CN114752776A - Electroslag smelting slag system for high-purity beryllium copper QBe2 alloy and smelting method thereof - Google Patents
Electroslag smelting slag system for high-purity beryllium copper QBe2 alloy and smelting method thereof Download PDFInfo
- Publication number
- CN114752776A CN114752776A CN202210389961.0A CN202210389961A CN114752776A CN 114752776 A CN114752776 A CN 114752776A CN 202210389961 A CN202210389961 A CN 202210389961A CN 114752776 A CN114752776 A CN 114752776A
- Authority
- CN
- China
- Prior art keywords
- smelting
- electroslag
- slag system
- alloy
- beryllium copper
- 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
- 238000003723 Smelting Methods 0.000 title claims abstract description 130
- 239000002893 slag Substances 0.000 title claims abstract description 97
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000956 alloy Substances 0.000 title claims abstract description 52
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000010953 base metal Substances 0.000 claims abstract description 25
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000006698 induction Effects 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000009749 continuous casting Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- 229910001632 barium fluoride Inorganic materials 0.000 claims abstract description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 3
- 238000005266 casting Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910052790 beryllium Inorganic materials 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 229910000979 O alloy Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- C22B9/18—Electroslag remelting
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides an electroslag smelting slag system for high-purity beryllium copper QBe2 alloy and a smelting method thereof, wherein the electroslag smelting slag system comprises the following chemical components in percentage by weight: CaF2：34～56％、BaF2：30～35％、MgF2：10～15％、Al2O3：2～8％、SiO2：1～5％、CeO2: 1-3% and the balance of unavoidable impurities. The smelting method comprises the following steps: mixing the beryllium copper mother alloy with Be of 3.8-4.1%, electrolytic copper, electrolytic nickel and old beryllium copper QBe2 alloy materials, and preparing a consumable electrode parent metal by adopting a vacuum induction melting and semi-continuous casting method; after electroslag smelting slag system is melted into a molten slag pool, the consumable electrode base metal is vertically inserted into the slag pool under the protection of argon gas for electroslag smelting, and meanwhile, Ca powder is added in batches, so that the high-purity beryllium copper QBe2 alloy without air holes, inclusion or few inclusion is obtained after smelting is finished.
Description
Technical Field
The invention belongs to the technical field of metal material metallurgy, and particularly relates to an electroslag smelting slag system for high-purity beryllium copper QBe2 alloy and a smelting method thereof.
Background
Beryllium copper alloys are known as "elastic king" in copper alloys and classified into high-beryllium high-strength alloys (Be: 1.6 to 2.1%) and low-beryllium high-conductivity alloys (Be: 0.2 to 0.7%) according to the content of beryllium. The QBe2 alloy is a high-beryllium high-strength elastic alloy with the largest aerospace use amount, and is mainly used for manufacturing aeronautical instruments, servo valves, elastic elements, structural parts and the like. However, the aerospace industry has very high requirements on the product quality of the beryllium copper QBe2 alloy, particularly on the aspects of purity, fracture and ultrasonic detection performance. Beryllium copper QBe2 alloy ingots produced by the conventional process of induction melting plus semi-continuous casting, the processed material of which has difficulty meeting the standard requirements in these respects.
Electroslag smelting is a process for refining and purifying metals by using resistance heat generated when current passes through slag as a heat source. Compared with the conventional process, the beryllium copper QBe2 alloy ingot prepared by electroslag smelting is greatly improved in the aspects of pure smelting and solidification structure control, the structure of the processed material is compact, the components are uniform, the beta phase is obviously reduced and distributed in a point shape, and the fracture and flaw detection results can meet the standard requirements. However, the problems of micro-pores and micro-nonmetal inclusions in the beryllium copper QBe2 alloy ingot cannot be fundamentally improved and solved because: firstly, the existing slag system is derived from a common ANF slag system, CaO contained in the slag system is easy to absorb moisture to generate pores, and the high-melting-point oxide component content is high, so that the slag system is easy to enter a metal molten pool during smelting to cause non-metal inclusion; secondly, because the melting point of the existing slag system is higher and is close to that of beryllium copper QBe2 alloy, the melting speed is too high and the current is unstable, so that double slag crust is generated and local inclusions are formed on the surface layer of the cast ingot, and the defects of folds, ripples and the like frequently appear on the surface of the cast ingot; thirdly, the common non-vacuum casting method for preparing the consumable electrode base metal makes pores and inclusions in the base metal difficult to control and can not be effectively removed during electroslag smelting; fourthly, the balance and matching of parameters such as current of electroslag smelting, water temperature of a crystallizer, smelting speed and the like and slag resistance cannot reach the optimal level, so that the degree of superheat of a molten pool is large and deep, and effective control of inclusions is not facilitated.
Therefore, how to effectively reduce or remove air holes and non-metal impurities and obtain high-purity beryllium copper QBe2 alloy ingots is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide an electroslag melting slag system for high purity beryllium copper QBe2 alloy, wherein the melting point of the electroslag melting slag system is lower than that of beryllium copper QBe2 alloy, and the electroslag melting slag system can perform refining and purification functions well.
The second purpose of the invention is to provide a smelting method of an electroslag smelting slag system, which adopts vacuum induction smelting to prepare a consumable electrode base metal and can reduce pores and nonmetallic inclusions in the base metal.
In order to achieve one of the purposes, the invention adopts the following technical scheme:
an electroslag smelting slag system for high-purity beryllium copper QBe2 alloy comprises the following chemical components in percentage by weight: CaF2：34～56％、BaF2：30～35％、MgF2：10～15％、Al2O3：2～8％、SiO2：1～5％、CeO2: 1-3% and the balance of inevitable impurities.
Further, the loose packed ratio of the chemical components is more than or equal to 1.0g/cm3。
Further, the CaF2、BaF2、MgF2、Al2O3、SiO2Has a particle size of 0.18mm or less<The content of 0.075mm is less than 30%; the CeO2The particle size is less than or equal to 10 mu m.
Further, the CaF2、CeO2、SiO2The purity of (A) is more than 99%; the BaF 2、MgF2The purity of (2) is more than 98%; the Al is2O3The purity of (2) is 95% or more.
Further, the weight percentage of the impurities is less than 0.5%.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a smelting method of an electroslag smelting slag system comprises the following steps:
step one, mixing beryllium copper mother alloy with Be weight percent of 3.8-4.1%, electrolytic copper, electrolytic nickel and old beryllium copper QBe2 alloy materials, and preparing a consumable electrode parent metal by adopting a vacuum induction melting and semi-continuous casting method;
and step two, placing the electroslag smelting slag system into an electroslag furnace crystallizer for slagging to form a molten slag pool, then vertically inserting the consumable electrode base metal in the step one into the slag pool for electroslag smelting under the protection of argon, simultaneously adding Ca powder in batches in the electroslag smelting process, and obtaining a high-purity beryllium copper QBe2 alloy ingot after smelting.
The slag system is melted under the action of current and chemically reacts to form a slag pool, a large amount of generated heat melts the consumable electrode parent metal into stable metal molten drops, when the metal molten drops penetrate through the slag system, a large amount of impurities are adsorbed by the slag system and then float to the surface of a molten pool, and pure metal molten drops continue to sink to the bottom of the crystallizer and are solidified into re-melted ingots under the water cooling action of the crystallizer.
Further, before the second step, the electroslag smelting slag is baked at a temperature of 420 to 680 ℃ for 8 to 12 hours.
Further, the smelting vacuum degree during vacuum induction smelting in the first step is less than or equal to 0.6Pa, and the smelting temperature is 1230-1410 ℃; in the first step, the casting temperature during semi-continuous casting is 1160-1340 ℃, and the casting speed is 58-76 mm/min.
Furthermore, the diameter of the consumable electrode base metal is 110-145 mm, and the diameter of the electroslag furnace crystallizer is 185-220 mm.
Further, the filling ratio of the consumable electrode base metal to the electroslag furnace crystallizer is 0.35-0.43.
Further, the slagging current of the electroslag smelting slag system in the second step is 1250-2000A; the stable-state given current of electroslag smelting is 3120-3830A, the smelting speed is 120-150 kg/h, and the cooling water temperature of an electroslag furnace crystallizer is 28-34 ℃.
Further, the Ca powder is added in the electroslag smelting process in the second step at the initial, middle and later stages of smelting, and the total amount of the Ca powder added in the third stage is 0.1-0.4% of the weight of the electroslag smelting slag system;
the purity of the Ca powder is 99.99%.
Further, the flow rate of argon in the second step is 3-5L/min.
Compared with the prior art, the electroslag smelting slag system and the smelting method provided by the invention have the following beneficial effects:
(1) the melting point of the electroslag smelting slag system provided by the invention is 950-980 ℃, which is far lower than that of beryllium copper QBe2 alloy, and the control of the melting speed in the electroslag smelting process is facilitated; in addition, the slag system does not contain CaO, thereby greatly reducing the probability of generating pores due to moisture absorption.
(2) According to the smelting method of the electroslag smelting slag system, the consumable electrode base metal is prepared by adopting a vacuum induction smelting method, so that pores and nonmetallic inclusions in the base metal are reduced to a certain extent.
(3) The Ca powder added in the electroslag smelting process can play a role in homogenization treatment, so that air holes and nonmetallic inclusions are effectively removed, and the requirement of high purity of beryllium copper QBe2 alloy in aerospace is met.
Drawings
FIG. 1(a) is a polished structure of a beryllium copper QBe2 alloy prepared according to example 1 of the present invention;
FIG. 1(b) is a graph showing the post acid corrosion grain structure of beryllium copper QBe2 alloy prepared in example 1 of the present invention;
FIG. 2(a) is a polished structure of a beryllium copper QBe2 alloy prepared according to example 2 of the present invention;
FIG. 2(b) is the grain structure of beryllium copper QBe2 alloy prepared in example 2 of the present invention after acid etching;
FIG. 3(a) shows the polished structure of a beryllium copper QBe2 alloy prepared according to example 3 of the present invention;
FIG. 3(b) is a graph showing the post-acid corrosion grain structure of beryllium copper QBe2 alloy prepared in example 3 of the present invention.
Detailed Description
The technical solution and the embodiments of the present invention are explained in detail below with reference to the accompanying drawings.
The embodiment provides an electroslag smelting slag system for high-purity beryllium copper QBe2 alloy, which comprises the following chemical components in percentage by weight: CaF2：34～56％、BaF2：30～35％、MgF2：10～15％、Al2O3：2～8％、SiO2：1～5％、CeO2: 1-3% and the balance of unavoidable impurities. And the weight percentage of the impurities is less than 0.5 percent.
The electroslag smelting slag system provided by the invention does not contain CaO, so that the gas suction probability of the cast ingot is greatly reduced; the reduction of oxide components reduces the melting point and viscosity of the slag system; small amount of SiO2The addition of the additive enables the pH value of the slag system to be reasonably controlled, is beneficial to obtaining long slag with better plasticity, and the surface layer of the cast ingot is easy to form thin and uniform slag crust; BaF2The melting point of the slag system can be reduced, the effect of stabilizing current can be achieved, and the resistivity tends to be constant, so that the frequent occurrence of skin effect is avoided; more importantly, CeO2The slag system can continuously adsorb the nonmetallic inclusion dissolved in the slag pool by the parent metal and drive the nonmetallic inclusion to float up to the surface of the slag system, thereby achieving the effect of removing the inclusion.
Wherein CaF2、BaF2、MgF2、Al2O3、SiO2Has a particle size of 0.18mm or less<The content of 0.075mm is less than 30%; CeO (CeO)2The particle size is less than or equal to 10 mu m.
The requirements on the loose charge ratio and the granularity are made, so that the current density of the electrode end is relatively concentrated in the melting period of the slag system, the slag system is uniformly melted, and the temperature field of a slag pool is consistent.
CeO2The particle size of (C) is required to be less than or equal to 10 mu m, and the function of (C) is to make CeO2The particles are uniformly dispersed in the slag pool, and the non-metallic inclusion dissolved in the slag pool by the base metal is promoted to float upwards under the strong adsorption effect of the particles.
Wherein, CaF2、CeO2、SiO2The purity of (A) is more than 99%; BaF2、MgF2The purity of (A) is more than 98%; al (Al)2O3The purity of (A) is 95% or more.
The electroslag smelting slag system provided by the invention has the advantages that the purity of each chemical component is high, the impurity introduction is reduced to a great extent, and meanwhile, the selected components have the advantages of low melting point and stable resistivity, can meet the thermodynamic and kinetic conditions of beryllium copper QBe2 alloy smelting, and can well play refining and purifying roles.
Another embodiment of the present invention provides a method for melting an electroslag melting slag system, including the steps of:
firstly, mixing beryllium copper mother alloy, electrolytic copper, electrolytic nickel and beryllium copper QBe2 alloy old materials with Be weight percent of 3.8-4.1%, and preparing a consumable electrode parent metal by adopting a vacuum induction melting and semi-continuous casting method;
In the first step, the smelting vacuum degree during vacuum induction smelting is less than or equal to 0.6Pa, and the smelting temperature is 1230-1410 ℃. The casting temperature in the semi-continuous casting is 1160-1340 ℃, and the casting speed is 58-76 mm/min. The diameter of the consumable electrode base material is 110-145 mm, and the diameter of an electroslag furnace crystallizer of the electroslag furnace is 185-220 mm; the filling ratio of the consumable electrode base metal to the electroslag furnace crystallizer is 0.35-0.43.
The vacuum induction melting has the function of reducing pores and nonmetallic inclusions in the consumable electrode base metal to a certain extent.
The filling ratio of the consumable electrode base metal to the electroslag furnace crystallizer is controlled to be 0.35-0.43, so that under the condition of the optimal filling ratio, the end of the electrode can obtain stable current density; meanwhile, the radiation heat flow of the liquid slag surface on the surface of the consumable electrode parent metal is convenient to control, so that the temperature of the end part of the electrode in the radius direction tends to be uniform, and the improvement of the crystallization quality of the beryllium copper QBe2 alloy ingot solidification area is facilitated.
And step two, placing the electroslag smelting slag system in an electroslag furnace crystallizer for slagging to form a molten slag pool, then vertically inserting the consumable electrode base metal in the step one into the slag pool for electroslag smelting under the protection of argon with the flow of 3-5L/min, simultaneously adding trace Ca powder with the purity of 99.99% in batches in the electroslag smelting process, and obtaining a high-purity beryllium copper QBe2 alloy ingot after the smelting is finished.
Wherein, before the second step, the electroslag smelting slag is baked at 420-680 ℃ for 8-12 h.
The smelting under the protection of argon can prevent the oxidation and burning loss of beryllium in the consumable electrode parent metal under the high-temperature heat radiation condition of a molten pool, and reduce the air suction caused by the contact of a molten slag system and air.
Wherein, the slagging current of the electroslag smelting slag system in the second step is 1250-2000A; the steady-state given current of the electroslag smelting is 3120-3830A, the smelting speed is 120-150 kg/h, and the cooling water temperature of an electroslag furnace crystallizer is 28-34 ℃.
The purpose of the steady-state given current is to ensure that a stable heat source is provided for a molten pool, so that a stable metal molten drop can be formed when the consumable electrode base metal is melted.
The melting speed is controlled to be 120-150 kg/h, so that the temperature distribution of the molten pool is uniform, the molten pool is ensured to have enough cylinder height and proper superheat degree, a shallow flat molten pool with the height of 110-160 mm is obtained, and floating of inclusions is facilitated.
The cooling water temperature of the electroslag furnace crystallizer is controlled to be 28-34 ℃, so that the beryllium-copper QBe2 alloy ingot can be solidified more uniformly, and the formation of segregation is avoided.
In the second step, the Ca powder is added at the initial stage, the middle stage and the later stage of the electroslag smelting, and the total amount of the Ca powder added in the third stage is 0.1-0.4% of the weight of the electroslag smelting slag system;
The Ca powder plays a role of homogenization treatment, so that cluster inclusions are converted into plastic low-melting-point spherical composite Ca salt, and sulfide inclusions are adhered to the spherical inclusions and flocculated, grown and floated to the surface of a slag system to further remove the non-metal inclusions.
Example 1
1. An electroslag smelting slag system comprises the following chemical components:
CaF2：56％；BaF2：30％；MgF2：10％；Al2O3:2％；SiO2：1％；CeO2：1％。
wherein CaF2The purity of (D) is 99.95%; SiO 22Has a purity of 99.2%; BaF2The purity of (2) is 98.4%; MgF2The purity of (2) is 98.7%; al (Al)2O3The purity of the sum was 95.8%; CeO (CeO)2The purity of (2) was 99.99%.
2. The slag system is applied to smelting of beryllium copper QBe2.0 alloy, and the smelting process comprises the following steps:
step one, mixing beryllium copper master alloy with Be percentage by weight of 3.88%, electrolytic copper, electrolytic nickel and beryllium copper QBe2 alloy old materials, smelting in a vacuum induction furnace under the vacuum degree of 0.6Pa, and preparing the consumable electrode parent metal with the diameter of 110mm through semi-continuous casting.
Wherein the smelting temperature is 1230 ℃; the casting temperature was 1160 ℃ and the casting speed was 76 mm/min.
And step two, placing 13kg of electroslag smelting slag system into an electroslag furnace crystallizer with the diameter of 185mm for slagging, forming a molten slag pool, vertically inserting the consumable electrode base metal in the step one into the slag pool for electroslag smelting under the protection of argon with the flow of 3-5L/min, adding 13g of Ca powder with the purity of 99.99% in the early stage, the middle stage and the later stage of smelting, and obtaining a beryllium copper QBe2 alloy ingot after the smelting is finished.
Wherein, before the second step, the electroslag smelting slag is baked for 12 hours at the temperature of 420 ℃.
The filling ratio of the consumable electrode base metal to the electroslag furnace crystallizer is 0.35, the slagging current of an electroslag smelting slag system is 1250A, the steady-state given current of electroslag smelting is 3100A, the smelting speed is 120kg/h, and the cooling water temperature of the electroslag furnace crystallizer is controlled to be 28-30 ℃.
3. The middle of an ingot of beryllium copper QBe2 was sliced, and a sample was taken in the height direction, and the metallographic structure obtained was as shown in fig. 1(a) and 1 (b). Detecting that no air holes exist after the embedded sample is polished, wherein the size of the impurities is less than 5 mu m and the impurities are in dispersion distribution; the grain size is detected to be slightly uneven after acid corrosion.
Example 2
1. An electroslag smelting slag system comprises the following chemical components:
CaF2：34％；BaF2：35％；MgF2：15％；Al2O3:8％；SiO2：5％；CeO2：3％。
wherein CaF2The purity of (2) was 99.91%; SiO 22Has a purity of 99.2%; BaF2The purity of (2) is 98.5%; MgF2The purity of (2) is 99.1%; al (Al)2O3The purity of the sum was 95.5%; CeO (CeO)2The purity of (2) was 99.99%.
2. The slag system is applied to smelting of beryllium copper QBe2.0 alloy, and the smelting process comprises the following steps:
step one, mixing beryllium copper master alloy with Be percentage by weight of 3.91%, electrolytic copper, electrolytic nickel and beryllium copper QBe2 alloy old materials, smelting in a vacuum induction furnace under the smelting vacuum degree of 0.5Pa, and preparing the consumable electrode parent metal with the diameter of 145mm through semi-continuous casting.
Wherein the smelting temperature is 1410 ℃; the casting temperature is 1340 ℃, and the casting speed is 58 mm/min.
And step two, placing 16kg of electroslag smelting slag system into an electroslag furnace crystallizer with the diameter of 220mm for slagging, forming a molten slag pool, vertically inserting the consumable electrode base metal in the step one into the slag pool for electroslag smelting under the protection of argon with the flow of 3-5L/min, adding 64g of Ca powder with the purity of 99.99% in the early stage, the middle stage and the later stage of smelting, and obtaining a beryllium copper QBe2 alloy ingot after the smelting is finished.
Wherein, before the second step, the electroslag smelting slag is baked at 680 ℃ for 8 h.
The filling ratio of the consumable electrode base metal to the electroslag furnace crystallizer is 0.43, the slagging current of an electroslag smelting slag system is 2000A, the steady-state given current of electroslag smelting is 3800A, the melting speed is 150kg/h, and the cooling water temperature of the electroslag furnace crystallizer is controlled to be 32-34 ℃.
3. The middle part of an ingot of beryllium copper QBe2 was sliced, and a part of the sample was taken in the height direction, and the metallographic structure obtained was as shown in fig. 2(a) and 2 (b). After the embedded sample is polished, no air holes are detected, the size of the inclusions is less than 5 mu m, and the inclusions are distributed dispersedly and sporadically; the grain size is more uniform after acid corrosion detection.
Example 3
1. An electroslag smelting slag system comprises the following chemical components:
CaF2：45％；BaF2：33％；MgF2：12％；Al2O3:5％；SiO2：3％；CeO2：2％。
wherein CaF2The purity of (D) is 99.95%; SiO 22Has a purity of 99.4%; BaF2Has a purity of 99%; MgF2The purity of (2) is 99.1%; al (aluminum)2O3The purity of the sum was 95.8%; CeO (CeO)2The purity of (2) was 99.99%.
2. The slag system is applied to smelting of beryllium copper QBe2.0 alloy, and the smelting process comprises the following steps:
firstly, beryllium copper master alloy with Be weight percent of 4.01%, electrolytic copper, electrolytic nickel and beryllium copper QBe2 alloy old materials are mixed, smelted in a vacuum induction furnace under the smelting vacuum degree of 0.4Pa, and the consumable electrode parent metal with the diameter of 125mm is prepared through semi-continuous casting.
Wherein the smelting temperature is 1296 ℃; the casting temperature is 1210 ℃ and the casting speed is 65 mm/min.
And step two, placing 14.5kg of electroslag smelting slag system into an electroslag furnace crystallizer with the diameter of 200mm for slagging to form a molten slag pool, vertically inserting the consumable electrode base metal in the step one into the slag pool for electroslag smelting under the protection of argon with the flow of 3-5L/min, adding 36.25g of Ca powder with the purity of 99.99% in the early stage, the middle stage and the later stage of smelting, and obtaining a beryllium copper QBe2 alloy ingot after the smelting is finished.
Wherein, before the second step, the electroslag smelting slag is baked for 10 hours at the temperature of 500 ℃.
The filling ratio of the consumable electrode base metal to the electroslag furnace crystallizer is 0.39, the slagging current of an electroslag smelting slag system is 1800A, the steady-state given current of electroslag smelting is 3450A, the melting speed is 135kg/h, and the cooling water temperature of the electroslag furnace crystallizer is controlled to be 30-32 ℃.
3. The middle of an ingot of beryllium copper QBe2 was sliced, and a sample was taken in the height direction, and the metallographic structure obtained was as shown in fig. 3(a) and 3 (b). No air holes and no impurities are detected after sample embedding and polishing; the grain size is detected to be uniform after acid corrosion.
It will be evident to those skilled in the art that the embodiments of the present invention are not limited to the details of the foregoing illustrative embodiments, and that the embodiments of the present invention are capable of being embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the embodiments being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the embodiments of the present invention and not for limiting, and although the embodiments of the present invention are described in detail with reference to the above preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the embodiments of the present invention without departing from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An electroslag smelting slag system for high-purity beryllium copper QBe2 alloy is characterized in that the electroslag smelting slag system comprises the following chemical components in percentage by weight: CaF2：34～56％、BaF2：30～35％、MgF2：10～15％、Al2O3：2～8％、SiO2：1～5％、CeO2: 1-3% and the balance of unavoidable impurities.
2. The electroslag smelting slag system of claim 1, wherein a loose packed ratio of the chemical component is not less than 1.0g/cm3。
3. The electroslag melting slag system of claim 1, wherein the CaF2、BaF2、MgF2、Al2O3、SiO2Has a particle size of less than or equal to 0.18mm<The content of 0.075mm is less than 30%; the CeO2The particle size is less than or equal to 10 mu m.
4. The electroslag smelting slag system of claim 1, wherein the CaF is2、CeO2、SiO2The purity of (A) is more than 99%; the BaF2、MgF2The purity of (A) is more than 98%; the Al is2O3The purity of (A) is 95% or more.
5. The electroslag smelting slag system of claim 1, wherein the weight percent of the impurities is < 0.5%.
6. A smelting method of an electroslag smelting slag system for high-purity beryllium copper QBe2 alloy, which is characterized in that the electroslag smelting slag system is the electroslag smelting slag system as defined in any one of claims 1 to 5, and the smelting method comprises the following steps:
firstly, mixing beryllium copper mother alloy, electrolytic copper, electrolytic nickel and beryllium copper QBe2 alloy old materials with Be weight percent of 3.8-4.1%, and preparing a consumable electrode parent metal by adopting a vacuum induction melting and semi-continuous casting method;
And step two, placing the electroslag smelting slag system into an electroslag furnace crystallizer for slagging to form a molten slag pool, then vertically inserting the consumable electrode base metal in the step one into the slag pool for electroslag smelting under the protection of argon, simultaneously adding Ca powder in batches in the electroslag smelting process, and obtaining a high-purity beryllium copper QBe2 alloy ingot after smelting is finished.
7. The smelting method as claimed in claim 6, wherein in the first step, the smelting vacuum degree during the vacuum induction smelting is less than or equal to 0.6Pa, and the smelting temperature is 1230-1410 ℃;
in the first step, the casting temperature during semi-continuous casting is 1160-1340 ℃, and the casting speed is 58-76 mm/min.
8. The melting method according to claim 6, wherein the consumable electrode base metal has a diameter of 110 to 145mm, and the electroslag furnace crystallizer has a diameter of 185 to 220 mm;
the filling ratio of the consumable electrode base metal to the electroslag furnace crystallizer is 0.35-0.43.
9. Smelting process according to claim 6, wherein:
the slagging current of the electroslag smelting slag system in the second step is 1250-2000A;
the stable-state given current of the electroslag smelting is 3120-3830A, the smelting speed is 120-150 kg/h, and the cooling water temperature of the electroslag furnace crystallizer is 28-34 ℃.
10. The smelting method as claimed in claim 6, wherein the Ca powder is added in the second step of electroslag smelting at the initial, middle and later stages of smelting, and the added Ca powder has the same mass each time, and the total amount of the added Ca powder is 0.1-0.4% of the weight of the electroslag smelting slag system; the purity of the Ca powder is 99.99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210389961.0A CN114752776B (en) | 2022-04-14 | 2022-04-14 | Electroslag smelting slag system for high-purity beryllium copper QBe alloy and smelting method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210389961.0A CN114752776B (en) | 2022-04-14 | 2022-04-14 | Electroslag smelting slag system for high-purity beryllium copper QBe alloy and smelting method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114752776A true CN114752776A (en) | 2022-07-15 |
| CN114752776B CN114752776B (en) | 2023-11-03 |
Family
ID=82330679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210389961.0A Active CN114752776B (en) | 2022-04-14 | 2022-04-14 | Electroslag smelting slag system for high-purity beryllium copper QBe alloy and smelting method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114752776B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116426775A (en) * | 2023-04-12 | 2023-07-14 | 烟台万隆真空冶金股份有限公司 | Method for efficiently preparing beryllium copper master alloy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4297132A (en) * | 1980-02-25 | 1981-10-27 | Allegheny Ludlum Steel Corporation | Electroslag remelting method and flux composition |
| JPS61183419A (en) * | 1985-02-08 | 1986-08-16 | Taiheiyo Seiko Kk | Electroslag remelting method of copper and copper alloy |
| CN1580300A (en) * | 2003-10-24 | 2005-02-16 | 河南中原特殊钢厂 | Copper alloy electroslag remelting process |
| CN114032399A (en) * | 2021-11-12 | 2022-02-11 | 成都先进金属材料产业技术研究院股份有限公司 | Ultralow oxygen control slag system for electroslag remelting |
-
2022
- 2022-04-14 CN CN202210389961.0A patent/CN114752776B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4297132A (en) * | 1980-02-25 | 1981-10-27 | Allegheny Ludlum Steel Corporation | Electroslag remelting method and flux composition |
| JPS61183419A (en) * | 1985-02-08 | 1986-08-16 | Taiheiyo Seiko Kk | Electroslag remelting method of copper and copper alloy |
| CN1580300A (en) * | 2003-10-24 | 2005-02-16 | 河南中原特殊钢厂 | Copper alloy electroslag remelting process |
| CN114032399A (en) * | 2021-11-12 | 2022-02-11 | 成都先进金属材料产业技术研究院股份有限公司 | Ultralow oxygen control slag system for electroslag remelting |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116426775A (en) * | 2023-04-12 | 2023-07-14 | 烟台万隆真空冶金股份有限公司 | Method for efficiently preparing beryllium copper master alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114752776B (en) | 2023-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109112319B (en) | Slag for nuclear-grade stainless steel electroslag remelting and method for electroslag remelting by using slag | |
| CN108339953B (en) | Production process of non-vacuum down-leading continuous casting chromium zirconium copper slab ingot | |
| CN103774017B (en) | The semicontinuous casting technique of strength heatproof magnesium alloy ingot casting in major diameter | |
| KR20140054427A (en) | Cu-ga alloy sputtering target and method for producing same | |
| JP5246529B2 (en) | Copper metal powder | |
| CN114752776B (en) | Electroslag smelting slag system for high-purity beryllium copper QBe alloy and smelting method thereof | |
| CN110819817B (en) | Basic slag system for aluminum-titanium-containing nickel-based high-temperature alloy and electroslag remelting method | |
| CN113373320A (en) | Purification method of ultra-high purity aluminum | |
| CN108118114B (en) | Electroslag remelting slag system suitable for medium carbon steel material and smelting method | |
| JP6365395B2 (en) | Method for producing nickel sulfate | |
| KR101516064B1 (en) | Cu-Ga ALLOY SPUTTERING TARGET AND METHOD FOR MANUFACTURING THE SAME | |
| TW201400634A (en) | Indium target and manufacturing method thereof | |
| CN115948669A (en) | Intermediate alloy containing zirconium and magnesium, production method and use thereof | |
| CN102925733B (en) | Multifunctional covering agents of copper alloy suitable for lead frame | |
| JP2011012300A (en) | Copper alloy and method for producing copper alloy | |
| CN114134356A (en) | Zinc alloy production process | |
| JP6127938B2 (en) | Removal of tellurium from sulfuric acid leachate of copper electrolytic slime | |
| CN114231804A (en) | 7050 alloy ingot casting material and preparation method thereof | |
| JP2007211324A (en) | Raw material phosphor bronze alloy for casting half-melted alloy | |
| EP3546605B1 (en) | Method for casting articles from aluminium alloys | |
| WO2012027992A1 (en) | Preparation method of al-zr-c master alloy | |
| CN110592397A (en) | Casting method of aluminum ingot | |
| CN101667639A (en) | Method for manufacturing rare earth alloy battery zinc powder | |
| CN104232952A (en) | Recycling technology for silver-tin oxide waste material electrolysis anode sludge | |
| CN117265235B (en) | Method for preparing low-carbon rare earth metal or alloy and application thereof |
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 |