US3660173A - Method of preparing corrosion resistant metallic articles - Google Patents

Method of preparing corrosion resistant metallic articles Download PDF

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US3660173A
US3660173A US49052A US3660173DA US3660173A US 3660173 A US3660173 A US 3660173A US 49052 A US49052 A US 49052A US 3660173D A US3660173D A US 3660173DA US 3660173 A US3660173 A US 3660173A
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percent
oxide layer
zirconium
titanium
article
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Akira Matsuno
Takao Sasame
Ikuzo Shimizu
Humio Kizu
Hiroyuki Kagawa
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Toshiba Corp
Mazda Motor Corp
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Tokyo Shibaura Electric Co Ltd
Toyo Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • NOJ 49,052 pounds thereof or to general oxidation which comprises the steps of heating in an oxidizing atmosphere at a temperature of 1,000 to l,400 C for a suitable number of hours articles
  • Foreign Application Priority Data prepared from a metal consisting of 10 to 25 percent of chromium, 2 to 5 percent of aluminum, less than 0.04 percent June 25, 1969 Japan ..44/50588 f carbon, to 105 percent of nitrogen to 0 p cent of titanium, 0.01 to 0.5 percent of zirconium, iron as the [52]
  • the present invention relates to a method of preparing metallic articles which are resistant to corrosion, particularly that exerted by hot corrosive gases containing halogens or compounds thereof and general oxidation.
  • exhaust gases from automobiles contain halogens and compounds thereof such as Cl Br PbCl PbBr C H CI and C l-I Br other lead compounds and phosphur compounds in addition to unburned carbon monoxide and hydrocarbons. Since these ingredients are extremely corrosive to general metallic materials, members involved in the exhaust system of an automobile, for example, a muffler is subject to damage by corrosion and consequently deemed as a consumable article. Where there is fitted to an automobile a reaction vessel according to the above-mentioned afterburner method, said vessel, if made of conventional materials, would fail to withstand the strong corrosive action of gases burning therein at a temperature of at least 900 C and sometimes rising to l200 C.
  • ferroalloys containing nickel, chromium and cobalt are generally known to withstand heat, they are unadapted for long use under such severe conditions as prevailing in the aforementioned reaction vessel. Further, even the chromizing or aluminizing treatment of the surface of these heat-resistant ferroalloys does not display any prominent effect.
  • a method oflining or spray coating a material of ceramic with very corrosion-resistant ceramics to improve the resistance of the reaction vessel to corrosion and oxidation.
  • the present invention has been accomplished with the view of settling the aforesaid problems associated with the material of a reaction vessel for treating or detoxicating exhaust gases from automobiles.
  • the method ofthe present invention is not limited to use in detoxicating automobile exhaust gases, but generally applicable in preparing metallic articles which are required fully to withstand long application in an atmosphere where there prevail very corrosive hot gases such as those containing halogens or compounds thereof.
  • metallic articles as used herein, include raw materials obtained by rolling or drawing, intermediate products worked by pressing, welding or cutting and end articles.
  • An object of the present invention is to provide ferroalloy articles which are prominently resistant to corrosion caused by very corrosive hot gases containing halogens or compounds thereof and general oxidation.
  • Another object of the present invention is to form a compact and firm corrosionand oxidation-resistant oxide layers mainly consisting of cit-A1 0 in close contact with the surface of a metallic base body, and enable it to maintain a stable state free from the possibility of coming off even when it is subjected to repeated heating under exposure to corrosive gases introduced at high temperature and speed.
  • FIG. I is a schematic longitudinal sectional view of an apparatus used in testing the degree of corrosion occurring in a ferroalloy article
  • FIG. 2 is a curve diagram indicating the relationship of the ratio of (Ti Zr)/N associated with the components of a ferroalloy article versus increased weight due to oxidation;
  • FIG. 3 is a curve diagram showing the relationship of'the aforesaid ratio of (Ti Zr )/N versus the percentage removal of an oxide layer;
  • FIG. 4 is a longitudinal sectional view of an oxide layer obtained by the method of the present invention, illustrating a typical structure thereof;
  • FIG. 5 is a longitudinal sectional view of an oxide layer obtained by the method of the invention, illustrating another typical structure thereof;
  • FIG. 6 is a curve diagram presenting the relationship of heating time and increased weight due to oxidation according to Example 3.
  • FIG. 7 is a plotted diagram from all Examples according to the contents of Ti and Zr, showing the different areas of two oxide layer types.
  • Corrosion resistance tests on metallic materials are generally conducted by an apparatus illustrated in FIG. 1 wherein there are placed a sample 3 and a substance 4 evolving corrosive gas in a quartz tube 2 kept at a constant temperature by a heater 1 and, while they are continuously heated, there is introduced into the quartz tube 2 air at the rate of 200 c.c. per minute in the direction of the indicated arrow.
  • this apparatus there were made experiments to determine how far the aforesaid metal alloys of the prior art could withstand the action of hot corrosive gases.
  • Aluminum (Al) is also indispensable to render metallic particles resistant to high temperature oxidation.
  • lf aluminum is contained in less than 2 percent, there will result an insufficient growth of aAl O in an oxide layer, leading to the increased formation of such oxides, for example, (Fe, C 0 as will exhibit less resistance to oxidation and erosion. Beyond 5 percent of aluminum, there will occur decrease in the room temperature workability of metalsas is the case with chromi urn. Accordingly, the suitable range of aluminum content is between 2 and 5 percent, the most preferable content being about 3 percent.
  • the method of the present invention is characterized by preparing articles from a metallic material consisting of 10 to 25 of Cr, 2 to 5 of Al, less than 0.04 of C,
  • Chromium (Cr) is an indispensable component for imparting an oxidationrresistant quality to metallic articles; However, its content of less than 10 percent will be insufficient to provide a desired degree of oxidation resistance. If the content exceeds 25 percent, there will be presented difficulties in rolling, drawing or press work. Accordingly, it is preferred that the content be ranged from 10 to 25 percent, the most desirable amount being around percent.
  • cal heating, chromium and aluminum are indispensable not only for formation of an oxide layer but also for elevation of the fatigue strength and oxidation resistance of a metallic base body when it is repeatedly heated at high temperature. Amounts of these materials incorporated in the metallic articles prepared by the method of the present invention are much the'same as in these of the prior art.
  • the carbon (C) component of the metallic base body combines with the content of titanium (Ti), zirconium (Zr) or chromium (Cr) to form carbides, which do not constitute solid solutions in the base body. Generation of large amounts of such carbides will not only lead to the occurrence of hot corrosion, but also to the reduced effect of titanium and zircocium which are added to increase the mechanical strength of an oxide layer. Accordingly, it is preferred that the carbon content be as little as possible, its allowable limit being 0.04 percent.
  • Nitrogen (N) contained in the metallic base body suppresses the diffusion of carbon and presents the coarse growth of carbide particles. Since, however, nitrogen has greater affinity with titanium'and zirconium than carbon, it will combine with them to form TiN and ZrN, far more decreasing the effect of titanium and zirconium than does the carbon. Therefore, it is desired that nitrogen be contained in the base body in as small amounts as possible, its permissible limit being 0.05 percent. Further, nitrogen largely affects the properties of the oxide layer as described later, according to the ratio of Ti Zr to N. From this point of view, the lower limit of the nitrogen content is set at 0.005 percent.
  • titanium and zirconium serve by their diffusion to cause an unremovable oxide layer to be formed compact and firm on the surface of the metallic base body. Titanium is dissolved in the solid aAl O to render it compact. However, if the content of titanium falls to below 0.1 percent, it will not display a noticeable effect, whereas its content of more than 0.6 percent will reduce the room temperature workability of metals, Accordingly, it is advisable that the titanium content be ranged from 0.1 to 0.6 percent. Even within said range, the properties of a resultant oxide layer appreciably vary with the titanium content as described later.
  • Zirconium fixes nitrogen to promote the effect of titanium, and aids in causing the oxide layer to be deeply settled in the metallic base body, taking a rooty form, thereby reducing its possibility of coming off the base body.
  • the zirconium content should be at least 0.01 percent. Since, however, the zirconium content of more than 0.5 percent greatly decreases the oxidation resistance of a resultant oxide layer, the preferable range of said content is between 0.01 and 0.5 percent. Even within this range, the properties of the oxide layer vary, as described later, with the zirconium content in relation to the titanium content.
  • Metallic silicon is generally used as a deoxidant in melting metals, and in addition is incorporated together with zirconium in the form of Fe-Si-Zr alloy in the present case, so that Si is to exist in the base metal of the invention as an impurity.
  • metallic manganese Mn is added to fix both the deoxidant and sulfur contained in metals so as to eliminate the harmful effect of them.
  • silicon and manganese will not affect the present invention, provided that they are used in customary proportions of less than 0.5 percent and 0.6 percent respectively.
  • the value of the ratio (Ti% Zr%)/N% is considered as a parameter common to the increased weight in heat treatment and the peel resistance of the oxide layer. If the ratio decreases from 10, there will result the reduced peel resistance of the oxide layer and if the ratio exceeds 60, the layer will be degraded in oxidation resistance and peel resistance. Accordingly, it is necessary to limit the ratio to within the range of from to 60, the most preferable ratio lying between and 50.
  • FIG. 2 represents curves showing the relationship of the ratio (Ti% Zr%)/N% versus the increased weight due to oxidation of metal samples having a typical composition embodying the present invention which were heat-treated in an oxidizing atmosphere at a temperature of 1,300 C for different lengths of time.
  • FIG. 3 gives curves illustrating the relationship of the ratio (Ti% Zr%)/N% versus the peel resistance of oxide layers deposited on the surface of the samples subjected to heat-treatment under the similar condition as in the preceding case.
  • the rate of peeling is expressed in the percentage decrease in weight of the aforementioned heat-treated samples which were subjected 5 minutes to sand blasting generally used in surface grinding.
  • Numerals 8 and 9 denote the samples heat-treated 50 and 100 hours respectively.
  • the ratio (Ti% Zr%)/N% and the properties of the resultant oxide layer have interrelationships.
  • the reason has not yet been clearly defined.
  • the oxidation resistance of an oxide layer decreases with the increasing amounts of titanium and zirconium capable of diffusion, insofar as they do not form compounds of TiN and ZrN respectively, and contrary the peel resistance of the oxide layer is elevated. Said peel resistances would reach maximums when the ratio (Ti% Zr%)/N% stands at 40 to 50, but decrease when the ratio exceeds 60, or when the ratio falls to below 10. Accordingly, we have found that with the ratio (Ti% Zr%)/N% limited to within the range of from 10 to 60 there can be reliably manufactured metallic articles protected with an oxide layer having a desired resistance to erosion and peelmg.
  • heating temperature is largely governed by an oxygen potential in the atmosphere in which heat-treatment is performed. Where heating is carried out in the air, it is desired to last for at least 2 hours, and may also be extended to 200 hours according to the required thickness of an oxide layer. Upon completion of heating, the metal article in the furnace is allowed to cool in the air.
  • the oxide layer deposited on the surface of a metallic base body consists of a main component of aAl,O having minor amounts of titanium and zirconium dissolved therein in solids and some mixed crystals of aAl o with some proportions of ZrO (Fe,Cr) O and other oxides.
  • the layer itself is compact and firm and tightly adheres to the metallic base body. It has so strong a resistance to peeling that even where ground with sand paper, it does not readily come off.
  • the oxide layer displays a prominent resistance to erosion by halogens, Pb or its compounds and vanadium, which characterizes the properties of metallic articles obtained by the method of the present invention.
  • the aforesaid reaction vessel for treating exhaust gases from automobiles which is coated inside and outside with an oxide layer according to the present invention is not affected at all by halogens, compounds thereof, Pb, Pb compounds or P compounds.
  • the general oxidation resistance of the metallic article it only slightly increases in weight by oxidation where it is employed at lower temperatures than those at which the oxide layer is formed, always presenting excellent oxidation resistance.
  • Type A represents an oxide layer mainly consisting of aAl O and minor amounts of ZrO the outermost region of said layer being constituted by a thin film of Al O TiO This type of oxide layer is not deeply settled in the metallic base body taking a rooty form, displaying a somewhat weaker resistance to peeling than the later described Type B.
  • Type A mainly results from the diffusing behavior of titanium and is formed under the conditions where the metallic base body contains large amounts of titanium dissolved in solids and minor volumes of TiN as an intervening substance, namely, where the greater part of the zirconium only serves to fix nitrogen.
  • Type A oxide layer Formation of a Type A oxide layer is supposed to proceed by the following mechanism.
  • the alloy elements involved in the metallic base body are diffused at a velocity of decreasing order as Al Ti Zr, where there prevails a sufficientoxygen potential for diffusion of aluminum and titanium, aluminum is first diffused at the initial stage of diffusion to form aAl O Since the affinity of alloy elements with oxygen progressively decreases in the order of Zr Ti Al Cr Fe, the titanium which starts diffusion after aluminum is dissolved in aAl O in solids only to a small extent. Most of the titanium passes through the stratum of aAl Q and is diffused up to the outermost region to produce a thin film of aAl O 'TiO which has an extremely compact orthorhombic crystal structure.
  • the proportionsof titanium and zirconium involved in the aforementioned composition of a metallic base body according to the present invention are selected to fall within the v ranges of 0.2 to 0.6 percent and more than 0.2 to 0.5 percent respectively and the weight ratio of titanium to zirconium is set'at a larger value than 0.9, then the oxide layer formed on the surface ofa metallic base body according to the method of the present invention will assume such a structure as illustrated in FIG. 5. Said structure will hereinafter be designated as Type B.
  • This type of oxide layer entirely consists of mixed crystals of aAl O and small amounts of ZrO and is deeply set in the metallic base body taking a rooty form, and the outermost part of the layer being constituted of a-Al O mixed with a small amount of ZrO .and (Fe,Cr) O crystals. Accordingly, the layer of Type B presents a very strong resistance to peeling, and its surface withstands far severer conditions than Type A with respect to attacks by halogens or PhD. This layer is slightly less resistant to general oxidation than Type A, but only to such extent that there will not be presented any practical difficulties.
  • Type A presents less weight increase due to oxidation, but a somewhat larger rate of peeling
  • Type B displayed a .smaller rate of peeling but greater weight increase due to oxidation.
  • Type B exhibits an extremely strong resistance to peeling, so that even if it is sand blasted, it does not readily come off, except for its outermost surface.
  • FIG. 5 illustrates the structure of a Type B oxide layer wherein the aAl O occupies the greater part of every region, (Fe,Cr)-,,O;, and ZrO- being present in minor weights. Further, ZrO does not combine with the aAl O to form stable crystals, being simply mixed therewith in the form of separate crystals.
  • Types A and B typically illustrated in FIGS. 4 and 5 respectively can not be rigidly distinguished from each other, but depending on the composition of metals involved, there may occur an oxide layer having an intermediate form between Types A and B.
  • the metallic base body to be used may be obtained by melting it in the atmosphere with a conventional method.
  • the oxide layer in this invention is easily formed on the surface of the article by heat-treating in a suitable furnace.
  • the Type A oxide layer can be forcibly removed by sand blasting, so that 1 The rate of peeling includes the removed amounts of n metallic base body itself, indicating that. till the oxide layer cznne off.
  • Type B of oxide layer is grown mainly by diffusion of zirconium, on to a surface layer and that of oxygen ion in to a metallic base body. Said growth is realized where there are dispersed in the metallic base body'relatively large amounts of zirconium without generating a compound of ZrN.
  • increasing addition of zirconium leads to the decreased oxidation resistance of metals, so that to obtain Type B of oxide layer it is necessary that the ratio of titanium to zirconium be set at 0.9 minimum. This will minimize decrease in the oxidation resistance of the metal and at the same time elevate its resistance to peeling and erosion. If the ratio of titanium to zirconium falls to below 0.9 the resistance ofthe metal to general oxidation will sharply drop.
  • Type B oxide layer Formation of a Type B oxide layer may be assumed to proceed by the undermentioned mechanism, though not clearly understood.
  • aluminum is first diffused in the surface of a metallic base body as in Type A to form a stratum of aAl O
  • Some amounts of oxidized Fe and Cr crystallize with the stratum of the aAl O in the form of (Fe,Cr) O;,.
  • Titanium is next diffused and then free zirconium dispersed in a metallic base body begins to be diffused through the loose body forward its surface, because zirconium does not have a nature to form a solid solution where the oxide layer becomes degraded by long use, it may be all removed by sand blasting and there can be again produced a fresh oxide layer having the same type as the preceding one by heat-treatment in an oxidizing atmosphere.
  • an oxide layer deposited on the surface of ferroalloy articles by the method of the present invention mainly consists of aAl O as a main component and oxides of titanium, zirconium and other elements mixed therewith.
  • Said oxide layer is really of quite a novel type in the sense that it is formed compact and firm on the surface of a metallic base body and displays a very strong resistance to erosion and peeling even where it is repeatedly heated by corrosive gases containing halogens of compounds thereof which are introduced at high temperature and speed, and moreover well withstands general oxidation.
  • the method of the present invention is adapted for use not only in a reaction vessel for treating exhaust gases from automobiles, but also widely in metallic articles which are exposed to general severely corrosive gases containing halogens or compounds thereof with a high temperature.
  • FIG. 7 is a co-ordinate system where the titanium content is plotted on the ordinate and the zirconium content on the abscissa. As seen from this figure, if, with 0.2 percent taken as the base point, the zirconium content decreases therefrom, there will result Type A of oxide layer. Where the zirconium content rises above the above-mentioned base point of 0.2 percent, the resultant oxide layer will TABLE 3. COMPOSITIONS OF SAMPLE METALS
  • Example EXAMPLE I An alloy melted in the atmosphere was rolled into a thin plate. Samples cut out of the plate were divided into three groups.
  • the samples were heated in an open small electric furnace at l,200 C for 2, l0 and 50 hours for the respective groups. After said heat-treatment, the samples were allowed to cool in the air. On their surfaces were formed oxide layers of Type A varying in thickness for each group. The samples were subjected to an erosion test for 2 hours at 900 C by the aforementioned method. None of the samples presented any erosion at all, namely, they all displayed an excellent resistance to erosion and oxidation, though they indicated 100 percent in the previously defined rate of peeling. The thickness of an oxide layer formed averaged 4.5 microns for 2 hours of heating, microns for 10 hours of heating and microns for 50 hours of heating.
  • Example 2 Samples obtained in the similar manner as in Example I were divided into three groups as in Example 1 by the different numbers of hours used in heating them at l,300 C. On the surfaces of the samples were deposited oxide layers of Type A varying in thickness for each group. Said thickness averaged 3.5 microns for 2 hours of heating, 8 microns for 10 hours of heating and 15 microns for 50 hours of heating. The samples presented the same resistance to erosion and oxidation and rate of peeling as in Example 1.
  • EXAMPLE 3 Samples obtained in the same manner as in Example I were divided into five groups by different lengths of time, that is, I0, 20, 50, I00 and 200 hours used in heating them at L300 C. On the surfaces of the samples were formed oxide layers of Type A varying in thickness of each group. Said thickness averaged 8, 11, l5, l7 and 19 microns for the respective groups. The relationship of the numbers of hours used in heating each group and the weight increase due to oxidation is presented in FIG. 6.
  • the thin metal plate prepared according to Example 3 was worked into an after burner type reaction vessel for treating exhaust gases from automobiles.
  • the vessel was heated 20 hours in an electric furnace kept at a temperature of l,300 C to form inside and outside thereof an oxide layer of Type A about l0 microns thick.
  • An after burner in which there was incorporated the reaction vessel was fitted to a 1,500 c.c. engine. After a 500 hours continuous run of the engine at 5,000 r.p.m., the exhaust gas therefrom was burnt again.
  • This bench test corresponded to the actual run of an automobile exceeding 50,000 kilometers. The test proved that the reaction vessel was not attacked at all by the exhaust gas, nor presented cracks, giving very satisfactory results from a practical point of view.
  • EXAMPLE 4 A sample obtained in the same manner as in Example I was heated 20 hours at I,300 C. An oxide layer formed thereon was ofType A and had a thickness of l l microns.
  • EXAMPLE 5 An oxide layer deposited on the surface of a sample treated as in Example 4 had a structure intermediate between Types A and B and was 30 microns thick. The layer was relatively deeply settled in the metallic base body, so that its rate of peeling was reduced to 48 percent.
  • EXAMPLE 6 Samples obtained in the same manner as in Example 3 were heated under the same condition as in said example to form oxide layers of Type B varying in thickness for each group of samples. The thickness averaged 10 microns for 2 hours of heating, 22 microns for 10 hours of heating and 35 microns for 50 hours of heating. An erosion test conducted 2 hours at 900 C showed that all the samples displayed an excellent resistance to erosion and oxidation, the rate of peeling being around 30 percent.
  • EXAMPLE 7 Samples prepared in the same manner as in Example I were divided into three groups which were heated 2, l0 and 50 hours respectively at l,300 C. On the surfaces of the samples were formed oxide layers of Type B varying in thickness for each group. The thickness averaged 19 microns for 2 hours of heating, 43 microns for 10 hours of heating and 99 microns for 50 hours of heating. An erosion test conducted 2 hours at l,l00 C showed that all the samples displayed an excellent re sistance to erosion and oxidation, the rate of peeling being around 30 percent.
  • EXAMPLE 8 Samples obtained in the same manner as in Example I were divided into three groups which were heated 20, 50 and I00 hours respectively at l,300 C to form on the surfaces of the samples oxide layers of Type B varying in thickness for each group. The thickness averaged 58 microns for 20 hours of heating, 1 10 microns for 50 hours of heating and 150 microns for 100 hours of heating.
  • a thin metal plate prepared according to this example was worked into an after burner type reaction vessel for treating exhaust gas from an automobile.
  • the vessel was heated 20 hours in an electric furnace kept at l,300 C to form inside and outside of the vessel an oxide layer of Type B about 50 to 60 microns thick.
  • An after-burner in which the vessel was incorporated was fitted to an automobile equipped with a Wankel type rotary piston engine of 500 c.c. X 2 rotor type. After the automobile was actually made to run 50,000 kilometers, the after burner was checked, showing that the inner wall of the reaction vessel was not attacked at all by the-exhaust gas, nor presented a creep phenomenon due to a continuous run, giving very desirable results from a practical standpoint.
  • a method of preparing corrosion-resistant metallic arti-v cles which comprises forming articles from a metal consisting of 10 to 25 percent of chromium, 2 to percent of aluminum, less than 0.04 percent of carbon, 0.005 to 0.05 percent of nitrogen, 0.1 to 0.6 percent of titanium, 0.01 to 0.5 percent of zirconium, iron as the remainder and.
  • a method of preparing corrosi0n-resistant metallic articles which comprises forming articles from a metal consisting of 10 to 25 percent of chromium, 2 to 5 percent of aluminum, less than 0.04 percent of carbon, 0.005 to 0.05 percent of nitrogen, 0.1 to 0.6 percent of titanium; 001 to 0.2 percent of zirconium, iron as the remainder and further containing ordi nary impurities, in which constitution ratio of Ti% Zr% to N% ranges from 10 to 60, heating the article in an oxidizing atmosphere for a suitable number of hours at a temperature of from 1,000 to 1,400 C to diffuse by migration in the surface layer of the base body of the article part of oxidizable elements contained therein, thereby forming on said surface an oxide layer averaging from 3 to I00 microns in thickness which mainly consists of 1,0,, and the outermost region of which is constituted by a thin film of Al O -TiO 3.
  • a method of preparing corrosion-resistant metallic articles which comprises forming articles from a metal consisting of 10 to 25 percent of chromium, 2 to 5 percent of aluminum, less than 0.04 percent of carbon, 0.005 to 0.05 percent of nitrogen, 0.2 to 0.6 percent of titanium, more than 0.2 to 0.5 percent of zirconium, iron as the remainder and further containing ordinary impurities, in which constitution ratio of Ti% Zr% to N ranges from 10 to 60 and the ratio of Ti% to Zr% is set at a larger value than 0.9, heating the article in an oxidizing atmosphere for a suitable number of hours at a temperature of from l,000 to l,400 C to diffuse by migration in the surface layer of the base body of the article part of oxidizable elements contained therein, thereby forming on said surface an oxide layer 3 to 300 microns thick on average mainly consisting of 04.41 0 settled in the metallic base body in a rooty form.
  • Corrosion-resistant metallic article comprising 10 to 25 percent of chromium, 2 to 5 percent of aluminum, less than 0.04 percent of carbon, 0.005 to 0.05 percent of nitrogen, 01 to 0.6 percent of titanium, 0.01 to 0.5 percent of zirconium, iron as the remainder and further containing ordinary impurities, in which the constitution ratio of Ti Zr to N ranges from 10 to 60, and having a surface oxide layer consisting essentially of aAl O 3 to 300 microns thick.

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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Resistance Heating (AREA)
US49052A 1969-06-25 1970-06-23 Method of preparing corrosion resistant metallic articles Expired - Lifetime US3660173A (en)

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JP44050588A JPS4945456B1 (enrdf_load_stackoverflow) 1969-06-25 1969-06-25

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JP (1) JPS4945456B1 (enrdf_load_stackoverflow)
BE (1) BE752536A (enrdf_load_stackoverflow)
CA (1) CA920488A (enrdf_load_stackoverflow)
DE (1) DE2031495A1 (enrdf_load_stackoverflow)
FR (1) FR2051325A5 (enrdf_load_stackoverflow)
GB (1) GB1269916A (enrdf_load_stackoverflow)
NL (1) NL7009318A (enrdf_load_stackoverflow)
SE (1) SE354491B (enrdf_load_stackoverflow)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873306A (en) * 1973-07-20 1975-03-25 Bethlehem Steel Corp Ferritic alloy with high temperature strength containing dispersed intermetallic TiSi
US3907611A (en) * 1972-11-10 1975-09-23 Toyo Kogyo Co Method for making ferrous metal having highly improved resistances to corrosion at elevated temperatures and to oxidization
US4082575A (en) * 1976-04-21 1978-04-04 Thermacore, Inc. Production of liquid compatible metals
EP0010138A1 (en) * 1978-09-25 1980-04-30 International Business Machines Corporation A method of treating aluminium microcircuits
US4266987A (en) * 1977-04-25 1981-05-12 Kennecott Copper Corporation Process for providing acid-resistant oxide layers on alloys
US4268324A (en) * 1979-04-20 1981-05-19 Sharma Vinod C Fabrication of spectrally selective solar surfaces by the thermal treatment of austenitic stainless steel AISI 321
US4668585A (en) * 1984-06-08 1987-05-26 Osaka Prefecture, Horonobu Oonishi and Kyocera Corporation Fe-Cr-Al type implant alloy composite for medical treatment
US4963200A (en) * 1988-04-25 1990-10-16 Doryokuro Kakunenryo Kaihatsu Jigyodan Dispersion strengthened ferritic steel for high temperature structural use
US5407493A (en) * 1993-03-08 1995-04-18 Nkk Corporation Stainless steel sheet and method for producing thereof
US5413642A (en) * 1992-11-27 1995-05-09 Alger; Donald L. Processing for forming corrosion and permeation barriers
US5496514A (en) * 1993-03-08 1996-03-05 Nkk Corporation Stainless steel sheet and method for producing thereof
WO1996034122A1 (en) * 1995-04-25 1996-10-31 Alger Donald L Processing for forming nitride, carbide and oxide protective coatings
WO1997041274A1 (en) * 1996-04-30 1997-11-06 American Scientific Materials Technologies, L.P. Thin-walled monolithic metal oxide structures made from metals, and methods for manufacturing such structures
US5786296A (en) * 1994-11-09 1998-07-28 American Scientific Materials Technologies L.P. Thin-walled, monolithic iron oxide structures made from steels
US6461562B1 (en) 1999-02-17 2002-10-08 American Scientific Materials Technologies, Lp Methods of making sintered metal oxide articles
US6655369B2 (en) 2001-08-01 2003-12-02 Diesel Engine Transformations Llc Catalytic combustion surfaces and method for creating catalytic combustion surfaces
US20040009359A1 (en) * 2000-10-31 2004-01-15 Alger Donald L. Alpha Al2O3 and Ti2O3 protective coatings on aluminide substrates
US6835449B2 (en) * 2001-09-12 2004-12-28 Mogas Industries, Inc. Nanostructured titania coated titanium
US12017176B2 (en) 2014-01-07 2024-06-25 Donaldson Company, Inc. Filtration media pack, filter elements, and air filtration media

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS518806B2 (enrdf_load_stackoverflow) * 1972-04-06 1976-03-22
JPS5541290B2 (enrdf_load_stackoverflow) * 1973-11-02 1980-10-23
JPS5183277U (enrdf_load_stackoverflow) * 1974-12-25 1976-07-03
FR2594144A1 (fr) * 1986-02-10 1987-08-14 Ugine Gueugnon Sa Tole en acier inoxydable ferritique et son utilisation pour la fabrication d'un recipient embouti et poli
DE3606804A1 (de) * 1986-03-01 1987-09-10 Thyssen Huette Ag Metallisches halbzeug und verfahren zu seiner herstellung sowie verwendung
DE3706415A1 (de) * 1987-02-27 1988-09-08 Thyssen Edelstahlwerke Ag Halbfertigerzeugnis aus ferritischem stahl und seine verwendung
DE3908526A1 (de) * 1989-03-16 1990-09-20 Vdm Nickel Tech Ferritische stahllegierung
FR2647122A1 (fr) * 1989-05-22 1990-11-23 Commissariat Energie Atomique Acier inoxydable ferritique contenant notamment de l'aluminium et du titane
JP2876627B2 (ja) * 1989-07-11 1999-03-31 大同特殊鋼株式会社 耐食性に優れたステンレス鋼

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2191790A (en) * 1938-05-07 1940-02-27 Electro Metallurg Co Steels and electrical resistance elements
US2442223A (en) * 1944-09-22 1948-05-25 Gen Electric Method of improving the corrosion resistance of chromium alloys
US2635164A (en) * 1951-08-21 1953-04-14 Kanthal Ab Electric heating unit
US2987394A (en) * 1959-03-25 1961-06-06 John J Mueller Iron-aluminum base alloys
US3068094A (en) * 1959-01-27 1962-12-11 Ford Motor Co Alloy of iron, aluminum, and chromium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2191790A (en) * 1938-05-07 1940-02-27 Electro Metallurg Co Steels and electrical resistance elements
US2442223A (en) * 1944-09-22 1948-05-25 Gen Electric Method of improving the corrosion resistance of chromium alloys
US2635164A (en) * 1951-08-21 1953-04-14 Kanthal Ab Electric heating unit
US3068094A (en) * 1959-01-27 1962-12-11 Ford Motor Co Alloy of iron, aluminum, and chromium
US2987394A (en) * 1959-03-25 1961-06-06 John J Mueller Iron-aluminum base alloys

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907611A (en) * 1972-11-10 1975-09-23 Toyo Kogyo Co Method for making ferrous metal having highly improved resistances to corrosion at elevated temperatures and to oxidization
US3873306A (en) * 1973-07-20 1975-03-25 Bethlehem Steel Corp Ferritic alloy with high temperature strength containing dispersed intermetallic TiSi
US4082575A (en) * 1976-04-21 1978-04-04 Thermacore, Inc. Production of liquid compatible metals
US4266987A (en) * 1977-04-25 1981-05-12 Kennecott Copper Corporation Process for providing acid-resistant oxide layers on alloys
EP0010138A1 (en) * 1978-09-25 1980-04-30 International Business Machines Corporation A method of treating aluminium microcircuits
US4268324A (en) * 1979-04-20 1981-05-19 Sharma Vinod C Fabrication of spectrally selective solar surfaces by the thermal treatment of austenitic stainless steel AISI 321
US4668585A (en) * 1984-06-08 1987-05-26 Osaka Prefecture, Horonobu Oonishi and Kyocera Corporation Fe-Cr-Al type implant alloy composite for medical treatment
US4963200A (en) * 1988-04-25 1990-10-16 Doryokuro Kakunenryo Kaihatsu Jigyodan Dispersion strengthened ferritic steel for high temperature structural use
US5599404A (en) * 1992-11-27 1997-02-04 Alger; Donald L. Process for forming nitride protective coatings
US5413642A (en) * 1992-11-27 1995-05-09 Alger; Donald L. Processing for forming corrosion and permeation barriers
US5407493A (en) * 1993-03-08 1995-04-18 Nkk Corporation Stainless steel sheet and method for producing thereof
US5496514A (en) * 1993-03-08 1996-03-05 Nkk Corporation Stainless steel sheet and method for producing thereof
US5786296A (en) * 1994-11-09 1998-07-28 American Scientific Materials Technologies L.P. Thin-walled, monolithic iron oxide structures made from steels
US5814164A (en) * 1994-11-09 1998-09-29 American Scientific Materials Technologies L.P. Thin-walled, monolithic iron oxide structures made from steels, and methods for manufacturing such structures
WO1996034122A1 (en) * 1995-04-25 1996-10-31 Alger Donald L Processing for forming nitride, carbide and oxide protective coatings
US6077370A (en) * 1996-04-30 2000-06-20 American Scientific Materials Technologies, L.P. Thin-walled monolithic metal oxide structures made from metals, and methods for manufacturing such structures
US6045628A (en) * 1996-04-30 2000-04-04 American Scientific Materials Technologies, L.P. Thin-walled monolithic metal oxide structures made from metals, and methods for manufacturing such structures
US6051203A (en) * 1996-04-30 2000-04-18 American Scientific Materials Technologies, L.P. Thin-walled monolithic metal oxide structures made from metals, and methods for manufacturing such structures
US6071590A (en) * 1996-04-30 2000-06-06 American Scientific Materials Technologies, L.P. Thin-walled monolithic metal oxide structures made from metals, and methods for manufacturing such structures
WO1997041274A1 (en) * 1996-04-30 1997-11-06 American Scientific Materials Technologies, L.P. Thin-walled monolithic metal oxide structures made from metals, and methods for manufacturing such structures
US6461562B1 (en) 1999-02-17 2002-10-08 American Scientific Materials Technologies, Lp Methods of making sintered metal oxide articles
US20040009359A1 (en) * 2000-10-31 2004-01-15 Alger Donald L. Alpha Al2O3 and Ti2O3 protective coatings on aluminide substrates
US6933053B2 (en) 2000-10-31 2005-08-23 Donald L. Alger Alpha Al2O3 and Ti2O3 protective coatings on aluminide substrates
US6655369B2 (en) 2001-08-01 2003-12-02 Diesel Engine Transformations Llc Catalytic combustion surfaces and method for creating catalytic combustion surfaces
US20050016512A1 (en) * 2001-08-01 2005-01-27 Gillston Lionel M. Catalytic combustion surfaces and method for creating catalytic combustion surfaces
US7527048B2 (en) 2001-08-01 2009-05-05 Diesel Engine Transformation Llc Catalytic combustion surfaces and method for creating catalytic combustion surfaces
US6835449B2 (en) * 2001-09-12 2004-12-28 Mogas Industries, Inc. Nanostructured titania coated titanium
US12017176B2 (en) 2014-01-07 2024-06-25 Donaldson Company, Inc. Filtration media pack, filter elements, and air filtration media

Also Published As

Publication number Publication date
SE354491B (enrdf_load_stackoverflow) 1973-03-12
DE2031495A1 (de) 1971-01-07
GB1269916A (en) 1972-04-06
FR2051325A5 (enrdf_load_stackoverflow) 1971-04-02
BE752536A (fr) 1970-12-01
CA920488A (en) 1973-02-06
JPS4945456B1 (enrdf_load_stackoverflow) 1974-12-04
NL7009318A (enrdf_load_stackoverflow) 1970-12-29

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