CN104419858A - Chromium-based alloy and preparation method thereof - Google Patents

Chromium-based alloy and preparation method thereof Download PDF

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Publication number
CN104419858A
CN104419858A CN201310366077.6A CN201310366077A CN104419858A CN 104419858 A CN104419858 A CN 104419858A CN 201310366077 A CN201310366077 A CN 201310366077A CN 104419858 A CN104419858 A CN 104419858A
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sintering
chromium
dewaxing
powder
croloy
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CN201310366077.6A
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包崇玺
周国燕
柳睿
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NBTM New Materials Group Co Ltd
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NBTM New Materials Group Co Ltd
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Priority to CN201310366077.6A priority Critical patent/CN104419858A/en
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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 V, 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. In the invention, original components comprising 5% of Fe and 1% of Y2O3 of the chromium-based alloy is improved with addition of vanadium, thereby further improving a corrosion resistance and a high-temperature-resistant performance. In addition, the vanadium can refine crystal grains and enhance the strength of the material. The vanadium is similar to a main element, chromium, in the chromium-based alloy in melting point and can form a solid solution with the chromium at a high temperature for improving strength of an alloy base body. Meanwhile, the vanadium does not much influent the coefficient of thermal expansion of the material. The chromium-based alloy 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

A kind of croloy and manufacture method thereof
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, containing Fe:5% and Y 2o 3: at high temperature corrosion resistance is more excellent for the croloy of 1%, 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%, V: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%, V: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, V and Cr tri-kinds of elements can adopt the form of element powders to add, and the form of mother alloy also can be adopted to add.
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 1200 ~ 1550 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 powder forming 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, the density of compacting is 5.3 ~ 7.0g/cm 3.
Improve again, when using continuous print sintering oven in described step 3), dewaxing and sintering process complete continuously, when using discrete sintering oven, dewaxing is separated with sintering process, and described dewaxing temperature is 300 ~ 800 DEG C, and the dewaxing time is 5 ~ 60 minutes, sintering temperature is 1430 ~ 1490 DEG C, sintering time is 10 ~ 200 minutes, when using vacuum as sintering atmosphere, needs the anti-rare gas element filled lower than 100KPa.
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: present invention improves over original Fe:5% and Y 2o 3: the structure composition of the croloy of 1%, by adding vanadium in Chrome metal powder, and then improves corrosion resisting property and the high-temperature behavior of material, and in addition, vanadium can crystal grain thinning, improves the intensity of material; The principal element chromium fusing point of vanadium and Chrome metal powder is close, at high temperature can form sosoloid with chromium, improve the intensity of alloy substrate; Simultaneously little on the thermal expansivity impact of material.The present invention can be used as fuel cell connecting board and uses, and use temperature is higher, work-ing life will be longer, and 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 v 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 vanadium is 12%, Yu Weige.Iron adds with the form of straight iron powder, and vanadium adds with the form of vanadium powder, and chromium adds to reduce the form of chromium powder or electrolytic chromium powder.Concrete proportioning is as follows: straight iron powder: 5%; Vanadium powder: 12%; Yttrium oxide powder: 1%; Reduction chromium powder or electrolytic chromium powder: 81.7%, 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, and shaping density is 6.2g/cm 3;
3) dewax, sinter: carry out in dewaxing and sintering integrated vacuum sintering, dewaxing temperature is 400 DEG C, and 20 minutes time, sintering temperature is 1510 DEG C, 30 minutes time, anti-applying argon gas during sintering, partial pressure of ar gas 50Kpa;
4) 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;
5) 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 vanadium, 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%, and yttrium oxide is 1.0%, and vanadium is 8%, Yu Weige; Iron adds with the form of 434L stainless steel and ferrovanadium mother alloy powder, (content of vanadium is for 75% with ferro-vanadium powder for vanadium, carbon is less than 0.2%, 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.Concrete proportioning is as follows: 434L Stainless Steel Powder: 2.8%; Ferro-vanadium powder 10.7%; Yttrium oxide powder: 1%; Reduction chromium powder or electrolytic chromium powder: 85.0%; Powder lubricant: 0.5%; 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 650MPa.Shaping density is 6.1g/cm 3;
3) dewax, sinter: carry out in dewaxing and sintering integrated vacuum sintering, dewaxing temperature is 600 DEG C, and 20 minutes time, sintering temperature is 1490 DEG C, 30 minutes time, anti-applying argon gas during sintering, partial pressure of ar gas 30KPa;
4) cool: after terminating, can furnace cooling be adopted; Or sintering oven is as cold as 900 DEG C, passes into argon gas and force cooling;
5) 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%, and yttrium oxide is 1.0%, and vanadium is 2%, Yu Weige; Iron adds with the stainless form of 434L, and vanadium adds with the form of pure vanadium powder, and chromium major part adds to reduce the form of chromium powder or electrolytic chromium powder, and small portion adds with the stainless form of 434L; Concrete proportioning is as follows: 434L stainless steel: 6%; Vanadium 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.Shaping density is 6.3g/cm 3;
3) dewax, sinter: carry out in dewaxing and sintering integrated vacuum sintering, dewaxing temperature is 600 DEG C, and 20 minutes time, sintering temperature is 1450 DEG C, 30 minutes time, anti-applying argon gas during sintering, partial pressure of ar gas 50KPa;
4) 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;
5) 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%, V: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%, V: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, V and Cr tri-kinds of elements can adopt the form of element powders to add, and the form of mother alloy also can be adopted to add.
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: 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 is 300 ~ 800 DEG C, 5 ~ 60 minutes time, sintering temperature is 1200 ~ 1550 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 powder forming 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 5.3 ~ 7.0g/cm 3.
7. manufacture method according to claim 4, it is characterized in that: when using continuous print sintering oven in described step 3), dewaxing and sintering process complete continuously, when using discrete sintering oven, dewaxing is separated with sintering process, and described dewaxing temperature is 300 ~ 800 DEG C, and the dewaxing time is 5 ~ 60 minutes, sintering temperature is 1430 ~ 1490 DEG C, 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.
CN201310366077.6A 2013-08-20 2013-08-20 Chromium-based alloy and preparation method thereof Pending CN104419858A (en)

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Application Number Priority Date Filing Date Title
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Citations (5)

* Cited by examiner, † Cited by third party
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
JPH0633166A (en) * 1992-07-21 1994-02-08 Kubota Corp Manufacture of oxide dispersion-strengthened heat resistant alloy sintered compact
JPH0633108A (en) * 1992-07-21 1994-02-08 Kubota Corp Production of oxide dispersion strengthened heat resistant alloy sintered body
JPH06188004A (en) * 1992-07-16 1994-07-08 Siemens Ag Material for metal component of high-temperature fuel-cell equipment
US5608174A (en) * 1992-05-14 1997-03-04 Eck; Ralf Chromium-based alloy

Patent Citations (5)

* Cited by examiner, † Cited by third party
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
JPH06188004A (en) * 1992-07-16 1994-07-08 Siemens Ag Material for metal component of high-temperature fuel-cell equipment
JPH0633166A (en) * 1992-07-21 1994-02-08 Kubota Corp Manufacture of oxide dispersion-strengthened heat resistant alloy sintered compact
JPH0633108A (en) * 1992-07-21 1994-02-08 Kubota Corp Production of oxide dispersion strengthened heat resistant alloy sintered body

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