CN114350994B - Preparation method of iron-containing zirconium alloy ingot - Google Patents
Preparation method of iron-containing zirconium alloy ingot Download PDFInfo
- Publication number
- CN114350994B CN114350994B CN202210027857.7A CN202210027857A CN114350994B CN 114350994 B CN114350994 B CN 114350994B CN 202210027857 A CN202210027857 A CN 202210027857A CN 114350994 B CN114350994 B CN 114350994B
- Authority
- CN
- China
- Prior art keywords
- smelting
- zirconium
- iron
- ingot
- electrode
- 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.)
- Active
Links
Images
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a preparation method of a zirconium alloy ingot containing iron, which comprises the steps of mixing and smelting sponge zirconium and zirconium-iron intermediate alloy particles and one or more alloy components of tin, niobium, chromium and nickel to finally prepare the zirconium alloy ingot with uniform iron element content. The zirconium alloy prepared by the method has good ingot casting performance, meets the requirements of subsequent finished products, solves the problem of uniform control of iron elements in the zirconium alloy, has wide application prospect, is easy to realize industrial production, has high automation degree, and has stable quality and better economical efficiency.
Description
Technical Field
The invention belongs to the technical field of zirconium alloy preparation, and particularly relates to a preparation method of an iron-containing zirconium alloy ingot.
Background
After the 21 st century, the nuclear power industry of China enters a rapid development stage, the demand of zirconium alloy as a cladding material for nuclear power is greatly increased, and the localization of zirconium alloy is gradually carried out. In order to improve the nuclear power economy, the requirement of a new-generation reactor technology on fuel consumption is higher and higher, the refueling time of the zirconium alloy cladding tube is further prolonged, and the content of iron element in the new-generation zirconium alloy developed in developed countries in the world is increased and tends to be increased gradually. At present, the addition of iron element in the commonly used zirconium alloy is basically pure metallic iron, but the uniformity of the iron element in the zirconium alloy ingot is poor, and the control difficulty of the iron element in zirconium is increased along with the increase of the iron content in the novel zirconium alloy, so that a method for preparing the iron-containing zirconium alloy ingot is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the preparation method of the iron-containing zirconium alloy ingot, the zirconium alloy ingot has good performance, completely meets the requirements of subsequent finished products, well solves the problem of uniform control of iron element in the zirconium alloy, and has the advantages of wide application prospect, easy realization of industrial production, high automation degree, stable quality of the prepared product and better economical efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an iron-containing zirconium alloy ingot is characterized in that sponge zirconium and zirconium-iron intermediate alloy particles are mixed with one or more alloy components of tin, niobium, chromium and nickel and then are smelted, and finally the zirconium alloy ingot with uniform iron element content is prepared.
Further, the method specifically comprises the following steps:
s1, pressing the mixture into an electrode block, and welding the electrode block into a consumable electrode in a vacuum plasma welding box;
and S2, smelting the consumable electrode in a vacuum consumable arc furnace, and cooling to obtain a zirconium alloy ingot.
Further, the mixture in step S1 includes sponge zirconium, zirconium-iron intermediate alloy particles, and one or more of tin, niobium, chromium, and nickel, and the preparation of the zirconium-iron intermediate alloy particles specifically includes the following steps:
s11, pressing the mixture of the pure iron chips and the sponge zirconium into an electrode block, and welding the electrode block into a consumable electrode in a vacuum plasma welding box;
s12, smelting the consumable electrode in a vacuum consumable arc furnace, and cooling to obtain a zirconium-iron intermediate alloy cast ingot;
and S13, machining the zirconium-iron intermediate alloy cast ingot to prepare zirconium-iron intermediate alloy particles.
Further, the weight of the pure iron filings in the step S11 accounts for 10-20% of the total weight, and the sizes of the iron filings are as follows: the length is 3-8 mm, the width is 2-5 mm, and the thickness is 0.1-0.2 mm.
Further, the step S11 specifically includes the following steps:
s111, according to the required weight of each electrode block, dividing the sponge zirconium and the scrap iron into a plurality of equal parts, wherein each equal part is used for pressing one electrode block: dividing each equal part of the zirconium sponge into half parts, adding the half parts into a die cavity of a pressing machine, uniformly scattering scrap iron on the zirconium sponge in the die cavity, adding the other half part of the zirconium sponge, and finally pressing;
and S112, welding the plurality of electrode blocks into a consumable electrode in a vacuum plasma welding box, and cooling to room temperature after welding.
Further, in step S12, the arc voltage control is adopted in the arc striking stage of the melting, and the melting is changed into a droplet after the melting is stable until the melting is finished.
Further, the step S12 specifically includes:
primary smelting: carrying out primary smelting on the consumable electrode in a vacuum consumable arc furnace to obtain a primary ingot, setting the smelting speed to be 2 kg/min-3 kg/min, the smelting current to be 3000A-4000A, the smelting voltage to be 23V-25V, and the cooling time after smelting to be more than or equal to 3h, wherein in order to improve the cooling speed of the ingot, the water inlet and outlet temperatures of crucible cooling water are respectively as follows: not more than 20 ℃ and not more than 30 ℃;
secondary smelting: carrying out secondary smelting on the primary cast ingot in a vacuum consumable arc furnace to obtain a secondary cast ingot, setting the smelting speed to be 4 kg/min-5 kg/min, the smelting current to be 5000A-6000A and the smelting voltage to be 24V-26V when controlling the smelting of molten drops, wherein the cooling time after smelting is more than or equal to 4h, and in order to improve the cooling speed of the cast ingot, the water inlet and outlet temperatures of crucible cooling water are respectively as follows: not more than 20 ℃ and not more than 31 ℃;
and (3) smelting for the third time: carrying out three times of smelting on the secondary ingot in a vacuum consumable arc furnace to obtain a zirconium-iron intermediate alloy ingot, setting the smelting speed to be 5 kg/min-6 kg/min, the smelting current to be 6500A-7500A and the smelting voltage to be 25V-27V during molten drop control smelting, wherein the cooling time after smelting is more than or equal to 5h, and in order to improve the cooling speed of the ingot, the water inlet and outlet temperatures of crucible cooling water are respectively as follows: not more than 20 ℃ and not more than 32 ℃.
Further, the zirconium-iron master alloy ingot in the step S13 is cut into slices with a thickness of 5-10 mm on a sawing machine after the chemical components of the zirconium-iron master alloy ingot are qualified, and then the slices are cut into blocks with side lengths of 5-20 mm on a shearing machine.
Compared with the prior art, the invention has the following beneficial effects:
the application provides a preparation method of an iron-containing zirconium alloy ingot, which is characterized in that zirconium iron intermediate alloy particles are used for replacing scrap iron and sponge zirconium to prepare the zirconium alloy ingot, so that the distribution of iron elements in the zirconium alloy ingot is more uniform; the molten drop control smelting technology is adopted during preparation of the zirconium-iron intermediate alloy, the cooling strength in smelting is increased, the problem of uniform distribution of iron elements in the matrix zirconium is further solved, no stirring magnetic field needs to be added in the smelting process, the zirconium alloy has good ingot casting performance, the requirements of subsequent finished products are met, the problem of uniform control of the iron elements in the zirconium alloy is solved, the application prospect is wide, industrial production is easy to realize, the automation degree is high, the prepared product is stable in quality, and the economical efficiency is good.
The method is not only suitable for preparing the iron-containing zirconium alloy ingot containing one or more of tin, niobium, chromium and nickel, but also suitable for preparing the iron-containing zirconium alloy ingot containing other alloy elements.
Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments thereof, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
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 for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a schematic diagram of a zirconium-iron master alloy ingot casting sampling according to an embodiment of the invention.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of apparatus consistent with certain aspects of the invention, as detailed in the appended claims.
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings and examples.
A preparation method of an iron-zirconium-containing alloy ingot comprises the following steps:
firstly, selecting sponge zirconium and pure iron scraps/particles, wherein the weight of the pure iron scraps/particles accounts for 10-20% of the total weight, and the size of the iron scraps is as follows: 3 ~ 8mm long, wide 2 ~ 5mm, thick 0.1 ~ 0.2mm, according to the required weight of every electrode block, divide into a plurality of equal portions of part with sponge zirconium and iron fillings respectively, every equal portion is used for suppressing an electrode block: dividing each equal part of the sponge zirconium into half parts, adding the half parts into a die cavity of a pressing machine, uniformly scattering scrap iron on the sponge zirconium in the die cavity, then adding the other half part of the sponge zirconium, and finally pressing on a 50MN press, wherein an electrode block is a rod-shaped electrode;
and step two, welding a plurality of electrode blocks into a consumable electrode in a vacuum plasma welding box, wherein the welding current is 400-450A, and cooling to room temperature after welding.
Step three, smelting the prepared consumable electrode in a vacuum arc furnace for three times:
primary smelting: and melting the prepared consumable electrode into a primary cast ingot in a vacuum consumable electric arc furnace. In the stage of melting and arcing, arc pressure control is adopted to set a melting voltage of 28V, after 2.5kg of consumable electrode is melted, the consumable electrode is turned into molten drops, the melting speed is set to be 2 kg/min-3 kg/min, the melting current is set to be 3000A-4000A, the melting voltage is set to be 23V-25V, the cooling time after melting is more than or equal to 3h, the vacuum degree before melting is less than or equal to 0.3Pa, the pressure rise rate before melting is less than or equal to 0.1Pa, and argon is filled into the furnace for protection during cooling after melting so as to improve the cooling speed of cast ingots. Simultaneously, for further improving the cooling strength, the temperatures of the cooling water in and out of the crucible in the melting process and the cooling process are respectively as follows: not more than 20 ℃ and not more than 30 ℃;
secondary smelting: cleaning the primary cast ingot, then using the cleaned primary cast ingot as a consumable electrode to carry out secondary smelting to obtain a secondary cast ingot, setting a smelting voltage of 28V by adopting arc pressure control in a smelting and arc striking stage, controlling the molten drop after 4kg of the consumable electrode is smelted until the whole smelting is finished, setting a smelting speed of 4 kg/min-5 kg/min, a smelting current of 5000A-6000A, a smelting voltage of 24V-26V, cooling time after smelting is more than or equal to 4h, vacuum degree before smelting is less than or equal to 0.3Pa, pressure rise rate before smelting is less than or equal to 0.1Pa, and filling argon gas into the furnace for protection when cooling after smelting is carried out so as to improve the cooling speed of the cast ingot. Simultaneously, for further improving the cooling strength, the temperatures of the cooling water in and out of the crucible in the melting process and the cooling process are respectively as follows: not more than 20 ℃ and not more than 31 ℃;
and (3) smelting for the third time: and cleaning the secondary cast ingot, then using the cleaned secondary cast ingot as a consumable electrode to carry out tertiary smelting to obtain a zirconium-iron intermediate alloy cast ingot, setting a smelting voltage of 28V by adopting arc pressure control in a smelting and arc striking stage, controlling the molten drop after 6kg of consumable electrode is smelted until the whole smelting is finished, setting a smelting speed of 5 kg/min-6 kg/min during smelting, setting a smelting current of 6500A-7500A, a smelting voltage of 25V-27V, cooling time after smelting to be not less than 5h, vacuum degree before smelting to be not more than 0.3Pa, pressure rise rate before smelting to be not more than 0.1Pa, and filling argon gas into the furnace for protection during cooling after smelting to improve the cooling speed of the cast ingot. Simultaneously, for further improving the cooling strength, the temperature of cooling water in and out of the crucible in the melting process and the cooling process is respectively as follows: not more than 20 ℃ and not more than 32 ℃;
the arc voltage control mode is adopted only in the arc striking stage in the smelting process of the third smelting, and the remaining consumable electrode is controlled by molten drops, so that the arc voltage in the arc striking stage is very low, the cooling intensity is very high, the smelted metal can be immediately solidified, the consumable electrode can be directly adhered to the bottom of the crystallizer, the arc length is properly increased by the arc voltage control, and the molten drop control is switched after the liquid metal is fully distributed on the bottom of the crystallizer. And when molten drops are controlled, the arc length is very short, the concentration ratio of the arc is higher, the temperature of the end face of the electrode is also higher, and along with the increase of the number of the molten drops, particles become small, so that volatile impurities can be removed, and the smelting speed is stabilized. A stirring magnetic field is not added in the smelting process, because the stirring magnetic field outside the furnace is a longitudinal magnetic field, so that the splashing of iron elements in smelting is increased, the uniform distribution in a molten pool is not facilitated, and particularly the iron content at the edge of an ingot is higher.
And step four, cutting the zirconium-iron intermediate alloy ingot into slices with the thickness of 5-10 mm on a sawing machine after the chemical components of the zirconium-iron intermediate alloy ingot are qualified, and then shearing the slices into blocks with the side length of 5-20 mm on a shearing machine.
Step five, mixing and pressing the zirconium-iron intermediate alloy particles and one or more of sponge zirconium, tin, niobium, chromium and nickel into an electrode block, and welding the electrode block into a consumable electrode in a vacuum plasma welding box; and smelting the consumable electrode in a vacuum consumable arc furnace, and cooling to obtain the zirconium alloy ingot.
The homogeneous distribution of iron in zirconium is very well controlled by these measures.
The following is described with reference to specific process procedures:
example 1:
step one, selecting sponge zirconium and prepared pure iron filings (the trade name YT-1), and calculating the weight of the needed sponge zirconium and the iron filings according to the content and the feeding amount of Fe element in the sponge zirconium, wherein the weight of Fe accounts for 10% of the total feeding proportion, the total feeding amount is 500kg, and the size of the iron filings is as follows: length × width × thickness: 3mm × 2mm × 0.2 mm;
step two, preparing the prepared sponge zirconium and scrap iron into an electrode; the preparation process of the electrode comprises the following steps:
and (3) electrode pressing: pressing the weighed sponge zirconium and the scrap iron into 20 electrode blocks with the weight of 25 kg/block, wherein the specification is phi 110mm multiplied by 300mm, dividing the weighed sponge zirconium into half parts and adding the half parts into a die cavity of a pressing machine during pressing, adding the weighed scrap iron and uniformly scattering the weighed sponge zirconium in the die cavity, then adding the other half part of the sponge zirconium and finally pressing;
electrode welding: welding 20 electrode blocks into 4 electrodes in a vacuum plasma welding box, wherein each electrode block consists of 5 electrode blocks, the welding current is 400A, and the cooling time after welding is more than or equal to 1 h;
step three: 4 electrodes are melted into ingots in a vacuum consumable arc furnace.
Primary smelting: carrying out primary smelting on 4 electrodes in a vacuum consumable arc furnace to obtain 4 primary cast ingots, wherein the specification of the smelted ingots is phi 160mm multiplied by 770mm, the smelting speed is set to be 2kg/min, the smelting current is 3000A, the smelting voltage is 23V, and the cooling time after smelting is more than or equal to 3 h; the temperature of the cooling water entering and leaving the crucible is respectively as follows: not more than 20 ℃ and not more than 30 ℃;
secondary smelting: carrying out secondary smelting on 4 primary ingots in a vacuum consumable arc furnace to obtain 2 secondary ingots, wherein the specification of the smelted ingots is phi 220mm multiplied by 1620mm, the smelting speed is set to be 4kg/min during smelting, the smelting current is 5000A, the smelting voltage is 24V, and the cooling time after smelting is more than or equal to 4 h; the temperature of the cooling water in and out of the crucible is respectively as follows: not more than 20 ℃ and not more than 31 ℃;
and (3) smelting for the third time: carrying out three times of smelting on 2 secondary ingots in a vacuum consumable arc furnace to obtain 1 zirconium-iron intermediate alloy ingot, wherein the specification of the smelted zirconium-iron intermediate alloy ingot is phi 280mm multiplied by 1000mm, the smelting speed is set to be 5kg/min during smelting, the smelting current is 6500A, the smelting voltage is 25V, and the cooling time after smelting is more than or equal to 5 h; the temperature of the cooling water in and out of the crucible is respectively as follows: not more than 20 ℃ and not more than 32 ℃;
sampling the cast ingot of the ferrozirconium intermediate alloy after the third smelting, and analyzing the chemical components of the cast ingot, wherein the sampling schematic diagram is shown in fig. 1, and the iron element content of each sampling point is shown in table 1 (wt%):
TABLE 1
As can be seen from table 1, the distribution of the iron element in the cast ingot of the zirconium-iron master alloy was uniform.
Step four: after the chemical components of the zirconium-iron intermediate alloy cast ingot are qualified, the zirconium-iron intermediate alloy cast ingot is cut into slices with the thickness of 5mm on a sawing machine, and then the slices are cut into small blocks with the side length of 5mm on a shearing machine.
Pressing a mixture of the zirconium-iron intermediate alloy particles, tin, niobium and the sponge zirconium into an electrode block, and welding the electrode block into a consumable electrode in a vacuum plasma welding box; and smelting the consumable electrode in a vacuum consumable arc furnace, and cooling to obtain the zirconium alloy ingot.
Example 2
Step one, selecting sponge zirconium and prepared pure iron filings (the brand YT-1), and calculating the weight of the needed sponge zirconium and the iron filings according to the content and the feeding amount of Fe element in the sponge zirconium, wherein the weight of Fe accounts for 15% of the total feeding proportion, the total feeding proportion is 660kg, and the size of the iron filings is as follows: length × width × thickness: 5mm × 3mm × 0.2 mm;
step two, preparing the prepared sponge zirconium and scrap iron into an electrode; the preparation process of the electrode comprises the following steps:
and (3) electrode pressing: pressing weighed sponge zirconium and scrap iron into 22 electrode blocks with the specification of phi 160mm multiplied by 300mm, wherein the weighed sponge zirconium is divided into half and added into a die cavity of a pressing machine, the weighed scrap iron is added and uniformly scattered on the sponge zirconium in the die cavity, then the other half of the sponge zirconium is added, and finally pressing is carried out;
electrode welding: welding 22 electrode blocks into 2 electrodes in a vacuum plasma welding box, wherein each electrode block consists of 11 electrode blocks, the welding current is 420A, and the cooling time after welding is more than or equal to 1 h;
step three: and melting the 2 electrodes into ingots in a vacuum consumable arc furnace.
Primary smelting: carrying out primary smelting on 2 electrodes in a vacuum consumable arc furnace to obtain 2 primary ingots, wherein the specification of the smelted ingots is phi 220mm multiplied by 825mm, the smelting speed is set to be 2.5kg/min during smelting, the smelting current is 3500A, the smelting voltage is 24V, and the cooling time after smelting is more than or equal to 3 h; the temperature of the cooling water in and out of the crucible is respectively as follows: not more than 20 ℃ and not more than 30 ℃;
secondary smelting: carrying out secondary smelting on 2 primary ingots in a vacuum consumable arc furnace to obtain 1 secondary ingot, wherein the specification of the smelted ingots is phi 280mm multiplied by 1650mm, the smelting speed is set to be 4.5kg/min, the smelting current is 5500A, the smelting voltage is 25V, and the cooling time after smelting is more than or equal to 4 h; the temperature of the cooling water in and out of the crucible is respectively as follows: not more than 20 ℃ and not more than 31 ℃;
and (3) smelting for the third time: carrying out three times of smelting on 1 secondary ingot in a vacuum consumable arc furnace to obtain 1 zirconium-iron intermediate alloy ingot, wherein the specification phi after smelting is 360mm multiplied by 1000mm, the smelting speed is set to be 5.5kg/min during smelting, the smelting current is 7000A, the smelting voltage is 26V, and the cooling time after smelting is more than or equal to 5 h; the temperature of the cooling water in and out of the crucible is respectively as follows: not more than 20 ℃ and not more than 32 ℃;
sampling the cast ingot of the ferrozirconium intermediate alloy after the third smelting, and analyzing the chemical components of the cast ingot, wherein the sampling schematic diagram is shown in fig. 1, and the iron element content of each sampling point is shown in table 2 (wt%):
TABLE 2
As can be seen from table 2, the distribution of the iron element in the cast ingot of the zirconium-iron master alloy was uniform.
Step four: and (3) crushing the zirconium-iron intermediate alloy, namely cutting the zirconium-iron intermediate alloy ingot prepared in the step three into sheets with the thickness of 8mm on a sawing machine after the chemical components of the zirconium-iron intermediate alloy ingot are qualified, and then cutting the sheets into small blocks with the side length of 15mm on a shearing machine.
Pressing a mixture of the zirconium-iron intermediate alloy particles, tin, chromium, nickel and sponge zirconium into an electrode block, and welding the electrode block into a consumable electrode in a vacuum plasma welding box; and smelting the consumable electrode in a vacuum consumable arc furnace, and cooling to obtain the zirconium alloy ingot.
Example 3
The embodiment comprises the following steps:
step one, selecting sponge zirconium and prepared pure scrap iron (the brand YT-1), and calculating the weight of the needed sponge zirconium and scrap iron according to the content and the feeding amount of Fe element in the sponge zirconium, wherein the weight of Fe accounts for 20% of the total feeding proportion, the total feeding amount is 980kg, and the size of the scrap iron is as follows: length × width × thickness: 8mm × 5mm × 0.2 mm;
step two, preparing the prepared sponge zirconium and scrap iron into an electrode; the preparation process of the electrode comprises the following steps:
and (3) electrode pressing: pressing the weighed sponge zirconium and scrap iron into 14 electrode blocks with the weight of 70 kg/block, wherein the specification is phi 220mm multiplied by 400mm, dividing the weighed sponge zirconium into half parts and adding the half parts into a die cavity of a pressing machine during pressing, then adding the weighed scrap iron and uniformly spreading the weighed sponge zirconium on the sponge zirconium in the die cavity, then adding the other half part of the sponge zirconium and finally pressing;
electrode welding: welding 14 electrode blocks into 2 electrodes in a vacuum plasma welding box, wherein each electrode block consists of 7 electrode blocks, the welding current is 450A, and the cooling time after welding is more than or equal to 1 h;
step three: and melting the 2 electrodes into ingots in a vacuum consumable arc furnace.
Primary smelting: carrying out primary smelting on 2 electrodes in a vacuum consumable arc furnace to obtain 2 primary cast ingots, wherein the specification of the smelted ingots is phi 280mm multiplied by 1225mm, the smelting speed is set to be 3kg/min, the smelting current is 4000A, the smelting voltage is 25V, and the cooling time after smelting is more than or equal to 3 h; the temperature of the cooling water in and out of the crucible is respectively as follows: not more than 20 ℃ and not more than 30 ℃;
secondary smelting: carrying out secondary smelting on 2 primary ingots in a vacuum consumable arc furnace to obtain 1 secondary ingot, wherein the specification of the smelted ingots is phi 360mm multiplied by 1485mm, the smelting speed is set to be 5kg/min, the smelting current is 6000A, the smelting voltage is 26V, and the cooling time after smelting is more than or equal to 4 h; the temperature of the cooling water in and out of the crucible is respectively as follows: not more than 20 ℃ and not more than 31 ℃;
and (3) smelting for the third time: carrying out three times of smelting on 1 secondary ingot in a vacuum consumable arc furnace to obtain 1 zirconium-iron intermediate alloy ingot, wherein the specification phi of the smelted ingot is 450mm multiplied by 950mm, the smelting speed is set to be 6kg/min during smelting, the smelting current is 7500A, the smelting voltage is 27V, and the cooling time after smelting is more than or equal to 5 h; the temperature of the cooling water in and out of the crucible is respectively as follows: not more than 20 ℃ and not more than 32 ℃;
sampling the cast ingot of the ferrozirconium intermediate alloy after the third smelting, and analyzing the chemical components of the cast ingot, wherein the sampling schematic diagram is shown in fig. 1, and the iron element content of each sampling point is shown in table 3 (wt%):
TABLE 3
As can be seen from table 3, the distribution of the iron element in the cast ingots of the zirconium-iron master alloy was uniform.
Step four: and (3) crushing the zirconium-iron intermediate alloy, namely cutting the zirconium-iron intermediate alloy ingot prepared in the step three into slices with the thickness of 10mm on a sawing machine after the chemical components of the zirconium-iron intermediate alloy ingot are qualified, and then cutting the slices into small blocks with the side length of 20mm on a shearing machine.
Pressing a mixture of the zirconium-iron intermediate alloy particles, tin, niobium, chromium, zirconium dioxide and sponge zirconium into an electrode block, and welding the electrode block into a consumable electrode in a vacuum plasma welding box; and smelting the consumable electrode in a vacuum consumable arc furnace, and cooling to obtain the zirconium alloy ingot.
The zirconium alloy ingots prepared by the embodiments 1-3 of the invention are respectively R90004-1, R90004-2 and R90004-3 in number, and meanwhile, the pure metal iron adding mode and the ingot number R90004-4 prepared by sponge zirconium are adopted, so that the uniformity of the Fe element content in the zirconium alloy ingot prepared by the zirconium-iron intermediate alloy is obviously better than that in the zirconium alloy ingot prepared by the pure metal iron adding mode, and the Fe element content in each ingot is shown in the following table 4:
TABLE 4
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (4)
1. The preparation method of the iron-containing zirconium alloy ingot is characterized by comprising the following steps:
s1, pressing the mixture into an electrode block, and welding the electrode block into a consumable electrode in a vacuum plasma welding box;
s2, smelting the consumable electrode in a vacuum consumable arc furnace, and cooling to obtain a zirconium alloy ingot with uniform iron element content;
the mixture in the step S1 includes sponge zirconium, zirconium-iron intermediate alloy particles and one or more of tin, niobium, chromium and nickel, and the preparation of the zirconium-iron intermediate alloy particles specifically includes the following steps:
s11, pressing the mixture of the pure iron chips and the sponge zirconium into an electrode block, and welding the electrode block into a consumable electrode in a vacuum plasma welding box;
s12, smelting the consumable electrode in a vacuum consumable arc furnace, and cooling to obtain a zirconium-iron intermediate alloy cast ingot;
s13, machining the zirconium-iron intermediate alloy cast ingot into zirconium-iron intermediate alloy particles;
in the step S12, arc voltage control is adopted in the arc starting stage of the smelting, and the stable smelting is converted into molten drops until the smelting is finished; the step S12 specifically includes:
primary smelting: carrying out primary smelting on the consumable electrode in a vacuum consumable arc furnace to obtain a primary ingot, setting the smelting speed to be 2 kg/min-3 kg/min, the smelting current to be 3000A-4000A, the smelting voltage to be 23V-25V, and the cooling time after smelting to be more than or equal to 3h, wherein in order to improve the cooling speed of the ingot, the water inlet and outlet temperatures of crucible cooling water are respectively as follows: not more than 20 ℃ and not more than 30 ℃;
secondary smelting: carrying out secondary smelting on the primary cast ingot in a vacuum consumable arc furnace to obtain a secondary cast ingot, setting the smelting speed to be 4 kg/min-5 kg/min, the smelting current to be 5000A-6000A and the smelting voltage to be 24V-26V when controlling the smelting of molten drops, wherein the cooling time after smelting is more than or equal to 4h, and in order to improve the cooling speed of the cast ingot, the water inlet and outlet temperatures of crucible cooling water are respectively as follows: not more than 20 ℃ and not more than 31 ℃;
and (3) smelting for the third time: carrying out three times of smelting on the secondary ingot in a vacuum consumable arc furnace to obtain a zirconium-iron intermediate alloy ingot, setting the smelting speed to be 5 kg/min-6 kg/min, the smelting current to be 6500A-7500A and the smelting voltage to be 25V-27V during molten drop control smelting, wherein the cooling time after smelting is more than or equal to 5h, and in order to improve the cooling speed of the ingot, the water inlet and outlet temperatures of crucible cooling water are respectively as follows: not more than 20 ℃ and not more than 32 ℃.
2. The method for preparing the iron-containing zirconium alloy ingot according to claim 1, wherein the weight of the pure iron filings in the step S11 accounts for 10-20% of the total weight, and the sizes of the iron filings are as follows: 3-8 mm long, 2-5 mm wide and 0.1-0.2 mm thick.
3. The method for preparing the alloy ingot containing iron and zirconium according to claim 1, wherein the step S11 specifically comprises the following steps:
s111, according to the required weight of each electrode block, dividing the sponge zirconium and the scrap iron into a plurality of equal parts, wherein each equal part is used for pressing one electrode block: dividing each equal part of the zirconium sponge into half parts, adding the half parts into a die cavity of a pressing machine, uniformly scattering scrap iron on the zirconium sponge in the die cavity, adding the other half part of the zirconium sponge, and finally pressing;
and S112, welding the plurality of electrode blocks into a consumable electrode in a vacuum plasma welding box, and cooling to room temperature after welding.
4. The method for preparing the cast ingot containing the iron-zirconium alloy according to claim 1, wherein the cast ingot of the zirconium-iron intermediate alloy in the step S13 is cut into slices with the thickness of 5-10 mm on a sawing machine after the chemical components of the cast ingot are qualified, and then the slices are cut into blocks with the side length of 5-20 mm on a shearing machine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210027857.7A CN114350994B (en) | 2022-01-11 | 2022-01-11 | Preparation method of iron-containing zirconium alloy ingot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210027857.7A CN114350994B (en) | 2022-01-11 | 2022-01-11 | Preparation method of iron-containing zirconium alloy ingot |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114350994A CN114350994A (en) | 2022-04-15 |
| CN114350994B true CN114350994B (en) | 2022-08-05 |
Family
ID=81108346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210027857.7A Active CN114350994B (en) | 2022-01-11 | 2022-01-11 | Preparation method of iron-containing zirconium alloy ingot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114350994B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664727A (en) * | 1982-06-21 | 1987-05-12 | Hitachi, Ltd. | Zirconium alloy having superior corrosion resistance |
| SU1440643A1 (en) * | 1987-05-08 | 1988-11-30 | Институт Электросварки Им.Е.О.Патона | Method of arc welding of zirconium with titanium |
| CN101597705A (en) * | 2009-05-26 | 2009-12-09 | 宝鸡钛业股份有限公司 | The production method of the above big specification zirconium ingot of a kind of Ф 600mm |
| CN107008998A (en) * | 2012-03-16 | 2017-08-04 | 松下知识产权经营株式会社 | Arc welding control method and arc-welding apparatus |
| CN111961895A (en) * | 2020-09-03 | 2020-11-20 | 西部新锆核材料科技有限公司 | Preparation method of zirconium alloy ingot |
-
2022
- 2022-01-11 CN CN202210027857.7A patent/CN114350994B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664727A (en) * | 1982-06-21 | 1987-05-12 | Hitachi, Ltd. | Zirconium alloy having superior corrosion resistance |
| SU1440643A1 (en) * | 1987-05-08 | 1988-11-30 | Институт Электросварки Им.Е.О.Патона | Method of arc welding of zirconium with titanium |
| CN101597705A (en) * | 2009-05-26 | 2009-12-09 | 宝鸡钛业股份有限公司 | The production method of the above big specification zirconium ingot of a kind of Ф 600mm |
| CN107008998A (en) * | 2012-03-16 | 2017-08-04 | 松下知识产权经营株式会社 | Arc welding control method and arc-welding apparatus |
| CN111961895A (en) * | 2020-09-03 | 2020-11-20 | 西部新锆核材料科技有限公司 | Preparation method of zirconium alloy ingot |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114350994A (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108326427B (en) | Method for manufacturing high-entropy alloy double-arc fuse in synergistic additive mode | |
| CN110951974B (en) | Titanium alloy ingot and preparation method thereof | |
| CN111378848B (en) | Pre-melted slag for electroslag remelting for improving purity of GH4169 alloy return and preparation method thereof | |
| CN110079719B (en) | Method for increasing hafnium content in tantalum-tungsten alloy | |
| CN108165866B (en) | Preparation method of multi-element high-entropy alloy | |
| CN101701298B (en) | Manufacture method of nuclear grade zirconium-niobium alloy cast ingot | |
| CN107686902B (en) | A kind of nuclear grade zirconium alloy cast ingot preparation method | |
| CN202164343U (en) | Electrode device used for waste titanium recycling and remelting process | |
| CN104846225A (en) | Preparation method for high-uniformity WSTi62441S titanium alloy ingot | |
| CN111961895B (en) | Preparation method of zirconium alloy ingot | |
| CN105861877A (en) | WSTi64311SC heat-resistant titanium alloy and preparation method thereof | |
| CN109136995B (en) | Method for producing rare earth metal and alloy | |
| CN114350994B (en) | Preparation method of iron-containing zirconium alloy ingot | |
| KR20150022994A (en) | Inert alloy anode used for aluminum electrolysis and preparation method therefor | |
| CN106636744A (en) | WSTi64E high-damage-tolerance super-large-size titanium alloy cast ingot and preparation method thereof | |
| CN106435209B (en) | A kind of method that current-conductive mold electroslag remelting prepares H13 steel | |
| CN105950912B (en) | A kind of preparation method of medical Zr 2.5Nb alloy cast ingots | |
| CN111945023A (en) | Vacuum induction melting method of titanium and titanium alloy ingots | |
| CN104498770B (en) | A kind of WSTi2815SC Burn-Resistant Titanium Alloys and preparation method thereof | |
| CN114507788A (en) | Vacuum consumable melting method of TC10 titanium alloy ingot | |
| CN110669974A (en) | Preparation method of niobium-zirconium alloy cast ingot | |
| CN106636668B (en) | A kind of waste and old electromagnetic wire copper refining agent and its preparation method and application | |
| CN100402681C (en) | Preparation method of Al-TiC master alloy | |
| CN113234944A (en) | Preparation method of zirconium alloy ingot | |
| CN107723515B (en) | A kind of high-quality aluminum vanadium series titanium alloy EB furnace+VAR furnace joint founding production method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 710299 No. 19, east section of Jinggao North Road, Jingwei new town, Xi'an Economic and Technological Development Zone, Xi'an City, Shaanxi Province Patentee after: Xi'an Western New Zirconium Technology Co.,Ltd. Address before: 710299 No. 19, east section of Jinggao North Road, Jingwei new town, Xi'an Economic and Technological Development Zone, Xi'an City, Shaanxi Province Patentee before: WESTERN ENERGY MATERIAL TECHNOLOGIES CO.,LTD. |