.

11. The thickened ammoniacal wood treating composition of claim l wherein the preservative component includes 0.1 to 4% by weight of at least one of copper arsenate, zinc arsenate, copper arsenite and zinc arsenite (as Zn or Cu or Zn + Cu metal) of the total aqueous solution; 0.15 to 10%
by weight of the total aqueous solution of a carbonate or a bicarbonate; and from 15 - 26% ammonia.

12. The thickened ammoniacal wood treating composition of claims 2, 3, or 4 wherein the ratio of active preserva-tive/ammonia/water in the preservative component (A) is 20-40/15-25/65-35.

13. The thickened ammoniacal wood treating composition of claims 2, 3, or 4 wherein the ratio of preservative component (A)/thickener component (B) is 31-85/69-15.

14. The thickened ammoniacal wood treating composition of claim 1 wherein the composition is selected from one of the following:
(i) an ammoniacal solution of copper arsenate as the preservative and zinc stearate as the thickener;
(ii) an ammoniacal solution of copper arsenate as the preservative and stearic acid as the thickener;
(iii) an ammoniacal solution of copper arsenate as the preservative and lauric acid as the thickener;
(iv) an ammoniacal solution of copper arsenate as the preservative and asbestos screenings as the thickener;
(v) an ammoniacal solution of copper arsenate as the preservative and a mastic of adipic acid and asbestos screenings as the thickener;
(vi) an ammoniacal solution of copper arsenate as the preservative and a mastic of a petroleum grease and asbestos screenings as the thickener;
(vii) an ammoniacal solution of copper arsenate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener;
(viii) an ammoniacal solution of copper chromate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener;
(ix) an ammoniacal solution of copper metaborate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener;

(x) an ammoniacal solution of copper arsenite as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener;
(xi) an ammoniacal solution of zinc arsenate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener;
(xii) an ammoniacal solution of zinc arsenate and copper arsenate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener;
(xiii) an ammoniacal solution of copper borate as the preservative and zinc stearate as the thickener;
(xiv) an ammoniacal solution of copper naphthenate as the preservative and a mastic of a petroleum grease and natural serpentine fibrous fragments as the thickener;
(xv) an ammoniacal solution of copper naphthenate as the preservative and a mastic of a petroleum grease and asbestos fibers as the thickener;
(xvi) an ammoniacal solution of copper borate as the preservative and a mastic of natural serpentine fibrous fragments and a petroleum grease as the thickener;
(xvii) an ammoniacal solution of copper ammonium arsenate as the preservative and a mastic of natural serpentine fibrous fragements and a petroleum grease as the thickener;
(xviii) an ammoniacal solution of zinc ammonium arsenate as the preservative and a mastic of natural serpentine fibrous fragments and a petroleum grease as the thickener.

15. The wood treating composition of claim 1 including sufficient thickener (B) to provide a composition for dip treatment having a viscosity of 30 - 120 poises.

16. The wood treating composition of claim 1 including sufficient thickener (B) to provide a composition for brush, roller or trowel treatment having a viscosity greater than 120 poises.

17. The wood treating composition of claim 1 including sufficient thickener (B) to provide a composition for brush, roller or trowel treatment having a viscosity of 250-800 poises.

18. The wood treating composition of claim 1 including sufficient thickener (B) to provide a composition for trowelling which does not flow spontaneously but is thixotropic.

19. The method of preserving wooden poles which comprises the steps of:
(a) applying a coating thereto of the composition of claim 15 to give a covered layer thereby to provide a substantially uniform layer which is at least 1/8" thick;
(b) providing a substantially ammonia impervious enclosed atmosphere around such coated wooden poles for a time sufficient to permit penetration into said poles;
and (c) removing the enclosure providing said ammonia impervious enclosed atmosphere, thereby to permit volatile material to escape and provide a preservative treated wooden pole.

20. The method of preserving wooden poles which comprises the steps of:
(a) applying a coating thereto of the composition of claim 16 to give a covered layer thereby to provide a substantially uniform layer of at least 1/8" thick;
(b) providing a substantially ammonia impervious enclosed atmosphere around such wooden poles for a time sufficient to permit penetration into said poles;
and (c) removing the enclosure providing said ammonia impervious enclosed atmosphere, thereby to permit volatile material to escape and provide a preservative treated wooden pole.

21. The method of claims 19 and 20 wherein the ammonia impervious enclosed atmosphere is provided by a polyethylene sheet enclosure.

22. The method of prolonging the service life of wooden poles, which comprises the steps of: applying a thickened ammonia composition as claimed in claim 15 to a preselected groundline area of a wooden pole to provide a substantially uniform coating thereto; and applying a substantially ammonia impervious and water-impervious bandage including means for sealing such bandage around its edges to said coated groundline area of said wooden pole, said bandage providing enforced contact between the wooden pole and said coating.

23. The method of prolonging the service life of wooden poles, which comprises the steps of : applying a thickened ammonia composition as claimed in claim 16 to a preselected groundline area of a wooden pole to provide a substantially uniform coating thereto; and applying a substantially ammonia-impervious and water-impervious bandage including means for sealing such bandage around its edges to the coated groundline area of said wooden pole, said bandage providing enforced contact between the wooden pole and said coating.

24. The method of claims 22 or 23 wherein the bandage is formed of polyethylene tape.