EP1522601B1 - Sintered component made of stainless steel with high corrosion resistance and production method therefor - Google Patents
Sintered component made of stainless steel with high corrosion resistance and production method therefor Download PDFInfo
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- EP1522601B1 EP1522601B1 EP04023061.7A EP04023061A EP1522601B1 EP 1522601 B1 EP1522601 B1 EP 1522601B1 EP 04023061 A EP04023061 A EP 04023061A EP 1522601 B1 EP1522601 B1 EP 1522601B1
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- 229910001220 stainless steel Inorganic materials 0.000 title claims description 70
- 239000010935 stainless steel Substances 0.000 title claims description 60
- 238000005260 corrosion Methods 0.000 title claims description 39
- 230000007797 corrosion Effects 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000843 powder Substances 0.000 claims description 95
- 239000000203 mixture Substances 0.000 claims description 46
- 239000002131 composite material Substances 0.000 claims description 38
- 239000011159 matrix material Substances 0.000 claims description 33
- 229910002262 LaCrO3 Inorganic materials 0.000 claims description 32
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910002340 LaNiO3 Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910002321 LaFeO3 Inorganic materials 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 36
- 230000003647 oxidation Effects 0.000 description 26
- 238000007254 oxidation reaction Methods 0.000 description 26
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 22
- 230000003247 decreasing effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 239000002436 steel type Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- HKRXOWGILGJWPT-UHFFFAOYSA-N oxygen(2-) yttrium(3+) zirconium(4+) Chemical compound [O-2].[Y+3].[Zr+4] HKRXOWGILGJWPT-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000004881 precipitation hardening Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
-
- 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
- C22C33/0207—Using a mixture of prealloyed powders or a master alloy
- C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
Definitions
- the invention relates to an improvement in a sintered component made of stainless steel with high corrosion resistance, and specifically relates to a sintered component made of stainless steel with high corrosion resistance having the following property; oxidation and corrosion do not easily occur even when the sintered component is exposed to corrosive atmospheres in a high temperature.
- the present invention is relates to a production method therefor.
- Patent Document No.1 Japanese Published Unexamined Application No. 10-183315 : sections [0014] and [0015]
- Patent Document No.1 Japanese Published Unexamined Application No. 10-183315 : sections [0014] and [0015]
- Patent Document No.1 Japanese Published Unexamined Application No. 10-183315 : sections [0014] and [0015]
- a Fe-Cr based sintered alloy in which Cr is 14 to 35 mass%, compound of at least La and Y including O is a predetermined mass% of multiplying the Cr mass% by a coefficient "a" (range of the "a” is 0.11 to 0.16.), and the balance is Fe and inevitable impurities
- the sintered alloy has a structure in which particles of compound of at least La and Y including O are dispersed in a matrix, is disclosed.
- chrome oxide (Cr 2 O 3 ) in the alloy surface and at least lanthanum oxide and yttrium oxide added thereto are reacted in an oxidizing atmosphere according to the reaction formula mentioned below, whereby a stable perovskite composite oxide is formed.
- the perovskite composite oxide acts as a protective coating, thereby suppressing the advancing of the oxidation.
- lanthanum oxide powder is added in the case of producing the sintered component made of stainless steel with high corrosion resistance, this production method has a problem mentioned below.
- the lanthanum oxide powder is easily agglomerated, whereby uniform mixing is difficult. Therefore, in order to uniformly disperse the lanthanum oxide powder, cumbersome treatments, in which stainless steel powder is immersed in alcohol etc. dissolved lanthanum oxide, and is dried, whereby lanthanum oxide coating is coated stainless steel powder, are necessary.
- lanthanum oxide inside of the green compact is hydrated with moisture in the air. Then the hydroxide is formed to generate expansion, and cracks are formed in the green compact. In order to prevent the phenomenon, it is necessary to perform sintering immediately after the forming, and to carefully control the processes.
- GB 2 219 004 A discloses a sintered component made of stainless steel containing a steel base-material comprising 8 - 12wt% Cr.
- Composite oxide particles are homogeneously dispersed in the base material, wherein the composite oxide particles comprise Y 2 O 3 and TiO 2 and are dispersed in the base-material in an amount of 0,1 to 1,0 wt% in total of Y 2 O 3 and TiO 2 and a TiO 2 to Y 2 O 3 molar ratio of 0,5 to 2,0.
- the TiO 2 and the Y 2 O 3 are present in the form of a thermal stable composite.
- JP 11 335 771 A discloses a sintered steel containing 7,5 to 13 wt% Cr and 0,1-3wt% zirconium-yttrium oxide, wherein the zirconium-yttrium oxide is dispersed in the steel matrix. Powders of Y 2 O 3 and Zr are mixed in a vibration mill and subsequently mixed with a steel powder.
- the invention according to claim 1 aims to provide a sintered component made of stainless steel with high corrosion resistance in which corrosion resistance is increased without parts of decreasing Cr concentration and precise production processes and process control are not necessary.
- the invention according to claim 6 aims to provide a production method therefor.
- a sintered component made of stainless steel with high corrosion resistance of the present invention is characterized in that a rare earth element is contained at 0.1 to 12 mass%, and the rare earth element is dispersed with a transition metal element and oxygen as a perovskite composite oxide in a matrix of the stainless steel.
- the rare earth element is dispersed with a transition metal element and oxygen as a perovskite composite oxide in a matrix of the stainless steel. Therefore, corrosion resistance is increased without parts of decreasing Cr concentration. That is, the Cr amount in the matrix of the sintered stainless steel with high corrosion resistance of the present invention is substantially uniform.
- a production method of a sintered component made of stainless steel with high corrosion resistance of the present invention is characterized in that a powder of perovskite composite oxide containing a rare earth element, transition metal element and oxygen is prepared, a stainless steel powder or a mixed powder having a stainless steel composition is prepared, and these powders are mixed, whereby a raw powder in which the rare earth element is 0.1 to 12 mass% is prepared, the raw powder is compacted in a predetermined shape, and is sintered.
- the perovskite composite oxide containing a rare earth element, transition metal element and oxygen is added as a powder. Therefore, the reaction formula is not generated. Accordingly, the transition metal element, for example Cr, is not absorbed from the matrix to the oxide coating, whereby the concentration of the transition metal element in every part of the matrix is uniform, resulting in increasing the corrosion resistance. Moreover, the powder of the perovskite composite oxide is not easily agglomerated, and the powder is stable, whereby the above-mentioned hydration reaction is not generated.
- corrosion resistance can be increased by no part of decreasing the concentration of the transition metal element in the matrix. Moreover, in the present invention, cumbersome processes to uniformly disperse the rare earth element are not necessary, and the problem in which cracks are formed in the green compact does not occur even in the case of having a pause between compacting and sintering.
- Any stainless steel can be used to form the matrix.
- ferritic stainless steel in which 11 to 32 mass% of Cr is contained and corrosion resistance to oxidizing acid is high can be used.
- martensitic stainless steel in which 0.15 to 1.2 mass% of C is additionally contained in the ferritic stainless steel and strength and wear resistance are comparatively increased is obtained, and this stainless steel can be used.
- an austenitic stainless steel in which 11 to 32 mass% of Cr and 3.5 to 22 mass% of Ni is contained and corrosion resistance to nonoxidizing acid is increased, can be used.
- 0.3 to 7 mass% of Mo can be contained in the above-mentioned stainless steels in order to improve creep resistance, acid resistance, corrosion resistance, pitting corrosion resistance or machinability.
- 1 to 4 mass% of Cu can be contained in the above-mentioned stainless steels in order to improve acid resistance, corrosion resistance or pitting corrosion resistance, or to give precipitation hardening performance.
- 0.1 to 5 mass% of Al can be contained in the above-mentioned stainless steels in order to improve weldability or heat resistance, or to give precipitation hardening performance.
- N 0.3 mass% or less of N can be contained in the above-mentioned stainless steels in order to arrange crystal grains and to decrease Ni content
- Mn 5.5 to 10 mass% of Mn can be contained in the above-mentioned stainless steels in order to decrease Ni content.
- 0.15 to 5 mass% of Si can be contained in the above-mentioned stainless steels in order to improve oxidation resistance, heat resistance or sulfuric acid resistance, 0.45 mass% or less of Nb can be contained in the above-mentioned stainless steels in order to improve grain boundary corrosion resistance or weldability, and 0.15 mass% or less of Se, 0.2 mass% or less of P or 0.15 mass% or less of S can be contained in the above-mentioned stainless steels in order to improve machinability.
- the rare earth element can be selected from at least one of Sc, Y, La, Ce and Gd, and representative elements mentioned above are Y and La.
- the transition metal element can be selected from at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo and W.
- Cr is selected in the elements to form perovskite composite oxide
- stability of the oxide is specifically excellent, and handling performance and corrosion resistance of the oxide are good.
- RMO 3 , R 2 MO 4 , R 3 M 2 O 7 and R 4 M 3 O 10 R: rare earth element, M: metal element
- at least one of R and M are formed by multiple elements in some perovskite composite oxides.
- Average grain diameter in the perovskite composite oxide powder is preferably 30 ⁇ m or less, whereby dispersion performance in mixing the powder and stainless steel powder can be improved. That is, when the grain diameter is increased, segregation in the matrix is increased, whereby some parts in which corrosion resistance is improved and other parts in which corrosion resistance is not improved are generated.
- the sintering after compacting the raw powder into predetermined shape is preferably performed at a sintering at 1000°C or more.
- the overall composition of the sintered component made of stainless steel with high corrosion resistance of the present invention is, basically, Cr: 7.51 to 31.96 mass%, rare earth element: 0.1 to 12 mass%, O: 0.02 to 6.48 mass%, and balance: Fe and inevitable impurities.
- This overall composition is changed by selecting transition metal elements in perovskite composite oxide. For example, when Cr is selected as a transition metal element, Cr is 7.51 to 31.99 mass%.
- Ni is selected instead of selecting Cr, a composition in which 0.04 to 7.82 mass% of Ni is added to the above-mentioned composition is obtained.
- Ti a composition in which 0.02 to 6.47 mass% of Ti is added to the above-mentioned composition is obtained.
- V When V is selected, a composition in which 0.02 to 6.88 mass% of V is added to the above-mentioned composition is obtained.
- Mn a composition in which 0.02 to 7.42 mass% of Mn is added to the above-mentioned composition is obtained.
- Co a composition in which 0.02 to 7.95 mass% of Co is added to the above-mentioned composition is obtained.
- Zr a composition in which 0.03 to 12.13 mass% of Zr is added to the above-mentioned composition is obtained.
- Nb a composition in which 0.03 to 12.54 mass% of Nb is added to the above-mentioned composition is obtained.
- Ni content in the overall composition becomes 2.39 to 21.97 mass%.
- Ni content in the overall composition becomes 3.59 to 30.34 mass%.
- C content in the matrix of the stainless steel is 0.15 to 1.2 mass%
- C content in the overall composition becomes 0.12 to 1.20 mass%.
- at least one of Mo, Cu, Al, N, Mn, Si, Nb, P, S and Se are contained in the matrix of the stainless steel, at least one of Mo: 0.21 to 18 mass%, Cu: 0.68 to 4 mass%, Al: 0.07 to 4.99 mass%, N: 0.3 mass% or less, Mn: 3.76 to 9.99 mass%, Si: 0.1 to 4.99 mass%, Nb: 0.44 mass% or less, P: 0.2 mass% or less, S: 0.15 mass% or less, and Se: 0.15 mass% or less are added to the overall composition.
- SUS310 powder which was defined by the JIS (Japan Industrial Standards) and was equal to 310 defined by the AISI (American Iron and Steel Institute) was prepared as a stainless steel powder forming a matrix, and LaCrO 3 powder and La 2 O 3 powder which had average grain diameters of 5 ⁇ m were prepared as a rare earth-oxygen composite powder. These powders were dispensed at a rate shown in Table 1, and were mixed, whereby a raw powder was obtained.
- the raw powder was compacted into a cylindrical shape (diameter: 10mm, height: 10mm) and to a square block having a square cross-section (width: 60 mm, depth: 10 mm, height: 10 mm), in order to set the green density to be 6.7 g/cm 3 , obtained green compacts were sintered in a hydrogen atmosphere at a sintering temperature of 1250 °C for 1 hour, whereby samples shown by sample Nos. 1 to 12 were produced.
- each sample was set in a crucible made of aluminum per test piece, all the crucibles were set in a muffle furnace, whereby oxidation test was performed by heating in an air atmosphere at 850 °C for 50 hours. Estimation was performed by measuring the difference in weight between before and after the test, by dividing the measured value by surface area, and by defining the divided value as an increase in weight by oxidation (g/m 2 ). The results are also shown in Table 1 and are shown in Fig. 1 as a graph.
- each sample was machined into a tensile test piece shape in a manner conforming to JIS Z 2241, whereby tensile strength was measured.
- the results are also shown in Table 1 and are shown in Fig. 2 as a graph.
- the effect of using the perovskite composite oxide powder was confirmed.
- the added amount of rare earth element content in the perovskite composite oxide powder was not less than 0.1 mass%, the effect of improving the corrosion resistance was obtained.
- the added amount of rare earth element content in the perovskite composite oxide powder was more than 12 mass%, strength was greatly decreased. Therefore, it was confirmed that the rare earth element content should be 0.1 to 12 mass%.
- LaCrO 3 powder and La 2 O 3 powder used in the Practical Example 1 were added to the stainless steel powder shown in the Table 2, in order to set the La content in the overall composition to 2 mass%, whereby a mixed raw powder was obtained.
- Test pieces were produced by using the raw powder in the same process of Practical Example 1, and oxidation testing was performed. The results are also shown in Table 2 and are shown in Fig. 3 as a graph.
- SUS304 JIS
- SUS430 JIS
- SUS310 balance LaCrO 3 3.44 2.00 188
- SUS310 balance La 2 O 3 2.35 2.00 254
- SUS304 balance LaCrO 3 3.44 2.00 335 17
- SUS304 balance La 2 O 3 4.69 2.00 407
- Perovskite composite oxide powder having an average grain diameter of 5 ⁇ m shown in Table 3 was added to the stainless steel powder (SUS310 powder), in order to set rare earth metal element content in the overall composition to 2 mass%, and these powders were mixed, whereby a mixed raw powder was obtained.
- Test pieces were produced by using the raw powder in the same process of Practical Example 1, and oxidation testing was performed. The results are also shown in Table 3 and are shown in Fig. 4 as a graph.
- SUS310 balance LaCrO 3 3.44 2.00 188
- SUS310 balance YCrO 3 4.25 2.00 195
- SUS304 balance CeCrO 3 3.43 2.00 196
- SUS304 balance LaFeO 3 3.50 2.00 210
- SUS430 balance LaNiO 3 3.53 2.00 199
- LaCrO 3 powders having various average grain diameters shown in the Table 4 were prepared. These LaCrO 3 powders were added to stainless steel powder (SUS310 powder), in order to set the rare earth element content in the overall composition to 2 mass%, whereby a mixed raw powder was obtained. Test pieces were produced by using the raw powder in the same process as in Practical Example 1, and oxidation testing was performed. The results are also shown in Table 4 and are shown in Fig. 5 as a graph.
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- Inorganic Chemistry (AREA)
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Description
- The invention relates to an improvement in a sintered component made of stainless steel with high corrosion resistance, and specifically relates to a sintered component made of stainless steel with high corrosion resistance having the following property; oxidation and corrosion do not easily occur even when the sintered component is exposed to corrosive atmospheres in a high temperature. The present invention is relates to a production method therefor.
- As a sintered component made of stainless steel with high corrosion resistance mentioned above, for example, a sintered component disclosed in Patent Document No.1 (Japanese Published Unexamined Application No.
10-183315 - In the above-mentioned sintered component made of stainless steel with high corrosion resistance, chrome oxide (Cr2O3) in the alloy surface and at least lanthanum oxide and yttrium oxide added thereto are reacted in an oxidizing atmosphere according to the reaction formula mentioned below, whereby a stable perovskite composite oxide is formed. The perovskite composite oxide acts as a protective coating, thereby suppressing the advancing of the oxidation.
Cr2O3 + La2O3 =2 LaCrO3
- According to research by the present inventors, it is apparent that although LaCrO3 is evidently formed in the above-mentioned reaction described in the Patent Document No.1, a certain portion of the Cr used in the above-mentioned reaction is supplied from the Cr solved in a matrix. Therefore, the Cr concentration is decreased in the vicinity of an area where the LaCrO3 is formed, whereby corrosion resistance in the vicinity is decreased.
- Moreover, it is apparent that although lanthanum oxide powder is added in the case of producing the sintered component made of stainless steel with high corrosion resistance, this production method has a problem mentioned below. The lanthanum oxide powder is easily agglomerated, whereby uniform mixing is difficult. Therefore, in order to uniformly disperse the lanthanum oxide powder, cumbersome treatments, in which stainless steel powder is immersed in alcohol etc. dissolved lanthanum oxide, and is dried, whereby lanthanum oxide coating is coated stainless steel powder, are necessary. When a green compact is formed by raw powder, lanthanum oxide inside of the green compact is hydrated with moisture in the air. Then the hydroxide is formed to generate expansion, and cracks are formed in the green compact. In order to prevent the phenomenon, it is necessary to perform sintering immediately after the forming, and to carefully control the processes.
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GB 2 219 004 A -
JP 11 335 771 A - The invention according to claim 1 aims to provide a sintered component made of stainless steel with high corrosion resistance in which corrosion resistance is increased without parts of decreasing Cr concentration and precise production processes and process control are not necessary. The invention according to claim 6 aims to provide a production method therefor.
- A sintered component made of stainless steel with high corrosion resistance of the present invention is characterized in that a rare earth element is contained at 0.1 to 12 mass%, and the rare earth element is dispersed with a transition metal element and oxygen as a perovskite composite oxide in a matrix of the stainless steel.
- In the sintered component made of stainless steel with high corrosion resistance of the present invention, the rare earth element is dispersed with a transition metal element and oxygen as a perovskite composite oxide in a matrix of the stainless steel. Therefore, corrosion resistance is increased without parts of decreasing Cr concentration. That is, the Cr amount in the matrix of the sintered stainless steel with high corrosion resistance of the present invention is substantially uniform.
- When a content of the rare earth element in the overall composition is less than 0.1 mass%, oxide coating in the matrix is not effectively strengthened. On the other hand, when the content is more than 12 mass%, perovskite composite oxide in the matrix is excessive, whereby the amount of the matrix is low, resulting in decreasing strength and wear resistance of the component.
- Moreover, a production method of a sintered component made of stainless steel with high corrosion resistance of the present invention is characterized in that a powder of perovskite composite oxide containing a rare earth element, transition metal element and oxygen is prepared, a stainless steel powder or a mixed powder having a stainless steel composition is prepared, and these powders are mixed, whereby a raw powder in which the rare earth element is 0.1 to 12 mass% is prepared, the raw powder is compacted in a predetermined shape, and is sintered.
- In the production method of a sintered component made of stainless steel with high corrosion resistance of the present invention, the perovskite composite oxide containing a rare earth element, transition metal element and oxygen is added as a powder. Therefore, the reaction formula is not generated. Accordingly, the transition metal element, for example Cr, is not absorbed from the matrix to the oxide coating, whereby the concentration of the transition metal element in every part of the matrix is uniform, resulting in increasing the corrosion resistance. Moreover, the powder of the perovskite composite oxide is not easily agglomerated, and the powder is stable, whereby the above-mentioned hydration reaction is not generated.
- According to the present invention, corrosion resistance can be increased by no part of decreasing the concentration of the transition metal element in the matrix. Moreover, in the present invention, cumbersome processes to uniformly disperse the rare earth element are not necessary, and the problem in which cracks are formed in the green compact does not occur even in the case of having a pause between compacting and sintering.
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Fig. 1 is a graph showing a relationship between increase in weight by oxidation and La content in the overall composition in the Practical Example 1 of the present invention. -
Fig. 2 is a graph showing a relationship between tensile strength and La content in the overall composition in the Practical Example 1 of the present invention. -
Fig. 3 is a graph showing increase in weight by oxidation in the case of using various powders in the Practical Example 2 of the present invention. -
Fig. 4 is a graph showing increase in weight by oxidation in the case of using various powders in the Practical Example 3 of the present invention. -
Fig. 5 is a graph showing a relationship between increase in weight by oxidation and grain diameter of the LaCrO3 powder in the Practical Example 4 of the present invention. - Hereinafter, the preferable embodiments of the present invention will be described.
- Any stainless steel can be used to form the matrix. For example, ferritic stainless steel in which 11 to 32 mass% of Cr is contained and corrosion resistance to oxidizing acid is high can be used. Moreover, martensitic stainless steel in which 0.15 to 1.2 mass% of C is additionally contained in the ferritic stainless steel and strength and wear resistance are comparatively increased is obtained, and this stainless steel can be used. Furthermore, an austenitic stainless steel, in which 11 to 32 mass% of Cr and 3.5 to 22 mass% of Ni is contained and corrosion resistance to nonoxidizing acid is increased, can be used.
- Furthermore, 0.3 to 7 mass% of Mo can be contained in the above-mentioned stainless steels in order to improve creep resistance, acid resistance, corrosion resistance, pitting corrosion resistance or machinability. Moreover, 1 to 4 mass% of Cu can be contained in the above-mentioned stainless steels in order to improve acid resistance, corrosion resistance or pitting corrosion resistance, or to give precipitation hardening performance. Furthermore, 0.1 to 5 mass% of Al can be contained in the above-mentioned stainless steels in order to improve weldability or heat resistance, or to give precipitation hardening performance. Additionally, 0.3 mass% or less of N can be contained in the above-mentioned stainless steels in order to arrange crystal grains and to decrease Ni content, and 5.5 to 10 mass% of Mn can be contained in the above-mentioned stainless steels in order to decrease Ni content.
- 0.15 to 5 mass% of Si can be contained in the above-mentioned stainless steels in order to improve oxidation resistance, heat resistance or sulfuric acid resistance, 0.45 mass% or less of Nb can be contained in the above-mentioned stainless steels in order to improve grain boundary corrosion resistance or weldability, and 0.15 mass% or less of Se, 0.2 mass% or less of P or 0.15 mass% or less of S can be contained in the above-mentioned stainless steels in order to improve machinability.
- The rare earth element can be selected from at least one of Sc, Y, La, Ce and Gd, and representative elements mentioned above are Y and La. The transition metal element can be selected from at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo and W. When Cr is selected in the elements to form perovskite composite oxide, stability of the oxide is specifically excellent, and handling performance and corrosion resistance of the oxide are good. Additionally, as the perovskite composite oxide, RMO3, R2MO4, R3M2O7 and R4M3O10 (R: rare earth element, M: metal element) can be cited, at least one of R and M are formed by multiple elements in some perovskite composite oxides.
- Average grain diameter in the perovskite composite oxide powder is preferably 30 µm or less, whereby dispersion performance in mixing the powder and stainless steel powder can be improved. That is, when the grain diameter is increased, segregation in the matrix is increased, whereby some parts in which corrosion resistance is improved and other parts in which corrosion resistance is not improved are generated. Moreover, the sintering after compacting the raw powder into predetermined shape is preferably performed at a sintering at 1000°C or more.
- Next, the overall composition of the sintered component made of stainless steel with high corrosion resistance of the present invention is, basically, Cr: 7.51 to 31.96 mass%, rare earth element: 0.1 to 12 mass%, O: 0.02 to 6.48 mass%, and balance: Fe and inevitable impurities. This overall composition is changed by selecting transition metal elements in perovskite composite oxide. For example, when Cr is selected as a transition metal element, Cr is 7.51 to 31.99 mass%. Moreover, when Ni is selected instead of selecting Cr, a composition in which 0.04 to 7.82 mass% of Ni is added to the above-mentioned composition is obtained. Similarly, when Ti is selected, a composition in which 0.02 to 6.47 mass% of Ti is added to the above-mentioned composition is obtained.
When V is selected, a composition in which 0.02 to 6.88 mass% of V is added to the above-mentioned composition is obtained.
When Mn is selected, a composition in which 0.02 to 7.42 mass% of Mn is added to the above-mentioned composition is obtained. When Co is selected, a composition in which 0.02 to 7.95 mass% of Co is added to the above-mentioned composition is obtained.
When Zr is selected, a composition in which 0.03 to 12.13 mass% of Zr is added to the above-mentioned composition is obtained. When Nb is selected, a composition in which 0.03 to 12.54 mass% of Nb is added to the above-mentioned composition is obtained. When Mo is selected, a composition in which 0.03 to 13.21 mass% of Mo is added to the above-mentioned composition is obtained. In the ranges of the respective transition metal elements, at least one of the above-mentioned transition metal elements can be added, and the overall composition becomes compositions in which at least one of the transition metal elements is added to the above-mentioned composition. - Moreover, when a stainless steel containing 3.5 to 22 mass% of Ni is selected as a matrix of stainless steel and Ni is not selected as a metal element in perovskite composite oxide, Ni content in the overall composition becomes 2.39 to 21.97 mass%. On the other hand, when a stainless steel containing 3.5 to 22 mass% of Ni is selected as a matrix of stainless steel and Ni is selected as a metal element in perovskite composite oxide, Ni content in the overall composition becomes 3.59 to 30.34 mass%.
- Furthermore, when the C content in the matrix of the stainless steel is 0.15 to 1.2 mass%, C content in the overall composition becomes 0.12 to 1.20 mass%. Additionally, when at least one of Mo, Cu, Al, N, Mn, Si, Nb, P, S and Se are contained in the matrix of the stainless steel, at least one of Mo: 0.21 to 18 mass%, Cu: 0.68 to 4 mass%, Al: 0.07 to 4.99 mass%, N: 0.3 mass% or less, Mn: 3.76 to 9.99 mass%, Si: 0.1 to 4.99 mass%, Nb: 0.44 mass% or less, P: 0.2 mass% or less, S: 0.15 mass% or less, and Se: 0.15 mass% or less are added to the overall composition.
- Hereinafter, the invention will be described in more detail along with Examples.
- SUS310 powder which was defined by the JIS (Japan Industrial Standards) and was equal to 310 defined by the AISI (American Iron and Steel Institute) was prepared as a stainless steel powder forming a matrix, and LaCrO3 powder and La2O3 powder which had average grain diameters of 5 µm were prepared as a rare earth-oxygen composite powder. These powders were dispensed at a rate shown in Table 1, and were mixed, whereby a raw powder was obtained. The raw powder was compacted into a cylindrical shape (diameter: 10mm, height: 10mm) and to a square block having a square cross-section (width: 60 mm, depth: 10 mm, height: 10 mm), in order to set the green density to be 6.7 g/cm3, obtained green compacts were sintered in a hydrogen atmosphere at a sintering temperature of 1250 °C for 1 hour, whereby samples shown by sample Nos. 1 to 12 were produced.
- In the samples having the cylindrical shape, each sample was set in a crucible made of aluminum per test piece, all the crucibles were set in a muffle furnace, whereby oxidation test was performed by heating in an air atmosphere at 850 °C for 50 hours. Estimation was performed by measuring the difference in weight between before and after the test, by dividing the measured value by surface area, and by defining the divided value as an increase in weight by oxidation (g/m2). The results are also shown in Table 1 and are shown in
Fig. 1 as a graph. - In the samples having the square block shape, each sample was machined into a tensile test piece shape in a manner conforming to JIS Z 2241, whereby tensile strength was measured. The results are also shown in Table 1 and are shown in
Fig. 2 as a graph.Table 1 sample number composition rate (mass%) rare earth element content in the overall composition (mass%) increase in weight by oxidation (g/m2) tensile strength (MPa) stainless steel powder LaCrO3 powder steel type addition amount type addition amount 01 SUS310 balance - - 0.00 360 412 02 SUS310 balance LaCrO3 0.17 0.10 322 410 03 SUS310 balance LaCrO3 1.72 1.00 252 411 04 SUS310 balance LaCrO3 3.44 2.00 188 401 05 SUS310 balance LaCrO3 6.88 4.00 154 389 06 SUS310 balance LaCrO3 13.75 8.00 97 361 07 SUS310 balance LaCrO3 20.63 12.00 87 335 08 SUS310 balance LaCrO3 27.51 16.00 84 276 09 SUS310 balance La2O3 0.12 0.10 327 410 10 SUS310 balance La2O3 1.17 1.00 289 395 11 SUS310 balance La2O3 2.35 2.00 254 377 12 SUS310 balance La2O3 4.69 4.00 205 355 13 SUS310 balance La2O3 9.38 8.00 240 317 14 SUS310 balance La2O3 14.07 12.00 480 263 15 SUS310 balance La2O3 18.76 16.00 680 190 - According to the Table 1 and
Fig. 1 , increases in weight by oxidation of samples in which LaCrO3 powder was used as a rare earth-oxygen composite powder were smaller than those of samples in which La2O3 powder was used as a rare earth-oxygen composite powder, whereby the samples obtained by using LaCrO3 powder were apparently improved in corrosion resistance. This effect was seen in the samples having La content of 0.1 mass% or more. Moreover, when more than 8 mass% of La2O3 powder was used, the increase in weight by oxidation was adversely increased. On the other hand, in the samples in which LaCrO3 powder was used, as the La content was increased, the increase in weight by oxidation tended to be decreased. However, when the La content was more than 8 mass%, the effect in which the increase in weight by oxidation was decreased by adding La became small for the addition. - In these samples, distribution of Cr and La in a surface layer of metal structure cross section was confirmed by an EPMA (Electron Probe Micro Analyzer) after the oxidation test. In the samples obtained by using LaCrO3 powder, uniform distribution of Cr in the matrix was confirmed. On the other hand, in the samples obtained by using La2O3 powder, La and Cr were detected in the same area and a part decreasing Cr concentration was confirmed around the area.
- As mentioned above, it was found that when a rare earth element was supplied as a rare earth oxide, the rare earth oxide absorbed Cr in the matrix during the oxidation test. Then a part in the matrix decreasing corrosion resistance was generated. On the other hand, it was found that when a rare earth element was supplied as a stable perovskite composite oxide, corrosion resistance in the matrix was not decreased because Cr concentration is uniform. Moreover, it was found that as the amount of La2O3 added was increased, decrease of corrosion resistance in the matrix was large.
- As shown in the Table 1 and
Fig. 2 , as the added amount of the rare earth-oxygen composite powder was increased, tensile strength tended to be decreased. The tendency in the decrease of the strength was dominant in the samples using La2O3 powder rather than those using LaCrO3 powder. This fact was also caused by decrease of Cr content in the matrix. In the samples using La2O3 powder, the strength of a part decreasing Cr content in the matrix was decreased, and thus total strength was decrease. Moreover, it is confirmed that when the La content is more than 12 mass% in both samples using LaCrO3 powder and La2O3 powder, the strength is greatly decreased. - As mentioned above, the effect of using the perovskite composite oxide powder was confirmed. When the added amount of rare earth element content in the perovskite composite oxide powder was not less than 0.1 mass%, the effect of improving the corrosion resistance was obtained. While the added amount of rare earth element content in the perovskite composite oxide powder was more than 12 mass%, strength was greatly decreased. Therefore, it was confirmed that the rare earth element content should be 0.1 to 12 mass%.
- LaCrO3 powder and La2O3 powder used in the Practical Example 1 were added to the stainless steel powder shown in the Table 2, in order to set the La content in the overall composition to 2 mass%, whereby a mixed raw powder was obtained. Test pieces were produced by using the raw powder in the same process of Practical Example 1, and oxidation testing was performed. The results are also shown in Table 2 and are shown in
Fig. 3 as a graph. Additionally, SUS304 (JIS) is a steel type equal to 304 defined by the AISI, and SUS430 (JIS) is a steel type equal to 430 defined by the AISI.Table 2 sample number composition rate (mass%) rare earth element content in the overall composition (mass%) increase in weight by oxidation (g/m2) stainless steel powder rare earth-oxygen composite powder steel type addition amount type addition amount 04 SUS310 balance LaCrO3 3.44 2.00 188 11 SUS310 balance La2O3 2.35 2.00 254 16 SUS304 balance LaCrO3 3.44 2.00 335 17 SUS304 balance La2O3 4.69 2.00 407 18 SUS430 balance LaCrO3 3.44 2.00 343 19 SUS430 balance La2O3 9.38 2.00 417 - As shown in the Table 2 and
Fig. 3 , even when the steel type of the stainless steel powder was changed, increases in weight by oxidation of samples in which LaCrO3 powder was used as a rare earth-oxygen composite powder were smaller than those of samples in which La2O3 powder was used as a rare earth-oxygen composite powder, as in the Practical Example 1. Therefore, it was confirmed that the effect of the perovskite composite oxide powder was obtained for any steel type. - Perovskite composite oxide powder having an average grain diameter of 5µm shown in Table 3 was added to the stainless steel powder (SUS310 powder), in order to set rare earth metal element content in the overall composition to 2 mass%, and these powders were mixed, whereby a mixed raw powder was obtained. Test pieces were produced by using the raw powder in the same process of Practical Example 1, and oxidation testing was performed. The results are also shown in Table 3 and are shown in
Fig. 4 as a graph.Table 3 sample number composition rate (mass%) rare earth element content in the overall composition (mass%) increase in weight by oxidation (g/m2) stainless steel powder rare earth-oxygen composite powder steel type addition amount type addition amount 04 SUS310 balance LaCrO3 3.44 2.00 188 11 SUS310 balance YCrO3 4.25 2.00 195 16 SUS304 balance CeCrO3 3.43 2.00 196 17 SUS304 balance LaFeO3 3.50 2.00 210 18 SUS430 balance LaNiO3 3.53 2.00 199 19 SUS430 balance La2O3 2.35 2.00 254 - As shown in the Table 3 and
Fig. 4 , even when the rare earth element and the metal element in the perovskite composite oxide were changed, increase in weight by oxidation was slightly suppressed in comparison with the case of supplying the rare earth element in the rare earth oxide. Moreover, it was confirmed that stable corrosion resistance improvement was observed for any rare earth oxide and any metal element. - LaCrO3 powders having various average grain diameters shown in the Table 4 were prepared. These LaCrO3 powders were added to stainless steel powder (SUS310 powder), in order to set the rare earth element content in the overall composition to 2 mass%, whereby a mixed raw powder was obtained. Test pieces were produced by using the raw powder in the same process as in Practical Example 1, and oxidation testing was performed. The results are also shown in Table 4 and are shown in
Fig. 5 as a graph.Table 4 sample number composition rate (mass%) rare earth element content in the overall composition mass% increase in weight by oxidation (g/m2) tensile strength (MPa) stainless steel powder LaCrO3 powder steel type addition amount grain diameter (µm) addition amount 04 SUS310 balance 5 3.44 2.00 188 411 24 SUS310 balance 15 3.44 2.00 206 378 25 SUS310 balance 30 3.44 2.00 222 367 26 SUS310 balance 75 3.44 2.00 560 278 - As shown in the Table 4 and
Fig. 5 , when the average grain diameter of the LaCrO3 powder was increased, increase in weight by oxidation tended to be slightly increased. However, when the average grain diameter was more than 30µm, increase in weight by oxidation was greatly increased. Therefore, it is confirmed that perovskite composite oxide powder having an average grain diameter of 30µm or less is preferably used. The reason is that, in a condition of setting the added amount of LaCrO3 powder to be constant, as the average grain diameter is increased, segregation in the matrix is increased, whereby some parts in which corrosion resistance is improved and other parts in which corrosion resistance is not improved are produced.
Claims (12)
- A sintered component made of a stainless steel with high corrosion resistance, comprising 0.1 to 12 mass% of a rare earth element selected from at least one of La and Y, the rare earth element being dispersed as a perovskite composite oxide selected from at least one of LaCrO3, YCrO3, CeCrO3, LaFeO3 and LaNiO3 in a matrix of the stainless steel and Cr amount in the matrix of the stainless steel is uniform.
- The sintered component according to claim 1, wherein the matrix of the stainless steel is made of a stainless steel containing 11 to 32 mass% of Cr.
- The sintered component according to claim 1, wherein the matrix of the stainless steel is made of a stainless steel containing 11 to 32 mass% of Cr and 3.5 to 22 mass% of Ni.
- The sintered component according to claim 2, wherein the matrix of the stainless steel contains 0.15 to 1.2 mass% of C.
- The sintered component according to any one of claims 2 to 4, wherein the matrix of the stainless steel contains at least one of 0.3 to 7 mass% of Mo, 1 to 4 mass% of Cu, 0.1 to 5 mass% of Al, 0.3 mass% or less of N, 5.5 to 10 mass% of Mn, 0.15 to 5 mass% of Si, 0.45 mass% or less of Nb, 0.2 mass% or less of P, 0.15 mass% or less of S, and 0.15 mass% or less of Se.
- A production method for a sintered component made of a stainless steel with high corrosion resistance, comprising the following steps of
preparing a perovskite composite oxide powder made of rare earth element, transition metal element and oxygen, and a stainless steel powder or a mixed powder having a stainless steel composition,
mixing the perovskite composite oxide powder selected from at least one of LaCrO3, YCrO3, CeCrO3, LaFeO13 and LaNiO3 and the stainless steel powder or the powder having a stainless steel composition, thereby preparing a raw powder in which the rare earth element is 0.1 to 12 mass%,
compacting the raw powder in a predetermined shape, thereby obtaining a green compact, and
sintering the green compact. - The production method according to claim 6, wherein the stainless steel powder or the mixed powder having a stainless steel composition contains 11 to 32 mass% of Cr.
- The production method according to claim 6, wherein the stainless steel powder or the mixed powder having a stainless steel composition contains 11 to 32 mass% of Cr and 3.5 to 22 mass% of Ni.
- The production method according to claim 7, wherein the stainless steel powder or the mixed powder having a stainless steel composition contains 0.15 to 1.2 mass% of C.
- The production method according to any one of claims 7 to 9, wherein the stainless steel powder or the mixed powder having a stainless steel composition contains at least one of 0.3 to 7 mass% of Mo, 1 to 4 mass% of Cu, 0.1 to 5 mass% of Al, 0.3 mass% or less of N, 5.5 to 10 mass% of Mn, 0.15 to 5 mass% of Si, 0.45 mass% or less of Nb, 0.2 mass% or less of P, 0.15 mass% or less of S, and 0.15 mass% or less of Se.
- The production method according to any one of claims 6 to 10, wherein an average grain diameter of the perovskite composite oxide powder is 30 µm or less.
- The production method according to any one of claims 6 to 11, wherein the sintering is performed at a sintering at 1000°C or more.
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CN100446898C (en) * | 2007-05-11 | 2008-12-31 | 北京工业大学 | Method for sintering multielement composite electron emission material of rare earth tungsten |
JP5311941B2 (en) * | 2007-11-13 | 2013-10-09 | セイコーエプソン株式会社 | Metal powder for powder metallurgy, sintered body and method for producing sintered body |
JP5604981B2 (en) | 2009-05-28 | 2014-10-15 | Jfeスチール株式会社 | Iron-based mixed powder for powder metallurgy |
JP5663974B2 (en) * | 2009-06-26 | 2015-02-04 | Jfeスチール株式会社 | Iron-based mixed powder for powder metallurgy |
CN103801693B (en) * | 2012-11-08 | 2016-01-06 | 沈阳中北通磁科技股份有限公司 | RE permanent magnetic alloy flexible sintered process |
JP6229277B2 (en) | 2013-03-01 | 2017-11-15 | 日立化成株式会社 | Sintered alloy and method for producing the same |
JP6489684B2 (en) * | 2015-03-27 | 2019-03-27 | 株式会社ダイヤメット | Heat-resistant sintered material with excellent oxidation resistance, high-temperature wear resistance, and salt damage resistance, and method for producing the same |
CN105312577A (en) * | 2015-06-17 | 2016-02-10 | 洛阳名力科技开发有限公司 | Manufacturing method for abrasion-resistant stainless steel |
CN105312571A (en) * | 2015-06-17 | 2016-02-10 | 洛阳名力科技开发有限公司 | Manufacturing method for stainless steel easy to polish |
CN106048441A (en) * | 2016-06-12 | 2016-10-26 | 无锡辛德华瑞粉末新材料科技有限公司 | Die steel powder for 3D printing and manufacturing method of die steel powder |
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US5529604A (en) * | 1995-03-28 | 1996-06-25 | Ametek, Specialty Metal Products Division | Modified stainless steel powder composition |
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