EP0264811B1 - Procédé d'obtention de revêtements de phosphate - Google Patents

Procédé d'obtention de revêtements de phosphate Download PDF

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Publication number
EP0264811B1
EP0264811B1 EP87115011A EP87115011A EP0264811B1 EP 0264811 B1 EP0264811 B1 EP 0264811B1 EP 87115011 A EP87115011 A EP 87115011A EP 87115011 A EP87115011 A EP 87115011A EP 0264811 B1 EP0264811 B1 EP 0264811B1
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Prior art keywords
phosphate
content
paint
coating
zinc
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Expired - Lifetime
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EP87115011A
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German (de)
English (en)
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EP0264811A1 (fr
Inventor
Atsunori Yoshida
Toshi Miyawaki
Takanobu Nihon Parkerizing Saito
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/362—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 fluorides or complex fluorides containing also phosphates containing also zinc cations
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/364—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 fluorides or complex fluorides containing also phosphates containing also manganese cations

Definitions

  • the invention relates to a method for producing phosphate coatings on surfaces of cold-rolled steel, one-sided or double-sided galvanized steel in dipping with a phosphating solution containing zinc, phosphate, nitrate and fluoride.
  • Zinc-phosphate coatings play a special role here. Such coatings can be produced from phosphating solutions with a comparatively high zinc content (normal zinc technology). In recent years, however, phosphating processes that use solutions with relatively low zinc contents have become increasingly important (low-zinc technology).
  • the zinc concentrations are generally in the range from 0.9 to 1.5 g / l. With decreasing zinc content, the ratio of phosphophyllite (P) (Zn2Fe (PO4) 2. 4H2O) to Hopeit (H) (Zn3 (PO4) 2. 4H2O) or P / P + H is higher, which indicates a very high paint film quality affects.
  • the treatment temperature is an important factor in the production of the phosphate coating. In general, depending on the surface to be treated and the requirements for the quality of the paint film, temperatures above 40 ° C are used. The use of lower temperatures can create difficulties in the production of phosphate coatings that the posed Should meet requirements. For example, coatings can be formed which have a too low layer weight, are not opaque, have coarse crystals and / or tend to rust.
  • a phosphating solution which contains the same ions, but with 10 to 40 ppm iron III has a relatively high content of this ion, which is due to the increased risk of rust formation in the coating and on the other hand, is disadvantageous because of undesired sludge formation.
  • the object of the invention is to provide a process for the production of phosphate coatings on surfaces of cold-rolled steel, one- or two-sided galvanized steel, which allows the use of working temperatures as low as possible and yet to phosphate coatings of high quality, in particular with regard to the appearance of the phosphate coating, layer weight, crystal size and phosphophyllite content and - after painting - impart high corrosion resistance and high paint adhesion.
  • the phosphate coatings should therefore have essentially the same quality as that which is produced at higher temperatures.
  • metal surfaces Before the metal surfaces are subjected to the phosphating process according to the invention, they are cleaned and activated as usual. Aqueous phosphate solutions containing a colloidal titanium compound are used for activation.
  • the phosphate concentration falls below 10 g / l, the phosphate coatings become thin and uneven. At concentrations above 20 g / l, the coating quality is no longer improved, instead the chemical consumption is increased.
  • Zinc concentrations below 1.5 g / l do not lead to phosphate coatings with the desired layer weight, those above 2.5 g / l lead to layers that are too heavy. In addition, the desired high phosphophyllite content is not obtained. The result is that paint adhesion and corrosion resistance deteriorate.
  • Nitrate serves as an oxidizing agent.
  • a content below 5 g / l is associated with a loss of the oxidation potential; such a content above 15 g / l does not improve the effect. It would only affect the economics of the process.
  • Fluoride is responsible both for the uniform etching of the steel surface and for the formation of a dense phosphate coating.
  • the layer formation on certain qualities of galvanized steel, in particular hot-dip galvanized steel with aluminum contents, is improved in the zinc layer.
  • Complex fluorides such as fluorosilicate, fluoroborate and fluorozirconate, but also simple fluorides or mixtures of complex and simple fluorides can be used as the source of fluoride.
  • F concentration below 0.5 g / l (calculated as F)
  • the etching effect is uneven and the phosphate coating is not sufficiently dense.
  • concentrations above 1.5 g / l the phosphate coating becomes too thin and the desired properties are not achieved.
  • the nickel content also has an effect on the formation of a dense phosphate coating; moreover, it improves the corrosion resistance and the adhesion of the varnish applied subsequently.
  • Nickel concentrations below 0.5 g / l do not result in the desired compression of the phosphate crystals, and there is no possible improvement in the corrosion resistance of the paint adhesion. Concentrations higher than 1.5 g / l do not improve the effect.
  • the iron III content maintains a certain supersaturation in the phosphating solution, i.e. allows an increase in the pH at which the deposition of phosphate takes place. This facilitates the formation of the phosphate coating. If the iron III concentration is below 2 mg / l, the effect is not yet sufficiently pronounced. At concentrations above 20 mg / l, the phosphating solutions tend to form sludge and are therefore impaired with regard to their ability to form phosphate coatings.
  • the nitrite content of 160 to 300 mg / l which is significantly higher than that of phosphating baths that are used at higher temperatures, is largely responsible for the iron dissolution from the steel surface and the deposition of phosphophyllite. Only if the specified range is observed is there a guarantee for the desired high phosphophyllite content in the coating and for the high quality of the coating. In addition, the rate of formation of the phosphate coating decreases with a lower nitrite content. At higher Nitrite content tends to form iron-phosphate coatings.
  • the content of nitrite points is usually determined using the saccharometer method. For this, 50 ml of bath solution are mixed with 2 to 5 g of sulfamic acid. The amount of gas generated in ml is equal to the number of points. A gas point corresponds to a content of 46 mg / l NO2 in the phosphating solution.
  • the free acid content of the phosphating solution essentially depends on the zinc concentration. The higher the zinc content, the higher the free acid content.
  • the exact free acid to be set when using the method according to the invention is shown in the figure. If their content is below the lower limit line, the phosphating solution becomes unstable and deposits begin to form. If the free acid content is above the upper limit, the phosphate coating formation is delayed and it is difficult to obtain dense phosphate coatings.
  • the hatched field illustrates the permissible free acid content, based on the respective zinc concentration.
  • a 10 ml bath sample is titrated against bromophenol blue as an indicator. If the solution is yellow to yellow-green when the indicator is added, titrate with 0.1 N sodium hydroxide solution until it changes to blue. If the bath sample is blue-violet after adding the indicator, titrate with 0.1 N sulfuric acid until it changes to blue. In this case, the free acid value obtained is negative. The score of free acid is equal to the respective consumption of titration solution in ml.
  • the metal surfaces are immersed in a phosphating solution which additionally contains 0.2 to 1 g / l of manganese (calculated as Mn).
  • a manganese content has a particularly positive effect on the paint adhesion when exposed to high levels of moisture, so that objects which are claimed in this respect should be treated in accordance with this preferred embodiment.
  • concentrations lower than 0.2 g / l the effect mentioned is not yet sufficiently pronounced. Concentrations above 1 g / l lead in particular to a reduction in the rate of formation of the phosphate coating.
  • Another advantageous embodiment of the invention consists in immersing the surfaces in a phosphating solution at a temperature in the range from 20 to 30 ° C.
  • the duration of exposure of the phosphating solution should generally be 90 to 180 seconds for the treatment of cold-rolled steel and 30 to 180 seconds for the galvanized steel. If workpieces are to be treated that have areas made of cold-rolled steel and galvanized steel (composite metals), it is recommended to use the treatment time for cold-rolled steel.
  • the particular advantage of the method according to the invention is that at temperatures which are practically room temperature, high quality Phosphate coatings are obtained which advantageously influence the properties of a subsequently applied lacquer.
  • the low temperatures in turn have the advantage that the expenditure on equipment for heating the phosphating baths and the energy expenditure itself can be considerably reduced.
  • the permissible tolerances with regard to temperature and zinc concentration are comparatively large, so that the process is easy to carry out.
  • the sheets were treated with a conventional alkaline cleaner (pH 12, score 19 ⁇ 1) at 40 ⁇ 2 ° C while diving for 180 seconds, sprayed with tap water at room temperature for 20 seconds, then with a 1 g / l titanium phosphate Activation solution from room temperature conditioned by immersion for 30 seconds and then phosphated in immersion for 120 seconds (except for comparative example 3, in which the phosphating was carried out by spraying).
  • a conventional alkaline cleaner pH 12, score 19 ⁇ 1
  • rinsing was carried out first with tap water at room temperature for 30 seconds, then with fully demineralized water (electrical conductivity 0.2 ⁇ S x cm ⁇ 1) for 20 seconds and at 100 ° C. for a period dried for 180 sec.
  • the paint is built up in three stages. First, a cationic electrocoat (Elecron 9400 from Kansai Paint Co., Ltd.) was applied. Bath temperature 28 ° C; Voltage 250 V. Treatment duration 180 sec. The layer thickness was 20 ⁇ m.
  • a cationic electrocoat (Elecron 9400 from Kansai Paint Co., Ltd.) was applied. Bath temperature 28 ° C; Voltage 250 V. Treatment duration 180 sec. The layer thickness was 20 ⁇ m.
  • the intermediate layer was produced with a lacquer based on melamine / alkyd resin (Amilac N-2 Sealer from Kansai Paint Co., Ltd.) in a spraying process with air as the blowing agent.
  • the film with a thickness of 30 microns was after a waiting time of 10 to 20 minutes. at 140 ° C for 30 min. branded.
  • a lacquer based on melamine / alkyd resin (Amilac White M3 from Kansai Paint Co., Ltd.) was used as the topcoat, which in the aforementioned manner, but with a film thickness of 40 microns was applied. The follow-up was done as mentioned above.
  • the evaluation of the phosphate coating was carried out in terms of the appearance of the coating, layer weight, crystal size and phosphophyllite content in the phosphate coating (in the treatment of steel sheet).
  • the weight difference between phosphated and phosphate-coated sheets was determined.
  • the phosphate coating was detached with a chromic acid solution with a concentration of 50 g / l.
  • the hot-dip galvanized sheets (plated) were freed from the phosphate coating with a solution which had been obtained by filling 20 g of ammonium dichromate and 480 g of concentrated ammonia solution with distilled water to 1 liter.
  • the layer weight is given in g / m2.
  • the size of the phosphate crystals was measured with an electron microscope by scanning line by line. The crystal size is listed in ⁇ m.
  • the proportion of phosphophyllite in the phosphate coating was determined by the method of X-ray diffractometry using the diffraction intensities for the area (100) for phosphophyllite and (020) for hopeit. It is given as the ratio of phosphophyllite to phosphophyllite + hopeit (P / P + H).
  • Sheets that had only been treated with the cationic electrocoat were cross-cut and exposed to the salt spray test with a 5% saline solution in accordance with JIS-Z-2371 for 1000 hours.
  • the test result is given as paint infiltration along the cutting lines in mm.
  • Sheets provided with the complete paint structure were immersed in deionized water of 40 ⁇ 1 ° C. after a waiting time of 24 h 120 h in such a way that the sheets did not come into contact with one another. The mixture was then dried in air at room temperature for 1 h.
  • test sheets were then fixed at an angle of 45 ° C with the paint film upwards and exposed to 100 screw nuts with a diameter of approx. 6 mm, which came from a height of 4.5 m - calculated from the intersection of the cutting lines - through a guide tube with an internal diameter of approx. 50 mm (total weight of the screw nuts 198 ⁇ 0.5 g).
  • the panels were then subjected to the salt spray test according to JIS-Z-2371 for 72 hours and then 92 hours of outdoor weathering.
  • Test sheets provided with the complete paint structure were immersed in fully demineralized water at 40 ° C. for 20 days and then provided with a cross cut in such a way that 100 squares each having an edge length of 2 mm were produced.
  • adhesive tape was pressed onto the surface having the squares and pulled off again. The evaluation was made by counting the paint squares remaining on the test sheet.
  • Table 1 shows that if all process-essential parameters are observed exactly, excellent results are achieved in every respect.
  • Table 2 clearly shows that Even changing just one parameter, even changing the way the phosphating solution is applied, is associated with considerable impairments in the quality of the paint film.
  • the process according to the invention can achieve properties which are at least as good as when working at higher temperatures in accordance with the prior art.

Claims (3)

  1. Procédé de formation de revêtements phosphatés sur des surfaces d'acier laminé à froid, d'acier galvanisé sur une ou deux faces, par immersion dans une solution de phosphatation contenant des ions phosphate, zinc, nitrate, fluorure, nickel, fer et nitrite,
    caractérisé en ce qu'on plonge les surfaces dans une solution de phosphatation à une température de 15 à 39°C, qui contient
    Figure imgb0006
    dans laquelle le rapport en poids de zn:POy est réglé à (0,08 à 0,21):1, la teneur en acides libres (AS) à une valeur à l'intérieur de la surface hachurée dans la figure, et le rapport P: (P=H) (P=phosphophyllite, H=hopéite) dans le revêtement phosphaté à 0,82 ou plus.
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'on plonge la surface dans une solution de phosphatation qui contient additionnellement 0,2 à 1 g/l de manganèse (calculé par Mn).
  3. Procédé selon la revendication 1 ou 2,
    caractérisé en ce qu'on plonge les surfaces dans une solution de phosphatation à une température dans la plage de 20 à 30°C.
EP87115011A 1986-10-16 1987-10-14 Procédé d'obtention de revêtements de phosphate Expired - Lifetime EP0264811B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP61246088A JPS63100185A (ja) 1986-10-16 1986-10-16 冷延鋼板または亜鉛めっき鋼板のりん酸塩化成処理方法
JP246088/86 1986-10-16

Publications (2)

Publication Number Publication Date
EP0264811A1 EP0264811A1 (fr) 1988-04-27
EP0264811B1 true EP0264811B1 (fr) 1991-06-26

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EP87115011A Expired - Lifetime EP0264811B1 (fr) 1986-10-16 1987-10-14 Procédé d'obtention de revêtements de phosphate

Country Status (8)

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EP (1) EP0264811B1 (fr)
JP (1) JPS63100185A (fr)
AU (1) AU7978387A (fr)
BR (1) BR8705531A (fr)
DE (2) DE3734596A1 (fr)
ES (1) ES2022854B3 (fr)
GB (1) GB2199047B (fr)
NZ (1) NZ222135A (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595424A (en) * 1985-08-26 1986-06-17 Parker Chemical Company Method of forming phosphate coating on zinc
JPH0633465B2 (ja) * 1986-04-26 1994-05-02 日本パ−カライジング株式会社 りん酸塩処理した自動車車体の後処理方法
AU593156B2 (en) * 1986-12-09 1990-02-01 Nihon Parkerizing Company Limited Process for the phosphate chemical conversion treatment of a steel material
JPH0730455B2 (ja) * 1988-09-27 1995-04-05 日本パーカライジング株式会社 リン酸塩化成処理液
ES2036023T3 (es) * 1988-11-25 1993-05-01 Metallgesellschaft Aktiengesellschaft Procedimiento para la aplicacion de recubrimiento de fosfato.
US5200000A (en) * 1989-01-31 1993-04-06 Nihon Parkerizing Co., Ltd. Phosphate treatment solution for composite structures and method for treatment
DE4326388A1 (de) * 1993-08-06 1995-02-09 Metallgesellschaft Ag Verfahren zur phosphatierenden Behandlung von einseitig verzinktem Stahlband
JP3417653B2 (ja) * 1994-05-11 2003-06-16 日本パーカライジング株式会社 アルミニウム材の塗装前処理方法
US20050145303A1 (en) 2003-12-29 2005-07-07 Bernd Schenzle Multiple step conversion coating process
DE102019134298A1 (de) 2019-12-13 2021-06-17 Thyssenkrupp Steel Europe Ag Verfahren zum Herstellen eines Stahlflachprodukts mit einer metallischen Schutzschicht auf Basis von Zink und einer auf einer Oberfläche der metallischen Schutzschicht erzeugten Phosphatierschicht und derartiges Stahlflachprodukt

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3239088A1 (de) * 1982-10-22 1984-04-26 Chemische Werke Kluthe GmbH & Co, 6900 Heidelberg Verfahren zur phosphatierung von metalloberflaechen
JPH06169974A (ja) * 1992-12-09 1994-06-21 Terumo Corp ポリオレフィン系医療容器用基材

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US3597283A (en) * 1969-10-08 1971-08-03 Lubrizol Corp Phosphating solutions for use on ferrous metal and zinc surfaces
US3676224A (en) * 1970-10-16 1972-07-11 Lubrizol Corp Phosphating solution with scale suppressing characteristics
GB1414484A (en) * 1972-05-03 1975-11-19 Pyrene Chemical Services Ltd Treatment of zinc surfaces
GB1591039A (en) * 1977-05-03 1981-06-10 Pyrene Chemical Services Ltd Processes and compositions for coating metal surfaces
DE2907094A1 (de) * 1979-02-23 1980-09-04 Metallgesellschaft Ag Phosphatierungsloesungen
JPS5811515B2 (ja) * 1979-05-11 1983-03-03 日本ペイント株式会社 金属表面にリン酸亜鉛皮膜を形成するための組成物
DE3101866A1 (de) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
DE3118375A1 (de) * 1981-05-09 1982-11-25 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung
ZA826595B (en) * 1981-09-17 1983-07-27 Amchem Prod Composition and process for treating steel
US4486241A (en) * 1981-09-17 1984-12-04 Amchem Products, Inc. Composition and process for treating steel
JPS58224172A (ja) * 1982-06-24 1983-12-26 Nippon Parkerizing Co Ltd カチオン電着塗装前処理方法
GB8329250D0 (en) * 1983-11-02 1983-12-07 Pyrene Chemical Services Ltd Phosphating processes
DE3407513A1 (de) * 1984-03-01 1985-09-05 Gerhard Collardin GmbH, 5000 Köln Verfahren zur zink-calcium-phosphatierung von metalloberflaechen bei niedriger behandlungstemperatur
JPS60251279A (ja) * 1984-05-25 1985-12-11 Nippon Parkerizing Co Ltd 鉄系材料のリン酸亜鉛系皮膜化成法
JPS6169974A (ja) * 1984-09-12 1986-04-10 Nippon Parkerizing Co Ltd 電着塗装前処理用リン酸亜鉛系皮膜化成法
JPS6179782A (ja) * 1984-09-27 1986-04-23 Nippon Parkerizing Co Ltd りん酸塩処理方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3239088A1 (de) * 1982-10-22 1984-04-26 Chemische Werke Kluthe GmbH & Co, 6900 Heidelberg Verfahren zur phosphatierung von metalloberflaechen
JPH06169974A (ja) * 1992-12-09 1994-06-21 Terumo Corp ポリオレフィン系医療容器用基材

Also Published As

Publication number Publication date
EP0264811A1 (fr) 1988-04-27
JPH055899B2 (fr) 1993-01-25
GB2199047B (en) 1990-12-12
DE3734596A1 (de) 1988-04-21
ES2022854B3 (es) 1991-12-16
DE3771026D1 (de) 1991-08-01
NZ222135A (en) 1989-12-21
BR8705531A (pt) 1988-05-24
JPS63100185A (ja) 1988-05-02
GB8724339D0 (en) 1987-11-18
AU7978387A (en) 1988-04-21
GB2199047A (en) 1988-06-29

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