CN115786801A - Production method of low-impurity ferrovanadium alloy and ferrovanadium alloy without oxidation impurity on surface layer - Google Patents
Production method of low-impurity ferrovanadium alloy and ferrovanadium alloy without oxidation impurity on surface layer Download PDFInfo
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- CN115786801A CN115786801A CN202211485141.8A CN202211485141A CN115786801A CN 115786801 A CN115786801 A CN 115786801A CN 202211485141 A CN202211485141 A CN 202211485141A CN 115786801 A CN115786801 A CN 115786801A
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- 239000000956 alloy Substances 0.000 title claims abstract description 95
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 79
- 239000002344 surface layer Substances 0.000 title claims abstract description 39
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims description 38
- 229910000628 Ferrovanadium Inorganic materials 0.000 title claims description 34
- 239000012535 impurity Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 230000003647 oxidation Effects 0.000 title claims description 8
- 238000007254 oxidation reaction Methods 0.000 title claims description 8
- 238000005422 blasting Methods 0.000 claims abstract description 53
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 239000010410 layer Substances 0.000 claims abstract description 32
- 238000003723 Smelting Methods 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 17
- 229910002064 alloy oxide Inorganic materials 0.000 abstract description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 10
- 229910001935 vanadium oxide Inorganic materials 0.000 description 10
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010301 surface-oxidation reaction Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
According to the invention, the high-valence oxides on the surface layer of the alloy are removed by shot blasting, whether the oxides are removed or not is detected by detecting the oxygen content of the surface layer, the shot blasting is to treat the alloy with the alloy granularity meeting the requirement and in a room temperature state after crushing, the surface of the alloy is bright silvery after shot blasting, the alloy valence state is stable, and the alloy cannot be oxidized any more; because the influence of the crushing process on the alloy surface layer cannot be detected, the invention grasps the thickness of the alloy oxide layer by detecting the oxygen content of different thicknesses of the surface layer before shot blasting, thereby adjusting the shot blasting process, controlling the thickness of the shot blasting removed surface, further controlling the thickness of the oxide layer removed, and ensuring the oxide layer to be removed completely.
Description
Technical Field
The invention relates to the technical field of ferrovanadium alloy preparation, in particular to a low-impurity ferrovanadium alloy production method and a ferrovanadium alloy without oxidation impurities on the surface layer.
Background
The ferrovanadium alloy is applied to an additive in roll production, and can improve the hardness and strength of the roll. In the ferrovanadium alloy product, vanadium metal and iron metal exist in a simple substance eutectic state, two main metal elements in the ferrovanadium alloy exist in a simple substance state by controlling a smelting process, and the contents of other elements meet the process requirements.
The melting point of ferrovanadium alloys is lower with lower vanadium content, especially in the range of 1400-1500 ℃ for 50 ferrovanadium. However, for manufacturers, after the ferrovanadium alloy is smelted, the ferrovanadium alloy is cooled to form a metal cake, and then the metal cake can be discharged, and in addition, the alloy cake needs to be crushed to the specified particle size requirement, which is usually 10-15mm. Because the surface temperature of the ferrovanadium alloy is 500-600 ℃ when the ferrovanadium alloy is cooled and discharged, vanadium metal exposed in the air is easily oxidized by the air at the temperature to form high-valence vanadium oxide; in addition, during crushing, during high-strength extrusion crushing, when jaw-type crushed teeth extrude the alloy blocks, the alloy surfaces and the alloy sections are oxidized due to instant high temperature, the instant alloy temperature is very high (according to field observation, a red state is presented), the temperature reaches 500-600 ℃ at the moment, and high-valence vanadium oxide is formed due to oxidation and presents oxidation colors with different valence states. One skilled in the art can make a preliminary determination of the presence of oxides, or the composition of oxides, based on color. The surface of part of the alloy block is in dark blue or black due to the high temperature at the moment of crushing, wherein the dark blue is formed by tetravalent vanadium (VO 2) on the surface of the alloy, the melting point is 1967 ℃, and the black is formed by trivalent vanadium (V2O 3) on the surface of the alloy, and the melting point is 2000 ℃. The high-valence vanadium oxide has a higher melting point which is far higher than that of the ferrovanadium alloy.
When the ferrovanadium alloy is applied to the additive in the roller, if the content of the high-valence vanadium oxide in the ferrovanadium alloy is higher, in the roller smelting preparation process, after the ferrovanadium alloy is melted, the high-valence vanadium oxide is difficult to melt into molten steel due to the high melting point of the high-valence vanadium oxide, so that black spots (inclusion of unfused high-valence vanadium oxide impurity particles with higher hardness) appear on the surface of the formed roller, and defects such as air holes, cracks or impurity particles appear on the surface of the roller formed in the later period.
Disclosure of Invention
In view of the above, there is a need for a method for producing a low-impurity ferrovanadium alloy, comprising the steps of:
raw material proportioning;
smelting: putting the prepared mixed material into a reaction furnace, and igniting for smelting;
standing: after smelting, standing, settling and cooling the alloy liquid;
discharging: after the alloy liquid is solidified into solid, pulling out the furnace body, and pulling out the alloy material cake;
crushing: crushing the material cake by using a jaw crusher to form an alloy material block;
shot blasting: and (3) throwing the alloy material block into a shot blasting machine for shot blasting, wherein the shot blasting medium adopts aluminum shots and steel shots with the mixture ratio of 2-3 to 7-8, and removing a surface oxide layer to form the vanadium-iron alloy without oxidation on the surface layer.
Has the beneficial effects that: in the invention, because the high-valence vanadium oxide is generated in the processes of discharging and crushing after smelting, the generation of the oxide cannot be controlled by controlling the early smelting, and only can be realized by post-treatment, and because the high-valence vanadium oxide is generated on the surface layer which is in contact with air, the oxygen content of the whole alloy cannot represent or react with the high-valence oxide on the surface layer in the background technical problem, and only can be controlled by treating the surface layer oxide. According to the invention, the high-valence oxides on the surface layer of the alloy are removed by shot blasting, whether the oxides are removed is detected by detecting the oxygen content on the surface layer, the shot blasting is to treat the alloy with the granularity meeting the requirement and in a room temperature state after crushing, the surface of the alloy is bright silver after shot blasting, the valence state of the alloy is stable, and the alloy cannot be oxidized any more.
Because the influence of the crushing process on the alloy surface layer cannot be detected, the method provided by the invention can be used for controlling the thickness of the alloy oxide layer by detecting the oxygen content of different thicknesses of the surface layer before shot blasting, so that the shot blasting process is adjusted, the thickness of the surface removed by shot blasting is controlled, the thickness of the oxide layer removed is further controlled, and the oxide layer is ensured to be removed cleanly.
Drawings
FIG. 1 is a diagram showing the positions of an alloy block at 1mm, 2mm and 5mm from the surface layer of an example. In the figure, 01 represents a position 5mm from the skin layer, 02 represents a position 2mm from the skin layer, and 03 represents a position 1mm from the skin layer.
Detailed Description
The invention provides a production method of a low-impurity ferrovanadium alloy, which comprises the following steps:
raw material proportioning (the following raw materials are weighed and prepared according to the corresponding weight ratio, 40-50 parts of V2O5, 35-45 parts of aluminum powder, 4-6 parts of CaO, 3-4 parts of CaF2 and 6-7 parts of foundry returns);
smelting: putting the prepared mixed material into a reaction furnace, and igniting for smelting;
standing: after smelting, standing, settling and cooling the alloy liquid (for at least 40 h);
discharging: after the alloy liquid is solidified into a solid, pulling out the furnace body, and pulling out the alloy material cake;
crushing: crushing the material cake by using a jaw crusher to form an alloy material block;
shot blasting: and (3) throwing the alloy material block into a shot blasting machine for shot blasting, wherein shot blasting media adopt aluminum shots and steel shots with the mixture ratio of 2-3.
Furthermore, the thickness detection of the surface oxidation layer is also set before the shot blasting step, and the thickness of the alloy surface oxidation layer is detected by adopting an oxygen content detection method.
Further, the thickness detection of the surface oxidation layer is set after the shot blasting step, and the oxygen content of the alloy surface layer is detected by adopting an oxygen content detection method.
Further, the oxygen content in the surface layer of 2mm is less than 0.5%.
Furthermore, the particle size of the ferrovanadium alloy is 10-15mm, and the deviation between the oxygen content in the surface layer within 2mm and the internal oxygen content is less than 0.03%.
Further, in the components of the ferrovanadium alloy, by mass percent: v:48-52 percent of O is less than or equal to 0.5 percent (the content of other elements is the same as the content of national standard marks or is not strictly controlled), wherein the O is less than or equal to 0.5 percent within 2mm from the surface layer.
The method comprises the following steps: the raw material proportioning, smelting, standing, discharging and crushing are all conventional operations in the field or are the existing operation steps of the applicant, and are not described in detail herein.
Example 1 shot blasting after crushing of ferrovanadium alloy material with particle size of 15 +/-1 mm
(1) Forming a shot blasting medium by adopting 2mm aluminum shots and 2mm steel shots according to the proportion of 3;
(2) The alloy material formed after crushing is put into a shot blasting machine, the speed of the shot blasting machine is controlled to be 2900r/min, the output power of a motor is controlled to be 11KW, the shot blasting amount is 170Kg/min, and the shot blasting speed is controlled>82m/s; the transmission speed of the crawler belt is 1000r/min, and the dust removal storm speed is 5000m 3 /h；
(3) The loading amount of the alloy material blocks loaded into the feeder is 0.6m 3 ；
(4) And separating the shot-blasted alloy material block from the shot blasting medium, and detecting the performance of the finished product of the alloy material block. See table 2 for test data.
Example 2
The method is the same as that in the embodiment 1, and is different in that in the embodiment 1, (3) a shot blasting medium is formed by 2mm aluminum shots and 2mm steel shots according to a ratio of 2.5; and (5) detecting the performance of the finished product. See table 2 for test data.
Example 3
The method is the same as that in the embodiment 1, and is different in that in the embodiment 1, (3) a 2mm aluminum shot and a 2mm steel shot are adopted to form a shot blasting medium according to a ratio of 2; and (5) detecting the performance of the finished product. See table 2 for test data.
Comparative example 1
The method is the same as that in the embodiment 1, and is different in that in the embodiment 1, (3) a 2mm aluminum shot and a 2mm steel shot are adopted to form a shot blasting medium according to a ratio of 4; and (5) detecting the performance of the finished product. See table 2 for test data.
Comparative example 2
The method is the same as that in the embodiment 1, and is different in that in the embodiment 1, (3) a shot blasting medium is formed by 2mm aluminum shots and 2mm steel shots according to a proportion of 1; and (5) detecting the performance of the finished product. See table 2 for test data.
Generally speaking, for different alloys, the thickness of an oxide layer formed during crushing is different, and the scheme is that for V48-52 ferrovanadium, after crushing, the thickness of the oxide layer is determined by detecting the oxygen content of the surface layer, then the material quality and the proportion of shot blasting shot materials are determined according to the thickness of the oxide layer, and a proper shot blasting process is determined.
See table 1, fig. 1. Before the shot blasting, get 1mm, 2mm, 3mm department from the top layer, it is higher through detecting oxygen content, 1mm, 2mm department oxygen content all is higher than the oxygen content of 5mm position, this thickness of surface has formed high valence vanadium oxide, and the position of 3mm from the top layer, it is close to with the oxygen content of 5mm position to detect oxygen content, thereby confirm that the thickness of oxide layer is about 2mm, before the shot blasting or throw the back, at the position measurement oxygen content of 5mm apart from the top layer, this position is basically the central point of alloy piece, can represent the oxygen content of this alloy piece self. The above tests also further verify that the oxide described in the background art is an oxide layer formed by the contact of the high temperature surface with air during tapping or crushing. Therefore, after shot blasting, whether the oxide layer is completely removed after shot blasting can be detected only by detecting whether the oxygen content at the positions of 1mm and 2mm of the surface layer is close to the oxygen content at the position of 5mm. And the oxide layer can be removed only by shot blasting after crushing, and if shot blasting is carried out at other stages, the effect of removing the surface oxide layer of the crushed alloy quickly cannot be achieved.
TABLE 1
TABLE 2
The data of the examples 1, 2 and 3 show that the proportion of the aluminum shots and the steel shots is proper, the shot blasting strength is strong, after detection, the oxygen content in the depth of 1mm and 2mm is basically equal to the oxygen content in the depth of 5mm (namely the inside of the alloy block), which shows that the oxide layer on the surface layer is completely removed, the oxygen content on the surface layer is almost the same as the oxygen content in the alloy block, and the deviation is less than 0.03%. And the color is the natural silver color of the ferrovanadium alloy, and the ferrovanadium alloy is dark blue or black, so that the oxide layer is completely removed, and the shot blasting effect is good.
In comparative example 1, the proportion of the aluminum shots is larger than that of the aluminum shots in examples 1, 2 and 3, the shot blasting strength is reduced, after detection, the oxygen content in the depth of 1mm and 2mm is higher than that in the depth of 5mm, obviously, the shot blasting strength is insufficient due to the high proportion of the aluminum shots, and the oxide layer is not removed completely.
In comparative example 2, the proportion of the aluminum shot is smaller than that of the aluminum shots in examples 1, 2 and 3, the shot blasting strength is obviously enhanced, after detection, the oxygen content in the depth of 1mm and 2mm is basically equal to that in the depth of 5mm (namely the center of the alloy block), which indicates that the oxide layer on the surface layer is completely removed, but after observation, the surface layer is gray black, which indicates that the alloy surface layer is polished to be damaged by the steel shot, or iron oxide in the steel shot adheres to the alloy surface layer to cause gray black. Therefore, although the surface oxide layer can be removed by the proportion, the appearance can not meet the process requirement.
In the above embodiment, after the shot blasting treatment is performed by the present invention, firstly, by observing the color change, the surface oxide is removed cleanly without the dark blue color and the black color, and secondly, by detecting the oxygen element content of the surface layer (1 mm and 2mm positions), the oxygen content is not more than 0.5%, and the deviation from the core oxygen content of the alloy block is not more than 0.03%, it is indicated that the oxide is removed cleanly, and the uniformity and the consistency of the surface layer removal are good, indicating that the surface layer oxide is removed uniformly.
When alloy products are produced, no matter the alloy products are sold in a block shape or a particle shape by manufacturers, or when a user crushes alloys with larger particle sizes to form smaller particles, the crushing process in the background technology exists, and oxides are generated on the surface locally. The oxygen content in the alloy is controlled by alloy manufacturers mostly by controlling the oxygen content in the smelting process, surface oxides generated by crushing cold alloy materials cannot be avoided, and the oxides are also a way for increasing oxygen during the subsequent smelting or adding of the alloy materials, so the removal of the surface oxides is also a technical difficulty generally existing in the field.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (6)
1. The production method of the low-impurity ferrovanadium alloy is characterized by comprising the following steps of:
preparing raw materials;
smelting: putting the prepared mixed material into a reaction furnace, and igniting for smelting;
standing: after smelting, alloy liquid is stood, settled and cooled;
discharging: after the alloy liquid is solidified into solid, pulling out the furnace body, and pulling out the alloy material cake;
crushing: crushing the material cake by using a jaw crusher to form an alloy material block;
shot blasting: and (3) throwing the alloy material block into a shot blasting machine for shot blasting, wherein the shot blasting medium adopts aluminum shots and steel shots with the mixture ratio of 2-3 to 7-8, and removing a surface oxide layer to form the vanadium-iron alloy without oxidation on the surface layer.
2. The method for producing the low-impurity ferrovanadium alloy as claimed in claim 1, wherein the thickness of the surface oxide layer of the alloy is detected by an oxygen content detection method after the shot blasting step.
3. The method for producing the low-impurity ferrovanadium alloy as claimed in claim 1, wherein the step of shot blasting is followed by a step of detecting the thickness of the surface oxide layer and a step of detecting the oxygen content of the surface layer of the alloy by an oxygen content detection method.
4. A vanadium iron alloy without oxidation impurities on the surface layer is characterized in that: the surface layer is within 2mm, and the oxygen content is less than or equal to 0.5 percent.
5. The ferrovanadium alloy having a surface layer free of oxidizing impurities as claimed in claim 4, wherein: the vanadium-iron alloy has a particle size of 10-15mm, and the deviation between the oxygen content in the surface layer of 2mm and the internal oxygen content is less than or equal to 0.03%.
6. The ferrovanadium alloy having a surface layer free of oxidizing impurities as claimed in claim 5, wherein: the ferrovanadium alloy comprises the following components in percentage by mass: v:48-52 percent of oxygen and less than or equal to 0.5 percent of oxygen, wherein the oxygen is less than or equal to 0.5 percent within 2mm from the surface layer.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB709869A (en) * | 1951-07-24 | 1954-06-02 | Fischer Ag Georg | Process for the surface treatment of light alloy components by abrasive blast |
| CN108300880A (en) * | 2018-02-02 | 2018-07-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of vanadium iron |
| CN109234533A (en) * | 2018-10-30 | 2019-01-18 | 攀钢集团钒钛资源股份有限公司 | Low-grade aluminum shot smelting ferrovanadium |
| US20200199712A1 (en) * | 2017-06-13 | 2020-06-25 | Northeastern University | Method for preparing ferrovanadium alloys based on aluminothermic self-propagating gradient reduction and slag washing refining |
| US20200246875A1 (en) * | 2019-01-31 | 2020-08-06 | Chengde Branch Of Hbis Group | Method for preparing vanadium and vanadium alloy powder from vanadium-containing materials through shortened process |
| CN113151730A (en) * | 2021-04-25 | 2021-07-23 | 攀钢集团北海特种铁合金有限公司 | External smelting method of ferrovanadium |
| CN113913677A (en) * | 2021-09-29 | 2022-01-11 | 河钢承德钒钛新材料有限公司 | 50 ferrovanadium alloy and smelting method thereof |
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- 2022-11-24 CN CN202211485141.8A patent/CN115786801B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB709869A (en) * | 1951-07-24 | 1954-06-02 | Fischer Ag Georg | Process for the surface treatment of light alloy components by abrasive blast |
| US20200199712A1 (en) * | 2017-06-13 | 2020-06-25 | Northeastern University | Method for preparing ferrovanadium alloys based on aluminothermic self-propagating gradient reduction and slag washing refining |
| CN108300880A (en) * | 2018-02-02 | 2018-07-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of vanadium iron |
| CN109234533A (en) * | 2018-10-30 | 2019-01-18 | 攀钢集团钒钛资源股份有限公司 | Low-grade aluminum shot smelting ferrovanadium |
| US20200246875A1 (en) * | 2019-01-31 | 2020-08-06 | Chengde Branch Of Hbis Group | Method for preparing vanadium and vanadium alloy powder from vanadium-containing materials through shortened process |
| CN113151730A (en) * | 2021-04-25 | 2021-07-23 | 攀钢集团北海特种铁合金有限公司 | External smelting method of ferrovanadium |
| CN113913677A (en) * | 2021-09-29 | 2022-01-11 | 河钢承德钒钛新材料有限公司 | 50 ferrovanadium alloy and smelting method thereof |
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