CN101234426A - Composite powder with nano Fe, Mo coating Si3N4 and preparation thereof - Google Patents

Composite powder with nano Fe, Mo coating Si3N4 and preparation thereof Download PDF

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CN101234426A
CN101234426A CNA2008100306670A CN200810030667A CN101234426A CN 101234426 A CN101234426 A CN 101234426A CN A2008100306670 A CNA2008100306670 A CN A2008100306670A CN 200810030667 A CN200810030667 A CN 200810030667A CN 101234426 A CN101234426 A CN 101234426A
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CN101234426B (en
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范景莲
银锐明
刘涛
田家敏
成会朝
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Central South University
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Abstract

The invention relates to a compound powder preparation method of a nanometer Fe, Mo coated with Si3N4 particles. A heterogeneous phase precipitation method is adopted to sediment Fe, Mo oxygen compounds on the surface of the Si3N4 particles, and the nanometer Fe, Mo coated with Si3N4 compound particle powder can be obtained through thermal reduction after filtering, drying and calcining. The method includes the following steps: preparing evenly-scattered Si3N4 suspension; preparing ferric salt solution, molybdate solution and alkaline solution; adding the ferric salt solution, molybdate solution and alkaline solution into the Si3N4 suspension under the condition of stirring and ultrasound; obtaining nanometer Fe, Mo coated with Si3N4 particle compound powder through repeatedly washing, filtering, drying, calcining in the air and thermal reduction. The quality ratio of Fe, Mo in the compound powder provided by the invention varies from 1 percent to 90 percent, and quality content of the Fe element between Fe element and Mo element can be adjusted from 1 percent to 99 percent and is coated evenly.

Description

Nanometer Fe, Mo coated Si 3N 4Composite powder of particle and preparation method thereof
Technical field
The present invention relates to nanometer Fe, Mo coated Si 3N 4Particle composite powder and preparation method thereof.
Background technology
Cermet had not only had high strength, the high rigidity of ceramic material as a kind of metal/ceramic composite but also had had advantages such as the toughness of metal material, machinability, became a main effective means of present material modification.In recent years, the technology of compound especially core-shell type nano material is risen, for brand-new road has been opened up in ceramic-metallic development.Metal and pottery are combined on nanoscale and the compound particle that constitutes in some way, can not only improve the performance of material effectively, and tend to produce many new excellent specific properties, as improve the stability of nano particle, regulate its optical property, magnetic performance, thermal property, electric property and surface-active and sensitivity characteristic, make it satisfy multiple specific demand, have higher using value.
Metal plays decisive role with the selection of ceramic phase to the cermet performance.Si 3N 4As a kind of refractory ceramics, than other refractory ceramics incomparable balanced advantage is arranged at high-temperature field, by comparison, the aluminium oxide ceramics heat shock resistance is poor, and intensity is low; The zirconia ceramics elevated temperature strength is low, and hardness is low; The bending strength of silicon carbide ceramics only reaches half of silicon nitride ceramics.Refractory metal Mo intensity is higher, toughness is relatively poor relatively, it is studied seldom mutually as ceramic-metallic metal, but performance of composites also depends on tissue, if high-melting point metal be on good terms with nano level size disperse be distributed in the ceramic matrix, the high strength that not only can keep material itself, also has good toughness, metal Fe compares with other metal, has medium fusing point and good intensity and toughness, and the solubility of refractory metal Mo (2617 ℃ of fusing points) in middle melting point metals Fe (1535 ℃ of fusing points) can reach 37.5%, Fe, Mo generates solid solution and can effectively improve ferritic hardness and improve austenitic hardenability significantly.Mo can make the high non-alloy iron and steel of intensity produce good toughness, and can further improve tensile strength and hardness.In addition, when molybdenum content surpassed certain proportion in the molybdenum-iron, its fusing point then can significantly rise.So, with Fe, Mo and Si 3N 4At the cermet of the compound preparation of nanoscale, can effectively improve the toughness of pottery, and can bear high temperature.Can be used to make the high strength that requires certain toughness, parts such as wear-resistant, high temperature resistant, have purposes widely in fields such as defence and military, Aero-Space, medical treatment, automobile engine, electronic components.
Summary of the invention
The object of the invention is: adopt nanometer technology, at the Si of nanometer or micron size 3N 4Particle surface evenly coats last layer nanometer Fe, Mo, in the composite particles between Fe, the Mo constituent content ratio adjustable, Si 3N 4Adjustable with the covering amount proportioning, coat thickness of thin layer and have controllability.
For achieving the above object, scheme of the present invention is:
Select Si 3N 4Powder, granular size are controlled between the 10nm-20um;
Use dispersant such as organic amine and salt thereof, surfactant, silane coupler, titanate coupling agent, polymer etc., add scope control in solute amount quality percentage composition 0.01-10% scope, ultrasonic wave and stirring obtain finely disseminated Si 3N 4Suspension.Obtain Si by adjusting ultrasonic intensity, mixing speed, the quantity of dispersant, aqueous ph value 3N 4The dispersion effect that suspension is best.
The final pH value that control iron salt solutions, molybdate and aqueous slkali add speed, solution is controlled at 6-12, so that the full and uniform reaction of solution, the iron of generation, molybdenum oxygen compound finally can evenly be coated on Si 3N 4Particle surface;
Adopt substep coating method, obtain nanometer Fe, Mo coated Si 3N 4Metal quality ratio content in the particle composite powder is up to 90%, and coating evenly.
Composite powder is placed in the iron container, and the high temperature thermal reduction obtains nanometer Fe, Mo coated Si 3N 4The composite powder of particle, reducing gas are H 2, CO, NH 3Or its mist, the recovery time is 1-9 hour, reduction temperature is in 500-1000 ℃ of scope.
The present invention has obtained preparation nanometer Fe, Mo coated Si 3N 4The composite powder method of particle adopts substep coating method, can obtain Fe, Mo coated Si 3N 4Metal and metallic compound quality can be regulated in the 0-100% scope up to Fe element mass content scope between 90%, Fe, the Mo element than content in the particle composite powder, and coat evenly.
The specific embodiment:
Embodiment 1:
(1) takes by weighing respectively big or small sheet α-Si about 15 gram 1u 3N 4Powder and 5ml gather diethanol 400, insert in one liter of deionized water solution; Powder, take by weighing 5 the gram FeSO 4.7H 2O, 5 gram (NH 4) 6Mo 7O 24.4H 2The poly-diethanol 400 of O and 5ml is inserted 1.5 liters of deionized water solutions; Prepare ammonia spirit by 0.25mol/L;
(2) mechanical agitation and ultrasonic oscillation Si 3N 4, FeSO 4.7H 2O, (NH 4) 6Mo 7O 24.4H 2O and poly-diethanol 400 mixture aqueous solutions slowly were added dropwise to the ammonia spirit for preparing after 20 minutes, stopped to drip when solution PH=11.5, and mechanical agitation and ultrasonic oscillation are continued until that this process finishes rear ten minutes;
(3) solution is filtered the sediment that obtains and add washed with de-ionized water, more after filtration, the number of occurrence at least three times is with the oven dry about 80 ℃ in air of gained sediment;
(4) with the 500 ℃ of calcinings 2 hours in air of gained sediment, obtain Fe, Mo oxide coated Si 3N 4Powder.
(5) with above-mentioned Fe, the Mo oxide coated Si of making 3N 4The composite particles powder is placed the iron container, pushes in the hydrogen reducing furnace and reduces, and its reducing process is:
Figure S2008100306670D00031
Acquisition nanometer Fe, Mo quality are coated Si 3N 4Particle powder, wherein to be about 12.6%, Fe element mass content between composite powder Fe, Mo element be 27% for Fe, Mo element mass content in composite powder.
Embodiment 2:
(1) takes by weighing respectively big or small sheet α-Si about 15 gram 1u 3N 4Powder and 5ml gather diethanol 400, insert in one liter of deionized water solution; Powder, take by weighing 10 the gram FeSO 4.7H 2O, 2 gram (NH 4) 6Mo 7O 24.4H 2The poly-diethanol 400 of O and 5ml is inserted 1.5 liters of deionized water solutions; Prepare ammonia spirit by 0.25mol/L;
(2) mechanical agitation and ultrasonic oscillation Si 3N 4, FeSO 4.7H 2O, (NH 4) 6Mo 7O 24.4H 2O and poly-diethanol 400 mixture aqueous solutions slowly were added dropwise to the ammonia spirit for preparing after 20 minutes, stopped to drip when solution PH=11.5, and mechanical agitation and ultrasonic oscillation are continued until that this process finishes rear ten minutes;
(3) solution is filtered the sediment that obtains and add washed with de-ionized water, more after filtration, the number of occurrence at least three times is with the oven dry about 80 ℃ in air of gained sediment;
(4) with the 500 ℃ of calcinings 2 hours in air of gained sediment, obtain Fe, Mo oxide coated Si 3N 4Powder.
(5) with above-mentioned Fe, the Mo oxide coated Si of making 3N 4The composite particles powder is placed the iron container, pushes in the hydrogen reducing furnace and reduces, and its reducing process is:
Figure S2008100306670D00032
Acquisition nanometer Fe, Mo quality are coated Si 3N 4Particle powder, wherein to be about 12.6%, Fe element mass content between composite powder Fe, Mo element be 96.7% for Fe, Mo element mass content in composite powder.
Embodiment 3:
(1) takes by weighing respectively big or small sheet α-Si about 15 gram 1u 3N 4Powder, take by weighing 5 the gram FeSO 4.7H 2O, 10 gram (NH 4) 6Mo 7O 24.4H 2The poly-diethanol 400 of O and 5ml is inserted 1.5 liters of deionized water solutions; Prepare ammonia spirit by 0.25mol/L;
(2) mechanical agitation and ultrasonic oscillation Si 3N 4, FeSO 4.7H 2O, (NH 4) 6Mo 7O 24.4H 2O and poly-diethanol 400 mixture aqueous solutions slowly were added dropwise to the ammonia spirit for preparing after 20 minutes, stopped to drip when solution PH=9, and mechanical agitation and ultrasonic oscillation are continued until that this process finishes rear ten minutes;
(3) solution is filtered the sediment that obtains and add washed with de-ionized water, more after filtration, the number of occurrence at least three times is with the oven dry about 80 ℃ in air of gained sediment;
(4) with the 500 ℃ of calcinings 2 hours in air of gained sediment, obtain Fe, Mo oxide coated Si 3N 4Powder.
(5) with the above-mentioned Fe that makes, Mo oxide coated Si 3N 4Composite particles powder, 5 gram FeSO 4.7H 2O, 10 gram (NH 4) 6Mo 7O 24Insert 1.5 liters of deionized water solutions with the poly-diethanol 400 of 5ml;
(6) the above-mentioned Fe that makes of mechanical agitation and ultrasonic oscillation 2O 3Coated Si 3N 4Composite particles powder solution slowly was added dropwise to ammonia spirit after 20 minutes, o'clock stopped in solution PH=8.8 dripping, and mechanical agitation and ultrasonic oscillation are continued until that this process finishes rear ten minutes;
(7) solution is filtered the sediment that obtains and add washed with de-ionized water, more after filtration, the number of occurrence at least three times is with the oven dry about 80 ℃ in air of gained sediment;
(8) repeat 15 times by (5), (6), (7) step;
(9) with the 500 ℃ of calcinings 2 hours in air of gained sediment, obtain high-load nanometer Fe, Mo oxide coated Si 3N 4Powder;
(10) with above-mentioned Fe, the Mo oxide coated Si of making 3N 4The composite particles powder is placed the iron container, pushes in the hydrogen reducing furnace and reduces, and its reducing process is:
Figure S2008100306670D00041
Acquisition nanometer Fe, Mo quality are coated Si 3N 4Particle powder, wherein Fe, Mo element mass content in composite powder are about 86%, Fe element mass content between composite powder Fe, Mo element and are about 15%.

Claims (5)

1. nanometer Fe, Mo coated Si 3N 4The composite powder of particle is characterized in that: the total ratio of Fe, Mo is Si 3N 4The 1%-90% of percentage by weight, Fe element mass content scope is 1-99% between Fe, the Mo.
2. a nanometer Fe as claimed in claim 1, Mo coated Si 3N 4The preparation method of particle composite powder is characterized in that may further comprise the steps:
(1) with Si 3N 4Add in the solution, under the condition of ultrasonic and stirring, obtain finely dispersed Si 3N 4Particle suspension liquid;
(2) under the condition of ultrasonic and stirring, dispersant is added the Si of step (1) preparation 3N 4In the suspension, dispersant is organic amine, organic amine salt, surfactant, silane coupler, titanate coupling agent or polymer, and addition is the 0.01-10% of solution quality;
(3) preparation divalence or ferric salt solution, molybdate, alkali salt solution;
(4) under ultrasonic and churned mechanically condition, iron salt solutions, water-soluble molybdate and aqueous slkali are added in the suspension of step (2) preparation, the pH value scope of control solution is 6-12, obtains nanometer Fe, the even coated Si of Mo oxygen compound 3N 4The composite particles of particle;
(5) composite particles solution filter or the supercentrifuge of preparation are separated, repeatedly cleaned, filter, oven dry is calcined 1-10h in 200 ℃ of-1000 ℃ of scopes in air, obtains nanometer Fe, Mo oxide coated Si 3N 4The composite powder of particle;
(6) step (5) system composite particles is added in the aqueous solution, under ultrasonic and churned mechanically condition, obtain finely dispersed suspension, obtain second layer nanometer Fe, the coating of Mo thin oxide layer by (2) (3) (4) (5) step then, repeatedly repeat, obtain the clad required thickness;
(7) composite powder of step (5) or (6) system is placed in the iron container, the high temperature thermal reduction obtains nanometer Fe, Mo coated Si 3N 4The composite powder of particle.
3. as requested 2 described preparation nanometer Fe, Mo coated Si 3N 4The method of particle is characterized in that: described Si 3N 4The powder particle size is between 10nm-20um.
4. 2 described preparation nanometer Fe, Mo coated Si as requested 3N 4The method of particle is characterized in that: the molysite of described divalence or trivalent is chloride, the sulfate, (NH of iron 4) 2SO 4.FeSO 4.6H 2O or oxalates; Described alkali salt is Na 2CO 3, NaHCO 3, NH 3.H 2O, NH 3HCO 3, NaOH, KOH, kHCO 3, or K 2CO 3
5. as requested 2 described preparation nanometer Fe, Mo coated Si 3N 4The method of particle composite powder is characterized in that: the described reducing gas of step (7) is H 2, CO, NH 3Or its mist, the recovery time is 1-9 hour, reduction temperature is in 500-1000 ℃ of scope.
CN2008100306670A 2008-02-22 2008-02-22 Preparation of composite powder with nano Fe, Mo coating Si3N4 Expired - Fee Related CN101234426B (en)

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Cited By (7)

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CN102145270A (en) * 2011-01-14 2011-08-10 银锐明 Nano Fe/Cr-coated Si3N4 powder and preparation method thereof
CN101805867B (en) * 2009-12-01 2012-11-21 中南大学 Si3N4-based metal ceramic and preparation method thereof
CN103003485A (en) * 2010-04-12 2013-03-27 塞罗斯有限公司 Method to clean a moistened soiled substrate with polymeric particles
CN104312096A (en) * 2013-10-11 2015-01-28 南亚塑胶工业股份有限公司 Inorganic filler with molybdenum compound coated on surface and application thereof
CN106925773A (en) * 2017-04-21 2017-07-07 深圳市创艺工业技术有限公司 A kind of 3D printing material with self-cleaning performance
CN113828770A (en) * 2021-09-17 2021-12-24 湖南工业大学 Nickel-reinforced particle composite powder with gradient structure and preparation method thereof
WO2022088151A1 (en) * 2020-10-31 2022-05-05 宁德时代新能源科技股份有限公司 Positive electrode active material and fabrication method therefor, secondary battery, battery module, battery pack, and apparatus

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CN101805867B (en) * 2009-12-01 2012-11-21 中南大学 Si3N4-based metal ceramic and preparation method thereof
CN103003485A (en) * 2010-04-12 2013-03-27 塞罗斯有限公司 Method to clean a moistened soiled substrate with polymeric particles
CN103003485B (en) * 2010-04-12 2016-04-20 塞罗斯有限公司 The method of moistening solid substrate is cleaned with polymer beads
CN102145270A (en) * 2011-01-14 2011-08-10 银锐明 Nano Fe/Cr-coated Si3N4 powder and preparation method thereof
CN104312096A (en) * 2013-10-11 2015-01-28 南亚塑胶工业股份有限公司 Inorganic filler with molybdenum compound coated on surface and application thereof
CN104312096B (en) * 2013-10-11 2018-07-17 南亚塑胶工业股份有限公司 Inorganic filler with molybdenum compound coated on surface and application thereof
CN106925773A (en) * 2017-04-21 2017-07-07 深圳市创艺工业技术有限公司 A kind of 3D printing material with self-cleaning performance
WO2022088151A1 (en) * 2020-10-31 2022-05-05 宁德时代新能源科技股份有限公司 Positive electrode active material and fabrication method therefor, secondary battery, battery module, battery pack, and apparatus
CN113828770A (en) * 2021-09-17 2021-12-24 湖南工业大学 Nickel-reinforced particle composite powder with gradient structure and preparation method thereof
CN113828770B (en) * 2021-09-17 2023-03-14 湖南工业大学 Nickel-reinforced particle composite powder with gradient structure and preparation method thereof

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