EP0366655A1 - Oxidation resistant iron base alloy compositions. - Google Patents
Oxidation resistant iron base alloy compositions.Info
- Publication number
- EP0366655A1 EP0366655A1 EP88903643A EP88903643A EP0366655A1 EP 0366655 A1 EP0366655 A1 EP 0366655A1 EP 88903643 A EP88903643 A EP 88903643A EP 88903643 A EP88903643 A EP 88903643A EP 0366655 A1 EP0366655 A1 EP 0366655A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- percent
- dopant
- composition according
- present
- level
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Definitions
- This invention relates to iron-base alloy compositions and methods for preparing these compositions.
- the compositions and methods relate to nickel containing austenitic ferrous alloy compositions, especially low nickel compositions.
- this invention relates to dopants added to low nickel austenitic alloys as a means of improving the elevated temperature oxidation resistance. This invention may be extended to apply to cast alloys.
- Low nickel ferrous alloys containing chromium and having nickel present in amounts of about 5 to 15 percent by weight and having manganese, nitrogen and carbon present to aid in forming and stabilizing any austenite present are known.
- sheet metal automotive exhaust system parts would offer the advantages of both lighter weight and reduced thermal mass.
- the metal thickness of wrought automotive engine parts such as thermal reactors and turbocharger housings, should be minimized. This can be accomplished by constructing the engine parts from stainless steels, austenitic where hot strength is required, and with alloying suitable for resistance to deterioration by engine exhaust gases on the inside surface of the engine parts and atmospheric air on the outside surface of the engine parts where the surface operating temperature is at a maximum.
- Such a construction is not cost effective because the resistance to oxidation of the lower cost stainless steel sheet metal alloys at elevated temperatures of 1,500 degrees F to 2,200 degrees F is not sufficient to allow their use in, applications where the alloy is exposed to the combustion products normally formed by gasoline fueled internal combustion engines. Because the presently available low-cost alloys do not resist oxidation in elevated temperature combustion environments, it is necessary to use a more expensive alloy with a higher nickel and/or chromium content in automotive emission control devices such as thermal reactors. Therefore, the limitation to using currently available, adequate alloy content stainless steels is the high cost and excessive strategic element content. Degradation of alloy materials, such as stainless steels, at elevated temperatures is largely dependent on the protective capacity of surface oxide films formed from the alloy during exposure to heat in oxygen containing atmospheres. In one respect, this invention deals with an effective method of improving the protective capacity of oxide scales formed on alloy materials such as low nickel austenitic stainless steels.
- compositions of the present invention relate to the discovery that certain elements can be added to iron-base alloy materials to dramatically improve their resistance to oxidation. More particularly, the invention relates to the discovery that the addition of these elements (referred to herein as "dopants") yields lower cost materials suitable for use in heretofore impractical environments.
- the compositions of the present invention comprise iron-base alloy compositions exhibiting improved resistance to oxidation comprising: (i)iron;
- At least one alloy element selected from the group consisting of nickel, chromium, molybdenum, manganese, silicon, carbon, vanadium, cobalt, copper, nitrogen, aluminum, titanium, zirconium, and mixtures thereof;
- a dopant selected from the group consisting of lithium, sodium, potassium, yttrium, lanthanum, cerium, calcium, magnesium, barium, aluminum, beryllium, strontium, and mixtures thereof.
- alloy materials such as low nickel austenitic (LNA) stainless steel alloys containing chromium and ferritic stainless steel alloys containing medium to high levels of chromium with the additions of an effective amount, preferably at least about 0.02, and more preferably about 0.1 to 2 percent by weight, of the dopants or doping elements or alloys disclosed herein.
- Alloy compositions of the present invention would be made in a conventional manner, i.e., typical of the alloy content without the dopant of the present invention, but with provision for the addition of dopant elements, in the melt process or later, in later alloy processing, or by surface treatment.
- barium, calcium, lithium, lanthanum/cerium, magnesium, potassium and sodium or mixtures thereof are added to the alloy as dopants.
- the methods disclosed herein involve the addition of small quantities of elements (appearing for the most part in Groups IA, IIA, and IIB of the Periodic Table of Elements) to the base alloy composition. These elements, as ions, enter into the protective oxide scale and modify predominantly anion and to a lesser extent cation transport through the oxide scale, greatly reducing the amount of oxidation observed due to elevated temperature exposure. Research leading to this invention was based upon low nickel austenitic
- Austenite Stabilizers Alloys of this invention are designed to maintain a stable austenitic matrix at use temperatures up to 2200 degrees F. Elements identified as promoting this austenite stability are Mn, Co, Ni, Cu, C, Sn, Sb, Bi and N. Throughout the course of this alloy development, it was necessary to periodically adjust the choice and quantity of austenite stabilizer elements to balance the counteracting effects of La-Ce, Ti, Zr, V, Cr, Al and Si as these elements were introduced or changed in concentration as part of the effort to determine their effect on oxidation resistance.
- An object of this invention is to improve the protective nature of surface oxides formed during exposure to elevated temperatures and, therefore, a stable surface oxide is required.
- Elements identified as significant contributors to stable surface oxide formation on these iron base alloys are: Cr, Co,
- Dopants are elements found to have a major effect on the protective nature of the host oxide. Typically, they are found in groups IA, IIA and
- IIIB of the Periodic Table of Elements include, without limitation, those described herein, as well as mixtures of these materials. Their function in improving oxidation resistance is judged to be due to their effect on predominantly anion and to a lesser extent cation transport through the surface oxide film.
- Fig. 1 graphs the still-air cyclic oxidation resistance of LNA with other commercial high-temperature alloys at 2,200 degrees F (1,204 degrees C);
- Fig. 2 graphs the still-air cyclic oxidation resistance of LNA with other commercial high-temperature alloys at 1,900 degrees F (1,038 degrees C);
- Fig. 3 illustrates an engine dynamometer installation for alloy evaluation
- Fig. 4 shows the cyclic oxidation resistance of high-temperature alloy rings tested on an engine dynamometer at 1,800 to 1,900 degrees F (982 to 1,038 degrees C) oxidizing exhaust atmosphere, unleaded fuel;
- Fig. 5 shows a photomicrograph of LNA alloy after 1,600 hours in the 1800-1950 degrees F zone of the engine installation shown in Fig. 3;
- Fig. 6 shows a photomicrograph of commercial RA333 alloy after 1600 hours in the 1800-1950 degrees F zone of the engine installation shown in Fig. 3; and Fig. 7 shows the -progressive improvement in oxidation resistance of alloys of this invention as a result of dopant additions.
- compositions produced by the methods of the present invention demonstrate many advantages over art-disclosed compositions including, without limitation, excellent strength; amenability to mass production techniques such as forming, joining and the like; and excellent resistance to oxidation under extreme conditions such as high temperatures.
- compositions of the present invention relate to the discovery that certain elements can be added to iron-base alloy materials to dramatically improve their resistance to oxidation. More particularly, the invention relates to the discovery that the addition of these elements (referred to herein as "dopants") yields materials suitable for use in heretofore impractical environments thereby avoiding the use of expensive, higher alloy-content materials.
- the compositions of the present invention comprise iron-base alloy compositions exhibiting improved resistance to oxidation comprising: (i)iron;
- At least one alloy element selected from the group consisting of nickel, chromium, molybdenum, manganese, silicon, carbon, vanadium, cobalt, copper, nitrogen, aluminum, titanium, zirconium, and mixtures thereof; and (iii) an effective amount of a dopant selected from the group consisting of lithium, sodium, potassium, yttrium, lanthanum, cerium, calcium, magnesium, barium, aluminum, beryllium, strontium, and mixtures thereof.
- iron-base is meant that iron is the predominate alloy element present, by weight of the final composition. Thus, while one or more other alloy elements may be employed, iron may be present at a level greater than any other single element by weight. Iron need not comprise 50 percent of the composition; by way of illustration (without limitation), a composition comprising 30 percent iron, by weight, and 29 percent nickel by weight, as well as other elements each being less than 30 percent by weight, but in aggregate totaling more than 50 percent by weight (including the nickel), would be iron-base as defined herein.
- an effective amount an amount of the dopant sufficient to show a significant and reproducible improvement in one or more oxidation-resistant properties of the final compositions. Such properties would include weight change, surf ace. appearance as measured by gross observation and micro observation by metallography as described herein. For example, when two alloy compositions, differing in only that one contains an effective amount of a dopant, and the other containing less than an effective amount or no dopant are compared, the alloy containing an effective amount will demonstrate a significant and reproducible improvement in one or more oxidation-resistant properties.
- Preferred alloy elements include those selected from the group consisting of silicon, nickel, chromium, cobalt, manganese, nitrogen, and mixtures thereof. Silicon, nickel, and chromium are particularly preferred. Iron, as well as the alloy elements described above, can be employed at levels generally known in the art.
- the dopants of the present invention may be employed in AISI types 201, 202, 301, 302, 302B, 303, 303Se, 304, 304L, 305, 308, 309, 309S, 310, 315, 316, 316L, 317, 321, 347, 348, 384 and 385 austenitic stainless steels.
- compositions prepared by the methods of the present invention can also employ lower levels, of strategic or expensive elements than generally disclosed in the art, but at the same time demonstrating equivalent or improved oxidation resistant properties.
- Stainless steel (RA 333) and non-stainless steel (INCO 330) may also employ the dopants of the present invention.
- Preferred compositions include those where nickel is present at a level of about 5 to about 15 percent, and where chromium is present at a level of about 10 to about 30 percent, by weight of the final composition.
- compositions and methods of the present invention employ an effective amount of a dopant.
- Preferred dopants are primarily selected from the group consisting of elements from Groups IA, IIA, IIIB of the Periodic Table of Elements. These include lithium, sodium, potassium, yttrium, lanthanum, cerium, calcium, magnesium, barium, aluminum, beryllium, and strontium. Mixtures of such materials may also be employed. Highly preferred materials include lithium, sodium, potassium, yttrium, lanthanum, cerium, calcium, magnesium, barium, aluminum and mixtures thereof. Preferred mixtures include magnesium and calcium with lithium, sodium, potassium, lithium and sodium, and lithium and potassium.
- the dopant is employed in the compositions and methods of the present invention in an effective amount.
- a level will vary with many factors, including, without limitation, the level of the various other elements, materials or impurities present, such as iron, nickel, chromium and the like, as well as the desired improvement in oxidation resistance. The selection of such a level is well within the skill of the artisan in light of the present disclosure and teachings.
- aluminum can play many roles in the compositions of the present invention. It can be used as an effective dopant when employed at In general, the dopant is present at a level of about at least about 0.02 percent, by weight of the final composition.
- the dopant is present at a level of about 0.05 to about 5 percent; still more preferably at a level of about 0.1 to about 3.5 percent; and still more preferably at a level of about 0.1 to about 2.0 percent.
- the dopant comprises magnesium, calcium, lithium, sodium, and potassium; the magnesium is present at a level of about 0.1 to about 1.5 percent; the calcium is present at a level of about 0.1 to about 1.5 percent; the lithium is present at a level of about 0.1 to about 0.5 percent; the sodium is present at a level of about 0.1 to about 0.5 percent; the potassium is present at a level of about 0.5 to about 1.0 percent.
- an alloy of this invention would be made with about 20 to 30 percent by weight chromium, about 0.1 to 1.5 percent by weight carbon, about 3 to 4 percent by weight manganese, about 0 to 12 percent by weight cobalt, about 5 to 15 percent by weight nickel and about 0.5 to 2 percent by weight dopant, with the balance being iron and normal residual impurities.
- the alloys of this invention can be described as oxidation resistance steels having iron as the base material with the addition of chromium and other alloying elements to increase oxidation resistance.
- the preferred alloys of this invention have a stable austenitic structure with the further feature that they contain minor quantities of dopant elements.
- Nickel, cobalt, nitrogen, carbon and manganese are strong austenite stabilizers in ferrous alloys and the concentration of one or more of these elements in the alloy should be maintained at a level high enough to ensure that the alloy's structure remains austenitic over the temperature range normally encountered by parts formed from the alloy.
- Alloying element ranges of 3 to 4 percent by weight, manganese; 5 to 15 percent by weight, nickel; 0 to 12 percent by weight, cobalt; 0.1 to 0.5 percent by weight, nitrogen; and 0.5 to 1.5 percent by weight, carbon provide good austenite stabilizing levels in normal ferrous alloys. Because excessive manganese (an austenite stabilizer) promotes the formation of a thick non-adherent oxide which spalls off and promotes further oxidation, its concentration in the alloys of this invention is needed but controlled to lessen the tendency for oxide spalling consistent with other requirements like formability, weldability and strength.
- Heat sizes were either 2500 or 5000 grams with resulting ingots weighing approximately 1800 grams. These ingots were hot forged and/or hot rolled into slabs with sufficient thermal-mechanical working to destroy the original cast micro-structure. Hot and cold rolling, with inter-stage annealing was employed to produce final strip form, typically 0.030" thick. Special melting procedures were employed for the addition of Mg wherein Mg metal or NiMg was encased in iron foil and plunged into the melt to facilitate high recovery levels of Mg. For convenience, halogen salts of Li, Na, K, Mg, Ca, Sr and Ba were often employed for small quantity (less than 1 percent) additions of these elements.
- the magnesium dopant modified silicon-containing alloys show an average oxidation resistance improvement at 2,200 degrees F of 24 percent compared to the undoped base composition. Further addition of calcium dopant yields a 36 percent improvement compared to the undoped base composition.
- Introduction of sodium, lithium, potassium, barium and lanthanum/cerium dopants, in addition to magnesium and calcium results in an average oxidation resistance improvement at 2,200 degrees F of 78 percent compared to the undoped base composition.
- Procedures used to evaluate experimental and commercial alloys range from simple still air cyclic oxidation tests with small coupons in laboratory furnaces, to vehicle tests with full size components.
- several of the following tests were performed: still-air cyclic oxidation in laboratory furnaces; cyclic endurance tests on engines loaded by dynamometers; controlled exhaust environment tests in tube furnaces; component endurance tests on engines loaded by dynamometers; and on-vehicle tests at the proving grounds for durability.
- Fig. 1 shown are graphs of the still-air cyclic oxidation resistance of LNA with other commercial high-temperature alloys at 2200 degrees F.
- the LNA alloy outperforms the stainless steel (RA 333) and non-stainless steel
- alloy test rings were utilized in various segments of an engine/dynamometer installation. Also employed were experimental alloy liners on exhaust manifolds of the engine driving the dynamometer.
- Fig. 3 is a schematic drawing of the alloy test ring pipe arrangement. The test conditions were controlled readily by injecting air at strategic points in the manifold, and adjusting carburetor jets to produce desired carbon monoxide levels and robot control of engine speed, load, spark and air injection.
- Elements are the active ingredients in this dopant concept, other elements such as Y, Si and Al have shown second order interaction benefits with the dopants. While not intending to be bound by theory, this is thought to be due to their contribution to the formation of a stable host oxide along with the other active oxide formers such as chromium, nickel and iron. Both Al and Si are strong ferrite formers and their presence required the further addition of nitrogen as an austenitic stabilizer to maintain the required austenitic microstructure. Accordingly, aluminum can be effective as a dopant when employed at levels below those typically taught in the art and necessary to employ it as an oxide former.
- Fig. 7 illustrates the progressive improvement in cyclic oxidation resistance of the alloys of this invention as additional dopant elements were introduced.
- the final low nickel austenitic alloy, with oxidation resistance superior to commercial RA333 contained dopants from the group of elements Li, Na, K, Mg, Ca, Ba and La, all of which are found in Groups IA, IIA or IIIB of the Periodic Table of Elements.
- Fig. 7 summarizes the experimental-design development of these alloys.
- oxidation resistance is generally characterized by weight loss per unit area of a 0.030" thick test panel shown as the ordinate.
- the band “RA333” represents a common commercial oxidation resistant austenitic alloy used as the standard of reference in all oxidation tests.
- Tabulated along the abscissa are two rows of element designations.
- the "investigated” row identifies those elements selected by the fractional factorial experiment to be of potential interest and worthy of incorporation into detailed full factorial experimental schemes.
- the "accepted” row identifies those elements which were found to offer significant improvements in oxidation resistance following detailed analysis of full factorial experiments. Moving from left to right on Fig.
Abstract
La présente invention se rapporte à des compositions d'alliages à base de fer, à une composition d'alliage ferreux osténitique contenant du nickel (en particulier des compositions à faible teneur en nickel) et à des dopants ajoutés à des alliages osténitiques à faible teneur en nickel comme moyens d'améliorer la résistance à l'oxydation à température élevée du matériau qui en résulte. L'oxydation cyclique en air tranquille d'une telle composition d'alliage et une comparaison d'un tel alliage avec deux alliages de la technique antérieure sont représentées sur le graphique.The present invention relates to iron-based alloy compositions, to an ostenitic ferrous alloy composition containing nickel (in particular compositions with a low nickel content) and to dopants added to low-content ostenitic alloys. of nickel as a means of improving the resistance to oxidation at high temperature of the resulting material. The cyclic oxidation in still air of such an alloy composition and a comparison of such an alloy with two alloys of the prior art are shown in the graph.
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1988/000982 WO1989009843A1 (en) | 1988-04-04 | 1988-04-04 | Oxidation resistant iron base alloy compositions |
CA000563292A CA1340700C (en) | 1988-04-04 | 1988-04-05 | Oxidation resistant iron base alloy compositions |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0366655A1 true EP0366655A1 (en) | 1990-05-09 |
EP0366655A4 EP0366655A4 (en) | 1991-07-24 |
EP0366655B1 EP0366655B1 (en) | 1996-02-28 |
Family
ID=33565659
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88903643A Expired - Lifetime EP0366655B1 (en) | 1988-04-04 | 1988-04-04 | Oxidation resistant iron base alloy compositions |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0366655B1 (en) |
CA (1) | CA1340700C (en) |
DE (1) | DE3855047T2 (en) |
WO (1) | WO1989009843A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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SE516583C2 (en) * | 1997-12-05 | 2002-01-29 | Sandvik Ab | Austenitic stainless steel with good oxidation resistance |
AUPP042597A0 (en) * | 1997-11-17 | 1997-12-11 | Ceramic Fuel Cells Limited | A heat resistant steel |
DE102008005803A1 (en) * | 2008-01-17 | 2009-07-23 | Technische Universität Bergakademie Freiberg | Component used for armoring vehicles and in installations and components for transporting and recovering gases at low temperature is made from a high carbon-containing austenitic cryogenic steel cast mold |
CN104032220B (en) * | 2014-05-09 | 2016-05-25 | 无锡市华尔泰机械制造有限公司 | A kind of high-pressure hydro operating mode flange |
US10316694B2 (en) | 2014-07-31 | 2019-06-11 | Garrett Transportation I Inc. | Stainless steel alloys, turbocharger turbine housings formed from the stainless steel alloys, and methods for manufacturing the same |
US9534281B2 (en) | 2014-07-31 | 2017-01-03 | Honeywell International Inc. | Turbocharger turbine housings formed from the stainless steel alloys, and methods for manufacturing the same |
US9896752B2 (en) | 2014-07-31 | 2018-02-20 | Honeywell International Inc. | Stainless steel alloys, turbocharger turbine housings formed from the stainless steel alloys, and methods for manufacturing the same |
DE102016005531A1 (en) * | 2016-05-02 | 2017-11-02 | Vladimir Volchkov | Low carbon steel |
CN107326293A (en) * | 2017-06-02 | 2017-11-07 | 太仓市龙华塑胶有限公司 | A kind of wear-resisting handware |
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Also Published As
Publication number | Publication date |
---|---|
CA1340700C (en) | 1999-08-10 |
WO1989009843A1 (en) | 1989-10-19 |
DE3855047T2 (en) | 1996-09-12 |
DE3855047D1 (en) | 1996-04-04 |
EP0366655A4 (en) | 1991-07-24 |
EP0366655B1 (en) | 1996-02-28 |
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