CN111235400A - Cutting, recombining and smelting process for hafnium - Google Patents

Cutting, recombining and smelting process for hafnium Download PDF

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CN111235400A
CN111235400A CN202010164503.8A CN202010164503A CN111235400A CN 111235400 A CN111235400 A CN 111235400A CN 202010164503 A CN202010164503 A CN 202010164503A CN 111235400 A CN111235400 A CN 111235400A
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hafnium
ingot
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CN111235400B (en
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白新房
武宇
朱波
王松茂
赵永庆
周恺
李蛟
杨军红
李波
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Xi'an Hantang Analysis Detection Co ltd
Northwest Institute for Non Ferrous Metal Research
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Xi'an Hantang Analysis Detection Co ltd
Northwest Institute for Non Ferrous Metal Research
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/22—Remelting metals with heating by wave energy or particle radiation
    • C22B9/228—Remelting metals with heating by wave energy or particle radiation by particle radiation, e.g. electron beams
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium

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Abstract

The invention discloses a hafnium slitting, recombining and smelting process, which comprises the following steps: firstly, welding crystal bar hafnium to obtain a hafnium smelting electrode; secondly, mounting a hafnium smelting electrode in the electron beam smelting furnace, and then carrying out first smelting to obtain a primary ingot; thirdly, mounting a primary ingot in the electron beam smelting furnace and then smelting for the second time to obtain a secondary ingot; fourthly, carrying out cutting recombination treatment on the secondary ingot to obtain a cut combined ingot; fifthly, mounting the split combined ingot in the electron beam melting furnace, and then carrying out third melting to obtain a hafnium finished product ingot. The method realizes effective control of the component uniformity of the hafnium finished ingot and improves the component distribution uniformity of the hafnium finished ingot by implementing slitting recombination in the smelting process.

Description

Cutting, recombining and smelting process for hafnium
Technical Field
The invention belongs to the technical field of high-purity metal smelting processes, and particularly relates to a hafnium slitting recombination smelting process.
Background
The hafnium metal has special physicochemical properties and nuclear performance, has wide application prospects in the industrial fields of nuclear reactors, aerospace and the like, and the uniformity of the hafnium metal directly influences the service performance of products, so that the control of ingot component distribution needs to be carried out from the melting process stage to ensure the uniformity of the distribution of other micro-content elements in the hafnium metal.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a hafnium slitting, recombining and smelting process aiming at the defects of the prior art. The method adopts the slitting recombination treatment in the smelting process of the hafnium ingot, realizes the effective control of the uniformity of the components of the hafnium ingot, improves the uniformity of the distribution of the components of the hafnium ingot, is easy to realize, has simple operation, and can effectively meet the requirement of the actual hafnium ingot on the control of the uniformity of the distribution of the components.
In order to solve the technical problems, the invention adopts the technical scheme that: a cutting, reforming and smelting process for hafnium is characterized by comprising the following steps:
step one, welding crystal bar hafnium to obtain a hafnium smelting electrode;
step two, a hafnium crucible and a bottom pad are arranged in the electron beam melting furnace, and then a hafnium melting electrode obtained in the step one is arranged in the hafnium crucible for first melting to obtain a primary ingot;
step three, mounting a hafnium crucible and a bottom pad in the electron beam melting furnace, and then mounting the primary ingot obtained in the step two in the hafnium crucible and then carrying out secondary melting to obtain a secondary ingot;
step four, carrying out cutting recombination treatment on the secondary ingot obtained in the step three to obtain a cut combined ingot; the cutting and recombining process comprises the following steps: cutting the secondary ingot into four equal parts along two mutually perpendicular diameters on the end surface, respectively marking the four equal parts as A, B, C and D along the clockwise direction, then cutting the cut secondary ingot into four equal parts along the height direction, respectively marking the four equal parts as I, II, III and IV from top to bottom to obtain 16 divided blocks as I-A, II-A, III-A, IV-A, I-B, II-B, III-B, IV-B, I-C, II-C, III-C, IV-C, I-D, II-D, III-D and IV-D, recombining the divided secondary ingots in a mode that the I-A, II-A, III-A and the IV-A are butted along the clockwise direction to form a first layer, I-B, II-B, I-C, III-B, III-B and IV-B are butted in a clockwise direction to form a second layer, I-C, II-C, III-C and IV-C are butted in a clockwise direction to form a third layer, I-D, II-D, III-D and IV-D are butted in a clockwise direction to form a fourth layer, and then welding treatment is carried out;
and step five, mounting a hafnium crucible and a bottom pad in the electron beam melting furnace, then mounting the split combined ingot obtained in the step four in the hafnium crucible, and then carrying out third melting to obtain a hafnium finished product ingot.
The cutting, reforming and smelting process for hafnium is characterized in that the welding conditions in the first step and the fourth step are as follows: a vacuum welding box with the vacuum degree of 2-10 Pa is adopted, wherein the vacuum welding box is filled with argon and keeps the pressure intensity of 0.08-0.12 MPa, the welding current intensity is 300-500A, and the cooling time after welding is 30-50 min. The vacuum degree of the vacuum welding box is 2 Pa-10 Pa, the defects that the early preparation time is long and the production efficiency is reduced due to overhigh vacuum degree and the pollution is easy to generate in the welding process due to overlow vacuum degree are avoided, the vacuum welding box is filled with argon and the pressure is kept to be 0.08 MPa-0.12 MPa, so that the welding treatment is protected by the argon, the argon has the advantages of good protection, low cost and high safety, the defects that the heat generated in the welding process due to overhigh pressure causes overlarge gas expansion in the welding box, the rubber glove of an operation window is damaged, the vacuum is damaged, and the argon amount due to overlow pressure cannot play a role in protecting inert gas are avoided, the welding current intensity is 300A-500A, the defects that the overmelting is easy and the ingot casting is polluted due to overhigh current are avoided, the invention also avoids the defect of low melting efficiency caused by over-small current, and the invention adopts the cooling time after welding of 30-50 min to realize complete cooling, thereby avoiding the defects of low production efficiency caused by over-long cooling time and easy oxidation caused by incomplete cooling caused by over-short cooling time.
The cutting, recombining and smelting process of the hafnium is characterized in that the diameter of the hafnium crucible in the second step is phi 94 mm-phi 114mm, and the diameter of the hafnium crucible in the third step and the fifth step is phi 120 mm-phi 150 mm. The diameter of the hafnium crucible adopted in the second step of the invention is phi 94 mm-phi 114mm, so that the obtained cast ingot is convenient for subsequent processing, the diameter of the hafnium crucible adopted in the third and fifth steps of the invention is phi 120 mm-phi 150mm, so that the obtained cast ingot is convenient for subsequent processing, and meanwhile, the diameter is larger than that of the hafnium crucible used in the second step, thereby being beneficial to the uniformity of the components of the cross section of the cast ingot.
The cutting, reforming and smelting process for hafnium is characterized in that the first smelting in the second step and the second smelting in the third step are carried out in the following steps: leak detection is carried out on the electron beam melting furnace for 3min to 10min, and when the leak rate is not more than 10-1Beginning smelting at Pa/min, wherein the vacuum degree in the furnace before smelting is not more than 2 multiplied by 10-2Pa, low vacuum degree in the furnace during smeltingAt 3X 10-2Pa, the smelting power is 60 kW-75 kW, the ingot pulling speed is 4 mm/min-6 mm/min, and the cooling time after smelting is 6 min-15 min. The invention carries out leak detection on the electron beam melting furnace for 3min to 10min, avoids the defect of low integral melting efficiency caused by overlong leak detection time, and also avoids the defect of influencing the quality of the melting ingot because the real leak rate can not be obtained due to short leak detection time, and the invention adopts the method that the leak rate is not more than 10-1The smelting is started when Pa/min, the defect that the smelting quality of the cast ingot is influenced due to overlarge leakage rate is avoided, and the defect that the smelting efficiency is low due to overlarge leakage rate is also avoided, the vacuum degree in the furnace before the smelting is not more than 2 multiplied by 10-2Pa and the vacuum degree in the furnace is not more than 3X 10-2Pa, the defect that the smelting quality of the ingot is influenced due to overlarge vacuum degree is avoided, and the defect that the smelting efficiency is low due to the overlarge vacuum degree is also avoided, the smelting power adopted by the invention is 60-75 kW, the defect that the ingot is easy to over-smelt and pollute due to the overlarge smelting power is avoided, and the defect that the smelting efficiency is low due to the overlarge smelting power is also avoided, the speed of pulling the ingot is 4-6 mm/min, the defect that the components in a melting area cannot be fully and uniformly mixed due to the overlarge speed of pulling the ingot is adopted, the defect that the efficiency is low due to the overlarge speed of pulling the ingot is also avoided, the defect that the cooling time after smelting is 6-15 min is adopted, the defect that the efficiency is low due to the overlong cooling is avoided, and the defect that the ingot is easy to oxidize due to the incomplete cooling caused by the overlong cooling time is also avoided.
The cutting, reforming and smelting process for the hafnium is characterized in that in the fifth step, the third smelting process comprises the following steps: leak detection is carried out on the electron beam melting furnace for 5min to 10min, and when the leak rate is not more than 10-1Beginning smelting at Pa/min, wherein the vacuum degree in the furnace before smelting is not more than 2 multiplied by 10-2Pa, vacuum degree in the furnace in smelting is not more than 3 x 10-2Pa, the smelting power is 75 kW-80 kW, the ingot pulling speed is 4 mm/min-6 mm/min, and the cooling time after smelting is 20 min-30 min. The invention carries out leak detection on the electron beam melting furnace for 5min to 10min, avoids the defect of low integral melting efficiency caused by overlong leak detection time, and also avoids leak detectionThe defect that the real leakage rate cannot be obtained due to short time and the quality of the smelting ingot casting is influenced is adopted, and the leakage rate is not more than 10-1The smelting is started when Pa/min, the defect that the smelting quality of the cast ingot is influenced due to overlarge leakage rate is avoided, and the defect that the smelting efficiency is low due to overlarge leakage rate is also avoided, the vacuum degree in the furnace before the smelting is not more than 2 multiplied by 10-2Pa and the vacuum degree in the furnace during smelting is not more than 3 x 10-2Pa, the defect that the smelting quality of the ingot is influenced due to overlarge vacuum degree is avoided, and the defect that the smelting efficiency is low due to the overlarge vacuum degree is also avoided, the smelting power is 75-80 kW, the defect that the ingot is easily overflown and polluted due to the overlarge smelting power is avoided, the defects that the smelting power is too small and the smelting efficiency is low are also avoided, the speed of pulling the ingot is 4-6 mm/min, the defect that components in a melting area cannot be sufficiently and uniformly mixed due to the overlarge speed of pulling the ingot is adopted, the defect that the efficiency is low due to the overlarge speed of pulling the ingot is also avoided, the defect that the cooling time after smelting is 20-30 min is adopted, the defect that the efficiency is low due to the overlong cooling is avoided, and the defect that the ingot is not completely cooled and is easily oxidized due to the overlong cooling time is also avoided.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the secondary ingot is cut and recombined, so that the uniformity control of the components of the hafnium finished ingot is realized, the uniformity guarantee of the components of the hafnium finished ingot is improved, the component content distribution of the hafnium finished ingot meets the requirement of ingot uniformity initial inspection for standard substances, and the uniformity of the corrosion performance of a subsequent hafnium finished bar processed and formed on the basis of the hafnium finished ingot is facilitated.
2. According to the hafnium finished product ingot obtained by the process, the distribution of elements at the head, the middle, the tail, the edges, the middle, the center and the like of the finished product ingot is detected to be uniform, so that the component distribution consistency of the hafnium finished product ingot is effectively guaranteed.
3. The method comprises the steps of performing primary smelting, secondary smelting, ingot casting slitting recombination and tertiary smelting on hafnium in sequence, and realizing effective control on the uniformity of components of the ingot casting by controlling the smelting process parameters.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic view of the structure of the secondary ingot of the present invention after slitting.
Fig. 2 is a schematic structural view of the divided composite ingot of the invention.
Detailed Description
Fig. 1 is a schematic structural diagram of the secondary ingot after being cut, and as can be seen from fig. 1, the secondary ingot is firstly cut into four equal parts along two mutually perpendicular diameters in the end face of the secondary ingot, and then is cut into four equal parts along the height direction of the secondary ingot, and the four equal parts are totally cut into 16 cut blocks which are respectively marked as I-A, II-A, III-A, IV-A, I-B, II-B, III-B, IV-B, I-C, II-C, III-C, IV-C, I-D, II-D, III-D and IV-D.
FIG. 2 is a schematic structural view of a composite slit ingot of the present invention, and it can be seen from FIG. 2 that the composite slit ingot is composed of a first layer formed by butting I-A, II-A, III-A and IV-A in a clockwise direction, a second layer formed by butting I-B, II-B, III-B and IV-B in a clockwise direction, a third layer formed by butting I-C, II-C, III-C and IV-C in a clockwise direction, and a fourth layer formed by butting I-D, II-D, III-D and IV-D in a clockwise direction.
Example 1
The embodiment comprises the following steps:
step one, welding crystal bar hafnium to obtain a hafnium smelting electrode; the welding conditions are as follows: a vacuum welding box with the vacuum degree of 3Pa is adopted, wherein the vacuum welding box is filled with argon and keeps the pressure intensity at 0.1MPa, the welding current intensity is 350A, and the cooling time after welding is 35 min;
step two, installing a hafnium crucible with the diameter of phi 104mm and a bottom pad in the electron beam melting furnace, then installing the hafnium melting electrode obtained in the step one in the hafnium crucible, and carrying out leak detection on the electron beam melting furnace for 4min, wherein when the leak rate is not more than 10-1Beginning to smelt for the first time at Pa/min to obtain a primary ingot(ii) a The vacuum degree in the furnace before the first smelting is not more than 2 multiplied by 10-2Pa, the vacuum degree in the furnace in the first smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 65kW, the ingot pulling speed is 5mm/min, and after a primary ingot is obtained, the primary ingot is cooled for 10 min;
step three, installing a hafnium crucible with the diameter of phi 124mm and a bottom pad in the electron beam melting furnace, then installing the primary ingot obtained in the step two in the hafnium crucible, and carrying out leak detection on the electron beam melting furnace for 8min when the leak rate is not more than 10-1Beginning to smelt for the second time when Pa/min, and obtaining a secondary ingot; the vacuum degree in the furnace body before the second smelting is not more than 2 multiplied by 10-2Pa, the vacuum degree in the furnace in the second smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 75kW, the ingot pulling speed is 5mm/min, and the secondary ingot is obtained and then cooled for 15 min;
step four, carrying out cutting recombination treatment on the secondary ingots obtained in the step three to obtain cut combined ingots; the cutting and recombining process comprises the following steps: cutting the secondary ingot into four equal parts along two mutually perpendicular diameters on the end surface, respectively marking the four equal parts as A, B, C and D along the clockwise direction, then cutting the cut secondary ingot into four equal parts along the height direction, respectively marking the four equal parts as I, II, III and IV from top to bottom to obtain 16 divided blocks, respectively marking the divided blocks as I-A, II-A, III-A, IV-A, I-B, II-B, III-B, IV-B, I-C, II-C, III-C, IV-C, I-D, II-D, III-D and IV-D, and recombining the divided secondary ingots as shown in figure 1 in a way that I-A, II-A, III-A and IV-A are butted along the clockwise direction to form a first layer, I-B, I-A, III-A and IV-A are butted to form a first layer, I-B, III and IV-D are butted along the clockwise direction, II-B, III-B and IV-B are butted along the clockwise direction to form a second layer, I-C, II-C, III-C and IV-C are butted along the clockwise direction to form a third layer, I-D, II-D, III-D and IV-D are butted along the clockwise direction to form a fourth layer, and then welding treatment is carried out to obtain a split combined ingot, as shown in figure 2; the welding conditions are as follows: a vacuum welding box with the vacuum degree of 3Pa is adopted, wherein the vacuum welding box is filled with argon and keeps the pressure intensity at 0.1MPa, the welding current intensity is 350A, and the cooling time after welding is 35 min;
step five, installing a hafnium crucible with the diameter of phi 124mm and a bottom pad in the electron beam melting furnace, and then placing the hafnium crucible and the bottom pad in the electron beam melting furnaceInstalling the split combined ingot obtained in the fourth step in the hafnium crucible, and performing leak detection on the electron beam melting furnace for 8min when the leak rate is not more than 10-1Beginning to smelt for the third time at Pa/min to obtain a hafnium finished product ingot; the vacuum degree in the furnace body before the third smelting is not more than 2 multiplied by 10- 2Pa, the vacuum degree in the furnace in the third smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 78kW, the ingot pulling speed is 4.5mm/min, and the hafnium finished product ingot is cooled for 20 min.
Performing component uniformity test on the strip hafnium used in the first step and the hafnium finished ingot obtained in the fifth step, wherein the detection results are shown in table 1 below; in the component uniformity testing process, the end face of one end of the ingot is used as a head part, the other end face of the ingot is used as a tail part, a face with equal distance between the end faces of the two ends is used as a middle part, the edge of the face is used as an edge, the circle center of the face is used as a center, and the part with equal distance between the edge and the center on the face is used as a middle part.
Table 1 mass contents of impurity elements in the hafnium ingot for the boule and the hafnium ingot used in example 1
Figure BDA0002406919700000071
Figure BDA0002406919700000081
As can be seen from table 1, the fluctuation range of the mass content of each impurity element in the hafnium ingot used in this embodiment is relatively large, which indicates that the distribution of the impurity elements in each part of the hafnium ingot is not uniform, and the distribution of the impurity elements in each part of the hafnium ingot obtained by the cutting, reforming and melting process is more uniform.
Comparative example 1
This comparative example comprises the following steps:
step one, welding crystal bar hafnium to obtain a hafnium smelting electrode; the welding conditions are as follows: a vacuum welding box with the vacuum degree of 3Pa is adopted, wherein the vacuum welding box is filled with argon and keeps the pressure intensity at 0.1MPa, the welding current intensity is 350A, and the cooling time after welding is 35 min;
step two, installing a hafnium crucible with the diameter of phi 104mm and a bottom pad in the electron beam melting furnace, then installing the hafnium melting electrode obtained in the step one in the hafnium crucible, and carrying out leak detection on the electron beam melting furnace for 4min, wherein when the leak rate is not more than 10-1Beginning to smelt for the first time when Pa/min, and obtaining a primary ingot; the vacuum degree in the furnace before the first smelting is not more than 2 multiplied by 10-2Pa, the vacuum degree in the furnace in the first smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 65kW, the ingot pulling speed is 5mm/min, and after a primary ingot is obtained, the primary ingot is cooled for 10 min;
step three, installing a hafnium crucible with the diameter of phi 124mm and a bottom pad in the electron beam melting furnace, then installing the primary ingot obtained in the step two in the hafnium crucible, and carrying out leak detection on the electron beam melting furnace for 8min when the leak rate is not more than 10-1Beginning to smelt for the second time when Pa/min, and obtaining a secondary ingot; the vacuum degree in the furnace body before the second smelting is not more than 2 multiplied by 10-2Pa, the vacuum degree in the furnace in the second smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 75kW, the ingot pulling speed is 5mm/min, and the secondary ingot is obtained and then cooled for 15 min;
step four, installing a hafnium crucible with the diameter of phi 124mm and a bottom pad in the electron beam melting furnace, then installing the split combined ingot obtained in the step three in the hafnium crucible, and carrying out leak detection on the electron beam melting furnace for 8min, wherein when the leak rate is not more than 10-1Beginning to smelt for the third time at Pa/min to obtain a hafnium finished product ingot; the vacuum degree in the furnace body before the third smelting is not more than 2 multiplied by 10- 2Pa, the vacuum degree in the furnace in the third smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 78kW, the ingot pulling speed is 4.5mm/min, and the hafnium finished product ingot is cooled for 20 min.
Performing component uniformity test on the crystal strip hafnium used in the first step and the hafnium finished product ingot obtained in the fourth step, wherein the detection results are shown in the following table 2; in the component uniformity testing process, the end face of one end of the ingot is used as a head part, the other end face of the ingot is used as a tail part, a face with equal distance between the end faces of the two ends is used as a middle part, the edge of the face is used as an edge, the circle center of the face is used as a center, and the part with equal distance between the edge and the center on the face is used as a middle part.
Table 2 mass contents of respective impurity elements in the strip hafnium and the hafnium finished ingot used in comparative example 1
Figure BDA0002406919700000091
Figure BDA0002406919700000101
As can be seen from Table 2, the variation range of the mass content of each impurity element in the hafnium ingot used in the comparative example is large, which indicates that the distribution of the impurity elements in each part of the hafnium ingot is not uniform, and the distribution uniformity of Al, Cr, Fe, Mg, Mo, Pb, Ti, W, O and H elements in the processed hafnium ingot is still poor.
As can be seen by comparing the example 1 with the comparative example 1, the distribution of each impurity element in the hafnium finished product ingot obtained by the slitting and recombining treatment is more uniform.
Example 2
The embodiment comprises the following steps:
step one, welding crystal bar hafnium to obtain a hafnium smelting electrode; the welding conditions are as follows: a vacuum welding box with the vacuum degree of 2Pa is adopted, wherein the vacuum welding box is filled with argon and keeps the pressure intensity at 0.12MPa, the welding current intensity is 300A, and the cooling time after welding is 30 min;
step two, a hafnium crucible with the diameter of phi 114mm and a bottom pad are arranged in the electron beam melting furnace, then the hafnium melting electrode obtained in the step one is arranged in the hafnium crucible, the electron beam melting furnace is subjected to leak detection for 10min, and when the leak rate is not more than 10-1Beginning to smelt for the first time when Pa/min, and obtaining a primary ingot; the vacuum degree in the furnace before the first smelting is not more than 2 multiplied by 10-2Pa, the vacuum degree in the furnace in the first smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 60kW, the ingot pulling speed is 6mm/min, and after a primary ingot is obtained, the primary ingot is cooled for 15 min;
step three, in the electricityA hafnium crucible with the diameter of phi 150mm and a bottom pad are arranged in the electron beam melting furnace, then a primary ingot obtained in the second step is arranged in the hafnium crucible, the electron beam melting furnace is subjected to leak detection for 10min, and when the leak rate is not more than 10-1Beginning to smelt for the second time when Pa/min, and obtaining a secondary ingot; the vacuum degree in the furnace body before the second smelting is not more than 2 multiplied by 10-2Pa, the vacuum degree in the furnace in the second smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 70kW, the ingot pulling speed is 6mm/min, and after a secondary ingot is obtained, cooling is carried out for 10 min;
step four, carrying out cutting recombination treatment on the secondary ingots obtained in the step three to obtain cut combined ingots; the cutting and recombining process comprises the following steps: cutting the secondary ingot into four equal parts along two mutually perpendicular diameters on the end surface, respectively marking the four equal parts as A, B, C and D along the clockwise direction, then cutting the cut secondary ingot into four equal parts along the height direction, respectively marking the four equal parts as I, II, III and IV from top to bottom to obtain 16 divided blocks, respectively marking the divided blocks as I-A, II-A, III-A, IV-A, I-B, II-B, III-B, IV-B, I-C, II-C, III-C, IV-C, I-D, II-D, III-D and IV-D, and recombining the divided secondary ingots as shown in figure 1 in a way that I-A, II-A, III-A and IV-A are butted along the clockwise direction to form a first layer, I-B, I-A, III-A and IV-A are butted to form a first layer, I-B, III and IV-D are butted along the clockwise direction, II-B, III-B and IV-B are butted along the clockwise direction to form a second layer, I-C, II-C, III-C and IV-C are butted along the clockwise direction to form a third layer, I-D, II-D, III-D and IV-D are butted along the clockwise direction to form a fourth layer, and then welding treatment is carried out to obtain a split combined ingot, as shown in figure 2; the welding conditions are as follows: a vacuum welding box with the vacuum degree of 2Pa is adopted, wherein the vacuum welding box is filled with argon and keeps the pressure intensity at 0.12MPa, the welding current intensity is 300A, and the cooling time after welding is 30 min;
step five, installing a hafnium crucible with the diameter of phi 150mm and a bottom pad in the electron beam melting furnace, then installing the split combined ingot obtained in the step four in the hafnium crucible, and carrying out leak detection on the electron beam melting furnace for 5min when the leak rate is not more than 10-1Beginning to smelt for the third time at Pa/min to obtain a hafnium finished product ingot; the vacuum degree in the furnace body before the third smelting is not more than 2 multiplied by 10- 2Pa, the firstThe vacuum degree in the furnace in the third smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 75kW, the ingot pulling speed is 6mm/min, and the obtained hafnium finished product ingot is cooled for 25 min.
Performing component uniformity test on the strip hafnium used in the first step and the hafnium finished ingot obtained in the fifth step, wherein the detection results are shown in table 3 below; in the component uniformity testing process, the end face of one end of the ingot is used as a head part, the other end face of the ingot is used as a tail part, a face with equal distance between the end faces of the two ends is used as a middle part, the edge of the face is used as an edge, the circle center of the face is used as a center, and the part with equal distance between the edge and the center on the face is used as a middle part.
Table 3 mass contents of impurity elements in the hafnium ingot for the boule and the hafnium ingot for the final product used in example 2
Figure BDA0002406919700000121
As can be seen from table 3, the fluctuation range of the mass content of each impurity element in the hafnium ingot used in this embodiment is relatively large, which indicates that the distribution of the impurity elements in each part of the hafnium ingot is not uniform, and the distribution of the impurity elements in each part of the hafnium ingot obtained by the cutting, reforming and melting process is more uniform.
Example 3
Step one, welding crystal bar hafnium to obtain a hafnium smelting electrode; the welding conditions are as follows: a vacuum welding box with the vacuum degree of 10Pa is adopted, wherein the vacuum welding box is filled with argon and keeps the pressure at 0.08MPa, the welding current intensity is 500A, and the cooling time after welding is 50 min;
step two, installing a hafnium crucible with the diameter of phi 94mm and a bottom pad in the electron beam melting furnace, then installing the hafnium melting electrode obtained in the step one in the hafnium crucible, and carrying out leak detection on the electron beam melting furnace for 3min, wherein when the leak rate is not more than 10-1Beginning to smelt for the first time when Pa/min, and obtaining a primary ingot; the vacuum degree in the furnace before the first smelting is not more than 2 multiplied by 10-2Pa, the vacuum degree in the furnace in the first smelting is not more than 3 multiplied by 10-2Pa, smelting power of 75kW, ingot pullingThe rate of (3) is 4mm/min, and a primary ingot is obtained and then cooled for 6 min;
step three, installing a hafnium crucible with the diameter of phi 120mm and a bottom pad in the electron beam melting furnace, then installing the primary ingot obtained in the step two in the hafnium crucible, and carrying out leak detection on the electron beam melting furnace for 3min when the leak rate is not more than 10-1Beginning to smelt for the second time when Pa/min, and obtaining a secondary ingot; the vacuum degree in the furnace body before the second smelting is not more than 2 multiplied by 10-2Pa, the vacuum degree in the furnace in the second smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 60kW, the ingot pulling speed is 4mm/min, and the secondary ingot is obtained and then cooled for 6 min;
step four, carrying out cutting recombination treatment on the secondary ingots obtained in the step three to obtain cut combined ingots; the cutting and recombining process comprises the following steps: cutting the secondary ingot into four equal parts along two mutually perpendicular diameters on the end surface, respectively marking the four equal parts as A, B, C and D along the clockwise direction, then cutting the cut secondary ingot into four equal parts along the height direction, respectively marking the four equal parts as I, II, III and IV from top to bottom to obtain 16 divided blocks, respectively marking the divided blocks as I-A, II-A, III-A, IV-A, I-B, II-B, III-B, IV-B, I-C, II-C, III-C, IV-C, I-D, II-D, III-D and IV-D, and recombining the divided secondary ingots as shown in figure 1 in a way that I-A, II-A, III-A and IV-A are butted along the clockwise direction to form a first layer, I-B, I-A, III-A and IV-A are butted to form a first layer, I-B, III and IV-D are butted along the clockwise direction, II-B, III-B and IV-B are butted along the clockwise direction to form a second layer, I-C, II-C, III-C and IV-C are butted along the clockwise direction to form a third layer, I-D, II-D, III-D and IV-D are butted along the clockwise direction to form a fourth layer, and then welding treatment is carried out to obtain a split combined ingot, as shown in figure 2; the welding conditions are as follows: a vacuum welding box with the vacuum degree of 10Pa is adopted, wherein the vacuum welding box is filled with argon and keeps the pressure at 0.08MPa, the welding current intensity is 500A, and the cooling time after welding is 50 min;
step five, installing a hafnium crucible with the diameter of phi 120mm and a bottom pad in the electron beam melting furnace, then installing the split combined ingot obtained in the step four in the hafnium crucible, and carrying out leak detection on the electron beam melting furnace for 10min when the leak rate is not more than 10-1Beginning to smelt for the third time at Pa/min to obtain hafniumCasting a finished ingot; the vacuum degree in the furnace body before the third smelting is not more than 2 multiplied by 10- 2Pa, the vacuum degree in the furnace in the third smelting is not more than 3 multiplied by 10-2Pa, the smelting power is 80kW, the ingot pulling speed is 4mm/min, and the hafnium finished product is cooled for 30min after ingot casting.
Performing component uniformity test on the strip hafnium used in the first step and the hafnium finished ingot obtained in the fifth step, wherein the detection results are shown in table 4 below; in the component uniformity testing process, the end face of one end of the ingot is used as a head part, the other end face of the ingot is used as a tail part, a face with equal distance between the end faces of the two ends is used as a middle part, the edge of the face is used as an edge, the circle center of the face is used as a center, and the part with equal distance between the edge and the center on the face is used as a middle part.
Table 4 mass contents of impurity elements in the hafnium ingot for the boule and the hafnium ingot used in example 3
Figure BDA0002406919700000141
Figure BDA0002406919700000151
As can be seen from table 4, the fluctuation range of the mass content of each impurity element in the hafnium ingot used in this embodiment is relatively large, which indicates that the distribution of the impurity elements in each part of the hafnium ingot is not uniform, and the distribution of the impurity elements in each part of the hafnium ingot obtained by the cutting, reforming and melting process is more uniform.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (5)

1. A cutting, reforming and smelting process for hafnium is characterized by comprising the following steps:
step one, welding crystal bar hafnium to obtain a hafnium smelting electrode;
step two, a hafnium crucible and a bottom pad are arranged in the electron beam melting furnace, and then a hafnium melting electrode obtained in the step one is arranged in the hafnium crucible for first melting to obtain a primary ingot;
step three, mounting a hafnium crucible and a bottom pad in the electron beam melting furnace, and then mounting the primary ingot obtained in the step two in the hafnium crucible and then carrying out secondary melting to obtain a secondary ingot;
step four, carrying out cutting recombination treatment on the secondary ingot obtained in the step three to obtain a cut combined ingot; the cutting and recombining process comprises the following steps: cutting the secondary ingot into four equal parts along two mutually perpendicular diameters on the end surface, respectively marking the four equal parts as A, B, C and D along the clockwise direction, then cutting the cut secondary ingot into four equal parts along the height direction, respectively marking the four equal parts as I, II, III and IV from top to bottom to obtain 16 divided blocks as I-A, II-A, III-A, IV-A, I-B, II-B, III-B, IV-B, I-C, II-C, III-C, IV-C, I-D, II-D, III-D and IV-D, recombining the divided secondary ingots in a mode that the I-A, II-A, III-A and the IV-A are butted along the clockwise direction to form a first layer, I-B, II-B, I-C, III-B, III-B and IV-B are butted in a clockwise direction to form a second layer, I-C, II-C, III-C and IV-C are butted in a clockwise direction to form a third layer, I-D, II-D, III-D and IV-D are butted in a clockwise direction to form a fourth layer, and then welding treatment is carried out;
and step five, mounting a hafnium crucible and a bottom pad in the electron beam melting furnace, then mounting the split combined ingot obtained in the step four in the hafnium crucible, and then carrying out third melting to obtain a hafnium finished product ingot.
2. The hafnium slitting, recombining and melting process according to claim 1, wherein the welding conditions in step one and step four are as follows: a vacuum welding box with the vacuum degree of 2-10 Pa is adopted, wherein the vacuum welding box is filled with argon and keeps the pressure intensity of 0.08-0.12 MPa, the welding current intensity is 300-500A, and the cooling time after welding is 30-50 min.
3. The cutting, reforming and melting process of hafnium according to claim 1, wherein the diameter of the hafnium crucible in step two is phi 94mm to phi 114mm, and the diameter of the hafnium crucible in step three and step five is phi 120mm to phi 150 mm.
4. The slitting, recombining and melting process of hafnium according to claim 1, wherein the first melting in step two and the second melting in step three are performed by: leak detection is carried out on the electron beam melting furnace for 3min to 10min, and when the leak rate is not more than 10-1Beginning smelting at Pa/min, wherein the vacuum degree in the furnace before smelting is not more than 2 multiplied by 10-2Pa, vacuum degree in the furnace in smelting is not more than 3 x 10-2Pa, the smelting power is 60 kW-75 kW, the ingot pulling speed is 4 mm/min-6 mm/min, and the cooling time after smelting is 6 min-15 min.
5. The hafnium slitting, recombining and melting process according to claim 1, wherein the third melting in step five is performed by: leak detection is carried out on the electron beam melting furnace for 5min to 10min, and when the leak rate is not more than 10-1Beginning smelting at Pa/min, wherein the vacuum degree in the furnace before smelting is not more than 2 multiplied by 10-2Pa, vacuum degree in the furnace in smelting is not more than 3 x 10- 2Pa, the smelting power is 75 kW-80 kW, the ingot pulling speed is 4 mm/min-6 mm/min, and the cooling time after smelting is 20 min-30 min.
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JP2002294354A (en) * 2001-03-30 2002-10-09 Japan Steel Works Ltd:The Method for manufacturing hydrogen storage alloy
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JP2002294354A (en) * 2001-03-30 2002-10-09 Japan Steel Works Ltd:The Method for manufacturing hydrogen storage alloy
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* Cited by examiner, † Cited by third party
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CN114277255A (en) * 2021-12-15 2022-04-05 西安诺博尔稀贵金属材料股份有限公司 Method for improving uniformity of components of niobium-tungsten alloy ingot
CN114277255B (en) * 2021-12-15 2024-05-14 西安诺博尔稀贵金属材料股份有限公司 Method for improving component uniformity of niobium-tungsten alloy cast ingot

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