CN113481545B - Lanthanum-iron alloy - Google Patents
Lanthanum-iron alloy Download PDFInfo
- Publication number
- CN113481545B CN113481545B CN202110377619.4A CN202110377619A CN113481545B CN 113481545 B CN113481545 B CN 113481545B CN 202110377619 A CN202110377619 A CN 202110377619A CN 113481545 B CN113481545 B CN 113481545B
- Authority
- CN
- China
- Prior art keywords
- lanthanum
- iron
- alloy
- intermediate alloy
- rare earth
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
- C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
Abstract
The invention discloses a lanthanum-iron alloy, which comprises 10.04-50.05 wt% of lanthanum, 59.97-95.06 wt% of iron and unavoidable impurities with the total amount less than 0.5wt%, wherein oxygen is less than or equal to 0.01wt%, carbon is less than or equal to 0.01wt%, phosphorus is less than or equal to 0.01wt% and sulfur is less than or equal to 0.005wt%. Compared with rare earth iron alloy prepared by a consumable cathode method, the lanthanum iron alloy prepared by the method has more uniform components and can accurately control the lanthanum content.
Description
This patent application is application number: 201611168972.7, name: lanthanum-iron alloy and preparation method thereof, application date: division of the application into 2016, 12 and 16.
Technical Field
The invention belongs to the technical field of rare earth iron alloy, and particularly relates to lanthanum iron alloy.
Background
At present, steel is the first large metal structural material and is widely applied to the fields of construction, energy, transportation, aerospace and the like. The application of rare earth in steel and the research thereof have also been developed rapidly, the rare earth added into molten steel can play the roles of desulfurizing, deoxidizing, changing the form of inclusions, etc., and the plasticity, stamping performance, wear resistance and welding performance of steel can be improved. Various rare earth steels such as rare earth steel plates for automobiles, die steels, steel rails and the like are widely used.
The adding method of rare earth in the production process of rare earth steel is always the focus of research of scientific research, the existing adding method comprises a wire feeding method, a cored wire, a rare earth iron intermediate alloy and other forms, and the existing effect is obvious. The technology for preparing the rare earth iron intermediate alloy mainly comprises the following steps:
(1) A miscibility method.
The miscibility method is also called a pair-blending method, and mainly utilizes an electric arc furnace or an intermediate frequency induction furnace to mix rare earth metals and iron to prepare an alloy. The method is a commonly adopted method at present, has simple process technology, can prepare a multi-element intermediate alloy or an application alloy, but has the following defects: 1) The rare earth metal is easy to have overhigh local concentration in the molten iron, and segregation is generated; 2) The raw materials adopted by the method are rare earth metals, and particularly for medium and heavy rare earth metals, the preparation process is complex and the cost is high; 3) The smelting temperature is high, and the rare earth metal and the pure iron are used as raw materials, so that the smelting temperature is high.
(2) Molten salt electrolysis.
The molten salt electrolysis process is mainly to prepare rare earth iron intermediate alloy by adopting an iron consumable cathode method. For example, chinese patent CN1827860 discloses a process and apparatus for producing dysprosium-iron alloy by molten salt electrolysis, which proposes that under the high temperature condition, dysprosium oxide dissolved in fluoride solution is ionized, dysprosium ion is separated out on the surface of iron cathode under the action of dc electric field, and reduced into metal dysprosium, and dysprosium and iron are alloyed to form dysprosium-iron alloy. The method has low production cost and simple process, but has the following defects: the rare earth and iron in the alloy have large distribution fluctuation, difficult control and distribution error as high as 3% -5%, and influence the consistency of products.
Disclosure of Invention
The invention aims to provide a lanthanum-iron alloy, which has more uniform components and accurately controllable lanthanum content compared with rare earth iron alloy prepared by a consumable cathode method.
In order to achieve the above purpose, the technical solution adopted by the invention is as follows:
lanthanum-iron alloy, wherein the content of lanthanum is 10.04-50.05 wt% and 59.97-95.06 wt%, and the balance is iron and unavoidable impurities with the total amount less than 0.5wt%, wherein oxygen is less than or equal to 0.01wt%, carbon is less than or equal to 0.01wt%, phosphorus is less than or equal to 0.01wt%, and sulfur is less than or equal to 0.005wt%.
Further: the lanthanum content is 10.04-50.03 wt%.
Further: the lanthanum content is 10.11-50.05 wt%.
Further: the lanthanum content is 29.98-50.05 wt%.
Further: the lanthanum content is 30.05-50.05 wt%.
Further: the lanthanum content is 59.97-69.98 wt%.
Further: in equipment for electrolyzing lanthanum-iron intermediate alloy, under a fluoride molten salt electrolyte system of lanthanum fluoride and lithium fluoride, lanthanum oxide is taken as an electrolysis raw material, and direct current is introduced for electrolysis to obtain the lanthanum-iron intermediate alloy; lanthanum-iron intermediate alloy and iron are used as raw materials, and a smelting method is adopted to prepare the lanthanum-iron alloy.
Further: the equipment for melting lanthanum-iron intermediate alloy is an intermediate frequency induction furnace, the melting process is carried out under vacuum condition, and a rare earth oxide crucible is adopted as the crucible.
Further: the material of the receiver is iron, rare earth oxide or boron nitride.
Further: lanthanum or iron is added during the vacuum melting process.
The technical effects of the invention include:
compared with the prior art, the invention has the technical effects that: aiming at the problems existing in the prior art, the invention develops a novel molten salt electrolysis process, and the prepared lanthanum-iron alloy has the advantages of uniform components, small segregation, low impurity content, high rare earth yield, low cost, no pollution, high rare earth yield and obvious effect when being applied to rare earth steel, and is suitable for large-scale industrial production.
1. In the invention, the lanthanum-iron alloy has the advantages that:
(1) The impurity content is low.
The lanthanum-iron alloy provided by the invention adopts pure lanthanum oxide as a raw material, and the smelting crucible is made of iron and rare earth oxide substances, so that the introduced impurity content is low.
(2) The components are uniform, and the lanthanum content is controllable.
Compared with a consumable cathode, the lanthanum-iron alloy provided by the invention has more uniform components and can accurately control the lanthanum content. Practice proves that the alloy can be used for preparing high-performance rare earth steel products.
2. The preparation method of the lanthanum-iron alloy disclosed by the invention has the advantages that:
(1) Lanthanum oxide is used as an electrolysis raw material, so that only CO, CO2 and a very small amount of fluorine-containing gas are generated in the electrolysis process, and the environment pollution is small.
(2) The pure iron rod is used as a consumable cathode, and lanthanum and iron separated by electrolysis form lanthanum-iron alloy with low melting point, which is beneficial to reducing the electrolysis temperature.
(3) The lanthanum-iron intermediate alloy obtained by molten salt electrolysis is subjected to vacuum melting, so that the components of the obtained lanthanum-iron intermediate alloy are accurately controlled, and the rare earth is small in burning loss, high in yield and high in product quality due to the fact that the lanthanum-iron intermediate alloy is melted under vacuum.
3. Has wide development and market prospect.
Along with the development of national economy construction, the steel is required to have high strength and toughness and good corrosion resistance, and the rare earth plays a key role. Rare earth also plays an important role in improving the toughness, plasticity, heat resistance, oxidation resistance and wear resistance of steel. The method is a first large country of steel yield, and has great significance in strengthening the application of rare earth in such a wide-ranging field. One of the important influencing factors limiting the industrialization process of rare earth steel is the adding mode of rare earth in steel, and the most effective mode developed at present is to add the rare earth in a mode of rare earth iron intermediate alloy. Taking 500 ten thousand tons of rare earth steel plates produced by steel-clad (group) companies as an example, 2.5 ten thousand tons of 10% rare earth ferroalloy is required to be consumed, and the economic benefit is remarkable. The implementation of the invention has a certain promotion effect on improving the industrial structure of the region and improving the technological strength of the region; on the other hand, the rare earth alloy is smelted every year and is fully applied to the rare earth steel, so that not only can great economic benefit be generated, but also the situation of non-ideal iron and steel situation in China can be turned, and the application prospect is wide; can find a way for low-cost rare earth, and assist the healthy and sustainable development of the rare earth industry and the steel industry.
Drawings
FIG. 1 is a schematic structural view of an apparatus for electrolyzing lanthanum-iron master alloy in the present invention;
FIG. 2 is a flow chart of a lanthanum-iron alloy preparation process in the invention.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. However, the exemplary embodiments can be embodied in many forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the example embodiments to those skilled in the art.
FIG. 1 is a schematic structural diagram of a lanthanum-iron intermediate alloy electrolysis device in the invention; as shown in FIG. 2, the lanthanum-iron alloy preparation process flow chart in the invention is shown.
The device for electrolyzing lanthanum-iron intermediate alloy used in the invention structurally comprises: 1 refractory brick, 2 iron cover, rare earth oxide crucible 3, lanthanum-iron alloy 4, anode plate 5, iron cathode 6, electrolyte 7, electrolytic bath 8, heat preservation 9, carbon ramming layer 10.
The electrolytic bath 8 is a graphite bath, and the outside of the graphite bath body is sequentially covered with a carbon ramming layer 10, a heat preservation layer 9, refractory bricks 1 and an iron sleeve 2; an iron cathode 6 is arranged in the middle of the graphite tank; an anode plate 5 is arranged around the iron cathode 6 in the graphite tank; a rare earth oxide crucible 3 is arranged at the bottom center of the graphite tank, and the rare earth oxide crucible 3 is opposite to the iron cathode 6. When in use, the electrolyte 7 is filled in the graphite tank, the electrolyte 7 adopts lanthanum fluoride and lithium fluoride molten salt electrolyte, and the rare earth oxide crucible 3 is filled with lanthanum-iron alloy 4.
The preparation process of lanthanum-iron alloy for producing rare earth steel comprises the following steps:
step 1: graphite is used as an electrolytic tank, a graphite plate is used as an anode, an iron rod is used as a consumable cathode, and a receiver for containing alloy is arranged below the cathode;
the material of the receiver can be one of iron, rare earth oxide and boron nitride.
Step 2: in a fluoride molten salt electrolyte system of lanthanum fluoride and lithium fluoride, lanthanum oxide is taken as an electrolysis raw material, and direct current is introduced to electrolyze to obtain lanthanum-iron intermediate alloy;
step 3: lanthanum-iron intermediate alloy and iron are used as raw materials, and a smelting method is adopted to prepare the lanthanum-iron alloy meeting the requirements.
The equipment for melting the lanthanum-iron intermediate alloy is an intermediate frequency induction furnace. The melting process is carried out under vacuum condition, and the crucible adopts a rare earth oxide crucible.
In the lanthanum-iron alloy, the content of lanthanum is 0-95wt%, and the balance is iron and unavoidable impurities with the total amount less than 0.5wt%, wherein oxygen is less than or equal to 0.01wt%, carbon is less than or equal to 0.01wt%, phosphorus is less than or equal to 0.01wt%, and sulfur is less than or equal to 0.005wt%.
The metal detection is carried out by adopting ICP-MS test according to national standards such as GB/T18115.1-2006 and the like; c is detected by a high-frequency combustion-infrared method according to GB/T12690.13-1990; o is tested according to GB/T12690.4-2003 by the inert gas pulse-infrared method. The standard deviation S of the chemical composition is calculated from the following formula:
wherein X is i Is the chemical composition of the sample; the X average is the average of the n-point chemical components of the sample, n=20 in the present invention.
Example 1
Adopting a round graphite electrolytic tank with phi of 650mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride and 20wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the anode current density is 0.5-1.0A/cm 2 Cathode current density of 5-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is continuously carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90%, the current efficiency is 80%, and the alloy composition results are shown in Table 1.
TABLE 1 lanthanum-iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 90.0 | 9.85 | 0.0085 | 0.0094 | ＜0.01 | ＜0.005 | 0.012 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 1.7kg of the lanthanum-iron intermediate alloy is added with 13.3kg of an iron rod, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron alloy components obtained after smelting are shown in Table 2.
TABLE 2 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 10.11 | 89.73 | 0.0080 | 0.0095 | ＜0.01 | ＜0.005 | 0.008 | ＜0.005 |
Example 2
Adopting a round graphite electrolytic tank with phi of 650mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride and 20wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the anode current density is 0.5-1.0A/cm 2 Cathode current density of 5-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is continuously carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90%, the current efficiency is 80%, and the alloy composition results are shown in Table 3.
TABLE 3 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 90.0 | 9.85 | 0.0085 | 0.0094 | ＜0.01 | ＜0.005 | 0.012 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 5kg of the lanthanum-iron intermediate alloy is added with 10kg of an iron rod, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in Table 4.
TABLE 4 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 29.98 | 69.74 | 0.0088 | 0.0089 | ＜0.01 | ＜0.005 | 0.004 | ＜0.005 |
Example 3
Adopting a round graphite electrolytic tank with phi of 650mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride and 20wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the anode current density is 0.5-1.0A/cm 2 Cathode current density of 5-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is continuously carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90%, the current efficiency is 80%, and the alloy composition results are shown in Table 5.
TABLE 5 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 90.0 | 9.85 | 0.0085 | 0.0094 | ＜0.01 | ＜0.005 | 0.012 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 8.4kg of the lanthanum-iron intermediate alloy is added with 6.6kg of an iron rod, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in Table 6.
TABLE 6 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 50.05 | 49.74 | 0.0074 | 0.0093 | ＜0.01 | ＜0.005 | 0.003 | ＜0.005 |
Example 4
Adopting a round graphite electrolytic tank with phi of 650mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride and 20wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the anode current density is 0.5-1.0A/cm 2 Cathode current density of 5-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is continuously carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90%, the current efficiency is 80%, and the alloy composition results are shown in Table 7.
TABLE 7 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 90.0 | 9.85 | 0.0085 | 0.0094 | ＜0.01 | ＜0.005 | 0.012 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 11.7kg of the lanthanum-iron intermediate alloy is added with 3.3kg of an iron rod, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in Table 8.
TABLE 8 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 70.04 | 29.66 | 0.0076 | 0.0086 | ＜0.01 | ＜0.005 | 0.0024 | ＜0.005 |
Example 5
Adopting a round graphite electrolytic tank with phi of 650mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride and 20wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the anode current density is 0.5-1.0A/cm 2 Cathode current density of 5-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is continuously carried out for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90%, the current efficiency is 80%, and the alloy composition results are shown in Table 9.
TABLE 9 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 90.0 | 9.85 | 0.0085 | 0.0094 | ＜0.01 | ＜0.005 | 0.012 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 7.5kg of lanthanum-iron intermediate alloy and 7.5kg of lanthanum metal are added, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in Table 10.
TABLE 10 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 95.03 | 4.76 | 0.0097 | 0.0076 | ＜0.01 | ＜0.005 | 0.010 | ＜0.005 |
Example 6
Adopting a round graphite electrolytic tank with phi of 700mm, wherein an anode consists of four graphite plates, the electrolyte contains 75wt% of lanthanum fluoride and 25wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 75mm, the average current intensity is 5500A, and the anode current density is 0.4-0.8A/cm 2 Cathode current density of 8-25A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is continuously carried out for 300 hours, 2688kg of lanthanum oxide is consumed, 2615kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 85.02%, the current efficiency is 78%, and the alloy composition results are shown in Table 11.
TABLE 11 lanthanum-iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 85.02 | 14.84 | 0.0075 | 0.0084 | ＜0.01 | ＜0.005 | 0.017 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 1.8kg of the lanthanum-iron intermediate alloy is added with 13.2kg of an iron rod, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in Table 12.
TABLE 12 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 10.04 | 89.66 | 0.0070 | 0.0080 | ＜0.01 | ＜0.005 | 0.003 | ＜0.005 |
Example 7
Adopting a round graphite electrolytic tank with phi of 700mm, wherein an anode consists of four graphite plates, the electrolyte contains 75wt% of lanthanum fluoride and 25wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 75mm, the average current intensity is 5500A, and the anode current density is 0.4-0.8A/cm 2 Cathode current density of 8-25A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is continuously carried out for 300 hours, 2688kg of lanthanum oxide is consumed, 2615kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 85.02%, the current efficiency is 78%, and the alloy composition results are shown in Table 13.
TABLE 13 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 85.02 | 14.84 | 0.0075 | 0.0084 | ＜0.01 | ＜0.005 | 0.017 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 5.3kg of the lanthanum-iron intermediate alloy is added with 9.7kg of an iron rod, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in table 14.
TABLE 14 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 30.05 | 69.77 | 0.0070 | 0.0086 | ＜0.01 | ＜0.005 | 0.0024 | ＜0.005 |
Example 8
Adopting a round graphite electrolytic tank with phi of 700mm, wherein an anode consists of four graphite plates, the electrolyte contains 75wt% of lanthanum fluoride and 25wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 75mm, the average current intensity is 5500A, and the anode current density is 0.4-0.8A/cm 2 Cathode current density of 8-25A/cm 2 The electrolysis temperature is maintained between 900 and 1050 ℃ and continuous electrolysis is carried out for 300 hours, and 2688kg of lanthanum oxide is consumed to prepare 2615kg of lanthanum-iron intermediate alloy with the average lanthanum content of 85.02%, current efficiency 78%, alloy composition results are shown in table 15.
TABLE 15 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 85.02 | 14.84 | 0.0075 | 0.0084 | ＜0.01 | ＜0.005 | 0.017 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 8.8kg of the lanthanum-iron intermediate alloy is added with 6.2kg of an iron rod, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in Table 16.
TABLE 16 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 50.03 | 49.78 | 0.0064 | 0.0087 | ＜0.01 | ＜0.005 | 0.0021 | ＜0.005 |
Example 9
Adopting a round graphite electrolytic tank with phi of 700mm, wherein an anode consists of four graphite plates, the electrolyte contains 75wt% of lanthanum fluoride and 25wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 75mm, the average current intensity is 5500A, and the anode current density is 0.4-0.8A/cm 2 Yin, yinPolar current density of 8-25A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is continuously carried out for 300 hours, 2688kg of lanthanum oxide is consumed, 2615kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 85.02%, the current efficiency is 78%, and the alloy composition results are shown in Table 17.
TABLE 17 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 85.02 | 14.84 | 0.0075 | 0.0084 | ＜0.01 | ＜0.005 | 0.017 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 12.4kg of lanthanum intermediate alloy and 2.6kg of iron rod are added, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in table 18.
TABLE 18 lanthanum-iron alloy composition analysis results/wt%
| RE | Fe | C | O | P | S | Si | Mn |
| 69.98 | 29.74 | 0.0078 | 0.0090 | ＜0.01 | ＜0.005 | 0.0018 | ＜0.005 |
Example 10
Adopts a round graphite electrolytic tank with phi of 700mm, and the anode is made of four stonesInk plate composition, 75wt% lanthanum fluoride, 25wt% lithium fluoride in electrolyte, 75mm pure iron rod as cathode, 5500A average current intensity and 0.4-0.8A/cm anode current density 2 Cathode current density of 8-25A/cm 2 The electrolysis temperature was maintained at 900-1050 ℃ and continuous electrolysis was carried out for 300 hours, consuming 2688kg of lanthanum oxide, producing 2615kg of lanthanum-iron intermediate alloy, the average lanthanum content being 85.02%, the current efficiency being 78%, and the alloy composition results being shown in table 19.
TABLE 19 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 85.02 | 14.84 | 0.0075 | 0.0084 | ＜0.01 | ＜0.005 | 0.017 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 5kg of the lanthanum-iron intermediate alloy is added with 10kg of lanthanum metal, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in table 20.
TABLE 20 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 95.06 | 4.69 | 0.0094 | 0.0093 | ＜0.01 | ＜0.005 | 0.0034 | ＜0.005 |
Example 11
Adopting a round graphite electrolytic tank with phi of 700mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride, 20wt% of lithium fluoride, the cathode is a 60mm pure iron rod, the average current intensity is 6000A, and the anode current density is 0.3-0.7A/cm 2 Cathode current density 10-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is carried out continuously for 200 hours, 2030kg of lanthanum oxide is consumed, 1766kg of lanthanum-iron alloy is prepared, the average lanthanum content is 95.06%, the current efficiency is 81%, and the alloy composition results are shown in Table 21.
TABLE 21 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 95.06 | 4.64 | 0.0042 | 0.0065 | ＜0.01 | ＜0.005 | 0.014 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 3.2kg of the lanthanum-iron intermediate alloy is added with 11.8kg of lanthanum metal, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in table 22.
TABLE 22 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 19.98 | 79.76 | 0.0040 | 0.0071 | ＜0.01 | ＜0.005 | 0.0088 | ＜0.005 |
Example 12
Adopting a round graphite electrolytic tank with phi of 700mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride, 20wt% of lithium fluoride, the cathode is a 60mm pure iron rod, the average current intensity is 6000A, and the anode current density is 0.3-0.7A/cm 2 Cathode current density 10-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is carried out continuously for 200 hours, 2030kg of lanthanum oxide is consumed, 1766kg of lanthanum-iron alloy is prepared, the average lanthanum content is 95.06%, the current efficiency is 81%, and the alloy composition results are shown in Table 23.
TABLE 23 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 95.06 | 4.64 | 0.0042 | 0.0065 | ＜0.01 | ＜0.005 | 0.014 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 6.3kg of lanthanum-iron intermediate alloy and 8.7kg of lanthanum metal are added, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in Table 24.
TABLE 24 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 40.06 | 59.63 | 0.0038 | 0.0072 | ＜0.01 | ＜0.005 | 0.0079 | ＜0.005 |
Example 13
Adopting a round graphite electrolytic tank with phi of 700mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride, 20wt% of lithium fluoride, the cathode is a 60mm pure iron rod, the average current intensity is 6000A, and the anode current density is 0.3-0.7A/cm 2 Cathode current density 10-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is carried out continuously for 200 hours, 2030kg of lanthanum oxide is consumed, 1766kg of lanthanum-iron alloy is prepared, the average lanthanum content is 95.06%, the current efficiency is 81%, and the alloy composition results are shown in Table 25.
TABLE 25 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 95.06 | 4.64 | 0.0042 | 0.0065 | ＜0.01 | ＜0.005 | 0.014 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 9.5kg of lanthanum-iron intermediate alloy and 5.5kg of lanthanum metal are added, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in table 26.
TABLE 26 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 59.97 | 39.62 | 0.0041 | 0.0075 | ＜0.01 | ＜0.005 | 0.0080 | ＜0.005 |
Example 14
Adopting a round graphite electrolytic tank with phi of 700mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride, 20wt% of lithium fluoride, the cathode is a 60mm pure iron rod, the average current intensity is 6000A, and the anode current density is 0.3-0.7A/cm 2 Cathode current density 10-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is carried out continuously for 200 hours, 2030kg of lanthanum oxide is consumed, 1766kg of lanthanum-iron alloy is prepared, the average lanthanum content is 95.06%, the current efficiency is 81%, and the alloy composition results are shown in Table 27.
TABLE 27 lanthanum iron master alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 95.06 | 4.64 | 0.0042 | 0.0065 | ＜0.01 | ＜0.005 | 0.014 | ＜0.005 |
The lanthanum-iron intermediate alloy prepared in the embodiment is taken as a raw material, 12.6kg of lanthanum-iron intermediate alloy is added with 2.4kg of metal lanthanum, smelting is carried out in a 30kg medium-frequency vacuum induction furnace, the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron composition obtained after smelting is shown in a table 28.
TABLE 28 lanthanum-iron alloy composition analysis results/wt%
| La | Fe | C | O | P | S | Si | Mn |
| 80.03 | 19.74 | 0.0046 | 0.0066 | ＜0.01 | ＜0.005 | 0.0079 | ＜0.005 |
The terminology used herein is for the purpose of description and illustration only and is not intended to be limiting. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.
Claims (1)
1. A lanthanum-iron alloy, characterized in that:
adopting a round graphite electrolytic tank with phi of 650mm, wherein an anode consists of four graphite plates, the electrolyte contains 80wt% of lanthanum fluoride and 20wt% of lithium fluoride, the cathode is a pure iron rod with the diameter of 70mm, the average current intensity is 5000A, and the anode current density is 0.5-1.0A/cm 2 Cathode current density of 5-20A/cm 2 The electrolysis temperature is maintained at 900-1050 ℃, the electrolysis is carried out continuously for 150 hours, 1250kg of lanthanum oxide is consumed, 1151kg of lanthanum-iron intermediate alloy is prepared, the average lanthanum content is 90%, the current efficiency is 80%, and the prepared lanthanum-iron intermediate alloy comprises the following components: la 90.0 wt%, fe 9.85 wt%, C0.0085 wt%, O0.0094 wt%, P < 0.01wt%, S < 0.005wt%, si 0.012 wt%, mn < 0.005 wt%;
taking 11.7kg of the prepared lanthanum-iron intermediate alloy as a raw material, adding 3.3kg of an iron rod, smelting in a 30kg medium-frequency vacuum induction furnace, wherein the protective gas is argon, a lanthanum oxide crucible is selected as the crucible, and the lanthanum-iron alloy obtained after smelting comprises the following components: la 70.04 wt%, fe 29.66 wt%, C0.0076 wt%, O0.0086 wt%, P < 0.01wt%, S < 0.005wt%, si 0.0024 wt%, mn < 0.005wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110377619.4A CN113481545B (en) | 2016-12-16 | 2016-12-16 | Lanthanum-iron alloy |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110377619.4A CN113481545B (en) | 2016-12-16 | 2016-12-16 | Lanthanum-iron alloy |
| CN201611168972.7A CN106757170A (en) | 2016-12-16 | 2016-12-16 | Lanthanum ferroalloy and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611168972.7A Division CN106757170A (en) | 2016-12-16 | 2016-12-16 | Lanthanum ferroalloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113481545A CN113481545A (en) | 2021-10-08 |
| CN113481545B true CN113481545B (en) | 2023-07-14 |
Family
ID=58893233
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611168972.7A Pending CN106757170A (en) | 2016-12-16 | 2016-12-16 | Lanthanum ferroalloy and preparation method thereof |
| CN202110377619.4A Active CN113481545B (en) | 2016-12-16 | 2016-12-16 | Lanthanum-iron alloy |
| CN202110377144.9A Active CN113430579B (en) | 2016-12-16 | 2016-12-16 | Preparation method of lanthanum-iron alloy |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611168972.7A Pending CN106757170A (en) | 2016-12-16 | 2016-12-16 | Lanthanum ferroalloy and preparation method thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110377144.9A Active CN113430579B (en) | 2016-12-16 | 2016-12-16 | Preparation method of lanthanum-iron alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN106757170A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517457B (en) * | 2018-05-15 | 2021-01-08 | 鞍钢股份有限公司 | Preparation method of rare earth-containing alloy |
| JP7192811B2 (en) * | 2020-03-06 | 2022-12-20 | トヨタ自動車株式会社 | Positive electrode active material and fluoride ion battery |
| CN111235604A (en) * | 2020-03-11 | 2020-06-05 | 赣州有色冶金研究所 | Rare earth additive and preparation method and application thereof |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO854899L (en) * | 1984-12-07 | 1986-06-09 | Rhone Poulenc Spec Chim | METHOD AND APPARATUS FOR ELECTROLYTIC PREPARATION OF RARE EARTH ELEMENTS. |
| CN85102283A (en) * | 1985-04-01 | 1986-08-06 | 中国科学院长春应用化学研究所 | The novel method of neodium iron intermediate alloy preparation |
| US4747924A (en) * | 1984-10-03 | 1988-05-31 | Sumitomo Light Metal Industries, Ltd. | Apparatus for producing neodymium-iron alloy |
| CN1064510A (en) * | 1992-03-18 | 1992-09-16 | 冶金工业部包头稀土研究院 | The preparation method of neodymium and Nd-Pr base heavy rare-earth alloy |
| CA2062636A1 (en) * | 1991-04-17 | 1992-10-18 | Frank H. Feddrix | Electrolytic process for making alloys of rare earth and other metals |
| CN1435513A (en) * | 2002-11-08 | 2003-08-13 | 包头市长河稀土材料有限公司 | Lanthanum and cerium composite alloy additive and preparing method thereof |
| WO2008095448A1 (en) * | 2007-02-07 | 2008-08-14 | Grirem Advanced Materials Co., Ltd. | A rare earth alloy, the preparing method and use thereof |
| CN101560628A (en) * | 2008-04-17 | 2009-10-21 | 北京有色金属研究总院 | Rare-earth ferroalloy and preparation process thereof |
| CN101724769A (en) * | 2008-10-13 | 2010-06-09 | 北京有色金属研究总院 | Rare earth aluminum alloy, and method and device for preparing same |
| CN102140656A (en) * | 2011-03-09 | 2011-08-03 | 赣州晨光稀土新材料股份有限公司 | Method for preparing Dy-Fe alloy through oxide molten salt electrolysis |
| WO2012099092A1 (en) * | 2011-01-21 | 2012-07-26 | Jx日鉱日石金属株式会社 | Method for producing high-purity lanthanum, high-purity lanthanum, sputtering target formed from high-purity lanthanum, and metal gate film having high-purity lanthanum as main component |
| JP2013197240A (en) * | 2012-03-19 | 2013-09-30 | Jx Nippon Mining & Metals Corp | Neodymium-iron-boron-based rare earth sintered magnet, and method of manufacturing the same |
| CN103820698A (en) * | 2014-03-11 | 2014-05-28 | 包头稀土研究院 | Rare earth iron intermediate alloy and application thereof |
| CN103924265A (en) * | 2014-04-28 | 2014-07-16 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Method for preparing rare-earth dysprosium alloy by molten salt electrolysis |
| CN103924266A (en) * | 2014-04-28 | 2014-07-16 | 包头稀土研究院 | Method for preparing rare earth-gadolinium alloy by adopting co-deposition method |
| CN105624737A (en) * | 2015-12-31 | 2016-06-01 | 包头稀土研究院 | Method for preparing rare earth magnesium alloy and yttrium-neodymium magnesium alloy |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100748B (en) * | 1985-04-01 | 1988-05-25 | 冶金工业部包头稀土研究院 | Electrolysis tank for continuous production of nd-metal and nd-fe alloy |
| JPS61253391A (en) * | 1985-04-30 | 1986-11-11 | Sumitomo Light Metal Ind Ltd | Method and apparatus for manufacturing praseodymiumi-iron or praseodymium-neodymium-iron alloy |
| US4737248A (en) * | 1985-12-19 | 1988-04-12 | Sumitomo Light Metal Industries, Ltd. | Process for producing dysprosium-iron alloy and neodymium-dysprosium-iron alloy |
| JPH0684551B2 (en) * | 1988-08-22 | 1994-10-26 | 昭和電工株式会社 | Process for producing praseodymium or praseodymium-containing alloy |
| CN1827860A (en) * | 2005-02-28 | 2006-09-06 | 包头市稀土应用技术研究所 | Process and apparatus for producing Dy-Fe alloy by molten salt electrolysis method |
| CN101200806B (en) * | 2006-12-13 | 2010-05-19 | 北京有色金属研究总院 | Method for preparing gadolinium-iron alloy by molten salt electrolysis |
| CN102383028A (en) * | 2011-11-03 | 2012-03-21 | 内蒙古包钢钢联股份有限公司 | Fe and mixed rare earth intermediate alloy for adding rare earth into steel and preparation method for Fe and mixed rare earth intermediate alloy |
| CN103572329B (en) * | 2012-07-31 | 2016-01-20 | 有研稀土新材料股份有限公司 | A kind of fusion electrolysis prepares the method for rare earth alloys |
-
2016
- 2016-12-16 CN CN201611168972.7A patent/CN106757170A/en active Pending
- 2016-12-16 CN CN202110377619.4A patent/CN113481545B/en active Active
- 2016-12-16 CN CN202110377144.9A patent/CN113430579B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4747924A (en) * | 1984-10-03 | 1988-05-31 | Sumitomo Light Metal Industries, Ltd. | Apparatus for producing neodymium-iron alloy |
| NO854899L (en) * | 1984-12-07 | 1986-06-09 | Rhone Poulenc Spec Chim | METHOD AND APPARATUS FOR ELECTROLYTIC PREPARATION OF RARE EARTH ELEMENTS. |
| CN85102283A (en) * | 1985-04-01 | 1986-08-06 | 中国科学院长春应用化学研究所 | The novel method of neodium iron intermediate alloy preparation |
| CA2062636A1 (en) * | 1991-04-17 | 1992-10-18 | Frank H. Feddrix | Electrolytic process for making alloys of rare earth and other metals |
| CN1064510A (en) * | 1992-03-18 | 1992-09-16 | 冶金工业部包头稀土研究院 | The preparation method of neodymium and Nd-Pr base heavy rare-earth alloy |
| CN1435513A (en) * | 2002-11-08 | 2003-08-13 | 包头市长河稀土材料有限公司 | Lanthanum and cerium composite alloy additive and preparing method thereof |
| WO2008095448A1 (en) * | 2007-02-07 | 2008-08-14 | Grirem Advanced Materials Co., Ltd. | A rare earth alloy, the preparing method and use thereof |
| CN101560628A (en) * | 2008-04-17 | 2009-10-21 | 北京有色金属研究总院 | Rare-earth ferroalloy and preparation process thereof |
| CN101724769A (en) * | 2008-10-13 | 2010-06-09 | 北京有色金属研究总院 | Rare earth aluminum alloy, and method and device for preparing same |
| WO2012099092A1 (en) * | 2011-01-21 | 2012-07-26 | Jx日鉱日石金属株式会社 | Method for producing high-purity lanthanum, high-purity lanthanum, sputtering target formed from high-purity lanthanum, and metal gate film having high-purity lanthanum as main component |
| CN102140656A (en) * | 2011-03-09 | 2011-08-03 | 赣州晨光稀土新材料股份有限公司 | Method for preparing Dy-Fe alloy through oxide molten salt electrolysis |
| JP2013197240A (en) * | 2012-03-19 | 2013-09-30 | Jx Nippon Mining & Metals Corp | Neodymium-iron-boron-based rare earth sintered magnet, and method of manufacturing the same |
| CN103820698A (en) * | 2014-03-11 | 2014-05-28 | 包头稀土研究院 | Rare earth iron intermediate alloy and application thereof |
| CN103924265A (en) * | 2014-04-28 | 2014-07-16 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Method for preparing rare-earth dysprosium alloy by molten salt electrolysis |
| CN103924266A (en) * | 2014-04-28 | 2014-07-16 | 包头稀土研究院 | Method for preparing rare earth-gadolinium alloy by adopting co-deposition method |
| CN105624737A (en) * | 2015-12-31 | 2016-06-01 | 包头稀土研究院 | Method for preparing rare earth magnesium alloy and yttrium-neodymium magnesium alloy |
Non-Patent Citations (1)
| Title |
|---|
| 石富."稀土冶金".《稀土冶金》.内蒙古大学出版社,1994,第363-364页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113430579B (en) | 2023-07-14 |
| CN106757170A (en) | 2017-05-31 |
| CN113430579A (en) | 2021-09-24 |
| CN113481545A (en) | 2021-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113046789B (en) | Preparation method of rare earth iron alloy | |
| CN111411372B (en) | Preparation method of rare earth iron alloy | |
| CN107312937B (en) | method and equipment for manufacturing high-silicon stainless steel for high-temperature-resistant concentrated sulfuric acid | |
| CN105624737B (en) | A kind of method for preparing magnesium-rare earth and rare-earth yttrium neodymium magnesium alloy | |
| CN113481545B (en) | Lanthanum-iron alloy | |
| CN109280842B (en) | Microalloyed high-silicon-manganese nitrogen-containing austenitic stainless steel material and preparation method thereof | |
| CN106834889A (en) | Cerium-iron alloy and preparation method thereof | |
| CN103924266A (en) | Method for preparing rare earth-gadolinium alloy by adopting co-deposition method | |
| US20230265547A1 (en) | Nickel-Based Superalloy Steel And Preparation Method Thereof | |
| CN113279018B (en) | Use of praseodymium neodymium iron alloy in rare earth steel | |
| Mimura et al. | Purification of chromium by hydrogen plasma-arc zone melting | |
| CN106834890A (en) | Lanthanum cerium-iron alloy and preparation method thereof for producing rare earth steel | |
| CN113279020B (en) | Preparation method of praseodymium-iron alloy | |
| CN106811644A (en) | Neodymium-iron alloy and preparation method thereof | |
| CN109852881B (en) | Steel for 45CrNiMoVA drill tool and production method thereof | |
| CN113046609A (en) | Yttrium iron alloy | |
| CN1724715A (en) | Method of preparing aluminium-iron base alloy in electrolytic tank using iron and its alloy as anode | |
| CN110117746B (en) | Manufacturing method of high-performance non-magnetic stainless steel | |
| CN110846515A (en) | Preparation method of nickel-based alloy 690 with ultralow gas content | |
| Block et al. | Electrodeposition of High‐Purity Chromium | |
| CN106884074B (en) | Method for controlling hairline defect of steel for high-temperature bolt | |
| Ryabchikov et al. | Concerning the Production and Application of Ferroalloys with REM and AEM for Steel Modification and Microalloying | |
| Liu et al. | Direct Alloying of Silicon in Liquid Steel by Molten Slag Electrolysis | |
| CN116904883A (en) | Age hardening type plastic die steel and preparation method thereof | |
| CN111705182A (en) | Method for manufacturing 15-5PH rare earth martensitic stainless steel |
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 |