EP0241364A1 - Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas - Google Patents

Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas Download PDF

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Publication number
EP0241364A1
EP0241364A1 EP87400751A EP87400751A EP0241364A1 EP 0241364 A1 EP0241364 A1 EP 0241364A1 EP 87400751 A EP87400751 A EP 87400751A EP 87400751 A EP87400751 A EP 87400751A EP 0241364 A1 EP0241364 A1 EP 0241364A1
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EP
European Patent Office
Prior art keywords
solution
glass
solutions
gel
mixture
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Application number
EP87400751A
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English (en)
French (fr)
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EP0241364B1 (de
Inventor
Bruno Aubert
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Societe Generale pour les Techniques Nouvelles SA SGN
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Societe Generale pour les Techniques Nouvelles SA SGN
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Priority to AT87400751T priority Critical patent/ATE64669T1/de
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Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/16—Processing by fixation in stable solid media
    • G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28—Treating solids
    • G21F9/30—Processing
    • G21F9/301—Processing by fixation in stable solid media
    • G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
    • G21F9/305—Glass or glass like matrix

Definitions

  • High-level nuclear waste - such as fission products - or long-lived waste such as actinides is currently immobilized in borosilicate glasses which offer sufficient guarantees of safety for man and the environment.
  • the French Atomic Energy Commission has developed an industrial vitrification process for fission products (PF).
  • This process (known as AVM) consists in calcining the FP solution and in sending the calcinate obtained, simultaneously with a glass frit, to a melting furnace. In a few hours, at a temperature of the order of 11OO ° C., a glass is obtained which is poured into metal containers.
  • the glass frit is composed mainly of silica and boric anhydride, plus the other oxides (sodium, aluminum, etc.) necessary for the total formulation of calcinate + frit to give a glass which can be produced by known glass techniques and fulfilling the conditions of safety for storage (conditions on leaching, mechanical strength, etc.).
  • the temperature should be chosen high enough to hasten digestion but without having a detrimental effect on the life of the oven.
  • the applicant has developed a process in which the constituents of the glass are mixed in an aqueous medium so as to form a gelled solution.
  • the main objective is the manufacture by gels of glasses before the same formulation as those currently prepared by the oxide route, as the examples will show, but any borosilicate formulation acceptable for packaging waste can be prepared.
  • vitrification adjuvant it is all the constituents of the final glass other than the constituents originating from nuclear waste and except B and Si. This adjuvant therefore does not contain active nuclear elements.
  • AVM process it is included in a glass frit; in the process which is the subject of the invention, it is an aqueous solution, . final glass : this is the glass in which nuclear waste is immobilized, . soil : it is a solution of orthosilicic acid; this unstable evolves by polymerizing.
  • sol-gel method A way is known for preparing the gels in an aqueous medium, known as the sol-gel method, which consists in using a sol in water and in destabilizing it by modifying the pH, thus causing this solution to gel.
  • the literature describes the preparation of a SiO2-B2O3 glass by the sol-gel method: - addition of a Ludox solution brought to pH: 2 to a solution of aqueous ammonium tetraborate also brought to pH: 2; - mixture with stirring for 1 h (with possible addition of ammonia to bring the medium to pH: 3.5 very favorable for gelling) if the solution obtained is free of precipitation or flocculation, it is considered to be a satisfactory gel - drying 8 h at 100 ° C then 15 h at 175 ° C under vacuum of 0.1 mm Hg - hot pressing (45O bars - 5OO to 9OO ° C - 15 min to 5 h) to densify and vitrify (fusion is another means).
  • the boron makes gelation very difficult (in the HITACHI process described below, the boron is also added after formation of the gel) in particular due to the high insolubility of many boron compounds and promotes recrystallization in mixed gels, - aluminum promotes precipitation to the detriment of gelling, which is opposed to the desired result, - Sodium, calcium and zirconium lead to the formation of crystals which later constitute fragile points which can cause local destruction.
  • the Applicant has found a process for the immobilization of nuclear waste in a borosilicate glass, characterized in that all the constituents of the glass are introduced at the same time into a mixing zone, the mixing taking place with vigorous stirring in an aqueous medium in temperature conditions (25-1OO ° C, 65-7O ° C preferably), pH (acid and between 2.5 and 3.5 preferably) and determined proportions (depending on the composition desired for the final glass), the constituents glass being composed of: - a silica-based gel precursor, - a concentrated aqueous solution of a boron compound, - concentrated aqueous solutions of the other constituents, that is to say: . the solution of the nuclear waste to be treated, . the vitrification aid solution.
  • the mixture obtained is dried, calcined (3OO-5OO ° C) and finally melted (1OOO-115O ° C) to obtain the final glass.
  • Strong stirring is defined by the stirring speed: the stirring device rotates at more than 5000 rpm, preferably 2OOO rpm, and the thickness of the stirred layer (distance between the wall of the container and a stirring blade) does not exceed 10% of the diameter of the blade. It can for example be a turbine, a mixer or more simply a mechanical agitator rotating in a narrow section.
  • the solutions used are concentrated solutions, with the aim of rapidly manufacturing a gel and minimizing the amount of water to be evaporated, as will be explained in the description and the examples. It is difficult to give an exact concentration limit for each of the compounds, but the concentration of the solutions can reasonably be situated at least 75% of the saturation concentration.
  • the method can be applied to various nuclear waste solutions. It is particularly suitable for the vitrification of FP solutions alone or with other active effluents, for example the soda solution for washing tributylphosphate used for the extraction of uranium and plutonium; the sodium washing solution can even be treated alone by this process.
  • FP solutions are nitric solutions resulting from the reprocessing of fuels, they contain a large number of elements in various chemical forms and a certain amount of insolubles. An example of composition is given below.
  • the soda effluent is based on sodium carbonate and possibly contains organic phosphorus traces entrained by washing (example 3).
  • a substance containing silica particles, possibly partially hydrolyzed, which is either in the form of a powder which, when dissolved in acid, can produce a sol, or directly in the form of a gel, will be called a gel precursor. 'a floor.
  • Gel precursors sold commercially and advantageously used in the process can for example be a sol such as Ludox® or else Aerosil® which is formed by hydrolysis in the gas phase of silicon tetrachloride. In an acidic environment, the Aerosil leads to a soil then to a firm gelled mass.
  • the Ludox is brought in a solution. Aerosil on the other hand can be taken either in solution or directly in the form of powder, depending on the technology used.
  • the gel precursor is placed in an acidic aqueous medium, according to the process which is the subject of the invention, so that it becomes a gelled solution by polymerization from Si-OH- bonds.
  • the boron necessary to form the borosilicate structure is brought by the aqueous solution of a boron compound sufficiently soluble such as ammonium tetraborate (TBA) which has a solubility of approximately 3OO g / l or 15.1% B2O3.
  • TSA ammonium tetraborate
  • the solution is prepared and used at 65-7O ° C.
  • Boric acid can just as easily be used, its solubility is around 13O g / l at 65 ° C or 6.5% B2O3, it is increased in the presence of Na+ ions when Na / B ⁇ O, 23 .
  • the vitrification aid To prepare the solution of the vitrification aid, it is necessary to use compounds containing the desired elements which are soluble in water, at process temperature, which are compatible with each other, which do not unnecessarily add other ions and whose ions not participating in the structure of the final glass are easily removed by heating. They are, for example, nitrate solutions when nitric FP solutions are treated.
  • the solid compounds are always preferably dissolved in the minimum quantity of water so as to minimize the volumes treated and the quantities of water to be evaporated.
  • the mixing is carried out between 20 ° and 80 ° C.
  • the solutions to be treated are taken at the temperature at which they are; the FP solution, due to the fact that its activity arrives at the treatment unit between 20 ° and 40 ° C.
  • the concentrated solution of the boron compound is maintained to avoid precipitation between 50 ° and 80 ° C.
  • the other solutions are developed at room temperature. It is then possible either to mix the solutions at the temperature at which they are developed or brought, either to bring all the solutions (except those of the waste taken as is) to a higher temperature before mixing them.
  • the latter has the following advantage. After mixing has taken place and the gelled solution has started to form, the polymerization (gelling) takes place during a so-called maturation time. The rise in temperature favors it. It is therefore very advantageous to prepare the mixture between 50 ° C. and 80 ° C.
  • the gelling solution matures in the process which is the subject of the invention, during drying, preferably at 100-150 ° C.
  • the solutions of the glass constituents have different pH values: the gel precursor in solution is acid (such as Aerosil in nitric solution) or alkaline (Ludox), the solution of acidic vitrification adjuvant, the solution of acid waste ( in the case of FP) or alkaline (non-neutralized washing effluent) solutions, the solution of the boron acid (boric acid) or alkaline (ammonium tetraborate) compound.
  • the pH of the mixture must be less than 7 and preferably between 2.5 and 3.5. An adjustment of the pH can be undertaken if necessary.
  • the mixture - from which the final glass is obtained by heating - is prepared from all the components in aqueous solution introduced simultaneously into the mixing zone.
  • a so-called solution is obtained gelled, its viscosity and its texture changing over time and going from a fluid solution to a gel.
  • the mixture obtained is dried (at 1OO-1O5 ° C preferably) in an oven for example, drying under vacuum is also possible. During this operation, the gel continues to form.
  • a calcination is then carried out between 3OO and 5OO ° C (35O to 4OO ° C preferably) during which the water finishes evaporating and the nitrates decompose in part, the analysis shows that after 2 h at 4OO ° C 30% of the nitrates are still present under the conditions of the example.
  • the calcination can be done either in a conventional calciner (of the type used in the AVM vitrification process) or in a melting furnace of the ceramic melter type for example.
  • drying-calcination-melting steps described correspond to heat treatments in defined temperature zones and in different equipment. It is obvious that similar heat treatments in other devices are suitable, for example drying in an oven followed by introduction into a melting furnace designed in several zones, in general any technique for making glass from a gel can be used.
  • the composition of the borosilicate matrix prepared in an aqueous medium is adjusted to the type of waste treated.
  • a borosilicate matrix low in sodium (or even possibly without sodium) can be developed, as the examples will show.
  • Group 1 represents the inactive elements of the fission product solution and group 2 the PF and insolubles of the same solution.
  • the simulated FP solution has a pH: 1.3.
  • the final glass composition to be obtained is:
  • the solutions of the vitrification aid are prepared according to the composition of the glass to be obtained and that of the waste solution to be treated.
  • the separate vitrification aid solutions are thus prepared at room temperature:
  • Ludox In another beaker, 56 cm3 of Ludox are acidified to pH 2, to avoid the subsequent precipitation of hydroxides such as Al (OH) 3 at pH: 5-6 or Zn (OH) 2 at pH: 4.8.
  • the Ludox solution is introduced, with stirring, into the ammonium tetraborate, the reaction taking place at 65 ° C.-70 ° C. Stirred (magnetic or mechanical stirrer) 30 min while maintaining the temperature. To accelerate the gelation, a small amount of dilute ammonia (0.15 N) is added to obtain pH: 3. There is gel formation.
  • the mixture is left to stand at 65 ° C.-70 ° C., it takes at least 20 h to obtain a mass which is dried in the oven (90 h at 110 ° C.) immediately after its obtaining, then melted between 1OOO and 115O ° C.
  • a glass of good quality was defined as being a homogeneous glass, not presenting any unfused and bubbles and moreover not showing on the surface traces of molybdate.
  • molybdate coming from FP solutions poses a major problem: part of the active Mo tends to separate from the solution and sediment so that this phase is not completely dispersed in the mixture therefore it is not fully included in the gelled solution.
  • the vitrification aid solution is prepared as follows: each of the compounds is dissolved in the minimum amount of water, ie a total of 640 g of water at 65 ° C .; pH: 0.6.
  • a conventional turbine comprising a mixing zone of small volume in which a propeller with several blades rotates so that a mixture with a high rate of shear is produced. In this example, it rotates at 2OOO rpm.
  • the turbine used for the tests is manufactured by the company STERMA, the mixing zone has a volume of 1 cm3, the thickness of the agitated layer is of the order of mm.
  • the mixing zone has a volume of 1 cm3
  • the thickness of the agitated layer is of the order of mm.
  • the vitrification and PF adjuvant solutions are pumped at the indicated flow rate, and it is their mixture at the overall flow rate of 25.4 kg / h which is sent to the turbine. Thus, there is a flow rate of 36 kg / h in gel.
  • the pH of the gelled solution leaving the turbine is 3.
  • this AVM process uses the vitrification adjuvant in the form of solid glass frit, a known composition is: SiO2 55-6O% by weight B2O3 16-18% by weight Al2O3 6-7% by weight Na2O 6-7% by weight CaO 4.5-6% by weight ZnO 2.5-3.5% by weight Li2O 2-3% by weight
  • This composition limits the amount of admissible sodium in the effluent to be vitrified, since the sodium content cannot be increased too much which lowers the resistance to leaching.
  • the present invention makes it possible to manufacture a borosilicate glass with the soda effluent having a composition close to that giving any satisfaction in the AVM process.
  • the ripening temperature can be significantly lowered or the ripening times shortened.
  • the following vitrification aid solution is prepared for one liter of aqueous solution: Al (NO3) 3, 9H2O 2O9, O g Ca (NO3) 2, 3H2O 98.5 g LiNO3 53.7 g Zn (NO3) 2, 6H2O 49.7 g Fe (NO3) 3, 6H2O 73.5 g Mn (NO3) 3, 6H2O 18.2 g Ba (NO3) 2 5.5 g Co (NO3) 2, 6H2O 11.3 g Sr (NO3) 2 4.1 g CsNO3 8, O g Y (NO3) 3, 4H2O 71, O g Na2MoO4, 2H2O 16.6 g Monoammonium phosphate 2.8 g
  • Each of the solutions is kept in a thermostatically controlled bath (temperature 65 ° C).
  • thermostatically controlled bath temperature 65 ° C.
  • diaphragm pumps that have been adjusted beforehand to obtain the desired flow rates.
  • the debits set are: . TBA solution ............ O, 12 kg / h .
  • Ludox solution .......... O 15 kg / h .
  • Na2CO3 solution ........ O, 21 kg / h
  • the operation is carried out for 1.5 h still in the form of agitation.
  • the contents of the mixer bowl are poured into a beaker and left to stand for 2 hours.
  • a homogeneous, practically solid mass of opalescent color is formed. This mass is distributed on a plate to form a layer of approximately 20 to 30 mm thick and the plate is placed in an oven heated to 105 ° C. for 24 h.
  • Dry particles of the order of cm3 are thus obtained. It is placed in an oven to calcine, the temperature is regularly raised over 3 hours to 400 ° C. and it is maintained for 3 hours. The calcinate obtained is crushed into particles of 1 to 3 mm.
  • a Joule effect electric oven with sufficient capacity is set at 115O ° C.
  • This example shows how the composition of the vitrification aid can be adjusted.
  • the vitrification adjuvant, TBA and waste solution solutions are the same.
  • the Aerosil ® sold by the company DEGUSSA.
  • the gel precursor is formed by gradually pouring, with stirring, the Aerosil into water acidified with HNO33N (pH: 2.5) so as to obtain a solution of 150 g of silica per liter.
  • the two examples 3 and 4 illustrate the invention for the treatment of soda effluent with different gel precursors, but they do not constitute a limitation thereof.
  • the neutralized soda effluent was treated alone. It is obviously advantageous to simultaneously treat the non-neutralized soda effluent (therefore as it leaves the extraction units) and the FP solutions which are nitric, so as not to consume nitric acid and increase the volumes of waste. For this, the washing water of the nitrous vapors, loaded with nitric acid, is added to the soda effluent to neutralize it, the resulting liquid being mixed with the FP solution in predetermined proportions. The vitrification adjuvant solution will then be suitable for this treatment.
  • the boron compound used is ammonium tetraborate tetrahydrate, this to allow comparison with the prior art easier.
  • TBA in existing vitrification plants, the use of TBA poses problems in the treatment of gaseous effluents rich in ammonia and nitrous vapors which are capable of recombining to produce dangerous ammonium nitrate under certain conditions.
  • boric acid is preferred under the conditions of the process which is the subject of the invention.
  • the Applicant believes that the gelled solution produced according to the invented process forms more quickly than the compounds react with one another to precipitate.
  • the gelled solution obtained has the structure of the desired final glass and in this solution the ions can no longer migrate.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Glass Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
EP87400751A 1986-04-08 1987-04-06 Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas Expired - Lifetime EP0241364B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87400751T ATE64669T1 (de) 1986-04-08 1987-04-06 Verfahren zur verfestigung von nuklearen abfaellen in borsilikatglas.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8605009A FR2596909B1 (fr) 1986-04-08 1986-04-08 Procede d'immobilisation de dechets nucleaires dans un verre borosilicate
FR8605009 1986-04-08

Publications (2)

Publication Number Publication Date
EP0241364A1 true EP0241364A1 (de) 1987-10-14
EP0241364B1 EP0241364B1 (de) 1991-06-19

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EP87400751A Expired - Lifetime EP0241364B1 (de) 1986-04-08 1987-04-06 Verfahren zur Verfestigung von nuklearen Abfällen in Borsilikatglas

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US (1) US4772431A (de)
EP (1) EP0241364B1 (de)
JP (1) JPH0833493B2 (de)
AT (1) ATE64669T1 (de)
CA (1) CA1332504C (de)
DE (1) DE3770855D1 (de)
ES (1) ES2023920B3 (de)
FR (1) FR2596909B1 (de)

Cited By (4)

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FR2659784A1 (fr) * 1990-03-15 1991-09-20 Doryokuro Kakunenryo Procede de traitement de dechets fortement radioactifs.
FR2677798A1 (fr) * 1991-06-13 1992-12-18 Doryokuro Kakunenryo Procede de vitrification reductrice de volume de dechets hautement radioactifs.
DE4136188C1 (en) * 1991-11-02 1992-12-24 Forschungszentrum Juelich Gmbh, 5170 Juelich, De Radioactive waste esp. for bonding caesium@ giving not too small ceramic prod. - bonded to alumina matrix, by introducing into silica sol, adding reactive alumina, kneading and extruding obtd. gel then drying and calcining
FR2943835A1 (fr) * 2009-03-31 2010-10-01 Onectra Procede de conditionnement de dechets radioactifs sous forme de roche synthetique

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US4898692A (en) * 1988-11-16 1990-02-06 The United States Of America As Represented By The United States Department Of Energy Process for direct conversion of reactive metals to glass
US5154899A (en) * 1991-06-28 1992-10-13 Sturcken Edward F Metal recovery from porous materials
US5249608A (en) * 1991-12-06 1993-10-05 Lee W. Tower Process and flushing device for removing oil from waste oil filters
US5508236A (en) * 1993-08-20 1996-04-16 The Research Foundation Of State University Of New York Ceramic glass composition
US5369062A (en) * 1993-08-20 1994-11-29 The Research Foundation Of State University Of Ny Process for producing ceramic glass composition
US5494863A (en) * 1994-12-13 1996-02-27 Vortec Corporation Process for nuclear waste disposal
JP2989508B2 (ja) * 1995-02-28 1999-12-13 核燃料サイクル開発機構 高レベル放射性廃液のガラス固化方法
US6145343A (en) * 1998-05-02 2000-11-14 Westinghouse Savannah River Company Low melting high lithia glass compositions and methods
RU2168225C1 (ru) * 1999-10-28 2001-05-27 Московское государственное предприятие - объединенный эколого-технологический и научно-исследовательский центр по обезвреживанию РАО и охране окружающей среды (Мос НПО "Радон") Способ остекловывания радиоактивных отходов в охлаждаемом металлическом индукционном плавителе
RU2168226C1 (ru) * 1999-10-28 2001-05-27 Московское государственное предприятие - объединенный эколого-технологический и научно-исследовательский центр по обезвреживанию РАО и охране окружающей среды (Мос НПО "Радон") Способ остекловывания радиоактивных отходов в охлаждаемом металлическом индукционном плавителе
DE10141103B4 (de) * 2001-08-22 2007-01-18 Schott Ag Verfahren zur Herstellung optischer Gläser und Farbgläser bei niederen Temperaturen
GB0808805D0 (en) * 2008-05-15 2008-06-18 Permastar Ltd Electrical power generating systems using spent nuclear fuel and other radioactive materials
WO2011152909A2 (en) 2010-03-09 2011-12-08 Kurion, Inc. Isotope-specific separation and vitrification using ion-specific media
US20110224474A1 (en) * 2010-03-09 2011-09-15 Kurion, Inc. Advanced Microwave System for Treating Radioactive Waste
CN101857355B (zh) * 2010-06-02 2012-09-05 天台精工西力玻璃珠有限公司 一种用于固化高放射性核废料的玻璃珠的生产方法
US10364176B1 (en) * 2016-10-03 2019-07-30 Owens-Brockway Glass Container Inc. Glass precursor gel and methods to treat with microwave energy
EP3687751A4 (de) 2017-09-26 2021-08-04 Delta Faucet Company Wässriges gelgiessverfahren für keramische produkte

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GB1050818A (de) * 1963-09-17 1900-01-01
DE2611689A1 (de) * 1976-03-19 1977-09-29 Kernforschungsanlage Juelich Verfahren zum einschliessen von radioaktiven spaltprodukten
FR2485243A1 (fr) * 1980-06-20 1981-12-24 Kraftwerk Union Ag Procede de stockage definitif, par vitrification, de dechets radioactifs contenant des borates
EP0168218A1 (de) * 1984-07-10 1986-01-15 Westinghouse Electric Corporation Verfahren zur Verfestigung von schlammigen Abfällen die eine hohe Konzentration von Borsäure enthalten

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2659784A1 (fr) * 1990-03-15 1991-09-20 Doryokuro Kakunenryo Procede de traitement de dechets fortement radioactifs.
FR2677798A1 (fr) * 1991-06-13 1992-12-18 Doryokuro Kakunenryo Procede de vitrification reductrice de volume de dechets hautement radioactifs.
DE4136188C1 (en) * 1991-11-02 1992-12-24 Forschungszentrum Juelich Gmbh, 5170 Juelich, De Radioactive waste esp. for bonding caesium@ giving not too small ceramic prod. - bonded to alumina matrix, by introducing into silica sol, adding reactive alumina, kneading and extruding obtd. gel then drying and calcining
FR2943835A1 (fr) * 2009-03-31 2010-10-01 Onectra Procede de conditionnement de dechets radioactifs sous forme de roche synthetique
WO2010112732A1 (fr) * 2009-03-31 2010-10-07 Onectra Procédé de conditionnement de déchets radioactifs sous forme de roche synthétique

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ES2023920B3 (es) 1992-02-16
CA1332504C (en) 1994-10-18
US4772431A (en) 1988-09-20
DE3770855D1 (de) 1991-07-25
EP0241364B1 (de) 1991-06-19
JPS632000A (ja) 1988-01-06
FR2596909A1 (fr) 1987-10-09
ATE64669T1 (de) 1991-07-15
JPH0833493B2 (ja) 1996-03-29
FR2596909B1 (fr) 1993-05-07

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