Stock material or miscellaneous articles – Composite – Of metal
Reexamination Certificate
1998-10-26
2001-04-10
Jones, Deborah (Department: 1775)
Stock material or miscellaneous articles
Composite
Of metal
C428S472000, C428S701000, C428S702000, C428S937000
Reexamination Certificate
active
06214474
ABSTRACT:
The invention concerns a body, of a high-melting metal base such as chromium, molybdenum, tungsten, tantalum, niobium, and their alloys or composite materials and an oxidation protective layer of silicides or aluminides.
High-melting metals have the characteristic of retaining their strength up to the highest temperatures. However, it is problematic that these metals and alloys have only a low resistance with respect to oxidation, if they are exposed to air or other oxidizing media at high temperatures of over 400° C.
In order to improve this strong susceptibility to oxidation, a method is known for providing the surface of the high-melting metals with corresponding protective layers. For many uses, the application of coatings of silicides or aluminides has proved good.
U.S. Pat. No. 3,540,863 describes, for example, CrFe silicide layers as an oxidation protective layer for a basic material made of niobium or niobium base alloys.
Such coatings are melted by a diffusion annealing treatment after the application. This dead melting is the unavoidable prerequisite for the diffusion annealing of the layer component and for the production of the required barrier of the layer to oxygen permeation in these silicide or aluminide layers, which nowadays are almost exclusively applied by dross coating or plasma spraying.
By this diffusion annealing treatment, the layer composition is modified by dissolving the base material and incorporating the base material components into the coating, and multiphase and multilayer oxidation protective coatings are formed, which have one or more layers of intermetallic phases at the interface of the nondissolved base material; according to current teaching, the phases have an advantageous effect on the layer adhesion of the oxidation protective layer.
The disadvantage, on the one hand, is that dissolution of the components of the base material inevitably takes place, whether the components have a positive or negative influence on the function of the oxidation protective layer; and on the other hand, that diffusion processes which transfer the fractions of the basic material into the oxidation protective layer continue even during the proper high-temperature use of the coated base body. In the oxidation layer, these processes, however, are undesired in any case, since they change the chemical and physical behavior of layer and continuously worsen its lifetime and its composite with the base material.
European Patent No. A2 0,304,176 describes an object provided with an oxidation protective layer and which is made of a high-melting metal, which is provided with a melted silicide layer, for example, with the composition 20% Cr, 20% Fe, remainder Si. In order to increase the thermal load capacity in the use of the coated object, the oxidation protective layer is provided with an external ceramic layer, which fulfills the function of a thermal barrier.
Such a measure does not have the effect of preventing the uncontrolled dissolution processes between the base material and oxidation protective layer during use.
In isolated cases, objects with oxidation protective layers have also become known which have a reaction barrier layer between the base material and oxidation protective layer. Such layer structures have been accepted, however, in actual practice only in very special fields of application (for example, in the glass industry) and there, in turn, only for very special applications and in combination with an oxidation protective layer made of metal or an alloy of the platinum group, as, for example, described in United Kingdom Patent No. 1,195,349.
The object of the invention under consideration, therefore, is to create an article comprised of a base body made of a high-melting metal and an oxidation protective layer made of silicides or aluminides, wherein the layer is optimized with regard to use, independent of the composition of the base material. At the same time, dissolution processes of the base material in the oxidation protective layer or vice versa, uncontrolled in such an object, are to be ruled out during the production of the coated component and during use.
In accordance with the invention, this is attained in that a reaction barrier layer is placed between the base body and the oxidation protective layer and that the oxidation protective layer is alloyed with one or more metals from the group molybdenum, niobium, tantalum, and hafnium in a total fraction of 2-35 at. %.
Thus, the invention goes a completely new way in that it prevents the unavoidable incorporation of high-melting metals from the base material in a concentration prespecified from the process technology and from use and which changes according to the temperature, by the placement of a reaction barrier layer, but instead purposefully incorporates high-melting metals, in the optimized concentration, in the oxidation protective layer, so as to obtain, as before, the advantages of these metals in the oxidation layer and, at the same time, to reliably prevent an uncontrollable dissolution and diffusion of these metals from the basic material during production and during use.
In this way, on the one hand, a composition of the oxidation protective layer, independent of the basic material and the production process, can be attained and, on the other hand, a continuous, cyclic change of the composition of the oxidation protective layer can be prevented during changing temperature loads or over very long periods of time with constant temperatures.
In particular, a continuous formation of brittle, intermetallic phases, uncontrolled during use, at the base material/oxidation protective layer transition zone, which bring about a reduction in the thickness of the effective oxidation protective layer, is stopped. Also a critical embrittlement of the base material/oxidation protective layer composite, which is frequently the cause of reduced service lives, is thereby prevented in the long term.
By preventing the reaction of layer components with the base material and diffusion of layer components into the base material, service lives with constant characteristics of the layer system in the composite zone are attained, which are considerably longer, with comparatively thinner protective layers.
“Silicides” are understood to be, in particular, alloys based on silicon with at least 60 at. % Si and 5-40 at. % of one or more elements from the group Cr, Fe, Ti, Zr, Hf, B, and C and “aluminides,” in particular, alloys based on aluminum with at least 60 at. % Al and 5-40 at. % of one or more elements from the group Si, Cr, Ti, Zr, Hf, Pt, B, and C.
The selection of the metal or metals, with which the oxidation protective layer is alloyed, in accordance with the invention, is based not only on the minimization of the cinder constant, but rather also on the usage conditions with regard to the steady-state or cyclical temperature load. Also the thermal expansion coefficients of the base body under consideration have to be taken into consideration in the selection.
As a rule, an optimal adaptation of the thermal expansion coefficients of the base material, reaction barrier layer, and oxidation protective layer substantially increase the temperature change resistance of the individual composite object.
Depending on the application case, an alloying of the same metal that the base body is essentially made of (for example, SiCrFe oxidation protective layer, alloyed with niobium, in a base body of niobium or a niobium base alloy) or the alloying of another metal (for example, SiCrFe layer, alloyed with molybdenum, in a base body of niobium or a niobium base alloy) produce the best service life results in use.
The essential advantage attained by the invention is that the user is no longer restricted to the automatically resulting alloy formation of the oxidation protective layer with very specific fractions of the basic material in accordance with the state of the art, and the possibility exists of optimizing the oxidation protective layer with freely selectable alloy fractions, taking into consideration th
Barbist Roland
Knabl Wolfram
Martinz Hans-Peter
Rodhammer Peter
Jones Deborah
Morgan & Finnegan , LLP
Plansee Aktiengesellschaft
Young Bryant
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