CN112143923A - Preparation method of 3mm Zn-Cu-Ti alloy wire for spraying - Google Patents
Preparation method of 3mm Zn-Cu-Ti alloy wire for spraying Download PDFInfo
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- CN112143923A CN112143923A CN202011041617.XA CN202011041617A CN112143923A CN 112143923 A CN112143923 A CN 112143923A CN 202011041617 A CN202011041617 A CN 202011041617A CN 112143923 A CN112143923 A CN 112143923A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
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- B21C25/00—Profiling tools for metal extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C18/00—Alloys based on zinc
- C22C18/02—Alloys based on zinc with copper as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
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Abstract
A preparation method of a 3mm Zn-Cu-Ti alloy wire for spraying comprises the following steps: 1. weighing pure copper blocks and sponge titanium according to a proportion, smelting the pure copper blocks and the sponge titanium into a Cu-Ti intermediate alloy by adopting a non-consumable vacuum arc furnace, and breaking the alloy into small blocks after cooling; 2. smelting Zn-Cu-Ti alloy by using a resistance furnace, then respectively putting Cu-Ti intermediate alloy into a zinc melt, preserving heat until the Cu-Ti intermediate alloy is completely dissolved into the zinc melt, and pouring the Zn-Cu-Ti alloy melt into a graphite mold; 3. putting the cylindrical cast ingot into a resistance furnace, heating to 150-180 ℃, taking out, and brushing a layer of graphite emulsion lubricant on the cast ingot; 4. and (2) putting the Zn-Cu-Ti ingot into an extrusion die, heating the ingot and the extrusion die together, carrying out isothermal extrusion, and carrying out one-step deformation to obtain the alloy wire. The preparation method solves the problem of large volatilization of zinc in the smelting process, and the method prepares the zinc-copper-titanium alloy wire material in one step, reduces the preparation procedures, greatly reduces the production cost and improves the productivity.
Description
Technical Field
The invention particularly relates to a preparation method of a Zn-Cu-Ti alloy wire for spraying, belonging to the field of material preparation.
Background
Through the development of nearly half a century, the application of zinc alloy in the world is becoming more and more extensive. The zinc alloy has the advantages of good fluidity, excellent mechanical property, short production process flow, low energy consumption and the like, and China has abundant zinc resources accounting for about 36% of the total amount of the world, geological reserves are the first in the world and are found to be 4200 ten thousand tons from the end of 2011, and the novel zinc alloy material is developed, has remarkable social and economic benefits and is also beneficial to relieving the condition of domestic resource shortage. Because of abundant resources and low price of raw materials, the research and application of zinc alloy arouse wide attention of the nonferrous metal world. According to the research at home and abroad, the zinc is alloyed in a series, so that the comprehensive mechanical property and the corrosion resistance of the zinc are improved, and the special protection mechanism of the metal zinc is also reserved. At present, the copper alloy and the cast iron are widely applied to the fields of hardware, daily decoration, building materials, automobile parts and the like as substitute materials of partial materials such as copper alloy, cast iron and the like. The investigation shows that the zinc alloy coating has the advantages of better compactness, higher adhesion with a matrix and the like compared with the traditional zinc plating, so that the zinc alloy is used as a spraying material. Zn-Cu-Ti is one kind of zinc alloy, is widely applied to structural materials and anticorrosive materials, and has high strength, good plasticity, excellent creep resistance and excellent corrosion resistance. Nowadays, zinc alloy is widely applied to the fields of bridges, navigation, pipelines, storage tanks and the like due to good corrosion resistance, and is also used for electroplating, spraying and the like. The zinc alloy is used as a spraying material, and the traditional method is to perform hot extrusion on a cast ingot and then perform multi-pass drawing, so as to obtain the required wire.
The traditional method for preparing the zinc alloy wire needs to be drawn in multiple passes, and although the required wire can be obtained finally, the method has obvious defects: the preparation process is complicated due to the multi-pass drawing, the preparation period is prolonged, and the preparation cost is increased.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a 3mm Zn-Cu-Ti alloy wire for spraying, so as to solve the problem of complicated preparation procedures of the zinc alloy wire.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a 3mm Zn-Cu-Ti alloy wire for spraying comprises the following steps:
(1) according to the mass ratio of 4: 3. 2: 1 or 8: 3, weighing pure copper blocks and sponge titanium in any proportion, smelting the pure copper blocks and the sponge titanium into a Cu-Ti intermediate alloy by adopting a non-consumable vacuum arc furnace, carrying out electromagnetic stirring treatment on the alloy melt in the smelting process, wherein the smelting frequency is not less than 3 times, and crushing the alloy into small blocks after cooling;
(2) smelting Zn-Cu-Ti alloy by using a resistance furnace, namely firstly melting pure zinc, then respectively putting Cu-Ti intermediate alloy into a zinc melt, preserving heat until the Cu-Ti intermediate alloy is completely dissolved into the zinc melt, pouring the Zn-Cu-Ti alloy melt into a graphite mold with the inner diameter of 36mm and the height of 75mm, and respectively obtaining Zn-0.4Cu-0.3Ti, Zn-0.6Cu-0.3Ti and Zn-0.8Cu-0.3Ti alloy cast ingots according to pure copper blocks and sponge titanium mixed in different mass ratios in the step (1);
(3) putting a Zn-Cu-Ti cylindrical cast ingot with the diameter of 36mm into a resistance furnace, heating to 150-180 ℃, keeping the temperature for 15min, taking out, and brushing a layer of graphite emulsion lubricant on the cast ingot;
(4) putting the Zn-Cu-Ti cast ingot into an extrusion die, wherein the diameter of a die hole is 3mm, heating the cast ingot and the extrusion die together, heating the cast ingot and the extrusion die to 398-408 ℃, keeping the temperature for 20-30min, then carrying out isothermal extrusion, wherein the extrusion speed is 0.8-1.2mm/s, the extrusion ratio is 144, and carrying out one-step deformation to obtain Zn-0.4Cu-0.3Ti, Zn-0.6Cu-0.3Ti and Zn-0.8Cu-0.3Ti alloy wires with the diameter of 3 mm.
Preferably, the temperature of the zinc melt in the step (2) is controlled to be 650-720 ℃.
Preferably, the holding time in step (2) is controlled within 4 to 6 hours.
Preferably, the pieces formed by the step (1) of cooling and then breaking are not more than 8g in mass.
According to the preparation method, the copper-titanium intermediate alloy is obtained by arc melting, and the copper-titanium alloy block is introduced into the zinc melt to prepare the zinc-copper-titanium alloy ingot. Putting the Zn-Cu-Ti ingot into an extrusion die, wherein the diameter of a die hole is 3mm, heating the ingot and the extrusion die together, keeping the temperature for a period of time after heating to a certain temperature, and then carrying out isothermal extrusion. In the process of preparing the zinc-copper-titanium alloy ingot, low-temperature smelting is adopted, so that the problem of large amount of volatilization of zinc in the smelting process is solved, the zinc-copper-titanium alloy wire is prepared in one step by the method, the preparation procedures are reduced, the required 3mm wire can be rapidly produced in the mass production process, the production cost is greatly reduced, and the productivity is improved.
Drawings
FIG. 1 is a pictorial representation of 3mm diameter Zn-Cu-Ti alloy ingots and wires.
FIG. 2 is a phase diagram of a Zn-0.4Cu-0.3Ti alloy.
FIG. 3 is a phase diagram of a Zn-0.6Cu-0.3Ti alloy.
FIG. 4 is a phase diagram of a Zn-0.8Cu-0.3Ti alloy.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A preparation method of a 3mm Zn-Cu-Ti alloy wire for spraying comprises the following steps:
(1) according to the mass ratio of 4: 3, weighing pure copper blocks and sponge titanium in proportion, smelting the pure copper blocks and the sponge titanium into a Cu-Ti intermediate alloy by adopting a non-consumable vacuum arc furnace, carrying out electromagnetic stirring treatment on an alloy melt in the smelting process, wherein the smelting frequency is not lower than 3 times, breaking the alloy into small blocks after cooling, and in order to ensure uniform dissolution and increase the contact surface, the mass of each small alloy block is not more than 8 g;
(2) smelting Zn-Cu-Ti alloy by using a resistance furnace, namely firstly melting pure zinc, and then respectively putting Cu-Ti intermediate alloy into a zinc melt as the most preferable process parameter, wherein the temperature of the zinc melt is controlled at 650 ℃, and the volatilization of zinc elements can be caused by overhigh temperature to influence the components of the prepared finished product; too low a temperature will result in too long a cycle time for melting the zinc alloy. Meanwhile, the heat preservation time of 4-6 hours is also the most preferable time period, the even mixing of the components is influenced by too short time, and the energy cost is wasted due to too long time. After the Cu-Ti intermediate alloy is completely dissolved into the zinc melt, pouring the Zn-Cu-Ti alloy melt into a graphite mold with the inner diameter of 36mm and the height of 75mm, and mixing pure copper blocks and sponge titanium according to different mass ratios in the step (1) to obtain a Zn-0.4Cu-0.3Ti alloy ingot;
(3) putting a Zn-Cu-Ti cylindrical cast ingot with the diameter of 36mm into a resistance furnace, heating to 150-180 ℃, keeping the temperature for 15min, taking out, and brushing a layer of graphite emulsion lubricant on the cast ingot;
(4) putting the Zn-Cu-Ti ingot into an extrusion die, wherein the diameter of a die hole is 3mm, heating the ingot and the extrusion die together, heating the ingot and the extrusion die to 398 ℃, keeping the temperature for 20-30min, then carrying out isothermal extrusion, wherein the extrusion speed is 0.8-1.2mm/s, the extrusion ratio is 144, carrying out one-step deformation to obtain a Zn-0.4Cu-0.3T alloy wire with the diameter of 3mm, and the phase characteristics of the Zn-0.4Cu-0.3Ti alloy are shown in figure 2.
Example 2:
a preparation method of a 3mm Zn-Cu-Ti alloy wire for spraying comprises the following steps:
(1) according to the mass ratio of 2: 1, weighing pure copper blocks and sponge titanium, smelting the pure copper blocks and the sponge titanium into a Cu-Ti intermediate alloy by adopting a non-consumable vacuum arc furnace, carrying out electromagnetic stirring treatment on an alloy melt in the smelting process, wherein the smelting frequency is not lower than 3 times, breaking the alloy into small blocks after cooling, and in order to ensure uniform dissolution and increase the contact surface, the mass of each small alloy block is not more than 8 g;
(2) smelting Zn-Cu-Ti alloy by using a resistance furnace, namely firstly melting pure zinc, and then respectively putting Cu-Ti intermediate alloy into a zinc melt as an optimal process parameter, wherein the temperature of the zinc melt is controlled at 680 ℃, and the zinc element is volatilized due to overhigh temperature, so that the components of a prepared finished product are influenced; too low a temperature will result in too long a cycle time for melting the zinc alloy. Meanwhile, the heat preservation time of 4-6 hours is also the most preferable time period, the even mixing of the components is influenced by too short time, and the energy cost is wasted due to too long time. After the Cu-Ti intermediate alloy is completely dissolved into the zinc melt, pouring the Zn-Cu-Ti alloy melt into a graphite mold with the inner diameter of 36mm and the height of 75mm, and mixing pure copper blocks and sponge titanium according to different mass ratios in the step (1) to obtain a Zn-0.6Cu-0.3Ti alloy ingot;
(3) putting a Zn-Cu-Ti cylindrical cast ingot with the diameter of 36mm into a resistance furnace, heating to 150-180 ℃, keeping the temperature for 15min, taking out, and brushing a layer of graphite emulsion lubricant on the cast ingot;
(4) putting the Zn-Cu-Ti ingot into an extrusion die, wherein the diameter of a die hole is 3mm, heating the ingot and the extrusion die together, heating the ingot and the extrusion die at 400 ℃, keeping the temperature for 20-30min, then carrying out isothermal extrusion, wherein the extrusion speed is 0.8-1.2mm/s, the extrusion ratio is 144, and carrying out one-step deformation to obtain a Zn-0.6Cu-0.3Ti alloy wire with the diameter of 3mm, wherein the phase characteristics of the Zn-0.4Cu-0.3Ti alloy are shown in figure 3.
Example 3:
a preparation method of a 3mm Zn-Cu-Ti alloy wire for spraying comprises the following steps:
(1) according to the mass ratio of 8: 3, weighing pure copper blocks and sponge titanium in any proportion, smelting the pure copper blocks and the sponge titanium into a Cu-Ti intermediate alloy by adopting a non-consumable vacuum arc furnace, carrying out electromagnetic stirring treatment on an alloy melt in the smelting process, wherein the smelting frequency is not less than 3 times, breaking the alloy into small blocks after cooling, and in order to ensure uniform dissolution and increase the contact surface, the mass of each small alloy block is not more than 8 g;
(2) smelting Zn-Cu-Ti alloy by using a resistance furnace, namely firstly melting pure zinc, and then respectively putting Cu-Ti intermediate alloy into a zinc melt, wherein the temperature of the zinc melt is controlled to be 720 ℃, and the zinc element is volatilized due to overhigh temperature to influence the components of a prepared finished product as an optimal process parameter; too low a temperature will result in too long a cycle time for melting the zinc alloy. Meanwhile, the heat preservation time of 4-6 hours is also the most preferable time period, the even mixing of the components is influenced by too short time, and the energy cost is wasted due to too long time. After the Cu-Ti intermediate alloy is completely dissolved into the zinc melt, pouring the Zn-Cu-Ti alloy melt into a graphite mold with the inner diameter of 36mm and the height of 75mm, and mixing pure copper blocks and sponge titanium according to different mass ratios in the step (1) to obtain a Zn-0.8Cu-0.3Ti alloy ingot;
(3) putting a Zn-Cu-Ti cylindrical cast ingot with the diameter of 36mm into a resistance furnace, heating to 150-180 ℃, keeping the temperature for 15min, taking out, and brushing a layer of graphite emulsion lubricant on the cast ingot;
(4) putting the Zn-Cu-Ti ingot into an extrusion die, wherein the diameter of a die hole is 3mm, heating the ingot and the extrusion die together, heating the ingot and the extrusion die at 408 ℃, keeping the temperature for 20-30min, then carrying out isothermal extrusion, wherein the extrusion speed is 0.8-1.2mm/s, the extrusion ratio is 144, carrying out one-step deformation to obtain a Zn-0.8Cu-0.3Ti alloy wire with the diameter of 3mm, and the phase characteristics of the Zn-0.8Cu-0.3Ti alloy are shown in figure 4.
FIG. 1 is a drawing of a 3mm wire material, FIG. 2 is a gold phase drawing of Zn-0.4Cu-0.3Ti after extrusion, the grains are equiaxial, the granular material is detected as CuTi3, the granules are few, and the granules are distributed in the grains. FIG. 3 is a diagram of the gold phase of Zn-0.6Cu-0.3Ti after extrusion, compared with FIG. 2, the grains are larger and more granular, most grains are distributed in the grains, and a small amount of grains are distributed in the grain boundary. FIG. 4 is a diagram of the gold phase of Zn-0.8Cu-0.3Ti after extrusion, in which the crystal grains are larger than in FIG. 1, smaller than in FIG. 2, and smaller in number than in FIG. 2, and most of the grains are distributed in the interior of the crystal grains.
Claims (3)
1. A preparation method of a 3mm Zn-Cu-Ti alloy wire for spraying is characterized by comprising the following steps:
(1) according to the mass ratio of 4: 3. 2: 1 or 8: 3, weighing pure copper blocks and sponge titanium in any proportion, smelting the pure copper blocks and the sponge titanium into a Cu-Ti intermediate alloy by adopting a non-consumable vacuum arc furnace, carrying out electromagnetic stirring treatment on the alloy melt in the smelting process, wherein the smelting frequency is not less than 3 times, and crushing the alloy into small blocks after cooling;
(2) smelting Zn-Cu-Ti alloy by using a resistance furnace, namely firstly melting pure zinc, then respectively putting Cu-Ti intermediate alloy into a zinc melt, preserving heat until the Cu-Ti intermediate alloy is completely dissolved into the zinc melt, pouring the Zn-Cu-Ti alloy melt into a graphite mold with the inner diameter of 36mm and the height of 75mm, and respectively obtaining Zn-0.4Cu-0.3Ti, Zn-0.6Cu-0.3Ti and Zn-0.8Cu-0.3Ti alloy cast ingots according to pure copper blocks and sponge titanium mixed in different mass ratios in the step (1);
(3) putting a Zn-Cu-Ti cylindrical cast ingot with the diameter of 36mm into a resistance furnace, heating to 150-180 ℃, keeping the temperature for 15min, taking out, and brushing a layer of graphite emulsion lubricant on the cast ingot;
(4) putting the Zn-Cu-Ti cast ingot into an extrusion die, wherein the diameter of a die hole is 3mm, heating the cast ingot and the extrusion die together, heating the cast ingot and the extrusion die to 398-408 ℃, keeping the temperature for 20-30min, then carrying out isothermal extrusion, wherein the extrusion speed is 0.8-1.2mm/s, the extrusion ratio is 144, and carrying out one-step deformation to obtain Zn-0.4Cu-0.3Ti, Zn-0.6Cu-0.3Ti and Zn-0.8Cu-0.3Ti alloy wires with the diameter of 3 mm.
2. The method of manufacturing 3mm Zn-Cu-Ti alloy wire according to claim 1, wherein the temperature of the zinc melt in the step (2) is controlled to 650 ℃ to 720 ℃.
3. The method for manufacturing a 3mm Zn-Cu-Ti alloy wire according to claim 1, wherein the soaking time in the step (2) is controlled within 4 to 6 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262820A (en) * | 2021-12-22 | 2022-04-01 | 江苏中矿大正表面工程技术有限公司 | Novel zinc alloy wire for electric arc spraying and preparation method of coating |
| CN114293038A (en) * | 2021-12-27 | 2022-04-08 | 江苏中矿大正表面工程技术有限公司 | Preparation method of corrosion-resistant cerium-containing Zn-Cu-Ti coating |
| CN114293039A (en) * | 2021-12-27 | 2022-04-08 | 江苏中矿大正表面工程技术有限公司 | Preparation method of Zn-Cu-Ti-Mg alloy for thermal spraying |
| CN114309068A (en) * | 2021-12-22 | 2022-04-12 | 江苏中矿大正表面工程技术有限公司 | Continuous casting and rolling preparation method of novel zinc alloy wire |
| CN114309124A (en) * | 2021-12-27 | 2022-04-12 | 江苏中矿大正表面工程技术有限公司 | Preparation process of high-toughness zinc-based copper-titanium alloy wire |
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| CN106319424A (en) * | 2016-09-18 | 2017-01-11 | 梁振西 | Zinc-copper-titanium alloy wire for electric arc spraying and preparation process of zinc-copper-titanium alloy wire |
| CN108330307A (en) * | 2018-02-05 | 2018-07-27 | 南通鑫祥锌业有限公司 | A kind of electric arc spraying zinc-copper-titanium alloy silk material and its preparation process |
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| JPS59190336A (en) * | 1983-04-11 | 1984-10-29 | Sumitomo Electric Ind Ltd | Production of aluminum alloy wire |
| CN102534299A (en) * | 2012-02-06 | 2012-07-04 | 南京达迈科技实业有限公司 | Beryllium-free polybasic copper alloy |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262820A (en) * | 2021-12-22 | 2022-04-01 | 江苏中矿大正表面工程技术有限公司 | Novel zinc alloy wire for electric arc spraying and preparation method of coating |
| CN114309068A (en) * | 2021-12-22 | 2022-04-12 | 江苏中矿大正表面工程技术有限公司 | Continuous casting and rolling preparation method of novel zinc alloy wire |
| CN114262820B (en) * | 2021-12-22 | 2022-07-22 | 江苏中矿大正表面工程技术有限公司 | Novel zinc alloy wire for electric arc spraying and preparation method of coating |
| CN114309068B (en) * | 2021-12-22 | 2024-04-19 | 江苏中矿大正表面工程技术有限公司 | Continuous casting and rolling preparation method of novel zinc alloy wire |
| CN114293038A (en) * | 2021-12-27 | 2022-04-08 | 江苏中矿大正表面工程技术有限公司 | Preparation method of corrosion-resistant cerium-containing Zn-Cu-Ti coating |
| CN114293039A (en) * | 2021-12-27 | 2022-04-08 | 江苏中矿大正表面工程技术有限公司 | Preparation method of Zn-Cu-Ti-Mg alloy for thermal spraying |
| CN114309124A (en) * | 2021-12-27 | 2022-04-12 | 江苏中矿大正表面工程技术有限公司 | Preparation process of high-toughness zinc-based copper-titanium alloy wire |
| CN114293039B (en) * | 2021-12-27 | 2022-07-12 | 江苏中矿大正表面工程技术有限公司 | Preparation method of Zn-Cu-Ti-Mg alloy for thermal spraying |
| CN114309124B (en) * | 2021-12-27 | 2024-04-19 | 江苏中矿大正表面工程技术有限公司 | Preparation process of high-toughness zinc-based copper-titanium alloy wire |
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