DE7434875U - ELECTRODE FOR USE IN AN ELECTROCHEMICAL PROCESS - Google Patents
ELECTRODE FOR USE IN AN ELECTROCHEMICAL PROCESSInfo
- Publication number
- DE7434875U DE7434875U DE7434875U DE7434875U DE7434875U DE 7434875 U DE7434875 U DE 7434875U DE 7434875 U DE7434875 U DE 7434875U DE 7434875 U DE7434875 U DE 7434875U DE 7434875 U DE7434875 U DE 7434875U
- Authority
- DE
- Germany
- Prior art keywords
- metal
- nickel
- electrode
- layer
- core
- 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
Links
- 238000000034 method Methods 0.000 title claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002923 metal particle Substances 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011162 core material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/16—Electrodes characterised by the combination of the structure and the material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inert Electrodes (AREA)
Description
« C«C
He./KnHe./Kn
BBC Aktiengesellschaft Brown, Boveri'& Cie., Baden (Schweiz)BBC Aktiengesellschaft Brown, Boveri '& Cie., Baden (Switzerland)
Elektrode, Verfahren zur Herstellung der Elektrode und Verwendung der Elektrode in einem elektrochemischen Verfahren.Electrode, method of manufacturing the electrode and use of the electrode in an electrochemical process.
Die Neuerung bezieht sich auf eine Elektrode zur Anwendung in einem elektrochemischen Verfahren, bestehend aus ein.em Kern, welcher zumindest teilweise aus Metall besteht, und mindestens einer die Kernoberfläche zumindest teilweise überdeckenden Oberflachenschicht.The innovation relates to an electrode for use in an electrochemical process, consisting of a Core, which consists at least partially of metal, and at least one of the core surface at least partially covering surface layer.
Inerte Elektroden, wie sie beispielsweise die gasentwickelnden Elektroden darstellen, können durch spezifische Oberflächenvergrösserung aktiviert werden. Die aktivierende WirkungInert electrodes, such as those that generate gas Electrodes can be represented by specific surface enlargement to be activated. The activating effect
7434875 30.12.767434875 12/30/76
119/7Ί119 / 7Ί
ItI IItI I
beruht auf einer Senkung der Ueberspannung, die durch dieis based on a reduction in the overvoltage caused by the
al&/ Art sind z. B .(MSK-E lektroden (Monoskelettkatalysatoren) oderal & / Type are z. B. (MSK electrodes (monoskeleton catalysts) or als DSK-Elektroden (Doppelskelettkatalysatoren) bekannt geworden (vgl. Buch "Brennstoffelemente" von W.Vielstich, Verlag Chemie, Weinheim/Bergstrasse, 1965, Seiten IHM ff., insbesondere S.116). Diese Elektroden werden durch Sinterung bei hohem Druck und hohen Temperaturen aus Metallpulvern mit verschiedenen Porositäten hergestellt. Anschliessend werden bestimmte Metallbestandteile herausgelöst, wodurch sich sehr viele und feine Poren bilden. Während Sinterelektroden gegenüber solchen aus Legierungen gewonnenen sich durch hohe Formbeständigkeit auszeichnen, ist ihre Herstellung sehr teuer. Sie können nicht rationell gefertigt werden und lassen sich zudem nur in kleinen Dimensionen (wenige dm ) herstellen.known as DSK electrodes (double skeleton catalysts) (see book "fuel elements" by W.Vielstich, Verlag Chemie, Weinheim / Bergstrasse, 1965, pages IHM ff., especially page 116). These electrodes are made from metal powders with different porosities by sintering at high pressure and high temperatures. Then certain metal components are dissolved out, which a large number of fine pores are formed. While sintered electrodes compared to those obtained from alloys characterized by high dimensional stability, their production is very expensive. They cannot be manufactured efficiently are and can only be produced in small dimensions (a few dm).
Es ist Aufgabe der Erfindung, eine Elektrode zu schaffen, die hinsichtlich ihrer mechanischen und elektrochemischen Eigenschaften den bekannten MSK- und DSK-Elektroden gleichwertig ist, sich jedoch durch einfachere und wirtschaftlichere Herstellung auszeichnet und zudem in nahezu beliebigen Abmessungen gefertigt werden kann. Aufgabe der Erfindung ist es ferner, ein Verfahren zur Herstellung derartiger Elektroden anzugeben.It is the object of the invention to create an electrode which, in terms of its mechanical and electrochemical Properties is equivalent to the known MSK and DSK electrodes, but is characterized by simpler and more economical production and also in almost any Dimensions can be manufactured. Another object of the invention is to provide a method for producing such electrodes to specify.
7434875 30.t2.767434875 30.t2.76
Diese Aufgabe wird bei einer Elektrode der eingangs genannten Gattung neuerungsgemäss dadurch gelöst, dass sich an den Kern eine poröse, aus Metallteilchen gebildete Schicht anschliesst, welche mittels auf elektrochemischem Wege abgeschiedenen Metall mit dem Kern verbunden ist.In the case of an electrode, this task becomes the one mentioned at the beginning The genus is solved according to the innovation in that an the core is adjoined by a porous layer formed from metal particles, which is deposited by means of electrochemical means Metal is connected to the core.
Das rteuerungsgemässe Verfahren zur Herstellung der Elektrode besteht darin, auf einen zumindest teilweise aus Metall bestehenden Kern Metallteilchen aufzubringen und diese Metallteilchen durch elektrochemische Metallabscheidung aus einem Galvanisierbad mit dem Kern zu verbinden.The control-based method for manufacturing the electrode consists in applying metal particles to an at least partially metal core and these metal particles to connect to the core by electrochemical metal deposition from an electroplating bath.
Derartige Elektroden werden vorzugsweise als Anoden oder * Kathoden in elektrochemischen Verfahren verwendet.Such electrodes are preferably used as anodes or * Cathodes used in electrochemical processes.
Elektroden nach der Neuerung weisen grosse Unempfindlichkeit gegenüber thermischen und mechanischen Belastungen auf. Ihre poröse Oberflächenschicht ergibt eine grosse spezifische Oberfläche. Als Metall eignen sich grundsätzlieh alle Materialien, welche die beabsichtigte Reaktion bei der Verwendung der Elektrode katalysieren. Als Bäder kommen solche,Electrodes according to the innovation are very insensitive to thermal and mechanical loads on. Their porous surface layer results in a large specific surface. In principle, they are suitable as metal any materials which catalyze the intended reaction in the use of the electrode. As baths come those
7434875 30.12.767434875 12/30/76
J.lS/71J.lS/71
aus denen sich die geeignete Metallart abscheidet, in Frage. Diese Bäder sollen ein gutes Mikrostreuvermögen aufweisen.from which the suitable type of metal is deposited, in question. These baths should have a good micro-scattering power.
Die Erfindung wird nachstehend anhand eines AusfOhrungsbeispiels näher erläutert. Der Kern der in der Zeichnung dargestellten Elektrode ist eine Stahlplatte 1, die mit einer Ni-Schicht 2 Oberzogen ist. Die sich an die Nickelsnhicht 2 anschliessende Schicht besteht aus Nickelfeilspänen 3. Mittels Nickelabscheidung aus einem Nickelbad sind die Nickelteilchen 3 auf der Nickelschicht 2 fixiert. Der durch die Ni-Abscheidung hergestellte Ueberzug ist mit Ί bezeichnet.The invention is explained below using an exemplary embodiment explained in more detail. The core of the electrode shown in the drawing is a steel plate 1 covered with a Ni layer 2 is raised. The one following the nickel layer 2 Layer consists of nickel filings 3. The nickel particles are deposited by means of nickel deposition from a nickel bath 3 fixed on the nickel layer 2. The coating produced by the Ni deposition is denoted by Ί.
Zur Herstellung der Elektrode wird von einer in üblicher Weise präparierten Stahlplatte 1 ausgegangen und diese auf galvanischem Wege mit einer dünnen Nickelschicht 2 übersogen. Die vernickelte Stahlplatte wird in ein Nickelbad eingebracht. Die Nickelteilchen werden als Nickelfeilspäne auf die vorverniekelte Platte aufgestreut. Die Fixierung der Nickelteilchen 3 kann nun auf zweierlei Weise erfolgen:For the production of the electrode one is used in the usual way prepared steel plate 1 and this galvanically coated with a thin nickel layer 2. The nickel-plated Steel plate is placed in a nickel bath. The nickel particles are pre-nickelized as nickel filings on the Scattered plate. The nickel particles 3 can now be fixed in two ways:
a) durch Nickelabscheidung aus einem Galvanisierbad vom Hype— phosphit- oder Boranattyp, die Nickelabscheidung erfolgt dabei stromlos, also ohne äussere Stromquelle,a) by nickel deposition from a hype electroplating bath- phosphite or boranate type, the nickel is deposited without electricity, i.e. without an external power source,
b) durch Nickelabscheidung aus einem Galvanisierbad vom Wattsoder Sulfamattyp, b) by nickel deposition from a galvanizing bath of the Watts or sulfamate type,
Beide Bäder sind z.B. in dem Buch "Handbuch der Galvanotechnik"Both baths are e.g. in the book "Handbuch der Galvanotechnik"
7434875 30.12.767434875 12/30/76
von Dettner/Elze, Carl Hanser Verlag, München, Bd.II, S.729-743, insbesondere S.731 u. 7«*0 bzw. S.87-im, insbesondere S.102 u.von Dettner / Elze, Carl Hanser Verlag, Munich, Volume II, pp.729-743, especially p.731 and 7 «* 0 or p.87-im, especially p.102 and 113, eingehend beschrieben.113, described in detail.
Bei der unter b) genannten Nickelabscheidung wird die vernickelte Stahlplatte mit dem Plus-Pol, eine in das Bad eingetauchte Gegenelektrode bzw. der (metallische)BehMlter, in dem die Galvanisierung erfolgt, wird mit dem Minuspol verbunden. In beiden Verfahren wird die Behandlungszeit im Bad so gewählt, dass zwar eine gute Fixierung der Nickelteilchen gewährleistet ist, das Nickel jedoch nicht die zwischen den einzelnen Nickelteilchen befindlichen Zwischenräume ausfüllt. Vorteilhaft ist es, die Nickelteilchen nach und nach in möglichst gleichmässiger Verteilung auf die vorvernickelte Platte aufzustreuen, so dass die Fixierung der Teilchen untereinander und mit der Platte in optimaler Weise erfolgt.In the case of the nickel deposition mentioned under b), the nickel-plated steel plate with the plus pole is immersed in the bath The counter electrode or the (metallic) container in which the electroplating takes place is connected to the negative pole. In both Procedure, the treatment time in the bath is chosen so that although a good fixation of the nickel particles is guaranteed, but not the nickel between the individual nickel particles fills the interstices. It is advantageous to gradually sprinkle the nickel particles onto the pre-nickel-plated plate in as uniform a distribution as possible, so that the fixing of the particles with one another and with the plate takes place in an optimal manner.
Die beschriebene Elektrode eignet sich in hervorragender Weise als Sauerstoff-Elektrode für Wasserelektrolyseure. Elektroden für andere chemische Verfahren, z.B. Brennstoffelemente, Inertanoden für den kathodischen Korrosionsschutz, lassen sich in entsprechender Weise einfach in nahezu beliebigen Abmessungen und wirtschaftlich herstellen.The electrode described is extremely suitable as an oxygen electrode for water electrolysers. Electrodes for other chemical processes, e.g. fuel elements, inert anodes for cathodic corrosion protection, can be used in Easily and economically produce in a corresponding manner in almost any dimensions.
Elektroden für allgemeine Anwendungen weisen eine Oberflächenschicht 3 auf, die aus einem der Metalle Nickel, Eisen, Kobalt, Silber, einem Metall aus der Platingruppe des Perioden-Electrodes for general applications have a surface layer 3 made of one of the metals nickel, iron, cobalt, Silver, a metal from the platinum group of the period
7434875 30.12.7e7434875 12/30/7e
Systems der Elenente oder einer Legierung dieser Metalle besteht. Gleiches gilt fflr die den Kern bedeckende Schicht 2, die bei geeignetem Kernmaterial selbstverständlich weggelassen werden kann, und auch bezüglich*.des der Fixierung dienenden Metalls.System of elements or an alloy of these metals. The same applies to the layer 2 covering the core, which of course can be omitted if the core material is suitable, and also to the metal used for fixing.
Als zweckmSssig hat es sich erwiesen, für Elektrolyseure in den OberfISchenschichten der Anode Nickel oder Silber zu verwenden. Die Kathode, an die weit geringere Anforderungen gestellt werden, kann aus Wirtschaftlichkeitsgrönden aus Eisen bestehen.It has proven to be useful for electrolysers in the surface layers of the anode nickel or silver to use. The cathode, which is subject to far less stringent requirements, can be used for reasons of economy consist of iron.
7434875 30.12.767434875 12/30/76
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1353974A CH576529A5 (en) | 1974-10-09 | 1974-10-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE7434875U true DE7434875U (en) | 1976-12-30 |
Family
ID=4393290
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE7434875U Expired DE7434875U (en) | 1974-10-09 | 1974-10-18 | ELECTRODE FOR USE IN AN ELECTROCHEMICAL PROCESS |
| DE19742449603 Withdrawn DE2449603A1 (en) | 1974-10-09 | 1974-10-18 | Electrodes for electrochemical processes - using porous outer layer of filings bonded to the core by electroplating |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19742449603 Withdrawn DE2449603A1 (en) | 1974-10-09 | 1974-10-18 | Electrodes for electrochemical processes - using porous outer layer of filings bonded to the core by electroplating |
Country Status (2)
| Country | Link |
|---|---|
| CH (1) | CH576529A5 (en) |
| DE (2) | DE7434875U (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54112785A (en) * | 1978-02-24 | 1979-09-03 | Asahi Glass Co Ltd | Electrode and manufacture thereof |
| US4230543A (en) * | 1978-04-07 | 1980-10-28 | Showa Denko K.K. | Cathode for electrolysis of aqueous solution of alkali metal halide |
| DE2835506C2 (en) * | 1978-08-12 | 1981-11-19 | Deutsche Automobilgesellschaft Mbh, 3000 Hannover | Biporous Raney nickel electrode and process for making same |
| DE2914094C2 (en) | 1979-04-07 | 1983-02-10 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Porous nickel electrode for alkaline electrolysis, process for producing the same and its use |
| US4242183A (en) * | 1979-04-13 | 1980-12-30 | The Dow Chemical Company | Highly active silver cathode, preparation of same and use to make 2,3,5-trichloropyridine |
| DE3102306A1 (en) * | 1980-02-02 | 1982-01-14 | Basf Ag, 6700 Ludwigshafen | ELECTRODES |
| GB8323390D0 (en) * | 1983-08-31 | 1983-10-05 | Ici Plc | Production of cathode |
| RU178966U1 (en) * | 2017-07-19 | 2018-04-24 | Общество с ограниченной ответственностью "Завод нефтегазовой аппаратуры "Анодъ" | Device for electrochemical corrosion protection |
-
1974
- 1974-10-09 CH CH1353974A patent/CH576529A5/xx not_active IP Right Cessation
- 1974-10-18 DE DE7434875U patent/DE7434875U/en not_active Expired
- 1974-10-18 DE DE19742449603 patent/DE2449603A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE2449603A1 (en) | 1976-05-20 |
| CH576529A5 (en) | 1976-06-15 |
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