EP0077703B1 - Revêtement à base de chrome pour acier résistant à l'usure et procédé de préparation - Google Patents

Revêtement à base de chrome pour acier résistant à l'usure et procédé de préparation Download PDF

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Publication number
EP0077703B1
EP0077703B1 EP82401775A EP82401775A EP0077703B1 EP 0077703 B1 EP0077703 B1 EP 0077703B1 EP 82401775 A EP82401775 A EP 82401775A EP 82401775 A EP82401775 A EP 82401775A EP 0077703 B1 EP0077703 B1 EP 0077703B1
Authority
EP
European Patent Office
Prior art keywords
fact
per
chromium
iron
steel
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
EP82401775A
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German (de)
English (en)
French (fr)
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EP0077703A1 (fr
Inventor
Guy Nicolas
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Nicolas Guy
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Nicolas Guy
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Publication date
Application filed by Nicolas Guy filed Critical Nicolas Guy
Publication of EP0077703A1 publication Critical patent/EP0077703A1/fr
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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
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces

Definitions

  • the technical sector of the present invention is that of chromium-based coatings for steel with high resistance to friction wear and of processes using chromium-plating in the vapor phase.
  • French patents 2,018,609 and 2,450,286 describe boronization processes according to which a metal part is subjected to a boriding activator at a temperature between 850 ° C. and 1100 ° C. for a sufficient time. An iron boride layer is thus obtained, which improves the wear resistance of the treated steel.
  • chromium to the surface of the material to be treated is done by means of halides which are the only chromium compounds found in the vapor state at diffusion temperatures.
  • the layer formed by chromization consists of carbides of chrome. These carbides are, in the most superficial part, carbide M 23 C 6 and, in the underlying layers, carbide M 7 C 3 .
  • M designates here a metal which, apart from chromium (Cr), can be iron (Fe), molybdenum (Mo), vanadium (V) etc ...
  • Cr chromium
  • Mo molybdenum
  • V vanadium
  • French patent 2,439,824 proposes a process according to which an ionic nitriding of a steel containing at least 0.2% carbon is first carried out, then a conventional chromization by gas route at a temperature between 850 ° C. and 1100 ° C.
  • Nitriding requires ion bombardment of the sample at a temperature between 450 and 570 ° C at a pressure of 2.5 to 8 millibar. It is specified that such a treatment makes it possible to almost completely eliminate the carbide M 7 C 3 at the origin of the formation of cracks or flaking of the steel. This would form a single surface layer of carbide M 23 C 6 greater than 30pm.
  • the various coatings were carried out on the various coatings and they made it possible to specify, in the case of chromization, the morphology, the composition and the wear resistance capacity of the layers obtained.
  • the said layers may also contain nitrides Cr 2 N when the halogen introduced into the cement is chloride NH 4 CI ammonium.
  • These coatings have a fairly high wear resistance, but the morphology and internal stresses of M 7 C 3 carbide limit their capacity.
  • the nitriding mode ionic or gaseous
  • carbonitrides had no major influence on the nature of the constituent phases of the layers obtained.
  • the predominant criterion turns out to be in fact the initial thickness of the nitride layer.
  • the coatings obtained are divided into two main sub-layers. One, on the surface, consists of the majority phase Cr 2 (C, N) and the carbide M 23 C 6 .
  • the other, underlying, consists, for approximately half of the thickness of the coating, of carbide M 7 C 3 . But this carbide again retains a columnar structure harmful to good wear resistance.
  • the layers obtained by chromizing or nitriding treatment followed by chromizing comprise a sublayer of chromium carbide M 7 C 3 . In its crystallized state, this carbide reduces the wear resistance of the chromized layers.
  • the object of the present invention is to provide a person skilled in the art with a new coating and a process for obtaining this, in which the formation of the carbide M 7 C 3 with its basalt crystallization is avoided.
  • the invention of dune relates to a coating for high tensile steel to wear by friction, characterized in that it comprises at least two surface layers, the first surface consists essentially of the phase (Cr, Fe) 2 B and the other internal mainly constituted by the phase (Fe, Cr) 2 B, Cr, Fe, B, denoting respectively chromium, iron, boron.
  • the (Cr, Fe) 2 B phase may contain another phase, of the M 23 C 6 type in which M mainly represents the chromium optionally substituted by iron, vanadium, molybdenum, nickel, manganese.
  • the thickness of the first layer can be at least 12 ⁇ m and the thickness of the second at least 18 ⁇ m.
  • This coating is preferably applied to a steel whose carbon content is at least 0.15%, by mass.
  • the invention also relates to a method for obtaining a coating on a steel, characterized in that in a first step, a boronization of the steel in the austenitic state is carried out at a temperature lower than or substantially equal to 950 ° C. for a time greater than or substantially equal to 4 hours and in that in a second step chromization is carried out at a temperature less than or substantially equal to 980 ° C. for a time greater than or substantially equal to 10 hours, steps possibly followed by a heat treatment of quenching and tempering.
  • Boronization can be carried out in the presence of a borating agent of the B 4 C + Na 2 B 4 07 type in a vinyl binder in order to produce a layer of iron borides FeB and Fe 2 B at least 30 ⁇ m thick.
  • the layer of iron borides has a thickness close to 40 ⁇ m.
  • the chromization can be carried out in the vapor phase in the presence of a cement comprising an iron-chromium powder 60-40, an anti-sintering agent (AI 2 0 3 ) a transporter (NH 4 CI) and a hydrogen flow rate of approximately 300 liters per hour.
  • a cement comprising an iron-chromium powder 60-40, an anti-sintering agent (AI 2 0 3 ) a transporter (NH 4 CI) and a hydrogen flow rate of approximately 300 liters per hour.
  • the boriding is carried out at 950 ° C for 4 hours and the chromization at 950 ° C for 15 hours.
  • the method according to the invention is applied to a low alloy steel of the 35 C D4 type.
  • the main advantage of the invention is to avoid for the first time the formation of the carbide M 7 C 3 both in the surface layer and in the deeper layers.
  • Another advantage lies in the fact that the invention makes it possible to provide coatings containing on the surface a phase notably containing chromium boride, which has never been obtained before.
  • those skilled in the art have for the first time a coating containing chromium boride, the tribological properties of which are also known, without significantly modifying the chromization treatment.
  • the method according to the invention can be applied to all types of steel regardless of their carbon content.
  • a boriding treatment is first carried out. This treatment, regardless of the technique used (powder carburizing, salt baths, EKABOR, slury coating, ionic, etc.), must result in a compact layer of iron boride of at least 15 ⁇ m.
  • the barrier layer which, during chromization, will make it possible to build up sublayers based on chromium boride Cr 2 B and iron boride enriched in chromium (Fe, Cr) 2 B.
  • the initial iron boride layer more or less limits the flow of carbon which can, after having migrated through it, combine with the chromium deposited during chromization. Together with the boride Cr 2 B, only the carbide M 23 C 6 can then be formed; but this provided that the initial layer of iron boride has a sufficient thickness.
  • thermochemical treatments After thermochemical treatments, the necessary thermal treatments can be carried out: the acquisition of the internal characteristics of the substrate. In this respect, it is preferable to carry out a new austenitization after chromization, avoiding if possible the water quenching.
  • the treatment process is carried out conventionally, but under the above conditions, by "slury-coating" in the presence of BçC + Na 2 B 4 0 7 in a vinyl binder.
  • the three samples include a compact layer of FeB and Fe 2 B iron borides with respective thicknesses of 4, 15 and 40 ⁇ m.
  • the steel substrates are austenitized at 850 ° C, quenched in oil and returned to 250 ° C for 2 h.
  • the iron boride layer was consumed and gave rise to the formation of a chromium carbide coating M 23 C 6 and M 7 C 3 without particularly appreciable improvement in the state of crystallization of the latter carbide.
  • the carbide layer M 7 C 3 has almost disappeared. Its thickness is less than 1 ⁇ m.
  • the M 23 C 6 carbide in the form of an independent sublayer remains. But it appears here the chromium boride Cr 2 B with enrichment in chromium of the iron boride Fe 2 B.
  • the coating system is completely different.
  • the initial thickness of iron boride no longer lets the carbon reach the surface with a sufficient content compared to the transport kinetics of chromium. And therefore, the formation of the carbide layer M 7 C 3 is retracted, the diffusion path in the system Fe, Cr, B, C at the isotherm T of chromization being then modified.
  • the layer over a thickness of about 16 ⁇ m, consists of the Cr 2 B and Cr 23 C a phases in which iron is substituted (Fe ⁇ 18%). Underlying this layer is the iron boride enriched in chromium by diffusion (Fe, Cr) 2 B.
  • the morphology of the layers is typically that of the M 23 C 6 phase.
  • crystals of chromium carbonitride Cr 2 (C, N) are very rare in the case of borochromization.
  • the coating of sample 1 consists of two sub-layers M 23 C 6 and M 7 C 3 with the same appearance as the chromized layers.
  • the coating of sample 2 is composed of three sublayers M 23 C 6 , M 7 C 3 and (Cr, Fe) 2 B before finding the general morphology of the layer of iron boride which does not was not completely consumed during the exchanges.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
EP82401775A 1981-10-06 1982-09-30 Revêtement à base de chrome pour acier résistant à l'usure et procédé de préparation Expired EP0077703B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8118779 1981-10-06
FR8118779A FR2514032A1 (fr) 1981-10-06 1981-10-06 Revetement a base de chrome pour acier resistant a l'usure et procede de preparation

Publications (2)

Publication Number Publication Date
EP0077703A1 EP0077703A1 (fr) 1983-04-27
EP0077703B1 true EP0077703B1 (fr) 1986-01-15

Family

ID=9262783

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82401775A Expired EP0077703B1 (fr) 1981-10-06 1982-09-30 Revêtement à base de chrome pour acier résistant à l'usure et procédé de préparation

Country Status (4)

Country Link
US (1) US4469532A (enExample)
EP (1) EP0077703B1 (enExample)
DE (1) DE3268575D1 (enExample)
FR (1) FR2514032A1 (enExample)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4485148A (en) * 1983-07-08 1984-11-27 United Technologies Corporation Chromium boron surfaced nickel-iron base alloys
AU3391184A (en) * 1983-08-15 1985-03-12 Clark, Eugene V. Turbine components having increased life cycle and method
US6007922A (en) * 1984-09-18 1999-12-28 Union Carbide Coatings Service Corporation Chromium boride coatings
US5595601A (en) * 1990-09-14 1997-01-21 Valmet Corporation Coating bar for a bar coater
DE19834394A1 (de) * 1998-07-30 2000-02-03 Rheinmetall W & M Gmbh Waffenrohr mit einer verschleißmindernden Hartchromschicht
DE19919688A1 (de) * 1999-04-30 2000-11-02 Rheinmetall W & M Gmbh Verfahren zur Innenbeschichtung eines Waffenrohres
US6197125B1 (en) * 1999-12-13 2001-03-06 Mcdermott Technology, Inc. Modification of diffusion coating grain structure by nitriding
US6602550B1 (en) 2001-09-26 2003-08-05 Arapahoe Holdings, Llc Method for localized surface treatment of metal component by diffusion alloying
DE10328450A1 (de) * 2003-06-25 2005-01-20 Rheinmetall W & M Gmbh Verfahren zur Beseitigung von Beschichtungs- und/oder Erosionsschäden
DE102013221403A1 (de) * 2013-10-22 2015-04-23 Robert Bosch Gmbh Verfahren zur Herstellung eines lokal borierten oder chromierten Bauteils
CN110722846A (zh) * 2019-09-03 2020-01-24 仙居县精鑫金属材料股份有限公司 一种改良型耐磨精密钢带及生产工艺

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622402A (en) * 1969-02-04 1971-11-23 Avco Corp Erosion-corrosion resistant coating
US3712798A (en) * 1970-01-06 1973-01-23 Surface Technology Corp Chromium boride coated articles
SU523962A1 (ru) * 1974-12-23 1976-08-05 Одесский ордена Трудового Красного Знамени политехнический институт Способ комплексной химико-термической обработки стали
SU637460A1 (ru) * 1976-05-04 1978-12-18 Одесский ордена Трудового Красного Знамени политехнический институт Способ диффузионного борохромировани
SU863709A1 (ru) * 1978-11-10 1981-09-15 Белорусский Ордена Трудового Красного Знамени Политехнический Институт Состав дл борохромировани стальных деталей
JPS55138076A (en) * 1979-11-02 1980-10-28 Teritsuku Corp Method and apparatus for generating glow discharge

Also Published As

Publication number Publication date
DE3268575D1 (en) 1986-02-27
FR2514032B1 (enExample) 1984-01-06
US4469532A (en) 1984-09-04
EP0077703A1 (fr) 1983-04-27
FR2514032A1 (fr) 1983-04-08

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