Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/66—Electroplating: Baths therefor from melts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
  • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
  • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
  • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
  • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
  • C08G59/1461—Unsaturated monoacids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
  • C09D163/10—Epoxy resins modified by unsaturated compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/922—Static electricity metal bleed-off metallic stock
  • Y10S428/9335—Product by special process
  • Y10S428/936—Chemical deposition, e.g. electroless plating
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S525/922—Polyepoxide polymer having been reacted to yield terminal ethylenic unsaturation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12701—Pb-base component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12708—Sn-base component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12708—Sn-base component
  • Y10T428/12722—Next to Group VIII metal-base component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12736—Al-base component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12736—Al-base component
  • Y10T428/12743—Next to refractory [Group IVB, VB, or VIB] metal-base component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12736—Al-base component
  • Y10T428/1275—Next to Group VIII or IB metal-base component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12736—Al-base component
  • Y10T428/1275—Next to Group VIII or IB metal-base component
  • Y10T428/12757—Fe

Definitions

• This invention relates to a process for coating steel, copper and other metallic surfaces with aluminum as protecting films by means of molten salt electrolysis in a fused bath containing aluminum halide and the like.
• Another object of the invention is to provide a process of the above kind, capable of obtaining aluminum-coated metallic products having superior bond of the coating to the metallic stock electrolytically treated.
• hydrogen ions are supplied in either or both positive and negative sense while the process proceeds.
• electrochemically ionized hydrogen for instance, by contact with platinum black, and/ or hydrogen chloride gas may be fed directly to the electrolytic bath.
• aqueous acetone solution of any desired concentration may preferably be used. According to the our experiments, superior results may be obtained when the aqueous wetting solution contains, solely or in combination, inorganic and/or organic substances or chemicals which have a high afiinity to water. For this purpose, methyl and/or ethyl alcohol, ethylene glycol, glycerine, lactic acid and/or formic acid may be employed.
• Starch, sugar, casein, egg albumen, gelatin, water glass or the like organic and inorganic substances may be utilized for the same purpose, in the form of syrup or paste.
• inorganic compounds such as sodium chloride, magnesium chloride, potassium chloride, calcium sulfate, magnesium perchlorate, caustic soda, calcium chloride, aluminum chloride, barium chloride, zinc chloride, chromium chloride, titanium tetrachloride, and the like may also be used in the form of an aqueous or alcoholic solution for the same purpose.
• conventional surface active agents for instance, soap, various known organic derivatives, such as sodium salts of .high molecular alkyl sulfates, or sulphonates may also be used. These agents may be used in the form of a dilute aqueous or alcohol solution for the purpose of this invention.
• the supply of hydrogen ions to the electrolytically reacting zone can be carried out in negative sense in the following way:
• the metal stock is preparatorily and cathodically subjected to an electrolytic treatment in the presence of an acid solution containing cations of those metals which have higher hydrogen overvoltage than that for aluminum, such as Pb, Sn, Ti, Zn, Bi, Cr, Cd and/ or the like.
• an acid solution containing cations of those metals which have higher hydrogen overvoltage than that for aluminum such as Pb, Sn, Ti, Zn, Bi, Cr, Cd and/ or the like.
• these metals are deposited on the stock and carried by the stock to the electrolytically reacting zone in the next succeeding electrolytic aluminum coating process.
• hydrogen ions contained in the fused salt bath especially those existing in close proximity of the electrolytically reacting zone, more specifically in the neighborhood of the metallic surface to be subjected to the aluminum coating process, are retarded in the transformation into hydrogen molecules. Although this retarding period is short, it is enough to carry out the electrolytic aluminum coating process under favorable conditions. In this way, hydrogen ions may be supplied in negative sense
• Example 1 Using a molten bath, 200 00., comprising 60 mole percent of aluminum chloride and 40 mole percent of sodium chloride, a steel stock having the size of x x 0.2 mm, was in a conventional manner electrolytically treated as cathode, below which a length, say cm., of coiled platinum wire of 0.5 mm. thickness and 10 mm. coil diameter was held as anode under tension at a distance of 2 cm. while being submerged in the bath. The cathodic current density was 2 amp/din. and the electrolysis was continued for 10 minutes at 160 C. In the course of the electrolysis, hydrogen gas was supplied in the form of small bubbles at a rate of cc./min. to the bath from below so as to contact the coiled anode. In this way, an aluminum coating having a thickness of 3 microns and superior surface conditions and an excellent bonding strength could be formed on both surfaces of the sheet stock.
• Example 2 For comparison, argon gas, again in the form of small bubbles, was introduced instead of hydrogen under the same operating conditions and at the same feeding rate as before and throughout the whole electrolytic period, which was again 10 minutes. An aluminum coating was produced on the steelstock, with no appreciable improvements in the quality of the coating. Though agitation of the bath was utilized, no appreciable gain in the desired results were achieved, because of the lack of the hydrogen ion.
• Example 3 1180 gms. of aluminum chloride and 320 gms. of sodium chloride were thoroughly mixed together, heated to melting temperature, charged into a glass vessel and kept at a temperature of 160 C., whereupon the vessel was sealingly closed off from the ambient atmosphere. Before the vessel was sealed, a sheet of aluminum plate, having the dimensions of x 150 x 0.2 mm., was arranged in the melt as anode and a piece of steel sheet having the same dimensions as cathode; current was con- Wt. of Current Al-coil, efiieiency, Time lapsed gms. State of Al-coatmg percent None 44. 9408 Smooth, tight and Well- 83 bonded. 24 hours... 41. 5588 Same as above 69 hours 40. 4352 Formatlon of trees, 68
• Example 4' Using a molten bath comprising 62 mole percent aluminum chloride and 38 mole percent sodium chloride, but without any addition of conventional metal mist suppressing agent such as potassium chloride so as to clearly observe the aforementioned adverse effects by the presence of superfluous aluminum solute as set forth in the foregoing Example 3, the electrolytic treatment was carried out at C. for about 10 minutes with a cathodic current density: 2 amp./dm. taking an aluminum plate as anode and a steel sheet as cathode, having the same dimensions as before, respectively, the voltage being 0.3- 0.4 volt and the treatment being repeatedly performed from several times to about 20 times per day and for an extended time period, such as 10 months.
• a cathodic current density 2 amp./dm.
• Example 5 A steel sheet stock, having the same dimensions as set forth in Example 3, was degreased, pickled and Well water-cleaned, and then was treated as cathode in an aqueous solution containing 1% of HCl and 0.005% of PbCl at a-current density of l amp./dm. for about 10 seconds, using a carbon electrode of equal dimensions as above as anode. The stock was then water-cleaned to a satisfying degree. In this case, the stock should preferably be subjected to the influence of mechanical vibration, preferably at several to about 100 cycles per second.
• the treated steel surface represented, to a slight degree, a brown to gray coloring; but still exhibiting the natural glazing color of steel.
• the thus treated stock was then subjected to a conventional electrolytic treatment in a molten salt bath comprising 5 8 mole percent of AlCl and 42 mole percent of NaCl according to the conventional technique for the formation of aluminum coating, providing thus a smooth, glazing and well-bonded aluminum film on the stock and capable of being subjected, without any cracks in the coating, to a subsequent mechanical working for the fabrication of finished products.
• the thickness of the aluminum could be adjusted with ease to a value thicker than microns which constitutes a considerable progress in the art.
• Example 6 In this experiment, the content of PbCl was adjusted to 0.005% and the concentration of HCl was 3 N, the current density being 1 amp./dm. The preliminary treatment was carried out for about 30 seconds, further conditions for the preliminary step being same as described in Example 5.
• the pretreated stock was further treated electrolytically with a current density of 2 amp./dm. as in the preceding Example 5, thus providing an aluminum coating, 17.4,u thick, with a current efliciency of 88%.
• the coating was beautiful, of metal glazing tone, and well-bonded with superior quality.
• Example 7 In this experiment, the content of PbCl was adjusted to 0.0006% and the concentration of HCl was 0.3 N, the current density being 1 amp./dm. The preliminary treatment was carried out for about 30 seconds, further conditions for the preliminary step being same as described in Example 5.
• test piece was further treated electrolytically with a current density of l amp./dm. in a bath which had become highly deteriorated so that only a degreased and pickled stock could not have been treated therewith effectively, other conditions being similar to those as employed in Example 5.
• the thus formed aluminum coating was beautiful in its metal glazing tone, and well-bonded with superior quality.
• Example 8 In this case, the aqueous preliminarily treating bath contained 0.1% of bismuth oxide and 1.0% of perchloric acid. The treatment was carried out with a current density of 1 amp./dm. for about 30 seconds.
• the treated stock was subjected further to an electrolytic treatment while using the same molten salt bath as was set forth in Example 7, and using a current density of l amp./dm. Superior results in the formed aluminum coating were obtained.
• the coating thus produced should be exposed to the open atmosphere at least once in the course of the next succeeding water-cleaning step, so as to convert the produced coating into an inactivated one.
• Example 9 In this case, an aqueous solution of hydrochloric acid having a concentration of l N and containing 0.05% of stannous chloride was used as preliminarily treating liquor. The treatment was carried out with a current density of 1 amp./dm. for about 30 seconds.
• the treated stock was subjected further to an electrolytic treatment while using the same molten bath as was set forth in Example 7, and with a current density of 1 amp./dm. again.
• Aluminum film was coated on the stock with superior results.
• Example 10 In this case, the preliminarily treating aqueous liquor contained 0.5% of lead acetate. The treatment was carried out with a current density of 0.3 amp./dm. for about 2 minutes.
• the thus treated stock was then subjected to the second treatment, as before, for coating it with aluminum, yet while using same bath composition as set forth in Example 6.
• the coating was slightly inferior in its characteristics, yet having a superior metallic glaze.
• Example 11 The preliminary treatment was carried out with use of an aqueous 2 N hydrochloric acid solution, containing 0.5 of titanium chloride at a current density of 20 amp./dm. t
• the thus treated stock was further subjected to an electrolytic coating treatment while using the same molten salt bath as set forth in Example 7.
• the current density was 1 amp./dm. as before.
• the thus obtained aluminum coating had a superior metal glaze, providing in addition, superior tightness, smoothness and bond.
• Example 12 A steel sheet stock was preliminarily coated with a thin film of acetone, of purity, by the way of dipping.
• the treated stock was subjected to an ordinary electrolytic treatment utilizing a used up molten bath comprising 58 mole percent of AlCl and 42 mole percent of NaCl and kept at C., which bath had so deteriorated as to be considered unusable for conventional operations.
• the electrolysis was carried out with a current density of 1.5 amp./dm. for about 10 minutes.
• the thus resulting aluminum coating was highly smooth, tight, closely adhering and highly durable to scratching.
• the acetone was replaced in subsequent tests by methyl alcohol, ethyl alcohol of 96% purity; ethylene glycol, 95 glycerin, 95 lactic acid, 87%; and formic acid, 87%; the effects were similar.
• Example 13 An aqueous syrup (concentration: 1%) made of starch was used in place of the acetone used in Example 12, and the treating conditions were the same as set forth in that example. Similar superior results were obtained.
• Example 14 A dilute aqueous solution of common salt (concentration: 5%) was used and other treating conditions were the same as set forth in Example 13. Same superior aluminum coating was obtained.
• the dipped metal stock was dried at normal temperature and then left in the open air so as to absorb a certain quantity of water content from the ambient air, so as to form a thin aqueous film on the stock surface.
• Example A combination of two or more of the substances referred to in the foregoing Examples 12-14 could be employed with equal results when other operating conditions Were similar to those set forth therein.

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Citations (9)

• 1965
  • 1965-11-09 US US507034A patent/US3480521A/en not_active Expired - Lifetime
  • 1965-11-12 GB GB48121/65A patent/GB1132696A/en not_active Expired
  • 1965-11-12 DE DE19651496937 patent/DE1496937B2/de not_active Withdrawn
  • 1965-11-13 FR FR38285A patent/FR1455523A/fr not_active Expired
  • 1965-11-15 CH CH1573265A patent/CH437958A/fr unknown
• 1969
  • 1969-03-24 US US828049*A patent/US3699012A/en not_active Expired - Lifetime
  • 1969-03-24 US US828050*A patent/US3616301A/en not_active Expired - Lifetime
  • 1969-12-18 US US886419A patent/US3697619A/en not_active Expired - Lifetime
• 1970
  • 1970-07-06 US US00060994A patent/US3778356A/en not_active Expired - Lifetime
• 1971
  • 1971-09-03 US US00177849A patent/US3775356A/en not_active Expired - Lifetime

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