CN109852840B - Copper-titanium alloy and preparation method thereof - Google Patents

Copper-titanium alloy and preparation method thereof Download PDF

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CN109852840B
CN109852840B CN201910261814.3A CN201910261814A CN109852840B CN 109852840 B CN109852840 B CN 109852840B CN 201910261814 A CN201910261814 A CN 201910261814A CN 109852840 B CN109852840 B CN 109852840B
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copper
titanium alloy
sintering
powder
alloy
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CN109852840A (en
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王聪
范永刚
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Shenyang Neu New Industrial Technology Research Institute Co ltd
Northeastern University China
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Shenyang Neu New Industrial Technology Research Institute Co ltd
Northeastern University China
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Abstract

The invention relates to a copper-titanium alloy and a preparation method thereof, wherein the alloy comprises components and mass thereofThe percentage is as follows: cu powder: 64 to 66 percent of TiH2Powder: 34-36 percent. The preparation method comprises the following steps: mixing Cu powder and TiH according to the component proportion of the copper-titanium alloy2And uniformly mixing the powder, preparing a mixture, performing compression molding at the molding pressure of 35-100 MPa and the pressure maintaining time of 10-30 min to prepare an alloy green body, sintering in an inert gas atmosphere at the temperature rising rate of 5-10 ℃/min from room temperature to the sintering temperature of 1085-1150 ℃, cooling and discharging after the sintering time is 10-60 min to prepare the copper-titanium alloy. The copper-titanium alloy prepared by the method has extremely high hardness and toughness, and simultaneously has good brittleness and thermal conductivity. And the raw materials are easy to obtain, and the mixing time is short. By accurately controlling the sintering temperature, the heating rate and the heat preservation time, the prepared alloy not only has the components meeting the requirements, but also has the performance guaranteed.

Description

Copper-titanium alloy and preparation method thereof
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a copper-titanium alloy and a preparation method thereof.
Background
Since the thirties of the twentieth century, copper-titanium alloys have been studied and various intermetallic compounds of copper and titanium have been discovered, and although the research has been relatively early, the copper-titanium alloys have not been paid sufficient attention. At present, most of research on copper-titanium alloys focuses on copper-rich areas, which are areas where only part of titanium is dissolved in copper and where the solubility of titanium changes greatly with temperature, so that aging strengthening can be easily performed. Research shows that the mechanical and physical properties of age-hardened copper-titanium alloy (1-6 wt.% Ti) can be compared favorably with those of copper-beryllium alloy. Although copper-beryllium alloy has excellent physical properties and mechanical properties, beryllium has certain toxicity and can harm human health in the using process, so that the research on the copper-titanium alloy as a substitute of the toxic copper-beryllium alloy becomes very significant.
The microhardness test of the reaction layer formed by the diffusion of copper and titanium simultaneously shows that the hardness of the intermetallic compound is far higher than that of the pure copper or pure titanium metal matrix, so that the intermetallic compound can be used as a reinforcing phase of certain materials. For example, in the copper-based boron nitride grinding wheel, titanium element is added as an active element to react with boron nitride to generate titanium nitride and titanium boride, so that chemical connection between a metal matrix and a boron nitride grinding material is established, the holding force of the matrix on the boron nitride is enhanced, and the grinding wheel can be effectively prevented from losing efficacy due to falling of the boron nitride grinding material. Meanwhile, copper and titanium also react to generate intermetallic compounds which can be used as a reinforcing phase to obviously improve the strength of a copper matrix and prolong the service life of the grinding wheel. The conductive material has good conductivity, and thus can be used as a cable, a transformer coil or a conductive sheet, a high-strength spring, an electrical contact, a lead frame in an integrated circuit package, a separator, or the like. And the related data show that both copper and titanium are excellent marine corrosion resistant materials, and titanium ingots are taken out after being placed on the seabed for decades to remain bright, so that the copper-titanium intermetallic compound has excellent marine corrosion resistance and can be used as a corrosion resistant coating or a structural material under marine working conditions. However, little research has been done specifically on the copper-titanium alloy in the intermediate region, and research in this area is almost blank.
Disclosure of Invention
In order to solve the problems, the invention provides a copper-titanium alloy and a preparation method thereof, wherein the alloy has high hardness, excellent toughness and good brittleness, and the specific technical scheme is as follows:
the copper-titanium alloy comprises the following components in percentage by mass: cu powder: 64 to 66 percent of TiH2Powder: 34-36 percent.
The microhardness of the copper-titanium alloy is 450-500 HV, and the impact toughness is 28-45J/cm2The fracture toughness is 5 to 11 MPa.m1/2。
The preparation method of the copper-titanium alloy comprises the following steps:
step 1, mixing materials: mixing Cu powder and TiH according to the component proportion of the copper-titanium alloy2Uniformly mixing the powder to prepare a mixture;
step 2, forming and demolding:
pressing and forming the mixture to obtain an alloy green body, wherein the forming pressure is 35-100 MPa, and the pressure maintaining time is 10-30 min;
and 3, sintering:
(1) sintering the alloy green body, raising the temperature from room temperature to a sintering temperature of 1085-1150 ℃ at a temperature raising rate of 5-10 ℃/min, and sintering for 10-60 min, wherein: the sintering operation is carried out in an inert gas atmosphere;
(2) cooling to less than or equal to 40 ℃ after sintering, and discharging to obtain the copper-titanium alloy.
In the step 1, Cu powder and TiH2The particle size range of the powder is 45-60 mu m.
In the step 1, the material mixing time is 0.5-2 h.
In the step 2, the compression molding is carried out at room temperature, and the process is as follows: and uniformly putting the mixture into a die, and performing compression molding under corresponding parameters.
And in the step 2, a hydraulic press is adopted for compression molding.
In the step 2, a steel mould is used for demoulding.
In the step 3(1), the inert gas atmosphere is used for isolating air, so that the sintering process is carried out under oxygen-free conditions, and the inert gas is argon.
In the step 3(2), the prepared copper-titanium alloy comprises Cu3Ti2And Cu4Ti3Phase, component structure homogeneous, Cu3Ti2And Cu4Ti3The tissues are mutually wrapped and are distributed uniformly, and hardness tests show that the material not only has extremely high hardness, but also has excellent toughness and good fracture performance.
In the preparation process of the copper-titanium alloy, TiH2Firstly decomposing to provide active metal Ti, then carrying out a reaction between Ti and Cu, and carrying out a series of phase changes to finally generate a target alloy phase, wherein the specific final reaction formula is as follows:
TiH2＝Ti+H2and 7Cu +5Ti ═ Cu3Ti2+Cu4Ti3
Compared with the existing copper-titanium alloy, the copper-titanium alloy has the beneficial effects that:
(1) the copper-titanium alloy disclosed by the invention has extremely high hardness, and has good brittleness and good thermal conductivity while keeping high hardness and excellent toughness.
(2) The preparation method provided by the invention has the advantages of easily-obtained raw materials, low cost and short mixing time. By accurately controlling the sintering temperature, the heating rate and the heat preservation time, the prepared alloy not only has the components meeting the requirements, but also has the performance guaranteed.
Drawings
FIG. 1 shows Cu in the Cu-Ti alloy prepared in example 34Ti3An alloy phase metallographic microscopic morphology map;
FIG. 2 shows Cu in the Cu-Ti alloy prepared in example 34Ti3A metallographic microscopic morphology graph of the alloy phase after the microhardness experiment is carried out;
FIG. 3 shows Cu in the Cu-Ti alloy prepared in example 33Ti2An alloy phase metallographic microscopic morphology map;
FIG. 4 shows Cu in the Cu-Ti alloy prepared in example 33Ti2And (4) carrying out a metallographic microscopic morphology graph after the alloy phase is subjected to a microhardness experiment.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to these examples.
Example 1
The copper-titanium alloy comprises the following components in percentage by mass: cu powder: 64% of TiH2Powder: 36 percent; cu powder and TiH2The sum of the mass percentages of the powders is 100 percent.
The preparation method of the copper-titanium alloy comprises the following steps:
step 1, mixing materials: according to the component proportion of the copper-titanium alloy, Cu powder and TiH with the grain size range of 45 mu m2Uniformly mixing the powder for 1h to prepare a mixture A;
step 2, forming: uniformly putting the mixture A into a die, cold-pressing and molding under the pressure of 100MPa for 10min to obtain an alloy green body;
step 3, demolding: demolding the pressed alloy green body;
and 4, sintering:
(1) sintering the alloy green body in an inert gas atmosphere, heating the alloy green body from room temperature to a sintering temperature of 1085 ℃ at a heating rate of 10 ℃/min, and sintering for 60 min;
(2) cooling to less than or equal to 40 ℃ after sintering, and discharging to obtain the copper-titanium alloy, wherein the copper-titanium alloy comprises Cu3Ti2And Cu4Ti3Phase, component structure homogeneous, Cu3Ti2And Cu4Ti3The tissues are mutually wrapped and are distributed uniformly, and the microhardness is 450HV and the impact toughness is 45J/cm through testing2Fracture toughness of 5MPa m1/2。
Example 2
The copper-titanium alloy comprises the following components in percentage by mass: cu powder: 65% of TiH2Powder: 35 percent.
The preparation method of the copper-titanium alloy comprises the following steps:
step 1, mixing materials:
mixing Cu powder and TiH according to the component proportion of the copper-titanium alloy2The powders are mixed evenly for 1h to prepare a mixture A, the Cu powder and the TiH2The particle size range of the powder is 60 mu m;
step 2, forming:
uniformly putting the mixture A into a die, cold-pressing and molding at the pressure of 35MPa for 30min to obtain an alloy green body;
step 3, demolding:
demolding the pressed alloy green body;
and 4, sintering:
(1) sintering the alloy green body in an inert gas atmosphere, raising the temperature from room temperature to 1150 ℃ at the temperature raising rate of 5 ℃/min, and sintering for 10 min;
(2) cooling to less than or equal to 40 ℃ after sintering, discharging to obtain the copper-titanium alloy comprising Cu3Ti2And Cu4Ti3Phase, component structure homogeneous, Cu3Ti2And Cu4Ti3The tissues are mutually wrapped and are distributed uniformly, and the microhardness is 460HV and the impact toughness is 40J/cm through testing2The fracture toughness is 6 MPa.m1/2。
Example 3
The copper-titanium alloy comprises the following components in percentage by mass: cu powder: 66% of TiH2Powder: 36 percent.
The preparation method of the copper-titanium alloy comprises the following steps:
step 1, mixing materials:
mixing Cu powder and TiH according to the component proportion of the copper-titanium alloy2The powders are mixed evenly for 1h to prepare a mixture A, the Cu powder and the TiH2The particle size range of the powder is 50 mu m;
step 2, forming:
uniformly putting the mixture A into a die, cold-pressing and molding at the pressure of 75MPa for 20min to obtain an alloy green body;
step 3, demolding:
demolding the pressed alloy green body;
and 4, sintering:
(1) sintering the alloy green body in an inert gas atmosphere, heating the alloy green body from room temperature to the sintering temperature of 1100 ℃ at the heating rate of 10 ℃/min, and sintering for 40 min;
(2) cooling to less than or equal to 40 ℃ after sintering, and discharging to obtain the copper-titanium alloy, wherein the copper-titanium alloy comprises Cu3Ti2And Cu4Ti3Phase, Cu3Ti2And Cu4Ti3The tissues are mutually wrapped and are distributed more uniformly, and Cu in the alloy4Ti3The metallographic microstructure of the alloy phase is shown in figure 1, Cu3Ti2The metallographic microscopic morphology of the alloy phase is shown in FIG. 3, and after the hardness test of the copper-titanium alloy, Cu is obtained4Ti3The metallographic microscopic morphology of the alloy phase after the microhardness test is shown in FIG. 2, Cu3Ti2The metallographic microscopic morphology of the alloy phase after the microhardness test is shown in FIG. 4, and the microhardness is 500HV and the impact toughness is 28J/cm after the test2Fracture toughness of 11MPa m1/2。
Example 4
The copper-titanium alloy comprises the following components in percentage by mass: cu powder: 64.5% by weight, TiH2Powder: 35.5 percent.
The preparation method of the copper-titanium alloy comprises the following steps:
step 1, mixing materials:
according to the component proportion of the copper-titanium alloy, Cu powder and TiH with the grain size range of 40 mu m2Uniformly mixing the powder for 1h to prepare a mixture A;
step 2, forming:
uniformly putting the mixture A into a die, cold-pressing and molding at the pressure of 50MPa for 25min to obtain an alloy green body;
step 3, demolding:
demolding the pressed alloy green body;
and 4, sintering:
(1) sintering the alloy green body in an inert gas atmosphere, heating from room temperature to a sintering temperature of 1125 ℃ at a heating rate of 7 ℃/min, and sintering for 25 min;
(2) cooling to less than or equal to 40 ℃ after sintering, discharging to obtain the copper-titanium alloy comprising Cu3Ti2And Cu4Ti3Phase, component structure homogeneous, Cu3Ti2And Cu4Ti3The tissues are mutually wrapped and are distributed uniformly, and the microhardness is 470HV and the impact toughness is 35J/cm through testing2The fracture toughness is 8 MPa.m1/2。
Example 5
The copper-titanium alloy comprises the following components in percentage by mass: cu powder: 65.5% of TiH2Powder: 34.5 percent.
The preparation method of the copper-titanium alloy comprises the following steps:
step 1, mixing materials:
mixing Cu powder and TiH according to the component proportion of the copper-titanium alloy2The powders are mixed evenly for 1h to prepare a mixture A, the Cu powder and the TiH2The particle size range of the powder is 50 mu m;
step 2, forming:
uniformly putting the mixture A into a die, cold-pressing and molding at the pressure of 50MPa for 20min to obtain an alloy green body;
step 3, demolding:
demolding the pressed alloy green body;
and 4, sintering:
(1) sintering the alloy green body in an inert gas atmosphere, heating the alloy green body from room temperature to the sintering temperature of 1100 ℃ at the heating rate of 10 ℃/min, and sintering for 30 min;
(2) cooling to less than or equal to 40 ℃ after sintering, discharging to obtain the copper-titanium alloy comprising Cu3Ti2And Cu4Ti3Phase, component structure homogeneous, Cu3Ti2And Cu4Ti3The tissues are mutually wrapped and are distributed uniformly, and the microhardness is 490HV and the impact toughness is 30J/cm through testing2A fracture toughness of 10MPa m1/2。

Claims (7)

1. The preparation method of the copper-titanium alloy is characterized in that the copper-titanium alloy comprises the following components in percentage by mass: cu powder: 64 to 66 percent of TiH2Powder: 34-36%; the method comprises the following steps:
step 1, mixing materials: mixing Cu powder and TiH according to the component proportion of the copper-titanium alloy2Uniformly mixing the powder to prepare a mixture;
step 2, forming and demolding:
pressing and forming the mixture to obtain an alloy green body, wherein the forming pressure is 35-100 MPa, and the pressure maintaining time is 10-30 min;
and 3, sintering:
(1) sintering the alloy green body, raising the temperature from room temperature to a sintering temperature of 1085-1150 ℃ at a temperature raising rate of 5-10 ℃/min, and sintering for 10-60 min, wherein: the sintering operation is carried out in an inert gas atmosphere;
(2) cooling to less than or equal to 40 ℃ after sintering, and discharging to obtain the copper-titanium alloy.
2. The method of claim 1, wherein in step 1, the Cu powder and the TiH powder are mixed2Particle size range of powderThe circumference is 45-60 mu m.
3. The method for preparing a copper-titanium alloy according to claim 1, wherein in the step 2, the press forming is performed at room temperature by the following steps: and uniformly putting the mixture into a die, and performing compression molding under corresponding parameters.
4. The method of claim 1, wherein in step 3(1), the inert gas atmosphere is designed to exclude air, so that the sintering process is performed under oxygen-free conditions, and the inert gas is argon.
5. The method for preparing the copper-titanium alloy according to claim 1, wherein in the step 3(1), the following reactions occur in sequence during the sintering process:
TiH2=Ti+H2；
7Cu+ 5Ti = Cu3Ti2+ Cu4Ti3。
6. the method of claim 1, wherein in step 3(2), the prepared copper-titanium alloy comprises Cu3Ti2And Cu4Ti3Phase, component structure homogeneous, Cu3Ti2And Cu4Ti3The tissues are wrapped around each other.
7. The method for preparing the copper-titanium alloy according to claim 1, wherein in the step 3(2), the prepared copper-titanium alloy has microhardness of 450-500 HV and impact toughness of 28-45J/cm2The fracture toughness is 5 to 11 MPa.m1/2。
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