EP2822718B1 - Thermal spray applications using iron based alloy powder - Google Patents
Thermal spray applications using iron based alloy powder Download PDFInfo
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- EP2822718B1 EP2822718B1 EP13712412.9A EP13712412A EP2822718B1 EP 2822718 B1 EP2822718 B1 EP 2822718B1 EP 13712412 A EP13712412 A EP 13712412A EP 2822718 B1 EP2822718 B1 EP 2822718B1
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- EP
- European Patent Office
- Prior art keywords
- thermal spray
- spraying
- metal material
- powder
- powder metal
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- 239000000843 powder Substances 0.000 title claims description 108
- 239000007921 spray Substances 0.000 title claims description 98
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 80
- 229910052742 iron Inorganic materials 0.000 title claims description 33
- 229910045601 alloy Inorganic materials 0.000 title claims description 24
- 239000000956 alloy Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 claims description 52
- 229910052799 carbon Inorganic materials 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 239000011651 chromium Substances 0.000 claims description 33
- 150000001247 metal acetylides Chemical class 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 229910052804 chromium Inorganic materials 0.000 claims description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims description 20
- 229910052720 vanadium Inorganic materials 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 15
- 239000010937 tungsten Substances 0.000 claims description 15
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 claims description 14
- 239000007769 metal material Substances 0.000 claims description 14
- 238000002485 combustion reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000007750 plasma spraying Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010285 flame spraying Methods 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 238000007751 thermal spraying Methods 0.000 claims description 5
- 238000010288 cold spraying Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 15
- 230000008018 melting Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 238000005275 alloying Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000000889 atomisation Methods 0.000 description 5
- 238000009689 gas atomisation Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000009692 water atomization Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910001567 cementite Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 206010063601 Exposure to extreme temperature Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000010284 wire arc spraying Methods 0.000 description 1
Images
Classifications
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- 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%
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
-
- 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
- B22F5/02—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of piston rings
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
Definitions
- This invention relates generally to wear resistant thermal spray powders, methods of forming the same, and applications thereof.
- Thermal spray techniques are used to apply wear resistant coatings to automotive engine components, such as pistons and piston rings.
- the coatings can protect the surface of the piston rings from wear as the piston slides along the cylinder.
- the coatings also reduce corrosion and oxidation of the piston caused by exposure to extreme temperatures and pollutants in the combustion chamber of the engine.
- wear resistant coatings have been formed from various ceramic materials, chromium-based powders, and molybdenum based powders. Examples of thermal spraying techniques include combustion, electrical discharge, cold spraying, and laser.
- WO2009/126674 describes a pre-sintered powder metal composition with over 3.0 wt % carbon, about 13 wt % chromium, about 2.5 wt % tungsten, about 4 wt % vanadium, about 1.5 wt % molybdenum and an oxygen content less than about 0.5 wt %.
- US 6887 585 B2 describes a wear-resistant coating for the bearing surfaces and flanks of piston rings, the wear-resistant coating comprising a mechanically alloyed powder mixture obtainable by mechanical alloying, said powder mixture including a metallic matrix comprising at least one of nickel land iron, and further comprising an iron-alloying element.
- EP 0266149 A2 describes a method of producing a wear-resistant metal member comprising the steps of spraying an alloy onto a surface of a metal member in a reduced pressure atmosphere by plasma spraying to form a sprayed layer on said surface, said alloy consisting essentially of by weight, 2 to 10% C, 18 to 60% Cr, 0.3 to 20% V, 25% or less Mo, 25% or less W, 10% or less Hf and the balance being Fe in a proportion of 20% or greater.
- the sprayed layer is subjected to a hardening treatment, followed by quenching and then a tempering treatment.
- the present disclosure describes a method of forming a wear resistant component comprising the steps of: spraying a powder metal material, wherein the powder metal material consists of 3.0 to 7.0 wt. % carbon, 10.0 to 25.0 wt. % chromium, 1.0 to 5.0 wt. % tungsten, 3.5 to 7.0 wt. % vanadium, 1.0 to 5.0 wt. % molybdenum, not greater than 0.5 wt. % oxygen, the balance being iron and impurities, based on the total weight of the powder metal material.
- the thermal spray powder provides exceptional wear resistance at a low cost relative to other materials used in thermal spray techniques.
- the thermal spray powder also has a lower melting point and therefore requires lower temperatures during the thermal spray technique, which conserves energy.
- the thermal spray powder may also be applied to a metal body, such as a piston or piston ring, without causing damage to the body.
- the thermal spray powder may provide improved oxidation resistance compared to other ferrous based materials used in thermal spray techniques.
- the powder metal material also referred to as a thermal spray powder 20
- the thermal spray powder 20 is iron-based and optionally includes other components, such as cobalt (Co), niobium (Nb), titanium (Ti), manganese (Mn), sulfur (S), silicon (Si), phosphorous (P), zirconium (Zr), and tantalum (Ta).
- the thermal spray powder 20 includes chromium, tungsten, vanadium, and molybdenum in amounts sufficient to provide exceptional wear resistance at a reduced cost, compared to other thermal spray materials. These elements are also present in amounts sufficient to form metal carbides.
- the thermal spray powder 20 includes 10.0 to 25.0 wt. % chromium, preferably 11.0 to 15.0 wt. % chromium, and most preferably 13.0 wt. % chromium; 1.0 to 5.0 wt. % tungsten, preferably 1.5 to 3.5 wt. % tungsten, and most preferably 2.5 wt. % tungsten; 3.5 to 7.0 wt.
- % vanadium preferably 4.0 to 6.5 wt. % vanadium, and most preferably 6.0 wt. % vanadium; 1.0 to 5.0 wt. % molybdenum, preferably 1.0 to 3.0 wt. % molybdenum, and most preferably 1.5 wt. % molybdenum.
- the thermal spray powder 20 includes the carbon in an amount sufficient to provide metal carbides in an amount greater than 15 vol. %, based on the total volume of the thermal spray powder 20.
- the thermal spray powder 20 includes at least 3.0 wt. % carbon, or 3.0 to 7.0 wt. % carbon, and preferably about 3.8 wt. % carbon, based on the total weight of the thermal spray powder 20.
- the amount of carbon in the thermal spray powder 20 is referred to as carbon total (C tot ).
- the thermal spray powder 20 also includes a stoichiometric amount of carbon (C stoich ), which represents the total carbon content that is tied up in the alloyed carbides at equilibrium.
- C stoich stoichiometric amount of carbon
- the type and composition of the carbides vary as a function of the carbon content and of the alloying elements content.
- the C stoich necessary to form the desired amount of metal carbides during atomization depends on the amount of carbide- forming elements present in the thermal spray powder 20.
- the C stoich for a particular composition is obtained by multiplying the amount of each carbide-forming element by a multiplying factor specific to each element.
- the multiplying factor is equal to the amount of carbon required to precipitate 1 wt. % of that particular carbide-forming element.
- the multiplying factors vary based on the type of precipitates formed, the amount of carbon, and the amount of each of the alloying elements.
- the multiplying factor for a specific carbide will also vary with the amount of carbon and the amount of the alloying elements.
- the multiplying factors of the carbide- forming elements are calculated as follows. First, the atomic ratio of the M 8 C 7 carbide is determined: 1.88 atoms of Cr, 0.58 atoms of Fe, 5.05 atoms of V, 0.26 atoms of Mo, 0.23 atoms of W, and 7 atoms of C.
- V 257.15 grams
- Cr 97.76 grams
- Fe 32.62 grams
- Mo 24.56 grams
- W 42.65 grams
- C 84.07 grams.
- the weight ratio indicates 47.73 grams of V will react with 15.60 grams of C, which means 1 gram of V will react with 0.33 grams of C.
- the thermal spray powder 20 includes a Ct ot / C stoich amount less than 1.1. Therefore, when the thermal spray powder 20 includes carbon at the upper limit of 7.0 wt. %, the C stoich will be 6.36 wt. % carbon (7.0 wt. % carbon / 1.1).
- the table below provides examples of other carbide types that can be found in the thermal spray powder 20, and multiplying factors for Cr, V, Mo, and W for generic carbide stoichiometry.
- the metal atoms in each of the carbides listed in the table could be partly replaced by other atoms, which would affect the multiplying factors.
- the metal carbides are formed during the atomization process and are present in an amount of at least 15.0 vol. %, but preferably in an amount of 40.0 to 60.0 vol. %, or 47.0 to 52.0 vol. %, and typically about 50.0 vol. %.
- the thennal spray powder 20 includes chromium-rich carbides, molybdenum-rich carbides, tungsten-rich carbides and vanadium-rich carbides in a total amount of about 50.0 vol. %.
- the metal carbides have a nanoscale microstructure.
- the metal carbides have a diameter between 1 and 400 nanometers.
- the fine nano-carbide structure may improve the adherence of the thennal spray powder 20 to an outer surface 22, 122 of a metal body 24, 124. Therefore, a wear resistant coating formed of the thermal spray powder 20 is less prone to flaking, chipping, and delamination.
- the fine carbide structure may also provide a more homogeneous microstructure, and therefore an improved impact and fatigue resistance compared to thermal spray materials with coarser carbide microstructures.
- the carbides can be of various types, including M 8 C 7 , M 7 C 3 , MC, M 6 C, M 23 C 6 , and M 3 C, wherein M is at least one metal atom, such as Fe, Cr, V, Mo, and/or W, and C is carbon.
- the metal carbides are selected from the group consisting of: M 8 C 7 , M 7 C 3 , MC, M 6 C, wherein M a C 7 is (V 63 Fe 37 ) 8 C 7 , M 7 C 3 is selected from the group consisting of: (Cr 34 Fe 66 ) 7 C 3 , Cr 3 5 Fe 3 . 5 C 3 , and Cr 4 Fe 3 C 3 ; and M 6 C is selected from the group consisting of: Mo 3 Fe 3 C, Mo2Fe4C, W 3 Fe 3 C, and W 2 Fe 4 C.
- the microstructure of the thermal spray powder 20 also includes nanoscale austenite, and may include nanoscale martensite, along with the nanoscale carbides.
- the carbon is also present in an amount sufficient to limit oxidation of the thermal spray powder 20 during the thermal spray process. Oxidation can occur due to poor atmosphere control, lack of cleanliness, and temperature during the thermal spray process.
- the remaining balance of the thermal spray powder 20 composition is iron.
- the thermal spray powder 20 typically has a microhardness of 800 to 1 ,500 Hv 50.
- the high hardness contributes to the exceptional wear resistance of the wear resistant coating 26 and the fine structure should improve toughness.
- the microhardness of the thermal spray powder 20 increases with increasing amounts of carbon.
- the thermal spray powder 20 includes 3.8 wt. % carbon, 13.0 wt. % chromium, 2.5 wt. % tungsten, 4.0-6.0 wt. % vanadium, 1.5 wt. % molybdenum, 0.2 wt. % oxygen, impurities in an amount not greater than 2.0 wt. % and the balance being iron, based on the total weight of said thermal-sprayed powder metal material.
- the thermal spray powder 20 of the exemplary embodiment has a melting point of about 1,235° C (2,255° F), and it will be completely melted at that temperature.
- the melting point of thermal spray powder 20 will however vary slightly as a function of the carbon content and alloying element content.
- the thermal spray powder 20 may include a small fraction of a liquid phase at a temperature as low as 1 ,150° C. The low melting point provides several advantages during the thermal spray process, compared to thermal spray materials having higher melting points. Less energy is needed to apply the thermal spray powder 20 to the outer surface 22 of the body 24 being coated.
- the thermal spray powder 22 can be sprayed at a lower temperature, which may provide less heat input to the body 24 being coated, less manufacturing equipment wear, possibly lower porosity in the wear resistant coating 26, and less oxidation of the thermal spray powder 20 during the spraying process.
- the lower melting point also provides the opportunity to use a cold spraying technique.
- the thermal spray powder 20 is formed by water or gas atomizing a melted iron based alloy.
- An exemplary process of forming the thermal spray powder 20 using water atomization is shown in Figure 5 .
- the water atomization step could be replaced by a gas atomization step.
- the iron based alloy provided prior to atomization includes 3.0 to 7.0 wt. % carbon, 10.0 to 25.0 wt. % chromium, 1.0 to 5.0 wt. % tungsten, 3.5 to 7.0 wt. % vanadium, 1.0 to 5.0 wt. % molybdenum, and at least 40.0 wt. % iron.
- the iron based alloy is typically provided as a pre-alloy including the carbon, chromium, tungsten, vanadium, molybdenum, and iron.
- the iron based alloy also has a low oxygen content, preferably not greater than 0.5 wt. %.
- the carbon content of the iron based alloy is sufficient to protect the alloy from oxidizing during the melting and atomizing steps.
- the iron based alloy is melted, it is fed to a water atomizer or a gas atomizer.
- the high carbon content of the iron based alloy decreases the solubility of the oxygen in the melted iron based alloy. Depleting the oxygen level in the melted iron based alloy has the benefit of shielding the carbide-forming elements from oxidizing during the melting and atomizing steps.
- the relatively high carbon content allows the austenite, or possibly martensite, to form in the matrix of the thermal spray powder 20, in which the carbides precipitate, during the atomizing step.
- Increasing the amount of carbide-forming alloying elements in the iron based alloy can also increase the amount of carbides formed in the matrix during the atomizing step.
- each droplet possesses the fully alloyed chemical composition of the melted batch of metal, including at least 3.0 wt. % carbon, 10.0 to 25.0 wt. % chromium, 1.0 to 5.0 wt. % tungsten, 3.5 to 7.0 wt. % vanadium, 1.0 to 5.0 wt.
- Each droplet also preferably includes a uniform distribution of carbides.
- the main elements of the droplets are protected from oxidation by the high carbon content of the powder during the melting and atomizing steps.
- the high carbon content and low oxygen content also limits the oxidization during the atomizing step.
- the outside surface of the droplets may become oxidized, possibly due to exposure to water or unprotected atmosphere.
- the atomized droplets are then passed through a dryer and into a grinder where the atomized material is mechanically ground or crushed, and then sieved.
- the hard and very fine nano-structure of the droplets improves the ease of grinding.
- a ball mill or other mechanical size reducing device may be employed.
- the droplets could be annealed prior to grinding the droplets, but no annealing step is required prior to grinding the droplets, and typically no annealing step is conducted. If an outer oxide skin is formed on the atomized droplets during the atomization step, the mechanical grinding fractures and separates the outer oxide skin from the bulk of the droplets.
- the ground droplets are then separated from the oxide skin to yield the atomized thermal spray powder 20 and oxide particles 30, as shown in Figure 5 .
- the outer oxide skin is minimal and can be tolerated without removal.
- the mechanical grinding step can still be used to fracture and reduce the size of the droplets.
- the thermal spray powder 20 may be further sorted for size, shape and other characteristics normally associated with powder metal.
- the thermal spray powder 20 can then be used to form a wear resistant component 28, 128, 228 such as a piston or piston ring.
- FIG 1 illustrates an example of the wear resistant component 28 including the thermal spray powder 20.
- the wear resistant component 28 is a piston including a body 24, specifically a skirt, presenting an outer surface 22.
- the thermal spray powder 20 is applied to the outer surface 22 of the body 24 by a thermal spraying technique to form a wear resistant coating on the outer surface 22.
- the wear resistant coating typically has a microhardness of 800 to 1 ,500 Hv 5o .
- Figure 2 illustrates another example of the wear resistant component 128 including the thermal spray powder 20.
- the wear resistant component 128 includes a body 124, specifically an uncoated piston ring, presenting an inner surface 136 surrounding a center axis A and an outer surface 122 facing opposite the inner surface 136.
- the thermal spray powder 20 is applied to the outer surface 122 by a thermal spraying technique to form a wear resistant coating on the outer surface 122.
- the thermal spray powder 20 can also be used to form wear resistant coatings on other components (not shown), for example turbine blades, transmission parts, exhaust system components, crankshafts, other automotive components, pulp and paper rollers, oil and petrochemical drilling components, golf clubs, and surgical applications.
- other components for example turbine blades, transmission parts, exhaust system components, crankshafts, other automotive components, pulp and paper rollers, oil and petrochemical drilling components, golf clubs, and surgical applications.
- FIG 4 is another example of the wear resistant component 228, specifically a piston ring, wherein the wear resistant component 228 consists entirely of the thermal spray powder 20.
- the wear resistant component 228 presents an inner surface 236 surrounding a center axis A and an outer surface 222 facing opposite the inner surface 236.
- This wear resistant component 228 is referred to as a spray-formed part.
- the spray-formed part typically has a microhardness of 800 to 1 ,500 Hv 5o .
- thermal spray techniques can be used to form the wear resistant component 28, 128, 228.
- Four typical thermal spray techniques are combustion, electrical discharge, cold spray, and laser.
- Each thermal spray technique includes spraying the thermal spray powder 20, either onto the outer surface 22, 122 of the body 24, 124 to form the wear resistant coating, or onto a substrate 238 to form the spray-formed part.
- the spraying step includes accelerating the thermal spray powder 20 at a high velocity, which can be up to a supersonic velocity.
- the combustion, electrical discharge, and laser techniques include melting the thermal spray powder 20 before spraying the melted powder. These techniques include heating the thermal spray powder 20 and then accelerating the heated thermal spray powder 20 to the outer surface 22, 122 of the body 24, 124 or onto the substrate 238, at a high velocity while the thermal spray powder 20 is heated.
- combustion technique includes flame spraying, such as powder flame spraying or wire flame spraying.
- flame spraying such as powder flame spraying or wire flame spraying.
- HVOF high velocity oxygen fuel spraying
- HVOF-G oxygen and gaseous fuels
- HVOF-K liquid fuels
- the electrical discharge technique can include plasma spraying or wire arc spraying.
- the plasma spraying is typically conducted under inert gas (IPS), a vacuum (VPS), or by dispersing the thermal spray powder 20 in a liquid suspension before injecting the thermal spray powder into a plasma jet (SPS).
- the plasma spraying can also include atmospherical plasma spraying (APS), high pressure plasma spraying (HPPS), water-stabilized plasma spraying (WSPS), reactive plasma spraying (RPS), or underwater plasma spraying (UPS).
- APS atmospherical plasma spraying
- HPPS high pressure plasma spraying
- WSPS water-stabilized plasma spraying
- RPS reactive plasma spraying
- UPS underwater plasma spraying
- nitrogen is used as the inert gas during the plasma spraying process, there is a potential to form vanadium carbonitrides, thus improving hardness and wear resistance. This potential is controlled by the processing parameters and the chemistry of the thermal spray powder 20 before the spraying process.
- FIGS 1 , 2, and 4 illustrate a step in the HVOF process, wherein a HVOF chamber gun sprays the thermal spray powder 20 on the outer surface 22, 122 of the body 24, 124, or onto the substrate 238.
- the HVOF chamber gun includes a pressurized combustion chamber 32 in fluid communication with a nozzle 34.
- the combustion chamber 32 contains a mixture of carrier gas, such as oxygen, and fuel, such as of acetylene, hydrogen, propane, or propylene. The mixture is ignited to produce a high-pressure flame and creating a pressure in the combustion chamber.
- the flame is formed through the nozzle 34 to accelerate the earner gas to a high velocity, which can be up to a supersonic velocity.
- the thermal spray powder 20 is then fed axially into the high pressure combustion chamber 32 or directly through the side of the nozzle 34.
- the carrier gas accelerates the thermal spray powder 20 out of the HVOF chamber gun at a high velocity.
- the thermal spray powder 20 is applied to the outer surface 22, 122 of the body 24, 124 to form the wear resistant coating.
- Figure 3 shows a thickness t of the wear resistant coating applied to the body 124 of Figure 2 . The thickness depends on the thermal spray technique used, design of the body 124, and application of the wear resistant component 28. In one embodiment, the thickness of the wear resistant coating is 20 to 200 microns.
- the method of forming the wear resistant component 28 can optionally include a post-spraying heat treatment.
- the method includes annealing the thermal spray powder 20 after it is applied to the body 24, 124 or formed into the spray-formed part.
- the annealing or other heat treatment step could modify the micro structure of the thermal spray powder 20 by making it coarser.
- the metal carbides could have diameter of at least one micron, rather than between 1 and 400 nanometers.
- Another aspect of the invention provides a method of forming the wear resistant component 228, wherein the wear resistant component 228 is a spray-formed part consisting of the thermal spray powder 20, such as the piston ring of Figure 4 .
- the spray- formed part is manufactured by spraying the thermal spray powder 20 onto the substrate 238 to a thickness of up to 500 millimeters.
- the spray-forming process is a near-net-shape process and includes capturing a spray of powder on a moving substrate, as described in the ASM Handbook, Volume 7 .
- This process provides several advantages, including densities greater than 98%, fine equiaxed grains, no macroscopic segregation, absence of prior particle boundaries, enhanced mechanical properties, material/ alloying flexibility, and a high rate of deposition, such as greater than 2 kg/second.
- thermal spray powder 20 could be co-sprayed with other powders to form the wear resistant component 28, 128, 228, either the resistant coating or the spray-formed part.
- other powders that could be co-sprayed with the thermal spray powder 20 of the present invention include intermetallics, other hard phases, and metallic alloys.
- the wear resistant coatings 26 and spray-formed parts including the co- sprayed powders could provide a wide range of microstructures, different from the microstructures provided by the thermal spray powder 20 alone.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Coating By Spraying Or Casting (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Pistons, Piston Rings, And Cylinders (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US201261608853P | 2012-03-09 | 2012-03-09 | |
PCT/US2013/029792 WO2013134606A2 (en) | 2012-03-09 | 2013-03-08 | Thermal spray applications using iron based alloy powder |
Publications (2)
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EP2822718A2 EP2822718A2 (en) | 2015-01-14 |
EP2822718B1 true EP2822718B1 (en) | 2019-08-07 |
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EP13712412.9A Active EP2822718B1 (en) | 2012-03-09 | 2013-03-08 | Thermal spray applications using iron based alloy powder |
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EP (1) | EP2822718B1 (ko) |
JP (1) | JP6199909B2 (ko) |
KR (1) | KR20140138180A (ko) |
CN (1) | CN104302426A (ko) |
WO (1) | WO2013134606A2 (ko) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
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US9624568B2 (en) | 2008-04-08 | 2017-04-18 | Federal-Mogul Corporation | Thermal spray applications using iron based alloy powder |
US9546412B2 (en) | 2008-04-08 | 2017-01-17 | Federal-Mogul Corporation | Powdered metal alloy composition for wear and temperature resistance applications and method of producing same |
US9162285B2 (en) | 2008-04-08 | 2015-10-20 | Federal-Mogul Corporation | Powder metal compositions for wear and temperature resistance applications and method of producing same |
CA2904887A1 (en) * | 2013-03-15 | 2014-09-25 | Federal-Mogul Corporation | Powder metal compositions for wear and temperature resistance applications and method of producing same |
CN104789895A (zh) * | 2015-04-21 | 2015-07-22 | 苏州统明机械有限公司 | 一种用于热喷涂的抗冲击合金钢粉末及其制备方法 |
CN104878305B (zh) * | 2015-05-15 | 2017-10-10 | 安泰科技股份有限公司 | 耐磨损耐腐蚀合金钢 |
CN104874802B (zh) * | 2015-05-15 | 2017-10-10 | 安泰科技股份有限公司 | 粉末冶金耐磨损耐腐蚀合金棒材 |
CN104889400B (zh) * | 2015-05-15 | 2017-10-10 | 安泰科技股份有限公司 | 粉末冶金耐磨耐蚀合金管材 |
CN104988359A (zh) * | 2015-06-24 | 2015-10-21 | 安徽再制造工程设计中心有限公司 | 一种Co-ZrO2-Ni-Fe涂层材料及制备方法 |
CN106475439B (zh) * | 2016-10-17 | 2018-05-08 | 武汉春禾科技有限公司 | 一种剥壳轮 |
CN106975742A (zh) * | 2017-04-27 | 2017-07-25 | 天津成立航空技术有限公司 | 一种航空发动机耐磨零件用钴基喷涂粉末及其制备方法 |
EP3655182A4 (en) * | 2017-07-21 | 2021-05-26 | National Research Council of Canada | PROCESS FOR THE PREPARATION OF POWDERS INTENDED FOR A COLD SPRAY TREATMENT, AND RELATED POWDERS |
CN109108297B (zh) * | 2018-09-14 | 2021-10-08 | 宁波瑞丰汽车零部件有限公司 | 一种汽车转向动力缸活塞 |
WO2020089666A1 (ja) * | 2018-11-02 | 2020-05-07 | 日産自動車株式会社 | 摺動部材用溶射被膜及び該摺動部材用溶射被膜を備える摺動装置 |
CN111266585A (zh) * | 2020-03-02 | 2020-06-12 | 合肥尚德新材料有限公司 | 一种制备液相不混溶的金属复合材料的方法 |
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EP0266149A2 (en) * | 1986-10-27 | 1988-05-04 | Hitachi, Ltd. | High wear-resistant member, method of producing the same, and valve gear using the same for use in internal combustion engine |
US6887585B2 (en) * | 2000-09-21 | 2005-05-03 | Federal-Mogul Burscheid Gmbh | Thermally applied coating of mechanically alloyed powders for piston rings |
WO2009126674A2 (en) * | 2008-04-08 | 2009-10-15 | Federal-Mogul Corporation | Powdered metal alloy composition for wear and temperature resistance applications and method of producing same |
US7998238B2 (en) * | 2003-07-31 | 2011-08-16 | Komatsu Ltd. | Sintered sliding member and connecting device |
CN102286702A (zh) * | 2011-08-15 | 2011-12-21 | 奥美合金材料科技(北京)有限公司 | 一种铁基粉末及其零件 |
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US5108493A (en) * | 1991-05-03 | 1992-04-28 | Hoeganaes Corporation | Steel powder admixture having distinct prealloyed powder of iron alloys |
JP2002309361A (ja) * | 2001-04-11 | 2002-10-23 | Sanyo Special Steel Co Ltd | 溶射用粉末の製造方法および溶射粉末 |
JP2006316745A (ja) * | 2005-05-13 | 2006-11-24 | Mitsubishi Materials Pmg Corp | 高温乾燥条件下ですぐれた耐摩耗性を発揮するFe基焼結合金製バルブシートの製造方法及びそのバルブシート |
-
2013
- 2013-03-08 WO PCT/US2013/029792 patent/WO2013134606A2/en active Application Filing
- 2013-03-08 KR KR1020147026116A patent/KR20140138180A/ko not_active Application Discontinuation
- 2013-03-08 EP EP13712412.9A patent/EP2822718B1/en active Active
- 2013-03-08 CN CN201380023676.6A patent/CN104302426A/zh active Pending
- 2013-03-08 JP JP2014561140A patent/JP6199909B2/ja active Active
Patent Citations (5)
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EP0266149A2 (en) * | 1986-10-27 | 1988-05-04 | Hitachi, Ltd. | High wear-resistant member, method of producing the same, and valve gear using the same for use in internal combustion engine |
US6887585B2 (en) * | 2000-09-21 | 2005-05-03 | Federal-Mogul Burscheid Gmbh | Thermally applied coating of mechanically alloyed powders for piston rings |
US7998238B2 (en) * | 2003-07-31 | 2011-08-16 | Komatsu Ltd. | Sintered sliding member and connecting device |
WO2009126674A2 (en) * | 2008-04-08 | 2009-10-15 | Federal-Mogul Corporation | Powdered metal alloy composition for wear and temperature resistance applications and method of producing same |
CN102286702A (zh) * | 2011-08-15 | 2011-12-21 | 奥美合金材料科技(北京)有限公司 | 一种铁基粉末及其零件 |
Also Published As
Publication number | Publication date |
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JP6199909B2 (ja) | 2017-09-20 |
WO2013134606A2 (en) | 2013-09-12 |
JP2015515542A (ja) | 2015-05-28 |
EP2822718A2 (en) | 2015-01-14 |
WO2013134606A3 (en) | 2013-10-31 |
KR20140138180A (ko) | 2014-12-03 |
CN104302426A (zh) | 2015-01-21 |
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