CN110193601B - Preparation method of double-layer or multi-layer refractory metal composite pipe - Google Patents
Preparation method of double-layer or multi-layer refractory metal composite pipe Download PDFInfo
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- CN110193601B CN110193601B CN201910511075.9A CN201910511075A CN110193601B CN 110193601 B CN110193601 B CN 110193601B CN 201910511075 A CN201910511075 A CN 201910511075A CN 110193601 B CN110193601 B CN 110193601B
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- 239000003870 refractory metal Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 50
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 238000003754 machining Methods 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 238000003825 pressing Methods 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000011049 filling Methods 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 13
- 230000003179 granulation Effects 0.000 claims description 13
- 238000009966 trimming Methods 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000009694 cold isostatic pressing Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 59
- 229910052750 molybdenum Inorganic materials 0.000 description 36
- 239000011733 molybdenum Substances 0.000 description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 33
- JZLMRQMUNCKZTP-UHFFFAOYSA-N molybdenum tantalum Chemical compound [Mo].[Ta] JZLMRQMUNCKZTP-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 229910001182 Mo alloy Inorganic materials 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- UNQHSZOIUSRWHT-UHFFFAOYSA-N aluminum molybdenum Chemical compound [Al].[Mo] UNQHSZOIUSRWHT-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- HTIKCTPIJXASKS-UHFFFAOYSA-N aluminum molybdenum(4+) oxygen(2-) Chemical compound [O-2].[Al+3].[Mo+4] HTIKCTPIJXASKS-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910000753 refractory alloy Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/03—Press-moulding apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
- B22F5/106—Tube or ring forms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Powder Metallurgy (AREA)
- Press-Shaping Or Shaping Using Conveyers (AREA)
Abstract
The invention discloses a preparation method of a double-layer or multi-layer refractory metal composite pipe, which comprises the following steps: firstly, granulating a binder to obtain refractory metal granulating powder required by each layer of the composite pipe; then, respectively carrying out layer-by-layer compression molding on the obtained refractory metal granulated powder through a refractory metal composite pipe isostatic pressing molding die from inside to outside to obtain a double-layer or multi-layer refractory metal pipe blank; and sintering and machining the tube blank to obtain the double-layer or multi-layer refractory metal composite tube. The tube blank is pressed and formed layer by layer from inside to outside, and the deviation of the size and the form and position tolerance of the tube blank is smaller than that before sintering; the prepared pipe has good interface combination and high inner dimension precision, reduces the reserved processing amount and improves the utilization rate of raw material powder.
Description
Technical Field
The invention belongs to the technical field of metal composite pipes, and relates to a preparation method of a double-layer or multi-layer refractory metal composite pipe.
Background
The refractory metal and the refractory metal alloy have the advantages of high melting point, high-temperature strength and the like, and are important high-temperature structural materials. The use temperature of refractory metals and their alloys is directly related to their melting points, and molybdenum alloys, tungsten alloys, niobium alloys, and the like are used in many cases. The molybdenum alloy has the defects of low-temperature brittleness, welding brittleness, difficult processing, poor high-temperature oxidation resistance and the like, so that the application range of the molybdenum alloy is limited. Mo-Nb, Mo-W, Mo-Ta and the like are infinite solid solution alloys, and the problems of high-temperature phase transformation, brittleness and the like do not exist, so that the addition of W, Nb and Ta in a certain proportion to Mo is one of effective ways for improving the performance of the molybdenum-based alloy. Meanwhile, a proper amount of second-phase reinforcing particles (rare earth oxide or ceramic phase) are introduced into the refractory metal matrix, and the performance of the refractory metal matrix composite is obviously higher than that of the refractory alloy.
In consideration of the specificity of the requirements on the material properties in practical application, the double-layer or multi-layer pipe can meet the functional realization of refractory metals. There are several possible processes for the preparation of double or multilayer pipes. The casting process, namely designing the special casting mould tube as the core, and casting and molding the core outer tube, has high requirements on equipment and high production cost due to the high melting point of refractory metals, and is not suitable for refractory metals. The welding process is to fill soft solder with low melting point and corresponding flux, such as lead-based solder, in the area of the pipe-to-pipe mating interface. The flux layer with a certain thickness on the interface can reduce and eliminate the thermal stress generated in the cooling process of the welding part through the self yield deformation while realizing the metallurgical bonding of the interface, and the proper flux and the welding process need to be further explored in consideration of the welding brittleness of molybdenum and molybdenum alloy. And the pressure forming process is to perform pressure forming after the pipes are assembled. Through the respective certain amount of deformation of the interface areas of the steel pipes, the interface metallurgical bonding of the fresh surfaces of the steel pipes and the fresh surfaces of the steel pipes is realized under the action of higher temperature and higher pressure stress, and the bonding rate is higher. The process has the defect that the deformation amount of the tube cannot be accurately controlled in the pressure forming process, so that the sizes of the tube, such as the wall thickness, the roundness of an inner hole, the coaxiality of the inner hole and the like, deviate.
Disclosure of Invention
The invention aims to provide a preparation method of a double-layer or multi-layer refractory metal composite pipe, which is used for preparing the refractory metal composite pipe with high dimensional precision and good performance.
The technical scheme adopted by the invention is that the preparation method of the double-layer or multi-layer refractory metal composite pipe is implemented according to the following steps:
step 1, respectively granulating raw material powder required by each layer of the composite pipe through a binder to obtain refractory metal granulated powder;
and 3, sintering the double-layer or multi-layer refractory metal pipe blank obtained in the step 2 to obtain a composite pipe sintered blank, and machining to obtain the double-layer or multi-layer refractory metal composite pipe.
The present invention is also characterized in that,
the flow speed of the refractory metal granulated powder obtained in the step 1 is not more than 45s/50g, and the apparent density is not less than 1.5g/cm3。
And 2, forming pressure is 160-200 MPa, and pressure maintaining time is 6-15 min.
The sintering in the step 3 specifically comprises the following steps: and (3) putting the pressed compact into a sintering furnace, heating and sintering under a wet hydrogen atmosphere, and then changing into a dry hydrogen atmosphere to continue heating and sintering.
The dew point of the wet hydrogen atmosphere is required to be 35-60 ℃, the sintering temperature under the wet hydrogen atmosphere is 600-900 ℃, and the heat preservation time is 2-5 h; the sintering temperature is 1800-2000 ℃ under the dry hydrogen atmosphere, and the heat preservation time is 2-5 h.
The isostatic pressing forming die adopted in the step 2 comprises a core die, a rubber cylinder and a fixed cylinder which are sequentially sleeved from inside to outside, a cavity is formed between the rubber cylinder and the core die, and end plugs are arranged at two ends of the cavity to form a sealed forming cavity; and an injection hole is formed in the position of the cavity on the fixed cylinder.
The core mould is tubular, and the outer wall of the core mould is provided with anti-skidding structures around the core mould close to the two ends.
The anti-skid structure is a plurality of groove rings arranged on the outer wall of the core mould.
The longitudinal section of the fixed cylinder is convex.
The step 2 specifically comprises the following steps:
2.1 filling the refractory metal granulated powder required by the first layer of the pipe obtained in the step 1 into a cavity, sealing the isostatic pressing forming die, putting the isostatic pressing forming die into a cold isostatic pressing machine for pressing, then releasing pressure, and lifting the isostatic pressing forming die;
2.2 removing the fixed cylinder and the rubber cylinder of the isostatic pressing mould, exposing the core blank formed at the cavity, trimming the core blank with the core mould to ensure the regular appearance of the core blank, replacing the end plug, the rubber cylinder and the fixed cylinder with corresponding sizes according to the thickness of the next layer of the pipe to be pressed, reassembling the end plug, the rubber cylinder and the fixed cylinder with the core blank with the core mould, and filling the second layer of refractory metal granulation powder of the pipe obtained in the step 1 into the cavity of the mould for pressing;
and 2.3, repeating the step 2.2, and pressing the pipe blank layer by layer from inside to outside until the last layer of refractory metal granulated powder is pressed, trimming the pipe blank, and removing the core mold to obtain the double-layer or multi-layer refractory metal pipe blank.
The beneficial effect of the invention is that,
1. the invention adopts the binder granulation powder as the raw material, the powder filling performance is good, and the binder effectively improves the strength of the double-layer or multi-layer composite pipe blank of the pipe, thereby being beneficial to the subsequent process operation; and the isostatic pressing formed pipe blank has good density consistency and small later-stage sintering deformation.
2. The invention adopts the rigid core mould, the inner wall of the tube blank has high dimensional accuracy, the inner wall of the base material tube is directly positioned and pressed and formed layer by layer from inside to outside, and the size and the form and position tolerance of the tube blank deviate little compared with those before sintering.
3. The interface of the double-layer or multi-layer refractory metal composite pipe prepared by the method is well combined, and the use performance of the product is greatly improved by partially using high-performance powder.
4. The invention has high inner dimension precision, reduces the reserved processing amount and improves the utilization rate of raw material powder.
5. The invention is not only suitable for preparing refractory metal double-layer or multi-layer composite metal pipes, but also can be applied to the composite forming of other double-layer or multi-layer metal pipes.
Drawings
FIG. 1 is a schematic structural view of an isostatic pressing mold used in the present invention;
fig. 2 is a schematic view of the anti-slip structure on the core mold.
In the figure, 1-1 is an upper end plug, 1-2 is a lower end plug, 2 is a core die, 2-1 is an anti-skid structure, 2-2 is a groove ring, 3 is a core blank, 4 is a cavity, 5 is a rubber cylinder, and 6 is a fixed cylinder.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a double-layer or multi-layer refractory metal composite pipe, which is implemented by the following steps:
step 1, respectively granulating raw material powder required by each layer of the composite pipe by using a binder to obtain refractory metal granulated powder, wherein the powder is different from conventional molybdenum and molybdenum alloy powder, has high apparent density and good fluidity and is beneficial to filling, and the binder can effectively improve the strength of a pressed compact and the bonding strength of each layer in the pressing process;
the method for granulating the refractory metal can be spray granulation, shot blasting granulation and the like, and the obtained refractory metal granulating powder is required to have the flow speed of not more than 45s/50g and the apparent density of not less than 1.5g/cm3。
the adopted isostatic pressing forming die structure of the refractory metal composite pipe is shown in figure 1, and comprises a core die 2, a rubber cylinder 5 and a fixed cylinder 6 which are sequentially sleeved from inside to outside, wherein a cavity 4 is formed between the rubber cylinder 5 and the core die 2, and two ends of the cavity 4 are respectively provided with an upper end plug 1-1 and a lower end plug 1-2 to form a sealed forming cavity.
Wherein the core mould 2 and the fixed cylinder 6 are both rigid moulds.
The core mold 2 is tubular, the outer surface is smooth, the anti-skid structures 2-1 are arranged on the periphery of the outer wall of the core mold 2 close to the two ends, as shown in fig. 2, the anti-skid structures 2-1 are a plurality of groove rings 2-2 arranged on the outer wall of the core mold 2. The outer diameter of the core mold 2 near the two ends is 0.02-0.05mm smaller than the outer diameter of other parts.
The fixed cylinder 6 is a convex cylinder, namely the longitudinal section is convex, and the diameter of the cylinder body close to the lower end is larger than that of the rest part of the cylinder body. The bottom of the convex cylinder is ensured to be level with the bottoms of the core mould 2 and the rubber cylinder 5, so that the rubber cylinder can be fixed to ensure the overall dimension.
The fixed cylinder 6 is provided with an injection hole for injecting a cold isostatic pressing medium between the fixed cylinder 6 and the rubber cylinder 5, and the injection hole is positioned at the position of the cavity 4.
The heights of the core mold 2 and the rubber tube 5 are higher than that of the fixed tube 6, and the height of the part with the small diameter of the fixed tube 6 is slightly higher than that of the molding cavity.
The height of the upper end plug 1-1 and the height of the lower end plug 1-2 are both 40-100 mm, the thickness of the rubber cylinder 5 is 5-10 mm, the thickness of the fixing cylinder 6 is 5-10 mm, and the aperture of the injection hole is 10-15 mm.
The end plug, the rubber cylinder and the fixed cylinder need to be matched with the core mould 2 and other structures to be replaced according to different structural layers of the pipe.
The compaction forming process of the refractory metal granulation powder comprises the following specific steps:
2.1 selecting a core mould 2 according to the requirement of the inner diameter size of the composite pipe, placing a lower end plug 1-2, an external rubber cylinder 5, sealing the bottom of the contact part of the rubber cylinder 5 and the core mould 2 at the lower part of the core mould 2 close to the outer wall, and installing a fixed cylinder 6 outside the rubber cylinder 5; and (3) filling the first layer of refractory metal granulation powder A in the tube blank obtained in the step (1) into the cavity (4), and installing and sealing an end plug 1-1 at the upper part of the rubber cylinder 5.
The sealing method can be to install a binding structure outside the cylinder body for sealing, for example, a metal wire is wound around the position to be sealed. The seal is wound around the periphery of the rubber tube 5 where the end plug is located.
2.2, placing the filled mold into a cold isostatic press for pressing, controlling the forming pressure to be 160-200 MPa, maintaining the pressure for 6-15 min, and releasing the pressure.
In the pressing process, cold isostatic pressing medium enters a gap between the rubber cylinder 5 and the fixed cylinder 6 of the die through the injection hole, and acts on the rubber cylinder 5 to enable the rubber cylinder 5 to be compressed inwards and form a tube blank.
2.3 lifting the mould from the cold isostatic press, removing the fixed cylinder 6 and the rubber cylinder 5, exposing the core blank 3 formed in the cavity 4, finishing the core blank 3 with the core mould 2 to ensure the regular appearance of the core blank 3, then replacing the end plug, the rubber cylinder 5 and the fixed cylinder 6 with corresponding sizes according to the thickness of the next layer of the pipe to be pressed, reassembling the core blank with the core mould 2, loading the second layer of refractory metal granulation powder B of the pipe obtained in the step 1 into the isostatic press mould, and pressing according to the requirement of the step 2.1;
and 2.4, repeating the step 2.3, and pressing the pipe blank layer by layer from inside to outside until the last layer of refractory metal granulated powder is pressed, trimming the pipe blank, and removing the core mold 2 to obtain the double-layer or multi-layer refractory metal pipe blank.
The method ensures that the inner cavity of the pressed blank is accurate in size, the pressed blank is directly positioned through the inner hole of the base material pipe, the reserved processing amount is reduced, and meanwhile, a double-layer or multi-layer refractory metal pipe blank with good density consistency of the pressed blank is obtained.
And 3, putting the pressed blank obtained in the step 2 into a sintering furnace, heating to 600-900 ℃ in a wet hydrogen atmosphere with the dew point of 35-60 ℃, preserving heat for 2-5 h, then heating to 1800-2000 ℃ in a dry hydrogen atmosphere, preserving heat for 2-5 h, and obtaining the double-layer or multi-layer refractory metal composite pipe sintering blank.
And 4, machining the sintered blank obtained in the step 3 to obtain the double-layer or multi-layer refractory metal composite pipe.
Example 1
Step 1, carrying out centrifugal spray granulation on pure molybdenum powder and molybdenum-alumina powder respectively by adding a binder PVA to obtain granulated powder, wherein the powder flow rates are respectively 38s/50g and 39s/50g, and the apparent density is 1.75g/cm3、1.72g/cm3。
And 3, putting the pressed blank obtained in the step 2 into a sintering furnace, heating to 750 ℃ in a wet hydrogen atmosphere with a dew point of 60 ℃, preserving heat for 5 hours, then heating to 1800 ℃ in a dry hydrogen atmosphere, preserving heat for 4 hours, and sintering and compacting to obtain a molybdenum-alumina/pure molybdenum double-layer composite tube sintered blank.
And 4, machining the sintered blank of the composite pipe obtained in the step 3 to obtain a molybdenum-aluminum oxide/pure molybdenum double-layer composite pipe, wherein the compactness of the pipe is 97.3%, the bonding strength of the two layers is high, and the outer wall of the pipe is good in wear resistance.
Example 2
Step 1, carrying out shot blasting granulation on pure molybdenum powder and molybdenum-tantalum powder respectively by adding a bonding agent PVB to obtain granulated powder, wherein the powder flow rates are 45s/50g and 41s/50g respectively, and the apparent density is 1.57g/cm3、1.74g/cm3。
Step 2, pressing the molybdenum-tantalum granulated powder obtained in the step 1 into a cold isostatic press through a double-layer or multi-layer refractory metal composite pipe isostatic pressing forming die at 190MPa for 10mim forming to obtain a molybdenum-tantalum core blank 3, and finishing the molybdenum-tantalum core blank 3 with the core die 2 to ensure that the core blank has a regular shape; replacing an end plug, a rubber cylinder and a fixed cylinder with corresponding sizes according to the thickness of the next layer of the pipe needing to be pressed, reassembling the end plug, the rubber cylinder and the fixed cylinder with the core mould with the molybdenum-tantalum core blank 3, sealing the bottom of the core mould 2, filling the pure molybdenum granules obtained in the step 1 into a forming cavity formed by the molybdenum-tantalum core blank 3, the rubber cylinder 5 and the end plug 1-2, installing the end plug 1-1 at the upper part of the rubber cylinder 5, sealing, putting the whole mould into a cold isostatic press to be pressed for 15mim forming at 190MPa to obtain a pure molybdenum/molybdenum-tantalum core blank 3, trimming the pure molybdenum/molybdenum-tantalum core blank 3 with the core mould 2, and ensuring the regular appearance of the core blank; replacing the end plug, the rubber cylinder 5 and the fixed cylinder 6 with corresponding sizes according to the thickness of the next layer of the pipe to be pressed, reassembling the end plug, the rubber cylinder 5 and the fixed cylinder with the pure molybdenum/molybdenum-tantalum core blank 3 with the core mould 2, sealing the bottom of the core mould 2, filling the molybdenum-tantalum granules obtained in the step 1 into a forming cavity formed by the pure molybdenum core blank 3, the rubber cylinder 5 and the end plug 1-2, installing the end plug 1-1 on the upper part of the rubber cylinder 5, placing the whole mould into isostatic pressing at 190MPa for 15mim forming after sealing, trimming the molybdenum-tantalum/pure molybdenum/molybdenum-tantalum composite pressed blank, and removing the core mould 2 to obtain the molybdenum-tantalum/pure molybdenum/molybdenum-tantalum composite pipe blank.
And 3, putting the pressed blank obtained in the step 2 into a sintering furnace, heating to 800 ℃ under a wet hydrogen atmosphere with a dew point of 35 ℃, preserving heat for 2h, then heating to 1900 ℃ under a dry hydrogen atmosphere, preserving heat for 2h, and sintering and compacting to obtain a molybdenum-tantalum/pure molybdenum/molybdenum-tantalum composite pipe sintered blank.
And 4, machining the sintered blank of the composite tube obtained in the step 3 to obtain the molybdenum-tantalum/pure molybdenum/molybdenum-tantalum composite tube, wherein the compactness of the tube is 97.1%, the bonding strength of each layer is high, and the inner wall and the outer wall of the tube have good corrosion resistance.
Example 3
Step 1, carrying out spray granulation on pure molybdenum powder and molybdenum-tungsten powder respectively by adding binders PVA and PVB to obtain granulated powder, wherein the powder flow rates are 39.6s/50g and 35.3s/50g respectively, and the apparent density is 1.68g/cm3、1.81g/cm3。
Step 2, pressing the pure molybdenum granulated powder obtained in the step 1 in a cold isostatic press through a double-layer or multi-layer refractory metal composite pipe isostatic pressing forming die at 200MPa for 6mim forming to obtain a pure molybdenum core blank 3, and finishing the pure molybdenum core blank 3 with the core die 2 to ensure the regular appearance of the core blank; replacing an end plug, a rubber cylinder 5 and a fixed cylinder 6 with corresponding sizes according to the thickness of the next layer of the pipe to be pressed, then reassembling the end plug, the rubber cylinder 5 and the fixed cylinder 6 with a pure molybdenum core blank 3 with a core mould, sealing the bottom of the core mould 2, then filling molybdenum-tungsten granules obtained in the step 1 into a forming cavity formed by the pure molybdenum core blank 3, the rubber cylinder 5 and the end plug 1-2, installing the end plug 1-1 at the upper part of the rubber cylinder 5, sealing, and then putting the whole mould into a cold isostatic press to be pressed for 10mim forming at 200MPa to obtain a molybdenum-tungsten/pure molybdenum core blank 3; trimming the molybdenum-tungsten/pure molybdenum double-layer composite pressed compact, and removing the core mold 2 to obtain the molybdenum-tungsten/pure molybdenum double-layer composite pipe blank.
And 3, putting the pressed blank obtained in the step 2 into a sintering furnace, heating to 900 ℃ and preserving heat for 3 hours under a wet hydrogen atmosphere with a dew point of 55 ℃, then heating to 2000 ℃ under a dry hydrogen atmosphere and preserving heat for 3 hours, and sintering and compacting to obtain a molybdenum-tungsten/pure molybdenum double-layer composite tube sintered blank.
And 4, machining the sintered blank of the composite tube obtained in the step 3 to obtain a molybdenum-tungsten/pure molybdenum double-layer composite tube, wherein the compactness of the tube is 97%, the bonding strength of the two layers is high, and the outer wall of the tube is fine in structure and has high strength and high hardness.
Example 4
Step 1, respectively carrying out spray granulation on pure molybdenum powder and molybdenum-zirconia powder by adding a binder PVA (polyvinyl alcohol) to obtain granulated powder, wherein the powder flow rates are respectively 40s/50g and 38.7s/50g, and the apparent density is 1.59g/cm3、1.70g/cm3。
Step 2, pressing the pure molybdenum granulated powder obtained in the step 1 in a cold isostatic press through a double-layer or multi-layer refractory metal composite pipe isostatic pressing forming die at 180MPa for 6mim forming to obtain a pure molybdenum core blank 3, and finishing the pure molybdenum core blank 3 with the core die 2 to ensure the regular shape of the core blank; replacing an end plug, a rubber cylinder 5 and a fixed cylinder 6 with corresponding sizes according to the thickness of the next layer of the pipe to be pressed, then reassembling the end plug, the rubber cylinder 5 and the fixed cylinder 6 with a pure molybdenum core blank 3 with a core mould, sealing the bottom of the core mould 2, then filling molybdenum-zirconia granules obtained in the step 1 into a forming cavity formed by the pure molybdenum core blank 3, the rubber cylinder 5 and the end plug 1-2, installing the end plug 1-1 at the upper part of the rubber cylinder 5, sealing, putting the whole mould into a cold isostatic press, pressing at 180MPa for 10mim forming, and obtaining the molybdenum-zirconia/pure molybdenum core blank 3; and trimming the molybdenum-zirconia/pure molybdenum composite pressed compact, and removing the core mold 2 to obtain the molybdenum-zirconia/pure molybdenum double-layer composite pipe blank.
And 3, putting the pressed blank obtained in the step 2 into a sintering furnace, heating to 600 ℃ in a wet hydrogen atmosphere with a dew point of 45 ℃, preserving heat for 4 hours, then heating to 1850 ℃ in a dry hydrogen atmosphere, preserving heat for 5 hours, and sintering and compacting to obtain the molybdenum-zirconia/pure molybdenum double-layer composite tube sintered blank.
And 4, machining the sintered blank of the composite tube obtained in the step 3 to obtain the molybdenum-zirconia/pure molybdenum double-layer composite tube, wherein the density of the tube is 98.4%, the bonding strength of the two layers is high, and the outer wall of the tube has good corrosion resistance.
Example 5
Step 1, respectively adding pure molybdenum powder, molybdenum-2% aluminum oxide and molybdenum-10% aluminum oxide powderAdding binder PVA, performing centrifugal spray granulation to obtain granulated powder with powder flow rate of 39s/50g, 40s/50g and 43s/50g, and apparent density of 1.67g/cm3、1.64g/cm3、1.54g/cm3。
Step 2, pressing the molybdenum-2% alumina granulated powder obtained in the step 1 in a cold isostatic press by a double-layer or multi-layer refractory metal composite pipe isostatic pressing forming die at 160MPa for 10mim forming to obtain a molybdenum-2% alumina core blank 3, and finishing the molybdenum-2% alumina core blank 3 with the core die 2 to ensure that the core blank has a regular shape; replacing an end plug, a rubber cylinder and a fixed cylinder with corresponding sizes according to the thickness of the next layer of the pipe to be pressed, reassembling the end plug, the rubber cylinder and the fixed cylinder with molybdenum-2% alumina core blank 3 with a core mould, sealing the bottom of the core mould 2, then granulating and filling pure molybdenum obtained in the step 1 into a forming cavity formed by the molybdenum-2% alumina core blank 3, the rubber cylinder 5 and the end plug 1-2, installing the end plug 1-1 on the upper part of the rubber cylinder 5, after sealing, putting the whole mould into a cold isostatic press to be pressed for 10mim forming at 170MPa to obtain the pure molybdenum/molybdenum-2% alumina core blank 3, and finishing the pure molybdenum/molybdenum-2% alumina core blank 3 with the core mould 2 to ensure the regular appearance of the core blank; the end plugs, the rubber cylinders 5 and the fixed cylinders 6 with corresponding sizes are replaced according to the thickness of the next layer of the pipe to be pressed, and reassembled with a pure molybdenum/molybdenum-2% alumina core blank 3 with a core model, the bottom of the core model 2 is sealed, then the molybdenum-2 percent alumina obtained in the step 1 is granulated and filled in a forming cavity formed by a pure molybdenum/molybdenum-2 percent alumina core blank 3, a rubber cylinder 5 and an end plug 1-2, installing an end plug 1-1 on the upper part of a rubber cylinder 5, sealing, putting the whole mould into a cold isostatic press, pressing at 190MPa for 10mim molding to obtain a molybdenum-2% alumina/pure molybdenum/molybdenum-2% alumina core blank 3, trimming a molybdenum-2% alumina/pure molybdenum/molybdenum-2% alumina core blank 3 with a core mold 2 to ensure that the core blank has a regular shape; replacing an end plug, a rubber cylinder 5 and a fixed cylinder 6 with corresponding sizes according to the thickness of the next layer of the pipe needing to be pressed, reassembling the end plug, the rubber cylinder 5 and the fixed cylinder 6 with a molybdenum-2% alumina/pure molybdenum/molybdenum-2% alumina core blank 3 with a core mould 2 to seal the bottom of the core mould 2, then filling the molybdenum-10% alumina granules obtained in the step 1 into a forming cavity formed by the molybdenum-2% alumina/pure molybdenum/molybdenum-2% alumina core blank 3, the rubber cylinder 5 and the end plug 1-2, installing the end plug 1-1 on the upper part of the rubber cylinder 5, after sealing, putting the whole mould into isostatic pressing at 190MPa to press 15mim for forming, trimming the molybdenum-10% alumina/molybdenum-2% alumina/pure molybdenum/molybdenum-2% alumina composite core mould, and removing the core mould 2 to obtain molybdenum-10% alumina/molybdenum-2% alumina/pure molybdenum/2% alumina And (3) aluminum composite tube blanks.
And 3, putting the pressed blank obtained in the step 2 into a sintering furnace, heating to 850 ℃ under a wet hydrogen atmosphere with a dew point of 40 ℃, preserving heat for 2h, then heating to 1920 ℃ under a dry hydrogen atmosphere, preserving heat for 4h, and sintering and compacting to obtain a molybdenum-10% alumina/molybdenum-2% alumina/pure molybdenum/molybdenum-2% alumina composite pipe sintered blank.
And 4, machining the sintered blank of the composite pipe obtained in the step 3 to obtain a molybdenum-10% aluminum oxide/molybdenum-2% aluminum oxide/pure molybdenum/molybdenum-2% aluminum oxide composite pipe, wherein the compactness of the pipe is 97.5%, the multilayer bonding strength is high, and the inner wall and the outer wall of the pipe are good in wear resistance.
Claims (1)
1. The preparation method of the double-layer or multi-layer refractory metal composite pipe is characterized by comprising the following steps:
step 1, respectively granulating raw material powder required by each layer of the composite pipe through a binder to obtain refractory metal granulated powder;
the flow rate of the refractory metal granulated powder is not more than 45s/50g, and the apparent density is not less than 1.5g/cm3；
Step 2, respectively carrying out layer-by-layer compression molding on the refractory metal granulated powder obtained in the step 1 from inside to outside through a refractory metal composite pipe isostatic pressing molding die to obtain a double-layer or multi-layer refractory metal pipe blank; the forming pressure is 160-200 MPa, and the pressure maintaining time is 6-15 min;
the adopted isostatic pressing forming die comprises a core die (2), a rubber cylinder (5) and a fixed cylinder (6) which are sequentially sleeved from inside to outside, wherein a cavity (4) is formed between the rubber cylinder (5) and the core die (2), and end plugs are arranged at two ends of the cavity (4) to form a sealed forming cavity; an injection hole is formed in the position of the cavity (4) on the fixed cylinder (6); the core mold (2) is tubular, and anti-skid structures (2-1) are arranged on the periphery of the outer wall of the core mold (2) close to two ends; the anti-skid structure (2-1) is a plurality of groove rings (2-2) arranged on the outer wall of the core mold (2); the longitudinal section of the fixed cylinder (6) is convex; the fixed cylinder (6) is a convex cylinder, and the bottom of the convex cylinder is ensured to be level with the bottoms of the core mold (2) and the rubber cylinder (5); the outer diameter of the core mould (2) close to the two ends is 0.02-0.05mm smaller than that of other parts;
the step 2 specifically comprises the following steps:
2.1 filling the refractory metal granulated powder required by the first layer of the pipe obtained in the step 1 into a cavity (4), sealing the isostatic pressing forming die, putting the isostatic pressing forming die into a cold isostatic pressing machine for pressing, then releasing pressure, and lifting the isostatic pressing forming die;
2.2 removing the fixed cylinder (6) and the rubber cylinder (5) of the isostatic pressing mould, exposing the core blank formed at the cavity (4), finishing the core blank with the core mould (2) to ensure the regular appearance of the core blank, then replacing the end plug, the rubber cylinder (5) and the fixed cylinder (6) with corresponding sizes according to the thickness of the next layer of the pipe to be pressed, reassembling the core blank with the core mould (2), and filling the second layer of refractory metal granulation powder of the pipe obtained in the step 1 into the cavity (4) of the mould for pressing;
2.3, repeating the step 2.2, and pressing the tube blank layer by layer from inside to outside until the last layer of refractory metal granulated powder is pressed, trimming the tube blank, and removing the core mold to obtain a double-layer or multi-layer refractory metal tube blank;
step 3, sintering the double-layer or multi-layer refractory metal pipe blank obtained in the step 2 to obtain a composite pipe sintered blank, and machining to obtain the double-layer or multi-layer refractory metal composite pipe;
the sintering is specifically as follows: putting the pressed compact into a sintering furnace, heating and sintering under a wet hydrogen atmosphere, and then changing into a dry hydrogen atmosphere to continue heating and sintering; the dew point of the wet hydrogen atmosphere is required to be 35-60 ℃, the sintering temperature under the wet hydrogen atmosphere is 600-900 ℃, and the heat preservation time is 2-5 h; the sintering temperature is 1800-2000 ℃ under the dry hydrogen atmosphere, and the heat preservation time is 2-5 h.
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| CA2357713A1 (en) * | 1999-01-06 | 2000-07-13 | Ceramight Composites Ltd. | Metal-ceramic laminar-band composite |
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