US20100018613A1 - High Strength, High Toughness Steel Alloy - Google Patents
High Strength, High Toughness Steel Alloy Download PDFInfo
- Publication number
- US20100018613A1 US20100018613A1 US12/488,112 US48811209A US2010018613A1 US 20100018613 A1 US20100018613 A1 US 20100018613A1 US 48811209 A US48811209 A US 48811209A US 2010018613 A1 US2010018613 A1 US 2010018613A1
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- United States
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- alloy
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- molybdenum
- tempered
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Classifications
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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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING 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
- C21D6/00—Heat treatment of ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
-
- 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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
-
- 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
- C21D1/32—Soft annealing, e.g. spheroidising
Definitions
- This invention relates to high strength, high toughness steel alloys, and in particular, to such an alloy that can be tempered at a significantly higher temperature without significant loss of tensile strength.
- the invention also relates to a high strength, high toughness, tempered steel article.
- Age-hardenable martensitic steels that provide a combination of very high strength and fracture toughness are known.
- the known steels are those described in U.S. Pat. No. 4,706,525 and U.S. Pat. No. 5,087,415.
- the former is known as AF1410 alloy and the latter is sold under the registered trademark AERMET.
- AERMET The combination of very high strength and toughness provided by those alloys is a result of their compositions which include significant amounts of nickel, cobalt, and molybdenum, elements that are typically among the most expensive alloying elements available. Consequently, those steels are sold at a significant premium compared to other alloys that do not contain such elements.
- the alloy described in the '019 patent is not a stainless steel and therefore, it must be plated to resist corrosion.
- Material specifications for aerospace applications of the alloy require that the alloy be heated at 375° F. for at least 23 hours after being plated in order to remove hydrogen adsorbed during the plating process. Hydrogen must be removed because it leads to embrittlement of the alloy and adversely affects the toughness provided by the alloy. Because this alloy is tempered at 400° F., the 23 hour 375° F. post-plating heat treatment results in over-tempering of parts made from the alloy such that a tensile strength of at least 280 ksi cannot be provided.
- the foregoing tabulation is provided as a convenient summary and is not intended to restrict the lower and upper values of the ranges of the individual elements for use in combination with each other, or to restrict the ranges of the elements for use solely in combination with each other.
- one or more of the ranges can be used with one or more of the other ranges for the remaining elements.
- a minimum or maximum for an element of a broad or preferred composition can be used with the minimum or maximum for the same element in another preferred or intermediate composition.
- the alloy according to the present invention may comprise, consist essentially of, or consist of the constituent elements described above and throughout this application.
- percent or the symbol “%” means percent by weight or mass percent, unless otherwise specified.
- a hardened and tempered steel alloy article that has very high strength and fracture toughness.
- the article is formed from an alloy having the broad or preferred weight percent composition set forth above.
- the alloy article according to this aspect of the invention is further characterized by being tempered at a temperature of about 500° F. to 600° F.
- the alloy according to the present invention contains at least about 0.35% and preferably at least about 0.37% carbon. Carbon contributes to the high strength and hardness capability provided by the alloy. Carbon is also beneficial to the temper resistance of this alloy. Too much carbon adversely affects the toughness provided by the alloy. Therefore, carbon is restricted to not more than about 0.55%, better yet to not more than about 0.50%, and preferably to not more than about 0.45%.
- At least about 0.6%, better yet at least about 0.7%, and preferably at least about 0.8% manganese is present in this alloy primarily to deoxidize the alloy. It has been found that manganese also benefits the high strength provided by the alloy. If too much manganese is present, then an undesirable amount of retained austenite may result during hardening and quenching such that the high strength provided by the alloy is adversely affected. Therefore, the alloy contains not more than about 1.2% and preferably not more than about 0.9% manganese.
- Silicon benefits the hardenability and temper resistance of this alloy. Therefore, the alloy contains at least about 0.9% silicon and preferably, at least about 1.3% silicon. Too much silicon adversely affects the hardness, strength, and ductility of the alloy. In order to avoid such adverse effects silicon is restricted to not more than about 2.5% and preferably to not more than about 2.1% in this alloy.
- the alloy contains at least about 0.75% chromium because chromium contributes to the good hardenability, high strength, and temper resistance provided by the alloy.
- the alloy contains at least about 1.0%, and better yet at least about 1.2% chromium. More than about 2% chromium in the alloy adversely affects the impact toughness and ductility provided by the alloy.
- chromium is restricted to not more than about 1.5% in this alloy and better yet to not more than about 1.35%.
- Nickel is beneficial to the good toughness provided by the alloy according to this invention. Therefore, the alloy contains at least about 3.5% nickel and preferably at least about 3.7% nickel. The benefit provided by larger amounts of nickel adversely affects the cost of the alloy without providing a significant advantage. In order to limit the upside cost of the alloy, nickel is restricted to not more than about 7% and preferably to not more than about 4.5% in the alloy.
- Molybdenum is a carbide former that is beneficial to the temper resistance provided by this alloy.
- the presence of molybdenum boosts the tempering temperature of the alloy such that a secondary hardening effect is achieved at about 500° F.
- Molybdenum also contributes to the strength and fracture toughness provided by the alloy.
- the benefits provided by molybdenum are realized when the alloy contains at least about 0.4% molybdenum and preferably at least about 0.5% molybdenum.
- the alloy contains not more than about 1.3% molybdenum and preferably not more than about 1.1% molybdenum.
- Tungsten may be substituted for some or all of the molybdenum in this alloy.
- tungsten is substituted for molybdenum on a 2:1 basis.
- the alloy contains less than about 0.01% molybdenum, about 0.8 to about 2.6 percent, preferably about 1.0 to 2.2% tungsten is included to benefit the temper resistance, strength, and toughness provided by the alloy.
- This alloy preferably contains at least about 0.5% copper which contributes to the hardenability and impact toughness of the alloy. Too much copper can result in precipitation of an undesirable amount of free copper in the alloy matrix and adversely affect the fracture toughness of the alloy. Therefore, not more than about 0.6% copper is present in this alloy.
- Vanadium contributes to the high strength and good hardenability provided by this alloy. Vanadium is also a carbide former and promotes the formation of carbides that help provide grain refinement in the alloy and that benefit the temper resistance and secondary hardening of the alloy. For those reasons, the alloy preferably contains at least about 0.25% vanadium. Too much vanadium adversely affects the strength of the alloy because of the formation of larger amounts of carbides in the alloy which depletes carbon from the alloy matrix material. Accordingly, the alloy contains not more than about 0.35% vanadium. Niobium can be substituted for some or all of the vanadium in this alloy because like vanadium, niobium combines with carbon to form M 4 C 3 carbides that benefit the temper resistance and hardenability of the alloy. When present, niobium is substituted for vanadium on 1.8:1 basis. When vanadium is restricted to not more than about 0.01%, the alloy contains about 0.2 to about 1.0% niobium.
- This alloy may also contain a small amount of calcium up to about 0.005% retained from additions during melting of the alloy to help remove sulfur and thereby benefit the fracture toughness provided by the alloy.
- Silicon, copper, vanadium, and when present, niobium are preferably balanced within their above-described weight percent ranges to benefit the novel combination of strength and toughness that characterize this alloy. More specifically, the ratio (% Si+% Cu)/(% V+(5/9) ⁇ % Nb) is preferably about 2 to 14, and better yet, about 6 to 12. It is believed that when the amounts of silicon, copper, and vanadium present in the alloy are balanced in accordance with the ratio, the grain boundaries of the alloy are strengthened by preventing brittle phases and tramp elements from forming on the grain boundaries.
- the balance of the alloy is essentially iron and the usual impurities found in commercial grades of similar alloys and steels.
- the alloy preferably contains not more than about 0.01%, better yet, not more than about 0.005% phosphorus and not more than about 0.001%, better yet not more than about 0.0005% sulfur.
- the alloy preferably contains not more than about 0.01% cobalt. Titanium may be present at a residual level from deoxidation additions and is preferably restricted to not more than about 0.01%.
- the elements can be balanced to provide different levels of tensile strength.
- an alloy composition containing about 0.38% C, 0.84% Mn, 1.51% Si, 1.25% Cr, 3.78% Ni, 0.50% Mo, 0.55% Cu, 0.29% V, balance essentially Fe has been found to provide a tensile strength in excess of 290 ksi in combination with a K Ic fracture toughness greater than 80 ksi ⁇ in, after being tempered at about 500° F. for 3 hours.
- An alloy composition containing about 0.40% C, 0.84% Mn, 1.97% Si, 1.26% Cr, 3.78% Ni, 1.01% Mo, 0.56% Cu, 0.30% V, balance essentially Fe, has been found to provide a tensile strength in excess of 310 ksi in combination with a K Ic fracture toughness greater than 60 ksi ⁇ in, after being tempered at about 500° F. for 3 hours.
- an alloy composition containing about 0.50% C, 0.69% Mn, 1.38% Si, 1.30% Cr, 3.99% Ni, 0.50% Mo, 0.55% Cu, 0.29% V, balance essentially Fe, has been found to provide a tensile strength in excess of 340 ksi in combination with a K Ic fracture toughness greater than 30 ksi ⁇ in, after being tempered at about 300° F. for 2 1 ⁇ 2 hours plus 21 ⁇ 2 hours.
- the alloy is preferably vacuum induction melted (VIM) and, when desired as for critical applications, refined using vacuum arc remelting (VAR). It is believed that the alloy can also be arc melted in air. After air melting, the alloy is preferably refined by electroslag remelting (ESR) or VAR.
- VIM vacuum induction melted
- ESR electroslag remelting
- the alloy of this invention is preferably hot worked from a temperature of about 2100° F. to form various intermediate product forms such as billets and bars.
- the alloy is preferably heat treated by austenitizing at about 1585° F. to about 1635° F. for about 30 to 45 minutes.
- the alloy is then air cooled or oil quenched from the austenitizing temperature.
- the alloy is preferably deep chilled to either ⁇ 100° F. or ⁇ 320° F. for at least about one hour and then warmed in air.
- the alloy is preferably tempered at about 500° F. for about 3 hours and then air cooled.
- the alloy may be tempered at up to 600° F. when an optimum combination of strength and toughness is not required.
- the alloy of the present invention is useful in a wide range of applications.
- the very high strength and good fracture toughness of the alloy makes it useful for machine tool components and also in structural components for aircraft, including landing gear.
- the alloy of this invention is also useful for automotive components including, but not limited to, structural members, drive shafts, springs, and crankshafts. It is believed that the alloy also has utility in armor plate, sheet, and bars.
- VIM heats were produced for evaluation.
- the weight percent compositions of the heats are set forth in Table 1 below. All heats were melted using ultra-clean raw materials and used calcium as a desulfurizing addition.
- the heats were cast as 4 in. square ingots. The ingots were forged to 21 ⁇ 4 in. square bars from a starting temperature of about 2100° F. The bars were cut to shorter lengths and half of the shorter length bars were further forged to 1 in. square bars, again from a starting temperature of 2100° F. The 1 in. bars were cut to still shorter lengths which were forged to 3 ⁇ 4 in. square bars from 2100° F.
- the 3 ⁇ 4 in. square bars and the remainder of the 21 ⁇ 4 in. square bars were annealed at 1050° F. for 6 hours and then cooled in air to room temperature.
- Standard specimens for tensile testing and standard specimens for Charpy V-notch impact testing were prepared from the 3 ⁇ 4 in. bars of each heat.
- Standard compact tension blocks for fracture toughness testing were prepared from the 21 ⁇ 2 in. square bars of each heat. All of the specimens were heat treated at 1585° F. for 30 minutes and then air cooled. The test specimens were then chilled at ⁇ 100° F. for 1 hour and warmed in air to room temperature.
- Duplicate specimens of each heat were then tempered at one of three different temperatures, 400° F., 500° F., and 600° F., by holding at the respective temperature for 3 hours. The tempered specimens were then air cooled to room temperature.
- Heat 1484 which has a weight percent composition in accordance with the alloy described herein, is the only alloy composition that provides a tensile strength of 280 ksi and a fracture toughness of at least 90 ksi ⁇ in after tempering a 500° F.
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/488,112 US20100018613A1 (en) | 2008-07-24 | 2009-06-19 | High Strength, High Toughness Steel Alloy |
US13/016,606 US20110165011A1 (en) | 2008-07-24 | 2011-01-28 | High strength, high toughness steel alloy |
US13/645,596 US9518313B2 (en) | 2008-07-24 | 2012-10-05 | High strength, high toughness steel alloy |
US13/646,988 US20130146182A1 (en) | 2008-07-24 | 2012-10-08 | High Strength, High Toughness Steel Alloy |
US15/463,445 US20180030579A1 (en) | 2008-07-24 | 2017-03-20 | High Strength, High Toughness Steel Alloy |
US16/396,950 US10472706B2 (en) | 2008-07-24 | 2019-04-29 | High strength, high toughness steel alloy |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US8324908P | 2008-07-24 | 2008-07-24 | |
US17209809P | 2009-04-23 | 2009-04-23 | |
US12/488,112 US20100018613A1 (en) | 2008-07-24 | 2009-06-19 | High Strength, High Toughness Steel Alloy |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US13/016,606 Continuation-In-Part US20110165011A1 (en) | 2008-07-24 | 2011-01-28 | High strength, high toughness steel alloy |
US13/646,988 Continuation US20130146182A1 (en) | 2008-07-24 | 2012-10-08 | High Strength, High Toughness Steel Alloy |
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US20100018613A1 true US20100018613A1 (en) | 2010-01-28 |
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Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
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US12/488,112 Abandoned US20100018613A1 (en) | 2008-07-24 | 2009-06-19 | High Strength, High Toughness Steel Alloy |
US13/646,988 Abandoned US20130146182A1 (en) | 2008-07-24 | 2012-10-08 | High Strength, High Toughness Steel Alloy |
US15/463,445 Abandoned US20180030579A1 (en) | 2008-07-24 | 2017-03-20 | High Strength, High Toughness Steel Alloy |
US16/396,950 Active US10472706B2 (en) | 2008-07-24 | 2019-04-29 | High strength, high toughness steel alloy |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
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US13/646,988 Abandoned US20130146182A1 (en) | 2008-07-24 | 2012-10-08 | High Strength, High Toughness Steel Alloy |
US15/463,445 Abandoned US20180030579A1 (en) | 2008-07-24 | 2017-03-20 | High Strength, High Toughness Steel Alloy |
US16/396,950 Active US10472706B2 (en) | 2008-07-24 | 2019-04-29 | High strength, high toughness steel alloy |
Country Status (13)
Country | Link |
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US (4) | US20100018613A1 (ja) |
EP (1) | EP2313535B8 (ja) |
JP (1) | JP5868704B2 (ja) |
KR (1) | KR101363674B1 (ja) |
CN (1) | CN102165086B (ja) |
AR (1) | AR072388A1 (ja) |
BR (1) | BRPI0911732B1 (ja) |
CA (1) | CA2731754C (ja) |
IL (1) | IL210783A0 (ja) |
MX (1) | MX2011000918A (ja) |
RU (1) | RU2482212C2 (ja) |
TW (1) | TWI440723B (ja) |
WO (1) | WO2010011447A2 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2012103539A1 (en) | 2011-01-28 | 2012-08-02 | Crs Holdings, Inc. | High strength, high toughness steel alloy |
US20130189146A1 (en) * | 2012-01-19 | 2013-07-25 | Gesenkschmiede Schneider Gmbh | Low-alloyed steel and components made thereof |
US9616529B2 (en) | 2011-04-15 | 2017-04-11 | Federal-Mogul Corporation | Piston and method of making a piston |
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US9499890B1 (en) | 2012-04-10 | 2016-11-22 | The United States Of America As Represented By The Secretary Of The Navy | High-strength, high-toughness steel articles for ballistic and cryogenic applications, and method of making thereof |
CN103451568A (zh) * | 2013-08-02 | 2013-12-18 | 安徽三联泵业股份有限公司 | 高碳不锈钢叶轮轴不锈钢材料及其制造方法 |
CN104674121B (zh) * | 2015-03-10 | 2017-03-08 | 山东钢铁股份有限公司 | 一种高抗弹性装甲用钢板及其制造方法 |
KR102245002B1 (ko) | 2020-02-28 | 2021-04-27 | 동우 화인켐 주식회사 | 양극활물질 전구체 재료 및 리튬 이차전지용 양극활물질의 제조방법, 및 이에 따라 제조된 리튬 이차전지용 양극활물질 |
KR102242170B1 (ko) | 2020-02-28 | 2021-04-20 | 동우 화인켐 주식회사 | 양극활물질 전구체 재료 및 리튬 이차전지용 양극활물질의 제조방법, 및 이에 따라 제조된 리튬 이차전지용 양극활물질 |
WO2021208181A1 (zh) * | 2020-04-14 | 2021-10-21 | 北京科技大学 | 一种低温高韧高温高强及高淬透性热模钢及制备技术 |
CN113249645B (zh) * | 2021-04-13 | 2022-02-25 | 北京科技大学 | 一种高延性超高强韧钢及其制备方法 |
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2009
- 2009-06-17 EP EP09789838.1A patent/EP2313535B8/en active Active
- 2009-06-17 RU RU2011106360/02A patent/RU2482212C2/ru active
- 2009-06-17 CN CN200980137486.0A patent/CN102165086B/zh active Active
- 2009-06-17 CA CA2731754A patent/CA2731754C/en active Active
- 2009-06-17 BR BRPI0911732-6A patent/BRPI0911732B1/pt active IP Right Grant
- 2009-06-17 KR KR1020117004217A patent/KR101363674B1/ko active IP Right Grant
- 2009-06-17 MX MX2011000918A patent/MX2011000918A/es active IP Right Grant
- 2009-06-17 WO PCT/US2009/047636 patent/WO2010011447A2/en active Application Filing
- 2009-06-17 JP JP2011520066A patent/JP5868704B2/ja active Active
- 2009-06-19 US US12/488,112 patent/US20100018613A1/en not_active Abandoned
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- 2009-06-29 AR ARP090102397A patent/AR072388A1/es active IP Right Grant
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- 2011-01-20 IL IL210783A patent/IL210783A0/en active IP Right Grant
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2012
- 2012-10-08 US US13/646,988 patent/US20130146182A1/en not_active Abandoned
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2017
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2012103539A1 (en) | 2011-01-28 | 2012-08-02 | Crs Holdings, Inc. | High strength, high toughness steel alloy |
KR20130114261A (ko) * | 2011-01-28 | 2013-10-16 | 씨알에스 홀딩즈 인코포레이티드 | 고강도 고인성 강합금 |
CN103502498A (zh) * | 2011-01-28 | 2014-01-08 | Crs控股公司 | 高强度、高韧性钢 |
KR101696967B1 (ko) * | 2011-01-28 | 2017-01-16 | 씨알에스 홀딩즈 인코포레이티드 | 고강도 고인성 강합금 |
US9616529B2 (en) | 2011-04-15 | 2017-04-11 | Federal-Mogul Corporation | Piston and method of making a piston |
US20130189146A1 (en) * | 2012-01-19 | 2013-07-25 | Gesenkschmiede Schneider Gmbh | Low-alloyed steel and components made thereof |
US10041157B2 (en) * | 2012-01-19 | 2018-08-07 | Gesenkschmiede Schneider Gmbh | Low-alloyed steel and components made thereof |
Also Published As
Publication number | Publication date |
---|---|
US10472706B2 (en) | 2019-11-12 |
CA2731754A1 (en) | 2010-01-28 |
MX2011000918A (es) | 2011-04-11 |
RU2482212C2 (ru) | 2013-05-20 |
RU2011106360A (ru) | 2012-08-27 |
WO2010011447A3 (en) | 2010-03-18 |
AR072388A1 (es) | 2010-08-25 |
TWI440723B (zh) | 2014-06-11 |
US20190249281A1 (en) | 2019-08-15 |
EP2313535B8 (en) | 2021-09-29 |
BRPI0911732A2 (pt) | 2015-10-06 |
WO2010011447A2 (en) | 2010-01-28 |
BRPI0911732B1 (pt) | 2018-07-24 |
CA2731754C (en) | 2015-11-03 |
EP2313535A2 (en) | 2011-04-27 |
KR20110036628A (ko) | 2011-04-07 |
CN102165086A (zh) | 2011-08-24 |
KR101363674B1 (ko) | 2014-02-14 |
US20130146182A1 (en) | 2013-06-13 |
EP2313535B1 (en) | 2021-07-28 |
JP5868704B2 (ja) | 2016-02-24 |
IL210783A0 (en) | 2011-03-31 |
CN102165086B (zh) | 2017-02-08 |
US20180030579A1 (en) | 2018-02-01 |
JP2011529137A (ja) | 2011-12-01 |
TW201009095A (en) | 2010-03-01 |
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