CN112322918A - Method for producing large-size copper-titanium alloy ingot in non-vacuum mode - Google Patents

Method for producing large-size copper-titanium alloy ingot in non-vacuum mode Download PDF

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CN112322918A
CN112322918A CN202011243300.4A CN202011243300A CN112322918A CN 112322918 A CN112322918 A CN 112322918A CN 202011243300 A CN202011243300 A CN 202011243300A CN 112322918 A CN112322918 A CN 112322918A
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copper
titanium alloy
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CN112322918B (en
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陈佳程
程万林
马吉苗
夏彬
杨文强
陈鹏
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NINGBO XINGYE SHENGTAI GROUP CO Ltd
NINGBO XINGYE XINTAI NEW ELECTRONIC MATERIAL CO Ltd
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Abstract

The invention belongs to the technical field of cast alloy, and particularly relates to a method for producing a large-size copper-titanium alloy ingot in a non-vacuum circulation mode. According to the invention, the large-size copper-titanium alloy ingot casting is carried out under a non-vacuum condition, Zr element is added in the production process according to the thermodynamic analysis result to protect Ti from being burnt, and the cost is greatly reduced compared with the copper-titanium alloy ingot casting produced by adopting a vacuum furnace. After casting, the furnace slag is roasted, then Zr and Ti are obtained by separation through oxidation, chlorination, magnesiothermic reduction, vacuum distillation and other means in sequence, and then the Zr, the Ti and the Cu are smelted in vacuum and poured to obtain Cu-Ti and Cu-Zr intermediate alloy which is continuously used as a raw material for producing copper-titanium alloy cast ingots, so that material recycling and continuous production process are realized, and the production cost of enterprises is further reduced.

Description

Method for producing large-size copper-titanium alloy ingot in non-vacuum mode
Technical Field
The invention belongs to the technical field of cast alloy, and particularly relates to a method for producing a large-size copper-titanium alloy ingot in a non-vacuum mode.
Background
The high-strength high-elasticity copper alloy is widely applied to connectors, switches, contact springs, terminals and the like, wherein the most widely applied copper alloy is beryllium bronze, and the beryllium bronze has high strength, high elasticity, high hardness, high wear resistance and very excellent comprehensive performance. Although beryllium bronze is honored as the king of elasticity of nonferrous metal, beryllium is a highly toxic element and has great harm to human bodies in the processing process. Copper-titanium alloy has gained wide attention as a material replacing beryllium copper, and the copper-titanium alloy has performances comparable to those of beryllium copper and is very environment-friendly in the processing process. However, titanium is extremely high in burning loss during smelting in the atmospheric environment, and the titanium has very high activity and also has very high reducibility. The burning loss of titanium smelted in the atmospheric environment mainly comprises the following three parts: ti reduces some metal compounds in the slag by virtue of high reducibility of Ti so as to enable Ti elements to enter the slag; reacting Ti with oxygen in the air to generate titanium oxide; and the Ti can react with nitrogen in the air at the temperature of over 800 ℃ to form TiN. Therefore, the copper-titanium alloy ingot is usually produced by a vacuum furnace, and the investment of the large vacuum furnace is huge, thereby greatly increasing the production cost of enterprises. In addition, slag generated in the alloy casting process cannot be recycled due to improper treatment, and resource waste is caused.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a method for circularly producing a copper-titanium alloy ingot under a non-vacuum condition, which not only prevents Ti from being burnt and oxidized under the non-vacuum condition, but also realizes the recycling of casting residues.
The above object of the present invention can be achieved by the following technical solutions: a method for producing large-size copper-titanium alloy ingots in a non-vacuum mode is characterized by comprising the following steps:
s1, batching: the materials are prepared according to the following mass percent: ti: 1-5%, Zr0.8-1%, and the balance of Cu and inevitable impurities;
s2, smelting: heating a smelting furnace, adding a copper electrolytic plate, adding a Cu-Mg intermediate alloy for deoxidation after the copper electrolytic plate is completely added, preserving heat, fishing slag, degassing, adding the Cu-Zr intermediate alloy after degassing is finished, adding the Cu-Ti intermediate alloy, and obtaining alloy liquid after smelting is finished;
s3, casting: pouring the alloy liquid into a mold for molding, adding Cu-Zr intermediate alloy into the furnace at intervals in the casting process, and casting to obtain a copper-titanium alloy cast ingot;
s4, oxygen-enriched roasting: after casting, intensively placing the furnace slag for roasting;
s5, chlorination: using Cl as main component after roasting2Chlorination is carried out, and C is added in the reaction process;
s6, magnesiothermic reduction: reducing the chloridized furnace slag by using Mg, and carrying out vacuum distillation and separation to obtain Ti and Zr;
s7, vacuum melting and pouring: and respectively smelting Ti and Zr with Cu in a vacuum furnace, and pouring to obtain Cu-Ti and Cu-Zr intermediate alloys which are continuously used as raw materials for producing copper-titanium alloy ingots.
In the production process of the large-size copper-titanium alloy ingot, Zr is selected to protect Ti from being burnt, and the Zr has the advantages that: zr and Ti can be infinitely dissolved in solid solution without forming a compound, which is shown in figure 4; as is clear from fig. 5, 6, 7 and 8, the gibbs free energy of the reaction of Zr with oxygen, nitrogen, carbon dioxide and water vapor is more negative than the gibbs free energy of the reaction of Ti with oxygen, nitrogen, carbon dioxide and water vapor, and in the Cu — Ti — Zr system, Zr reacts with oxygen, nitrogen, carbon dioxide and water vapor preferentially to Ti. In addition, Zr can play a role in refining grains, inhibiting the formation of an early amplitude modulation structure and inhibiting the growth of a lamellar structure in the Cu-Ti alloy; zr is kept lower than Ti in the melt, which can effectively reduce the reaction rate with oxygen and nitrogen from the kinetic point of view; the production process of Zr and Ti is very similar, and adopts chlorination and then magnesium thermal reduction, thereby facilitating subsequent recovery and reutilization.
After the casting is finished, the slag is roasted so as to oxidize Zr and Ti in the slag into ZrO2、TiO2In the form of (a); then the slag is chloridized to make ZrO2、TiO2Conversion to ZrCl4、TiCl4(ii) a ZrCl is subjected to magnesiothermic reduction4、TiCl4Reduction, the products after reduction are Zr, Ti, Mg and MgCl2And then by utilizing the property of different vapor pressures of the substances, separating the substances by vacuum distillation to obtain Zr and Ti, then carrying out vacuum melting and pouring on the Zr, the Ti and the Cu to obtain Cu-Ti and Cu-Zr intermediate alloy, and continuously using the Cu-Ti and Cu-Zr intermediate alloy as a raw material for producing the copper-titanium alloy ingot, thereby realizing the recycling of materials and the continuous production process and effectively reducing the production cost of enterprises.
Preferably, in the step S1, the raw material needs to be dried and moisturized during blending.
Preferably, the smelting temperature in the step S2 is 1200-1300 ℃, the addition amount of the Cu-Mg intermediate alloy is 0.05-0.3% of the mass of the fed material, and the content of Mg in the Cu-Mg intermediate alloy is 20%. The Cu-Mg intermediate alloy with the proportion can remove oxygen in the melt to the maximum extent and basically has no magnesium element in the melt in the later stage of smelting.
Preferably, in the step S2, the content of Ti in the Cu-Ti master alloy is 20-40 wt%, and the content of Zr in the Cu-Zr master alloy is 30-50 wt%.
Preferably, in the step S2, the melt is covered with a covering agent I during the process of adding the copper electrolytic plate, and the covering thickness is 9-12 cm; adding a Cu-Mg intermediate alloy for deoxidation, keeping the temperature for 10-30 min, fishing out slag, and covering the melt with a covering agent II, wherein the covering thickness is 8-15 cm; the degassing gas is argon, and the degassing time is 20-35 min.
Further preferably, the covering agent I is charcoal, and the covering agent II is CaF consisting of the following components in percentage by mass2：30～45％，MgF2：2～15％，NaF：2～15％，MgO：10～20％，CaO：10～20％，NaCl：4～10％，CaCl2: 4-10%. According to the invention, two covering agents are selected, wherein one covering agent, namely charcoal, has a heat preservation effect and can also play a reducing role to remove oxygen in copper liquid, but Ti can react with C at high temperature, so that the performance of the produced copper-titanium alloy ingot can not meet the use requirement. Therefore, after the copper liquid is deoxidized and insulated, the charcoal is thoroughly removed by fishing slag, and the covering agent is replaced to protect the two melts. The covering agent II mainly selects oxides, fluorides and chlorides of calcium, sodium and magnesium, and has the advantages that: firstly, Ti and Zr do not react with a covering agent; the covering agent has proper fluidity and good spreadability, and plays roles in preserving heat of the melt and isolating air; thirdly, the covering agent can well absorb slag in the copper liquid and play a role in purifying the copper liquid.
Preferably, the casting temperature in the step S3 is 1150-1250 ℃, the casting speed is 70-100 mm/min, and the cooling water flow is 50-75 m3And h, the vibration frequency is 40-60 times/min, and 30-100 g of Cu-Zr intermediate alloy is added into the furnace every 30-70 s in the casting process. Into the casting furnace at short intervals during the casting processA Cu — Zr master alloy is added in order to keep Zr in the melt and protect Ti from burning.
Preferably, the large-size copper-titanium alloy ingot cast in step S3 has a composition of, by mass, Ti: 1-5 wt%, Zr less than or equal to 0.5 wt%, and the balance of copper and inevitable impurities.
Preferably, the temperature of the calcination in the step S4 is 850-900 ℃.
Preferably, the addition amount of C in the step S5 is 10-16% of the mass of the roasted slag. The addition of C can promote the chlorination reaction.
Preferably, the smelting in the step S7 is finished, the mixture is kept stand for 10-30 min and then is poured, and the pouring temperature is 1200-1300 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention can cast the large-size copper-titanium alloy ingot in the atmospheric environment, and greatly reduces the production cost compared with the investment of producing the large-size copper-titanium alloy ingot by the traditional large-size vacuum furnace.
2. From the basic thermodynamic angle, the reaction Gibbs free energy of Zr and oxygen and nitrogen is more negative than that of Ti and oxygen and nitrogen, and the method of abandoning Zr and protecting Ti is adopted, so that Ti can be prevented from being burnt as long as Zr exists in the system in the smelting process.
3. According to the invention, Ti and Zr in the smelted furnace slag are recycled and reused to prepare the Cu-Zr intermediate alloy and the Cu-Ti intermediate alloy which are continuously used as raw materials for producing the copper-titanium alloy ingot, so that the production cost of enterprises can be effectively reduced.
Drawings
FIG. 1 is a production flow diagram of a copper-titanium alloy ingot of the present invention;
FIG. 2 is a Cu-Ti binary phase diagram;
FIG. 3 is a Cu-Zr binary phase diagram;
FIG. 4 is a Ti-Zr binary phase diagram;
FIG. 5 is a graph of Gibbs free energy as a function of temperature for the reaction of Ti, Zr and nitrogen;
FIG. 6 is a graph of Gibbs free energy of reactions relating Ti, Zr and oxygen as a function of temperature;
FIG. 7 is a graph of Gibbs free energy of reactions relating Ti, Zr and carbon dioxide as a function of temperature;
FIG. 8 is a graph of Gibbs free energy of reaction associated with Ti, Zr and water vapor as a function of temperature;
FIG. 9 is a plot of the elemental analysis site-selected cutting profiles of the ingots of examples 1-8.
Detailed Description
The following are specific examples of the present invention and illustrate the technical solutions of the present invention for further description, but the present invention is not limited to these examples.
Example 1
The following raw materials were used in this example: the copper electrolytic plate, the Cu-Ti intermediate alloy, the Cu-Zr intermediate alloy and the Cu-Mg intermediate alloy are produced by the following specific steps:
s1, batching according to 6t of materials, wherein the alloy comprises the following components in mass: 1 wt% of Ti, 0.8 wt% of Zr, and the balance of Cu and inevitable impurities, and fully drying moisture before feeding the materials into a furnace, wherein the Ti is added in a Cu-Ti intermediate alloy mode, the content of Ti in the Cu-Ti intermediate alloy is 20%, the Zr is added in a Cu-Zr intermediate alloy mode, and the content of Zr in the Cu-Zr intermediate alloy is 50%;
s2, heating a smelting furnace, adding copper electrolytic plates at 1300 ℃, covering with charcoal in the period of time, wherein the covering thickness is 9cm, adding 15kg of 20% Cu-Mg intermediate alloy into the melt after all the electrolytic plates are added, deoxidizing, preserving heat for 30min, and fishing slag; covering the melt with a second covering agent, wherein the second covering agent comprises CaF in percentage by mass2：30％，MgF2：15％，NaF：2％，MgO：10％，CaO：20％，NaCl：4％，CaCl2: 10 percent, covering the alloy liquid with the thickness of 15cm, degassing by adopting argon gas for 10min, adding a Cu-Zr intermediate alloy after the degassing is finished, and adding a Cu-Ti intermediate alloy after the Cu-Zr intermediate alloy is melted to prepare an alloy liquid;
s3, casting the alloy liquid, wherein the casting temperature is 1220 ℃, the casting speed is 90mm/min, and the cooling water flow is 50m3H, the vibration frequency is 60 times/min; casting processContinuously adding Cu-Zr intermediate alloy into the furnace in the process, starting to add 60g of Cu-Zr intermediate alloy into the furnace every 30s, casting for 30min, adding 40g of Cu-Zr intermediate alloy into the furnace every 40s, and casting to obtain a copper-titanium alloy ingot;
s4, collecting slag after casting, and then carrying out oxygen-enriched roasting at 850 ℃ to ensure that Zr and Ti completely exist in the form of oxides;
s5, chloridizing the roasted slag, adding C in the reaction process, wherein the adding amount of C is 10 percent of the mass of the roasted slag, and ZrO is added2、TiO2Conversion to ZrCl4、TiCl4；
S6 reaction of ZrCl with Mg4、TiCl4Reduction followed by vacuum distillation separated out Ti and Zr.
And S7, respectively adding Ti and Zr into a small vacuum furnace, respectively adding electrolytic copper, standing for 30min after the Ti and the Zr are completely melted, and then casting at 1200 ℃.
The ingot was cut according to FIG. 9 and the composition was measured, the elemental composition being shown in Table 1.
Table 1: EXAMPLE 1 ingot elemental composition
Figure BDA0002769073680000061
Figure BDA0002769073680000071
Example 2
The following raw materials were used in this example: the copper electrolytic plate, the Cu-Ti intermediate alloy, the Cu-Zr intermediate alloy and the Cu-Mg intermediate alloy are produced by the following specific steps:
s1, batching according to 5.5t of materials, wherein the alloy comprises the following components in percentage by mass: 3 wt% of Ti, 0.9 wt% of Zr, and the balance of Cu and inevitable impurities, and fully drying moisture before feeding the materials into a furnace, wherein the Ti is added in a Cu-Ti intermediate alloy mode, the content of Ti in the Cu-Ti intermediate alloy is 20%, the Zr is added in a Cu-Zr intermediate alloy mode, and the content of Zr in the Cu-Zr intermediate alloy is 40%.
S2, heating a smelting furnace, adding copper electrolytic plates, covering with charcoal at 1250 ℃ during the heating, wherein the covering thickness is 10cm, adding 12kg of 20% Cu-Mg intermediate alloy into the melt for deoxidation after all the electrolytic plates are added, preserving heat for 20min, and fishing slag; covering the melt with a second covering agent, wherein the second covering agent comprises CaF in percentage by mass2：40％，MgF2：7％，NaF：7％，MgO：14％，CaO：14％，NaCl：7％，CaCl2: 7%, covering the alloy liquid with the thickness of 13cm, degassing by adopting argon gas for 20min, adding a Cu-Zr intermediate alloy after degassing is finished, and adding a Cu-Ti intermediate alloy after the Cu-Zr intermediate alloy is melted to prepare an alloy liquid;
s3, casting the alloy liquid, wherein the casting temperature is 1200 ℃, the casting speed is 85mm/min, and the cooling water flow is 60m3H, the vibration frequency is 50 times/min; continuously adding Cu-Zr intermediate alloy into the furnace in the casting process, beginning to add 45g of Cu-Zr intermediate alloy into the furnace every 30s, adding 30g of Cu-Zr intermediate alloy into the furnace every 40s after casting for 25min, and casting to obtain a copper-titanium alloy ingot;
s4, collecting slag after casting, and then carrying out oxygen-enriched roasting at 860 ℃ to ensure that Zr and Ti completely exist in the form of oxides;
s5, chloridizing the roasted slag, adding C in the reaction process, wherein the adding amount of C is 12% of the mass of the roasted slag, and ZrO is added2、TiO2Conversion to ZrCl4、TiCl4；
S6 reaction of ZrCl with Mg4、TiCl4Reduction, followed by vacuum distillation to separate out Ti and Zr;
and S7, respectively adding Ti and Zr into a small vacuum furnace, respectively adding electrolytic copper, standing for 20min after the Ti and the Zr are completely melted, and then casting at 1250 ℃.
The ingot was cut according to FIG. 9 and the composition was measured, the elemental composition being shown in Table 2.
Table 2: EXAMPLE 2 ingot elemental composition
Figure BDA0002769073680000081
Example 3
The following raw materials were used in this example: the copper electrolytic plate, the Cu-Ti intermediate alloy, the Cu-Zr intermediate alloy and the Cu-Mg intermediate alloy are produced by the following specific steps:
s1, batching according to 6t of materials, wherein the alloy comprises the following components in mass: 4 wt% of Ti, 1 wt% of Zr, and the balance of Cu and inevitable impurities, and fully drying the materials before the materials are put into a furnace, wherein the Ti is added in a Cu-Ti intermediate alloy mode, the content of Ti in the Cu-Ti intermediate alloy is 40%, the Zr is added in a Cu-Zr intermediate alloy mode, and the content of Zr in the Cu-Zr intermediate alloy is 50%;
s2, heating a smelting furnace, adding copper electrolytic plates at 1280 ℃, covering with charcoal in the period of 10cm in thickness, adding 16kg of 20% Cu-Mg intermediate alloy into the melt after all the electrolytic plates are added, deoxidizing, keeping the temperature for 30min, and fishing slag; covering the melt with a second covering agent, wherein the second covering agent comprises CaF in percentage by mass2：44％，MgF2：8％，NaF：8％，MgO：15％，CaO：15％，NaCl：5％，CaCl2: 5%, covering with the thickness of 14cm, degassing by adopting argon gas for 30min, adding a Cu-Zr intermediate alloy after degassing is finished, and adding a Cu-Ti intermediate alloy after melting to prepare an alloy liquid;
s3, casting the alloy liquid, wherein the casting temperature is 1200 ℃, the casting speed is 80mm/min, and the cooling water flow is 65m3H, the vibration frequency is 60 times/min; continuously adding Cu-Zr intermediate alloy into the furnace in the casting process, beginning to add 50g of Cu-Zr intermediate alloy into the furnace every 30s, adding 30g of Cu-Zr intermediate alloy into the furnace every 40s after casting for 20min, and casting to obtain a copper-titanium alloy ingot;
s4, collecting slag after casting, and then carrying out oxygen-enriched roasting at 880 ℃ to ensure that Zr and Ti completely exist in the form of oxides;
s5, chloridizing the roasted slag, adding C in the reaction process, wherein the adding amount of C is 14% of the mass of the roasted slag, and ZrO is added2、TiO2Conversion to ZrCl4、TiCl4；
S6 reaction of ZrCl with Mg4、TiCl4Reduction, followed by vacuum distillation to separate out Ti and Zr;
and S7, respectively adding Ti and Zr into a small vacuum furnace, respectively adding electrolytic copper, standing for 30min after the Ti and the Zr are completely melted, and then casting at 1300 ℃.
The ingot was cut according to FIG. 9 and the composition was measured, the elemental composition being shown in Table 3.
Table 3: EXAMPLE 3 ingot elemental composition
Figure BDA0002769073680000101
Example 4
The following raw materials were used in this example: the copper electrolytic plate, the Cu-Ti intermediate alloy, the Cu-Zr intermediate alloy and the Cu-Mg intermediate alloy are produced by the following specific steps:
s1, batching according to 5.5t of materials, wherein the alloy comprises the following components in percentage by mass: 5 wt% of Ti, 1 wt% of Zr, and the balance of copper and inevitable impurities, fully drying the materials before the materials are put into a furnace, wherein the Ti is added in a Cu-Ti intermediate alloy mode, the content of Ti in the Cu-Ti intermediate alloy is 20%, the Zr is added in a Cu-Zr intermediate alloy mode, and the content of Zr in the Cu-Zr intermediate alloy is 30%;
s2, heating a smelting furnace, firstly adding copper electrolytic plates, wherein the smelting temperature is 1230 ℃, covering with charcoal during the heating, after all the electrolytic plates are added, adding 15kg of 20% Cu-Mg intermediate alloy into the melt for deoxidation, keeping the temperature for 30min, and fishing slag; covering the melt with a second covering agent, wherein the second covering agent comprises CaF in percentage by mass2：45％，MgF2：7％，NaF：7％，MgO：20％，CaO：10％，NaCl：5％，CaCl2: 6 percent, covering the alloy liquid with the thickness of 15cm, degassing by adopting argon gas for 30min, adding a Cu-Zr intermediate alloy after degassing is finished, and adding a Cu-Ti intermediate alloy after melting to prepare an alloy liquid;
s3, casting the alloy liquid, wherein the casting temperature is 1300 ℃, the casting speed is 100mm/min, the Cu-Zr intermediate alloy is not added into the furnace continuously in the casting process, 100g of the Cu-Zr intermediate alloy is added into the furnace every 40S, 60g of the Cu-Zr intermediate alloy is added into the furnace every 70S after casting for 25min, and a copper-titanium alloy ingot is obtained by casting;
s4, collecting slag after casting, and then carrying out oxygen-enriched roasting at 900 ℃ to ensure that Zr and Ti completely exist in the form of oxides;
s5, chloridizing the roasted slag, adding C in the reaction process, wherein the adding amount of C is 16% of the mass of the roasted slag, and ZrO is added2、TiO2Conversion to ZrCl4、TiCl4；
S6 reaction of ZrCl with Mg4、TiCl4Reduction, followed by vacuum distillation to separate out Ti and Zr;
and S7, respectively adding Ti and Zr into a small vacuum furnace, respectively adding electrolytic copper, standing for 30min after the Ti and the Zr are completely melted, and then casting at 1250 ℃.
The ingot was cut according to FIG. 9 and the composition was measured, the elemental composition being shown in Table 4.
Table 4: EXAMPLE 4 ingot elemental composition
Figure BDA0002769073680000111
Figure BDA0002769073680000121
Example 5
In this example, the following raw materials were used for melting: a copper electrolytic plate and a Cu-Ti intermediate alloy are smelted by a vacuum furnace, and the Cu-Mg intermediate alloy and a covering agent are not required to be added in a vacuum environment, and the specific production process comprises the following steps:
s1, batching according to 6t of materials, wherein the alloy comprises the following components in mass: 4 wt% of Ti (without Zr element), the balance of Cu and inevitable impurities, and fully drying the materials before the materials are put into a furnace, wherein the Ti is added in a copper-titanium intermediate alloy mode, and the content of Ti in the copper-titanium alloy is 40%;
s2, adding a copper electrolytic plate and a Cu-Ti intermediate alloy into a vacuum smelting furnace according to the ingredients, and smelting to obtain an alloy liquid;
s3, casting the alloy liquid, wherein the casting temperature is 1200 ℃, the casting speed is 80mm/min, and the cooling water flow is 65m3The vibration frequency is 60 times/min.
The ingot was cut according to FIG. 9 and the composition was measured, the elemental composition being shown in Table 5.
Table 5: EXAMPLE 5 ingot elemental composition
Figure BDA0002769073680000122
Figure BDA0002769073680000131
Example 6
In this example, the following raw materials were used for melting: copper electrolytic plates, Cu-Ti master alloys, Cu-Mg master alloys; the Cu-Zr intermediate alloy is smelted in the atmospheric environment by adopting a conventional method without adding the Cu-Zr intermediate alloy, and the specific production process is as follows:
s1, batching according to 6t of materials, wherein the alloy comprises the following components in mass: 4 wt% of Ti (without Zr element), the balance of Cu and inevitable impurities, and fully drying the materials before the materials are put into a furnace, wherein the Ti is added in a Cu-Ti intermediate alloy mode, and the content of Ti in the Cu-Ti intermediate alloy is 40%;
s2, adopting non-vacuum melting, heating a melting furnace, adding a copper electrolytic plate at 1280 ℃, covering with charcoal at a thickness of 10cm during the heating, adding 16kg of 20% Cu-Mg intermediate alloy into the melt for deoxidation after all the electrolytic plates are added, preserving heat for 30min, and fishing slag; covering the melt with a second covering agent, wherein the second covering agent comprises CaF in percentage by mass2：44％，MgF2：8％，NaF：8％，MgO：15％，CaO：15％，NaCl：5％，CaCl2: 5% and a cover thickness of 14cm, using argon gasDegassing for 30min, and adding a Cu-Ti intermediate alloy after degassing to prepare an alloy liquid;
s3, casting the alloy liquid, wherein the casting temperature is 1200 ℃, the casting speed is 80mm/min, and the cooling water flow is 65m3And h, the vibration frequency is 60 times/min, and copper-titanium alloy cast ingots are obtained by casting.
The ingot was cut according to FIG. 9 and the composition was measured, the elemental composition being shown in Table 6.
Table 6: EXAMPLE 6 ingot elemental composition
Figure BDA0002769073680000132
Figure BDA0002769073680000141
Example 7
The only difference from example 3 is that only covering agent one was used as the covering agent.
Table 7: EXAMPLE 7 ingot elemental composition
Figure BDA0002769073680000142
Figure BDA0002769073680000151
Example 8
The only difference from example 3 is that only covering agent two was used as the covering agent.
Table 8: EXAMPLE 8 ingot elemental composition
Figure BDA0002769073680000152
The copper-titanium alloy ingots of the above examples 1 to 8 were made into finished copper-titanium alloy strips, and the performance parameters of the finished strips were tested as shown in table 9.
After the copper-titanium alloy cast ingot is prepared into a finished copper-titanium alloy strip, the performance of the strip is tested, wherein the test standards comprise tensile strength, yield strength, electric conductivity, hardness and the like, and the specific test standards are as follows:
tensile strength according to part 1 of the national standard GT/B228.1-2010 metal material tensile test: test method for Room temperature test
The yield strength is according to the part 1 of the tensile test of the metal material of the national standard GT/B228.1-2010: test method for Room temperature test
The conductivity is tested according to the national standard GB/T32791-2016 copper and copper alloy conductivity eddy current test method
The Vickers hardness is determined according to the national standard GB/T4340.1-2009 Vickers hardness test part 1: test method test
Table 9: properties of finished strips made of copper-titanium alloy ingots in examples 1 to 8
Figure BDA0002769073680000161
As can be seen from the analysis of the ingot casting elements in tables 1 to 8, when the ingot casting is in a non-vacuum state and no zirconium element is added, the content of the titanium element in the ingot casting is low, mainly because most of the titanium is burned due to the presence of impurities such as oxygen, the mechanical property and the conductivity of the finished ingot casting are greatly reduced, which is specifically seen in the comparison of the properties of the finished copper-titanium alloy ingot casting in table 9. When the technical scheme of the invention is adopted, the zirconium element is added under non-vacuum condition, and the zirconium element is preferentially reacted with impurities such as titanium and oxygen according to thermodynamic analysis, so that a large amount of titanium element can be prevented from being burnt when a copper-titanium alloy ingot is prepared by adding a proper amount of zirconium element, the content of titanium in the copper-titanium alloy ingot is further ensured, and the copper-titanium alloy ingot has good comprehensive performance.
In view of the numerous embodiments of the present invention, the experimental data of each embodiment is huge and is not suitable for being listed and explained herein one by one, but the contents to be verified and the final conclusions obtained by each embodiment are close. While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (10)

1. A method for producing large-size copper-titanium alloy ingots in a non-vacuum mode is characterized by comprising the following steps:
s1, batching: the materials are prepared according to the following mass percent: ti: 1-5%, Zr0.8-1%, and the balance of Cu and inevitable impurities;
s2, smelting: heating a smelting furnace, adding a copper electrolytic plate, adding a Cu-Mg intermediate alloy for deoxidation after the copper electrolytic plate is completely added, preserving heat, fishing slag, degassing, adding the Cu-Zr intermediate alloy after degassing is finished, adding the Cu-Ti intermediate alloy, and obtaining alloy liquid after smelting is finished;
s3, casting: pouring the alloy liquid, adding Cu-Zr intermediate alloy into the furnace at intervals in the casting process, and casting to obtain a copper-titanium alloy cast ingot;
s4, oxygen-enriched roasting: after casting, intensively placing the furnace slag for roasting;
s5, chlorination: using Cl as main component after roasting2Chlorination is carried out, and C is added in the reaction process;
s6, magnesiothermic reduction: reducing the chloridized furnace slag by using Mg, and carrying out vacuum distillation and separation to obtain Ti and Zr;
s7, vacuum melting and pouring: and respectively smelting Ti and Zr with Cu in a vacuum furnace, and pouring to obtain Cu-Ti and Cu-Zr intermediate alloys which are continuously used as raw materials for producing copper-titanium alloy ingots.
2. The non-vacuum production method of large-size copper-titanium alloy ingots according to claim 1, wherein the smelting temperature in the step S2 is 1200-1300 ℃, the addition amount of the Cu-Mg intermediate alloy is 0.05-0.3% of the mass of the fed materials, and the content of Mg in the Cu-Mg intermediate alloy is 20%.
3. The non-vacuum production method for large-size copper-titanium alloy ingots according to claim 1, wherein the content of Ti in the Cu-Ti master alloy in the step S2 is 20-40 wt%, and the content of Zr in the Cu-Zr master alloy is 30-50 wt%.
4. The method for non-vacuum production of large-format copper-titanium alloy ingots according to claim 1, wherein the step S2 is to cover the melt with a covering agent during the process of adding copper electrolytic plates, wherein the covering thickness is 9-12 cm; adding a Cu-Mg intermediate alloy for deoxidation, keeping the temperature for 10-30 min, fishing out slag, and covering the melt with a covering agent II, wherein the covering thickness is 8-15 cm; the degassing gas is argon, and the degassing time is 20-35 min.
5. The non-vacuum large format copper titanium alloy ingot production method of claim 4, wherein the first covering agent is charcoal and the second covering agent is CaF consisting of the following components in percentage by mass2：30～45％，MgF2：2～15％，NaF：2～15％，MgO：10～20％，CaO：10～20％，NaCl：4～10％，CaCl2：4～10％。
6. The non-vacuum production method of large-size copper-titanium alloy ingots according to claim 1, wherein the casting temperature in step S3 is 1150-1250 ℃, the casting speed is 70-100 mm/min, and the cooling water flow rate is 50-75 m3And h, the vibration frequency is 40-60 times/min, and 30-100 g of Cu-Zr intermediate alloy is added into the furnace every 30-70 s in the casting process.
7. The method for non-vacuum production of large-size copper-titanium alloy ingots according to claim 1, wherein the large-size copper-titanium alloy ingots cast in the step S3 have the following composition in percentage by mass: 1-5 wt%, Zr less than or equal to 0.5 wt%, and the balance of copper and inevitable impurities.
8. The non-vacuum production method for large-size copper-titanium alloy ingots according to claim 1, wherein the roasting temperature in the step S4 is 850-900 ℃.
9. The non-vacuum production method of large-size copper-titanium alloy ingots according to claim 1, wherein the amount of C added in the step S5 is 10-16% of the mass of the roasted slag.
10. The non-vacuum production method for large-size copper-titanium alloy ingots according to claim 1, wherein the casting is performed after the completion of the melting in the step S7 and standing for 10-30 min, and the casting temperature is 1200-1300 ℃.
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