CN104419857A - Chromium-based alloy and preparation method thereof - Google Patents
Chromium-based alloy and preparation method thereof Download PDFInfo
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- CN104419857A CN104419857A CN201310366075.7A CN201310366075A CN104419857A CN 104419857 A CN104419857 A CN 104419857A CN 201310366075 A CN201310366075 A CN 201310366075A CN 104419857 A CN104419857 A CN 104419857A
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Abstract
A chromium-based alloy and a preparation method thereof. The chromium-based alloy is characterized by comprising following components, by mass: 4-6% of Fe, 0.8-1.2% of Y2O3, 0.1-15% of Mo, not more than 2% of unavoidable impurities and the balance chromium. The preparation method includes following steps: designing the components, mixing the components, pressing the components to obtain a material, dewaxing the material, sintering the material, cooling the material and analyzing and detecting the material. Because molybdenum is added to the chromium-based alloy, the chromium-based alloy is effectively improved in corrosion-resistant performance and high-temperature performance. Meanwhile, the molybdenum does not much influent the coefficient of thermal expansion of the material. The chromium-based alloy is excellent in high-temperature-resistant performance and corrosion resistance, meanwhile is effectively reduced in sintering temperature and improved in sintering deformation, can be used as a fuel cell connection plate, is higher in operation temperature, is longer in service life, is matched with other assemblies in the cell in the coefficient of thermal expansion and is free from generating much influence on assembly and usage.
Description
Technical field
The invention belongs to croloy technical field, relate to the powder metallurgy croloy of high temperature application, be especially applied to croloy and the manufacture method thereof of fuel cell connecting board.
Background technology
Chromium metal fusing point high (1857 DEG C), specific tenacity large (ratio of intensity and density), there is good antioxidant property and anti-high-sulfur, diesel oil fuel, sea-water corrosion performance and high thermal conductivity, therefore have huge potential application foreground at high-temperature field.But the tough crisp conversion temp of chromium is high, secondly, when being exposed in air under high temperature, because of the infiltration of nitrogen, alloy plasticity is degenerated, impelling strength can not reach requirement.The application of croloy of these drawbacks limit.
" the pure chromium of powder metallurgy and chromium alloy material " (Rare Metals Materials and engineering, Vol.27.Supp.October1998, pp265-267) literary composition reports fuel cell connecting board and uses containing Fe:5% and Y
2o
3: the croloy of 1%.It is high that Solid Oxide Fuel Cell has generating efficiency, and discharge is few, low noise advantages.When adopting Solid Oxide Fuel Cell to generate electricity, single battery need be connected into high-power pile.This battery pile needs high temperature oxidation resisting, and electrical and thermal conductivity is good, and thermal expansion characteristics and other assemblies of battery match, and the material of energy long-term stable operation is as connecting material.The excellent specific property of chromium and chromium alloy material can meet the requirement of fuel cell.Compared with pure chromium material, the croloy containing Fe:5% and Y2O3:1% at high temperature corrosion resistance is more excellent, also has its hot expansibility more to mate with other assemblies of battery, can meet the various requirement of plate SOFC.
Generally speaking, temperature is higher, and fuel cell power generation efficiency is higher, but to the requirement of web plate also higher (major requirement web plate has stronger high-temperature behavior and intensity), Fe:5% and Y
2o
3: the croloy use temperature of 1% is generally at 750 ~ 900 DEG C, duration of service was at 9,000 hours, although had large increase compared with pure chromium material, if but for fuel cell connecting board or inadequate (fuel battery service life is approximately 40000 hours), therefore need to develop a kind of new croloy to meet the requirement of high temperature life-time service.
Summary of the invention
First technical problem to be solved by this invention be to provide a kind of under the high temperature conditions can the croloy of life-time service, be applied to fuel cell connecting board.
Second technical problem to be solved by this invention be to provide a kind of under the high temperature conditions can the manufacture method of croloy of life-time service.
The present invention solves the technical scheme that above-mentioned first technical problem adopt: a kind of croloy, is characterized in that: the composition of this croloy is: Fe:4 ~ 6%, Y
2o
3: 0.8 ~ 1.2%, Mo:0.1 ~ 15%, is no more than the inevitable impurity of 2%, Cr: surplus, and above-mentioned per-cent is mass percent.
As preferably, described composition is: Fe:5%, Y
2o
3: 1%, Mo:2%, is no more than the inevitable impurity of 2%, Cr: surplus, and above-mentioned per-cent is mass percent.
As preferably, the interpolation of described Fe, Mo and Cr tri-kinds of elements is added with the form of element powders, or adds with the form of mother alloy.
The present invention solves the technical scheme that above-mentioned second technical problem adopt: a kind of manufacture method of croloy, is characterized in that comprising the following steps:
1) mix according to each component proportion of alloy, during mixing, add the powder forming lubricant being no more than alloy mass 1%;
2) above-mentioned mixed powder is suppressed on shaping press, adopt common mold pressing, compacting pressure 400 ~ 2000MPa, shaping density 5.3g/cm
3~ 7.0g/cm
3;
3) dewaxing and sintering: adopt continuous print sintering oven or discrete sintering oven to sinter, sintering atmosphere is vacuum or pure hydrogen or rare gas element, and dewaxing temperature can be 300 ~ 800 DEG C, 5 ~ 60 minutes time, sintering temperature is 1250 ~ 1600 DEG C, 10 ~ 200 minutes time;
4) cool after terminating;
5) finally carry out analyzing to obtained alloy and detect.
As improvement, described step 1) in powder forming lubricant be organic lubricant powder, the add-on of lubricant accounts for 0.3 ~ 0.5% of alloy mass.
As improvement, described step 2) compacting be not limited to common mold pressing, also can adopt warm-pressing formation or warm contour forming, to reduce compacting pressure, improve green strength, the density of compacting is 6.1 ~ 6.5g/cm
3.
Improve, the detailed process of the sintering in described step 3) is again: use continuous print sintering oven, and dewaxing and sintering process complete continuously, or use discrete sintering oven, dewaxes to be separated with sintering process; Described dewaxing temperature is 300 ~ 800 DEG C, and the dewaxing time is 5 ~ 60 minutes, and sintering temperature is 1440 ~ 1550 DEG C, sintering time is 10 ~ 200 minutes, when using vacuum as sintering atmosphere, need the anti-rare gas element filled lower than 100KPa, to stop the evaporation of chromium.
As preferably, described rare gas element is argon gas, and pressure is 30 ~ 50Kpa.
Improve, the cooling in described step 4) can adopt and pass into rare gas element pressure cooling, also can furnace cooling again.
Compared with prior art, the invention has the advantages that: owing to the addition of molybdenum element in Chrome metal powder, effectively can improve corrosion resisting property and the high-temperature behavior of Chrome metal powder, simultaneously little on the thermal expansivity impact of material.Croloy of the present invention has excellent resistance to elevated temperatures and solidity to corrosion, effectively can reduce sintering temperature simultaneously, improve sintering warpage, can be used as fuel cell connecting board to use, use temperature is higher, work-ing life will be longer, thermal expansivity and other assemblies of battery match simultaneously, on assembling and can not use the impact that generation is large.
Accompanying drawing explanation
Fig. 1 is the distribution plan that the embodiment of the present invention 1 sinters rear ferro element;
Fig. 2 is the distribution plan that the embodiment of the present invention 1 sinters rear molybdenum element;
Fig. 3 is the hole figure that the embodiment of the present invention 1 sinters rear alloy;
Fig. 4 is the distribution plan that the embodiment of the present invention 1 sinters rear yttrium;
Fig. 5 is the distribution plan that the embodiment of the present invention 1 sinters rear chromium element.
Fig. 6 is the oxidation weight gain curve (pyro-oxidation resistance) at 1000 DEG C after the embodiment of the present invention 3 sinters;
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1:
1) designing material composition and mixing: the composition iron of croloy material is 5%, and yttrium oxide is 1.0%, and molybdenum is 13%, Yu Weige; Iron adds with the form of straight iron powder, and molybdenum adds with the form of molybdenum powder, and chromium adds to reduce the form of chromium powder or electrolytic chromium powder; Concrete proportioning is as follows: straight iron powder: 5%; Molybdenum powder: 13%; Yttrium oxide powder: 1%; Reduction chromium powder or electrolytic chromium powder: 80.7%, powder lubricant: 0.3%; Mix at bipyramid or V-arrangement mixer or other mixers according to proportioning.
2) suppress, suppressed on shaping press by above-mentioned mixed powder, compacting can adopt common mold pressing, and compacting pressure is 700MPa.Shaping density is 6.4g/cm
3.
4) dewax, sinter: carry out in dewaxing and sintering integrated vacuum sintering, dewaxing temperature is 400 DEG C, and 20 minutes time, sintering temperature is 1530 DEG C, 30 minutes time, anti-applying argon gas during sintering, partial pressure of ar gas 50Kpa.
5) cool: can adopt after terminating and pass into rare gas element pressure cooling, also can furnace cooling.As sintering oven is as cold as 1200 DEG C, pass into argon gas and force cooling.
6) analyze and detect: as required, detecting chemical composition and/or metallographic structure and/or other performances, after sintering, Fig. 1 and Fig. 2 is shown in the distribution of iron and molybdenum, and hole situation is shown in Fig. 3, and after sintering, the distribution of yttrium and chromium is shown in Fig. 4 and Fig. 5 respectively.
Embodiment 2:
1) designing material composition and mixing: the composition iron of croloy material is 5%, yttrium oxide is 1%, and molybdenum is 7%, Yu Weige, iron adds with the form of 434L stainless steel and iron molybdenum mother alloy powder, with ferro-molybdenum powder, (for 60%, carbon is less than 0.1% to molybdenum content to molybdenum, and other are less than 2%, Yu Weitie) form adds, chromium part adds to reduce the form of chromium powder or electrolytic chromium powder, and part adds with the form of 434L stainless steel master alloy powder, and concrete proportioning is as follows: 434L Stainless Steel Powder: 0.5%; Ferro-molybdenum powder 11.7%; Yttrium oxide powder: 1%; Reduction chromium powder or electrolytic chromium powder: 86.3%; Powder lubricant: 0.5%, mixes at bipyramid or V-arrangement mixer or other mixers according to proportioning.
2) suppress, suppressed on shaping press by above-mentioned mixed powder, compacting can adopt common mold pressing, and compacting pressure is 650MPa.Shaping density is 6.3g/cm
3.
4) dewax, sinter: carry out in dewaxing and sintering integrated vacuum sintering, dewaxing temperature is 600 DEG C, and 20 minutes time, sintering temperature is 1500 DEG C, 30 minutes time, anti-applying argon gas during sintering, partial pressure of ar gas 30Kpa.
5) cool: can furnace cooling after terminating.Or sintering oven is as cold as 900 DEG C, passes into argon gas and force cooling.
6) analyze and detect: as required, detecting chemical composition and/or metallographic structure and/or other performances.
Embodiment 3:
1) designing material composition and mixing: the composition iron of croloy material is 5%, yttrium oxide is 1.0%, molybdenum is 2%, Yu Weige, iron adds with the stainless form of 434L, and molybdenum adds with the form of pure molybdenum powder, and chromium major part adds to reduce the form of chromium powder or electrolytic chromium powder, small portion adds with the stainless form of 434L, and concrete proportioning is as follows: 434L stainless steel: 6%; Molybdenum powder: 2%; Yttrium oxide powder: 1%; Reduction chromium powder or electrolytic chromium powder: 90.7%, powder lubricant: 0.3%.Mix at bipyramid or V-arrangement mixer or other mixers according to proportioning.
2) suppress, suppressed on shaping press by above-mentioned mixed powder, compacting can adopt temperature and pressure mold pressing, and compacting pressure is 700Mpa, and shaping density is 6.3g/cm
3.
4) dewax, sinter: carry out in dewaxing and sintering integrated vacuum sintering, dewaxing temperature is 600 DEG C, and 20 minutes time, sintering temperature is 1480 DEG C, 30 minutes time, anti-applying argon gas during sintering, partial pressure of ar gas 50KPa.
5) cool: can adopt after terminating and pass into rare gas element pressure cooling.As sintering oven is as cold as 1200 DEG C, pass into argon gas and force cooling.
6) analyze and detect: as required, detecting chemical composition and/or metallographic structure and/or other performances.The rear sample of sintering is shown in Fig. 6 at the oxidation weight gain curve (pyro-oxidation resistance) of 1000 DEG C.
Claims (9)
1. a croloy, is characterized in that: the composition of this croloy is: Fe:4 ~ 6%, Y
2o
3: 0.8 ~ 1.2%, Mo:0.1 ~ 15%, is no more than the inevitable impurity of 2%, Cr: surplus, and above-mentioned per-cent is mass percent.
2. croloy according to claim 1, is characterized in that: described composition is: Fe:5%, Y
2o
3: 1%, Mo:2%, is no more than the inevitable impurity of 2%, Cr: surplus, and above-mentioned per-cent is mass percent.
3. croloy according to claim 1 and 2, is characterized in that: the interpolation of described Fe, Mo and Cr tri-kinds of elements is added with the form of element powders, or adds with the form of mother alloy.
4. a manufacture method for croloy according to claim 1 and 2, is characterized in that comprising the following steps:
1) mix according to each component proportion of alloy, during mixing, add the powder forming lubricant being no more than alloy mass 1%;
2) above-mentioned mixed powder is suppressed on shaping press, adopt common mold pressing, compacting pressure 400 ~ 2000MPa, shaping density 5.3g/cm
3~ 7.0g/cm
3;
3) dewaxing and sintering: sintering atmosphere is vacuum or pure hydrogen or rare gas element, dewaxing temperature 300 ~ 800 DEG C, and 5 ~ 60 minutes time, sintering temperature is 1250 ~ 1600 DEG C, 10 ~ 200 minutes time;
4) cool after terminating;
5) finally carry out analyzing to obtained alloy and detect.
5. manufacture method according to claim 4, is characterized in that: described step 1) in powder forming lubricant be organic lubricant powder, the add-on of lubricant accounts for 0.3 ~ 0.5% of alloy mass.
6. manufacture method according to claim 4, is characterized in that: described step 2) compacting be not limited to common mold pressing, also can adopt warm-pressing formation or warm contour forming, the shaping density of compacting is 6.1 ~ 6.5g/cm
3.
7. manufacture method according to claim 4, is characterized in that: the detailed process of the sintering in described step 3) is: use continuous print sintering oven, and dewaxing and sintering process complete continuously, or use discrete sintering oven, dewaxes to be separated with sintering process; Described dewaxing temperature is 300 ~ 800 DEG C, and the dewaxing time is 5 ~ 60 minutes, and sintering temperature is 1440 ~ 1550 DEG C, and sintering time is 10 ~ 200 minutes, when using vacuum as sintering atmosphere, needs the anti-rare gas element filled lower than 100KPa.
8. manufacture method according to claim 7, is characterized in that: described rare gas element is argon gas, and pressure is 30 ~ 50Kpa.
9. manufacture method according to claim 4, is characterized in that: the cooling in described step 4) can adopt and pass into rare gas element pressure cooling, also can furnace cooling.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310366075.7A CN104419857A (en) | 2013-08-20 | 2013-08-20 | Chromium-based alloy and preparation method thereof |
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|---|---|---|---|
| CN201310366075.7A CN104419857A (en) | 2013-08-20 | 2013-08-20 | Chromium-based alloy and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105695834A (en) * | 2016-02-20 | 2016-06-22 | 杨鑫 | Female forming die |
| CN113430398A (en) * | 2021-05-17 | 2021-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | JCr 98-grade chromium metal containing vanadium element and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0510495A1 (en) * | 1991-04-26 | 1992-10-28 | Kubota Corporation | Oxide-dispersion-strengthened heat-resistant sintered alloy |
| EP0578855A1 (en) * | 1992-07-16 | 1994-01-19 | Siemens Aktiengesellschaft | Material for the metallic components of high-temperature fuel cell stacks |
| JPH0633108A (en) * | 1992-07-21 | 1994-02-08 | Kubota Corp | Production of oxide dispersion strengthened heat resistant alloy sintered body |
| JPH0633166A (en) * | 1992-07-21 | 1994-02-08 | Kubota Corp | Manufacture of oxide dispersion-strengthened heat resistant alloy sintered compact |
| US5608174A (en) * | 1992-05-14 | 1997-03-04 | Eck; Ralf | Chromium-based alloy |
-
2013
- 2013-08-20 CN CN201310366075.7A patent/CN104419857A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0510495A1 (en) * | 1991-04-26 | 1992-10-28 | Kubota Corporation | Oxide-dispersion-strengthened heat-resistant sintered alloy |
| US5608174A (en) * | 1992-05-14 | 1997-03-04 | Eck; Ralf | Chromium-based alloy |
| EP0578855A1 (en) * | 1992-07-16 | 1994-01-19 | Siemens Aktiengesellschaft | Material for the metallic components of high-temperature fuel cell stacks |
| JPH0633108A (en) * | 1992-07-21 | 1994-02-08 | Kubota Corp | Production of oxide dispersion strengthened heat resistant alloy sintered body |
| JPH0633166A (en) * | 1992-07-21 | 1994-02-08 | Kubota Corp | Manufacture of oxide dispersion-strengthened heat resistant alloy sintered compact |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105695834A (en) * | 2016-02-20 | 2016-06-22 | 杨鑫 | Female forming die |
| CN113430398A (en) * | 2021-05-17 | 2021-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | JCr 98-grade chromium metal containing vanadium element and preparation method thereof |
| CN113430398B (en) * | 2021-05-17 | 2022-11-01 | 攀钢集团攀枝花钢铁研究院有限公司 | JCr 98-grade metallic chromium containing vanadium element and preparation method thereof |
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Application publication date: 20150318 |