CA1201865A - Photodecontamination - Google Patents
PhotodecontaminationInfo
- Publication number
- CA1201865A CA1201865A CA000425164A CA425164A CA1201865A CA 1201865 A CA1201865 A CA 1201865A CA 000425164 A CA000425164 A CA 000425164A CA 425164 A CA425164 A CA 425164A CA 1201865 A CA1201865 A CA 1201865A
- Authority
- CA
- Canada
- Prior art keywords
- additive
- radiation
- contaminant
- flash lamp
- frequency range
- 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
Links
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
- A62D3/176—Ultraviolet radiations, i.e. radiation having a wavelength of about 3nm to 400nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0035—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0035—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like
- B08B7/0042—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like by laser
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/04—Combined processes involving two or more non-distinct steps covered by groups A62D3/10 - A62D3/40
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Electromagnetism (AREA)
- Sampling And Sample Adjustment (AREA)
- Fire-Extinguishing Compositions (AREA)
- Cleaning In General (AREA)
- Detergent Compositions (AREA)
Abstract
PHOTODECONTAMINATION
ABSTRACT OF THE DISCLOSURE
Decontamination may be effected by adding to a contaminant an additive which is capable of absorbing radiation of a predetermined frequency range. The resultant contaminant/additive system may be exposed to high-intensity radiation of the predetermined frequency range until decontamination is complete. The method is particularly adapted to the removal or neutralization of contaminants which do not strongly absorb radiation from readily available sources.
ABSTRACT OF THE DISCLOSURE
Decontamination may be effected by adding to a contaminant an additive which is capable of absorbing radiation of a predetermined frequency range. The resultant contaminant/additive system may be exposed to high-intensity radiation of the predetermined frequency range until decontamination is complete. The method is particularly adapted to the removal or neutralization of contaminants which do not strongly absorb radiation from readily available sources.
Description
~Z~ S
PHOTODECONTAMINATION
BACRGROUND OF THE 1 N V ~:N '1' ION
The present invention relates to a method of decontamination and more particularl~, to the photoremoval of chemical warfare ~C.W.) agents and other contaminants.
One method of decontaminating a surface of a chemical deposit is to expose the surface to high-intensity radiation until the energy absorbed decomposes or evaporates the chemical.
"Decontamination", as used herein, refers to detoxification, cleaning, and other processes by which a chemical is removed or its noxious gualities are neutrali2ed. Vig, et al., U.SO Patent No. 4,208,135 disclose~ a method of removing contaminants from surfaces by precleaning the surface and air, and then irradiating the surface with shortwave ultraviolet radiation in the presence of oxygen. Shortwave ultraviolet is generally defined by the wavelength range of 1700 angstroms to 3000 angstroms. Di Vita, et al., U.S. Patent No. 4,028,080, discloses a similar method used to clean optical fibers.
A problem arises with respect to some C.W.
agentsO as well as other chemicals, in that they ~5 strongly absorb radiation only in the deep vacuum ultraviolet region, below 2000 angstroms. Vacuum ultraviolet radiation is strongly absorbed by air, and hence, irradiation of surfaces requires an evacuated ; chamber. Howevèr, it is not usually practical to place a surface in need of decontamination in an evacuated chamber. Furthermore, the deep vacuum ultraviolet region is generally devoid of economical high-intensity radiation sources. Hence, large scale decontamination of surfaces exposed to such C.W. agents is not feasible using known methods.
It is an object of the present invention to provide an improved method for decontamination that is ~X~
"
~L20~8~
applicable to contaminants which do not absorb strongly optical frequencies generated by readily available radiation sources.
SUMMARY OF THE PRESENT INVENTION
In accordance with the present invention, an improved method of decontamination employs a chemical additive capable of absorbing radiation of wavelengths greater than that of vacuum ultraviolet The additive may be mixed with the contaminant, or alternatively, disposed upon and in contact with the contaminant. The combined chemical system is then exposed to high-intensity radiation of a frequency range strong:Ly absorbed by the additive until a contaminant is destroyed, altered, or removed by evaporation, decomposition or alternative process. A laser or flash lamp may be used to supply the high-intensity radiation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In instances where a contaminant cannot be destroyed, altered or removed removed readily by irradiation because the contaminant does not strongly absorb radiation from readily available sources, a chemical additive which is strongly absorbed by radiation from a readily available source may be added to the contaminant~ The resulting contaminant/additive chemical system can be irradiated with radiation which is absorhed by the additive until decontamination is complete. The contaminant may be a chemical deposit or film upon a surface, or may be in another form.
The contaminant may be a C.W. agent or any other substance the removal, alteration, or destruction of which is re~uired. The additive strongly absorbs radiation characteristic of a predetermined radiation source. The radiation source may have narrow frequency spectrum, such as a laser, or a broad frequency range, such as a flash lamp.
The additive may be mixed with the contaminant, layered over the contaminant, or otherwise situated so ~Z~865 that an energy transfer may take place between the additive and the contaminant. The transfer may be thermal. More specifically, the radiation absorbed by the additive may be converted to therma:L agitation of S the additive. Molecular collisions between the additive and the contaminant then lead to the thermal agitation of the additive.
Other energy transfer mechanisms are appropriate for speciic contaminant systems. For example, radiation may induce vibrational or electronic excitation in the additive. The energy stored may be transferred by re-radiation or by collisions to excite molecules of the contaminant.
Depending upon the contaminant, the energy transfer may effect decontamination in a variety of ways. Thermal energy may result in the evaporation of the contaminant. Alternatively, the heat may lead to the decomposition of the contaminant. Heat or electron - excitation may lead to the ioniza~ion of the contaminant. The ionized contaminant molecules may combine with other chemicals so that the noxious qualities of the contaminant are neutralized. The neutralizing chemicals may be provided with the additive.
-- In a preferred embodiment of the present invention, a solution of para-aminobenzoic acid (PABA) is added to a contaminant such as a COW. agent. PABA
solutions strongly absorb radiation in the near ultraviolet region and thus is amenable to many high-intensity radia~ion sources. The C.W. agent/PABA
system may be irradiated by means of a high-intensity radiation source. The radiation source may be a laser such as an excimer, dye or N2 laser. Alternative~y, a high-intensity pulsed xenon flash lamp, or other incoherent flash lamp, may be used to irradiate the chemical system. Once the radiation is absorbed, some manner of energy transfer occurs to the C.W. agent, ~Z()~86S
leading to its photoremoval.
The PABA is particularly well suited for decontamination by means of a 1ash }amp, such as a xenon flash lamp. PABA which is widely used to pro~ect human skin ~rom ultraviolet rays from the sun, is widely available in large quantities and is nontoxic. PABA
absorbs ultraviolet radiation over a broad section of the near ultraviolet region. Hence, it is a safe and available chemical which is an efficient absorber of radiation over the frequency range of a flash lamp.
PABA is also well suited for absorbing the radiation of lasers. However, specific additives may be - more efficient energy absorbers in a narrow spectrum of a particular laser. For example, ferrocine might be used as an additive in conjunction with an argon-fluoride laser.
r Tests have been performed to evaluate the efficacy of the present method. PABA solution and malathion were mixed in a test tube and then layered on 2C a glass slide. Malathion is a C.W. agent analog, which means that it behaves physically and chemically like many of the chemicals developed for chemical warfare.
After evaporation of the solvents, a residue remained on the slide. Slides of this type were irradiated with KrF
laser pulses (248 nm). The residue was completely removed from the irradiated area. Removal was also ' complete when similar slides were irradiated with a Flashblaster. ~Flashblaster is a high-intensity pulsed xenon ~lash lamp developed by Maxwell Laboratories).
~ 30 In one set of control tests, pure PABA solution ; was deposited on a slide. The PABA was completely removed from the irradiated areas o~ the slides when exposed to either the KrF laser or the Flashblaster. In a second set of control tests, pure malathion was deposited on glass slides. The malathion residue was not removed when irradiated by either radiation source.
These ~ests support the proposition that the method of ,.
,~, .. . ... .. . , , . .. .. ~, . ... ~ . , . .. , . . . . . ,, . , . ,, . , , ~ ,, ~Z~i8~
the present invention permits the photoremoval of contaminants not always readily removable by economical radiation sources.
In accordance with the above disclosure, a method of decontamination is presented which allows the photoremoval of contaminants from surfaces. It is apparent that alternative chemicals may be applied.
These chemicals may absorb in the near ultraviolet or other portion of the spectrum in which high-intensity radiation sources are economic~1 and practical. Other embodiments are within the spirit and scope of the present invention.
f :
,~
, . . . , , .. , ,~ . .. . .. . . . .
PHOTODECONTAMINATION
BACRGROUND OF THE 1 N V ~:N '1' ION
The present invention relates to a method of decontamination and more particularl~, to the photoremoval of chemical warfare ~C.W.) agents and other contaminants.
One method of decontaminating a surface of a chemical deposit is to expose the surface to high-intensity radiation until the energy absorbed decomposes or evaporates the chemical.
"Decontamination", as used herein, refers to detoxification, cleaning, and other processes by which a chemical is removed or its noxious gualities are neutrali2ed. Vig, et al., U.SO Patent No. 4,208,135 disclose~ a method of removing contaminants from surfaces by precleaning the surface and air, and then irradiating the surface with shortwave ultraviolet radiation in the presence of oxygen. Shortwave ultraviolet is generally defined by the wavelength range of 1700 angstroms to 3000 angstroms. Di Vita, et al., U.S. Patent No. 4,028,080, discloses a similar method used to clean optical fibers.
A problem arises with respect to some C.W.
agentsO as well as other chemicals, in that they ~5 strongly absorb radiation only in the deep vacuum ultraviolet region, below 2000 angstroms. Vacuum ultraviolet radiation is strongly absorbed by air, and hence, irradiation of surfaces requires an evacuated ; chamber. Howevèr, it is not usually practical to place a surface in need of decontamination in an evacuated chamber. Furthermore, the deep vacuum ultraviolet region is generally devoid of economical high-intensity radiation sources. Hence, large scale decontamination of surfaces exposed to such C.W. agents is not feasible using known methods.
It is an object of the present invention to provide an improved method for decontamination that is ~X~
"
~L20~8~
applicable to contaminants which do not absorb strongly optical frequencies generated by readily available radiation sources.
SUMMARY OF THE PRESENT INVENTION
In accordance with the present invention, an improved method of decontamination employs a chemical additive capable of absorbing radiation of wavelengths greater than that of vacuum ultraviolet The additive may be mixed with the contaminant, or alternatively, disposed upon and in contact with the contaminant. The combined chemical system is then exposed to high-intensity radiation of a frequency range strong:Ly absorbed by the additive until a contaminant is destroyed, altered, or removed by evaporation, decomposition or alternative process. A laser or flash lamp may be used to supply the high-intensity radiation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In instances where a contaminant cannot be destroyed, altered or removed removed readily by irradiation because the contaminant does not strongly absorb radiation from readily available sources, a chemical additive which is strongly absorbed by radiation from a readily available source may be added to the contaminant~ The resulting contaminant/additive chemical system can be irradiated with radiation which is absorhed by the additive until decontamination is complete. The contaminant may be a chemical deposit or film upon a surface, or may be in another form.
The contaminant may be a C.W. agent or any other substance the removal, alteration, or destruction of which is re~uired. The additive strongly absorbs radiation characteristic of a predetermined radiation source. The radiation source may have narrow frequency spectrum, such as a laser, or a broad frequency range, such as a flash lamp.
The additive may be mixed with the contaminant, layered over the contaminant, or otherwise situated so ~Z~865 that an energy transfer may take place between the additive and the contaminant. The transfer may be thermal. More specifically, the radiation absorbed by the additive may be converted to therma:L agitation of S the additive. Molecular collisions between the additive and the contaminant then lead to the thermal agitation of the additive.
Other energy transfer mechanisms are appropriate for speciic contaminant systems. For example, radiation may induce vibrational or electronic excitation in the additive. The energy stored may be transferred by re-radiation or by collisions to excite molecules of the contaminant.
Depending upon the contaminant, the energy transfer may effect decontamination in a variety of ways. Thermal energy may result in the evaporation of the contaminant. Alternatively, the heat may lead to the decomposition of the contaminant. Heat or electron - excitation may lead to the ioniza~ion of the contaminant. The ionized contaminant molecules may combine with other chemicals so that the noxious qualities of the contaminant are neutralized. The neutralizing chemicals may be provided with the additive.
-- In a preferred embodiment of the present invention, a solution of para-aminobenzoic acid (PABA) is added to a contaminant such as a COW. agent. PABA
solutions strongly absorb radiation in the near ultraviolet region and thus is amenable to many high-intensity radia~ion sources. The C.W. agent/PABA
system may be irradiated by means of a high-intensity radiation source. The radiation source may be a laser such as an excimer, dye or N2 laser. Alternative~y, a high-intensity pulsed xenon flash lamp, or other incoherent flash lamp, may be used to irradiate the chemical system. Once the radiation is absorbed, some manner of energy transfer occurs to the C.W. agent, ~Z()~86S
leading to its photoremoval.
The PABA is particularly well suited for decontamination by means of a 1ash }amp, such as a xenon flash lamp. PABA which is widely used to pro~ect human skin ~rom ultraviolet rays from the sun, is widely available in large quantities and is nontoxic. PABA
absorbs ultraviolet radiation over a broad section of the near ultraviolet region. Hence, it is a safe and available chemical which is an efficient absorber of radiation over the frequency range of a flash lamp.
PABA is also well suited for absorbing the radiation of lasers. However, specific additives may be - more efficient energy absorbers in a narrow spectrum of a particular laser. For example, ferrocine might be used as an additive in conjunction with an argon-fluoride laser.
r Tests have been performed to evaluate the efficacy of the present method. PABA solution and malathion were mixed in a test tube and then layered on 2C a glass slide. Malathion is a C.W. agent analog, which means that it behaves physically and chemically like many of the chemicals developed for chemical warfare.
After evaporation of the solvents, a residue remained on the slide. Slides of this type were irradiated with KrF
laser pulses (248 nm). The residue was completely removed from the irradiated area. Removal was also ' complete when similar slides were irradiated with a Flashblaster. ~Flashblaster is a high-intensity pulsed xenon ~lash lamp developed by Maxwell Laboratories).
~ 30 In one set of control tests, pure PABA solution ; was deposited on a slide. The PABA was completely removed from the irradiated areas o~ the slides when exposed to either the KrF laser or the Flashblaster. In a second set of control tests, pure malathion was deposited on glass slides. The malathion residue was not removed when irradiated by either radiation source.
These ~ests support the proposition that the method of ,.
,~, .. . ... .. . , , . .. .. ~, . ... ~ . , . .. , . . . . . ,, . , . ,, . , , ~ ,, ~Z~i8~
the present invention permits the photoremoval of contaminants not always readily removable by economical radiation sources.
In accordance with the above disclosure, a method of decontamination is presented which allows the photoremoval of contaminants from surfaces. It is apparent that alternative chemicals may be applied.
These chemicals may absorb in the near ultraviolet or other portion of the spectrum in which high-intensity radiation sources are economic~1 and practical. Other embodiments are within the spirit and scope of the present invention.
f :
,~
, . . . , , .. , ,~ . .. . .. . . . .
Claims (8)
1. A method of cleaning a surface to remove a contaminant from a surface comprising: applying a chemical additive to the contaminant on the surface, said additive being characterized in that it absorbs radiation in a predetermined frequency range; and irradiating the contaminant/additive system on the surface with one or more flashes of a flash lamp of said predetermined frequency range until said surface is clean.
2. The method of Claim 1 further characterized in that said additive absorbs said flash lamp-emitted radiation, including radiation within the near ultraviolet region.
3. The method of Claim 1 further characterized in that said additive is a solution of para-aminobenzoic acid.
4. The method of any one of Claims 1, 2, or 3 further characterized in that said radiation is provided by a pulsed xenon flash lamp.
5. A method of preparing a potential contaminant for later removal from a surface and subsequently removing the contaminant from a surface, the method comprising: mixing said potential contaminant with a chemical additive, said additive being characterized in that it absorbs radiation in a predetermined frequency range, and irradiating the contaminant/additive system on the surface with one or more flashes of a flash lamp of said predetermined frequency range until said surface is decontaminated.
6. The method of Claim 5 further characterized in that said additive absorbs said flash lamp-emitted radiation, including radiation within the near ultraviolet region.
7. The method of Claim 5 further characterized in that said additive is a solution of para-aminobenzoic acid.
8. The method of any one of Claims 5, 6, or 7 further characterized in that said radiation is provided by a pulsed xenon flash lamp.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36524782A | 1982-04-05 | 1982-04-05 | |
| US365,247 | 1982-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1201865A true CA1201865A (en) | 1986-03-18 |
Family
ID=23438068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000425164A Expired CA1201865A (en) | 1982-04-05 | 1983-04-05 | Photodecontamination |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1201865A (en) |
| DE (1) | DE3310117A1 (en) |
| FR (1) | FR2524316B1 (en) |
| GB (1) | GB2118028B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3400776A1 (en) * | 1984-01-12 | 1985-07-25 | Erich Poehlmann | Method and apparatus for reducing the emissions of dangerous molecular substances |
| GB2169496B (en) * | 1985-01-16 | 1987-12-23 | Stc Plc | Cleaning metal surfaces |
| FR2674380A1 (en) * | 1991-03-19 | 1992-09-25 | Coudert Anne Marie | PROCESS FOR THE DISLOCATION OF COMPOUND CHEMICAL MOLECULES, APPARATUS FOR IMPLEMENTING SAME AND APPLICATION FOR NEUTRALIZING TOXIC GASES. |
| FR2674983B1 (en) * | 1991-04-05 | 1994-08-05 | Framatome Sa | LASER WORKING PROCESS AND EQUIPMENT IN A CONTAMINATED AREA OF A NUCLEAR FACILITY. |
| FR2678418B1 (en) * | 1991-06-26 | 1994-08-05 | Framatome Sa | LASER WORKING PROCESS IN A CONTAMINATED AREA OF A NUCLEAR FACILITY, AND EQUIPMENT FOR ITS IMPLEMENTATION. |
| DE4235750C2 (en) * | 1992-10-23 | 1994-09-22 | Bundesrep Deutschland | Protective clothing |
| FR2752386B1 (en) * | 1996-08-14 | 1998-09-11 | Commissariat Energie Atomique | METHOD FOR CLEANING OR DECONTAMINATION OF AN OBJECT USING AN ULTRAVIOLET LASER BEAM AND DEVICE FOR IMPLEMENTING IT |
| DE19633494A1 (en) * | 1996-08-20 | 1998-02-26 | Otto Barnickel | Apparatus for air treatment |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1497779A1 (en) * | 1966-04-27 | 1969-10-02 | Helmut Schneider | Method and device for generating sound or ultrasonic waves on surfaces |
| IT992983B (en) * | 1972-08-18 | 1975-09-30 | Gen Electric | METHOD FOR REMOVING PHOTORESISTANT MATERIAL FROM A SUPPORT |
| US4028135A (en) * | 1976-04-22 | 1977-06-07 | The United States Of America As Represented By The Secretary Of The Army | Method of cleaning surfaces by irradiation with ultraviolet light |
| US4028080A (en) * | 1976-06-23 | 1977-06-07 | The United States Of America As Represented By The Secretary Of The Army | Method of treating optical waveguide fibers |
| JPS55115484A (en) * | 1979-02-28 | 1980-09-05 | Asahi Chem Ind Co Ltd | Heterogeneous sensitizer for photosensitized oxidation |
-
1983
- 1983-03-21 DE DE19833310117 patent/DE3310117A1/en not_active Withdrawn
- 1983-03-21 GB GB08307747A patent/GB2118028B/en not_active Expired
- 1983-04-01 FR FR8305435A patent/FR2524316B1/en not_active Expired
- 1983-04-05 CA CA000425164A patent/CA1201865A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2118028B (en) | 1985-12-18 |
| DE3310117A1 (en) | 1983-10-06 |
| FR2524316A1 (en) | 1983-10-07 |
| GB8307747D0 (en) | 1983-04-27 |
| GB2118028A (en) | 1983-10-26 |
| FR2524316B1 (en) | 1987-08-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |