CN112760504A - Preparation method of copper-titanium alloy - Google Patents
Preparation method of copper-titanium alloy Download PDFInfo
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- CN112760504A CN112760504A CN202011563195.2A CN202011563195A CN112760504A CN 112760504 A CN112760504 A CN 112760504A CN 202011563195 A CN202011563195 A CN 202011563195A CN 112760504 A CN112760504 A CN 112760504A
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- C22C1/02—Making non-ferrous alloys by melting
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- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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Abstract
The invention belongs to the technical field of alloy smelting, in particular to a preparation method of a copper-titanium alloy, which aims at the problems that the purification degree of the copper-titanium alloy is low, copper and titanium metals cannot be effectively refined and purified and the hot workability of the copper-titanium alloy is poor in the existing preparation method, and the following scheme is proposed at present: the method comprises the following steps: (1) weighing materials: weighing quantitative copper, titanium, magnesium, zinc, nickel and iron in sequence for later use; (2) mixing raw materials: adding the various raw materials obtained in the step (1) into a container, and uniformly mixing the raw materials for 3-5 min by stirring to obtain a mixed material; (3) primary vacuum smelting: and adding the mixed material into a vacuum induction furnace for high-temperature treatment, and melting the mixed material to obtain an alloy liquid. The impurity content of the prepared copper-titanium alloy is low, and the purification degree of the copper-titanium alloy is high; copper and titanium metal are effectively refined, and the quality of the copper-titanium alloy is high; can eliminate the center looseness of the copper-titanium alloy, reduce the shrinkage cavity of the head and improve the hot processing performance.
Description
Technical Field
The invention relates to the technical field of alloy smelting, in particular to a preparation method of a copper-titanium alloy.
Background
The mechanical and physical properties of the copper-titanium alloy can be compared favorably with those of the copper-beryllium alloy, and compared with the copper-beryllium alloy, the copper-titanium alloy has the advantage of no toxicity, and does not harm the health of human bodies in the using process, so that the research on the fact that the copper-titanium alloy becomes a substitute of the toxic copper-beryllium alloy becomes very significant, and the copper-titanium alloy is suitable for manufacturing various dies, explosion-proof safety tools and wear-resistant parts such as cams, gears, worm gears, bearings and the like.
The existing preparation method can not strictly control the active titanium element in the alloy, so that the contents of hydrogen, oxygen, nitrogen, impurities and the like in the prepared copper-titanium alloy are high, the removal effect of harmful impurities such as lead, bismuth, arsenic, antimony and the like is poor, and the purification degree of the copper-titanium alloy is influenced; copper and titanium metals cannot be effectively refined, and gas, impurities and nonmetallic inclusions are removed in the refining process, so that the quality of the prepared copper-titanium alloy is poor; the columnar alloy crystal blocks along the axial direction from bottom to top can not be obtained, so that the copper-titanium alloy has the conditions of center looseness and head shrinkage, and the hot working performance of the copper-titanium alloy is poor.
Disclosure of Invention
The preparation method of the copper-titanium alloy provided by the invention solves the problems that the active titanium element in the alloy can not be strictly controlled, so that the prepared copper-titanium alloy has high contents of hydrogen, oxygen, nitrogen, impurities and the like, the removal effect of harmful impurities such as lead, bismuth, arsenic, antimony and the like is poor, and the purification degree of the copper-titanium alloy is influenced; copper and titanium metals cannot be effectively refined, and gas, impurities and nonmetallic inclusions are removed in the refining process, so that the quality of the prepared copper-titanium alloy is poor; the problem that the hot workability of the copper-titanium alloy is poor due to the fact that the copper-titanium alloy has loose center and shrinkage cavity at the head part because a columnar alloy crystal block along the axial direction from bottom to top cannot be obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the copper-titanium alloy comprises the following steps
1. The preparation method of the copper-titanium alloy is characterized by comprising the following steps
(1) Weighing materials: weighing quantitative copper, titanium, magnesium, zinc, nickel and iron in sequence for later use;
(2) mixing raw materials: adding the various raw materials obtained in the step (1) into a container, and uniformly mixing the raw materials for 3-5 min by stirring to obtain a mixed material;
(3) primary vacuum smelting: and adding the mixed material into a vacuum induction furnace for high-temperature treatment, and melting the mixed material to obtain an alloy liquid.
(4) And (3) casting molding: pouring the alloy liquid processed in the step (3) to obtain a blocky alloy electrode blank;
(5) remelting and smelting in a secondary electroslag furnace: and (4) putting the alloy electrode blank prepared by the treatment in the step (4) into an electroslag furnace, electrifying as a negative electrode, melting the electrode by utilizing heat emitted by electric arc, and remelting copper and titanium metal through the full action of molten metal and the molten blank to obtain the refined copper-titanium alloy.
(6) Water cooling treatment: in the process of the step (5), the crystallization speed is improved under the water cooling effect of the crystallizer, so that liquid metal is continuously supplemented through crystal precipitation, and the copper-titanium alloy is obtained;
(7) and (3) pressing and forming: and (4) placing the copper-titanium alloy processed in the step (6) into a die for compression molding to obtain an alloy green body.
(8) Demolding: opening the die, and taking out the alloy green compact obtained by pressing in the step (7);
(9) and (3) sintering: placing the alloy green body into a reaction kettle for sintering, and heating from room temperature to a sintering temperature of 1085-1150 ℃ at a heating rate of 5-10 ℃/min, wherein the sintering time is 10-60 min;
(10) cooling and discharging: and (3) carrying out water cooling treatment on the alloy green body for 20min, and taking out the prepared copper-titanium alloy when the temperature is reduced to 40-45 ℃.
Preferably, in the step (3), the smelting temperature is 2700-3000 ℃, and the treatment time is 6-9 h.
Preferably, the casting operation in step (4) is performed in an ambient temperature atmosphere.
Preferably, the operation temperature of the electroslag furnace in the step (5) is 1700-2000 ℃, and the remelting time is 2-3.5 h;
preferably, in the step (6), the copper-titanium alloy is in a columnar structure along the axial direction from bottom to top.
Preferably, the molding pressure in the step (7) is 35-100 MPa, and the pressure maintaining time is 10-30 min.
Preferably, the sintering operation described in step (9) is performed under an inert gas atmosphere.
Preferably, the copper-titanium alloy in the step (10) comprises the following components in percentage by mass: 58-63% of copper, 28-34% of titanium, 1-3% of magnesium, O.2-0.5% of zinc, 0-0.2% of nickel and 2-12.8% of iron, wherein the mass ratio of zinc to nickel is 1-5: 1.
preferably, the copper-titanium alloy in the step (10) comprises the following components in percentage by mass: 60-63% of copper, 30-34% of titanium, 2-3% of magnesium, 0.3-0.5% of zinc, 0.1-0.2% of nickel and 5-12.8% of iron.
Preferably, the copper-titanium alloy in the step (10) comprises the following components in percentage by mass: 60-63% of copper, 30-34% of titanium, 2-3% of magnesium, 0.3-0.5% of zinc, 0.1-0.2% of nickel and 5-12.8% of iron.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, a vacuum high-temperature smelting environment is provided through one-time vacuum smelting, so that the active titanium element in the alloy is strictly controlled, the contents of hydrogen, oxygen, nitrogen, impurities and the like in the prepared copper-titanium alloy are low, harmful impurities such as lead, bismuth, arsenic, antimony and the like are volatilized and removed in vacuum, and the purification degree of the copper-titanium alloy is high;
2. according to the invention, the specific surface area of the metal molten drop in contact with the molten blank is increased through remelting and smelting in the secondary electroslag furnace, copper and titanium are effectively refined through the full action of molten metal and the molten blank, gas, impurities and non-metallic inclusions are removed in the refining process, and the quality of the prepared copper-titanium alloy is improved;
3. according to the invention, through water cooling treatment, when secondary remelting smelting is carried out, the crystallization speed is improved through the water cooling effect of the crystallizer, so that crystals are precipitated and continuously supplemented with liquid metal, a columnar alloy crystal block along the axial direction from bottom to top is obtained, the center porosity of the copper-titanium alloy is eliminated, the head shrinkage cavity is reduced, and the hot working performance of the copper-titanium alloy is improved;
according to the preparation method provided by the invention, a vacuum high-temperature smelting environment is provided through one-time vacuum smelting, so that the active titanium element in the alloy is strictly controlled, the contents of hydrogen, oxygen, nitrogen, impurities and the like in the prepared copper-titanium alloy are low, harmful impurities such as lead, bismuth, arsenic, antimony and the like are volatilized and removed in vacuum, and the purification degree of the copper-titanium alloy is high; the specific surface area of the metal molten drop contacted with the molten blank is increased through the remelting and smelting processing of the secondary electroslag furnace, the copper and titanium metal are effectively refined through the full action of molten metal and the molten blank, gas, impurities and non-metallic inclusions are removed in the refining process, and the quality of the prepared copper-titanium alloy is improved; through water cooling treatment, when secondary remelting smelting is carried out, the crystallization speed is improved through the water cooling effect of the crystallizer, so that crystals are precipitated and continuously supplemented with liquid metal, columnar alloy crystal blocks along the axial direction from bottom to top are obtained, the center looseness of the copper-titanium alloy is eliminated, the head shrinkage cavity is reduced, and the hot working performance of the copper-titanium alloy is improved.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example one
Referring to fig. 1, a method for preparing a copper-titanium alloy includes the following steps
(1) Weighing materials: weighing quantitative copper, titanium, magnesium, zinc, nickel and iron in sequence for later use;
(2) mixing raw materials: adding the various raw materials obtained in the step (1) into a container, and stirring for 3min to uniformly mix to obtain a mixed material;
(3) primary vacuum smelting: and (3) adding the mixed material into a vacuum induction furnace for high-temperature treatment, wherein the smelting temperature is 2700 ℃, the treatment time is 9 hours, and the mixed material is melted to obtain alloy liquid.
(4) And (3) casting molding: pouring the alloy liquid prepared by the processing in the step (3) to obtain a blocky alloy electrode blank, wherein the pouring operation is carried out in a normal temperature atmosphere;
(5) remelting and smelting in a secondary electroslag furnace: and (3) putting the alloy electrode blank prepared by the treatment in the step (4) into an electroslag furnace, electrifying as a negative electrode, melting the electrode by using heat emitted by an electric arc, and remelting copper and titanium metal by full action of molten metal and the molten blank to obtain refined copper-titanium alloy, wherein the operation temperature of the electroslag furnace is 1700 ℃, and the remelting time is 3.5 hours.
(6) Water cooling treatment: in the process of the step (5), the crystallization speed is improved under the water cooling effect of the crystallizer, so that liquid metal is continuously supplemented through crystal precipitation to obtain copper-titanium alloy which is in a columnar structure along the axial direction from bottom to top;
(7) and (3) pressing and forming: and (4) placing the copper-titanium alloy processed in the step (6) into a die for compression molding to obtain an alloy green body, wherein the molding pressure is 35MPa, and the pressure maintaining time is 30 min.
(8) Demolding: opening the die, and taking out the alloy green compact obtained by pressing in the step (7);
(9) and (3) sintering: placing the alloy green body into a reaction kettle for sintering, heating from room temperature to a sintering temperature of 1085 ℃ at a heating rate of 5 ℃/min, wherein the sintering operation is carried out in an inert gas atmosphere;
(10) cooling and discharging: and (3) carrying out water cooling treatment on the alloy green body for 20min, and taking out the prepared copper-titanium alloy when the temperature is reduced to 40 ℃.
The copper-titanium alloy comprises the following components in percentage by mass: 58% of copper, 28% of titanium, 1% of magnesium, O.2% of zinc, 0.2% of nickel and 12.6% of iron.
Example two
(1) Weighing materials: weighing quantitative copper, titanium, magnesium, zinc, nickel and iron in sequence for later use;
(2) mixing raw materials: adding the various raw materials obtained in the step (1) into a container, and stirring for 4min to uniformly mix to obtain a mixed material;
(3) primary vacuum smelting: and adding the mixed material into a vacuum induction furnace for high-temperature treatment, wherein the smelting temperature is 2900 ℃, the treatment time is 7 hours, and the mixed material is melted to obtain alloy liquid.
(4) And (3) casting molding: pouring the alloy liquid prepared by the processing in the step (3) to obtain a blocky alloy electrode blank, wherein the pouring operation is carried out in a normal temperature atmosphere;
(5) remelting and smelting in a secondary electroslag furnace: and (3) putting the alloy electrode blank prepared by the treatment in the step (4) into an electroslag furnace, electrifying as a negative electrode, melting the electrode by using heat emitted by an electric arc, and remelting copper and titanium metal by full action of molten metal and the molten blank to obtain refined copper-titanium alloy, wherein the operation temperature of the electroslag furnace is 1900 ℃ and the remelting time is 2.5 hours.
(6) Water cooling treatment: in the process of the step (5), the crystallization speed is improved under the water cooling effect of the crystallizer, so that liquid metal is continuously supplemented through crystal precipitation to obtain copper-titanium alloy which is in a columnar structure along the axial direction from bottom to top;
(7) and (3) pressing and forming: and (4) placing the copper-titanium alloy processed in the step (6) into a die for compression molding to obtain an alloy green body, wherein the molding pressure is 50MPa, and the pressure maintaining time is 25 min.
(8) Demolding: opening the die, and taking out the alloy green compact obtained by pressing in the step (7);
(9) and (3) sintering: placing the alloy green body into a reaction kettle for sintering, heating from room temperature to a sintering temperature of 1120 ℃ at a heating rate of 6 ℃/min, wherein the sintering time is 30min, and the sintering operation is carried out in an inert gas atmosphere;
(10) cooling and discharging: and (3) carrying out water cooling treatment on the alloy green body for 20min, and taking out the prepared copper-titanium alloy when the temperature is reduced to 42 ℃.
The copper-titanium alloy comprises the following components in percentage by mass: 60% of copper, 30% of titanium, 2% of magnesium, 0.5% of zinc, 0.1% of nickel and 7.4% of iron.
EXAMPLE III
(1) Weighing materials: weighing quantitative copper, titanium, magnesium, zinc, nickel and iron in sequence for later use;
(2) mixing raw materials: adding the various raw materials obtained in the step (1) into a container, and stirring for 4min to uniformly mix to obtain a mixed material;
(3) primary vacuum smelting: and (3) adding the mixed material into a vacuum induction furnace for high-temperature treatment, wherein the smelting temperature is 2800 ℃, the treatment time is 8 hours, and melting the mixed material to obtain alloy liquid.
(4) And (3) casting molding: pouring the alloy liquid prepared by the processing in the step (3) to obtain a blocky alloy electrode blank, wherein the pouring operation is carried out in a normal temperature atmosphere;
(5) remelting and smelting in a secondary electroslag furnace: and (3) putting the alloy electrode blank prepared by the treatment in the step (4) into an electroslag furnace, electrifying as a negative electrode, melting the electrode by using heat emitted by electric arc, and remelting copper and titanium metal by full action of molten metal and the molten blank to obtain refined copper-titanium alloy, wherein the operation temperature of the electroslag furnace is 1800 ℃ and the remelting time is 3 hours.
(6) Water cooling treatment: in the process of the step (5), the crystallization speed is improved under the water cooling effect of the crystallizer, so that liquid metal is continuously supplemented through crystal precipitation to obtain copper-titanium alloy which is in a columnar structure along the axial direction from bottom to top;
(7) and (3) pressing and forming: and (4) placing the copper-titanium alloy processed in the step (6) into a die for compression molding to obtain an alloy green body, wherein the molding pressure is 80MPa, and the pressure maintaining time is 15 min.
(8) Demolding: opening the die, and taking out the alloy green compact obtained by pressing in the step (7);
(9) and (3) sintering: placing the alloy green body into a reaction kettle for sintering, heating from room temperature to the sintering temperature of 1100 ℃ at the heating rate of 8 ℃/min, wherein the sintering time is 40min, and the sintering operation is carried out in the atmosphere of inert gas;
(10) cooling and discharging: and (3) carrying out water cooling treatment on the alloy green body for 20min, and taking out the prepared copper-titanium alloy when the temperature is reduced to 43 ℃.
The copper-titanium alloy comprises the following components in percentage by mass: 62% of copper, 31% of titanium, 2% of magnesium, 0.3% of zinc, 0.2% of nickel and 4.5% of iron.
Example four
(1) Weighing materials: weighing quantitative copper, titanium, magnesium, zinc, nickel and iron in sequence for later use;
(2) mixing raw materials: adding the various raw materials obtained in the step (1) into a container, and stirring for 5min to uniformly mix to obtain a mixed material;
(3) primary vacuum smelting: and (3) adding the mixed material into a vacuum induction furnace for high-temperature treatment, wherein the smelting temperature is 3000 ℃, the treatment time is 6 hours, and melting the mixed material to obtain an alloy liquid.
(4) And (3) casting molding: pouring the alloy liquid prepared by the processing in the step (3) to obtain a blocky alloy electrode blank, wherein the pouring operation is carried out in a normal temperature atmosphere;
(5) remelting and smelting in a secondary electroslag furnace: and (3) putting the alloy electrode blank prepared by the treatment in the step (4) into an electroslag furnace, electrifying as a negative electrode, melting the electrode by using heat emitted by electric arc, and remelting copper and titanium metal by full action of molten metal and the molten blank to obtain refined copper-titanium alloy, wherein the operation temperature of the electroslag furnace is 2000 ℃, and the remelting time is 2 hours.
(6) Water cooling treatment: in the process of the step (5), the crystallization speed is improved under the water cooling effect of the crystallizer, so that liquid metal is continuously supplemented through crystal precipitation to obtain copper-titanium alloy which is in a columnar structure along the axial direction from bottom to top;
(7) and (3) pressing and forming: and (4) placing the copper-titanium alloy processed in the step (6) into a die for compression molding to obtain an alloy green body, wherein the molding pressure is 100MPa, and the pressure maintaining time is 10 min.
(8) Demolding: opening the die, and taking out the alloy green compact obtained by pressing in the step (7);
(9) and (3) sintering: sintering the alloy green body in a reaction kettle, raising the temperature from room temperature to 1150 ℃ at a heating rate of 10 ℃/min, wherein the sintering operation is carried out in an inert gas atmosphere;
(10) cooling and discharging: and (3) carrying out water cooling treatment on the alloy green body for 20min, and taking out the prepared copper-titanium alloy when the temperature is reduced to 45 ℃.
The copper-titanium alloy comprises the following components in percentage by mass: 63% of copper, 30% of titanium, 3% of magnesium, 0.4% of zinc, 0.1% of nickel and 3.5% of iron.
The working principle is as follows: through one-time vacuum smelting, a vacuum high-temperature smelting environment is provided, so that active titanium elements in the alloy are strictly controlled, the contents of hydrogen, oxygen, nitrogen, impurities and the like in the prepared copper-titanium alloy are low, harmful impurities such as lead, bismuth, arsenic, antimony and the like are volatilized and removed in vacuum, and the purification degree of the copper-titanium alloy is high; the specific surface area of the metal molten drop contacted with the molten blank is increased through the remelting and smelting processing of the secondary electroslag furnace, the copper and titanium metal are effectively refined through the full action of molten metal and the molten blank, gas, impurities and non-metallic inclusions are removed in the refining process, and the quality of the prepared copper-titanium alloy is improved; through water cooling treatment, when secondary remelting smelting is carried out, the crystallization speed is improved through the water cooling effect of the crystallizer, so that crystals are precipitated and continuously supplemented with liquid metal, columnar alloy crystal blocks along the axial direction from bottom to top are obtained, the center looseness of the copper-titanium alloy is eliminated, the head shrinkage cavity is reduced, and the hot working performance of the copper-titanium alloy is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The preparation method of the copper-titanium alloy is characterized by comprising the following steps
(1) Weighing materials: weighing quantitative copper, titanium, magnesium, zinc, nickel and iron in sequence for later use;
(2) mixing raw materials: adding the various raw materials obtained in the step (1) into a container, and uniformly mixing the raw materials for 3-5 min by stirring to obtain a mixed material;
(3) primary vacuum smelting: and adding the mixed material into a vacuum induction furnace for high-temperature treatment, and melting the mixed material to obtain an alloy liquid.
(4) And (3) casting molding: pouring the alloy liquid processed in the step (3) to obtain a blocky alloy electrode blank;
(5) remelting and smelting in a secondary electroslag furnace: and (4) putting the alloy electrode blank prepared by the treatment in the step (4) into an electroslag furnace, electrifying as a negative electrode, melting the electrode by utilizing heat emitted by electric arc, and remelting copper and titanium metal through the full action of molten metal and the molten blank to obtain the refined copper-titanium alloy.
(6) Water cooling treatment: in the process of the step (5), the crystallization speed is improved under the water cooling effect of the crystallizer, so that liquid metal is continuously supplemented through crystal precipitation, and the copper-titanium alloy is obtained;
(7) and (3) pressing and forming: and (4) placing the copper-titanium alloy processed in the step (6) into a die for compression molding to obtain an alloy green body.
(8) Demolding: opening the die, and taking out the alloy green compact obtained by pressing in the step (7);
(9) and (3) sintering: placing the alloy green body into a reaction kettle for sintering, and heating from room temperature to a sintering temperature of 1085-1150 ℃ at a heating rate of 5-10 ℃/min, wherein the sintering time is 10-60 min;
(10) cooling and discharging: and (3) carrying out water cooling treatment on the alloy green body for 20min, and taking out the prepared copper-titanium alloy when the temperature is reduced to 40-45 ℃.
2. The preparation method of the copper-titanium alloy according to claim 1, wherein the smelting temperature in the step (3) is 2700-3000 ℃, and the treatment time is 6-9 h.
3. The method for preparing a copper-titanium alloy according to claim 1, wherein the casting operation in the step (4) is performed in an ambient temperature atmosphere.
4. The method for preparing the copper-titanium alloy according to claim 1, wherein the operation temperature of the electroslag furnace in the step (5) is 1700-2000 ℃, and the remelting time is 2-3.5 hours.
5. The method for preparing the copper-titanium alloy according to claim 1, wherein the copper-titanium alloy in the step (6) has a columnar structure along the axial direction from bottom to top.
6. The method for preparing a copper-titanium alloy according to claim 1, wherein the forming pressure in step (7) is 35 to 100MPa, and the dwell time is 10 to 30 min.
7. The method of claim 1, wherein the sintering operation in step (9) is performed under an inert gas atmosphere.
8. The method for preparing the copper-titanium alloy according to claim 1, wherein the copper-titanium alloy in the step (10) comprises the following components in percentage by mass: 58-63% of copper, 28-34% of titanium, 1-3% of magnesium, O.2-0.5% of zinc, 0-0.2% of nickel and 2-12.8% of iron, wherein the mass ratio of zinc to nickel is 1-5: 1.
9. the method for preparing the copper-titanium alloy according to claim 1, wherein the copper-titanium alloy in the step (10) comprises the following components in percentage by mass: 60-63% of copper, 30-34% of titanium, 2-3% of magnesium, 0.3-0.5% of zinc, 0.1-0.2% of nickel and 5-12.8% of iron.
10. The method for preparing the copper-titanium alloy according to claim 1, wherein the copper-titanium alloy in the step (10) comprises the following components in percentage by mass: 60% of copper, 30% of titanium, 2% of magnesium, 0.5% of zinc, 0.1% of nickel and 7.4% of iron.
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| CN111041256A (en) * | 2019-12-26 | 2020-04-21 | 西安斯瑞先进铜合金科技有限公司 | Preparation method of vacuum induction melting CuTi alloy material |
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2020
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| JPH0748639A (en) * | 1993-08-04 | 1995-02-21 | Nikko Kinzoku Kk | Method for adding active metal at the time of melting copper alloy |
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