CN103606428A - Nano vanadium carbide ferrofluid and preparation method thereof - Google Patents
Nano vanadium carbide ferrofluid and preparation method thereof Download PDFInfo
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- CN103606428A CN103606428A CN201310486724.7A CN201310486724A CN103606428A CN 103606428 A CN103606428 A CN 103606428A CN 201310486724 A CN201310486724 A CN 201310486724A CN 103606428 A CN103606428 A CN 103606428A
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Abstract
The invention relates to a nano vanadium carbide ferrofluid and a preparation method thereof. High-energy ball milling nano magnetic vanadium carbide with the particle size between 30nm and 60nm is used as magnetic particles in the ferrofluid, the precursor is prepared through an aqueous solution batching method, and nano vanadium carbide is prepared through a direct carbonization method of vanadium oxides; nano magnetic vanadium carbide is prepared after high-energy ball milling, nano magnetic vanadium carbide particles are pre-dispersed in a base solution and subjected to surface modification to obtain the nano vanadium carbide ferrofluid. According to the nano vanadium carbide ferrofluid and the preparation method thereof, the nano vanadium carbide particle size is between 30nm and 60nm, aggregation is not serious, ferromagnetism is provided after high-energy ball milling, the saturated magnetization is 48.02 emu/g, the saturated magnetic field intensity is 4000 Oe, the nano vanadium carbide particles have good dispersity and stability in the base solution after surface modification, the ferrofluid saturated magnetization is 6.87 emu/g, and the ferrofluid can be used for ferrofluid sealing, lubrication, damping and the like and can be used in specific environments such as the strong oxidizing environment.
Description
Technical field
The invention belongs to magnetic fluid material and preparation field.
Background technology
Magnetic fluid, claims again magnetic fluid (Ferrofluid), is by nano level ferromagnetism or ferrimagnetism particulate, after surface modification, is distributed in to even dispersion a kind of high stability colloidal dispersion forming in liquid base fluid.Magnetic fluid, owing to having the magnetic of solid and the mobility of liquid concurrently, can show many good properties under magnetic fields, at aspects such as electronic information, Aero-Space, defence and military, accurate manufacture and biomedicines, show good application prospect.
Magnetic fluid can be divided into iron oxygen magnetic fluid, metal and alloy magnetic fluid and iron nitride magnetic fluid by magnetic particle kind.Studying at present and apply maximum is nano ferriferrous oxide (Fe
3o
4) magnetic fluid, it is nanometer Fe prepared by coprecipitation
3o
4magnetic particle, after surface modification, is scattered in base fluid and is prepared from.Although Fe
3o
4magnetic fluid has the advantages such as preparation technology is simple and convenient, with low cost, but due to nanometer Fe
3o
4have very high specific area, in preparation, storage and use procedure, easily oxidation, becomes Fe
2o
3cause magnetic property greatly to reduce, impact is used; Fe in addition
3o
4magnetic fluid requires higher to environment for use, can only under specific pH value, keep stable, peracid or alkali all can make magnetic fluid unstability, even can dissolve Fe
3o
4nanoparticle.
Adopt barium oxide direct carborization can prepare nano vanadium carbide (VC), high-energy ball milling can make originally the not magnetic nano vanadium carbide particulate of tool produce ferromagnetism, and this ferromagnetism is irreversible, after high-energy ball milling, the ferromagnetism of nano vanadium carbide also cannot be eliminated by annealing or other technique.Utilize this characteristic of high-energy ball milling nano vanadium carbide particulate, prepared nano vanadium carbide magnetic fluid.
Summary of the invention
The object of the invention is, for the deficiency in above-mentioned iron oxygen magnetic fluid material and preparation technology, provide that a kind of magnetic property is good, excellent in stability, sludge proof novel nano vanadium carbide magnetic fluid material.
The present invention also provides the preparation method that a kind of technique is simple, can be used for industrial nano vanadium carbide magnetic fluid, and this preparation method is also applicable to the preparation of other surface modification carbide magnetic fluids, applied widely.
The present invention is achieved by the following technical solutions.
The composition of nano vanadium carbide magnetic fluid of the present invention is: base fluid, nano-magnetic vanadium carbide particulate and surface modifier; Wherein the particle diameter of nano-magnetic vanadium carbide particulate is 30~60nm, and base fluid can be water, dimethicone or kerosene.
The mass ratio of nano-magnetic vanadium carbide particulate and base fluid is 1: 40~3: 10.
Surface modifier is 1: 20~1: 2 with nano-magnetic vanadium carbide particle mass ratio.
The concrete preparation process that the present invention adopts is as follows.
(1) batching: adopt the method for aqueous solution batching to prepare precursor powder.According to vanadium in vanadium source and carbon source: the mol ratio of carbon is the ratio of 1: 3~1: 1, by a certain amount of vanadium trioxide, (or other vanadium sources, as ammonium metavanadate [NH
4vO
3], ammonium poly-vanadate [(NH
4)
2v
6o
16], oxalic acid vanadyl [VOC
2o
4] etc.) and with glucose (or other water-soluble carbon sources, as fructose, sucrose, water-soluble phenolic resins etc.), be dissolved in the deionized water of heating, electric stirring fully mixes raw material, the temperature of deionized water should be not less than 80 ℃ even to guarantee batch mixing.Raw material mixes the spray-dired method of rear employing and prepares the precursor powder that carbonization will be used.
(2) carbonization: the precursor powder making in step (1) is put into tube-type atmosphere furnace, under hydrogen atmosphere, carry out carbonization, adopt substep to heat up, first at 550 ℃ of insulation 1h, make precursor powder resolve into barium oxide and free active carbon, then rising to carburizing temperature is 1100~1300 ℃, 8~10 ℃/min of heating rate, and carbonization temperature retention time is 2~5h.After carbonization finishes, before powder is come out of the stove, with inert gas, carry out Passivation Treatment, products therefrom is nano vanadium carbide particulate, and its particle diameter is 30~60nm.
(3) high-energy ball milling: by the nano vanadium carbide particulate making in step (2) high-energy ball milling 5~8h in stainless steel jar mill, ratio of grinding media to material 10: 1, rotating speed 400r/min, after ball milling, products therefrom is nano-magnetic vanadium carbide particulate.
(4) washing and pre-dispersed: utilize the settlement action of high-intensity magnetic field, by secondary deionized water and absolute ethyl alcohol cyclic washing for nano-magnetic vanadium carbide particulate, remove remaining carbon and other non-magnetic impurities; According to the mass ratio of nano-magnetic vanadium carbide particulate and base fluid, be the ratio of 1: 40~3: 10, add a certain amount of base fluid, churned mechanically supersonic oscillations 20~60 min that simultaneously use different frequency, carry out pre-dispersedly, are prepared into nano-magnetic vanadium carbide magnetic paint.Wherein base fluid can be water, dimethicone or kerosene.
(5) surface modification: be the ratio of 1: 20~1: 2 according to surface modifier and nano-magnetic vanadium carbide particle mass ratio, in pre-dispersed nano-magnetic vanadium carbide magnetic paint, add surface modifier, under electric stirring, carry out surface modification reaction, reaction temperature is 60~85 ℃, modification time is 2~5h, and product is nano vanadium carbide magnetic fluid.Three kinds of surface modifiers corresponding to base fluid are respectively: water-enuatrol, dimethicone-silane resin acceptor kh-550+silicone oil of carboxyl, kerosene-oleic acid.
The present invention adopts aqueous solution dosing method to prepare presoma, and the vanadium source in carbonization temperature-rise period in presoma can be changed vanadium oxide into, and carbon source can change active carbon into; Barium oxide direct carborization is prepared nano vanadium carbide, because vanadium source and carbon source after solution batching are the even mixing of molecular level, greatly shortened the diffusion length of reaction, reduced reaction temperature and reaction time, suppress growing up of crystal grain in carbonisation, thereby obtained nano vanadium carbide.After high-energy ball milling, make nano-magnetic vanadium carbide, then that nano-magnetic vanadium carbide particulate is pre-dispersed in base fluid, after surface modification, obtain nano vanadium carbide magnetic fluid.High-energy ball milling impels C to enter the lattice of V, and the lattice constant d of V is expanded, and produces exchange coupling effect and makes originally do not have magnetic vanadium carbide to have ferromagnetism.Surface modification reaction can form coating layer at nano-magnetic vanadium carbide microparticle surfaces, the compatibility that increases vanadium carbide and base fluid, reduces the density contrast between vanadium carbide and base fluid, and has certain sterically hindered effect, thereby maintain the stability of magnetic fluid, prevent to reunite and sedimentation.
The nano vanadium carbide diameter of particle that the present invention prepares is 30~60nm, and it is also not serious to reunite, and has ferromagnetism after high-energy ball milling, and saturation magnetization is 48.02emu/g, saturation magnetic field intensity 4000Oe.After surface modification, nano-magnetic vanadium carbide particulate has good dispersiveness in base fluid, and hydromagnetic stability is good, under gravitational field under standing 30 days, high-intensity magnetic field standing one week, does not all occur obvious sedimentation and reunion, magnetic fluid saturation magnetization 6.87emu/g.The nano vanadium carbide magnetic fluid that adopts this inventive method to prepare, magnetic property is good, excellent in stability and resistance to oxidation, can effectively advance the development of magnetic fluid technique, can be applicable to magnet fluid sealing, Used in Boundary Lubrication of Magnetic Fluids and magnetic fluid damping etc., and can be applicable under the special environment such as strong oxidizing property.
Accompanying drawing explanation
Fig. 1 is the TEM photo of the nano-magnetic vanadium carbide prepared of embodiment 1.
Fig. 2 is the magnetic hysteresis loop of the nano-magnetic vanadium carbide prepared of embodiment 1.
Fig. 3 is the magnetic hysteresis loop of the nano vanadium carbide water-based magnetic fluid prepared of embodiment 1.
Embodiment
The present invention will be described further by following examples, but protection scope of the present invention is not limited to this.
Embodiment 1.
Take vanadium trioxide 30g, DEXTROSE ANHYDROUS 12g, be dissolved in the deionized water of 80 ℃, after electric stirring fully mixes raw material, adopt spray-dired way to prepare the required presoma of carbonization.Precursor powder is put into tube-type atmosphere furnace, pass into hydrogen and carry out carbonization, after 550 ℃ of insulation 1h, rising to carburizing temperature is 1200 ℃, 10 ℃/min of heating rate, carbonization temperature retention time 3h.By the vanadium carbide particulate making after carbonization high-energy ball milling 6h in stainless steel jar mill, ratio of grinding media to material 10:1, rotating speed 400r/min.Utilize the settlement action of high-intensity magnetic field, by secondary deionized water and absolute ethyl alcohol cyclic washing for nano-magnetic vanadium carbide particulate, remove remaining carbon and other non-magnetic impurities, then join in a certain proportion of base fluid water, churned mechanically supersonic oscillations 30 min that simultaneously use different frequency, carry out pre-dispersed.In pre-dispersed nano-magnetic vanadium carbide magnetic paint, add surface modifier enuatrol according to a certain percentage, under electric stirring, carry out surface modification reaction, surface modification temperature is 75 ℃, modification time is 2.5h, wherein the ratio of each composition is: base fluid water quality mark is 80%, nano-magnetic vanadium carbide mass fraction is 17%, and surface modifier enuatrol mass fraction is 3%, and surface modification afterproduct is water-base nano vanadium carbide magnetic fluid.The nano-magnetic vanadium carbide saturation magnetization of gained is 48.02emu/g, saturation magnetic field intensity 4000Oe.After surface modification, nano-magnetic vanadium carbide particulate has good dispersiveness in base fluid, hydromagnetic stability is good, under gravitational field under standing 30 days, high-intensity magnetic field standing one week, all there is not obvious sedimentation and reunion, magnetic fluid saturation magnetization is 6.87emu/g.
Embodiment 2.
Take ammonium metavanadate 20g, DEXTROSE ANHYDROUS 8g, be dissolved in the deionized water of 80 ℃, after electric stirring fully mixes raw material, adopt spray-dired way to prepare the required presoma of carbonization.Precursor powder is put into tube-type atmosphere furnace, pass into hydrogen and carry out carbonization, after 550 ℃ of insulation 1h, rising to carburizing temperature is 1150 ℃, 8 ℃/min of heating rate, carbonization temperature retention time 4h.By the vanadium carbide particulate making after carbonization high-energy ball milling 7h in stainless steel jar mill, ratio of grinding media to material 10:1, rotating speed 400r/min.Utilize the settlement action of high-intensity magnetic field, by secondary deionized water and absolute ethyl alcohol cyclic washing for nano-magnetic vanadium carbide particulate, remove remaining carbon and other non-magnetic impurities, then join in a certain proportion of base fluid kerosene, churned mechanically supersonic oscillations 20 min that simultaneously use different frequency, carry out pre-dispersed.In pre-dispersed nano-magnetic vanadium carbide magnetic paint, add surface modifier oleic acid according to a certain percentage, under electric stirring, carry out surface modification reaction, surface modification temperature is 65 ℃, modification time is 4h, wherein the ratio of each composition is: base fluid kerosene mass fraction is 80%, nano-magnetic vanadium carbide mass fraction is 16%, and surface modifier oleic acid mass fraction is 4%, and surface modification afterproduct is keryl nano vanadium carbide magnetic fluid.The magnetic fluid saturation magnetization 6.32emu/g of gained.
Embodiment 3.
Take ammonium poly-vanadate 30g, DEXTROSE ANHYDROUS 15g, be dissolved in the deionized water of 80 ℃, after electric stirring fully mixes raw material, adopt spray-dired way to prepare the required presoma of carbonization.Precursor powder is put into tube-type atmosphere furnace, pass into hydrogen and carry out carbonization, after 550 ℃ of insulation 1h, rising to carburizing temperature is 1300 ℃, 10 ℃/min of heating rate, carbonization temperature retention time 2.5h.By the vanadium carbide particulate making after carbonization high-energy ball milling 8h in stainless steel jar mill, ratio of grinding media to material 10:1, rotating speed 400r/min.Utilize the settlement action of high-intensity magnetic field, by secondary deionized water and absolute ethyl alcohol cyclic washing for nano-magnetic vanadium carbide particulate, remove remaining carbon and other non-magnetic impurities, then join in a certain proportion of base fluid dimethicone, churned mechanically supersonic oscillations 40 min that simultaneously use different frequency, carry out pre-dispersed.In pre-dispersed nano-magnetic vanadium carbide magnetic paint, add surface modifier silane resin acceptor kh-550 and silicone oil of carboxyl according to a certain percentage, under electric stirring, carry out surface modification reaction, surface modification temperature is 80 ℃, modification time is 3h, wherein the ratio of each composition is: base fluid dimethicone mass fraction is 76%, nano-magnetic vanadium carbide mass fraction is 20%, surface modifier silane resin acceptor kh-550 mass fraction is 2%, silicone oil of carboxyl mass fraction is 2%, and surface modification afterproduct is Silicon-oil-based nano vanadium carbide magnetic fluid.Gained magnetic fluid saturation magnetization 7.17emu/g.
Embodiment 4.
Take oxalic acid vanadyl 25g, DEXTROSE ANHYDROUS 8g, be dissolved in the deionized water of 80 ℃, after electric stirring fully mixes raw material, adopt spray-dired way to prepare the required presoma of carbonization.Precursor powder is put into tube-type atmosphere furnace, pass into hydrogen and carry out carbonization, after 550 ℃ of insulation 1h, rising to carburizing temperature is 1250 ℃, 10 ℃/min of heating rate, carbonization temperature retention time 3.5h.By the vanadium carbide particulate making after carbonization high-energy ball milling 5h in stainless steel jar mill, ratio of grinding media to material 10:1, rotating speed 400r/min.Utilize the settlement action of high-intensity magnetic field, by secondary deionized water and absolute ethyl alcohol cyclic washing for nano-magnetic vanadium carbide particulate, remove remaining carbon and other non-magnetic impurities, then join in a certain proportion of base fluid water, churned mechanically supersonic oscillations 30 min that simultaneously use different frequency, carry out pre-dispersed.In pre-dispersed nano-magnetic vanadium carbide magnetic paint, add surface modifier enuatrol according to a certain percentage, under electric stirring, carry out surface modification reaction, surface modification temperature is 75 ℃, modification time is 3h, wherein the ratio of each composition is: base fluid water quality mark is 88%, nano-magnetic vanadium carbide mass fraction is 10%, and surface modifier enuatrol mass fraction is 2%, and surface modification afterproduct is water-base nano vanadium carbide magnetic fluid.Gained magnetic fluid saturation magnetization 4.03emu/g.
Claims (2)
1. a nano vanadium carbide magnetic fluid, is characterized in that composition is: base fluid, nano-magnetic vanadium carbide particulate and surface modifier; The particle diameter of described nano-magnetic vanadium carbide particulate is 30~60nm, and base fluid is water, dimethicone or kerosene; Wherein:
The mass ratio of nano-magnetic vanadium carbide particulate and base fluid is 1: 40~3: 10;
Surface modifier is 1: 20~1: 2 with nano-magnetic vanadium carbide particle mass ratio.
2. the preparation method of nano vanadium carbide magnetic fluid claimed in claim 1, is characterized in that step is as follows:
(1) batching: according to vanadium in vanadium source and carbon source: the mol ratio of carbon is the ratio of 1: 3~1: 1, by vanadium trioxide, ammonium metavanadate, ammonium poly-vanadate or oxalic acid vanadyl and glucose, fructose, sucrose or water-soluble phenolic resins, be dissolved in temperature higher than in the deionized water of 80 ℃, electric stirring fully mixes raw material, then adopts spray-dired method to prepare the precursor powder that carbonization will be used;
(2) carbonization: the precursor powder making in step (1) is put into tube-type atmosphere furnace, under hydrogen atmosphere, carry out carbonization, adopt substep to heat up, first at 550 ℃ of insulation 1h, then rising to carburizing temperature is 1100~1300 ℃, 8~10 ℃/min of heating rate, carbonization temperature retention time is 2~5h; After carbonization finishes, before powder is come out of the stove, with inert gas, carry out Passivation Treatment, products therefrom is nano vanadium carbide particulate, and its particle diameter is 30~60nm;
(3) high-energy ball milling: by the nano vanadium carbide particulate making in step (2) high-energy ball milling 5~8h in stainless steel jar mill, ratio of grinding media to material 10: 1, rotating speed 400r/min, after ball milling, products therefrom is nano-magnetic vanadium carbide particulate;
(4) washing and pre-dispersed: utilize the settlement action of high-intensity magnetic field, by secondary deionized water and absolute ethyl alcohol cyclic washing for nano-magnetic vanadium carbide particulate, remove remaining carbon and other non-magnetic impurities; It according to the mass ratio of nano-magnetic vanadium carbide particulate and base fluid, is the ratio of 1: 40~3: 10, add base fluid water, dimethicone or kerosene, churned mechanically supersonic oscillations 20~60 min that simultaneously use different frequency, carry out pre-dispersedly, are prepared into nano-magnetic vanadium carbide magnetic paint;
(5) surface modification: be the ratio of 1: 20~1: 2 according to surface modifier and nano-magnetic vanadium carbide particle mass ratio, in pre-dispersed nano-magnetic vanadium carbide magnetic paint, add surface modifier, under electric stirring, carry out surface modification reaction, reaction temperature is 60~85 ℃, modification time is 2~5h, and product is nano vanadium carbide magnetic fluid;
Three kinds of surface modifiers corresponding to base fluid are respectively: water-enuatrol, dimethicone-silane resin acceptor kh-550+silicone oil of carboxyl, kerosene-oleic acid.
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CN101198442A (en) * | 2005-07-22 | 2008-06-11 | Tdy工业公司 | Composite materials |
US7560160B2 (en) * | 2002-11-25 | 2009-07-14 | Materials Modification, Inc. | Multifunctional particulate material, fluid, and composition |
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