CN103680799B - A kind of perfluoro polyether oil based magnetic liquid - Google Patents
A kind of perfluoro polyether oil based magnetic liquid Download PDFInfo
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Abstract
The invention discloses a kind of perfluoro polyether oil based magnetic liquid, this magnetic liquid is by exposed Fe3O4Magnetic nanoparticle, PFPE carboxylic acids surfactant and PFPE oils base load liquid three part composition.Exposed Fe3O4Magnetic nanoparticle (g) with the proportioning of PFPE carboxylic acids surfactant (ml) is: 40:1～1:1；Fe after modification3O4Magnetic nanoparticle (g) with the proportioning of PFPE oils base load liquid (ml) is: 1:20～2:1.PFPE based magnetic liquid saturation magnetization is 14Gs～600Gs, this magnetic liquid has superior resistance to chemical attack, high-low temperature resistant and radiation hardness, the absolutely not property such as burning, can be at pH=1～14, long-term stable operation at a temperature of-40 DEG C～200 DEG C, this is that general type magnetic liquid is beyond one's reach, and is particularly suited for the military industry field such as space station and Aero-Space.
Description
Technical field
The present invention relates to a kind of magnetic liquid, be specifically related to a kind of perfluoro polyether oil based magnetic liquid.
Background technology
Magnetic liquid is a kind of Nano-function thin films, is the magnetic crossed through surfactant coating decoration
Property particle height be scattered in base load liquid, form a kind of nanoscale, the colloid of " solid-liquid " biphase stable homogeneous mixing
, in gravitational field, magnetic field, electromagnetism, centrifugal field, there is not delaminating deposition in suspension.Owing to it has solid concurrently
The magnetic of material and the mobility of fluent material, it is possible to be magnetized rapidly under the effect of externally-applied magnetic field and have
Magnetic, after externally-applied magnetic field removes, magnetic disappears the most immediately, without coercivity and remanent magnetism, i.e. shows excellent
Superparamagnetism, thus there is a series of special physical and chemical performance, nano-meter characteristic and mobility, by extensively
General it is applied to the fields such as Aero-Space, machinery, the energy, material, chemical industry, bio-pharmaceuticals.
Different with the kind of surfactant according to base load liquid, magnetic liquid can be divided into: water base, keryl,
The type magnetic liquid such as gasoline base, synthetic ester base, polyglycols base, polyphenyl ether, hydrocarbons base.Specially
Profit CN101225233A in surfactant use Hamposyl L, N-Oleoylsarcosine, Laurel glycine,
Oleic acid or its sodium salt, base load liquid uses ethyl silicon oil to make magnetic liquid；In patent CN102063992A every
Under anoxybiotic gas, use paraffin, as base load liquid using plasma activation method, carbonyl iron dust is made magnetic liquid
Body；Patent CN1218902C does not add any surfactant and relies solely on regulation acidity to prepare cobalt
Ferrum oxygen molten iron based magnetic liquid, magnetic liquid is unstable, and may be only available for weak acid environment；Patent
Using carbonyl polysaccharide in ZL200510100230.6 is that water-base magnetic liquid prepared by surfactant, this magnetic liquid
Body is only applicable to biological field；Patent ZL200610036839.6 use polyamide-based dendritic amine surface live
Property agent prepares water-base magnetic liquid for the field such as target drug-carrying, nuclear magnetic resonance, NMR.Surface activity in above data
Agent and base load liquid are hydrocarbon type organic, and the magnetic liquid prepared is unstable, it is impossible to enough acid and alkali-resistances, resistance to
High/low temperature, suitable application area is limited.
Ester group, keryl, gasoline base, water-base magnetic liquid have reached the ripe practical stage, but these kinds
The magnetic liquid of class is along with the expansion of the scope of application, and its drawback day by day highlights, such as: can not be applicable to height
Temperature environment, can not acid and alkali-resistance, can not seal erosion medium, can not radiation hardness, can not apply
The extreme special environment etc. such as in space station, and perfluoro polyether oil based magnetic liquid due to its surfactant and
Base load liquid is fluorine ether material, its stable chemical nature, has a lot of property, it is possible to overcome above-mentioned
The use defect of special environment, has extremely strong using value.
Summary of the invention
The technical problem to be solved is: overcome the problem that existing magnetic liquid exists, it is provided that a kind of
Acid-alkali-corrosive-resisting, high-low temperature resistant, do not burn, the intensity of magnetization is high, good stability can be applicable to extreme ring
The perfluoro polyether oil based magnetic liquid of the especially military industry field in border.
For achieving the above object, the present invention adopts the following technical scheme that:
A kind of perfluoro polyether oil based magnetic liquid, including magnetic nanoparticle, surfactant and base load liquid three
Part.
Above-mentioned magnetic nanoparticle is Fe3O4Granule, uses coprecipitation to prepare, and particle diameter is 6～18nm, flat
All particle diameters are 10nm.
Above-mentioned surfactant is PFPE carboxylic acids, and magnetic liquid preparation is come by the selection of surfactant
Saying most important, can be related to magnetic liquid be successfully prepared, and whether magnetic liquid has that using value etc. is great asks
Topic, is also the primary difficulties solved of magnetic liquid preparation, because it rises in magnetic liquid preparation process
Discrete particles, improves particle surface performance and mates effects such as mixing with base load liquid.Wherein, PFPE carboxylic
Acids surfactant has a structure that Rf[CF(CF3)CF2O]nCF(CF3) COOH, wherein Rf=F or
CF3, n=3～60.
Above-mentioned base load liquid is PFPE oils, mixes for one of which or the most several arbitrary proportion.Base load
The selection of liquid must consider the factors such as chemical structural formula, viscosity, molecular weight, use temperature, and sternly
Lattice match with above-mentioned PFPE carboxylic acids surfactant, it is possible to the most molten, and these are all systems
The premise of standby magnetic liquid.Wherein, PFPE oils base load liquid has a structure that
CF3-{[O-CF(CF3)-CF2]n-(O-CF2)m}-O-CF3, wherein m+n=4～60, m/n=18～1200.
The concrete preparation method of a kind of perfluoro polyether oil based magnetic liquid is as follows:
(1) exposed Fe3O4The preparation of magnetic nanoparticle
The ionic equation of its reaction is: Fe2++2Fe3++8OH-=Fe3O4+4H2O, weighs a certain amount of in advance
FeCl3Dissolve in deionized water, under room temperature, be configured to certain density solution for standby, control bath temperature and exist
At 32～92 DEG C；Installation and debugging reaction unit, reaction there-necked flask all uses sealing in the case of not having material to add
Plug seals.The Fe configured is poured in there-necked flask3+Solution, mixing speed 100～600r/min, work as temperature
During close to preparation reaction temperature, it is Fe according to molar ratio2+: Fe3+=1:1.5～2 adds FeCl2Or FeSO4
Powder, reduces mixing speed and continues stirring and dissolving uniformly under 100～150r/min, monitoring iron salt mixing at any time
Liquid internal temperature, when temperature exceedes preparation reaction temperature 1～2 DEG C, example Fe in molar ratio3+: ammonia=1:
4～8 slowly pour into the strong aqua ammonia of 25%, and reactant liquor immediately becomes black, and adjusting rotating speed is 300～600r/min,
The precipitation time is 5～30min, prepares exposed Fe3O4Magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe3O4The coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), PFPE carboxylic acids surfactant can be with 25% strong aqua ammonia
It is simultaneously introduced reaction there-necked flask, it is also possible to be initially charged the strong aqua ammonia of 25%, then add again after reaction 5～30min
Enter PFPE carboxylic acids surfactant.Both can add in the case of stirring, it is also possible to stand
Under the conditions of add.Both can be at preparation Fe3O4Process terminate, react there-necked flask still at first water-bath
Interior addition, it is also possible to add after reaction there-necked flask is moved into second water-bath being used for coating reaction.
Water-bath temperature for cladding controls at 52～92 DEG C.Use any one of above-mentioned feed postition equal
Can, according to the ratio of exposed magnetic-particle (g) with surfactant (ml) it is: 40:1～1:1 adds perfluor
Polyether carboxyl acids surfactant, then starts stirring 400～700r/min, and the cladding time is 30～120min,
Make the Fe after cladding3O4Magnetic nanoparticle.
(3) Fe after cladding3O4Magnetic nanoparticle processes
There-necked flask after above-mentioned steps (2) coating reaction being terminated takes out, and reactant liquor moves into 1000ml and burns
Cup, settles under magnetic support, and with deionized water cyclic washing 5～7 times, until checking in washing liquid without Cl-And SO4 2-
And till pH=7.Gained magnetic-particle is moved in surface plate, puts in vacuum drying oven and be dried, vacuum
Degree is-0.1Mpa, and heating-up temperature is 30～90 DEG C, is generally 24～48 hours drying time.
(4) high-energy ball milling or ultrasonic vibration make perfluoro polyether oil based magnetic liquid
The magnetic-particle that gained in above-mentioned steps (3) is dried is weighed with PFPE oil-based carrier liquid according to modification
After magnetic-particle (g) mix with the ratio of base load liquid (ml) 1:20～2:1.Now can also be toward mixture
In supplement and add PFPE carboxylic acids surfactant, additional proportion gathers according to magnetic-particle (g) and perfluor
Ether carboxylic acids surfactant (ml) is 50～20:0～5, modifies the magnetic making up not yet complete cladding further
Property granule.The method using high-energy ball milling or ultrasonic wave concussion carries out mixing dispersion, at a high speed temperature during concussion
Up to 50～80 DEG C, for preventing intensification from causing oxidation, the method using interval cooling, cooling extent is 0.7 DEG C
/ min～2 DEG C/min, high-energy ball milling or ultrasonic 1h～20h terminate.One of which can be used merely, or
By the way of two kinds, mixture is prepared perfluoro polyether oil based magnetic liquid crude product, by crude product at magnetic
On seat, precipitation or high speed centrifugation remove the bulky grain that bottom settles down, and this step 3～5 time are repeated,
Taking upper strata black even mixed liquor is perfluoro polyether oil based magnetic liquid.
The performance characterization of a kind of perfluoro polyether oil based magnetic liquid includes:
Vibrating specimen magnetometer (VSM) test magnetization curve, can be seen that PFPE from Fig. 1 curve
Oil-based magnetic liquid is superparamagnetism, is zero without remanent magnetism, coercivity, and the intensity of magnetization of magnetic liquid is high；
Transmission electron microscope (TEM) test microscopic appearance, as can be seen from Figure 2 PFPE carboxylic acids surface
The magnetic-particle profile major part of activating agent cladding is spherical, and without adhesion, even particle size distribution, for 6-18nm；
X-ray diffraction (XRD) test crystalline structure, as can be seen from Figure 3 in (200), (311), (400),
(422), (511), (440) peak value occurs, this and exposed Fe3O4Diffraction spectrogram has same peak value
And pattern, illustrate that PFPE carboxylic acids surfactant cladding can't affect Fe3O4Crystalline structure, entirely
Perfluoroalkyl polyether carboxylic acids surfactant cladding Fe3O4It is still that inverse spinel structure.
The magnetic of Fourier infrared spectrograph (FTIR) test PFPE carboxylic acids surfactant cladding
The modification situation of grain, can analyze: 587cm from Fig. 4-1The absworption peak of corresponding Fe-O, 1350～1100cm-1
For the stretching vibration of C-F, 1250cm-1Near be the stretching vibration corresponding to-O-ehter bond, 1725～1700cm-1
For the absworption peak of-C=O carboxylate group, 3500cm-1Near be that a small amount of moisture absorption of sample causes, so from
Above-mentioned analysis learns that PFPE carboxylic acids surfactant has been coated on Fe3O4Surface.
Fig. 5 and 6 is at-40 DEG C of low temperature tests carried out, and Fig. 5 is cone and plate viscometer sample cell, at-40 DEG C
Time frosting, but perfluoro polyether oil based magnetic liquid-40 DEG C only viscosity of the inside slightly raises, mobility
Unaffected, magnetic property does not declines, and contrasts now water-base magnetic liquid and has frozen inefficacy.
Fig. 7 is to take out after perfluoro polyether oil based magnetic liquid continues uninterrupted heating 260 hours at 80 DEG C,
The intensity of magnetization only declines 1.3%, and viscous warm nature is unaffected, and volatile quantity is only 6.4069*10-5g/h/m2.And with
The water-base magnetic liquid of sample volume is continuous heating 4 hours at 80 DEG C, and magnetic liquid has been completely dried, this
Time water-base magnetic liquid complete failure.
Fig. 8 is 5 kinds of perfluoro polyether oil based magnetic liquids and a kind of ester group magnetic liquid (magnetic in magnetic liquid
Particle loads is identical but magnetic fluid volume different) at 200 DEG C air blast volatilize after 8 hours, ester group magnetic
Liquid complete oxidation display rufous, illustrates magnetic-particle Fe3O4Complete oxidation becomes Fe2O3,
Magnetic only remains 45%, and 5 kinds of perfluoro polyether oil based magnetic liquids are in addition to No. 4 a small amount of magnetic-particles separate out,
Substantially having no effect, PFPE carboxylic acids surfactant is to Fe3O4Cladding complete, stability is excellent
Good, magnetic residue up to 92%.
Fig. 9 is perfluoro polyether oil based magnetic liquid and ester group magnetic liquid strong at pH=1 and pH=14 respectively
The result soaked in acid, highly basic.After 4 months, perfluoro polyether oil based magnetic liquid in strong acid and highly basic the most not
Being corroded, the intensity of magnetization is without being decreased obviously, and apparent property is unchanged；And ester group magnetic liquid is at pH=1 strong acid
There is layering in 7 days in middle placement, and magnetic declines 70%, soaks 4 days ester group magnetic liquids in the highly basic of pH=14
Destroyed, magnetic-particle and base load liquid phase separation, the most nonmagnetic.
Perfluoro polyether oil based magnetic liquid has the most superior characteristic, depend entirely on its surfactant and
The performance of base load liquid.PFPE carboxylic acids surfactant and PFPE oils base load liquid belong to fluorine ether
Class material, it has the most excellent chemical stability, and the outer nearly all medicine of fluorine removal does not the most occur with it instead
Should, the strong acid and strong base such as the sulphuric acid that do not seethed with excitement, fuming nitric aicd, HF, strong oxidizer, melted caustic soda is the most rotten
Erosion property material corrodes, and molecular structure and chemical composition are constant；High and low temperature resistance is superior, at low temperature-40 DEG C
Simply viscosity slightly raises, but mobility is unaffected, chemolysis and aging does not occur at 290 DEG C, does not has
There are knot carbon or deposit, do not give off poisonous gas；The outer nearly all medicine of fluorine removal solvent is unable to it
Dissolve, such as Hydrocarbon, water, steam, chemical solvent etc.；Can never burn, there is no flash-point, do not have
There is self-ignition point will not react with combustion medium oxygen, itself can serve as explosion-proof hot media.
The present invention compared with prior art, has the advantage that
1. prepared and can be competent at the perfluoro polyether oil based magnetic liquid using demand under extreme special environment,
In pH=1～14 acid & alkali liquids, long-term immersion has no effect, can work steadily in the long term at-40 DEG C～200 DEG C
Making, even particle distribution, do not reunite, not coagulation, mobility is constant, and some conventional magnetic liquid are already
Volatilize, freeze or crack and lose use value.So the magnetic liquid solution Aero-Space of the present invention,
The visual plant long-standing special seal needs of problems of the industries such as machinery, chemical industry, pharmacy, biology.Make
For critical material promote as the tip device production domesticization of the field such as national defence, military project, manned space flight breakthrough enter
Exhibition.Widen magnetic liquid applied environment and use medium, for can not use conventional surfactants or
Add the most unfruitful field of wide variety of conventional surfactant.
2. the perfluoro polyether oil based magnetic liquid that prepared by the present invention, uses vibrating specimen magnetometer to measure saturated magnetic
Changing intensity is 14～600Gs, and the intensity of magnetization and viscosity can arbitrarily adjust.
3. the perfluoro polyether oil based magnetic liquid of the present invention is the most flammable.
4. the preparation method of the perfluoro polyether oil based magnetic liquid that prepared by the present invention is simple, and productivity is high, to equipment
Require low.
Accompanying drawing explanation
Fig. 1 is the magnetization curve of perfluoro polyether oil based magnetic liquid.
Fig. 2 is the TEM figure of the magnetic-particle of PFPE carboxylic acids surfactant cladding.
Fig. 3 is the XRD figure spectrum of the magnetic-particle of PFPE carboxylic acids surfactant cladding.
Fig. 4 is the FTIR collection of illustrative plates of the magnetic-particle of PFPE carboxylic acids surfactant cladding.
Fig. 5,6 it is that perfluoro polyether oil based magnetic liquid is at-40 DEG C of low temperature tests carried out.
Fig. 7 is after perfluoro polyether oil based magnetic liquid and water-base magnetic liquid continue uninterrupted heating at 80 DEG C
Situation about taking out.
Fig. 8 is 5 kinds of perfluoro polyether oil based magnetic liquids and a kind of ester group magnetic liquid air blast volatilization at 200 DEG C
Situation is taken out after 8 hours.
Fig. 9 is perfluoro polyether oil based magnetic liquid and ester group magnetic liquid strong at pH=1 and pH=14 respectively
The result soaked in acid, highly basic.
Detailed description of the invention
Embodiment 1
(1) exposed Fe3O4The preparation of magnetic nanoparticle
Weigh 5.40g FeCl3It is dissolved in 400ml deionized water, under room temperature, is configured to the molten of 0.05mol/L
Liquid is standby, controls bath temperature at 32 DEG C.The Fe configured is poured in there-necked flask3+Solution, stirring speed
Degree 300r/min, when temperature is close to preparation reaction temperature 32 DEG C, adds 1.98g FeCl2Powder, reduction is stirred
Mixing speed is to continue stirring and dissolving under 100r/min uniformly, and monitoring iron salt mixed liquor internal temperature, works as temperature at any time
When degree reaches 31～32 DEG C, slowly pouring into the strong aqua ammonia 20ml of 25%, reactant liquor immediately becomes black, adjusts
Turn over speed is 200r/min, and the response time is 30min, and preparation draws exposed Fe3O4Magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe3O4The coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), reaction there-necked flask is not being taken out, in the case of not stopping stirring
Add PFPE carboxylic acids surfactant 1ml.Then reaction there-necked flask is moved into and be used for being coated with the most flatly
In the water-bath of reaction, the water-bath temperature of cladding controls at 62 DEG C, starts stirring 300r/min, during cladding
Between 100min, make the Fe after cladding3O4Magnetic nanoparticle.
(3) Fe after cladding3O4Magnetic nanoparticle processes
There-necked flask after above-mentioned steps (2) coating reaction being terminated takes out, and reactant liquor moves into 1000ml and burns
Cup, settles on magnetic support, and with deionized water cyclic washing 5～7 times, until checking in washing liquid without Cl-And
Till pH=7.Moving into gained magnetic-particle in surface plate to put in vacuum drying oven and be dried, vacuum is
-0.1Mpa, heating-up temperature is 80 DEG C, and drying time is 24 hours.
(4) high-energy ball milling or ultrasonic vibration make perfluoro polyether oil based magnetic liquid
The magnetic-particle (g) that gained in above-mentioned steps (3) is dried and PFPE oil-based carrier liquid (ml)
Proportionally mix for 1:20.The scattered method of ultrasound wave is used to disperse, ultrasonic 1h, obtain crude product,
Crude product is precipitated on magnetic support and removes the bulky grain that bottom settles down, this step 3 time is repeated, takes
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, it is possible at pH=1～14, stable at a temperature of-40 DEG C～200 DEG C
Work, can be used in magnetic fluid sealing liquid structure, is particularly suited for military project radar rotary joint, tank
Military project and the aerospace fields such as all visors, space station porthole and moonfall buffer unit.
Embodiment 2
(1) exposed Fe3O4The preparation of magnetic nanoparticle
Weigh 54.0g FeCl3It is dissolved in 400ml deionized water, under room temperature, is configured to the solution of 0.5mol/L
Standby, control bath temperature at 42 DEG C.The Fe configured is poured in there-necked flask3+Solution, mixing speed
300r/min, when temperature is close to preparation reaction temperature 42 DEG C, adds 27.80g FeSO4Powder, reduction is stirred
Mixing speed is to continue stirring and dissolving under 100r/min uniformly, and monitoring iron salt mixed liquor internal temperature, works as temperature at any time
When degree reaches 41～42 DEG C, slowly pouring into the strong aqua ammonia 120ml of 25%, reactant liquor immediately becomes black, adjusts
Turn over speed is 400r/min, and the response time is 15min, and preparation draws exposed Fe3O4Magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe3O4The coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), reaction there-necked flask is not being taken out, in the case of not stopping stirring
Add PFPE carboxylic acids surfactant 7ml.Then reaction there-necked flask is moved into and be used for being coated with the most flatly
In the water-bath of reaction, the water-bath temperature of cladding controls at 72 DEG C, starts stirring 400r/min, during cladding
Between 45min, make the Fe after cladding3O4Magnetic nanoparticle.
(3) Fe after cladding3O4Magnetic nanoparticle processes
There-necked flask after above-mentioned steps (2) coating reaction being terminated takes out, and reactant liquor moves into 1000ml and burns
Cup, settles on magnetic support, and with deionized water cyclic washing 5～7 times, until checking in washing liquid without Cl-And SO4 2-
And till pH=7.Move into gained magnetic-particle in surface plate to put in vacuum drying oven and be dried, vacuum
For-0.1Mpa, heating-up temperature is 30 DEG C, and drying time is 24 hours.
(4) high-energy ball milling or ultrasonic vibration make perfluoro polyether oil based magnetic liquid
The magnetic-particle (g) that gained in above-mentioned steps (3) is dried and PFPE oil-based carrier liquid (ml)
Proportionally mix for 1:12, do not add PFPE carboxylic acids surfactant.Employing ultrasound wave disperses
Method disperse, ultrasonic 5h, obtain crude product, crude product is precipitated on magnetic support remove bottom sedimentation under
The bulky grain come, is repeated this step 3 time, and taking upper strata black even mixed liquor is PFPE oil base magnetic
Property liquid, saturation magnetization is 205GS, and this magnetic liquid absolutely not fires, without flash-point, without self-ignition point,
Can be at pH=1～14, steady operation at a temperature of-40 DEG C～200 DEG C, can be used for magnetic fluid sealing liquid structure
In, it is particularly suited for military project radar rotary joint, tank week visor, space station porthole and moonfall buffer unit
Etc. military project and aerospace field.
Embodiment 3
(1) exposed Fe3O4The preparation of magnetic nanoparticle
Weigh 54.0g FeCl3It is dissolved in 400ml deionized water, under room temperature, is configured to the solution of 0.5mol/L
Standby, control bath temperature at 52 DEG C.The Fe configured is poured in there-necked flask3+Solution, mixing speed
300r/min, when temperature is close to preparation reaction temperature 52 DEG C, adds 27.80g FeSO4Powder, reduction is stirred
Mixing speed is to continue stirring and dissolving under 100r/min uniformly, and monitoring iron salt mixed liquor internal temperature, works as temperature at any time
When degree reaches 51～52 DEG C, slowly pouring into the strong aqua ammonia 150ml of 25%, reactant liquor immediately becomes black, adjusts
Turn over speed is 400r/min, and the response time is 10min, and preparation draws exposed Fe3O4Magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe3O4The coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), reaction there-necked flask is not being taken out, in the case of not stopping stirring
Add PFPE carboxylic acids surfactant 8ml.Then reaction there-necked flask is moved into and be used for being coated with the most flatly
In the water-bath of reaction, the water-bath temperature of cladding controls at 72 DEG C, starts stirring 500r/min, during cladding
Between 60min, make the Fe after cladding3O4Magnetic nanoparticle.
(3) Fe after cladding3O4Magnetic nanoparticle processes
There-necked flask after above-mentioned steps (2) coating reaction being terminated takes out, and reactant liquor moves into 1000ml and burns
Cup, settles on magnetic support, and with deionized water cyclic washing 5～7 times, until checking in washing liquid without Cl-And SO4 2-
And till pH=7.Move into gained magnetic-particle in surface plate to put in vacuum drying oven and be dried, vacuum
For-0.1Mpa, heating-up temperature is 50 DEG C, and drying time is 24 hours.
(4) high-energy ball milling or ultrasonic vibration make perfluoro polyether oil based magnetic liquid
The magnetic-particle (g) that gained in above-mentioned steps (3) is dried and PFPE oil-based carrier liquid (ml)
Proportionally mix for 1:8, do not add PFPE carboxylic acids surfactant.Use the side of high-energy ball milling
Method carries out disperseing 5h, obtains crude product, is precipitated by crude product and remove the bulky grain that bottom settles down on magnetic support,
This step 3 time is repeated, and taking upper strata black even mixed liquor is perfluoro polyether oil based magnetic liquid, saturated
The intensity of magnetization is 416GS, and this magnetic liquid absolutely not fires, without flash-point, without self-ignition point, it is possible at pH=1～14,
Steady operation at a temperature of-40 DEG C～200 DEG C, can be used for, in magnetic fluid sealing liquid structure, being particularly suited for army
Military project and the Aero-Space such as work radar rotary joint, tank week visor, space station porthole and moonfall buffer unit
Field.
Embodiment 4
(1) exposed Fe3O4The preparation of magnetic nanoparticle
Weigh 54.0g FeCl3It is dissolved in 400ml deionized water, under room temperature, is configured to the solution of 0.5mol/L
Standby, control bath temperature, at 72 DEG C, pours the Fe configured in there-necked flask3+Solution, mixing speed
400r/min, when temperature is close to preparation 72 DEG C, adds 30.80g FeSO4Powder, reducing mixing speed is
100r/min, continues stirring and dissolving uniform, at any time monitoring iron salt mixed liquor internal temperature, when temperature reaches
When 71～72 DEG C, slowly pouring into the strong aqua ammonia 150ml of 25%, reactant liquor immediately becomes black, adjusts rotating speed
For 500r/min, the response time is 13min, and preparation draws exposed Fe3O4Magnetic nanoparticle.
(2) PFPE carboxylic acids surfactant is to exposed Fe3O4The coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (1), reaction there-necked flask is moved in the water-bath of 80 DEG C, start stirring
600r/min, adds PFPE carboxylic acids surfactant 11ml, is coated with time 120min, makes bag
Fe after covering3O4Magnetic nanoparticle.
(3) Fe after cladding3O4Magnetic nanoparticle processes
There-necked flask after above-mentioned steps (2) coating reaction being terminated takes out, and reactant liquor moves into 1000ml and burns
Cup, settles on magnetic support, and with deionized water cyclic washing 5～7 times, until checking in washing liquid without Cl-And SO4 2-
And till pH=7.Move into gained magnetic-particle in surface plate to put in vacuum drying oven and be dried, vacuum
For-0.1Mpa, heating-up temperature is 60 DEG C, and drying time is 36 hours.
(4) high-energy ball milling or ultrasonic vibration make perfluoro polyether oil based magnetic liquid
The magnetic-particle (g) that gained in above-mentioned steps (3) is dried and PFPE oil-based carrier liquid (ml)
Proportionally mix for 2:1.8, in mixture, add PFPE carboxylic acids surfactant, according to magnetic
Granule (g) and PFPE carboxylic acids surfactant (ml) ratio are that 20:1 adds, and repair further
Decorations make up the magnetic-particle of not yet complete cladding.The method using high-energy ball milling is disperseed, every 1h～3h
Stopping instrument lowering the temperature once, high-energy ball milling 12h terminates.Obtain crude product, crude product is precipitated on magnetic support and goes
Falling the bulky grain precipitated, this step 3～5 time are repeated, taking upper strata black even mixed liquor is perfluor
Polyether oil based magnetic liquid, saturation magnetization is 600Gs, and this magnetic liquid absolutely not fires, without flash-point, nothing
Self-ignition point, it is possible at pH=1～14, steady operation at a temperature of-40 DEG C～200 DEG C, can be used for magnetic fluid sealing
In liquid structure, it is particularly suited for military project radar rotary joint, tank week visor, space station porthole and moonfall
The military projects such as buffer unit and aerospace field.
Claims (8)
1. a perfluoro polyether oil based magnetic liquid, by exposed Fe3O4Magnetic nanoparticle, PFPE carboxylic
Acids surfactant and PFPE oils base load liquid three part is organic is prepared from, it is characterised in that exposed
Fe3O4Magnetic nanoparticle is to be done precipitant by the strong aqua ammonia of 25% to prepare, and lives in PFPE carboxylic acids surface
Property agent has a structure that Rf[CF(CF3)CF2O]nCF(CF3) COOH, wherein Rf=F or CF3, n=3～60,
PFPE oils base load liquid has a structure that CF3-{[O-CF(CF3)-CF2]n-(O-CF2)m}-O-CF3,
Wherein m+n=4～60, m/n=18～1200.
A kind of perfluoro polyether oil based magnetic liquid the most according to claim 1, PFPE carboxylic to be used
Acids surfactant is to exposed Fe3O4Magnetic nanoparticle carries out surface coating decoration, it is characterised in that exposed
Fe3O4Magnetic nanoparticle g with the proportioning of PFPE carboxylic acids surfactant ml is: 40:1～1:1.
A kind of perfluoro polyether oil based magnetic liquid the most according to claim 1, it is characterised in that after modification
Fe3O4Magnetic nanoparticle g with the proportioning of PFPE oils base load liquid ml is: 1:20～2:1.
A kind of perfluoro polyether oil based magnetic liquid the most according to claim 1, it is characterised in that saturated magnetic
Changing intensity is 14～600Gs.
A kind of perfluoro polyether oil based magnetic liquid the most according to claim 1, it is characterised in that this magnetic
Liquid can be at pH=1～14, steady operation at a temperature of-40 DEG C～200 DEG C.
A kind of perfluoro polyether oil based magnetic liquid the most according to claim 1, it is characterised in that this magnetic
Liquid absolutely not fires, without flash-point, without self-ignition point.
A kind of perfluoro polyether oil based magnetic liquid the most according to claim 1, it is characterised in that this magnetic
Liquid can be used in magnetic fluid sealing liquid structure.
A kind of perfluoro polyether oil based magnetic liquid the most according to claim 1, it is characterised in that this magnetic liquid
Body is applicable to military project radar rotary joint, tank week visor, space station porthole and moonfall buffer unit.
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| 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 |
| 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 |
| CN115064330B (en) * | 2022-07-04 | 2023-04-07 | 清华大学 | Low-temperature-resistant perfluoropolyether-based magnetic liquid and preparation method thereof |
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| US5013471A (en) * | 1988-06-03 | 1991-05-07 | Matsushita Electric Industrial Co., Ltd. | Magnetic fluid, method for producing it and magnetic seal means using the same |
| CN1959870A (en) * | 2006-09-22 | 2007-05-09 | 中山大学 | Magnetic liquid of vacuum pump oil |
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|---|---|---|---|---|
| US5013471A (en) * | 1988-06-03 | 1991-05-07 | Matsushita Electric Industrial Co., Ltd. | Magnetic fluid, method for producing it and magnetic seal means using the same |
| CN1959870A (en) * | 2006-09-22 | 2007-05-09 | 中山大学 | Magnetic liquid of vacuum pump oil |
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| 氟碳化合物基磁性液体制备及性能研究;王凡;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20131215(第S2期);正文第30页倒数第1-6行、第31页第1-12页、第27页第2段第1行、正文第47页4.2.2节第1段、正文第48页4.2.3节第1段 * |
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