EP0823496B1 - Herstellung einer keramischen schicht mit plasmaunterstützter elektrolyse und so hergestelltes produkt - Google Patents

Herstellung einer keramischen schicht mit plasmaunterstützter elektrolyse und so hergestelltes produkt Download PDF

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Publication number
EP0823496B1
EP0823496B1 EP95930367A EP95930367A EP0823496B1 EP 0823496 B1 EP0823496 B1 EP 0823496B1 EP 95930367 A EP95930367 A EP 95930367A EP 95930367 A EP95930367 A EP 95930367A EP 0823496 B1 EP0823496 B1 EP 0823496B1
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EP
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Prior art keywords
napo
solution
process according
arc discharge
discharge voltage
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Revoked
Application number
EP95930367A
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English (en)
French (fr)
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EP0823496A1 (de
EP0823496A4 (de
Inventor
Qingshan High-tech. Dvping Zoom 14 KONG
Hongbo High-tech. Developing Zoom 14 ZUO
Donghui High-tech. Developing Zoom 14 MI
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Sunny Asia Co Ltd Harbin
Original Assignee
Harbin Huanya Micro - Arc Co Ltd
HARBIN HUANYA MICRO ARC CO Ltd
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Application filed by Harbin Huanya Micro - Arc Co Ltd, HARBIN HUANYA MICRO ARC CO Ltd filed Critical Harbin Huanya Micro - Arc Co Ltd
Publication of EP0823496A1 publication Critical patent/EP0823496A1/de
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Classifications

    • 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
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge

Definitions

  • the present invention concerns surface chemical treatment, in particular surface chemical treatment for metal material.
  • ceramic materials have become the third generation engineering materials because of their special performances, superiority of rich resources.
  • the whole ceramic materials are brittle, not easy to process, their wide application has been limited all the time.
  • cheap metal materials may be used instead of expensive metal materials with the prerequisite for guaranteeing the use performance, at the same time endow with the substrate metal material some special performances that can not be obtained by the other surface treatment methods and enlarge its suitable range.
  • using easy-processing materials as the substrate to apply surface ceramic coating can increase the shaping and processing performances for the ceramic materials, providing guarantee for making complicated shape spares with ceramic coating, and carving out a new way for widely using ceramic products.
  • the object of the invention is to overcome the above defects in the prior art and to provide a process for surface ceramic-coating on metal substrate in an electrolyte solution containing (NaPO 3 ) 6 and a product thereof.
  • Another object of the invention is to provide a kind of metal products coated by ceramic layer.
  • the subject matter of the present invention is a process for preparing a ceramic layer on a metal substrate comprising the steps of plasma arc discharging on the substrate metal as an anode under voltage of 100-400V and current density of 0.5-20A/dm 2 to electrochemically oxidize the anode in an electrolyte solution which essentially comprises 10-50 g/l of (NaPO 3 ) 6 and 5-20 g/l of H 3 BO 3 and/or Na 2 B 4 O 7 ⁇ 7H 2 O, and also comprises at least one oxyacid-salt selected from the group consisting of Na 3 PO 4 , Na 2 SO 4 , Na 2 SiO 3 , NH 4 VO 4 , NaVO 3 , Na 2 CrO 4 , Na 2 WO 4 , CoSO 4 , NiSO 4 , Fe 2 (SO 4 ) 3 , MnSO 4 ⁇ H 2 O and Cr 2 (SO 4 ) 3 , and optionally comprises additives selected from the group consisting of Ca(Ac) 2 ,
  • the growing course of the ceramic layer is: in electrochemical oxidizing electrolytic bath, the metal workpiece is as anode, adding direct current electrical field between the cathode and the anode, there will be the following anodic oxidation reactions on the surface of the workpiece.
  • the process of the present invention also comprises the steps of cleaning the substrate metal before anodic oxidization, and rinsing, then sealing the surface after anodic oxidation. Therefore, the process of the present invention comprises the following steps:
  • alkaline cleaning liquid which is formulated as Na 3 PO 4 ⁇ 12H 2 O 50-60g/l, Na 2 SiO 3 10-15g/l, Na 2 CO 3 10-20g/l and surfactant 0.1-10ml/l. It is required that the cleaning liquid must be forced to be stirred or to be sprayed to the surface of the workpiece in the bath, to make it clean up at the temperature of 40-60°C for 20-30 min. Then the workpiece is immersed in a potcher containing clean water at the temperature of 15-20°C and rinsed until there are no clean liquid aforementioned remained on the surface of the workpiece.
  • Products with different colors, pattern, designs and properties, which can be applied in various field, can be obtained by using various electrolyte solutions, controlling various operation current, voltage, temperature of the solutions, stirring strength and pattern.
  • the voltage for arc discharging is usually between 100-400V, the current density is 0.5-20A/dm 2 , and the temperature of the solution is 10-50°C.
  • the electrolyte solution is combined with distilled water.
  • the combining sequence is: first dissolving (NaPO 3 ) 6 thoroughly, then adding the other materials, and adjusting pH with H 3 PO 4 to pH 4.0-10.5. After combining the solution, it is required to be laid aside still for more than 24 hours, and the temperature is controlled at 15-45°C.
  • the solution is forced to be uniform by spraying and stirring.
  • a white ceramic film thus can be obtained with the thickness of the film being 5-28 ⁇ m.
  • To form a homogeneous blue film it is required to force to stir the solution to make the solution uniform completely for 5-20 min.
  • a blue dotted film with different size dots which have decorative effect can be formed by means of changing the stirring manner to the solution to decrease the numbers of the discharge centers on the surface of the workpiece, increase the current density of the discharge centers, thus cause some matters to discharge and produce different size pattern dots on the surface, and get excellent decorative effect.
  • the control time is 1-5min., to form different dots patterns decorative films.
  • the thickness of the film is 5-15 ⁇ m, and a blue film from light blue to dark blue is formed. This operation process also can be used in producing products of other colors.
  • Two types of products can be obtained.
  • a decorative film with various dots patterns or a homogeneous dark pink film can be obtained by using the method of ⁇ 2>.
  • the oxidizing time is 5-25 min, the thickness is 5-25 ⁇ m.
  • the film thus obtained is from light pink to dark pink.
  • the method for combining is the same as in ⁇ 1>.
  • the homogeneous color film in light grey to dark grey or dots patterns film in grey can be obtained.
  • the thickness is 5-20 ⁇ m.
  • any two kinds of them can be mixed together to produce different color film.
  • the white film oxidized in electrolyte ⁇ 1> can be overlapped by blue dots in electrolyte ⁇ 2> with the above stirring manner, and become another kind of product. The details are shown in the following examples.
  • Temperature of water is 15-60°C. The requirement is cleaning up the workpiece until there are no electrolyte solution remaining on the surface of it.
  • the workpiece After rinsing, the workpiece can be sealed by using the process of dip coating, pour coating, spray coating to improve the luster. Paints of water-soluble acrylic acid resin or water-soluble amino resin can be used, and according to the requirements of the paint, be baked at 150-250°C for 5-30min for the case that a water-soluble acrylic acid is used. After baking, the products must be inspected to be standard, and then packed.
  • the content of the material from the electrolyte in the layer by using the process of the present invention is higher than that of traditional anodic oxide film lay er, and there are no oxide hydrates of the substrate metal in the film.
  • the products obtained by using the process of the present invention are composed of substrate metal and the ceramic layer on the surface of the substrate.
  • the content of the substrate metal oxide is 70.0-95.0% by weight
  • the content of the other metal oxides, non-metal oxides, inorganic salts or their mixture is 5.0-3.0% by weight.
  • Said ceramic layer is formed by using the process of anodic oxidation enhanced plasma arc discharge.
  • the described other metal oxides, non-metal oxides, inorganic salts or their mixture come from the electrolyte solution.
  • the layer's appearance of the products is stacked in regular mosaic manner, and the rate of holes is very low, which is less than 0.5%. There are little macroscopic defect.
  • Each composition is uniformly dispersed in the layer. Because the metal atoms on the substrate surface take part in the reaction directly, the layer and the substrate are combined closely, and have no obvious boundary.
  • the homogeneity of the ceramic layer of the products in the present invention is good, and the combination strength between the layer and the substrate is higher.
  • the holes in the layer are little. Both ram resistance and corrosion resistance are good, and the colors are bright and there are many patterns, as well as the decorative effect is great.
  • the process of the present invention is suitable for surface treatment of the substrate workpiece of any dimension, shape and construction.
  • the oxidization treatment began when the solution in the bath was stirred in the case of the workpiece as anode and a stainless steel plate as cathode. Keeping the current being constant 1A, the voltage was slowly raised to 160-180V, on the surface of the workpiece, there was the phenomenon of plasma arc discharge. When the voltage raised to 210-240V, the current decreased. The duration for oxidization was 10 min., then the oxidization was stopped by adjusting the current to 0, the voltage to 0 and shutting off the power source. The workpiece was taken out form the bath and a white film was thus obtained. After cleaning, the holes were closed, and the workpiece was dip coated in water-soluble acrylic acid resin, and then baked for 5 min.
  • the sections were put into the cleaning bath, dipped for 25 min. After raised by a shop traveler, the sections were dropped water freely, then were put into a potcher. After raised, they were put into the second potcher and then to the oxide bath to begin electrifying and oxidizing.
  • the current was 1A/dm 2 , the voltage was raised slowly. Stirring the solution, cooling, when the voltage was raised to 150V, small arc light on the surface of the workpieces occurred.
  • the operation conditions described ahead were kept for 10min, the end voltage was 230V. Then the workpieces were put into potcher to rinse again, and dipped into resin bath, and baked in an oven. After unloading from the hanging, products were packed.
  • the color of the film was coffee-color, and the thickness was measured as 8-11 ⁇ m.
  • the appearance of the end products was homogeneous, and the microhardness (HV) was 260-480kg/mm 2 (0.049N), and wear resistance (judgment of the time of spraying sands) was 300-500 seconds.
  • the oxidizing time was controlled to 15min, voltage 150V, then current was decreased and the power source be shut off.
  • the workpiece was taken out and rinsed. After baking, the color of the workpiece was grey.
  • the thickness of the film was measured as 15 ⁇ m, CASS test: class 9.
  • the workpiece was taken out from the bath, rinsed and baked until to be an end product.
  • the thickness of the film was measured as 50-70 ⁇ m, the time for wear resistance of spray sands was 720-800 second, microhardness was 900-1300HV (0.098N), and the combination strength with substrate was 25.6-35.0kg/mm 2 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Detergent Compositions (AREA)

Claims (13)

  1. Verfahren zur Herstellung eines Keramiküberzugs auf der Oberfläche eines Substratmetalls, das die Stufe der Plasmabogenentladung auf dem Substratmetall als Anode unter einer Spannung von 100 - 400 V und bei einer Stromdichte von 0.5 - 20 A/dm2 zur elektrochemischen Oxidation der Anode in einer Elektrolytlösung umfaßt, die im wesentlichen 10 - 50 g/l (NaPO3)6 und 5 - 20 g/l H3BO3 und/ oder Na2B4O7.7H2O und außerdem noch wenigstens ein Salz einer Oxosäure, ausgewählt aus der Gruppe, bestehend aus Na3PO4, Na2SO4, Na2SiO3, NH4VO4, NaVO3, Na2CrO4, Na2WO4, CoSO4, NiSO4, Fe2(SO4)3, MnSO4.H2O und Cr2(SO4)3, und ggf. Zusätze, ausgewählt aus der Gruppe, bestehend aus Ca(Ac)2, Zn(Ac)2, Co(Ac)2, Ni(Ac)2, H2SiF6, KF und EDTA, enthält, wodurch auf der Oberfläche des Substrats eine Keramikschicht gebildet wird.
  2. Verfahren nach Anspruch 1, bei dem der Elektrolyt die Komponenten (NaPO3)6 10-50 g/l Na3PO4.12H2O 10-30 g/l, Na2B4O7.7H2O 5-20 g/l, Ca(Ac)2 0,1-5 g/l, Na2SiO3 0,1-10 g/l, Zn(Ac)2 0,1-12 g/l, Na2SO4 5-10 g/l, H3BO3 5-20 g/l
    enthält, der pH der Lösung 4.0 - 10,5 beträgt und die Bogenentladungsspannung 100 - 400 V beträgt.
  3. Verfahren nach Anspruch 1, bei dem der Elektrolyt die Komponenten (NaPO3)6 10-50 g/l, H3BO3 5-20 g/l, EDTA 1-6 g/l, Na2SO4 5-10 g/l, Na3PO4.12H2O 5-15 g/l, CoSO4 5-20 g/l, NiSO4 1-10 g/l, Co(Ac)2 10-20 g/l
    enthält, der pH der Lösung 4.0 - 6 beträgt und die Bogenentladungsspannung 150 - 300 V beträgt.
  4. Verfahren nach Anspruch 1, bei dem der Elektrolyt die Komponenten (NaPO3)6 10-50 g/l, Na3PO4.12H2O 5-10 g/l, Ni(Ac)2 2-15 g/l, H3BO3 5-10 g/l, Na2SO4 5-10 g/l, Na2B4O7.7H2O 5-10 g/l, Fe2(SO4)3 2-10 g/l, EDTA 1-6 g/l, MnSO4.H2O 2-10 g/l
    enthält und die Bogenentladungsspannung 125 - 350 V beträgt.
  5. Verfahren nach Anspruch 1, bei dem der Elektrolyt die Komponenten (NaPO3)6 10-50 g/l, Na2B4O7.7H2O 5-20 g/l, Na3PO4.12H2O 10-30 g/l, Na2SiO3 0,5-10 g/l, Zn(Ac)2 0,1-12 g/l, MnSO4.H2O 5-20 g/l
    enthält und die Bogenentladungsspannung 150 - 350 V beträgt.
  6. Verfahren nach Anspruch 1, bei dem der Elektrolyt die Komponenten (NaPO3)6 10-50 g/l Na2B4O7.7H2O 5-10 g/l, NH4VO3 2-10 g/l, NaVO3 2-10 g/l, Na2SO4 5-10 g/l
    enthält, der pH der Lösung 3 - 6 beträgt und die Bogenentladungsspannung 150 - 350 V beträgt.
  7. Verfahren nach Anspruch 1, bei dem der Elektrolyt die Komponenten (NaPO3)6 10-50 g/l, Na2B4O7.7H2O 5-10 g/l, NH4VO3 2-7 g/l, NaVO3 2-7 g/l, Ni(Ac)2 5-15 g/l, MnSO4 1-5 g/l, H3BO3 5-10 g/l
    enthält, der pH der Lösung 3 - 7 beträgt und die Bogenentladungsspannung 150 - 300 V beträgt.
  8. Verfahren nach Anspruch 1, bei dem der Elektrolyt die Komponenten (NaPO3)6 10-50 g/l, Na2B4O7.7H2O 10-15 g/l Na3PO4.12H2O 10-15 g/l, NH4VO3 1-10 g/l, Na2CrO4 2-10 g/l
    enthält und die Bogenentladungsspannung 125 - 350 V beträgt.
  9. Verfahren nach Anspruch 1, bei dem der Elektrolyt die Komponenten (NaPO3)6 10-50 g/l, Na2B4O7.7H2O 10-50 g/l, Na2SO4 5-10 g/l, Na3PO4.12H2O 10-15 g/l, CoSO4 2-15 g/l, Cr2(SO4)2 2-15 g/l, Co(Ac)2 2-10 g/l, Ni(Ac)2 2-10 g/l, NH4VO3 2-10 g/l
    enthält und die Bogenentladungsspannung 125 - 350 beträgt.
  10. Verfahren nach Anspruch 1, bei dem der Elektrolyt die Komponenten (NaPO3)6 10-50 g/l, H2SiF6 2-20 ml/l, KF 1-10 g/l, Na2B4O7.7H2O 7-20 g/l, Na2WO4 1-20 g/l
    enthält und die Bogenentladungsspannung 100 - 200 V beträgt.
  11. Verfahren nach einem der Ansprüche 1 - 10, bei dem die Elektrolytlösung zum Zwecke ihrer Homogenisierung während der Oxidation gerührt wird.
  12. Verfahren nach einem der Ansprüche 1 - 10, bei dem die Elektrolytlösung gleichmäßig gerührt wird, das Rühren dann eingestellt und unvermittelt wieder aufgenommen wird oder das Substrat der Lösung zugeführt wird.
  13. Erzeugnisse, hergestellt nach einem der Verfahren 1 - 12.
EP95930367A 1995-04-18 1995-09-11 Herstellung einer keramischen schicht mit plasmaunterstützter elektrolyse und so hergestelltes produkt Revoked EP0823496B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN95114880A CN1034522C (zh) 1995-04-18 1995-04-18 等离子体增强电化学表面陶瓷化方法及其制得的产品
CN95114880 1995-04-18
PCT/CN1995/000072 WO1996033300A1 (en) 1995-04-18 1995-09-11 Process for producing ceramic layer by plasma enhanced electrolysis and product thereof

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EP0823496A1 EP0823496A1 (de) 1998-02-11
EP0823496A4 EP0823496A4 (de) 1998-05-20
EP0823496B1 true EP0823496B1 (de) 2002-04-03

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EP95930367A Revoked EP0823496B1 (de) 1995-04-18 1995-09-11 Herstellung einer keramischen schicht mit plasmaunterstützter elektrolyse und so hergestelltes produkt

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EP (1) EP0823496B1 (de)
JP (1) JP2937484B2 (de)
CN (1) CN1034522C (de)
AU (1) AU3378895A (de)
DE (1) DE69526256T2 (de)
WO (1) WO1996033300A1 (de)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1050389C (zh) * 1997-04-21 2000-03-15 哈尔滨环亚微弧技术有限公司 等离子体增强电化学表面陶瓷化能量控制方法
US7452454B2 (en) 2001-10-02 2008-11-18 Henkel Kgaa Anodized coating over aluminum and aluminum alloy coated substrates
US7569132B2 (en) 2001-10-02 2009-08-04 Henkel Kgaa Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating
US7820300B2 (en) 2001-10-02 2010-10-26 Henkel Ag & Co. Kgaa Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to organic or inorganic coating
US7578921B2 (en) * 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
US20060016690A1 (en) 2004-07-23 2006-01-26 Ilya Ostrovsky Method for producing a hard coating with high corrosion resistance on articles made anodizable metals or alloys
EP2371996B1 (de) * 2008-12-26 2016-03-09 Nihon Parkerizing Co., Ltd. Verfahren für eine elektrolytische keramik-metallbeschichtung, elektrolyseanwendung für eine elektrolytische keramik-metallbeschichtung und metallisches material
US9701177B2 (en) 2009-04-02 2017-07-11 Henkel Ag & Co. Kgaa Ceramic coated automotive heat exchanger components
CN102102217A (zh) * 2009-12-18 2011-06-22 中国电子科技集团公司第四十九研究所 一种微弧氧化制造氧化铝薄膜方法
CN103290448A (zh) * 2013-05-07 2013-09-11 锡山区羊尖泓之盛五金厂 一种金属表面耐蚀处理方法
JP2015074825A (ja) * 2013-10-11 2015-04-20 株式会社栗本鐵工所 プラズマ電解酸化による皮膜形成方法及び金属材料
CN104404601B (zh) * 2014-12-19 2017-09-29 中北大学 Mg‑Gd‑Y‑Zr铸造镁合金的一种微弧氧化处理工艺
CN105862131B (zh) * 2016-06-03 2018-05-01 武汉工程大学 一种利用mpcvd制备碳化钼晶体时钼的引入方法
GB201610615D0 (en) * 2016-06-17 2016-08-03 Keronite Int Ltd Durable white inorganic finish for aluminium articles
CN107630185B (zh) * 2017-09-15 2020-01-17 芜湖通潮精密机械股份有限公司 一种干刻机台内壁板再生方法
CN111876811B (zh) * 2020-07-27 2022-02-25 上海交通大学 一种铝锂合金微弧氧化方法及其采用的电解液

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3834999A (en) * 1971-04-15 1974-09-10 Atlas Technology Corp Electrolytic production of glassy layers on metals
DE3328049A1 (de) * 1983-08-03 1985-02-21 Hoechst Ag, 6230 Frankfurt Verfahren zur einstufigen anodischen oxidation von traegermaterialien aus aluminium fuer offsetdruckplatten
CN87103694A (zh) * 1985-10-24 1988-11-09 鲁道夫·何拉德科夫斯基 铝制品的电镀方法及所用的电镀液
DE3870925D1 (de) * 1987-02-02 1992-06-17 Friebe & Reininghaus Ahc Verfahren zur herstellung dekorativer ueberzuege auf metallen.
DE3736240A1 (de) * 1987-10-27 1989-05-11 Flachglas Ag Vorrichtung zur galvanischen verstaerkung einer leiterspur auf einer glasscheibe
DD295198B5 (de) * 1990-06-14 1996-06-27 Physikalisch Tech Studien Gmbh Elektrolyt zur erzeugung duenner schwarzer konversionsschichten auf leichtmetallen
RU1812247C (ru) * 1990-08-24 1993-04-30 Институт Прикладной Физики Способ обработки деталей
CN2202135Y (zh) * 1994-08-30 1995-06-28 哈尔滨环亚微弧技术有限公司 铝合金表面弧增强电化学沉积装置

Also Published As

Publication number Publication date
EP0823496A1 (de) 1998-02-11
JP2937484B2 (ja) 1999-08-23
CN1034522C (zh) 1997-04-09
WO1996033300A1 (en) 1996-10-24
AU3378895A (en) 1996-11-07
DE69526256D1 (de) 2002-05-08
EP0823496A4 (de) 1998-05-20
JPH10509772A (ja) 1998-09-22
DE69526256T2 (de) 2002-11-07
CN1115793A (zh) 1996-01-31

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