CN104894623A - Multi-phase composite magnetic nano-wire array and preparation method thereof - Google Patents
Multi-phase composite magnetic nano-wire array and preparation method thereof Download PDFInfo
- Publication number
- CN104894623A CN104894623A CN201510199123.7A CN201510199123A CN104894623A CN 104894623 A CN104894623 A CN 104894623A CN 201510199123 A CN201510199123 A CN 201510199123A CN 104894623 A CN104894623 A CN 104894623A
- Authority
- CN
- China
- Prior art keywords
- electroplate liquid
- preparation
- nano
- composite magnetic
- wire array
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002070 nanowire Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910017061 Fe Co Inorganic materials 0.000 claims abstract description 67
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000004070 electrodeposition Methods 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000009713 electroplating Methods 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 82
- 239000000243 solution Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- 239000005030 aluminium foil Substances 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 239000004471 Glycine Substances 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 7
- 239000003292 glue Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000000151 deposition Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002288 cocrystallisation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- VMXUWOKSQNHOCA-UKTHLTGXSA-N ranitidine Chemical compound [O-][N+](=O)\C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-UKTHLTGXSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910002546 FeCo Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The present invention relates to a multi-phase composite magnetic nano-wire array and a preparation method thereof. According to the preparation method, an electric conduction glue for an AAO template with a gold-sprayed back surface and a Cu sheet are adhered to form a composite cathode, graphite with a smooth and clean surface is adopted as an anode, electrochemical deposition is alternately performed in a Fe-Co electroplating solution and a Sm-Co electroplating solution after the cathode and the anode are connected to a power supply so as to form nano-wires on the template, and the nano-wires in the template are subjected to annealing crystallization so as to obtain the multi-phase composite magnetic nano-wire array . Compared with the multi-phase composite magnetic nano-wire array in the prior art, the multi-phase composite magnetic nano-wire array prepared by the method of the present invention has characteristics of high length-diameter ratio, large coercive force and excellent magnetic anisotropy, can be used for high-density perpendicular magnetic recording medium, and is further a sensor element and electromagnetic device material having wide prospects.
Description
Technical field
The present invention relates to the preparation method of Magnetic Nanowire Arrays, especially relate to a kind of electro-deposition preparation method of heterogeneous composite magnetic nano wire.
Background technology
In recent decades, along with information technology develop rapidly, as the material carrier-electronic devices and components of information just progressively towards the future development of microminiaturized densification.Meanwhile, storing device then constantly will improve storage space, and requires to have the advantages that energy consumption is low, efficiency is high.These both increase requirement high-performance being stored to magneticsubstance undoubtedly.One-dimensional magnetic nano wire, owing to having the features such as the magneticanisotropy of height, high susceptibility and high-coercive force, low saturation magnetic moment and low magnetic consumption, has application prospect widely in super-high density vertical storage, sensor.At present, the system being commonly used to do nano magnetic material has rare earth permanent magnet and transition metal permanent magnetism etc.Rare-earth system has excellent magnetic characteristics but limits the development space of this system due to the high and expensive raw material price of its coercive force temperature coefficient; Transition metal systems is of a great variety, and between different system, magnetic property difference is also comparatively large, and the comprehensive magnetic of its single phase nano line can not be very good.
After Kneller in 1991 proposes the physical thought of nanocomposite permanent magnets first, multi-phase compound permanent-magnet material receives the extensive attention of scientific worker and has carried out large quantity research.High but the soft magnetism phase that coercive force is little of saturation magnetization and the large but Hard Magnetic phase that Ms is low of coercive force is generally comprised in compound system, then certain technique is utilized to be combined with each other, particularly two-phase intercrystalline there is ferromagnetic exchange coupling and the dimension of each phase in nanometer range time, just may integrant high performance permanent magnetic materials.The technique preparing multi-phase compound permanent-magnet material conventional at present has quick quenching technique, mechanical alloying method, vacuum masking method, discharge plasma sintering method etc.But these methods obviously and be not suitable for preparing one-dimensional nano-composite material, as quick quenching technique, discharge plasma sintering and mechanical alloying method often prepare block, band or powder; Vacuum masking method such as magnetron sputtering is commonly used to prepare single-phase or heterogeneous two-dimensional film.With regard to the preparation technology of one-dimensional nano line, the technique of development comparative maturity is template.
Wang Xuehua etc. (Wang Xuehua, oldly returns, Cai Peng, Fu Ping, Li Chengyong, Yang Liang, Cao Hong. material engineering .2002,13:79-82) in AAO template, deposit the FeCo alloy nano-wire even thickness that obtains and orientation is better.Publication number is the preparation method that the Chinese invention patent of CN101016650A discloses a kind of high square ratio magnetic one-dimensional nano line array, utilizes porous alumina to carry out the Fe nano wire that electrochemical deposition obtains high squareness ratio for template.These researchs obtaining single phase nano line by single preparation technology are more, and about the research of heterogeneous composite Nano linear array, being especially reported in domestic and international periodical rarely has and seeing of iron family element ting and the heterogeneous composite nano-line of rare earth element.Publication number is that the Chinese invention patent of CN103128305A discloses a kind of method preparing Ag/Co magnetic nanometer composite material, with Ag nano wire for substrate template, Co salt is that precursor adopts two-step synthesis method to obtain the Ag/Co magnetic composite nano line of one dimension, and its preparation technology there is pollution and structural stability is poor.
Summary of the invention
Object of the present invention is exactly provide that a kind of length-to-diameter ratio is high, magneticanisotropy is excellent and heterogeneous composite magnetic nano-wire array that coercive force is large and preparation method thereof to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
A kind of preparation method of heterogeneous composite magnetic nano-wire array, comprise the following steps: boning with back side metal spraying AAO template conductive resin and Cu sheet is formed composite cathode, using the clean graphite of surfacing as anode, after composite cathode and anode are switched on power, alternately in Fe-Co electroplate liquid and Sm-Co electroplate liquid, carry out electrochemical deposition, template forms nano wire, then Annealing Crystallization is carried out to the nano wire in template, obtain heterogeneous composite magnetic nano-wire array.
Described Fe-Co electroplate liquid moiety is: the CoSO of 0.1 ~ 0.3mol/L
4.7H
2the FeSO of O, 0.15 ~ 0.2mol/L
4.7H
2o, the Na of additive composition 0.6 ~ 0.8mol/L
2sO
4, the xitix of 0.05 ~ 0.1mol/L and the H of 0.4 ~ 0.5mol/L
3bO
3.
When carrying out electrochemical deposition in Fe-Co electroplate liquid, add buffer reagent regulator solution pH in described Fe-Co electroplate liquid between 3-4, Fe-Co temperature of electroplating solution is 45-55 DEG C, and current density is at 30mA/cm
2~ 50mA/cm
2between.
Described Sm-Co bath components consists of: the SmCl of 0.2 ~ 0.4mol/L
3with the CoCl of 0.05 ~ 0.1mol/L
2and additive; Wherein solution ratio ensures atomic ratio Sm:Co=4:1, and described additive comprises 0.1 ~ 0.2mol/L boric acid, 0.06 ~ 0.12mol/L xitix and 0.08 ~ 0.16mol/L glycine.The acting as of additive prevents that ion is oxidized, reaction is too violent and regulate codeposition current potential.
When carrying out electrochemical deposition in Sm-Co electroplate liquid, add buffer reagent regulator solution pH in described Sm-Co electroplate liquid between 2-3, Sm-Co temperature of electroplating solution is room temperature, and current density is at 20mA/cm
2~ 40mA/cm
2between.
When carrying out electrochemical deposition, galvanic deposition cell put into by anode graphite and composite cathode, and composite cathode and anode are parallel relative and spacing is 2-3cm.Because solution temperature required when two-phase deposits is different, so need to prepare different water bath.When alternately carrying out electrochemical deposition in Fe-Co electroplate liquid and Sm-Co electroplate liquid, adopt following steps:
(1) in Fe-Co electroplate liquid, 80-100s is deposited, to induce the formation of follow-up Sm-Co nano wire;
(2) Fe-Co electroplate liquid is poured out rapidly subsequently, Sm-Co electroplate liquid is poured into after being rinsed well by electrolyzer with deionized water, in Sm-Co electroplate liquid, deposit 20-30s, again Sm-Co electroplate liquid is changed to Fe-Co electroplate liquid afterwards, then deposit 50-60s in Fe-Co electroplate liquid;
(3) circulation step (2) 20-40 time, until nano wire covers with form plate hole.
Because the Sm-Co nano wire of deposited is non-crystalline state, magnetic property is poor, needs to carry out anneal with the Hard Magnetic phase impelling Sm-Co crystallization to obtain magnetic property excellence to the nano wire in template for this reason.During Annealing Crystallization, annealing temperature selects 500-550 DEG C, and ensures rate of heating≤5 DEG C/min, and destroy the orientation of nano wire with the too fast and internal stress that is that produce of preventing from heating up, soaking time is 1 ~ 3 hour.
The preparation method of AAO template is: annealing aluminium foil is cut into disk and flattens, then it is put into successively acetone, the cleaning of dehydrated alcohol sonic oscillation is deoiled, aluminium foil deionized water after process of deoiling is rinsed well repeatedly, then removing aluminium foil surface zone of oxidation is soaked in alkali lye, after deionized water rinsing is clean, electrochemically carry out polishing, electrolytic solution select dehydrated alcohol and perchloric acid by volume 4:1 join, obtain the consistent AAO template of uniform pore diameter finally by twice oxidizing process; Back side metal spraying AAO template conductive resin and Cu sheet are bondd and forms combined electrode, be connected with power cathode.Anode is the clean graphite of surfacing, needs graphite to rinse 4-5 time with deionized water and dehydrated alcohol successively before connection.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, adopt the technique of alternating deposit to deposit Fe-Co phase and Sm-Co phase successively, control the ratio of each phase by control galvanic deposit parameter and depositing time and then ensure the stability of structure and composition; The control of electrochemical deposition temperature relies on the water bath changing plating tank to realize.
2, due to rare earth element Sm more difficult deposition in solution environmental, therefore first deposit Fe-Co alloy/C 80-100s when alternating deposit to induce the formation of follow-up Sm-Co nano wire, thus improve the deposition of Sm-Co phase.
3, the heterogeneous composite magnetic nano-wire array prepared of the inventive method, length-to-diameter ratio is high, coercive force is large, has excellent magneticanisotropy, can be used for high-density perpendicular magnetic recording medium; Also be simultaneously a kind of sensor element of having a extensive future and electromagnetic device material.
Accompanying drawing explanation
Fig. 1 is the SEM image of embodiment 1 gained Fe-Co/Sm-Co heterogeneous composite nano-line when covering with form plate hole;
Fig. 2 is the TEM image after utilizing NaOH solution to be dissociated by embodiment 1 gained nano wire;
Fig. 3 is gained XRD diffractogram after the heterogeneous composite nano-line of embodiment 3 gained Fe-Co/Sm-Co 550 DEG C annealing 2h.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The preparation of AAO template and electrode pre-treatment
Annealing aluminium foil is cut into the disk that diameter is 2cm and flattens, then it is put into acetone, dehydrated alcohol successively, use ultrasonic washing instrument oscillation cleaning 5min respectively, aluminium foil deionized water after process of deoiling is rinsed well repeatedly, then the NaOH solution putting into 10%wt soaks 15min, removing aluminium foil surface zone of oxidation.Put afterwards and rinse 20min with clear water under a tap, finally clean with deionized water rinsing.Electrochemical method carries out polishing, electrolytic solution select dehydrated alcohol and perchloric acid by volume 4:1 join.Technique finally by twice oxidation obtains the consistent template of uniform pore diameter.Back side metal spraying AAO template conductive resin and Cu sheet are bondd and forms combined electrode, be connected with power cathode.Anode is the clean graphite of surfacing, needs graphite to rinse 4-5 time with deionized water and dehydrated alcohol successively before connection.
First prepare Fe-Co electroplate liquid and Sm-Co electroplate liquid respectively, wherein Fe-Co electroplate liquid consists of the CoSO of 0.2mol/L
4.7H
2the FeSO of O, 0.15mol/L
4.7H
2the Na of O, 0.7mol/L
2sO
4, the xitix of 0.05mol/L and the H of 0.4mol/L
3bO
3.Sm-Co electroplate liquid consists of the SmCl of 0.2mol/L
3with the CoCl of 0.05mol/L
2and additive 0.2mol/L boric acid, 0.1mol/L xitix and 0.15mol/L glycine.Plating tank will be put in pretreated Electrode connection circuit, and then place it on magnetic stirring apparatus and start to carry out alternating deposit.First deposit Fe-Co alloy/C 100s, pour out rapidly Fe-Co electroplate liquid subsequently, after being rinsed well by electrolyzer with deionized water, pour Sm-Co electroplate liquid deposition 20s into, again Sm-Co electroplate liquid is changed to Fe-Co electroplate liquid deposition 50s afterwards, Posterior circle 30 times.Wherein when depositing Fe-Co, temperature of electroplating solution is 45 DEG C, and current density is 30mA/cm
2; Sm-Co temperature of electroplating solution is room temperature, and current density is 20mA/cm
2, template forms nano wire, then Annealing Crystallization is carried out to the nano wire in template, annealing temperature 500 DEG C, soaking time 2h, obtain the heterogeneous composite nano-line of Fe-Co/Sm-Co.Now available nano wire length-to-diameter ratio can reach 100-130, and coercive force is about 2244Oe, and remanence ratic reaches 75%.
SEM image when the heterogeneous composite nano-line of the present embodiment Fe-Co/Sm-Co covers with form plate hole as shown in Figure 1, as can be seen from the figure the nano wire that the AAO template of " cellular " has been deposited state filled, and surface is for consistent nano wire cross section, aperture and be evenly distributed between nano wire.The process of post-depositional template NaOH solution can be realized one-dimensional nano line and observe its pattern with the SEM that is separated and then utilizes of template, the TEM image after utilizing NaOH solution to be dissociated by nano wire as shown in Figure 2.Clearly can see in figure and being separated from each other between nano wire, obvious Cluster Phenomenon does not occur, and its length is about 4-5 μm, has larger length-to-diameter ratio.Analyzing its reason is due to Fe
7co
3the introducing of phase compensate for the large deficiency of Sm-Co phase fragility, and then the length-to-diameter ratio of biphase line is increased substantially.
Embodiment 2
First prepare Fe-Co electroplate liquid and Sm-Co electroplate liquid respectively, wherein Fe-Co electroplate liquid consists of the CoSO of 0.2mol/L
4.7H
2the FeSO of O, 0.15mol/L
4.7H
2the Na of O, 0.7mol/L
2sO
4, the xitix of 0.05mol/L and the H of 0.4mol/L
3bO
3.Sm-Co electroplate liquid consists of the SmCl of 0.2mol/L
3with the CoCl of 0.05mol/L
2and binder component is 0.1mol/L boric acid, 0.12mol/L xitix and 0.16mol/L glycine.Plating tank will be put in pretreated Electrode connection circuit, and then place it on magnetic stirring apparatus and start to carry out alternating deposit.First deposit Fe-Co alloy/C 80s, pour out rapidly Fe-Co electroplate liquid subsequently, after being rinsed well by electrolyzer with deionized water, pour Sm-Co electroplate liquid deposition 30s into, again Sm-Co electroplate liquid is changed to Fe-Co electroplate liquid deposition 60s afterwards, Posterior circle 30 times.Wherein when depositing Fe-Co, temperature of electroplating solution is 50 DEG C, and current density is 40mA/cm
2; Sm-Co temperature of electroplating solution is room temperature, and current density is 20mA/cm
2.Annealing Crystallization is carried out to the nano wire of deposited in template, annealing temperature 550 DEG C, soaking time 1h, obtain the heterogeneous composite nano-line of Fe-Co/Sm-Co.The nano wire length-to-diameter ratio now obtained reaches 120-150, and coercive force is about 2656Oe, remanence ratic nearly 85%.
Embodiment 3
First prepare Fe-Co and Sm-Co electroplate liquid respectively, wherein Fe-Co plating solution consists of the CoSO of 0.2mol/L
4.7H
2the FeSO of O, 0.15mol/L
4.7H
2the Na of O, 0.7mol/L
2sO
4, the xitix of 0.05mol/L and the H of 0.4mol/L
3bO
3.Sm-Co electroplate liquid consists of the SmCl of 0.2mol/L
3with the CoCl of 0.05mol/L
2and binder component is 0.1mol/L boric acid, 0.12mol/L xitix and 0.16mol/L glycine.Plating tank will be put in pretreated Electrode connection circuit, and then place it on magnetic stirring apparatus and start to carry out alternating deposit.First deposit Fe-Co alloy/C 80s, pour out rapidly Fe-Co electroplate liquid subsequently, after being rinsed well by electrolyzer with deionized water, pour Sm-Co electroplate liquid deposition 30s into, again Sm-Co electroplate liquid is changed to Fe-Co electroplate liquid deposition 60s afterwards, Posterior circle 30 times.Wherein when depositing Fe-Co, temperature of electroplating solution is 55 DEG C, and current density is 50mA/cm
2; Sm-Co temperature of electroplating solution is room temperature, and current density is 30mA/cm
2.Annealing Crystallization is carried out to the nano wire of deposited in template, annealing temperature 550 DEG C, soaking time 2h, obtain the heterogeneous composite nano-line of Fe-Co/Sm-Co.The nano wire length-to-diameter ratio now obtained reaches 80-100, and coercive force is about 2021Oe remanence ratic nearly 70%.
The heterogeneous composite nano-line of Fe-Co/Sm-Co 550 DEG C annealing 2h after gained XRD diffractogram as shown in Figure 3, the thing after can obviously finding out Annealing Crystallization in figure mutually in there is SmCo
5phase and Sm
2co
17phase, and Fe-Co corresponding be Fe
7co
3phase, and then achieve the two-phase compound in nano wire after alternating deposit and anneal are described.The most obvious Al in XRD diffracting spectrum
2o
3peak is because the reason of AAO template produces.
Embodiment 4
A kind of preparation method of heterogeneous composite magnetic nano-wire array, comprise the following steps: boning with back side metal spraying AAO template conductive resin and Cu sheet is formed composite cathode, using the clean graphite of surfacing as anode, after composite cathode and anode are switched on power, alternately in Fe-Co electroplate liquid and Sm-Co electroplate liquid, carry out electrochemical deposition, template forms nano wire, then Annealing Crystallization is carried out to the nano wire in template, obtain heterogeneous composite magnetic nano-wire array.
Wherein, the preparation method of AAO template is: annealing aluminium foil is cut into disk and flattens, then it is put into successively acetone, the cleaning of dehydrated alcohol sonic oscillation is deoiled, aluminium foil deionized water after process of deoiling is rinsed well repeatedly, then removing aluminium foil surface zone of oxidation is soaked in alkali lye, after deionized water rinsing is clean, electrochemically carry out polishing, electrolytic solution select dehydrated alcohol and perchloric acid by volume 4:1 join, obtain the consistent AAO template of uniform pore diameter finally by twice oxidizing process; Back side metal spraying AAO template conductive resin and Cu sheet are bondd and forms combined electrode, be connected with power cathode.Anode is the clean graphite of surfacing, needs graphite to rinse 4 times with deionized water and dehydrated alcohol successively before connection.
Fe-Co electroplate liquid moiety is: the CoSO of 0.1mol/L
4.7H
2the FeSO of O, 0.15mol/L
4.7H
2o, the Na of additive composition 0.6mol/L
2sO
4, the xitix of 0.05mol/L and the H of 0.4mol/L
3bO
3.When carrying out electrochemical deposition in Fe-Co electroplate liquid, to add buffer reagent regulator solution pH in Fe-Co electroplate liquid be 3, Fe-Co temperature of electroplating solution is 45 DEG C, and current density is 30mA/cm
2.
Sm-Co bath components consists of: the SmCl of 0.2mol/L
3with the CoCl of 0.05mol/L
2and additive; Wherein solution ratio ensures atomic ratio Sm:Co=4:1, and additive comprises 0.1mol/L boric acid, 0.06mol/L xitix and 0.08mol/L glycine.The acting as of additive prevents that ion is oxidized, reaction is too violent and regulate codeposition current potential.When carrying out electrochemical deposition in Sm-Co electroplate liquid, to add buffer reagent regulator solution pH in described Sm-Co electroplate liquid be 2, Sm-Co temperature of electroplating solution is room temperature, and current density is 20mA/cm
2.
When carrying out electrochemical deposition, galvanic deposition cell put into by anode graphite and composite cathode, and composite cathode and anode are parallel relative and spacing is 2cm.Because solution temperature required when two-phase deposits is different, so need to prepare different water bath.When alternately carrying out electrochemical deposition in Fe-Co electroplate liquid and Sm-Co electroplate liquid, adopt following steps:
(1) in Fe-Co electroplate liquid, 80s is deposited, to induce the formation of follow-up Sm-Co nano wire;
(2) Fe-Co electroplate liquid is poured out rapidly subsequently, Sm-Co electroplate liquid is poured into after being rinsed well by electrolyzer with deionized water, in Sm-Co electroplate liquid, deposit 20s, again Sm-Co electroplate liquid is changed to Fe-Co electroplate liquid afterwards, then deposit 50s in Fe-Co electroplate liquid;
(3) circulation step (2) 20 times, until nano wire covers with form plate hole.
Because the Sm-Co nano wire of deposited is non-crystalline state, magnetic property is poor, needs to carry out anneal with the Hard Magnetic phase impelling Sm-Co crystallization to obtain magnetic property excellence to the nano wire in template for this reason.During Annealing Crystallization, annealing temperature selects 500 DEG C, and ensures rate of heating≤5 DEG C/min, and destroy the orientation of nano wire with the too fast and internal stress that is that produce of preventing from heating up, soaking time is 3 hours.
Embodiment 5
A kind of preparation method of heterogeneous composite magnetic nano-wire array, comprise the following steps: boning with back side metal spraying AAO template conductive resin and Cu sheet is formed composite cathode, using the clean graphite of surfacing as anode, after composite cathode and anode are switched on power, alternately in Fe-Co electroplate liquid and Sm-Co electroplate liquid, carry out electrochemical deposition, template forms nano wire, then Annealing Crystallization is carried out to the nano wire in template, obtain heterogeneous composite magnetic nano-wire array.
Wherein, the preparation method of AAO template is: annealing aluminium foil is cut into disk and flattens, then it is put into successively acetone, the cleaning of dehydrated alcohol sonic oscillation is deoiled, aluminium foil deionized water after process of deoiling is rinsed well repeatedly, then removing aluminium foil surface zone of oxidation is soaked in alkali lye, after deionized water rinsing is clean, electrochemically carry out polishing, electrolytic solution select dehydrated alcohol and perchloric acid by volume 4:1 join, obtain the consistent AAO template of uniform pore diameter finally by twice oxidizing process; Back side metal spraying AAO template conductive resin and Cu sheet are bondd and forms combined electrode, be connected with power cathode.Anode is the clean graphite of surfacing, needs graphite to rinse 5 times with deionized water and dehydrated alcohol successively before connection.
Fe-Co electroplate liquid moiety is: the CoSO of 0.3mol/L
4.7H
2the FeSO of O, 0.2mol/L
4.7H
2o, the Na of additive composition 0.8mol/L
2sO
4, the xitix of 0.1mol/L and the H of 0.5mol/L
3bO
3.When carrying out electrochemical deposition in Fe-Co electroplate liquid, to add buffer reagent regulator solution pH in Fe-Co electroplate liquid be 4, Fe-Co temperature of electroplating solution is 55 DEG C, and current density is 50mA/cm
2.
Sm-Co bath components consists of: the SmCl of 0.4mol/L
3with the CoCl of 0.1mol/L
2and additive; Wherein solution ratio ensures atomic ratio Sm:Co=4:1, and additive comprises 0.2mol/L boric acid, 0.12mol/L xitix and 0.16mol/L glycine.The acting as of additive prevents that ion is oxidized, reaction is too violent and regulate codeposition current potential.When carrying out electrochemical deposition in Sm-Co electroplate liquid, to add buffer reagent regulator solution pH in described Sm-Co electroplate liquid be 3, Sm-Co temperature of electroplating solution is room temperature, and current density is 40mA/cm
2.
When carrying out electrochemical deposition, galvanic deposition cell put into by anode graphite and composite cathode, and composite cathode and anode are parallel relative and spacing is 3cm.Because solution temperature required when two-phase deposits is different, so need to prepare different water bath.When alternately carrying out electrochemical deposition in Fe-Co electroplate liquid and Sm-Co electroplate liquid, adopt following steps:
(1) in Fe-Co electroplate liquid, 100s is deposited, to induce the formation of follow-up Sm-Co nano wire;
(2) Fe-Co electroplate liquid is poured out rapidly subsequently, Sm-Co electroplate liquid is poured into after being rinsed well by electrolyzer with deionized water, in Sm-Co electroplate liquid, deposit 30s, again Sm-Co electroplate liquid is changed to Fe-Co electroplate liquid afterwards, then deposit 60s in Fe-Co electroplate liquid;
(3) circulation step (2) 40 times, until nano wire covers with form plate hole.
Because the Sm-Co nano wire of deposited is non-crystalline state, magnetic property is poor, needs to carry out anneal with the Hard Magnetic phase impelling Sm-Co crystallization to obtain magnetic property excellence to the nano wire in template for this reason.During Annealing Crystallization, annealing temperature selects 550 DEG C, and ensures rate of heating≤5 DEG C/min, and destroy the orientation of nano wire with the too fast and internal stress that is that produce of preventing from heating up, soaking time is 1 hour.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. a preparation method for heterogeneous composite magnetic nano-wire array, is characterized in that, comprise the following steps:
Bond with back side metal spraying AAO template conductive resin and Cu sheet and formed composite cathode, using the clean graphite of surfacing as anode, after composite cathode and anode are switched on power, alternately in Fe-Co electroplate liquid and Sm-Co electroplate liquid, carry out electrochemical deposition, template forms nano wire, again Annealing Crystallization is carried out to the nano wire in template, obtain heterogeneous composite magnetic nano-wire array.
2. the preparation method of a kind of heterogeneous composite magnetic nano-wire array according to claim 1, is characterized in that, described Fe-Co electroplate liquid moiety is: the CoSO of 0.1 ~ 0.3mol/L
4.7H
2the FeSO of O, 0.15 ~ 0.2mol/L
4.7H
2o, the Na of additive composition 0.6 ~ 0.8mol/L
2sO
4, the xitix of 0.05 ~ 0.1mol/L and the H of 0.4 ~ 0.5mol/L
3bO
3.
3. the preparation method of a kind of heterogeneous composite magnetic nano-wire array according to claim 1, it is characterized in that, when carrying out electrochemical deposition in Fe-Co electroplate liquid, buffer reagent regulator solution pH is added between 3-4 in described Fe-Co electroplate liquid, Fe-Co temperature of electroplating solution is 45-55 DEG C, and current density is at 30mA/cm
2~ 50mA/cm
2between.
4. the preparation method of a kind of heterogeneous composite magnetic nano-wire array according to claim 1, it is characterized in that, described Sm-Co bath components consists of: the SmCl of 0.2 ~ 0.4mol/L
3with the CoCl of 0.05 ~ 0.1mol/L
2and additive; Wherein solution ratio ensures atomic ratio Sm:Co=4:1, and described additive comprises 0.1 ~ 0.2mol/L boric acid, 0.06 ~ 0.12mol/L xitix and 0.08 ~ 0.16mol/L glycine.
5. the preparation method of a kind of heterogeneous composite magnetic nano-wire array according to claim 1, it is characterized in that, when carrying out electrochemical deposition in Sm-Co electroplate liquid, buffer reagent regulator solution pH is added between 2-3 in described Sm-Co electroplate liquid, Sm-Co temperature of electroplating solution is room temperature, and current density is at 20mA/cm
2~ 40mA/cm
2between.
6. the preparation method of a kind of heterogeneous composite magnetic nano-wire array according to claim 1, is characterized in that, when alternately carrying out electrochemical deposition in Fe-Co electroplate liquid and Sm-Co electroplate liquid, adopts following steps:
(1) in Fe-Co electroplate liquid, 80-100s is deposited, to induce the formation of follow-up Sm-Co nano wire;
(2) in Sm-Co electroplate liquid, deposit 20-30s, in Fe-Co electroplate liquid, deposit 50-60s more afterwards;
(3) circulation step (2) 20-40 time, until nano wire covers with form plate hole.
7. the preparation method of a kind of heterogeneous composite magnetic nano-wire array according to claim 1, is characterized in that, during Annealing Crystallization, annealing temperature selects 500-550 DEG C, and ensures rate of heating≤5 DEG C/min, and soaking time is 1 ~ 3 hour.
8. the preparation method of a kind of heterogeneous composite magnetic nano-wire array according to claim 1, it is characterized in that, the preparation method of AAO template is:
Annealing aluminium foil is cut into disk and flattens, then it is put into successively acetone, the cleaning of dehydrated alcohol sonic oscillation is deoiled, aluminium foil deionized water after process of deoiling is rinsed well repeatedly, then removing aluminium foil surface zone of oxidation is soaked in alkali lye, after deionized water rinsing is clean, electrochemically carry out polishing, obtain the consistent AAO template of uniform pore diameter finally by twice oxidizing process;
During polished finish, electrolytic solution select dehydrated alcohol and perchloric acid by volume 4:1 join.
9. the preparation method of a kind of heterogeneous composite magnetic nano-wire array according to claim 1, is characterized in that, when carrying out electrochemical deposition, composite cathode and anode are parallel relative and spacing is 2-3cm.
10. the heterogeneous composite magnetic nano-wire array adopting method described in claim 1 to prepare.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510199123.7A CN104894623B (en) | 2015-04-23 | 2015-04-23 | A kind of multiphase composite magnetic nano-wire array and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510199123.7A CN104894623B (en) | 2015-04-23 | 2015-04-23 | A kind of multiphase composite magnetic nano-wire array and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104894623A true CN104894623A (en) | 2015-09-09 |
| CN104894623B CN104894623B (en) | 2017-04-05 |
Family
ID=54027566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510199123.7A Expired - Fee Related CN104894623B (en) | 2015-04-23 | 2015-04-23 | A kind of multiphase composite magnetic nano-wire array and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104894623B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112481666A (en) * | 2020-10-26 | 2021-03-12 | 中国计量大学 | Samarium-iron-cobalt-phosphorus amorphous film and preparation method thereof |
| CN112481665A (en) * | 2020-10-26 | 2021-03-12 | 中国计量大学 | Samarium-iron-cobalt film electroplating solution and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030189475A1 (en) * | 2002-04-09 | 2003-10-09 | The Electrodyne Company, Inc. | Bonded permanent magnets |
| CN103586465A (en) * | 2013-11-12 | 2014-02-19 | 河北工业大学 | Method for preparing Sm-Co based magnetic nano-material |
| CN104087976A (en) * | 2014-07-02 | 2014-10-08 | 河北工业大学 | Preparation method of Sm-Co alloy amorphous magnetic nanowire array |
-
2015
- 2015-04-23 CN CN201510199123.7A patent/CN104894623B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030189475A1 (en) * | 2002-04-09 | 2003-10-09 | The Electrodyne Company, Inc. | Bonded permanent magnets |
| CN103586465A (en) * | 2013-11-12 | 2014-02-19 | 河北工业大学 | Method for preparing Sm-Co based magnetic nano-material |
| CN104087976A (en) * | 2014-07-02 | 2014-10-08 | 河北工业大学 | Preparation method of Sm-Co alloy amorphous magnetic nanowire array |
Non-Patent Citations (1)
| Title |
|---|
| WEIYANG: "Fabrication and magnetic properties of Sm2Co17 and Sm2Co17/Fe7Co3 magnetic nanowires via AAO templates", 《JOURNAL OF CRYSTAL GROWTH》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112481666A (en) * | 2020-10-26 | 2021-03-12 | 中国计量大学 | Samarium-iron-cobalt-phosphorus amorphous film and preparation method thereof |
| CN112481665A (en) * | 2020-10-26 | 2021-03-12 | 中国计量大学 | Samarium-iron-cobalt film electroplating solution and preparation method thereof |
| CN112481665B (en) * | 2020-10-26 | 2021-08-17 | 中国计量大学 | Samarium-iron-cobalt film electroplating solution and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104894623B (en) | 2017-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107142503B (en) | A kind of Fe-Ni-P or Fe-Ni-P-RE amorphous alloy coating and its electro-deposition plating solution and electro-deposition method | |
| CN102108511A (en) | Electroplating and chemical plating composite protecting process for NdFeB permanent magnet and NdFeB permanent magnet with composite protective layer | |
| CN1838244A (en) | Soft magnetic thin film and magnetic recording head | |
| CN103898574A (en) | Electroplating Fe-Ni alloy magnetic shielding material and preparation method thereof | |
| WO2015085687A1 (en) | Heavy rare earth attachment method for sintered ndfeb magnet | |
| US20160053396A1 (en) | Fe-ni-p-re multicomponent alloy plating layer, and electrodeposition preparation method and application thereof | |
| CN100449038C (en) | Process for preparing invor alloy foil | |
| CN103060803B (en) | Method for preparing composite coating at surface of neodymium iron boron permanent magnet | |
| CN104936379A (en) | Fabrication method for embedding magnetic core induction of printed circuit board | |
| CN104894623A (en) | Multi-phase composite magnetic nano-wire array and preparation method thereof | |
| CN218666353U (en) | Protective layer structure of neodymium iron boron application graphite alkene electrophoresis lacquer | |
| CN101255580A (en) | Nd-added nd-fe-b permanent-magnetic material electroplating fluid and method of use thereof | |
| CN101593523B (en) | Method for preparing L10 type ultrahigh density magnetic record metal thin film | |
| Flynn et al. | Influence of pulse reverse plating on the properties of Ni-Fe thin films | |
| CN102545401B (en) | Permanent magnet member for voice coil motor and voice coil motor | |
| CN108660487A (en) | The preparation method of Nd-Fe-B Magnetic Nanowire Arrays | |
| CN109023446A (en) | A kind of method of neodymium-iron boron permanent magnetic material electroplating copper | |
| CN102416483B (en) | Method for preparing double-phase composite samarium cobalt-iron powder | |
| CN111926366B (en) | Sintered neodymium-iron-boron magnet surface corrosion-resistant coating and preparation method thereof | |
| JP2001250707A (en) | Permanent magnet material | |
| CN102568744B (en) | Composite permanent magnetic film and preparation method thereof | |
| CN112837884A (en) | Electroplated layer structure for improving fracture force of sintered neodymium-iron-boron sheet magnet and preparation method | |
| CN1862725B (en) | Chemical deposition of fine magnetic element and electrochemical deposition manufacturing method and system | |
| CN107460505A (en) | The preparation method of Tb Fe Co ternary RE alloy magnetic nanometer films | |
| Lim et al. | Soft-solution process of Fe–Tb–O films for use in high frequency micromagnetic devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170405 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |