EP0339728B1 - Verfahren zur Herstellung von Diaphragmen - Google Patents

Verfahren zur Herstellung von Diaphragmen Download PDF

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Publication number
EP0339728B1
EP0339728B1 EP89201031A EP89201031A EP0339728B1 EP 0339728 B1 EP0339728 B1 EP 0339728B1 EP 89201031 A EP89201031 A EP 89201031A EP 89201031 A EP89201031 A EP 89201031A EP 0339728 B1 EP0339728 B1 EP 0339728B1
Authority
EP
European Patent Office
Prior art keywords
powder
layer
thickness
metal powder
wire gauze
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
Application number
EP89201031A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0339728A1 (de
Inventor
Heinz Wüllenweber
Peter Dr. Kohl
Herbert Dr. Jung
Jürgen Borchardt
Wolfgang Bickle
Jürgen Dr. Braus
Hans-Joachim Hiedemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kolbenschmidt AG
GEA Group AG
Jean Hiedemann GmbH and Co KG
Original Assignee
Kolbenschmidt AG
Metallgesellschaft AG
Jean Hiedemann GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kolbenschmidt AG, Metallgesellschaft AG, Jean Hiedemann GmbH and Co KG filed Critical Kolbenschmidt AG
Publication of EP0339728A1 publication Critical patent/EP0339728A1/de
Application granted granted Critical
Publication of EP0339728B1 publication Critical patent/EP0339728B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1103—Making porous workpieces or articles with particular physical characteristics
    • B22F3/1118—Making porous workpieces or articles with particular physical characteristics comprising internal reinforcements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers

Definitions

  • the invention relates to a method for producing diaphragms with a thickness of 0.3 to 3.0 mm, consisting of a wire mesh serving as a carrier, preferably nickel wire mesh, and a porous ceramic layer connected to it and having a thickness of 0.1 to 2 , 8 mm, preferably for electrolysis, whereby a layer of a difficult-to-pour metal powder consisting of sputtered particles, in particular nickel powder, is applied to a layer, the wire mesh is rolled or pressed onto the powder layer with simultaneous compression of the same by 30 to 60% and the metal powder in oxidizing atmosphere at temperatures of 800 to 1500 ° C with a holding time of 1 to 30 minutes, preferably 5 to 15 minutes.
  • Diaphragms for electrolysis should be designed in such a way that they are resistant to temperature and corrosion, do not have their own electronic conductivity and have sufficient mechanical strength and have a very low resistance due to the smallest possible thickness against the transport of the electrical charges in the electrolyte.
  • EP-B-0 022 252 provides a 0.3 to 0.7 mm thick diaphragm made of porous sintered nickel, iron or copper with a framework structure formed from a wire mesh, preferably nickel wire mesh, the metal is at least partially oxidized to metal oxide.
  • a diaphragm is obtained in that a layer of the metal powder is applied to a wire mesh with a mesh size of 100 to 500 ⁇ m in such a way that this is done with binders or simply spread alcohol-sprayed metal powder on the wire mesh or spray it on and compress it by applying a pressure of about 200 kg / cm 2 and at the same time connect it to the wire mesh.
  • the metal powder is then subjected to a reducing sintering treatment at a temperature of 700 to 1000 ° C for 10 to 20 minutes and then an oxidizing treatment at a temperature of 1000 to 1200 ° C for up to 3 hours.
  • a reducing sintering treatment at a temperature of 700 to 1000 ° C for 10 to 20 minutes
  • an oxidizing treatment at a temperature of 1000 to 1200 ° C for up to 3 hours.
  • large-area diaphragms should be able to be produced, the strength of which is obtained by an oxidation which is not too extensive, ie by a metallic residual structure.
  • Sufficient electrical resistance is provided by the oxide formation penetrating from the surface over the entire body.
  • the diaphragms described above especially with larger dimensions, do not have uniform strength, density and thickness over the entire body.
  • a constant strength is the prerequisite for the safety of the surfaces of the diaphragms against erosion by gas and liquid flows that occur in the cells of a water electrolysis.
  • Constant density and thickness of the diaphragms are the prerequisite for a uniform current density and optimal gas purity; because with uneven current density, ie with local current concentrations, this can lead to local overheating and corrosion attacks and thus to hole formation in the diaphragms, so that, for example, detonating gas can be produced during alkaline water electrolysis.
  • the fine-meshed sieve in the manufacture of large diaphragms, the fine-meshed sieve must be kept at a uniform distance from the base by using spacers; because without the spacer, the screen would be bent by the nickel powder applied thereon and the pressure of the doctor blade guided over the nickel powder, so that the distance between the screen and the base would be uneven.
  • spacers cause interruptions in the nickel powder layer, so that the resulting defects significantly impair the gas separation and the uniformity of the passage of current.
  • the metal powder is evenly distributed and applied to the base according to the bulk volume and the powder layer is rotated under a distributor roller rotating counter to the direction of the powder to form a uniform layer thickness is passed through. This measure is the prerequisite for the uniform layer thickness of the porous ceramic layers connected to the wire mesh and their adhesive strength on the wire mesh.
  • the metal powder is expediently applied to the base in an amount of 25 to 500 mg / cm 2 .
  • the thickness is 1.0 to 7.0 mm, preferably 3.0 to 5.0 mm.
  • This object can also be achieved in such a way that the metal powder is evenly distributed and applied to a wire mesh resting on a base according to the bulk volume and the powder layer is passed under a distributor roller rotating counter to the direction of the powder to form a uniform layer thickness.
  • the wire mesh it is necessary for the wire mesh to be coated on both sides, to turn the wire mesh with the powder layer adhering to it upwards, and then to distribute and apply a layer of the same metal powder uniformly according to the bulk volume, to pass it under a distributor roller rotating counter to the direction in which the powder is fed, and then to compact by rolling.
  • the wire mesh has a porous ceramic layer on both sides
  • a layer of the same metal powder is evenly distributed according to the bulk volume and applied to the wire mesh rolled or pressed onto the compacted metal powder layer against the feed direction of the powder rotating distributor roller passed to form a uniform layer thickness and then compacted by rolling.
  • the device for carrying out the method consists of a cellular wheel feeder which allocates and applies the powdered metal, a distributor roller and compacting roller arranged downstream of it. by means of the latter, the wire mesh, which is preferably wound on a drum, is pressed onto the metal powder layer, so that the openings of the wire mesh are filled with metal powder.
  • cellular wheel feeder, distributor roller and compacting roller and, if appropriate, the drum interacting with the compacting roller, on which the wire mesh is wound, are combined to form a unit which can be moved along the base.
  • the unit consisting of cellular wheel feeder, distributor roller and compacting roller is assigned a further cellular wheel feeder and a distributor roller.
  • the wire mesh is pressed into the surface of the sintered metal powder layer brought to a uniform layer thickness by the compacting roller while simultaneously compressing the powder layer, and during the backward movement, the metal powder layer applied to the wire mesh and having a uniform layer thickness is compacted by the compacting roller, which makes the sputtering shaped particles of the metal powder are so firmly connected that the manufactured Composite material can be transported easily.
  • the metal powder particles are so closely hooked together that small-format diaphragms can be produced from them without using a wire mesh acting as a support.
  • the position of the cellular wheel feeder and the discharge opening of the storage container is selected such that the metal powder cannot be discharged when the cellular wheel feeder is at a standstill. This results in a direct dependence of the discharge amount of the metal powder and thus the layer thickness allocated and applied to the base on the speed of the cellular wheel feeder.
  • the layer thickness of the metal powder on the base can be controlled by the speed at which the unit formed by cellular wheel feeder, distributor roller and compacting roller is moved.
  • the composite material can be manufactured in sheet or strip form and is so flexible that it can be easily wound onto a drum.
  • Fig. 1 and Fig. 2 from the funnel-shaped storage container (1) carbonyl nickel powder (2) in a grain size of 2.2 to 2.8 microns by means of the discharge opening of the storage container (1) closing cellular wheel feeder (3) with a star shape arranged, coaxial trough-like cells in batches to the stationary base (4) in an amount of 50 mg / cm 2 and applied.
  • carbonyl nickel powder (10) is applied from the storage container (11) by means of the cellular wheel feeder (12) to the nickel wire mesh (9) in an amount of 50 mg / cm 2 , the powder layer through the distributor roller (14) rotating counter to the direction of the powder is brought to a uniform thickness and then compacted by the compacting roller (7) to a layer thickness of 0.45 mm.
  • the material composite which is then fired in an oxidizing atmosphere at a temperature of 1000 ° C and a holding time of 15 min, has a constant thickness and density over the entire surface, which means that the prerequisites for optimal abrasion resistance, uniform current distribution and good gas purity are met. Before firing the composite material, it can be profiled.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Chemically Coating (AREA)
EP89201031A 1988-04-23 1989-04-21 Verfahren zur Herstellung von Diaphragmen Expired - Lifetime EP0339728B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3813743A DE3813743A1 (de) 1988-04-23 1988-04-23 Verfahren und vorrichtung zur herstellung von diaphragmen
DE3813743 1988-04-23

Publications (2)

Publication Number Publication Date
EP0339728A1 EP0339728A1 (de) 1989-11-02
EP0339728B1 true EP0339728B1 (de) 1997-10-15

Family

ID=6352725

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89201031A Expired - Lifetime EP0339728B1 (de) 1988-04-23 1989-04-21 Verfahren zur Herstellung von Diaphragmen

Country Status (8)

Country Link
US (2) US4961901A (pt)
EP (1) EP0339728B1 (pt)
JP (1) JP2869487B2 (pt)
BR (1) BR8901906A (pt)
CA (1) CA1319474C (pt)
DE (2) DE3813743A1 (pt)
NO (1) NO891630L (pt)
ZA (1) ZA892958B (pt)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69024628T2 (de) * 1989-07-27 1996-08-29 Furukawa Electric Co Ltd Verfahren zur herstellung eines metallischen komplexes sowie so erzeugte komplexe
US7560067B2 (en) * 2001-07-16 2009-07-14 Sherman Andrew J Powder friction forming
US20140170012A1 (en) * 2012-12-18 2014-06-19 United Technologies Corporation Additive manufacturing using partially sintered layers
JP6379684B2 (ja) 2014-06-02 2018-08-29 株式会社リコー 立体造形装置
US10245786B2 (en) * 2014-12-17 2019-04-02 Xerox Corporation System for planarizing objects in three-dimensional object printing systems with reduced debris
WO2020092485A1 (en) * 2018-10-31 2020-05-07 Carbon, Inc. Apparatuses for additively manufacturing three-dimensional objects
US11376787B2 (en) * 2019-06-18 2022-07-05 Carbon, Inc. Additive manufacturing method and apparatus for the production of dental crowns and other objects

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1930287A (en) * 1927-12-21 1933-10-10 Moraine Products Company Method of compressing powdered materials
US2341732A (en) * 1941-04-04 1944-02-15 Gen Motors Corp Method and apparatus for briquetting of powdered metal
US2917821A (en) * 1954-04-01 1959-12-22 Mannesmann Ag Method for rolling metal powder
SU119772A1 (ru) * 1958-11-15 1958-11-30 Ю.Н. Семенов Устройство дл подачи металлического порошка в прокатные валки
US3050776A (en) * 1960-04-21 1962-08-28 Electric Storage Battery Co Nickel-powder leveling apparatus
US3194858A (en) * 1962-02-23 1965-07-13 Alloys Res & Mfg Corp Continuous powder metallurgical process
US3403999A (en) * 1965-10-13 1968-10-01 Texas Instruments Inc Manufacture of braze shim stock
GB1515420A (en) * 1976-03-10 1978-06-21 Davy Loewy Ltd Treatment of compacted metal powder strip
JPS55164162A (en) * 1979-06-06 1980-12-20 Hitachi Ltd Forming method for thin film
DE2927566C2 (de) * 1979-07-07 1986-08-21 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma für alkalische Elektrolyse, Verfahren zur Herstellung desselben und dessen Verwendung
SU980962A1 (ru) * 1981-05-15 1982-12-15 Ордена Трудового Красного Знамени Институт Проблем Материаловедения Ан Усср Технологическа лини дл производства биметалла
SU1041214A1 (ru) * 1982-02-08 1983-09-15 Витебский технологический институт легкой промышленности Способ получени покрытий из порошковых материалов
DE3318758C2 (de) * 1983-05-24 1985-06-13 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma auf Nickeloxidbasis und Verfahren zur Herstellung desselben
US4670214A (en) * 1986-05-12 1987-06-02 Energy Conversion Devices, Inc. Method for making electrode material from high hardness active materials
SU1444081A1 (ru) * 1987-06-04 1988-12-15 Коммунарский горно-металлургический институт Устройство дл прокатки порошка

Also Published As

Publication number Publication date
NO891630D0 (no) 1989-04-20
US4961901A (en) 1990-10-09
NO891630L (no) 1989-10-24
BR8901906A (pt) 1989-11-28
DE3813743A1 (de) 1989-11-02
EP0339728A1 (de) 1989-11-02
JP2869487B2 (ja) 1999-03-10
JPH01312097A (ja) 1989-12-15
DE58909821D1 (de) 1997-11-20
US5114326A (en) 1992-05-19
ZA892958B (en) 1990-12-28
CA1319474C (en) 1993-06-29

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