CN103680798A - Preparation method for perfluor polyether oil-based magnetic liquid - Google Patents
Preparation method for perfluor polyether oil-based magnetic liquid Download PDFInfo
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Abstract
The invention discloses a preparation method for a perfluor polyether oil-based magnetic liquid. The magnetic liquid is formed by bare Fe[3]O[4] magnetic nano-particles, a perfluor polyether carboxylic acid surface active agent and a perfluor polyether oil-based carrier liquid in a prepared mode. The bare Fe[3]O[4] nano-particles with the average particle diameter of 10 nanometers are firstly prepared by the adoption of a chemical coprecipitation method; the perfluor polyether carboxylic acid surface active agent is then adopted for modifying the bare Fe[3]O[4] nano-particles; finally, the modified Fe[3]O[4] magnetic nano-particles and the perfluor polyether oil-based carrier liquid are blended through a high-energy ball milling or ultrasonic shaking method to form the uniform and stable perfluor polyether oil-based magnetic liquid, and the saturation magnetization of the perfluor polyether oil-based magnetic liquid is 14-600 Gs. The magnetic liquid has the excellent special performance of resisting to chemical corrosion, high temperature, low temperature resistance and radiation and never burning, can work stably for a long time at the temperature of 40 DEG C below zero-200 DEG C at the pH value of 1-14, and is particularly suitable for space stations, aeronautics and astronautics and other military industry fields.
Description
Technical field
The present invention relates to surface modification and the field of dispersions thereof of nano-powder, be specifically related to a kind of preparation method of perfluoro polyether oil based magnetic liquid.
Background technology
Magnetic liquid is a kind of Nano-function thin films, that a magnetic-particle high degree of dispersion of crossing through surfactant coating decoration is in base load liquid,, in gravitational field, magnetic field, electric field, centrifugal field, there is not delaminating deposition in the soliquid that forms a kind of nanoscale, the mixing of " solid-liquid " two-phase stable homogeneous.Because it has the magnetic of solid material and the mobility of fluent material concurrently, can under the effect of externally-applied magnetic field, be magnetized rapidly and there is magnetic, after externally-applied magnetic field removes, magnetic disappears again immediately, without coercive force and remanent magnetism, show good superparamagnetism, thereby there is a series of special physical and chemical performances, nano-meter characteristic and mobility, be widely used in the fields such as Aero-Space, machinery, the energy, material, chemical industry, bio-pharmaceuticals.
Different according to the kind of base load liquid and surfactant, magnetic liquid can be divided into: water base, keryl, gasoline base, synthetic ester base, polyglycols base, polyphenyl ether, silicon hydrocarbon compound based magnetic liquid.Patent ZL95108828.9 inventor, adopt thermal decomposition method to prepare metal magnetic liquid in the device of special development, its preparation facilities is complicated, loaded down with trivial details, the required heat decomposition temperature of flow process is high, energy loss is large, is unsuitable for applying and large-scale production; In patent CN1741207A, do not add any surface activity, in acid solution, nano particle is carried out to peptization processing, only depending on electric double layer physical absorption to stop between particle reunites, at particle surface clad surface activating agent, not forming chemical bond stops the chemical interval power of particle agglomeration large, nano particle and the magnetic liquid of preparation are all unstable, and can only be applicable to weak acid environment; In patent CN102063992A, using paraffin as base load liquid, using plasma activation method is prepared magnetic liquid, need to be under the environment of complete starvation, reaction cavity temperature is up to 200 ℃ and need alternating-current pulse current/voltage up to 10kV, reaction unit is complicated, cost is high, especially operating personnel is had to danger; In patent ZL200510064275.2, adopt surfactant and base load liquid Hybrid Heating to 80 ℃～100 ℃, after cool to room temperature, add wherein concentrating agent of low volatilization point, in the reacting furnace of 182 ℃, react with the carbonyl iron dust of evaporation, the method needs special reacting furnace, and the concentrating agents adding is low boiling point hydrocarbon organic solvent of ketone, not only impurity has been introduced to magnetic liquid product, and the volatilization of these concentrating agents will cause murder by poisoning to operating personnel and environment, above-mentioned patent is the preparation of conventional magnetic liquid.In patent CN101514284B, mentioned fluorine ethers magnetic material, first using perfluoro polyether oil and silicone oil as base load liquid, put into autoclave 1MPa, 100 ℃ are stirred 90min, supercharging 2MPa, 150 ℃ are stirred 120min, when temperature, pressure returns to room temperature and normal pressure, the Fe-Ni alloy nano particle of Liquid preparation methods is added in reactor, at pressure 0.5MPa, at 60 ℃, stir 180min and make magnetic seal material, in its reaction, to adopt arc process to prepare oleic acid coated as surfactant for Fe-Ni alloy nano particle, require anoxybiotic high vacuum, in the reactor mixing with perfluoro polyether oil and silicone oil, also require high pressure-temperature, the most important thing is that the viscosity of the magnetic material prepared is up to 1.1*10
5mPas, close to semisolid, has been no longer traditional magnetic liquid.
Ester group, keryl, gasoline base, water-base magnetic liquid has reached the ripe practical stage, but the magnetic liquid of these kinds is along with the expansion of the scope of application, its drawback day by day highlights, as: can not be applicable to high and low temperature environment, can not acid and alkali-resistance, can not seal erosion medium, can not radiation hardness, can not be applied to extreme particular surroundingss such as space station etc., and perfluoro polyether oil based magnetic liquid is because its surfactant and base load liquid are fluorine ether material, its stable chemical nature, there are a lot of properties, can overcome the familiar lacunas of above-mentioned particular surroundings, there is extremely strong using value.
Summary of the invention
Technical problem to be solved by this invention is: overcome prior art deficiency, a kind of acid-alkali-corrosive-resisting, high-low temperature resistant be provided, do not burn, the magnetization is high, the preparation method of the perfluoro polyether oil based magnetic liquid that can be applicable to extreme environment of good stability, and preparation process is except the Fe after modifying
3o
4outside magnetic nanoparticle vacuum drying step, whole preparation flow, all without inflated with nitrogen or take other measures to get rid of oxygen and disturb, all completes under aerobic environment, and device is simple, and easy to operate, energy consumption is low.
For achieving the above object, the present invention takes following technical scheme:
A preparation method for perfluoro polyether oil based magnetic liquid, comprises magnetic nanoparticle, surfactant and base load liquid three parts.
Above-mentioned magnetic nanoparticle is Fe
3o
4particle, adopts coprecipitation preparation, and particle diameter is at 8～18nm, and average grain diameter is 10nm.
Above-mentioned surfactant is PFPE carboxylic acids, selecting concerning prepared by magnetic liquid of surfactant is most important, can be related to magnetic liquid be successfully prepared, whether magnetic liquid has the significant problems such as using value, also be the primary key issue solving of magnetic liquid preparation, because it plays discrete particles in magnetic liquid preparation process, improve particle surface performance and mate the effect such as mix with base load liquid.
Above-mentioned base load liquid is PFPE oils, the selection of base load liquid must consider the factors such as chemical structural formula, viscosity, molecular weight, serviceability temperature, and strict and above-mentioned PFPE carboxylic acids surfactant matches, can stablize with it altogether moltenly, these are all the prerequisites of preparing magnetic liquid.
A kind of preparation method's concrete operations of perfluoro polyether oil based magnetic liquid are as follows:
(1) exposed Fe
3o
4the preparation of magnetic nanoparticle
The ionic equation of its reaction is: Fe
2++ 2Fe
3++ 8OH
-=Fe
3o
4+ 4H
2o is Fe according to molar ratio
2+: Fe
3+=1:1.5～2 add deionized water preparation Fe
2+, Fe
3+molysite precursor solution, controls bath temperature at 32～92 ℃, Installation and Debugging reaction unit, and reaction there-necked flask does not all seal with seal rubber plug in the situation that having material to add.In there-necked flask, pour the Fe configuring into
3+solution, mixing speed 100～600r/min, when temperature approaches preparation feedback temperature, adds FeCl
2or FeSO
4powder, reduces to be stirred to that under 100～150r/min, to continue stirring and dissolving even, monitors at any time molysite mixed liquor internal temperature, when temperature surpasses 1～2 ℃ of preparation feedback temperature, and routine Fe in molar ratio
3+: ammoniacal liquor=1:4～8 slowly pour into 25% concentrated ammonia liquor, and reactant liquor becomes black immediately, and adjustment rotating speed is 300～600r/min, and the precipitation reaction time is 5～30min, and preparation draws exposed Fe
3o
4magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe
3o
4the coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), PFPE carboxylic acids surfactant can add simultaneously and react there-necked flask with 25% concentrated ammonia liquor, also can first add 25% concentrated ammonia liquor, adds PFPE carboxylic acids surfactant after then reacting 5～30min again.Both can in the situation that stirring, add, also can under standing condition, add.Both can be at preparation Fe
3o
4process finish, react there-necked flask and still in first water-bath, add, also can after reaction there-necked flask is moved into second water-bath for coating reaction, add again.For coated water-bath temperature, be controlled at 52～92 ℃.Adopt and above-mentionedly add any in mode all can, according to exposed magnetic-particle (g) and the ratio of surfactant (ml), be: 40:1～1:1 adds PFPE carboxylic acids surfactant, then start and stir 400～700r/min, the coated time is 30～120min, makes the Fe after being coated
3o
4magnetic nanoparticle.
(3) Fe after coated
3o
4magnetic nanoparticle is processed
There-necked flask after above-mentioned steps (2) coating reaction is finished takes out, and reactant liquor is moved into 1000ml beaker, sedimentation under magnetic support, and with deionized water cyclic washing 5～7 times, until check without Cl
-and SO
4 2-and till pH=7.Gained magnetic-particle is moved in surface plate, put into vacuum drying chamber dry, vacuum degree is-0.1Mpa that heating-up temperature is 30～90 ℃, is generally 24～48 hours drying time.
(4) perfluoro polyether oil based magnetic liquid is made in high-energy ball milling or ultrasonic concussion
The dry magnetic-particle of gained in above-mentioned steps (3) is weighed and mixed with the ratio of base load liquid (ml) 1:20～2:1 according to the magnetic-particle (g) after modifying with PFPE oil-based carrier liquid.Now also supplemented and added PFPE carboxylic acids surfactant in mixture in the past, additional proportion is 50～20:0～5 according to magnetic-particle and PFPE carboxylic acids surfactant (g:ml), further modifies and makes up not yet complete coated magnetic-particle.Adopt the method for high-energy ball milling or ultrasonic oscillation to mix dispersion, while shaking at a high speed, temperature can reach 50～80 ℃, for preventing from heating up, causes oxidation, adopts the method for interval cooling, cooling extent is 0.7 ℃/min～2 ℃/min, and high-energy ball milling or ultrasonic 1h～20h finish.Can adopt merely wherein a kind of, or the mode of two kinds and use is prepared perfluoro polyether oil based magnetic liquid crude product by mixture, crude product is precipitated on magnetic support or high speed centrifugation removes the bulky grain that bottom settles down, repeatedly carry out this step 3～5 time, getting upper strata black even mixed liquor is perfluoro polyether oil based magnetic liquid.
Deionized water used in above-mentioned steps (1) (3), is to adopt ultrapure water machine to manufacture, and deionization resistivity of water is 18.2 Μ Ω .cm(25 ℃).
The ultrasonic disperser frequency that above-mentioned steps (4) is used is 40kHZ, and high energy ball mill mill amount is 50ml*3, and power is 50kW.
Perfluoro polyether oil based magnetic liquid has so superior characteristic, depends on the performance of its surfactant and base load liquid completely.PFPE carboxylic acids surfactant and PFPE oils base load liquid all belong to fluorine ether material, it has very good chemical stability, the outer nearly all medicine of defluorination does not react with it, the strong acid and strong base strong corrosive materials such as the sulfuric acid not seethed with excitement, fuming nitric aicd, HF, strong oxidizer, melting caustic soda corrode, and molecular structure and chemical composition are constant; High and low temperature resistance is superior, and at low temperature-40 ℃, just viscosity slightly raises, but mobility is unaffected, chemical breakdown and aging does not occur at 290 ℃, does not tie carbon or deposit, does not give off poisonous gas; Except fluorous solvent, nearly all medicine all can not be dissolved, as hydrocarbon, water, steam, chemical solvent etc.; Can never burn, there is no flash-point, there is no self-ignition point, can not react with combustion medium oxygen, itself just can be used as explosion-proof hot media.
Compared with prior art, tool has the following advantages in the present invention:
1. prepared the perfluoro polyether oil based magnetic liquid that can be competent at user demand under extreme particular surroundings, in the acid & alkali liquid of pH=1～14, long-term immersion has no effect, can long-term stable operation at-40 ℃～200 ℃, even particle distribution, do not reunite, coagulation not, mobility is constant, and some conventional magnetic liquids volatilize already, freeze or cracking and lose use value.Magnetic liquid of the present invention has solved the long-standing special seal needs of problems of visual plant of the industries such as Aero-Space, machinery, chemical industry, pharmacy, biology.As critical material, promoted as the breakthrough of the field tip device production domesticization such as national defence, military project, manned space flight.Widen applied environment and the working medium of magnetic liquid, for can not use conventional surfactants or add also unfruitful field of wide variety of conventional surfactant.
2. the perfluoro polyether oil based magnetic liquid that prepared by the present invention, adopting vibrating specimen magnetometer to measure saturation magnetization is 14～600Gs, and the magnetization and viscosity can be adjusted arbitrarily.
3. perfluoro polyether oil based magnetic liquid of the present invention is absolutely not flammable.
4. the preparation method of the perfluoro polyether oil based magnetic liquid that prepared by the present invention is simple, and productive rate is high, low for equipment requirements.
Accompanying drawing explanation
Fig. 1 is the magnetization curve of perfluoro polyether oil based magnetic liquid.
Fig. 2 is the TEM figure of the coated magnetic-particle of PFPE carboxylic acids surfactant.
Fig. 3 is the XRD collection of illustrative plates of the coated magnetic-particle of PFPE carboxylic acids surfactant.
Fig. 4 is the FTIR collection of illustrative plates of the coated magnetic-particle of PFPE carboxylic acids surfactant.
Embodiment
Embodiment 1
(1) exposed Fe
3o
4the preparation of magnetic nanoparticle
Take 5.40g FeCl
3be dissolved in 400ml deionized water, under room temperature, be configured to the solution for standby of 0.05mol/L, control bath temperature at 32 ℃.In there-necked flask, pour the Fe configuring into
3+solution, mixing speed 300r/min, when temperature approaches 32 ℃ of preparation feedback temperature, adds 1.98g FeCl
2powder, reduce mixing speed and be that under 100r/min, to continue stirring and dissolving even, monitor at any time molysite mixed liquor internal temperature, when temperature reaches 31～32 ℃, slowly pour into 25% concentrated ammonia liquor 20ml, reactant liquor becomes black immediately, and adjustment rotating speed is 200r/min, reaction time is 30min, and preparation draws exposed Fe
3o
4magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe
3o
4the coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), will not react there-necked flask taking-up, in the situation that does not stop stirring, add PFPE carboxylic acids surfactant 1ml.Then reaction there-necked flask is moved into the other water-bath that is used for flatly coating reaction, coated water-bath temperature is controlled at 62 ℃, starts and stirs 300r/min, and coated time 120min, makes the Fe after being coated
3o
4magnetic nanoparticle.
(3) Fe after coated
3o
4magnetic nanoparticle is processed
There-necked flask after above-mentioned steps (2) coating reaction is finished takes out, and reactant liquor is moved into 1000ml beaker, sedimentation on magnetic support, and with deionized water cyclic washing 5～7 times, until check in washing lotion without Cl
-and till pH=7.Gained magnetic-particle is moved into in surface plate, to put into vacuum drying chamber dry, vacuum degree is-0.1Mpa, and heating-up temperature is 80 ℃, and be 24 hours drying time.
(4) perfluoro polyether oil based magnetic liquid is made in high-energy ball milling or ultrasonic concussion
By the dry magnetic-particle (g) of gained in above-mentioned steps (3) with PFPE oil-based carrier liquid (ml) proportionally for 1:20 mixes.The method that adopts ultrasonic wave to disperse is disperseed, and ultrasonic 1h, obtains crude product, crude product is precipitated and removes the bulky grain that bottom settles down on magnetic support, repeatedly carry out this step 3 time, getting upper strata black even mixed liquor is perfluoro polyether oil based magnetic liquid, and saturation magnetization is 14GS.This magnetic liquid absolutely not fires, without flash-point, without self-ignition point, can be in pH=1～14, steady operation at-40 ℃～200 ℃ temperature, can be used in magnetic fluid sealing liquid structure, be particularly useful for military project and the aerospace fields such as military project radar rotary joint, all visors of tank, space station porthole and moonfall buffer unit.
Embodiment 2
(1) exposed Fe
3o
4the preparation of magnetic nanoparticle
Take 54.0g FeCl
3be dissolved in 400ml deionized water, under room temperature, be configured to the solution for standby of 0.5mol/L, control bath temperature at 42 ℃.In there-necked flask, pour the Fe configuring into
3+solution, mixing speed 300r/min, when temperature approaches 42 ℃ of preparation feedback temperature, adds 27.80g FeSO
4powder, reduce mixing speed and be that under 100r/min, to continue stirring and dissolving even, monitor at any time molysite mixed liquor internal temperature, when temperature reaches 41～42 ℃, slowly pour into 25% concentrated ammonia liquor 120ml, reactant liquor becomes black immediately, and adjustment rotating speed is 400r/min, reaction time is 15min, and preparation draws exposed Fe
3o
4magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe
3o
4the coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), will not react there-necked flask taking-up, in the situation that does not stop stirring, add PFPE carboxylic acids surfactant 7ml.Then reaction there-necked flask is moved into the other water-bath that is used for flatly coating reaction, coated water-bath temperature is controlled at 72 ℃, starts and stirs 400r/min, and coated time 45min, makes the Fe after being coated
3o
4magnetic nanoparticle.
(3) Fe after coated
3o
4magnetic nanoparticle is processed
There-necked flask after above-mentioned steps (2) coating reaction is finished takes out, and reactant liquor is moved into 1000ml beaker, sedimentation on magnetic support, and with deionized water cyclic washing 5～7 times, until check in washing lotion without Cl
-and SO
4 2-and till pH=7.Gained magnetic-particle is moved into in surface plate, to put into vacuum drying chamber dry, vacuum degree is-0.1Mpa, and heating-up temperature is 30 ℃, and be 24 hours drying time.
(4) perfluoro polyether oil based magnetic liquid is made in high-energy ball milling or ultrasonic concussion
By the dry magnetic-particle (g) of gained in above-mentioned steps (3) with PFPE oil-based carrier liquid (ml) proportionally for 1:12 mixes, do not add PFPE carboxylic acids surfactant.The method that adopts ultrasonic wave to disperse is disperseed, ultrasonic 5h, obtain crude product, crude product is precipitated and removes the bulky grain that bottom settles down on magnetic support, repeatedly carry out this step 3 time, getting upper strata black even mixed liquor is perfluoro polyether oil based magnetic liquid, saturation magnetization is 205GS, this magnetic liquid absolutely not fires, without flash-point, without self-ignition point, can be in pH=1～14, steady operation at-40 ℃～200 ℃ temperature, can be used in magnetic fluid sealing liquid structure, be particularly useful for military project radar rotary joint, the all visors of tank, military project and the aerospace fields such as space station porthole and moonfall buffer unit.
Embodiment 3
(1) exposed Fe
3o
4the preparation of magnetic nanoparticle
Take 54.0g FeCl
3be dissolved in 400ml deionized water, under room temperature, be configured to the solution for standby of 0.5mol/L, control bath temperature at 52 ℃.In there-necked flask, pour the Fe configuring into
3+solution, mixing speed 300r/min, when temperature approaches 52 ℃ of preparation feedback temperature, adds 27.80g FeSO
4powder, reduce mixing speed and be that under 100r/min, to continue stirring and dissolving even, monitor at any time molysite mixed liquor internal temperature, when temperature reaches 51～52 ℃, slowly pour into 25% concentrated ammonia liquor 150ml, reactant liquor becomes black immediately, and adjustment rotating speed is 400r/min, reaction time is 10min, and preparation draws exposed Fe
3o
4magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe
3o
4the coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), will not react there-necked flask taking-up, in the situation that does not stop stirring, add PFPE carboxylic acids surfactant 8ml.Then reaction there-necked flask is moved into the other water-bath that is used for flatly coating reaction, coated water-bath temperature is controlled at 72 ℃, starts and stirs 500r/min, and coated time 60min, makes the Fe after being coated
3o
4magnetic nanoparticle.
(3) Fe after coated
3o
4magnetic nanoparticle is processed
There-necked flask after above-mentioned steps (2) coating reaction is finished takes out, and reactant liquor is moved into 1000ml beaker, sedimentation on magnetic support, and with deionized water cyclic washing 5～7 times, until check in washing lotion without Cl
-and SO
4 2-and till pH=7.Gained magnetic-particle is moved into in surface plate, to put into vacuum drying chamber dry, vacuum degree is-0.1Mpa, and heating-up temperature is 50 ℃, and be 24 hours drying time.
(4) perfluoro polyether oil based magnetic liquid is made in high-energy ball milling or ultrasonic concussion
By the dry magnetic-particle (g) of gained in above-mentioned steps (3) with PFPE oil-based carrier liquid (ml) proportionally for 1:8 mixes, do not add PFPE carboxylic acids surfactant.Adopt the method for high-energy ball milling to disperse 5h, obtain crude product, crude product is precipitated and removes the bulky grain that bottom settles down on magnetic support, repeatedly carry out this step 3 time, getting upper strata black even mixed liquor is perfluoro polyether oil based magnetic liquid, saturation magnetization is 416GS, this magnetic liquid absolutely not fires, without flash-point, without self-ignition point, can be in pH=1～14, steady operation at-40 ℃～200 ℃ temperature, can be used in magnetic fluid sealing liquid structure, be particularly useful for military project radar rotary joint, the all visors of tank, military project and the aerospace fields such as space station porthole and moonfall buffer unit.
Embodiment 4
(1) exposed Fe
3o
4the preparation of magnetic nanoparticle
Take 54.0g FeCl
3be dissolved in 400ml deionized water, under room temperature, be configured to the solution for standby of 0.5mol/L, control bath temperature at 72 ℃, in there-necked flask, pour the Fe configuring into
3+solution, mixing speed 400r/min, when temperature approaches 72 ℃ of preparations, adds 30.80g FeSO
4powder, reduction mixing speed is 100r/min, continue stirring and dissolving even, monitor at any time molysite mixed liquor internal temperature, when temperature reaches 71～72 ℃, slowly pour into 25% concentrated ammonia liquor 150ml, reactant liquor becomes black immediately, adjustment rotating speed is 500r/min, and the reaction time is 13min, and preparation draws exposed Fe
3o
4magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe
3o
4the coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), by the water-bath of 80 ℃ of reaction there-necked flask immigrations, start and stir 600r/min, then add PFPE carboxylic acids surfactant 11ml, coated time 120min, makes the Fe after being coated
3o
4magnetic nanoparticle.
(3) Fe after coated
3o
4magnetic nanoparticle is processed
There-necked flask after above-mentioned steps (2) coating reaction is finished takes out, and reactant liquor is moved into 1000ml beaker, sedimentation on magnetic support, and with deionized water cyclic washing 5～7 times, until check in washing lotion without Cl
-and SO
4 2-and till pH=7.Gained magnetic-particle is moved into in surface plate, to put into vacuum drying chamber dry, vacuum degree is-0.1Mpa, and heating-up temperature is 60 ℃, and be 36 hours drying time.
(4) perfluoro polyether oil based magnetic liquid is made in high-energy ball milling or ultrasonic concussion
By the dry magnetic-particle (g) of gained in above-mentioned steps (3) with PFPE oil-based carrier liquid (ml) proportionally for 2:1.8 mixes, in mixture, add PFPE carboxylic acids surfactant, according to magnetic-particle (g), be that 20:1 adds with PFPE carboxylic acids surfactant (ml) ratio, further modify and make up not yet complete coated magnetic-particle.Adopt the method for high-energy ball milling to disperse, every 1h～3h, stop instrument cooling once, high-energy ball milling 12h finishes.Obtain crude product, crude product is precipitated and removes the bulky grain precipitating on magnetic support, repeatedly carry out this step 3～5 time, getting upper strata black even mixed liquor is perfluoro polyether oil based magnetic liquid, saturation magnetization is 600Gs, this magnetic liquid absolutely not fires, without flash-point, without self-ignition point, can be in pH=1～14, steady operation at-40 ℃～200 ℃ temperature, can be used in magnetic fluid sealing liquid structure, be particularly useful for military project and the aerospace fields such as military project radar rotary joint, all visors of tank, space station porthole and moonfall buffer unit.
Claims (8)
1. a preparation method for perfluoro polyether oil based magnetic liquid, first prepares exposed Fe by coprecipitation
3o
4magnetic nanoparticle, average grain diameter 10nm, then uses PFPE carboxylic acids surfactant to exposed Fe
3o
4magnetic nanoparticle carries out surface coating decoration, Fe after then modifying by high-energy ball milling method or ultrasonic oscillation method again
3o
4magnetic nanoparticle stable suspersion is in PFPE oils base load liquid, finally adopt magnetic support precipitation or ultracentrifugal method remove can not stable suspersion bulky grain obtain perfluoro polyether oil based magnetic liquid, it is characterized in that PFPE oils base load liquid has following structure: R
f[CF (CF
3) CF
2o]
ncF
2cF
3, R
f=F and CF
3, n=10～60 or CF
3-{ [O-CF (CF
3)-CF
2]
n-(O-CF
2)
m}-O-CF
3, m+n=4～60 wherein, m/n=18～1200, and PFPE oils base load liquid is that one or more in the chemical substance of above-mentioned two kinds of structure representatives are mixed in any proportion.
2. the preparation method of a kind of perfluoro polyether oil based magnetic liquid according to claim 1, is characterized in that exposed Fe
3o
4magnetic nanoparticle (g) with the additional proportion of PFPE carboxylic acids surfactant (ml) is: 40:1～1:1.
3. the preparation method of a kind of perfluoro polyether oil based magnetic liquid according to claim 1, is characterized in that the Fe after modifying
3o
4magnetic nanoparticle (g) with the additional proportion of PFPE oils base load liquid (ml) is: 1:20～2:1.
4. the preparation method of a kind of perfluoro polyether oil based magnetic liquid according to claim 1, is characterized in that again adding PFPE carboxylic acids surfactant in the process of high-energy ball milling or ultrasonic oscillation, and additional proportion is according to the Fe after modifying
3o
4magnetic nanoparticle (g) is 50～20:0.1～5 with PFPE carboxylic acids surfactant (ml), further modifies and makes up not yet complete coated magnetic-particle.
5. the preparation method of a kind of perfluoro polyether oil based magnetic liquid according to claim 1, is characterized in that except the Fe after modifying
3o
4outside magnetic nanoparticle vacuum drying step, whole preparation flow, all without inflated with nitrogen or take other measures to get rid of oxygen and disturb, all completes under aerobic environment.
6. the preparation method of a kind of perfluoro polyether oil based magnetic liquid according to claim 1, usings deionized water as reaction medium and washing agent in preparation, it is characterized in that the resistivity at 25 ℃ of deionized waters is 18.2 Μ Ω .cm.
7. the preparation method of a kind of perfluoro polyether oil based magnetic liquid according to claim 1, it is characterized in that used high energy ball mill mill amount is 50ml*3, power is 50kW, and abrading-ball is agate material, particle diameter is respectively 2mm, 4mm, 6mm, and ultrasonic disperser frequency is 40kHZ.
8. the preparation method of a kind of perfluoro polyether oil based magnetic liquid according to claim 1, is characterized in that for reducing Fe in high-energy ball milling and ultrasonic procedure
3o
4due to the oxidation that intensification causes, take interval cool-down method, cooling extent is 0.7 ℃/min～2 ℃/min.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996480A (en) * | 2014-06-11 | 2014-08-20 | 黑龙江工程学院 | Perfluoropolyether-grease-based magnetic fluid and preparation method thereof |
| CN105174317A (en) * | 2015-09-08 | 2015-12-23 | 北京交通大学 | Novel technology for synthesizing nanometer Fe3O4 particles for magnetic liquid |
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| CN106782966A (en) * | 2016-11-18 | 2017-05-31 | 合肥工业大学 | Process for dispersing of the friction induction magnetic nanoparticle in bio oil |
| CN107393675A (en) * | 2017-07-14 | 2017-11-24 | 四川大学 | A kind of fluorine ether acid@Fe3O4The preparation method of the compound fluorine ether oil based magnetic rheologic liquids of@GO |
| CN107545973A (en) * | 2017-06-26 | 2018-01-05 | 中国科学院理化技术研究所 | Liquid metal magnetofluid and preparation method thereof |
| CN107799262A (en) * | 2017-11-17 | 2018-03-13 | 四川大学 | A kind of high saturation and magnetic intensity Mn0.8Zn0.2Fe2O4The preparation method of nano particle and its magnetic liquid |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996480A (en) * | 2014-06-11 | 2014-08-20 | 黑龙江工程学院 | Perfluoropolyether-grease-based magnetic fluid and preparation method thereof |
| CN103996480B (en) * | 2014-06-11 | 2016-09-21 | 黑龙江工程学院 | A kind of fluorine element oil-based magnetic fluid and preparation method thereof |
| CN105174317A (en) * | 2015-09-08 | 2015-12-23 | 北京交通大学 | Novel technology for synthesizing nanometer Fe3O4 particles for magnetic liquid |
| CN105225786A (en) * | 2015-11-02 | 2016-01-06 | 江苏海纳精密装备有限公司 | A kind of preparation method of PFPE oil-based magnetic fluids material |
| CN106782966A (en) * | 2016-11-18 | 2017-05-31 | 合肥工业大学 | Process for dispersing of the friction induction magnetic nanoparticle in bio oil |
| CN107545973A (en) * | 2017-06-26 | 2018-01-05 | 中国科学院理化技术研究所 | Liquid metal magnetofluid and preparation method thereof |
| CN107393675A (en) * | 2017-07-14 | 2017-11-24 | 四川大学 | A kind of fluorine ether acid@Fe3O4The preparation method of the compound fluorine ether oil based magnetic rheologic liquids of@GO |
| CN107799262A (en) * | 2017-11-17 | 2018-03-13 | 四川大学 | A kind of high saturation and magnetic intensity Mn0.8Zn0.2Fe2O4The preparation method of nano particle and its magnetic liquid |
| CN107799262B (en) * | 2017-11-17 | 2019-10-29 | 四川大学 | A kind of high saturation and magnetic intensity Mn0.8Zn0.2Fe2O4The preparation method of nano particle and its magnetic liquid |
| CN108611156A (en) * | 2018-04-13 | 2018-10-02 | 天津长芦新材料研究院有限公司 | A kind of graphite oxide ene-type perfluoroalkyl polyether grease additive and preparation method thereof |
| CN108611156B (en) * | 2018-04-13 | 2022-03-18 | 天津长芦新材料研究院有限公司 | Graphene oxide type fluoropolyether oil additive and preparation method thereof |
| CN109065319A (en) * | 2018-09-12 | 2018-12-21 | 自贡兆强密封制品实业有限公司 | A kind of superelevation saturation magnetization Fe3O4The preparation method of nano particle and its magnetic fluid |
| CN113921222A (en) * | 2021-10-27 | 2022-01-11 | 南京晶脉科技有限公司 | Magnetic fluid material, preparation method, fluid dynamic sealing method and application thereof |
| CN113921222B (en) * | 2021-10-27 | 2022-06-21 | 南京晶脉科技有限公司 | Magnetic fluid material, preparation method, fluid dynamic sealing method and application thereof |
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