CA1320221C - Asbestos contamination control method and formulas used therein - Google Patents
Asbestos contamination control method and formulas used thereinInfo
- Publication number
- CA1320221C CA1320221C CA000582523A CA582523A CA1320221C CA 1320221 C CA1320221 C CA 1320221C CA 000582523 A CA000582523 A CA 000582523A CA 582523 A CA582523 A CA 582523A CA 1320221 C CA1320221 C CA 1320221C
- Authority
- CA
- Canada
- Prior art keywords
- volume
- materials
- dangerous
- formula
- asbestos
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/0066—Disposal of asbestos
-
- 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
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
- C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
Abstract
ABSTRACT OF THE DISCLOSURE
A method of removing dangerous asbestos containing materials from a first location and controlling environmental contamination therefrom comprising the steps of applying an encapsulating formula to said dangerous asbestos containing materials in said first location in an amount sufficient to penetrate said dangerous asbestos containing materials, removing said wetted encapsulated materials from said first location to a second location, mixing said removed materials with a hardening formula whereby said wetting and encapsulating formula initially renders said dangerous asbestos containing material non-friable and said hardening formula solidifies and permanently holds said dangerous asbestos containing materials in a non-friable safely disposable solid mass.
A method of removing dangerous asbestos containing materials from a first location and controlling environmental contamination therefrom comprising the steps of applying an encapsulating formula to said dangerous asbestos containing materials in said first location in an amount sufficient to penetrate said dangerous asbestos containing materials, removing said wetted encapsulated materials from said first location to a second location, mixing said removed materials with a hardening formula whereby said wetting and encapsulating formula initially renders said dangerous asbestos containing material non-friable and said hardening formula solidifies and permanently holds said dangerous asbestos containing materials in a non-friable safely disposable solid mass.
Description
t 32022 1 ASBESTOS CONTAMINATION CONT~OL METIIOD
AND FORMULAS USED TIIEREIN
Back~round of the Invention Technical Field: `
This invention relates to a method of asbestos contamination control and the formulas used therein and the use of the method on friable or cementitious asbestos containing coatings or articles that are being removed from a building being renovated or demolished.
Descri~tion of the Prior Art:
U.S. Patent 3,972,972 discloses a process for producing a board oi' cement-like material reinforced by fibrous material, such as asbestos, wherein the fibrous material is airborne during the i'ormation oi' the material~
U.~. Patent 4,271,115 discloses a method of producing a prewet dust-i'ree form of asbestos short Iibers by agglomerating thc asbestos i'ibers with a re].atively slrlal.l. amounl; O r hydro-philic liquids such as water and a polymeric material such as eth~lene glycol. The asbestos agglomerate is designed l'or use in connection with non-polar materials such as solvents, oils, rubber, polyethylene, and polyesters.
U.S. Patent 4,489,109 discloses a process i'or the production ~k -1- ~
of a vulcanized latex protective coating bonded to the surface of an asbestos-cement article to prevent the subsequent release of asbestos fibers from the same.
Patent No. 4,604,111 discloses a negative air pressure method and apparatus for the protection of a job site from air-borne asbestos fibers in a specified enclosure defining the job site.
The present invention differs from the known prior art in avoiding the release of friable asbestos into the environment by an initial step of wetting the asbestos containing material and simultaneously encapsulating the asbestos fibers in the material thus preventing the release of friable asbestos into the environment whereas the prior art relates to utilizing fri-able asbestos in a product where the friable asbestos is airborne during some or all of the stated process or in the case of Patent 4,604,111, friable asbestos in the environment is air-borne and is theoretically circulated through filters in communication with an exhaust means.
The United States Environmental Protection Agency has established regulations setting certain standards for the handling of friable asbestos in various work environments including demolition.
The demolition of structures containing friable asbestos is controlled by these regulations and requires very expensive handling and disposal techniques. The disposal techniques for friable asbestos are particularly budensome and expensive including wetting, double bagging, and disposal in only certain licensed disposal sites which are often a great distance from a demoltion site.
Summarv of the Invention The present invention is directed to a method of converting i'riable asbestos in insulating coatings and coverings to non-friable asbestos and is particularly useful in protecting the environment from contamination with friable asbestos when asbestos containing insulating coatings, coverings and similar ~orms are being removed and/or the structures inwhich they are located are demolished. The method of the present invention comprlses converting friable asbestos to non-friable asbestos by wettlng and encapsulating the asbestos and/or asbestos containing material with water containing propylene glycol, vinyl acetate/ethylene copolymer and preIerably a dye to indicate satuation and depth of penetration of the wetting liquid in the material whicll can then be saIely removed and following such removal further encapsulating the asbestos with an additional treatment o~ the same material.
The remove~ material including the encapsulated asbestos is then mixed with a hardening Ivrmula oI water, Portland cement, . and a small amount of propylene glycol so as to form a pourable mixture that will harden and forlll a mass completely and saIely containing the non-Iriable asbestos. The propylene glycol acts to bond the larger molecules of the water, vinyl acetate/ethylene copolymer and Portland cemen-t to the asbestos fibers to a much greater extent than has heretofore been believed possible.
Descriotion of the Preferred ~mbodilllent ~ s used throughou~ ~his specification, the term friable asbestos n~ean6 any ma~elial containing asbestos that by ~land pre~sure can crumble, I)ulveriæe, or be reduced to powder-like Il~ers which can be airborlle. Tlle term asbes~os mealls any of ~lle asbestiform varities oL cllrysotile, crocidolite, cumlllingtonite-grunerite, antlloplloyllite, and actinolite-trelllolite. Tlle llerein disclosed method and Iorolulas for convertillg friable asbestos to non-friable asbestos have mally advantages in botll elimillatillg a potential health hazard and in greatly reducing the cost and difficulties of disposing of friable asbestos in accordance with the National Emission Standards for Hazardous Air Pollutants (49 Federal Register, page 13658 et seq.). The wetting and encapsulation formulas may comprise from about 60% by volume to about 99% by volume water and from about .011% by volume to about .02% by volume propylene glycol and from about 6.09% by volume to about 29.34% by volume of one of a group comprising Portland cement and vinyl acetate/ethylene copolymer and acrylic polymer. If desired .0003% by volume F,D and C Blue No. 1 and .0007% by volume F,D and C Yellow No. 5 may be added to obtain the color green in the formula. The hardening or solidifying formula may comprise from about 67.72% by volume to about 94% by volume water, irom about .0062% by volume to about .011~% by volume propylene glycol and from about 24% by volume to about 29.50% by volume Por~land cement or an equal amount of vinyl acetate/ethylene copolymer may be substituted for the Portland cement. The color dyes above referred to may be added to the hardening formula if desired. The quantity of asbestos fibers in different articles varies and an improved wetting and encapsulation formula can be ~ 32022~
obtained by increasing the vinyl acetate/ethylene copolymer to 11.49% by volume with a similar increase in the propylene glycol and reducing the water content to 88.50% by volume.
The vinyl acetate/ethylene copolymer is a water soluble, dry white powder commercially available as AIRFLEX RP 226* a product of Air Products and Chemicals, Inc. of Allentown, Pennsylvania.
If desired, flame retardants may and should be added to the above formulas and may comprise 75 to 150 grams of ammonium polyphosphate for each gallon of the wetting and encapsulation iormula or alternately from 12 to 20 ounces of liquid sodium silicate grade 40 added to each gallon of the wetting and encapsu-lation formula.
A still further improved wetting and encapsulation formula can be obtained by additionally increasing the content of vinyl acetate/ethylene copolymer to 17.04% by volume with a similar increase of the propylene glycol and reducing the water content to 82.6% by volume.
A still further modification of the wetting and encapsulation formulas hereinbefore given may be employed wherein Portland cement i8 substituted for the vinyl acetate/ethylene copolymer of the *Registered Trademark 'A
earlier examples. One generally satisfactory mixture comprises water 75.46% by volume, Portland cement 24.53% by volume and propylene glycol .011% by volume in which mixture the amount of water may be varied depending upon a desired consistency. The propylene glycol bonds the larger molecules of the Portland cement to the smaller molecules of the asbestos fibers.
A still further modification of the wetting and encapsulation formula may comprise water 67.7270 by volume, Portland cement 29.34% by volume, vinyl acetate/ethylene copolymer 2.93% by volume and propylene glycol .006270 by volume.
A still further modification of the wetting and encapsulation formula may comprise water 95.83% by volume, vinyl acetate/ethylene copolymer 4.15% by vol~ume and propylene glycol .0152% by volume.
A stlll i'urther modification of the wetting and encapsulation ~ormula can be made by substituting an acrylic polymer such as commercially available from Rohm and Hass Company of Philadelphia, Pennsylvania 19105, as RHOPLEX ~C 76*Emulsion (an aqueous acrylic emulsion) for the vinyl acetate/ethylene copolymer of the formulas hereinbefore disclosed and adding Portland cement. For example, the wetting and encapsulation formula so modified may comprise * Registered Trademark substantially 67.6570 by volume water, .00076% by volume propylene glycol, 7.81% by volume acrylic polymer and24.53% by volume Portland cement. The formula may be colored by adding .00038% by volume F,D and C ~lue No. 1 and .00076% by volume F,D and C Yellow No.
5 to obtain the color green. The acrylic polymer is an emulsion of 47% acrylic polymer solids and water.
Those skilled in the art will observe that the application oi' the above formulas in the herein disclosed method may be quickly periormed and that the materials used in the formulas are relatively inexpensive as the asbestos and/or asbestos containing material to be removed is simply sprayed or otherwise wet with the wetting and encapsulation iormulas above described so that the asbestos and/or asbestos containing material is suf~iciently saturated and/or penetrated as may be visibly determined by the color thereo~ when the coloring dyes are used. The asbestos material is then removed and ~urther encapsulated by mixing with the hard-enlng ~ormula including the Portland cement so as to completely enclose and bond the asbestos containing wetted material rendering it sa~e ~or disposal as all oi the asbestos and the particles o~
other materials, such as binders, are advantageously bonded in a 1 320~
solid mass by the hardening formula hereinbefore given.
It will thus be seen that the asbestos and/or asbestos con-taining material, such as insulation, may be quickly and safely removed from an article or structure without enclosing the area or otherwise attempting to control air quality in the removal area.
It will also be observed that there can be no air contamination as no friable asbestos is present in the material being removed.
The hardening formula with the Portland cement may be used by mixing the wetted and encapsulated asbestos containing material in a ratio of 7 parts by volume to 1 part by volume of the Portland cement containing hardening formula. The ratio may change depending on the asbestos containing material composition from 2 to 14 parts by volume to one part of the Portland cement containing hardening formula. The resulting mix which contains no friable asbestos will harden into a solidified mass which may be sa~ely and easily dlsposed of in any land fill or the llke.
It will occur to those skilled in the art that when the result-ing mass has dried and hardened, the same may be sprayed with any of the wetting and encapsulating formulas hereinbefore disclosed if desired to additionally coat and seal the mass before final ~ 3~02~1 disposal.
It will occur to those skilled in the art that the several formulas hereinbefore set forth may be adapted for use in lower temperature or winter removal operations to prevent freezing by increasing the percentage ratio of propylene glycol to that of water, propylene glycol is 1,2-propanediol, sometimes known as 1,2-dihydroxypropane.
Numerous tests of the wetting and encapsulation material formulas hereinbefore given have been made with tests samples formulated as follows. One wetting and encapsulation formula sample comprises 38 ounces of water and .187 grams of propylene glycol with the addition of saturation and penetrating indicating dye comprising .013 grams of F,D, and C. Blue No. 1 and .027 grams o~ F,D, and C Yellow No. 5 to obtain the color green. The wetting and encapsulation formula sprayed or similarly applied on asbestos containing material penetrates the same rapidly and to a depth oi four inches in approximately one hour's time. The degree o~
penetration and/or saturation is visible due to the color occasioned by the dye in the formula. Removing the treated asbestos contain-ing material such as insulation from an object is facilitated by the freeing of the bonding agents by the wetting and encapsulationformula and disclosed no friable asbestos or other material capable of being airborne. The wetting and encapsulation (bonding) soften-ing action is maintained for a number of hours (from 6 to 12 hours) and may be repeated in the event the time element is extended and some drying of the asbestos containing material occurs before removal. The bonding of the removed asbestos containing material with the hardening formulas hereinbefore given insures the stability of the removed material and the continued absence of friable 10 asbestOS.
The hereinbefore modified wetting and encapsulating formula in which an acrylic polymer is subsituted for the vinyl acetate/
ethylene copolymer specii'ied 7.81~ by volume acrylic polymer and tests o~ this particular modified i'ormula indicate that the acrylic polymer may be used ef~ectively in amounts from 6.09%
by volume to 7.81% by volume which is the same range as that of the vinyl acetate/ethylene copolymer hereinbefore appearing.
Several embodiments of the present invention have been described and it will be apparent that various changes and modifications of the hardening formula may be made without departing from the scope oi the invention and having thus
AND FORMULAS USED TIIEREIN
Back~round of the Invention Technical Field: `
This invention relates to a method of asbestos contamination control and the formulas used therein and the use of the method on friable or cementitious asbestos containing coatings or articles that are being removed from a building being renovated or demolished.
Descri~tion of the Prior Art:
U.S. Patent 3,972,972 discloses a process for producing a board oi' cement-like material reinforced by fibrous material, such as asbestos, wherein the fibrous material is airborne during the i'ormation oi' the material~
U.~. Patent 4,271,115 discloses a method of producing a prewet dust-i'ree form of asbestos short Iibers by agglomerating thc asbestos i'ibers with a re].atively slrlal.l. amounl; O r hydro-philic liquids such as water and a polymeric material such as eth~lene glycol. The asbestos agglomerate is designed l'or use in connection with non-polar materials such as solvents, oils, rubber, polyethylene, and polyesters.
U.S. Patent 4,489,109 discloses a process i'or the production ~k -1- ~
of a vulcanized latex protective coating bonded to the surface of an asbestos-cement article to prevent the subsequent release of asbestos fibers from the same.
Patent No. 4,604,111 discloses a negative air pressure method and apparatus for the protection of a job site from air-borne asbestos fibers in a specified enclosure defining the job site.
The present invention differs from the known prior art in avoiding the release of friable asbestos into the environment by an initial step of wetting the asbestos containing material and simultaneously encapsulating the asbestos fibers in the material thus preventing the release of friable asbestos into the environment whereas the prior art relates to utilizing fri-able asbestos in a product where the friable asbestos is airborne during some or all of the stated process or in the case of Patent 4,604,111, friable asbestos in the environment is air-borne and is theoretically circulated through filters in communication with an exhaust means.
The United States Environmental Protection Agency has established regulations setting certain standards for the handling of friable asbestos in various work environments including demolition.
The demolition of structures containing friable asbestos is controlled by these regulations and requires very expensive handling and disposal techniques. The disposal techniques for friable asbestos are particularly budensome and expensive including wetting, double bagging, and disposal in only certain licensed disposal sites which are often a great distance from a demoltion site.
Summarv of the Invention The present invention is directed to a method of converting i'riable asbestos in insulating coatings and coverings to non-friable asbestos and is particularly useful in protecting the environment from contamination with friable asbestos when asbestos containing insulating coatings, coverings and similar ~orms are being removed and/or the structures inwhich they are located are demolished. The method of the present invention comprlses converting friable asbestos to non-friable asbestos by wettlng and encapsulating the asbestos and/or asbestos containing material with water containing propylene glycol, vinyl acetate/ethylene copolymer and preIerably a dye to indicate satuation and depth of penetration of the wetting liquid in the material whicll can then be saIely removed and following such removal further encapsulating the asbestos with an additional treatment o~ the same material.
The remove~ material including the encapsulated asbestos is then mixed with a hardening Ivrmula oI water, Portland cement, . and a small amount of propylene glycol so as to form a pourable mixture that will harden and forlll a mass completely and saIely containing the non-Iriable asbestos. The propylene glycol acts to bond the larger molecules of the water, vinyl acetate/ethylene copolymer and Portland cemen-t to the asbestos fibers to a much greater extent than has heretofore been believed possible.
Descriotion of the Preferred ~mbodilllent ~ s used throughou~ ~his specification, the term friable asbestos n~ean6 any ma~elial containing asbestos that by ~land pre~sure can crumble, I)ulveriæe, or be reduced to powder-like Il~ers which can be airborlle. Tlle term asbes~os mealls any of ~lle asbestiform varities oL cllrysotile, crocidolite, cumlllingtonite-grunerite, antlloplloyllite, and actinolite-trelllolite. Tlle llerein disclosed method and Iorolulas for convertillg friable asbestos to non-friable asbestos have mally advantages in botll elimillatillg a potential health hazard and in greatly reducing the cost and difficulties of disposing of friable asbestos in accordance with the National Emission Standards for Hazardous Air Pollutants (49 Federal Register, page 13658 et seq.). The wetting and encapsulation formulas may comprise from about 60% by volume to about 99% by volume water and from about .011% by volume to about .02% by volume propylene glycol and from about 6.09% by volume to about 29.34% by volume of one of a group comprising Portland cement and vinyl acetate/ethylene copolymer and acrylic polymer. If desired .0003% by volume F,D and C Blue No. 1 and .0007% by volume F,D and C Yellow No. 5 may be added to obtain the color green in the formula. The hardening or solidifying formula may comprise from about 67.72% by volume to about 94% by volume water, irom about .0062% by volume to about .011~% by volume propylene glycol and from about 24% by volume to about 29.50% by volume Por~land cement or an equal amount of vinyl acetate/ethylene copolymer may be substituted for the Portland cement. The color dyes above referred to may be added to the hardening formula if desired. The quantity of asbestos fibers in different articles varies and an improved wetting and encapsulation formula can be ~ 32022~
obtained by increasing the vinyl acetate/ethylene copolymer to 11.49% by volume with a similar increase in the propylene glycol and reducing the water content to 88.50% by volume.
The vinyl acetate/ethylene copolymer is a water soluble, dry white powder commercially available as AIRFLEX RP 226* a product of Air Products and Chemicals, Inc. of Allentown, Pennsylvania.
If desired, flame retardants may and should be added to the above formulas and may comprise 75 to 150 grams of ammonium polyphosphate for each gallon of the wetting and encapsulation iormula or alternately from 12 to 20 ounces of liquid sodium silicate grade 40 added to each gallon of the wetting and encapsu-lation formula.
A still further improved wetting and encapsulation formula can be obtained by additionally increasing the content of vinyl acetate/ethylene copolymer to 17.04% by volume with a similar increase of the propylene glycol and reducing the water content to 82.6% by volume.
A still further modification of the wetting and encapsulation formulas hereinbefore given may be employed wherein Portland cement i8 substituted for the vinyl acetate/ethylene copolymer of the *Registered Trademark 'A
earlier examples. One generally satisfactory mixture comprises water 75.46% by volume, Portland cement 24.53% by volume and propylene glycol .011% by volume in which mixture the amount of water may be varied depending upon a desired consistency. The propylene glycol bonds the larger molecules of the Portland cement to the smaller molecules of the asbestos fibers.
A still further modification of the wetting and encapsulation formula may comprise water 67.7270 by volume, Portland cement 29.34% by volume, vinyl acetate/ethylene copolymer 2.93% by volume and propylene glycol .006270 by volume.
A still further modification of the wetting and encapsulation formula may comprise water 95.83% by volume, vinyl acetate/ethylene copolymer 4.15% by vol~ume and propylene glycol .0152% by volume.
A stlll i'urther modification of the wetting and encapsulation ~ormula can be made by substituting an acrylic polymer such as commercially available from Rohm and Hass Company of Philadelphia, Pennsylvania 19105, as RHOPLEX ~C 76*Emulsion (an aqueous acrylic emulsion) for the vinyl acetate/ethylene copolymer of the formulas hereinbefore disclosed and adding Portland cement. For example, the wetting and encapsulation formula so modified may comprise * Registered Trademark substantially 67.6570 by volume water, .00076% by volume propylene glycol, 7.81% by volume acrylic polymer and24.53% by volume Portland cement. The formula may be colored by adding .00038% by volume F,D and C ~lue No. 1 and .00076% by volume F,D and C Yellow No.
5 to obtain the color green. The acrylic polymer is an emulsion of 47% acrylic polymer solids and water.
Those skilled in the art will observe that the application oi' the above formulas in the herein disclosed method may be quickly periormed and that the materials used in the formulas are relatively inexpensive as the asbestos and/or asbestos containing material to be removed is simply sprayed or otherwise wet with the wetting and encapsulation iormulas above described so that the asbestos and/or asbestos containing material is suf~iciently saturated and/or penetrated as may be visibly determined by the color thereo~ when the coloring dyes are used. The asbestos material is then removed and ~urther encapsulated by mixing with the hard-enlng ~ormula including the Portland cement so as to completely enclose and bond the asbestos containing wetted material rendering it sa~e ~or disposal as all oi the asbestos and the particles o~
other materials, such as binders, are advantageously bonded in a 1 320~
solid mass by the hardening formula hereinbefore given.
It will thus be seen that the asbestos and/or asbestos con-taining material, such as insulation, may be quickly and safely removed from an article or structure without enclosing the area or otherwise attempting to control air quality in the removal area.
It will also be observed that there can be no air contamination as no friable asbestos is present in the material being removed.
The hardening formula with the Portland cement may be used by mixing the wetted and encapsulated asbestos containing material in a ratio of 7 parts by volume to 1 part by volume of the Portland cement containing hardening formula. The ratio may change depending on the asbestos containing material composition from 2 to 14 parts by volume to one part of the Portland cement containing hardening formula. The resulting mix which contains no friable asbestos will harden into a solidified mass which may be sa~ely and easily dlsposed of in any land fill or the llke.
It will occur to those skilled in the art that when the result-ing mass has dried and hardened, the same may be sprayed with any of the wetting and encapsulating formulas hereinbefore disclosed if desired to additionally coat and seal the mass before final ~ 3~02~1 disposal.
It will occur to those skilled in the art that the several formulas hereinbefore set forth may be adapted for use in lower temperature or winter removal operations to prevent freezing by increasing the percentage ratio of propylene glycol to that of water, propylene glycol is 1,2-propanediol, sometimes known as 1,2-dihydroxypropane.
Numerous tests of the wetting and encapsulation material formulas hereinbefore given have been made with tests samples formulated as follows. One wetting and encapsulation formula sample comprises 38 ounces of water and .187 grams of propylene glycol with the addition of saturation and penetrating indicating dye comprising .013 grams of F,D, and C. Blue No. 1 and .027 grams o~ F,D, and C Yellow No. 5 to obtain the color green. The wetting and encapsulation formula sprayed or similarly applied on asbestos containing material penetrates the same rapidly and to a depth oi four inches in approximately one hour's time. The degree o~
penetration and/or saturation is visible due to the color occasioned by the dye in the formula. Removing the treated asbestos contain-ing material such as insulation from an object is facilitated by the freeing of the bonding agents by the wetting and encapsulationformula and disclosed no friable asbestos or other material capable of being airborne. The wetting and encapsulation (bonding) soften-ing action is maintained for a number of hours (from 6 to 12 hours) and may be repeated in the event the time element is extended and some drying of the asbestos containing material occurs before removal. The bonding of the removed asbestos containing material with the hardening formulas hereinbefore given insures the stability of the removed material and the continued absence of friable 10 asbestOS.
The hereinbefore modified wetting and encapsulating formula in which an acrylic polymer is subsituted for the vinyl acetate/
ethylene copolymer specii'ied 7.81~ by volume acrylic polymer and tests o~ this particular modified i'ormula indicate that the acrylic polymer may be used ef~ectively in amounts from 6.09%
by volume to 7.81% by volume which is the same range as that of the vinyl acetate/ethylene copolymer hereinbefore appearing.
Several embodiments of the present invention have been described and it will be apparent that various changes and modifications of the hardening formula may be made without departing from the scope oi the invention and having thus
2 described my invention what I claim is:
Claims (18)
1. A method of removing dangerous asbestos containing materials from a first location and controlling environmental contamination therefrom comprising the steps of wetting and encapsulating said dangerous materials in said first location with a wetting formula comprising from about 60% to about 99%
by volume water, from .0062% to about .011% by volume propylene glycol and from about 6.09% to about 17.04% by volume vinyl acetate/ethylene copolymer in an amount sufficient to penetrate said dangerous material, removing said wetted encapsulated materials from said first location to a second location, mixing said removed materials with a hardening formula comprising from about 67.72%
to about 94% by volume water, from about 24 % to about 29.34 %
by volume of one of a group comprising Portland cement and vinyl acetate/ethylene copolymer and from about .0062% to about .011%
by volume propylene glycol whereby said wetting and encapsulating formula initially renders said dangerous asbestos containing material non-friable and said hardening formula solidifies and permanently holds said dangerous material in a non-friable safely disposable solid mass.
by volume water, from .0062% to about .011% by volume propylene glycol and from about 6.09% to about 17.04% by volume vinyl acetate/ethylene copolymer in an amount sufficient to penetrate said dangerous material, removing said wetted encapsulated materials from said first location to a second location, mixing said removed materials with a hardening formula comprising from about 67.72%
to about 94% by volume water, from about 24 % to about 29.34 %
by volume of one of a group comprising Portland cement and vinyl acetate/ethylene copolymer and from about .0062% to about .011%
by volume propylene glycol whereby said wetting and encapsulating formula initially renders said dangerous asbestos containing material non-friable and said hardening formula solidifies and permanently holds said dangerous material in a non-friable safely disposable solid mass.
2. The method of claim 1 wherein said dangerous materials include friable asbestos.
3. The method of claim 1 wherein said dangerous materials comprise asbestos containing insulation on pipes and the like.
4. The method of claim 1 wherein said dangerous materials comprise asbestos containing thermal insulation bats.
5. The method of claim 1 wherein the amount of said wetting and encapsulation formula is sufficient to saturate the asbestos containing materials.
6. The method of claim 1 wherein dye is present in said wetting and encapsulation formula in an amount sufficient to render said formula visible in said asbestos containing materials.
7. The method of claim 1 wherein said wetting and encapsulation formula comprises water 93.88% by volume, propylene glycol .015%
by volume, and vinyl acetate/ethylene copolymer 6.9% by volume.
by volume, and vinyl acetate/ethylene copolymer 6.9% by volume.
8. The method of claim 1 wherein said hardening formula comprises 75.46% water by volume, 24.53% Portland cement by volume, and .011% propylene glycol by volume.
9 . A method of removing dangerous asbestos containing materials from a first location and controlling environmental contamination therefrom comprising the steps of wetting and encapsulating said dangerous asbestos containing materials in said first location with a wetting and encapsulation forming comprising water 93.88% by volume, propylene glycol .015% by volume and vinyl acetate/ethylene copolymer 6.09% by volume in an amount sufficient to saturate said dangerous asbestos containing material, removing said dangerous asbestos containing material from said first location to a second location, mixing said removed materials with a solidifying formula comprising water about 75.46% by volume, vinyl acetate/ethylene copolymer about 24.53% by volume and propylene glycol about .011% by volume whereby said wetting and encapsulation formula lenders asbestos in said dangerous asbestos containing materials non-friable and said solidifying formula permanently holds said dangerous asbestos containing materials in a non-friable safely disposable solid mass.
10. A method of removing dangerous asbestos containing materials from a first location and controlling environmental contamination therefrom comprising the steps of wetting and encapsulating said dangerous materials in said first location with a wetting and encapsulating formula comprising water, propylene glycol and acrylic polymer in an amount sufficient to saturate said dangerous materials, removing said wetted dangerous material from said first location to a second location, saturating said removed dangerous materials with a hardening formula comprising water, Portland cement, and propylene glycol whereby said wetting and encapsulating formula renders asbestos in said dangerous materials non-friable and said hardening formula permanently holds said dangerous materials in a non-friable, safely disposable solid mass.
11. A method of removing dangerous asbestos containing materials from a first location and controlling environmental contamination therefrom comprising the steps of wetting and encapsulation said dangerous materials in said first location with a wetting and encapsulating formula comprising water 93.88 %
by volume, propylene glycol .015% by volume and vinyl acetate/
ethylene copolymer 6.09% by volume in an amount sufficient to saturate said dangerous materials, removing said wetted dangerous materials from said first location to a second location, mixing said removed dangerous materials with a hardening formula comprising water 75.45% by volume, Portland cement 24.53% by volume, and propylene glycol .011% by volume whereby said wetting and encapsulation formula renders asbestos in said dangerous materials non-friable and said hardening formula permanently holds said asbestos in said materials in a non-friable safely disposable solidified mass.
by volume, propylene glycol .015% by volume and vinyl acetate/
ethylene copolymer 6.09% by volume in an amount sufficient to saturate said dangerous materials, removing said wetted dangerous materials from said first location to a second location, mixing said removed dangerous materials with a hardening formula comprising water 75.45% by volume, Portland cement 24.53% by volume, and propylene glycol .011% by volume whereby said wetting and encapsulation formula renders asbestos in said dangerous materials non-friable and said hardening formula permanently holds said asbestos in said materials in a non-friable safely disposable solidified mass.
12. A method of removing dangerous asbestos materials from a first location and controlling environmental contamination therefrom comprising the steps of wetting and encapsulating said dangerous materials in said first location with a wetting formula comprising water 75.43% by volume, propylene glycol .011% by volume, and Portland cement 24.53% by volume in an amount sufficient to saturate said dangerous materials, removing said wetted and encapsulated dangerous materials from said first location to a second location and mixing said removed dangerous materials with a hardening formula comprising about 75.45%
by volume, vinyl acetate/ethylene copolymer about 24.53% by volume, and propylene glycol about .0107% by volume whereby said wetting and encapsulation formula renders said asbestos in said dangerous materials non-friable and said hardening ing formula permanent holds said dangerous solid materials in a non-friable safely disposable solidified condition.
by volume, vinyl acetate/ethylene copolymer about 24.53% by volume, and propylene glycol about .0107% by volume whereby said wetting and encapsulation formula renders said asbestos in said dangerous materials non-friable and said hardening ing formula permanent holds said dangerous solid materials in a non-friable safely disposable solidified condition.
13. A method of removing dangerous asbestos containing materials from a first location and controlling environmental contamination therefrom comprising the steps of wetting and encapsulating said dangerous materials in said first location with a wetting and encapsulation formula comprising from 60 %
to 99 % by volume water, from .011% to .02% by volume propylene glycol and from 6.9% to 7.81% vinyl acetate/ethylene copolymer in an amount sufficient to penetrate and saturate said dangerous materials, removing said wetted and encapsulated materials from said first location to a second location and mixing said removed wetted and encapsulated materials with a hardening formula comprising from 75% to 94% by volume water, from 24% to 29.50%
by volume Portland cement and from .0062% to .001% by volume propylene glycol whereby said wetting and encapsulating formula renders said asbestos in said dangerous materials non-friable and said hardening formula permanently holds said dangerous materials in a solid non-friable safely disposable mass.
to 99 % by volume water, from .011% to .02% by volume propylene glycol and from 6.9% to 7.81% vinyl acetate/ethylene copolymer in an amount sufficient to penetrate and saturate said dangerous materials, removing said wetted and encapsulated materials from said first location to a second location and mixing said removed wetted and encapsulated materials with a hardening formula comprising from 75% to 94% by volume water, from 24% to 29.50%
by volume Portland cement and from .0062% to .001% by volume propylene glycol whereby said wetting and encapsulating formula renders said asbestos in said dangerous materials non-friable and said hardening formula permanently holds said dangerous materials in a solid non-friable safely disposable mass.
14. The method of removing dangerous asbestos containing materials from a first location and controlling environmental contamination therefrom comprising the steps of saturating said dangerous materials in said first location with a wetting formula comprising 60? to 95% by volume water, from .016% to .02% by volume propylene glycol, from 25.50% to 29.34% by volume Portland cement in an amount sufficient to penetrate and saturate said asbestos containing materials, removing said wetted materials from said first location to a second location, mixing said removed materials with a hardening formula comprising from 67.72% to 94% by volume water, from 6.09% to 17.50% by volume vinyl acetate/ethylene copolymer, and from .0128% to .012% by volume propylene glycol whereby said wetting formula renders said asbestos in said materials non-friable and said hardening formula permanently holds said asbestos containing materials in a non-friable safely disposable mass.
15. The method of removing dangerous asbestos containing materials from a fixed location in a job site so as to avoid airborne asbestos fibers comprising the sequential steps of wetting said materials with a first formula comprising from 60%
to 99% by volume water, from .011% to .02% by volume propylene glycol, and from 6.9% to 7.81% by volume acrylic polymer in an amount sufficient to penetrate and saturate said asbestos contain-ing materials, removing said wetted materials from said fixed location, mixing said removed wetted materials with a second formula comprising from 75% to 94% by volume water, from 24%
to 29.50% by volume Portland cement, and from .0062% to .011%
by volume propylene glycol so that said formulas join the molecules of said asbestos to the molecules of said acrylic polymer and Portland cement to render said asbestos non-friable.
to 99% by volume water, from .011% to .02% by volume propylene glycol, and from 6.9% to 7.81% by volume acrylic polymer in an amount sufficient to penetrate and saturate said asbestos contain-ing materials, removing said wetted materials from said fixed location, mixing said removed wetted materials with a second formula comprising from 75% to 94% by volume water, from 24%
to 29.50% by volume Portland cement, and from .0062% to .011%
by volume propylene glycol so that said formulas join the molecules of said asbestos to the molecules of said acrylic polymer and Portland cement to render said asbestos non-friable.
16. A formula for treating dangerous asbestos fiber containing materials so as to render said asbestos fibers non-friable, said formula comprising from 60% to 99% by volume water, from .011%
to .02% by volume propylene glycol and from 6.9% to 7.81% by volume vinyl acetate/ethylene copolymer wherein said propylene glycol acts to bond the larger molecules of said vinyl acetate/
ethylene copolymer to the smaller molecules of said asbestos fibers.
to .02% by volume propylene glycol and from 6.9% to 7.81% by volume vinyl acetate/ethylene copolymer wherein said propylene glycol acts to bond the larger molecules of said vinyl acetate/
ethylene copolymer to the smaller molecules of said asbestos fibers.
17. A formula for treating dangerous asbestos fiber containing materials so as to render said asbestos fibers non-friable, said formula comprising from 60% to 99% by volume water, from .011%
to .02% by volume propylene glycol and from 6.9% to 7.81% by volume acrylic polymer wherein said propylene glycol acts to bond the larger molecules of said acrylic polymer to the smaller molecules of said asbestos fibers.
to .02% by volume propylene glycol and from 6.9% to 7.81% by volume acrylic polymer wherein said propylene glycol acts to bond the larger molecules of said acrylic polymer to the smaller molecules of said asbestos fibers.
18. A formula for treating dangerous asbestos fiber containing materials so as to render said asbestos fibers non-friable, said formula comprising from 60% to 95% by volume water, from .016%
to .02% by volume propylene glycol, from 24.50% to 29.34% by volume Portland cement wherein said propylene glycol acts to bond the larger molecules of said Portland cement to the smaller molecules of said asbestos fibers.
to .02% by volume propylene glycol, from 24.50% to 29.34% by volume Portland cement wherein said propylene glycol acts to bond the larger molecules of said Portland cement to the smaller molecules of said asbestos fibers.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/041,200 US4828883A (en) | 1987-04-22 | 1987-04-22 | Asbestos contamination control method and formulas used therein |
| GB8721480A GB2204308B (en) | 1987-04-22 | 1987-09-11 | Asbestos contamination removal methods |
| DE3733938A DE3733938C2 (en) | 1987-04-22 | 1987-10-07 | Process for the disposal of asbestos-containing materials by wetting and consolidation and suitable means |
| CA000582523A CA1320221C (en) | 1987-04-22 | 1988-11-08 | Asbestos contamination control method and formulas used therein |
| AU24987/88A AU608381B2 (en) | 1987-04-22 | 1988-11-10 | Asbestos contamination control method and formulas used therein |
| JP63285992A JPH02131280A (en) | 1987-04-22 | 1988-11-12 | Peeling tape for display and its manufacture |
| NL8802782A NL8802782A (en) | 1987-04-22 | 1988-11-14 | METHOD FOR REMOVING ASBESTOS CONTAINING MATERIALS |
| FR8815915A FR2639852A1 (en) | 1987-04-22 | 1988-12-05 | METHOD FOR CONTROLLING THE ASBESTOS CONTAMINATION AND FORMULAS USED IN THIS PROCESS |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/041,200 US4828883A (en) | 1987-04-22 | 1987-04-22 | Asbestos contamination control method and formulas used therein |
| CA000582523A CA1320221C (en) | 1987-04-22 | 1988-11-08 | Asbestos contamination control method and formulas used therein |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1320221C true CA1320221C (en) | 1993-07-13 |
Family
ID=25672226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000582523A Expired - Fee Related CA1320221C (en) | 1987-04-22 | 1988-11-08 | Asbestos contamination control method and formulas used therein |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4828883A (en) |
| JP (1) | JPH02131280A (en) |
| AU (1) | AU608381B2 (en) |
| CA (1) | CA1320221C (en) |
| DE (1) | DE3733938C2 (en) |
| FR (1) | FR2639852A1 (en) |
| GB (1) | GB2204308B (en) |
| NL (1) | NL8802782A (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4828883A (en) * | 1987-04-22 | 1989-05-09 | Allied Gator, Inc. | Asbestos contamination control method and formulas used therein |
| US5034247A (en) * | 1988-06-30 | 1991-07-23 | H. B. Fuller Company | Method of using a composition for wetting and encapsulating asbestos |
| ATE83759T1 (en) * | 1988-07-20 | 1993-01-15 | Kluge Umweltschutz Gmbh | METHOD FOR EMBEDING ASBESTOS-CONTAINING RUBBISH TO BE DISPOSED IN CONCRETE BODY AND DEVICE FOR CARRYING OUT THE METHOD. |
| DE3902717A1 (en) * | 1989-01-31 | 1990-08-02 | Bilfinger Berger Bau | Process for the disposal of asbestos fibres and/or building materials containing asbestos fibres and equipment for carrying out the process |
| DE3908913C1 (en) * | 1989-03-18 | 1990-09-27 | Wolfgang Dipl.-Chem. Dr. 1000 Berlin De Ortlepp | Process for the disposal of asbestos-containing dusts |
| DE3915656A1 (en) * | 1989-05-16 | 1990-11-22 | Wolfgang Rowedder | Asbestos fibre dust binding - using combination of calcium chloride soln. and calcium chloride paste |
| DE3919838A1 (en) * | 1989-06-17 | 1990-12-20 | Putzmeister Maschf | METHOD AND DEVICE FOR THE DISPOSAL OF CONTAMINATED BUILDING WASTE |
| US5039365A (en) * | 1989-09-14 | 1991-08-13 | Wall & Floor Treatments, Inc. | Method for encapsulating and barrier containment of asbestos fibers in existing building structures |
| DE3932208A1 (en) * | 1989-09-27 | 1990-03-08 | Erich Wild | Fibre binding of hazardous fibre layers - e.g. sprayed asbestos, using sodium methyl silicate and hardener |
| US5032328A (en) * | 1989-11-08 | 1991-07-16 | Griffis Steven C | Method for casting friable asbestos-containing material into a non-friable mass |
| DE4004201A1 (en) * | 1990-02-12 | 1991-08-14 | Ortlepp Wolfgang | Disposal of harmful matter esp. asbestos waste - by melting with coal or coke and flux giving prods. useful for making building material and in metallurgy |
| GB9018206D0 (en) * | 1990-08-18 | 1990-10-03 | Gwilliam Graham J | Asbestos encapsulation |
| US5108788A (en) * | 1990-09-10 | 1992-04-28 | Eastman Kodak Company | Method for treating inorganic fiber insulation to minimize dust and airborne particulates or to accomplish waterproofing |
| DE4029830A1 (en) * | 1990-09-20 | 1992-03-26 | T I B Chemie Gmbh | METHOD FOR REFURBISHING ASBESTINE-BASED SURFACE ELEMENTS, preferably COMPONENT ELEMENTS LIKE PANELS, WALLS AND CORRUGATED PANELS |
| DE4039541C1 (en) * | 1990-12-11 | 1992-05-07 | Jakob 5210 Troisdorf De Knoben | Handling and removal of electric heat storage units contg. asbestos - comprises sealing all air inlets and outlets before dismantling, placing film sleeve around units and immersing in liq. to bind loose fibres |
| US5034075A (en) * | 1991-02-26 | 1991-07-23 | Mcmath William H | Method for encapsulating and containing asbestos on power plant equipment |
| DE4106066C1 (en) * | 1991-02-27 | 1991-12-19 | Institut Fuer Asbesterhebung Erler Gmbh, 5060 Bergisch Gladbach, De | Asbestos building element treatment appts. - applies mixture of wax and plastics to suppress dust |
| US5229437A (en) * | 1991-12-31 | 1993-07-20 | The Gibson-Homans Company | Encapsulating material for asbestos tile |
| DE4229885C2 (en) * | 1992-09-04 | 1997-09-18 | Kemmer Gmbh Geb | Process for the disposal of asbestos fibers |
| DE4244099C1 (en) * | 1992-12-24 | 1994-06-01 | Inst Umwelttechnologie Und Umw | Deposition of smallest mineral fibres or dust particles - by producing fine particle mist, wetting surfaces of fibres and depositing particles |
| DE4420635A1 (en) * | 1994-06-14 | 1995-12-21 | Sika Chemie Gmbh | Process for cleaning and refurbishing asbestos cement slabs |
| US5552179A (en) * | 1995-06-16 | 1996-09-03 | Allied Gator, Inc. | Method for treating concrete |
| DE19549302A1 (en) * | 1995-12-22 | 1997-06-26 | Gustav Pegel & Sohn Gmbh & Co | Disposal of water conditioned asbestos material |
| FR2756861B1 (en) * | 1996-12-06 | 1999-01-15 | Brouckaert Michel | PROCESS FOR THE SANITARY NEUTRALIZATION OF ASBESTOS USED IN THE BUILDING |
| WO1999043627A1 (en) * | 1998-02-26 | 1999-09-02 | Antonino Ancione S.P.A. | An adhesive mixture of synthetic polymers for encapsulating amianthus |
| US20100229756A1 (en) * | 2009-03-10 | 2010-09-16 | Japan Corn Starch Co., Ltd. | Additive composition for spraying water to prevent dust scattering |
| DE102014010465B4 (en) * | 2014-07-15 | 2022-03-24 | Bundesrepublik Deutschland, vertreten durch das Bundesministerium der Verteidigung, vertreten durch das Bundesamt für Ausrüstung, Informationstechnik und Nutzung der Bundeswehr | Fibre-binding paint for CFRP fire damage |
| AU2022256704A1 (en) | 2021-04-13 | 2023-11-23 | Fiberbinder Aps | A fibre binder composition for retaining fibres and other particles on a building site |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD44097A1 (en) * | 1965-03-15 | 1965-12-23 | Covering layer and method for producing the cover layer for asbestos spray insulation | |
| JPS5328932B2 (en) * | 1973-05-21 | 1978-08-17 | ||
| JPS53138699A (en) * | 1977-05-10 | 1978-12-04 | Sanwa Purasuchitsuku Kk | Method of making pattern on panel |
| US4271115A (en) * | 1979-08-09 | 1981-06-02 | Megaloid Chemical Corporation | Method of producing a pre-wet, dust-free form of asbestos short fibers |
| US4604111A (en) * | 1981-11-23 | 1986-08-05 | Anthony Natale | Particulate contamination control method and filtration device |
| JPS5981188A (en) * | 1982-11-02 | 1984-05-10 | General Kk | Hot stamping foil |
| US4489109A (en) * | 1982-12-10 | 1984-12-18 | Asarco Incorporated | Process for applying latex rubber coatings to asbestos-cement products |
| US4828883A (en) * | 1987-04-22 | 1989-05-09 | Allied Gator, Inc. | Asbestos contamination control method and formulas used therein |
-
1987
- 1987-04-22 US US07/041,200 patent/US4828883A/en not_active Expired - Fee Related
- 1987-09-11 GB GB8721480A patent/GB2204308B/en not_active Expired - Fee Related
- 1987-10-07 DE DE3733938A patent/DE3733938C2/en not_active Expired - Fee Related
-
1988
- 1988-11-08 CA CA000582523A patent/CA1320221C/en not_active Expired - Fee Related
- 1988-11-10 AU AU24987/88A patent/AU608381B2/en not_active Ceased
- 1988-11-12 JP JP63285992A patent/JPH02131280A/en active Pending
- 1988-11-14 NL NL8802782A patent/NL8802782A/en not_active Application Discontinuation
- 1988-12-05 FR FR8815915A patent/FR2639852A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB8721480D0 (en) | 1987-10-21 |
| DE3733938C2 (en) | 1996-10-10 |
| US4828883A (en) | 1989-05-09 |
| NL8802782A (en) | 1990-06-01 |
| AU608381B2 (en) | 1991-03-28 |
| GB2204308B (en) | 1991-11-06 |
| JPH02131280A (en) | 1990-05-21 |
| AU2498788A (en) | 1990-05-17 |
| FR2639852A1 (en) | 1990-06-08 |
| GB2204308A (en) | 1988-11-09 |
| DE3733938A1 (en) | 1988-11-03 |
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| MKLA | Lapsed |