CN1485466A - Process of electricity sedimentation in aqueous solution for producing rare earth magnetic film alloy material - Google Patents
Process of electricity sedimentation in aqueous solution for producing rare earth magnetic film alloy material Download PDFInfo
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- CN1485466A CN1485466A CNA021396485A CN02139648A CN1485466A CN 1485466 A CN1485466 A CN 1485466A CN A021396485 A CNA021396485 A CN A021396485A CN 02139648 A CN02139648 A CN 02139648A CN 1485466 A CN1485466 A CN 1485466A
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Abstract
The electroplating solution of the invention comprises rare earth chloride, FeCl2, complexe agent, additive I, II, CaCl2. The process comprises, an inert anode or transition metal anode or two anodes; introducing pure argon or nitrogen to dispel oxygen, the whole electroplating process conducting in the protective environment of pure argon or nitrogen, the working current density is 20mA/cm2-200mA/cm2, the time is 15min-48hours, the temperature is 0-70degree C, taking out of the electroplated members, washing ,drying and sealing; placing the electroplated film in the protective environment of pure argon or nitrogen, heating at 700-800 degree C for 15min-20hours, sealing and storing. The electroplating solution is stable and has a wide range of working conditions. The rare earth alloy has more than 11% of rare earth.
Description
Technical field
The present invention relates to the aqueous solution electrodeposition method and produce the technology of rare earth permanent magnet thin film alloys material.
Background technology
The alloy material of rare earth metal and transition-metal Fe, Co, Ni is the extraordinary magneticsubstance of a class, at Aeronautics and Astronautics, automobile, electrical equipment, computer, communication, in control and the military affairs purposes is very widely arranged all automatically.The technology that is used for preparing this type of material at present has: 1, melt-quenching method; promptly be prepared into mother alloy with vacuum induction melting method; in vacuum quick quenching equipment; under the protection of inert gas; in silica tube, mother alloy is melted; under the argon pressure effect, alloy solution is mapped on the copper roller of high speed rotating, with 10 through the nozzle of silica tube bottom
5～10
6℃/speed of s is rapidly solidificated into amorphous, again through thermal treatment, forms the nano-crystal composite permanent magnetic strip.2, hydrogenation disproportionation dehydrogenation recombination method: alloy is broken into meal → vacuum oven hydrogen treatment → hydrogenation disproportionation reaction → hydrogen is extracted out → be combined to rare earth permanent magnet powder with fine particle.These method processing condition and parameter request are quite harsh.3, mechanical alloying method: with the constituent element element is raw material, utilizes planetary ball mill to grind, and makes it to take place at low temperatures solid state reaction, and then obtains required alloy or compound.This method shortcoming is: the micropowders that makes can not contact with air, otherwise oxidation and spontaneous combustion very easily, the technology harshness.4, vacuum system embrane method comprises high-frequency sputtering, vacuum-evaporation, magnetron sputtering.All these methods all are to be raw material with pure metal rare earth simple substance and pure transition metal, the starting material costliness, and it is big to add facility investment, and therefore, the price of this class material is very expensive.As being used to make the magnetic recording material of the read-write magneto-optic disk of 430M memory size, commercially available price is more than 200 yuan.About the alloy of aqueous solution electrodeposition method production rare earth and transition metal, existing patent documentation report (seeing Patent:WO99/18265).This report in, only provided mishmetal La, Ce, Nd respectively with Fe, Co, Ni galvanic deposit situation.And Sm, the Dy, the Gd that are commonly used to do rare earth permanent-magnetic material do not appear in the newspapers.And in the alloy of Nd and Fe, the percentage composition major part of Nd is 3.4% (mass percent), and maximum only 7.5% can not satisfy the requirement of producing permanent magnet material.And the not mentioned magneticsubstance of this patent documentation is made.
Summary of the invention
The objective of the invention is, propose a kind of aqueous solution electrodeposition method and produce the technology of rare-earth magnetic thin film alloys material, it is a raw material with cheap rare earth oxide or muriate, prepare the magneticthin film alloy material of rare earth transition alloy, utilize this production technique, can greatly reduce the cost of this series products, boost productivity, satisfy the requirement of the electronics, computer, information industry of develop rapidly this series products.
Technical scheme of the present invention is that the technology that described aqueous solution electrodeposition method is produced rare-earth magnetic thin film alloys material comprises:
1. adopt the electrolytic solution of following component:
Rare earth chloride 0.2-0.6mol/L
FeCl
2 0.05-0.20mol/L
Complexing agent 0.5-1.5mol/L
Additive I 0.01-0.2g/200ml
CaCl
2 0.2-1.0mol/L
H
3BO
3 0.1-0.5mol/L
Additive II 0.01-0.2g/200ml
Described rare earth chloride is the muriate of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy;
Described complexing agent is glycine, nitrilotriacetic acid(NTA), trolamine, ammonia oxalic acid, any of citric acid, tartrate, sulfosalicylic acid, oxyacetic acid, glycol acid or wantonly two kinds mixing acid;
Described additive I is any among polyoxyethylene glycol, dextran, gelatin, OP, EDTA, poly amic acid, the KI;
Described additive II is ammoniacal liquor+H
3BO
3, N.F,USP MANNITOL+H
3BO
3, benzylamine+H
3BO
3, xylidine+NaBH
4, benzylamine+NaBH
4, methyl alcohol+NaBH
4In any, (ammoniacal liquor: the H for example of the former with the latter in every kind of additive II component
3BO
3) weight ratio be 2-4: 1;
The pH value of described aqueous electrolysis liquid is 1-6.5;
2. electrode: the anode as the galvanic deposit substrate material adopts inert anode or magnesium-yttrium-transition metal anode, or the double anode of being made up of inert anode and magnesium-yttrium-transition metal anode;
3. electroplate: plating piece is put into electroplate liquid, feed high-purity argon gas in the electroplate liquid or nitrogen carries out deoxygenation, and whole plating carries out in the protective atmosphere of high-purity argon gas or nitrogen, working current density is 20mA/cm
2-200mA/cm
2, the time is 15 minutes-48 hours, temperature is 0--70 ℃, has plated the back and take out plating piece under electriferous state, washes, dries up, seals;
4. thermal treatment: will electroplate the protective atmosphere that good noncrystal membrane places high-purity argon gas or nitrogen, and heat-treat under 700--800 ℃ of temperature, 15 minutes-20 hours time, sealing is afterwards preserved.
Below the present invention made further specify.
Technology utilization rare earth oxide of the present invention and transition metal, add suitable complexing agent and additive again, can go out the non-crystaline amorphous metal of rare earth and transition metal at aqueous solution electrodeposition, by suitable thermal treatment, amorphous can be changed into nanocrystalline, thereby make the magneticthin film alloy material.
Described rare earth chloride can be that the oxide compound of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy makes with dissolving with hydrochloric acid; Described inert anode can be graphite, Ti.Pt alloy; And FeCl
2Can generate by iron powder and hydrochloric acid reaction.
The present invention has studied the influence of related process factor to product, and existing division is as follows.
(1) influence of .PH value: see Fig. 1;
(2). the influence of current density: see Fig. 2;
(3). the influence of additive I: in plating bath, add a small amount of trolamine, polyoxyethylene glycol, dextran, gelatin, OP, EDTA, KI, poly amic acid, all improve the content (see figure 3) of coating middle-weight rare earths to some extent.Simultaneously also can the refinement particle, improve the homogeneity (see figure 4) of coating.It is an amount of that the add-on of additive is wanted, and Fig. 5 and Fig. 6 are respectively to having taken the influence to coating middle-weight rare earths content of gelatin consumption and polyoxyethylene glycol consumption out of.
(4). add other metal ion influence: add other codeposition metal ion on a small quantity in plating bath, found that, the adding of a small amount of Ti, Cu, Ni will significantly increase the content (seeing Fig. 7 A) of coating middle-weight rare earths.Fig. 7 B has gone through the situation of the add-on of Ti in the plating bath to coating middle-weight rare earths content influence.
(5). the influence of additive II: additive II (comprises ammoniacal liquor+H
3BO
3, methyl alcohol+sodium borohydride, N.F,USP MANNITOL+H
3BO
3, benzylamine+boric acid, xylidine+NaBH
4, benzylamine+NaBH
4) Fig. 8 A, Fig. 8 B are seen in the influence of the content of B in the coating and rare earth.The result shows that the adding of additive II greatly improves the content of B in the coating, also can increase the content of coating middle-weight rare earths simultaneously.
(6) .O
2Influence: before the plating, electroplate liquid must lead to high-purity Ar or N
2Remove, remove O
2Fully, whole electroplanting device is in high-purity Ar or high-purity N
2In the atmosphere, avoid the oxidation of rare earth.
(7). the XRD figure of coating: be shown in Fig. 9, as known in the figure, shown typical amorphous.Figure 10 shows before the coating thermal treatment metallograph of (b) behind (a) and thermal treatment.
By technology of the present invention, comprise the electroplate liquid and the electroplating technical conditions of the specific components that employing is developed through the present invention, having obtained granular size is about 20nm, Sm, Nd content surpass the non-crystalline state coating of 11% (mass ratio); After thermal treatment, test its permanent magnetism performance, its Bs=2 * 10
4Gs, Hc=1600Oe, Mr=1 * 10
4Gs.The result has realized the two-phase coupling as can be known, can be used as the starting material of producing magneto-optic memory technique fully.
Technology of the present invention is simple, and it is easy to control to form component and thickness, and technology is simple, automatization easy to operate, easy, and starting material are mainly rare earth oxide or salt, and cost reduces greatly.
The electroplating solution of technology of the present invention is stable, the processing condition wide ranges, and in the amorphous rare earth alloy of gained, content of rare earth can reach more than 11%, coating surface light flawless, after Overheating Treatment, be transformed into nanocrystallinely, the magnetic property after the crystallization obviously is better than amorphous rare earth alloy.
Description of drawings
Fig. 1 be in the electrolytic solution pH value to the influence of Sm content in coating relation;
Fig. 2 is the influence relation of current density to Sm content in the coating, and wherein stain is that the concentration of glycine is that 0.33mol/ rises gained, and the concentration that empty circle is a glycine is that 0.84mol/ rises gained;
Fig. 3 is the influence of additive to Sm content in the coating, among the figure transverse axis from left to right add that the black bar is followed successively by not doping, adds trolamine, polyoxyethylene glycol, dextran, gelatin, OP, polyoxyethylene glycol+OP, EDTA, KI, poly amic acid be to the influence of coating middle-weight rare earths content;
Fig. 4 is the sem photograph of reflection associated additives energy refinement particle, raising coating uniformity;
Fig. 5 adds the influence of gelatin to Sm content in the coating;
Fig. 6 adds the influence of polyoxyethylene glycol to Sm content in the coating;
Fig. 7 A is the influence of added metal to Sm content in the coating;
Fig. 7 B adds the influence of Ti to Sm content in the coating;
Fig. 8 A is the influence of additive to B content in the coating;
Fig. 8 B is the influence of additive to Nd content in the coating;
Fig. 9 is the X-ray diffractogram of one group of non-crystalline state iron-based alloy;
Figure 10 is the metallograph of (b) after (a) and the thermal treatment before the coating thermal treatment;
Figure 11 is the magnetic tester performance map of coating.
Embodiment
Embodiment 1: preparation Nd-Fe-B alloy
Plating bath: 0.08mFeCl
2+ 0.8m glycine+0.5mNdCl
3+ 0.8mCaCl
2+ H
3BO
3(0.5ml+ benzylamine 10.857g), PH=6.0, D=2500A/m
2, T=30 ℃
Coating component: weight ratio Fe%=87.46, Nd=11.5%, B%=1.04
Coating testing method: with 1: behind the 1HCl dissolved samples, be decided to be 50ml, content with aas determination Fe, measure the content of Nd and B respectively with spectrophotometry, the coating of gained is heat-treated, material after the thermal treatment is measured its magnetic property with vibrating sample magnetometer, and it the results are shown in Figure 11.As can be known, the Bs of this material is 2 * 10
4Gs.Br=Hc is 1600Oe, is the superior permanent magnet film material of magnetic property.
Embodiment 2: another group electroplate liquid component is FeCl
2(0.08m)+glycine (0.9m)+CaCl
2(0.8m)+RE (0.5m) (Sm, Nd etc.)+Macrogol 2000 0 (or: OP, bright acid, dextran, KI, poly amic acid), H
3BO
3(0.5m)+benzylamine (or mannitic acid, ammoniacal liquor, xylidine).
Embodiment 3: technological process
1. the preparation of solution
Starting material: rare earth oxide+hydrochloric acid or rare earth chloride, Fe powder+HCl or iron protochloride, complexing agent, CaCl
2, additive I, H
3BO
3, additive II.
Process for preparation is as follows:
Solution A: rare earth oxide with dissolving with hydrochloric acid after, add the part complexing agent again.
Solution B: the transition metal chloride dissolving adds another part complexing agent.
Solution C: solution A adds CaCl again with after solution B is mixed
2And H
3BO
3
Transferring pH value is 1～6.5
Solution D: solution C+additive I+ additive II.
Transferring PH again is 1～6.5
2. galvanic deposit
Electrode: anode inert anode, magnesium-yttrium-transition metal anode or double anode, anode is the substrate material of galvanic deposit.
Plating piece is handled:
Brass: polishing → HCl etch → water washes → dries up.
Aluminium flake: oil removing (Na
1OH+Na
2CO
3+ Na
3PO
4) → etch (H
2SO
4+ CrO
3) → bright dipping (nitric acid) → pre-plating → Direct Electroplating.
Stainless steel: anode electrolysis oil removing → hot water wash → cold wash → pickling → cold wash → flash nickel → cold wash → dry up.
3. plating
Plating piece is put into electroplate liquid after treatment, is 20mA/cm in current density
2～200mA/cm
2Following plating, whole electroplanting device places argon gas (or high-purity N
2) in the protection, after having plated, under electriferous state, take out the plating sheet, wash, dry up, seal.
4. thermal treatment
Electroplating the film that comes out is noncrystal membrane, at high-purity argon gas (or N
2) protect down, to heat-treat, thermal treatment temp is 700 ℃～800 ℃, and heat treatment time is 15 minutes to 20 hours, and after finishing, sealing is preserved.
More excellent operational condition is: 30 ℃, current density is 20mA/cm
2, PH is 6.0, double anode (inert anode+soluble anode).
Claims (3)
1. an aqueous solution electrodeposition method is produced the technology of rare-earth magnetic thin film alloys material, it is characterized in that it comprises:
(1). adopt the electrolytic solution of following component:
Rare earth chloride 0.2-0.6mol/L
FeCl
2 0.05-0.20mol/L
Complexing agent 0.5-1.5mol/L
Additive I 0.01-0.2g/200ml
CaCl
2 0.2-1.0mol/L
H
3BO
3 0.1-0.5mol/L
Additive II 0.01-0.2g/200ml
Described rare earth chloride is the muriate of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy;
Described complexing agent is glycine, nitrilotriacetic acid(NTA), trolamine, ammonia oxalic acid, any ground or wantonly two kinds mixing acid of citric acid, tartrate, sulfosalicylic acid, oxyacetic acid, glycol acid;
Described additive I is any among polyoxyethylene glycol, dextran, gelatin, OP, EDTA, poly amic acid, the KI;
Described additive II is ammoniacal liquor+H
3BO
3, N.F,USP MANNITOL+H
3BO
3, benzylamine+H
3BO
3, xylidine+NaBH
4, benzylamine+NaBH
4, methyl alcohol+NaBH
4In any, the weight ratio of the former with the latter is 2-4 in every kind of additive II component: 1;
The pH value of described aqueous electrolysis liquid is 1-6.5;
(2). electrode: adopt inert anode or magnesium-yttrium-transition metal anode as the anode of galvanic deposit substrate material, or the double anode of forming by inert anode and magnesium-yttrium-transition metal anode;
(3). electroplate: plating piece is put into electroplate liquid, feed high-purity argon gas in the electroplate liquid or nitrogen carries out deoxygenation, and whole plating carries out in the protective atmosphere of high-purity argon gas or nitrogen, working current density is 20mA/cm
2-200mA/cm
2, the time is 15 minutes-48 hours, temperature is 0--70 ℃, has plated the back and take out plating piece under electriferous state, washes, dries up, seals;
(4). thermal treatment: will electroplate the protective atmosphere that good noncrystal membrane places high-purity argon gas or nitrogen, and heat-treat under 700--800 ℃ of temperature, 15 minutes-20 hours time, sealing is afterwards preserved.
2. aqueous solution electrodeposition method according to claim 1 is produced the technology of rare-earth magnetic thin film alloys material, it is characterized in that, described rare earth chloride is got with dissolving with hydrochloric acid by the oxide compound of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy.
3. aqueous solution electrodeposition method according to claim 1 is produced the technology of rare-earth magnetic thin film alloys material, it is characterized in that FeCl
2Generate by iron powder and hydrochloric acid reaction.
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|---|---|---|---|
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| CN1217035C CN1217035C (en) | 2005-08-31 |
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| CN103617884A (en) * | 2013-12-11 | 2014-03-05 | 北京科技大学 | Heavy rear earth adhering method of sintered NdFeB magnet |
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| CN1300382C (en) * | 2004-04-12 | 2007-02-14 | 昆明理工大学 | Steel components and parts covered by Zn-Fe-RE cladding material, electroplating method and electrolyte |
| CN102400191A (en) * | 2011-11-22 | 2012-04-04 | 沈阳理工大学 | Method for preparing Sm-Fe (samarium-ferrum) alloy magnetic thin film under intense magnetic field |
| CN102400191B (en) * | 2011-11-22 | 2014-04-09 | 沈阳理工大学 | Method for preparing Sm-Fe (samarium-ferrum) alloy magnetic thin film under intense magnetic field |
| CN105112973A (en) * | 2013-09-03 | 2015-12-02 | 天津大学 | Preparation method of citric acid-doped cerium conversion film |
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| CN107268031B (en) * | 2016-03-31 | 2019-06-07 | 蔚山大学产学合作部 | The electrochemistry recovery method of heavy rare earth metalloid |
| CN107268031A (en) * | 2016-03-31 | 2017-10-20 | 蔚山大学产学合作部 | The electrochemistry recovery method of heavy rare earth metalloid |
| JP2017193750A (en) * | 2016-04-20 | 2017-10-26 | 株式会社Ｊｃｕ | Electroplating bath for forming porous cylindrical iron group element plating film and method for forming porous cylindrical iron group element plating film using the same |
| CN107460505B (en) * | 2017-08-23 | 2019-02-12 | 河北工业大学 | The preparation method of Tb-Fe-Co ternary RE alloy magnetic nanometer film |
| CN107460505A (en) * | 2017-08-23 | 2017-12-12 | 河北工业大学 | The preparation method of Tb Fe Co ternary RE alloy magnetic nanometer films |
| CN108660487A (en) * | 2018-06-05 | 2018-10-16 | 河北工业大学 | The preparation method of Nd-Fe-B Magnetic Nanowire Arrays |
| CN108914174A (en) * | 2018-08-07 | 2018-11-30 | 河北工业大学 | The preparation method of Tb-Dy-Fe-Co alloy Magnetic nano-pipe array |
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| CN111705332B (en) * | 2020-05-20 | 2021-07-20 | 上海应用技术大学 | Simple electrodeposited Co-Ce/NF electrode material and preparation and application thereof |
| CN112481666A (en) * | 2020-10-26 | 2021-03-12 | 中国计量大学 | Samarium-iron-cobalt-phosphorus amorphous film and preparation method thereof |
| WO2022267384A1 (en) * | 2021-06-23 | 2022-12-29 | 中国科学院深圳先进技术研究院 | Fe-ni-p alloy electroplating solution, electro-deposition method for fe-ni-p alloy coating, and alloy coating |
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