US3864164A - Method for depositing protective coatings on carbon articles - Google Patents

Method for depositing protective coatings on carbon articles Download PDF

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Publication number
US3864164A
US3864164A US299455A US29945572A US3864164A US 3864164 A US3864164 A US 3864164A US 299455 A US299455 A US 299455A US 29945572 A US29945572 A US 29945572A US 3864164 A US3864164 A US 3864164A
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US
United States
Prior art keywords
aluminium
refractory material
refractory
carbon
spray
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
US299455A
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English (en)
Inventor
Alan Hinchcliffe
Kenneth Johnson
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.)
British Steel Corp
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British Steel Corp
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 British Steel Corp filed Critical British Steel Corp
Priority to US05/506,581 priority Critical patent/US3951103A/en
Application granted granted Critical
Publication of US3864164A publication Critical patent/US3864164A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • B05B7/22Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc
    • B05B7/222Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc
    • B05B7/224Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed electrically, magnetically or electromagnetically, e.g. by arc using an arc the material having originally the shape of a wire, rod or the like
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B13/00Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
    • B05B13/02Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work
    • B05B13/0278Arrangement or mounting of spray heads
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B13/00Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
    • B05B13/02Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work
    • B05B13/04Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work the spray heads being moved during spraying operation
    • B05B13/0442Installation or apparatus for applying liquid or other fluent material to separate articles rotated during spraying operation
    • 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16Wires; Tubes

Definitions

  • ABSTRACT The invention relates to a method and apparatus for coating carbon articles, such as carbon electrodes for use in steelmaking, with aluminium and refractory materials.
  • the method comprises in a single operation, spraying aluminium in a molten state on to the surface, and immediately spraying refractory material on to the aluminium coating so formed.
  • the apparatus includes spray heads, by which the aluminium and refractory materials are sprayed, the spray heads being located alongside each other and moved relatively to the carbon electrode simultaneously, the distance apart of the spray heads being sufficient to ensure that there is virtually no interference between the sprays of aluminium and refractory material, and also to ensure that the heat of the molten aluminium does not dry out the refractory material before it reaches the surface of the carbon article.
  • This invention relates to methods of and apparatus for creating protective coatings on the surfaces of carbon articles.
  • the invention is a modification of the basic process described and claimed in British Pat. Nos. 1,026,055 and 1,15 1,071.
  • these patent specifications are described methods of coating carbon articles with aluminum layers and then applying to the aluminium layer a layer of refractory material.
  • these methods have involved applying the aluminium by use of an electric arc to atomise the aluminium and compress air to blow the atomised aluminium on to the surface of the carbon article.
  • the article is then allowed to cool sufficiently to paint on to the aluminium surface a slurry containing refractory material.
  • a method of creating a protective coating on the surface of a carbon article comprises, in a single operation, spraying aluminium in molten state on to the surface and immediately spraying refractory material on to the aluminium coating so formed.
  • the spray heads by which the aluminium and refractory materials are sprayed can be located alongside each other and moved relatively to the carbon electrode simultaneously, the distance apart of the spray heads being sufficient to ensure that there is virtually no interference between the sprays of aluminum and refractory material, and also to ensure that the heat of the molten aluminium does not dry out the refractory material before it reaches the surface of the carbon article.
  • the refractory spray is a pneumatic spray and the refractory is contained in a slurry having a water base together with a thickening agent.
  • a preferred thickening agent is Cellofas 8.50 which is produced by Imperial Chemical Industries Ltd. Cellofas 8.50 is sodium carboxymethyl cellulose and is available in both granulated and powder form.
  • a possible refractory material which may be used comprises aluminium powder, titanium dioxide, silicon metal powder, silicon carbide boric acid ferrochrome, bichromium trioxide and zirconium silicate.
  • the invention com prises apparatus for applying a protective coating to the surface of a carbon article
  • the apparatus consisting of means to support and rotate the carbon article and two spray heads, one for aluminium and the other for refractory material, the spray heads being mounted on a carriage, movable longitudinally of the carbon article, the spacing of the spray heads being such that they allow two sprays to reach the surface of the carbon article without interference with each other and also such that the heat of the molten aluminium will not dry out the refractory spray before it reaches the carbon article.
  • FIG. 1 is a diagrammatic plan of an apparatus, embodying the invention, for creating a protective coating on the surface of a large carbon electrode.
  • FIG. 2 is an end elevation, partly in section and on a reduced scale, of the same apparatus.
  • a carbon electrode, of the kind used in large electric furnaces for steel refining, is preheated to about 100 150C to remove moisture and to ensure that when material is subsequently sprayed on to the electrode it dries rapidly.
  • the three stages of coating then commence. In the first stage there are three steps:
  • the second stage repeats the first three steps identically.
  • the third stage there is no refractory spray but graphite is sprayed.
  • the third stage consists of:
  • the electrode 10 which is to be sprayed is supported in a lathe.
  • a nipple 11 is screwed into the central bore at each end of the I electrode 10. This central bore is already threaded because it is normally used to attach one electrode to the next as they are consumed.
  • the electrode surface is prepared by removal of dirt, paint and grease by a very light machining process. During this process gramophone type grooves 12 are formed which assist in the bonding of the material subsequently and also increase surface area.
  • the carbon electrode surface is then sprayed with aluminium by an electric arc process in which aluminium rods 13, wound on drums 13a, are fed into a gap 14 between arc electrodes 15 and the atomised aluminium is blown by an air jet on to the carbon electrode surface.
  • the carbon electrode 10 is slowly rotated and a band of aluminium about 1 inch wide is sprayed so as to form continuous spiral coating of aluminium on the electrode surface.
  • a refractory spray head is mounted alongside the aluminium spray, about 4-5 inches laterally displaced from the aluminium spray.
  • a 1 inch band of refractory is sprayed on top of the aluminium at the same time as the aluminium is being sprayed further along the electrode. This gap between the two sprays is necessary for two reasons.
  • the distances separating the two sprays are important, but these are variable and are dependent upon the rate at which the aluminium spray operates, eg at lower current settings, say 200 amperes, the aluminium spraying generator requires a lower volume of air to deposit the aluminium on the electrode, causing the overspray to be much less and consequently, in this case,
  • the refractory spray gun could be located much closer, approx. 3 inches distant. Conversely, when spraying at 450-500 amps, the separation needs to be 5 inches minimum. ln all cases the spray heads are separated in the vertical plane by some 4 inches.
  • the aluminium spray and refractory spray heads are both mounted on a carriage which is supported on a grooved rail 21 and by a wheel 22 running in another rail 23.
  • the carriage is traversed automatically by lead screw 24.
  • the refractory spray is provided by a normal pneumatic paint spry gun, comprising spray head 17 and pipes 18 for the supply of air and 19 for supply of refractory, the refractory being in the form of a slurry contained in a normal paint pressure pot.
  • the slurry may, for example, consist of aluminium powder, silicon carbide, silicon, titanium dioxide, boric acid, ferrochrome, birchromium trioxide, zirconium silicate water and Cellofas.
  • the Cellofas is a thickening agent and is mixed with the water first. The other ingredients are powdered and mixed together and then thoroughly mixed in the Cellofas/water.
  • This spray technique replaces a technique in which refractory material was hand-painted on to the aluminium. Hand-painting takes much longer and it was necessary to wait until the electrode had been completely coated in aluminium before hand-painting could commence and it was also necessary to wait until the electrode had cooled.
  • the refractory spray can be used simultaneously with the aluminium spray thus cutting out one of the steps in the manufacturing process. The saving in time is particularly valuable after the second aluminium coating because at this stage the time required for cooling prior to hand-painting is quite large.
  • the graphite is applied preferably by spraying.
  • the titanium tends to form small globules which clog the spray nozzle and this can be overcome by adequate mixing of the, titanium with the other powdered materials before they are mixed into the Cellofas/water mixture.
  • the Cellofas/water mixture is made up by mixing 2-2 /2% by weight of Cellofas in warm water at a temperature of about 6080C which ensures that the Cellofas dissolves quickly.
  • Ferrochrome Boric Acid Bichromium Tioxidc Zirconium Silicate These components are thoroughly mixed in dry powder form. 1250 grams of the dry mixture are then mixed into 1250 c.c. of water which already contains 2-2%% by weight of Cellofas. This quantity of slurry is sufficient to coat an electrode 8 feet long and 24 inches diameter, i.e. about 50 sq. ft. of surface. The above mixture is used for the refractory spray coating.
  • a method of creating a protective coating on the surface of a carbon article comprising, in a single operation, directing a spray of aluminium in molten state against said surface, and immediately thereafter directing a spray ofa water-slurry of refractory material onto the aluminium coating so formed without drying out said slurry before it reaches the surface of said carbon article, there being substantially no interference between the sprays.
  • a method as set forth in claim 1 including moving the sprays of aluminium and refractory slurry longitudinally of said carbon article while said carbon article is rotated.
  • the refractory material comprises at least one member selected from the group consisting of aluminium powder, titanium dioxide, silicon metal powder, silicon carbide and boric acid, ferrochrome, bichromium trioxide and zirconium silicate.
  • a method according to claim 8 comprising applying a first coating of aluminium and refractory material, the refractory material being in accordance with claim 8, and then applying a second coating of aluminium and refractory material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
US299455A 1971-10-22 1972-10-20 Method for depositing protective coatings on carbon articles Expired - Lifetime US3864164A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/506,581 US3951103A (en) 1971-10-22 1974-09-16 Apparatus for creating protective coatings on carbon articles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB4926171A GB1378384A (en) 1971-10-22 1971-10-22 Apparatus for creating protective coatings on carbon articles

Related Child Applications (1)

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US299455A Expired - Lifetime US3864164A (en) 1971-10-22 1972-10-20 Method for depositing protective coatings on carbon articles

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US (1) US3864164A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS4851008A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AR (1) AR194757A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (1) AU465279B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE790211A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BR (1) BR7207378D0 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (1) CA981123A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2251590C2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR2156889B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1378384A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL7213955A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ZA (1) ZA727377B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951103A (en) * 1971-10-22 1976-04-20 British Steel Corporation Apparatus for creating protective coatings on carbon articles
US4077357A (en) * 1975-02-12 1978-03-07 Dso "Cherna Metalurgia" Apparatus for the application of a protective coating to a graphite electrode
US4259919A (en) * 1979-01-26 1981-04-07 Dso "Cherna Metalurgia" Apparatus for coating graphite electrodes
USRE33876E (en) * 1975-09-11 1992-04-07 United Technologies Corporation Thermal barrier coating for nickel and cobalt base super alloys
WO1993025731A1 (en) * 1992-04-01 1993-12-23 Moltech Invent S.A. The application of refractory borides to protect carbon-containing components of aluminium production cells
US5275983A (en) * 1989-06-19 1994-01-04 Bp Chemicals (Hitco) Inc. Pack mixture composition for SiC pack cementation coating of carbonaceous substrates
US5527442A (en) * 1992-04-01 1996-06-18 Moltech Invent S.A. Refractory protective coated electroylytic cell components
US5651874A (en) * 1993-05-28 1997-07-29 Moltech Invent S.A. Method for production of aluminum utilizing protected carbon-containing components
US5683559A (en) * 1994-09-08 1997-11-04 Moltech Invent S.A. Cell for aluminium electrowinning employing a cathode cell bottom made of carbon blocks which have parallel channels therein
US5753163A (en) * 1995-08-28 1998-05-19 Moltech. Invent S.A. Production of bodies of refractory borides
US6001236A (en) * 1992-04-01 1999-12-14 Moltech Invent S.A. Application of refractory borides to protect carbon-containing components of aluminium production cells
CN104475286A (zh) * 2014-12-24 2015-04-01 金华职业技术学院 圆柱形套类零件外表面喷涂机
CN104492637A (zh) * 2015-01-08 2015-04-08 金华职业技术学院 非圆截面柱形套类零件喷涂机
CN104525417A (zh) * 2014-12-24 2015-04-22 金华职业技术学院 一种喷漆机

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3028348C2 (de) * 1980-07-25 1985-05-15 C. Conradty Nürnberg GmbH & Co KG, 8505 Röthenbach Kohlenstoffelektrode für Lichtbogenöfen
ZA824333B (en) 1981-06-26 1983-04-27 Foseco Trading Ag Protection of graphite electrodes
CH654030A5 (fr) * 1983-02-16 1986-01-31 Castolin Sa Procede pour former un revetement resistant a l'usure sur la surface d'un substrat metallique.
GB8627308D0 (en) * 1986-11-14 1986-12-17 Alcan Int Ltd Composite metal deposit
CN113578610A (zh) * 2021-08-05 2021-11-02 太仓黎江不锈钢有限公司 一种全角度喷涂装置
CN117816450A (zh) * 2024-01-09 2024-04-05 高梵(浙江)信息技术有限公司 一种面料生产用涂层加工设备

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1256599A (en) * 1916-07-03 1918-02-19 Max Ulrich Schoop Process and mechanism for the production of electric heaters.
US1978415A (en) * 1931-12-24 1934-10-30 Moore Drop Forging Company Method of uniting metals
US3019014A (en) * 1961-03-20 1962-01-30 Edward J Miksis Folding roll
US3348929A (en) * 1962-04-16 1967-10-24 Metalurgitschen Zd Lenin Protecting carbon materials from oxidation
US3553010A (en) * 1967-07-26 1971-01-05 Sigri Elektrographit Gmbh Carbon or graphite formed body

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1026055A (en) * 1962-10-02 1966-04-14 Metalurgitchen Zd Lenin Coating of carbon
FR1434642A (fr) * 1965-03-29 1966-04-08 Metalurgitchen Zd Lenin Procédé et appareil pour la réalisation d'enduits protecteurs sur des produits en carbone, notamment des électrodes en graphite ainsi que les produits pourvus d'une couche protectrice conforme à celle ainsi obtenue

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1256599A (en) * 1916-07-03 1918-02-19 Max Ulrich Schoop Process and mechanism for the production of electric heaters.
US1978415A (en) * 1931-12-24 1934-10-30 Moore Drop Forging Company Method of uniting metals
US3019014A (en) * 1961-03-20 1962-01-30 Edward J Miksis Folding roll
US3348929A (en) * 1962-04-16 1967-10-24 Metalurgitschen Zd Lenin Protecting carbon materials from oxidation
US3476586A (en) * 1962-04-16 1969-11-04 Metalurgitschen Z Lenin Method of coating carbon bodies and the resulting products
US3553010A (en) * 1967-07-26 1971-01-05 Sigri Elektrographit Gmbh Carbon or graphite formed body

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951103A (en) * 1971-10-22 1976-04-20 British Steel Corporation Apparatus for creating protective coatings on carbon articles
US4077357A (en) * 1975-02-12 1978-03-07 Dso "Cherna Metalurgia" Apparatus for the application of a protective coating to a graphite electrode
USRE33876E (en) * 1975-09-11 1992-04-07 United Technologies Corporation Thermal barrier coating for nickel and cobalt base super alloys
US4259919A (en) * 1979-01-26 1981-04-07 Dso "Cherna Metalurgia" Apparatus for coating graphite electrodes
US5275983A (en) * 1989-06-19 1994-01-04 Bp Chemicals (Hitco) Inc. Pack mixture composition for SiC pack cementation coating of carbonaceous substrates
US6001236A (en) * 1992-04-01 1999-12-14 Moltech Invent S.A. Application of refractory borides to protect carbon-containing components of aluminium production cells
WO1993025731A1 (en) * 1992-04-01 1993-12-23 Moltech Invent S.A. The application of refractory borides to protect carbon-containing components of aluminium production cells
US5527442A (en) * 1992-04-01 1996-06-18 Moltech Invent S.A. Refractory protective coated electroylytic cell components
US5651874A (en) * 1993-05-28 1997-07-29 Moltech Invent S.A. Method for production of aluminum utilizing protected carbon-containing components
US5683559A (en) * 1994-09-08 1997-11-04 Moltech Invent S.A. Cell for aluminium electrowinning employing a cathode cell bottom made of carbon blocks which have parallel channels therein
US5888360A (en) * 1994-09-08 1999-03-30 Moltech Invent S.A. Cell for aluminium electrowinning
US5753163A (en) * 1995-08-28 1998-05-19 Moltech. Invent S.A. Production of bodies of refractory borides
CN104475286A (zh) * 2014-12-24 2015-04-01 金华职业技术学院 圆柱形套类零件外表面喷涂机
CN104525417A (zh) * 2014-12-24 2015-04-22 金华职业技术学院 一种喷漆机
CN104492637A (zh) * 2015-01-08 2015-04-08 金华职业技术学院 非圆截面柱形套类零件喷涂机
CN104492637B (zh) * 2015-01-08 2016-09-07 金华职业技术学院 非圆截面柱形套类零件喷涂机

Also Published As

Publication number Publication date
ZA727377B (en) 1973-06-27
BE790211A (fr) 1973-02-15
AR194757A1 (es) 1973-08-14
AU465279B2 (en) 1975-09-25
JPS4851008A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1973-07-18
AU4782072A (en) 1974-04-26
BR7207378D0 (pt) 1973-09-27
CA981123A (en) 1976-01-06
FR2156889A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1973-06-01
DE2251590A1 (de) 1973-04-26
DE2251590C2 (de) 1982-07-29
NL7213955A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1973-04-25
FR2156889B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1975-03-14
GB1378384A (en) 1974-12-27

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