CN115740458A - Preparation method of molybdenum-copper alloy section bar - Google Patents
Preparation method of molybdenum-copper alloy section bar Download PDFInfo
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Abstract
The invention discloses a preparation method of a molybdenum-copper alloy section, which comprises the following steps: step 1, preparing copper-coated molybdenum composite powder; step 2, preparing mixed powder according to the product obtained in the step 1, supplemented molybdenum powder and induced copper powder; step 3, performing cold press molding treatment on the mixed powder prepared in the step 2, and step 4, performing cold press molding in the step 3, and performing infiltration sintering to obtain a molybdenum-copper alloy billet; step 5, carrying out lamination rolling on the molybdenum-copper alloy billet subjected to solution infiltration sintering in the step 4 to obtain a molybdenum-copper alloy plate; and 6, grinding the molybdenum-copper alloy plate obtained in the step 5 to obtain the molybdenum-copper alloy plate. The copper-molybdenum alloy section prepared by the invention solves the problems of low density, poor heat and electric conductivity and high expansion coefficient in the traditional molybdenum-copper alloy preparation process.
Description
Technical Field
The invention belongs to the technical field of composite material preparation and modification processing, and relates to a preparation method of a molybdenum-copper alloy profile.
Background
With the development of integrated circuits in the field of microelectronics to large storage capacity and high speed and the development of assemblies in the direction of miniaturization and thinning, the packaging heat sink material is required to meet the requirements of high-low (three-high-low), namely, (1) the material has good heat conductivity and electrical conductivity and can timely dissipate heat generated by a semiconductor chip during operation, (2) the material has low thermal expansion coefficient, good matching property, solderability and corrosion resistance, (3) the material has sufficient strength, rigidity and formability, and (4) the material has low cost as much as possible so as to meet the requirements of large-scale commercial application. To date, conventional single metals (Al, cu, mo, W) or alloys (Kovar, invar) have not been able to meet the requirements for high-integration chips and circuits. The metal-based molybdenum-copper composite material is a structure formed by uniformly mixing two-phase monomers which are formed by molybdenum and copper and are not mutually soluble and form intermetallic compounds, the molybdenum-copper alloy has the excellent characteristics of high melting point, high density, strong electric corrosion resistance, low thermal expansion coefficient of Mo, high electric conductivity, thermal conductivity, certain plasticity and the like of Cu, and the corresponding mechanical and physical properties of the material can be controlled and adjusted by changing the composition proportion. Due to the characteristics, the molybdenum-copper alloy can be widely applied to the fields of electronic packaging, radiators and the like. However, because the melting point difference between molybdenum and copper is large, the solubility is extremely low under a balanced condition, and the electronegativity difference is obvious, the alloy material prepared by adopting the traditional process has low density and poor electric and heat conducting properties. Therefore, it is necessary to find an economical and efficient technique for preparing the molybdenum-copper alloy material with more excellent performance.
Disclosure of Invention
The invention aims to provide a preparation method of a molybdenum-copper alloy profile, and the copper-molybdenum alloy profile prepared by the method solves the problems of low density, poor heat and electric conductivity and high expansion coefficient in the traditional molybdenum-copper alloy preparation process.
The technical scheme adopted by the invention is that the preparation method of the molybdenum-copper alloy section bar specifically comprises the following steps:
step 5, carrying out lamination rolling on the molybdenum-copper alloy billet subjected to solution infiltration sintering in the step 4 to obtain a molybdenum-copper alloy plate;
and 6, grinding the molybdenum-copper alloy plate obtained in the step 5 to obtain the molybdenum-copper alloy plate.
The invention is also characterized in that:
the specific process of the step 1 is as follows:
step 1.1, carrying out ultrasonic cleaning on molybdenum powder in an absolute ethyl alcohol solvent for 15-30 min, and drying; step 1.2, cleaning the sample prepared in the step 1.1 in a sodium hydroxide solution with the concentration of 10-20 g/L for 25-40 min to remove grease attached to the surface, soaking the molybdenum powder after deoiling in hydrochloric acid with the concentration of 35-40%, and coarsening for 25-40 min;
step 1.3, adding the molybdenum powder treated in the step 1.2 into chemical plating solution, wherein the chemical plating process is carried out in a heat collection type magnetic stirrer, the heat collection type magnetic stirrer keeps the temperature of the plating solution at 55-60 ℃, 10% -15% of sodium hydroxide solution is dropwise added into the chemical plating solution, the pH value of the plating solution is adjusted to 12-13, when the specified pH value interval is reached, after 25-30 s incubation period, the reaction starts, bubbles gradually escape, and when the bubbles of the plating solution disappear, the chemical plating is finished;
step 1.4, curing and sintering for 1-2 hours at 300-500 ℃ in a reducing atmosphere to obtain copper-coated molybdenum composite powder, wherein the copper content in the coated powder accounts for 17% -19%.
The specific process of the step 2 is as follows: mechanically mixing the copper-coated molybdenum composite powder prepared in the step 1 with complementary molybdenum powder and induced copper powder in a mixer for 30-90 min, and adding 10-20 mL/kg of gasoline solvent during mixing to finally obtain uniform mixed powder.
The specific process of the step 3 is as follows: and (3) weighing the mixed powder obtained in the step (2), filling the mixed powder into a cavity of a steel pressing die, performing cold press molding, selecting the pressing pressure of 600-800 MPa, keeping the pressure for 10-15 s, and finally demolding to obtain a billet with determined size and shape.
The specific process of the step 4 is as follows: and (3) loading the green body formed by cold pressing in the step (3) into a graphite boat or a ceramic boat, burying the periphery of the copper block to be dissolved and infiltrated with alumina sand, heating to 1300-1350 ℃ at the speed of 6-10 ℃/min under a protective atmosphere, keeping the temperature for 90-120 min at the gas flow of 1-2L/h, cooling along with the furnace, and then obtaining the sintered molybdenum-copper alloy.
The specific process of the step 5 is as follows: respectively adding a layer of cold-rolled steel plate with the thickness of about 5-10 mm on the upper part and the lower part of the molybdenum-copper alloy billet obtained by the solution infiltration sintering in the step 4, and smearing anti-adhesion nano Al between the rolled plate layers 2 O 3 And coating, wherein the rolling temperature is 700-800 ℃, then rolling in different passes on a rolling mill, finally performing heat preservation for 1-2 h at 300-330 ℃, and performing annealing heat treatment and machine tool processing to obtain the molybdenum-copper alloy plate.
The specific process of the step 6 is as follows: and (5) removing the oxide on the surface of the molybdenum-copper alloy plate obtained in the step (5) by using solid sand blasting, then grinding the upper surface and the lower surface on a surface grinding machine, wherein the surface roughness is not lower than Ra0.3, and finally cutting the molybdenum-copper alloy plate into required sizes to obtain the molybdenum-copper alloy plate.
The preparation method of the molybdenum-copper alloy section bar has the advantages that the thickness variation range of the obtained plate is large (can meet any requirement between 0.1 mm and 5 mm), the problems of poor tissue distribution uniformity, low density, poor heat and electric conductivity and high linear expansion coefficient of the prepared molybdenum-copper alloy plate are effectively solved, and the prepared molybdenum-copper composite material has the characteristics of good comprehensive properties such as mechanical property, physical property and the like, no cutting scrap, less cutting scrap, economy and high speed.
Drawings
FIG. 1 is a schematic view of a sheet pack rolling assembly used in the method for preparing the Mo-Cu alloy profile of the invention;
FIGS. 2 (a) - (c) are SEM and EDS photographs of copper-clad molybdenum composite powder prepared by chemical plating in example 1 of the preparation method of molybdenum-copper alloy section bar according to the present invention;
FIGS. 3 (a) and (b) are photographs showing the metallographic structure of Mo70Cu obtained in example 1 of the method for producing a Mo-Cu alloy structural material of the present invention before and after rolling.
In the figure, 1. Roll, 2. Cold rolled steel sheet, 3.Al 2 O 3 Coating, 4. Alloy compact.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
The preparation method of the molybdenum-copper alloy section bar specifically comprises the following steps:
carrying out ultrasonic cleaning on original molybdenum powder (with the particle size of 5-10 microns) sold in the market in an absolute ethyl alcohol solvent for 15-30 min, and drying. Subsequently, the sample is washed in a sodium hydroxide solution with the concentration of 10-20 g/L for 25-40 min to remove residues such as grease attached to the surface. Soaking the molybdenum powder after deoiling in hydrochloric acid with the concentration of 35-40% and coarsening for 25-40 min to improve the surface appearance of the molybdenum powder and enable copper to be better attached to the surface of the molybdenum powder. And finally, adding the pretreated molybdenum powder into the chemical plating solution, wherein the chemical plating process is carried out in a heat collection type magnetic stirrer, the heat collection type magnetic stirrer keeps the temperature of the plating solution at 55-60 ℃, the rotating speed of a rotor is 300r/min, 10% -15% of sodium hydroxide solution is dropwise added into the plating solution, the pH value of the plating solution is regulated to 12-13, when the specified pH value interval is reached, after an incubation period of 25-30 s, the reaction starts, bubbles gradually escape, and when the plating solution is changed from initial blue gray to dark red, the bubbles of the plating solution disappear, the chemical plating is finished. After each reaction stage is finished, deionized water is used for washing for 3-5 times, and then alcohol is used for washing for 2-4 times. The composition of the electroless plating solution is shown in table 1. Finally, the mixture is solidified and sintered for 1 to 2 hours at the temperature of between 300 and 500 ℃ in a reducing atmosphere (hydrogen or vacuum) to obtain copper-coated molybdenum composite powder with adjustable components, particle size and sphericity, wherein the copper content in the coated powder accounts for 17 to 19 percent.
TABLE 1 electroless plating solution parameters and formulation
| Composition (I) | Concentration of | Content (%) |
| Blue vitriod | 20g/L | 27.8 |
| Formaldehyde solution | 20ml/L | 14.8 |
| Tartaric acid potassium sodium salt | 10g/L | 19.1 |
| Ethylenediaminetetraacetic acid disodium salt | 18g/L | 38.3 |
taking the coating powder value of the copper-coated molybdenum composite powder (the copper content in the coating powder is calculated according to 18 percent) prepared in the step 1 according to the priority principle, mutually matching the coating powder with the supplement molybdenum powder and the induction copper powder (the particle size is 50-80 micrometers), calculating the proportion of the three powders according to the required percentage as shown in the table 2, and mechanically mixing the calculated copper powder, molybdenum powder and copper-coated molybdenum powder in a mixer for 30-90 min. When mixing materials, 10-20 mL/kg of solvent gasoline is added to accelerate the mixing efficiency, and simultaneously 2% of sodium butadiene rubber solution (sodium butadiene rubber is dissolved in the solvent gasoline to reach saturated solution) is added to finally obtain uniform mixed powder.
TABLE 2 proportioning ratio (%)
firstly, determining the forming size of the molybdenum-copper alloy billet into a cuboid of 100mm multiplied by 60mm multiplied by 10mm, and calculating the mass of the molybdenum-copper alloy plates with different components (the method is that the mass of the molybdenum-copper alloy billet = the volume of the billet is 60 cm) 3 The theoretical density of the compositions is shown as 2 multiplied by 85 percent), then the mixed powder corresponding to the step 2 is weighed and put into a cavity of a high-speed steel pressing die for cold press molding, the pressing pressure is 600 to 800MPa, the pressure maintaining time is 10 to 15s, and finally the die is removed to obtain a billet with determined size and shape.
loading the green compact formed by cold pressing in the step 3 into a graphite boat or a ceramic boat, and placing a copper block (which can be processed by a pure copper section bar and can also be formed by pure copper powder) to be dissolved and infiltratedPlacing on the upper end of the compact (calculation method of specific amount, copper infiltrated mass = volume of compact 60 cm) 3 The theoretical density of the composition is shown in Table 2X 15%), and the periphery is filled with alumina sand of 100 mesh size. And then slowly heating (the heating rate is 6-10 ℃/min) in a high-temperature atmosphere protective furnace to 1300-1350 ℃, wherein the used protective atmosphere is hydrogen, which can reduce oxygen adsorbed by the powder or the compact and is also beneficial to atomic diffusion in the compact, accelerate the densification of the compact, the gas flow is 1-2L/h, the mixture is cooled along with the furnace after staying for 90-120 min, and then the sintered molybdenum-copper alloy is obtained.
Step 5, laminating and rolling;
respectively adding a layer of cold-rolled steel plate with the thickness of about 5-10 mm (the plane size of the steel plate is 1-3 times larger than that of the billet) on the upper part and the lower part of the molybdenum-copper alloy billet obtained by the solution infiltration sintering in the step 4, and smearing anti-adhesion nano Al between the rolled plate layers 2 O 3 Coating, pack rolling assembly as shown in figure 1, pack rolling assembly comprising roll 1, cold rolled steel sheet 2, al 2 O 3 Coating 3 and alloy billet 4; the rolling temperature is 700-800 ℃, then different passes of rolling are carried out on a rolling mill (after each pass is finished, the rolling mill is put into a heating furnace to be heated to the temperature), and finally the molybdenum-copper alloy block is rolled into a plate with the required size and thickness and high surface flatness. Finally, the thin composite board with the size structure and the performance meeting the requirements is obtained by heat preservation for 1 to 2 hours at the temperature of between 300 and 330 ℃, annealing heat treatment and machine tool processing. The laminated rolling can not only prevent the surface from being oxidized, but also obtain a thin plate (the thickness can reach about 0.1 mm) with uniform thickness and smooth surface. And multi-layer rolling (stacking a plurality of alloy billets at the same time, but separating the alloy billet layers by using steel plates) can be carried out for improving the rolling efficiency.
Step 6, grinding;
and (5) removing oxides on the surface of the molybdenum-copper alloy plate meeting the size requirement obtained in the step (5) by using solid sand blasting, then grinding the upper surface and the lower surface on a surface grinding machine, wherein the surface roughness is not lower than Ra0.3, and finally cutting the molybdenum-copper alloy plate into the required size to meet the user requirement.
Example 1
Mo70Cu30 alloy plates with the size of 100X 1mm are prepared.
carrying out ultrasonic cleaning on original molybdenum powder (with the particle size of 5-10 microns) sold in the market in an absolute ethyl alcohol solvent for 15min, and drying. Subsequently, the sample was washed in a sodium hydroxide solution having a concentration of 10g/L for 25min to remove residues such as grease attached to the surface. And soaking the deoiled molybdenum powder in 35% hydrochloric acid, and coarsening for 25min to improve the surface appearance of the molybdenum powder and enable copper to be better attached to the surface of the molybdenum powder. And finally, adding the pretreated molybdenum powder into chemical plating solution, wherein the chemical plating process is carried out in a heat collection type magnetic stirrer, the temperature of the plating solution is kept at 60 ℃ by the heat collection type magnetic stirrer, the rotating speed of a rotor is 300r/min, 15% of sodium hydroxide solution is dropwise added into the plating solution, the pH value of the plating solution is adjusted to 13, and when the specified pH value interval is reached, the reaction starts after 25s incubation period. Bubbles gradually escape in the reaction process, and the chemical plating is finished when the plating solution is changed from the initial blue-gray color to dark-red color. After each reaction stage is finished, deionized water is used for cleaning for 3 times, and then alcohol is used for cleaning for 2 times. Finally, the powder is solidified and sintered for 1 hour at 300 ℃ in a reducing atmosphere (hydrogen or vacuum) to obtain coating powder with the components, the grain diameter and the sphericity being controllable and the coating proportion being 18 percent.
586.26g of coating powder are directly weighed according to the proportion.
and (3) loading the powder weighed in the step (2) into a high-speed steel pressing die for cold press molding, wherein the selected pressing pressure is 450MPa, the pressure maintaining time is 10s, and demolding to obtain the Mo70Cu30 green compact.
and (3) placing the pressed blank formed by cold pressing in the step (3) in a graphite boat, placing a copper block (directly using a pure copper section) to be dissolved and infiltrated at the upper end of the pressed blank, and burying the periphery of the pressed blank by using alumina sand with the granularity of 100 meshes. Then the mixture is put into a high-temperature atmosphere protective furnace to be heated slowly (the heating rate is 8 ℃/min) to 1300 ℃, the used protective atmosphere is hydrogen, and the gas flow is 1.1L/h. And (5) standing for 90min, cooling along with the furnace, and then obtaining a sintered molybdenum-copper alloy billet.
Step 5, laminating and rolling;
respectively adding a layer of cold-rolled steel plate with the thickness of about 5-10 mm (the plane size of the steel plate is 1-3 times larger than that of the billet) on the upper part and the lower part of the molybdenum-copper alloy billet obtained by the solution infiltration sintering in the step 4, and smearing anti-adhesion nano Al between the plate layers 2 O 3 And coating, namely heating the assembly to 800 ℃, then performing different rolling passes on a rolling mill (after each pass is finished, putting the assembly into a heating furnace to be heated to the temperature), and finally rolling the molybdenum-copper alloy block into a plate with the required thickness and high surface flatness. And then preserving heat for 1.5h at 300 ℃, annealing, heat treating and then machining by a lathe to obtain the thin composite board with the structural shape and the performance meeting the requirements.
Step 6, grinding;
and (5) removing oxides on the surface of the molybdenum-copper alloy plate meeting the size requirement obtained in the step (5) by using solid sand blasting, and then grinding the upper surface and the lower surface on a surface grinding machine, wherein the surface roughness is not lower than Ra0.3, and finally the molybdenum-copper alloy plate meets the user requirement.
In the preparation process of this embodiment 1, fig. 2 (a) is an SEM topography of the copper-coated molybdenum composite powder, it can be seen that fine and uniform spherical or dumbbell-shaped particles grow on the surface of the Mo powder, the surface of the Mo powder is completely coated, the coating effect is good, the shape of the coated powder tends to spherical, the particle diameter of the coated powder is about 4-6 μm, in order to verify the core-shell structure of the composite powder, fig. 2 (b) (c) is a cross-sectional structure and a line scanning distribution diagram of the core-shell structure copper-coated molybdenum composite powder, it can be seen that the outer layer element of a single powder particle is Cu, the inner layer element is Mo, the coating is clearly visible, and the coating thickness is 1 μm.
Fig. 3 (a) is a photograph of the microstructure of the Mo70Cu30 alloy before rolling, wherein the granular part is copper and the matrix is molybdenum, and it can be seen from the figure that the granular copper phase is uniformly distributed in the matrix molybdenum phase, the copper phase accounts for about 30% of the total volume, the two-phase structure is uniformly distributed, and has no defects such as obvious holes and agglomeration, and no other phase exists in the structure. FIG. 3 (b) is a photograph of the structure of a Mo70Cu30 alloy in a longitudinal section in the rolling direction. It can be seen from the figure that the molybdenum particles undergo significant plastic deformation after hot rolling, i.e. elongation to a certain extent along the rolling direction, and that the alloy has significant rolling flow lines after rolling, the copper network structure is more significant, and the copper phase is more uniformly dispersed. The compactness of the molybdenum-copper alloy is greatly improved due to the dense and uniform network distribution of the copper phase, and the electric and thermal conductivity of the material can be effectively improved.
Example 2
Mo60Cu40 alloy plate material with the size of 200X 1mm is prepared.
Carrying out ultrasonic cleaning on commercial original molybdenum powder (with the particle size of 5-10 microns) in an absolute ethyl alcohol solvent for 20min, and drying. Subsequently, the sample was washed in a sodium hydroxide solution having a concentration of 10g/L for 25min to remove residues such as grease attached to the surface. And soaking the deoiled molybdenum powder in 35% hydrochloric acid, and coarsening for 25min to improve the surface appearance of the molybdenum powder and enable copper to be better attached to the surface of the molybdenum powder. And finally, adding the pretreated molybdenum powder into chemical plating solution, wherein the chemical plating process is carried out in a heat collection type magnetic stirrer, the heat collection type magnetic stirrer keeps the temperature of the plating solution at 60 ℃, the rotating speed of a rotor is 300r/min, 15% of sodium hydroxide solution is dropwise added into the plating solution, the pH value of the plating solution is adjusted to 13, and when the specified pH value interval is reached, after a 25-second incubation period, the reaction starts. Bubbles will gradually escape during the reaction process, and when the plating solution is changed from the initial blue-gray color to dark-red color, the chemical plating is completed. After each reaction stage is finished, deionized water is used for washing for 3 times, and then alcohol is used for washing for 2 times. Finally, the mixture is solidified and sintered for 1 hour at 300 ℃ in a reducing atmosphere (hydrogen or vacuum) to obtain coating powder with the components, the grain diameter and the sphericity being controllable and the coating proportion being 18 percent.
703.54g of coating powder and 115.66g of induction copper powder are weighed according to the proportion. And mechanically mixing the weighed induced copper powder and the coating powder in a mixer for 50min. 18mL/kg of solvent gasoline is added during mixing to accelerate the mixing efficiency, and finally uniform mixed powder is obtained.
and (3) loading the powder weighed in the step (2) into a high-speed steel pressing die for cold press molding, wherein the selected pressing pressure is 520MPa, the pressure maintaining time is 12s, and demolding to obtain the Mo60Cu40 green compact.
And (3) placing the pressed blank formed by cold pressing in the step (3) in a graphite boat, placing a copper block (directly using a pure copper section) to be dissolved and infiltrated at the upper end of the pressed blank, and burying the periphery of the pressed blank by using alumina sand with the granularity of 100 meshes. Then the mixture is put into a high-temperature atmosphere protective furnace to be slowly heated (the heating rate is 8 ℃/min) to 1300 ℃, the used protective atmosphere is hydrogen, and the gas flow is 1.1L/h. And (5) standing for 90min, cooling along with the furnace, and then obtaining a sintered molybdenum-copper alloy billet.
Step 5, laminating and rolling;
respectively adding a layer of cold-rolled steel plate with the thickness of about 5-10 mm (the plane size of the steel plate is 1-3 times larger than that of the billet) on the upper part and the lower part of the molybdenum-copper alloy billet obtained by the solution infiltration sintering in the step 4, and smearing anti-adhesion nano Al between the plate layers 2 O 3 And coating, namely heating the assembly to 800 ℃, then performing different rolling passes on a rolling mill (after each pass is finished, putting the assembly into a heating furnace to be heated to the temperature), and finally rolling the molybdenum-copper alloy block into a plate with the required thickness and high surface flatness. And then preserving heat for 1.5 hours at 300 ℃, and performing annealing heat treatment and lathe machining to obtain the thin composite board with the size structure and the performance meeting the requirements.
Step 6, grinding;
and (5) removing oxides on the surface of the molybdenum-copper alloy plate meeting the size requirement obtained in the step (5) by using solid sand blasting, and then grinding the upper surface and the lower surface on a surface grinding machine, wherein the surface roughness is not lower than Ra0.3, and finally the molybdenum-copper alloy plate meets the user requirement.
Example 3
Mo50Cu50 alloy sheet material with the size of 150X 0.5mm is prepared.
Carrying out ultrasonic cleaning on commercial original molybdenum powder (with the particle size of 5-10 microns) in an absolute ethyl alcohol solvent for 25min, and drying. Subsequently, the sample was washed in a sodium hydroxide solution having a concentration of 10g/L for 25min to remove residues such as grease attached to the surface. And soaking the molybdenum powder after deoiling in hydrochloric acid with the concentration of 35%, and coarsening for 25min to improve the surface appearance of the molybdenum powder and enable copper to be better attached to the surface of the molybdenum powder. And finally, adding the pretreated molybdenum powder into chemical plating solution, wherein the chemical plating process is carried out in a heat collection type magnetic stirrer, the temperature of the plating solution is kept at 60 ℃ by the heat collection type magnetic stirrer, the rotating speed of a rotor is 300r/min, 15% of sodium hydroxide solution is dropwise added into the plating solution, the pH value of the plating solution is adjusted to 13, and when the specified pH value interval is reached, the reaction starts after 25s incubation period. Bubbles will gradually escape during the reaction process, and when the plating solution is changed from the initial blue-gray color to dark-red color, the chemical plating is completed. After each reaction stage is finished, deionized water is used for cleaning for 3 times, and then alcohol is used for cleaning for 2 times. Finally, the powder is solidified and sintered for 1 hour at 300 ℃ in a reducing atmosphere (hydrogen or vacuum) to obtain coating powder with the components, the grain diameter and the sphericity being controllable and the coating proportion being 18 percent.
353.62g of coating powder and 131.18g of induction copper powder are weighed according to the proportion. And mechanically mixing the weighed induced copper powder and the coating powder in a mixer for 35min. 18mL/kg of solvent gasoline is added during mixing to accelerate the mixing efficiency, and finally uniform mixed powder is obtained.
and (3) loading the powder weighed in the step (2) into a high-speed steel pressing die for cold press molding, wherein the selected pressing pressure is 500MPa, the pressure maintaining time is 10s, and demolding to obtain the Mo50Cu50 pressed compact.
and (3) placing the pressed blank formed by cold pressing in the step (3) in a graphite boat, placing a copper block (directly using a pure copper section) to be dissolved and infiltrated at the upper end of the pressed blank, and burying the periphery of the pressed blank by using alumina sand with the granularity of 100 meshes. Then the mixture is put into a high-temperature atmosphere protective furnace to be slowly heated (the heating rate is 8 ℃/min) to 1300 ℃, the used protective atmosphere is hydrogen, and the gas flow is 1.1L/h. And (5) standing for 90min, cooling along with the furnace, and then obtaining a sintered molybdenum-copper alloy billet.
Step 5, laminating and rolling;
respectively adding a layer of cold-rolled steel plate with the thickness of about 5-10 mm (the plane size of the steel plate is 1-3 times larger than that of the billet) on the upper and lower parts of the molybdenum-copper alloy billet obtained by the solution infiltration sintering in the step 4, and smearing anti-adhesion nano Al between the plate layers 2 O 3 And coating, namely heating the assembly to 800 ℃, then performing different rolling passes on a rolling mill (after each pass is finished, putting the assembly into a heating furnace to be heated to the temperature), and finally rolling the molybdenum-copper alloy block into a plate with the required thickness and high surface flatness. And then preserving heat for 1.5h at 300 ℃, annealing, heat treating and then machining by a lathe to obtain the thin composite board with the size structure and the performance meeting the requirements.
Step 6, grinding;
and (5) removing oxides on the surface of the molybdenum-copper alloy plate meeting the size requirement obtained in the step (5) by using solid sand blasting, and then grinding the upper surface and the lower surface on a surface grinding machine, wherein the surface roughness is not lower than Ra0.3, and finally the molybdenum-copper alloy plate meets the user requirement.
Example 4
A Mo80Cu20 alloy sheet material with dimensions of phi 100mm by 1mm was prepared.
carrying out ultrasonic cleaning on original molybdenum powder (with the particle size of 5-10 microns) sold in the market in an absolute ethyl alcohol solvent for 30min, and drying. Subsequently, the sample was washed in a sodium hydroxide solution having a concentration of 10g/L for 25min to remove residues such as grease attached to the surface. And soaking the molybdenum powder after deoiling in hydrochloric acid with the concentration of 35%, and coarsening for 25min to improve the surface appearance of the molybdenum powder and enable copper to be better attached to the surface of the molybdenum powder. And finally, adding the pretreated molybdenum powder into chemical plating solution, wherein the chemical plating process is carried out in a heat collection type magnetic stirrer, the temperature of the plating solution is kept at 60 ℃ by the heat collection type magnetic stirrer, the rotating speed of a rotor is 300r/min, 15% of sodium hydroxide solution is dropwise added into the plating solution, the pH value of the plating solution is adjusted to 13, and when the specified pH value interval is reached, the reaction starts after 25s incubation period. Bubbles will gradually escape during the reaction process, and when the plating solution is changed from the initial blue-gray color to dark-red color, the chemical plating is completed. After each reaction stage is finished, deionized water is used for washing for 3 times, and then alcohol is used for washing for 2 times. Finally, the powder is solidified and sintered for 1 hour at 300 ℃ in a reducing atmosphere (hydrogen or vacuum) to obtain coating powder with the components, the grain diameter and the sphericity being controllable and the coating proportion being 18 percent.
582.76g of coating powder is directly weighed according to the proportion.
and (3) loading the powder weighed in the step (2) into a high-speed steel pressing die for cold press molding, wherein the selected pressing pressure is 500MPa, the pressure maintaining time is 10s, and demolding to obtain a Mo50Cu50 pressed compact.
and (3) placing the pressed blank formed by cold pressing in the step (3) in a graphite boat, placing a copper block (directly using a pure copper section) to be dissolved and infiltrated at the upper end of the pressed blank, and burying the periphery of the pressed blank by using alumina sand with the granularity of 100 meshes. Then the mixture is put into a high-temperature atmosphere protective furnace to be heated slowly (the heating rate is 8 ℃/min) to 1300 ℃, the used protective atmosphere is hydrogen, and the gas flow is 1.1L/h. And standing for 90min, and cooling along with the furnace to obtain a sintered molybdenum-copper alloy billet.
Step 5, laminating and rolling;
respectively adding a layer of cold-rolled steel plate with the thickness of about 5-10 mm (the plane size of the steel plate is 1-3 times larger than that of the billet) on the upper and lower parts of the molybdenum-copper alloy billet obtained by the solution infiltration sintering in the step 4, and smearing anti-adhesion nano Al between the plate layers 2 O 3 And coating, namely heating the assembly to 800 ℃, then performing different rolling passes on a rolling mill (after each pass is finished, putting the assembly into a heating furnace to be heated to the temperature), and finally rolling the molybdenum-copper alloy block into a plate with the required thickness and high surface flatness. And then preserving heat for 1.5h at 300 ℃, annealing, heat treating and then machining by a lathe to obtain the thin composite board with the size structure and the performance meeting the requirements.
Step 6, grinding;
and (5) removing oxides on the surface of the molybdenum-copper alloy plate meeting the size requirement obtained in the step (5) by using solid sand blasting, and then grinding the upper surface and the lower surface on a surface grinding machine, wherein the surface roughness is not lower than Ra0.3, and finally the molybdenum-copper alloy plate meets the user requirement.
TABLE 3 Properties of the Mo-Cu alloy sheets or tablets produced
Claims (7)
1. The preparation method of the molybdenum-copper alloy section is characterized by comprising the following steps: the method specifically comprises the following steps:
step 1, preparing copper-coated molybdenum composite powder;
step 2, preparing mixed powder according to the product obtained in the step 1, supplemented molybdenum powder and induced copper powder;
step 3, performing cold press molding treatment on the mixed powder prepared in the step 2;
step 4, performing cold press molding in the step 3 to perform infiltration sintering to obtain a molybdenum-copper alloy billet;
step 5, carrying out lamination rolling on the molybdenum-copper alloy billet subjected to solution infiltration sintering in the step 4 to obtain a molybdenum-copper alloy plate;
and 6, grinding the molybdenum-copper alloy plate obtained in the step 5 to obtain the molybdenum-copper alloy plate.
2. The method for preparing molybdenum-copper alloy profile according to claim 1, wherein: the specific process of the step 1 is as follows:
step 1.1, carrying out ultrasonic cleaning on molybdenum powder in an absolute ethyl alcohol solvent for 15-30 min, and drying; step 1.2, cleaning the sample prepared in the step 1.1 in a sodium hydroxide solution with the concentration of 10-20 g/L for 25-40 min to remove grease attached to the surface, soaking the molybdenum powder after deoiling in hydrochloric acid with the concentration of 35-40%, and coarsening for 25-40 min;
step 1.3, adding the molybdenum powder treated in the step 1.2 into chemical plating solution, wherein the chemical plating process is carried out in a heat collection type magnetic stirrer, the heat collection type magnetic stirrer keeps the temperature of the plating solution at 55-60 ℃, 10-15% of sodium hydroxide solution is dropwise added into the chemical plating solution, the pH value of the plating solution is adjusted to 12-13, when the specified pH value interval is reached, after 25-30 s incubation period, the reaction starts, bubbles gradually escape, and when the bubbles of the plating solution disappear, the chemical plating is finished;
step 1.4, curing and sintering for 1-2 hours at 300-500 ℃ in a reducing atmosphere to obtain copper-coated molybdenum composite powder, wherein the copper content in the coated powder accounts for 17% -19%.
3. The method for preparing the molybdenum-copper alloy profile according to claim 1, wherein the method comprises the following steps: the specific process of the step 2 comprises the following steps: mechanically mixing the copper-coated molybdenum composite powder prepared in the step 1 with complementary molybdenum powder and induced copper powder in a mixer for 30-90 min, and adding 10-20 mL/kg of solvent gasoline during mixing to finally obtain uniform mixed powder.
4. The method for preparing the molybdenum-copper alloy profile according to claim 1, wherein the method comprises the following steps: the specific process of the step 3 is as follows: and (3) weighing the mixed powder obtained in the step (2), putting the mixed powder into a cavity of a steel pressing die for cold press molding, selecting the pressing pressure of 600-800 MPa, keeping the pressure for 10-15 s, and finally demoulding to obtain a billet with determined size and shape.
5. The method for preparing molybdenum-copper alloy profile according to claim 1, wherein: the specific process of the step 4 is as follows: and (4) placing the green body formed by cold pressing in the step (3) in a graphite boat or a ceramic boat, burying the periphery of the copper block to be dissolved and infiltrated with alumina sand, heating to 1300-1350 ℃ at the speed of 6-10 ℃/min under a protective atmosphere, keeping the temperature for 90-120 min, and cooling along with the furnace to obtain the sintered molybdenum-copper alloy.
6. The method for preparing the molybdenum-copper alloy profile according to claim 1, wherein the method comprises the following steps: the specific process of the step 5 comprises the following steps: respectively adding a layer of cold-rolled steel plate with the thickness of about 5-10 mm on the upper part and the lower part of the molybdenum-copper alloy billet obtained by the solution infiltration sintering in the step 4, and smearing the rolled plate layersAnti-sticking nano Al 2 O 3 Coating, rolling at 700-800 ℃, then rolling on a rolling mill for different passes, finally performing heat preservation for 1-2 h at 300-330 ℃, and performing annealing heat treatment and machine tool machining to obtain the molybdenum-copper alloy plate.
7. The method for preparing molybdenum-copper alloy profile according to claim 6, wherein: the specific process of the step 6 is as follows: firstly spraying the molybdenum-copper alloy plate obtained in the step 5 with solid
Removing oxide on the surface by using sand, then grinding the upper surface and the lower surface on a surface grinder,
surface roughness is not less than Ra0.3, and cutting into required size.
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| CN116618647B (en) * | 2023-07-21 | 2023-10-13 | 安徽诺星航空科技有限公司 | Molybdenum-copper alloy composite material and preparation process thereof |
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