CN1053844C - Cobaltfree nickel based rare-earth alloy and production thereof - Google Patents
Cobaltfree nickel based rare-earth alloy and production thereof Download PDFInfo
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- CN1053844C CN1053844C CN 96115538 CN96115538A CN1053844C CN 1053844 C CN1053844 C CN 1053844C CN 96115538 CN96115538 CN 96115538 CN 96115538 A CN96115538 A CN 96115538A CN 1053844 C CN1053844 C CN 1053844C
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 45
- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 12
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 7
- 229910052759 nickel Inorganic materials 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000005096 rolling process Methods 0.000 claims abstract description 21
- 238000007670 refining Methods 0.000 claims abstract description 7
- 229910018505 Ni—Mg Inorganic materials 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 230000006698 induction Effects 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005097 cold rolling Methods 0.000 claims description 6
- 238000005098 hot rolling Methods 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 238000004080 punching Methods 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000005482 strain hardening Methods 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 abstract description 8
- 239000010432 diamond Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 239000006104 solid solution Substances 0.000 abstract 1
- 238000007668 thin rolling process Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 4
- 229910001573 adamantine Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The present invention relates to a catalyst alloy suitable for producing excellent crystal artificial diamond with high strength. The present invention is characterized in that a group of multiple single-phase solid solution alloys are prepared from Ni as base materials, Mn, Cr, Mg, RE, etc. A production method of the catalyst alloy is characterized in that vacuum is broken to add Mn after smelting; Ni-Mg master alloys and mixed rare earth are added during the later period of refining, and a second rolling process is well controlled during precision rolling. The present invention solves the problem of consumption of noble metal Co, and diamond synthesized by the alloy has the advantages of high yield per unit and excellent quality. Additionally, the alloy has good moderate temperature plasticity and low notch sensitivity, and provides basic guarantee for precise and thin rolling.
Description
The present invention relates to a kind of being applicable to and produce the adamantine catalyst alloy of the excellent brilliant high-strength artificial of bulky grain.
Catalyst alloy is catalysis (activity) material that the class that grows up along with the demand of diamond has specific function, has become to be used for one of indispensable main raw material(s) of diamond synthesis.In the diamond industry, play a part very importantly, therefore, update and develop novel catalyst alloy and be the effective way that improves the diamond quality and reduce cost.But the used raw material of catalyst alloy contain precious metal Co, and cost is very high, make the price of diamond also high.Though the inventor is the disclosed catalyst alloy that does not contain Co in 95110188.9 the technology at number of patent application, it is a kind of powder, can not make sheet stock, and the bortz powder of making can not be used for cutting.Used main powder raw material cost is very high, is difficult for obtaining.The catalyst alloy of producing uses the vacuum induction melting of 25-50 kilogram more at present, and technology point is unsuitable for big-and-middle-sized vacuum induction melting, can not effective use of energy sources.
At problem set forth above, the invention provides a kind of catalyst alloy sheet, its purpose is that workout cost height, adamantine synthetic per unit area yield are lower, can not realize the problem of large-scale production.
The present invention is achieved through the following technical solutions:
A kind of Ni base rare earth does not have the preparation method of Co catalyst alloy sheet, and it is characterized in that: this preparation method carries out in the following order:
At first the host element of this catalyst alloy is prepared burden, vacuum induction melting is adopted in batching back, vacuumizes after closing stove, and vacuum reaches 20Pa～1Pa, send electrofusion, and clear back fusion vacuum breaker adds manganese metal charging under the argon shield; Close stove evacuation afterwards once more and keep the refining of high temperature high vacuum, vacuum degree control more than 1Pa, 1500 ℃ of temperature, duration 15-20 branch; Refining finishes to have a power failure and adds rare earth and Ni-Mg alloy, pours into a mould when temperature is controlled at 1350-1400 ℃, and cooled alloy pig is stripped off the skin, and passes through hot rolling cogging and pickling afterwards, carries out the cold rolling of two rolling process multi-pass again, carries out punching and polishing after finishing; Poring rate will be to guarantee that steel stream constantly is standard; The alloy pig resistance furnace of packing into heats heating-up temperature in the hot rolling cogging operation: 1020 ℃ ± 10 ℃, and time 40-60 branch, 1000 ℃ ± 10 ℃ of start rolling temperatures, finishing temperature: be controlled at more than 750 ℃; In the first cold rolling rolling process, eliminate work hardening through recrystallization annealing, its temperature is 850 ℃ ± 10 ℃, the time is 60 minutes; To be less than 0.5mm thick for the finished product band after second rolling process.
Design concept of the present invention is to be converted into adamantine crystal structure and the electronic structure respective conditions is a foundation with graphite.And be criterion with d electronics percentage (percentage concentration)～40% of alloy constituent element, to consider that simultaneously synthesis technique T and economic effect factors advance decision design.The institutional framework of this series alloy is stable single-phase austenite.
Advantage of the present invention:
1. Ni base rare earth disclosed in this invention does not have the Co catalyst alloy and has very high economic benefit as a technical products.Profit for output value is all very high.Compare with the present catalyst alloy of the domestic widely used Co of containing, only its raw material ton cost can reduce and reaches more than 30%, has the very strong market competitiveness.
2. rare earth element and Mg (or Zr, B), this serial catalyst alloy is allocated proper amount of rare-earth element La, Ce, Pr, Na, Sm into, and to add this in the mishmetal mode be the present invention's one big characteristics.Though the rare earth element amount of allocating into is few, its effect can not be underestimated, and can not only purify alloy liquid, and refined cast structure improves hot-working character, and can obviously improve adamantine synthetic per unit area yield, and can improve diamond quality, crystalline form and color and luster etc.
Owing to contain in the alloy constituent element disclosed in this invention the trace active element make this serial catalyst alloy have preferably in warm plasticity and lower notch sensitivity.Improved the processing characteristics of alloy, thereby made this catalyst alloy provide effective technical guarantee to ultra-thin band finish rolling.
4. by melting main points disclosed in this invention, promptly be used in the small size vacuum induction furnace melting.Be more suitable for 0.1～0.5 ton of medium-sized vacuum induction melting.This will be effective use of energy sources, realize large-scale production, and reducing production costs provides advantage.
Accompanying drawing 1 is the proportioning figure of host element of the present invention in 6 groups of embodiment;
Accompanying drawing 2 is that technology of the present invention is carried out sketch.
The present invention is specified by embodiment below in conjunction with accompanying drawing:
This catalyst alloy is allocated into percentage by weight with 6 groups of embodiment in accompanying drawing 1 table, upper and lower limit as shown in the figure, the impurity content control range of alloy: C-0.02/0.04 in the table; Si-＜0.05; S-0.06; P-＜0.03; O2-0.015; H2, N2-0.003, its production technology is following in order carries out:
1. prepare burden:
Carry out full element (comprising impurity content) burdening calculation by the listed alloy constituent element of subordinate list:
Wherein host element adopt high-purity electrolysis nickel, electrolytic manganese Mn, iron Fe, chromium Cr, vanadium V ,-Cu adopts technical purity.
The essential element of mishmetal R has La, Ce, Pr, and they account for the 70-80% of mishmetal gross weight; The essential element of mishmetal R also comprises Nd, Sm.
The Ni-Mg intermediate alloy that magnesium elements adopts.
2. melting:
This serial catalyst alloy adopts vacuum induction melting, and present embodiment adopts the 200Kg type.
(1) melting stage-confected materials ECDC removing the work material is packed in the crucible.Close stove evacuation, send electrofusion.Manganese metal is added in clear back vacuum breaker argon shield fusion down.Vacuum 20Pa-1Pa, 1500 ℃ of temperature, time 15-20min.
(2) refining period-purpose is to remove gas and objectionable impurities, and this phase will keep high temperature and high vacuum, and vacuum should be controlled at more than the 1Pa, to guarantee abundant refined alloyization.Refining finishes to have a power failure and adds rare earth and Ni-Mg intermediate alloy.And the reaction condition and the liquid level conjunctiva process of noting observing molten steel simultaneously, to regulate molten steel temperature.
(3) cast-cast is quality and the lumber recovery that important step in the smelting technology is directly connected to alloy pig.Need grasp for this reason and annotate the gentle speed of annotating, to guarantee that steel stream constantly is standard.Pouring temperature generally is controlled at 1350 ℃-1400 ℃.
All fusion process can be with reference to accompanying drawing.
3. must strip off the skin to alloy pig,, press from both sides macro defects such as quarrel and table split to remove dimple.After leveling, the surface changes hot rolling cogging over to.
4. hot rolling cogging
To heat the heating cogging technics through the resistance furnace of packing into of the alloy pig after stripping off the skin:
Heating-up temperature: 1020 ℃ ± 10 ℃
Temperature retention time: 40 minutes～60 minutes
Start rolling temperature: 1000 ℃ ± 10 ℃
Finishing temperature :～750 ℃
The cogging size:
Before the cogging: φ 40～60mm (thick) * 60～90mm (wide) * 500～550mm (length)
After the cogging: 3～4mm (thick) * 100～150mm (wide) *～1500mm long (slab)
5. to the blank pickling:
Pickling can adopt three acid mother liquors to use after diluting
Adopt H2O2 (hydrogen peroxide) to embathe with the clean surface.
6. cold rolling:
Cold rolling is that the blank finish rolling after leveling is become less than the thick strip of 0.5mm.This serial catalyst alloy adopts two repeatedly rolling finishing of rolling process.
First rolling process by the thick made-up belt of～4mm through the thick strip of multi-pass finish rolling to 0.8～1.0mm, after recrystallization annealing is eliminated work hardening and adjusted autstenitic grain size 5-7 level.
Temperature is 850 ℃ ± 10 ℃, time 60min,
Second rolling process is by 0.8～1.0mm, and finish rolling is to being the finished product band less than the thick strip of 0.5mm, and the key problem in technology in the K rolling process is only to allow to finish total deformation with two passage finish rolling.
7. punching:
The catalyst sheet that the strip punching that general＜0.5mm is thick on request becomes different size is promptly: φ 18mm ± 0.05; φ 20mm ± 0.05; φ 23mm ± 0.05.
8. polishing:
Polishing is that the catalyst sheet that dashes good different size is removed crimping, burr and polished surface through barreling.After be the finished product catalyst sheet after the chip select.
Claims (1)
1, a kind of Ni base rare earth does not have the preparation method of Co catalyst alloy sheet, and it is characterized in that: this preparation method carries out in the following order:
At first the host element of this catalyst alloy is prepared burden, vacuum induction melting is adopted in batching back, vacuumizes after closing stove, and vacuum reaches 20Pa～1Pa, send electrofusion, and clear back fusion vacuum breaker adds manganese metal charging under the argon shield; Close stove evacuation afterwards once more and keep the refining of high temperature high vacuum, vacuum degree control more than 1Pa, 1500 ℃ of temperature, duration 15-20 branch; Refining finishes to have a power failure and adds rare earth and Ni-Mg alloy, pours into a mould when temperature is controlled at 1350-1400 ℃, and cooled alloy pig is stripped off the skin, and passes through hot rolling cogging and pickling afterwards, carries out the cold rolling of two rolling process multi-pass again, carries out punching and polishing after finishing; Poring rate will be to guarantee that steel stream constantly is standard; The alloy pig resistance furnace of packing into heats heating-up temperature in the hot rolling cogging operation: 1010-1030 ℃, and time 40-60 branch, start rolling temperature 990-1010 ℃, finishing temperature: be controlled at more than 750 ℃; In the first cold rolling rolling process, eliminate work hardening through recrystallization annealing, its temperature is 840-860 ℃, the time is 60 minutes; To be less than 0.5mm thick for the finished product band after second rolling process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96115538 CN1053844C (en) | 1996-08-19 | 1996-08-19 | Cobaltfree nickel based rare-earth alloy and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96115538 CN1053844C (en) | 1996-08-19 | 1996-08-19 | Cobaltfree nickel based rare-earth alloy and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1149001A CN1149001A (en) | 1997-05-07 |
| CN1053844C true CN1053844C (en) | 2000-06-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96115538 Expired - Fee Related CN1053844C (en) | 1996-08-19 | 1996-08-19 | Cobaltfree nickel based rare-earth alloy and production thereof |
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| Country | Link |
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| CN (1) | CN1053844C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103629C (en) * | 1999-11-21 | 2003-03-26 | 张晓� | Clearing agent for synthetizing artificial diamond in conjunction with catalyst and its preparing process |
| CN102851564B (en) * | 2012-05-18 | 2014-06-25 | 中国科学院合肥物质科学研究院 | Vacuum melting method of high-strength high-elongation alloy steel |
| CN106244833B (en) * | 2016-08-31 | 2018-06-12 | 攀钢集团江油长城特殊钢有限公司 | A kind of preparation method containing magnesium alloy |
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- 1996-08-19 CN CN 96115538 patent/CN1053844C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1149001A (en) | 1997-05-07 |
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