CN1164782C - Vacuum induction smelting process of Ti-Ni and Ti-Ni-Nb marmem - Google Patents
Vacuum induction smelting process of Ti-Ni and Ti-Ni-Nb marmem Download PDFInfo
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- CN1164782C CN1164782C CNB011389184A CN01138918A CN1164782C CN 1164782 C CN1164782 C CN 1164782C CN B011389184 A CNB011389184 A CN B011389184A CN 01138918 A CN01138918 A CN 01138918A CN 1164782 C CN1164782 C CN 1164782C
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Abstract
The present invention relates to a vacuum induction melting process for a Ti-Ni shape memory alloy and a Ti-Ni-Nb shape memory alloy. A CaO crucible is adopted to melt alloys. Raw materials are put into a furnace according to the required proportion of an alloy. Requirements for a Ti-Ni alloy comprise: Ni and 15 to 25% Ti are put into the crucible, and the rest 75 to 85% of Ti and a strong deoxidizing agent Ca are added to an alloy feed hopper. Requirements for a Ti-Ni-Nb alloy comprise: Ni, Nb and 20% of Ti are put into the crucible, and the rest 75 to 85% of Ti and the strong deoxidizing agent Ca are added to the alloy feed hopper. The furnace is pumped into vacuum until the furnace pressure is lower than 2 Pa, and argon is supplied to the furnace until the furnace pressure reach 0.3 to 0.6 atm. Electric power is supplied to the furnace. When the materials are melted, the residual 75 to 85% of Ti is added to the crucible, and then the mixed material is stirred intermittently. When the mixed material is completely melted, the alloy liquid is refined at the temperature of 20 to 100 DEG C for 10 to 20 minutes, wherein the temperature is higher than the melting point of the alloy. The alloy liquid is condensed by stopping the power, the condensed alloy liquid is heated to be melted, and 0.01 to 0.1 wt% of Ca is added to the alloy liquid for strong deoxidation after the condensed alloy liquid is melted. The temperature of the alloy liquid is regulated to be higher than a melting point by 80 to 120 DEG C, and then the alloy liquid is cast into Ti-Ni shape memory alloy cast ingots and Ti-Ni-Nb shape memory alloy cast ingots. The components of the alloys can be effectively controlled by the process, oxygenation in the melting process is avoided, and alloy processing performance is enhanced.
Description
Technical field
The invention belongs to the vacuum metallurgy field, specifically is the technology of pure Ti-Ni of a kind of vacuum induction melting and Ti-Ni-Nb shape memory alloy.
Background technology
Ti-Ni and Ti-Ni-Nb shape memory alloy are active strong, existing vacuum metallurgy technology is (as electron beam, the vacuum induction melting of water-cooled scull, plumbago crucible) such alloy of melting, its technological difficulties are: the principal constituent control out of true of alloy, carburetting, influence the performances such as transformation temperature (common composition deviation 0.5 weight percent promptly has a strong impact on the transformation temperature and the performance of alloy) of alloy; In addition, use MgO, the Al of conventional thermodynamic stability difference
2O
3The reactive alloys of crucible for smelting the type, since active fusion T' and above-mentioned crucible material kickback, the oxygenation of alloy melting process, and the ingot casting hot workability degenerates, and also influences the cold-forming property of high temperature deformation material simultaneously.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can accurately control the alloy principal constituent, avoid the oxygenation in the fusion process, thereby improve pureization of the vacuum induction melting Ti-Ni of alloy processing characteristics and the technology of Ti-Ni-Nb shape memory alloy.
Technical solution of the present invention is:
Adopt the CaO crucible, concrete technology is: feed → vacuumize → alloy melting phase → refining and modifying phase → the alloy liquid cooling coagulates → adjusts temperature cast alloy cast ingot; Operation steps is as follows:
1. alloy raw material: get industry 1 by the weight ratio of Ti-Ni or the requirement of Ti-Ni-Nb alloy
#-Ni, 0
#-Ti and Nb-1 bar;
2. the charging of alloy raw material: be for Ti-Ni alloy loading sequence: Ni and 15～25% Ti pack in the described crucible, and the Ti of residue 75～85% and strong reductor Ca add in the material alloying bucket; For Ti-Ni-Nb alloy loading sequence be: Ni, Nb and 15～25% Ti pack in the described crucible, and the Ti of residue 75～85% and strong reductor Ca add in the material alloying bucket; Described strong reductor Ca add-on is 0.02～0.1% of total raw material weight;
3. vacuumize: when being evacuated to furnace pressure and being lower than 2Pa, applying argon gas to 0.03～0.06MPa scope;
4. the fusing of alloy: send electricity, melt starting material in the crucible of packing into, after the material melts in the crucible, in crucible, add remaining 75～85% Ti, intermittently stir;
5. refining and modifying: change clear after, alloy liquid is refining 10～20min in the temperature range that is higher than 20～100 ℃ of alloy melting points;
6. the alloy liquid cooling is coagulated: finish refining period, alloy liquid power failure condensation;
7. final deoxygenation: with the fusing that heats up of the above-mentioned alloy liquid that solidifies, the fusing back adds strong reductor Ca by described weight percent and carries out strong deoxidation in alloy liquid;
8. alloy liquid cast: the temperature of adjusting alloy liquid is higher than 80～120 ℃ of fusing points, and cast gets Ti-Ni and Ti-Ni-Nb shape memory alloy ingot casting.
Advantage of the present invention is:
1. the present invention adopts the good CaO ceramic crucible molten alloy of thermodynamic stability, has avoided the reaction of Ti and crucible in the alloy greatly.
2. the present invention adopts the CaO crucible in conjunction with the refining in the alloy smelting process, condensation and the effective deoxidation of reinforcement reductor Ca, high purified Ti-Ni of oxygen and Ti-Ni-Nb shape memory alloy have been obtained, oxygen level is stable less than 0.06 weight percent, the control of alloy principal constituent is accurate, and the composition deviation is less than 0.3 weight percent; The ingot casting crystal structure is even, and segregation is low, high temperature deformation excellent property, stable performance.
3. smelting technique of the present invention is compared with water-cooled scull, the electron beam melting technology of employing, equipment cost is low, technology is simple, easy to operate, reduced the cost of preparation alloy greatly, the Ti-Ni of melting of the present invention and Ti-Ni-Nb shape memory alloy are widely used in national defence and civilian's high-tech development project.
Embodiment
Embodiment 1
Adopt the CaO crucible, preparation Ti-Ni alloy, concrete technology is: feed → vacuumize → alloy melting phase → refining and modifying phase → the alloy liquid cooling coagulates → adjusts temperature cast alloy cast ingot, and operation steps is as follows:
1. the charging of alloy raw material: get starting material 0 by the Ti44Ni56 part by weight
#-Ti and 1
#-Ni, loading sequence is: Ni and 20% Ti pack in the described crucible, and the Ti of residue 80% and strong reductor Ca add in the material alloying bucket;
2. vacuumize: when being evacuated to furnace pressure and equaling 1.5Pa, applying argon gas is to 0.03MPa;
3. the fusing of alloy: send electricity, melt starting material in the crucible of packing into, after the material melts in the crucible, in crucible, add remaining 80% Ti, intermittently stir; The purpose that stirs is top and the crucible reaction that prevents to float over after low-density Ti from melting alloy liquid;
4. refining and modifying: change clear after, alloy liquid is being higher than the temperature refining 20min of 50 ℃ of alloy melting points, purpose is dissolved H, O, N, especially a dissolved oxygen in removing molten steel, because of dissolved oxygen in the starting material sponge Ti is about 0.07 weight percent;
5. the alloy liquid cooling is coagulated: finish refining period, alloy liquid power failure condensation, and the effect of this operation is in the liquation process of setting, solution gas is known from experience further removal;
6. final deoxygenation: with the fusing that heats up of the above-mentioned alloy liquid that solidifies, the fusing back adds 0.05 weight percent in alloy liquid Ca carries out strong deoxidation; Because of the vapour pressure height of Ca, the residual quantity of the alloy cast ingot of melting is lower than 0.005 weight percent, can not influence the performance of alloy;
7. alloy liquid cast: the temperature of adjusting alloy liquid is higher than 90 ℃ of fusing points, and cast gets Ti-Ni shape memory alloy ingot casting.
Wherein: the CaO ceramic crucible has the good performance of thermodynamic stability, and the preparation method is: starting material CaO sand is with high-purity Wingdale CaCO
3Be raw material, adopt high temperature crystallization method, make through broken, screening; Make binding agent isostatic cool pressing forming of green body with dehydrated alcohol, forming pressure 150～240MPa, 2～8 minutes dwell times, sintering schedule is incubated 2～4 hours for to be warming up to 1600～1750 ℃ with stove, and stove is cold, finally obtain the CaO crucible, CaO grain graininess proportioning in the raw materials of Ca O sand that is wherein adopted: 1～2mm accounts for 40～45% weight, and 0.5～1mm accounts for 15～25% weight, and＜0.5mm accounts for 30～45% weight; Other add granularity be 1～2mm account for gross weight 1～3%ZrO
2Particle is as additive; Its concrete preparation technology is:
The a.CaO grain size proportion: 1～2mm accounts for 40%, 0.5～1mm and accounts for 20%, and＜0.5mm accounts for 40%;
B. forming of green body method: isostatic cool pressing;
C. forming pressure: 200MPa;
D. dwell time: 4 minutes;
E. sintering schedule: be warming up to 1650 ℃ with stove, it is cold to be incubated 2 hours stoves;
F. additive: 2%ZrO
2Particle, its granularity are 1～2mm;
G. binding agent: dehydrated alcohol.
Present embodiment is smelted the Ti-Ni shape memory alloy, and capacity is from the ingot casting of 10Kg to 20Kg, and forgeability is good, and the composition analysis after wherein the Ti-Ni alloy cast ingot forges the results are shown in Table 1:
The composition (weight percent) of table 1Ti-Ni shape memory alloy ingot casting
| Ingot casting | Ni | Ti | C | O | N | H | Fe | Si |
| Require composition | 55.6/56.00 | Surplus | ≤0.050 | ≤0.060 | ≤0.050 | ≤0.015 | ≤0.150 | ≤0.100 |
| 1 | 56.0 | Surplus | 0.0058 | 0.046 | 0.0035 | 0.00046 | ＜0.05 | 0.03 |
| 2 | -- | Surplus | -- | 0.039 | 0.0030 | 0.00060 | -- | -- |
| 3 | -- | Surplus | -- | 0.029 | 0.0030 | 0.00064 | -- | -- |
| 4 | 55.9 | Surplus | 0.0054 | 0.031 | 0.0031 | -- | ＜0.05 | 0.03 |
Annotate: ingot casting 1,2,3 is the 10kg ingot casting, and (undetermined H contains ingot casting 4 for the 20kg ingot casting
Amount), ingot casting 2 and 3 have spot-check H, O and three main harmful impurity components of N.
From The above results as can be known, the shape memory alloy of present embodiment melting has obtained accurate Composition Control, and homogeneous is pure, stable performance.
Embodiment 2
Difference from Example 1 is:
Preparation Ti-Ni-Nb alloy, operation steps is as follows:
1. the charging of alloy raw material: Ti36.96-Ni48.38-Nb14.66 gets starting material 1 by weight proportion
#-Ni, Nb-1 bar, 0
#-Ti, loading sequence is: Ni, Nb and 20% Ti pack in the described crucible, and the Ti of residue 80% and strong reductor Ca add in the material alloying bucket;
2. vacuumize: when being evacuated to furnace pressure and equaling 1.2Pa, applying argon gas is to 0.05MPa;
3. the fusing of alloy: send electricity, melt starting material in the crucible of packing into, after the material melts in the crucible, in crucible, add remaining 80% Ti, intermittently stir; The purpose that stirs is top and the crucible reaction that prevents to float over after low-density Ti from melting alloy liquid;
4. refining and modifying: change clear after, alloy liquid is being higher than the temperature refining 10min of 90 ℃ of alloy melting points, purpose is dissolved H, O, N, especially a dissolved oxygen in removing molten steel, because of dissolved oxygen in the starting material sponge Ti is about 0.07 weight percent;
5. the alloy liquid cooling is coagulated: finish refining period, alloy liquid power failure condensation, and the effect of this operation is in the liquation process of setting, solution gas is known from experience further removal;
6. final deoxygenation: with the fusing that heats up of the above-mentioned alloy liquid that solidifies, the fusing back adds 0.1 weight percent in alloy liquid Ca carries out strong deoxidation; Because of the vapour pressure height of Ca, the residual quantity of the alloy cast ingot of melting is lower than 0.005 weight percent, can not influence the performance of alloy;
7. alloy liquid cast: the temperature of adjusting alloy liquid is higher than 90 ℃ of fusing points, and cast gets Ti-Ni-Nb shape memory alloy ingot casting.
The Ti-Ni-Nb shape memory alloy that is obtained, capacity are the ingot casting of 10Kg, and forgeability is good, and table 2 has provided the composition of Ti-Ni-Nb shape memory alloy and forged the performance of bar and the measuring result of transformation temperature.
The Ti-Ni-Nb shape memory alloy component and the performance of table 2CaO crucible for smelting
| Ingot casting | Ni | Ti | Nb | O | C | σ 0.2(MPa) | Ms(℃) |
| 1 | 48.38 | 37.00 | Surplus | 0.040 | 0.015 | 534 | -90 |
| 2 | 48.36 | 36.89 | Surplus | 0.035 | 0.013 | 521 | -94 |
| 3 | 48.36 | 37.88 | Surplus | 0.038 | 0.015 | 527 | -86 |
| 4 | 48.38 | 37.05 | Surplus | 0.053 | 0.018 | 521 | -91 |
| 5 | 48.56 | 37.04 | Surplus | 0.038 | 0.010 | 523 | -85 |
From The above results as can be known, the shape memory alloy of the technology of the present invention melting has obtained accurate Composition Control, and homogeneous is pure, stable performance.
Claims (1)
1. the technology of pureization of vacuum induction melting Ti-Ni and Ti-Ni-Nb shape memory alloy, it is characterized in that: adopt the CaO crucible, concrete technology is: feed → vacuumize → alloy melting phase → refining and modifying phase → the alloy liquid cooling coagulates → adjusts temperature cast alloy cast ingot; Operation steps is as follows:
1) alloy raw material: get industry 1 by the weight ratio of Ti-Ni or the requirement of Ti-Ni-Nb alloy
#-Ni, 0
#-Ti and Nb-1 bar;
2) charging of alloy raw material: be for Ti-Ni alloy loading sequence: Ni and 15～25% Ti pack in the described crucible, and the Ti of residue 75～85% and strong reductor Ca add in the material alloying bucket; For Ti-Ni-Nb alloy loading sequence be: Ni, Nb and 15～25% Ti pack in the described crucible, and the Ti of residue 75～85% and strong reductor Ca add in the material alloying bucket; Described strong reductor Ca add-on is 0.02～0.1% of total raw material weight;
3) vacuumize: when being evacuated to furnace pressure and being lower than 2Pa, applying argon gas to 0.03～0.06MPa scope;
4) fusing of alloy: send electricity, melt starting material in the crucible of packing into, after the material melts in the crucible, in crucible, add remaining 75～85% Ti, intermittently stir;
5) refining and modifying: after changing clearly, alloy liquid is refining 10～20min in the temperature range that is higher than 20～100 ℃ of alloy melting points;
6) the alloy liquid cooling is coagulated: finish refining period, alloy liquid power failure condensation;
7) final deoxygenation: with above-mentioned alloy liquid intensification fusing of solidifying, the fusing back adds strong reductor Ca by described weight percent and carries out strong deoxidation in alloy liquid;
8) alloy liquid cast: the temperature of adjusting alloy liquid is higher than 80～120 ℃ of fusing points, and cast gets Ti-Ni and Ti-Ni-Nb shape memory alloy ingot casting.
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| CNB011389184A CN1164782C (en) | 2001-12-25 | 2001-12-25 | Vacuum induction smelting process of Ti-Ni and Ti-Ni-Nb marmem |
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| CNB011389184A CN1164782C (en) | 2001-12-25 | 2001-12-25 | Vacuum induction smelting process of Ti-Ni and Ti-Ni-Nb marmem |
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| CN1164782C true CN1164782C (en) | 2004-09-01 |
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| CN100348760C (en) * | 2004-10-22 | 2007-11-14 | 中国科学院金属研究所 | Fastening ring made of wide thermal hysteresis Ti-Ni-based shape-memory alloy, preparation method and application thereof |
| CN100547095C (en) * | 2007-07-05 | 2009-10-07 | 沈阳天贺新材料开发有限公司 | The technology of TiNi shape memory alloy smelting ultra-pure |
| US8430981B1 (en) * | 2012-07-30 | 2013-04-30 | Saes Smart Materials | Nickel-titanium Alloys, related products and methods |
| CN102965529B (en) * | 2012-11-30 | 2014-12-03 | 上海大学 | Preparation method of short-process titanium alloy Ti-Ni-Nb |
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| CN103740984B (en) * | 2013-12-31 | 2016-01-20 | 常州中钢精密锻材有限公司 | A kind of melting technology of abros |
| CN107170599A (en) * | 2017-07-19 | 2017-09-15 | 云南电网有限责任公司电力科学研究院 | A kind of fingertip spring for disconnecting switch |
| CN111979466B (en) * | 2020-08-12 | 2022-02-15 | 西北工业大学 | Shape memory alloy and laser 3D printing method thereof |
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Assignee: Danyang Precision Alloy Factory Co., Ltd. Assignor: Institute of metal research, Chinese Academy of Sciences Contract fulfillment period: 2007.1.18 to 2012.1.18 Contract record no.: 2008320001061 Denomination of invention: Process of vacuum induction smelting Ti-Ni and Ti-Ni-Nb shape memory alloy Granted publication date: 20040901 License type: Exclusive license Record date: 20081027 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.1.18 TO 2012.1.18; CHANGE OF CONTRACT Name of requester: DANYANG CITY PRECISE ALLOY FACTORY CO., LTD. Effective date: 20081027 |
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