US3723160A - Zinc-plating compositions - Google Patents

Zinc-plating compositions Download PDF

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Publication number
US3723160A
US3723160A US00078798A US3723160DA US3723160A US 3723160 A US3723160 A US 3723160A US 00078798 A US00078798 A US 00078798A US 3723160D A US3723160D A US 3723160DA US 3723160 A US3723160 A US 3723160A
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zinc
plating
composition
flux
chloride
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US00078798A
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J Tanaka
T Taguchi
M Watanabe
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C24/00Coating starting from inorganic powder
    • C23C24/08Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/106Coating with metal alloys or metal elements only

Definitions

  • This composition gives good zinc plating on the surface of steel materials by simply being applied to the surface and heated. Up to 1% aluminum may be added to said zinc powder. Aluminum prevents growth of the zinc-ion alloy layer. Also a primary flux solution consisting of zinc chloride, ammonium chloride, stannous chloride, hydrochloric acid and Water is provided, which is used for pretreating the surface to be zinc-plating for activation thereof. Use of these compositions makes possible zinc plating of large size steel materials and structures including ship bottoms.
  • This invention relates to a material for zinc plating.
  • Iron and steel are tough materials but they have a disadvantage in that they are easily corroded.
  • zinc which is a base metal, the zinc is corroded in preference to iron, and thus iron is protected.
  • zinc is the most widely and abundantly employed metal for coating iron materials for the purpose of inhibiting corrosion and rust formation.
  • Zinked steel tubing, zinked iron wire and zinked steel plate or sheet are a few examples of such materials. That is, zinc is applied to the surface of iron materials for rust prevention by means of hot dip plating, electrolytic plating, sheradizing or melt spray.
  • zinc-rich paint which contains a large amount of zinc powder is now being used. But zincrich paint has the following defects:
  • the object of this invention is to overcome the abovementioned defect of the prior art and to provide a novel material and process to effect zinc plating on the surface of iron and steel in a short period.
  • an easy method of zinc-plating iron and steel materials comprises applying by a brush or the like to the surface of steel and iron a composition comprising 30-80 parts by weight of a flux having the following formula:
  • the first and most important feature of this invention is that an organic compound having polarity is used as the medium of the plating composition.
  • an organic compound having polarity is included formamide, acetamide, dimethyl formamide, urea, guanidine, etc. But the compounds other than formamide, acetamide and a mixture thereof are not suitable for the reason that is explained later.
  • Formamide, acetamide and the mixture thereof are good solvents for the abovementioned metallic salts and protect the powder of zinc, zinc-aluminum alloy or mixed powder of zinc and aluminum which is in contact with said active metallic salts, and thus form a paste together with said salts and the metal powders which is easily coated and preserved for a long period. Also these organic compounds are less carbonizable when heated for plating.
  • the flux of the plating material of this invention there is a specific feature in the formula of the flux of the plating material of this invention.
  • a eutectic mixture (zinc chloride/ammonium chloride 3:1 by weight) is employed.
  • the flux of the plating composition of this invention is best in fluidity and plating effect when the ratio of zinc chloride to ammonium chloride is 5:1 by weight.
  • the upper limit of the zinc chloride content is about 60% for the reason that when more than 60% zinc chloride is used, the plating composition which is formed together with formamide and/ or acetamide is close to being solid, and therefore the coating operation is difficult and the preservability is poor.
  • the lower limit is about 35% because with less than 35% zinc chloride the composition is close to being liquid and thus it has a tendency to drip down when coated on the surface.
  • the ammonium chloride content is one fifth of the zinc chloride content mentioned above, that is, about 6 to about 12% by weight.
  • stannous chloride The purpose of incorporating stanuous chloride is to improve the plating effect of the composition. Addition of stannous chloride improves the plating effect, but if the content thereof exceeds 5%, it tends to oxidize the zinc powder. It is necessary to add at least 1% stannous chloride to exhibit its effects. That is, the stannous chloride content should be 15% by weight.
  • the purpose of incorporating lead chloride is to improve the plating effect of the composition in combination with stannous chloride.
  • the effect of lead chloride is especially to improve fluidity of the molten zinc. At least 1% is necessary in order to exhibit this effect. If more than 7% lead chloride is added, the composition becomes thick and stiff; and yet the plating effect does not improve in proportion with the content. Therefore the lead chloride content should be 1-7%.
  • the flux of the abovementioned composition is mixed with zinc powder, powder of zinc-aluminum alloy or mixed powder of zinc and aluminum (in both cases the aluminum content is up to 1%) to form a zinc plating paste.
  • the metal powder occupies 70 parts by Weight at most. If the flux is less than 30 parts by weight, the plating composition becomes close to being solid, and the coating operation is made difiicult. If the flux occupies more than parts by weight (accordingly the metal powder content is less than 20 parts by weight), the plating composition drips down from the coated surface because of the excess amount of the flux when heated for plating. Therefore the preferred ratio of the flux and the metal powder is 30-80z70-20 by weight.
  • the reason why aluminum is added to zinc powder is that aluminum is effective to prevent growth of the interface layer (zinc-iron alloy layer) formed between the iron or steel substrate and the coated zinc layer. If said interface layer grows thick, the plated layer easily scales off when bending stress is applied, since the alloy is brittle. Aluminum has also an effect to inhibt the reaction between the metal powder and the flux ingredients.
  • the upper limit of the aluminum content is 1%, since addition of more than 1% aluminum is not only ineffective for preventing said reaction but accelerating oxidation of the metal powder.
  • the abovementioned zinc-plating composition is characterized by good preservability or long shelf life and excellent plating effect. But even better plating is effected by pre-treating the surface of the iron or steel to be plated with the primary flux composition. This is the third feature of this invention.
  • primary flux is applied to the surface of iron or steel by means of a brush or the like and heated by a gas burner, a torch lamp or oxygen-acetylene flame, etc. When heated,
  • the non-volatile ingredients (corresponding to the flux part of the abovementioned plating composition) remain, and melt and dissolve rust and scale on the surface of the iron materials, and then turns brown. At this stage, heating is discontinued and the zinc-plating composition is applied.
  • the primary flux cleans and activates the surface of iron materials and also acts as the auxiliary flux for plating.
  • the use of primary flux improves the plating effect of the zinc-plating composition, prevents dripping of the coated plating composition, and inhibts oxidation of the metal powder which is caused when the flux is heated because of insufficiency of the active flux ingredients in the plating composition.
  • the zinc-plating composition a rather reserved amount the active metallic salt ingredients is used in order to prolong the shelf life.
  • That is the use of the primary flux doubles or triples the benefits brought about by plating with the zinc-plating composition of this invention.
  • the composition of the thus used primary flux is determined in conjunction with the composition of the flux part of the zinc-plating composition, and therefore it is a little different from that of the normally used flux for hot dip galvanizng. That is, the primary flux composition must contain as much amount of the non-volatile ingredient such as zinc chloride as possible, and must be miscible with the zinc plating composition which is later applied to the surface to be plated and thus must function as the plating flux.
  • the primary flux is, therefore, comprised of 5075% by weight of zinc chloride, up to by weight of ammonium chloride, 1-10% by weight of stannous chloride, 1-3% by weight of hydrochloric acid (sp. gr. 1.18) the balance being water.
  • the amount of zinc chloride varies correlatively with the amount of ammonium chloride, but if the zinc chloride content is less 50%, the water content is relatively high and thus the flux does not leave a suflicient amount of active salts after the water is vaporized. If the zinc chloride content exceeds 75% the flux is nolonger a solution. Consequently, the preferred zinc chloride contentis 50-70%.
  • Ammonium chloride is added in order to improve the fluidity of the molten zinc chloride during plating. When 7075% zinc chloride is used, ammonium chloride does no more dissolve in the flux solution. In this case, the fluidity of the zinc chloride is improved by addition of stannous chloride, and therefore ammonium chloride is not necessary.
  • stannous chloride improves the fluidty of the molten zinc chloride by lowering the melting point of the zinc chloride. Further, when the primary flux is applied on the surface of an iron material, it dissolves the scale and at the same time tin is deposited and forms a coating layer which helps zinc plating because tin is nobler than iron. Therefore stannous chloride is an indispensable ingredient for the zinc-plating composition, but it has a tendency to oxidize or dissolve the metal powder and therefore it cannot be incorporated in the flux part of the zinc-plating composition in large amount.
  • stannous chloride must be contained at least in an amount of 1%, use of more than 10% stannous chloride only increases the cost of the primary flux unnecessarily.
  • Hydrochloric acid is added to stabilize the stannous chloride and prevent it from being converted to tin hydroxide. The amount of hydrochloric acid varies from 1 to 3% depending upon the amount of the added stannous chloride. A small amount of a surface active agent may be incorporated in the flux so as to improve coating and wetting properties of the flux, too.
  • the abovementioned zinc-plating composition is applied thereon and heated so as to effect zinc plating.
  • FIG. 1 is a photomicrograph showing the cross section of a steel sheet zinc-plated with the zinc-plating composition of this invention.
  • FIG. 2 is a photomicrograph showing the cross section of a steel sheet zinc-plated by using the primary flux and zinc-plating composition of this invention.
  • FIG. 3 is a graph showing corrosion of pure zinc by the flux of the zinc-plating composition of this invention as the weight loss (in percent) as days pass in comparison with a prior art flux comprising an aqueous solution of inorganic salts.
  • This composition was uniformly applied with a brush on the sandpapered surface of a steel sheet (JIS 63310 SPCI) 0.8 mm. in thickness.
  • the applied composition was heated by sweeping the flame of a torch over the coated surface so as to vaporize the liquid component of the composition at -200 C. Then the flame was let stay longer in one place so that the zinc was molten and plated at 400-500 C. Thus the torch was slowly moved to melt the zinc powder portion by portion until the whole surface of the steel sheet was plated. The surface was cleaned with steel wool to remove the residual flux and the surplus molten zinc.
  • the thickness of the zinc plating was about 20* microns, about 10 microns of which was an iron-zinc alloy layer. The test results are summarized in Table 1, too.
  • EXAMPLE 2 All the flux ingredients shown in Table 1 except for acetamide were taken each in the indicated amount and melted and mixed in a vessel at about 250 C. After completely molten and mixed the mixture was cooled. To this the indicated amount of acetamide was added and the mixture was heated at 170480 C. so as to dissolve the solid salts. After the solid salts were completely dissolved, the mixture was rapidly cooled as being agitated. The thus obtained flux is in the state of paste or ointment. The metal powder was mixed well into the flux and a zinc plating composition was obtained.
  • This composition was uniformly applied with a brush on the sandpapered surface of a steel plate (HS 63106 SM41B) 1-0 mm. in thickness.
  • the applied composition was heated by an oxygen-acetylene flame so as to effect the zinc plating.
  • the residual flux was washed away with water. The results are summarized in Table 1.
  • EXAMPLE 3 A zinc plating material having the composition indicated in Table 1 was prepared pursuant to the operation of Example 1.
  • EXAMPLE 4 All the flux ingredients shown in Table 1 except for acetamide and formamide were taken each in the indicated amount and melted and mixed in a vessel at about 250 C. After completely molten and mixed, the mixture was cooled. To this the indicated amount of acetamide and formamide were added and the mixture was heated at 170-1S0 C. so as to dissolve the solid salts. After the solid salts were completely dissolved, the mixture was cooled rapidly as being agitated. The thus obtained flux was in the state of paste or ointement. The metal powder was mixed well into the flux and a zinc plating composition was obtained.
  • EXAMPLE 5 A zinc plating material having the composition indicated in Table 1 was prepared pursuant to the operation of Example 1.
  • EXAMPLE 6 Primary flux composition All the primary flux ingredients shown in Table l were taken each in the indicated amount and were mixed well in a vessel to give a clear solution, which was used as the primary flux.
  • Zinc-plating composition The composition of Example 1 was used as the zinc plating composition.
  • the primary flux was applied with a brush on the sandpapered surface of a steel sheet (JIS G33l0 SPCl) 0.8 mm. in thickness.
  • the surface was uniformly heated by the flame of a torch, so as to vaporize the water, whereby the steel surface was activated.
  • the flux turned slightly brown, heating was stopped and the zinc-plating composition was uniformly applied with a brush on the steel surface, which was heated evenly by sweeping the flame of a torch over said coated surface so as to vaporize the liquid component of the composition at 150- 200 C.
  • the flame was let stay longer in one place so that the zinc was molten and plated at 400500 C.
  • the torch was slowly moved to melt the zinc portion by portion until the whole surface of the steel sheet was plated.
  • the surface was cleaned with steel wool to remove the residual flux was surplus molten zinc.
  • the thickness of the zinc plating was about 20 microns, about microns of which was an iron-zinc alloy layer.
  • the test results are summarize
  • EXAMPLE 7 Primary flux composition All the primary flux ingredients shown in Table 1 were taken each in the indicated amount and were mixed well in a vessel to give a clear solution, which is a primary flux.
  • Zinc-plating composition The composition of Example 2 was used as the zincplating composition.
  • EXAMPLE 8 Primary flux composition All the primary flux ingredients shown in Table 1 were taken each in the indicated amount and were mixed well in a vessel to give a clear solution, which was used as the primary flux.
  • Zinc-plating composition The composition of Example 3 was used as the zincplating composition.
  • EXAMPLE 9 Primary flux composition All the primary flux ingredients shown in Table 1 were taken in the indicated amount and were mixed well in a vessel to give a clear solution, which was used as primary flux to be used.
  • Zinc-plating composition The composition of Example 4 was used as the zincplating composition.
  • Comparative Example 1 All the flux ingredients of the zinc-plating composition shown in Table 1 except for dimethyl formamide were taken each in the indicated amount and were melted and mixed in a vessel at about 250 C. After completely molten the mixture was cooled. To this, the indicated amount of dimethyl formamide was added and heated at C. so as to dissolve the solid salts. After the solid salts were completely dissolved, the mixture was rapidly cooled as being agitated. The thus obtained flux is in an ointment-like state. The metal powder was mixed well into the flux and a zinc-plating composition was obtained.
  • Comparative Example 2 All the flux ingredients shown in Table 1 except for urea were taken each in the indicated amount and were mixed and melted well in a vessel at about 250 C. To this, urea was added and the mixture was heated at 140- 150 C. and thereafter was rapidly cooled as being agitated. The metal powder was mixed well into the flux. The thus obtained plating composition was nearly in a solid state.
  • Zinc-plating composition The composition of Comparative Example 1 was used as the zinc-plating composition.
  • a steel sheet (JIS 63310 SPCl) 0.2 mm. in thickness was zinc-plated by means of the torch flame pursuant to the operation of Example 6 and the residual flux was washed away with water. The results are summarized in Table 1.
  • Zinc-plating composition The zinc-plating composition used in Comparative Example 2 was used.
  • a steel plate (JIS 63106 SM41B) mm. in thickness was zinc-plated by means of an oxygen-acetylene flame following the operation of Example 6 and the residual flux was washed away with water.
  • the test results are summarized in Table 1. It was extremely difiicult to apply this composition by a brush.
  • Comparative Example 7 Primary flux composition All the flux primary ingredients shown in Table 1 were 10 taken each in the indicated amount and were mixed well in a vessel to give a clear solution, which was used as the primary flux.
  • Zinc-plating composition The zinc-plating composition used in Comparative Example 3 was used.
  • Comparative Example 8 Primary flux composition All the primary flux ingredients shown in Table l were taken each in the indicated amount and were mixed Well in a vessel to give a clear solution which was used as the primary flux.
  • Zinc-plating composition The plating composition used in Comparative Example 4 was used.
  • a steel sheet (JIS 63308 SPMA) 1 mm. in thickness was plated by means of the gas burner flame pursuant to the operation of Example 1. The residual flux was washed away with water. The test results are summarized in Table 1. To apply this plating composition by a brush was possible but very diflicult.
  • a steel sheet (JIS 63310 SPCl) 0.8 mm. in thickness was coated with said composition several times by means of a brush, and was heated with a torch flame so as to eifect zinc plating. After the sheet was plated, the residual flux was washed with water.
  • Table 1 It was extremely difficult to apply this composition by a brush.
  • a steel tube 63454 STP 638) 3 mm. in thickness and 50 mm. in outer diameter was coated with said composition several times by a brush, and was heated with a torch flame so as to effect zinc plating. After the tube was plated, the residual flux was washed with water.
  • Table 1 The test results are summarized in Table 1. It was extremely difficult to apply this composition uniformly on the surface of the steel tube.
  • the figure shows test results of the study on the corrosiveness of fluxes of this invention and of the prior art. Corrosiveness against pure zinc (represented by weight loss in percent) of the flux of the zinc-plating composition of Examples 1 and 6 (curve B) and a prior art flux comprising 42.2% by weight zinc chloride, 9.1% by weight ammonium chloride, 1.6% by weight lead chloride, 0.3% by weight stannous chloride and balance water (curve F) is shown as the change as days pass. It is clear that the flux of the plating composition of this invention is extremely non-corrosive to zinc at the normal temperature and pressure.
  • the method and composition for zinc plating of this invention makes possible rust-preventive zinc plating of large size steel materials, steel constructions, already constructed steel materials and ship bottoms, which have been regarded as impossible to

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Chemically Coating (AREA)
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US00078798A 1969-10-22 1970-10-07 Zinc-plating compositions Expired - Lifetime US3723160A (en)

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JP (1) JPS494135B1 (fr)
BE (1) BE757770A (fr)
DE (1) DE2051925C3 (fr)
DK (1) DK138605B (fr)
FR (1) FR2066380A5 (fr)
GB (1) GB1304876A (fr)
NL (1) NL145603B (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3943270A (en) * 1973-03-01 1976-03-09 Foseco International Limited Aqueous flux for hot dip galvanising process
US4647308A (en) * 1984-06-18 1987-03-03 Copper Development Association, Inc. Soldering compositions, fluxes and methods of use
US5100486A (en) * 1989-04-14 1992-03-31 The United States Of America As Represented By The United States Department Of Energy Method of coating metal surfaces to form protective metal coating thereon
US5814126A (en) * 1994-01-12 1998-09-29 Cook; Thomas H. Method and apparatus for producing bright and smooth galvanized coatings
US20140120367A1 (en) * 2012-10-25 2014-05-01 Fontaine Holdings Nv Flux compositions for steel galvanization
US20140120368A1 (en) * 2012-10-25 2014-05-01 Fontaine Holdings Nv Flux compositions for steel galvanization
KR20140052904A (ko) * 2012-10-25 2014-05-07 퐁텐느 홀딩스 엔베 긴 강 제품의 Zn-Al-Mg 합금으로의 연속적인 단일 침적의 아연도금 공정
US20150251236A1 (en) * 2014-03-04 2015-09-10 Fontaine Holdings Nv Galvanized metal objects and their manufacturing process
CN113122791A (zh) * 2021-04-12 2021-07-16 中山市华锌工材料科技有限公司 金属粉块及其制备方法与热镀锌合金浴的制备方法
EP4328353A3 (fr) * 2022-08-24 2024-05-08 Seppeler Holding und Verwaltungs GmbH & Co. KG Procédé pour améliorer la galvanisation de pièces dans un procédé de galvanisation normale

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5187263U (fr) * 1975-01-09 1976-07-13
JPS58178503A (ja) * 1982-04-12 1983-10-19 三菱電機株式会社 チツプ抵抗器

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3943270A (en) * 1973-03-01 1976-03-09 Foseco International Limited Aqueous flux for hot dip galvanising process
US4647308A (en) * 1984-06-18 1987-03-03 Copper Development Association, Inc. Soldering compositions, fluxes and methods of use
US5100486A (en) * 1989-04-14 1992-03-31 The United States Of America As Represented By The United States Department Of Energy Method of coating metal surfaces to form protective metal coating thereon
US5814126A (en) * 1994-01-12 1998-09-29 Cook; Thomas H. Method and apparatus for producing bright and smooth galvanized coatings
KR20140052904A (ko) * 2012-10-25 2014-05-07 퐁텐느 홀딩스 엔베 긴 강 제품의 Zn-Al-Mg 합금으로의 연속적인 단일 침적의 아연도금 공정
US20140120368A1 (en) * 2012-10-25 2014-05-01 Fontaine Holdings Nv Flux compositions for steel galvanization
US20140120367A1 (en) * 2012-10-25 2014-05-01 Fontaine Holdings Nv Flux compositions for steel galvanization
KR20140052903A (ko) * 2012-10-25 2014-05-07 퐁텐느 홀딩스 엔베 긴 강 제품의 Zn-Al-Mg 합금으로의 연속적인 단일 침적의 아연도금 공정
KR20150035343A (ko) * 2012-10-25 2015-04-06 퐁텐느 홀딩스 엔베 강 아연도금용 플럭스 조성물
KR20150035342A (ko) * 2012-10-25 2015-04-06 퐁텐느 홀딩스 엔베 강의 아연도금용 플럭스 조성물
US10793940B2 (en) * 2012-10-25 2020-10-06 Fontaine Holdings Nv Flux compositions for steel galvanization
US20150251236A1 (en) * 2014-03-04 2015-09-10 Fontaine Holdings Nv Galvanized metal objects and their manufacturing process
JP2015168885A (ja) * 2014-03-04 2015-09-28 フォンテーン ホールディングス ナムローゼ フェンノートシャップFontaine Holdings Nv 亜鉛メッキ金属物体およびその製造方法
CN113122791A (zh) * 2021-04-12 2021-07-16 中山市华锌工材料科技有限公司 金属粉块及其制备方法与热镀锌合金浴的制备方法
EP4328353A3 (fr) * 2022-08-24 2024-05-08 Seppeler Holding und Verwaltungs GmbH & Co. KG Procédé pour améliorer la galvanisation de pièces dans un procédé de galvanisation normale

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GB1304876A (fr) 1973-01-31
DE2051925B2 (de) 1974-01-31
NL145603B (nl) 1975-04-15
JPS494135B1 (fr) 1974-01-30
DK138605C (fr) 1979-03-05
DE2051925A1 (de) 1971-05-06
DE2051925C3 (de) 1974-09-05
BE757770A (fr) 1971-04-01
NL7015112A (fr) 1971-04-26
DK138605B (da) 1978-10-02
FR2066380A5 (fr) 1971-08-06

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