EP0716154B1 - Utilisation d'un alliage en aluminium et titane et matériau de revêtemens pour telle utilisation - Google Patents

Utilisation d'un alliage en aluminium et titane et matériau de revêtemens pour telle utilisation Download PDF

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Publication number
EP0716154B1
EP0716154B1 EP95118740A EP95118740A EP0716154B1 EP 0716154 B1 EP0716154 B1 EP 0716154B1 EP 95118740 A EP95118740 A EP 95118740A EP 95118740 A EP95118740 A EP 95118740A EP 0716154 B1 EP0716154 B1 EP 0716154B1
Authority
EP
European Patent Office
Prior art keywords
atom
titanium
coating material
alloy
aluminium
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
EP95118740A
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German (de)
English (en)
Other versions
EP0716154A2 (fr
EP0716154A3 (fr
Inventor
Michael Dr.-Ing. Schütze
Michael Dipl.-Ing. Schulte
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.)
DECHEMA GESELLSCHAFT FUER CHEMISCHE TECHNIK UND BI
Original Assignee
Dechema Deutsche Gesellschaft fur Chemisches Apparatewesen Chemische Technik und Biotechnologie Ev
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium

Definitions

  • the invention relates to the use of an alloy made of aluminum and titanium with an alloy content Aluminum from 22 to 56 atom%.
  • the invention further relates to a coating material for such use.
  • a high-temperature-resistant, corrosion-resistant alloy of aluminum and titanium is described in DE-A-42 15 017 as a material for, for example, turbine blades.
  • the material When used at high temperatures up to 900 ° C, the material should become resistant to oxidation and corrosion by forming a slowly growing Al 2 O 3 layer instead of a rapidly growing TiO 2 layer.
  • EP-A-04 95 454 also describes a material made of aluminum and titanium, in which a protective layer made of Al 2 O 3 is intended to prevent corrosion of the material.
  • the proposed aluminum-titanium alloy is intended as a material for engine parts, in particular valves and piston pins.
  • atmospheres that the materials used so far are not able to withstand sufficiently.
  • Such atmospheres are characterized by low oxygen partial pressures, for example in the range from 1x10 -34 to 1x10 -27 bar and, for example, H 2 S contents of up to 1% by volume and higher (Ullmann's Encyclopedia of Industrial Chemistry, Volumes A12, p. 169 - 306 and A18, pp. 52 - 99, VCH Verlag, Weinheim 1989 and 1991).
  • processes in which such atmospheres are present are the distillation and gasification of tar and heavy oil residues, the gasification of coal and the gasification of (special) waste (B. Glaser, M.
  • intermetallic titanium aluminide materials offer themselves as materials for use due to their properties lying between the metallic and the ceramic materials these conditions without exhibiting the toughness problems mentioned.
  • the object underlying the invention was an advantageous use of an alloy of aluminum and find Titan. Furthermore, a coating material discovered for such use become.
  • the first-mentioned object is achieved according to the invention by using an alloy of aluminum and titanium with an alloy content of aluminum of 22-56 atom% as a high-temperature-resistant, corrosion-resistant coating material for an unalloyed or low-alloy steel for protection against corrosion in plants with process gases, which are reducing Atmospheres have an oxygen partial pressure in the range of 1x10 -34 bar to 1x10 -26 bar and have a sulfiding effect due to their content of sulfur-containing compounds.
  • the coating material according to the invention stands out characterized in that the alloy with appropriate reduction titanium content up to 7 atomic% niobium or up to 3 atom% chromium or up to 2 atom% silicon or up to 7 atomic% tungsten or up to 7 atomic% molybdenum contains.
  • Such a material has a high resistance to corrosion attack both under isothermal and under thermal cycling.
  • the basic idea of the invention is that a material is only stable in a corrosive environment at high temperatures if, when reacting with the surrounding atmosphere, very thin, dense and extremely slow-growing corrosion product layers are formed, which act as a barrier between the external environment and develop the metal. With the materials previously used in technology in the environments mentioned, this is not the case at temperatures above 400 ° C. and generally also at temperatures below it, since rapidly growing sulfides of the elements Fe, Cr, Ni or mixed sulfides result from these Form elements, cf. S. Mrowec, K. Przybylski: High Temp. Mat.
  • Plasma spraying methods are available for the coating on. Because the coefficient of thermal expansion the titanium aluminide and the unalloyed and low-alloyed heat-resistant steels are very close together, see J.H. Schneibel et al .: Materials Science and Engineering, A152 (1992), 126-131, and TAPP, A Database of Thermochemical and Physical Properties, ES Microware, Inc .; OH (USA), In 1991, this combination of materials offered itself as a layered composite for high temperature applications, because when cooling no critical mechanical from the operating temperature Stresses induced in the layer / substrate composite that in other cases (e.g. ceramic coatings) led to flaking of the coating to have. Furthermore, one follows from these aspects particularly good resistance to temperature changes during operation.
  • an alloy with 51 atom% aluminum and 49 atom% titanium is exposed to a sulfidating gas atmosphere with 1 vol.% Hydrogen sulfide in a carrier gas made of argon and with 5 vol.% Hydrogen.
  • the reactor is electrically heated by a tube furnace surrounding it.
  • T 700 ° C
  • the equilibrium partial pressure of the sulfur in the reaction gas due to the dissociation reaction of the hydrogen sulfide is 1x10 -6 bar, while the oxygen partial pressure is below 1x10 -26 bar.
  • the alloy has conditions under which commercially used, high-alloy steels massively damaged be, up to three orders of magnitude reduced rate of corrosion.
  • Titanium-aluminum alloys of different compositions a gas atmosphere containing hydrogen sulfide exposed at elevated temperature.
  • Example 2 In addition to the alloy mentioned in Example 1 with 51 atom% Aluminum becomes samples with 50 or 46 atom% aluminum as well as 0.8 - 2 atom% niobium, 0 - 1.4 atom% chromium and 0.1 - 0.2 atom% silicon tested.
  • thermocyclic test with rapid cooling processes is carried out with the help of movable half-shells that open and close under computer control.
  • T 500 ° C
  • the reaction gas is cooled to 350 ° C in 24-hour cycle intervals and then reheated. This procedure is continued for a total of 504 hours.
  • the area-specific mass changes of the titanium-aluminum alloys are 0.03 - 0.04 mg / cm 2 .
  • the values are between 21 mg / cm 2 (St37, material no. 1.0212) and 10 mg / cm 2 (X10CrNiTi18 9, material no. 1.4541).
  • Metallographic follow-up examinations of the samples taken from commercially available heat exchanger tubes show that under the reaction conditions, sulfidic cover layers have formed which have been detached from the substrate several times as a result of the temperature changes and thus have lost any diffusion barrier effect. No external corrosion products can be found on the surfaces of the titanium-aluminum alloys in the scanning electron microscope, even with a magnification factor of 4500.
  • the tested alloys based on titanium and aluminum thus also exhibit in a sulfidating gas atmosphere excellent under thermal cycling Corrosion resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (6)

  1. Utilisation d'un alliage d'aluminium et de titane, l'alliage ayant une teneur en aluminium de 22 à 56 % en atomes, en tant que matériau de revêtement anti-corrosion et résistant aux hautes températures pour un acier non allié ou faiblement allié destiné à la protection, contre la corrosion, d'installations contenant des gaz de procédé, qui en tant qu'atmosphères réductrice présentent une pression partielle d'oxygène comprise entre 1x10-34 bar et 1x10-26 bar, et qui, du fait de leur teneur en composés sulfurés, ont une action de sulfatation.
  2. Utilisation selon la revendication 1, caractérisée en ce que les gaz de procédé ont une teneur en H2S de 1 % en volume, et chauffent le matériau de revêtement jusqu'à 700°C.
  3. Matériau de revêtement pour l'utilisation selon les revendications 1 ou 2, qui contient du titane et de 22 à 56 % en atomes aluminium, caractérisé en ce que l'alliage, avec une réduction correspondante de la teneur en titane, contient jusqu'à 7 % en atome de niobium.
  4. Matériau de revêtement pour l'utilisation selon les revendications 1 ou 2, qui content du titane et de 22 à 56 % en atomes aluminium, caractérisé en ce que l'alliage, avec une réduction correspondante de la teneur en titane, contient jusqu'à 3 % en atome de chrome.
  5. Matériau de revêtement pour l'utilisation selon les revendications 1 ou 2, qui contient du titane et de 22 à 56 % en atomes aluminium, caractérisé en ce que l'alliage, avec une réduction correspondante de la teneur en titane, contient jusqu'à 2 % en atome de silicium.
  6. Matériau de revêtement pour l'utilisation selon les revendications 1 ou 2, qui contient du titane et de 22 à 56 % en atomes aluminium, caractérisé en ce que l'alliage, avec une réduction correspondante de la teneur en titane, contient jusqu'à 7 % en atome de molybdène.
EP95118740A 1994-12-05 1995-11-29 Utilisation d'un alliage en aluminium et titane et matériau de revêtemens pour telle utilisation Expired - Lifetime EP0716154B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4443147A DE4443147A1 (de) 1994-12-05 1994-12-05 Korrosionsbeständiger Werkstoff für Hochtemperaturanwendungen in sulfidierenden Prozeßgasen
DE4443147 1994-12-05

Publications (3)

Publication Number Publication Date
EP0716154A2 EP0716154A2 (fr) 1996-06-12
EP0716154A3 EP0716154A3 (fr) 1996-10-16
EP0716154B1 true EP0716154B1 (fr) 2000-01-19

Family

ID=6534891

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95118740A Expired - Lifetime EP0716154B1 (fr) 1994-12-05 1995-11-29 Utilisation d'un alliage en aluminium et titane et matériau de revêtemens pour telle utilisation

Country Status (3)

Country Link
EP (1) EP0716154B1 (fr)
JP (1) JPH08218138A (fr)
DE (2) DE4443147A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19748874C2 (de) * 1996-11-09 2000-03-23 Max Planck Inst Eisenforschung Verwendung einer TiAl-Legierung
EP0906967B1 (fr) * 1997-10-01 2003-11-12 DECHEMA Gesellschaft für Chemische Technik und Biotechnologie e.V. Emploi d'un alliage d'aluminium et de titane
DE10151716A1 (de) * 2001-10-19 2003-05-08 Bayerische Motoren Werke Ag Legierungspulver zur Beschichtung insbesondere des Ventilsitzbereiches eines Zylinderkopfes einer Brennkraftmaschine sowie Beschichtungsverfahren
KR100887315B1 (ko) * 2006-03-29 2009-03-06 이인환 근관치료용 합금
DE102007060587B4 (de) * 2007-12-13 2013-01-31 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH Titanaluminidlegierungen

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4879092A (en) * 1988-06-03 1989-11-07 General Electric Company Titanium aluminum alloys modified by chromium and niobium and method of preparation
US5304344A (en) * 1989-06-02 1994-04-19 General Electric Company Gamma titanium aluminum alloys modified by chromium and tungsten and method of preparation
JP2678083B2 (ja) * 1990-08-28 1997-11-17 日産自動車株式会社 Ｔｉ―Ａｌ系軽量耐熱材料
JPH0543958A (ja) * 1991-01-17 1993-02-23 Sumitomo Light Metal Ind Ltd 耐酸化性チタニウムアルミナイドの製造方法
US5149497A (en) * 1991-06-12 1992-09-22 General Electric Company Oxidation resistant coatings of gamma titanium aluminum alloys modified by chromium and tantalum
US5264051A (en) * 1991-12-02 1993-11-23 General Electric Company Cast gamma titanium aluminum alloys modified by chromium, niobium, and silicon, and method of preparation
DE4215017C2 (de) * 1992-05-12 2000-01-13 Forschungszentrum Juelich Gmbh Verfahren zur Herstellung einer Komponente auf der Basis intermetallischer Phasen des Systems Titan-Aluminium

Also Published As

Publication number Publication date
EP0716154A2 (fr) 1996-06-12
JPH08218138A (ja) 1996-08-27
EP0716154A3 (fr) 1996-10-16
DE59507645D1 (de) 2000-02-24
DE4443147A1 (de) 1996-06-27

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