CN108161156B - Vacuum brazing method for molybdenum alloy and graphite - Google Patents
Vacuum brazing method for molybdenum alloy and graphite Download PDFInfo
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- CN108161156B CN108161156B CN201711184154.0A CN201711184154A CN108161156B CN 108161156 B CN108161156 B CN 108161156B CN 201711184154 A CN201711184154 A CN 201711184154A CN 108161156 B CN108161156 B CN 108161156B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/008—Soldering within a furnace
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
- B23K1/206—Cleaning
Abstract
The invention belongs to the technical field of heterogeneous material connection, and particularly relates to a vacuum brazing method for molybdenum alloy and graphite. The method comprises a graphite activation step and a vacuum brazing step. The process has reasonable design and good use effect, and the molybdenum alloy and graphite composite piece obtained by the method has high joint remelting temperature, can be used below 1500 ℃, has stable performance and does not crack.
Description
Technical Field
The invention belongs to the technical field of heterogeneous material connection, and particularly relates to a vacuum brazing method for molybdenum alloy and graphite.
Background
The molybdenum alloy has the characteristics of high melting point, small thermal expansion coefficient, good heat conduction and electric conductivity, good thermodynamic stability and the like, and is widely applied to wall materials, high-temperature thermal field materials, electric vacuum component materials and X-ray tube matching materials (target discs, rotor supporting rods, bearing sleeves and the like) of nuclear fusion devices. Graphite is a hexagonal crystalline form of carbon, has a relatively low density as a low atomic weight material, has an extremely high melting point and thermal shock resistance, and is an excellent high temperature resistant material. Based on the fact that molybdenum alloy and graphite both have high melting point and good heat and electricity conduction performance, the graphite has small density and can effectively reduce the weight of the material, and welding composite parts of the molybdenum alloy and the graphite are widely applied to nuclear fusion reactor materials and anode target materials for industrial and medical CT machines.
In the connection technology of molybdenum and its alloy and graphite, a lot of studies have been made by many scholars in China. In patent CN102240836B "molybdenum and graphite vacuum brazing method", a pretreatment is performed to increase the specific surface area in the molybdenum and graphite area to be welded, then a foil brazing filler metal is put in, and then vacuum pressure welding is performed. The pretreatment process for increasing the specific surface area of molybdenum and graphite is complex in actual production operation and is not suitable for mass production. Patent CN101290852B preparation method of WMo graphite composite anode target material for high-power X-ray tube, research on W/Mo/graphite anode target material of medical CT machine X-ray tube and research on molybdenum/graphite composite connection characteristic prepare composite green compact of WMo and TiNiCr binder layer by powder metallurgy method, then put three high graphite and composite green compact with the same diameter into graphite mould in sequence, the binder layer of the composite green compact contacts with graphite, and the composite green compact is put into a vacuum hot-pressing sintering furnace for hot-pressing sintering and forming. In patent CN105397264A, "a molybdenum and graphite vacuum hot pressing diffusion welding method", a hot pressing technique is used to perform diffusion at high temperature, so as to form a carbide layer of Mo as a welding transition layer, and finally form an effective connection between molybdenum and graphite. The research on the graphite and molybdenum alloy brazing material and the brazing process is mainly carried out on the welding process of the graphite and TZM and the welding performance of joints by three solders, namely Ti-Si solder, Zr solder and Ti solder. Document "diffusion welding of molybdenum and graphite" studies the interface structure and joint performance of a joint when molybdenum and graphite are directly diffusion-welded without an intermediate layer, and studies the change of the structure and performance of the joint when foil-shaped and powdery titanium and nickel are used as intermediate layer materials. The welding methods of molybdenum, molybdenum alloy and graphite related to the methods are all brazing by using different added elements, different brazing filler metal layers and different adding forms, including powder, foil, plating layers and the like, and the welding methods aiming at changing the welding surface structure to increase the contact area of the brazing filler metal and the base metal and increase the wettability and the cohesiveness all need pressure welding.
Disclosure of Invention
The invention aims to provide a vacuum brazing method of molybdenum alloy and graphite aiming at the defects of the prior art, which comprises the steps of carrying out activation treatment on the to-be-welded surface of the graphite, then putting brazing filler metal in the graphite, and directly carrying out vacuum brazing on the to-be-welded surface of the graphite and the molybdenum alloy to obtain a composite piece of the molybdenum alloy and the graphite.
In order to achieve the purpose, the invention adopts the following technical scheme:
a vacuum brazing method of molybdenum alloy and graphite sequentially comprises the following steps:
activating graphite: placing the titanium alloy sheet on a to-be-welded surface of graphite to be subjected to activation treatment to obtain activated graphite;
vacuum brazing: and placing brazing solder between the molybdenum alloy to be welded and the graphite subjected to the active treatment for vacuum brazing treatment to obtain a molybdenum alloy and graphite composite part.
In the invention, the graphite to be welded mainly contains covalent bonds, shows very stable electronic coordination and is difficult to be wetted by the metal solder with metal bonds, so that the inventor adopts titanium alloy to activate the graphite surface, thereby being more beneficial to wetting the solder and the graphite surface.
In the vacuum brazing method of molybdenum alloy and graphite, as a preferred embodiment, a high vacuum degassing step is further included before the graphite activation step: the molybdenum alloy to be welded and the graphite to be welded are subjected to vacuum degree of not less than 5 multiplied by 10-4Pa (e.g. 4X 10)-4Pa、2×10-4Pa、1×10-4Pa、9×10-5Pa) is carried out; more preferably, the degassing heat treatment is performed at 1500-1800 ℃ (such as 1510 ℃, 1550 ℃, 1580 ℃, 1600 ℃, 1620 ℃, 1650 ℃, 1670 ℃, 1690 ℃, 1720 ℃, 1750 ℃ and 1790 ℃), and the holding time is 30-60 min (such as 32min, 35min, 38min, 42min, 45min, 48min, 50min, 55min and 58 min); further preferably, the degassing heat treatment is performed in a vacuum furnace. Because graphite adsorptivity is stronger, in order to avoid producing the gas pocket in the brazing process, adopt the high vacuum treatment in order to arrange the impurity gas in the graphite completely.
In the above vacuum brazing method of a molybdenum alloy and graphite, as a preferred embodiment, in the graphite activation step, the activation treatment is performed in a vacuum furnace.
In the above vacuum brazing method of a molybdenum alloy and graphite, as a preferred embodiment, in the graphite activation step, the size of the titanium alloy sheet is the same as the size of the surface to be welded of the graphite to be welded (i.e., the titanium alloy sheet can just cover the surface to be welded of the graphite to be welded); more preferably, the thickness of the titanium alloy sheet is 0.2-0.5 mm (such as 0.21mm, 0.25mm, 0.28mm, 0.30mm, 0.35mm, 0.40mm, 0.45mm, 0.49mm), and the thickness of the titanium alloy sheet is too thin or too thick, which may reduce the connection strength between the molybdenum alloy and the graphite.
In the vacuum brazing method for molybdenum alloy and graphite, the titanium alloy sheet may be a titanium alloy with a titanium content of more than 80% by mass, and since pure titanium has high activity and can react with graphite to generate TiC, the titanium alloy sheet is preferably a pure titanium sheet, and further, the pure titanium sheet meets the relevant regulation of TA1 specified in the standard GB/T3622-2012 "titanium and titanium alloy strip and foil".
In the method for vacuum brazing of a molybdenum alloy and graphite, as a preferred embodiment, in the step of activating graphite, the temperature of the activation treatment is 1700 to 1800 ℃ (such as 1710 ℃, 1730 ℃, 1750 ℃, 1760 ℃, 1770 ℃, 1780 ℃, 1790 ℃ and 1799 ℃), the heat preservation time is 10 to 30min (such as 12min, 15min, 18min, 22min, 25min, 28min and 30min), and the vacuum degree is not less than 5 × 10-4Pa (e.g. 4X 10)-4Pa、2×10-4Pa、1×10- 4Pa、9×10-5Pa); more preferably, in the step of activating graphite, the activation treatment is followed by furnace cooling to 60 ℃ or lower (e.g., 40 ℃, 45 ℃, 50 ℃, 55 ℃, 59 ℃). The titanium material is evaporated too fast due to the over-high activation temperature and the over-long heat preservation time, which is not beneficial to forming a stable activation layer; and the titanium material has strong activity and is easy to oxidize when the vacuum degree is too low.
In the above method of vacuum brazing a molybdenum alloy and graphite, as a preferred embodiment, in the step of vacuum brazing, the composition of the brazing material includes: ti, Cr and Ta; more preferably, the brazing material consists of the following components in percentage by mass: 80-90% of Ti, 5-10% of Cr and 5-10% of Ta; further preferably, the brazing material is prepared by adopting a process of combining vacuum melting and rolling.
In the vacuum brazing method of the molybdenum alloy and graphite, as a preferred embodiment, in the vacuum brazing step, the brazing material is in a flake shape, and the thickness is preferably 0.15 to 0.30mm (for example, 0.16mm, 0.18mm, 0.20mm, 0.22mm, 0.25mm, 0.27mm, 0.29 mm). Too thin or too thick a brazing material may reduce the joining strength of the molybdenum alloy and graphite.
In the above method for vacuum brazing of a molybdenum alloy and graphite, as a preferred embodiment, in the vacuum brazing step, the temperature of the vacuum brazing treatment is 1820-1900 ℃ (such as 1830 ℃, 1840 ℃, 1850 ℃, 1860 ℃, 1870 ℃, 1880 ℃, 1890 ℃, 1899 ℃), the holding time is 10-30 min (such as 12min, 15min, 18min, 22min, 25min, 28min, 30min), and the degree of vacuum is not less than 5 × 10-3Pa (e.g. 3X 10)-3Pa、1×10-3Pa、9×10-4Pa、5×10-4Pa、3×10-4Pa、1×10-4Pa) is added. Too high brazing temperature can cause too much volatilization of brazing filler metal and recrystallization of base metal, and too low vacuum degree can cause difficult discharge of gas in brazing seams to form air holes.
In the above-described vacuum brazing method of a molybdenum alloy and graphite, as a preferred embodiment, in the vacuum brazing step, the vacuum brazing process is performed in a vacuum brazing furnace.
In the above vacuum brazing method of molybdenum alloy and graphite, as a preferred embodiment, no external pressure is applied during the vacuum brazing process, and the method of the present invention satisfies the element diffusion condition without applying any external pressure.
In the above method for vacuum brazing of molybdenum alloy and graphite, the molybdenum alloy to be welded may be pure molybdenum, or a molybdenum alloy doped with other metals, such as TZM, MHC, ML, MRe, etc., and as a preferred embodiment, the mass percentage of the molybdenum element in the molybdenum alloy to be welded is 90% or more.
The preferred embodiments described in the present invention may be combined arbitrarily.
According to the invention, the surface of the graphite is activated, and the molybdenum alloy and the graphite are further subjected to high-vacuum degassing treatment before the graphite activation step, so that the interface energy among the liquid brazing material, the molybdenum alloy and the graphite is greatly reduced, and the wettability of the brazing material, the molybdenum alloy and the graphite is effectively improved. In addition, the invention uses the brazing solder containing Ti, Cr and Ta, wherein the Ti element and molybdenum are infinitely dissolved in solid solution and react with graphite to generate TiC with high melting point, and the Cr and Ta elements can effectively improve the wettability of the liquid brazing solder and the graphite. Therefore, the molybdenum alloy and graphite composite part obtained by the method has high joint remelting temperature, can be used below 1500 ℃, has stable performance and does not crack. In addition, the method of the invention does not need to apply extra pressure to the workpiece to be welded in the brazing treatment process, simplifies the process, saves energy, and can ensure that a plurality of products are welded in each furnace because no pressure is needed, thereby improving the production efficiency, reducing the cost and being suitable for mass production.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for the purpose of the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
The molybdenum alloy used in the following examples is a TZM molybdenum alloy in which, in mass percent, Ti: 0.4-0.55%, Zr: 0.06-0.12%, C: 0.01-0.04% and the balance of Mo. The titanium sheets used in the following examples meet the relevant specifications of TA1 specified in the GB/T3622-2012 Standard for titanium and titanium alloy strips and foils.
The brazing material used in the following examples was prepared as follows: according to the specified mass ratio, Ti sheets, Ta sheets and Cr sheets are made into consumable electrodes, the consumable electrodes are remelted for 3 times in a vacuum arc furnace to obtain alloy ingot blanks, then the alloy ingot blanks are forged and rolled to deform to obtain brazing filler metal sheets, and the brazing filler metal sheets can be used after acid washing.
Example 1
The vacuum brazing method of the molybdenum alloy and the graphite in the embodiment is concretely as follows:
(1) cleaning the molybdenum alloy to be welded and the graphite to be welded, placing the molybdenum alloy to be welded and the graphite to be welded into a high-temperature vacuum furnace for high-temperature vacuum degassing treatment, wherein the treatment temperature is 1600 ℃, the heat preservation time is 60min, and the treatment vacuum degree is 4 multiplied by 10-4Pa, cooling to within 100 ℃ and discharging.
(2) Vacuum packaging the molybdenum alloy to be welded discharged from the furnace, placing a titanium sheet with the same shape and the same size and the thickness of 0.3mm on the surface to be welded of the graphite to be welded, putting the titanium sheet and the graphite to be welded into a vacuum furnace together for activating the graphite to be welded, wherein the treatment temperature is 1720 ℃, the heat preservation time is 20min, and the vacuum degree is 4.5 multiplied by 10-4And Pa, cooling to within 60 ℃, discharging, and obtaining the activated graphite.
(3) Placing Ti90Cr5Ta5 (i.e. in the brazing material, the mass percent of Ti is 90%, the mass percent of Cr is 5%, and the mass percent of Ta is 5%) brazing material with the thickness of 0.2mm (i.e. the upper and lower surfaces of the brazing material are respectively contacted with the to-be-welded surface of the to-be-welded molybdenum alloy and the to-be-welded surface of the activated graphite) between the to-be-welded surface of the to-be-welded molybdenum alloy subjected to vacuum degassing treatment and the to-be-welded surface of the activated graphite, and then placing the brazing material and the to-be-welded surface of the to-be-welded molybdenum alloy into a vacuum brazing furnace for brazing treatment at the brazing temperature of 1870 ℃-3Pa。
Performing ultrasonic flaw detection on the molybdenum alloy and graphite composite piece obtained by brazing, displaying that the interface bonding rate is more than 95%, simultaneously sampling and performing mechanical property test, wherein in the sample, the molybdenum alloy and the graphite are cuboids, and the sizes (width, height and length) are as follows: 5 × 25cm, the size of the overlapped part of the two end parts is 5 × 5mm, the composite piece sample with the specification is placed into a testing tool, then the test is carried out on an Instron3369 universal material testing machine, and the room-temperature shear strength is measured to be 19.5MPa by referring to GB/T6396 and 2008 composite steel plate mechanics and process performance testing method.
Example 2
The vacuum brazing method of the molybdenum alloy and the graphite in the embodiment is concretely as follows:
(1) cleaning the molybdenum alloy to be welded and the graphite to be welded, placing the molybdenum alloy to be welded and the graphite to be welded into a high-temperature vacuum furnace for high-temperature vacuum degassing treatment, wherein the treatment temperature is 1550 ℃, the heat preservation time is 50min, and the treatment vacuum degree is 3 multiplied by 10-4Pa, cooling to within 100 ℃ and discharging.
(2) Vacuum packaging the molybdenum alloy to be welded discharged from the furnace, placing a titanium sheet with the same shape and size and the thickness of 0.4mm on the surface to be welded of the graphite to be welded, putting the titanium sheet and the surface to be welded of the graphite to be welded into a vacuum furnace together for activating treatment, wherein the treatment temperature is 1750 ℃, the heat preservation time is 30min, and the vacuum degree is 4.5 multiplied by 10-4And Pa, cooling to within 60 ℃, discharging, and obtaining the activated graphite.
(3) Placing Ti85Cr5Ta10 (i.e. in the brazing material, the mass percent of Ti is 85%, the mass percent of Cr is 5%, and the mass percent of Ta is 10%) with the thickness of 0.25mm between the to-be-welded surface of the molybdenum alloy subjected to vacuum degassing treatment and the to-be-welded surface of the activated graphite, and then placing the brazing material and the brazing material together into a vacuum brazing furnace for brazing treatment, wherein the brazing temperature is 1820 ℃, the heat preservation time is 30min, and the vacuum degree is 3 multiplied by 10-3Pa。
And (3) carrying out ultrasonic flaw detection on the molybdenum alloy and graphite composite piece obtained by brazing, displaying that the interface bonding rate is more than 95%, simultaneously sampling and carrying out mechanical property test according to the method described in the embodiment 1, and measuring that the room-temperature shear strength is 20.5 MPa.
Example 3
The vacuum brazing method of the molybdenum alloy and the graphite in the embodiment is concretely as follows:
(1) cleaning the molybdenum alloy to be welded and the graphite to be welded, placing the molybdenum alloy to be welded and the graphite to be welded into a high-temperature vacuum furnace for high-temperature vacuum degassing treatment, wherein the treatment temperature is 1550 ℃, the heat preservation time is 35min, and the molybdenum alloy and the graphite to be welded are positioned at the high-temperature vacuum furnaceThe degree of vacuum is 3.5 multiplied by 10-4Pa, cooling to within 100 ℃ and discharging.
(2) Vacuum packaging the molybdenum alloy to be welded discharged from the furnace, placing a titanium sheet with the same shape and size and the thickness of 0.2mm on the surface to be welded of the graphite to be welded, putting the titanium sheet and the graphite to be welded into a vacuum furnace together for activating the graphite to be welded, wherein the treatment temperature is 1700 ℃, the heat preservation time is 25min, and the vacuum degree is 3 multiplied by 10-4And Pa, cooling to within 60 ℃, discharging, and obtaining the activated graphite.
(3) Placing Ti85Cr10Ta5 (i.e. in the brazing material, the mass percent of Ti is 85%, the mass percent of Cr is 10%, and the mass percent of Ta is 5%) with the thickness of 0.20mm between the to-be-welded surface of the molybdenum alloy subjected to vacuum degassing treatment and the to-be-welded surface of the activated graphite, and then placing the brazing material and the brazing material together into a vacuum brazing furnace for brazing treatment, wherein the brazing temperature is 1800 ℃, the heat preservation time is 25min, and the vacuum degree is 2 multiplied by 10-3Pa。
And (3) carrying out ultrasonic flaw detection on the molybdenum alloy and graphite composite piece obtained by brazing, displaying that the interface bonding rate is more than 95%, simultaneously sampling and carrying out mechanical property test according to the method described in the embodiment 1, and measuring that the room-temperature shear strength is 18.5 MPa.
Example 4
The vacuum brazing method of the molybdenum alloy and the graphite in the embodiment is concretely as follows:
(1) cleaning the molybdenum alloy to be welded and the graphite to be welded, placing the molybdenum alloy and the graphite into a high-temperature vacuum furnace for high-temperature vacuum degassing treatment at 1750 ℃, keeping the temperature for 60min, and treating the vacuum degree of 2 multiplied by 10-4Pa, cooling to within 100 ℃ and discharging.
(2) Vacuum packaging the molybdenum alloy to be welded discharged from the furnace, placing a titanium sheet with the same shape and size and the thickness of 0.4mm on the surface to be welded of the graphite to be welded, putting the titanium sheet and the surface to be welded of the graphite to be welded into a vacuum furnace together for activating treatment, wherein the treatment temperature is 1750 ℃, the heat preservation time is 20min, and the vacuum degree is 2.5 multiplied by 10-4And Pa, cooling to within 60 ℃, discharging, and obtaining the activated graphite.
(3) Placing Ti90Cr5Ta5 (i.e. in the brazing material, the mass percent of Ti is 90%, the mass percent of Cr is 5% and the mass percent of Ta is 5%) with the thickness of 0.30mm between the to-be-welded surface of the molybdenum alloy subjected to vacuum degassing treatment and the to-be-welded surface of the activated graphite, and then placing the brazing material (i.e. the upper surface and the lower surface of the brazing material are respectively contacted with the to-be-welded surface of the molybdenum alloy to be welded and the to-be-welded surface of the activated graphite) together in a vacuum brazing furnace for brazing treatment, wherein the brazing temperature is 1860 ℃, the heat preservation time is 25min, and the vacuum degree is 1.5 multiplied by 10-3Pa。
And (3) carrying out ultrasonic flaw detection on the molybdenum alloy and graphite composite piece obtained by brazing, displaying that the interface bonding rate is more than 95%, simultaneously sampling and carrying out mechanical property test according to the method described in the embodiment 1, and measuring that the room-temperature shear strength is 21 MPa.
Example 5
(1) Cleaning the molybdenum alloy to be welded and the graphite to be welded, placing the molybdenum alloy and the graphite to be welded into a high-temperature vacuum furnace for high-temperature vacuum degassing treatment, wherein the treatment temperature is 1650 ℃, the heat preservation time is 30min, and the treatment vacuum degree is 6 multiplied by 10-5Pa, cooling to within 100 ℃ and discharging.
(2) Vacuum packaging the molybdenum alloy to be welded after being discharged from the furnace, placing a titanium sheet with the same shape and size and the thickness of 0.3mm on the surface to be welded of the graphite to be welded, putting the titanium sheet and the graphite to be welded into a vacuum furnace together for activating the graphite, wherein the treatment temperature is 1770 ℃, the heat preservation time is 10min, and the vacuum degree is 3 multiplied by 10-4Pa, cooling to within 60 ℃ and discharging.
(3) Placing a brazing material (namely the upper surface and the lower surface of the brazing material are respectively contacted with the to-be-welded surface of the molybdenum alloy to be welded and the to-be-welded surface of the activated graphite) of Ti90Cr5Ta5 (namely the mass percent of Ti is 90%, the mass percent of Cr is 5% and the mass percent of Ta is 5% in the brazing material) with the thickness of 0.15mm between the to-be-welded surface of the molybdenum alloy to be subjected to vacuum degassing treatment and the to-be-welded surface of the graphite to be welded, and then placing the brazing material and the to-be-welded surface of the molybdenum alloy to be welded and the to-be-welded surface of the activated graphite together in a vacuum brazing furnace for-4Pa。
And (3) carrying out ultrasonic flaw detection on the molybdenum alloy and graphite composite piece obtained by brazing, displaying that the interface bonding rate is more than 95%, simultaneously sampling and carrying out mechanical property test according to the method described in the embodiment 1, and measuring that the room-temperature shear strength is 20.5 MPa.
Example 6
In this example, the titanium alloy sheet used for the activation treatment of the to-be-welded graphite surface is a TiCrTa alloy in which the mass percent of Ti is 90%, the mass percent of Cr is 5%, and the mass percent of Ta is 5%, except that the titanium alloy sheet used for the activation treatment of the to-be-welded graphite surface is different from that in example 4, and the other process steps and parameters are the same as those in example 4.
The molybdenum alloy and graphite composite piece obtained by brazing in the embodiment is subjected to ultrasonic flaw detection, the interface bonding rate is more than 85%, meanwhile, the sample is sampled and subjected to mechanical property test according to the method described in the embodiment 1, and the room-temperature shear strength is measured to be 17.5 MPa.
Example 7
In this example, except that the brazing material used in the brazing treatment is different from that in example 4, other process steps and parameters are the same as those in example 4, and the components and the mixture ratio of the brazing material in this example are as follows: the mass percent of Ti is 80%, the mass percent of Cr is 10%, and the mass percent of Ta is 10%.
The molybdenum alloy and graphite composite piece obtained by brazing in the embodiment is subjected to ultrasonic flaw detection, the interface bonding rate is over 90 percent, and meanwhile, the sample is sampled and subjected to mechanical property test according to the method described in the embodiment 1, and the room-temperature shear strength is measured to be 19 MPa.
Example 8
In this example, except that the brazing material used in the brazing treatment is different from that in example 4, other process steps and parameters are the same as those in example 4, and the components and the mixture ratio of the brazing material in this example are as follows: the mass percent of Ti is 70%, the mass percent of Cr is 15%, and the mass percent of Ta is 15%.
The molybdenum alloy and graphite composite piece obtained by brazing in the embodiment is subjected to ultrasonic flaw detection, the interface bonding rate is below 80%, and meanwhile, a sample is taken to perform a mechanical property test according to the method described in the embodiment 1, and the room-temperature shear strength is measured to be 15 MPa.
Example 9
In this example, except that the brazing material used in the brazing treatment is different from that in example 4, other process steps and parameters are the same as those in example 4, and the components and the mixture ratio of the brazing material in this example are as follows: the mass percent of Ti is 90%, and the mass percent of Cr is 10%.
The molybdenum alloy and graphite composite piece obtained by brazing in the embodiment is subjected to ultrasonic flaw detection, the interface bonding rate is below 80%, and meanwhile, a sample is taken to perform a mechanical property test according to the method described in the embodiment 1, and the room-temperature shear strength is measured to be 15 MPa.
Example 10
The process steps and parameters of this example were the same as those of example 4 except that the brazing material used in the brazing treatment was different from those of example 4, and the brazing material in this example was pure Ti.
The molybdenum alloy and graphite composite piece obtained by brazing in the embodiment is subjected to ultrasonic flaw detection, the interface bonding rate is below 90%, and meanwhile, a sample is taken to perform a mechanical property test according to the method described in the embodiment 1, and the room-temperature shear strength is measured to be 18 MPa.
Examples 11 to 13
Examples 11-13 the process steps and parameters were the same as in example 4 except that the process conditions for the brazing treatment were different from those of example 4, and the process conditions for the brazing treatment of examples 11-13 are shown in table 1.
The mechanical properties of the molybdenum alloys and graphite composites brazed according to examples 11-13 were measured as described in example 1 and the room temperature shear strength was determined as shown in table 1.
TABLE 1 braze Process conditions for examples 11-13 and mechanical Properties of the resulting composites
Examples 14 to 16
Examples 14-16 the process steps and parameters were the same as in example 4 except that the process conditions for the vacuum degassing treatment were different from those of example 4, and the process conditions for the vacuum degassing treatment of examples 14-16 are shown in Table 2.
The molybdenum alloys and graphite composites obtained from examples 14-16 by vacuum degassing were tested for mechanical properties as described in example 1 and the room temperature shear strength was measured as shown in Table 2.
TABLE 2 examples 14-16 vacuum degassing Process conditions and mechanical Properties of the resulting composites
Claims (9)
1. A vacuum brazing method of molybdenum alloy and graphite is characterized by sequentially comprising the following steps:
high vacuum degassing step: the molybdenum alloy to be welded and the graphite to be welded are not less than 5 multiplied by 10 under the vacuum degree-4Degassing heat treatment is carried out under the condition of Pa; the temperature of the degassing heat treatment is 1500-1800 ℃, and the heat preservation time is 30-60 min;
activating graphite: placing a titanium alloy sheet on a to-be-welded surface of graphite to be subjected to activation treatment to obtain activated graphite, wherein the thickness of the titanium alloy sheet is 0.2-0.5 mm; the temperature of the activation treatment is 1700-1800 ℃, the heat preservation time is 10-30 min, and the vacuum degree is not less than 5 multiplied by 10-4Pa；
After the activation treatment, cooling to below 60 ℃ along with the furnace, and discharging;
vacuum brazing: placing brazing solder between the molybdenum alloy to be welded and the graphite subjected to the active treatment for vacuum brazing treatment to obtain a molybdenum alloy and graphite composite part; the temperature of the vacuum brazing treatment is 1820-1900 ℃, the heat preservation time is 10-30 min, and the vacuum degree is not less than 5 multiplied by 10-3Pa; the brazing solder comprises the following components: ti, Cr and Ta, wherein the brazing solder is in a flake shape, and the thickness of the brazing solder is 0.15-0.30 mm.
2. The vacuum brazing method of molybdenum alloy and graphite according to claim 1, wherein the degassing heat treatment is performed in a vacuum furnace.
3. The vacuum brazing method of molybdenum alloy and graphite according to claim 1, wherein in the graphite activation step, the activation treatment is performed in a vacuum furnace.
4. A method of vacuum brazing of molybdenum alloy and graphite according to any one of claims 1 to 3, wherein in the graphite activation step, the size of the titanium alloy flakes is the same as the size of the to-be-welded surface to which the graphite is to be welded.
5. A method for vacuum brazing of molybdenum alloy and graphite according to any one of claims 1 to 3, wherein the titanium alloy sheet is a pure titanium sheet, and the pure titanium sheet meets the relevant specification of TA1 specified in the standard GB/T3622-2012 "titanium and titanium alloy strip and foil".
6. A method of vacuum brazing of molybdenum alloy and graphite according to any one of claims 1 to 3,
the brazing material comprises the following components in percentage by mass: 80-90% of Ti, 5-10% of Cr and 5-10% of Ta.
7. The vacuum brazing method of molybdenum alloy and graphite according to claim 6, wherein the brazing material is prepared by a process of vacuum melting combined with rolling.
8. A method of vacuum brazing of molybdenum alloy and graphite according to any one of claims 1 to 3, wherein in the step of vacuum brazing, the vacuum brazing process is performed in a vacuum brazing furnace; no external pressure is applied during the vacuum brazing process.
9. A method for vacuum brazing of molybdenum alloy and graphite according to any one of claims 1-3, wherein the mass percentage of molybdenum element in the molybdenum alloy to be welded is 90% or more.
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| CN111014869B (en) * | 2019-12-18 | 2021-05-07 | 西安瑞福莱钨钼有限公司 | Vacuum welding method of molybdenum-based graphite |
| CN112317907B (en) | 2020-10-27 | 2022-01-28 | 西门子爱克斯射线真空技术(无锡)有限公司 | Brazing device and method for anode target disc |
| CN113770467B (en) * | 2021-09-07 | 2023-06-20 | 安徽尚欣晶工新材料科技有限公司 | SPS pressureless brazing method for TZM alloy and graphite |
| CN113478062B (en) * | 2021-09-08 | 2021-12-07 | 北京机电研究所有限公司 | Reaction diffusion connection method for titanium-zirconium-molybdenum alloy high-temperature-resistant joint |
| CN114055864A (en) * | 2021-11-05 | 2022-02-18 | 河北宇天材料科技有限公司 | Composite-structure heat-conducting plate and preparation method and application thereof |
| CN114043174A (en) * | 2021-11-25 | 2022-02-15 | 合肥工业大学 | High-strength welding joint structure of molybdenum alloy and graphite and processing method thereof |
| CN114260614A (en) * | 2021-12-22 | 2022-04-01 | 合肥工业大学 | Ti-Cr brazing filler metal of TZM alloy/graphite and brazing process thereof |
| CN114749746B (en) * | 2022-04-20 | 2024-01-23 | 合肥工业大学 | Reaction brazing process for connecting graphite and molybdenum alloy by Ti/Zr foil |
| CN114932334B (en) * | 2022-06-14 | 2024-03-08 | 武汉联影医疗科技有限公司 | Welding method of anode target plate |
| CN115255703A (en) * | 2022-08-31 | 2022-11-01 | 武汉工程大学 | Graphite-molybdenum joint and preparation method thereof |
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