US3765953A - Niobium-based oxidation resistant materials and process for their preparation - Google Patents

Niobium-based oxidation resistant materials and process for their preparation Download PDF

Info

Publication number
US3765953A
US3765953A US00169932A US3765953DA US3765953A US 3765953 A US3765953 A US 3765953A US 00169932 A US00169932 A US 00169932A US 3765953D A US3765953D A US 3765953DA US 3765953 A US3765953 A US 3765953A
Authority
US
United States
Prior art keywords
niobium
type
oxidation
layer
based alloy
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
US00169932A
Other languages
English (en)
Inventor
J Chevillon
G Gauje
J Grammagnac
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.)
Safran Aircraft Engines SAS
Original Assignee
Societe Nationale dEtude et de Construction de Moteurs dAviation SNECMA
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 Societe Nationale dEtude et de Construction de Moteurs dAviation SNECMA filed Critical Societe Nationale dEtude et de Construction de Moteurs dAviation SNECMA
Application granted granted Critical
Publication of US3765953A publication Critical patent/US3765953A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • 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
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C23C8/06—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 using gases
    • C23C8/08—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 using gases only one element being applied
    • C23C8/10—Oxidising

Definitions

  • SHEET 2 BF 3 IAcK RENE PAUL. CuawLLoN, Ciemzces WumcaCELEs-vm ALOlS GAuIE. IAc ues Leopow EMILE GRAMMAGNAC e7 ma m -wuiak% amma NlOBIUM-BASED OXIDATION RESISTANT MATERIALS AND PROCESS FOR THEIR PREPARATION
  • the present invention concerns a procedure for improving the hot oxidation resistance of niobium and niobium based alloys.
  • niobium and niobium-based alloys pose considerable problems as regards the possibility of effective protection against oxidation of the work-pieces or their surfaces produced using these materials. Attempts have been made in practice to resolve these problems by depositing on the surface materials, metals, mixtures of metals, or metallic alloys or compounds which can be made to adhere to the underlying material by heating in vacuum or in a neutral or reactive atmosphere at a high temperature. These metals or alloys form a thin protective layer which to some degree ensures protection of the underlying material against the oxidation which can develop after utilisation of the pieces at high temperature.
  • the metallic oxides of niobium of the B-Nb O type are thermally stable and the transformation a B is irreversible; certain complex oxides of niobium of B-(Nb, M M
  • M M0 0 type form a protective barrier effective at high or low temperature against oxygen
  • the metallic oxides of niobium of the B-(Nb, M M M M,,) O type can be prepared by oxidising the superficial protective coating without dislodging it as long as one operates in conditions where the oxides formed, in particular the oxides of a-(Nb, M M M M0 0 type transform into oxides of the B-(Nb, M M M M0 0 type to the same extent as they are formed.
  • This oxidation of the superficial layer should be effected without oxidation of niobium or of the alloy of niobium which is situated below this layer; this result can be obtained by effecting the oxidation reaction in conditions such that the speed of transformation of metallic oxides of the a-(Nb, M M M M0 0 type into metallic oxides of the B-(Nb, M M M M,,) O, type is at least equal the speed of formation of the metallic oxides of the a-(Nb, M M M M O type.
  • the protection surface is oxidised without penetration of oxygen into the niobium or niobium alloy beneath.
  • the invention thus concerns a procedure for preparation of pieces of new material, as defined above, characterised in that the said pieces, previously treated according to known processes for formation of superficial metallic protective layers, are subjected to an oxidation reaction under operating conditions in which the speed of formation of the metallic oxides of B-(Nb, M M Mhd 3, M0 0 type from the metallic oxides of a-(Nb, M M M M,,) O type is greater than the speed of formation of the metallic oxides of a-( Nb, M M M M0 0 type.
  • This oxidation reaction should be effected while maintaining the material, coated with a metallic layer which is in itself known, in air at atmospheric pressure at a temperature between 700 and l,200C for a time exceeding 50 h and, preferably, for 50-300 h according to the composition of the layer.
  • the treatment is conducted in still air, at a temperature between 700 and 900C.
  • Niobium pentoxide Nb O can occur in two different crystalline forms; one orthorhombic form, a, and one monoclinic, B.
  • a thin layer of metal alloys is deposited on the surface of the niobium or the niobium alloy to be protected.
  • niobium a paint containing nickel, titanium, chromium, and aluminium is deposited on the surface of the niobium.
  • a chemical reaction between these metals and the underlying niobium with formation of chemical compounds containing niobium.
  • alloyed niobium aluminide will be formed.
  • this superficial layer is subjected to oxidation, the atoms of niobium will oxidise as welll as the other metallic atoms, leading to the formation of various oxides.
  • the protective layer ofB type (Nb, M M M M0 0 oxides is obtained by depositing on the surface of the piece made of niobium or niobium alloys 2. powder comprising at least three of the following elements, Si, Al, Cr, Fe, Ti, Ni and Co, and subjecting the piece thus coated to a controlled oxidation in the conditions given above.
  • the powder contains, according to one characteristic of the invention, silicon or aluminium, the silicon or aluminium being always associated with niobium and chromium, the fourth constituent being chosen among the remaining metals of the list given above, i. e., iron, titanium, nickel and cobalt.
  • the preferred powders are those comprising:
  • FIGS. 1 and 2 relate to modes of heating of the pieces during the tests carried out (the ordinate gives temperature, the abscissa gives time).
  • FIGS. 3, 4 and 5 show the comparative speed of oxidation of samples, treated according to the invention, or untreated;
  • FIG. 3 gives the results obtained with isothermal heating;
  • FIGS. 4 and 5 the results obtained with cyclic heating.
  • the ordinate gives the variation of weight of the sample and the abscissa gives the time.
  • thermal cycles these thermal cycles are of two types: type A, in which the samples are kept during considerable times at high temperature, or type C in which the samples are not kept for a long time at a high constant temperature.
  • the type A cycle consists in keeping the sample isothermally for a longer or shorter time at the maximum test temperature, which is usually between 1,000C and 1,400C, with the heating to temperature and the cooling to ambient temperature effected rapidly enough, that is in a time between several seconds and several minutes.
  • FIG. 1 shows schematically two cycles of this type, a cycle A of 90 minutes duration and a cycle A of 24 hours duration.
  • the type C cycle is as follows: a slow rise to the test temperature, holding for a short time and rapid cooling.
  • FIG. 2 shows schematically a type C cycle of 4 hours duration, where the rate of temperature rise is 300C per hour approximately.
  • life times are compared of an ordinary sample of niobium, obtained with the two types of test, it is observed that for a same maximum test temperature, fixed in this case at 1,100C, and in spite of a holding time equal to percent of the test duration with cycle A, of minutes duration against only 2 to 3 for cycle C, of 4 hours duration, that is about 30 times shorter duration, the life time is however divided by a factor of the order of 10 to 20 when one passes from cycle A to cycle C.
  • FIG. 3 shows the difference between the speed of oxidation at a constant temperature of 700C between Sample 1, which had not undergone the previous treatment according to the invention, and Sample 2, which had undergone a previous treatment of hours at 900C. These two samples were protected by a mixture of powder based on silicon-chromium-iron of about 0.15 mm thickness. This example is to show the improvement obtained during prolonged maintenance in the dangerous temperature zone.
  • FIG. 4 shows the gain in weight of two samples during an oxidation test according to a cycle of type C with a maximum temperature of 1,100C.
  • the 2 samples had simultaneously received the same protection by a mixture of powders based on Si-Cr-Fe, but sample number I was tested as it was, while sample number 2 was additionally subjected to a controlled thermal oxidation and aging treatment of 200 hours at 900C.
  • Final failure characterised by a considerable fall in weight, is shown around 80 hours for sample number 1 and at 875 hours for sample number 2, which represents an improvement factor of the order of 10.
  • the first non treated sample had a life time of hours
  • the second sample having received a previous controlled thermal oxidation and ageing treatment according to the invention of 240 hours at 900C in air, at atmospheric pressure, had a life time of 300 hours.
  • FIG. 5 permits examination of the gains in weight obtained in oxidation tests following a type A cycle at 800C with durations of 24 hours.
  • the weight gain was obtained by weighing after each period.
  • the samples of niobium alloy were protected by a coating of 0.03 mm comprising chromium, titanium, and aluminium deposited in the vapour phase.
  • Sample number 1 was untreated, but sample number 2 had undergone a controlled thermal oxidation and aging treatment of 264 hours at 700C. A spectacular difference is seen between the two tests, sample number 1 being rapidly destroyed and sample number 2 being still intact at the end of 792 hours of testing.
  • EXAMPLE 5 This example is given to show the importance of not exceeding 900C, this temperature constituting the approximate limit above which the oxidation rate of niobium and the elements associated with it into a a-type Nb O become prohibitive for the control of the process.
  • test pieces Two sets of test pieces were coated using a powder of Si, Cr, Fe. In each set the test pieces were either subject to a preliminary oxidation at atmospheric pressure in still air, or were not subject to the said oxidation.
  • the life time according to cycle C is shown in Table I below.
  • Niobium or a niobium-based alloy having a protective coating formed of mixed metalic oxides of the B-(Nb, Me) O type, wherein Me includes a metal having a major amount of aluminum or silicon alloyed with chromium and at least one other metal taken from the group consisting essentially of iron, titanium, nickel, cobalt, or mixtures thereof.
  • Niobium or a niobium-based alloy according to claim 2 are 50 parts aluminum and/or silicon to 1 part each of chromium, iron, nickel, titanium and/or cobalt.
  • Niobium or a niobium-based alloy according to claim 1 wherein the protective coating composition is taken from the group comprising the following combination of metals:
  • Process for the manufacture of niobium or a niobium-based alloy comprising the steps of forming a protective coating of the (Nb, Me) O type wherein Me includes a metal having a major amount of aluminum or silicon alloyed with chromium and at least one other metal taken from the group consisting essentially of iron, titanium, nickel, cobalt, or mixtures thereof, heating and oxidizing said (Nb, Me),O layer at 700 to 1,200C for a time sufficient to convert a major portion of said layer to the B-oxide form.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Powder Metallurgy (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
US00169932A 1970-08-12 1971-08-09 Niobium-based oxidation resistant materials and process for their preparation Expired - Lifetime US3765953A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR7029740A FR2102632A5 (OSRAM) 1970-08-12 1970-08-12

Publications (1)

Publication Number Publication Date
US3765953A true US3765953A (en) 1973-10-16

Family

ID=9060136

Family Applications (1)

Application Number Title Priority Date Filing Date
US00169932A Expired - Lifetime US3765953A (en) 1970-08-12 1971-08-09 Niobium-based oxidation resistant materials and process for their preparation

Country Status (3)

Country Link
US (1) US3765953A (OSRAM)
FR (1) FR2102632A5 (OSRAM)
GB (1) GB1365377A (OSRAM)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931447A (en) * 1973-05-04 1976-01-06 The United States Of America As Represented By The United States National Aeronautics And Space Administration Fused silicide coatings containing discrete particles for protecting niobium alloys
EP0196093A1 (en) * 1985-03-27 1986-10-01 Liu Yu Zhong A process for treating an article made of metal selectec from tantalum, niobium and tantalum-niobium alloy
US5100486A (en) * 1989-04-14 1992-03-31 The United States Of America As Represented By The United States Department Of Energy Method of coating metal surfaces to form protective metal coating thereon
US5804499A (en) * 1996-05-03 1998-09-08 Siemens Aktiengesellschaft Prevention of abnormal WSix oxidation by in-situ amorphous silicon deposition
US6303075B1 (en) * 1999-11-12 2001-10-16 Agency Of Industrial Science And Technology High temperature oxidation resistant alloy materials and method of producing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3057048A (en) * 1958-11-06 1962-10-09 Horizons Inc Protection of niobium
US3078554A (en) * 1960-06-08 1963-02-26 Gen Electric Columbium base alloy article
US3102044A (en) * 1960-09-12 1963-08-27 United Aircraft Corp Applying protective coating from powdered material utilizing high temperature and low pressure
US3219474A (en) * 1962-05-11 1965-11-23 Priceman Seymour Protective coatings for columbium and its alloys

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3057048A (en) * 1958-11-06 1962-10-09 Horizons Inc Protection of niobium
US3078554A (en) * 1960-06-08 1963-02-26 Gen Electric Columbium base alloy article
US3102044A (en) * 1960-09-12 1963-08-27 United Aircraft Corp Applying protective coating from powdered material utilizing high temperature and low pressure
US3219474A (en) * 1962-05-11 1965-11-23 Priceman Seymour Protective coatings for columbium and its alloys

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931447A (en) * 1973-05-04 1976-01-06 The United States Of America As Represented By The United States National Aeronautics And Space Administration Fused silicide coatings containing discrete particles for protecting niobium alloys
EP0196093A1 (en) * 1985-03-27 1986-10-01 Liu Yu Zhong A process for treating an article made of metal selectec from tantalum, niobium and tantalum-niobium alloy
US5100486A (en) * 1989-04-14 1992-03-31 The United States Of America As Represented By The United States Department Of Energy Method of coating metal surfaces to form protective metal coating thereon
US5804499A (en) * 1996-05-03 1998-09-08 Siemens Aktiengesellschaft Prevention of abnormal WSix oxidation by in-situ amorphous silicon deposition
US6303075B1 (en) * 1999-11-12 2001-10-16 Agency Of Industrial Science And Technology High temperature oxidation resistant alloy materials and method of producing the same

Also Published As

Publication number Publication date
FR2102632A5 (OSRAM) 1972-04-07
GB1365377A (en) 1974-09-04

Similar Documents

Publication Publication Date Title
DE2020697C3 (de) Verfahren zum Herstellen eines titanhaltigen Trägers mit einer Beschichtung
DE2327250A1 (de) Verfahren zur herstellung eines metallurgisch abgedichteten ueberzugs
US3547673A (en) Method of forming cermet-type protective coatings on heat resistant alloys
US3741791A (en) Slurry coating superalloys with fecraiy coatings
US5288345A (en) Method for treating sintered alloy
US2771666A (en) Refractory bodies
US3078554A (en) Columbium base alloy article
US3765953A (en) Niobium-based oxidation resistant materials and process for their preparation
US3620693A (en) Ductile, high-temperature oxidation-resistant composites and processes for producing same
DE3742944C1 (de) Oxidationsschutzschicht
US4969960A (en) Method for increasing the resistance to thermal shocks in heating conductor materials
US2857297A (en) Process of coating molybdenum
US3055088A (en) Composite metal body for high temperature use
DE1925482C3 (de) Verfahren zur Diffusionsbeschichtung einer Oberfläche eines Metallgegenstandes
US3216806A (en) Oxidation resistant coatings on niobium
GB2127040A (en) Internal oxidation of ag alloys
US6340398B1 (en) Oxidation protective coating for Mo-Si-B alloys
US3761301A (en) Processes for producing ductile high temperature oxidation resistant composites
US3446655A (en) Method of producing refractory metal articles
DE3842301A1 (de) Hochtemperatur-schutzschicht
US4119761A (en) Heat radiation anode
US3574572A (en) Coatings for high-temperature alloys
US3573996A (en) Silicide coatings for refractory metals
US3753763A (en) Coatings for columbium and columbium base alloys
Reznik Coatings for columbium and columbium base alloys