CN103606428B - A kind of nano vanadium carbide ferrofluid and preparation method thereof - Google Patents
A kind of nano vanadium carbide ferrofluid and preparation method thereof Download PDFInfo
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- CN103606428B CN103606428B CN201310486724.7A CN201310486724A CN103606428B CN 103606428 B CN103606428 B CN 103606428B CN 201310486724 A CN201310486724 A CN 201310486724A CN 103606428 B CN103606428 B CN 103606428B
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Abstract
A kind of nano vanadium carbide ferrofluid and preparation method thereof, adopt particle diameter be the high-energy ball milling nano-magnetic vanadium carbide of 30 ~ 60nm as the magnetic particle in magnetic fluid, adopt aqueous solution dosing method to prepare presoma, barium oxide direct carborization prepares nano vanadium carbide; After high-energy ball milling, obtained nano-magnetic vanadium carbide, then by pre-dispersed in base fluid for nano-magnetic vanadium carbide particulate, obtains nano vanadium carbide ferrofluid after surface modification.Nano vanadium carbide particle diameter prepared by the present invention is 30 ~ 60nm, and reunite and not serious, after high-energy ball milling, there is ferromagnetism, saturation magnetization is 48.02emu/g, saturation magnetic field intensity 4000Oe, after surface modification, nano-magnetic vanadium carbide particulate has well dispersed and stability in base fluid, magnetic fluid saturation magnetization 6.87emu/g, can be applicable to magnet fluid sealing, Used in Boundary Lubrication of Magnetic Fluids and magnetic fluid damping etc., and under can be applicable to the special environment such as strong oxidizing property.
Description
Technical field
The invention belongs to magnetic fluid material and preparation field.
Background technology
Magnetic fluid, also known as magnetic fluid (Ferrofluid), is by nano level ferromagnetism or ferri-magnetic material, after surface modification, is distributed in even dispersion a kind of high stability colloidal dispersion formed in liquid base fluid.Magnetic fluid, due to the mobility of the magnetic and liquid that have solid concurrently, can show many excellent properties, in electronic information, Aero-Space, defence and military, precision manufactureing and biomedicine etc., show good application prospect under magnetic fields.
Magnetic fluid can be divided into iron oxygen magnetic fluid, metal and alloy magnetic fluid thereof and iron nitride magnetic fluid by magnetic particle kind.That current investigation and application is maximum is nano ferriferrous oxide (Fe
3o
4) magnetic fluid, it is nanometer Fe coprecipitation prepared
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
4there is very high specific area, be easily oxidized in preparation, storage and use procedure, become Fe
2o
3cause magnetic property greatly to reduce, impact uses; Fe in addition
3o
4magnetic fluid requires higher to environment for use, can only keep stable under specific pH value, and peracid or excessively 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, namely 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, prepare nano vanadium carbide ferrofluid.
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.
Present invention also offers the preparation method that a kind of technique is simple, can be used for industrial nano vanadium carbide ferrofluid, 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 ferrofluid 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) prepare burden: 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], vanadyl oxalate [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 makes raw material fully mix, the temperature of deionized water should be not less than 80 DEG C even to ensure batch mixing.Raw material mixes the precursor powder that the spray-dired method of rear employing prepares carbonization.
(2) carbonization: precursor powder obtained in step (1) is put into tube-type atmosphere furnace, carry out carbonization in a hydrogen atmosphere, substep is adopted to heat up, first at 550 DEG C of insulation 1h, precursor powder is made to resolve into barium oxide and free active carbon, then rising to carburizing temperature is 1100 ~ 1300 DEG C, heating rate 8 ~ 10 DEG C/min, and carbonization temperature retention time is 2 ~ 5h.After carbonization terminates, before powder is come out of the stove, carry out Passivation Treatment with inert gas, products therefrom is nano vanadium carbide particulate, and its particle diameter is 30 ~ 60nm.
(3) high-energy ball milling: by nano vanadium carbide particulate high-energy ball milling 5 ~ 8h in stainless steel jar mill obtained in step (2), 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: the settlement action utilizing high-intensity magnetic field, by nano-magnetic vanadium carbide particulate secondary deionized water and absolute ethyl alcohol cyclic washing, the remaining carbon of removing and other non-magnetic impurities; Be the ratio of 1: 40 ~ 3: 10 according to the mass ratio of nano-magnetic vanadium carbide particulate and base fluid, add a certain amount of base fluid, the churned mechanically supersonic oscillations 20 ~ 60min simultaneously using different frequency, carries out pre-dispersed, is 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, surface modifier is added in pre-dispersed nano-magnetic vanadium carbide magnetic paint, surface modification reaction is carried out under electric stirring, reaction temperature is 60 ~ 85 DEG C, modification time is 2 ~ 5h, and product is nano vanadium carbide ferrofluid.The surface modifier that three kinds of base fluids are corresponding is 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 change vanadium oxide into, and carbon source can change active carbon into; Barium oxide direct carborization prepares nano vanadium carbide, because vanadium source and carbon source are the Homogeneous phase mixing of molecular level after solution batching, substantially reduce the diffusion length of reaction, reduce reaction temperature and reaction time, inhibit growing up of crystal grain in carbonisation, thus obtain nano vanadium carbide.After high-energy ball milling, obtained nano-magnetic vanadium carbide, then by pre-dispersed in base fluid for nano-magnetic vanadium carbide particulate, obtains nano vanadium carbide ferrofluid after surface modification.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, increase the compatibility of vanadium carbide and base fluid, reduce the density contrast between vanadium carbide and base fluid, and there is certain sterically hindered effect, thus 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 reunite and not serious, after high-energy ball milling, have ferromagnetism, 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, leaves standstill 30 days, leaves standstill one week under high-intensity magnetic field, all do not occur obvious sedimentation and reunion, magnetic fluid saturation magnetization 6.87emu/g under gravitational field.Adopt nano vanadium carbide ferrofluid prepared by this inventive method, magnetic property is good, excellent in stability and resistance to oxidation, effectively can 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 under can be applicable to the special environment such as strong oxidizing property.
Accompanying drawing explanation
Fig. 1 is the TEM photo of the nano-magnetic vanadium carbide that embodiment 1 is prepared.
Fig. 2 is the magnetic hysteresis loop of the nano-magnetic vanadium carbide that embodiment 1 is prepared.
Fig. 3 is the magnetic hysteresis loop of the nano vanadium carbide water-based magnetic fluid that embodiment 1 is prepared.
Embodiment
The present invention will be described further by following examples, but protection scope of the present invention is not limited thereto.
Embodiment 1.
Take vanadium trioxide 30g, DEXTROSE ANHYDROUS 12g, be dissolved in the deionized water of 80 DEG C, after electric stirring makes raw material fully mix, adopt spray-dired way to prepare presoma needed for carbonization.Precursor powder is put into tube-type atmosphere furnace, passes into hydrogen and carry out carbonization, rising to carburizing temperature after 550 DEG C of insulation 1h is 1200 DEG C, heating rate 10 DEG C/min, carbonization temperature retention time 3h.By the vanadium carbide particulate high-energy ball milling 6h, the ratio of grinding media to material 10:1 in stainless steel jar mill that obtain after carbonization, rotating speed 400r/min.Utilize the settlement action of high-intensity magnetic field, by nano-magnetic vanadium carbide particulate secondary deionized water and absolute ethyl alcohol cyclic washing, the remaining carbon of removing and other non-magnetic impurities, then join in a certain proportion of base fluid water, the churned mechanically supersonic oscillations 30min simultaneously using different frequency, carries out pre-dispersed.Surface modifier enuatrol is added according to a certain percentage in pre-dispersed nano-magnetic vanadium carbide magnetic paint, surface modification reaction is carried out under electric stirring, surface modification temperature is 75 DEG C, 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, leave standstill 30 days under gravitational field, leave standstill one week under high-intensity magnetic field, all do not occur 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 DEG C, after electric stirring makes raw material fully mix, adopt spray-dired way to prepare presoma needed for carbonization.Precursor powder is put into tube-type atmosphere furnace, passes into hydrogen and carry out carbonization, rising to carburizing temperature after 550 DEG C of insulation 1h is 1150 DEG C, heating rate 8 DEG C/min, carbonization temperature retention time 4h.By the vanadium carbide particulate high-energy ball milling 7h, the ratio of grinding media to material 10:1 in stainless steel jar mill that obtain after carbonization, rotating speed 400r/min.Utilize the settlement action of high-intensity magnetic field, by nano-magnetic vanadium carbide particulate secondary deionized water and absolute ethyl alcohol cyclic washing, the remaining carbon of removing and other non-magnetic impurities, then join in a certain proportion of base fluid kerosene, the churned mechanically supersonic oscillations 20min simultaneously using different frequency, carries out pre-dispersed.Surface modifier oleic acid is added according to a certain percentage in pre-dispersed nano-magnetic vanadium carbide magnetic paint, surface modification reaction is carried out under electric stirring, surface modification temperature is 65 DEG C, 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 ferrofluid.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 DEG C, after electric stirring makes raw material fully mix, adopt spray-dired way to prepare presoma needed for carbonization.Precursor powder is put into tube-type atmosphere furnace, passes into hydrogen and carry out carbonization, rising to carburizing temperature after 550 DEG C of insulation 1h is 1300 DEG C, heating rate 10 DEG C/min, carbonization temperature retention time 2.5h.By the vanadium carbide particulate high-energy ball milling 8h, the ratio of grinding media to material 10:1 in stainless steel jar mill that obtain after carbonization, rotating speed 400r/min.Utilize the settlement action of high-intensity magnetic field, by nano-magnetic vanadium carbide particulate secondary deionized water and absolute ethyl alcohol cyclic washing, the remaining carbon of removing and other non-magnetic impurities, then join in a certain proportion of base fluid dimethicone, the churned mechanically supersonic oscillations 40min simultaneously using different frequency, carries out pre-dispersed.Surface modifier silane resin acceptor kh-550 and silicone oil of carboxyl is added according to a certain percentage in pre-dispersed nano-magnetic vanadium carbide magnetic paint, surface modification reaction is carried out under electric stirring, surface modification temperature is 80 DEG C, 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 ferrofluid.Gained magnetic fluid saturation magnetization 7.17emu/g.
Embodiment 4.
Take vanadyl oxalate 25g, DEXTROSE ANHYDROUS 8g, be dissolved in the deionized water of 80 DEG C, after electric stirring makes raw material fully mix, adopt spray-dired way to prepare presoma needed for carbonization.Precursor powder is put into tube-type atmosphere furnace, passes into hydrogen and carry out carbonization, rising to carburizing temperature after 550 DEG C of insulation 1h is 1250 DEG C, heating rate 10 DEG C/min, carbonization temperature retention time 3.5h.By the vanadium carbide particulate high-energy ball milling 5h, the ratio of grinding media to material 10:1 in stainless steel jar mill that obtain after carbonization, rotating speed 400r/min.Utilize the settlement action of high-intensity magnetic field, by nano-magnetic vanadium carbide particulate secondary deionized water and absolute ethyl alcohol cyclic washing, the remaining carbon of removing and other non-magnetic impurities, then join in a certain proportion of base fluid water, the churned mechanically supersonic oscillations 30min simultaneously using different frequency, carries out pre-dispersed.Surface modifier enuatrol is added according to a certain percentage in pre-dispersed nano-magnetic vanadium carbide magnetic paint, surface modification reaction is carried out under electric stirring, surface modification temperature is 75 DEG C, 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 ferrofluid, 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 ferrofluid according to claim 1, is characterized in that step is as follows:
(1) prepare burden: 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 vanadyl oxalate and glucose, fructose, sucrose or water-soluble phenolic resins, be dissolved in temperature higher than in the deionized water of 80 DEG C, electric stirring makes raw material fully mix, and then adopts spray-dired method to prepare the precursor powder of carbonization;
(2) carbonization: precursor powder obtained in step (1) is put into tube-type atmosphere furnace, carry out carbonization in a hydrogen atmosphere, substep is adopted to heat up, first at 550 DEG C of insulation 1h, then rising to carburizing temperature is 1100 ~ 1300 DEG C, heating rate 8 ~ 10 DEG C/min, carbonization temperature retention time is 2 ~ 5h; After carbonization terminates, before powder is come out of the stove, carry out Passivation Treatment with inert gas, products therefrom is nano vanadium carbide particulate, and its particle diameter is 30 ~ 60nm;
(3) high-energy ball milling: by nano vanadium carbide particulate high-energy ball milling 5 ~ 8h in stainless steel jar mill obtained in step (2), ball material mass ratio 10: 1, rotating speed 400r/min, after ball milling, products therefrom is nano-magnetic vanadium carbide particulate;
(4) washing and pre-dispersed: the settlement action utilizing high-intensity magnetic field, by nano-magnetic vanadium carbide particulate secondary deionized water and absolute ethyl alcohol cyclic washing, the remaining carbon of removing and other non-magnetic impurities; Be the ratio of 1: 40 ~ 3: 10 according to the mass ratio of nano-magnetic vanadium carbide particulate and base fluid, add base fluid water, dimethicone or kerosene, the churned mechanically supersonic oscillations 20 ~ 60min simultaneously using different frequency, carries out pre-dispersed, is 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, surface modifier is added in pre-dispersed nano-magnetic vanadium carbide magnetic paint, surface modification reaction is carried out under electric stirring, reaction temperature is 60 ~ 85 DEG C, modification time is 2 ~ 5h, and product is nano vanadium carbide ferrofluid;
The surface modifier that three kinds of base fluids are corresponding is respectively: water-enuatrol, dimethicone-silane resin acceptor kh-550+silicone oil of carboxyl, kerosene-oleic acid.
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