EP0102284A1 - Lösung und Verfahren zur chemischen Konversion metallischer Oberflächen - Google Patents

Lösung und Verfahren zur chemischen Konversion metallischer Oberflächen Download PDF

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Publication number
EP0102284A1
EP0102284A1 EP83401608A EP83401608A EP0102284A1 EP 0102284 A1 EP0102284 A1 EP 0102284A1 EP 83401608 A EP83401608 A EP 83401608A EP 83401608 A EP83401608 A EP 83401608A EP 0102284 A1 EP0102284 A1 EP 0102284A1
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EP
European Patent Office
Prior art keywords
acid
solution
solution according
zinc
conversion
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Granted
Application number
EP83401608A
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English (en)
French (fr)
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EP0102284B1 (de
Inventor
Jean-Claude Lumaret
Serge Gosset
Didier Boulinguiez
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Roquette Freres SA
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Roquette Freres SA
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Priority to AT83401608T priority Critical patent/ATE27971T1/de
Publication of EP0102284A1 publication Critical patent/EP0102284A1/de
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Publication of EP0102284B1 publication Critical patent/EP0102284B1/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
    • C23C22/47—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/23—Condensed phosphates

Definitions

  • the invention relates to an acidic aqueous solution for the chemical conversion of metallic substrates, in particular based on iron or its alloys.
  • chemical conversion denotes the surface chemical transformations of metals, in particular in an acid medium, making it possible to modify their intrinsic properties and to confer on them new physical or physico-chemical characteristics, in particular with a view to increasing their resistance. corrosion and / or to promote the adhesion of film-forming coatings applied subsequently.
  • This phosphating layer can have a so-called amorphous or crystalline structure.
  • the amorphous structure is obtained by a conversion based on iron phosphate; the phosphating layer is then essentially composed of an iron phosphate, vivianite Fe 3 (PO 4 ) 2 , 8 H 2 O and iron oxide of the magnetite type Fe 3 0 4 .
  • This type of layer allows excellent adhesion of paints and a significant increase in corrosion resistance.
  • the crystal structure is obtained when the treatment solution contains for example phosphate zinc; the essential constituents of the layer are then the homeopathy Zn 3 (PO 4 ) 2 , 4 H 2 O and the phosphophyllite Zn 2 Fe (PO 4 ) 2 , 4 H 2 O which are in the form of crystals oriented with respect to the support.
  • This type of layer has a certain porosity due to the existence of intercrystalline gaps, which give it good wettability with respect to products such as paints and varnishes.
  • the essential property of the crystalline layers is however to slow corrosion; this property is related to the dielectric strength of the phosphate coating which opposes the passage of local currents generated by the formation of galvanic microcouples on the surface of the metal.
  • chelating agents to conventional phosphating baths having as essential component primary phosphates; these chelating agents were chosen from the group comprising EDTA (ethylene-diamine-tetracetic acid), monohydroxycarboxylic acids (in particular gluconic acid) and polycarboxylic acids such as citric acid, oxalic acid, l tartaric acid and others.
  • EDTA ethylene-diamine-tetracetic acid
  • monohydroxycarboxylic acids in particular gluconic acid
  • polycarboxylic acids such as citric acid, oxalic acid, l tartaric acid and others.
  • one of the major drawbacks of conventional phosphating processes lies in the fact that, even after chromating passivation, the behavior of the chemical conversion layers obtained and the resistance to corrosion of the treated substrates are only very limited in time. .
  • the polyphosphate forming part of the solution in accordance with the invention can be chosen in particular from sodium trimeta-, tetrameta- and hexametaphosphate, sodium hexametaphosphate or HMPP being preferred.
  • Glucoheptonic acid and very particularly gluconic acid or their salts are preferred.
  • the zinc ion can be brought in any suitable way and in particular in the form of its salts, such as nitrate or sulphate or its oxide.
  • the amounts of polyphosphate, chelating agents and zinc ion present in the solutions according to the invention are at least 0.2 mmol, 0.3 mmol and 0.15 atg, respectively. per liter.
  • the zinc is brought in combined form with the chelating agent, preferably in the form of citrate, tartrate, glucoheptonate and, most particularly, gluconate.
  • the amounts of polyphosphate and zinc salts of at least one of the above-mentioned chelating agents present in the solutions according to the invention are respectively at least 0.2 mmol and 0.3 mmol per liter; in the case of HMPP and zinc gluconate, these lower limit quantities are 0.122 and 0.136 g / l respectively.
  • the chemical conversion solution according to the invention comprises from 0.25 g / l to 150 g / l of the composition consisting of the polyphosphate and the zinc salt of the chelating agent; preferably, this amount is from 2 to 100 g / l and, more preferably still, from 10 to 80 g / l.
  • the weight ratio between zinc gluconate and sodium hexametaphosphate is between approximately 10/1 and 1/7, preferably between approximately 8/1 and 1/4 and, more preferably again, between about 5/1 and 1/3.
  • the amount of zinc gluconate is from 10 to 60 g / l and the amount of hexametaphosphate from 2 to 30 g / l.
  • the pH of the solution is initially, that is to say before implementation, brought to a value less than 2, preferably between approximately 0.7 and 1, 7.
  • the chemical conversion process according to the invention is characterized in that it comprises the implementation of the chemical conversion solution according to the invention by spraying onto the metal substrate to be treated or by immersion of the substrate in the solution , immersion being preferred.
  • the objects treated by implementing the method according to the invention can be stored in the open air, without any protective treatment (for example lubrication) beforehand and without any degradation phenomena appearing. layer.
  • the temperature of the solution is between around 40 and 100 ° C, more particularly above 60 ° C and preferably between 65 and 98 ° C.
  • the contact between the solution and the may substrate metal is maintained for a time varying, in practice, from 2 seconds to 60 minutes.
  • the pH value when it is the preferred treatment solution comprising zinc gluconate and sodium hexametaphosphate which is used on a metal substrate, it is found that the pH value, initially between approximately 0.7 and 1.7 , increases as a function of the number of objects treated or of the surface treated, by describing a curve which has two characteristic zones similar to landings. Most generally, the first of said zones is in a pH range between about 1.9 and 2.6 and the second is in a pH range between about 2.2 to 3.5, this depending in particular on treated surfaces and treatments prior to the actual conversion step.
  • layer weights of the order of 40 to 60 g / m 2 were obtained by immersing steel plates in a conversion solution according to the invention for a period of 15 to 25 minutes and at a temperature of 90 ° C.
  • the weight of the conversion layer obtained at a pH value corresponding to the first level is less than that of the layers obtained at a pH value corresponding to the second level (or layers “second zone”).
  • “Second zone” layers have exceptional corrosion resistance; but even the “first zone” layers have resistance to the horn significantly higher than that of the conversion layers obtained by conventional phosphating processes.
  • the pH of this solution is first brought to an initial value of approximately 0.7 to 1.7 by means of one of the above-mentioned mineral acids and then, before the actual application, the bath is ripened, in particular by contacting with metallic iron, so as to bring the pH of the solution to a treatment value corresponding to one or the other of the two aforementioned stages, that is to say comprised either between approximately 1.9 and 2.6, or between approximately 2.2 and 3.5.
  • the pH can be maintained at this level if necessary by adding sufficient quantities of one of the above-mentioned mineral acids.
  • the pH of the chemical conversion solution is changed from the initial value the between approximately 0.7 and 1.7 up to a value corresponding to the first and / or second level by adding to the solution a sufficient quantity of iron filings, generally from 0.5 to 4 g and, more preferably , from 0.75 to 3 g per liter of solution; the solution thus "matured" is implemented by immersion or spraying.
  • the contact time between the bath and the metal object to be treated can be reduced, from a value commonly situated between 60 and 30 minutes in the absence of filings, to a value of 15 minutes and even 5 minutes.
  • manganese nitrate is particularly preferred and makes it possible to considerably improve the rate of crystallization of the deposit.
  • the effectiveness of the manganese nitrate is illustrated by the fact that treatment with the solu- tion according to the invention containing Mn (N0 3) 2 gives rise to a crystalline deposit of expansion similar to that which is obtained in the absence of manganese nitrate but in the presence of iron filings and after baking at 135 ° C for 15 minutes. This observation can be made by comparative examination with a scanning electron microscope.
  • the preferred manganese concentration is between 0.5 and 1.5 g / 1 and, more preferably, between 0.75 g / 1 and 1.25 g / 1.
  • the presence of manganese contributes to improving the stabilization of the pH at the preferred values, which offers, unlike the phosphating methods according to the prior art, a much greater reproducibility of the tests.
  • the conversion layers obtained by implementing the process in accordance with the invention constitute an excellent bonding base for all organic coatings of the glycerophthalic, vinyl, epoxide, polyurethane type. , water-soluble alkyd, air or oven dried, as well than for all metallic coatings such as zinc, cadmium, tin and the like.
  • organic or metallic coatings can be applied by brush, by dipping or by pneumatic gun or by spray gun under high pressure without air or also by electrostatic or by electrodeposition by anodic or cathodic way, on the chemical conversion layers obtained. beforehand.
  • the baths obtained using the conversion solutions in accordance with the invention do not give rise to the formation of the amounts of sludge encountered in the baths of the prior art , thus eliminating the problems of pollution and guaranteeing excellent stability without renewal, the baths of the prior art requiring, for their part, frequent renewals.
  • Another advantage lies in the fact that the preferred conversion solution according to the invention is essentially based on biodegradable products.
  • metallic test pieces of steel E 24 - 1 (0.22 X of carbon - 0.075 X of phosphate - 0.062 ⁇ of sulfur) of dimensions approximately equal to 9.5 x 6.5 cm, having previously undergone a cold chemical pickling in 6N hydrochloric medium, are immersed for 60 minutes in one liter baths based three conversion solutions maintained at 95 ° C (solutions A, B, C).
  • Solution A contains 0.25 g / 1 of zinc gluconate or GZ dihydrate (the concentration is expressed without taking into account the two molecules of water of crystallization).
  • Solution B contains 0.25 g / 1 of sodium hexametaphosphate or HMPP.
  • Solution C is obtained by mixing equal volumes of solutions A and B.
  • the pH of each of solutions A, B and C is adjusted to the value of 2 by adding a few ml of nitric acid.
  • the treated plates were subjected to the salt spray test for 24 hours.
  • the pH of the conversion bath is measured after the treatment of each of the plates.
  • a pH meter of the type 601 A / Digital IONALYSER marketed by the company ORION RESEARCH ' , is used, provided with a high temperature electrode and calibrated at 95 ° C.
  • the experimental method used is identical to that described in Example 2 (influence of the HMPP concentration), except for the treatment time which is limited to 15 minutes.
  • the concentration of the conversion solutions is maintained whatever the composition.
  • HMPP concentration is unchanged regardless of the combination studied.
  • This example illustrates the use of citric acid as a chelating agent.
  • the solution tested has the following composition:
  • This example also shows the advantage of introducing the zinc ion in the form of the salt of the chelating agent.
  • the performances obtained are compared, on the one hand, with a solution based on sodium gluconate plus zinc nitrate in mixture with hexametaphosphate and, on the other hand, with a solution based on zinc gluconate and sodium hexametaphosphate.
  • the experimental conditions used are those described in Example 2 with regard to the study of the influence of the HMPP concentration.
  • the test pieces analyzed are those treated at a pH value corresponding to the second pH zone.
  • the concentration of hexametaphosphate is the same in both cases.
  • composition of the two solutions studied is as follows:
  • Table IV shows the appearance of the test pieces after treatment and their resistance to salt spray expressed in hours.
  • This example illustrates the advantage of using the polyphosphate ion in place of the phosphate ion provided by sodium dihydrogen phosphate.
  • the operating mode is that described above.
  • the immersion time is 30 minutes.
  • the pH of the bath was successively brought directly to 2, 2.5 and 3 with nitric acid and iron filings.
  • the samples are degreased with acetone then with trichlorethylene and then pickled in an aqueous solution of 6N hydrochloric acid for 5 minutes at 40 ° C.
  • Mn nitrate acts more sensitively than iron filings on the crystallization of the deposit.
  • the method used consists in measuring the force necessary to tear off a pad with a surface area of 3.14 cm 2 , glued to a film-forming coating deposited on the surface of a test piece.
  • the measurements are carried out with an Instron type dynamometer.
  • the film-forming coatings examined are industrial type paints, applied in a single layer with an automatic film applicator.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Chemically Coating (AREA)
  • Laminated Bodies (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP83401608A 1982-08-03 1983-08-03 Lösung und Verfahren zur chemischen Konversion metallischer Oberflächen Expired EP0102284B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83401608T ATE27971T1 (de) 1982-08-03 1983-08-03 Loesung und verfahren zur chemischen konversion metallischer oberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8213550A FR2531457A1 (fr) 1982-08-03 1982-08-03 Solution et procede pour la conversion chimique de substrats metalliques
FR8213550 1982-08-03

Publications (2)

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EP0102284A1 true EP0102284A1 (de) 1984-03-07
EP0102284B1 EP0102284B1 (de) 1987-06-24

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EP83401608A Expired EP0102284B1 (de) 1982-08-03 1983-08-03 Lösung und Verfahren zur chemischen Konversion metallischer Oberflächen

Country Status (10)

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US (1) US4474626A (de)
EP (1) EP0102284B1 (de)
JP (1) JPS5943883A (de)
AT (1) ATE27971T1 (de)
AU (1) AU544167B2 (de)
CA (1) CA1233733A (de)
DE (1) DE3372218D1 (de)
ES (1) ES524686A0 (de)
FR (1) FR2531457A1 (de)
ZA (1) ZA835616B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2184109A (en) * 1985-10-29 1987-06-17 Grace W R & Co The treatment of aqueous systems
EP0298827A1 (de) * 1987-06-25 1989-01-11 Roquette FrÀ¨res Lösung und Verfahren zur gemischten Phosphatisierung

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3800834A1 (de) * 1988-01-14 1989-07-27 Henkel Kgaa Verfahren und mittel zum gleichzeitigen gleitschleifen, reinigen und passivieren metallischer werkstuecke
JP2781844B2 (ja) * 1988-10-20 1998-07-30 日本ペイント株式会社 塗装用下地処理剤
US5137589A (en) * 1990-02-09 1992-08-11 Texo Corporation Method and composition for depositing heavy iron phosphate coatings
US5258078A (en) * 1990-02-09 1993-11-02 Texo Corporation Method and composition for depositing heavy iron phosphate coatings
JP5463609B2 (ja) * 2005-03-31 2014-04-09 Ｊｆｅスチール株式会社 クロムフリー表面処理亜鉛系めっき鋼板およびその製造方法ならびに表面処理液
US7989078B2 (en) * 2006-12-28 2011-08-02 United Technologies Coporation Halogen-free trivalent chromium conversion coating
US8536106B2 (en) 2010-04-14 2013-09-17 Ecolab Usa Inc. Ferric hydroxycarboxylate as a builder
CN111996522B (zh) * 2020-08-03 2022-08-16 鞍钢股份有限公司 一种锌铝镁钢板环保钝化剂及制备使用方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1045929A (fr) * 1951-11-19 1953-12-02 Parker Ste Continentale Procédé perfectionné de phosphatation
FR1138208A (fr) * 1955-12-26 1957-06-11 Walterisation Company Ltd Perfectionnements aux traitements de surfaces de métaux
GB825485A (en) * 1956-03-31 1959-12-16 Pyrene Co Ltd Improvements in the production of oxalate coatings
FR1243081A (fr) * 1958-11-28 1960-10-07 Parker Ste Continentale Procédé de phosphatation de métaux, en particulier de métaux ferreux
DE974196C (de) * 1942-12-11 1960-10-13 Metallgesellschaft Ag Verfahren zur Erzeugung von geschmeidigen Phosphatueberzuegen auf metallischen Gegenstaenden
DE975008C (de) * 1952-08-06 1961-08-03 American Chem Paint Co Verfahren zur Herstellung von Phosphatueberzuegen auf Zink und dessen Legierungen
FR1362202A (fr) * 1962-11-13 1964-05-29 Parker Ste Continentale Procédé perfectionné de formation de revêtements phosphatés sur des surfaces métalliques
FR1530050A (fr) * 1966-07-01 1968-06-21 Procédé et produit pour la préparation de la surface de métaux en vue d'opérations de peinture ou de finissage

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA565717A (en) * 1958-11-04 The Walterisation Company Limited Surface treatment of metals
US2067007A (en) * 1934-03-05 1937-01-05 Patents Corp Method of coating metal
US2528787A (en) * 1947-09-08 1950-11-07 Hall Lab Inc Protection of metals from corrosion
US2826517A (en) * 1954-01-11 1958-03-11 Kelite Products Inc Process and composition for phosphatizing steel
US3152018A (en) * 1961-11-01 1964-10-06 Wyandotte Chemicals Corp Room temperature phosphate coating composition
JPS4893552A (de) * 1972-03-11 1973-12-04
US4110128A (en) * 1975-12-17 1978-08-29 International Lead Zinc Research Organization, Inc. Solution and procedure for depositing a protective coating on galvanized steel parts, and solution regeneration procedure
JPS6038464B2 (ja) * 1978-08-01 1985-08-31 三菱重工業株式会社 鉄鋼材の防錆処理法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE974196C (de) * 1942-12-11 1960-10-13 Metallgesellschaft Ag Verfahren zur Erzeugung von geschmeidigen Phosphatueberzuegen auf metallischen Gegenstaenden
FR1045929A (fr) * 1951-11-19 1953-12-02 Parker Ste Continentale Procédé perfectionné de phosphatation
DE975008C (de) * 1952-08-06 1961-08-03 American Chem Paint Co Verfahren zur Herstellung von Phosphatueberzuegen auf Zink und dessen Legierungen
FR1138208A (fr) * 1955-12-26 1957-06-11 Walterisation Company Ltd Perfectionnements aux traitements de surfaces de métaux
GB825485A (en) * 1956-03-31 1959-12-16 Pyrene Co Ltd Improvements in the production of oxalate coatings
FR1243081A (fr) * 1958-11-28 1960-10-07 Parker Ste Continentale Procédé de phosphatation de métaux, en particulier de métaux ferreux
FR1362202A (fr) * 1962-11-13 1964-05-29 Parker Ste Continentale Procédé perfectionné de formation de revêtements phosphatés sur des surfaces métalliques
FR1530050A (fr) * 1966-07-01 1968-06-21 Procédé et produit pour la préparation de la surface de métaux en vue d'opérations de peinture ou de finissage

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2184109A (en) * 1985-10-29 1987-06-17 Grace W R & Co The treatment of aqueous systems
US4778655A (en) * 1985-10-29 1988-10-18 W. R. Grace & Co. Treatment of aqueous systems
EP0298827A1 (de) * 1987-06-25 1989-01-11 Roquette FrÀ¨res Lösung und Verfahren zur gemischten Phosphatisierung
FR2618164A1 (fr) * 1987-06-25 1989-01-20 Roquette Freres Solution et procede de phosphatation mixte.
US5045130A (en) * 1987-06-25 1991-09-03 Compagnie Francaise De Produits Industriels Solution and process for combined phosphatization

Also Published As

Publication number Publication date
CA1233733A (en) 1988-03-08
FR2531457A1 (fr) 1984-02-10
JPS5943883A (ja) 1984-03-12
JPH0411629B2 (de) 1992-03-02
ES8403981A1 (es) 1984-05-01
DE3372218D1 (en) 1987-07-30
EP0102284B1 (de) 1987-06-24
AU544167B2 (en) 1985-05-16
AU1753183A (en) 1984-02-09
FR2531457B1 (de) 1985-03-01
US4474626A (en) 1984-10-02
ATE27971T1 (de) 1987-07-15
ZA835616B (en) 1984-09-26
ES524686A0 (es) 1984-05-01

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