EP2047007A1 - Heat and corrosion resistant cast austenitic stainless steel alloy with improved high temperature strength - Google Patents

Heat and corrosion resistant cast austenitic stainless steel alloy with improved high temperature strength

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Publication number
EP2047007A1
EP2047007A1 EP07751919A EP07751919A EP2047007A1 EP 2047007 A1 EP2047007 A1 EP 2047007A1 EP 07751919 A EP07751919 A EP 07751919A EP 07751919 A EP07751919 A EP 07751919A EP 2047007 A1 EP2047007 A1 EP 2047007A1
Authority
EP
European Patent Office
Prior art keywords
cast
cf8c
stainless steel
creep
weight percent
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.)
Withdrawn
Application number
EP07751919A
Other languages
German (de)
French (fr)
Inventor
Philip J. Maziasz
John P. Shingledecker
Michael J. Pollard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Caterpillar Inc
UT Battelle LLC
Original Assignee
Caterpillar Inc
UT Battelle LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Caterpillar Inc, UT Battelle LLC filed Critical Caterpillar Inc
Publication of EP2047007A1 publication Critical patent/EP2047007A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/004Heat treatment of ferrous alloys containing Cr and Ni
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/001Austenite

Definitions

  • This disclosure relates generally to cast austenitic stainless steel alloys of the CF8C type with improved high temperature strength. More particularly, this disclosure relates to CF8C type stainless steel alloys and articles cast therefrom having excellent high temperature creep strength, and aging resistance, and which exhibit a stable austenitic microstructure with substantially no delta ferrite after casting and high temperature aging.
  • Nickel based super alloys are candidate materials for other high temperature applications like gas turbines, due to its excellent high temperature properties.
  • the cost of nickel makes nickel based super alloys expensive, and turbine manufacturers are considering lower-cost alternatives for casings and large structural components. These material issues are not unique to diesel engines and combustion turbines.
  • Distributed power applications that utilize advanced natural gas reciprocating engines need low-cost high-temperature capable materials as expectations for efficiency and service temperature increase. Any new material for these applications should have low cost and good high temperature creep and fatigue resistance.
  • any new material should have good casting characteristics like melt fluidity, hot tear resistance, and weldability.
  • a significant factor in the cost of producing a casting is the post casting stress relief or solution heat treatment typically required for stainless steel castings. Eliminating the need for post casting heat treatments can result in substantial time and money savings for casting manufacturers. These cost savings can be even higher for large components like steam turbine casings where large furnaces have to be used. Therefore, any new material should have the desired properties in the as-cast state, that is, without the need for post casting heat treatment.
  • CF8C is a commercially available cast austenitic stainless steel that is relatively inexpensive. However, standard practice is to solution treat CF8C castings at 1050 0 C, which like discussed above, may increase its cost for some applications.
  • Currently-available cast austenitic stainless CF8C steels may include from 18 wt. % to 21 wt. % chromium, 9 wt. % to 12 wt. % nickel and smaller amounts of carbon, silicon, manganese, phosphorous, sulfur and niobium.
  • CF8C typically includes about 2 wt. % silicon, about 1.5 wt. % manganese and about 0.04 wt. % sulfur.
  • CF8C is a niobium stabilized grade of austenitic stainless steel most suitable for applications at temperatures below 500 0 C. In the standard form CF8C has poor strength at temperatures above 600 0 C. It also does not provide adequate cyclic oxidation resistance at temperatures exceeding 700 0 C, does not provide sufficient ductility, does not have the requisite long- term stability of the original microstructure after high temperature aging, and lacks long-term resistance to cracking during severe thermal cycling.
  • delta ferrite is present in the as-cast microstructure.
  • This delta-ferrite in the microstructure transforms to sigma ( ⁇ ) phase during prolonged high-temperature exposure, decreasing the ductility of the material, particularly at lower or ambient temperatures.
  • sigma
  • the absence of delta ferrite and sigma phase in the microstructure in the as-cast state and after prolonged exposure to high temperatures (high temperature aging) is an important advantage to preserve the as-cast properties of the material during the lifetime of a component created with the material.
  • a class of stainless steel alloys is described in U.S.
  • Patent 5,340,534 issued to Magee (hereinafter, "the '534 patent”.)
  • the '534 patent seeks to improve the galling resistance and corrosion resistance of stainless steel alloys.
  • a concentration of silicon above 2.25% is an important contributor to the improved galling resistance of the alloy.
  • Silicon is also important for metal fluidity of casting steels.
  • silicon promotes the formation of ferrite, sigma phases and niobium rich lanes or other suicide phases in the steel, and ferrite volume measurements indicate ferrite volumes between 2.3 and 7 percent in different heats of alloys described in the '534 patent.
  • presence of ferrite and sigma phases deteriorates the properties of steels exposed to high temperatures.
  • Another class of stainless steel alloys is described in U.S.
  • Patent 4,341,555 issued to Douthett et al. (hereinafter, "the '555 patent”.)
  • the concentration of carbon is restricted to 0.06%, and a concentration of molybdenum is kept between 2 and 4.5% for good pitting and acid corrosion resistance.
  • the alloys described in the '555 patent rely on post casting stress relief heat treatments to improve their mechanical properties.
  • a modified CF8C type steel alloy which has good casting characteristics, improved strength and creep properties at temperatures above 600°C in the as-cast state, and which exhibits a stable and completely austenitic microstructure after casting and high temperature aging, so that the improved strength and ductility of the material is maintained over the lifetime of the alloy.
  • Completely austenitic microstructure refers to a nearly 100% austenitic microstructure which is substantially free of delta ferrite and sigma phases of steel.
  • the disclosed system is directed to overcoming one or more of the problems set forth above.
  • the present disclosure is directed to a heat and corrosion resistant cast austenitic stainless steel alloy which contains less than about 15% nickel.
  • the alloy has a completely austenitic microstructure in an as- cast state, and a creep rupture life exceeding 20,000 hrs at a stress of 35 MPa and a temperature of 850°C, when creep tested in the as-cast state under ASTM E 139 test conditions.
  • the present disclosure is directed to a heat and corrosion resistant cast austenitic stainless steel alloy containing less than 15% nickel.
  • the alloy has a creep rupture life exceeding 3,000 hrs and a minimum creep rate of less than 1 x 10 "3 at a stress of 100 MPa and a temperature of 750 0 C, when creep tested in the as-cast state under ASTM El 39 test conditions.
  • the alloy also has a 0.2% yield strength exceeding 130 MPa at 750 0 C in the as-cast state, and a decrease in 0.2% yield strength from 750 to 900 0 C of less than 20%; and, a completely austenitic microstructure after casting.
  • the present disclosure is directed to an article made of a heat and corrosion resistant cast austenitic stainless steel alloy which contains less than about 15% nickel and has a completely austenitic microstructure.
  • the article also shows no detectable ferromagnetic phases like ferrite or martensite when measured with a measurement device after casting and after high temperature aging for 3000 hrs at 750 0 C.
  • the article has a creep rupture life exceeding 20,000 hrs at a stress of 35 MPa and a temperature of 85O 0 C, when creep tested in the as-cast state under ASTM El 39 test conditions and a creep rupture life exceeding 2000 hours and a minimum creep rate less than 5 x 10 3 at a stress of 100 MPa and a temperature of 75O 0 C, when creep tested in the as-cast state under ASTM El 39 test conditions.
  • the present disclosure also discloses a heat and corrosion resistant cast austenitic stainless steel alloy which has a completely austenitic microstructure in the as-cast state.
  • the alloy includes about 0.05 weight percent to about 0.15 weight percent of carbon, about 1.5 weight percent to about 3.5 weight percent copper, about 0.25 weight percent to about 1.0 weight percent tungsten, and about 0.6 weight percent to about 1.5 weight percent of niobium.
  • FIG. Ia is an SEM micrograph of the microstructure of an exemplary polished and etched as-cast CF8C alloy.
  • FIG. Ib is an SEM micrograph of the microstructure of an exemplary polished and etched as-cast CF8C-Plus alloy.
  • FIG. 2a shows the microstructure of an exemplary CF8C alloy before high temperature aging.
  • FIG. 2b shows the microstructure of an exemplary CF8C alloy after high temperature aging.
  • FIG. 3a shows the microstructure of an exemplary CF8C-Plus alloy before high temperature aging.
  • FIG. 3b shows the microstructure of an exemplary CF8C-Plus alloy after high temperature aging.
  • FIG. 4a is a TEM image of the microstructure of an exemplary CF8C-Plus alloy after high temperature aging.
  • FIG. 4b is a TEM image of the microstructure of an exemplary CF8C-Plus alloy after creep testing at 850 0 C and 35MPa.
  • CF8C is the traditional cast equivalent of type 347 stainless steel.
  • the chemistry of CF8C-Plus is based on the composition of CF8C with precise additions of nickel (Ni), manganese (Mn), and nitrogen (N) combined with a reduction in silicon (Si) and adjustments of other minor alloying elements. These alloy modifications were made to improve the high-temperature mechanical properties and the casting characteristics of the CF8C steel using inexpensive alloying elements without the need for post casting heat treatments.
  • Table I is directed towards the maximum and minimum ranges of the compositional elements made in accordance with the present disclosure.
  • Table I also includes (in column labeled "Example alloy") an example of an embodiment of an alloy made in accordance with the present disclosure.
  • Embodiments covered by the present disclosure include alloys with any subset of compositional ranges falling within the minimum and maximum ranges shown in Table I.
  • allowable ranges of cobalt (Co), vanadium (V), and titanium (Ti) may not significantly alter the performance of the resulting material.
  • Co may range from 0 to about 5 weight percent
  • V may range from 0 to about 3 weight percent
  • Ti may range from 0 to about 0.2 weight percent without significantly altering the performance of the alloys.
  • FIG. Ia shows the microstructure of an exemplary polished and etched as-cast CF8C alloy
  • FIG. Ib shows the microstructure of an exemplary polished and etched as-cast CF8C-Plus alloy.
  • the microstructure of the as-cast CF8C alloy includes an austenite matrix with delta ferrite 10 pools in the interdentrite core regions, and niobium carbide (NbC) 12 in the interdentritic regions.
  • NbC niobium carbide
  • the microstructure of the as-cast CF8C-Plus alloy does not show any delta ferrite 10.
  • the microstructure of CF8C-Plus alloy is fully austenitic with a mixture of chromium carbide (Cr 23 C 6 ) and NbC 12 in the interdentritic regions.
  • a digital Fisher ® Feritscope ® was used to measure the ferrite content of both the CF8C and CF8C-Plus steel castings.
  • the CF8C had a ferrite number of about 16.8 +/-1.1, which is equivalent to about 14% delta ferrite, and the CF8C-Plus did not register any detectable ferromagnetic behavior, meaning it has less than about 0.1% delta ferrite. Both these macroscopic measurements and microscopic studies indicate that the CF8C-Plus material in the as-cast state is substantially free of delta ferrite 10 in the as-cast state.
  • sand cast keel bars were encapsulated in quartz tubes, evacuated, and backfilled with argon. These were aged in an air box furnace at 750 0 C for 3,000 hours. These specimens were polished and etched for optical microscopy using an etchant composed of glycerin, hydrochloric acid, nitric acid, and acetic acid having a volumetric ratio of 3:3 : 1 : 1. Scanning Electron Microscopy (SEM) analysis was performed on polished and unetched specimens using backscatter electron (BSE) imaging, and x-ray energy dispersive spectroscopy (XEDS) was performed on areas of interest.
  • SEM Scanning Electron Microscopy
  • BSE backscatter electron
  • XEDS x-ray energy dispersive spectroscopy
  • FIG. 2a shows a BSE image of the microstructure of an exemplary CF8C alloy before high temperature aging
  • FIG. 2b shows a BSE image of the microstructure of an exemplary CF8C alloy after high temperature aging at
  • FIGS. 2a and 2b indicate a change in BSE image contrast in delta ferrite 10 of the aged material.
  • XEDS analysis of these regions in the aged material indicates that they are enriched in silicon (Si) and chromium (Cr) compared to the delta- ferrite 10 found in the as-cast structure.
  • Comparison of FIGS. 2a and 2b indicates that delta-ferrite 10 has transformed into sigma phase 14 after high temperature aging. Based on the chemical composition of the phase and the knowledge that delta-ferrite 10 can transform rapidly to sigma phase 14 in stainless steels, it is concluded that aging for 3,000 hours at 750 0 C transforms a majority of the delta ferrite 10 in CF8C steel into sigma phase 14. Electron diffraction patterns from these regions were studied using transmission electron microscopy (TEM) and confirmed the presence of body centered tetragonal (bet) sigma phase.
  • TEM transmission electron microscopy
  • FIG. 3a shows a BSE image of the microstructure of an exemplary CF8C-Plus alloy before high temperature aging
  • FIG. 3b shows a BSE image of the microstructure of an exemplary CF8C-Plus alloy after high temperature aging at 750 0 C for 3,000 hours.
  • the CF8C-Plus steel alloys in FIG 3a and FIG 3b do not show the formation of any delta ferrite 10 or sigma phases 14 after high temperature aging.
  • the structure of CF8C-Plus alloy before and after high temperature aging samples is austenitic with interdendritic carbides 16. No obvious change was observed in carbide size or morphology after aging.
  • Table II compares the average tensile properties, namely 0.2% offset yield strength (YS), ultimate tensile strength (UTS), and ductility as measured as the percentage elongation at fracture (Elong.), and percentage reduction of cross sectional area at fracture (RA), for CF8C, and CF8C-Plus (CF8C+) steels as a function of temperature.
  • the average yield strength of CF8C-Plus changes very little above 700 0 C, while that of CF8C steel shows significant weakening.
  • the average ultimate tensile strength of the CF8C-Plus steel is higher for the entire temperature range compared to CF8C. This increase is significantly higher (> 70 Mpa) at temperatures above 700 0 C.
  • the ductility, as measured by elongation and reduction of area, of CF8C-PIus steel are both higher than that of CF8C steel above 700 0 C.
  • Table III compares the average creep rupture life of CF8C and CF 8C-Plus (CF8C+) alloys at different stresses and temperatures. As seen in the table, the creep rupture life of CF8C-Plus steel is over an order of magnitude higher than that of CF8C steel in all cases.
  • the creep ductility of CF8C-Plus steel both as measured as a percentage change in elongation and percentage change in area, also shows a significant improvement over that of CF8C steel. In most cases, this improvement in ductility over CF8C steel is over 100%.
  • the minimum creep rate of CF8C-Plus steel also shows a significant decrease over that of CF8C. In most cases, this decrease in minimum creep rate is over an order of magnitude lower than that of CF8C. Table III
  • FIG. 4a is a TEM image of the microstructure of CF8C after 493 hours of creep testing at 850 0 C and 35MPa.
  • FIG. 4b is the TEM image of the microstructure of CF8C-Plus after over 20,000 hours of creep testing at 85O 0 C and 35MPa.
  • Comparison of FIGS. 4a and 4b shows that the NbC 12 precipitates in the CF8C-Plus steel were less than about 50 nanometers in average diameter (as shown in FIG. 4b,) while the average diameter of these precipitates was over about 250 nanometers, with much larger spacing after only 493 hours of testing, in CF8C alloys (as shown in FIG. 4a.)
  • This alloy is used as the baseline to compare the effect of additional alloying elements in the alloy.
  • the columns titled 'CF8C+B', 'CF8C+W, 'CF8C+Cu', and 'CF8C+AF list the composition of the alloys obtained by adding about 0.005 weight percent of boron, about 0.45 weight percent of tungsten, about 2.5 weight percent of copper, and about 1.3 weight percent of aluminum, respectively, to the composition of the CF8C-Plus alloy.
  • Table VII compares the tensile test and creep test results of the four alloy additions to the CF8C material. As the results indicate, samples with Al and B additions exhibited worse creep life than CF8C-Plus material, and were not, therefore, chosen for creep testing at 750 0 C and 140MPa. The results indicate that the alloys with the Cu and W additions performed better than the base CF8C-Plus material in high temperature creep.
  • the disclosed heat and corrosion resistant cast austenitic stainless steel alloy can be used for the production of any articles exposed to extreme temperatures and/or extreme thermal cycling conditions.
  • the disclosed alloy can be used for components in engines and power systems.
  • the present disclosure is not limited to these applications, as other applications will become apparent to those skilled in the art.
  • CF8C-Plus steel results in increased low cycle fatigue life and creep rupture strength. Increased low cycle fatigue life and creep rupture strength allows components made of CF8C+ to be long lasting.
  • the increased creep strength and fatigue life of the disclosed CF8C-Plus steel alloys over traditional CF8C material is unexpected because both these materials are castings, and therefore, deformation processes are not involved in creating a dislocation structure upon cooling.
  • Potential reasons for the significant improvement of low cycle fatigue life and creep rupture life of CF8C-Plus over traditional CF8C alloys are that the presence of Mn alters the stacking fault energy of the CF8C-Plus alloy giving rise to higher energy stacking faults, and the presence of manganese and nitrogen in the alloy composition helps nucleation of NbC.
  • the size and density of the NbC 12 precipitates in the matrix may also contribute to the observed improvement in fatigue life and creep rupture life.
  • the presence of these fine particulates of NbC 12 could likely pin dislocations, improving the creep rupture life of CF8C-Plus alloys.
  • the increased fatigue and creep rupture life, the decreased creep strain rate, and the lower decrease in 0.2% yield strength at high temperatures may allow engine and turbine manufacturers to increase power density by allowing engines and turbines to run at higher temperatures, thereby providing possible increase in fuel efficiency.
  • Engine and turbine manufacturers may also reduce the weight of components as a result of the increased power density by thinner section designs allowed by increased high temperature strength and corrosion resistance compared to conventional high-silicon molybdenum ductile irons. Further, the stainless steel alloys of the present disclosure provide superior performance over other cast stainless steels for a comparable or lower cost. Finally, stainless steel alloys disclosed herein will assist manufacturers in meeting emission regulations for diesel, turbine and gasoline engine applications.

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Abstract

A heat and corrosion resistant cast austenitic stainless steel alloy which contains less than about 15% nickel. The alloy has a creep rupture life exceeding 3,000 hrs and a minimum creep rate of less than 1 x 10-3 at a stress of 100 MPa and a temperature of 75O°C, when creep tested in the as-cast state under ASTM El 39 test conditions. The alloy also has a 0.2% yield strength exceeding 130 MPa at 750°C in the as-cast state, and a decrease in 0.2% yield strength from 750 to 900°C of less than 20%; and, a completely austenitic microstructure after casting.

Description

HEAT AND CORROSION RESISTANT CAST AUSTENITIC STAINLESS STEEL ALLOY WITH IMPROVED HIGH TEMPERATURE STRENGTH
Technical Field
This disclosure relates generally to cast austenitic stainless steel alloys of the CF8C type with improved high temperature strength. More particularly, this disclosure relates to CF8C type stainless steel alloys and articles cast therefrom having excellent high temperature creep strength, and aging resistance, and which exhibit a stable austenitic microstructure with substantially no delta ferrite after casting and high temperature aging.
Background
There is a need for high strength, oxidation resistant and crack resistant cast alloys for use in components subject to extreme temperature environments. Advanced diesel engines must continue to have high fuel efficiency as well as reduced exhaust emissions, without sacrificing durability and reliability. More demanding duty cycles require exhaust manifolds and turbocharger housing materials to withstand temperatures above 7500C. Such materials must withstand both prolonged, steady high-temperature exposure as well as more rapid and severe thermal cycling. New emissions reduction technology and transient power excursions can push temperatures in these critical components even higher. The current material of choice for diesel engine components is Silicon-Molybdenum (SiMo) cast iron. However, it is being pushed beyond its high temperature strength and corrosion limitations. Nickel based super alloys are candidate materials for other high temperature applications like gas turbines, due to its excellent high temperature properties. However, the cost of nickel makes nickel based super alloys expensive, and turbine manufacturers are considering lower-cost alternatives for casings and large structural components. These material issues are not unique to diesel engines and combustion turbines. Distributed power applications that utilize advanced natural gas reciprocating engines need low-cost high-temperature capable materials as expectations for efficiency and service temperature increase. Any new material for these applications should have low cost and good high temperature creep and fatigue resistance.
Because these components are made by casting processes, any new material should have good casting characteristics like melt fluidity, hot tear resistance, and weldability. A significant factor in the cost of producing a casting is the post casting stress relief or solution heat treatment typically required for stainless steel castings. Eliminating the need for post casting heat treatments can result in substantial time and money savings for casting manufacturers. These cost savings can be even higher for large components like steam turbine casings where large furnaces have to be used. Therefore, any new material should have the desired properties in the as-cast state, that is, without the need for post casting heat treatment.
CF8C is a commercially available cast austenitic stainless steel that is relatively inexpensive. However, standard practice is to solution treat CF8C castings at 10500C, which like discussed above, may increase its cost for some applications. Currently-available cast austenitic stainless CF8C steels may include from 18 wt. % to 21 wt. % chromium, 9 wt. % to 12 wt. % nickel and smaller amounts of carbon, silicon, manganese, phosphorous, sulfur and niobium. CF8C typically includes about 2 wt. % silicon, about 1.5 wt. % manganese and about 0.04 wt. % sulfur. CF8C is a niobium stabilized grade of austenitic stainless steel most suitable for applications at temperatures below 5000C. In the standard form CF8C has poor strength at temperatures above 6000C. It also does not provide adequate cyclic oxidation resistance at temperatures exceeding 7000C, does not provide sufficient ductility, does not have the requisite long- term stability of the original microstructure after high temperature aging, and lacks long-term resistance to cracking during severe thermal cycling.
In austenitic stainless steel castings, such as CF8C, delta ferrite is present in the as-cast microstructure. This delta-ferrite in the microstructure transforms to sigma (σ) phase during prolonged high-temperature exposure, decreasing the ductility of the material, particularly at lower or ambient temperatures. The absence of delta ferrite and sigma phase in the microstructure in the as-cast state and after prolonged exposure to high temperatures (high temperature aging) is an important advantage to preserve the as-cast properties of the material during the lifetime of a component created with the material. A class of stainless steel alloys is described in U.S. Patent 5,340,534 issued to Magee (hereinafter, "the '534 patent".) The '534 patent seeks to improve the galling resistance and corrosion resistance of stainless steel alloys. A concentration of silicon above 2.25% is an important contributor to the improved galling resistance of the alloy. Silicon is also important for metal fluidity of casting steels. However, silicon promotes the formation of ferrite, sigma phases and niobium rich lanes or other suicide phases in the steel, and ferrite volume measurements indicate ferrite volumes between 2.3 and 7 percent in different heats of alloys described in the '534 patent. As described earlier, presence of ferrite and sigma phases deteriorates the properties of steels exposed to high temperatures. Another class of stainless steel alloys is described in U.S. Patent 4,341,555 issued to Douthett et al. (hereinafter, "the '555 patent".) In the alloys described in the '555 patent, the concentration of carbon is restricted to 0.06%, and a concentration of molybdenum is kept between 2 and 4.5% for good pitting and acid corrosion resistance. The alloys described in the '555 patent rely on post casting stress relief heat treatments to improve their mechanical properties.
It is, therefore, desirable to have a modified CF8C type steel alloy which has good casting characteristics, improved strength and creep properties at temperatures above 600°C in the as-cast state, and which exhibits a stable and completely austenitic microstructure after casting and high temperature aging, so that the improved strength and ductility of the material is maintained over the lifetime of the alloy. Completely austenitic microstructure refers to a nearly 100% austenitic microstructure which is substantially free of delta ferrite and sigma phases of steel.
The disclosed system is directed to overcoming one or more of the problems set forth above.
Summary of the Invention In one aspect, the present disclosure is directed to a heat and corrosion resistant cast austenitic stainless steel alloy which contains less than about 15% nickel. The alloy has a completely austenitic microstructure in an as- cast state, and a creep rupture life exceeding 20,000 hrs at a stress of 35 MPa and a temperature of 850°C, when creep tested in the as-cast state under ASTM E 139 test conditions.
In another aspect, the present disclosure is directed to a heat and corrosion resistant cast austenitic stainless steel alloy containing less than 15% nickel. The alloy has a creep rupture life exceeding 3,000 hrs and a minimum creep rate of less than 1 x 10"3 at a stress of 100 MPa and a temperature of 7500C, when creep tested in the as-cast state under ASTM El 39 test conditions. The alloy also has a 0.2% yield strength exceeding 130 MPa at 7500C in the as-cast state, and a decrease in 0.2% yield strength from 750 to 9000C of less than 20%; and, a completely austenitic microstructure after casting.
In another aspect, the present disclosure is directed to an article made of a heat and corrosion resistant cast austenitic stainless steel alloy which contains less than about 15% nickel and has a completely austenitic microstructure. The article also shows no detectable ferromagnetic phases like ferrite or martensite when measured with a measurement device after casting and after high temperature aging for 3000 hrs at 7500C. The article has a creep rupture life exceeding 20,000 hrs at a stress of 35 MPa and a temperature of 85O0C, when creep tested in the as-cast state under ASTM El 39 test conditions and a creep rupture life exceeding 2000 hours and a minimum creep rate less than 5 x 103 at a stress of 100 MPa and a temperature of 75O0C, when creep tested in the as-cast state under ASTM El 39 test conditions.
The present disclosure also discloses a heat and corrosion resistant cast austenitic stainless steel alloy which has a completely austenitic microstructure in the as-cast state. The alloy includes about 0.05 weight percent to about 0.15 weight percent of carbon, about 1.5 weight percent to about 3.5 weight percent copper, about 0.25 weight percent to about 1.0 weight percent tungsten, and about 0.6 weight percent to about 1.5 weight percent of niobium.
Brief Description of the Drawings
FIG. Ia is an SEM micrograph of the microstructure of an exemplary polished and etched as-cast CF8C alloy. FIG. Ib is an SEM micrograph of the microstructure of an exemplary polished and etched as-cast CF8C-Plus alloy.
FIG. 2a shows the microstructure of an exemplary CF8C alloy before high temperature aging.
FIG. 2b shows the microstructure of an exemplary CF8C alloy after high temperature aging.
FIG. 3a shows the microstructure of an exemplary CF8C-Plus alloy before high temperature aging.
FIG. 3b shows the microstructure of an exemplary CF8C-Plus alloy after high temperature aging. FIG. 4a is a TEM image of the microstructure of an exemplary
CF8C alloy after creep testing at 8500C and 35MPa.
FIG. 4b is a TEM image of the microstructure of an exemplary CF8C-Plus alloy after creep testing at 8500C and 35MPa. Detailed Description
CF8C is the traditional cast equivalent of type 347 stainless steel. The chemistry of CF8C-Plus is based on the composition of CF8C with precise additions of nickel (Ni), manganese (Mn), and nitrogen (N) combined with a reduction in silicon (Si) and adjustments of other minor alloying elements. These alloy modifications were made to improve the high-temperature mechanical properties and the casting characteristics of the CF8C steel using inexpensive alloying elements without the need for post casting heat treatments.
Table I
Table I is directed towards the maximum and minimum ranges of the compositional elements made in accordance with the present disclosure. Table I also includes (in column labeled "Example alloy") an example of an embodiment of an alloy made in accordance with the present disclosure. Embodiments covered by the present disclosure include alloys with any subset of compositional ranges falling within the minimum and maximum ranges shown in Table I. It should be noted that allowable ranges of cobalt (Co), vanadium (V), and titanium (Ti) may not significantly alter the performance of the resulting material. Specifically, based upon current information, Co may range from 0 to about 5 weight percent, V may range from 0 to about 3 weight percent, and Ti may range from 0 to about 0.2 weight percent without significantly altering the performance of the alloys.
To study the effect of these modifications on the mechanical properties and creep behavior of the materials, mechanical testing was carried out, and the test results of the modified alloy (named CF8C-Plus) samples are compared with those of the traditional CF8C steel alloy. Samples of the traditional CF8C and the CF8C-Plus material were cast for experiments using centrifugal casting. Table I also shows the composition of CF8C and CF8C-Plus steel alloys that were used for these studies.
FIG. Ia shows the microstructure of an exemplary polished and etched as-cast CF8C alloy, and FIG. Ib shows the microstructure of an exemplary polished and etched as-cast CF8C-Plus alloy. The microstructure of the as-cast CF8C alloy includes an austenite matrix with delta ferrite 10 pools in the interdentrite core regions, and niobium carbide (NbC) 12 in the interdentritic regions. In contrast, the microstructure of the as-cast CF8C-Plus alloy does not show any delta ferrite 10. The microstructure of CF8C-Plus alloy is fully austenitic with a mixture of chromium carbide (Cr23C6) and NbC 12 in the interdentritic regions. A digital Fisher® Feritscope® was used to measure the ferrite content of both the CF8C and CF8C-Plus steel castings. The CF8C had a ferrite number of about 16.8 +/-1.1, which is equivalent to about 14% delta ferrite, and the CF8C-Plus did not register any detectable ferromagnetic behavior, meaning it has less than about 0.1% delta ferrite. Both these macroscopic measurements and microscopic studies indicate that the CF8C-Plus material in the as-cast state is substantially free of delta ferrite 10 in the as-cast state.
To investigate the microstructural evolution of CF8C and CF8C- Plus steel during aging, sand cast keel bars were encapsulated in quartz tubes, evacuated, and backfilled with argon. These were aged in an air box furnace at 7500C for 3,000 hours. These specimens were polished and etched for optical microscopy using an etchant composed of glycerin, hydrochloric acid, nitric acid, and acetic acid having a volumetric ratio of 3:3 : 1 : 1. Scanning Electron Microscopy (SEM) analysis was performed on polished and unetched specimens using backscatter electron (BSE) imaging, and x-ray energy dispersive spectroscopy (XEDS) was performed on areas of interest.
FIG. 2a shows a BSE image of the microstructure of an exemplary CF8C alloy before high temperature aging, and FIG. 2b shows a BSE image of the microstructure of an exemplary CF8C alloy after high temperature aging at
750°C for 3,000 hours. Comparison of FIGS. 2a and 2b indicate a change in BSE image contrast in delta ferrite 10 of the aged material. XEDS analysis of these regions in the aged material indicates that they are enriched in silicon (Si) and chromium (Cr) compared to the delta- ferrite 10 found in the as-cast structure. Comparison of FIGS. 2a and 2b indicates that delta-ferrite 10 has transformed into sigma phase 14 after high temperature aging. Based on the chemical composition of the phase and the knowledge that delta-ferrite 10 can transform rapidly to sigma phase 14 in stainless steels, it is concluded that aging for 3,000 hours at 7500C transforms a majority of the delta ferrite 10 in CF8C steel into sigma phase 14. Electron diffraction patterns from these regions were studied using transmission electron microscopy (TEM) and confirmed the presence of body centered tetragonal (bet) sigma phase.
FIG. 3a shows a BSE image of the microstructure of an exemplary CF8C-Plus alloy before high temperature aging, and FIG. 3b shows a BSE image of the microstructure of an exemplary CF8C-Plus alloy after high temperature aging at 7500C for 3,000 hours. In contrast to the CF8C alloys shown in FIG 2a and FIG 2b, the CF8C-Plus steel alloys in FIG 3a and FIG 3b do not show the formation of any delta ferrite 10 or sigma phases 14 after high temperature aging. The structure of CF8C-Plus alloy before and after high temperature aging samples is austenitic with interdendritic carbides 16. No obvious change was observed in carbide size or morphology after aging. These studies indicate that in contrast to CF8C alloy, the CF8C-Plus alloy is substantially free of delta ferrite 10 or sigma phases 14 of steel after high temperature aging at 7500C for 3,000 hours.
From the centrifugal castings, tensile, creep, and fatigue specimens were machined in both the hoop and longitudinal orientations. Room temperature and elevated temperature tensile tests were performed in accordance with ASTM E8 and E21. Air creep testing was performed in accordance with ASTM El 39 at constant load in lever-arm type creep machines with extensometers attached to the shoulders of the specimens to measure creep deformation. Low cycle fatigue (LCF) and creep-fatigue (C-F) testing was performed in servo-hydraulic test systems in strain control using induction heating in accordance with ASTM E606. For the creep-fatigue tests, a strain hold was imposed at maximum tensile strain during the cycle.
Table II compares the average tensile properties, namely 0.2% offset yield strength (YS), ultimate tensile strength (UTS), and ductility as measured as the percentage elongation at fracture (Elong.), and percentage reduction of cross sectional area at fracture (RA), for CF8C, and CF8C-Plus (CF8C+) steels as a function of temperature. The average yield strength of CF8C-Plus changes very little above 7000C, while that of CF8C steel shows significant weakening. The average ultimate tensile strength of the CF8C-Plus steel is higher for the entire temperature range compared to CF8C. This increase is significantly higher (> 70 Mpa) at temperatures above 7000C. The ductility, as measured by elongation and reduction of area, of CF8C-PIus steel are both higher than that of CF8C steel above 7000C.
Table II
Table III compares the average creep rupture life of CF8C and CF 8C-Plus (CF8C+) alloys at different stresses and temperatures. As seen in the table, the creep rupture life of CF8C-Plus steel is over an order of magnitude higher than that of CF8C steel in all cases. The creep ductility of CF8C-Plus steel, both as measured as a percentage change in elongation and percentage change in area, also shows a significant improvement over that of CF8C steel. In most cases, this improvement in ductility over CF8C steel is over 100%. The minimum creep rate of CF8C-Plus steel also shows a significant decrease over that of CF8C. In most cases, this decrease in minimum creep rate is over an order of magnitude lower than that of CF8C. Table III
Fig. 4a is a TEM image of the microstructure of CF8C after 493 hours of creep testing at 8500C and 35MPa. FIG. 4b is the TEM image of the microstructure of CF8C-Plus after over 20,000 hours of creep testing at 85O0C and 35MPa. Comparison of FIGS. 4a and 4b shows that the NbC 12 precipitates in the CF8C-Plus steel were less than about 50 nanometers in average diameter (as shown in FIG. 4b,) while the average diameter of these precipitates was over about 250 nanometers, with much larger spacing after only 493 hours of testing, in CF8C alloys (as shown in FIG. 4a.)
To study the effect on low cycle fatigue, fully reversed (R-ratio = - 1) strain controlled low cycle fatigue tests were run at 6500C and 8000C at constant frequency. Table IV compares the low cycle fatigue life of CF8C and CF8C-Plus (CF 8C+) steels at different strain ranges at the two different temperatures. At 6500C both materials show similar behavior at high strains, but CF8C-Plus alloys show significant improvement in cycles to failure for the lowest strain ranges. A similar result is found at 8000C.
Table IV
Additionally, low cycle fatigue tests were run at 7500C with an R- ratio of 0 to 0.45% strain (0 to 0.45% total strain) at a strain rate of 0.001/sec. For these creep-fatigue experiments, a 180 second hold time at the maximum strain (0.45%) was utilized. Table V shows the results for these tests. For the low cycle fatigue tests, the cycles to failure for the CF8C was 50% that of the CF8C-Plus. Both materials had a reduction in cycle life when the 180 second peak strain hold was added, but the CF8C showed a more dramatic reduction (75%) compared to the CF8C (60%). The creep-fatigue cycle life of the CF8C- Plus steel was three times that of the CF8C steel.
Table V
The effects of further alloying elements in CF8C-Plus material was also studied. Four separate alloying additions, B, W, Cu, and Al, were chosen for evaluation on CF8C-Plus steel. Fifteen pound lab-scale heats of CF8C-Plus with minor alloy additions were produced by induction melting with an argon cover gas and cast into graphite blocks (152mm 102mm X 25.4mm). One heat was cast to the CF8C-Plus composition, and four other heats contained a single alloy addition each. The approximate measured compositions of these five castings (wt%) are given in Table VI. The column titled 'CF8C+' lists the approximate composition of an embodiment of an alloy made in accordance with the present disclosure. This alloy is used as the baseline to compare the effect of additional alloying elements in the alloy. The columns titled 'CF8C+B', 'CF8C+W, 'CF8C+Cu', and 'CF8C+AF list the composition of the alloys obtained by adding about 0.005 weight percent of boron, about 0.45 weight percent of tungsten, about 2.5 weight percent of copper, and about 1.3 weight percent of aluminum, respectively, to the composition of the CF8C-Plus alloy.
Table VI
No post-casting stress-relief or solution annealing treatment was given to these castings. Tensile bars were machined from the casting blocks, and tensile tests and creep tests were performed on these materials. The test condition chosen to screen all the specimens was 8500C and 75MPa. Alloy samples that had creep rupture lives comparable to the CF8C-Plus material were then tested at 7500C and 140MPa.
Table VII compares the tensile test and creep test results of the four alloy additions to the CF8C material. As the results indicate, samples with Al and B additions exhibited worse creep life than CF8C-Plus material, and were not, therefore, chosen for creep testing at 7500C and 140MPa. The results indicate that the alloys with the Cu and W additions performed better than the base CF8C-Plus material in high temperature creep.
Based upon these results, both Cu and W together were added to the CF8C-Plus material to obtain and alloy having the approximate composition (in weight percent) of 0.09C, 3.9Mn, 0.46Si, 13.1Ni, 20.1Cr, 0.28Mo, 0.008V, 0.77Nb, 0.28N, 2.94Cu, IW, and the balance Fe. Tensile bars were machined from the casting blocks, and tensile tests and creep tests were repeated on this new alloy. Table VIII lists the results of these tensile and creep tests.
Unexpectedly, the inventors found that adding both the Cu and W together introduced synergistic effects that decreased the creep rate and increased the creep rupture life of the material significantly Microscopic analyses of this alloy indicated that its microstructure was substantially free of delta ferrite 10 or sigma phases 14 of steel in the as-cast and the post high temperature aged microstructure.
Table VIII
Industrial Applicability
The disclosed heat and corrosion resistant cast austenitic stainless steel alloy can be used for the production of any articles exposed to extreme temperatures and/or extreme thermal cycling conditions. The disclosed alloy can be used for components in engines and power systems. However, the present disclosure is not limited to these applications, as other applications will become apparent to those skilled in the art.
By employing the stainless steel alloys of the present disclosure, manufacturers can provide a more reliable and durable high temperature component. The absence of delta- ferrite 10 in the microstructure after casting produces a stable austenitic microstructure in CF8C-Plus. Delta-ferrite 10 transforms to sigma phase 14 during prolonged high-temperature exposure causing embrittlement. CF8C-Plus has a nearly 100% austenite microstructure, substantially free of delta ferrite and sigma phase. The improved creep ductility combined with a lower creep rate for
CF8C-Plus steel results in increased low cycle fatigue life and creep rupture strength. Increased low cycle fatigue life and creep rupture strength allows components made of CF8C+ to be long lasting. The increased creep strength and fatigue life of the disclosed CF8C-Plus steel alloys over traditional CF8C material is unexpected because both these materials are castings, and therefore, deformation processes are not involved in creating a dislocation structure upon cooling. Potential reasons for the significant improvement of low cycle fatigue life and creep rupture life of CF8C-Plus over traditional CF8C alloys are that the presence of Mn alters the stacking fault energy of the CF8C-Plus alloy giving rise to higher energy stacking faults, and the presence of manganese and nitrogen in the alloy composition helps nucleation of NbC. The size and density of the NbC 12 precipitates in the matrix may also contribute to the observed improvement in fatigue life and creep rupture life. The presence of these fine particulates of NbC 12 could likely pin dislocations, improving the creep rupture life of CF8C-Plus alloys. The increased fatigue and creep rupture life, the decreased creep strain rate, and the lower decrease in 0.2% yield strength at high temperatures may allow engine and turbine manufacturers to increase power density by allowing engines and turbines to run at higher temperatures, thereby providing possible increase in fuel efficiency.
Engine and turbine manufacturers may also reduce the weight of components as a result of the increased power density by thinner section designs allowed by increased high temperature strength and corrosion resistance compared to conventional high-silicon molybdenum ductile irons. Further, the stainless steel alloys of the present disclosure provide superior performance over other cast stainless steels for a comparable or lower cost. Finally, stainless steel alloys disclosed herein will assist manufacturers in meeting emission regulations for diesel, turbine and gasoline engine applications.
While only certain embodiments have been set forth, alternative embodiments and various modifications will be apparent from the above description to those skilled in the art. These and other alternatives are considered equivalents and within the spirit and scope of the present disclosure.

Claims

Claims
1. A heat and corrosion resistant cast austenitic stainless steel alloy comprising; less than about 15% nickel; a creep rupture life exceeding 3,000 hrs and a minimum creep rate less than 1 x 10"3 at a stress of 100 MPa and a temperature of 75O0C, when creep tested in the as-cast state under ASTM E 139 test conditions; a 0.2% yield strength exceeding 130 MPa at 7500C in the as-cast state; less than 20% decrease in 0.2% yield strength from 750 to 9000C; and completely austenitic microstructure after casting.
2. The cast austenitic stainless steel alloy of claim 1 further including, niobium carbide (12) precipitates in the microstructure that are less than or equal to about 50 nanometers after 20,000 hours of creep test at a stress of 35 MPa and a temperature of 8500C under ASTM El 39 test conditions.
3. The cast austenitic stainless steel alloy of claim 1 further including, about 0.05 weight percent to about 0.15 weight percent carbon, about 1.5 weight percent to about 3.5 weight percent copper, and about 0.2 weight percent to about 1 weight percent silicon.
4. The cast austenitic stainless steel alloy of claim 3 further including, about 0.1 weight percent to about 1 weight percent molybdenum, about 0.1 weight percent to about 1.5 weight percent niobium, and about 0.25 weight percent to about 1.0 weight percent tungsten
5. The cast austenitic stainless steel alloy of claim 1 further including, a creep rupture life exceeding 200 hours and a minimum creep rate less than 5 x 10'3 at a stress of 140 MPa and a temperature of 75O0C, when creep tested in the as-cast state under ASTM El 39 test conditions.
6. The cast austenitic stainless steel alloy of claim 5 further including, a creep ductility exceeding 20% elongation at a stress of 140 MPa and a temperature of 7500C, when creep tested in the as-cast state under ASTM El 39 test conditions.
7. The cast austenitic stainless steel alloy of claim 1 further including, an ultimate tensile strength exceeding 250 MPa at 75O0C in the as-cast state and, an ultimate tensile strength exceeding 140 MPa at 9000C in the as-cast state.
8. The cast austenitic stainless steel alloy of claim 7 further including, a ductility exceeding 10% elongation when tensile tested in the as-cast state at 7500C, and a ductility exceeding 30% elongation when tensile tested in the as-cast state at 9000C.
9. The cast austenitic stainless steel alloy of claim 1 further including, a completely austenitic microstructure after high temperature aging.
10. An article made from the cast austenitic stainless steel alloy of any one of claims 1 through 9.
EP07751919A 2006-07-31 2007-02-28 Heat and corrosion resistant cast austenitic stainless steel alloy with improved high temperature strength Withdrawn EP2047007A1 (en)

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