CN116694959A - High-purity high-homogeneity nickel-tungsten intermediate alloy and preparation method thereof - Google Patents
High-purity high-homogeneity nickel-tungsten intermediate alloy and preparation method thereof Download PDFInfo
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- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000000956 alloy Substances 0.000 title claims abstract description 127
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 70
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000003723 Smelting Methods 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- 238000003825 pressing Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000004663 powder metallurgy Methods 0.000 claims abstract description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 41
- 239000011812 mixed powder Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- 230000006698 induction Effects 0.000 claims description 7
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 238000000462 isostatic pressing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 abstract description 27
- 229910052721 tungsten Inorganic materials 0.000 abstract description 27
- 229910000601 superalloy Inorganic materials 0.000 abstract description 11
- 238000005204 segregation Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000000265 homogenisation Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a high-purity high-homogeneity nickel-tungsten intermediate alloy, which comprises the following elements in percentage by mass: 43% -65% of Ni, and the balance of W and unavoidable impurities; the preparation method of the nickel-tungsten intermediate alloy comprises the following steps: 1. selecting carbonyl nickel powder and tungsten powder; 2. weighing and uniformly mixing carbonyl nickel powder and tungsten powder; 3. cold pressing the mould; 4. powder metallurgy sintering is carried out after the tantalum foil or the titanium foil is wrapped; 5. and (5) casting after vacuum melting to obtain the nickel-tungsten intermediate alloy. The nickel tungsten element in the nickel tungsten intermediate alloy is uniformly distributed, segregation, high density and high melting point phases are not present, the impurity content is low, the nickel tungsten intermediate alloy is used as a tungsten element additive material prepared from the nickel-based superalloy, the smelting temperature is low, the smelting time is short, and the composition and the tissue uniformity of the alloy material of the product are ensured; the invention strictly controls the raw material selection and the preparation process, avoids the pollution of the external environment, improves the homogenization degree of the alloy and obtains the high-purity and high-homogeneity nickel-tungsten intermediate alloy.
Description
Technical Field
The invention belongs to the technical field of alloy preparation, and particularly relates to a high-purity high-homogeneity nickel-tungsten intermediate alloy and a preparation method thereof.
Background
Nickel-based superalloys are currently used mainly for manufacturing the hottest end components of aviation jet engines and various industrial gas turbines because of their good high temperature strength, oxidation resistance, and excellent gas corrosion resistance. With the rapid development of important fields such as aerospace, nuclear industry, metallurgical chemical industry and the like, higher requirements are put forward on the performance of nickel-based superalloy. The solid solution strengthening and dispersion strengthening effects can be achieved by adding tungsten element into the nickel-based alloy, and the high-temperature tissue stability, high-temperature strength and heat-resistant durability of the material are effectively improved.
The main mode of adding tungsten element in the existing nickel-based superalloy is to directly add elemental tungsten metal in the smelting process, but the melting point of the tungsten metal is high (3422 ℃) and the density is large (19.26 g/cm) 3 ) In the smelting process, the smelting temperature needs to be increased, the smelting time is prolonged, and finally, high-melting-point and high-density slag inclusion is still easy to form, which is not beneficial to the performance of the final product. Compared with the simple substance of tungsten, the nickel-tungsten intermediate alloy has low melting point, and the nickel-tungsten intermediate alloy is used as a tungsten element addition material of the nickel-based superalloy, so that the required smelting temperature is low, the smelting time is short, the tungsten element segregation can be avoided during smelting, high-density inclusion and high-melting-point W blocks are formed, and the composition and tissue uniformity of a final product are ensured.
The invention discloses a nickel-tungsten intermediate alloy with a patent publication number of CN106756243A and a preparation method thereof, wherein metal nickel and metal tungsten (41-44 wt%) are directly used as raw materials for vacuum induction smelting, the vacuum degree is 5-30 Pa, the power is 40-80 kW, and the refining temperature is 1550-1650 ℃. The method is carried out at a higher temperature, has high energy consumption and high cost, and does not relate to a preparation method of the nickel-tungsten intermediate alloy with higher tungsten content ratio.
The invention patent with publication number of CN109182843A discloses a method for preparing a nickel-tungsten intermediate alloy by electron beam melting, wherein tungsten accounts for 35.1-45% by mass, and the vacuum degree during melting is less than 5 multiplied by 10 -2 Pa, the number of refining was twice. The method is similar to the patent, and the metal nickel and the metal niobium are directly smelted, and two electron beam smelting processes are needed.
The invention patent with publication number CN110358947A discloses a method for preparing a nickel-tungsten intermediate alloy by an out-of-furnace aluminothermic process, wherein raw materials mainly comprise tungsten oxide and atomized nickel powder, and the tungsten content of a final nickel-tungsten intermediate alloy product is 40% -42%. The method takes metal oxide as a raw material, and utilizes a metallothermic reduction method to prepare the intermediate alloy, so that the alloy has poor uniformity, segregation is easy to occur, the alloy components are not easy to control, and the alloy compactness is poor. In addition, a certain amount of aluminum element can be introduced into the alloy, and the impurity content is higher.
The invention patent with publication number of CN109825752A discloses a nickel-tungsten intermediate alloy prepared by a sintering process, wherein the proportion of tungsten powder is 38% -55%, the balance is nickel powder, a sample is not protected in the sintering process, and a large-scale sintering furnace cavity in actual industrial production is a graphite cavity, so that serious carbon pollution is caused to the sample. In addition, the patent does not specifically require the vacuum degree during sample sintering, but sintering under a high vacuum degree can also cause the oxygen and nitrogen contents of the sample to be too high. This can result in the final nickel-base alloy product having too high a carbon, oxygen, nitrogen content, which increases the likelihood of forming carbides, oxides, nitrides, and compromises product performance. Furthermore, compared with nickel metal (density of 8.9 g/cm 3 ) Density of tungsten metal (19.26 g/cm 3 ) The nickel-tungsten master alloy finished product is very high, and the formation of tungsten blocks is difficult to avoid by a one-step powder sintering process.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a high-purity and high-homogeneity nickel-tungsten intermediate alloy aiming at the defects in the prior art. The nickel tungsten elements in the nickel tungsten intermediate alloy are uniformly distributed, segregation, high density and high melting point phases are not present, and the impurity content is low; the nickel-tungsten intermediate alloy is used as a tungsten element additive material in the preparation process of the nickel-based superalloy, so that the smelting temperature is low, the smelting time is short, the composition and structure uniformity of the alloy material of the product are ensured, and the service performance of the product is improved.
In order to solve the technical problems, the invention adopts the following technical scheme: the high-purity high-homogeneity nickel-tungsten intermediate alloy is characterized by comprising the following elements in percentage by mass: 43% -65% of Ni, and the balance of W and unavoidable impurities; the mass percentages of the elements in the unavoidable impurities are as follows: less than or equal to 0.005% of C, less than or equal to 0.007% of O, less than or equal to 0.003% of N, less than or equal to 0.0005% of S, less than or equal to 0.0035% of Al, less than or equal to 0.0015% of As, less than or equal to 0.00025% of Bi, less than or equal to 0.00025% of Co, less than or equal to 0.00025% of Cr, less than or equal to 0.001% of Cu, less than or equal to 0.01% of Fe, less than or equal to 0.0001% of Mn, less than or equal to 0.002% of Mo, less than or equal to 0.001% of P, less than or equal to 0.0001% of Pb, less than or equal to 0.01% of Si, less than or equal to 0.0005% of Sn, less than or equal to 0.003% of Ti, and less than or equal to 0.0003% of Zn.
The invention uses Ni as a matrix, uses W with strengthening and heat-resisting functions as main alloy elements to form a nickel-tungsten intermediate alloy, is used for manufacturing intermediate alloy materials for high-temperature alloys of aviation jet engines and hottest end parts of various industrial gas turbines, and forms Ni within the content range of alloy design components by controlling the content of each element 4 W is single phase. Compared with simple substance tungsten metal, the melting point of the nickel-tungsten intermediate alloy is obviously reduced, the difference from the melting point of the matrix nickel metal is within 300 ℃, and the specific heat, the specific gravity and the latent heat of fusion are similar to those of the matrix nickel metal, so that the requirement of the nickel-base superalloy on refractory metal component ingredients can be met, and the metallurgical defects of high-density high-melting-point tungsten blocks, segregation and the like which are easily formed in the smelting process of the nickel-base superalloy are effectively solved. Meanwhile, the hardness of the nickel-tungsten intermediate alloy prepared by the method is moderate and is 20HRC, the nickel-tungsten intermediate alloy has good processing performance, and is convenient for subsequent cutting into small slices, so that the nickel-tungsten intermediate alloy can be conveniently added as an intermediate alloy material in the nickel-based superalloy smelting process.
In addition, the invention also discloses a method for preparing the high-purity high-homogeneity nickel-tungsten intermediate alloy, which is characterized by comprising the following steps of:
step one, powder preparation: nickel carbonyl powder and tungsten powder are selected as raw material powder;
step two, powder mixing: weighing and uniformly mixing the nickel carbonyl powder and the tungsten powder selected in the first step according to the element composition of the target product nickel-tungsten intermediate alloy to obtain mixed powder;
step three, powder cold pressing: filling the mixed powder obtained in the second step into a die, and then adopting an electric isostatic pressing machine to perform cold pressing at room temperature to obtain a nickel-tungsten blank;
step four, sintering the blank: wrapping and compacting the nickel-tungsten blank obtained in the third step by adopting tantalum foil or titanium foil with the mass purity of more than 99%, and then placing the nickel-tungsten blank in a vacuum sintering furnace for powder metallurgy sintering to obtain a nickel-tungsten intermediate alloy block;
step five, vacuum smelting: and (3) carrying out vacuum smelting on the nickel-tungsten intermediate alloy block obtained in the step (IV), and then casting into an ingot to obtain the high-purity and high-homogeneity nickel-tungsten intermediate alloy.
The invention strictly controls the impurity content of the raw material and the preparation process of the nickel-tungsten intermediate alloy, avoids impurity elements introduced from the outside in the raw material or the preparation process, and controls the impurity content of the nickel-tungsten intermediate alloy at an extremely low level. Meanwhile, the nickel and tungsten elements of the nickel-tungsten intermediate alloy prepared by the method are uniformly distributed, and a high-density high-melting-point tungsten block is not existed, so that the quality of the nickel-based superalloy of the downstream material is further ensured, and the production efficiency and the qualification rate of the alloy are effectively improved.
The method is characterized in that the mass purity of the nickel carbonyl powder and the tungsten powder in the first step is more than 99.5%, the granularity is more than 200 meshes, and the granularity ratio of the nickel carbonyl powder to the tungsten powder is 1:7. The invention effectively reduces the impurity content of the nickel-tungsten intermediate alloy by strictly controlling the mass purity and the granularity of the raw material nickel carbonyl powder and tungsten powder, ensures the purity and the machinability of the nickel-tungsten intermediate alloy, and simultaneously controls the granularity ratio of the nickel-tungsten intermediate alloy to be the optimal granularity ratio, thereby being beneficial to the uniform mixing of the two powders.
The method is characterized in that the rotating speed of the uniformly mixed powder mixer charging barrel in the second step is 20-60 revolutions per minute, and the time is 3-8 hours. According to the invention, the high-melting-point alloy component tungsten powder and the low-melting-point alloy component nickel powder are mixed, and the rotation speed and time are controlled to obtain uniformly mixed powder, so that the component uniformity of the nickel-tungsten intermediate alloy is improved.
The method is characterized in that in the third step, the mixed powder is filled into a die, vacuum sealing is carried out by a vacuum sealing machine, and then cold pressing is carried out. According to the invention, the mixed powder is filled into the mold with the specific shape and is sealed by a vacuum machine, so that the powder overflow phenomenon can not occur in the subsequent cold pressing process, and the nickel-tungsten blank with the specific shape is obtained.
The method is characterized in that the mixed powder in the third step is subjected to cold pressing within 8 hours after being uniformly mixed. According to the invention, the cold pressing process is completed within 8 hours after the nickel-tungsten powder is mixed, so that uneven components of the nickel-tungsten intermediate alloy and even high-melting-point tungsten blocks caused by tungsten powder with larger specific gravity sedimentation due to long-time placement are avoided.
The method is characterized in that the cold pressing pressure in the third step is 100-250 MPa, and the pressure maintaining time is 3-8 min. The mixed powder is pressurized under the pressure and kept for the time, so that the formability of the nickel-tungsten blank is ensured, and the subsequent sintering forming is facilitated.
The method is characterized in that the vacuum degree of the system in the powder metallurgy sintering process in the step four is 0.05 Pa-0.001Pa, the sintering temperature is 800 ℃ -1550 ℃, the sintering time is 1 h-5 h, and titanium sponge is placed beside the wrapped nickel tungsten blank. According to the invention, the vacuum degree of a sintering system is strictly controlled, and the nickel-tungsten blank is wrapped by the tantalum foil or the titanium foil, so that the nickel-tungsten blank is effectively prevented from introducing impurity elements such as carbon, oxygen, nitrogen and the like in the external environment, and the purity of the nickel-tungsten intermediate alloy is improved; meanwhile, a small amount of titanium sponge is placed, and oxygen can be combined with titanium preferentially compared with nickel and tungsten according to a free energy diagram of metal oxide, so that the titanium sponge absorbs oxygen in the surrounding environment of the wrapped nickel-tungsten blank, and the nickel-tungsten intermediate alloy block is prevented from being oxidized.
The method is characterized in that in the fifth step, the vacuum smelting is one or more of vacuum induction smelting, vacuum suspension smelting and electron beam smelting, the vacuum degree of the vacuum smelting is 0.01 Pa-0.001 Pa, the smelting temperature is 1000 ℃ -1600 ℃, and the smelting time is 10 min-20 min. According to the invention, the secondary smelting purification process is added after the sintering of the nickel-tungsten blank, so that the high-density inclusion and high-melting-point tungsten block are further ensured not to exist in the nickel-tungsten intermediate alloy, and the impurity elements such as oxygen and nitrogen in the nickel-tungsten intermediate alloy are reduced, thereby further improving the purity and the homogenization degree of the nickel-tungsten intermediate alloy. Meanwhile, compared with direct smelting tungsten metal simple substance, the sintered nickel-tungsten intermediate alloy block has lower melting point, avoids high energy consumption caused by high-temperature smelting, and is not easy to be biased to gather by the nickel-tungsten element after sintering prealloying, thereby being more beneficial to the homogenization of the nickel-tungsten intermediate alloy.
Compared with the prior art, the invention has the following advantages:
1. the nickel tungsten elements in the nickel tungsten intermediate alloy are uniformly distributed, segregation, high density and high melting point phases are not present, and the impurity content is low; the nickel-tungsten intermediate alloy is used as a tungsten element additive material in the preparation process of the nickel-based superalloy, so that the smelting temperature is low, the smelting time is short, the composition and structure uniformity of the alloy material of the product are ensured, and the service performance of the product is improved.
2. Compared with the preparation of the nickel-tungsten intermediate alloy by simple sintering, the preparation method has the advantages that the raw materials are strictly controlled from selection to preparation, the nickel carbonyl powder and the tungsten powder are proportionally selected according to the brand requirements of the nickel-tungsten intermediate alloy, the components of the nickel-tungsten intermediate alloy are controllable, the particle size ratio of the nickel-tungsten intermediate alloy is limited, the uniform mixing of the powder is facilitated, and the component uniformity of the nickel-tungsten intermediate alloy is ensured; then, after cold press molding, the nickel tungsten blank is wrapped by adopting titanium foil or tantalum foil, so that the nickel tungsten blank is prevented from being polluted by a graphite cavity of a sintering furnace, sponge titanium is placed beside the blank in the sintering process, powder metallurgy sintering is performed under high vacuum degree, the pollution of impurity elements such as carbon, oxygen and nitrogen in the atmosphere to the alloy is avoided, the content of the impurity elements such as carbon and oxygen is strictly controlled, the impurity elements such as oxygen and nitrogen of the nickel tungsten intermediate alloy are reduced through vacuum melting purification, the high-density high-melting-point W block is avoided in the alloy, the homogenization degree of the alloy is improved, and pollution is reduced, so that the high-purity high-homogeneity nickel tungsten intermediate alloy is obtained.
3. Compared with the method for preparing the nickel-tungsten intermediate alloy by directly smelting the nickel metal simple substance and the tungsten metal simple substance, the method provided by the invention has the advantages that the pre-sintering is used for pre-alloying the nickel-tungsten, the smelting temperature and the smelting time required by the subsequent vacuum smelting are reduced, the pre-alloyed nickel-tungsten alloy is not easy to cause element segregation in the subsequent smelting process to form a W block with high density and high melting point, and the high purity and high homogeneity of the nickel-tungsten intermediate alloy are ensured; in addition, the prealloyed nickel-molybdenum alloy can be obtained by only carrying out vacuum melting once, so that the preparation process is simplified.
4. Compared with the method for preparing the nickel-tungsten intermediate alloy by the out-of-furnace aluminothermic method, the whole preparation process is carried out under high vacuum degree, the alloy is effectively prevented from being polluted by the external environment, the high-purity raw materials are mixed in proportion, the controllable alloy components are ensured, and the impurity content of the finally obtained alloy material is very low.
5. The nickel-tungsten intermediate alloy prepared by the method has high purity and homogeneity, and the process is simple and effective, and is suitable for large-scale factory production.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is an XRD pattern of a nickel-tungsten master alloy prepared in example 1 of the present invention.
Fig. 2a is a scan of a nickel-tungsten master alloy prepared in example 1 of the present invention.
FIG. 2b is a diagram showing the distribution of Ni element in the nickel-tungsten master alloy prepared in example 1 of the present invention.
FIG. 2c is a graph showing the W element distribution in the nickel-tungsten master alloy prepared in example 1 of the present invention.
Detailed Description
Example 1
Example 1
The high-purity high-homogeneity nickel-tungsten intermediate alloy of the embodiment comprises the following elements in percentage by mass: ni 65%, and the balance W and unavoidable impurities.
The preparation method of the high-purity and high-homogeneity nickel-tungsten intermediate alloy comprises the following steps:
step one, powder preparation: nickel carbonyl powder with the mass purity of more than 99.5 percent and the granularity of 2.50 mu m and tungsten powder with the mass purity of more than 99.5 percent and the granularity of 16.71 mu m are selected as raw material powder;
step two, powder mixing: according to the element composition of the target product nickel-tungsten intermediate alloy, weighing and uniformly mixing the nickel carbonyl powder and the tungsten powder selected in the first step, wherein the rotating speed of a charging barrel is 20 revolutions per minute, and the time is 3 hours, so as to obtain mixed powder;
step three, powder cold pressing: loading the mixed powder obtained in the second step into a die, vacuum sealing by adopting a vacuum sealing machine, and then cold pressing by adopting an electric isostatic pressing machine under the condition of room temperature, wherein the cold pressing pressure is 100MPa, the pressure maintaining time is 8min, and a nickel-tungsten blank is obtained, wherein the interval time between the mixing process and the cold pressing process of the mixed powder is 2h;
step four, sintering the blank: wrapping the nickel-tungsten blank obtained in the third step by adopting titanium foil with the mass purity of more than 99%, compacting, then placing the nickel-tungsten blank in a vacuum sintering furnace for powder metallurgy sintering, wherein the vacuum degree of the system is 0.05 Pa-0.001Pa, the sintering temperature is 800 ℃, the sintering time is 5 hours, and placing a small amount of titanium sponge beside the wrapped nickel-tungsten blank to obtain a nickel-tungsten intermediate alloy block;
step five, vacuum smelting: and (3) placing the nickel-tungsten intermediate alloy block obtained in the step (IV) into a vacuum induction furnace for vacuum induction smelting, wherein the vacuum degree is 0.01 Pa-0.001Pa, the smelting temperature is 1000 ℃, the smelting time is 20min, and then casting into an ingot to obtain the high-purity and high-homogeneity nickel-tungsten intermediate alloy.
The nickel-tungsten master alloy composition prepared in this example was tested and the results are shown in table 1:
as can be seen from Table 1, the impurity elements in the nickel-tungsten intermediate alloy are very low, especially the carbon, oxygen, nitrogen and sulfur elements, which shows that the nickel-tungsten intermediate alloy prepared by the invention completely avoids the pollution of external environment.
FIG. 1 shows XRD patterns of a nickel-tungsten master alloy prepared according to the present embodiment, in which the phase is Ni alone as shown in FIG. 1 4 The W phase, the absence of W phase peaks and Ni phase peaks, indicates that the nickel and tungsten particles are fully alloyed.
Fig. 2a is a scanned view of the nickel-tungsten intermediate alloy prepared in example 1 of the present invention, and fig. 2b to 2c are graphs of Ni element and W element in the nickel-tungsten intermediate alloy prepared in this example, respectively, as can be seen from fig. 2a to 2c, the nickel-tungsten element in the nickel-tungsten intermediate alloy is uniformly distributed as a whole, no segregation exists, and no high-melting-point and high-density tungsten block is formed.
Example 2
The high-purity high-homogeneity nickel-tungsten intermediate alloy of the embodiment comprises the following elements in percentage by mass: 43% of Ni, and the balance of W and unavoidable impurities.
The preparation method of the high-purity and high-homogeneity nickel-tungsten intermediate alloy comprises the following steps:
step one, powder preparation: nickel carbonyl powder with the mass purity of more than 99.5 percent and the granularity of 2.50 mu m and tungsten powder with the mass purity of more than 99.5 percent and the granularity of 16.71 mu m are selected as raw material powder;
step two, powder mixing: according to the element composition of the target product nickel-tungsten intermediate alloy, weighing and uniformly mixing the nickel carbonyl powder and the tungsten powder selected in the first step, wherein the rotating speed of a charging barrel is 60 revolutions per minute, and the time is 8 hours, so as to obtain mixed powder;
step three, powder cold pressing: loading the mixed powder obtained in the second step into a die, vacuum sealing by adopting a vacuum sealing machine, and then cold pressing by adopting an electric isostatic pressing machine under the condition of room temperature, wherein the cold pressing pressure is 250MPa, the pressure maintaining time is 8min, and a nickel-tungsten blank is obtained, wherein the interval time between the mixing process and the cold pressing process of the mixed powder is 4h;
step four, sintering the blank: the nickel-tungsten blank obtained in the third step is tightly wrapped by adopting tantalum foil with the mass purity of more than 99%, then the nickel-tungsten blank is placed in a vacuum sintering furnace for powder metallurgy sintering, the vacuum degree of the system is 0.05 Pa-0.001Pa, the sintering temperature is 1550 ℃ and the sintering time is 1h, and a small amount of titanium sponge is placed beside the wrapped nickel-tungsten blank to obtain a nickel-tungsten intermediate alloy block;
step five, vacuum smelting: and (3) placing the nickel-tungsten intermediate alloy block obtained in the step (IV) into a vacuum suspension induction furnace for vacuum suspension induction smelting, wherein the vacuum degree is 0.01 Pa-0.001Pa, the smelting temperature is 1600 ℃, the smelting time is 10min, and then casting into an ingot to obtain the high-purity high-homogeneity nickel-tungsten intermediate alloy.
The nickel-tungsten master alloy composition prepared in this example was tested and the results are shown in table 2:
as can be seen from Table 2, the impurity elements in the nickel-tungsten intermediate alloy are very low, especially the carbon, oxygen, nitrogen and sulfur elements, which shows that the nickel-tungsten intermediate alloy prepared by the invention completely avoids the pollution of external environment.
Example 3
The high-purity high-homogeneity nickel-tungsten intermediate alloy of the embodiment comprises the following elements in percentage by mass: 50% of Ni, and the balance of W and unavoidable impurities.
The preparation method of the high-purity and high-homogeneity nickel-tungsten intermediate alloy comprises the following steps:
step one, powder preparation: nickel carbonyl powder with the mass purity of more than 99.5 percent and the granularity of 2.50 mu m and tungsten powder with the mass purity of more than 99.5 percent and the granularity of 16.71 mu m are selected as raw material powder;
step two, powder mixing: according to the element composition of the target product nickel-tungsten intermediate alloy, weighing and uniformly mixing the nickel carbonyl powder and the tungsten powder selected in the first step, wherein the rotating speed of a charging barrel is 40 revolutions per minute, and the time is 5 hours, so as to obtain mixed powder;
step three, powder cold pressing: loading the mixed powder obtained in the second step into a die, vacuum sealing by adopting a vacuum sealing machine, and then cold pressing by adopting an electric isostatic pressing machine under the condition of room temperature, wherein the cold pressing pressure is 180MPa, the pressure maintaining time is 6min, and a nickel-tungsten blank is obtained, wherein the interval time between the mixing process and the cold pressing process of the mixed powder is 6h;
step four, sintering the blank: the nickel-tungsten blank obtained in the third step is tightly wrapped by adopting tantalum foil with the mass purity of more than 99 percent, then the nickel-tungsten blank is placed in a vacuum sintering furnace for powder metallurgy sintering, the vacuum degree of the system is 0.05 Pa-0.001Pa, the sintering temperature is 1200 ℃, the sintering time is 2 hours, and a small amount of titanium sponge is placed beside the wrapped nickel-tungsten blank to obtain a nickel-tungsten intermediate alloy block;
step five, vacuum smelting: and (3) placing the nickel-tungsten intermediate alloy block obtained in the step (IV) into a vacuum electron beam melting furnace for vacuum electron beam melting, wherein the vacuum degree is 0.01 Pa-0.001Pa, the melting temperature is 1500 ℃, the melting time is 15min, and then casting into an ingot to obtain the high-purity high-homogeneity nickel-tungsten intermediate alloy.
The nickel-tungsten master alloy composition prepared in this example was tested and the results are shown in table 3:
as can be seen from Table 3, the impurity elements in the nickel-tungsten intermediate alloy are very low, especially the carbon, oxygen, nitrogen and sulfur elements, which shows that the nickel-tungsten intermediate alloy prepared by the invention completely avoids the pollution of external environment.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (9)
1. The high-purity high-homogeneity nickel-tungsten intermediate alloy is characterized by comprising the following elements in percentage by mass: 43% -65% of Ni, and the balance of W and unavoidable impurities; the mass percentages of the elements in the unavoidable impurities are as follows: less than or equal to 0.005% of C, less than or equal to 0.007% of O, less than or equal to 0.003% of N, less than or equal to 0.0005% of S, less than or equal to 0.0035% of Al, less than or equal to 0.0015% of As, less than or equal to 0.00025% of Bi, less than or equal to 0.00025% of Co, less than or equal to 0.00025% of Cr, less than or equal to 0.001% of Cu, less than or equal to 0.01% of Fe, less than or equal to 0.0001% of Mn, less than or equal to 0.002% of Mo, less than or equal to 0.001% of P, less than or equal to 0.0001% of Pb, less than or equal to 0.01% of Si, less than or equal to 0.0005% of Sn, less than or equal to 0.003% of Ti, and less than or equal to 0.0003% of Zn.
2. A method of preparing a high purity, high homogeneity nickel tungsten master alloy as claimed in claim 1, comprising the steps of:
step one, powder preparation: nickel carbonyl powder and tungsten powder are selected as raw material powder;
step two, powder mixing: weighing and uniformly mixing the nickel carbonyl powder and the tungsten powder selected in the first step according to the element composition of the target product nickel-tungsten intermediate alloy to obtain mixed powder;
step three, powder cold pressing: filling the mixed powder obtained in the second step into a die, and then adopting an electric isostatic pressing machine to perform cold pressing at room temperature to obtain a nickel-tungsten blank;
step four, sintering the blank: wrapping and compacting the nickel-tungsten blank obtained in the third step by adopting tantalum foil or titanium foil with the mass purity of more than 99%, and then placing the nickel-tungsten blank in a vacuum sintering furnace for powder metallurgy sintering to obtain a nickel-tungsten intermediate alloy block;
step five, vacuum smelting: and (3) carrying out vacuum smelting on the nickel-tungsten intermediate alloy block obtained in the step (IV), and then casting into an ingot to obtain the high-purity and high-homogeneity nickel-tungsten intermediate alloy.
3. The method according to claim 2, wherein in the first step, the mass purity of the nickel carbonyl powder and the tungsten powder is 99.5% or more, the particle size is 200 mesh or more, and the particle size ratio of the nickel carbonyl powder to the tungsten powder is 1:7.
4. The method according to claim 2, wherein the rotation speed of the uniformly mixed powder mixer charging barrel in the second step is 20-60 rpm, and the time is 3-8 h.
5. The method according to claim 2, wherein in the third step, the mixed powder is filled into a mold, vacuum-sealed by a vacuum sealer, and then cold-pressed.
6. The method according to claim 2, wherein the mixed powder in step three is cold-pressed within 8 hours after being uniformly mixed.
7. The method according to claim 2, wherein the cold pressing pressure in the third step is 100mpa to 250mpa and the dwell time is 3min to 8min.
8. The method according to claim 2, wherein the vacuum degree of the system in the powder metallurgy sintering process in the fourth step is 0.05 pa-0.001pa, the sintering temperature is 800-1550 ℃, the sintering time is 1-5 h, and titanium sponge is placed beside the wrapped nickel-tungsten blank.
9. The method according to claim 2, wherein in the fifth step, the vacuum melting is one or more of vacuum induction melting, vacuum suspension melting and electron beam melting, the vacuum degree of the vacuum melting is 0.01 pa-0.001pa, the melting temperature is 1000 ℃ -1600 ℃, and the melting time is 10 min-20 min.
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