US3388049A - Method of electrodepositing microcrack chromium coatings - Google Patents
Method of electrodepositing microcrack chromium coatings Download PDFInfo
- Publication number
- US3388049A US3388049A US440019A US44001965A US3388049A US 3388049 A US3388049 A US 3388049A US 440019 A US440019 A US 440019A US 44001965 A US44001965 A US 44001965A US 3388049 A US3388049 A US 3388049A
- Authority
- US
- United States
- Prior art keywords
- nickel
- chromium
- deposit
- cracking
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/625—Discontinuous layers, e.g. microcracked layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- 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
- Y10S428/934—Electrical process
- Y10S428/935—Electroplating
-
- 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
- Y10T428/12472—Microscopic interfacial wave or roughness
-
- 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.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12826—Group VIB metal-base component
- Y10T428/12847—Cr-base component
- Y10T428/12854—Next to Co-, Fe-, or Ni-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.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
Definitions
- Chromium plating with increased resistance to corrosion and flaking is produced by first electrodepositing on the substrate a nickel layer with a high internal stress level, sufiicient to produce micro-cracks therein during the electrodepositing of th chromium layer, and then electrodepositing the chromium layer.
- the electrolyte bath from which the cracking nickel is electrodeposited preferably includes (a) nickel chloride, nickel sulphamate or nickel fiuoborate and (b) acetic acid ammonium acetate or nickel acetate, or mixtures of them.
- So-called decorative chromium deposits usually comprise, by way of terminal deposits, a deposit of nickel followed by a deposit of electrolytic chromium.
- the physical condition of the chromium plating plays a predominant part.
- the metal may be deposited in the form of a tight coating, but because of the brittleness of electrolytic chroming, this tightness is destroyed fairly soon owing to the appearance of cracks or holes.
- the chromium immediately after it is deposited, the chromium may be porous to some extent or embody minute cracks in a more or less large number per unit area, resulting in the formation of. individual elements placed more or less closely together.
- chromium with a microcrack structure (cracks spaced from one another by a few ten microns). This can be obtained either by a double-coating chroming process, which requires chromium thicknesses in excess of 0.5 micron, or by a single-coating chroming process in chromium baths containing a small quantity of selenium, in which the microcrack structure is produced with a chromium thickness of approximately 0.3 micron.
- Another method aiming at obtaining microporous chromium deposits consists in applying, onto the terminal nickel coating (usually bright nickel), a thin nickel coat- 3,388,649 Patented June 11, 1968 ing about one micron thick containing non-conductive particle inclusions.
- the chromium coating deposited on this nickel is itself deposited in .porous form due to the presence of these non-conductive particles.
- the present invention has for its object to provide a method of obtaining microcracked chromium under unusually simple, readily applicable conditions.
- This method consists in depositing on the metal, for instance on the nickel normally constituting the ultimate protective coating prior to the chromium coating, a thin metal coating under conditions such as to cause the metal to be highly stressed and barely ductile. During the subsequent chroming operation, this last coating of metal and the coating of chromium undergo simultaneous microcracking, thereby imparting excellent resistance to corrosion to the object treated in this way.
- this intermediate metal deposited tor subsequent cracking The thinner the coating of this intermediate metal deposited tor subsequent cracking, the more advantageous it will be for its electrochemical potential to lie between that of the subjacent metal and that of the terminal chromium plating (in the state of surface oxidation to which it is normally brought after a few hours or a few days have elapsed).
- thin coating is to be understood a coating whose thickness is included between a fraction of a micron and approximately 3 or 4 microns.
- nickel Whilst various metals, or alloys based on nickel or cobalt in particular, can be employed, a coating of nickel is entirely suitable for the deposit designed to become cracked, provided its potential is slightly higher than that of the previous metal coating. Furthermore, this intermediate coating must not detract from the final appearance of the chromium-plated part.
- Example 1 Principal protective nickel plating, for example bright nickel plating Rinsing operations Depositing of the cracking nickel under the following conditions:
- Such brightening substances must not appreciably aiiect the potential of the cracking-nickel deposit, so that the electrochemical protective process may be maintained as described precedingly. Nor must they reduce the propensity for cracking of the ultimate coat of nickel which generates the microcracking in the subsequent chromium plating.
- the sodium salt of sulfonimide ortho-benzoyl acid can be added in proportions ranging from 0.5 to 3 g./l., the optimum being around 1 g./liter, through this is by no means critical.
- butyne 1-4 diol will enable very bright deposits of cracking nickel to be obtained, regardless of the thickness of the deposits. This compound is added to the bath in the proportion of 0.1 to 3 g./liter.
- brightening agents which will enable particularly bright cracking-nickel deposits to be obtained, regardlessof their thickness, are the amino derivatives of heterocyclic compounds such as 2-aminothiazole.
- Example 3 Bath with addition of butyne 1-4 diol Optimum Anhydrous nickel acetate, g./l. to
- Example 4 Bath with addition of Z-amino-thiazole: Optimum Anhydrous nickel acetate, 50 g./l. to
- Example 5 Optional agitation (with compressed air or the cathodes).
- the thickness of the cracking-nickel deposit can be considerably increased by the aid of the brightening agents utilized in accordance with the invention. This enables the method to be used in existing installations with minimum or no modification.
- this operating sequence permits of combining the advantages offered by duplex nickel plating and microcrack chromium-plating; moreover, this sequence can be executed without the need to seek a more noble cracking nickel than the subjacent coating of levelling nickel.
- This delay will vary with operating conditions and with the structure and stress specific to the subjacent nickel deposit. By way of indication, however, it may be stated that spontaneous cracking in the ultimate nickel deposit egins after approximately a quarter of an hour has elapsed.
- the microcracked structure can be developed over all the chromium-plated surfaces, using conventional chromiumplaiing baths comprising, as catalysts, the sulphuric, hydrofluoric, fluosilicic, and like ions.
- Vlhat is claimed is:
- a method of depositing a corrosion resistant microcracked coating on a substrate which comprises electro depositing nickel on said substrate from an aqueous acidic bath and thereafter electrodepositing chromium on said nickel, said nickel being deposited with a high internal stress level, said stress level being suit'icient to produce micro-cracks therein during the deposition of the chromium layer which in turn produces a micro-crack pattern in the chrom um layer.
- the said brigten-ing agent is selected from the group consisting of the sulphonates, sulphonarnides, and sulphoninsides of aromatic derivatives, butyne 1-4 diol, cobalt salts, the amino derivatives of hetcrocyclic compounds such as Z-aminothiazols, and mixtures of at least two of these agents.
- a method in accordance with claim 8 in which the previous metallic deposit is a semi-bright or bright nickel plating, and this nickel plating is subjected to a depassivation operation before the deposit of cracking nickel t-here- 10.
- the said electrodcposited nickel coating is a duplex nickel plating consisting of a first deposit of dull or levelling nickel and a second deposit of a coating of cracking nickel.
- said aqueous acidic bath consists essentially of (a) nickel chloride, and (b) a member of the group consisting of ammonium acetate, nickel acetate, and mixtures thereof.
- the bath contains (a) a compound from the group consisting of nickel chloride, nickel sulphamate and nickel fluoborate and (b) a member of the group consisting of acetic acid, ammonium acetate, nickel acetate and mixtures thereof.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR991133A FR1447970A (fr) | 1964-10-12 | 1964-10-12 | Dépôts de chrome décoratif résistant à la corrosion |
FR996104A FR88318E (fr) | 1964-10-12 | 1964-11-24 | Dépôts de chrome décoratif résistant à la corrosion |
FR3489A FR89217E (fr) | 1964-10-12 | 1965-01-27 | Dépôts de chrome décoratif résistant à la corrosion |
FR11348A FR89657E (fr) | 1964-10-12 | 1965-03-31 | Dépôts de chrome décoratif résistant à la corrosion |
FR57477A FR90417E (fr) | 1964-10-12 | 1966-04-13 | Dépôts de chrome décoratif résistant à la corrosion |
Publications (1)
Publication Number | Publication Date |
---|---|
US3388049A true US3388049A (en) | 1968-06-11 |
Family
ID=27514668
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US440019A Expired - Lifetime US3388049A (en) | 1964-10-12 | 1965-03-15 | Method of electrodepositing microcrack chromium coatings |
US626938A Expired - Lifetime US3620936A (en) | 1964-10-12 | 1967-03-30 | Electroplating a decorative chromium-plating resistant to corrosion |
US00184251A Expired - Lifetime US3759802A (en) | 1964-10-12 | 1971-09-27 | Corrosion resistant ornamental chromium plating |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US626938A Expired - Lifetime US3620936A (en) | 1964-10-12 | 1967-03-30 | Electroplating a decorative chromium-plating resistant to corrosion |
US00184251A Expired - Lifetime US3759802A (en) | 1964-10-12 | 1971-09-27 | Corrosion resistant ornamental chromium plating |
Country Status (13)
Country | Link |
---|---|
US (3) | US3388049A (xx) |
JP (2) | JPS5024248B1 (xx) |
AT (1) | AT276893B (xx) |
BE (2) | BE670116A (xx) |
BR (1) | BR6788420D0 (xx) |
CH (1) | CH445999A (xx) |
DE (2) | DE1496974B2 (xx) |
ES (1) | ES339183A2 (xx) |
FR (5) | FR1447970A (xx) |
GB (2) | GB1122795A (xx) |
NL (2) | NL140902B (xx) |
OA (1) | OA117E (xx) |
SE (2) | SE327875B (xx) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3471271A (en) * | 1965-08-16 | 1969-10-07 | Udylite Corp | Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate |
US3474010A (en) * | 1966-10-26 | 1969-10-21 | M & T Chemicals Inc | Method of electroplating corrosion resistant coating |
US3528894A (en) * | 1966-08-25 | 1970-09-15 | M & T Chemicals Inc | Method of electrodepositing corrosion resistant coating |
US3866289A (en) * | 1969-10-06 | 1975-02-18 | Oxy Metal Finishing Corp | Micro-porous chromium on nickel-cobalt duplex composite plates |
FR2508936A1 (fr) * | 1981-07-06 | 1983-01-07 | Occidental Chem Co | Composition et procede de revetement electrolytique avec des couches de nickel composites |
US4416738A (en) * | 1980-01-28 | 1983-11-22 | The Boeing Company | Chromium plating |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1541118A (en) * | 1976-12-03 | 1979-02-21 | Bnf Metals Tech Centre | Nickel plating |
JPS54119436U (xx) * | 1978-02-09 | 1979-08-21 | ||
US4432843A (en) * | 1982-07-29 | 1984-02-21 | Omi International Corporation | Trivalent chromium electroplating baths and processes using thiazole addition agents |
JPH02116220U (xx) * | 1989-03-04 | 1990-09-18 | ||
EP0785296B1 (en) * | 1995-12-29 | 2000-03-15 | AT&T Corp. | Electroplating of nickel on nickel ferrite devices |
EP2975162B1 (de) * | 2014-07-18 | 2018-09-05 | FRANZ Oberflächentechnik GmbH & Co KG | Verfahren zum schutzbeschichten eines werkstücks |
US10138884B2 (en) * | 2014-12-22 | 2018-11-27 | Weatherford Technology Holdings, Llc | Nickel corrosion barrier under chrome for sucker rod pumps |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2678908A (en) * | 1951-07-26 | 1954-05-18 | Eastman Kodak Co | Method of forming ferrotyping surfaces |
US3282810A (en) * | 1961-11-27 | 1966-11-01 | Res Holland Nv | Method of electrodepositing a corrosion resistant nickel-chromium coating and products thereof |
US3298802A (en) * | 1962-02-23 | 1967-01-17 | Res Holland S Hertogenbosch Nv | Method for covering objects with a decorative bright-nickel/chromium coating, as well as objects covered by applying this method |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1176956B (de) * | 1958-08-27 | 1964-08-27 | Bosch Gmbh Robert | Verfahren zum mehrstufigen galvanischen Abscheiden glaenzender Nickelueberzuege |
GB871276A (en) * | 1959-02-26 | 1961-06-28 | Hanson Van Winkle Munning Co | Improvements in electrodeposition of nickel |
GB1091526A (en) * | 1963-07-24 | 1967-11-15 | Canning & Co Ltd W | Improvements in electrodeposition of chromium |
US3471271A (en) * | 1965-08-16 | 1969-10-07 | Udylite Corp | Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate |
-
1964
- 1964-10-12 FR FR991133A patent/FR1447970A/fr not_active Expired
- 1964-11-24 FR FR996104A patent/FR88318E/fr not_active Expired
-
1965
- 1965-01-27 FR FR3489A patent/FR89217E/fr not_active Expired
- 1965-03-15 US US440019A patent/US3388049A/en not_active Expired - Lifetime
- 1965-03-31 FR FR11348A patent/FR89657E/fr not_active Expired
- 1965-09-24 BE BE670116D patent/BE670116A/xx not_active IP Right Cessation
- 1965-09-28 CH CH1335465A patent/CH445999A/fr unknown
- 1965-10-04 GB GB41936/65A patent/GB1122795A/en not_active Expired
- 1965-10-07 DE DE1965R0041715 patent/DE1496974B2/de active Granted
- 1965-10-11 SE SE13121/65A patent/SE327875B/xx unknown
- 1965-10-11 JP JP40062000A patent/JPS5024248B1/ja active Pending
- 1965-10-12 NL NL656513216A patent/NL140902B/xx not_active IP Right Cessation
-
1966
- 1966-04-13 FR FR57477A patent/FR90417E/fr not_active Expired
-
1967
- 1967-03-24 BE BE696105D patent/BE696105A/xx unknown
- 1967-03-29 NL NL6704452A patent/NL6704452A/xx unknown
- 1967-03-30 US US626938A patent/US3620936A/en not_active Expired - Lifetime
- 1967-04-04 GB GB05291/67A patent/GB1187843A/en not_active Expired
- 1967-04-06 OA OA52895A patent/OA117E/xx unknown
- 1967-04-10 DE DE1621151A patent/DE1621151C3/de not_active Expired
- 1967-04-10 AT AT338167A patent/AT276893B/de not_active IP Right Cessation
- 1967-04-11 BR BR188420/67A patent/BR6788420D0/pt unknown
- 1967-04-12 ES ES339183A patent/ES339183A2/es not_active Expired
- 1967-04-12 SE SE05064/67A patent/SE335935B/xx unknown
- 1967-04-12 JP JP42022950A patent/JPS4827183B1/ja active Pending
-
1971
- 1971-09-27 US US00184251A patent/US3759802A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2678908A (en) * | 1951-07-26 | 1954-05-18 | Eastman Kodak Co | Method of forming ferrotyping surfaces |
US3282810A (en) * | 1961-11-27 | 1966-11-01 | Res Holland Nv | Method of electrodepositing a corrosion resistant nickel-chromium coating and products thereof |
US3298802A (en) * | 1962-02-23 | 1967-01-17 | Res Holland S Hertogenbosch Nv | Method for covering objects with a decorative bright-nickel/chromium coating, as well as objects covered by applying this method |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3471271A (en) * | 1965-08-16 | 1969-10-07 | Udylite Corp | Electrodeposition of a micro-cracked corrosion resistant nickel-chromium plate |
US3528894A (en) * | 1966-08-25 | 1970-09-15 | M & T Chemicals Inc | Method of electrodepositing corrosion resistant coating |
US3474010A (en) * | 1966-10-26 | 1969-10-21 | M & T Chemicals Inc | Method of electroplating corrosion resistant coating |
US3866289A (en) * | 1969-10-06 | 1975-02-18 | Oxy Metal Finishing Corp | Micro-porous chromium on nickel-cobalt duplex composite plates |
US4416738A (en) * | 1980-01-28 | 1983-11-22 | The Boeing Company | Chromium plating |
FR2508936A1 (fr) * | 1981-07-06 | 1983-01-07 | Occidental Chem Co | Composition et procede de revetement electrolytique avec des couches de nickel composites |
Also Published As
Publication number | Publication date |
---|---|
ES339183A2 (es) | 1968-04-16 |
US3620936A (en) | 1971-11-16 |
GB1122795A (en) | 1968-08-07 |
FR88318E (fr) | 1967-01-20 |
FR89217E (fr) | 1967-05-26 |
SE335935B (xx) | 1971-06-14 |
OA117E (xx) | 1970-12-15 |
DE1496974A1 (de) | 1969-12-18 |
NL6704452A (xx) | 1967-10-16 |
BE696105A (xx) | 1967-09-01 |
BR6788420D0 (pt) | 1973-07-10 |
SE327875B (xx) | 1970-08-31 |
FR89657E (fr) | 1967-07-28 |
FR90417E (fr) | 1967-12-08 |
CH445999A (fr) | 1967-10-31 |
BE670116A (xx) | 1966-01-17 |
FR1447970A (fr) | 1966-08-05 |
NL6513216A (xx) | 1966-04-13 |
DE1621151B2 (de) | 1978-03-23 |
DE1621151A1 (de) | 1970-07-16 |
JPS4827183B1 (xx) | 1973-08-20 |
GB1187843A (en) | 1970-04-15 |
DE1621151C3 (de) | 1978-11-23 |
NL140902B (nl) | 1974-01-15 |
AT276893B (de) | 1969-12-10 |
US3759802A (en) | 1973-09-18 |
JPS5024248B1 (xx) | 1975-08-14 |
DE1496974B2 (de) | 1971-11-04 |
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