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WO2004011391A1 - Materiaux de construction impermeabilisants renfermant des esters a haut poids moleculare - Google Patents

Materiaux de construction impermeabilisants renfermant des esters a haut poids moleculare Download PDF

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Publication number
WO2004011391A1
WO2004011391A1 PCT/AU2003/000963 AU0300963W WO2004011391A1 WO 2004011391 A1 WO2004011391 A1 WO 2004011391A1 AU 0300963 W AU0300963 W AU 0300963W WO 2004011391 A1 WO2004011391 A1 WO 2004011391A1
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WO
WIPO (PCT)
Prior art keywords
waterproofing
repelling
emulsion
water
wool grease
Prior art date
Application number
PCT/AU2003/000963
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English (en)
Other versions
WO2004011391A8 (fr
Inventor
Anthony Allen Pynsent
Michael Susic
Original Assignee
Cooee Biosciences Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2002950460A external-priority patent/AU2002950460A0/en
Priority claimed from AU2002950459A external-priority patent/AU2002950459A0/en
Priority claimed from AU2003900472A external-priority patent/AU2003900472A0/en
Priority claimed from AU2003902375A external-priority patent/AU2003902375A0/en
Application filed by Cooee Biosciences Limited filed Critical Cooee Biosciences Limited
Priority to AU2003281673A priority Critical patent/AU2003281673A1/en
Publication of WO2004011391A1 publication Critical patent/WO2004011391A1/fr
Publication of WO2004011391A8 publication Critical patent/WO2004011391A8/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/47—Oils, fats or waxes natural resins
    • C04B41/474—Natural resins, e.g. rosin
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/06—Waxes
    • 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
    • B27K2240/00—Purpose of the treatment
    • B27K2240/70—Hydrophobation treatment
    • 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
    • B27K3/34—Organic impregnating agents
    • 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
    • B27K3/34—Organic impregnating agents
    • B27K3/36—Aliphatic compounds
    • 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
    • B27K3/34—Organic impregnating agents
    • B27K3/50—Mixtures of different organic impregnating agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials

Definitions

  • Wool grease is relatively stable; it does not go rancid and therefore is useful for products that must be stored; is tacky and adheres to a range of surfaces; has no tendency to dry, so it is invaluable where prolonged plasticity is required; and does not crystallize but rather hinders the crystallization of waxes with which it is blended, making it ideal for a number of end uses.
  • Road construction involves the use of road base aggregates and the like to form a foundation for the upper bitumen layer on surfaced roads. Both surfaced and unsurfaced roads are subject to erosion and break down from the effects of water, particularly rain. Rain or water typically ingress into road base layers by seepage through the porous bitumen layer or by capillary action through the shoulders of the road.
  • Partial stabilization of particulate matter such as road base aggregates and the like has been achieved through the addition of binders, such as calcium lignosulfonate.
  • binders such as calcium lignosulfonate.
  • These lignosulfonates are typically water-soluble and are leached from unsurfaced roads during rain episodes. The leached product is brown in color and very unsightly.
  • the binding properties are removed and the road surface becomes subject to the usual problems caused by water.
  • US patent 4,666,522 describes the use of lignosulfonates as binders for coal, road surfaces, animal feeds and the like. The formulation described in US patent 4,666,522 has 1-50 parts hydrophobe to 100 parts lignosulfonate.
  • hydrophobes such as waxes, plant oils and fats, including animal and plant fatty acids.
  • US patent 4,666,522 only teaches the use of such a composition for binding particulate matter, which is due to the known binding action of lignosulfonates. There is no teaching of waterproofing these materials or the specific use of wool grease.
  • US patent 561 ,266 uses insoluble calcium or aluminum salts of fatty acids treated with mineral based oils/waxes; lanolin; naphthalene; stearic acid; palmitic acid or aliphatic alcohols with a flocculent such as calcium hydroxide or aluminum sulfate to provide a water repelling flexible film for use in airfield construction.
  • US patent 575,479 describes the use of ammonium salts of waxes, resins or fatty acids (oleic, stearic, and palmitic) and rendering them insoluble with a multivalent metal salt such as aluminum, iron, copper, and chromium to prevent them from being leached from road bases and the like.
  • US patent 605,057 uses a combination of wool grease, soap of rosin acids and a hydrophobic substance such as bitumen, a heavy metal (litharge) and a filler to create a waterproof plastic compound used in construction.
  • a hydrophobic substance such as bitumen, a heavy metal (litharge) and a filler.
  • the use of soaps does not render reliable stabilization as they break down and leach from the soil, and their effectiveness is short lived.
  • Excess trivalent metal salt is required to react with the soaps applied to the soil, and the trivalent metal salts are usually soluble and toxic. Any excess is leached to the environment and has detrimental effects on the ecosystems that they enter.
  • the invention resides in a waterproofing or repelling agent comprising; naturally-occurring high molecular weight esters, selected from the group consisting of wool grease, bees wax, carnauba wax, spermaceti wax and the like; a carboxylic acid; and a hydrocarbon solvent.
  • the hydrocarbon solvent is selected from D-60 (e.g. Exxsol D-60, Trade Mark), n-decane, methoxy propoxy propanol, cineole
  • hydrocarbon solvent is D-60.
  • the carboxylic acid is selected from straight chain or branched fatty acids, tertiary carboxylic acids produced by a Koch reaction of olefins and carbon monoxide, or naphthenic carboxylic acids.
  • the straight and branched chain fatty acids may be selected from palmitic acid, stearic acid, isopalmitic acid, isostearic acid, palmitoleic acid, oleic acid or myristic acids.
  • the naphthenic carboxylic acids are preferably obtained from crude oil and may include 2-naphthoic acid. More preferably the carboxylic acid is a straight chain fatty acid such as stearic acid.
  • the waterproofing or repelling agent comprises:
  • the water proofing or repelling agent comprises: 30-70% (w/v) wool grease; and
  • the waterproofing or repelling agent may be added to an aqueous solution of alkali hydroxide, comprising 1 part alkali hydroxide in 5,000 to 10,000 parts water, to form a waterproofing or repelling emulsion.
  • the alkali hydroxide is selected from sodium or potassium hydroxide. More preferably the alkali hydroxide is sodium hydroxide.
  • the waterproofing or repelling emulsion may be diluted to comprise
  • the water proofing or repelling agent may further comprise binders, such as lignosulfonate or bitumen; preservatives and/or termite repellents, such as quaternary ammonium compounds, benzalkonium lignosulfonates and benzalkonium lauryl sulfates.
  • binders such as lignosulfonate or bitumen; preservatives and/or termite repellents, such as quaternary ammonium compounds, benzalkonium lignosulfonates and benzalkonium lauryl sulfates.
  • the binder is calcium or sodium lignosulfonate.
  • the invention provides a method of producing waterproofing or repelling agent comprising naturally occurring high molecular weight esters, selected from the group consisting of wool grease, bees wax, carnauba wax, spermaceti wax and the like; comprising the step of; forming a solution of naturally occurring high molecular weight esters by mixing said high molecular weight ester and a carboxylic acid with a hydrocarbon solvent and heating to temperatures greater than 50°C.
  • the solution of high molecular weight ester is formed by heating between 60°C to 80°C.
  • the method of producing a waterproofing or repelling agent may further comprise the steps of; adding a solution of naturally occurring high molecular weight ester to an aqueous solution of alkali hydroxide, comprising 1 part alkali hydroxide in 5,000-25,000 parts of water; and agitating to form a stable
  • W/O/W emulsion which may also be in equilibrium with an O/W emulsion.
  • the waterproofing agent or emulsion further comprises high molecular weight waxy hydrocarbons; binding agents, selected from lignosulfonate and salts thereof, and bitumen, and/or preservatives or termite repellents, selected from quaternary ammonium compounds, quaternary ammonium lignosulfonates or quaternary ammonium lauryl sulfates.
  • binding agents selected from lignosulfonate and salts thereof, and bitumen, and/or preservatives or termite repellents, selected from quaternary ammonium compounds, quaternary ammonium lignosulfonates or quaternary ammonium lauryl sulfates.
  • the high molecular weight waxy hydrocarbon is microcrystalline wax.
  • the waterproofing agent comprises 4-12% (w/v) of microcrystalline wax per volume of hydrocarbon solvent.
  • the waterproofing or repelling agent or emulsion may be used to waterproof porous building materials, such as timber, concrete, and the like; provide water repelling properties to road base to assist in the stabilization; or preserving timber when the emulsion includes one or more preservative and/or termite repellent agents.
  • the invention provides a method of waterproofing or water repelling in road construction comprising the steps of; applying the said waterproofing agent or emulsion of high molecular weight esters to the surface of particulate material and distributing the waterproofing agent or emulsion throughout an upper layer of the particulate material; and compressing the particulate material to form a road base.
  • the particulate material may include crusher dust, aggregate, decomposed granite and laterite soils, crushed shale, corona, and the like.
  • FIG 1 is a graph of the time taken for water to ingress into timber treated with different concentrations of wool grease emulsions
  • FIG 2 is a graph of the change in area of ingressing water, which is inversely proportional to the ingression time, on a wooden surface painted with an inexpensive acrylic water based paint as a function of the concentration of wool grease added to the paint;
  • FIG 3 is a graph of time taken for water to ingress into treated crusher dust as a function of crusher dust particle size;
  • FIG 4 is a computer generated graph showing the rainfall absorbed by treated crusher dust as a function of waterproofing agent concentration;
  • FIG 5 is a computer generated graph showing the amount of rainfall absorbed by treated (1.5% wool grease) and untreated crusher dust as a function of rainfall intensity;
  • FIG 6 is a graph of water ingression and evaporation of a laterite soil as a function of waterproofing agent concentration;
  • FIG 7 is a graph of the time taken for a crusher dust mold (60 mm diameter x 5 mm thick) to totally disintegrate under water as a function of waterproofing agent.
  • DETAILED DESCRIPTION OF THE INVENTION For ease of description
  • the waterproofing agent is formed using one of the following processes.
  • Wool grease and stearic acid are dissolved in a hydrocarbon solvent, preferably D-60, by heating to temperatures greater than 50°C, preferably 60°C, and mixing thoroughly.
  • D-60 is a proprietary paraffinic, dearomatized solvent with a boiling point of 180°C, similar to n-decane. It was selected as it is readily available, inexpensive, and environmentally friendly.
  • the stearic acid is required to fortify the wool grease/D-60 mixture.
  • the concentration of wool grease is typically between 30-70% (w/v) of D-60, and the concentration of stearic acid is typically between 1- 5% (w/v) of D-60. At higher concentrations of wool grease in D-60 a gel is formed whilst at lower concentrations in D-60 a solution is formed.
  • Wool grease, stearic acid and microcrystalline wax are dissolved in a hydrocarbon solvent, preferably D-60, by heating to temperatures greater than 70°C, preferably 80°C, and mixing thoroughly.
  • the concentration of wool grease is typically between 40-60% (w/v) of D-60
  • the concentration of stearic acid is typically between 1-5% (w/v) of D-60
  • the concentration of microcrystalline wax is typically between 4-12% (w/v) of D-60.
  • the wool grease, stearic acid and microcrystalline wax are dissolved in a hydrocarbon solvent, preferably D-60, by heating to temperatures greater than 70°C, preferably 80°C, and mixing thoroughly.
  • the concentration of wool grease is typically between 8-12% (w/v) of D-60
  • the concentration of stearic acid is typically between 1-2% (w/v) of D-60
  • the concentration of microcrystalline wax is typically between 4-6% (w/v) of D-60.
  • hydrophobic solvents such as kerosene, diesel, paraffinic solvents, methoxy propoxy propanol, cineole (eucalyptus oil), d-limonene, and turpentines may be used to form a solution of wool grease and stearic acid.
  • the solution of A above may be added into water containing sodium hydroxide to form a stable emulsion.
  • Sodium hydroxide is dissolved in water at a ratio of between 1 part sodium hydroxide to 5,000 - 25,000 parts water.
  • the solution of A above is then added to the water containing sodium hydroxide and agitated, either by pumping, stirring, or air agitation to form an O ⁇ /V— W/O/W equilibrium mixture containing approximately 5-12% (w/v) of wool grease.
  • the emulsion pH is between 8 and 8.5.
  • Commercial stearic acid (a mixture of stearic and palmitic acids) is added to give a concentration range of 0.15-0.25% (w/v) in the emulsion.
  • the emulsion formed by this process has been found to be stable for several hours without agitation, and stable indefinitely with gentle agitation.
  • the stearic acid facilitates the formation of a stable W/O ⁇ V emulsion at low concentrations of wool grease, such as 1-5% (w/v) wool grease. Above this concentration range there are usually enough fatty acids present in commercial wool grease to readily facilitate emulsion formation. However, above about 5% (w/v) wool grease in the emulsion the amount of sodium hydroxide must be 1 part to 5,000 parts water to prevent the W/O ⁇ /V emulsion from forming a W/O emulsion that is not water miscible.
  • the stearic acid or naturally present fatty acids are converted to an alkali metal salt, preferably a sodium salt, during emulsion formation due to the presence of the sodium hydroxide in the water.
  • stearic, palmitic, myristic or similar acids may be used to facilitate the formation of a stable emulsion. It has been found that only the sodium or potassium salts of the fatty acids have substantial W/O/W and O/W emulsifying power. Sodium bicarbonate was found to be required in high concentration which resulted in a "salting out” effect occurring, converting the W/O ⁇ /V and O ⁇ /V emulsions to a W/O emulsion, which is not miscible with water. However, sodium hydroxide was found to be very effective in forming the sodium salt of stearic acid and stabilizing the resulting emulsion.
  • the waterproofing agent may further comprise small amounts of microcrystalline wax (or any other similar wax) to form a harder, less greasy surface coating, and as a side benefit it also contributes to waterproofing. This is for both solution and emulsion application.
  • the microcrystalline waxes are not completely soluble in any known solvent, but ultimately form a gel when heated above their melting point and mixed with any of the solvents listed above and allowed to cool. This gel can then be added to the hot or cool wool grease solution, usually in the range of 1-2 parts microcrystalline wax to 10 parts wool grease. However, in the above examples the microcrystalline wax is added directly to the hot mixture.
  • Palmitic acid, stearic acid and commercially available stearic acid where found to stabilize or fortify the W/O ⁇ /V and O ⁇ /V wool grease emulsions to the same level.
  • a wool grease solution of Example 1 is generally restricted to low volume applications such as hardwood timber, paint, and concrete blocks due to its gel like consistency and cost restraints resulting from the high volume of D-60 that would be required.
  • the wool grease emulsion of Example 1 is cost effective for high volume applications such as waterproofing larger areas of timber, particularly softwood timbers.
  • Computer-aided modeling eliminates the need for expensive pre- trial field tests and provides an indication as to the waterproofing properties of the emulsion and/or solution of the invention when applied to various materials.
  • This equation can be modified to test waterproofing ability.
  • the time taken for a certain volume of water to ingress the substance is given by the parameter t.
  • the model is valid for an unsaturated system where the water volume is far less than the total pore volume. All the individual pores can be summed to approximate a single theoretical capillary. As water ingresses this theoretical capillary, its length will shorten until it is zero (full of water), assuming that water does not leave the material. Since the change in theoretical capillary length cannot be measured, the length is kept approximately constant by using a small volume of water compared to its total capacity.
  • the theoretical capillary volume is measured by immersing a mold of the substance in a container of water and allowing it to absorb all the water that it can.
  • the ingression time against water volume can be readily measured and the data analyzed by linear regression analysis.
  • An important measurement is to determine the waterproofing ability of a waterproofing agent that has been added to the material under test.
  • Pine wood was painted with patches of emulsions of varying wool grease concentrations applied at 120 mL/ m 2 and dried for 3 days at 22°C. Water (20 ⁇ L) was applied to each patch and allowed to ingress and/or evaporate. This is demonstrated in FIG. 1, and modeling the data gives total waterproofing at a wool grease concentration of 10.0%(w/v), and the time taken for evaporation is 5800 sec.
  • A (a - b i) 4 + c
  • the above model assumed a constant particle size, which is not necessarily the case with road base aggregate.
  • FIG. 4 demonstrates the amount of rainfall absorbed by crusher dust containing various concentrations of wool grease of Example 1. With just small additions of wool grease, much of the rainfall is repelled, thereby maintaining the moisture content and optimum binding and strength of the crusher dust.
  • FIG. 5 demonstrates the difference in rainfall absorbed by untreated and treated (1.5% w/w wool grease) crusher dust. At low rainfall the water is allowed to enter the crusher dust (maintaining its optimum moisture content), but as the rainfall becomes heavier it is repelled, which protects the crusher dust. This means that an automatic protection process is built into the road base, vital for areas of heavy rainfall such as the tropics.
  • the Poiseuille equation may be modified to model water ingression into road base materials and also allowing for water evaporation. For some materials that may be used for road bases, water evaporation dominates over water ingression.
  • the value of (a/b) 2 gives the concentration of water repelling agent at which total waterproofing is achieved, and the value of c is the evaporation time at total waterproofing.
  • FIG. 6 demonstrates this for a laterite soil, and total waterproofing is achieved at 0.91% (w/w) of waterproofing agent, and the evaporation time for 20 ⁇ L of water is 4490 sec.
  • Example 1 Paint, spraying, dipping, etc. with waterproofing agent of Example 1 can readily waterproof hardwood and plywood. Microcrystalline wax is added to the solution to give a harder, less greasy surface. Typical concentrations and application rates are: Wool grease 5% (w/v) Microcrystalline wax 0.5% (w/v) Application rate 200 mL/m 2
  • the waterproofing agent can also be applied by vacuum or pressure ingression, or as is more common, sequentially by both techniques. However, the product should be diluted about 100x with solvent to obtain more efficient ingression and cover that is not excessive. 2.1.2 Softwood and Hardwood
  • the emulsion has been found to give superior waterproofing properties compared to the wool grease dissolved in D-60, especially when applied to softwood timbers. It appears initially contradictory that a water-based emulsion is superior to an organic solvent for waterproofing timber. Without wanting to be bound to a theory that the inventors hypothesize, the more favorable results with the water based emulsion may be due to the cellulose fibers being hollow and they and/or their gates collapsing in the presence of an organic solvent, which would result in larger voids within the timber structure.
  • the waterproofing agent can also be applied by vacuum or pressure ingression, or as is more common, sequentially by both techniques. However, the product should be diluted about 20-1 OOx with water to obtain more efficient ingression and cover that is not excessive.
  • a surfactant such as sodium lauryl sulfate needs to be added at about 0.1 % to maintain emulsion stability.
  • Example 2.4 Application to Road Base, Crusher Dust or Aggregate
  • solution in a hydrocarbon or similar solvent can be used, it is generally preferable to use the emulsion of Example 1 above for high volume applications such as waterproofing road base aggregates, crusher dust, decomposed granite and laterite soils, crushed shale, and corona (crushed coral) for roads, piles of dirt, gravel, coal, ash, etc.
  • Road base materials are often expensive, high quality aggregates.
  • Crusher dust is a plentiful and inexpensive material that under normal conditions is useless for road base construction because the ingression of water rapidly destroys its strength and it falls apart.
  • the application of the emulsions of Example 1 to crusher dust results in water being repelled and optimum moisture content can be maintained within the crusher dust structure.
  • the crusher dust becomes a high-quality, inexpensive, road base material.
  • the invention can use any soil, rock, aggregate, etc. as long as there are some small particles and shrinkage on drying is not a problem.
  • the emulsions of Example 1 are delivered to the road base material by gravity feed or pumping through a spray device normally found on water trucks used for road construction.
  • the road base is then bladed or mixed by other means to obtain an even spread of the product in the road base material.
  • Another means of applying the product to road base material or aggregates is to spray it onto the material on a conveyor belt or similar device, and then pugging or mixing the material by suitable means, after which the final product is delivered to the construction site.
  • lignosulfonate or other known binders to the emulsion to provide additional binding properties.
  • the lignosulfonate in no way adds to the waterproofing properties of the wool grease.
  • the use of the waterproofing agent has been found to prevent the leaching of any water-soluble binders such as lignosulfonate by rain or ground water when used in road base type applications.
  • Waterproofing Tests - Crusher Dust and Laterite Soils 50 g of crusher dust or laterite soil was mixed with water to give an added moisture concentration of 4% (w/w), complementing the approximately 2% (w/w) moisture already present.
  • a wool grease emulsion was prepared in accordance with Example 1 and added to the moistened crusher dust in varying amounts. The application rate of the wool grease emulsion was around 1 L/m 2 surface area of crusher dust. However, levels from 0.5-5 L/m 2 surface area can be used.
  • the treated crusher dust was then compacted into molds of 60 mm diameter by 5 mm thick by hitting the mixture with a bolt within the confines of an egg ring.
  • the resulting "biscuits" mimicked a road base and were allowed to dry (22 & 38°C) for appropriate times.
  • Fig. 7 demonstrates the enormous difference between treated and untreated crusher dust. Disintegration time without added waterproofing agent was 3 seconds, but with 1% (w/w) added waterproofing agent the time was 582 seconds, a 194-fold increase in resistance to disintegration. Coloring Crusher Dust
  • Iron oxide can be purchased in many other colors, such a green, blue and yellow, should other colors be desired.
  • the wool grease emulsions of Example 1 above were applied in a number of outside locations to assess its effectiveness in assisting in the stabilization of road bases.
  • calcium lignosulfonate was added to the emulsion to act as a binder.
  • the binder was used in a 50% (w/v) aqueous solution.
  • the wool grease emulsion of Example 1 is referred to as "WaterBloc" and the calcium lignosulfonate is simply referred to as "binder".
  • Location B was an all weather sand horse training track. WaterBloc and binder were added to 1800 tonnes of 2.5 grade road base at the quarry, transported to the track, spread over the 1400 metre area, and compacted with a multi-tyre roller. 150mm of sand was put over the top when dry.
  • Section One was a slope, which was treated with WaterBloc only. Minimal erosion after 6 months was observed. This is considered to be a good result due to the slope of the road. This section was subsequently treated with WaterBloc and binder in October 2002. No wear or erosion occurred despite considerable rainfall.
  • Section Two was treated with WaterBloc and binder and experienced minimal erosion. No maintenance was needed.
  • Location E was completed in two unsealed sections. The first section was 1 km over a crest in the hill with an S bend and was treated with WaterBloc only. The drought meant very little rain on the road and it dusted up fairly quickly on the S bend. Results showed that WaterBloc alone does not add any shear strength to the roadbase.
  • the first section was retreated with WaterBloc and binder mixed into the top 50mm instead of 100mm, thus doubling the concentration of the waterproofing emulsion without extra cost.
  • This section after re- treatment received some heavy rains and has experienced no erosion to date.
  • the second section was 0.5 kilometres down the slope of the hill, treated with WaterBloc and binder. This section has performed very well and has not needed to be graded.
  • Laterite material was treated with WaterBloc before applying a 2 coat seal. No erosion or wear was observed after a major wet season.
  • a section of trial was treated with WaterBloc and binder.
  • the trial was located in a position where trucks turn sharply.
  • the treated surface was found to dust up. Additional binder would be required to withstand such shear forces and wear. It is suggested that in a similar location the binder volume be increased 3 times.
  • Laterite type soil under heavy transport This trial was done with WaterBloc and binder. Total success, no wear or erosion at this point.
  • the waterproofing agent of the invention when applied as a surface coat to timber or similar materials has been found to have maximum surface ingression; provide a non-greasy surface and high waterproofing ability when compared to the current commercially available solvent based wool grease formulations.
  • Surface ingression has been found to be on average 3mm for softwood.
  • the treated surface is non-greasy in nature when the wool grease concentration in the emulsion is at or below 8% (w/v).
  • the waterproofing ability of the wool grease emulsion is high at concentrations above 2% (w/v) wool grease.
  • the optimum application rate of a 5-8% (w/v) wool grease emulsion is 1 L/ m 2 for softwood and 1 L/ 20 m 2 for hardwood.
  • wool grease emulsions of the invention has been found to protect timber against termite infestation.
  • Termites infest timber that is infected with an active microbial growth, such as dry rot. Microbial colonies containing fungal spores and/or bacteria develop, or become active, when timber is moist or wet for an extended period of time. Termites have been known to bore through plastic conduits, lead sheeting, PVC coatings on wiring and healthy or green timber to reach microbe infected timber. Whilst the termites may make their way through PVC tubing, coatings and the like, it is believed that they do not ingest these materials.
  • Termite prevention is preferably attained through the application of a wool grease emulsion containing greater than 7.5% (w/v) wool grease. More suitably the wool grease emulsion contains greater than 10% (w/v) wool grease.
  • the wool grease emulsion may be painted or sprayed onto the timber.
  • the timber may be pressure treated with a wool grease emulsion.
  • the waterproofing or repelling agent of the invention has been found to provide anti-termite activity to timber, either on its own or in combination with other anti-termite agents.
  • Pieces of pine wood (40x20x10 mm) were painted with the O ⁇ /V emulsion, of Example 1 , containing 10%, 5%, 2.5%, and 1.2% (w/v) wool grease at the rate of 1 L/ 6 m 2 and allowed to dry overnight. Control samples of timber were painted with water and treated in the same manner.
  • timber is treated with an emulsion comprising 12% (w/v) of wool grease for effective waterproofing and termite prevention.
  • the waterproofing properties of the wool grease emulsion prevent the formation of bacterial and/or fungal infections in treated timber and as a result render the treated timber somewhat, although not totally, unappealing to termites. It is likely that the digestive flora balance of a termite is affected or interfered with by the presence or digestion of the timber treated with a wool grease emulsion. An imbalance in a termite's digestive bacterial flora may lead to death, thus the termite endeavors to maintain the symbiotic relationship with its digestive flora by avoiding timber treated with wool grease. If resistance to termite infestation is a function of taste or smell the wool grease emulsion may further comprise lignosulfonates, bitumen and the like.
  • wool grease emulsion may further comprise antimicrobial treatments such as quaternary ammonium compounds or fungicides, to further control the development of fungal infections in timber, such as illustrated in the following example.
  • antimicrobial treatments such as quaternary ammonium compounds or fungicides
  • Wood blocks of Pinus radiata (50 x 40 x 40 mm, with the grain in the 50 mm direction) were treated with quaternary ammonium lignosulfonates with and without wool grease emulsion treatment, and solvent controls of both ethanol and water.
  • the timber samples treated with a range of formulations were placed within PVC tube containers, and inserted into aboveground mound colonies of Coptotermes species.
  • Table 2 summarizes the location of treated timber within the termite mound and the treatment used on the respective sample.
  • Base Wood block nearest cap with wire-vent hole.
  • Randomized treated wood blocks were placed within each of five tube containers (300 x 90 mm), and inserted into aboveground mound colonies of C. lacteus. Termites were allowed to forage into the tube containers for 28 days. After this period, all the tube containers were withdrawn from the mound colonies and the feeding response of the natural populations of C. lacteus towards the various treated wood blocks was measured using a simple objective rating system of attack and damage, as outlined in Table 3 above.
  • Table 7 summarizes the results. All the solvent control blocks were severely damaged at every mound. Blocks treated with two coats of wool grease emulsion were less palatable to the termites than to those treated with a single coat. Though the specimens were limited, termites were not completely deterred by blocks treated with the anti-microbial treatments alone at the stated concentrations.
  • Blocks treated with the highest loadings of anti-microbial and one coat of wool grease emulsion showed mostly termite visits and only a single termite nibble.
  • the anomalous responses of the termites to the 0.5 and 1.0% anti-microbial blocks are considered to be due to differences in ingression rates.
  • the wood blocks treated with a 1.5% solution of antimicrobial and wool grease emulsion showed the lowest feeding response after the 28 day test period.
  • Example 5 The process of Example 5 was repeated using benzalkonium stearate (BSt), benzalkonium dodecyl (lauryl) sulfate (BDS) and benzalkonium lignosulfonate (BLS), but where they were used in combination with wool grease emulsions they were mixed with the emulsion rather than applied separately. Results are summarized below in Table 8. TABLE 8.
  • Wool grease emulsion is a W/O/W emulsion containing wool grease.
  • O ⁇ /V, W/O and O ⁇ //O emulsions comprising wool grease and bitumen are also useful for preserving timber against rot or fungi, termites, and against mechanical stress due to contraction and expansion. Mechanical stresses due to contraction and expansion appear to be prevented because water is prevented from ingressing into the treated timber and then evaporating.
  • An O ⁇ /V wool grease-bitumen emulsion may comprise 2-10% (w/v) wool grease and 1-20% (w/v) bitumen.
  • O ⁇ /V emulsions may also contain carboxylic acid, such as stearic acid, and microcrystalline waxes, such as paraffin.
  • a W/O wool grease-bitumen emulsion may comprise: 1-5% (w/v) wool grease; 5-15% (w/v) bitumen; 0-10% (w/v) microcrystalline wax; 60- 90% (v/v) D-60; and 2-20% (v/v) water.
  • O ⁇ /V/O wool grease- bitumen emulsion may comprise: 0.2-0.5% (w/v) wool grease; 0.2-0.5% (w/v) bitumen; 0-1 % (w/v) microcrystalline wax; 7-40% (v/v) D-60; and 55- 92% (v/v) water.
  • the O ⁇ /V emulsion is applied by diluting 3-5 times with water, and sprayed or painted onto timber at about 1 L/ 6 m 2 .
  • the W/O emulsion is applied by diluting 2-5 times with D-60, and sprayed or painted onto timber at about 1 L/ 6 m 2 .
  • the O ⁇ /V/O emulsion is applied undiluted at an application rate of about 1 L/ 2 m 2 . Drying times are 1-2 hrs.
  • Studies in which timber was painted with the emulsions and left in damp conditions and within termite nests showed no rotting and no termite attack, respectively, within two months. Untreated samples showed extensive rotting and termite attack, respectively, within two weeks.
  • Softwood samples treated with the wool grease emulsion of the invention under accelerated UV light conditions showed no deterioration in the waterproofing properties of the treated surface over a period of 1 , 2 & 6 months.
  • Softwood timber pieces were allowed to soak overnight in solutions of wool grease emulsions described above but containing 2% (w/v) benzalkonium lignosulfonate, 2% (w/v) benzalkonium lauryl sulfate, and 2% (w/v) benzalkonium 5-amino-2-naphthalene sulfonate, and allowed to dry for 3 days.
  • 2% (w/v) benzalkonium lignosulfonate 2% (w/v) benzalkonium lauryl sulfate
  • 2% (w/v) benzalkonium 5-amino-2-naphthalene sulfonate 2% (w/v) benzalkonium 5-amino-2-naphthalene sulfonate
  • Benzalkonium lignosulfonate can be added to the wool grease emulsions up to a concentration of 1.2% (w/v) without compromising emulsion stability. At this concentration, together with 7% (w/v) of the high molecular weight esters, the mixture becomes an effective antitermite/ antifungal product, and prevents mould and algal growth.
  • Benzalkonium lauryl sulfate is an antimicrobial, water resistant, wax-like compound that forms an emulsion and can be added at higher concentrations (up to about 10% (w/v)) to wool grease emulsions used for timber treatment.
  • the benzalkonium lauryl sulfate enhances the water repelling properties of the high molecular weight esters contained in the wool grease emulsions, and at 2% (w/v) provides antimicrobial properties, and the mixture strongly repels termites and prevents rot and mould from attacking timber.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

L'invention concerne un agent imperméabilisant ou hydrofuge comprenant des esters à haut poids moléculaire existant à l'état naturel, sélectionnés dans le groupe comprenant des graisses de suint, de la cire d'abeille, de la cire de carnauba, du blanc de baleine et analogues ; un acide carboxylique ; et un solvant hydrocarbure. L'agent imperméabilisant peut être utilisé sur des produits de construction poreux tels que bois d'oeuvre et maçonnerie. L'agent imperméabilisant peut également être utilisé pour rendre hydrophobes des couches de fondation en vue d'améliorer la stabilisation de couches de fondation formées de matériaux en particules. L'agent imperméabilisant peut également comprendre des agents de conservation ou des agents répulsifs des termites en vue d'améliorer la conservation des bois d'oeuvre.
PCT/AU2003/000963 2002-07-30 2003-07-30 Materiaux de construction impermeabilisants renfermant des esters a haut poids moleculare WO2004011391A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003281673A AU2003281673A1 (en) 2002-07-30 2003-07-30 Waterproofing construction materials with high molecular weight esters

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
AU2002950459 2002-07-30
AU2002950460A AU2002950460A0 (en) 2002-07-30 2002-07-30 Porous building and construction materials with high molecular weight esters
AU2002950459A AU2002950459A0 (en) 2002-07-30 2002-07-30 High molecular weight esters as water repelling agents in road construction
AU2002950460 2002-07-30
AU2003900472 2003-02-04
AU2003900472A AU2003900472A0 (en) 2003-02-04 2003-02-04 Porous building and construction materials with high molecular weight esters
AU2003902375A AU2003902375A0 (en) 2003-05-16 2003-05-16 Porous building and construction materials with high molecular weight esters
AU2003902375 2003-05-16

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007016725A1 (fr) * 2005-08-08 2007-02-15 Robert Churchill Hylands Protection semi-siccative et semi-solidifiante pour bois d’oeuvre et huile de paraffine protectrice presentant un bouclier resistant aux intemperies a base de lanoline (graisse pour laine de brebis)
FR2931093A1 (fr) * 2008-05-16 2009-11-20 Arc Nucleart Groupement D Inte Procede de sechage et de stabilisation du bois
US7658794B2 (en) 2000-03-14 2010-02-09 James Hardie Technology Limited Fiber cement building materials with low density additives
US7998571B2 (en) 2004-07-09 2011-08-16 James Hardie Technology Limited Composite cement article incorporating a powder coating and methods of making same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007115379A1 (fr) 2006-04-12 2007-10-18 James Hardie International Finance B.V. Element de construction renforce a surface etanche

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JPS546002A (en) * 1977-06-17 1979-01-17 Chuo Yuka Lithium soappbase lubricating grease compositions and production thereof
JPS5863769A (ja) * 1981-10-09 1983-04-15 Kao Corp 艶出し剤組成物
JPH10212445A (ja) * 1997-01-29 1998-08-11 Car Mate Mfg Co Ltd 塗装用保護はつ水剤組成物
DE19952563A1 (de) * 1999-11-01 2001-05-03 Romonta Gmbh Wachscompound

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Publication number Priority date Publication date Assignee Title
JPS546002A (en) * 1977-06-17 1979-01-17 Chuo Yuka Lithium soappbase lubricating grease compositions and production thereof
JPS5863769A (ja) * 1981-10-09 1983-04-15 Kao Corp 艶出し剤組成物
JPH10212445A (ja) * 1997-01-29 1998-08-11 Car Mate Mfg Co Ltd 塗装用保護はつ水剤組成物
DE19952563A1 (de) * 1999-11-01 2001-05-03 Romonta Gmbh Wachscompound

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Title
DATABASE WPI Derwent World Patents Index; Class E19, AN 1979-14896B/08 *
FURNITUREKNOWLEDGE.COM, 1999, Retrieved from the Internet <URL:http://www.furnitureknowledge.com/tiparkiv.htm> [retrieved on 200311] *
PATENT ABSTRACTS OF JAPAN *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7658794B2 (en) 2000-03-14 2010-02-09 James Hardie Technology Limited Fiber cement building materials with low density additives
US7727329B2 (en) 2000-03-14 2010-06-01 James Hardie Technology Limited Fiber cement building materials with low density additives
US8182606B2 (en) 2000-03-14 2012-05-22 James Hardie Technology Limited Fiber cement building materials with low density additives
US8603239B2 (en) 2000-03-14 2013-12-10 James Hardie Technology Limited Fiber cement building materials with low density additives
US7998571B2 (en) 2004-07-09 2011-08-16 James Hardie Technology Limited Composite cement article incorporating a powder coating and methods of making same
WO2007016725A1 (fr) * 2005-08-08 2007-02-15 Robert Churchill Hylands Protection semi-siccative et semi-solidifiante pour bois d’oeuvre et huile de paraffine protectrice presentant un bouclier resistant aux intemperies a base de lanoline (graisse pour laine de brebis)
FR2931093A1 (fr) * 2008-05-16 2009-11-20 Arc Nucleart Groupement D Inte Procede de sechage et de stabilisation du bois

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