CN113234947B - Nano copper-titanium alloy and preparation method thereof - Google Patents

Nano copper-titanium alloy and preparation method thereof Download PDF

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CN113234947B
CN113234947B CN202110545833.6A CN202110545833A CN113234947B CN 113234947 B CN113234947 B CN 113234947B CN 202110545833 A CN202110545833 A CN 202110545833A CN 113234947 B CN113234947 B CN 113234947B
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titanium alloy
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蒋燕
黄平
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Panzhihua University
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
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Abstract

The invention relates to a nano copper-titanium alloy and a preparation method thereof, belonging to the technical field of alloy preparation. The invention aims to provide a preparation method of a nano copper-titanium alloy with good high-temperature stability. The method comprises the following steps: a. putting copper and titanium into the same copper crucible of an electric arc melting furnace, and then sealing to remove oxygen in the electric arc melting furnace; b. adjusting current to melt copper and titanium, then stirring and melting for 40-60 s, and then closing current for cooling; c. and repeating the step b at least once to obtain the nano copper-titanium alloy. The method can obtain the nano copper-titanium alloy at one time, has simple steps, simple required equipment, quick operation, short preparation period and low cost, and can realize the preparation of the alloy within a few minutes. The prepared nano copper-titanium alloy has good high-temperature stability, better plastic deformation capability at room temperature and wider application range.

Description

Nano copper-titanium alloy and preparation method thereof
Technical Field
The invention relates to a nano copper-titanium alloy and a preparation method thereof, belonging to the technical field of alloy preparation.
Background
Copper materials have been widely used in electronic components and industrial parts due to their high electrical and thermal conductivity, and are also important parts for the military industry and aircraft manufacturing industry in the future. The copper-titanium alloy is a representative copper material, has good mechanical properties, is a potential substitute material for copper-beryllium alloy, and has wide market application prospect. Most current-carrying components have been made of copper beryllium alloy, but the high cost of beryllium and the long-term environmental and health hazards that it presents require the development of materials with comparable properties. The preparation cost of the copper-titanium alloy is far lower than that of copper-beryllium, the copper-titanium alloy is environment-friendly, and if the copper-titanium alloy can simultaneously meet the requirements of electrical conductivity, mechanical property and high-temperature thermal stability, the application of the copper-titanium alloy is not limited to current-carrying components and can also be expanded to the military industry and the aircraft manufacturing industry.
Titanium plays a role in solid solution strengthening in copper, the alloy strength tends to increase along with the increase of the titanium content, but the alloy conductivity obviously decreases along with the increase of the titanium content. In order to balance mechanical properties and electrical conductivity, the titanium content is generally within 5%. At present, most of research focuses on improving the comprehensive performance of the copper-titanium alloy by adding a plurality of trace elements, the mechanical properties of the prepared multi-element copper-titanium alloy are increased compared with those of the binary copper-titanium alloy, but the thermal conductivity of other elements is lower than that of pure copper, and the electron scattering is increased. The ternary or multi-element copper-titanium alloy not only needs to adjust the optimized content of each element, but also needs to adjust the final structure proportion to solve the contradiction between the mechanical property and the conductivity, the preparation process is complex, and the obtained alloy material usually has higher tensile strength and lower elongation, and has no remarkable comprehensive effect. In the aspect of the preparation method, the performance is improved mainly through a series of deformation and aging treatment, and oxygen impurities are inevitably introduced in the process, so that the cost is increased.
The Chinese patent with the application number of 201410474358.8 discloses a copper-titanium alloy material and a preparation method thereof, wherein the copper-titanium alloy comprises Ti, Cr, Ca, Ni, V, Zn and Cu, is a seven-element copper-titanium alloy, has more alloy elements, adopts a step-by-step smelting method in the preparation method, lasts for more than 6 hours, and has lower smelting efficiency. The tensile strength of the alloy at room temperature exceeds 1000MPa, and the elongation and other properties are unknown.
The Chinese patent with application number 201410471560.5 discloses a CuTi elastic copper alloy and a preparation method thereof, and the multi-element copper-titanium alloy is prepared by smelting, rolling and heat treatment in sequence, wherein the strength of the copper-titanium alloy exceeds 1000MPa, but the elongation is only about 5%, which is not enough to be used at high temperature.
The Chinese patent with the application number of 201910334755.8 discloses a preparation method of an ultrafine grain copper-titanium alloy wire, which adopts a powder metallurgy route preparation method to obtain a copper-titanium alloy material containing nano-titanium, wherein the alloy has good hardness, strength and conductivity, the elongation is 5-8%, the method is complicated, and the high-temperature stability of the prepared alloy needs to be improved.
The Chinese patent application No. 201911368576.2 discloses a high-strength high-conductivity copper-titanium alloy material and a preparation method thereof, which still adopts a powder metallurgy route preparation method, realizes the high conductivity of the formed copper-titanium alloy material by adding less titanium powder, and controls the growth of crystal grains in the sintering process by lower sintering temperature, thereby keeping the copper-titanium alloy material with higher strength.
It can be seen that the currently developed copper-titanium alloy completely meets the mechanical property requirement at room temperature, but the copper-titanium alloy with high-temperature thermal stability is still lacking.
Disclosure of Invention
Aiming at the defects, the first technical problem solved by the invention is to provide a preparation method of the nano copper-titanium alloy with better high-temperature stability.
The preparation method of the nano copper-titanium alloy comprises the following steps:
a. putting copper and titanium into the same copper crucible of an electric arc melting furnace, and then sealing to remove oxygen in the electric arc melting furnace;
b. adjusting current to melt copper and titanium, then stirring and melting for 40-60 s, and then closing current for cooling;
c. and repeating the step b at least once to obtain the nano copper-titanium alloy.
In one embodiment of the invention, in the step a, the method for removing oxygen in the arc melting furnace comprises the following steps: putting zirconium into another crucible of the arc melting furnace, vacuumizing the arc melting furnace, introducing inert gas, and before alloy melting, starting arc to melt the zirconium in the other crucible.
In one embodiment of the invention, the vacuum is applied to10-1Introducing inert gas to 0.01-0.05 MPa below Pa.
In one embodiment of the present invention, the temperature is cooled to 25 ℃ or lower, and the gas pressure in the arc melting furnace is 0.04 to 0.06 MPa.
In one embodiment of the present invention, the current is adjusted to 200 to 250A during melting.
In one embodiment of the present invention, in the step c, the step b is repeated three times.
In one embodiment of the present invention, the nano copper-titanium alloy contains 0.1 to 5 wt% of titanium, and the balance is copper and inevitable impurities.
In one embodiment of the present invention, the nano-copper-titanium alloy contains 4 wt% of titanium, and the balance is copper and inevitable impurities.
The invention also provides the nano copper-titanium alloy prepared by the preparation method of the nano copper-titanium alloy.
The nano copper-titanium alloy is a binary alloy, has simple components, low cost, good high-temperature stability, good plastic deformation capability at room temperature and wide application range.
Compared with the prior art, the invention has the following beneficial effects:
the method can obtain the nano copper-titanium alloy at one time, has simple required equipment, quick operation, short preparation period and low cost, can realize the preparation of the alloy within a few minutes, and has the whole process from startup to shutdown within 1 hour. Because the density difference exists between the copper and the titanium, the continuous stirring and mixing are carried out in a molten state, so that the uniform mixing between the copper and the titanium solution can be better promoted, and the titanium can be quickly and uniformly dissolved in the copper; meanwhile, the smelting time is short, the precipitation of titanium is less, the content of intermetallic compounds is low, and the size of the copper matrix can reach nanometer. The prepared nano copper-titanium alloy has good high-temperature stability, better plastic deformation capability at room temperature and wider application range.
Drawings
FIG. 1 shows the metallographic morphology (left) and the metallographic SEM morphology (right) of the Cu-4Ti alloy prepared in example 1.
FIG. 2 is a surface-scanning distribution diagram of the Cu-4Ti alloy prepared in example 1.
FIG. 3 shows the morphology and size of Cu grains in the Cu-4Ti alloy prepared in example 1.
FIG. 4 shows tensile properties of Cu-4Ti alloy prepared in example 1 at different temperatures.
Detailed Description
The preparation method of the nano copper-titanium alloy comprises the following steps:
a. putting copper and titanium into the same copper crucible of an electric arc melting furnace, and then sealing to remove oxygen in the electric arc melting furnace;
b. adjusting current to melt copper and titanium, then stirring and melting for 40-60 s, and then closing current for cooling;
c. and repeating the step b at least once to obtain the nano copper-titanium alloy.
The method can obtain the nano copper-titanium alloy at one time, has simple steps, simple required equipment, quick operation, short preparation period and low cost, and can realize the preparation of the alloy within a few minutes. The prepared nano copper-titanium alloy has good high-temperature stability, better plastic deformation capability at room temperature and wider application range.
For low melting point materials, smelting is the best method for obtaining nearly full densification, but most smelting ingots are coarse-grained structures at present; and because titanium is easily precipitated at high temperature and forms intermetallic compounds with copper, the elongation is significantly reduced. The method of the invention can better promote the uniform mixing between the copper and the titanium solution by continuously stirring and mixing in a molten state, so that the titanium can be quickly and uniformly dissolved in the copper; meanwhile, the smelting time is short, because of the intermittent current-carrying mode, and because the copper crucible is fast in water cooling, the precipitation of titanium is less, the content of intermetallic compounds is low, and the size of the copper matrix can reach nanometer, so that the nanometer copper-titanium alloy is obtained.
Step a is mainly a preparation step before smelting, copper and titanium are put into the same copper crucible of an electric arc smelting furnace, and then the copper crucible is sealed to remove oxygen in the electric arc smelting furnace.
The method for removing oxygen in the arc melting furnace, which is commonly used in the field, can be applied to the invention, such as introducing protective gas after vacuumizing and the like.
In one embodiment of the present invention, oxygen is removed from an arc melting furnace using the following method: putting zirconium into another crucible of the arc melting furnace, vacuumizing the arc melting furnace, introducing inert gas, and before alloy melting, starting arc to melt the zirconium in the other crucible. Because zirconium has a strong oxygen affinity, zirconium can adsorb free oxygen in the cavity. By adopting the method, oxygen can be further removed, and impurities can be reduced.
In one embodiment of the invention, the vacuum is applied to 10 deg.C-1Pa or less, e.g. 10-3~10-1Pa, and introducing inert gas to 0.01-0.05 MPa. The pressure interval is adopted, and the result after the experimental temperature and the bearable pressure of the cavity are considered, so that the positive pressure in the cavity can be smaller than the bearable pressure of the cavity even if the pressure in the cavity is heated and expanded at the working temperature, and the safety of equipment is ensured.
The inert gas in the invention is a gas which does not participate in the reaction, such as helium, neon, argon and the like. In one embodiment of the invention, the inert gas is high purity argon.
The step b is a primary smelting process. Adjusting the current to melt the copper and the titanium, then stirring and melting for 40-60 s, and then closing the current for cooling. When smelting, the magnetic stirring equipment needs to be opened, so that the copper and the titanium are mixed more uniformly. After the smelting is carried out for a period of time, cooling is needed, the air pressure is reduced, the atmosphere in the protective cavity is clean, and equipment accessories are safe.
In one embodiment of the invention, the temperature is reduced to below 25 ℃, generally, a water-cooled copper crucible is adopted, the temperature can be displayed by observing the air pressure value and the cooling water, when the air pressure value is reduced to about 0.05MPa and the temperature of the cooling water is reduced to below 25 ℃, the current is started again, and the next smelting is carried out.
The current is related to the melting point of the material, and when the current is adjusted, the melting condition of the material needs to be observed so as to achieve melting. In one embodiment of the present invention, the current is adjusted to 200 to 250A during melting.
The smelting of the invention is repeated intermittent smelting, namely, the current is closed after the smelting is carried out for a certain time, and the current is opened for continuous smelting after the smelting is cooled for a certain time, so as to protect the clean atmosphere in the cavity and the safety of the cavity parts. In one embodiment of the invention, in step c, step b is repeated three times, i.e. four heats in total.
The method of the invention is suitable for smelting alloys with various copper and titanium contents. Copper-titanium alloys with different titanium contents and different properties can be obtained by adjusting the content ratio of copper to titanium. In one embodiment of the present invention, the nano copper-titanium alloy contains 0.1 to 5 wt% of titanium, and the balance is copper and inevitable impurities.
In one embodiment of the present invention, the nano-copper-titanium alloy contains 4 wt% of titanium, and the balance is copper and inevitable impurities.
The invention also provides the nano copper-titanium alloy prepared by the preparation method of the nano copper-titanium alloy.
The nano copper-titanium alloy is a binary alloy, has simple components, low cost, good high-temperature stability, good plastic deformation capability at room temperature and wide application range.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
The binary Cu-4Ti alloy comprises 4 wt% of Ti and the balance of copper and inevitable impurities. The preparation method comprises the following specific steps:
step 1: placing a zirconium block in one of the crucibles in a chamber of the arc melting furnace;
step 2: putting a copper block and a titanium block into one copper crucible of an electric arc melting furnace together according to the mass fraction ratio of 96: 4; and then cleaning the cavity to reduce impurities such as oxygen, nitrogen and the like. The cleaning method comprises the following steps: vacuum pumping is carried out to 10-1Pa, and then filling high-purity argon to ensure that the air pressure in the cavity is 0.05 MPa.
And step 3: firstly, arc striking is carried out to melt the zirconium ingot in one of the crucibles, so as to remove oxygen again and reduce impurities.
And 4, step 4: and 3, after the step 3 is finished, adjusting the current to melt the copper and the titanium blocks in the crucible, simultaneously turning on the magnetic stirring equipment to mix the copper and the titanium blocks more uniformly, turning off the current after the melting is carried out for about 60 seconds, and cooling the water to below 25 ℃ when the air pressure value is reduced to about 0.05MPa so as to protect the atmosphere in the cavity to be clean and the cavity parts to be safe.
And 5: repeating the step 4 for three times to uniformly mix the titanium and the copper and fully dissolve the titanium into the copper. I.e., four heats in total, takes about 4 minutes to heat, and samples were taken for about 1 hour in total from start-up to shut-down. Finally obtaining the nano copper-titanium alloy which is marked as Cu-4Ti alloy.
The metallographic morphology of the alloy is shown in the left side of the figure 1, and the metallographic SEM morphology is shown in the right side of the figure 1. The surface scanning distribution diagram is shown in figure 2, the crystal grain appearance and size are shown in figure 3, the tensile property at different temperatures is shown in figure 4, and #1 and #2 in figure 4 are two parallel samples of the Cu-4Ti alloy.
The hardness of the obtained Cu-4Ti alloy was 268. + -. 4(HV0.2), and XRD detected copper and a small amount of Cu3Peak of the Ti two phases. The metallographic phase and SEM morphology of the alloy are shown in figure 1, the alloy is composed of two different structures, the energy spectrum surface scanning result is shown in figure 2, and the results show that the middle part of the precipitate is mainly copper (a small amount of dissolved titanium), the edge of the precipitate is a braided copper-titanium intermetallic compound, and the rest part is copper (a large amount of dissolved titanium), wherein the grain size of the copper is less than 100nm, and is shown in figure 3. The tensile curves of the obtained Cu-4Ti alloy at different temperatures are shown in fig. 4. The average mechanical properties of the alloy are shown in table 1.
TABLE 1
Figure BDA0003073467330000051
Therefore, the yield strength of the copper-titanium alloy obtained by the method is equivalent to the room temperature at 450 ℃, the high-temperature elongation is higher, and the tensile strength is reduced by less than 4% compared with the room temperature. The high temperature stability remained good.

Claims (7)

1. The preparation method of the nano copper-titanium alloy is characterized by comprising the following steps of:
a. putting copper and titanium into the same copper crucible of an electric arc melting furnace, and then sealing to remove oxygen in the electric arc melting furnace;
b. adjusting current to melt copper and titanium, then stirring and melting for 40-60 s, then closing current for cooling, cooling to below 25 ℃, and reducing the pressure in the arc melting furnace to 0.04-0.06 MPa;
c. repeating the step b at least once to obtain the nano copper-titanium alloy;
the copper crucible is a water-cooled copper crucible, and the nano copper-titanium alloy contains 0.1-5 wt% of titanium and the balance of copper and inevitable impurities.
2. The method for preparing a nano copper-titanium alloy according to claim 1, wherein the method comprises the following steps: in the step a, the method for removing oxygen in the arc melting furnace comprises the following steps: putting zirconium into another crucible of the arc melting furnace, vacuumizing the arc melting furnace, introducing inert gas, and before alloy melting, starting arc to melt the zirconium in the other crucible.
3. The method for preparing a nano copper-titanium alloy according to claim 2, wherein: vacuum pumping is carried out to 10-1Introducing inert gas to 0.01-0.05 MPa below Pa.
4. The method for preparing a nano copper-titanium alloy according to claim 1, wherein the method comprises the following steps: in the step b, the current is 200-250A.
5. The method for preparing a nano copper-titanium alloy according to claim 1, wherein the method comprises the following steps: in the step c, the step b is repeated for 3 times.
6. The method for preparing a nano copper-titanium alloy according to claim 1, wherein the method comprises the following steps: the titanium content was 4 wt%.
7. The nano copper-titanium alloy prepared by the preparation method of the nano copper-titanium alloy according to any one of claims 1 to 6.
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