EP1664230A2 - Matieres composites et particulaires hydrophobes et applications associees - Google Patents

Matieres composites et particulaires hydrophobes et applications associees

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Publication number
EP1664230A2
EP1664230A2 EP04744975A EP04744975A EP1664230A2 EP 1664230 A2 EP1664230 A2 EP 1664230A2 EP 04744975 A EP04744975 A EP 04744975A EP 04744975 A EP04744975 A EP 04744975A EP 1664230 A2 EP1664230 A2 EP 1664230A2
Authority
EP
European Patent Office
Prior art keywords
hydrophobic
free
particulates
aggregate
flowing
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP04744975A
Other languages
German (de)
English (en)
Other versions
EP1664230A4 (fr
Inventor
Zeev Birger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SEALSAND Inc
Original Assignee
Superseal Ltd
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 IL15743703A external-priority patent/IL157437A0/xx
Application filed by Superseal Ltd filed Critical Superseal Ltd
Publication of EP1664230A2 publication Critical patent/EP1664230A2/fr
Publication of EP1664230A4 publication Critical patent/EP1664230A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/30—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic using agents to prevent the granules sticking together; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/12—Multiple coating or impregnating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3072—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/65—Water proofers or repellants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to hydrophobic composites, particulates and free- flowing aggregates, methods of producing same, and applications thereof. More particularly, the present invention relates to hydrophobic composites having a core material coated by a hydrophobic powder having an impure element pre-treated with a hydrophobic hydrocarbon, and optionally with additional coating agents, such that the resulting composites are characterized by superior water-repellency and durability, suitable for various applications.
  • the present invention further related to hydrophobic composites that are prepared in aqueous solutions. In many applications it is desired to prevent moisture from reaching critical regions using hydrophobic materials which repel water.
  • Moisture may percolate into the construction, either vertically, for example because of accumulation of water on roofs or floors of construction/foundations, or horizontally, by leakage of water through external walls of a building for example, because of extreme weather conditions.
  • a sever problem of horizontal leakage is in buried walls or portions thereof, where hydrostatic pressure generated by excess moisture in the surrounding soil pushing in on the outside of the foundation wall, significantly contributes to horizontal leakage.
  • the percolation of moisture through concrete walls is explained by the porosity of the concrete (about 12 % - 20 %), formed during the curing process when surplus water creates a network of interconnected capillaries, about 10-100 nm in diameter. As used herein, the term about refers to ⁇ 10 %.
  • the sand under the floor tiles becomes a thermal conductor, thus reducing any isolation pretended to be achieved in the design stages of the building.
  • an electrical heating system is constructed under the floor. The contact between these systems and the wet sand may cause a sever damage to the system, or, in extreme cases, even fire may occur.
  • all prior art methods are directed at positioning a waterproofing material such as a sealing sheet, a bituminous membrane or a solvent based elastomeric coat, under the bed sand supporting the floor tiles.
  • Radon is an invisible and odourless radioactive gas, produced by the decay of radioactive heavy metals uranium and thorium, dispersed throughout the Earth's crust.
  • the by-products of the radioactive decay of these metals are lighter radioactive heavy metals which also decay into lighter metals and so on.
  • the decay chain continuously produces radium, which decays into radon isotopes, mainly Radon-222 and Radon-220 (the latter also known as Thoron), where the Radon-222 isotope is the most common indoors radioactive gas.
  • Radon decay products are tiny radioactive solid particles which float in the air and, breathed by human, get trapped in the lungs, trachea and bronchi. Because of these decay products, the Radon, at the levels common in homes, is about 1,000 times more lethal than the safety limits on any other toxin or carcinogen. Being the heaviest known gas (nine times heavier than air), the Radon gas naturally moves into the permeable soil and the gravel bed surrounding the foundations of the house and subsequently diffusively penetrates into the house through the above mentioned openings and pores in concrete. Radon is soluble in water and therefore carried to the vicinity of the house by underground streams, and further into the house by the percolation of water, e.g., through the concrete.
  • hydrophobic materials which repel water. Design considerations for hydrophobic materials depend on the application for which such materials are designated, and include water intrusion pressure, thickness, chemical compatibility, airflow, temperature compatibility and the like.
  • Water intrusion pressure is a measure of a critical pressure under which water are forced through the hydrophobic material. Chemical compatibility is important in applications where the hydrophobic material comes in contact with corrosive material
  • Another structure for which wate ⁇ roof ⁇ ng is required is a water reservoir, where the base and the walls thereof need to be impermeable so as to prevent water from leaking out. The problem of leaking reservoir is crucial in arid regions where one desire to maintain the content of the reservoir for as much as time possible.
  • a typical reservoir is a flat area surrounded by a sloping embankment.
  • the sealing sheet tends to be damaged by hard objects, being in contact therewith either from above or from below.
  • the sealing sheets may be ruptured. Forth, forces induce earth movements or cracks formation (e.g., in a man made concrete reservoir) rupture the sealing sheets.
  • An additional limitation of prior art method is originated by colonies of insects and organisms present under the sealing sheets. In which case purification chemicals are required to purify the content of the reservoir. Wate ⁇ roofing is often required also in agriculture or gardening where irrigation is employed. When an area is artificially irrigated by water, only a relatively small portion of water reach the plants growing on the soil. Most of the water seeps through the earth or evaporates.
  • the need to save water is also related to other agricultural problems, such as salty soil and underground salty water.
  • other agricultural problems such as salty soil and underground salty water.
  • Design considerations for hydrophobic materials to be used for wate ⁇ roofing any of the above structures include water intrusion pressure, thickness, chemical compatibility, airflow, temperature compatibility and the like. Water intrusion pressure is a measure of a critical pressure under which water are forced through the hydrophobic material. Chemical compatibility is important in applications where the hydrophobic material comes in contact with corrosive material.
  • the oil absorbent compositions of the Tully et al. patent are obtained by treating a liquid absorbent material, which may be particulate, granular or fibrous in nature, with a colloidal metal or metalloid oxide which is chemically bonded to an organosilicon compound to render the metal or metalloid oxide hydrophobic.
  • the hydrophobic oxide-treated absorbent composition is contacted with the oil-contaminated water and selectively removes the oil therefrom.
  • hydrophobic composites having superior water repellency are obtainable by depositing on a particulate and granular core material an adherent first coat which comprises a film- forming polyurethane and asphalt, as an optional additive, and applying to the thus coated core material a second coat comprising a hydrophobic colloidal oxide such as, for example, hydrophobic fumed silica. Craig teaches that the adherent first coat should not exceed 1 weight percentage of the total dry aggregate weight while the second coat is between 0.025 and 0.25 weight percentage of this total weight. Further according to the teachings of Craig, hydrophobic composites prepared in this manner not only prevent water from adhering to the surfaces of the individual composite particles, but also from entering the interstitial spaces of the aggregates of the composites.
  • WO 03/044124 which is also inco ⁇ orated by reference as if fully set forth herein, also discloses a method of preparing hydrophobic aggregates, which is based on the teachings of Craig (U.S. Patent No. 4,474,852). According to the teachings of WO 03/044124, the hydrophobic aggregates disclosed in U.S. Patent No. 4,474,852 are not satisfactory as they do not withstand water pressure higher than 2-3 centimeters.
  • the method disclosed in WO 03/044124 includes depositing on a particulate or granulate core material an adherent first coat which comprises a film- forming agent such as polyurethane and optionally a gluing agent such as liquid asphalt, and applying to the thus coated core material a second coat which comprises a hydrophobic fumed silicate or any other superhydrophobic powder.
  • the adherent first coat constitutes about 1-2 weight percentages of the total dry aggregate weight while the second coat constitutes more than 5 weight percentages of this total weight.
  • such hydrophobic aggregate is capable of holding a water pressure of up to 20-30 cm.
  • WO 03/044124 teaches the use of superhydrophobic powders other than hydrophobic fumed silica, this reference neither specifies nor exemplifies such a superhydrophobic powder. This reference also fails to demonstrate any performance of the hydrophobic aggregates disclosed therein with regard to both, water repellency and its behavior under high water pressures. Furthermore, it is well known in the art that using such a large amount of hydrophobic fumed silica as the second coat, as taught by WO 03/044124, reduces the cost-effectiveness as well as the simplicity of the process.
  • hydrophobic fumed silica as well as other metal oxides treated with organosilicon compounds, such as those disclosed in the Craig patent, are characterized as acidic substances, aggregates coated by such materials are susceptible to reactions with alkaline reagents such as detergents. This feature limits the use of such aggregates in applications where detergents may be in contact with the hydrophobic aggregates, such as, for example, top-coatings of various surfaces.
  • US Patent 4,474,852 mentioned hereinabove describes several applications for its hydrophobic composites in wate ⁇ roofing applications.
  • a flood coat of asphalt sealer should first be applied over the surface, immediately after which a heavy coat of the hydrophobic composites may be sprayed over and rolled into the asphalt sealer, providing a watertight top coat.
  • the same top coating technique may be used in pothole repairs in roadways.
  • the composites may also be used as a substitute for common aggregate in asphalt roofing or shingles, or in built-up roofing. In such applications, the hydrophobic composites are effective in preventing water penetration and resulting damage caused by freeze-thaw cycles as well as dimensional changes due to wetting and drying.
  • US Patent 4,474,852 also claims utility as a top coat on paved surfaces, such as asphalt or concrete road surfaces or bridge decking, providing a water-tight finish, which substantially reduces freeze-thaw damage, and which is unaffected by salt compositions normally used for ice removal.
  • these hydrophobic composites may be applied to painted surfaces to provide a durable, wate ⁇ roof finish over wood, metal, concrete, stone, brick and certain synthetic substrates.
  • Such hydrophobic composites may also be blended with suitable binding agents to provide a water-repellent coat.
  • the hydrophobic composite of US Patent 4,474,852 may also be used as a wate ⁇ roofing agent in pavement construction, as a fill or bed material under concrete slabs or as a gravel fill or ballast for road beds or sidewalks.
  • free-flowing aggregate are made of extremely small particulates hence being easily carried in the wind and washed out by running water. Therefore, without specific and enabling instructions, it would be very difficult and probably not practical to use the hydrophobic aggregate in its flowing form.
  • hydrophobic composites do not result in satisfactory products and are limited by other parameters, such as, for example, cost effectiveness. There is thus a widely recognized need for, and it would be highly advantageous to have hydrophobic composites, particulates and free-flowing aggregates, methods of producing same and applications thereof, devoid the above limitations.
  • hydrophobic composite comprising a core material coated by a hydrophobic powder, the hydrophobic powder comprises at least one impure element having a hydrocarbon chain attached thereto.
  • the element is selected from the group consisting of a metallic element, a semi-metallic element and a transition metallic element.
  • the hydrophobic powder is bonded to the core material via an adherent layer.
  • the hydrophobic composite further comprising at least one additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • the coloring agent constitutes between about 0.1 and about 2 weight percentages of the hydrophobic composite.
  • the UV resistant agent and the bleaching agent each constitutes between about 0.01 and about 2 weight percentages of the hydrophobic composite.
  • the abrasive agent constitutes between about 0.1 and about 0.5 weight percentages of the hydrophobic composite.
  • a method of preparing a hydrophobic composite comprising coating a core material with a hydrophobic powder, the hydrophobic powder comprises at least one impure element having a hydrocarbon chain attached thereto, to thereby provide the hydrophobic composite.
  • the method further comprising, prior to the coating, applying onto the core material an adherent layer, the adherent layer bonding the hydrophobic powder to the core material.
  • the step of applying onto the core material an adherent layer comprises admixing the core material with an adherent mixture containing a film-forming agent and a volatile solvent, while removing all of the volatile solvent from the mixture of the core material and the adherent mixture, to thereby provide the core material having applied thereon the adherent layer.
  • the step of applying onto the core material an adherent layer comprises admixing the core material with an aqueous adherent mixture containing a water-based gluing agent and an aqueous solvent (e.g., water), while removing all of the aqueous solvent from the mixture of the core material and the adherent mixture, to thereby provide the core material having applied thereon the adherent layer.
  • the method further comprising drying the core material prior to the coating.
  • the method further comprising drying the core material prior to the admixing.
  • the method further comprising, after the coating, curing the hydrophobic composite.
  • the volatile solvent is an organic solvent having a boiling temperature ranging between about 80 °C and about 200 °C.
  • the method further comprising, prior to the coating, admixing the core material with an additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • the method further comprising, prior to the coating, admixing the core material having thereon the adherent layer with an additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • an additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • the core material is selected from the group consisting of a particulate material and a granulate material.
  • the core material is selected from the group consisting of sand, gravel, slag, porcelanit, dolomite, porcelain, basalt, quartz sand, coal ash, chalk, zeolite, montmorillonite, agapultite, flint, bentonite, perlite, mica, wood chips, nut shells, sawdust and combinations thereof.
  • the core material has an average particle size ranging between 25 millimeters and 5 microns.
  • the core material is quartz sand.
  • the adherent layer constitutes between about 0.5 and about 7 weight percentages of the hydrophobic composite.
  • the hydrophobic powder constitutes between about 0.1 and about 5 weight percentages of the hydrophobic composite.
  • a hydrophobic particulate comprising a particulated core material coated by a hydrophobic powder, the hydrophobic powder comprises at least one impure element having a hydrocarbon chain attached thereto.
  • the hydrocarbon chain comprises at least 10 carbon atoms.
  • the hydrocarbon is a residue of a fatty acid having at least 12 carbon atoms.
  • the fatty acid is selected from the group consisting of stearic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linolenic acid and arachidonic acid.
  • the at least one element is selected from the group consisting of a metallic element, a semi-metallic element, a transition metallic element and combinations thereof.
  • the at least one element is selected from the group consisting of magnesium, calcium, aluminum, zinc, sodium, barium, zirconium, manganese, titanium, vanadium, chromium, iron and combinations thereof.
  • the hydrophobic composite and particulate are characterized as being inactive toward alkaline reagents. According to still further features in the described preferred embodiments the hydrophobic composite and particulate is capable of preventing water adherence thereto and water penetration therein under an external pressure of up to about 4.5 atmospheres. According to still further features in the described preferred embodiments the hydrophobic composite and particulate is characterized by being durable to dynamic water wear for at least 2 months. According to still further features in the described preferred embodiments the gluing agent constitutes between about 0.1 and about 50 weight percentages of the adherent layer.
  • the hydrophobic particulate further comprising at least one additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • the coloring agent constitutes between about 0.1 and about 2 weight percentages of the hydrophobic particulate.
  • the UV resistant agent and the bleaching agent each constitutes between about 0.01 and about 2 weight percentages of the hydrophobic particulate.
  • the abrasive agent constitutes between about 0.1 and about 0.5 weight percentages of the hydrophobic particulate.
  • a method of preparing a hydrophobic particulate comprising coating a particulated core material with a hydrophobic powder, the hydrophobic powder comprises at least one impure element having a hydrocarbon chain attached thereto, to thereby provide the hydrophobic particulate.
  • the method further comprising, prior to the coating, applying onto the particulated core material an adherent layer, the adherent layer bonding the hydrophobic powder to the particulated core material.
  • the step of applying onto the particulated core material an adherent layer comprises admixing the particulated core material with an adherent mixture containing a film- forming agent and a volatile solvent, while removing all of the volatile solvent from the mixture of the particulated core material and the adherent mixture, to thereby provide the particulated core material having applied thereon the adherent layer.
  • the step of applying onto the particulated core material an adherent layer comprises admixing the particulated core material with an aqueous adherent mixture containing a water-based gluing agent and an aqueous solvent (e.g., water), while removing all of the aqueous solvent from the mixture of the particulated core material and the adherent mixture, to thereby provide the particulated core material having applied thereon the adherent layer.
  • the method further comprising drying the particulated core material prior to the coating.
  • the method further comprising drying the particulated core material prior to the admixing.
  • the method further comprising, after the coating, curing the hydrophobic particulate.
  • the curing is performed for a time period ranging between 1 and 30 days.
  • the removing of the volatile solvent is performed by evaporative heating.
  • the removing of the volatile solvent is performed at room temperature.
  • the volatile solvent is an organic solvent having a boiling temperature ranging between about 80 °C and 200 °C.
  • the method further comprising, prior to the coating, admixing the particulated core material with an additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • the method further comprising, prior to the coating, admixing the particulated core material having thereon the adherent layer with an additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • the particulated core material has an average particle size ranging between 25 millimeters and 5 microns.
  • the particulated core material is quartz sand.
  • the film forming agent is a film forming polyurethane.
  • the adherent mixture further comprises a gluing agent.
  • the gluing agent is a volatile hydrocarbon having at least 12 carbon atoms.
  • the gluing agent is selected from the group consisting of liquid asphalt, paraffin wax, beeswax, lanolin wax, linseed oil and combinations thereof.
  • the hydrophobic powder has an average particle size ranging between 0.02 micron and 50 microns. According to still further features in the described preferred embodiments the hydrophobic powder has a surface area ranging between 1 m /gram and 60 m /gram. According to still further features in the described preferred embodiments the hydrophobic fumed silica constitutes between 1 and 99 weight percentages of the hydrophobic powder. According to still further features in the described preferred embodiments the adherent layer constitutes between about 0.5 and about 7 weight percentages of the hydrophobic particulate. According to still further features in the described preferred embodiments the hydrophobic powder constitutes between about 0.1 and about 5 weight percentages of the hydrophobic particulate.
  • a hydrophobic composite comprising a core material coated by a hydrophobic material bonded tehreof via a water-based adherent layer.
  • the water-based adherent layer comprises a water-based gluing agent.
  • the water-based gluing agent is a bitumen-latex paste.
  • the hydrophobic material is selected from the group consisting of a hydrophobic powder comprising at least one impure element having a hydrocarbon chain attached thereto, hydrophobic fumed silica, molten polypropylene and any mixture thereof.
  • hydrophobic composite the core material and the hydrophobic powder, are as described hereinabove.
  • a method preparing the hydrophobic composite described above which comprises admixing a core material and an aqueous adherent mixture including a water-based gluing agent and an aqueous solvent; removing the aqueous solvent to thereby to thereby provide the core material having applied thereon the water-based adherent layer; and coating the core material having applied thereon the water-based adherent layer with the hydrophobic material, thereby providing the hydrophobic composite.
  • the concentration of the water-based gluing agent in the aqueous adherent mixture ranges between about 1 weight percentage and about 99 weight percentages.
  • the method further comprises drying the core material prior to the admixing.
  • the method further comprises drying the core material having applied thereon the water- based adherent layer prior to the coating.
  • the method further comprises, after the coating, curing the hydrophobic composite.
  • the curing is performed for a time period ranging between 1 and 30 days.
  • the removing the aqueous solvent is performed by tumble drying.
  • the method further comprises, prior to the coating, admixing the core material having thereon the water-based adherent layer with an additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • a free-flowing hydrophobic aggregate capable of repelling a predetermined maximal pressure of liquid
  • the free-flowing hydrophobic aggregate comprising a plurality of differently sized particulates, wherein at least one of a size distribution of the particulates, a contact angle between the liquid and the particulates and a characteristic distance between adjacent particulates is selected so that when a layer of the free- flowing hydrophobic aggregate is in contact with a liquid having a pressure lower than or equal to the predetermined maximal pressure, percolation of the liquid through the free-flowing hydrophobic aggregate is prevented.
  • the layer has a thickness from about 1 cm to about 10 cm and further wherein the predetermined maximal pressure is equivalent to a column of water having a height above 100 cm.
  • the free-flowing hydrophobic aggregate further comprising inflatable particulates size wise compatible with capillaries formed between the particulates and capable of absorbing the liquid.
  • a freezing temperature of the inflatable particulates below about -20 degrees centigrade, both in an inflated state and in a deflated state of the inflatable particulates.
  • the size distribution is selected so that the free-flowing hydrophobic aggregate is characterized by a minimal water abso ⁇ tion capability.
  • the predetermined thermal properties are selected from the group consisting of thermal conductivity, specific heat capacity and latent heat.
  • the size distribution is selected so that the free-flowing hydrophobic aggregate is capable of allowing evaporation of the liquid.
  • the size distribution is proportional to the predetermined maximal pressure.
  • a cosine of the contact angle is proportional to the predetermined maximal pressure, the contact angle is measured from a tangent to a surface defined by the free-flowing hydrophobic aggregate.
  • the characteristic distance is inversely proportional to the predetermined maximal pressure.
  • the plurality of differently sized particulates comprises a particulated core material coated by a hydrophobic powder selected so as to provide the contact angle.
  • the hydrophobic powder comprises inflatable particulates capable of absorbing the fluid.
  • a diameter of the inflatable particulates is from about 1 micrometer to about 100 micrometers.
  • a freezing temperature of the inflatable particulates is below about -20 degrees centigrade, both in an inflated state and in a deflated state of the inflatable particulates.
  • the inflatable particulates when in a deflated state, constitute less than 1 percent of the free-flowing hydrophobic aggregate by volume.
  • the free-flowing hydrophobic aggregate further comprising at least one additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • a hydrophobic brick comprising a protective encapsulation having a predetermined shape, and a free-flowing hydrophobic aggregate being encapsulated in the protective encapsulation.
  • the hydrophobic brick further comprising inflatable particulates size wise compatible with capillaries formed between the particulates and capable of absorbing the fluid.
  • a method of wate ⁇ roofing a portion of a structure being in contact with a ground comprising: providing a bed of a free-flowing hydrophobic aggregate; and positioning the structure over or in the bed of the free- flowing hydrophobic aggregate.
  • the method further comprising protecting the bed of free-flowing hydrophobic aggregate by enclosing the bed in a protective structure.
  • a thickness of the bed of free-flowing hydrophobic aggregate is between 1 and 15 cm.
  • a thickness of the bed of free-flowing hydrophobic aggregate is between 4 and 10 cm.
  • the method further comprising protecting the sidewall of free- flowing hydrophobic aggregate by enclosing the sidewall in a protective structure.
  • the method further comprising refilling the sidewall of free-flowing hydrophobic aggregate, with time.
  • the sidewall of the free-flowing hydrophobic aggregate comprises an arrangement of hydrophobic bricks, each being a protective encapsulation having a predetermined shape and encapsulating the free-flowing hydrophobic aggregate.
  • the method further comprising coating the underground wall of the structure with a wate ⁇ roofing substance selected from the group consisting of a liquid and a paste.
  • the structure is an existing structure, and the method is applied as a repair method.
  • the structure is a new structure, and the method is applied during construction.
  • a method of wate ⁇ roofing a floor of a structure comprising providing a bed of a free- flowing hydrophobic aggregate onto the structure and positioning the floor of the structure over the bed of the free-flowing hydrophobic aggregate.
  • the method further comprising protecting the bed of the free-flowing hydrophobic aggregate by enclosing the bed in a protective structure.
  • the method further comprising embedding a pipe in the bed of the free-flowing hydrophobic aggregate.
  • a method of wate ⁇ roofing a roof of a structure, the roof having sidewalls comprising: applying a bed of a free- flowing hydrophobic aggregate on the roof; and covering the bed of the free-flowing hydrophobic aggregate, to protect the bed.
  • the covering comprises applying a floor over the bed of the free-flowing hydrophobic aggregate.
  • the bed of the free-flowing hydrophobic aggregate comprises an arrangement of hydrophobic bricks, each being a protective encapsulation having a predetermined shape and encapsulating the free-flowing hydrophobic aggregate.
  • a thickness of the bed of the free-flowing hydrophobic aggregate is between 1 and 15 cm.
  • a thickness of the bed of the free-flowing hydrophobic aggregate is between 4 and 7 cm.
  • a method of wate ⁇ roofing a reservoir comprising: placing a flooring bed of a free-flowing hydrophobic aggregate over a base of the reservoir; and placing walls of the free-flowing hydrophobic aggregate over walls of the reservoir; wherein at least one of the flooring bed and the walls of the free-flowing hydrophobic aggregate are covered by a protective structure designed and constructed to maintain the free- flowing hydrophobic aggregate in place.
  • a thickness of the flooring bed of free-flowing hydrophobic aggregate is between 4 and 15 cm.
  • the method further comprising mixing the free-flowing hydrophobic aggregate with lightweight aggregates.
  • the protective structure is selected from the group consisting of tiles, geotechnic fabric, concrete, plastic and combination thereof.
  • at least one of the flooring bed and the sidewalls of the free-flowing hydrophobic aggregate comprises an arrangement of hydrophobic bricks, each being a protective encapsulation having a predetermined shape and encapsulating the free-flowing hydrophobic aggregate.
  • the free-flowing hydrophobic aggregate further comprises inflatable particulates size wise compatible with capillaries formed between the particulates and capable of absorbing the fluid.
  • a method of protecting an object buried underground comprising providing a free-flowing hydrophobic aggregate and surrounding the object by a layer of the free- flowing hydrophobic aggregate in a manner such that the layer of the free-flowing hydrophobic aggregate is inte ⁇ osed between the object and the ground.
  • the size distribution is selected so that a maximal diameter of capillaries formed between the particulates is suitable for repelling the liquid.
  • the size distribution is selected so that the free-flowing hydrophobic aggregate is characterized by predetermined acoustical isolation ability.
  • the free- flowing hydrophobic aggregate comprises a particulated core material coated by a hydrophobic powder
  • the hydrophobic powder comprises at least one impure element having a hydrocarbon chain attached thereto.
  • the hydrophobic powder comprises inflatable particulates capable of absorbing fluid when being in contact therewith.
  • the free-flowing hydrophobic aggregate further comprises at least one additive selected from the group consisting of a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent.
  • a hydrophobic composition for protecting an underground object comprising a thermally conductive free-flowing hydrophobic aggregate and a dielectric free-flowing hydrophobic aggregate, the thermally conductive free-flowing hydrophobic aggregate and the dielectric free-flowing hydrophobic aggregate being mixed in a predetermined ratio selected so as to electrically isolate the underground object while allowing transportation of heat therefrom.
  • the hydrophobic composition further comprising inflatable particulates size wise compatible with capillaries formed between particulates of the thermally conductive free-flowing hydrophobic aggregate and/or the dielectric free-flowing hydrophobic aggregate, the inflatable particulates being capable of absorbing fluid.
  • a freezing temperature of the inflatable particulates below about -20 degrees centigrade, both in an inflated state and in a deflated state of the inflatable particulates.
  • the hydrophobic composition further comprising at least one additive selected from the group consisting of a UV resistant agent, a bleaching agent and an abrasive agent.
  • a method of protecting an underground object comprising: providing a hydrophobic composition having a thermally conductive free-flowing hydrophobic aggregate and a dielectric free-flowing hydrophobic aggregate; and surrounding the object by a layer of the hydrophobic composition in a manner such that the layer of the hydrophobic composition is inte ⁇ osed between the object and the ground; the thermally conductive free-flowing hydrophobic aggregate and the dielectric free- flowing hydrophobic aggregate being mixed in a predetermined ratio selected so as to electrically isolate the underground object while allowing transportation of heat therefrom.
  • the hydrophobic composition further comprises inflatable particulates, size wise compatible with capillaries formed between particulates of the thermally conductive free-flowing hydrophobic aggregate and/or the dielectric free-flowing hydrophobic aggregate, the inflatable particulates being capable of absorbing fluid.
  • a freezing temperature of the inflatable particulates below about -20 degrees centigrade, both in an inflated state and in a deflated state of the inflatable particulates.
  • the hydrophobic composition further comprises at least one additive selected from the group consisting of a UV resistant agent, a bleaching agent and an abrasive agent.
  • a method of manufacturing a hydrophobic composition for protecting an underground object comprising providing a thermally conductive free-flowing hydrophobic aggregate; providing a dielectric free-flowing hydrophobic aggregate; and mixing the thermally conductive free-flowing hydrophobic aggregate and the dielectric free-flowing hydrophobic aggregate in a predetermined ratio; the predetermined ratio being selected so as to allow electrical isolation of the underground object and transportation of heat therefrom.
  • the underground object is selected from the group consisting of an underground electrical cable, an underground electrical wire, an underground communication cable and an underground communication wire.
  • At least one of the thermally conductive free-flowing hydrophobic aggregate and the dielectric free-flowing hydrophobic aggregate comprises a particulated core material coated by a hydrophobic powder.
  • the hydrophobic powder has a distinguishable color.
  • the particulated core material is further coated by a coloring coat.
  • the coloring coat is water resistant.
  • the method further comprising mixing the thermally conductive free-flowing hydrophobic aggregate and the dielectric free-flowing hydrophobic aggregate with inflatable particulates being size wise compatible with capillaries formed between particulates of the thermally conductive free-flowing hydrophobic aggregate and/or the dielectric free-flowing hydrophobic aggregate, the inflatable particulates being capable of absorbing fluid.
  • an abso ⁇ tion capability of the inflatable particulates is from about 100 to about 5000 by weight.
  • a freezing temperature of the inflatable particulates below about -20 degrees centigrade, both in an inflated state and in a deflated state of the inflatable particulates.
  • a diameter of the inflatable particulates is from about 1 micrometer to about 1000 micrometers.
  • the method further comprising mixing the thermally conductive free-flowing hydrophobic aggregate and the dielectric free-flowing hydrophobic aggregate with at least one additive selected from the group consisting of a UV resistant agent, a bleaching agent and an abrasive agent.
  • the particulated core material is selected from the group consisting of sand, gravel, slag, porcelanit, dolomite, porcelain, basalt, quartz sand, coal ash, chalk, zeolite, montmorillonite, agapultite, flint, bentonite, perlite, mica, wood chips, nut shells, sawdust and combinations thereof.
  • at least one of the thermally conductive free-flowing hydrophobic aggregate and the dielectric free-flowing hydrophobic aggregate comprises a plurality of differently sized particulates.
  • At least one of a size distribution of the differently sized particulates, a contact angle between a liquid and the differently sized particulates and a characteristic distance between adjacent particulates is selected so that when a layer of the hydrophobic composition is in contact with a liquid having a pressure lower than or equal to a predetermined maximal pressure, percolation of the liquid through the hydrophobic composition is prevented.
  • the liquid is water.
  • the layer has a thickness from about 1 cm to about 10 cm and further wherein the predetermined maximal pressure is equivalent to a column of water having a height above 30 cm.
  • the size distribution is characterized by a variance ranging from 1 micrometer to 1400 micrometer. According to still further features in the described preferred embodiments the size distribution is selected so that a maximal diameter of capillaries formed between the particulates is suitable for repealing the predetermined maximal pressure of the liquid. According to still further features in the described preferred embodiments the size distribution is 'Selected so that a maximal diameter of capillaries formed between the particulates is from 1 nanometer to 500 nanometers.
  • a method of preparing an area for plants cultivating comprising providing a bed of a free-flowing hydrophobic aggregate onto the area and covering the bed of a free- flowing hydrophobic aggregate by a layer of soil, thereby preparing an area for plants cultivating.
  • the bed of the free-flowing hydrophobic aggregate comprises an arrangement of hydrophobic patches, each being a protective encapsulation having a predetermined shape and encapsulating the free-flowing hydrophobic aggregate.
  • the protective encapsulation is made from a degradable material.
  • the hydrophobic patches are arranged such that at least one space is formed between adjacent hydrophobic patches.
  • the method further comprising covering the bed of the free-flowing hydrophobic aggregate by a super absorbent polymer.
  • the method further comprising positioning at least one water collection channel for allowing conveyance of water into the soil.
  • the method further comprising surrounding the layer of soil by a protective barrier.
  • the protective barrier comprises the free-flowing hydrophobic aggregate.
  • a plant cultivating method comprising: providing a bed of a free- flowing hydrophobic aggregate an area; covering the bed of a free-flowing hydrophobic aggregate by a layer of soil; planting a plant in the layer of soil; and applying aqueous liquid under the bed of a free- flowing hydrophobic aggregate thereby cultivating the plant.
  • the aqueous liquid is salty water.
  • the method further comprising positioning at least one water collection channel for allowing conveyance of water under the bed of the free-flowing hydrophobic aggregate.
  • a method of preparing a salt-free area on a salty soil comprising providing a bed of a free-flowing hydrophobic aggregate onto the salty soil and covering the bed of the free-flowing hydrophobic aggregate by non-salty soil, thereby preparing the salt-free area.
  • the further comprising mixing the free-flowing hydrophobic aggregate with lightweight aggregates.
  • the method further comprising covering the bed of free-flowing hydrophobic aggregate by a super absorbent polymer.
  • the bed of free-flowing hydrophobic aggregate is designed and constructed to facilitate desalination of non-desalted water present thereunder, the desalination being effected by passage of desalted vapors of the non-desalted water through the bed of the free- flowing hydrophobic aggregate.
  • the free-flowing hydrophobic aggregate comprises a plurality of differently sized particulates, and further wherein at least one of a size distribution of the particulates, a contact angle between a liquid and the particulates and a characteristic distance between adjacent particulates is selected so that when the free-flowing hydrophobic aggregate is in contact with a liquid having a pressure lower than or equal to a predetermined maximal pressure, percolation of the liquid through the free-flowing hydrophobic aggregate is prevented.
  • the method further comprising inflatable particulates size wise compatible with capillaries formed between the particulates and capable of absorbing the fluid.
  • the inflatable particulates when in a deflated state, constitute less than 2 percent of the free-flowing hydrophobic aggregate by volume.
  • the inflatable particulates comprise a super absorbent polymer.
  • the inflatable particulates comprises sodium being cross linked with polyacrylic acid.
  • the inflatable particulates comprises anti-caking agent.
  • the size distribution is selected so that the free-flowing hydrophobic aggregate is characterized by a predetermined specific weight.
  • the size distribution is selected so that the free-flowing hydrophobic aggregate is characterized by a minimal abso ⁇ tion capability. According to still further features in the described preferred embodiments the size distribution is selected so that the free-flowing hydrophobic aggregate is characterized by predetermined thermal properties. According to still further features in the described preferred embodiments the size distribution is selected so that the free-flowing hydrophobic aggregate is capable of allowing evaporation of liquid.
  • the free-flowing hydrophobic aggregate preferably comprises one or more of the hydrophobic composites described hereinabove.
  • the present invention successfully addresses the shortcomings of the presently known configurations by providing hydrophobic composites and particulates, having properties far exceeding prior art, and suitable for being implemented in various applications. Additionally, the present invention successfully addresses the shortcomings of the presently known manufacturing methods by providing methods of producing the hydrophobic composites and particulates.
  • all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In case of conflict, the patent specification, including definitions, will control.
  • the materials, methods, and examples are illustrative only and not intended to be limiting.
  • FIGs. 1 schematically illustrates a free-flowing hydrophobic aggregate, having a plurality of differently sized particulates, in accordance with a preferred embodiment of the present invention
  • FIGs. 2A-B schematically illustrate prior-art methods of wate ⁇ roofing a foundation of a house
  • FIGs. 3 A-C schematically illustrate methods of wate ⁇ roofing a foundation of a house, in accordance with a preferred embodiment of the present invention
  • FIGs. 4A-B schematically illustrate a hydrophobic brick and a hydrophobic brick wall, in accordance with a preferred embodiment of the present invention
  • FIG. 5A-B schematically illustrate methods of wate ⁇ roofing a floor of a house, in accordance with a preferred embodiment of the present invention
  • FIGs. 6A-B schematically illustrate prior-art methods of wate ⁇ roofing a roof
  • FIG. 7 schematically illustrates a method of wate ⁇ roofing a flat roof, in accordance with a preferred embodiment of the present invention
  • FIG. 8 schematically illustrates a method of wate ⁇ roofing a reservoir, in accordance with a preferred embodiment of the present invention
  • FIG. 9 schematically illustrates tiles with toothed edges, used for holding hydrophobic aggregate in place, in accordance with a preferred embodiment of the present invention
  • FIG. 10 is a schematic illustration of a hydrophobic composition for protecting an underground object, according to a preferred embodiment of the present invention
  • FIG. 11 is a flowchart of a method of protecting an underground object according to a preferred embodiment of the present invention
  • FIG. 12a is a schematic illustration of a an object buried in the ground and surrounded by a layer of the hydrophobic composition, according to a preferred embodiment of the present invention
  • FIG. 12b is a schematic illustration of an above ground object positioned in a dike and surrounded by a layer of the hydrophobic composition, according to a preferred embodiment of the present invention
  • FIG. 13 is a flowchart of a method of manufacturing a hydrophobic composition for protecting an underground object, according to a preferred embodiment of the present invention.
  • the present invention is of novel hydrophobic composites and particulates that have superior chemical and physical performances, which can be beneficially used in various wate ⁇ roofing and oil-absorbing applications, and of methods of their production.
  • the present invention is further of the use of free-flowing hydrophobic aggregate while providing protection to the free-flowing aggregates from wind and water erosion.
  • the hydrophobic composites, particulates and free- flowing hydrophobic aggregate of the present invention comprise a core and coating compositions which render the resulting product durable toward a myriad of parameters encountered in water-proofing and desalination applications such as, for example, high water pressures, wear, reactive detergents and more.
  • hydrophobic composites, particulates and free-flowing hydrophobic aggregate of the present invention are manufacturable far cost effectively as compared with the prior art hydrophobic composites described in the background section above.
  • the principles and operation of the hydrophobic composites, particulates, free- flowing hydrophobic aggregate and the methods utilizing same according to the present invention may be better understood with reference to the drawings and accompanying descriptions.
  • hydrophobic composites disclosed in WO 03/044124 include a hydrophobic coating that is consisted essentially of hydrophobic fumed silica, which is both highly expensive and render the composite's surface acidic and hence susceptible to reactive detergents.
  • Such hydrophobic composites apart from being economically inefficient, and are typically further characterized as environmentally unfriendly, cannot be efficiently used in various applications such as topcoats of various surfaces.
  • a hydrophobic powder of one or more impure elements having one or more hydrocarbons attached thereto can be prepared in an environmental-friendly and economically-efficient process and exert superior water-repellency as well as durability toward parameters such as high water pressures, dynamic water wear and reactive detergents.
  • a hydrophobic composite which comprises a core material coated by a hydrophobic powder, the powder comprises one or more impure elements having a hydrocarbon chain attached thereto.
  • the hydrophobic powder can also be used for providing hydrophobic particulates and, more preferably, a hydrophobic free- flowing aggregate.
  • impure element includes chemical elements of the periodic table which are not used in their pure form.
  • the impure elements can be naturally impure elements such as, for example, oxidized elements or carbonated elements or can be pure or impure elements which have been further impurified by, for example, small quantities of other elements and/or various organic substances.
  • the impurity of the element(s) is required so as to render the element susceptible to a surface reaction with an organic substance bearing the hydrocarbon chain, as is further detailed hereinbelow.
  • the selected elements are preferably metallic, semi-metallic or transition metallic elements.
  • preferred elements that are usable in context of the present invention, in an impure form, include, without limitation, magnesium, calcium, aluminum, zinc, sodium, barium, zirconium, manganese, titanium, vanadium, chromium, iron and combinations thereof.
  • the elements are selected according to the desired application of the final hydrophobic product.
  • hydrophobic powder that includes impure calcium, magnesium and/or zinc bearing a hydrocarbon chain is preferable in cases where the final product is used for building and construction applications.
  • hydrocarbon chain describes a chain of carbon atoms that are covalently attached therebetween and are substituted by hydrogen atoms.
  • the hydrocarbon chain can be linear or branched, saturated or unsaturated chain and therefore can be in he form of alkylene chains that are optionally interrupted or substituted by, for example, one or more aryl groups.
  • the hydrocarbon chain of the present invention includes at least 10 carbon atoms, preferably at least 12 carbon atoms or more, e.g., 13, 14, 15, 16, 17, 18, 19, 20 or more carbon atoms.
  • Such a hydrocarbon chain is highly hydrophobic and therefore, when used for coating, renders the powder hydrophobic.
  • the hydrocarbon chain can be attached to the impure element(s) via various interactions such as electrostatic interactions and Van der Vaals interactions.
  • a preferred hydrocarbon chain according to the present invention is a residue of a hydrophobic organic substance that is capable of reacting with the impure element(s).
  • Such an organic substance has a functional group that can react with the surface of an impure element, the functional group is connected to the hydrocarbon chain.
  • a representative example of such an organic substance is a fatty acid that has at least 12 carbon atoms. Fatty acids can react with various functional groups that are present on the impure elements' surface via its carboxylic end, to thereby provide the hydrophobic derivative described above.
  • the hydrophobic powder of the present invention preferably includes an impure element or a mixture of impure elements, as is defined hereinabove, whereby the selected impurity renders the surface of the element(s) susceptible to chemically reacting with the organic substance described above, which have been reacted with the organic substance to thereby provide the impure element(s) having the hydrocarbon residue of the organic substance covalently attached thereto.
  • a representative example of a hydrophobic powder that is usable in context of the present invention therefore includes, without limitations, a powder obtained by surface reaction of oxidized element(s) (e.g., colloidal particles of calcium oxide, magnesium oxide and the like), which bear free hydroxyl groups on their surfaces, and a fatty acid such as, for example, stearic acid.
  • oxidized element(s) e.g., colloidal particles of calcium oxide, magnesium oxide and the like
  • a fatty acid such as, for example, stearic acid.
  • the free hydroxyl groups react with the carboxylic group of the fatty acid, so as to form the corresponding ester.
  • a powder prepared by reacting the surface of calcium carbonate, which have been further impurified, with stearic acid is commercially available (for example, from Kfar-Gilaadi Quarries, Israel).
  • the hydrophobic powder of the present invention is typically characterized by a surface area ranging between 1 Vgram and 20 m 2 /gram. However, in cases where higher surface area is required, the hydrophobic powder can be grinded so as to enhance the surface area up to more than 50 m /gram (e.g., 60 m /gram). It should be noted in this respect that the presently known hydrophobic coatings, e.g., the hydrophobic coatings described in U.S. patent No. 4,474,852 and in WO 03/044124, are characterized by surface areas of about 50 m /gram.
  • hydrophobic powder having a surface area of about 60 m /gram is highly efficient due to other physical parameters (e.g., air entrapment, as is detailed hereinbelow) as well as its low cost. Due to its particular chemical structure, the hydrophobic powder of the present invention exerts "soap-like" properties and hence it is further characterized as being inactive toward alkaline reagents, such as detergents.
  • hydrophobic coatings that are based on hydrophobic colloidal oxides are characterized as being susceptible to such reagents and hence cannot be used in applications that involve the use of detergents.
  • the hydrophobic powder of the present invention has an average particles size ranging between 0.02 micron and 50 microns, preferably between 0.1 micron and 20 microns, and more preferably between 0.1 micron and 10 microns.
  • hydrophobic composites coated by the hydrophobic powder of the present invention are characterized by high water-repellency performance.
  • the use of a combination of the hydrophobic powder of the present invention and hydrophobic fumed silica can be beneficial.
  • the hydrophobic powder further comprises hydrophobic fumed silica.
  • hydrophobic fumed silica describes a colloidal form of silica made by combustion of silicon tetrachloride in hydrogen-oxygen furnaces, in which individual particles on the surface thereof have been chemically bonded to hydrophobic trirnethoxysiloxyl groups.
  • Hydrophobic fumed silica is a commercially available powder typically having an average particles size smaller than 1 micron and, if present in the hydrophobic powder of the present invention, it can constitute between 1 and 99 weight percentages of the powder.
  • the resulting mixed powder typically has an average particle size of between 0.02 micron and 20 microns.
  • hydrophobic composites according to the present invention may include a core material that is coated by a combination of the hydrophobic powder described hereinabove and hydrophobic fumed silica, whereas the partial amount of each of these powders is predetermined either by the selected core material and/or by the intended use of the final product.
  • the hydrophobic composite or particulates should have smaller particles size and hence the mixed powder should consist a higher amount of the hydrophobic fumed silica.
  • the hydrophobic composite or particulates can have larger particles size and hence the mixed powder consists a higher amount of the hydrophobic powder described hereinabove.
  • hydrophobic powder of the present invention constitutes between about 0.1 and 5 weight percentages of the hydrophobic composite, whereby powders that include higher amount of the hydrophobic powder described hereinabove constitute between about 2 and about 5 weight percentages of the composite and powders that include higher amount of the hydrophobic fumed silica constitute between about 0.1 and about 2 weight percentages of the composite.
  • the term "about” refers to ⁇ 10 %.
  • the core material coated by the hydrophobic powder of the present invention may be selected from a wide variety of organic and inorganic substances, with inorganic substances (e.g., minerals) being favored from standpoint of cost and availability.
  • the physical form of the core material may vary, with particulate and granulate material being preferred.
  • Preferred core materials have an average particles size ranging between about 25 millimeters (25,000 microns) and 5 microns, more preferably between 10 millimeters and 20 microns, more preferably between 5 millimeters and 100 microns and most preferably between 1,000 microns and 200 microns.
  • Such a core material is also referred to herein throughout as aggregate.
  • Non- particulated, non-granulated, integral core materials are also within the scope of the present invention.
  • core materials that are preferably usable in context of the present invention include, without limitation, sand, gravel, slag, porcelanit, dolomite, porcelain, basalt, quartz sand, coal ash, chalk, zeolite, montmorillonite, agapultite, flint, bentonite, perlite, mica, wood chips, nut shells, sawdust and combinations thereof.
  • a representative example of a preferred core material according to the present invention is quartz sand having a particle size of between 600 and 800 microns.
  • the hydrophobic composite of the present invention preferably further comprises an adherent layer, which bonds the hydrophobic powder to the core material.
  • the adherent layer serves as a first coat layer deposited on the core material, which anchors the hydrophobic outer coat thereto.
  • the adherent layer preferably comprises a film forming agent such as a film forming polyurethane.
  • a film forming agent such as a film forming polyurethane.
  • Any of the film-forming polyurethanes commonly employed in the field of coatings may be used in the practice of the present invention. Included in this category are the well-known two-component and one-component polyurethane coating systems.
  • the two-component systems are formed by the reaction of an aliphatic or aromatic isocyanate with a hydroxyl-bearing compound, such as polyfunctional polyesters based on adipic acid, phthalic anhydride, ethylene glycol and trimethylolpropane, for example.
  • one-component polyurethane coating systems that may be employed as the adherent layer are those derived from stable isocyanate-terminated prepolymers formed from an aliphatic or aromatic isocyanate and polyfunctional polyether or polyester. These one-component systems are commonly referred to as "moisture cured" polyurethane coatings because drying results from the reaction of the free-isocyanate groups of the pre-polymer with water or atmospheric moisture.
  • Another one-component polymer coating which may be used in the preparation of the hydrophobic composites is the "urethane oil” or "uralkyd", which is the reaction product of a diisocyanate with a hydroxyl-containing drying oil derivative, e.g., that produced by alcoholysis of an unsaturated glyceride with a polyol, such as trimethylolpropane.
  • the adherent layer of the present invention may further comprise a gluing agent in combination with the film-forming agent, so as to provide an increase in the anchoring quality of the adherent layer over a longer period of time and an increased attraction for oil and oil related products.
  • the gluing agent preferably comprises a volatile hydrocarbon that has at least 12 carbon atoms, such as, for example, asphalt.
  • asphalt describes a dark brown to black cementitious material in which the predominate constituents are bitumens that occur in nature or are obtained in petroleum processing, the latter being preferred, primarily because of its greater availability.
  • the asphalt may be solid, semi-solid or liquid, with the latter being preferred.
  • the adherent layer is a water-based adherent layer, preferably comprising a water-based gluing agent.
  • the adherent layer of the present invention preferably constitutes between about 0.5 and about 7 weight percentages of the hydrophobic composite, more preferably between 1 and 5 weight percentages of the hydrophobic composite, depending on the particles size of the core material, the selected process of preparing the hydrophobic composite, particulate or free-flowing aggregate and the intended application of the final product.
  • the core material has an average particles size ranging between 150 microns and 1000 microns
  • a smaller amount of the adherent layer e.g., between 0.5 and 1 weight percentage of the hydrophobic composite, is used.
  • a higher amount of the adherent layer is preferred.
  • compositions of the adherent layer mixture include a film-forming polyurethane in an amount ranging between 5 and 25 weight percentages of the adherent layer mixture, depending on the size and type of the core material; a gluing agent in an amount ranging between 0 and 25 weight percentages of the adherent layer mixture, depending on the core material used, the gluing agent used and the intended use of the final product; and a volatile solvent in an amount of between 50 and 95 weight percentages of the mixture, depending on the amounts of the other components.
  • the volatile solvent merely functions as a vehicle for depositing the adherent layer on the core materials, virtually any volatile solvent in which the components of the adherent layer are soluble may be used.
  • preferred solvents include petroleum distillates, such as mineral spirits or paint thinner, which have a boiling temperature of between about 80 °C and about 200 °C.
  • a representative example of a preferred volatile solvent is toluene, which is readily evaporated at relatively low temperatures and results in rapid spread of the mixture onto the core materials.
  • a water-based adherent layer is easily applied to the core materials by dissolving a water-based gluing agent in an aqueous solvent, preferably water, so as to form a homogeneous composition and to provide a uniform deposition of the adherent layer over the surfaces of the core materials.
  • the hydrophobic composites of the present invention can further comprise various additives which, in accordance with the intended application and the core material used, provide hydrophobic composites with improved characteristics.
  • additives include, without limitations, coloring agents, UV resistant agents, bleaching agents and abrasive agents.
  • Coloring agents that are usable in context of the present invention include any of the presently known mineral or organic coloring agents, with mineral coloring agents being preferred.
  • a preferred amount of the coloring agent added to the composite ranges between about 0.1 and 2 weight percentages of the hydrophobic composite.
  • the resulting colored hydrophobic composites may be beneficially used in various applications, such as applications that require easy identification of the hydrophobic composite or applications that involve external coating.
  • a representative example of such an application is the use of colored hydrophobic sand to mark submerged cables, so as to warn against excavation nearby.
  • the addition of a coloring agent to the hydrophobic composite is further beneficial as it can sometimes improve the surface tension of the composite, thus rendering it more hydrophobic.
  • UV resistant agents are added to the hydrophobic composites of the present invention in order to improve the durability of the composites against UV irradiation, and are hence particularly useful in high radiation geographical sites, e.g., for topcoats of roofs or other surfaces.
  • UV resistant agents that are usable in context of the present invention include, without limitation, titanium dioxide and zinc oxide, both may also serve as bleaching agents.
  • a preferred amount of the UV resistant agent and the beaching agent added to the composite ranges between about 0.01 and 2 weight percentages of the hydrophobic composite.
  • Abrasive agents are typically added to the hydrophobic composite in order to improve the wear resistance of the composites and are therefore typically used in applications where the composites are exposed to continuous wear.
  • abrasive agents that are usable in context of the present invention include, without limitation, powdered abrasives such as titanium dioxide and aluminium oxide (Al 2 O 3 , corundum).
  • a preferred amount of the abrasive agent added to the composite ranges between about 0.1 and 0.25 weight percentages of the hydrophobic composite.
  • the hydrophobic composites of the present nvention are therefore comprised of a core material, as is described hereinabove, whi ch is coated by the hydrophobic powder described hereinabove, preferably in combi nation with hydrophobic fumed silica, and preferably further include an adherent layer, as is described hereinabove.
  • the hydrophobic composites of the present invention further comprise additives for improving their properties in accordance with their intended application.
  • a representative example of a hydrophobic composite according to the present invention is quartz sand coated by a mixture of the hydrophobic powder described herein and hydrophobic fumed silica, in a ratio that ranges between 20:1 and 2:1, whereby this hydrophobic mixture is bonded to the sand via an adherent layer.
  • the hydrophobic composites of the present invention are superior to the presently known composites as they include inexpensive and available materials, they are characterized as inactive toward alkaline reagents such as detergents, and, as is demonstrated in the Examples section that follows, they exert superior water- repellency and are further characterized as being capable of preventing water adherence thereto and water penetration therein under an external pressure of at least 2 atmospheres and up to almost 5 atmospheres, and as being highly durable toward dynamic water wear, namely, as remaining hydrophobic under continuous dynamic water wear for at least two months.
  • hydrophobic composites of the present invention can therefore be utilized in a myriad of applications, such as, but not limited to, as wate ⁇ roofing agents in building and pavement construction, as fill or bed materials under concrete slabs or as wall coatings, both below and above ground, as gravel fill or ballast for road beds or sidewalks, as top coats on paved surfaces, in top hole repairs in roadways, as substitutes for common aggregates in asphalt roofing or shingles, or in built-up roofing.
  • these hydrophobic composites may be applied to painted surfaces to provide a durable, wate ⁇ roof finish over wood, metal, concrete, stone, brick, and certain synthetic substrates.
  • a method of preparing the hydrophobic composites described above there is provided a method of preparing the hydrophobic composites described above.
  • the method is effected by coating a core material, as is described hereinabove, with the hydrophobic powder of the present invention, optionally in combination with hydrophobic fumed silica.
  • the amount of the hydrophobic powder and the relative amount of the hydrophobic fumed silica are predetermined as is discussed hereinabove.
  • the mixture is prepared is a separate vessel prior to applying thereof to the core material.
  • the method further comprises, prior to coating with the hydrophobic powder, applying onto the core material such an adherent layer, and, more specifically, admixing a pre-prepared adherent layer mixture that contains a film forming agent, a volatile solvent and optionally a gluing agent, as is described hereinabove, with the core material, while removing all of the volatile solvent from the resulting mixture, so as to provide a core material having the adherent layer applied thereon.
  • the adherent layer is a water-based adherent layer and the method further comprises, prior to coating with the hydrophobic powder, applying onto the core material such an adherent layer, and, more specifically, admixing a pre-prepared adherent layer mixture that contains a water-based gluing agent and an aqueous solvent, as is described hereinabove, with the core material, while removing all of the aqueous solvent from the resulting mixture, so as to provide a core material having the water-based adherent layer applied thereon.
  • the adherent layer mixture is prepared by mixing its components under heat and is preferably added to the core material while hot.
  • the relative amount of each component in the mixture is predetermined as is discussed hereinabove, while the total amount of the required adherent layer can be also predetermined, as is described and exemplified in the Examples section that follows.
  • the removal of the volatile solvent is typically performed by evaporative heating, but can alternatively be performed at room temperature. Hence, the entire process can be performed under heat or alternatively can be performed as a "cold” process, whereas no external heat is applied, as is exemplified in the Examples section that follows.
  • the "cold" process typically involves higher amount of the adherent layer.
  • the core material should contain no more than 1 weight percentage moisture, so as to ensure uniform coatings of the particles, the core material is preferably dried to this extent prior to the coating procedure.
  • the core material is typically dried at a temperature ranging between 90 °C and 120 °C, preferably at about 104 °C. Upon being dried, the core material can be used hot or can be stored in a closed vessel and be thereafter coated while cold.
  • the hydrophobic composite Once the hydrophobic composite has been prepared, it is preferably cured so as to obtain the final product.
  • the curing time typically ranges between 1 and 30 days, depending on the composition of the hydrophobic powder. For example, in cases where only the hydrophobic powder of the present invention is used, a curing time of 30 days is required. In cases where the hydrophobic powder is in combination with hydrophobic fumed silica, the curing time is shortened proportionally to the relative amount of the hydrophobic fumed silica, and down to 1 day.
  • hydrophobic composites which include a core material and a hydrophobic material bonded thereto via a water- based adherent layer can be easily prepared, while still achieving the desired characteristics of the resulting hydrophobic composites.
  • hydrophobic composites are highly advantageous since they involve the use of a cost-effective, easy to handle, safe and environmentally friendly aqueous medium.
  • a hydrophobic composite comprising a core material coated by a hydrophobic material, whereby the hydrophobic material is bonded to the core material via a water-based adherent layer.
  • a water-based adherent layer which will effectively bind a hydrophobic material to a core material
  • two requirements should be met: (i) the core material having applied tehreof a water-based adherent layer must be effectively dried, so as to provide a substantially water-free adherent layer, prior to its coating with the hydrophobic material; and (ii) the adherent layer should retain its tackiness (its gluing property) in its substantially dried form, so as to allow efficient binding of the hydrophobic material thereto.
  • hydrophobicity of the resulting composites depends on the contact angle, as described hereinbelow, and further since the contact angle depends on the physical entrapment of air within the composites, it is highly desirable to select an adherent layer which enables the formation of a physical structure of the hydrophobic layer that entraps as much air as physically possible.
  • An appropriate and efficient water-based adherent layer is therefore selected so as to meet the above requirements, as well as ease of use, cost, other physical requirements and its interaction with the selected hydrophobic coating material.
  • a water-based adherent layer, according to the present invention can be used in any hydrophobic composite, regardless of the core material and the hydrophobic material.
  • the water-based adherent layer according to the present invention preferably comprises a water-based gluing agent, which can be selected from a wide variety of commercially available water-based gluing agents.
  • gluing agents include, without limitation, Bitumen-Latex and Bitumen-Polymer binders such as Bitumflex (by Bitum, Israel), Elastopaz and Elastobrush (by Pazkar, Israel), Specef 10 and Specef 52 (by Wacker, Germany), Dispercoll c, Dispercoll u, Dispercoll s and Desmodur d (by Bayer, Germany), EnimorU Hiniplast and Hidropren 40-20 (by Enecol, Spain) and many more.
  • Bitumen-Latex and Bitumen-Polymer binders such as Bitumflex (by Bitum, Israel), Elastopaz and Elastobrush (by Pazkar, Israel), Specef 10 and Specef 52 (by Wacker, Germany), Dispercoll c, Dispercoll u, Dispercoll s and Desmodur d (by Bayer, Germany), EnimorU Hiniplast and Hidropren 40-20 (by Enecol, Spain) and
  • the water-based bitumen binders are collectively referred to herein as a bitumen-latex paste.
  • the water-based gluing agent preferably include one or more water-based gluing agent(s), optionally and preferably selected from the commercially available water-based gluing agents listed above.
  • the water-based adherent layer is easily applied onto a core material by simply dissolving it in water, or in any other aqueous medium, and applying the resulting mixture onto the core material.
  • the resulting core material should thereafter be substantially dried, as is described hereinabove.
  • the drying is preferably performed by heating the core material as described herein, optionally and preferably, in combination with a blower or any other technique that may accelerate and enhance the drying process at this stage.
  • the core material used can be any core material, and is preferably a core material as described hereinabove.
  • the hydrophobic material can be, for example, the hydrophobic powder described hereinabove, alone or in combination with hydrophobic fumed silica, hydrophobic fumed silica per se or any other silicon-based hydrophobic powder, molten polypropylene and other hydrophobic polymers, as well as any other hydrophobic material or superhydrophobic powder usable in hydrophobic composites, and any combination of the forgoing.
  • the hydrophobic composite and particulates described above can be employed, according to preferred embodiments of the present invention.
  • the hydrophobic composite of the present invention can be used for manufacturing a free-flowing hydrophobic aggregate, referred to herein as aggregate 1, having enhanced wate ⁇ roofing properties.
  • Aggregate 1 is capable of repealing a predetermined maximal pressure of liquid.
  • a layer of the aggregate of relatively small thickness (of the order of centimeters) is sufficient to withstand a column of water or any other liquid of interest.
  • the column is above 30 cm in height, more preferably above 100 cm in height, most preferably above 10 m in height.
  • a typical thickness of the layer is from about 1 cm to about 20 cm.
  • the ability of any hydrophobic material to repeal water basically depends on the surface tension of the liquid being in contact with the hydrophobic material. In any liquid, the cohesive forces between molecules present deep in the liquid are shared with all neighboring atoms.
  • the surface molecules of the liquid have no neighboring atoms of the same type above and exhibit stronger cohesive forces upon the molecules directly associated with them on the surface. From a macroscopic point of view, the enhanced intermolecular interaction at the surface of the liquid is observed as the surface tension of the liquid.
  • the cohesive forces between like molecules compete with external forces existing between the molecules of the liquid and molecules of the material contacting the liquid. When this material is hydrophobic, the cohesive forces significantly dominate, the free surface of the liquid becomes film-like and the liquid is incapable of wetting the hydrophobic material.
  • Figure 1 is a schematic illustration of aggregate 1, which preferably comprises a plurality of differently sized particulates 2 characterized by several (specifically selected) parameters which influence the level of the external forces and thereby the hydrophobic properties of the aggregate.
  • These parameters includes, but are not limited to, a size distribution, M, of particulates 2, a contact angle, ⁇ , defined between the liquid and particulates 2 and a characteristic distance, r, defined between adjacent particulates.
  • M, ⁇ and r are preferably selected depending on the wate ⁇ roofing application for which the aggregate is designed to be used, and in accordance with the maximal liquid pressure expected in the specific application.
  • M and the cosine of ⁇ are preferably proportional to the pressure and r is preferably inversely proportional to the pressure.
  • P kMcosQ/r, (EQ. 1) where k is a constant of the proportionality and the angle, ⁇ , is measured from the tangent to a surface defined by the layer of the free-flowing aggregate.
  • ⁇ is selected from 90° to 180°, where larger values of ⁇ within this range correspond to larger pressure under which the aggregate remains dry and vise versa.
  • the contact angle, ⁇ depends on the materials from which the hydrophobic aggregate of the present invention is made. A detailed description of materials which were found to be suitable to various wate ⁇ roofing applications is provided hereinafter.
  • a non-uniform size distribution allows for better control on the capillary size of aggregate 1.
  • Capillary size is a measure of the diameter of capillaries formed between the particulates of the aggregate.
  • the size distribution, M is selected so that a maximal diameter of the capillaries is suitable for repelling the liquid at the pressure, P.
  • a typical diameter of the capillaries is from 1 nanometer to 500 nanometers. Such diameter is size wise compatible with capillaries formed in concrete matrices.
  • the size of the particulates may vary between about 25 millimeters (25,000 microns) and 5 microns, more preferably between 10 millimeters and 20 microns, more preferably between 5 millimeters and 100 microns and most preferably between 1,000 microns and 200 microns. In a construction site, large size particulates are easier to handle.
  • the manufacture can select the characteristic variance of the size distribution of the aggregate.
  • the particulates are preferably smaller in size and larger in variance.
  • the preferred variance is about 50 micrometers
  • the preferred variance is about 30 micrometers
  • for a column of liquid of about 10-50 m the preferred variance is about 10 micrometers.
  • M Other physical quantities which can be affected by M include, but are not limited to, the specific weight of the aggregate, water abso ⁇ tion capability, thermal properties (e.g., thermal conductivity, specific heat capacity, latent heat) and acoustical isolation.
  • thermal properties e.g., thermal conductivity, specific heat capacity, latent heat
  • acoustical isolation e.g., thermal conductivity, specific heat capacity, latent heat
  • an application-oriented aggregate may be formed. For example, in an acoustical isolated wate ⁇ roofing application M is selected so as to maximize the acoustical isolation of the aggregate, in temperature isolated wate ⁇ roofing application M is selected so as to minimize the thermal conductivity of the aggregate, etc.
  • a judicious selection of the size distribution can also be used to control the ability of the aggregate to allow evaporation of the liquid there through.
  • M is selected so that the aggregate is capable of allowing evaporation of the liquid.
  • aggregate 1 may exhibits statistical fluctuations in which locally the capillaries exceed their average size by several standard deviations.
  • a relatively large capillary size is typically formed in interfaces between hydrophobic and non hydrophobic layers. The problem of large interface capillaries is non statistical and affects the overall pressure under which aggregate 1 can be used. This problem may be solved by applying adhesives between hydrophobic and non hydrophobic layers, as further detailed herein under.
  • the capillary size of aggregate 1 may be significantly reduced using inflatable particulates capable of absorbing fluid (e.g., water).
  • the inflatable particulates Once being in contact with the liquid, the inflatable particulates dynamically adjust to the liquid pressure, even when this pressure exceeds its expected value. Due to the judicious selection of the static parameters of aggregate 1 (e.g., the size distribution, M), the inflatable particulates inflate only when the pressure excides the expected pressure to which aggregate 1 is designed. As the pressure rise, the inflatable particulates start to inflate thus establishing a dynamic pressure barrier.
  • the inflation of the inflatable particulates increases internal forces within aggregate 1, blocking residual capillaries and thus enhancing the ability of aggregate 1 to prevent percolation of liquid and passage of water vapor.
  • the inflatable particulates may be inco ⁇ orated into aggregate 1 in more than one way.
  • the inflatable particulates may be integrated in, or attached to particulates 2, already in the manufacturing stage thereof. This embodiment is further detailed hereinafter, following the description of the suitable materials which may be used to manufacture aggregate 1.
  • the inflatable particulates are in the form of free particulates (e.g., a powder).
  • an inflatable particulate 3 is present in void 4 between particulates 2.
  • particulates 2 When a local increase of liquid occurs, particulates 2 are pressed one against its neighbors, while, at the same time, inflatable particulate 3 absorb the liquid and begins to inflate, hence operates as a small "balloon" having a dynamically expanding surface area.
  • External forces, caused by particulates 2 and acting inwards to void 4 limit the inflating process so that particulate 3 becomes a three-dimensional structure whose shape is similar to the shape of void 4.
  • the inflating process is terminated when particulate 3 essentially occupies void 4, thus reducing the characteristic distance, r, and increasing the pressure, P, under which aggregate 1 is effective.
  • the average size of inflatable particulates is selected so that, when the inflatable particulates are in deflated state, at least one inflatable particulate or, more preferably, several inflatable particulates, occupy void 4.
  • a typical size of the inflatable particulates is from about 1 micrometer to about 1000 micrometers, preferably, 5-500 micrometers.
  • the inflatable particulates preferably are devoid of any fluid communication there amongst, so that even when the inflatable particulates are in inflated state, the free- flowing nature of aggregate 1 is maintained.
  • the inflatable particulates constitute a sufficiently small volume percentage of aggregate 1.
  • the inflatable particulates constitute less than 1 % of aggregate 1 by volume, more preferably about 0.2 %.
  • the voids between the hydrophobic surfaces of particulates 2 form a network, at least partially interconnected, in which the largest voids determine the entire behavior of aggregate 1.
  • the swelling time of the inflatable particulates is sufficiently small (preferably under 10 seconds) so that aggregate 1 quickly responses to any contact with water.
  • the abso ⁇ tion capability of the inflatable particulates is preferably from about 100 to about 5000 by weight, more preferably from about 200 to about 2000. by weight.
  • the freezing temperature of the inflatable particulates is preferably below about -20 °C (both in inflated and in deflated states) so that aggregate 1 maintains its free-flowing nature even at low temperatures.
  • a judicious selection of the material from which the inflatable particulates are made may result in that cycles of abso ⁇ tion-deso ⁇ tion thereof can be is repeated endlessly. Any material known capable of swelling when in contact with a liquid can be used for the inflatable particulates, provided that the combination of the inflatable particulates and particulates 2 maintains the free-flowing nature of aggregate 1.
  • the inflatable particulates are made of a super absorbent polymer (SAP), also known as Polyols polymers.
  • SAPs are known in the art for many years. What makes SAP water absorbent is the presence of a chemical such as sodium or potassium molecules that cross-links between the hydrocarbon chains of a polymer. These cross-links allow the polymer to form into a single super-molecule capable of holding significant amounts of water.
  • the polymer is typically polyurethane, urethane or polypropylene, but other polymers may also be used.
  • SAPs There are hundreds types of SAPs, characterized by various parameters, such as their water pick-up capabilities, the temperature at which water is absorbed and desorbed, abruptness of water release and the like.
  • a representative example of a SAP include, without limitations, sodium cross linked with polyacrylic acid.
  • Similar SAPs include, but are not limited to, LiquiBlockTM 80, LiquiBlockTM 88, LiquiBlockTM At-03S, LiquiBlockTM 80HS, LiquiBlockTM 88Hs, LiquiBlockTM 144, LiquiBlockTM 144TRS, NorsocrylTM S-35, NorsocrylTM D-60, NorsocrylTM XFS, all of which are purchasable from Emerging Technologies, Inc., North Carolina, USA. These SAPs were experimentally found to be suitable for inco ⁇ orating with the aggregate 1. Other SAPs are presently manufactured by, and are available from, Union Carbide, BASF Co ⁇ oration and many other companies.
  • the inflatable particulates may comprise an anti-caking agent to minimize liquid communication between adjacent inflatable particulates.
  • an anti-caking agent for example, NorsocrylTM XFS and LiquiBlockTM 144TRS, above, include an anti-caking agent.
  • SAP is used only for the pu ⁇ ose of bridging between capillaries, while most of the wate ⁇ roofing is accomplished by the inherent hydrophobic properties of aggregate 1.
  • only a small amount of SAP is needed, as further detailed hereinabove.
  • the hydrophobic aggregate may be mixed with hydrophobic coated lightweight aggregates, for example, Pumis, Perlite, volcanic aggregate, crashed foam concrete, etc.
  • the lightweight aggregates serve for reducing the overall weight of the mixture. The reduced weight is important, for example, when the mixture is used for wate ⁇ roofing roofs, flooring or any wate ⁇ roofing done indoors.
  • Figures 2A-B schematically illustrate prior-art methods of wate ⁇ roofing a foundation of a structure 10 on a ground 12.
  • a foundation layer of pebbles 22, and sidewalls of pebbles 20 are provided as water channels to allow for water flow adjacent to underground section 14 of structure 10.
  • the foundation walls of underground section 14 may be covered with tar or a similar material, as an additional water protection.
  • a method of wate ⁇ roofing a portion of a structure being in contact with a ground comprises the following method steps in which in a first step a bed of a free- flowing hydrophobic aggregate is provided, and in a second step the structure is positioned over or in the bed.
  • any free-flowing hydrophobic aggregate may be used, such as, but not limited to, aggregate 1 mentioned hereinabove or another commercially available free- flowing hydrophobic aggregate (also known in the literature as "magic sand"), manufactured, for example, by Clifford W. Estes Co. Inc., New Jersey, USA, and Educational Innovations, Connecticut, USA.
  • additional aggregates useable in context of the present invention are described in U.S. Provisional Patent Application Nos. 60/486,419 and 60/486,420, WO 03/044124 and U.S. Patent No. 4,474,852, all of which are hereby inco ⁇ orated by reference.
  • FIGS 3A-C schematically illustrate wate ⁇ roofing of a foundation of a construction, in accordance with a preferred embodiment of the present invention.
  • a bed 32 of free-flowing hydrophobic aggregate is applied over pebble layer 22, preferably remains as a drainage channel under bed 32.
  • Bed 32 prevents water from applying upward pressure onto underground section 14.
  • the hydrophobic aggregate may be delivered to the construction site either in a free-flowing form, or encapsulated in one or protective encapsulations.
  • protective encapsulation is a hydrophobic brick, as further detailed herein under (see Figure 4 A and the description that follows).
  • bed 32 may comprise an arrangement of hydrophobic bricks.
  • bed 32 is preferably protected by a structure 23, for example, a concrete structure or a polymeric structure, to prevent erosion by underground water.
  • the thickness of bed 32 (designated dl in Figure 3B) is preferably from about 1 cm to about 15 cm, more preferably from about 4 cm to about 10 cm.
  • wall 15 of underground section 14 can also be wate ⁇ roofed by providing a sidewall 30 of the free-flowing hydrophobic aggregate (e.g., aggregate 1) adjacent to wall 15.
  • Wall 15 is preferably coated by a wate ⁇ roofing liquid or paste, e.g., tar layer 24.
  • Tar layer 24 adheres the hydrophobic aggregate to wall 15 hence serves as a vapor barrier, preventing a formation of gap between sidewall 30 and wall 15.
  • sidewall 30 of the hydrophobic aggregate is preferably protected by a structure 36, which may be, for example, one or more wood boards, polymeric (e.g., polystyrene) boards, plastic boards, metal boards, a brick wall or a concrete structure.
  • Structure 36 is inte ⁇ osed between sidewall 30 and ground 12 (or pebble layer 22) hence serves for protecting sidewall 30 from erosion, roots, rocks and the like.
  • structure 36 has a non-smooth surface 37, facing ground 12 or pebble layer 22 for so as to enlarge the contact area between structure 36 and the ground.
  • sidewall 30 may be done by more than one way, as further detailed herein below, both to a an existing structure, during repair procedure, and to a new structure, during its construction.
  • prior art methods typically include the use of foam or swollen materials injected along the existing walls into the interface between the wall and the ground surrounding the wall. In extreme cases the area near the underground wall is exposed or vacuumed using heavy machinery, so as to allow access to the external side of the wall.
  • the wall is than wate ⁇ roofed by a sealing material, such as elastomeric concrete or various foams.
  • underground wall 15 can be wate ⁇ roofed by the following procedure. First, a layer of ground adjacent to the external side of wall 15 is pulled out or vacuumed, leaving a gap of air, and second the gap is filled with the free-flowing hydrophobic aggregate.
  • the free- flowing nature of the hydrophobic aggregate allows for a substantially complete filling of the gap, in contrast to any other foamy or swollen material which does not allow an airflow there through, hence entrap air pockets and cannot fill the entire gap.
  • structure 36 is preferably constructed adjacent to wall 15, in a manner that a gap is formed between structure 36 and wall 15.
  • Structure 36 may be made in any way known in the art.
  • structure 36 may be an additional wall, e.g., a brick-concrete wall.
  • the advantage of this embodiment is that the additional wall maintains the hydrophobic aggregate in place for a prolonged period of time. Additional advantages of the additional wall include additional strength to the construction and an enhanced isolation (both thermal and acoustical).
  • structure 36 may be made of tiles (e.g., plastic tiles) having toothed edges, which fit into each other, tongue and groove fashion.
  • side wall 30 is constructed level by level as follows. Hard boards or other boards, such as, but not limited to, metal, wood and plastic boards) are temporarily positioned adjacent to wall 15, so that a first side of the hard boards is facing wall 15 (again, leaving a sufficient gap there between) and a second side of the hard boards is facing the ground. The gap is filled with the free-flowing hydrophobic aggregate and the ground is allowed to contact the second side of the hard boards.
  • protecting structure 36 is preferably positioned permanently between the hydrophobic aggregate and the ground.
  • the hard boards may be used as protecting structure 36.
  • the advantages of this embodiment are that (i) there is no need to build an additional wall near wall 15 and (ii) the filling of the gap is simpler as a relatively small volume is filled at each level.
  • the preferred thickness of sidewall 30 (designated d2 in Figure 3C) is from about 4 cm to about 10 cm. It is to be understood that other values may similarly be used, depending on the expected water pressure.
  • side wall 30 comprises an arrangement of hydrophobic bricks, each comprising a protective encapsulation having a predetermined shape and encapsulating a free-flowing hydrophobic aggregate.
  • Figures 4A-B schematically illustrate a hydrophobic brick 40 having a protective encapsulation 41 and a hydrophobic brick wall 42.
  • encapsulation 41 is made from a bio degradable material or water degradable material, for example, recycled cardboard devoid of water protection and the like.
  • the construction of hydrophobic brick wall 42 is by positioning bricks 40 one on top of the other, similarly to the construction of any other brick wall.
  • wall 42 is preferably watered in order to facilitate the degrading of bricks.
  • the brick thickness, in the direction of water protection, d3, is about 2-10 cm, preferably about 4 cm. It will be appreciated that other dimensions may similarly be used. It is known that structures in contact with the ground are dynamic, due to ground movements or crack formations.
  • a removable cover 38 is preferably provided on the top side thereof, to allow the refill of the gap, with time.
  • Removable cover 38 may be made from any water resistant material, such as, but not limited to, wate ⁇ roofed concrete stones.
  • Figures 5A-B schematically illustrate methods of wate ⁇ roofing floors 60 of structure 10, in accordance with a preferred embodiment of the present invention.
  • Structure 10 includes several levels 70 and side walls 52.
  • Bed 32 of hydrophobic aggregate e.g., aggregate 1
  • a typical thickness of bed 32 for this aspect of the invention is about 1-10 cm, however, it will be appreciated that other values may similarly be used.
  • Contact area 52' between wall 52 and bed 32 is preferably coated by a wate ⁇ roofing liquid or paste which adheres the hydrophobic aggregate to wall 52 hence serves as a vapor barrier, as further detailed hereinabove.
  • a pipe 68 e.g., water, sewage, gas, electricity, etc.
  • the advantage of the hydrophobic aggregate is that it allows water to evaporate there through without becoming wet.
  • a particular advantage of the present embodiment is that due to the improved isolating properties of the free-flowing aggregate, no additional isolating materials are necessary for the pipes as is commonly used for hot water pipes or the like. In addition, the free-flowing aggregate protects the pipes also from corrosion and wear.
  • bed 32 under floor 60, is that such an environment keeps away insects and other organisms which cannot dig holes or tunnels, or even survive in the dry environment of the hydrophobic aggregate.
  • An additional advantage is the thermal and acoustical isolation provided by bed 32.
  • bed 32 is ideal as a bed for placing hot/cold water pipes, for which it will be appreciated that thermal isolation is of utmost important.
  • Figures 6 A - 6B schematically illustrate prior- art methods of wate ⁇ roofing a roof 50. Numerous methods are known for wate ⁇ roofing roofs. One such method is illustrated in Figure 6 A, where a layer 54 of tar is applied to roof 50.
  • FIG 6B Another method is illustrated in Figure 6B, where a layer of ordinary sand 58 and flooring 60 is applied onto roof 50.
  • protective sheets 56 for example bituminous membranes, polyvinyl chloride (PVC) or ethylene propylene diene monomer (EPDM) layers may be used under layer of sand 58.
  • PVC polyvinyl chloride
  • EPDM ethylene propylene diene monomer
  • FIG 7 schematically illustrates structure 10 having a roof 50 and sidewalls 52.
  • bed 32 of hydrophobic aggregate e.g., aggregate 1
  • the contour of roof 50 may be treated by providing vapor barrier and inclined edges, as is well known in the art. Additionally, floor 60 may be applied over bed 32, thus preventing erosion thereof. In this manner, a high-level water-proofing protection is achieved even on severe weather conditions such as hail.
  • the thickness of bed 32 (designated d4 in Figure 7) is preferably about 5 cm. It will be appreciated that other values may similarly be used.
  • a method of wate ⁇ roofing a reservoir e.g., a water reservoir. Referring further to the drawings, Figure 8 schematically illustrates a reservoir
  • the method comprises the following method steps in which in a first step a flooring bed 84 of a free-flowing hydrophobic aggregate (e.g., aggregate 1) is placed over base 82 of the reservoir.
  • a flooring bed 84 of a free-flowing hydrophobic aggregate e.g., aggregate 1
  • walls 90 sloping walls or vertical, depending on the shape of reservoir 80
  • Flooring bed 84 and/or walls 90 are preferably covered by protective structure 86 and 92, respectively, so as to maintain free-flowing hydrophobic aggregate in place.
  • Structure 86 (covering bed 84) preferably comprises a flexible layer, for example, a geotechnic fabric, covered by a concrete slab, of preferably about 5 cm in thickness.
  • the flexible layer of structure 86 may be covered by concrete tiles.
  • a portion of the flexible layer of structure 86 may be covered by concrete tiles and another portion may be covered by a concrete slab.
  • the concrete is poured on the flexible layer devoid of metal wiring, to prevent flowing of the hydrophobic aggregate during the construction of structure 86.
  • Polymeric fibers may be added to the concrete mix to minimize crack formations in the structure 86.
  • the pouring of the concrete may be done in any way known in the art, preferably by leaving a sufficient number of gaps to allow the concrete to expand during its curing process.
  • Structure 86 may also be made of a plurality of protective boards or any other method known in the art.
  • the method for placing walls 90 depends on the shape of walls ⁇ 8 of reservoir 80. For vertical walls, walls 90 may be constructed similarly to walls 30 or 42 as further detailed hereinabove. For sloping walls, a sloping structure 92 is constructed.
  • FIG. 9 schematically illustrates a representative example of stabilizing means, in the form of tiles 98 with toothed edges 99, which fit into each other, tongue and groove fashion.
  • Tiles 98 may be made from polyvinyl chloride, polycarbonate or any other suitable material capable of holding the hydrophobic aggregate. The size and strength of the tiles is preferably selected so as to allow the installer to walk or stand thereon.
  • elongators 97 are preferably attached to the tiles so as to create a sufficient gap between the tiles and the ground.
  • a typical length of elongators 97 is 1-10 cm.
  • the procedure of constructing sloping structure 92 using tiles 98 is as follows. A first line of tiles is arranged on sloping wall 88 near base 82, so that elongators 97 keep tiles 98 above the walls. The volume defined by elongators 97 is then filled with the hydrophobic aggregate.
  • tiles 98 may be manufactured from a transparent material so as to allow the installer to verify that the entire volume is filled, and to vibrate the tiles if necessary, so as to better distribute the hydrophobic aggregate.
  • Mechanic or sonic vibration may also be used.
  • a second line is arranged adjacent to the first line, and the procedure is repeated.
  • the elongators of the previous line are removed so as to allow the hydrophobic aggregate to fill the volume engaged by the elongators.
  • wall ⁇ 8 is covered by tiles 98 and the hydrophobic aggregate, concrete or another suitable cover is preferably be applied on the other side of tiles 90. Toothed edges 99 serve for increasing the surface area of tiles 98 so as to maintain the hydrophobic aggregate and the concrete in place and to allow spray shot crating if so desired.
  • the upper line of tiles is preferably permanently attached to the ground to serve as a protective cover.
  • the tiles are arranged in a manner that allows refilling of the free-flowing hydrophobic aggregate with time. This can be done, for example, by leaving openings in the upper line of tiles or by providing a removable cover thereupon, as further detailed hereinabove.
  • the compositions, particulates and free-flowing aggregate of the present invention can also be used in the area of agriculture or gardening where it is often desired to prepare an area for plants cultivating. It is known that only a relatively small part of water used for irrigation finally arrives to the plants, whereby most of the water seeps through the earth or evaporates.
  • an area of interest can be prepared for plants cultivating by providing a bed of free-flowing hydrophobic aggregate (e.g., aggregate 1) onto the area of interest and covering the bed by a layer of soil. Additionally one or more water collection channels can be positioned in, under or above the soil for allowing conveyance of water.
  • the bed can be in a form of hydrophobic patches, made of a protective encapsulation and encapsulating the aggregate. The patches are preferably arranged such that one or more spaces are formed between adjacent patches, thereby allowing excess water (e.g., rain water), to drain of the area of interest. Since the hydrophobic aggregate is dry and presents a low resistance for vapor, the bed can conduct a passage for vapor underneath the trees or plants.
  • the sucking action of the roots is further enhanced by the sucking action of the roots.
  • the hydrophobic bed traps the condensed water and prevents it from escaping again.
  • water percentage in the top soil layer rises.
  • the effect of vapor and water trapping can be increased by positioning a layer of super absorbent polymer on the hydrophobic bed so as to utilize a larger proportion of vapor.
  • the layer of soil is surrounded by a protective barrier, which itself can be made of hydrophobic aggregate as further hereinabove.
  • the walls of the protective barrier and the bed form an enclosed reservoir, preventing the condensed water from escaping therefrom.
  • the height of the walls can vary as desired, depending on the amounts of condensed water, soil type and underground water level.
  • the hydrophobic bed facilitates desalination of non-desalted water present thereunder, because vapors, passing through the bed are substantially desalted, hence, upon condensation the water is being desalinated.
  • the hydrophobic bed can also be used in a preparation of a salt-free area on a salty soil. In many places around the world, underground water level is high and water is salty. This presents a real challenge both for agriculture and construction applications.
  • a salt-free area can be provided by providing a hydrophobic bed onto the area of interest and covering the bed by salt-free soil.
  • the bed prevents the salt from penetrating therethrough and at the same time facilitates passage of (non-salty) water vapor, in the aforementioned desalination process.
  • a layer of super absorbent polymer can be used, to allow formation of gel, as further detailed above. It would be appreciated that the use of hydrophobic bed of the present embodiment as a barrier against salts is advantageous over conventional methods in which barrier sheets are used, because there are no joints or welded parts. According to a further aspect of the present invention there is provided a method of protecting an object buried underground.
  • composition 110 a hydrophobic composition for protecting an underground object, generally referred to herein as composition 110.
  • Figure 10 is a schematic illustration of composition 110 which comprises a mix of at least two free-flowing hydrophobic aggregate, each of which may posses one or more properties of aggregate 1.
  • composition 110 comprises a thermally conductive free-flowing hydrophobic aggregate 112 and a dielectric free-flowing hydrophobic aggregate 114.
  • Aggregates 112 and 114 are mixed in a predetermined ratio which is selected so as to electrically isolate the underground object while allowing transportation of heat therefrom.
  • composition 110 has a distinguishable color, preferably different than the color of the ground.
  • composition 110 Even in cases where water vapors percolate through composition 110, these are not sufficient to initiate electrolytic corrosion.
  • hydrophobic aggregate 114 is made of a dielectric material (i.e., has substantially no electrical conductivity)
  • connection boxes, oil sensors or any other device filled with composition 110 can function without short circuits for a prolonged period of time.
  • the free-flowing form of composition 110 facilitates the removal of the aggregates from the wires and/or the connection boxes, if such a removal is needed, e.g., for maintenance.
  • the ohmic resistance of conductors being present in connection boxes, and of cables and wires carrying electrical current is known to release energy by generating a substantial amount of heat.
  • the resulting temperature increase often contributes to weakening of both the current carrier and its surrounding nonconducting elements. It is appreciated that lack of a proper heat transport mechanism may results in electrical discontinuities along the wires and cables, especially inside the connection boxes, where most of the heat is generated. Furthermore, in small connection boxes, the generated heat may cause fusion of several conducting elements thereby to create short circuits and damage the systems depending on the underground cable.
  • the thermal conductance of aggregate 112 allow composition 110 to transport heat away from the current carrier (e.g., to the ground) thereby to keep the underground connection boxes, cables and/or wires cool at all times and to maintain their functionality. Forth, various agents, and especially digesting agents, present in the ground in solid state are prevented from becoming liquefied and therefore from reaching and damaging the underground object.
  • the free-flowing form of the aggregates of the present invention minimizes axial stresses from acting upon the underground object.
  • the free- flowing hydrophobic aggregates are similar to a viscous fluid, which uniformly distributes the mechanical forces acting thereupon.
  • the aggregates of the present invention thus absorb a considerable amount of the mechanical forces and protects the underground object.
  • Sixth, being substantially water-free, the hydrophobic aggregates do not freeze and does not stick, hence facilitate an easy access to the underground object in cold regions, and improves resistance to frost.
  • composition 110 has a distinguishable color. This embodiment can be beneficially used when an identification of composition 110 is required.
  • composition 110 For example, for the pu ⁇ ose of warning against excavation near the submerged object which is covered by composition 110.
  • underground oil tanks often suffer from oil spills resulting from a leaking tank or an overflow.
  • one or more sensors are positioned near the underground oil tanks so as to generate a signal when the surroundings of the sensor become wet. These sensors, however, often generate false alarm due to the presence of, e.g., rain water.
  • the composites of the present invention can have an increased attraction for oil and oil related products.
  • the aggregates of the present invention can be used to selectively prevent water from reaching the sensors, hence substantially reducing the false alarms.
  • any free- flowing hydrophobic aggregate may be used for aggregates 112 and/or 114, provided they have the required properties, i.e., enhanced thermal conductance of aggregate 112, enhanced electrical resistivity of aggregate 114 and enhanced water repulsion for both aggregate
  • any hydrophobic material to repel water basically depends on the surface tension of the liquid being in contact with the hydrophobic material.
  • the cohesive forces between molecules present deep in the liquid are shared with all neighboring atoms.
  • the surface molecules of the liquid have no neighboring atoms of the same type above and exhibit stronger cohesive forces upon the molecules directly associated with them on the surface. From a macroscopic point of view, the enhanced intermolecular interaction at the surface of the liquid is observed as the surface tension of the liquid.
  • the cohesive forces between like molecules compete with external forces existing between the molecules of the liquid and molecules of the material contacting the liquid.
  • aggregates 112 and 114 are preferably selected such that the cohesive forces are sufficient for preventing the liquid from wetting composition 110.
  • Any of the aforementioned hydrophobic aggregates may be mixed in composition 110, according to preferred embodiments of the present invention.
  • the core material is preferably selected in accordance with the desired property of the free-flowing hydrophobic aggregate. For example, sea sand may be used as the particulated core material for thermally conductive aggregate 112, while coal ash may be used as the particulated core material for dielectric aggregate 114.
  • each of aggregates 112 and 114 of composition 110 may comprise differently sized particulates characterized by several parameters which influence the hydrophobic properties of composition 110. These parameters may includes the aforementioned size distribution, M, a contact angle, ⁇ . As stated capillary sizes may be significantly reduced using inflatable particulates, which, in one embodiment can be integrated in, or attached to the particulates of aggregates 112 and/or 114. Alternatively, inflatable particulates cane be in the form of free particulates (e.g., a powder).
  • an inflatable particulate 116 is present in a void 118 between particulates of aggregates 112 and 114, similarly to the way the inflatable particulate was inco ⁇ orated with aggregate 1.
  • an underground object e.g., a tank, a cable, a wire, a network etc.
  • the method comprises the following method steps which are illustrated in the flowchart of Figure 11.
  • a hydrophobic composition e.g., composition 110
  • a second step designated by Block 124 the object is surrounded by a layer of the hydrophobic composition in a manner that the layer is inte ⁇ osed between the object and the ground.
  • the second step my be performed in any way known in the art, for example, by forming a ditch in the ground, applying a first layer of the hydrophobic composition in the ditch, placing the object on the first layer and covering the object with an additional layer of the hydrophobic composition.
  • the upper layer of the hydrophobic composition may be subsequently covered by a layer of ground to prevent the composition from carried by the wind or the rain.
  • Figure 12a schematically illustrate an object 130 buried in ground 132, and surrounded by a layer 134 of the hydrophobic composition, in accordance with the present invention.
  • the underground object is an oil tank
  • one or more sensors 129 may be positioned near the object within layer 134 so as to monitor possible oil spills.
  • the hydrophobic composition is selected so as to allow abso ⁇ tion or adso ⁇ tion of oil therein, hence to facilitate proper operation of sensors 129 with minimal false alarms. This can be done, for example, by selecting the core material so as to maximize the adsorbing or absorbing capability of the aggregates.
  • core material includes, without limitation, granolas of cellulose which can provide about 1:1 abso ⁇ tion capability.
  • the surroundings of object 131 within dike 135 is filled by a layer 133 of hydrophobic particulates (e.g., aggregate 1, composition 110, etc.).
  • the core material of the hydrophobic particulates is selected so as to maximize the adsorbing or absorbing capability of layer 133.
  • oil spills 137 are attracted thereby, hence causing the water to overflow from dike 135 and keeping the contaminating oil therein.
  • a thermally conductive free-flowing hydrophobic aggregate e.g., aggregate 112
  • a dielectric free-flowing hydrophobic aggregate e.g., aggregate 114
  • the two aggregates are mixed.
  • the mixing ratio of the two aggregates is selected so as to allow both electrical isolation of the underground object and transportation of heat therefrom.
  • the method may further comprise an optional step, designated by Block 148, in which inflatable particulates (e.g., particulates 116) are mixed with the thermally conductive and the dielectric free-flowing hydrophobic aggregates, as further detailed hereinabove.
  • the method may further comprise an additional step, designated by Block 150, in which the two aggregates (and the inflatable particulates in the embodiment in which these particulates are included) are mixed with one or more additive, such as, but not limited to, a coloring agent, a UV resistant agent, a bleaching agent and an abrasive agent, as detailed above.
  • the hydrophobic powder of the present invention includes one or more selected impure elements that have a hydrocarbon attached thereto and optionally hydrophobic fumed silica.
  • the composition of the hydrophobic powder is predetermined according to the desired application.
  • the hydrophobic powder is preferably prepared by a surface reaction of colloidal particles of one or more selected impure element (e.g., calcium carbonate, magnesium carbonate, calcium oxide, etc.) with a fatty acid having at least 10 carbon atoms in its hydrocarbon chain, to thereby obtain a hydrophobic derivative of the element in a powder form.
  • one or more selected impure element e.g., calcium carbonate, magnesium carbonate, calcium oxide, etc.
  • a representative example of such a hydrophobic powder is Calcium Stearate, which is a commercially available powder that is presently used in pharmaceuticals and plastics.
  • a hydrophobic powder can be prepared, for example, by contaminating calcium carbonate with impurities such as magnesium oxide, iron oxide, aluminium oxide, silica and sulfates, and thereafter reacting the resulting impure calcium with stearic acid.
  • the hydrophobic powder further includes hydrophobic fumed silica
  • the resulting hydrophobic powder mixture is prepared by mixing predetermined amounts of each of the components until uniformity is attained. The mixing is typically continued for about 10 minutes.
  • a representative example of a hydrophobic powders according to the present invention include a mixture of Calcium Stearate having an average particles size of about 10 microns (obtained from Kfar-Gilaadi Quarries, Israel) and hydrophobic fumed silica having an average particles size not greater than 1 micron (Aerosil Fume Silica, R-812, by Degussa, Germany).
  • the calcium stearate and the fumed silica are mixed for about 10 minutes and the resulting hydrophobic powder has an average particles size not greater than 10 microns.
  • EJ ⁇ AMPlE l Preparation of Hydrophobic Composites — General Procedure Drying the core material: The core material (as is defined hereinabove) is dried at a temperature of at least 104 °C, until its moisture level is reduced to below 1 weight percentage. This procedure is carried out in a closed mixing vessel equipped with a suction port fitted with a valve enabling opening and closure. Alternatively, a pre-dried core material is placed in the mixing vessel described above and is heated to a temperature of at least 70 °C. Coating the core material with an adherent layer: Preliminary preparation of the adherent layer mixture is carried out in a mixing vessel at a temperature of 40-90
  • the composition of the mixture is determined as is described hereinabove.
  • the adherent mixture is then added hot as it is into the mixing vessel described hereinabove, which contains the dry core material.
  • the resulting mixture of the dry core material and the adherent layer mixture are thereafter heated and mixed, preferably at 30-60 rpm, such that the solvent is evaporated using the suction system described above.
  • this procedure is carried out without heating, by utilizing the self-heat of the core materials, which is formed during the drying process. This procedure continues until the solvent content reaches 0 % and typically lasts 10-45 minutes, depending on the type of solvent used in the adherent layer mixture.
  • the evaporated solvent e.g., an organic solvent
  • the evaporated solvent can be recycled for repeated use, both in order to protect the environment and from an economic standpoint.
  • other additives e.g., coloring agents, abrasive powder, UV resistance agents etc., as is detailed hereinabove
  • the additive is added to the mixing vessel at this stage and mixing is continued, preferably at 30-60 rpm, for additional 5 minutes, to obtain uniformity.
  • the added materials should be dried, so as to have a moisture content of less than 1 %.
  • Coating the core material coated with the adherent layer with a hydrophobic powder The hydrophobic powder is prepared as described hereinabove in a separate vessel.
  • the resulting hydrophobic mixture of choice is added into the core material mixture.
  • the suction port is closed in order to prevent loss of the hydrophobic material.
  • Mixing is continued for about 10 minutes, until the powder cloud completely disappears.
  • the resulting mixture is then cured for between 24 hours and 30 days, depending on the selected hydrophobic mixture, so as to produce the final hydrophobic composite.
  • the total time of the process between obtaining the dried core material and obtaining the core material coated by the hydrophobic powder ranges between 25 and 60 minutes.
  • the dried core material may be stored in a closed dry place to be used for coating when cold, without any need of re-heating.
  • An adherent layer mixture which preferably comprises in this procedure 7 % polyurethane and 93 % ethyl acetate, is prepared as described above and is then added to the dried core material.
  • the quantity of the obtained adherent layer in this process typically ranges between 3 and 7 weight percentages of the dry core material weight.
  • the resulting mixture is mixed at room temperature, for about 10 minutes, until the ethyl acetate is vaporized down to a level of 0 %.
  • the evaporated ethyl acetate may be recycled up to about 80 % of its content.
  • a hydrophobic coat mixture of choice is then added as is described above and the resulting mixture is mixed for about 5 minutes. The final product is obtained after curing between 24 hours and 30 days.
  • EXAMPLE 4 Preparation of Hydrophobic Sand Sand, such as, for example, quartz sand having particles size of 600-800 microns, was dried as is described hereinabove.
  • an adherent mixture containing 9 weight percentages of the polyurethane Alkydal F 48, 55 % in benzene-xylel (obtained from Bayer, Germany), 5 weight percentages of commercial liquid asphalt (Premier 1430, obtained from Paz-Kar, Israel) and 86 weight percentages of toluene (obtained from Frutarom, Israel) was mixed, at 70 °C, for about 10 minutes and was thereafter added to the hot sand. Mixing was continued for about 15 minutes, at 50 ⁇ m, during which the toluene content was reduced to 0 %.
  • a hydrophobic powder comprised of between 14:1 and 3:1 Calcium Stearate
  • This enhanced resistance occurs as a result of the following: when a water wave hits the hydrophobic sand, it pushes the grains somewhat apart and when the wave retreats a momentary under-pressure is created, which pulls out the lightweight granules first.
  • This "migration" of the lightweight particles is only carried out due to dynamic motion and the particles move towards the dynamic disturbance, so as to form a thin crust of hydrophobic particles forming an additional protection layer.
  • the retreating water does not pull away this crust and the next wave will then encounter a double hydrophobic defense line. It was found that such lightweight particles may be achieved by using an excessive amount of the adherent layer.
  • the adherent layer components which do not adjoin the sand, form free, light particles having a size of 1- 50 microns. These particles become hydrophobic in the second stage, together with the sand granules, and as they are much lighter in weight than the sand granules, they are attracted first to the momentary under-pressure following the wave and thus form, the described crust.
  • a detailed exemplary procedure of preparing such hydrophobic sand, improved with free particles is as follows: Quartz sand, obtained from a quarry, having particles size of 600-800 microns, was dried as is described hereinabove.
  • an adherent mixture containing 15 weight percentages of the polyurethane Alkydal F 48, 55 % in benzene-xylel obtained from Bayer, Germany
  • 5 weight percentages of commercial liquid asphalt Premier 1430, obtained from Paz-Kar, Israel
  • 80 weight percentages of toluene obtained from Frutarom
  • a hydrophobic powder comprised of 14:1 Calcium Stearate (obtained from Kfar-Gilaadi Quarries, Israel) and hydrophobic fumed silica (Aerosil Fume Silica, R- 812, by Degussa, Germany) was prepared in a separate vessel by mixing the components for about 10 minutes and was thereafter added to the hot mixing vessel containing the sand coated by the adherent layer. The suction port was closed and mixing was continued for about 10 minutes at 50 rpm. The product was then cured for 30 days.
  • EXAMPLE 6 A Hydrophobicity Test When hydrophobic sand is serially manufactured, on-going tests of the hydrophobic quality of the finished product are required.
  • Hydrophobic sand is then added to the funnel until the sand lump falls into the water.
  • the balance indicates the weight of the hydrophobic sand for comparison.
  • the underlying principle of this designed test is as follows: Since the sand is hydrophobic, it changes the surface tension of the water so that the sand floats on top of the water. The weight of the hydrophobic sand is practically balanced by the surface tension. Hydrophobic sand attempts to reach the minimum contact area possible with the water so that the sand grains cling to one another and the sand lump directs itself towards the beaker center.
  • the small funnel is constructed such that the streaming of the sand is practically constant and the closeness of the nozzle to the water warrants a practical "floating" of the sand and hardly transfers any kinetic energy which could drop down the sand lump prematurely.
  • the water must come from the same source, and should preferably be distilled;
  • the water temperature must be identical in all sample tests; Testing must begin when the water is in static conditions, preferably in an enclosed space; All other test data must be identical (beaker, funnel, sand, etc.);
  • a number of tests must be carried out in parallel, observing the statistical sampling rules.
  • the test can be carried out automatically by inserting an electric stopper at the funnel nozzle, and a detector that indicates the exact moment when the sand lump falls and then halts the sand flow by means of a shutdown valve.
  • EXAMPLE 7 Corrosivity Test In order to verify the protection capability of the hydrophobic sand of the present invention against corrosion of iron, the following corrosivity test has been performed: Into a container filled with sea-sand, three standard polygonal reinforcing iron construction bars of 10 mm diameter were inserted. The three bars were of identical length and weight. The first bar was dressed with concrete throughout its length in a diameter of about 10 cm, apart from the tip of the bar, which was left exposed for electric connection. Based on the assumption that corrosion level within cast and impacted concrete would be minimal, this bar was intended to serve as control against the two other bars and is referred to hereinafter as control bar.
  • the second bar was left in its natural state and sunk into the sea sand as is, apart from its tip which was left exposed for electric connection, and is referred to hereinafter as natural bar.
  • the third bar was sunk in sea sand surrounded throughout its length with the hydrophobic sand of the present invention (prepared as described in Example 4) in a diameter of about
  • hydrophobic bar 10 cm, apart from the its tip which was left exposed for electric connection, and is referred to hereinafter as hydrophobic bar.
  • the second (natural) and third (hydrophobic) bars were electrically connected to the concrete-encrusted bar (control) through 100 ohm resistors.
  • the sea sand was wetted with water including 8 % sodium chloride, added in order to accelerate the corrosion process.
  • the sand wetting was carried out once in a fortnight in order to allow natural drying-up by evaporation.
  • the electric potentials between the second natural bar (natural) and the control, as well as between the third bar (hydrophobic) and the control bar were measured every day.
  • Example 5 the hydrophobic sand improved with free particles of the present invention
  • Example 5 five samples of the hydrophobic sand improved with free particles of the present invention (Example 5) having varying thickness between 1 cm and 5 cm were tested for their water wear.
  • the tests were carried out as follows: A transparent glass beaker equipped with a screw-down metal lid was provided. Into the metal lid a layer of sponge on which the tested sealant was laid was inserted, so that the sample extended over the edge of the glass beaker.
  • the total rotation time of each beaker is noted down, considering that one water rotation in the glass simulates one wetting cycle or a single wave. Since the PVC sheet wear lifetime is known, a coefficient is determined for the number of wettings per day so that the test time can be compared based on sealant lifetime in months. The data obtained indicate that the beaker containing polystyrene was taken down after A days and further indicate that no water has been penetrated the sealant surface in the beakers containing the hydrophobic sands of the present invention after two months.
  • a wide and deep pail is perforated at its bottom with holes that are covered with a porous cloth, passing water but not sand.
  • the pail is filled with hydrophobic sand.
  • the nozzle of a long syringe is cut off, so as to provide a uniform cylinder.
  • the syringe cross-sectional area is chosen to be 1 cm 2 , for convenience.
  • Rubber bands are stretched on the syringe external surface, so as to roughen it, and the external surface of the syringe is further covered by a bitomenic paste (or any other gluing agent that is not water-based), so as to attach hydrophobic sand thereto and thereby prevent water passage from the syringe into the hydrophobic sand.
  • the syringe is inserted into the hydrophobic sand in the pail, so as to make the distance from the cut-off nozzle to the pail bottom serve as the thickness of the tested layer.
  • the syringe is anchored to the pail walls on two sides, such that the syringe distance from any wall is larger than the thickness of the tested layer, to prevent water from "taking the shorter path".
  • the piston handle top is widened to enable it to take weights, and the thus modified piston is accurately weighed.
  • the syringe is then half-filled with water and the piston is carefully inserted thereto.
  • By placing weights on the piston top it is possible to measure the pressure in the long run, as well as to establish the burst-out pressure.
  • Such a test allows performing comparative tests of the capability to withstand water pressure of various hydrophobic aggregates, assuming the aggregate is incompressible. This assumption must be carefully verified for each type of hydrophobic aggregate tested.
  • the test described above was performed with a hydrophobic sand prepared as described hereinabove, having a particles size of between 300 and 600 microns and a hydrophobic powder that forms with water a contact angle of 130 °C.
  • a weight of 3 kg (including the piston self-weight) was placed on the piston for 48 hours. The water head remained unchanged during this time period. The load was thereafter gradually increased until burst-out occurred at 4.6 kg.
  • the core materials that are usable in the hydrophobic composites of the present invention are granulated or particulate materials each characterized by a different shape, surface area, absorbency, surface texture and various other mechanical and chemical characteristics. Therefore, different core materials absorb different quantities of the adherent layer of the present invention until they become fully coated. It is therefore desirable to calculate the quantity of the adherent layer required to coat a specific core material, both from an economic standpoint and in order to produce hydrophobic composites improved by "free particles", which require excessive amount of the adherent layer, as is detailed hereinabove (see, Example 5).
  • the tested core material is sieved to remove small particles. Measured samples of the remaining material are thereafter accurately weighed.
  • the core material is then coated by an adherent layer and a hydrophobic powder, as is described hereinabove, whereby the amount of the adherent layer is much higher than in typical procedures and the amount of the hydrophobic powder is standard and is accurately weighed. As is described hereinabove (in Example 5), such high amounts of the adherent layer result in hydrophobic sand having a surfeit of free particles.
  • the resulting hydrophobic composite is then cured and is thereafter passed again through the same sieve as before to remove the free particles formed.
  • Hydrophobic composites having a core material and a hydrophobic material bonded thereto via a water-based adherent layer are generally prepared as follows: Drying the core material: The core material (as is defined hereinabove) is dried at a temperature of at least 90 °C, until its moisture level is reduced to below 1 weight percentage. This procedure is carried out in a closed mixing vessel equipped with a suction port fitted with a valve enabling opening and closure. Alternatively, a pre-dried core material is placed in an open fire furnace and is heated to a temperature of at least 70 °C.
  • Coating the core material with a water-based adherent layer Preliminary preparation of an adherent layer mixture containing a water-based gluing agent and water, in a ratio of 1: to 99:1, preferably 1:2, is carried out in a mixing vessel at a temperature of 40-90 °C, during about 10 minutes. The adherent mixture is then added hot as it is into the mixing vessel described hereinabove, which contains the dry core material. The resulting mixture of the dry core material and the adherent layer mixture is mixed, preferably at 30-60 ⁇ m, and is optionally further heated, and thereafter tumble-dried using the internal heat formed during the reaction, optionally in combination with an external heat and/or a blower, aimed at increasing the drying rate.
  • the additive is added to the mixing vessel at this stage and mixing is continued, preferably at 30-60 ⁇ m, for additional 5 minutes, to obtain uniformity.
  • the added materials should be dried, so as to have a moisture content of less than 1 %.
  • Coating the core material coated with the water-based adherent layer with a hydrophobic material A selected hydrophobic material, as is detailed hereinabove, is added into the core material mixture. Upon addition of the hydrophobic material, the suction port is closed in order to prevent loss of the hydrophobic material. The resulting mixture is then cured for between 24 hours and 7 days, depending on the selected hydrophobic material, the temperature and the humidity, so as to produce the final hydrophobic composite.
  • EXAMPLE 12 Preparation of Hydrophobic Sand having a Water-based Adherent Layer
  • Bitumen-Latex binders and Bitumen-Polymer binders were selected. These binders are commercially available water-based gluing agents, which are known and typically sold as wate ⁇ roofing pastes. A number of bitumen gluing agents are presently available, which differ one from the other by various physical and chemical properties such as temperature endurance, stability in acidic or alkali environment, ease of application and the like.
  • hydrophobic sand having a water-based adherent layer, and coated by a Calcium Stearate hydrophobic powder, prepared as described above, were prepared according to the procedures described above, using as the adherent layer a mixture of the following gluing agents and water: Bitumflex (by Bitum, 4 Ayezira str., Haifa Israel), and Elastopaz (by Pazkar, Alon Tavor, Afula,

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Abstract

L'invention concerne de nouvelles matières composites, en particulier des matières particulaires hydrophobes et des agrégats hydrophobes à écoulement libre, ainsi que des procédés pour les utiliser.
EP04744975A 2003-07-14 2004-07-14 Matieres composites et particulaires hydrophobes et applications associees Withdrawn EP1664230A4 (fr)

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IL15743703A IL157437A0 (en) 2003-07-14 2003-08-17 Hydrophobic aggregate and applications thereof
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WO2009156957A2 (fr) * 2008-06-24 2009-12-30 Neoseal Ltd. Utilisation de matériau hydrophobe
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WO2005005566A3 (fr) 2009-03-26
WO2005005566A2 (fr) 2005-01-20
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JP2007536387A (ja) 2007-12-13
CA2532191A1 (fr) 2005-01-20
KR20060065629A (ko) 2006-06-14

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