Method and device for solid-phase regeneration of high-homogeneity intermediate alloy from dissimilar metal filings

Abstract

The invention discloses a method for solid-phase regeneration of a high-homogeneity intermediate alloy from dissimilar metal chips. The method comprises the following steps that firstly, metal elementary substance chips and intermediate alloy chips are subjected to ultrasonic cleaning and drying; step 2, mixing; step 3, crushing processing; step 4, pressing; 5, pulse current assisted vacuum sintering is carried out under the pressurization condition; step 6, performing hot extrusion deformation; step 7, carrying out homogenization treatment; 8, surface oxide skin is removed; and ninthly, machining is conducted, and the granular or scrap-shaped high-homogeneity intermediate alloy is obtained. According to the method, the cost of raw materials for preparing the intermediate alloy is reduced through solid-phase recycling of the metal filing, after the metal filing is crushed and pressed, pulse current is used for assisting vacuum sintering and hot extrusion deformation, local heating and rapid pre-compounding of the filing interface are achieved, an oxidation film is crushed, and the mechanical occlusal force of the filing interface is improved; and the defect healing capacity is improved through the homogenization treatment process, and the solid-phase regenerated high-homogenization intermediate alloy with uniform components is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of low-cost master alloy preparation, and in particular relates to a method and a device for solid-phase regeneration of high-homogeneity master alloys from heterogeneous metal scraps. Background Art

[0002] The cost of master alloys containing large melting point differences, large density differences and expensive rare metal components is relatively high. At the same time, the high brittleness makes it difficult to use traditional large plastic deformation homogenization, and the preparation of highly homogeneous master alloys is difficult and costly. For master alloys containing expensive rare metal components, recycling and reuse is an important way to reduce costs and improve efficiency in the preparation of master alloys.

[0003] When the loose metal chips are directly remelted by the remelting method to obtain the intermediate alloy products, the metal chips with lower density will float on the surface of the molten pool, causing serious oxidation and burning, and the recovery rate is low. The remelting method has problems such as easy oxidation of recycled materials, high burning, low recovery efficiency and serious pollution. The solid phase regeneration method to prepare intermediate alloys does not require remelting, which reduces burning and waste slag, and can solve the problems of regeneration and reuse of intermediate alloy waste and sustainable development. However, the direct solid phase regeneration technology of chip-like and granular alloys has technical problems such as insufficient density and poor interface bonding effect, which affects the quality of the recycled alloy. Pulse current assisted deformation has an electroplastic effect, which can also break the oxide film and realize local transient liquid phase diffusion connection of dissimilar metals, efficiently obtain a bonding interface with uniform composition, and the thermal effect of the current will also cause local overheating and rapid healing of the interface.

[0004] The patent with application number 202310686772.4 discloses a pulse current assisted magnesium-based composite material sintering and forging integrated equipment, which forges the product without taking out the sintered product, meets the requirements of sintering and forging integrated processing, avoids internal defects of the product and difficult processing problems, but this method cannot effectively solve the problem of large plastic deformation of brittle intermediate alloys.

[0005] Patent application number 201410561656.0 discloses a solid recycled aluminum alloy and its preparation method, taking an appropriate amount of aluminum alloy fine chips and putting them into a steel mold cavity, and then pressing them into a prefabricated block by molding, putting the pressed prefabricated block into an induction coil for induction heating, and putting the heated prefabricated block into a mold for hot extrusion. This method can effectively solve the problem of poor mechanical properties caused by insufficient density in the process of solid phase recycled aluminum alloy from metal chips, but it still cannot effectively solve the problem of rapid healing of the fine chip interface and the problem of unbroken oxide film on the local interface.

[0006] Therefore, it is necessary to provide a method for solid phase regeneration of highly homogeneous master alloys from heterogeneous metal chips. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide a method for solid phase regeneration of high homogeneous master alloys from heterogeneous metal chips in view of the deficiencies of the above-mentioned prior art. The method uses metal single substance chips and master alloy chips to solid phase regenerate high homogeneous master alloys, realizes the preparation of master alloys with different rare metal component contents, recycles and reuses rare metals in solid phase, improves the utilization rate of raw materials, reduces the cost of raw materials for preparing master alloys, uses heterogeneous metal chips to prepare high homogeneous master alloys through solid phase regeneration technology, promotes the recycling and reuse of master alloys, improves production efficiency, and the prepared solid phase regenerated high homogeneous master alloy has uniform composition and structure.

[0008] In order to solve the above technical problems, the technical solution adopted by the present invention is: a method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips, characterized in that the method comprises the following steps:

[0009] Step 1: ultrasonically clean the metal chips and the intermediate alloy chips using a metal cleaning agent, and then dry them;

[0010] Step 2: Mixing the metal chips dried in step 1 with the intermediate alloy chips dried to obtain heterogeneous metal chips;

[0011] Step 3, crushing the heterogeneous metal chips obtained in step 2 to obtain flaky heterogeneous metal chips;

[0012] Step 4: Pressing the sheet-shaped heterogeneous metal chips obtained in step 3 to obtain block-shaped heterogeneous metal chips;

[0013] Step 5: Place the bulk heterogeneous metal chips obtained in step 4 into a pulse current assisted-hot extrusion multi-field coupling composite forming device, and then perform pulse current assisted vacuum sintering under pressure to obtain a sintered ingot;

[0014] Step 6: The sintered ingot obtained in step 5 is further subjected to hot extrusion deformation in a pulse current assisted-hot extrusion multi-field coupling composite forming device to obtain an extruded ingot;

[0015] Step 7: homogenizing the extruded ingot obtained in step 6 to obtain a billet;

[0016] Step 8: removing the surface oxide scale of the billet obtained in step 7 to obtain a high-homogeneity master alloy ingot;

[0017] Step 9: Process the high-homogeneity master alloy ingot obtained in step 8 to obtain a granular or chip-shaped high-homogeneity master alloy.

[0018] The present invention adopts metal single substance chips and intermediate alloy chips, solid phases of rare metal chips are recovered and reused, the raw material cost of preparing intermediate alloys is reduced, impurities on the surfaces of metal single substance chips and intermediate alloy chips are removed by ultrasonic cleaning with a metal cleaning agent, the raw material purity of high-homogeneity intermediate alloys is ensured, uniformly mixed heterogeneous alloy chips are obtained by crushing processing, the uniformity of intermediate alloys is ensured, the surface lamination of mixed chips is achieved by pressing, the interface diffusion connection during sintering is ensured, pulse current-assisted vacuum sintering is performed under pressure, the current-assisted hot pressing interface discharge effect is utilized to achieve local heating of chip interfaces, rapid pre-compounding and oxide film crushing, the mechanical bite force of alloy chip interfaces is improved by extrusion deformation, the healing ability of cavity defects is improved during homogenization treatment, a high-homogeneity intermediate alloy ingot is obtained, and the high-homogeneity intermediate alloy is conveniently prepared and used as an additive by processing into granular or chip shapes.

[0019] The above-mentioned method for solid phase regeneration of high homogeneous master alloy from heterogeneous metal chips is characterized in that the metal chips in step 1 are titanium chips, zirconium chips or nickel chips; the master alloy chips are TiTa60 master alloy chips, ZrNb50 master alloy chips or NiMo50 master alloy chips. The invention controls the composition of metal chips and master alloy chips, so that the application range of the prepared high homogeneous master alloy is wider.

[0020] The above-mentioned method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips is characterized in that the quality of the master alloy chips in the heterogeneous metal chips in step 2 satisfies: Wherein, M is the mass of the intermediate alloy chips, G is the mass of the target high homogeneous intermediate alloy, A is the mass percentage of the index required element in the target high homogeneous intermediate alloy, B is the mass percentage of the index required element in the metal single substance chips, H is the mass percentage of the index required element in the intermediate alloy chips, and the unit of mass is kg. The present invention calculates the mass of the intermediate alloy chips in the heterogeneous metal chips according to the composition of the intermediate alloy chips and the metal single substance chips, obtains the ratio of the intermediate alloy chips to the metal single substance chips, and realizes the design of different mass percentages under different high homogeneous intermediate alloy target elements.

[0021] The above-mentioned method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips is characterized in that the crushing process in step 3 is performed by a crusher, and the thickness of the flaky heterogeneous metal chips is not greater than 1 mm, the width is not greater than 5 mm, and the length is not greater than 5 mm. The present invention ensures the local uniformity of the prepared master alloy by controlling the specifications of the flaky heterogeneous metal chips.

[0022] The above-mentioned method for solid phase regeneration of high homogeneous master alloy from heterogeneous metal chips is characterized in that the pressing in step 4 is performed by a cold isostatic press, the pressing pressure is 200MPa to 300MPa, and the holding time is 5min to 10min. The present invention controls the pressing parameters to initially shape the flaky heterogeneous metal chips, which is convenient for subsequent pulse current assisted vacuum sintering.

[0023] The above-mentioned method for solid phase regeneration of high homogeneous master alloy from heterogeneous metal chips is characterized in that the pulse current assisted-hot extrusion multi-field coupling composite forming device in step five includes a hollow die, the upper part of the die is matched with an upper pressure head with one end inserted into the die, the lower part of the upper pressure head is sequentially installed with an upper insulating gasket and an upper copper electrode, the die is provided with an extrusion die, the extrusion die is provided with a funnel-shaped hole, the lower part of the die is provided with a backing plate with an opening, the aperture of the lower part of the funnel-shaped hole is smaller than the opening of the backing plate, the lower part of the backing plate is provided with a lower die pad with one end inserted into the opening of the pad, the upper part of the lower die pad is sequentially provided with a lower insulating gasket and a lower copper electrode, the upper copper electrode is connected to the pulse power supply through the upper insulating gasket and the wire in the first channel in the upper pressure head, the lower copper electrode is connected to the pulse power supply through the lower insulating gasket and the wire in the second channel in the lower die pad, the die is provided with a temperature measuring hole, and the pulse current assisted-hot extrusion multi-field coupling composite forming device is placed in a vacuum box.

[0024] It should be noted that the extrusion ratio is controlled by controlling the aperture of the lower portion of the funnel-shaped hole.

[0025] The above-mentioned method for solid phase regeneration of high homogeneous master alloy of heterogeneous metal chips is characterized in that the pressure of the pressurization condition in step 5 is 5MPa-40MPa, the temperature of the pulse current assisted vacuum sintering is 1000℃-1200℃, the sintering time is 30min-90min, and the vacuum degree is less than 1×10 -2 Pa. The present invention controls the parameters of pressure and pulse current-assisted vacuum sintering to fully alloy the master alloy.

[0026] The above-mentioned method for solid phase regeneration of high homogeneity master alloy of heterogeneous metal chips is characterized in that the pulse current in step 5 is adjusted by adjusting the current ratio of the pulse power supply and meets the following conditions: Among them I p is the peak current, S 0 is the cross-sectional area of ​​the sintered ingot, D c is the duty cycle, current ratio r a The pulse current assists vacuum sintering by 20% to 80%, with an output voltage of 5V to 12V, a peak current of 5A to 6000A, and a current density of 2A / mm 2 ~50A / mm2 The present invention obtains different output currents by adjusting the current ratio, thereby ensuring the effect of pulse current-assisted vacuum sintering.

[0027] The above-mentioned method for solid phase regeneration of high homogeneous master alloy from heterogeneous metal chips is characterized in that the temperature of the hot extrusion molding in step 6 is 800°C to 1000°C, the extrusion rate is 0.5mm / s to 5mm / s, and the extrusion ratio is 5 to 30: 1. The present invention ensures the effect of hot extrusion molding by controlling the parameters of hot extrusion molding, which is beneficial to the healing of cavity defects in the homogenization process.

[0028] The above-mentioned method for solid phase regeneration of high homogeneous master alloy from heterogeneous metal chips is characterized in that the temperature of the homogenization treatment in step 7 is 900°C to 1200°C and the time is 2h to 4h. The present invention ensures the effect of the homogenization treatment by controlling the parameters of the homogenization treatment, and improves the healing ability of the cavity defects.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] 1. The present invention uses metal single substance chips and master alloy chips to carry out solid phase regeneration of high homogeneous master alloys, realizes the preparation of master alloys with different rare metal component contents, recycles and reuses rare metals in the solid phase, improves the utilization rate of raw materials, reduces the cost of raw materials for preparing master alloys, uses heterogeneous metal chips to prepare high homogeneous master alloys through solid phase regeneration technology, promotes the recycling and reuse of master alloys, and improves production efficiency. The prepared solid phase regenerated high homogeneous master alloy has uniform composition and structure, and the segregation degree is not more than 15%.

[0031] 2. The present invention performs pulse current-assisted vacuum sintering under pressurized conditions and utilizes the current-assisted hot pressing interface discharge effect to achieve local heating of the chip interface to quickly pre-compound and break the oxide film, and to dissipate the oxide layer and impurities on the chip surface. Therefore, the sintering rate is high and the required sintering time is also shorter. During the entire sintering process, only the sample is heated after being turned on, and the sintered ingot is rapidly cooled after power is turned off.

[0032] 3. The present invention improves the mechanical bite force of the chip interface through extrusion deformation, realizes a high-homogeneous intermediate alloy product with high solid-phase regeneration density, solves the problem of insufficient solid-phase regeneration density, and improves the healing ability of void defects during the homogenization process to obtain a high-homogeneous intermediate alloy ingot.

[0033] 4. The present invention designs a pulse current assisted-hot extrusion multi-field coupled composite forming device so that pulse current assisted vacuum sintering and hot extrusion deformation can be carried out continuously in the forming device under pressurized conditions, thereby improving production efficiency and ensuring the performance of high-homogeneity master alloy.

[0034] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The present invention is a process flow chart for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips.

[0036] Figure 2 It is a schematic structural diagram of the flaky heterogeneous metal chips of the present invention.

[0037] Figure 3 It is a schematic structural diagram of the blocky heterogeneous metal chips of the present invention.

[0038] Figure 4 It is a schematic diagram of the structure of the pulse current assisted-hot extrusion multi-field coupling composite forming device of the present invention after pulse current assisted vacuum sintering.

[0039] Figure 5 It is a schematic structural diagram of the hot extrusion deformation performed by the pulse current assisted-hot extrusion multi-field coupling composite forming device of the present invention.

[0040] Figure 6 This is the SEM image of the solid phase regenerated high homogeneity TiTa40 alloy prepared in Example 1 of the present invention.

[0041] Figure 7 This is the element distribution diagram of Ti in the solid phase regenerated high homogeneity TiTa40 alloy prepared in Example 1 of the present invention.

[0042] Figure 8 This is the element distribution diagram of Ta in the solid phase regenerated high homogeneity TiTa40 alloy prepared in Example 1 of the present invention.

[0043] Fig. 9 This is the SEM image of the solid phase regenerated high homogeneity ZrNb45 alloy prepared in Example 2 of the present invention.

[0044] Fig.10 This is the element distribution diagram of Zr in the solid phase regenerated high homogeneity ZrNb45 alloy prepared in Example 2 of the present invention.

[0045] Fig.11 This is the element distribution diagram of Nb in the solid phase regenerated high homogeneity ZrNb45 alloy prepared in Example 2 of the present invention.

[0046] Fig.12 This is a SEM image of the solid-phase regenerated high-homogeneity NiMo30 alloy prepared in Example 3 of the present invention.

[0047] Fig.13 This is the element distribution diagram of Mo in the solid phase regenerated high homogeneity NiMo30 alloy prepared in Example 3 of the present invention.

[0048] Fig.14 This is the element distribution diagram of Ni in the solid phase regenerated high homogeneity NiMo30 alloy prepared in Example 3 of the present invention.

[0049] Description of reference numerals:

[0050] 1—die; 2—upper pressure head; 3—upper insulating gasket;

[0051] 4—Upper copper electrode; 5—Extrusion die; 6—Backing plate;

[0052] 7—lower die pad; 8—lower insulating gasket; 9—lower copper electrode;

[0053] 10—first channel; 11—pulse power supply; 12—second channel;

[0054] 13—temperature measuring hole; 14—sintering ingot. DETAILED DESCRIPTION

[0055] Figure 1 The process flow chart of the present invention for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips is as follows: Figure 1 It can be seen that the present invention sequentially cleans and dries the metal element chips and the intermediate alloy chips, mixes, crushes, presses, performs pulse current assisted vacuum sintering under pressure, performs hot extrusion deformation, homogenizes, removes surface oxide scale, and processes to obtain granular or chip-like highly homogeneous intermediate alloys.

[0056] Figure 2 The schematic diagram of the structure of the sheet-shaped heterogeneous metal chips of the present invention is as follows: Figure 2 It can be seen that the metal chips and intermediate alloy chips in the crushed flaky heterogeneous metal chips are of similar specifications and are evenly mixed.

[0057] Figure 3 The schematic diagram of the structure of the block-shaped heterogeneous metal chips of the present invention is as follows: Figure 3 It can be seen that the metal chips and the intermediate alloy chips are cold pressed into tightly fitted block-shaped heterogeneous metal chips.

[0058] Figure 4 This is a schematic diagram of the structure of the pulse current assisted-hot extrusion multi-field coupling composite forming device of the present invention after pulse current assisted vacuum sintering. Figure 4It can be seen that the pulse current assisted-hot extrusion multi-field coupling composite forming device includes a hollow die 1, the upper part of the die 1 is equipped with an upper pressure head 2 with one end inserted into the die 1, the lower part of the upper pressure head 2 is sequentially installed with an upper insulating gasket 3 and an upper copper electrode 4, the die 1 is provided with an extrusion die 5, the extrusion die 5 is provided with a funnel-shaped hole, the lower part of the die 1 is provided with a backing plate 6 with an opening, the aperture of the lower part of the funnel-shaped hole is smaller than the opening of the backing plate 6, and the lower part of the backing plate 6 is provided with an end inserted into the backing plate 6 opening. The lower die pad 7 in the hole, the upper part of the lower die pad 7 is sequentially provided with a lower insulating gasket 8 and a lower copper electrode 9, the upper copper electrode 4 is connected to the pulse power supply 11 through the upper insulating gasket 3 and the wire in the first channel 10 in the upper pressure head 2, the lower copper electrode 9 is connected to the pulse power supply 11 through the lower insulating gasket 8 and the wire in the second channel 12 in the lower die pad 7, the die 1 is provided with a temperature measuring hole 13, and the area between the die 1, the upper copper electrode 4, the extrusion die 5 and the lower copper electrode 9 is a sintered ingot 14.

[0059] Figure 5 The schematic diagram of the structure of the pulse current assisted-hot extrusion multi-field coupling composite forming device for hot extrusion deformation of the present invention is shown in FIG. Figure 5 It can be seen that the pulse current assisted-hot extrusion multi-field coupling composite forming device includes a hollow die 1, the upper part of the die 1 is equipped with an upper pressure head 2 with one end inserted into the die 1, the lower part of the upper pressure head 2 is sequentially installed with an upper insulating gasket 3 and an upper copper electrode 4, the die 1 is provided with an extrusion die 5, the extrusion die 5 is provided with a funnel-shaped hole, the lower part of the die 1 is provided with a backing plate 6 with an opening, the aperture of the lower part of the funnel-shaped hole is smaller than the opening of the backing plate 6, and the lower part of the backing plate 6 is provided with an end inserted into the backing plate 6 opening. The lower die pad 7 in the hole, the upper part of the lower die pad 7 is sequentially provided with a lower insulating gasket 8 and a lower copper electrode 9, the upper copper electrode 4 is connected to the pulse power supply 11 through the upper insulating gasket 3 and the wire in the first channel 10 in the upper pressure head 2, the lower copper electrode 9 is connected to the pulse power supply 11 through the lower insulating gasket 8 and the wire in the second channel 12 in the lower die pad 7, a temperature measuring hole 13 is opened on the die 1, and the upper pressure head 2 is used for downward pressing, and the sintered ingot 14 is extruded from the extrusion die 5 to realize hot extrusion deformation.

[0060] Example 1

[0061] This embodiment includes the following steps:

[0062] Step 1, ultrasonically clean Ti chips and TiTa60 master alloy chips respectively with a metal cleaning agent, and then dry them; the Ti chips are composed of the following components by mass fraction: O≤0.25%, H≤0.03%, N≤0.03%, C≤0.02%, Si≤0.02%, Mg≤0.01%, Fe≤0.04%, Mn≤0.01%, Cl≤0.04%, and the balance is Ti; the TiTa60 master alloy chips are composed of the following components by mass fraction: Ta 59.44%, Fe 0.031%, Si 0.01%, C0.011%, H 0.0008%, O 0.16%, N 0.007%, and the balance is Ti and unavoidable impurities;

[0063] Step 2: Mix 1 kg of the Ti chips dried in step 1 and 2 kg of the TiTa60 master alloy chips dried to obtain heterogeneous metal chips;

[0064] Step 3: crush the heterogeneous metal scraps obtained in step 2 using a crusher to obtain flaky heterogeneous metal scraps with a thickness of no more than 1 mm, a width of no more than 5 mm, and a length of no more than 5 mm;

[0065] Step 4: The sheet-shaped heterogeneous metal chips obtained in step 3 are pressed by a cold isostatic press at a pressing pressure of 200 MPa and a holding time of 5 min to obtain block-shaped heterogeneous metal chips with a diameter of 95 mm;

[0066] Step 5: Place the blocky dissimilar metal chips obtained in step 4 into a pulse current assisted-hot extrusion multi-field coupling composite forming device placed in a vacuum box, the inner diameter of the concave die of the forming device is 100 mm, and then perform pulse current assisted vacuum sintering under a pressure of 5 MPa, a temperature of 1000 ° C, a sintering time of 90 min, and a vacuum degree of 6×10 -3 Pa, the duty cycle in pulse current assisted vacuum sintering is 20%, the output voltage is 5V, the peak current is 5A, and the current density is 2A / mm 2 , obtaining a sintered ingot;

[0067] Step 6: The sintered ingot obtained in step 5 is further subjected to hot extrusion deformation at a temperature of 800° C., an extrusion rate of 0.5 mm / s, and an extrusion ratio of 30:1 in a pulse current assisted-hot extrusion multi-field coupling composite forming device to obtain an extruded ingot;

[0068] Step 7: homogenizing the extruded ingot obtained in step 6 at a temperature of 900° C. for 2 hours to obtain a billet;

[0069] Step 8: removing the surface oxide scale of the billet obtained in step 7 to obtain a high-homogeneity master alloy ingot;

[0070] Step nine: Process the high-homogeneity master alloy ingot obtained in step eight to obtain a chip-like solid-phase regenerated high-homogeneity TiTa40 master alloy.

[0071] The chemical composition of the solid phase regenerated high homogeneity TiTa40 master alloy prepared in this embodiment was tested, and the specific results are shown in Table 1 below.

[0072] Table 1

[0073] element Ti Ta Fe C O N Mass fraction (wt%) margin 39.52 0.027 0.012 0.18 0.011

[0074] Figure 6 This is a SEM image of the solid phase regenerated high homogeneity TiTa40 alloy prepared in Example 1 of the present invention. Figure 7 This is the element distribution diagram of Ti in the solid phase regenerated high homogeneity TiTa40 alloy prepared in Example 1 of the present invention, Figure 8 The element distribution diagram of Ta in the solid phase regenerated high homogeneity TiTa40 alloy prepared in Example 1 of the present invention is shown in FIG. Figures 6 to 8 It can be seen that the solid phase regenerated high homogeneity TiTa40 master alloy prepared in this embodiment has no high-density tantalum non-melting blocks and has uniform composition.

[0075] Example 2

[0076] This embodiment includes the following steps:

[0077] Step 1, respectively, ultrasonically clean the Zr chips and the ZrNb50 master alloy chips with a metal cleaning agent, and then dry them; the Zr chips meet the standard of nuclear-grade sponge zirconium HZr-01 in the YS / T397-2015 standard; the ZrNb50 master alloy chips are composed of the following components by mass fraction: Nb 49.21%, C 0.004%, H 0.003%, O 0.033%, N 0.004%, and the balance is Zr and unavoidable impurities;

[0078] Step 2: Mix 0.3 kg of the dried Zr chips in step 1 and 2.7 kg of the dried ZrNb50 master alloy chips to obtain heterogeneous metal chips;

[0079] Step 3: crush the heterogeneous metal scraps obtained in step 2 using a crusher to obtain flaky heterogeneous metal scraps with a thickness of no more than 1 mm, a width of no more than 5 mm, and a length of no more than 5 mm;

[0080] Step 4: The sheet-shaped heterogeneous metal chips obtained in step 3 are pressed by a cold isostatic press at a pressing pressure of 250 MPa and a holding time of 8 min to obtain block-shaped heterogeneous metal chips with a diameter of 95 mm;

[0081] Step 5: Place the blocky dissimilar metal chips obtained in step 4 into a pulse current assisted-hot extrusion multi-field coupling composite forming device placed in a vacuum box, the inner diameter of the concave die of the forming device is 100 mm, and then perform pulse current assisted vacuum sintering under a pressure of 20 MPa, a temperature of 1100 ° C, a sintering time of 60 min, and a vacuum degree of 8.5×10 -3 Pa, the duty cycle in pulse current assisted vacuum sintering is 50%, the output voltage is 6V, the peak current is 3000A, and the current density is 40A / mm 2 , obtaining a sintered ingot;

[0082] Step 6: The sintered ingot obtained in step 5 is further subjected to hot extrusion deformation at a temperature of 900° C., an extrusion rate of 2.5 mm / s, and an extrusion ratio of 20:1 in a pulse current assisted-hot extrusion multi-field coupling composite forming device to obtain an extruded ingot;

[0083] Step 7: homogenizing the extruded ingot obtained in step 6 at a temperature of 1000° C. for 3 hours to obtain a billet;

[0084] Step 8: removing the surface oxide scale of the billet obtained in step 7 to obtain a high-homogeneity master alloy ingot;

[0085] Step 9: Process the high-homogeneity master alloy ingot obtained in step 8 to obtain a chip-like solid-phase regenerated high-homogeneity ZrNb45 master alloy.

[0086] The chemical composition of the solid phase regenerated high homogeneity ZrNb45 master alloy prepared in this embodiment was tested, and the specific results are shown in Table 2 below.

[0087] Table 2

[0088] element Zr Nb C H O N Mass fraction (wt%) margin 45.44 0.003 0.0032 0.041 0.002

[0089] Fig. 9 This is the SEM image of the solid phase regenerated high homogeneity ZrNb45 alloy prepared in this example. Fig.10 This is the element distribution diagram of Zr in the solid phase regenerated high homogeneity ZrNb45 alloy prepared in this embodiment. Fig.11 The element distribution diagram of Nb in the solid phase regenerated high homogeneity ZrNb45 alloy prepared in this embodiment is as follows: Figures 9 to 11 It can be seen that the solid phase regenerated high homogeneity ZrNb45 alloy prepared in this embodiment has no inclusions, segregation and high melting point niobium infusible blocks, and has uniform composition.

[0090] Example 3

[0091] This embodiment includes the following steps:

[0092] Step 1: ultrasonically clean Ni chips and TiTa60 master alloy chips respectively with a metal cleaning agent, and then dry them; the mass purity of the Ni chips is 99.96%; the NiMo50 master alloy chips are composed of the following components by mass fraction: Mo 49.82%, Al < 0.01%, Fe < 0.005%, Si 0.006%, C < 0.005%, N < 0.001%, O 0.068%, and the balance is Ni and unavoidable impurities;

[0093] Step 2: Mix 4 kg of Ni chips dried in step 1 and 6 kg of NiMo50 master alloy chips dried to obtain dissimilar metal chips;

[0094] Step 3: crush the heterogeneous metal scraps obtained in step 2 using a crusher to obtain flaky heterogeneous metal scraps with a thickness of no more than 1 mm, a width of no more than 5 mm, and a length of no more than 5 mm;

[0095] Step 4: The sheet-shaped heterogeneous metal chips obtained in step 3 are pressed by a cold isostatic press at a pressing pressure of 300 MPa and a holding time of 10 min to obtain block-shaped heterogeneous metal chips with a diameter of 95 mm;

[0096] Step 5: Place the blocky dissimilar metal chips obtained in step 4 into a pulse current assisted-hot extrusion multi-field coupling composite forming device placed in a vacuum box, the inner diameter of the concave die of the forming device is 100 mm, and then perform pulse current assisted vacuum sintering under a pressure of 40 MPa, a temperature of 1200 ° C, a sintering time of 30 min, and a vacuum degree of 5×10 - 3 Pa, the duty cycle in pulse current assisted vacuum sintering is 80%, the output voltage is 12V, the peak current is 6000A, and the current density is 50A / mm 2 , obtaining a sintered ingot;

[0097] Step 6: The sintered ingot obtained in step 5 is further subjected to hot extrusion deformation at a temperature of 1000° C., an extrusion rate of 5 mm / s, and an extrusion ratio of 5:1 in a pulse current assisted-hot extrusion multi-field coupling composite forming device to obtain an extruded ingot;

[0098] Step 7: homogenizing the extruded ingot obtained in step 6 at a temperature of 1200° C. for 4 hours to obtain a billet;

[0099] Step 8: removing the surface oxide scale of the billet obtained in step 7 to obtain a high-homogeneity master alloy ingot;

[0100] Step nine: Process the high-homogeneity master alloy ingot obtained in step eight to obtain a granular solid-phase regenerated high-homogeneity NiMo30 master alloy.

[0101] The chemical composition of the solid phase regenerated high homogeneity NiMo30 master alloy prepared in this embodiment was tested, and the specific results are shown in Table 3 below.

[0102] Table 3

[0103] element Ni Mo Al Fe Si C N O Mass fraction (wt%) margin 29.87 0.005 0.007 0.005 0.005 0.001 0.011

[0104] Fig.12 This is the SEM image of the solid phase regenerated high homogeneity NiMo30 alloy prepared in this embodiment. Fig.13 This is the element distribution diagram of Mo in the solid phase regenerated high homogeneity NiMo30 alloy prepared in this embodiment, Fig.14 The element distribution diagram of Ni in the solid phase regenerated high homogeneity NiMo30 alloy prepared in this embodiment is as follows: Figure 12 to Figure 14 It can be seen that the solid phase regenerated high homogeneity NiMo30 alloy prepared in this embodiment has no high melting point molybdenum infusible block and has uniform composition.

[0105] The above is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent change made to the above embodiment according to the technical essence of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips, characterized in that: The method comprises the following steps: Step 1: ultrasonically clean the metal chips and the intermediate alloy chips using a metal cleaning agent, and then dry them; Step 2: Mixing the metal chips dried in step 1 with the intermediate alloy chips dried to obtain heterogeneous metal chips; Step 3, crushing the heterogeneous metal chips obtained in step 2 to obtain flaky heterogeneous metal chips; Step 4: Pressing the sheet-shaped heterogeneous metal chips obtained in step 3 to obtain block-shaped heterogeneous metal chips; Step 5: Place the bulk heterogeneous metal chips obtained in step 4 into a pulse current assisted-hot extrusion multi-field coupling composite forming device, and then perform pulse current assisted vacuum sintering under pressure to obtain a sintered ingot; Step 6: The sintered ingot obtained in step 5 is further subjected to hot extrusion deformation in a pulse current assisted-hot extrusion multi-field coupling composite forming device to obtain an extruded ingot; Step 7: homogenizing the extruded ingot obtained in step 6 to obtain a billet; Step 8: removing the surface oxide scale of the billet obtained in step 7 to obtain a high-homogeneity master alloy ingot; Step 9: Process the high-homogeneity master alloy ingot obtained in step 8 to obtain a granular or chip-shaped high-homogeneity master alloy.

2. The method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips according to claim 1, characterized in that: The metal chips in step 1 are titanium chips, zirconium chips or nickel chips; the intermediate alloy chips are TiTa60 intermediate alloy chips, ZrNb50 intermediate alloy chips or NiMo50 intermediate alloy chips.

3. The method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips according to claim 1, characterized in that: The quality of the intermediate alloy chips in the dissimilar metal chips in step 2 meets the following requirements: Wherein, M is the mass of the intermediate alloy chips, G is the mass of the target high-homogeneity intermediate alloy, A is the mass percentage of the index required element in the target high-homogeneity intermediate alloy, B is the mass percentage of the index required element in the metal single substance chips, H is the mass percentage of the index required element in the intermediate alloy chips, and the unit of mass is kg.

4. The method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips according to claim 1, characterized in that: The crushing process in step three is carried out by a crusher, and the thickness of the flaky heterogeneous metal chips is not greater than 1 mm, the width is not greater than 5 mm, and the length is not greater than 5 mm.

5. The method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips according to claim 1, characterized in that: The pressing in step 4 is performed using a cold isostatic press, the pressing pressure is 200 MPa to 300 MPa, and the holding time is 5 min to 10 min.

6. The method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips according to claim 1, characterized in that: The pulse current assisted-hot extrusion multi-field coupling composite forming device in step 5 comprises a hollow die (1), the upper part of the die (1) is matched with an upper pressure head (2) with one end inserted into the die (1), the lower part of the upper pressure head (2) is sequentially installed with an upper insulating gasket (3) and an upper copper electrode (4), the die (1) is provided with an extrusion die (5), the extrusion die (5) is provided with a funnel-shaped hole, the lower part of the die (1) is provided with a backing plate (6) with an opening, the aperture of the lower part of the funnel-shaped hole is smaller than the opening of the backing plate (6), and the lower part of the backing plate (6) is provided with an end inserted into the backing plate (6) A lower die pad (7) is provided in the opening, a lower insulating pad (8) and a lower copper electrode (9) are sequentially arranged on the upper part of the lower die pad (7), the upper copper electrode (4) is connected to a pulse power supply (11) through the upper insulating pad (3) and the wire in the first hole (10) in the upper pressure head (2), the lower copper electrode (9) is connected to the pulse power supply (11) through the lower insulating pad (8) and the wire in the second hole (12) in the lower die pad (7), a temperature measuring hole (13) is provided on the die (1), and the pulse current assisted-hot extrusion multi-field coupling composite forming device is placed in a vacuum box.

7. The method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips according to claim 1, characterized in that: The pressure of the pressurized condition in step 5 is 5MPa-40MPa, the temperature of the pulse current assisted vacuum sintering is 1000℃-1200℃, the sintering time is 30min-90min, and the vacuum degree is less than 1×10 -2 Pa.

8. The method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips according to claim 1, characterized in that: The pulse current in step 5 is adjusted by adjusting the current ratio of the pulse power supply and meets the following conditions: Among them I p is the peak current, S0 is the cross-sectional area of ​​the sintered ingot, D c is the duty cycle, current ratio r a The pulse current assists vacuum sintering by 20% to 80%, with an output voltage of 5V to 12V, a peak current of 5A to 6000A, and a current density of 2A / mm 2 ~50A / mm 2 .

9. The method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips according to claim 1, characterized in that: The temperature of the hot extrusion molding in step six is ​​800° C. to 1000° C., the extrusion rate is 0.5 mm / s to 5 mm / s, and the extrusion ratio is 5 to 30:

1.

10. The method for solid phase regeneration of high homogeneity master alloy from heterogeneous metal chips according to claim 1, characterized in that: The temperature of the homogenization treatment in step seven is 900° C. to 1200° C., and the time is 2 h to 4 h.

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