GB2159542A - Method for producing protective oxidic layers on metallic surfaces - Google Patents
Method for producing protective oxidic layers on metallic surfaces Download PDFInfo
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- GB2159542A GB2159542A GB08506428A GB8506428A GB2159542A GB 2159542 A GB2159542 A GB 2159542A GB 08506428 A GB08506428 A GB 08506428A GB 8506428 A GB8506428 A GB 8506428A GB 2159542 A GB2159542 A GB 2159542A
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- oxide
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 230000001681 protective effect Effects 0.000 title description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 116
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 116
- 238000000034 method Methods 0.000 claims abstract description 84
- 239000010410 layer Substances 0.000 claims abstract description 47
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 230000012010 growth Effects 0.000 claims abstract description 11
- 238000010899 nucleation Methods 0.000 claims abstract description 10
- 230000006911 nucleation Effects 0.000 claims abstract description 10
- 239000011241 protective layer Substances 0.000 claims abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 45
- 229910045601 alloy Inorganic materials 0.000 claims description 37
- 239000000956 alloy Substances 0.000 claims description 37
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000001965 increasing effect Effects 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910019974 CrSi Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 1
- 235000013980 iron oxide Nutrition 0.000 claims 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims 1
- 238000005496 tempering Methods 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 51
- 230000007547 defect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 230000009643 growth defect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000054817 Lycaena dione Species 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001063 inconels 617 Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005480 shot peening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000003887 surface segregation Methods 0.000 description 1
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
- 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
- C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
- C23C8/18—Oxidising of ferrous 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
- C23C8/06—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
- C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
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)
- Formation Of Insulating Films (AREA)
Abstract
A method for producing oxidic protective layers by the treatment of metallic surface in an oxidizing atmosphere in which the O2 pressure or partial pressure of the treatment medium, governing the oxidation potential as it does, is continuously varied during the oxidation process to control the nucleation and growth rate of the oxide being produced. The O2 supply of the treatment medium, which is continuously varied in the course of oxidation, results in a dense, isotropic structure of the resultant oxide layer with a minimum of defect concentration.
Description
SPECIFICATION
Method for producing protective oxidic layers on the surfaces of metals or metal alloys
This invention relates to a method for producing oxidic layers by surface treatment of metal or metal alloys. More particularly it relates to such a method in which the metal or metal alloy is treated at elevated temperature in an oxidizing atmosphere the oxidation potential of which is selected, by controlling the temperature and pressure of the atmosphere used or partial pressure of one or several constituents of the atmosphere, such that selective formation is achieved of a few, preselected alloying constituents or preferably of only one alloying constituent, or that selective formation of a metal oxide of a certain valence state is achieved.DAS 31 04112,31 08160 and 32 1 5 314, describe methods for producing oxide layers which by their homogeneity, provide a considerably enhanced protection from corrosion and permeation.
In view of the rapid development of engine and nuclear reactor engineering, however, the corrosion and permeation resistance requirements for the materials used are becoming increasingly stringent, and new ways must be sought to improve still further the chemical and physical surface resistance of the materials used.
One object of the present invention is to provide the surface of metallic materials with oxidic layers of improved chemical and physical resistance.
According to the present invention we propose a method for producing oxidic protective layers by surface treatment of metals or metal alloys in an oxidizing atmosphere at elevated temperature, wherein the 02 pressure or partial pressure of the treatment atmosphere, the pressure determining the oxidation potential, is continuously varied to control the nucleation or growth rate of the resultant oxidic layer. Control of the potential serves to selectively affect the nucleation and growth rates with a view to optimizing the properties of the resultant oxide layer.
Oxidation potential, as used in the present specification, is to express the absolute oxidation ability of the treatment atmosphere, as contrasted with its relative oxidation ability with reference to a certain substance to be oxidized. The measure of (absolute) oxidation potential is the pressure or partial pressure of the free oxygen in the oxidizing medium, which in turn varies with the type of oxidizing agent used, and with the composition, pressure and temperature of the treatment atmosphere.An oxidizing treatment atmosphere of a specific (absolute) oxidation potential may possess a high relative oxidation ability with reference too a very reactive metal (e.g. sodium), but only a rather modest oxidation ability with reference to a less active metal (e.g. zink), and ultimately it may have no relative oxidation ability at all with reference to a metal of even lower affinity (e.g. cop per).-It is emphasized, again, that "oxidation potential" here signifies no potential other than the absolute oxidation potential.
Conceptually the method of the present invention is to continuously adapt the physical and chemical conditions of the oxidation process to the actual progress of oxide formation and growth of the oxide layer. In practical applications this is achieved by the continuous adjustment of the oxidation potential to the optimum value for the respective stage in the formation of the layer. The principle of the process, accordingly, is to allow the oxidation potential to float.
Useful oxidizing constituents of the treatment atmosphere are oxygen and all oxygenic compounds that take a gaseous form and deoxidize at the process conditions applied. In this manner use can be made of oxygen under vacuum conditions or diluted with inert carrier gases. Preferred oxidation agents, however, are steam and carbon dioxide either alone or mixed one with the other, with or without the addition of inert gases. The H2/H2O or CO/
CO2 ratio and with it the oxidation potential, i.e. the 02 partial pressure supplied to the metal surface, can be controlled via the 2H20 2H2 + O2 and 2C02 r 2C02 + O2 equilibriums by varying the pressure and/or temperature of the treatment atmosphere.
The specific control of said oxygen supply varies individually with the respective alloy to be treated, and also with the rate of oxide nucleation at the start of oxidation and the rate of subsequent growth of the oxide layer, where the O2 supply is continuously varied to achieve a dense, isotropic oxide structure and minimize defect concentration.
In view of the great variety of metal alloys admitting of oxidizing, and of the differences in metal oxides to be produced on the surfaces of the alloys, there will be no hard and fast rule for the continuous control of the oxidation potential, yet it is considered to fall within the knowledge and working experience of the man skilled in the art that he determine by preliminary testing the exact process parameters to use for the alloy selected in keeping with the above considerations. Two representative versions of the inventive method shall nevertheless be highlighted at this point: a) After oxidation has been initiated at a rela
tively low oxidation potential the latter is
gradually increased in a transitional phase
and oxidation is finally continued at a
higher oxidation potential.
b) When oxidation is being initiated the oxida
tion potential is relatively high, and it is
continuously lowered from the start as oxi
dation progresses.
The process variant a) is advantageously used when owing to the composition of the alloy, a low-level partial oxygen pressure that does not essentially run above the decomposition pressure of the oxide is required for initiating selective oxidation of one or several alloying constituents, such as chrome or aluminum, to prevent the formation of undesirable further oxide phases.
The process variant b) finds preferred use when the element the oxidation of which is to form the protective layer, is present in the alloy in a concentration such that with the oxidant used (preferably steam and/or carbon dioxide), the selectivity of oxidation is independent of the O2 partial pressure. This generally is the case when the base element of the alloy, such as iron in steel, is to be used for oxidation.
The various process variants to suit the types of alloy to be coated are selected for the following considerations:
Process variant a):
Selective oxidation of an alloying constituent
Initiation of oxidation at a partial oxygen pressure adapted to the equilibrium pressure of the oxide to be formed, using an H2/H2O mixture or CO/CO2 mixture of a suitable composition will ensure selective nucleation of the intended oxide. (Use can naturally be made also of an H2/H2O/CO/CO2 mixture). This type of initiation of oxidation also requires suitable preparations to ensure maximum availability, on the surface, of the element to be oxidized.This chiefly involves mechanical surface treatment and annealing in a hydrogen atmosphere, which makes for greater movability of the metal atoms and for surface segregation, e.g. of chrome, which substantially promotes nucleation of the intended oxide (here Cr203) at a low oxidation potential.
Following nucleation the oxidation potential is raised to achieve an adequate growth rate.
It has also been observed that at a nearequilibrium oxidation potential, i.e. an
H2/H2O mixture with a high H2 surplus, porous oxide layers will form when it is used throughout oxidation. Whereas a dense, isotropic oxide structure develops when the oxidation potential is raised, after an initiation phase, by continuously replacing the H2 or CO content of the oxidation atmosphere with inert gas, such as He or Ar, and going through the growth phase of the layer using H2O or CO2 in inert gas. With surface layers produced in this manner, additional "aging" of the layers has proved beneficial. For the purpose, the layers are tempered after oxidation at a lower temperature but in the same atmosphere. This eliminates growth defects, via recrystallization processes, and compacts the structure of the layer.
The implementation of the entire process is described below in light of process variants used on various alloys.
Process variant b):
Oxidation of the base element of an alloy
In case where owing to the composition of the alloy the formation of the intended oxide is independent of the oxidation potential, it will be helpful, when H20 or CO2 are used as oxidants, to start oxidation with a relatively high oxidation potential, i.e. with a 100% H20 or CO2 atmosphere. This holds true for the formation of oxide layers by oxidation of the base element of an alloy, e.g. iron in steels, or of another element if it is present in high concentration and has a clearly higher affinity for oxygen than the base element (e.g.
chrome in a nickel-base alloy having a chrome content of some 24% by weight and over).
Under these conditions the initiation of oxidation using pure steam or pure CO2 causes the formation of a large number of oxide nucleii in the interest of an extremely fine-grained isotropic structure. In the process it is important that during the heating phase at the beginning of the process the oxidant is already present when the temperature level is reached at which oxidation can start. When use is made of steam, it cannot be admitted into the oxidation vessel before it has reached a temperature of some 200"C, so as to avoid condensation. Until then, flushing with inert gas is required.
Mechanical preparation, again, is helpful in that it promotes diffusion by inducing recrystallization processes in the surface zone.
As oxidation commences, a reducing gas species (H2 and/or CO2) forms from the oxidant used (H20 and/or CO2) via said equilibriums, the concentration of which steadily increases in the course of oxidation if the process is carried out in a closed system. This will continuously reduce the oxidation potential of the atmosphere. In an open system the same effect can be achieved by the increasingly liberal admixture of reducing gas species. This reduction in oxidation potential advances the quality of the resultant layer in two manners: It slows the oxide growth and so prevents the formation of growth defects, such as open-pore grain boundaries and the overgrowth of voids, as well as columnar growth with grain boundaries reaching to the material. Such imperfections would be inevitable of oxidation were continued with the starting oxidation potential remaining unchanged.
In the description of this process variant, the effect that flow velocity may have has been ignored in so far as it was assumed that it was optimized to suit the geometry of the component to be coated with a view to a uniform supply of oxidant to the surface to be coated and to the dwell time of the oxidant on the surface of the component. This will have to be covered in specific applications by preparatory testing and will be no problem to anyone skilled in the art.
The dense, fine-grained isotropic oxide structure achieved by the process variants a) and b) clearly augments the protective action against the penetration of injurious foreign elements, such as sulphur, carbon, halogen and hydrogen, and increases the tear resistance under thermocyclic load when compared witha more coarsely grained and often columnar structure, such as it results from conventional oxidation methods that use a treatment atmosphere with a constant oxidation potential.
The particular features of the method for producing protective oxide layers by selective oxidation using a floating oxidation potential will be described and demonstrated in light of the following embodiments of the present invention:
Embodiment 1 (Process variant a):
On objects made of a nickel-base alloy containing 15% to 22% by weight Cr, protective Cr2O3 were produced using the following process:
The surface was mechanically prepared by grinding, honing or shot peening and then cleaned. Thereafter the objects were annealed at approximately atmospheric pressure in dry
H2 at 1 000 C for 4 hours.
Gradual admixture of steam over a period of 1 hour at a rising pressure until a partial pressure of 2 kPa (20 mbar) was reached served to initiate selective oxidation of Cr into Cr2O3. The hydrogen was then continuously replaced, over a period of again 1 hour, by inert gas (argon or helium). Oxidation was continued for a duration of 4 hours in the
Ar/H20 atmosphere. This process produced a homogenously continuous layer of Cr2O3 about 2 ym thick that had a dense, finegrained isotropic structure.
Test specimens coated by the process just described were experimentally subjected to a carburizing process atmosphere at 900"C and proved that they fully prevented the penetration of carbon into the material and, thus, injurous carburization.
Embodiment 2 (Process variant a):
An object made of an iron-base alloy containing 32% Ni, 21% Cr, approximately 0.1%
C and about 0.5% each Mn, Si, Al and Ti (Material No. 1.4876) was prepared as described for embodiment 1 and then subjected to the following oxidation process:
The object was heated at atmospheric pressure in a gas mixture of hydrogen with 2 kPa (20 mbar) H20 to 950"C. After 1 hour, one part H2 was replaced with Ar until the composition was 2 kPa (20 mbar) H2O, 20 kPa (200 mbar) H2 and the remainder Ar. In this atmosphere oxidation was allowed to take place for 5 hours and a Cr2O3 layer was formed. Thereafter the temperature was lowered to 800"C and simultaneously the remaining H2 was completely replaced with Ar.The object with the Cr203 surface layer was held another 1 2 hours in the resultant Ar/H20 atmosphere.
This procedure produced a uniform Cr203 layer 2 to 3 ,um thick on the object that showed a dense structure and gave the object a clearly improved resistance to corrosion in an atmosphere containing SO2 as compared with an object that went without pre-oxidation and with an object that had been preoxidized in an oxidation atmosphere that had conventionally been held constant in its composition.
Embodiment 3 (Process variant a):
Following mechanical surface treatment, objects made of steel containing 12% to 22% chrome by weight were annealed for 3 hours in dry H2 at temperatures between 800 and 1000"C (depending on the Cr content) and then oxidized as described in the process for embodiment 2. The resultant Cr203 layers corresponded in both structure and effect to those described for embodiment 2.
Embodiment 4 (Process variant a):
An object made of an alloy containing 0.05% C, 12% Cr, 4.5% Mo, 6% Al, 2%
Nb, the remainder Ni, were annealed at 1 050'C in H2 after surface preparation by grinding and polishing. Thereafter, at a constant temperature, H20 vapor was admixed to the H2 for a period of 4 hours in continuously increasing concentration until the H2 was completely substituted. Oxidation was then continued in the straight H20 atmosphere for a duration of 2 hours. After the temperature was then lowered to 950"C, the object was allowed to remain another 6 hours in the H20 atmosphere.This process produced on the object an Awl203 surface layer 2 to 3 jum thick, which by its density and bond gave excellent protection from corrosion when the object was subsequently subjected to a sulphurous and halogenous hot gas atmosphere.
Embodiment 5 (Process variant b):
An object made of steel containing 18% Ni, 12% Co, 4% Mo, 1.5% Ti, remainder Fe (material No. 1.6356) was mechanically prepared and then subjected to the following oxidation process:
During the heating phase, steam was admixed at a temperature of about 250"C of the inert starting atmosphere (Ar or He) in a continuously increasing quantity that gradually displaced the inert gas such that when the specified 460 to 480 temperature was reached, the atmosphere was 100% steam.
When oxidation had been started the oxidation potential was continuously reduced by allowing the hydrogen concentration to rise continuously in the course of the 4-hour oxidation time. Two different process versions were used: In one case the system was closed when the specified temperature (e.g. 480'C) and the 100% H20 atmosphere were reached.
In this case the H2 concentration spontaneously increased as a measure of the reaction of H20 and, thus, of the oxide formation (Fe304). In the other case a continuously increasing amount of H2 was added in an open (flowing) system. The quantity depends on the surface area to be coated. For 1 mole Fe3O4 the maximum amount of H2 at the end of oxidation is 4 moles. In both cases the system was flushed dry with air at the end of oxidation to prevent H20 condensation during cooling. This selective oxidation process with a floating oxidation potential produced dense, fine-grained Fe304 surface layers 1 to 2 ym thick that gave excellent protection of the steel from corrosion in a sulphurous and halogeneous atmosphere at temperatures to about 300'C.
Embodiment 6 (Process variant b):
Objects made of steel containing less than 12% chrome were prepared and then subjected to oxidation as for embodiment 5, where the oxidation temperature was the higher the higher the chrome content (approximately 500"C for 2% Cr, 600"C for 5%, 680"C for 7%). This caused layers of chrome iron spinel (Fe,Cr)304 to form. The properties of the resultant layers corresponded to those for embodiment 5 at process temperature of about 50"C below the coating temperatures.
Embodiment 7 (Process variant b):
Objects of nonferrous, highly heat-resistant alloys and superalloys containg 24% chrome and more were mechanically prepared and then subjected to an oxidation process as described for embodiment 5, where the oxidation temperature was as high as 1 050 C and the oxidation time 8 hours. Following oxidation the objects were tempered at 900"C in a constant atmosphere for another 6 hours. This produced Cr203 layers 2 to 3 lim thick of an extremely uniform, dense structure. These layers have proved to give lasting protection from corrosion even at elevated temperatures in various atmospheres containing C, S and halogen.
Embodiment 8 (Process variant b):
An object of a heat-resistant steel containing about 0.15% C, 25% Cr, 20% Ni, 2%
Si, 2% Mn (X 1 5 CrNiSi 25 20) was subjected to mechanical surface preparation and annealing in H2 and then to the following oxidation treatment:
The object was heated to 1 000 C in an inert gas atmosphere (argon or helium). When this temperature had been reached, the inert gas was rapidly replaced with CO2 and oxidation was then initiated. Oxidation was maintained for 6 hours, in the course of which the oxidation potential was continuously reduced in a closed system as a result of the CO concentration, which increased as the oxidation progressed. In an open (flow) system, a continuously growing amount of CO was added to the CO2 atmosphere.As for embodiment 5 the uantity again depended on the surface area to be coated. The oxidation product essentially is Cr203. For 1 mole Cr203 the maximum amount of CO at the end of oxidation is 3 moles.
Oxidation produced a fine-grain, dense Cr2O3 layer about 2 itm thick containing some percent Mn and a thin top layer of Mn Cr204.
Playing an important role with regard to a good bond is the SiO2 formed underneath the
Cr203 layer. The bnd-promoting effect of the
SiO2 is attributed to the fact that as a result of the process used, with its spontaneous Cr2O3 nucleation, the SiO2 grows into the grain boundaries of the material through the mechanism of internal oxidation with its ramified roots. Otherwise a thin SiO2 film would develop at the metal-to-oxide interface and obviously cause the top coat over it to separate.
Embodiment 9 (Process variant a):
An object of a heat-resistant steel X 10 CrSi 1 3 containing Si raised to 5% by weight was mechanically prepared and then subjected to the following oxidation process:
The object was heated to an oxidation temperature of 950'C in a hydrogen atmosphere.
Thereafter a continuously increasing amount of CO2 was added to the H2 atmosphere for a duration of 1 hour until a concentration of 10% by volume was reached. In the course of another hour the H2 was continuously replaced with inert gas (Ar, He). Oxidation was continued in the inert gas/CO2 atmosphere for another 4 hours.
This treatment produced a practically straight SiO2 coating about 2.5 ,um thick that had a very fine-grain, dense structure. Intimate growth of the SiO2 into the grain boundaries of the material made for a good bond.
The SiO2 coating achieved by the procedure described above gave the object a clearly improved resistance to corrosion in a sulphidizing atmosphere at high temperatures, compared with an object of the same material but without the oxide coating here described.
Embodiment 10 (Process variant a):
An object made of an alloy derived from the material Alloy 800, having a composition of about 20 Cr, 33 Ni, 4 Mn, Si less than 1, Ti less than 1, Al less than 1, the remainder Fe (in % by weight) was mechanically prepared and then annealed at 950"C in an H2 atmosphere for 2 hours. Thereafter oxidation was initiated at the same temperature by the addition of CO2 of a concentration of initially about 5% by volume to the H2 atmosphere.
The CO2 content of the vapor phase was then raised continuously for 4 hours until the at mosphere was completely CO2, which was then used to continue oxidation for another 2 hours.
With this type of oxidation process and alloy, the first step in the process was the formation of a felt-like MnCr2O4 layer 1 to 2 ,um thick. In the further course of oxidation an extremely dense layer of Cr2O3 formed on the
Mn-depleted alloy below the MnCr204-layer.
Owing to the growth mechanism the Cr2O3 had penetrated into the grain boundaries, which made for an excellent bond, and on the other hand had grown, with fine-grain particles, into the felt-like MnCr2O4 layer, so that an extremely dense compound layer about 4 ym thick resulted.
Enhancement of the oxidation potential in the course of the oxidation process has here promoted the formation of Cr2O3 over that of the thermodynamically favored MnCr2O4 after the Mn-activity of the alloy had already been lowered by initial oxidation at low oxidation potential by the formation of MnCr2O4.
Also the process version producing a twolayer coating gave the alloy excellent protection from corrosion at elevated temperature.
Embodiment ii (Process variant b):
An object made of alloy 22 Cr, 12.5 Co, 9
Mo, 1 Al, remainder Ni (in % by weight), known by its tradename of Inconel 617, as a substratum plated with alloy 1 6 Cr, 5 Al, 0.4
Y, remainder Fe (in % by weight) was subjected to the following oxidation process to produce a surface layer on the plating material.
After heating to an oxidation temperature of 1 000 C in an inert gas atmosphere (Ar, He), oxidation was initiated by the rapid replacement of the inert gas with steam under atmospheric pressure. This caused intensive Al2O3 nucleation. After 1 hour continuously increasing addition of inert gas (Ar, He) was used to steadily decrease the H20 vapor content in the vapor phase such that after another 4 hours a residual partial pressure of 10 mbar H20 was reached. Thereafter the inert gas content was replaced with H2, which again lowered the oxidation potential. The An203 layer was tempered for another 4 hours in the H2 atmosphere under 10 mbar H2. This healed growth defects and improved the bond by progressive internal oxidation of Y.
The resultant, extremely dense An203 layer was about 4 mm thick, had an isotropic structure and gave a clearly improved resistance from sulphidization, carburization and halogen corrosion at elevated temperatures when compared with uncoated plating material.
The embodiments of the process as described above in the examples given refer to the alloys selected. For other alloys. modified procedures deviating from said embodiments may be of advantage, and these procedures may also be a combination of the abovementioned typical process variants a) and b).
In any case, however, the principle of floating oxidation potential must be maintained intact.
Claims (26)
1. A method for producing oxidic protective layers by surface treatment of metals or metal alloys in an oxidizing atmosphere at elevated temperature, wherein during oxidation the O2 pressure or partial pressure of the treatment atmosphere, which pressure determining the oxidation potential, is continuously varied to control the nucleation or growth rate of the oxidic layer being produced.
2. A method according to claim 1, wherein steam or a steam-laden atmosphere is selected as a treatment atmosphere.
3. A method according to claims 1 and 2, wherein continuous variations of the O2 partial pressure of the steam atmosphere is achieved by adding hydrogen or removing H2 from the hydrogenous H20 steam atmosphere.
4. A method according to claim 1, wherein carbon dioxide or a CO2 laden atmosphere is selected as a treatment atmosphere.
5. A method according to claims 1 and 4, wherein continuous variation of the O2 pressure of the carbon dioxide atmosphere is achieved by adding carbon monoxide or removing CO from the CO-laden CO2 atmosphere.
6. A method according to claims 1, 2 and 4, wherein the continuous variation of the O2 partial pressure of the treatment atmosphere is achieved by adding or removing inert gases.
7. A method according to claim 6, wherein rare gases, such as argon and/or helium, are used as inert gases.
8. A method according to any one of the preceding claims, wherein the continuous variation of the O2 partial pressure of the treatment atmosphere is achieved by varying the treatment temperature.
9. A method according to any one of claims 1 to 8, for alloys on whose surfaces the oxide of one or several, quantitatively subordinate alloy constituents is to be formed selectively, wherein selective oxidation is initiated, with an oxidation potential running below the decomposition pressure of the oxide or oxides to be formed, and wherein the oxidation potential is thereafter continuously increased to a predetermined final value above the decomposition pressure.
1 0. A method according to claim 9, wherein the metal surface to be oxidized is first subjected to mechanical and/or chemical preparation.
11. A method according to claim 10, wherein for chemical preparation, annealing in a hydrogen atmosphere is selected.
1 2. A method according to any one of claims 9 to 11, wherein the resultant oxide layer is aged by tempering in the treatment atmosphere at a lowered temperature.
1 3. A method according to any one of claims 9 to 12, wherein on an alloy containing approximately 1 2 to approximately 23% chrome, layers of Cr2O3 are formed.
14. A method according to claims 9 to 12, wherein on an alloy containing approximately 2.5 to approximately 8% aluminium, layers of Al2O3 are formed.
1 5. A method according to any one of claims 9 to 12, wherein on heat-resistance steel X 10 CrSi 1 3 with an Si content raised to about 5% by weight, layers of SiO2 are formed.
1 6. A method according to any one of claims 9 to 12, wherein on an alloy containing approximately 20% Cr, 33% Ni, 4% Mn, < 1% Si, < 1% Ti, < 1% Al (percent by weight) remainder Fe, layers of Mn Cr2O4 and Cr2O3 are formed.
1 7. A method according to any one of the claims 1 to 8, wherein on alloys whose surfaces the oxide of the base material of the alloy or of a highly concentrated alloying constituent of an affinity for oxygen greater than that of the base constituent is to be formed, a high oxidation potential is provided for initiating oxidation by using an essentially 100% H20 and/or CO2 atmosphere, after which the oxidation potential is continuously decreased.
18. A method according to claim 17, wherein the metal surface to be oxidized is first subjected to mechanical and/or chemical preparation.
1 9. A method according to claim 1 7 or 18, wherein for chemical preparation, annealing in a hydrogen atmosphere is used.
20. A method according to any one of claims 1 7 to 19, wherein the resultant oxide layers is tempered in the treatment atmosphere at a lowered temperature.
21. A method according to any one of claims 1 7 to 20, wherein on an iron-base alloy (steel) free of chrome, iron oxides are formed.
22. A method according to any one of claims 1 7 to 20, wherein on steels containing less than approximately 12% chrome, layers of chrome iron spinel (Fe,Cr)3O4 are formed.
23. A method according to any one of claims 1 7 to 20, wherein on an alloy containing approximately 24% by weight chrome or
more, chrome oxide is formed.
24. A method according to any one of claims 1 7 to 20, wherein on a heat-resistant steel containing approximately 0.15% C,
25% Cr, 20% Ni, 2% Si and 2% Mn (X 15
CrNiSi 25 20), layers of Cr203, MnCr2O4 and
SiO2 are formed.
25. A method according to any one of claims 1 7 to 20, wherein on an alloy contain
ing 22% Cr, 12.5% Co, 9% Mo, 1% Al (in
percent by weight), remainder Ni, as a substratum, a plating consisting of an alloy 16% Cr, 5% Al, 0.4% Y (percent by weight), remainder Fe, is deposited, on which layers of Awl203 are formed.
26. A method for producing oxide layers on metals or metal alloys substantially as hereinbefore described with reference to any one or more of the partial embodiments thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3419638A DE3419638C2 (en) | 1984-05-25 | 1984-05-25 | Process for the oxidative production of protective layers on an alloy |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8506428D0 GB8506428D0 (en) | 1985-04-17 |
| GB2159542A true GB2159542A (en) | 1985-12-04 |
| GB2159542B GB2159542B (en) | 1988-03-16 |
Family
ID=6236906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08506428A Expired GB2159542B (en) | 1984-05-25 | 1985-03-13 | Method for producing protective oxidic layers on metallic surfaces |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE3419638C2 (en) |
| GB (1) | GB2159542B (en) |
| SE (1) | SE8502590L (en) |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB462380A (en) * | 1934-06-02 | 1937-03-04 | Electro Chimie Metal | Process for the manufacture of articles resistant to gaseous corrosion |
| GB693921A (en) * | 1949-08-17 | 1953-07-08 | British Thomson Houston Co Ltd | Improvements in and relating to methods of providing magnetic sheet steel with an insulating film |
| GB870170A (en) * | 1958-02-10 | 1961-06-14 | Ca Atomic Energy Ltd | Zirconium bearings and process of producing same |
| GB959789A (en) * | 1959-11-16 | 1964-06-03 | Steatit Magnesia Ag | Improvements in the manufacture of thin magnetic anisotropic layers |
| GB1418880A (en) * | 1971-12-27 | 1975-12-24 | Eastman Kodak Co | Oxide-coated iron powder |
| GB1445650A (en) * | 1973-12-26 | 1976-08-11 | Midrex Corp | Passivating process for sponge iron |
| GB1477370A (en) * | 1973-08-06 | 1977-06-22 | Stephanois Rech Mec | Method for treating parts made of titanium or titanium alloy and parts produced thereby |
| US4078949A (en) * | 1976-09-02 | 1978-03-14 | United States Steel Corporation | Method for improving the surface quality of stainless steels and other chromium-bearing iron alloys |
| GB2092621A (en) * | 1981-02-06 | 1982-08-18 | Maschf Augsburg Nuernberg Ag | Forming oxide layer on alloy steels |
| GB2093073A (en) * | 1981-02-06 | 1982-08-25 | Maschf Augsburg Nuernberg Ag | A method of producing protective oxide layers |
| GB2118978A (en) * | 1982-04-23 | 1983-11-09 | Maschf Augsburg Nuernberg Ag | Forming oxide layer on titanium |
| GB2133422A (en) * | 1982-12-11 | 1984-07-25 | Maschf Augsburg Nuernberg Ag | Coating by chemical vapour-phase reaction between workpiece and reactants |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2269601A (en) * | 1934-06-02 | 1942-01-13 | Electrochimie D Electro Metall | Process for the manufacture of articles resistant to gaseous corrosion |
| US3259526A (en) * | 1962-04-24 | 1966-07-05 | Honeywell Inc | Method of heat treatment |
| DE1521998A1 (en) * | 1966-09-30 | 1969-08-21 | Siemens Ag | Process for the pre-oxidation of nuclear reactor components made of zirconium alloys |
| NL156193B (en) * | 1972-12-08 | 1978-03-15 | Philips Nv | METHOD OF COVERING A CHROME-NICKEL PART WITH A CHROME OXIDE-CONTAINING LAYER, AND PART PROVIDED WITH SUCH LAYER. |
-
1984
- 1984-05-25 DE DE3419638A patent/DE3419638C2/en not_active Expired
-
1985
- 1985-03-13 GB GB08506428A patent/GB2159542B/en not_active Expired
- 1985-05-24 SE SE8502590A patent/SE8502590L/en unknown
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB462380A (en) * | 1934-06-02 | 1937-03-04 | Electro Chimie Metal | Process for the manufacture of articles resistant to gaseous corrosion |
| GB693921A (en) * | 1949-08-17 | 1953-07-08 | British Thomson Houston Co Ltd | Improvements in and relating to methods of providing magnetic sheet steel with an insulating film |
| GB870170A (en) * | 1958-02-10 | 1961-06-14 | Ca Atomic Energy Ltd | Zirconium bearings and process of producing same |
| GB959789A (en) * | 1959-11-16 | 1964-06-03 | Steatit Magnesia Ag | Improvements in the manufacture of thin magnetic anisotropic layers |
| GB1418880A (en) * | 1971-12-27 | 1975-12-24 | Eastman Kodak Co | Oxide-coated iron powder |
| GB1477370A (en) * | 1973-08-06 | 1977-06-22 | Stephanois Rech Mec | Method for treating parts made of titanium or titanium alloy and parts produced thereby |
| GB1445650A (en) * | 1973-12-26 | 1976-08-11 | Midrex Corp | Passivating process for sponge iron |
| US4078949A (en) * | 1976-09-02 | 1978-03-14 | United States Steel Corporation | Method for improving the surface quality of stainless steels and other chromium-bearing iron alloys |
| GB2092621A (en) * | 1981-02-06 | 1982-08-18 | Maschf Augsburg Nuernberg Ag | Forming oxide layer on alloy steels |
| GB2093073A (en) * | 1981-02-06 | 1982-08-25 | Maschf Augsburg Nuernberg Ag | A method of producing protective oxide layers |
| GB2118978A (en) * | 1982-04-23 | 1983-11-09 | Maschf Augsburg Nuernberg Ag | Forming oxide layer on titanium |
| GB2133422A (en) * | 1982-12-11 | 1984-07-25 | Maschf Augsburg Nuernberg Ag | Coating by chemical vapour-phase reaction between workpiece and reactants |
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| CN113913713A (en) * | 2021-08-04 | 2022-01-11 | 常州大学 | A method for inhibiting the release of Co ions from Co-based biomaterials |
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| WO2025224187A1 (en) * | 2024-04-23 | 2025-10-30 | Terrabarrier Ab | Metallic alloy with protective oxide layer, method for making the same and apparatus for forming at least an oxide layer at the surface of a metallic alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8506428D0 (en) | 1985-04-17 |
| GB2159542B (en) | 1988-03-16 |
| SE8502590L (en) | 1985-11-26 |
| DE3419638A1 (en) | 1985-11-28 |
| SE8502590D0 (en) | 1985-05-24 |
| DE3419638C2 (en) | 1987-02-26 |
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