EP0302465A2 - Verfahren zur keramischen Beschichtung von Metallen - Google Patents

Verfahren zur keramischen Beschichtung von Metallen Download PDF

Info

Publication number
EP0302465A2
EP0302465A2 EP88112601A EP88112601A EP0302465A2 EP 0302465 A2 EP0302465 A2 EP 0302465A2 EP 88112601 A EP88112601 A EP 88112601A EP 88112601 A EP88112601 A EP 88112601A EP 0302465 A2 EP0302465 A2 EP 0302465A2
Authority
EP
European Patent Office
Prior art keywords
coating
ion
ceramic
grams
ceramic coating
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.)
Withdrawn
Application number
EP88112601A
Other languages
English (en)
French (fr)
Other versions
EP0302465A3 (de
Inventor
Yoshio Moriya
Souei Koizumi
Masanori Kanda
Yasunobu Matsushima
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.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
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 Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Publication of EP0302465A2 publication Critical patent/EP0302465A2/de
Publication of EP0302465A3 publication Critical patent/EP0302465A3/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C23C—COATING 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • C23C—COATING 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/20—Orthophosphates containing aluminium cations
    • 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
    • C23C—COATING 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising

Definitions

  • the present invention is a method for ceramic coating of metals.
  • ceramic coatings with carbides such as TiC, SiC, nitrides such as TiN, Si3N4, borides such as TiB2, oxides such as Al203 or silicides such as MoSi2 can provide metals with improved heat and oxidation resistance.
  • the ceramic coatings can be applied to metals by flame spray methods, ion sputtering methods, chemical vapour deposition methods (CVD), dry-in-place (coating-drying) methods, baking-in-­place (coating-baking) methods and the like.
  • flame spray methods ion sputtering methods, chemical vapour deposition methods (CVD), dry-in-place (coating-drying) methods, baking-in-­place (coating-baking) methods and the like.
  • one method is to treat a metal coated with frit at a temperature as high as 677-871°C (Jap.Pat.Publ SHO 55-26714/1980). Generally the method is carried out at a temperature used for inorganic coating materials. In the known processes the ceramic coating is applied directly on the surface of the metal which has been cleaned mecha­nically or chemically.
  • This material comprises a denatured silicone varnish binder and alumina-silica short fibers as the ceramic material (Nikkei New Material, p.101, 5-19, 1986). According to this article, one of the advantages of the material is the capability of the film to follow the expansion of the substrate metal.
  • the adhesion between the coating film and substrate metal is poor and the ceramic coatings delaminate because of the difference between the coefficient of thermal expansion of the substrate metal and the ceramic. Delamination can also be caused by oxidation of the substrate metal when exposed to high tem­perature.
  • An object of the present invention is to provide a method for ceramic coating of metals; which coated metals can be used at high temperature without delamination.
  • a further object of the invention is to provide a coating which protects the metal substrate from oxi­dation.
  • the metal article comprising the aluminum phosphate coated metal substrate with the ceramic coating overlay also comprises the invention.
  • aluminum phosphate coating refers to a film obtained by the method described in Jap.Pat.Pub.SHO 53-6945/1978 by the present applicants, wherein a coating is formed by a chemical conversion treatment or electrolytic treat­ment with an acidic liquid at a pH from 1.5 to 5 containing alumi­num ion in a concentration of from about 0.01 to about 10 g/l and phosphate ion in about 1.0 to about 100 g/l, the principal com­ponent of such a film being aluminum phosphate (AlPO4-xH2O).
  • Jap.Pat.Pub. SHO 53-6945/1978 is incorporated herein be reference.
  • Publication SHO 53-6945/1978 is directed to preventing ferrous materials from corrosion by providing an alternative coating as a substitute for coatings of zinc, manganese, and calcium phosphate or the like and chromate coating for painting, and particularly for painting with acrylic-based paint.
  • an aluminum phosphate coating is an excellent base coat for a ceramic coating.
  • the characteristics of an aluminum phosphate coating have been investigated in more detail.
  • Figure 1 shows thermal weight change and differential thermal analysis up to 500°C of an aluminum phosphate coating obtained according to the method described in the above-cited patent published herein.
  • the coating of aluminum phosphate is amorphous AlPO4-xH2O, undergoes loss of x ⁇ H2O at about 150°C to 200°C (weight loss of about 12%), then up to about 500°C it is the stable form of AlPO4.
  • the thermal analysis shows that the loss of adsorbed water and crystal water takes place respectively at 50-100°C and at about 150°C but at over 200°C no weight change occurs. This is an indication of the thermal stability of AlPO4.
  • the drying of the aluminum phosphate coating is not critical. With air-drying of the film, residual moisture and water of crystallization are removed during baking without affecting the adhesion of the ceramic coating.
  • the AlPO4 provides a base for high adhesion with the ceramic coating.
  • the AlPO4 undergoes no further decom­position than the above-mentioned dehydration.
  • a ceramic coating is deposited on cleaned metal surfaces according to known methods, the metal surface is oxidized when subjected to the heat resistance test and is accompanied by dela­mination of the ceramic coating.
  • the composition containing aluminum ion for use in forming the AlPO4 coating is a liquid prepared by adding an aluminum compound such as nitrate, hydroxide or sulphate in the form of a solid or liquid to an acidic phosphate solution. The pH is adjusted so that the mixture is acidic.
  • the content of aluminum ion in the mixture is from about 0.01 to 10 g/l, preferably 0.2 to 3 g/l. When less than about 0.01 g/l of Al ion is present, the deposit of aluminum phosphate is not sufficient. When the alumi­num ion content exceeds about 3 g/l, economical disadvantages result.
  • the acidic phosphate liquid mixture is prepared by diluting phosphoric acid, sodium dihydrogen phosphate or disodium hydrogen phosphate and the like with water so as to contain 1 to 100 g/l, preferably 5 to 50 g/l, of the phosphate ion.
  • the pH is less than about 1.5, the metal being treated receives a large amount of etching.
  • the pH is above about 5.0, precipitation of alu­minum phosphate and aluminum hydroxide take place in the treating bath.
  • nitrate ion in an amount of from 0 to about 20 g/l preferably 1 to 5 g/l, chlorate ion in an amount of from 0 to about 20 g/l preferably 1 to 5 g/l, or nickel ion in an amount of from 0 to about 5 g/l preferably 0.01 to 2 g/l. It is also useful, for the purpose of increasing coating weight, to add sulphate ion in an amount of from 0 to about 10 g/l.
  • the metals to which the method of the present invention is applicable are those metallic materials which require improved heat resistance and which can be etched by phosphoric acid. Metals such as iron, steel, stainless steel, heat-resistant steel, aluminum, aluminum alloy, etc., can be treated by the method of the present invention.
  • the metal substrate can be coated with the AlPO4 coating by:
  • the coating formed is dried and preferably baked at a tem­perature above about 150°C.
  • Ceramics such as carbides, nitrides, borides, oxides, sili­cides, mixtures or compositions containing these and the like are useful.
  • Alkali metal silicate type coating compositions, metal alcoholate type coating compositions, silica sol type compositions and silicone compositions and the like can be used in the process.
  • the baking-in-place (coating/baking) process of the present invention for ceramic coating can provide a coating film with adhesion to the substrate comparable to that provided by conven­tional CVD processes.
  • the substrate becomes hot so that the heat resistance of aluminum phosphate can be utilized in the ceramic coating. Heating the substrate, during the ceramic coating, up to about 200 to about 400°C is also useful. A similar effect occurs in the ion sputtering process or flame spray process.
  • Test piece SPCC steel sheet (70 x 150 x 0.8 mm) was used.
  • the composition of the treating liquid was as follows: PO43 ⁇ 22.8 g/l A13+ 0.9 g/l NO3 3.1 g/l This liquid was neutralized with sodium hydroxide to adjust the pH to about 2.5.
  • the metal test piece was surface cleaned and immersed in the treating liquid for 3 minutes.
  • the treating liquid was maintained at a temperature of 60°C.
  • the test piece was removed from the treating liquid, rinsed with water and dried. A coating weighing 1 g/m2 was formed on the test piece.
  • test piece was dip-coated with GLASCA 90 (a product of Nichiban R&D Ltd., metal alcoholate type: colorless transparent, ceramic component: alkoxysilane 19-23%), then baked at 150°C for 30 minutes to form a colorless, transparent ceramic coating.
  • the film thickness was 5 ⁇ m.
  • An SPCC steel sheet (70 x 150 x 0.8 mm) test piece which was previously surface cleaned was subject to an electrolytic treat­ment in a liquid of the composition PO43 ⁇ 25.0 g/l A13+ 1.2 g/l NO3 9.0 g/l
  • the liquid was neutralized with sodium hydroxide to adjust the pH to 2.5.
  • the test piece was immersed in the liquid and was electrolytically treated with direct current at a temperature of 65°C, a current density of 5A/dm2 for 30 seconds.
  • the opposite electrode was a graphite plate at an electrode distance of 40 mm and electrode ratio of 1:1. After the electrolytic coating, the test piece was rinsed with water and dried.
  • a ceramic coating as in Example 1 was applied to the coated test piece.
  • Example 1 For comparison, a ceramic coating as in Example 1 was applied to a test piece without precoating (the steel sheet was surface-­cleaned with a cleaner).
  • Example 1 and Example 2 were heated in an over at 250°C, 400°C or 500°C for 2 hours, then cooled in air.
  • the result of an appearance inspection is shown in Table 1.
  • the discoloring of the metal surface by oxi­dation was visually observed either through the transparent cera­mic coating or, in the case the ceramic coating was delaminated, directly on such portions of the metal.
  • Test pieces were coated by the conversion treatment of Example 1 or 2. The coated test pieces were then coated with various kinds of ceramic coating compositions and subjected to the following tests which results are shown in Table 3.
  • test pieces After receiving the base coat and ceramic coating, test pieces were heated to various temperatures and cooled to room temperature.
  • ceramic coating without precoating permits oxidation of the metal surface, often resulting in delamination.
  • delamination does not take place below about 500°C and oxidation of the metal surface is suppressed.
  • the heat resistance attained by means of the baking-in-place process of the invention is comparable to that obtained by a con­ventioned CVD process.
  • the method of the present invention is free of the disadvan­tages of the CVD process such as long treatment time (as much as 2 to 8 hrs), poor productivity and high apparatus cost.
  • the process of the invention when used with a baking-in-place process provides a simple treatment process with high productivity.
  • the method of the present invention is also applicable to a CVD process and the like, and provides for excellent adhesion and oxidation resistance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Electrochemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
EP88112601A 1987-08-03 1988-08-03 Verfahren zur keramischen Beschichtung von Metallen Withdrawn EP0302465A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP192591/87 1987-08-03
JP62192591A JPH0730459B2 (ja) 1987-08-03 1987-08-03 金属へのセラミックコ−ティング法

Publications (2)

Publication Number Publication Date
EP0302465A2 true EP0302465A2 (de) 1989-02-08
EP0302465A3 EP0302465A3 (de) 1990-01-31

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP88112601A Withdrawn EP0302465A3 (de) 1987-08-03 1988-08-03 Verfahren zur keramischen Beschichtung von Metallen

Country Status (5)

Country Link
EP (1) EP0302465A3 (de)
JP (1) JPH0730459B2 (de)
AU (1) AU606726B2 (de)
BR (1) BR8803842A (de)
MX (1) MX170165B (de)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0991365A4 (de) * 1997-04-30 2000-04-12 Medquest Products Inc Elektrochirurgische klinge mit einem leitenden nicht klebendem überzug
WO2005061218A1 (en) * 2003-11-19 2005-07-07 Applied Thin Films, Inc. Aluminum phosphate compounds, compositions, materials and related metal coatings
DE10014035B4 (de) * 2000-03-22 2006-07-13 Electro Chemical Engineering Gmbh Gefärbte Konversionsschicht, eine Lösung zu ihrer Herstellung sowie ihre Verwendung
EP1743955A2 (de) 2005-07-15 2007-01-17 NHK Spring Co., Ltd. Stahlteil mit hervorragendem Korrosionswiderstand und Korrosionsermüdungswiderstand, sowie Oberflächendbehandlung zur Herstellung
US7311944B2 (en) 2002-12-23 2007-12-25 Applied Thin Films, Inc. Aluminum phosphate coatings
US7678465B2 (en) 2002-07-24 2010-03-16 Applied Thin Films, Inc. Aluminum phosphate compounds, compositions, materials and related metal coatings
US7682700B2 (en) 2002-08-14 2010-03-23 Applied Thin Films, Inc. Aluminum phosphate compounds, compositions, materials and related composites
US7887917B2 (en) 2005-06-30 2011-02-15 Unifrax I Llc Inorganic fiber
CN103044995A (zh) * 2013-01-28 2013-04-17 陈立晓 一种柴油机排气管道高温涂料
US8497018B2 (en) 2010-01-27 2013-07-30 Applied Thin Films, Inc. High temperature stable amorphous silica-rich aluminosilicates
CN103741195A (zh) * 2013-12-23 2014-04-23 南通恒新金属工艺科技有限公司 钢丝电解磷化处理装置
US9556063B2 (en) 2014-07-17 2017-01-31 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9567256B2 (en) 2013-03-15 2017-02-14 Unifrax I Llc Inorganic fiber
US9708214B2 (en) 2014-07-16 2017-07-18 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9919957B2 (en) 2016-01-19 2018-03-20 Unifrax I Llc Inorganic fiber
US10023491B2 (en) 2014-07-16 2018-07-17 Unifrax I Llc Inorganic fiber
US10882779B2 (en) 2018-05-25 2021-01-05 Unifrax I Llc Inorganic fiber
US11203551B2 (en) 2017-10-10 2021-12-21 Unifrax I Llc Low biopersistence inorganic fiber free of crystalline silica

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008106340A (ja) * 2006-10-27 2008-05-08 Nhk Spring Co Ltd 鉄鋼用りん酸アルミニウム系化成処理液及びその作製方法
CN110438485A (zh) * 2019-07-29 2019-11-12 吴俊杰 一种pvc喷胶工艺的磷化处理系统

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR884852A (fr) * 1940-05-10 1943-08-30 Opel Adam Ag Procédé pour protéger contre la rouille la surface intérieure des réservoirs àessence et des canalisations pour combustibles liquides
JPS536945B2 (de) * 1973-02-27 1978-03-13
JPS51136539A (en) * 1975-05-22 1976-11-26 Ota Toshuki Process for coating aluminum with inorganic substance
JPS5481132A (en) * 1977-12-13 1979-06-28 Teikoku Kako Kk Steel materials for use in ferroconcretes
JPS54148139A (en) * 1978-04-24 1979-11-20 Nippon Steel Corp Bolt set excellent in ease to paint, corrosion resistance, lubricativity, and co-turning inhibition
US4592958A (en) * 1983-01-18 1986-06-03 Sermatech Coated part, coating therefor and method of forming same

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0991365A4 (de) * 1997-04-30 2000-04-12 Medquest Products Inc Elektrochirurgische klinge mit einem leitenden nicht klebendem überzug
DE10014035B4 (de) * 2000-03-22 2006-07-13 Electro Chemical Engineering Gmbh Gefärbte Konversionsschicht, eine Lösung zu ihrer Herstellung sowie ihre Verwendung
US7678465B2 (en) 2002-07-24 2010-03-16 Applied Thin Films, Inc. Aluminum phosphate compounds, compositions, materials and related metal coatings
US8124184B2 (en) 2002-07-24 2012-02-28 Applied Thin Films, Inc. Aluminum phosphate compounds, compositions, materials and related metal coatings
US7682700B2 (en) 2002-08-14 2010-03-23 Applied Thin Films, Inc. Aluminum phosphate compounds, compositions, materials and related composites
US7311944B2 (en) 2002-12-23 2007-12-25 Applied Thin Films, Inc. Aluminum phosphate coatings
WO2005061218A1 (en) * 2003-11-19 2005-07-07 Applied Thin Films, Inc. Aluminum phosphate compounds, compositions, materials and related metal coatings
AU2003304644B2 (en) * 2003-11-19 2010-09-30 Applied Thin Films, Inc. Aluminum phosphate compounds, compositions, materials and related metal coatings
US7887917B2 (en) 2005-06-30 2011-02-15 Unifrax I Llc Inorganic fiber
US8551897B2 (en) 2005-06-30 2013-10-08 Unifrax I Llc Inorganic fiber
EP1743955A2 (de) 2005-07-15 2007-01-17 NHK Spring Co., Ltd. Stahlteil mit hervorragendem Korrosionswiderstand und Korrosionsermüdungswiderstand, sowie Oberflächendbehandlung zur Herstellung
EP1743955A3 (de) * 2005-07-15 2007-01-24 NHK Spring Co., Ltd. Stahlteil mit hervorragendem Korrosionswiderstand und Korrosionsermüdungswiderstand, sowie Oberflächendbehandlung zur Herstellung
US8497018B2 (en) 2010-01-27 2013-07-30 Applied Thin Films, Inc. High temperature stable amorphous silica-rich aluminosilicates
CN103044995A (zh) * 2013-01-28 2013-04-17 陈立晓 一种柴油机排气管道高温涂料
US9919954B2 (en) 2013-03-15 2018-03-20 Unifrax I Llc Inorganic fiber
US9567256B2 (en) 2013-03-15 2017-02-14 Unifrax I Llc Inorganic fiber
CN103741195A (zh) * 2013-12-23 2014-04-23 南通恒新金属工艺科技有限公司 钢丝电解磷化处理装置
CN103741195B (zh) * 2013-12-23 2016-06-15 南通恒新金属工艺科技有限公司 钢丝电解磷化处理装置
US10023491B2 (en) 2014-07-16 2018-07-17 Unifrax I Llc Inorganic fiber
US9708214B2 (en) 2014-07-16 2017-07-18 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US10301213B2 (en) 2014-07-16 2019-05-28 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9926224B2 (en) 2014-07-17 2018-03-27 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9556063B2 (en) 2014-07-17 2017-01-31 Unifrax I Llc Inorganic fiber with improved shrinkage and strength
US9919957B2 (en) 2016-01-19 2018-03-20 Unifrax I Llc Inorganic fiber
US11203551B2 (en) 2017-10-10 2021-12-21 Unifrax I Llc Low biopersistence inorganic fiber free of crystalline silica
US12122704B2 (en) 2017-10-10 2024-10-22 Unifrax I Llc Low biopersistence inorganic fiber free of crystalline silica
US10882779B2 (en) 2018-05-25 2021-01-05 Unifrax I Llc Inorganic fiber

Also Published As

Publication number Publication date
AU2038688A (en) 1989-02-09
BR8803842A (pt) 1989-02-21
AU606726B2 (en) 1991-02-14
JPS6436774A (en) 1989-02-07
JPH0730459B2 (ja) 1995-04-05
EP0302465A3 (de) 1990-01-31
MX170165B (es) 1993-08-10

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