CN114166589A - Preparation method of nuclear-grade hafnium and hafnium alloy single-point spectrum standard sample - Google Patents
Preparation method of nuclear-grade hafnium and hafnium alloy single-point spectrum standard sample Download PDFInfo
- Publication number
- CN114166589A CN114166589A CN202111315980.0A CN202111315980A CN114166589A CN 114166589 A CN114166589 A CN 114166589A CN 202111315980 A CN202111315980 A CN 202111315980A CN 114166589 A CN114166589 A CN 114166589A
- Authority
- CN
- China
- Prior art keywords
- nuclear
- ingot
- hafnium
- hafnium alloy
- grade hafnium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001029 Hf alloy Inorganic materials 0.000 title claims abstract description 156
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 118
- 238000001228 spectrum Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000003723 Smelting Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000012958 reprocessing Methods 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 230000006698 induction Effects 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 238000007689 inspection Methods 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 17
- 238000004458 analytical method Methods 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000005266 casting Methods 0.000 claims description 14
- 238000009616 inductively coupled plasma Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 241001062472 Stokellia anisodon Species 0.000 claims description 5
- 238000005204 segregation Methods 0.000 claims description 5
- 238000009659 non-destructive testing Methods 0.000 claims description 4
- 230000003595 spectral effect Effects 0.000 claims description 2
- 238000005339 levitation Methods 0.000 claims 4
- 230000000694 effects Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000010309 melting process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005464 sample preparation method Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
-
- 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
- C22B9/04—Refining by applying a vacuum
-
- 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
- C22B9/20—Arc remelting
-
- 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
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N2001/2893—Preparing calibration standards
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Manufacturing & Machinery (AREA)
- Plasma & Fusion (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of nuclear grade hafnium alloy preparation, in particular to a method for preparing a nuclear grade hafnium and a hafnium alloy single-point spectrum standard sample, which comprises the following steps: the material comprises the following components in percentage by mass: 0.02-0.048% of Fe, 0.0015-0.009% of Cr, 0.58-0.65% of Zr, less than 0.01% of Al, less than 0.01% of Cu, less than 0.005% of Ni, less than 0.01% of Si and the balance of hafnium, and mixing to obtain a bulk nuclear-grade hafnium sponge mixed raw material; wherein, the hafnium is bulk nuclear grade sponge hafnium; performing vacuum consumable melting on the bulk nuclear grade sponge hafnium to obtain a nuclear grade hafnium alloy primary ingot; carrying out cold crucible magnetic suspension smelting on the nuclear grade hafnium alloy primary ingot for multiple times to obtain a nuclear grade hafnium alloy ingot; and (4) reprocessing the nuclear grade hafnium alloy cast ingot to obtain a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample. The method solves the technical problems that in the prior art, the melting control of the low-content element in the nuclear grade hafnium is extremely difficult, and the prepared low-content element in the nuclear grade hafnium has poor uniformity and low stability.
Description
Technical Field
The invention relates to the technical field of nuclear grade hafnium alloy preparation, in particular to a method for preparing a nuclear grade hafnium and a hafnium alloy single-point spectrum standard sample.
Background
The nuclear grade hafnium and the hafnium alloy have plasticity, easy processing, high temperature resistance and corrosion resistance, and are important materials for atomic energy industry. Hafnium has a large thermal neutron capture cross section, is an ideal neutron absorber, and can be used as a control rod and a protection device of a nuclear reactor. The content of chemical elements in nuclear grade hafnium and hafnium alloy control rods directly affects their efficiency in reactor control. In order to ensure the consistency and stability of the curve of the detection equipment, the development of the nuclear-grade hafnium and the hafnium alloy spectrum standard sample is a key technical task of nuclear materials, and can ensure that the detection result is more accurate and reliable, so that the production, research and development and localization work of the nuclear-grade hafnium alloy control bar is further accelerated. In the existing technology for preparing nuclear grade hafnium, the smelting control of low-content elements in the nuclear grade hafnium is extremely difficult, the prepared low-content elements in the nuclear grade hafnium have poor uniformity and low stability, and in addition, the production and research and development progress of the nuclear grade hafnium alloy in China is restricted to a certain extent due to the preparation capacity of the standard sample for single-point spectral analysis of the nuclear grade hafnium and the hafnium alloy in China.
Accordingly, the present invention is particularly set forth.
Disclosure of Invention
The invention aims to provide a preparation method of a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample, which can be used for controlling smelting of low-content elements in the nuclear grade hafnium, so that the prepared low-content elements in the nuclear grade hafnium have good uniformity and high stability.
The invention provides a preparation method of a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample, which comprises the following steps: the material comprises the following components in percentage by mass: 0.02-0.048% of Fe, 0.0015-0.009% of Cr, 0.58-0.65% of Zr, less than 0.01% of Al, less than 0.01% of Cu, less than 0.005% of Ni, less than 0.01% of Si and the balance of hafnium, and mixing to obtain a bulk nuclear-grade hafnium sponge mixed raw material; wherein, the hafnium is bulk nuclear grade sponge hafnium; performing vacuum consumable melting on the bulk nuclear-grade sponge hafnium mixed raw material to obtain a nuclear-grade hafnium alloy primary ingot; carrying out cold crucible magnetic suspension smelting on the nuclear grade hafnium alloy primary ingot for multiple times to obtain a nuclear grade hafnium alloy ingot; and (4) reprocessing the nuclear grade hafnium alloy cast ingot to obtain a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample.
Further, the method for carrying out multiple times of cold crucible magnetic suspension smelting on the primary nuclear-grade hafnium alloy ingot to obtain the nuclear-grade hafnium alloy ingot comprises the following steps: carrying out cold crucible magnetic suspension primary smelting on the nuclear grade hafnium alloy primary ingot to obtain a nuclear grade hafnium alloy primary ingot; performing cold crucible magnetic suspension secondary smelting on the nuclear grade hafnium alloy primary ingot to obtain a nuclear grade hafnium alloy secondary ingot;
further, the step of carrying out cold crucible magnetic suspension primary smelting on the primary nuclear grade hafnium alloy ingot to obtain the primary nuclear grade hafnium alloy ingot comprises the following steps: the vacuum degree in the crucible reaches 1.0 multiplied by 10-2Introducing high-purity argon into a nuclear-grade hafnium alloy primary ingot in a crucible under the MPa condition; controlling the power of the induction coil to smelt and keeping the temperature for 10-20 min; and cooling to obtain the primary nuclear-grade hafnium alloy ingot.
Further, controlling the power of the induction coil to smelt, and keeping the temperature for 10-20 min comprises the following steps: the primary smelting power is 160 KW-180 KW, and the heat preservation power is 140 KW-150 KW.
Further, performing cold crucible magnetic suspension secondary melting on the nuclear grade hafnium alloy primary ingot to obtain a nuclear grade hafnium alloy secondary ingot, wherein the steps of: the vacuum degree in the crucible reaches 1.0 multiplied by 10-2Introducing high-purity argon into a nuclear-grade hafnium alloy primary ingot in a crucible under the MPa condition; controlling the power of the induction coil to carry out smelting to obtain a nuclear grade hafnium alloy solution, and keeping the temperature for 10-20 min; and casting the nuclear-grade hafnium alloy solution into a mold, and cooling to obtain a secondary nuclear-grade hafnium alloy ingot.
Further, controlling the power of the induction coil to smelt, and keeping the temperature for 10-20 min comprises the following steps: the secondary smelting power is 260 KW-280 KW, and the heat preservation power is 240 KW-250 KW.
Further, the method for performing cold crucible magnetic suspension secondary melting on the nuclear grade hafnium alloy primary ingot to obtain the nuclear grade hafnium alloy secondary ingot further comprises the following steps: and (5) upside down placing the primary ingot of the nuclear grade hafnium alloy.
Further, casting the nuclear grade hafnium alloy solution into a mold to obtain a secondary nuclear grade hafnium alloy ingot, comprising: direct casting was performed by rotating the crucible.
Further, reprocessing the nuclear grade hafnium alloy ingot to obtain a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample, which comprises: primary detection of uniformity: after the surface of the cast ingot is treated, the upper end and the lower end of the cast ingot are cut by 100mm, the cast ingot is subjected to nondestructive testing, and then scrap-shaped samples are taken from the upper end surface, the lower end surface and the middle position of the nuclear-grade hafnium alloy cast ingot to be subjected to component segregation inspection and analytical data are processed; processing: processing the nuclear grade hafnium alloy ingot qualified by the uniformity initial inspection into a chip-shaped sample with the size of about 3mm multiplied by 1mm multiplied by 0.2mm (length multiplied by width multiplied by thickness); checking the uniformity of components: randomly selecting 3 groups of 15 samples in each group from the uniformly mixed nuclear-grade hafnium alloy chip-shaped samples, and respectively checking the 3 groups of data on an Agilent inductively coupled plasma emission spectrometer; setting the value: and (4) carrying out fixed value analysis on the sample with qualified component uniformity inspection.
The nuclear-grade hafnium and hafnium alloy single-point spectrum standard sample preparation method provided by the invention can be used for preparing nuclear-grade hafnium and hafnium alloy spectrum standard samples, and the nuclear-grade hafnium and hafnium alloy spectrum standard samples prepared by the method mainly aim at hafnium control rods and protection devices widely applied in China and used in atomic energy industry. The invention purifies the raw materials by one-time vacuum arc melting, removes volatile elements, prevents the influence of foreign impurities and has certain uniform effect. Utilize electromagnetic force to make molten metal and crucible keep non-contact state and carry out secondary cold crucible magnetic suspension smelting, avoid external pollution, the magnetic field is to the material effect among the melting process, makes the material more even, and surface skin effect strengthens, and the electromagnetic force increases, and capacity in-process stirring effect is more obvious, helps the material even. After the secondary cold crucible suspension smelting, the casting molding is carried out under the vacuum condition, the casting process is that the molten metal is more fully stirred, the components are thorough and uniform, and after the molding, the appearance is regular and the yield is high. The problems of analysis errors and stability caused by different production, research and use units and different analysis instruments are solved, the component design gives consideration to the application and popularization of a series of products such as hafnium sponge, hafnium bar, hafnium wire, hafnium plate and the like, and the method has positive significance for the industrial development of the atomic energy in China. The material comprises the following components in percentage by mass: 0.02-0.048% of Fe, 0.0015-0.009% of Cr, 0.58-0.65% of Zr, less than 0.01% of Al, less than 0.01% of Cu, less than 0.005% of Ni, less than 0.01% of Si, and the balance of mass percentage of hafnium, wherein the bulk nuclear-grade hafnium sponge is weighed, and nuclear-grade hafnium and hafnium alloy spectrum standard samples are prepared by mixing, so that the analysis requirements of the hafnium sponge, hafnium rods, hafnium wires and hafnium plates can be met. And advanced processes such as one-time vacuum arc melting, two-time cold crucible electromagnetic induction melting, casting, rapid cooling and the like are adopted, so that the problems of low-content element melting control and non-uniformity in nuclear-grade hafnium are solved. Eight qualified laboratories in China adopt different principles and reliable analysis methods to carry out cooperative rating, and the rating result is accurate and reliable. And the uniformity inspection is carried out by adopting a variance method, and the result shows that the single-point standard sample has good uniformity. According to the stability of the same kind of standard samples and the stability investigation of development units, the single-point standard sample also has good stability.
Therefore, the method for preparing the nuclear grade hafnium and the hafnium alloy single-point spectrum standard sample solves the technical problems that in the prior art, the melting control of low-content elements in the nuclear grade hafnium is extremely difficult, the prepared low-content elements in the nuclear grade hafnium have poor uniformity and low stability, and the production and research and development progress of the nuclear grade hafnium alloy in China is limited to a certain extent due to the preparation capability of the standard sample for the nuclear grade hafnium and the hafnium alloy single-point spectrum analysis in China at present.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing a single-point spectrum standard sample of nuclear grade hafnium and hafnium alloy according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a method for obtaining a nuclear-grade hafnium and hafnium alloy single-point spectrum standard sample by performing surface treatment, processing and detection on a nuclear-grade hafnium alloy ingot according to an embodiment of the present invention.
Detailed Description
In order to make the above and other features and advantages of the present invention more apparent, the present invention is further described below with reference to the accompanying drawings. It is understood that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that the specific details need not be employed to practice the present invention. In other instances, well-known steps or operations are not described in detail to avoid obscuring the invention.
The nuclear-grade hafnium and hafnium alloy single-point spectrum standard sample preparation method provided by the invention can be used for preparing nuclear-grade hafnium and hafnium alloy spectrum standard samples, and the nuclear-grade hafnium and hafnium alloy spectrum standard samples prepared by the method mainly aim at hafnium control rods and protection devices widely applied in China and used in atomic energy industry. The problems of analysis errors and stability caused by different production, research and use units and different analysis instruments are solved, the component design gives consideration to the application and popularization of a series of products such as hafnium sponge, hafnium bar, hafnium wire, hafnium plate and the like, and the method has positive significance for the industrial development of the atomic energy in China.
Example one
As shown in fig. 1, the method comprises:
step S101, according to the mass percentage of elements: 0.02-0.048% of Fe, 0.0015-0.009% of Cr, 0.58-0.65% of Zr, less than 0.01% of Al, less than 0.01% of Cu, less than 0.005% of Ni, less than 0.01% of Si and the balance of hafnium, and mixing to obtain a bulk nuclear-grade hafnium sponge mixed raw material; wherein, the hafnium is bulk sponge hafnium.
Specifically, the mass percent of Fe in the hafnium sponge mixed raw material can be controlled to be between 0.02% and 0.048%, the mass percent of Cr in the hafnium sponge mixed raw material is controlled to be between 0.0015% and 0.009%, the mass percent of Zr in the hafnium sponge mixed raw material is controlled to be between 0.58% and 0.65%, the mass percent of Al in other elements is controlled to be less than 0.01%, Cu is controlled to be less than 0.01%, Ni is controlled to be less than 0.005%, Si is controlled to be less than 0.01%, and the rest mass percent of hafnium can be bulk nuclear grade hafnium sponge, and the raw materials are mixed to obtain the bulk nuclear grade hafnium sponge mixed raw material.
Step S102, performing vacuum consumable melting on the bulk nuclear-grade hafnium sponge mixed raw material to obtain a nuclear-grade hafnium alloy primary ingot;
after preparing the bulk nuclear-grade hafnium sponge mixed raw material, performing vacuum consumable melting on the nuclear-grade hafnium sponge mixed raw material, wherein the vacuum consumable melting process may include: drying, mixing, pressing an electrode, welding an electrode, carrying out vacuum consumable melting and the like, wherein in the melting process, the current is set between 1800A and 2200A, the voltage is set between 28V and 36V, and the vacuum degree is controlled between 0.1Pa and 2 Pa. It should be noted that the vacuum consumable melting is performed after the steps of drying, mixing, pressing an electrode, welding the electrode, and the like are completed.
Step S103, carrying out cold crucible magnetic suspension smelting on the primary nuclear-grade hafnium alloy ingot for multiple times to obtain a nuclear-grade hafnium alloy ingot;
specifically, the scheme may include the following steps:
step S1031, carrying out cold crucible magnetic suspension primary smelting on the primary nuclear-grade hafnium alloy ingot to obtain a primary nuclear-grade hafnium alloy ingot;
first, the degree of vacuum in the crucible reached 1.0X 10-2Introducing high-purity argon into a nuclear-grade hafnium alloy primary ingot in a crucible under the MPa condition; controlling the power of the induction coil to smelt, and keeping the temperature for 10-20 min; wherein, the power of the induction coil, namely the power of primary smelting, is controlled between 160KW and 180KW, and the heat preservation power is controlled between 140KW and 150 KW; and finally, cooling the primary nuclear-grade hafnium alloy ingot in the crucible to obtain a primary nuclear-grade hafnium alloy ingot. Need to make sure thatThe outer wall of the crucible is provided with a certain thickness, a cooling water flow channel can be arranged in the outer wall, and cooling water flows through the cooling water flow channel to exchange heat with the inside of the crucible, so that the purpose of cooling the nuclear-grade hafnium alloy primary ingot in the crucible is achieved.
Step S1032, carrying out cold crucible magnetic suspension secondary smelting on the nuclear grade hafnium alloy primary ingot to obtain a nuclear grade hafnium alloy secondary ingot;
first, the degree of vacuum in the crucible reached 1.0X 10-2Introducing high-purity argon into a nuclear-grade hafnium alloy primary ingot in a crucible under the MPa condition; controlling the power of the induction coil to carry out smelting to obtain a nuclear grade hafnium alloy solution, and keeping the temperature for 10-20 min; wherein, the power of the induction coil, namely the secondary smelting power, is controlled between 260KW and 280KW, and the heat preservation power is between 240KW and 250 KW. And finally, casting the nuclear-grade hafnium alloy solution into a mold, and cooling to obtain a nuclear-grade hafnium alloy secondary ingot. When the nuclear-grade hafnium alloy solution is cast into a mold, in order to reduce external pollution, the nuclear-grade hafnium alloy solution can be directly cast in a magnetic suspension smelting chamber through a rotating crucible, and then cooled to obtain a secondary nuclear-grade hafnium alloy ingot. The primary ingot of nuclear grade hafnium alloy prepared in the previous step is placed at a different position, for example, the primary ingot of nuclear grade hafnium alloy is placed upside down, thereby improving the effect of the secondary melting.
And step S104, as shown in FIG. 2, reprocessing the nuclear grade hafnium alloy ingot to obtain nuclear grade hafnium and a hafnium alloy single-point spectrum standard sample.
Specifically, the scheme can further comprise the following specific steps:
step S1041, uniformity initial inspection: after the surface of the cast ingot is treated, the upper end and the lower end of the cast ingot are cut by 100mm, the cast ingot is subjected to nondestructive testing, and then scrap-shaped samples are taken from the upper end surface, the lower end surface and the middle position of the nuclear-grade hafnium alloy cast ingot to be subjected to component segregation inspection and analytical data are processed;
step S1042, processing: processing the nuclear grade hafnium alloy ingot qualified by the uniformity initial inspection into a chip-shaped sample with the size of about 3mm multiplied by 1mm multiplied by 0.2mm (length multiplied by width multiplied by thickness);
step S1043, component uniformity inspection: randomly selecting 3 groups of 15 samples in each group from the uniformly mixed nuclear-grade hafnium alloy chip-shaped samples, and respectively checking the 3 groups of data on an Agilent inductively coupled plasma emission spectrometer;
step S1044, constant value: and (4) carrying out fixed value analysis on the sample with qualified component uniformity inspection.
Compared with the prior art, the scheme has the advantages that the raw materials are purified through one-time vacuum arc melting, volatile elements are removed, the influence of foreign impurities is prevented, and a certain uniform effect is achieved. Utilize electromagnetic force to make molten metal and crucible keep non-contact state and carry out secondary cold crucible magnetic suspension smelting, avoid external pollution, the magnetic field is to the material effect among the melting process, makes the material more even, and surface skin effect strengthens, and the electromagnetic force increases, and capacity in-process stirring effect is more obvious, helps the material even. After the secondary cold crucible suspension smelting, the casting molding is carried out under the vacuum condition, the casting process is that the molten metal is more fully stirred, the components are thorough and uniform, and after the molding, the appearance is regular and the yield is high.
Example two
In an alternative embodiment, the following method can be used to prepare single-point spectral standard samples of nuclear grade hafnium and hafnium alloy:
step S201, the element mass percentage is as follows: 0.045% of Fe, 0.0040% of Cr, 0.62% of Zr, and weighing bulk nuclear grade sponge hafnium in the balance of hafnium;
and S202, performing vacuum consumable melting on the bulk nuclear grade hafnium sponge weighed in the step S201 once, and performing drying, material mixing, electrode pressing, electrode welding and one-time consumable melting on the hafnium sponge. In the smelting process, the current is 1800A-2200A, the voltage is 28V-36V, and the vacuum degree is 0.1 Pa-2 Pa;
step S203, carrying out cold crucible magnetic suspension primary smelting on the primary nuclear grade hafnium alloy ingot obtained in the step S202 until the vacuum degree reaches 1.0 multiplied by 10-2Introducing high-purity argon under the MPa condition, smelting with the induction coil power of 160KW, preserving heat with the power of 140KW for 20min, introducing cooling water into the crucible, and rapidly cooling to obtain a primary nuclear-grade hafnium alloy ingot;
step S204, carrying out cold crucible magnetic suspension secondary melting on the primary nuclear grade hafnium alloy ingot obtained in the step S203 until the vacuum degree reaches 1.0 multiplied by 10-2Introducing high-purity argon under the MPa condition, smelting with the induction coil power of 260KW, preserving heat with the power of 240KW for 20min, casting the nuclear-grade hafnium nuclear-grade solution into a mold with cold water, and rapidly cooling to obtain a nuclear-grade hafnium alloy secondary ingot;
and S205, carrying out surface treatment on the secondary ingot of the nuclear grade hafnium alloy obtained in the step S204, then carrying out detection processing, and obtaining a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample to finish the method, wherein the detection is qualified.
The standard sample prepared in this example was designated Hf-1.
EXAMPLE III
In an alternative embodiment, the following method can be used to prepare the nuclear grade hafnium and hafnium alloy single-point spectrum standard sample:
step S301, the element mass percentage is as follows: 0.033% of Fe, 0.0059% of Cr, 0.60% of Zr and the balance of hafnium, wherein bulk nuclear-grade sponge hafnium is weighed;
and S302, performing vacuum consumable melting on the bulk nuclear-grade hafnium sponge weighed in the S301 once, and performing drying, material mixing, electrode pressing, electrode welding and one-time consumable melting on the hafnium sponge. In the smelting process, the current is 1800A-2200A, the voltage is 28V-36V, and the vacuum degree is 0.1 Pa-2 Pa;
step S303, carrying out cold crucible magnetic suspension primary smelting on the primary nuclear grade hafnium alloy ingot obtained in the step S302, and carrying out primary smelting when the vacuum degree reaches 1.0 multiplied by 10-2Introducing high-purity argon under the MPa condition, smelting with the induction coil power of 160KW, preserving heat with the power of 140KW for 20min, introducing cooling water into the crucible, and rapidly cooling to obtain a primary nuclear-grade hafnium alloy ingot;
step S304, carrying out cold crucible magnetic suspension secondary melting on the primary nuclear grade hafnium alloy ingot obtained in the step S303 until the vacuum degree reaches 1.0 multiplied by 10-2Introducing high-purity argon under the MPa condition, smelting with the induction coil power of 260KW, preserving heat with the power of 240KW for 20min, and carrying out nuclear grade hafnium nuclear gradeCasting the solution into a mold filled with cold water, and rapidly cooling to obtain a secondary nuclear-grade hafnium alloy ingot;
and S305, carrying out surface treatment on the secondary ingot of the nuclear grade hafnium alloy obtained in the step S304, then carrying out detection processing, and obtaining a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample to finish the method, wherein the detection is qualified.
The standard sample prepared in this example was designated Hf-2.
Example four
In an alternative embodiment, the following method can be used to prepare the nuclear grade hafnium and hafnium alloy single-point spectrum standard sample:
step S401, according to the element mass percentage: 0.021% of Fe, 0.0030% of Cr and 0.64% of Zr, and weighing bulk nuclear-grade sponge hafnium in the balance of hafnium;
and S402, performing vacuum consumable melting on the bulk nuclear grade hafnium sponge weighed in the S401 once, and performing drying, material mixing, electrode pressing, electrode welding and one-time consumable melting on the hafnium sponge. In the smelting process, the current is 1800A-2200A, the voltage is 28V-36V, and the vacuum degree is 0.1 Pa-2 Pa;
step S403, carrying out cold crucible magnetic suspension primary melting on the primary nuclear grade hafnium alloy ingot obtained in the step S402, and carrying out primary melting when the vacuum degree reaches 1.0 multiplied by 10-2Introducing high-purity argon under the MPa condition, smelting with the induction coil power of 160KW, preserving heat with the power of 140KW for 20min, introducing cooling water into the crucible, and rapidly cooling to obtain a primary nuclear-grade hafnium alloy ingot;
step S404, performing cold crucible magnetic suspension secondary melting on the primary nuclear grade hafnium alloy ingot obtained in the step S403 until the vacuum degree reaches 1.0 multiplied by 10-2Introducing high-purity argon under the MPa condition, smelting with the induction coil power of 260KW, preserving heat with the power of 240KW for 20min, casting the nuclear-grade hafnium nuclear-grade solution into a mold with cold water, and rapidly cooling to obtain a nuclear-grade hafnium alloy secondary ingot;
and S405, carrying out surface treatment on the secondary ingot of the nuclear grade hafnium alloy obtained in the step 404, then carrying out detection processing, and obtaining a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample to finish the method, wherein the detection is qualified.
The standard sample prepared in this example was designated Hf-3.
In order to verify that the low-content elements in the nuclear-grade hafnium prepared by the preparation method of the nuclear-grade hafnium and the single-point spectrum standard sample of the hafnium alloy provided by the invention have good uniformity and high stability, the following comparative examples five to seven are specially made for comparison with the above examples two to four.
EXAMPLE five
Step S501, the element mass percentage is as follows: 0.021% of Fe, 0.0030% of Cr and 0.64% of Zr, and weighing bulk nuclear-grade sponge hafnium in the balance of hafnium;
step S502, carrying out cold crucible magnetic suspension once melting on the bulk nuclear grade hafnium sponge weighed in the step S501, and carrying out vacuum degree reaching 1.0 multiplied by 10-2Introducing high-purity argon under the MPa condition, smelting with the induction coil power of 170KW, preserving heat with the power of 145KW for 18min, introducing cooling water into the crucible, and rapidly cooling to obtain a primary nuclear-grade hafnium alloy ingot;
and S503, carrying out surface treatment on the primary ingot of the nuclear grade hafnium alloy obtained in the step S502, then carrying out detection processing, and obtaining a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample to finish the method, wherein the detection is qualified.
EXAMPLE six
Step S601, the element mass percentage is as follows: 0.021% of Fe, 0.0030% of Cr and 0.64% of Zr, and weighing bulk nuclear-grade sponge hafnium in the balance of hafnium;
step S602, the bulk nuclear grade sponge hafnium weighed in the step S601 is subjected to cold crucible magnetic suspension primary smelting, and the vacuum degree reaches 1.0 multiplied by 10-2Introducing high-purity argon under the MPa condition, introducing 170KW of induction coil power, smelting, preserving heat for 146KW, preserving heat for 17min, performing cold crucible magnetic suspension secondary smelting on the primary nuclear grade hafnium alloy ingot obtained in the step two, introducing high-purity argon and 260KW of induction coil power, smelting, preserving heat for 240KW under the condition that the vacuum degree reaches 1.0 x 10 < -2 > MPa, preserving heat for 20min, introducing cold water into the crucible, and rapidly cooling to obtain a secondary nuclear grade hafnium alloy ingot;
and step S603, carrying out surface treatment on the secondary ingot of the nuclear grade hafnium alloy obtained in the step S602, and then carrying out detection processing, wherein the detection is qualified, and thus obtaining single-point spectrum standard samples of the nuclear grade hafnium and the hafnium alloy.
EXAMPLE seven
Step S701, the method comprises the following steps according to the mass percentage of elements: 0.021% of Fe, 0.0030% of Cr and 0.64% of Zr, and weighing bulk nuclear-grade sponge hafnium in the balance of hafnium;
step S702, carrying out vacuum consumable electrode arc furnace smelting on the bulk nuclear grade hafnium sponge weighed in the step S701 for once;
and S703, carrying out surface treatment on the primary ingot of the nuclear grade hafnium alloy obtained in the step S702, and then carrying out detection processing, wherein the detection is qualified, and thus obtaining single-point spectrum standard samples of the nuclear grade hafnium and the hafnium alloy.
Effect detection
1. Primary detection of uniformity: after the surface of the cast ingot is treated, the upper end and the lower end of the cast ingot are cut by 100mm, the cast ingot is subjected to nondestructive testing, then scrap-shaped samples are taken from the upper end surface, the lower end surface (the center, the R/2 position and the R position) and the middle position of the side wall of the nuclear-grade hafnium alloy cast ingot for component segregation inspection, and analysis data are processed according to the requirements of YS/T409 Standard sample technical Specification for analyzing nonferrous metal products;
EXAMPLE two ingot uniformity
Example three ingot uniformity
| Position of | Zr element content% | The content of Fe element% | The content of Cr element% |
| Upper end face-center | 0.5995 | 0.0331 | 0.0037 |
| Upper end face-R/2 | 0.5997 | 0.0329 | 0.0037 |
| Upper end face-R | 0.5999 | 0.0328 | 0.0035 |
| Lower end face-center | 0.5997 | 0.0330 | 0.0036 |
| Lower end face-R/2 | 0.5998 | 0.0325 | 0.0037 |
| Lower end face-R | 0.6002 | 0.0326 | 0.0034 |
| Side wall | 0.5998 | 0.0328 | 0.0036 |
| Mean value of | 0.5998 | 0.0328 | 0.0036 |
| Standard deviation S | 0.0002 | 0.0002 | 0.0001 |
| 1.5S | 0.0003 | 0.0003 | 0.00015 |
| Limit of repeatability r | 0.05 | 0.0005 | 0.0003 |
| Conclusion | Qualified | Qualified | Qualified |
Example four ingot uniformity
| Position of | Zr element content% | The content of Fe element% | The content of Cr element% |
| Upper end face-center | 0.6395 | 0.0198 | 0.0025 |
| Upper end face-R/2 | 0.6397 | 0.0199 | 0.0027 |
| Upper end face-R | 0.6398 | 0.0201 | 0.0029 |
| Lower end face-center | 0.6395 | 0.0197 | 0.0025 |
| Lower end face-R/2 | 0.6396 | 0.0199 | 0.0026 |
| Lower end face-R | 0.6399 | 0.0200 | 0.0028 |
| Side wall | 0.6400 | 0.0196 | 0.0029 |
| Mean value of | 0.6397 | 0.0198 | 0.0027 |
| Standard deviation S | 0.0002 | 0.0002 | 0.0002 |
| 1.5S | 0.0003 | 0.0003 | 0.0003 |
| Limit of repeatability r | 0.05 | 0.0005 | 0.0003 |
| Conclusion | Qualified | Qualified | Qualified |
Example five ingot uniformity
Examples six ingot uniformity
| Position of | Zr element content% | The content of Fe element% | The content of Cr element% |
| Upper end face-center | 0.6395 | 0.0203 | 0.0028 |
| Upper end face-R/2 | 0.6392 | 0.0207 | 0.0026 |
| Upper end face-R | 0.6400 | 0.0200 | 0.0026 |
| Lower end face-center | 0.6354 | 0.0183 | 0.0020 |
| Lower end face-R/2 | 0.6360 | 0.0180 | 0.0019 |
| Lower end face-R | 0.6363 | 0.0187 | 0.0021 |
| Side wall | 0.6389 | 0.0200 | 0.0027 |
| Mean value of | 0.6379 | 0.0194 | 0.0024 |
| Standard deviation S | 0.0019 | 0.0011 | 0.0004 |
| 1.5S | 0.0028 | 0.0016 | 0.0006 |
| Limit of repeatability r | 0.05 | 0.0005 | 0.0003 |
| Conclusion | Qualified | Fail to be qualified | Fail to be qualified |
Example seven ingot uniformity
The above experimental data results show that: the nuclear grade hafnium alloy cast ingot cast by the method is qualified by inspection, all elements have no segregation phenomenon, and the nuclear grade hafnium and the hafnium alloy single-point spectrum standard sample prepared by the preparation method provided by the invention are further verified to have good uniformity and high stability of low-content elements in the nuclear grade hafnium.
2. Processing: processing the nuclear grade hafnium alloy ingot qualified by the uniformity initial inspection into a chip-shaped sample with the size of about 3mm multiplied by 1mm multiplied by 0.2mm (length multiplied by width multiplied by thickness);
3. checking the uniformity of components: randomly selecting 3 groups of uniformly mixed nuclear grade hafnium alloy scrap samples according to the technical specification of standard samples, numbering 15 samples in each group in sequence, and respectively inspecting the 3 groups of samples on an Agilent inductively coupled plasma emission spectrometer;
all standard samples are uniformly qualified through inspection;
4. setting the value: and (3) carrying out fixed value analysis on the sample with qualified component uniformity according to the requirements of YS/T409 technical Specification for non-ferrous metal product analysis.
And (3) carrying out fixed value analysis by selecting a unit with a qualification laboratory, an industry representative and a regional representative to participate in fixed value, and selecting an accurate and reliable analysis method for collaborative customized analysis.
Data summarization and processing
And (4) referring to data reported by each analysis unit, checking whether abnormal values exist in the group and among the units according to the allowable difference of a national standard method by extreme difference, and if necessary, requiring an original laboratory to check the suspicious values. The data is then processed in the following various ways. Then, the standard value and the expansion uncertainty of each group of data are calculated.
(1) And (4) normal test: (Shapiro-wilk) Charpiro-Wilk method
Summarizing the original data after the suspicious values are removed, and performing normal test on all data reported by each cooperation unit by using a Charperot-Wilck method.
Calculating the formula:
in the formula: k is 1 to h, and h is (n-1)/2 when the number of measurements n is an even number and h is (n-1)/2 when the number of measurements n is an odd number. Coefficient akIs a particular value for n relative to k. W < W (a, n) does not obey normal, otherwise it is normal.
All data were tested for normality or near normality.
(2) And (3) abnormal value test: (Grubbs) Grubbs' method
When the data are subjected to normal distribution or approximate normal, the average value of each group of data is regarded as a single measurement value, and a new group of data is formed. The test was carried out by the Grabbs method.
Here, significance level α is 0.05, critical value 2.126. And calculating the maximum residual error and the minimum residual error, if both are smaller than a critical value, and keeping all the residual errors.
(3) And (3) equal precision inspection: (cochran) Kokronen Process
And (5) using a Koclen criterion to test whether the results of each group have equal precision or not by using the standard sample.
Cocklun criterion test formula:
in the formula: m: number of data sets, n: the number of times of measurement was repeated.
If Cmax is less than or equal to C (a, m, n), each group of data is equal in precision.
If Cmax > C (a, m, n) indicates that the set of data is of poor accuracy.
The examination shows that all data are of equal or approximately equal precision.
(4) After each group of data is processed, the arithmetic mean value and the single measurement standard deviation of each group of data are calculated, and the effective number of the standard value is reduced according to GB/T8170 data reduction rule.
(5) Standard value and extended uncertainty:
since the tests were all of equal precision, the standard and extended uncertainties were calculated as follows:
measuring the characteristic quantity of the standard sample, wherein: m is the number of data sets, n is the number of repeated measurements,
the average value was determined.
Arithmetic total mean (standard value)
Standard deviation of single measurement
Standard deviation of arithmetic mean
Standard deviation (non-uniform uncertainty) S of non-uniform generation1：
When the F is less than 1, the silicon carbide powder is mixed,
synthetic uncertainty S:
expansion uncertainty U:
where K is an inclusion factor determined by the confidence probability and the degree of freedom, where K is 2.37(a ═ 0.05, a is the confidence level; V ═ 7, V is the degree of freedom).
The result of the fixed value of the standard sample is represented by (standard value, extended uncertainty).
EXAMPLE two Standard sample No. Hf-1 (%)
EXAMPLE three Standard No. Hf-2 (%)
Example four Standard No. Hf-3 (%)
Standard sample number Hf-1, standard sample number Hf-2, standard sample number Hf-3 Spectrum Standard sample rating results (%)
Production assessment
The standard sample is analyzed on a PE and Spiker inductively coupled plasma emission spectrometer and compared with a chemical method, and the test result is as follows.
Production evaluation results (%)
After two inductively coupled plasma emission spectrometers are tested, the obtained data is matched with the chemical test result. The three single-point calibration samples are reasonable in component design, good in uniformity and accurate and reliable in fixed value.
The respective technical features described above may be arbitrarily combined. Although not all possible combinations of features are described, any combination of features should be considered to be covered by the present specification as long as there is no contradiction between such combinations.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample is characterized by comprising the following steps:
the material comprises the following components in percentage by mass: 0.02-0.048% of Fe, 0.0015-0.009% of Cr, 0.58-0.65% of Zr, less than 0.01% of Al, less than 0.01% of Cu, less than 0.005% of Ni, less than 0.01% of Si and the balance of hafnium, and mixing to obtain a bulk nuclear-grade hafnium sponge mixed raw material; wherein the hafnium is bulk nuclear grade hafnium sponge;
performing vacuum consumable melting on the bulk nuclear-grade hafnium sponge mixed raw material to obtain a nuclear-grade hafnium alloy primary ingot;
carrying out cold crucible magnetic suspension smelting on the nuclear grade hafnium alloy primary ingot for multiple times to obtain a nuclear grade hafnium alloy ingot;
and reprocessing the nuclear grade hafnium alloy cast ingot to obtain a nuclear grade hafnium and hafnium alloy single-point spectrum standard sample.
2. The method of claim 1, wherein the step of performing multiple cold crucible magnetic levitation melting on the primary nuclear grade hafnium alloy ingot to obtain a nuclear grade hafnium alloy ingot comprises:
performing cold crucible magnetic suspension primary smelting on the nuclear grade hafnium alloy primary ingot to obtain a nuclear grade hafnium alloy primary ingot;
and carrying out cold crucible magnetic suspension secondary smelting on the nuclear grade hafnium alloy primary ingot to obtain a nuclear grade hafnium alloy secondary ingot.
3. The method of claim 2, wherein the step of performing cold crucible magnetic levitation primary melting on the nuclear grade hafnium alloy primary ingot to obtain the nuclear grade hafnium alloy primary ingot comprises the following steps:
the vacuum degree in the crucible reaches 1.0 multiplied by 10-2Introducing high-purity argon into the primary nuclear-grade hafnium alloy ingot in the crucible under the MPa condition;
controlling the power of the induction coil to smelt and keeping the temperature for 10-20 min;
and cooling to obtain the primary nuclear-grade hafnium alloy ingot.
4. The method of claim 3, wherein controlling the power of the induction coil to perform melting and maintaining the temperature for 10-20 min comprises:
the primary smelting power is 160 KW-180 KW, and the heat preservation power is 140 KW-150 KW.
5. The method of claim 2, wherein the step of performing cold crucible magnetic levitation secondary melting on the nuclear grade hafnium alloy primary ingot to obtain a nuclear grade hafnium alloy secondary ingot comprises:
the vacuum degree in the crucible reaches 1.0 multiplied by 10-2Under the condition of MPa,introducing high-purity argon into the nuclear-grade hafnium alloy primary ingot in the crucible;
controlling the power of the induction coil to carry out smelting to obtain a nuclear grade hafnium alloy solution, and keeping the temperature for 10-20 min;
and casting the nuclear grade hafnium alloy solution into a mold, and cooling to obtain a nuclear grade hafnium alloy secondary ingot.
6. The method of claim 5, wherein controlling the power of the induction coil to perform melting and maintaining the temperature for 10-20 min comprises:
the secondary smelting power is 260-280 KW, and the heat preservation power is 240-250 KW.
7. The method of claim 2, wherein the step of subjecting the primary nuclear grade hafnium alloy ingot to cold crucible magnetic levitation secondary melting to obtain a secondary nuclear grade hafnium alloy ingot further comprises:
and (3) upside down placing the primary nuclear-grade hafnium alloy ingot.
8. The method of claim 5, wherein casting the nuclear grade hafnium alloy solution into a mold and cooling to obtain a secondary nuclear grade hafnium alloy ingot comprises:
direct casting was performed by rotating the crucible.
9. The method of claim 1, wherein the reprocessing of the nuclear grade hafnium alloy ingot to obtain a nuclear grade hafnium and hafnium alloy single-point spectral standard sample comprises:
primary detection of uniformity: after the surface of the cast ingot is treated, the upper end and the lower end of the cast ingot are cut by 100mm, the cast ingot is subjected to nondestructive testing, and then scrap-shaped samples are taken from the upper end surface, the lower end surface and the middle position of the nuclear-grade hafnium alloy cast ingot to be subjected to component segregation inspection and analytical data are processed;
processing: processing the nuclear grade hafnium alloy ingot qualified by the uniformity initial inspection into a chip-shaped sample with the size of about 3mm multiplied by 1mm multiplied by 0.2mm (length multiplied by width multiplied by thickness);
checking the uniformity of components: randomly selecting 3 groups of 15 samples in each group from the uniformly mixed nuclear-grade hafnium alloy chip-shaped samples, and respectively checking the 3 groups of data on an Agilent inductively coupled plasma emission spectrometer;
setting the value: and (4) carrying out fixed value analysis on the sample with qualified component uniformity inspection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111315980.0A CN114166589B (en) | 2021-11-08 | 2021-11-08 | Preparation method of nuclear-grade hafnium and hafnium alloy single-point spectrum standard sample |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111315980.0A CN114166589B (en) | 2021-11-08 | 2021-11-08 | Preparation method of nuclear-grade hafnium and hafnium alloy single-point spectrum standard sample |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114166589A true CN114166589A (en) | 2022-03-11 |
| CN114166589B CN114166589B (en) | 2024-10-18 |
Family
ID=80478388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111315980.0A Active CN114166589B (en) | 2021-11-08 | 2021-11-08 | Preparation method of nuclear-grade hafnium and hafnium alloy single-point spectrum standard sample |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114166589B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115647733A (en) * | 2022-10-11 | 2023-01-31 | 中国核动力研究设计院 | Hafnium standard substance and preparation method thereof |
| CN115896501A (en) * | 2022-12-29 | 2023-04-04 | 苏州六九新材料科技有限公司 | Preparation method of titanium-aluminum alloy, titanium-aluminum alloy and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60177260A (en) * | 1984-02-23 | 1985-09-11 | Toshiba Corp | Method for measuring soundness of hafnium in nuclear reactor |
| KR20040027087A (en) * | 2002-09-27 | 2004-04-01 | 주식회사 포스코 | Sample compound method for alloy iron fluorescent x-ray analysis and the sample pretreatment method thereof |
| CN103759991A (en) * | 2013-12-10 | 2014-04-30 | 中国航空工业集团公司北京航空材料研究院 | Uniformity control method for trace element arsenic in cast superalloy standard substance |
| CN106885799A (en) * | 2015-03-30 | 2017-06-23 | 国核宝钛锆业股份公司 | A kind of method for determining content of magnesium in core level sponge zirconium particle |
| CN108152355A (en) * | 2017-11-02 | 2018-06-12 | 山东非金属材料研究所 | A kind of rare earth pyrophoric alloy Standard Reference Materials for Determination and preparation method thereof |
| CN113533014A (en) * | 2021-06-11 | 2021-10-22 | 中国科学院金属研究所 | Preparation method of internal control standard sample for spectral analysis of cast superalloy |
-
2021
- 2021-11-08 CN CN202111315980.0A patent/CN114166589B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60177260A (en) * | 1984-02-23 | 1985-09-11 | Toshiba Corp | Method for measuring soundness of hafnium in nuclear reactor |
| KR20040027087A (en) * | 2002-09-27 | 2004-04-01 | 주식회사 포스코 | Sample compound method for alloy iron fluorescent x-ray analysis and the sample pretreatment method thereof |
| CN103759991A (en) * | 2013-12-10 | 2014-04-30 | 中国航空工业集团公司北京航空材料研究院 | Uniformity control method for trace element arsenic in cast superalloy standard substance |
| CN106885799A (en) * | 2015-03-30 | 2017-06-23 | 国核宝钛锆业股份公司 | A kind of method for determining content of magnesium in core level sponge zirconium particle |
| CN108152355A (en) * | 2017-11-02 | 2018-06-12 | 山东非金属材料研究所 | A kind of rare earth pyrophoric alloy Standard Reference Materials for Determination and preparation method thereof |
| CN113533014A (en) * | 2021-06-11 | 2021-10-22 | 中国科学院金属研究所 | Preparation method of internal control standard sample for spectral analysis of cast superalloy |
Non-Patent Citations (3)
| Title |
|---|
| 李刚 等: "使用ICP-OES测定核级锆锭中7种痕量元素", 金属世界, no. 05, 15 September 2018 (2018-09-15), pages 54 - 56 * |
| 王立新 等: "铜铬锆合金光谱分析用标准物质的研制", 化学分析计量, vol. 25, no. 06, 30 November 2016 (2016-11-30), pages 4 - 8 * |
| 陈永君 等: "X射线荧光光谱用人工标准物质的研制", 岩矿测试, vol. 28, no. 05, 31 October 2009 (2009-10-31), pages 462 - 466 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115647733A (en) * | 2022-10-11 | 2023-01-31 | 中国核动力研究设计院 | Hafnium standard substance and preparation method thereof |
| CN115896501A (en) * | 2022-12-29 | 2023-04-04 | 苏州六九新材料科技有限公司 | Preparation method of titanium-aluminum alloy, titanium-aluminum alloy and application |
| CN115896501B (en) * | 2022-12-29 | 2024-06-07 | 苏州六九新材料科技有限公司 | Preparation method and application of titanium-aluminum alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114166589B (en) | 2024-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114166589B (en) | Preparation method of nuclear-grade hafnium and hafnium alloy single-point spectrum standard sample | |
| Matula | Electrical resistivity of copper, gold, palladium, and silver | |
| CN107340276B (en) | Method for rapidly determining contents of multiple elements in rare earth metal | |
| CN104614215B (en) | High manganic aluminum bronze standard substance and preparation method thereof | |
| CN102965541A (en) | Ti80 titanium alloy standard substance and preparation method thereof | |
| CN112816280B (en) | Preparation method of 7XXX series aluminum alloy as-cast single-point spectrum standard sample | |
| CN110686944A (en) | Preparation method of copper alloy standard sample | |
| CN102368052A (en) | Preparation method of copper alloy spectral standard sample | |
| Konopel’ko et al. | New metrological support for measurements of the concentration of hydrogen in solid samples | |
| WO2015156458A1 (en) | Method for preparing zirconium alloy with excellent low hydrogen absorption and hydrogen embrittlement resistance and zirconium alloy composition with excellent low hydrogen absorption and hydrogen embrittlement resistance | |
| CN103674652B (en) | Iron based nano crystal standard sample for spectrochemical analysis preparation method | |
| CN103528867B (en) | A kind of be used for spectral analysis and chemico-analytic fine copper standard model and preparation method | |
| CN105784530A (en) | Method for measuring contents of oxygen and nitrogen in neodymium iron boron (NdFeB) material | |
| CN110405122A (en) | A kind of production method and production system of high-strength and high ductility wrought alloy | |
| CN113670829B (en) | Low-alloy cast iron spectrum complete standard sample, preparation method and detection method thereof | |
| CN103163079B (en) | Low-carbon aluminum-containing silicon steel standard sample and preparation method thereof | |
| CN107941738A (en) | The method of inspection of nitrogen content in a kind of variety steel magnesium oxide coating | |
| CN117686291B (en) | Copper and copper alloy spectral analysis standard substance and preparation method thereof | |
| CN113984705B (en) | Method for measuring oxygen content of aluminum nitride crystal lattice | |
| CN100494959C (en) | Method for preparing X-ray austenite measuring and caliberating sample | |
| CN107543807A (en) | Detect TiO in high titanium powder2Method of content | |
| CN115808511A (en) | Method for determining additive manufacturing forming parameters of metal material | |
| Wallace | Chemical vapor deposition of ZrC in small bore carbon-composite tubes | |
| CN111189866A (en) | Detection method for monitoring direct-reading spectrometer by X-ray fluorescence spectrometer | |
| Hoggan et al. | Initial Microstructure Evaluation of a U 3 Si 2+ W Fuel Pin Fabricated Via Arc Melt Gravity Drop Casting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240914 Address after: 721000, No. 206 Gaoxin Avenue, High tech Development Zone, Baoji City, Shaanxi Province Applicant after: STATE NUCLEAR BAO TI ZIRCONIUM INDUSTRY Co. Country or region after: China Applicant after: STATE NUCLEAR ZIRCONIUM PHOSPHATE CHEMICAL TESTING CO.,LTD. Applicant after: STATE NUCLEAR WEC ZIRCONIUM AND HAFNIUM CO.,LTD. Address before: 721013 Baoji hi tech Avenue, Baoji, Shaanxi Applicant before: STATE NUCLEAR BAO TI ZIRCONIUM INDUSTRY Co. Country or region before: China Applicant before: STATE NUCLEAR ZIRCONIUM PHOSPHATE CHEMICAL TESTING CO.,LTD. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |