US20070086910A1 - Acid resistant austenitic alloy for valve seat insert - Google Patents
Acid resistant austenitic alloy for valve seat insert Download PDFInfo
- Publication number
- US20070086910A1 US20070086910A1 US11/251,308 US25130805A US2007086910A1 US 20070086910 A1 US20070086910 A1 US 20070086910A1 US 25130805 A US25130805 A US 25130805A US 2007086910 A1 US2007086910 A1 US 2007086910A1
- Authority
- US
- United States
- Prior art keywords
- alloy
- amount
- corrosion
- chromium
- iron
- 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.)
- Abandoned
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 124
- 239000000956 alloy Substances 0.000 title claims abstract description 124
- 239000002253 acid Substances 0.000 title description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000005260 corrosion Methods 0.000 claims abstract description 72
- 230000007797 corrosion Effects 0.000 claims abstract description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052742 iron Inorganic materials 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- 239000011651 chromium Substances 0.000 claims abstract description 38
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 32
- 239000010703 silicon Substances 0.000 claims abstract description 32
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 26
- 239000010937 tungsten Substances 0.000 claims abstract description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 23
- 239000011733 molybdenum Substances 0.000 claims abstract description 23
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010955 niobium Substances 0.000 claims abstract description 21
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 21
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 3
- 238000004663 powder metallurgy Methods 0.000 claims description 3
- 238000005552 hardfacing Methods 0.000 claims 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 239000010941 cobalt Substances 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229910001347 Stellite Inorganic materials 0.000 description 11
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910001311 M2 high speed steel Inorganic materials 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- -1 AISI 300 series Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 229910000753 refractory alloy Inorganic materials 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910000997 High-speed steel Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/008—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of engine cylinder parts or of piston parts other than piston rings
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
-
- 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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
- 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
-
- 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
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- 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
- C22C38/56—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.7% by weight of carbon
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
- F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L2301/00—Using particular materials
Definitions
- This invention relates to an acid corrosion resistant and wear resistant austenitic iron base alloy that possesses excellent resistance to sulfuric acid and is superior to high speed steels for many applications where both sulfuric acid corrosion and wear occur simultaneously.
- This invention further relates to such a corrosion resistant alloy useful for making valve seat inserts used in internal combustion engines with exhaust gas recirculation (EGR) system.
- EGR exhaust gas recirculation
- modified M2 tool steel and Silichrome XB are two common material choices for making diesel engine intake valve seat inserts.
- modified M2 tool steel comprises 1.2-1.5 wt % carbon, 0.3-0.5 wt % silicon, 0.3-0.6 wt % manganese, 6.0-7.0 wt % molybdenum, 3.5-4.3 wt % chromium, 5.0-6.0 wt % tungsten, up to 1.0 wt % nickel, and the balance being iron.
- Modified Silichrome XB contains 1.3-1.8 wt % carbon, 1.9-2.6 wt % silicon, 0.2-0.6 wt % manganese, 19.0-21.0 wt % chromium, 1.0-1.6 wt % nickel, and the balance being iron.
- Another common iron base alloy for intake valve seat inserts contains 1.8-2.3 wt % carbon, 1.8-2.1 wt % silicon, 0.2-0.6 wt % manganese, 2.0-2.5 wt % molybdenum, 33.0-35.0 wt % chromium, up to 1.0 wt % nickel, and the balance being substantially iron.
- U.S. Pat. No. 6,916,444 discloses an iron base alloy containing a large amount of residual austenite for intake valve seat insert material. This alloy contains 2.0-4.0% carbon, 3.0-9.0% chromium, 0.0-4.0% manganese, 5.0-15.0% molybdenum, 0.0-6.0% tungsten, 0.0-6.0% vanadium, 0.0-4.0 niobium, 7.0-15.0% nickel, 0.0-6.0% cobalt, and the balance being iron with impurities.
- U.S. Pat. No. 6,436,338 discloses a corrosion resistant iron base alloy for diesel engine valve seat insert applications.
- the alloy is composed of carbon 1.1-1.4%, chromium 11-14.5%, molybdenum 4.75-6.25%, tungsten 3.5-4.5%, cobalt 0-3%, niobium 1.5-2.5%, vanadium 1-1.75%, copper 0-2.5%, silicon 0-1%, nickel 0-0.8%, iron being the balance with impurities.
- U.S. Pat. No. 6,866,816 discloses an austenitic type iron base alloy with good corrosion resistance.
- the chemical composition of the alloy is 0.7-2.4% carbon, 1.5-4.0% silicon, 5.0-9.0% chromium, less than 6.0% manganese, 5.0-20.0% molybdenum and tungsten, the total of vanadium and niobium 0-4.0%, titanium 0-1.5%, aluminum 0.01-0.5%, nickel 12.0-25.0%, copper 0-3.0%, and at least 45.0% iron.
- carbon 0.7-2.4% carbon
- silicon 5.0-9.0%
- chromium less than 6.0%
- manganese 5.0-20.0%
- molybdenum and tungsten the total of vanadium and niobium 0-4.0%
- titanium 0-1.5% aluminum 0.01-0.5%
- nickel 12.0-25.0% nickel 12.0-25.0%
- copper 0-3.0% copper 0-3.0%
- at least 45.0% iron iron.
- more severe corrosion conditions in some engines with high sulfur fuel and high humidity demands materials with corrosion resistance much better than the above iron base alloys.
- High carbon and high chromium type nickel base alloys normally do not exhibit good wear resistance under intake valve seat insert working conditions due to lack of combustion deposits and insufficient amount of metal oxides to protect valve seat insert from direct metal-to-metal wear.
- Eatonite 2 is one example of the nickel base alloys used for making exhaust valve seat inserts, which contains 2.0-2.8 wt % carbon, up to 1.0 wt % silicon, 27.0-31.0 wt % chromium, 14.0-16.0 wt % tungsten, up to 8.0 wt % iron, and the balance being essentially nickel.
- Eatonite is a trademark of Eaton Corporation.
- Several similar nickel base alloys with added iron and/or cobalt are also available for exhaust valve seat inserts.
- U.S. Pat. 6,200,688 discloses high silicon and high iron-type nickel base alloy used as material for valve seat inserts. These nickel base alloys may possibly be used in EGR engines only when the wear rate of intake insert is moderate.
- Tribaloy® T400 contains 2.0-2.6 wt % silicon, 7.5-8.5 wt % chromium, 26.5-29.5 wt % molybdenum, up to 0.08 wt % carbon, up to 1.50 wt % nickel, up to 1.5 wt % iron, and the balance being essentially cobalt.
- Stellite® 3 contains 2.3-2.7 wt % carbon, 11.0-14.0 wt % tungsten, 29.0-32.0 wt % chromium, up to 3.0 wt % nickel, up to 3.0 wt % iron, and the balance being cobalt.
- the above cobalt base alloys possess both excellent corrosion and wear resistance. However, the cost of these cobalt base alloys only allows these alloys to be used in limited applications. (®Registered Trademarks of Deloro Stellite Company Inc.)
- Austenitic iron base valve alloys or valve facing alloys may also be classified into the same group of materials.
- U.S. Pat. No.4,122,817 discloses an austenitic iron base alloy with good wear resistance, PbO corrosion and oxidation resistance. The alloy contains 1.4-2.0 wt % carbon, 4.0-6.0 wt % molybdenum, 0.1 to 1.0 wt % silicon, 8.0-13.0 wt % nickel, 20.0-26.0 wt % chromium, 0-3.0 wt % manganese, with the balance being iron.
- 4,929,419 discloses a heat, corrosion and wear resistant austenitic steel for internal combustion exhaust valves, which contains 0.35-1.5 wt % carbon, 3.0-10.0 wt % manganese, 18.0-28.0 wt % chromium, 3.0-10.0 wt % nickel, up to 2.0 wt % silicon, up to 0.1 wt % phosphorus, up to 0.05 wt % sulfur, up to 10.0 wt % molybdenum, up to 4.0 wt % vanadium, up to 8.0 wt % tungsten, up to 1.0 wt % niobium, up to 0.03 wt % boron, and the balance being essentially iron.
- the present invention is an alloy with the following composition: Element wt. % Carbon 1.8-2.8 Silicon 0.5-3.5 Chromium 12.0-25.0 Molybdenum and 2.0-10.0 tungsten combined Nickel 12.0-25.0 Niobium and 1.0-4.0 vanadium combined Titanium 0-1.0 Aluminum 0.01-0.2 Copper 0.05-3.0 Iron and impurities Balance
- metal components are either made of the alloy, such as by casting, or by the powder metallurgy method by forming from a powder and sintering. Furthermore, the alloy can be used to hardface the components as the protective coating.
- Alloys with excellent corrosion resistance under static immersion type test may perform poorly under cyclic heating corrosion because of different corrosion behaviors at high temperature and the possible influence of oxidation to the corrosion process.
- the high temperature cyclic corrosion tester provides a tool to study corrosion behavior with the influence of oxidation under high temperature condition.
- a number of alloy elements can affect corrosion and hardness of the alloy, where it is preferred to have a minimum hardness of 34.0 HRC in order to achieve good wear resistance in the inventive austenitic alloy.
- the austenitic alloy can become too brittle when the hardness of the alloy exceeds 54.0 HRC due to formation of intermetallic compounds like sigma phase from excessive amount of alloy elements.
- Ring samples with 45 mm outer diameter, 32 mm inner diameter and 5 mm thickness were used as hardness samples and the hardness values of all samples were obtained using a Rockwell C hardness tester.
- a high temperature cyclic corrosion tester was built to simulate sulfuric acid corrosion at high temperature.
- the new corrosion tester provides a better corrosion measurement method than the traditional static immersion corrosion test as both oxidation and high temperature are also important factors contributing to the corrosion process in intake insert working environment.
- the high temperature cyclic corrosion test rig is composed of a heating coil, an air cylinder, a sample with its holder, a control unit, and an acid solution container.
- First the air cylinder lifts the sample up into the heating coil to heat the specimen.
- the sample is held inside the coil for about 22 seconds so that the specimen temperature reaches about 300 °F.
- the air cylinder moves the heated sample down into the sulfuric acid solution container, and the cycle continues to repeat. All acid solution left on the sample is vaporized when the sample is heated inside the heating coil. Therefore both corrosion and oxidation occur in this process, which is closer to the actual insert corrosion in EGR equipped engines than the static acid immersion test. Corrosion also occurs when the heated specimen is pushed into the sulfuric acid solution container.
- the testing time is one hour.
- the sample dimensions are 6.35 mm in diameter and 31.75 mm in length. About 12.7 mm length of the sample is immersed into the solution. 0.25 vol.%, 0.50 vol. %, and 1.0 vol.% sulfuric acid solutions are used for each sample.
- a precision balance is used to measure the weight of each sample before and after test and the precision of the balance is 0.0001 gram.
- the corrosion weight loss is the weight difference of a sample before and after corrosion test. The lower the corrosion weight loss the higher the corrosion resistance of an alloy sample.
- the composition of the invention alloy is such as to produce a corrosion weight loss preferably less than 5.0 mg, 10.0 mg, and 18 mg in 0.25, 0.5, and 1.0 vol.% sulfuric acid solutions in the high temperature cyclic corrosion tester, respectively.
- Samples 1-7 contain carbon contents from 1.2 to 2.7 wt % with silicon 1.0 wt %, chromium 18.0 wt %, tungsten 7.0 wt %, nickel 16 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials. Hardness increases TABLE 1 Alloy Hardness and Chemical Composition (wt %) Sample Hardness No. Alloy Name C Si Cr W Mo Fe V Nb Ni Al Cu (HRC) 1 Comparative 1.2 1.0 18.0 7.0 — Bal.
- the carbon content of the alloy is more than 3.0 wt %, shrinkage will become a major problem for insert type ring shaped castings. Therefore, the carbon content is defined to be within the range of from 1.8 to 3.0 % for good hardness and casting properties.
- Samples 8-15 contain chromium from 10.0 to 25.0 wt % with carbon 2.5 wt %, silicon 1.0 wt %, tungsten 7.0 wt %, nickel 16 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials.
- These different chromium contents containing samples illustrate the effects of chromium on hardness and corrosion resistance.
- Lower chromium containing alloy gives lower corrosion resistance while alloys with higher chromium contents have lower hardness. Therefore chromium content in the inventive alloy is defined to be within 12.0 to 25.0 wt %, preferably between 15.0 to 20.0 wt % for the balance of good corrosion resistance and adequate hardness.
- Samples 16-20 contain tungsten and/or molybdenum from 0 to 15.0 wt % with carbon 2.5 wt %, silicon 1.0-2.0 wt %, chromium 18.0 wt %, nickel 16.0-25.0 wt %, vanadium 1.0-2.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials.
- tungsten and/or molybdenum from 0 to 15.0 wt % with carbon 2.5 wt %, silicon 1.0-2.0 wt %, chromium 18.0 wt %, nickel 16.0-25.0 wt %, vanadium 1.0-2.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials.
- U.S. Pat. No. 6,866,816 where corrosion
- molybdenum and/or tungsten content it is not necessary to use high molybdenum and/or tungsten content for better corrosion or higher hardness in the inventive alloy. Similar to high speed steels, addition of molybdenum or tungsten improves hot hardness of the inventive alloy, which is important from the designed application view as the intake insert working temperature can reach 700° F.
- the molybdenum or tungsten content is defined to be within 3.0 to 15.0 wt %, and the combined contents of the two elements should be less than 16.0 wt %. Excessive amount of tungsten or molybdenum causes brittleness problem of castings made from the inventive alloy.
- Samples 6, 21, and 23 contain nickel from 12.0 to 25.0 wt % with carbon 2.5 wt %, silicon 1.0 wt %, chromium 18.0 wt %, tungsten 7.0 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials.
- Nickel has a positive contribution to the corrosion resistance of the alloy. First there is a minimum amount of nickel required in order to form stable austenite in the alloy, higher nickel content improves corrosion resistance of the alloy in all acid concentrations tested. However the improvement is at the expense of lower hardness and therefore lower wear resistance. Therefore, the nickel content is defined to be within the range of 12.0 to 25.0 wt %.
- Vanadium and niobium are strong MC carbide type forming alloy elements. A small addition of vanadium and niobium helps to improve corrosion resistance of the alloy. Too much vanadium or niobium decreases the hardness of the alloy. Samples 5 and 24 contain vanadium from 1.0 to 3.0 wt % with carbon 2.5 wt %, silicon 1.0 wt %, chromium 18.0 wt %, tungsten 7.0 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials. From the corrosion and hardness test results, vanadium content should be in the range of 0.02 to 3.0 wt %. Similarly, niobium content is between 0.02 to 3.0 wt %.
- Samples 6 and 25 contain silicon from 1.0 to 3.0 wt % with carbon 2.5 wt %, chromium 18.0 wt %, tungsten 7.0 wt %, nickel 16 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials. Silicon has deoxidizing and desulfurizing effects during alloy melting process. Silicon also has the effect of improving fluidity. However, the main reasons of using silicon in the inventive alloy are that silicon can also improve corrosion and wear resistance of the alloys.
- the Si content is less than 0.5%, the effects on wear and corrosion are not achieved. If the Si content is more than 3.5 wt %, specially in the high carbon austenitic alloy, excessive amount of silicon provides a too brittle alloy. Higher amount of silicon also decreases the hardness of the inventive alloy. Therefore, the silicon content is defined to be within the range of 0.5 to 3.5 wt %.
- the range of copper in the alloy is defined to be within 0.02 to 3.0 wt %.
- Manganese also has deoxidizing and desulfurizing effects to molten metals. However, manganese can deteriorate corrosion resistance if its content is too high. Therefore, the manganese range is defined to be less than 1.5 wt %.
- the range for aluminum is between about 0.01 and about 0.2 wt %, preferably between about 0.05 and about 0.1 wt %.
- the range for titanium is between about zero and about 1 wt %, preferably between about 0.05 wt % and about 0.5 wt %.
- alloys of the present invention are capable of being incorporated in the form of a variety of embodiments, only a few of which have been illustrated and described.
- the invention may be embodied in other forms without departing from its spirit or essential characteristics. It should be appreciated that the addition of some other ingredients, process steps, materials or components not specifically included will have an adverse impact on the present invention.
- the best mode of the invention may, therefore, exclude ingredients, process steps, materials or components other than those listed above for inclusion or use in the invention.
- the described embodiments are considered in all respects only as illustrative and not restrictive, and the scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Lift Valve (AREA)
- Heat Treatment Of Articles (AREA)
Abstract
A high carbon austenitic iron base alloy for wear and corrosion resistant applications is developed for valve seat insert applications when corrosion resistance is required. The alloy comprises 1.8-2.8 wt % carbon, 0.5-3.5 wt % silicon, 10.0-25.0 wt % chromium, less than 1.5 wt % manganese, 2.0-10.0 wt % molybdenum and tungsten combined, 1.0-4.0 wt % niobium and vanadium combined, 0-1.0 wt % titanium, 0.01-0.2 wt % aluminum, 12-25 wt % nickel, 0.5-3.0 wt % copper, and the balance being iron and a small amount of impurities.
Description
- 1. Technical Field
- This invention relates to an acid corrosion resistant and wear resistant austenitic iron base alloy that possesses excellent resistance to sulfuric acid and is superior to high speed steels for many applications where both sulfuric acid corrosion and wear occur simultaneously. This invention further relates to such a corrosion resistant alloy useful for making valve seat inserts used in internal combustion engines with exhaust gas recirculation (EGR) system.
- 2. Description of Related Art
- Internal combustion engines equipped with EGR systems require intake valve seat insert materials with excellent corrosion resistance due to formation of sulfuric acid in intake insert area when sulfur oxide that comes from diesel fuel after combustion meets with moisture from incoming air. Sulfur content in diesel fuel seems relatively low, however, the concentration of sulfuric acid will likely increase with engine running time as combustion deposits from exhaust gas accumulated around inner wall area of an intake insert will absorb more sulfuric acid. Severe corrosion can occur on intake valve seat inserts made from M2 tool steel once the amount of high concentration acid is enough. Cobalt base alloy Stellite 3 possess excellent corrosion resistance and good wear resistance under diesel engine intake working condition and therefore this cobalt alloy is normally the choice as the intake insert material to ensure the valve train service life in EGR device equipped diesel engines. (®Registered Trademarks of Deloro Stellite Company Inc.)
- Traditionally, modified M2 tool steel and Silichrome XB are two common material choices for making diesel engine intake valve seat inserts. In broad ranges, modified M2 tool steel comprises 1.2-1.5 wt % carbon, 0.3-0.5 wt % silicon, 0.3-0.6 wt % manganese, 6.0-7.0 wt % molybdenum, 3.5-4.3 wt % chromium, 5.0-6.0 wt % tungsten, up to 1.0 wt % nickel, and the balance being iron. Modified Silichrome XB contains 1.3-1.8 wt % carbon, 1.9-2.6 wt % silicon, 0.2-0.6 wt % manganese, 19.0-21.0 wt % chromium, 1.0-1.6 wt % nickel, and the balance being iron. Another common iron base alloy for intake valve seat inserts contains 1.8-2.3 wt % carbon, 1.8-2.1 wt % silicon, 0.2-0.6 wt % manganese, 2.0-2.5 wt % molybdenum, 33.0-35.0 wt % chromium, up to 1.0 wt % nickel, and the balance being substantially iron. There are also several high chromium-type iron base alloys available for making intake valve seat inserts.
- U.S. Pat. No. 6,916,444 discloses an iron base alloy containing a large amount of residual austenite for intake valve seat insert material. This alloy contains 2.0-4.0% carbon, 3.0-9.0% chromium, 0.0-4.0% manganese, 5.0-15.0% molybdenum, 0.0-6.0% tungsten, 0.0-6.0% vanadium, 0.0-4.0 niobium, 7.0-15.0% nickel, 0.0-6.0% cobalt, and the balance being iron with impurities. U.S. Pat. No. 6,436,338 discloses a corrosion resistant iron base alloy for diesel engine valve seat insert applications. The alloy is composed of carbon 1.1-1.4%, chromium 11-14.5%, molybdenum 4.75-6.25%, tungsten 3.5-4.5%, cobalt 0-3%, niobium 1.5-2.5%, vanadium 1-1.75%, copper 0-2.5%, silicon 0-1%, nickel 0-0.8%, iron being the balance with impurities. U.S. Pat. No. 6,866,816 discloses an austenitic type iron base alloy with good corrosion resistance. The chemical composition of the alloy is 0.7-2.4% carbon, 1.5-4.0% silicon, 5.0-9.0% chromium, less than 6.0% manganese, 5.0-20.0% molybdenum and tungsten, the total of vanadium and niobium 0-4.0%, titanium 0-1.5%, aluminum 0.01-0.5%, nickel 12.0-25.0%, copper 0-3.0%, and at least 45.0% iron. However, more severe corrosion conditions in some engines with high sulfur fuel and high humidity demands materials with corrosion resistance much better than the above iron base alloys.
- High carbon and high chromium type nickel base alloys normally do not exhibit good wear resistance under intake valve seat insert working conditions due to lack of combustion deposits and insufficient amount of metal oxides to protect valve seat insert from direct metal-to-metal wear. Eatonite 2 is one example of the nickel base alloys used for making exhaust valve seat inserts, which contains 2.0-2.8 wt % carbon, up to 1.0 wt % silicon, 27.0-31.0 wt % chromium, 14.0-16.0 wt % tungsten, up to 8.0 wt % iron, and the balance being essentially nickel. Eatonite is a trademark of Eaton Corporation. Several similar nickel base alloys with added iron and/or cobalt are also available for exhaust valve seat inserts. U.S. Pat. 6,200,688 discloses high silicon and high iron-type nickel base alloy used as material for valve seat inserts. These nickel base alloys may possibly be used in EGR engines only when the wear rate of intake insert is moderate.
- Wear resistant cobalt base alloys are another type of materials used in the industry, and the most commonly used ones are Stellite® 3 and Tribaloy® T-400 for more demanding applications. As disclosed in U.S. Pat. No. 3,257,178 and 3,410,732, Tribaloy® T400 contains 2.0-2.6 wt % silicon, 7.5-8.5 wt % chromium, 26.5-29.5 wt % molybdenum, up to 0.08 wt % carbon, up to 1.50 wt % nickel, up to 1.5 wt % iron, and the balance being essentially cobalt. Stellite® 3 contains 2.3-2.7 wt % carbon, 11.0-14.0 wt % tungsten, 29.0-32.0 wt % chromium, up to 3.0 wt % nickel, up to 3.0 wt % iron, and the balance being cobalt. The above cobalt base alloys possess both excellent corrosion and wear resistance. However, the cost of these cobalt base alloys only allows these alloys to be used in limited applications. (®Registered Trademarks of Deloro Stellite Company Inc.)
- Austenitic iron base valve alloys or valve facing alloys may also be classified into the same group of materials. U.S. Pat. No.4,122,817 discloses an austenitic iron base alloy with good wear resistance, PbO corrosion and oxidation resistance. The alloy contains 1.4-2.0 wt % carbon, 4.0-6.0 wt % molybdenum, 0.1 to 1.0 wt % silicon, 8.0-13.0 wt % nickel, 20.0-26.0 wt % chromium, 0-3.0 wt % manganese, with the balance being iron. U.S. Pat. No. 4,929,419 discloses a heat, corrosion and wear resistant austenitic steel for internal combustion exhaust valves, which contains 0.35-1.5 wt % carbon, 3.0-10.0 wt % manganese, 18.0-28.0 wt % chromium, 3.0-10.0 wt % nickel, up to 2.0 wt % silicon, up to 0.1 wt % phosphorus, up to 0.05 wt % sulfur, up to 10.0 wt % molybdenum, up to 4.0 wt % vanadium, up to 8.0 wt % tungsten, up to 1.0 wt % niobium, up to 0.03 wt % boron, and the balance being essentially iron.
- A new austenitic iron base alloy has been invented that possess corrosion resistance close to Stellite 3 under diluted hot sulfuric acid condition. The cost of the alloy is significantly lower than cobalt base alloys, such as Stellitee and Tribaloy®. In one aspect, the present invention is an alloy with the following composition:
Element wt. % Carbon 1.8-2.8 Silicon 0.5-3.5 Chromium 12.0-25.0 Molybdenum and 2.0-10.0 tungsten combined Nickel 12.0-25.0 Niobium and 1.0-4.0 vanadium combined Titanium 0-1.0 Aluminum 0.01-0.2 Copper 0.05-3.0 Iron and impurities Balance - In another aspect of the invention, metal components are either made of the alloy, such as by casting, or by the powder metallurgy method by forming from a powder and sintering. Furthermore, the alloy can be used to hardface the components as the protective coating.
- It is the object of this invention to develop an austenitic iron base alloy with excellent corrosion resistance to meet the specific demand from more severe corrosion condition in diesel engines with EGR systems.
- It is another object of this invention to develop a corrosion resistant iron base alloy with good wear resistance.
- Numerous experiments have been accomplished in order to achieve the above objectives. Alloys with excellent corrosion resistance under static immersion type test may perform poorly under cyclic heating corrosion because of different corrosion behaviors at high temperature and the possible influence of oxidation to the corrosion process. The high temperature cyclic corrosion tester provides a tool to study corrosion behavior with the influence of oxidation under high temperature condition. According to our studies, a number of alloy elements can affect corrosion and hardness of the alloy, where it is preferred to have a minimum hardness of 34.0 HRC in order to achieve good wear resistance in the inventive austenitic alloy. However, the austenitic alloy can become too brittle when the hardness of the alloy exceeds 54.0 HRC due to formation of intermetallic compounds like sigma phase from excessive amount of alloy elements. It is relatively easier to achieve enough corrosion resistance with higher chromium and nickel contents under low carbon content. In stainless steels, like AISI 300 series, carbon content is controlled to a minimum level in order to reduce both chromium content tied with carbon and carbide/matrix boundaries for better corrosion resistance. Unfortunately valve seat insert alloys almost always have much higher carbon content than corrosion resistant stainless steels because a large volume fraction of alloy carbides is mandatory for higher hardness and better wear resistance in wear resistant alloys using alloy carbides as primary hard phases, which is contrary to the high corrosion resistance requirement. U.S. Pat. No. 6,866,816 discloses an austenitic alloy using low to medium chromium content and high molybdenum with about 1.6 wt % carbon to achieve good corrosion resistance and wear resistance. To obtain an even higher corrosion resistance, much higher chromium content is used in the present inventive alloy with a higher carbon content to form more alloy carbides in order to compensate for the reduction of hardness and wear resistance due to higher chromium content. Unlike U.S. Pat. No. 6,866,816 in which high contents of refractory alloy elements, like molybdenum and tungsten, are used for higher corrosion resistance and higher hardness, high refractory alloy element contents 5 can cause brittleness problem in the present inventive alloys when these refractory alloy elements combine with chromium, silicon and other alloy elements to form harmful intermetallic phases. Other different approaches need to be tested in order to increase the hardness of the current high chromium type inventive alloy. Through many experimental tests we found that the hardness of the current inventive alloy can reach to U.S. Pat. No. 6,866,816 when carbon is between 2.2-2.7 wt %, chromium 10.0-17.0 wt %, silicon 0.5-3.0 wt %, tungsten 2.0-7.0 wt % or a combination of tungsten and molybdenum 2.0-14.0 wt %, nickel 12.0-20.0 wt %, copper 0.0-2.0 wt %, vanadium 0.0-3.0 wt %, niobium 0.0-2.0 wt %, and the balance being iron with other inevitable impurities.
- Chemical compositions of all samples are given in table 1. These alloy samples were prepared in a 60 pounds industry frequency induction furnace by conventional atmosphere melting process, and the corrosion and hardness samples were cast into shell molds. The comparative alloy samples have compositions outside the scope of this invention. There are also two commercial alloys Stellite 3 and M2 listed in the table as comparative alloys.
- Ring samples with 45 mm outer diameter, 32 mm inner diameter and 5 mm thickness were used as hardness samples and the hardness values of all samples were obtained using a Rockwell C hardness tester.
- A high temperature cyclic corrosion tester was built to simulate sulfuric acid corrosion at high temperature. The new corrosion tester provides a better corrosion measurement method than the traditional static immersion corrosion test as both oxidation and high temperature are also important factors contributing to the corrosion process in intake insert working environment.
- The high temperature cyclic corrosion test rig is composed of a heating coil, an air cylinder, a sample with its holder, a control unit, and an acid solution container. First the air cylinder lifts the sample up into the heating coil to heat the specimen. The sample is held inside the coil for about 22 seconds so that the specimen temperature reaches about 300 °F. Then the air cylinder moves the heated sample down into the sulfuric acid solution container, and the cycle continues to repeat. All acid solution left on the sample is vaporized when the sample is heated inside the heating coil. Therefore both corrosion and oxidation occur in this process, which is closer to the actual insert corrosion in EGR equipped engines than the static acid immersion test. Corrosion also occurs when the heated specimen is pushed into the sulfuric acid solution container. The testing time is one hour. The sample dimensions are 6.35 mm in diameter and 31.75 mm in length. About 12.7 mm length of the sample is immersed into the solution. 0.25 vol.%, 0.50 vol. %, and 1.0 vol.% sulfuric acid solutions are used for each sample. A precision balance is used to measure the weight of each sample before and after test and the precision of the balance is 0.0001 gram. The corrosion weight loss is the weight difference of a sample before and after corrosion test. The lower the corrosion weight loss the higher the corrosion resistance of an alloy sample. From actual engine with EGR corrosion tests, the composition of the invention alloy is such as to produce a corrosion weight loss preferably less than 5.0 mg, 10.0 mg, and 18 mg in 0.25, 0.5, and 1.0 vol.% sulfuric acid solutions in the high temperature cyclic corrosion tester, respectively.
- Samples 1-7 contain carbon contents from 1.2 to 2.7 wt % with silicon 1.0 wt %, chromium 18.0 wt %, tungsten 7.0 wt %, nickel 16 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials. Hardness increases
TABLE 1 Alloy Hardness and Chemical Composition (wt %) Sample Hardness No. Alloy Name C Si Cr W Mo Fe V Nb Ni Al Cu (HRC) 1 Comparative 1.2 1.0 18.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 29.0 2 Comparative 1.4 1.0 18.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 30.4 3 1.8 1.0 18.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 34.7 4 2.0 1.0 18.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 36.9 5 2.2 1.0 18.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 39.9 6 2.5 1.0 18.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 41.1 7 2.7 1.0 18.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 41.5 8 Comparative 2.5 1.0 10.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 45.3 9 2.5 1.0 12.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 45.3 10 2.5 1.0 13.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 45.6 11 2.5 1.0 15.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 44.8 12 2.5 1.0 17.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 43.0 13 2.5 1.0 20.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 38.3 14 2.5 1.0 22.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 38.1 15 2.5 1.0 25.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 39.0 16 2.5 1.0 18.0 2.0 — Bal. 1.0 1.0 16.0 0.04 1.5 41.6 17 2.5 1.0 18.0 4.0 — Bal. 1.0 1.0 16.0 0.04 1.5 41.0 18 2.5 1.5 18.0 7.0 7.0 Bal. 1.0 1.0 25.0 0.04 1.5 40.2 19 2.5 1.0 18.0 — 5.0 Bal. 1.0 1.0 16.0 0.04 1.5 41.1 20 2.5 2.0 18.0 — 15.0 Bal. 2.0 1.0 16.0 0.04 1.5 51.0 21 2.5 1.0 18.0 7.0 — Bal. 1.0 1.0 12.0 0.04 1.5 41.8 22 2.5 1.0 18.0 7.0 — Bal. 1.0 1.0 20.0 0.04 1.5 38.9 23 2.5 1.0 18.0 7.0 — Bal. 1.0 1.0 25.0 0.04 1.5 38.6 24 2.2 1.0 18.0 7.0 — Bal. 3.0 1.0 16.0 0.04 1.5 38.5 25 2.5 3.0 18.0 7.0 — Bal. 1.0 1.0 16.0 0.04 1.5 36.1 26 Stellite 3 2.4 — 30.0 12.8 2.0 — Co: 2.0 — — 55.0 50.8 27 M2 1.6 1.3 4.0 5.5 6.5 Bal. 1.5 — — — — 42.0 28 Tribaloy 0.08 2.6 8.5 — 28.5 — — Co: — — — 54.2 T400 60.4 29 US6866816 1.6 2.0 9.0 — 15.0 Bal. — 2.0 16.0 0.30 1.0 43.2 30 US6916444 2.4 1.5 6.0 — 15.0 Bal. 2.5 1.5 10.0 — — 46.6 31 US6436338 1.3 0.6 13.2 4.0 5.8 Bal. 1.3 2.1 0.6 — Co: 2.1 45.0 32 US4122817 1.7 0.5 24.0 Mn: 1.4 3.9 Bal. — — 9.2 — — 38.2 33 US6200688 1.7 3.0 15.0 12.0 — 35.0 — 2.0 32.0 — — 39.8
rapidly with carbon content increasing from 1.2 to 2.2 wt % and then slowly increases with further carbon content. Carbon content in the inventive alloy needs to be at least 1.8 or higher in order to achieve required hardness because the hardness of sample alloys with 1.2 and 1.4 wt % carbon is only 29.0 and 30.4 HRC. On the other hand, if the carbon content of the alloy is more than 3.0 wt %, shrinkage will become a major problem for insert type ring shaped castings. Therefore, the carbon content is defined to be within the range of from 1.8 to 3.0 % for good hardness and casting properties. - Samples 8-15 contain chromium from 10.0 to 25.0 wt % with carbon 2.5 wt %, silicon 1.0 wt %, tungsten 7.0 wt %, nickel 16 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials. These different chromium contents containing samples illustrate the effects of chromium on hardness and corrosion resistance. Lower chromium containing alloy gives lower corrosion resistance while alloys with higher chromium contents have lower hardness. Therefore chromium content in the inventive alloy is defined to be within 12.0 to 25.0 wt %, preferably between 15.0 to 20.0 wt % for the balance of good corrosion resistance and adequate hardness.
- Samples 16-20 contain tungsten and/or molybdenum from 0 to 15.0 wt % with carbon 2.5 wt %, silicon 1.0-2.0 wt %, chromium 18.0 wt %, nickel 16.0-25.0 wt %, vanadium 1.0-2.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials. Unlike U.S. Pat. No. 6,866,816 where corrosion resistance increase with the amount of molybdenum content, increasing tungsten and molybdenum have little effect in hardness and corrosion in the range tested. It is not necessary to use high molybdenum and/or tungsten content for better corrosion or higher hardness in the inventive alloy. Similar to high speed steels, addition of molybdenum or tungsten improves hot hardness of the inventive alloy, which is important from the designed application view as the intake insert working temperature can reach 700° F. The molybdenum or tungsten content is defined to be within 3.0 to 15.0 wt %, and the combined contents of the two elements should be less than 16.0 wt %. Excessive amount of tungsten or molybdenum causes brittleness problem of castings made from the inventive alloy.
- Samples 6, 21, and 23 contain nickel from 12.0 to 25.0 wt % with carbon 2.5 wt %, silicon 1.0 wt %, chromium 18.0 wt %, tungsten 7.0 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials. Nickel has a positive contribution to the corrosion resistance of the alloy. First there is a minimum amount of nickel required in order to form stable austenite in the alloy, higher nickel content improves corrosion resistance of the alloy in all acid concentrations tested. However the improvement is at the expense of lower hardness and therefore lower wear resistance. Therefore, the nickel content is defined to be within the range of 12.0 to 25.0 wt %.
- Vanadium and niobium are strong MC carbide type forming alloy elements. A small addition of vanadium and niobium helps to improve corrosion resistance of the alloy. Too much vanadium or niobium decreases the hardness of the alloy. Samples 5 and 24 contain vanadium from 1.0 to 3.0 wt % with carbon 2.5 wt %, silicon 1.0 wt %, chromium 18.0 wt %, tungsten 7.0 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials. From the corrosion and hardness test results, vanadium content should be in the range of 0.02 to 3.0 wt %. Similarly, niobium content is between 0.02 to 3.0 wt %.
- Samples 6 and 25 contain silicon from 1.0 to 3.0 wt % with carbon 2.5 wt %, chromium 18.0 wt %, tungsten 7.0 wt %, nickel 16 wt %, vanadium 1.0 wt %, niobium 1.0 wt %, copper 1.5 wt %, and the balance is iron with other impurities associated with casting raw materials. Silicon has deoxidizing and desulfurizing effects during alloy melting process. Silicon also has the effect of improving fluidity. However, the main reasons of using silicon in the inventive alloy are that silicon can also improve corrosion and wear resistance of the alloys. Increasing silicon content from 1.0 to 3.0 wt % improves
TABLE 2 Corrosion Test Results (Weight Loss; mg) Sample No. Alloy Name 0.25% 0.5% 1.0% 1 comparative 2.5 4.6 13.3 2 comparative 3.1 4.6 14.5 3 2.6 7.1 13.4 4 4.1 7.6 14.5 5 3.8 8.1 15.2 6 3.8 8.1 14.0 7 4.3 8.7 14.0 8 comparative 6.3 9.8 12.4 9 3.7 9.5 14.4 10 2.3 9.0 17.4 11 2.6 7.1 13.9 12 2.7 7.8 14.8 13 3.5 9.0 15.2 14 4.2 8.9 13.5 15 2.9 5.8 11.8 16 3.7 7.8 13.9 17 3.0 5.0 15.0 18 2.9 4.9 11.2 19 3.3 8.1 17.8 20 3.9 7.7 13.8 21 4.1 7.8 17.9 22 2.5 7.3 13.0 23 1.1 5.5 10.7 24 2.7 7.8 15.1 25 1.8 4.0 10.6 26 Stellite 3 2.6 5.8 7.5 27 M2 23.5 45.0 84.1 28 Tribaloy 1.2 4.7 11.9 T400 29 US6866816 5.2 10.3 15.0 30 US6916444 15.2 18.7 20.2 31 US6436338 13.9 19.4 33.4 32 US4122817 8.7 14.4 23.6 33 US6200688 4.4 8.5 12.2
corrosion resistance of the inventive alloy. If the Si content is less than 0.5%, the effects on wear and corrosion are not achieved. If the Si content is more than 3.5 wt %, specially in the high carbon austenitic alloy, excessive amount of silicon provides a too brittle alloy. Higher amount of silicon also decreases the hardness of the inventive alloy. Therefore, the silicon content is defined to be within the range of 0.5 to 3.5 wt %. - Addition of copper enhances the corrosion resistance of the alloy significantly. However excessive amount of copper decreases wear resistance of the alloy. Therefore, the range of copper in the alloy is defined to be within 0.02 to 3.0 wt %.
- Manganese also has deoxidizing and desulfurizing effects to molten metals. However, manganese can deteriorate corrosion resistance if its content is too high. Therefore, the manganese range is defined to be less than 1.5 wt %.
- A small amount of aluminum, and optionally titanium, is added in the inventive alloys for precipitation hardening purpose. The range for aluminum is between about 0.01 and about 0.2 wt %, preferably between about 0.05 and about 0.1 wt %. The range for titanium is between about zero and about 1 wt %, preferably between about 0.05 wt % and about 0.5 wt %. When these elements are added, and the alloys heat treated, wear resistance will be improved.
- Corrosion and hardness test results for M2 tool steel, Stellite 3, Tribaloy T400, U.S. Pat. No. 6,866,816, U.S. Pat. No. 6,916,444, U.S. Pat. No. 6,436,338, U.S. Pat. No. 3,257,178, U.S. Pat. No. 4,122,817, and U.S. Pat. No. 6,200,688 are also given in Table 1 and Table 2. It is clear that many inventive samples have much better corrosion and wear resistance than M2 tool steel. Some samples are even close to cobalt base alloys Stellite 3, Tribaloy T400, and nickel base alloy (U.S. Pat. No. 6,436,338) in terms of corrosion resistance. However, these samples are much less expensive than these cobalt base and nickel base alloys.
- It should be appreciated that the alloys of the present invention are capable of being incorporated in the form of a variety of embodiments, only a few of which have been illustrated and described. The invention may be embodied in other forms without departing from its spirit or essential characteristics. It should be appreciated that the addition of some other ingredients, process steps, materials or components not specifically included will have an adverse impact on the present invention. The best mode of the invention may, therefore, exclude ingredients, process steps, materials or components other than those listed above for inclusion or use in the invention. However, the described embodiments are considered in all respects only as illustrative and not restrictive, and the scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (30)
1. An austenitic iron base alloy with good corrosion and wear resistance, comprising:
a) about 1.8 to about 2.8 wt % carbon;
b) about 12.0 to about 25.0 wt % chromium;
c) about 0.5 to 3.5 wt % silicon;
d) about 12.0 to about 25.0 wt % nickel;
e) about 2.0 to about 10.0 wt % of tungsten and molybdenum combined;
f) about 1.0 to about 4 wt % niobium and vanadium combined;
g) about 0 to about 1.0 wt % titanium;
h) about 0.01 to about 0.2 wt % aluminum;
i) about 0.05 to about 3 wt % copper;
j) less than 1.5 wt % manganese;
g) The balance being iron and impurities.
2. A part for internal combustion engine component comprising the alloy of claim 1 .
3. The part of claim 2 where the part is formed by casting the alloy, hardfacing with the alloy either in wire or powder form,
4. The part of claim 2 where the part is formed by a powder metallurgy method.
5. The alloy of claim 1 wherein the amount of carbon is between about 2.3 and about 2.7 wt %.
6. The alloy of claim 1 wherein the amount of chromium is between about 16.0 and about 20.0 wt %.
7. The alloy of claim 1 wherein the amount of silicon is between about 0.5 and about 1.5 wt %.
8. The alloy of claim 1 wherein the amount of tungsten is between about 3.0 and about 7.0 wt %.
9. The alloy of claim 1 wherein the amount of nickel is between about 14.0 and about 18.0 wt %.
10. The alloy of claim 1 wherein the amount of niobium and vanadium combined is between about 1.5 and about 2.5 wt %.
11. The alloy of claim 1 wherein the amount of titanium is between about 0.02 and about 0.06 wt %.
12. The alloy of claim 1 wherein the amount of aluminum is between about 0.03 and about 0.06 wt %.
13. The alloy of claim 1 wherein the amount of copper is between about 1.0 and about 2.0 wt %.
14. The alloy of claim 1 wherein the amount of manganese is between about 0.2 and about 0.6 wt %.
15. The alloy of claim 1 wherein the amount of iron is greater than about 50 wt %.
16. An austenitic iron base alloy with good corrosion and wear resistance, comprising:
a) about 1.8 to about 2.8 wt % carbon;
b) about 12.0 to about 25.0 wt % chromium;
c) about 0.5 to about 3.5 wt % silicon;
d) about 12.0 to about 25.0 wt % nickel;
e) about 10.0 to about 16.0 wt % of molybdenum and tungsten combined;
f) about 1.0 to about 4 wt % niobium and vanadium combined;
g) about 0.01 to about 1.0 wt % titanium;
h) about 0.01 to about 0.2 wt % aluminum;
i) about 0.05 to about 3.0 wt % copper;
j) less than 1.5 wt % manganese;
g) The balance being iron and impurities.
16. A part for internal combustion engine component comprising the alloy of claim 15 .
17. The part of claim 16 where the part is formed by casting the alloy, hardfacing with the alloy either in wire or powder form,
18. The part of claim 16 where the part is formed by a powder metallurgy method.
19. The alloy of claim 15 wherein the amount of carbon is between about 2.3 and about 2.7 wt %.
20. The alloy of claim 15 wherein the amount of chromium is between about 16.0 and about 20.0 wt %.
21. The alloy of claim 15 wherein the amount of silicon is between about 0.5 and about 1.5 wt %.
22. The alloy of claim 15 wherein the amount of molybdenum is between about 12.0 and about 15.0 wt %.
23. The alloy of claim 15 wherein the amount of nickel is between about 14.0 and about 18.0 wt %.
24. The alloy of claim 15 wherein the amount of niobium and vanadium combined is between about 1.5 and about 2.5 wt %.
25. The alloy of claim 15 wherein the amount of titanium is between about 0.02 and about 0.06 wt %.
26. The alloy of claim 15 wherein the amount of aluminum is between about 0.03 and about 0.06 wt %.
27. The alloy of claim 15 wherein the amount of copper is between about 1.0 and about 2.0 wt %.
28. The alloy of claim 15 wherein the amount of manganese is between about 0.2 and about 0.6 wt %.
29. The alloy of claim 15 wherein the amount of iron is greater than about 50 wt %.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/251,308 US20070086910A1 (en) | 2005-10-14 | 2005-10-14 | Acid resistant austenitic alloy for valve seat insert |
| BRC10604291A BRPI0604291C1 (en) | 2005-10-14 | 2006-10-13 | homogeneous iron-based austenitic alloy with good corrosion and wear resistance |
| DE602006005757T DE602006005757D1 (en) | 2005-10-14 | 2006-10-13 | Acid-resistant austenitic alloy for valve seat ring |
| EP06255276A EP1775351B1 (en) | 2005-10-14 | 2006-10-13 | Acid resistant austenitic alloy for valve seat insert |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/251,308 US20070086910A1 (en) | 2005-10-14 | 2005-10-14 | Acid resistant austenitic alloy for valve seat insert |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20070086910A1 true US20070086910A1 (en) | 2007-04-19 |
Family
ID=37564345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/251,308 Abandoned US20070086910A1 (en) | 2005-10-14 | 2005-10-14 | Acid resistant austenitic alloy for valve seat insert |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20070086910A1 (en) |
| EP (1) | EP1775351B1 (en) |
| BR (1) | BRPI0604291C1 (en) |
| DE (1) | DE602006005757D1 (en) |
Cited By (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080292489A1 (en) * | 2007-01-04 | 2008-11-27 | Ut-Battelle, Llc | High Mn Austenitic Stainless Steel |
| US20080304996A1 (en) * | 2007-01-04 | 2008-12-11 | Ut-Battelle, Llc | High Nb, Ta, and Al Creep- and Oxidation-Resistant Austenitic Stainless Steels |
| US20090258250A1 (en) * | 2003-04-21 | 2009-10-15 | ATT Technology, Ltd. d/b/a Amco Technology Trust, Ltd. | Balanced Composition Hardfacing Alloy |
| US20110162612A1 (en) * | 2010-01-05 | 2011-07-07 | L.E. Jones Company | Iron-chromium alloy with improved compressive yield strength and method of making and use thereof |
| US20110300016A1 (en) * | 2009-02-17 | 2011-12-08 | Mec Holding Gmbh | Wear resistant alloy |
| US20130251585A1 (en) * | 2012-03-26 | 2013-09-26 | Hitachi Powdered Metals Co., Ltd. | Sintered alloy and production method therefor |
| US20140255245A1 (en) * | 2011-10-20 | 2014-09-11 | Borgwarner Inc. | Turbocharger and a component therefor |
| JP2014169468A (en) * | 2013-03-01 | 2014-09-18 | Hitachi Chemical Co Ltd | Sintered alloy and its manufacturing method |
| US20140284882A1 (en) * | 2011-07-12 | 2014-09-25 | Michael Zinnabold | Wear protection layer for piston rings |
| US9404400B2 (en) * | 2008-08-01 | 2016-08-02 | Daf Trucks N.V. | Cylinder head with valve seat and method for the production thereof |
| US9638075B2 (en) | 2013-12-02 | 2017-05-02 | L.E. Jones Company | High performance nickel-based alloy |
| CN109402518A (en) * | 2017-08-17 | 2019-03-01 | L.E.君斯公司 | High performance iron-based alloys for engine valve train applications, methods of making the same, and uses thereof |
| CN113832384A (en) * | 2021-08-27 | 2021-12-24 | 李春林 | Super-wear-resistant high-chromium cast iron rotor and machining method thereof |
| US11353117B1 (en) | 2020-01-17 | 2022-06-07 | Vulcan Industrial Holdings, LLC | Valve seat insert system and method |
| US11384756B1 (en) | 2020-08-19 | 2022-07-12 | Vulcan Industrial Holdings, LLC | Composite valve seat system and method |
| US11391374B1 (en) | 2021-01-14 | 2022-07-19 | Vulcan Industrial Holdings, LLC | Dual ring stuffing box |
| US11421680B1 (en) | 2020-06-30 | 2022-08-23 | Vulcan Industrial Holdings, LLC | Packing bore wear sleeve retainer system |
| US11421679B1 (en) | 2020-06-30 | 2022-08-23 | Vulcan Industrial Holdings, LLC | Packing assembly with threaded sleeve for interaction with an installation tool |
| US11434900B1 (en) | 2022-04-25 | 2022-09-06 | Vulcan Industrial Holdings, LLC | Spring controlling valve |
| US11479836B2 (en) | 2021-01-29 | 2022-10-25 | Ut-Battelle, Llc | Low-cost, high-strength, cast creep-resistant alumina-forming alloys for heat-exchangers, supercritical CO2 systems and industrial applications |
| EP4123048A1 (en) * | 2021-07-06 | 2023-01-25 | L.E. Jones Company | Low-carbon iron-based alloy useful for valve seat inserts |
| USD980876S1 (en) | 2020-08-21 | 2023-03-14 | Vulcan Industrial Holdings, LLC | Fluid end for a pumping system |
| USD986928S1 (en) | 2020-08-21 | 2023-05-23 | Vulcan Industrial Holdings, LLC | Fluid end for a pumping system |
| US20230220528A1 (en) * | 2022-01-11 | 2023-07-13 | Garrett Transportation I Inc | High silicon stainless steel alloys and turbocharger kinematic components formed from the same |
| USD997992S1 (en) | 2020-08-21 | 2023-09-05 | Vulcan Industrial Holdings, LLC | Fluid end for a pumping system |
| CN117165863A (en) * | 2023-11-03 | 2023-12-05 | 江苏星源电站冶金设备制造有限公司 | Wear-resistant fire grate segment and preparation method thereof |
| US11866809B2 (en) | 2021-01-29 | 2024-01-09 | Ut-Battelle, Llc | Creep and corrosion-resistant cast alumina-forming alloys for high temperature service in industrial and petrochemical applications |
| US11920684B1 (en) | 2022-05-17 | 2024-03-05 | Vulcan Industrial Holdings, LLC | Mechanically or hybrid mounted valve seat |
| US12049889B2 (en) | 2020-06-30 | 2024-07-30 | Vulcan Industrial Holdings, LLC | Packing bore wear sleeve retainer system |
| US12055221B2 (en) | 2021-01-14 | 2024-08-06 | Vulcan Industrial Holdings, LLC | Dual ring stuffing box |
| US12140240B1 (en) | 2022-01-19 | 2024-11-12 | Vulcan Industrial Holdings, LLC | Gradient material structures and methods of forming the same |
| USD1061623S1 (en) | 2022-08-03 | 2025-02-11 | Vulcan Industrial Holdings, LLC | Fluid end for a pumping system |
| US12292120B1 (en) | 2021-02-23 | 2025-05-06 | Vulcan Industrial Holdings, LLC | System and method for valve assembly |
| US12292121B2 (en) | 2023-08-10 | 2025-05-06 | Vulcan Industrial Holdings, LLC | Valve member including cavity, and related assemblies, systems, and methods |
| US12297922B1 (en) | 2022-03-04 | 2025-05-13 | Vulcan Industrial Holdings, LLC | Valve seat with embedded structure and related methods |
| US12345332B2 (en) | 2021-08-18 | 2025-07-01 | Vulcan Industrial Holdings, LLC | Self-locking plug |
| US12366245B1 (en) | 2020-08-27 | 2025-07-22 | Vulcan Industrial Holdings, LLC | Connecting rod assembly for reciprocating pump |
| US12510164B1 (en) | 2021-08-18 | 2025-12-30 | Vulcan Industrial Holdings, LLC | Sleeved fluid end |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7754142B2 (en) | 2007-04-13 | 2010-07-13 | Winsert, Inc. | Acid resistant austenitic alloy for valve seat inserts |
| CN107385317A (en) * | 2017-09-06 | 2017-11-24 | 马鞍山市万兴耐磨金属制造有限公司 | Austenite nodular cast iron and its processing technology |
| CN110468333A (en) * | 2019-09-03 | 2019-11-19 | 昆明理工大学 | A kind of semi-autogenous mill high abrasion ultra-high manganese steel liner plate and preparation method |
| CN111304535A (en) * | 2020-03-20 | 2020-06-19 | 江苏精研科技股份有限公司 | Corrosion-resistant steel powder, ultrahigh-strength steel feed and preparation process of corrosion-resistant steel complex part |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3257178A (en) * | 1966-06-21 | Coated metal article | ||
| US3410732A (en) * | 1965-04-30 | 1968-11-12 | Du Pont | Cobalt-base alloys |
| US4122817A (en) * | 1975-05-01 | 1978-10-31 | Trw Inc. | Internal combustion valve having an iron based hard-facing alloy contact surface |
| US4724000A (en) * | 1986-10-29 | 1988-02-09 | Eaton Corporation | Powdered metal valve seat insert |
| US4929419A (en) * | 1988-03-16 | 1990-05-29 | Carpenter Technology Corporation | Heat, corrosion, and wear resistant steel alloy and article |
| US5458703A (en) * | 1991-06-22 | 1995-10-17 | Nippon Koshuha Steel Co., Ltd. | Tool steel production method |
| US6200688B1 (en) * | 1998-04-20 | 2001-03-13 | Winsert, Inc. | Nickel-iron base wear resistant alloy |
| US6436338B1 (en) * | 1999-06-04 | 2002-08-20 | L. E. Jones Company | Iron-based alloy for internal combustion engine valve seat inserts |
| US6866816B2 (en) * | 2002-08-16 | 2005-03-15 | Alloy Technology Solutions, Inc. | Wear and corrosion resistant austenitic iron base alloy |
| US6916444B1 (en) * | 2002-02-12 | 2005-07-12 | Alloy Technology Solutions, Inc. | Wear resistant alloy containing residual austenite for valve seat insert |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS518808B2 (en) * | 1972-04-11 | 1976-03-22 | ||
| US5674449A (en) * | 1995-05-25 | 1997-10-07 | Winsert, Inc. | Iron base alloys for internal combustion engine valve seat inserts, and the like |
| US7611590B2 (en) * | 2004-07-08 | 2009-11-03 | Alloy Technology Solutions, Inc. | Wear resistant alloy for valve seat insert used in internal combustion engines |
-
2005
- 2005-10-14 US US11/251,308 patent/US20070086910A1/en not_active Abandoned
-
2006
- 2006-10-13 DE DE602006005757T patent/DE602006005757D1/en active Active
- 2006-10-13 BR BRC10604291A patent/BRPI0604291C1/en active IP Right Grant
- 2006-10-13 EP EP06255276A patent/EP1775351B1/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3257178A (en) * | 1966-06-21 | Coated metal article | ||
| US3410732A (en) * | 1965-04-30 | 1968-11-12 | Du Pont | Cobalt-base alloys |
| US4122817A (en) * | 1975-05-01 | 1978-10-31 | Trw Inc. | Internal combustion valve having an iron based hard-facing alloy contact surface |
| US4724000A (en) * | 1986-10-29 | 1988-02-09 | Eaton Corporation | Powdered metal valve seat insert |
| US4929419A (en) * | 1988-03-16 | 1990-05-29 | Carpenter Technology Corporation | Heat, corrosion, and wear resistant steel alloy and article |
| US5458703A (en) * | 1991-06-22 | 1995-10-17 | Nippon Koshuha Steel Co., Ltd. | Tool steel production method |
| US6200688B1 (en) * | 1998-04-20 | 2001-03-13 | Winsert, Inc. | Nickel-iron base wear resistant alloy |
| US6436338B1 (en) * | 1999-06-04 | 2002-08-20 | L. E. Jones Company | Iron-based alloy for internal combustion engine valve seat inserts |
| US6916444B1 (en) * | 2002-02-12 | 2005-07-12 | Alloy Technology Solutions, Inc. | Wear resistant alloy containing residual austenite for valve seat insert |
| US6866816B2 (en) * | 2002-08-16 | 2005-03-15 | Alloy Technology Solutions, Inc. | Wear and corrosion resistant austenitic iron base alloy |
Cited By (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090258250A1 (en) * | 2003-04-21 | 2009-10-15 | ATT Technology, Ltd. d/b/a Amco Technology Trust, Ltd. | Balanced Composition Hardfacing Alloy |
| US20080304996A1 (en) * | 2007-01-04 | 2008-12-11 | Ut-Battelle, Llc | High Nb, Ta, and Al Creep- and Oxidation-Resistant Austenitic Stainless Steels |
| US7754305B2 (en) | 2007-01-04 | 2010-07-13 | Ut-Battelle, Llc | High Mn austenitic stainless steel |
| US7754144B2 (en) | 2007-01-04 | 2010-07-13 | Ut-Battelle, Llc | High Nb, Ta, and Al creep- and oxidation-resistant austenitic stainless steel |
| US20080292489A1 (en) * | 2007-01-04 | 2008-11-27 | Ut-Battelle, Llc | High Mn Austenitic Stainless Steel |
| US9404400B2 (en) * | 2008-08-01 | 2016-08-02 | Daf Trucks N.V. | Cylinder head with valve seat and method for the production thereof |
| US20110300016A1 (en) * | 2009-02-17 | 2011-12-08 | Mec Holding Gmbh | Wear resistant alloy |
| WO2010147726A1 (en) * | 2009-06-17 | 2010-12-23 | Att Technology, Ltd. | Balanced composition hardfacing alloy |
| US20110162612A1 (en) * | 2010-01-05 | 2011-07-07 | L.E. Jones Company | Iron-chromium alloy with improved compressive yield strength and method of making and use thereof |
| US8479700B2 (en) | 2010-01-05 | 2013-07-09 | L. E. Jones Company | Iron-chromium alloy with improved compressive yield strength and method of making and use thereof |
| US20140284882A1 (en) * | 2011-07-12 | 2014-09-25 | Michael Zinnabold | Wear protection layer for piston rings |
| US9487855B2 (en) * | 2011-07-12 | 2016-11-08 | Federal-Mogul Bursheid Gmbh | Wear protection layer for piston rings |
| US20140255245A1 (en) * | 2011-10-20 | 2014-09-11 | Borgwarner Inc. | Turbocharger and a component therefor |
| US9359938B2 (en) * | 2011-10-20 | 2016-06-07 | Borgwarner Inc. | Turbocharger and a component therefor |
| US9340857B2 (en) * | 2012-03-26 | 2016-05-17 | Hitachi Powdered Metals Co., Ltd. | Sintered alloy and production method therefor |
| US20130251585A1 (en) * | 2012-03-26 | 2013-09-26 | Hitachi Powdered Metals Co., Ltd. | Sintered alloy and production method therefor |
| KR101607866B1 (en) * | 2013-03-01 | 2016-03-31 | 히타치가세이가부시끼가이샤 | Sintered alloy and manufacturing method thereof |
| JP2014169468A (en) * | 2013-03-01 | 2014-09-18 | Hitachi Chemical Co Ltd | Sintered alloy and its manufacturing method |
| US9982562B2 (en) | 2013-03-01 | 2018-05-29 | Hitachi Chemical Company, Ltd. | Sintered alloy and manufacturing method thereof |
| US9982563B2 (en) | 2013-03-01 | 2018-05-29 | Hitachi Chemical Company, Ltd. | Sintered alloy and manufacturing method thereof |
| US9638075B2 (en) | 2013-12-02 | 2017-05-02 | L.E. Jones Company | High performance nickel-based alloy |
| CN109402518A (en) * | 2017-08-17 | 2019-03-01 | L.E.君斯公司 | High performance iron-based alloys for engine valve train applications, methods of making the same, and uses thereof |
| US11353117B1 (en) | 2020-01-17 | 2022-06-07 | Vulcan Industrial Holdings, LLC | Valve seat insert system and method |
| US12345253B2 (en) | 2020-06-30 | 2025-07-01 | Vulcan Industrial Holdings, LLC | Packing assembly with threaded sleeve for interaction with an installation tool |
| US12480489B2 (en) | 2020-06-30 | 2025-11-25 | Vulcan Industrial Holdings, LLC | Packing bore wear sleeve retainer system |
| US12270394B2 (en) | 2020-06-30 | 2025-04-08 | Vulcan Industrial Holdings, LLC | Packing bore wear sleeve retainer system |
| US11421680B1 (en) | 2020-06-30 | 2022-08-23 | Vulcan Industrial Holdings, LLC | Packing bore wear sleeve retainer system |
| US11421679B1 (en) | 2020-06-30 | 2022-08-23 | Vulcan Industrial Holdings, LLC | Packing assembly with threaded sleeve for interaction with an installation tool |
| US12049889B2 (en) | 2020-06-30 | 2024-07-30 | Vulcan Industrial Holdings, LLC | Packing bore wear sleeve retainer system |
| US11384756B1 (en) | 2020-08-19 | 2022-07-12 | Vulcan Industrial Holdings, LLC | Composite valve seat system and method |
| USD980876S1 (en) | 2020-08-21 | 2023-03-14 | Vulcan Industrial Holdings, LLC | Fluid end for a pumping system |
| USD986928S1 (en) | 2020-08-21 | 2023-05-23 | Vulcan Industrial Holdings, LLC | Fluid end for a pumping system |
| USD997992S1 (en) | 2020-08-21 | 2023-09-05 | Vulcan Industrial Holdings, LLC | Fluid end for a pumping system |
| US12366245B1 (en) | 2020-08-27 | 2025-07-22 | Vulcan Industrial Holdings, LLC | Connecting rod assembly for reciprocating pump |
| US12404931B2 (en) | 2021-01-14 | 2025-09-02 | Vulcan Industrial Holdings, LLC | Dual ring stuffing box |
| US11391374B1 (en) | 2021-01-14 | 2022-07-19 | Vulcan Industrial Holdings, LLC | Dual ring stuffing box |
| US12055221B2 (en) | 2021-01-14 | 2024-08-06 | Vulcan Industrial Holdings, LLC | Dual ring stuffing box |
| US11479836B2 (en) | 2021-01-29 | 2022-10-25 | Ut-Battelle, Llc | Low-cost, high-strength, cast creep-resistant alumina-forming alloys for heat-exchangers, supercritical CO2 systems and industrial applications |
| US11866809B2 (en) | 2021-01-29 | 2024-01-09 | Ut-Battelle, Llc | Creep and corrosion-resistant cast alumina-forming alloys for high temperature service in industrial and petrochemical applications |
| US12292120B1 (en) | 2021-02-23 | 2025-05-06 | Vulcan Industrial Holdings, LLC | System and method for valve assembly |
| EP4123048A1 (en) * | 2021-07-06 | 2023-01-25 | L.E. Jones Company | Low-carbon iron-based alloy useful for valve seat inserts |
| US12540673B2 (en) | 2021-08-18 | 2026-02-03 | Vulcan Industrial Holdings, LLC | Self-locking plug |
| US12510164B1 (en) | 2021-08-18 | 2025-12-30 | Vulcan Industrial Holdings, LLC | Sleeved fluid end |
| US12345332B2 (en) | 2021-08-18 | 2025-07-01 | Vulcan Industrial Holdings, LLC | Self-locking plug |
| CN113832384A (en) * | 2021-08-27 | 2021-12-24 | 李春林 | Super-wear-resistant high-chromium cast iron rotor and machining method thereof |
| US20230220528A1 (en) * | 2022-01-11 | 2023-07-13 | Garrett Transportation I Inc | High silicon stainless steel alloys and turbocharger kinematic components formed from the same |
| US12140240B1 (en) | 2022-01-19 | 2024-11-12 | Vulcan Industrial Holdings, LLC | Gradient material structures and methods of forming the same |
| US12498051B2 (en) | 2022-01-19 | 2025-12-16 | Vulcan Industrial Holdings, LLC | Gradient material structures and methods of forming the same |
| US12297922B1 (en) | 2022-03-04 | 2025-05-13 | Vulcan Industrial Holdings, LLC | Valve seat with embedded structure and related methods |
| US12366244B2 (en) | 2022-04-25 | 2025-07-22 | Vulcan Industrial Holdings, LLC | Spring controlling valve |
| US11434900B1 (en) | 2022-04-25 | 2022-09-06 | Vulcan Industrial Holdings, LLC | Spring controlling valve |
| US11761441B1 (en) * | 2022-04-25 | 2023-09-19 | Vulcan Industrial Holdings, LLC | Spring controlling valve |
| US11920684B1 (en) | 2022-05-17 | 2024-03-05 | Vulcan Industrial Holdings, LLC | Mechanically or hybrid mounted valve seat |
| USD1061623S1 (en) | 2022-08-03 | 2025-02-11 | Vulcan Industrial Holdings, LLC | Fluid end for a pumping system |
| US12292121B2 (en) | 2023-08-10 | 2025-05-06 | Vulcan Industrial Holdings, LLC | Valve member including cavity, and related assemblies, systems, and methods |
| CN117165863A (en) * | 2023-11-03 | 2023-12-05 | 江苏星源电站冶金设备制造有限公司 | Wear-resistant fire grate segment and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1775351A1 (en) | 2007-04-18 |
| BRPI0604291C1 (en) | 2018-06-19 |
| EP1775351B1 (en) | 2009-03-18 |
| BRPI0604291A (en) | 2007-08-21 |
| DE602006005757D1 (en) | 2009-04-30 |
| BRPI0604291E2 (en) | 2009-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20070086910A1 (en) | Acid resistant austenitic alloy for valve seat insert | |
| US7754142B2 (en) | Acid resistant austenitic alloy for valve seat inserts | |
| US6866816B2 (en) | Wear and corrosion resistant austenitic iron base alloy | |
| US11215090B2 (en) | High performance iron-based alloys for engine valvetrain applications and methods of making and use thereof | |
| US8940110B2 (en) | Corrosion and wear resistant iron based alloy useful for internal combustion engine valve seat inserts and method of making and use thereof | |
| US10138766B2 (en) | Iron-based alloys and methods of making and use thereof | |
| US7611590B2 (en) | Wear resistant alloy for valve seat insert used in internal combustion engines | |
| US9334547B2 (en) | Iron-based alloys and methods of making and use thereof | |
| CN102369304A (en) | Hot working tool steel with excellent toughness and thermal conductivity | |
| CN109468522A (en) | The full form casting process of super-duplex stainless steel pump case | |
| CN109396348A (en) | The full form casting process of super-duplex stainless steel valve body | |
| US7326307B2 (en) | Thermal fatigue resistant cast steel | |
| EP4190931A1 (en) | Nickel-niobium intermetallic alloy useful for valve seat inserts | |
| JPS5940212B2 (en) | Co-based alloy for engine valves and valve seats of internal combustion engines | |
| HK40077639A (en) | High performance iron-based alloys for engine valvetrain applications and methods of making and use thereof | |
| BRPI0604291B1 (en) | AUSTENITIC LEATHER BASED ON IRON AND PART FOR AN INTERNAL COMBUSTION ENGINE | |
| HK40000431A (en) | High performance iron-based alloys for engine valvetrain applications and methods of making and use thereof | |
| HK40000431B (en) | High performance iron-based alloys for engine valvetrain applications and methods of making and use thereof | |
| JPS63199850A (en) | Low alloy heat resistant cast steel | |
| HK40074086A (en) | Martensitic wear resistant alloy strengthened through aluminum nitrides | |
| JPS6032711B2 (en) | Fe-based sintered alloy for valve seats | |
| BRC10604291F1 (en) | HOMOGENEOUS IRON BASED ALLOY WITH GOOD RESISTANCE TO CORROSION AND WEAR | |
| KR970001323B1 (en) | Small alloy for valve seat with excellent wear resistance | |
| JPS5855223B2 (en) | Heat-resistant and wear-resistant Cr↓-Fe↓-Ni↓-Co-based alloy | |
| JPH01301836A (en) | Corrosion-resistant soft magnetic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: ALLOY TECHNOLOG SOLUTIONS, INC., WISCONSIN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LIANG, XUECHENG;REEL/FRAME:017369/0602 Effective date: 20051209 |
|
| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |