WO2007107054A1 - Procédé de préparation d'un film de ferrite à partir de composés anioniques laminés - Google Patents

Procédé de préparation d'un film de ferrite à partir de composés anioniques laminés Download PDF

Info

Publication number
WO2007107054A1
WO2007107054A1 PCT/CN2006/001079 CN2006001079W WO2007107054A1 WO 2007107054 A1 WO2007107054 A1 WO 2007107054A1 CN 2006001079 W CN2006001079 W CN 2006001079W WO 2007107054 A1 WO2007107054 A1 WO 2007107054A1
Authority
WO
WIPO (PCT)
Prior art keywords
ldhs
film
prepared
suspension
solution
Prior art date
Application number
PCT/CN2006/001079
Other languages
English (en)
Chinese (zh)
Inventor
Lan Yang
Yingchao Zhang
Xue Duan
Lie Yin
Original Assignee
Beijing University Of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University Of Chemical Technology filed Critical Beijing University Of Chemical Technology
Publication of WO2007107054A1 publication Critical patent/WO2007107054A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

  • the invention belongs to the technical field of preparation of ferrite films, and in particular provides a method for preparing a ferrite film from an anionic layered compound. Background technique
  • Ferrite materials due to their magnetic, electrical properties, high chemical stability and high mechanical strength, are used in various magnetic cores for multi-channel communication and television, as well as recording heads for recording and video recording, magnetic memory for electronic computers. Core, ultrasonic and hydroacoustic devices as well as telecommunications, self-control, magneto-acoustic and metrology devices, as well as a variety of microwave devices in radar, communications, navigation, telemetry, remote control plasma devices.
  • soft magnetic ferrite film materials can also be used as pH electrodes, sensors for water, oxygen and urea, and hydrogenation catalysts.
  • the precursor solution is mostly a metal alkoxide and a citrate sol and a metal organic solution.
  • REvan de Leest et al. utilize metal alcohol.
  • a Ni-Zn ferrite film was prepared on a thermally oxidized silicon substrate by a sol-gel method using a salt as a precursor; in Thin Solid Films, 1999, 339: 109-113, Fuxiang Cheng et al. used citric acid chelation.
  • Predecessor A sol-gel method was used to prepare a Co ferrite film on a single crystal silicon substrate. Due to the high cost and low variety of metal alkoxide and metal organic precursors, the preparation of coating sintering methods accounts for a very small proportion in many ferrite film research reports. It is therefore imperative to seek new precursors to prepare a variety of ferrite film materials to meet the needs of high-tech development.
  • the spinel ferrite is prepared from the layered precursor LDHs. Due to the lowest lattice effect of the LDHs and the lattice localization effect, the metal ions and interlayer anions on the layer are evenly distributed in a certain way, that is, in the LDHs. In each structural unit, the chemical composition is unchanged, so that after calcination, a ferrite material having a uniform composition and a structural hook can be obtained. Summary of the invention
  • An object of the present invention is to provide a method for preparing a ferrite film from an anionic layered compound, which solves the drawbacks of the conventional ferrite film precursor prepared by the conventional coating sintering method, which is small in variety and expensive.
  • the invention adopts coating technology
  • the suspension was coated on a substrate to prepare
  • the composite film is then dried and solidified, and finally baked at a high temperature to obtain a dense granular ferrite film (please refer to FIG. 1 together).
  • the process steps are as follows:
  • Formulation a salt solution in which a molar concentration ratio of a divalent metal ion to a trivalent Fe ion [M 2+ ]/[Fe 3+ ] is 1 to 5, and An n is N0 3 -, S0 4 2 — or Cr;
  • the preparation of the LDHs suspension slurry may preferably be carried out by one of the following two methods: (1) preparing a mixed salt solution of M (A"') 2/ and Fe (A"") 3/n with deionized water, wherein The molar concentration ratio of the divalent metal ion to the trivalent Fe ion [M 2+ ]/[Fe 3+ ] is 1 to 5, and the A n - may
  • M"Fe m LDHs powder at 60 ⁇ 110 nm; the prepared M"Fe m LDHs powder is added to the deionized water solution, and the weight ratio of M"Fe"'LDHs powder to water is 1:30 ⁇ 60, ultrasonic dispersion for about l-2h, centrifugation to discard the precipitate, add adhesive in the M II Fe , I, LDHs centrifugation solution to obtain M"Fe m LDHs suspension;
  • a tackifier may be selectively added to adjust the viscosity of the suspension
  • the suspension prepared in the step a is applied onto a substrate, and then dried and solidified at a temperature of 10 - 10 CTC to obtain a dry coating film of LDHs, and the coating amount is > 20 g / m 2 ;
  • the dry coating film prepared in the step b is placed in a muffle furnace, and is heated at a temperature of about 1 to 10 ° C / min to be sintered at a temperature of 900 to 1200 ° C for 1 to 4 hours, and then about 1 hour.
  • the M (iI) Fe ( 0 2+ ( ⁇ ( ⁇ ) ) in the ii0 LDH S represents a divalent metal ion Mg 2+ , Zn 2 , ⁇ Co 2 '., Ni 2+ , Fe 2+ , Mn 2+ And any one of Cu 2+ , preferably Zn 2+ or Mg 2+ ;
  • the molar ratio of M 2+ /Fe 3 (Fe (m) ) is preferably 1.6 to 4.5:1, preferably molar The ratio is 2 ⁇ 4: 1.
  • the adhesive is one or a mixture of one or more of polyalcohol, polyamide, polyester, etc.; preferably polyvinyl alcohol; the adhesive may be added in an appropriate amount as needed, for example: the concentration of the adhesive is 1 to 5%, Its added volume and The volume ratio of the centrate or suspension can be 0.2 3:1.
  • the tackifier is preferably one or a mixture of polyethylene glycol, glycerin, carboxymethyl cellulose, phthalamide, and the tackifier may be added in an appropriate amount as needed, such as in a liquid form, The volume of addition can be about /40 ⁇ 1/10 times the total solution volume.
  • the substrate is an alumina ceramic substrate, a monocrystalline silicon wafer, a quartz substrate, a stainless steel substrate; preferably an alumina ceramic substrate.
  • the substrate should be cleaned in advance, and the cleaning agent may be one or more selected from the group consisting of detergent, acetone, ethanol, and deionized water; more preferably, acetone, ethanol, and deionized water are used for ultrasonic cleaning.
  • the cleaning agent may be one or more selected from the group consisting of detergent, acetone, ethanol, and deionized water; more preferably, acetone, ethanol, and deionized water are used for ultrasonic cleaning.
  • the invention has the advantages that: the method provided is a layered precursor method, and the conversion of LDHs to ferrite film materials is achieved by calcination using LDHs with a simple price, a simple synthesis process, and a structural component controllable as a starting material. A series of ferrite film materials with uniform particle dispersion, compactness, micron thickness and good adhesion are obtained. Using the characteristics of the type and quantity of divalent and trivalent metal ions in the LDHs laminate and the high dispersion between the divalent and trivalent metal ions, and evenly distributed on the main layer, can be based on the expected compound properties. To design the molecular structure of LDHs, a series of ferrite film materials with various functional properties were prepared. DRAWINGS
  • FIG. 1 is a schematic view showing a preparation process of a ferrite film according to the present invention.
  • Figure 2 is an XRD chart of an alumina substrate in Example 1 of the present invention.
  • Fig. 3 is an XRD chart of the powder of Ni-FeCO 3 LDHs in Example 1 of the present invention.
  • 4 is an XRD chart of a Ni-FeCO 3 LDHs film in Example 1 of the present invention.
  • Figure 5 is an XRD chart of a NiO/NiFe 2 0 4 film in Example 1 of the present invention.
  • Figure 6 is a SEM photograph of an alumina substrate in Example 1 of the present invention.
  • Figure 7 is a SEM photograph of a Ni-Fe C0 3 LDHs composite film in Example 1 of the present invention.
  • Figure 8 is a SEM photograph of a NiO NiFe 2 0 4 film in Example 1 of the present invention.
  • Figure 9 is a cross-sectional SEM photograph of a NiO NiFe 2 0 4 film in Example 1 of the present invention. detailed description
  • the prepared suspension was ultrasonicated for 10 minutes to make the composition distribution more uniform.
  • the film was prepared on the cleaned ct-Al 2 0 3 substrate (substrate) by coating technique and dried at room temperature for 72 hours.
  • the substrate cleaning was carried out using an acetone-deionized water-ethanol cleaning method. From the XRD in Fig. 4, it can be seen that in addition to the diffraction peak of the alumina matrix (please refer to Fig. 2), the (003) and (006) diffraction peaks unique to LDHs appear, combined with the SEM in Fig. 7, It is considered that a Ni-FeCO 3 LDHs/polyvinyl alcohol composite film is obtained.
  • the dried film was slowly heated at a temperature rise of rC/min for sintering, and kept at 900 ° C for 2 h, after which the temperature drop rate was controlled to 1.
  • the condition of C/min was cooled to 500 ° C, and then the furnace was cooled to cool down to the room temperature. From the comparison of Fig. 6 and Fig. 8, it can be considered that a dense and uniform particle film is successfully prepared on the alumina substrate. From the XRD pattern of the film of Fig. 5, the NiO/NiFe 2 0 4 composite film can be judged.
  • the cross-sectional SEM image of the film of Fig. 9 shows that the film thickness is about 1.8 M m.
  • Ni-FeCO 3 LDHs suspension was mixed with a 4% polyvinyl alcohol solution at a volume ratio of 1: 2, and a 1.5% aqueous solution of carboxymethyl cellulose was added as a tackifier in an amount of 5% of the total volume of the solution. After that, it can be further ultrasonically dispersed and homogenized to obtain a suspension of Ni-FeC0 3 LDHs, and a Ni-FeC0 3 LDHs/polyvinyl alcohol composite film is prepared on the already cleaned ct-Al 2 0 3 substrate by a coating technique. Dry at room temperature for 72 h.
  • Example 3 Sintering was carried out by the same operation as in Example 1, and a non-stoichiometric granular ferrite film (NiO/NiFe 2 0 4 film) having a thickness of micron order, dense and uniform was obtained.
  • a non-stoichiometric granular ferrite film NiO/NiFe 2 0 4 film having a thickness of micron order, dense and uniform was obtained.
  • Example 4 A stable suspension of Ni-FeCO 3 LDHs was prepared under the same conditions as in Example 1. A non-stoichiometric granular ferrite film having a thickness of micron order, dense and uniform was prepared by coating technique on the cleaned quartz substrate. Example 4
  • Example 5 A stable suspension of Ni-FeCO 3 LDHs was prepared under the same conditions as in Example 1.
  • Mg (N0 3 ) 2 and Fe (N0 3 ) 3 mixed salt solution with deionized water, wherein the concentration of metal ions is Mg: 0.8 molar, Fe: 0.4 molar; another sodium hydroxide and anhydrous carbonic acid are prepared.
  • the LDHs powder with a particle size of 60 ⁇ 100 nm can be obtained by crystallization for 6 hours at C.
  • the dried film is slowly heated at a heating rate of about rC/min for sintering, and incubated at 1 10 (TC for 2 h, then the controlled cooling rate is about rC/min, and slowly returns to room temperature.
  • the thickness can be obtained in the order of micrometer. , a dense, uniform non-stoichiometric granular ferrite film (MgO/MgFe 2 0 4 film).
  • the prepared suspension was prepared by coating technique on the cleaned ot-Al 2 0 3 substrate, and dried at room temperature for 24 hours.
  • the substrate was cleaned by acetone-deionized water-ethanol cleaning.
  • Example 7 The dried film was slowly heated at a temperature rise of 5 ° C / min for sintering, and kept at 1 10 CTC for 2 h, and then slowly returned to room temperature as the furnace was cooled.
  • a non-stoichiometric granular ferrite film having a thickness of micron, dense and uniform can be obtained.
  • the ZnFeS0 4 LDHs suspension was prepared under the same conditions as in Example 1, and then an LDHs/polyvinyl alcohol composite film was prepared on the alumina substrate by a coating method, and dried for 72 hours, and then sintered under the same conditions as in Example 1.
  • a micron-sized, dense, uniform, non-stoichiometric granular ferrite film (ZnO/ZnFe 2 0 4 film) is available.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Iron (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Chemically Coating (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'un film de ferrite à partir de composés anioniques laminés. Ledit procédé consistant: à former un coulis de MIIFeIIILDHs en tant que précurseur de revêtement d'un substrat pour obtenir le film; à sécher et faire durcir le film, et finalement à le calciner à haute température pour obtenir le produit final. Ledit film d'épaisseur micrométrique, de particules denses et uniformément dispersées, a un excellent pouvoir adhésif, ses matériaux constitutifs sont peu onéreux, et son procédé de synthèse est simple. FIG.1: 1 poudres de LDHs 2 solvant 3 brassage, traitement par ultra-sons, adjonction d'additifs 4 coulis de LDHs 5 substrat 6 revêtement 7 membrane composite 8 séchage et frittage 9 film de ferrite
PCT/CN2006/001079 2006-03-17 2006-05-24 Procédé de préparation d'un film de ferrite à partir de composés anioniques laminés WO2007107054A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200610011513.8 2006-03-17
CNB2006100115138A CN100497249C (zh) 2006-03-17 2006-03-17 一种由阴离子型层状化合物制备铁氧体薄膜的方法

Publications (1)

Publication Number Publication Date
WO2007107054A1 true WO2007107054A1 (fr) 2007-09-27

Family

ID=36922768

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2006/001079 WO2007107054A1 (fr) 2006-03-17 2006-05-24 Procédé de préparation d'un film de ferrite à partir de composés anioniques laminés

Country Status (2)

Country Link
CN (1) CN100497249C (fr)
WO (1) WO2007107054A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112275271A (zh) * 2020-10-20 2021-01-29 北京化工大学 水滑石浆料及其制备和结构化催化剂及其制备方法
CN114751460A (zh) * 2022-04-11 2022-07-15 北京化工大学 一种稀土铁氧体铁酸镥薄膜的溶胶凝胶制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100430132C (zh) * 2006-09-27 2008-11-05 北京化工大学 一种用于醇氧化反应合成水滑石薄膜催化剂的制备方法
CN101255556B (zh) * 2008-03-28 2010-06-16 北京化工大学 一种制备多孔氧化锌颗粒镶嵌复合薄膜的方法
CN104278231B (zh) * 2013-07-12 2017-02-15 中国科学院金属研究所 一种Ti68Zr32合金的热氧化阻氢方法
CN109336144A (zh) * 2018-11-14 2019-02-15 江苏隆昌化工有限公司 一种三氯化铝废水制备碳铝酸钙的方法
CN113070196B (zh) * 2021-03-01 2022-05-03 电子科技大学 一种改善旋转喷涂制备NiZn铁氧体薄膜性能的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4853294A (fr) * 1971-11-08 1973-07-26
JPH05221652A (ja) * 1992-02-10 1993-08-31 Nippon Steel Corp フェライトペースト及びその製造方法
CN1358691A (zh) * 2000-12-14 2002-07-17 北京化工大学 全返混液膜反应器及其在制备超细阴离子层状材料中的应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4853294A (fr) * 1971-11-08 1973-07-26
JPH05221652A (ja) * 1992-02-10 1993-08-31 Nippon Steel Corp フェライトペースト及びその製造方法
CN1358691A (zh) * 2000-12-14 2002-07-17 北京化工大学 全返混液膜反应器及其在制备超细阴离子层状材料中的应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112275271A (zh) * 2020-10-20 2021-01-29 北京化工大学 水滑石浆料及其制备和结构化催化剂及其制备方法
CN112275271B (zh) * 2020-10-20 2023-04-25 北京化工大学 水滑石浆料及其制备和结构化催化剂及其制备方法
CN114751460A (zh) * 2022-04-11 2022-07-15 北京化工大学 一种稀土铁氧体铁酸镥薄膜的溶胶凝胶制备方法

Also Published As

Publication number Publication date
CN1821169A (zh) 2006-08-23
CN100497249C (zh) 2009-06-10

Similar Documents

Publication Publication Date Title
CN102093045B (zh) 一种核壳结构钛酸钡-钡铁氧体复合粉体材料及制备方法
WO2007107054A1 (fr) Procédé de préparation d'un film de ferrite à partir de composés anioniques laminés
CN101857436B (zh) 一类铌酸钾钠基无铅压电陶瓷粉体的制备方法
CN107098700B (zh) 一种适用于直写打印的高固含量bmn悬浮液墨水及其制备方法
WO2004009233A1 (fr) Catalyseur a base solide nanometrique magnetique et son procede de preparation
WO2006128333A1 (fr) Matiere d'electrode d'oxyde de metal composite de type spinelle et procede de fabrication
CN114617298B (zh) 一种利用多卡耦合巨热效应的气溶胶发生系统和加热介质
WO2004011387A1 (fr) Procede de production d'un aimant en ferrite a partir d'un precurseur stratifie
CN113479918B (zh) 一种纳米球形α-氧化铝粉体制备方法
CN102241967A (zh) 三维有序大孔钙钛矿热致变色材料及其制备方法
CN102485692A (zh) 一种二维片状钡铁氧体的制备方法
CN101329921A (zh) 用于电磁吸波的铁氧体-镍复合粉体及制备方法
WO2006050648A1 (fr) Film hautement oriente d'hydroxydes doubles lamellaires metalliques, et son procede de preparation
CN101244931B (zh) 水滑石前驱法制备硅基体多孔铁氧体薄膜的制备方法
CN102863207B (zh) 一种单晶模板制备铁氧体薄膜的方法
CN102942361B (zh) 层状结构的钛铁钴酸铋陶瓷材料及其制备方法
CN101255556B (zh) 一种制备多孔氧化锌颗粒镶嵌复合薄膜的方法
Parikh et al. Recent progress in the synthesis of oxide films from liquid solutions
JP2002160924A (ja) 高周波用フェライト薄膜およびその製造方法
CN101462171B (zh) 一种纳米镍球的制法
Drmota et al. Synthesis of strontium hexaferrite nanoparticles prepared using co-precipitation method and microemulsion processing
CN101693622B (zh) 一种低温制备钡铁氧体的方法
CN110434326B (zh) 一种金属软磁粉体表面原位包覆锂铝氧化物绝缘层的方法
CN115070058A (zh) 一种抗氧化能力强的高结晶度高球形度钯粉的制备方法
CN113070196B (zh) 一种改善旋转喷涂制备NiZn铁氧体薄膜性能的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 06741967

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06741967

Country of ref document: EP

Kind code of ref document: A1