CN102766439B - High-temperature coefficient high stable room temperature switch nanocomposite - Google Patents
High-temperature coefficient high stable room temperature switch nanocomposite Download PDFInfo
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- CN102766439B CN102766439B CN201210230969.9A CN201210230969A CN102766439B CN 102766439 B CN102766439 B CN 102766439B CN 201210230969 A CN201210230969 A CN 201210230969A CN 102766439 B CN102766439 B CN 102766439B
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Abstract
The present invention relates to the preparation of high-temperature coefficient high stable room temperature switch nanocomposite and performances, belong to a kind of novel intelligent composite function nano material.The present invention proposes the nano material profit with excellent heat, electricity, magnetic transfer characteristic be prepared switch nanocomposite with the insulating properties base fluid flexible combination of fixed crystalline temperature, the interface affinity for enhancing itself and base fluid is modified by the surface to nano material so that the on-off ratio and stability of composite material greatly improve.In the energy, the fields such as biologic medical have broad application prospects this very strong intelligent nano composite functional material of practicability.
Description
Technical field
The invention belongs to a kind of novel intelligent composite function nano materials
Background technology
Since the thermistor effect that faraday has found silver sulfide, it includes ceramics that scientific research personnel, which has developed a series of,
Thermistor (thermistor) material including base and polymer matrix composite.Wherein there is critical-temperature coefficient (CTR)
Thermistor material have the function of " self-locking " near its phase transition temperature, and show special intelligent characteristic, receive
The extensive concern of industrial quarters is sensing, temperature control, current limliting, and the fields such as overload protection have a wide range of applications.These thermistor materials
The critical-temperature of material is determined by its phase transformation (ceramic base) or softening temperature (polymer matrix).In the material having been reported, VO2's
Phase transition temperature is closest to room temperature, about 340K.Although the adjusting of ingredient can change critical-temperature, its range adjusted
It is limited.For critical-temperature, the thermo-sensitive material of (0-40 DEG C) within the scope of room temperature has urgent demand to the mankind, because it can be straight
It scoops out for related fields such as room temperature control, energy saving, biologic medicals, the life to improving the mankind has great meaning.
Room temperature switch nanocomposite be insulating properties base fluid by crystalline temperature within the scope of room temperature and with excellent heat,
What the nano material of the transmission performances such as electricity, magnetic was combined, the composite material is in its base fluid by the process that liquid phase is solid phase
Middle nano material, which can be assembled into space and ooze, exceedes network, so that the transmission characteristics such as thermal conductivity, conductance, magnetic conductance of composite material are substantially
Improve, and during solid phase transformation becomes for liquid phase nano material ooze exceed network can due to the ablation of crystal and the convection current of liquid and
It is destroyed, to restore its original transmission characteristic.Both physical phenomenons rice is combined into, it will establish a kind of new intelligence
Energy working machine system, develops a series of novel nanocomposite materials with switching characteristic.
Courts of a feudal ruler Zheng Rui et al.[1]Nano graphite flakes room temperature switch nanocomposite is successfully prepared and has studied, this is compound
For material when using 16 alkane as base fluid, the conductivity variations of composite material reach 2 magnitudes, thermal conductivity near its crystalline temperature
Variation reaches 3 times, shows preferable intelligent switch characteristic, but due to the nano graphite flakes of non-surface modification and 16 alkane
The interface affinity of base fluid is poor, causes graphite flake during composite material repeats to freeze because being repeatedly extruded, and causes
Expendable serious agglomeration, to affect the practicability of composite material.
Currently, other nano materials with excellent physical chemical property and special construction are in room temperature in addition to nano graphite flakes
The application study in switch nanocomposite field is unfolded not yet.Carbon family nano material, such as：Carbon nanotube, graphene, richness
Strangle from alkene, carbon black, the self-discoveries such as carbon fiber just because its excellent physics, chemistry, mechanical performance and its unique structure by
Extensive concern has been arrived, has also achieved preferable achievement in the research and application of field of compound material, though it is foreseeable that carbon
Race's nano material also has larger application potential in switch nanocomposite field.By a series of technological means, such as
Replace the base fluid with different crystalline temperatures and be adjusted flexibly the switch temperature of composite material, adjust nano-composite material type and
Surface modification method improves different nano materials and variety classes base by surface modification to improve the on-off ratio of composite material
The interface affinity of liquid, enhance composite material will push this kind of material to move towards practical application using repeatability and stability.
Invention content
It is an object of the invention to：
(1) use the nano material of variety classes and different dimensions as the filling of novel Room Temperature switch nanocomposite
Material, and the switch temperature of composite material is adjusted flexibly by choosing the base fluid of different room temperature crystalline temperatures.
(2) it is directed to different types of base fluid, the correlation method that surface modification is carried out to nano-composite material is provided, to improve
The on-off ratio of composite material enhances the interface affinity of packing material and base fluid, improves stability of the composite material under liquid phase
And practicability.
In addition, all nano materials with excellent transmission characteristic and all insulating liquids with fixed crystalline temperature are all
It can be respectively as the packing material and base fluid of switch composite material.
Separately below to the working mechanism of room temperature switch nanocomposite, material selection, preparation method and performance characteristic
It is illustrated respectively.Room temperature switch nanocomposite is insulating properties base fluid by crystalline temperature within the scope of room temperature and with excellent
The nano materials of the transmission performances such as heat, electricity, magnetic be combined, the nano material filled is by liquid phase in its base fluid
By the extruding of base fluid crystal to mutually abut during solid phase, three-dimensional space is formed at crystal boundaries and is oozed exceed net
Network, so that the transmission characteristics such as thermal conductivity, conductance, magnetic conductance of composite material greatly improve, and by solid phase transformation be liquid phase change in base fluid
Nano material, which is oozed, in the process is exceeded network and can be destroyed due to the ablation of crystal and the convection current of liquid, original to restore its
Transmission characteristic.The preparation of composite material can choose all nano materials with excellent transmission characteristic as packing material, example
The carbon family nano material of such as metal nano material, metal oxide nano-material and different dimensions, can select room temperature range
Base fluid of the liquid of crystalline temperature as composite material within the scope of (0-40 DEG C) or non-room temperature, such as：20 alkane (36.4 DEG C), 19 alkane
(32 DEG C), 18 alkane (28 DEG C), 16 alkane (18.1 DEG C), methyl hexadecanoate (29 DEG C), glycerine (17.9 DEG C) and water (0 DEG C) etc..At this
In some embodiments of invention, the fullerene and carbon black of zero dimension, one-dimensional carbon fiber and carbon nanotube, two-dimensional nano graphite flakes
It is scattered in hydrophobicity base fluid with what graphene can be stablized, such as in 20 alkane, 19 alkane, 18 alkane, 16 alkane or methyl hexadecanoate.Not
Winding and aggregation easily occur during being squeezed by base fluid crystal for the carbon nanomaterial of surface modification, and then in base fluid crystalline substance
It cannot preferably restore to disperse after body ablation, show poor repetition practicality characteristic.In certain embodiments of the present invention
Pass through the carbon for selecting the functional group similar with base fluid molecular structure to be surface modified to be stablized to carbon nanomaterial
Nano material --- suspension and carbon nanomaterial of hydrophobicity base fluid --- suspension of hydrophily base fluid.By surface modification
Carbon nanomaterial base fluid crystal repeat melt during show good recovery dispersing characteristic, show preferably
Repetition practicality characteristic, room temperature switch carbon nano-composite material is near its base fluid transformation temperature in certain embodiments of the present invention
3 times are at least up to the modulation of thermal conductivity, the modulation to conductivity has been more than 5 magnitudes, and respectively in composite material base fluid
Crystal reaches stable after repeating ablation 3 times, and composite material under liquid phase is still steady after repeating to freeze and melt 20 times or more
Fixed suspension, is not separated.Therefore the present invention proposes a kind of room temperature switch at low cost, simple for process, highly practical
Nanocomposite preparation method can have high-temperature coefficient, the temperature sensor of high stability and temperature control as a kind of
Device processed.
Herein, it enumerates sensible to the object of the invention measure for the exemplary embodiments of the present invention.
The embodiment of the present invention is related to the preparation method and performance characterization of room temperature switch nanocomposite, for example, by
Insulating properties base fluid of the transformation temperature within the scope of room temperature and with high conductance, thermal conductivity, the nano material of magnetic conductance transmission characteristic it is compound and
At room temperature switch nanocomposite can be directly by the way that simply nano material ultrasonic disperse be obtained in base fluid, Huo Zhetong
It crosses and rear ultrasonic disperse is surface modified to nano material is obtained in base fluid.
Nano structural material refers to the average length in those at least one dimensions between 1 nanometer to 100 nanometers
Material.In some embodiments, it is about 100 nanometers as the nano material of filler at least one dimension, 50 nanometers,
40 nanometers, 30 nanometers, 20 nanometers, 10 nanometers or 5 nanometers.Therefore non-limiting nano structural material includes generally each side
To all the particle of size is being received, either has and receive the linear shape or have of cross section scale and receive piece/dish structure of thickness.It
Scale in each dimension can use scanning electron microscope (SEM) or transmission electron microscope (TEM), dynamic Laser
It scatters the technologies such as particle size analyzer and carries out accurate Characterization.
Corresponding surface modification, common surface modification method packet are taken to nano material according to the type of basis material
It includes：Chemical modification and physical modification；Chemical modification be using specific functional group by with nano-material surface atom formationization
Key is learned to achieve the purpose that surface modification, and then changes its surface characteristic, it is successfully scattered in corresponding basis material,
The advantage of chemical modification is that functional group is connected to carbon material surface by the chemical bond of the strong bonds such as covalent bond, ionic bond energy, therefore
Surface modification has preferable stability, is not easy to be affected by the surrounding environment, the disadvantage is that lattice can be brought to corresponding material surface
Defect, the intrinsic transmission characteristics such as conductance and thermal conductivity to reduce material.Common chemical reaction is modified：Carboxylated is oxygen-containing
Base group modification, metallic particles and inorganic matter modification, alkyl and aryl compound modification, aliphatic compound modification, sulfenyl chemical combination
Object is modified, and macrocycle molecule is compound-modified and biomolecule is modified etc..In certain illustrative embodiments of the present invention, first
Carboxylated oxygen-containing group modification is carried out to carbon nanomaterial, is then realized to carbon by 18 amine and carboxyl reacting forming ion key
The surface modification of nano material is finally successfully scattered in what carbon nanomaterial was stablized in hydrophobicity base fluid.
The effects that physical modification refers to non-bonding modification, and specific functional group is adsorbed by surface electrostatic or physics coats
It realizes the surface modification to nano material, and then changes its surface characteristic, make it easier to be scattered in corresponding matrix material
In material, its advantage is that surface is modified mildly, the variation of material intrinsic structure and transmission characteristic will not be usually brought, the disadvantage is that function
Group and material surface combine can be weaker, desorption is easy under certain condition, to lose the effect of surface modification.Common physics
Modification includes：Discrete dosage forms surface modification (lauryl sodium sulfate, neopelex, polyvinyl alcohol, polypyrrole alkane
Ketone, methylcellulose, saponin etc.) and macromolecule polyalcohol coating decoration (large biological molecule, organic polymer molecules etc.) etc..
In certain illustrative embodiments of the present invention, carbon nanomaterial is repaiied by ionic dispersant neopelex
Decorations are finally successfully scattered in what carbon nanomaterial was stablized in hydrophily base fluid.
In addition, the surface modification method of nano material, which also has, irradiates modification, pulse streamer discharge, microwave treatment etc..It is selecting
It, should be from being conducive to improve nano material and corresponding matrix when selecting the method being surface modified to relevant nanometer material and functional group
Synthesis is examined in terms of interface affinity between material, the stability of system and the cost and complexity of reduction surface modification processes
Consider
It is every other nano combined for switching other than the surface modification method described in illustrative embodiment of the present invention
The surface modification method of material preparation should all belong to the scope of protection of the present invention.
The present invention is a kind of composite system with room temperature high-temperature coefficient high stable temperature-sensitive intelligent transportation characteristic, phase
There are the advantages such as at low cost, simple for process, temperature control coefficient height, room temperature range for traditional temperature-sensitive intelligent control material, saving
Multiple biologies such as energy, automatic control, sensing, industrial circle have important application prospect.
The temperature-sensitive transmission characteristic of composite material is achieved through the following technical solutions.The measurement of thermal conductivity is to pass through
Y.Nagasaka and A.Nagashima[2]Design, the thermal transient linear system voluntarily built are united come what is realized, and the measurement of conductivity is logical
Cross what the two plate resistance test unit voluntarily built was completed, conductivity δ passes through formula：
δ=k/R,
It is calculated, k is test cell constant, and R is sample to be tested resistance value.The magnetic conductivity of composite material is to use the U.S.
LakeShore companies produce what 7400 type vibrating specimen magnetometers were characterized and tested.
The present invention has following major advantage compared with prior art：
First passage of the present invention experiments have shown that composite material liquid phase lower part surface functional group modification can be to nano material
Contact with each other generate space steric effect, to effectively prevent nano material under liquid phase 3 dimension exceed the shape for oozing transmission network
At so that transmission performance of the composite material under liquid phase is poor, during composite material base fluid crystallizes, part surface modification
Nano material contact with each other and squeeze under the great stress of crystal around, crystal growth stabilization after, nano material
It forms complete 3 and ties up to exceed and ooze transmission network so that the transmission characteristic of composite material significantly improves, compound to effectively increase
The on-off ratio of material, in certain embodiments of the present invention, composite material have been more than 5 orders of magnitude to the modulation of conductance, are realized
Insulator --- conductor changes.Surface modification equally destroys nano material in composite material Percolation network, material weight
It is played a crucial role during new dispersion.In the process, the close base fluid functional group of nano-material surface to receive
Rice material is more easy to remove from Percolation network under the drive of base fluid molecule, oozes net to effectively overcome nano material exceeding
Serious agglomeration in network and the problem of irrecoverable dispersion so that the practicability of room temperature switch nanocomposite effectively improves.This
In the energy, the fields such as biologic medical have broad application prospects the kind very strong intelligent nano composite functional material of practicability.
Description of the drawings
Attached drawing is used to provide further understanding of the present invention, and a part for constitution instruction, the allusion quotation with the present invention
Type embodiment is used to explain the present invention together, but does not constitute any restrictions to embodiment of the present invention.Wherein：
Fig. 1 shows the preparation flow figure of room temperature switch carbon nano-composite material in typical case；
Fig. 2 shows the high-resolution-ration transmission electric-lens comparison diagram of original state carbon nanotube and 18 amido long-chain carbon nano tubes,
Wherein 2-1 is original state carbon nanotube, and 2-2 is 18 amido long-chain carbon nano tubes；
Fig. 3 shows the mid-infrared light spectrogram of original state carbon nanotube and 18 amido long-chain carbon nano tubes, wherein 3-1
For original state carbon nanotube, 3-2 is 18 amido long-chain carbon nano tubes, and 3-3 is the poor spectrogram of 3-1 and 3-2；
Fig. 4 shows composite material using 16 alkane as base fluid, and for carbon nanotube as packing material, 18 amine are surface modification official
When can roll into a ball, the switching mechanism schematic diagram of composite material, wherein 4-1 is under original state liquid phase, and 4-2 is under solid phase, and 4-3 is solid phase
After ablation under liquid phase；
Fig. 5 shows composite material using 16 alkane as base fluid, and carbon nanotube is packing material, and loading is volume fraction
When 1.2% near base fluid crystalline temperature conductivity change schematic diagram；
Fig. 6 shows composite material using 16 alkane as base fluid, and carbon nanotube is packing material, and loading is volume fraction
When 0.4% near base fluid crystalline temperature thermal conductivity change schematic diagram；
Specific implementation mode
The specific implementation mode of exemplary embodiments of the present invention is illustrated below, it should be understood that allusion quotation described herein
Type embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Carbon nanomaterial is scattered in the intensive polar solvents such as glycerine and deionized water by embodiment one using Chemical modification
In, the step of preparing this kind of room temperature switch carbon nano-composite material, is as follows：
(1) it configures the concentrated sulfuric acid and the volume ratio of concentrated nitric acid is：3/1 mixed acid；
(2) carbon nano-particle is put into mixed acid and carries out carboxylation reaction, the reaction ratio of mixed acid and carbon nanomaterial
Example is 100ml: 0.1g；
(3) mixed acid and the mode of carbon nanomaterial reaction are respectively：Carbon nanotube, at room temperature 50W ultrasonic reactions 6h.Charcoal
Black, fullerene, nano graphite flakes, flow back in mixed acid solution 4h at room temperature.Graphene flows back in mixed acid solution at room temperature
2h；
(4) reaction product by supercentrifuge (10000rpm) repeated washing until nano-material surface pH value is close to 7,
Then the miillpore filter for being 0.2um with aperture filters product, and product is put into 90 DEG C of baking ovens dry 12h and obtains after filtration
Final product；
(5) nano material after surface modification is scattered in by corresponding base by the plug-in type ultrasonic device that power is 500W
In liquid, ultrasonic time is subject to form uniform suspension；
Carbon nanomaterial is scattered in 20 alkane (36.4 DEG C), 19 alkane (32 DEG C), 18 by embodiment two using Chemical modification
When the nonpolar solvents such as alkane (28 DEG C), 16 alkane (18.1 DEG C), methyl hexadecanoate (29 DEG C), it is multiple to prepare this kind of room temperature switch carbon nanometer
The step of condensation material, is as follows：
(1) carbon nanomaterial of carboxylated and 18 amine are uniformly mixed with the ratio that mass ratio is 1: 4；
(2) mixture is placed in closed container and reacts 96h under the conditions of 95 DEG C；
(3) reactant is cleaned with a large amount of ethyl alcohol after reaction, after repeating 3 to 5 times, the micropore for being 0.2um with aperture is filtered
Membrane filtration crosses reactant, and to ensure to wash away 18 extra amine impurity of nano-material surface, product after filtration is then placed in vacuum ring
Drying at room temperature is for 24 hours in border；
(4) nano material after surface modification is scattered in by corresponding base by the plug-in type ultrasonic device that power is 500W
In liquid, ultrasonic time is subject to form uniform suspension；
Embodiment three is modified using dispersant (lauryl sodium sulfate) carbon nanomaterial being scattered in glycerine and deionization
In the intensive polar solvents such as water, the step of preparing this kind of room temperature switch carbon nano-composite material, is as follows：
(1) lauryl sodium sulfate --- the deionized water mixture base fluid that configuration quality score is 1%；
(2) carbon nanomaterial is poured into the concentration of 50mg/l in above-mentioned base fluid；
(3) it is gone using the plug-in type ultrasonic device that power is 500W to being mixed with carbon nanomaterial and lauryl sodium sulfate
Ion aqueous mixtures base fluid is ultrasonically treated, and ultrasonic time is subject to form uniform suspension；
(4) by mixture using aperture be 0.2um miillpore filter be filtered, and in deionized water by high speed from
Scheming (10000rpm) repeated washing is to ensure to remove extra lauryl sodium sulfate；
(5) will consider wash after product practicality plug-in type ultrasonic device under lower power (100W) be scattered in again from
Sub- water or glycerine, to obtain the stabilization suspension for the carbon nano-particle that dispersant is modified.
Example IV, using macromolecule polyalcohol (polyvinylpyrrolidone) modification by carbon nanomaterial be scattered in glycerine and
In the intensive polar solvents such as deionized water, the step of preparing this kind of room temperature switch carbon nano-composite material, is as follows：
(1) preparation process is the same as embodiment three；
(2) polyvinyl pyrrole that mass fraction is 1% will be added in the uniform suspension obtained in embodiment three
Then mixture is placed 12h by alkanone at 50 DEG C；
(3) by mixture using aperture be 0.2um miillpore filter be filtered, and in deionized water by high speed from
Scheming (10000rpm) repeated washing is to ensure to remove extra polyvinylpyrrolidone；
(4) will consider wash after product practicality plug-in type ultrasonic device under lower power (100W) be scattered in again from
Sub- water or glycerine, to obtain the stabilization suspension for the carbon nano-particle that macromolecule polyalcohol wraps up.
Embodiment five, one-step method prepare hydrophobic group Fe3O4Ferrofluid is switched, it can be by Fe3O4Stable is scattered in 20 alkane
It is prepared by the nonpolar solvents such as (36.4 DEG C), 19 alkane (32 DEG C), 18 alkane (28 DEG C), 16 alkane (18.1 DEG C), methyl hexadecanoate (29 DEG C)
The step of this kind of room temperature magnetic switch nanocomposite, is as follows：
(1) at room temperature by FeCl3·6H2O and FeCl2·4H2The mixture of O presses Fe3∶Fe2Be dissolved in at=1.85: 1
In the NaCl solution of 0.1mol/L and filter；
(2) a certain amount of oleic acid and certain nonpolar solvent are mixed for use；
(3) iron salt solutions, nonpolar solvent mixed liquor are poured into three-necked flask, nitrogen is continually fed into the flow of 8L/min
And 10min is stirred to exclude the air in solution and reactor；It is quickly added by several times into reactor and analyzes pure ammonium hydroxide
(26.5w%) reaction a period of time obtains Fe3O4Black suspension (is continually fed into nitrogen)；
(4) its layering is enabled by obtained suspension is static, extracting the black liquor on upper layer, to obtain hydrophobic group nonpolarity molten
The switch ferrofluid of agent.
Finally, it should be noted that, it the above is only the exemplary embodiments for enumerating the present invention.On it is clear that the invention is not restricted to
Embodiment is stated, there are many more the operative combinations and material surface method of modifying of material preparation.Those skilled in the art's energy
The all scenario for directly exporting or associating from present disclosure should all be considered protection scope of the present invention.
[1]nature communication；Ruiting Zheng, Jinwei Gao, Jianjian Wang, Gang
Chen；nature publishing；2011.4.19；2：298；
[2]Journal of Physics E：Scientific Instruments；Y.Nagasaka,
A.Nagashima；IOP publishing；1981,14.1435.
Claims (10)
1. a kind of preparation method with switching characteristic nanocomposite, it is characterized in that：The nano material used is as switch
The packing material of nanocomposite, and adjust switch nanocomposite by choosing the base fluid of different temperatures crystalline temperature
Switch temperature；For different types of base fluid, corresponding surface modification is carried out to packing material, to enhance packing material and base fluid
Stability under liquid phase of interface affinity and switch nanocomposite；
The working mechanism of the switch nanocomposite refers to that switch nanocomposite is by liquid phase crystallization in its base fluid
Transmission network is formed by the extruding of crystal when solid phase, switch nanocomposite transmission characteristic is made to improve, in its base fluid by solid
Transmission network is destroyed due to the ablation of crystal when being mutually molten into liquid phase, and it is special that switch nanocomposite restores its original transmission
Property；
The switch nanocomposite refers to transmitting spy to the conductivity, thermal conductivity and magnetic conductivity of switch nanocomposite
Property temperature-sensitive intelligently connecting or disconnecting control.
2. according to the method described in claim 1, it is characterized in that：The switch temperature of the switch nanocomposite refers to room
Within the scope of warm range or non-room temperature, the room temperature range refers to 0-40 DEG C.
3. according to the method described in claim 1, it is characterized in that：The switch nanocomposite to the modulation of conductivity extremely
More than 5 orders of magnitude less realize transformation of the switch nanocomposite electric conductivity from insulator to conductor.
4. according to the method described in claim 1, it is characterized in that：The switch nanocomposite to the modulation of thermal conductivity extremely
3 times are reached less.
5. according to the method described in claim 1, it is characterized in that：The packing material refers to metal nano material, metal oxygen
The carbon family nano material of compound nano material and different dimensions.
6. according to the method described in claim 1, it is characterized in that：The base fluid of the selection different temperatures crystalline temperature refers to having
The liquid of fixed crystalline temperature.
7. according to the method described in claim 1, it is characterized in that：It is described corresponding surface carried out to packing material be modified be
Refer to：Use one or both of biomolecule modification or chemical modification method of modifying.
8. according to the method described in claim 1, it is characterized in that：Stability of the switch nanocomposite under liquid phase
Refer to switch nanocomposite it is stable suspension under liquid phase after the completion of preparation.
9. according to the method described in claim 1, it is characterized in that：The switch nanocomposite is repeating to freeze and melt 20
It is secondary it is above after be still stable suspension under liquid phase, be not separated.
10. according to the method described in claim 1, it is characterized in that：The switch nanocomposite can be used as a kind of tool
Have high-temperature coefficient, high stability temperature sensor and temperature control equipment.
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| CN109444053B (en) * | 2018-12-25 | 2020-10-02 | 南京大学 | Transient heat transfer microscope and method for measuring micro-area heat by using same |
| CN110556218B (en) * | 2019-01-21 | 2020-09-22 | 清华大学 | Flexible stretchable temperature-controlled conductor-insulator reversible transition material and application thereof |
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