EP0074211B1 - Überzogenes metallisches Substrat und Verfahren zum Überziehen dieses Substrates - Google Patents

Überzogenes metallisches Substrat und Verfahren zum Überziehen dieses Substrates Download PDF

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Publication number
EP0074211B1
EP0074211B1 EP82304451A EP82304451A EP0074211B1 EP 0074211 B1 EP0074211 B1 EP 0074211B1 EP 82304451 A EP82304451 A EP 82304451A EP 82304451 A EP82304451 A EP 82304451A EP 0074211 B1 EP0074211 B1 EP 0074211B1
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EP
European Patent Office
Prior art keywords
substrate
coating
ammonia
effected
produce
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
Application number
EP82304451A
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English (en)
French (fr)
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EP0074211A1 (de
Inventor
Cyril Dawes
John David Smith
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.)
ZF International UK Ltd
Original Assignee
Lucas Industries 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 Lucas Industries Ltd filed Critical Lucas Industries Ltd
Publication of EP0074211A1 publication Critical patent/EP0074211A1/de
Application granted granted Critical
Publication of EP0074211B1 publication Critical patent/EP0074211B1/de
Expired legal-status Critical Current

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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
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment

Definitions

  • This invention relates to a method of coating a non-alloy steel substrate with a corrosion resistant coating.
  • phosphating In order to improve the adhesion between the steel substrate and the paint composition, it is known to effect pretreatment of the steel substrate by a process known as phosphating.
  • a typical phosphating treatment the steel substrate is first cleaned for 2 to 5 minutes using an alkaline cleaner maintained at 50 to 70°C, then the cleaner is removed by rinsing the cleaned substrate in two successive rinsing operations with water at ambient temperature, each operation being of a duration of half to one minute. Then, the cleaned and rinsed steel substrate is sprayed with a zinc phosphate solution maintained at 40 to 70°C, the spraying operation taking about one and a half minutes.
  • the steel substrate can be immersed in a zinc phosphate solution for about 5 minutes.
  • the substrate is rinsed with water at ambient temperature and again rinsed with water at ambient temperature which is often de-ionized.
  • the substrate may be subjected to a chromate rinse.
  • a further rinse with deionised water at ambient temperature may be effected and will be effected if the above mentioned chromate rinse has been performed.
  • the component is dried in an oven and is then ready for painting with a paint composition.
  • the phosphating solution requires close chemical control to maintain consistent results. Control of effluent from the treatment plant is essential since excessive pollution of the site drainage system with zinc ions is not permitted. Additionally, it is likely that legislation will be enacted in the near future to restrict the phosphate ion concentration in site effluent discharge. High levels of plant maintenance are also required to maintain consistent results. The number of clean water rinsing operations required in the process makes itvulnerable to rising water costs. The process requires a high capital investment. The phosphating process is usually sited in a flow line arrangement organised for specific products and this greatly reduces or often eliminates any flexibility of product throughput. Lastly, the phosphating process is sensitive to the cleaniness of the components to be processed therefore requires close control at the cleaning stage.
  • An object of the present invention is to provide a method of coating a non-alloy steel substrate in which the above disadvantages can be obviated or mitigated and in which the corrosion resistance of the coated substrate can be materially improved.
  • GB-A-2026045 discloses a method of treating a steel substrate prior to painting, in which method the substrate is gas soft nitrided with gas components generating no free carbon to form a nitride layer, after which the substrate is cooled by standing in air and then directly painted.
  • GB-A-2026045 recommends the nitride layer to be mainly epsilon phase, although mixed epsilon and gamma' phases are not precluded as the nitride layer.
  • a method of coating a non-alloy steel substrate comprising the steps of effecting on the substrate a pre-treatment operation which includes heat treating the substrate so as to produce an epsilon iron nitride surface layer thereon, and subsequently coating the pre-treated substrate with a solid organic polymer coating composition, characterised in that after the heat treating step and before the coating step the heat treated substrate is quenched in oil, degreased and then heated to remove moisture from the micropores of the epsilon iron nitride surface layer.
  • the non-alloy steel is preferably one which contains up to 0.5 wt% carbon.
  • the epsilon iron nitride surface layer is formed by heat treating the steel substrate at a temperature of 550 to 720°C for up to 4 hours in an atmosphere of ammonia, ammonia and endothermic gas, ammonia and exothermic gas or ammonia and nitrogen, with the optional inclusion of at least one of carbon dioxide, carbon monoxide, air and methane, followed by cooling.
  • ammonia, ammonia and endothermic gas, ammonia and exothermic gas or ammonia and nitrogen with the optional inclusion of at least one of carbon dioxide, carbon monoxide, air and methane, followed by cooling.
  • exothermic gas and "endothermic gas” are well understood in the art.
  • Carbon dioxide, carbon monoxide, air and exothermic gas are oxidizing gases.
  • Carbon dioxide, methane and endothermic gas are carburizing gases.
  • the heating to remove moisture from the micropores is effected to a temperature of e.g. 200°C.
  • the invention is applicable to any non-alloy steel substrates which are required to be rendered corrosion resistant, for example steel sheets, tubes, rods or other articles of manufacture produced by, for example, rolling, pressing, forging or extruding.
  • the polymer coating composition may be applied by means of a wet process, for example one employing a solvent to disperse the polymer coating composition, but may alternatively be effected by powder coating.
  • the epsilon iron nitride layer produced as described above imparts other advantageous properties to the substrate.
  • increased strength in components made from thin strip or sheet can be obtained.
  • the epsilon iron nitride layer is very hard (approximately 1100HB) and has anti-seizure properties which can be exploited in certain applications merely by masking the required areas during the application of the polymer coating composition.
  • the processing costs are lower than for phosphating and a further reduction may be obtained when only corrosion resistance is required by the use of higher temperatures and shorter times within the above ranges.
  • the epsilon iron nitride surface layer has a thickness of about 25 pm. Thicknesses greater than about 25 pm can lead to spalling or cracking of the surface layer. Typically, such a layer thickness of about 25 pm can be obtained by heat treatment at 660°C for 45 minutes. Such a layer thickness may also be produced by heat treatment at 570°C for 3 hours or at 610°C for 90 minutes. However, heat treatment temperatures and times may be employed to produce layer thicknesses of less than 25 pm, eg down to 15 ⁇ m. For example, heat treatment at 570°C for 2 hours can be employed to produce a layer thickness of 16-20 um.
  • test plates of non-alloy steel having a carbon content of 0.10% were subjected to a phosphate pretreatment or a pretreatment according to the present invention and were then coated with one of three organic coating systems.
  • the resultant samples were subjected to a salt-spray test in accordance with ASTM Standard B117-64 in which 5 plus or minus 1 parts by weight of sodium chloride are dissolved in 95 parts by weight of distilled water, the pH of the solution being adjusted so that, when atomised at 35°C (95°F) the collected solution will have a pH in the range of 6.5 to 7.2 and the temperature in the exposure zone of the salt-spray chamber is maintained at about 35°C (95 plus 2 minus 3°F)
  • the steel samples were pretreated by heating them for two hours at 570°C in the case of samples (A)1 to 3, (A)5 and (B)1 and for 45 minutes at 660°C in the case of sample (A)4, in an atmosphere of 50% ammonia and 50% endothermic gas followed by slow cooling under a protective atmosphere of the same composition.
  • the resultant steel samples had an epsilon iron nitride surface layer of a thickness of 16-20 pm.
  • the resultant yoke body had a salt-spray resistance of more than 400 hours as measured according to the above-described Salt-Spray Test.
  • the epsilon iron nitride layer itself has an inherent resistance to corrosion by humidity and this property is particularly useful in cases where the organic coating becomes chipped in service or where it is desired to leave part of the surface of the epsilon iron nitride layer uncoated with the organic layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (7)

1. Verfahren zum Überziehen eines unlegierten Stahlsubstrats, das die Schritte der Durchführung eines Vorbehandlungsvorganges auf dem Substrat, der eine Wärmebehandlung des Substrats zur Erzeugung einer Epsiloneisennitrid-Oberflächenschicht darauf einschließt, und des nachfolgenden Überziehens des vorbehandelten Substrats mit einer festen organischen Polymerüberzugszusammensetzung vorsieht, dadurch gekennzeichnet, daß nach dem Wärmebehandlungsschritt und vor dem Überzugsschritt das wärmebehandelte Substrat in Öl abgeschreckt, entfettet und dann erhitzt wird, um Feuchtigkeit aus den Mikroporen der Epsiloneisennitrid-Oberflächenschicht zu entfernen.
2. Verfahren nach Anspruch 1, wobei der Wärmebehandlungsschritt durchgeführt wird, indem man das Stahlsubstrat bei einer Temperatur von 550 bis 720°C bis zu 4 Stunden in einer Atmosphäre von Ammoniak, Ammoniak und endothermem Gas, Ammoniak und exothermem Gas oder Ammoniak und Stickstoff, mit dem wahlweisen Zusatz wenigstens eines von Kohlendioxid, Kohlenmonoxid, Luft und Methan erhitzt.
3. Verfahren nach Anspruch 1 oder 2, wobei die Überzugszusammensetzung mittels eines Naßverfahren aufgebracht wird.
4. Verfahren nach Anspruch 1 oder 2, wobei die Überzugszusammensetzung durch Pulverbeschichtung aufgebracht wird.
5. Verfahren nach Anspruch 1 oder 2, wobei der Wärmebehandlungsvorgang so durchgeführt wird, daß eine Oberflächenschicht mit einer Dicke von nicht mehr als etwa 25 11m erzeugt wird.
6. Verfahren nach Anspruch 5, wobei der Wärmebehandlungsvorgang so durchgeführt wird, daß eine Dicke von etwa 15 bis 25 pm erzeugt wird.
7. Verfahren nach Anspruch 5, wobei der Wärmebehandlungsvorgang so durchgeführt wird, daß eine Dicke von etwa 25 µm erzeugt wird.
EP82304451A 1981-09-05 1982-08-24 Überzogenes metallisches Substrat und Verfahren zum Überziehen dieses Substrates Expired EP0074211B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8126928 1981-09-05
GB8126928 1981-09-05

Publications (2)

Publication Number Publication Date
EP0074211A1 EP0074211A1 (de) 1983-03-16
EP0074211B1 true EP0074211B1 (de) 1987-11-04

Family

ID=10524340

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82304451A Expired EP0074211B1 (de) 1981-09-05 1982-08-24 Überzogenes metallisches Substrat und Verfahren zum Überziehen dieses Substrates

Country Status (14)

Country Link
EP (1) EP0074211B1 (de)
JP (1) JPS5852474A (de)
AR (1) AR228794A1 (de)
AU (1) AU552307B2 (de)
BR (1) BR8205184A (de)
DE (1) DE3277585D1 (de)
ES (1) ES8307909A1 (de)
HU (1) HU186571B (de)
IN (1) IN159201B (de)
NZ (1) NZ201811A (de)
PL (1) PL238136A1 (de)
SU (1) SU1364242A3 (de)
YU (1) YU199782A (de)
ZA (1) ZA826202B (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5931864A (ja) * 1982-08-11 1984-02-21 Toyota Motor Corp 潤滑皮膜形成熱処理方法
GB8310102D0 (en) * 1983-04-14 1983-05-18 Lucas Ind Plc Corrosion resistant steel components
US4756774A (en) * 1984-09-04 1988-07-12 Fox Steel Treating Co. Shallow case hardening and corrosion inhibition process
GB8507230D0 (en) * 1985-03-20 1985-04-24 Lucas Ind Plc Thin flat article with hardened surfaces
US5037491A (en) * 1986-02-28 1991-08-06 Fox Patrick L Shallow case hardening and corrosion inhibition process
JPS63161420A (ja) * 1986-12-24 1988-07-05 Taiyo Kogyo:Kk ズ−ム機構に用いるガイドポ−ルの製造方法およびガイドポ−ル
CN100445032C (zh) * 2005-12-26 2008-12-24 张明亮 不锈钢饮用水压力容器内外表面处理工艺
FR3030578B1 (fr) * 2014-12-23 2017-02-10 Hydromecanique & Frottement Procede de traitement superficiel d'une piece en acier par nitruration ou nitrocarburation, oxydation puis impregnation
DE102016103866B3 (de) * 2016-03-03 2017-05-18 Nemak, S.A.B. De C.V. Verfahren zum Wärmebehandeln eines aus einem Metallwerkstoff bestehenden Bauteils mit mindestens einem mit einer Glasur- oder Emaille-Beschichtung beschichteten Flächenabschnitt
WO2019171157A1 (en) * 2018-03-09 2019-09-12 Arcelormittal A manufacturing process of press hardened parts with high productivity

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55129176A (en) * 1979-03-28 1980-10-06 Honda Motor Co Ltd Coating method

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1299308A (en) * 1971-05-01 1972-12-13 Ceskoslovenska Akademie Ved Improvements in or relating to blades for rotary flow machines
FR2428682A1 (fr) * 1978-06-16 1980-01-11 Stephanois Rech Meca Hydr Cent Procede de conditionnement de surface d'une piece metallique et surface obtenue
JPS553863A (en) * 1978-06-27 1980-01-11 Honda Motor Co Ltd Treating method of prime coat by gas softening nitriding
GB2027062B (en) * 1978-07-12 1982-08-25 Honda Motor Co Ltd Continuous process for brazing and nitriding
JPS5840650B2 (ja) * 1978-07-31 1983-09-07 マツダ株式会社 ロ−タリピストンエンジンのサイドハウジング
JPS5842570B2 (ja) * 1978-08-30 1983-09-20 オムロン株式会社 近接スイッチ
JPS5555072A (en) * 1978-10-18 1980-04-22 Honda Motor Co Ltd Preparation of fuel tank
JPS5824193B2 (ja) * 1979-01-30 1983-05-19 本田技研工業株式会社 軟窒化を防錆下地とする塗装前処理法
BR8107846A (pt) * 1980-12-03 1982-09-08 Lucas Industries Ltd Componente metalico de aco

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55129176A (en) * 1979-03-28 1980-10-06 Honda Motor Co Ltd Coating method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Dawes C. et al., Low pressure oxy-nitro-carburising at 570*C, Metallurgia and metal forming, February 1975, pages 58-60 *

Also Published As

Publication number Publication date
ES515496A0 (es) 1983-08-01
BR8205184A (pt) 1983-08-16
SU1364242A3 (ru) 1987-12-30
HU186571B (en) 1985-08-28
AU8796882A (en) 1983-03-17
EP0074211A1 (de) 1983-03-16
AU552307B2 (en) 1986-05-29
IN159201B (de) 1987-04-11
ZA826202B (en) 1983-07-27
NZ201811A (en) 1985-08-16
JPS5852474A (ja) 1983-03-28
ES8307909A1 (es) 1983-08-01
DE3277585D1 (en) 1987-12-10
PL238136A1 (en) 1983-03-28
AR228794A1 (es) 1983-04-15
YU199782A (en) 1985-10-31

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