CN103755958B - A kind of preparation method of polyimides/CaCu 3 Ti 4 O coated with silver nano particle composite material - Google Patents
A kind of preparation method of polyimides/CaCu 3 Ti 4 O coated with silver nano particle composite material Download PDFInfo
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Abstract
The invention discloses a kind of high dielectric, the preparation method of low-loss polyimides/CCTO@Ag nano particle composite material, the method is to prepare with polyimides for substrate, after the CCTO@Ag nano-particle prepared is carried out ultrasonic disperse in dehydrated alcohol, it is blended in solvent with polyimide monomers, monomer is the most at room temperature made to carry out home position polymerization reaction, realize simultaneously polyimides copolymerization and with the intercalation synthesis of CCTO@Ag nano-particle, the stock solution of gained uses coating method, polyimides/CCTO@Ag nanoparticle composite film is i.e. obtained through Gradient annealing.Use polyimides/CCTO@Ag nano particle composite material prepared by the inventive method compared with pure polyimides, its dielectric constant (103) improves 30 times, and there is relatively low dielectric loss (0.006), have broad application prospects in fields such as high energy-storage capacitor, artificial organ and high speed integrated circuits.
Description
Technical field
The present invention relates to a kind of high dielectric, low-loss polyimides/CaCu 3 Ti 4 O (CCTO) coated with silver (Ag) nucleocapsid structure
The preparation method of nano particle composite material, belongs to technical field of electronic materials.
Background technology
Polymer is owing to its excellent electricity, heat and ductility are in capacitor, integrated circuit and High-Voltage Insulation field
Have a wide range of applications, but the low characteristic of dielectric constant limits it and further develops.Along with current electronic applications device
Development integrated and that be miniaturized, it is desirable to provide the new material being provided simultaneously with high-k and low dielectric loss meets
Requirement.
In order to obtain required high performance material, current commonly used method is that polymeric material is doped modification,
Conventional doping method mainly has two kinds.One is with polymer as substrate, will have the ferroelectric ceramics of high-k
Grain is combined with it, prepares polymer/ferroelectric ceramics composite.But there are some problems in the method, one is the compound of synthesis
Its dielectric constant of material not high enough (typically smaller than 50), does not reaches the demand of actual application.The dielectric constant of composite can be with
The increase of the doping of ceramic particle and increase, but too high doping can cause again composite flexibility and other machines
The reduction of tool performance, also brings the increase of dielectric loss simultaneously.Excellent in order to obtain various aspects of performance under relatively low doping
Good composite, needs to find the material with more high-k；Two is that ferroelectric material has electrostriction effect, time long
Between use can bring Composites Fatigue, reduce the life-span of device；Three be pottery used be mostly a leaded class material,
This inevitably brings pollution to environment, it is therefore desirable to finds unleaded high dielectric constant material and is used as substituting；Four are
Ceramic particle size used is mostly in micron level, the problem that there is intercalation difficulty with polymer macromolecule compound tense so that multiple
Interaction zone biphase in fit system is little, and poor compatibility, the dielectric properties room for promotion that fundamentally result in material has
Limit.
Another method is that the nano material (metal nanoparticle or carbon nano-fiber etc.) mixing high conductivity is come
Preparation nanometer dielectric composite, this composite due to its excellent performance, is paid close attention to widely having obtained nearly ten years
Also achieving a lot of achievement, but there is problems of owing to exceeding the impact oozing theory, material can occur near percolation threshold
Phase transformation from insulator to conductor, thus cause its dielectric loss significantly to increase, bring difficulty to reality application.
Thus improve the dielectric topmost problem of nanometer and be present in the suitable method of searching to reduce the medium of material
Loss, there are some researches show that the dielectric loss of composite is higher, and topmost reason is that polymer and particles of inorganic material are biphase
More difficult compound, the most biphase dielectric constant values differs greatly and result in composite inner organic facies and bear bigger field intensity,
Limit the further raising of dielectric constant, it is therefore desirable to find new method to solve this problem.To inorganic particle surfaces
Carrying out processing and well solve this problem with Organic substance compound preparation nanometer electrolyte again, the surface of inorganic particle processes main
Increase polar group to be divided into, Coated with Organic Matter, this several method of inorganic particle cladding etc..
Leadless environment-friendly material CaCu 3 Ti 4 O (CCTO) is due to the huge dielectric constant of its abnormality and low-loss, in recent years
Paying close attention to increasing, its preparation method includes traditional solid state reaction and wet chemical method.Polyimides is combination property
One of optimal high-molecular organic material, high temperature resistant reaches more than 400 DEG C, life-time service temperature range-200 DEG C～300 DEG C,
Being particularly suitable for the use that works in harsh environment, at engineering field, microelectronic has a wide range of applications.At present for poly-
Acid imide is little with the report of CaCu 3 Ti 4 O (CCTO) composite, it is known that be reported as polyimides/micron CCTO composite wood
Material, it is dielectric constant the lowest (49) and dielectric loss higher (0.24) under higher doping ratio (40vol% CCTO),
The CCTO its preparation method of micron level used uses traditional solid reaction process, and the method needs higher temperature (to be more than
1000 DEG C) and time-consuming longer (more than 24 hours), additionally prepared its dispersibility of micron CCTO is poor, and macromole intercalation is relatively
For difficulty.
Summary of the invention
The present invention is directed to the biphase poor compatibility of composite in prior art and dielectric constant is low and dielectric loss is high
Problem, it is provided that a kind of polyimides/CCTO@Ag nano particle composite material with high-k and low dielectric loss
Preparation method.CCTO@Ag nano-particle, can be effectively due to the high electric conductivity of surface Argent grain and relatively low dielectric constant
Reduce percolation threshold, solve poor compatibility and difficult the asking of macromole intercalation that polymer exists with large-size particle compound tense
Topic, improves the compatibility between polyimides and CCTO@Ag nano-particle, promotes polyimides macromole and CCTO@Ag nanometer
The combination of granule, thus obtain the polyimides/CCTO@Ag nano particle composite material possessing premium properties.
The present invention prepares the CCTO@Ag nano-particle of good dispersion initially with wet chemistry method and crystal seed method, then
Utilize CCTO@Ag nano-particle that Kapton is doped, improve its dielectric constant.
The present invention provides the preparation method of a kind of polyimides/CCTO@Ag nano particle composite material, as it is shown in figure 1, should
Method is completed by following steps:
(1) prepare CCTO nano-particle, and coated with silver nano-particle outside CCTO granule with wet chemical method, formed
The nano-particle of CCTO@Ag nucleocapsid structure；
(2), after a kind of monomer of CCTO@Ag nano-particle Yu polyimides being uniformly dispersed in solvent, add another
A kind of monomer of polyimides, at starvation, under the conditions of 20～40 DEG C home position polymerization reaction 4-16 hour obtain polyimides/
The stock solution of CCTO@Ag nano particle composite material, wherein the cumulative volume of CCTO@Ag nano-particle and two kinds of monomers of polyimides it
Ratio is 1.5～5%；
(3) by (2) gained stock solution film in substrate, in the range of 60 DEG C～300 DEG C, in vacuum tank, Gradient annealing is carried out,
Polyimides/CCTO@Ag nanoparticle composite film is obtained after cleaning, drying.
In step (1), the crystal seed method after coated with silver nano-particle uses improvement outside CCTO granule is in nanometer CCTO
Granule periphery coated with silver nano-particle, the method specifically includes following steps:
(1) weigh the nanometer CCTO particle powder of 0.1 gram and the sodium hydroxide of 1.0204 grams is dissolved in the distilled water of 50 milliliters
In, ultrasonic 30 minutes, it is centrifuged drying, is obtained powders A.The stannic chloride of 0.5980 gram is joined 25 ml methanol and 25 millis
Rise in the solution of distilled water mixing, and the concentrated sulphuric acid (98wt%) adding 1 milliliter obtains solution B, and powders A is joined solution B
In, after stirring 1 hour, it is dried to obtain powder C through being repeatedly centrifuged washing.
(2) silver nitrate of 2.2932 grams and the ammonia of 1 milliliter are dissolved in the distilled water of 50 milliliters, obtain high concentration
Ammoniated silver nitrate solution D (0.27mol/L), is additionally dissolved in 50 milliliters by the silver nitrate of 0.4247 gram and the ammonia of 0.2 milliliter
In distilled water, obtain the ammoniated silver nitrate solution E (0.05mol/L) of low concentration.
(3) powder C is joined in solution D and react 30 minutes, after being centrifuged, again the powder obtained is joined solution E
In, it is sufficiently stirred for the CCTO@Ag nanoparticulate dispersion that reaction obtains being coated with for 17-24 hour, obtains institute through centrifugal drying
The CCTO@Ag powder of nanometric particles needed.
In one embodiment of the invention, the CCTO nano-particle that step (1) described wet chemical method is prepared straight
Footpath is 80 nanometers, a diameter of 35 nanometers of silver nano-grain of cladding.
In step (2), specifically include following steps:
(1) weigh a certain amount of CCTO@Ag powder of nanometric particles to be placed in glass container, then pour a certain amount of N into,
(DMAC) solution stirring in N-dimethyl acetylamide, is subsequently adding a certain amount of diaminodiphenyl ether (ODA) and is uniformly mixed,
And glass container is placed in ultrasonic dispersers process 0.5 hour～2 hours.
(2) weigh a certain amount of pyromellitic acid anhydride (PMDA) and add in above-mentioned mixed liquor, in starvation condition
Lower stirring reaction a period of time will obtain the stock solution of polyimides/CCTO@Ag nano particle composite material.
Described response hierarchy is optional first to be mixed CCTO@Ag nano-particle with diaminodiphenyl ether (ODA), and ultrasonic 0.5
Hour～mix with pyromellitic acid anhydride (PMDA) again after 2 hours, or first by CCTO@Ag nano-particle and equal benzene tetramethyl
Acid dianhydride (PMDA) mixes, and mixes with diaminodiphenyl ether (ODA) after ultrasonic 0.5 hour～2 hours again.Different proportioning tools
Body is, is first that the mol ratio of pyromellitic acid anhydride (PMDA) and diaminodiphenyl ether (ODA) is 1:1～1.2:1, secondly
CCTO@Ag nano-particle controls at 1.5vol%～5vol% with the ratio of the cumulative volume of two kinds of monomers of polyimides.Suitably reaction
Temperature is to keep 20 DEG C～40 DEG C in water-bath or oil bath.Starvation condition can be selected for nitrogen, noble gas or vacuum
Condition.
In step (3), specifically include following steps:
(1) select smooth surface and glass plate in uniform thickness, silicon chip or other there is the material conduct of higher melt
Substrate uses.
(2) by stock solution on the substrate, it is allowed to expansion pave.
(3) substrate is placed in container under the conditions of starvation annealing reaction and processes through the later stage that to obtain polyamides sub-
Amine/CCTO@Ag nanoparticle composite film.
Described container for baking oven or Muffle furnace or other container of higher temperature environment, starvation bar can be provided
Part can be selected for nitrogen, noble gas or vacuum condition.Annealing temperature is chosen several the most respectively in the range of 60 DEG C～300 DEG C
Value, 100 DEG C, 200 DEG C, is incubated 1 hour respectively by i.e. 60 DEG C at 300 DEG C, heating rate be maintained at 0.5 DEG C/min～2 DEG C/
Min, then Temperature fall.Later stage processes preferably by the glass plate immersion distilled water with laminated film 10 minutes～60 points
Clock, then takes laminated film off with tweezers, with distilled water flushing clean after put into baking oven, at 50 DEG C～90 DEG C, be incubated 2 little
Time～5 hours dry obtain polyimides/CCTO@Ag nanoparticle composite film.
The structural representation of the final composite prepared sees Fig. 4.
The present invention utilizes CCTO@Ag nano-particle to mix with two kinds of monomers of polyimides, on the one hand monomer and nanometer
Grain composite, on the other hand two kinds of monomers carry out in-situ polymerization and obtain polyimide molecule long-chain, to CCTO nano-particle table
After face processes by silver cladding, can effectively improve polyimides and CCTO being combined in interface so that CCTO@Ag nanometer
Granule is formed with polymeric matrix and uniformly and is firmly combined and effectively reduces percolation threshold, promotes the polarization at interface, improves
The Electric Field Distribution of composite inner, thus improve the dielectric constant of polyimides/CCTO@Ag composite, reduce its medium
Loss.The dielectric properties of prepared polyimides/CCTO@Ag nano particle composite material are significantly improved.
The polyimides that the present invention produces/CCTO@Ag nanoparticle composite film material is thin with the polyimides of pure phase
Film is compared, and under extremely low doping ratio (3vol%), the value of the high-k obtained improves about 30 times (103), and with
Time keep low dielectric loss (0.006).This composite is conducive to meeting the integrated of current capacitor and electronic device
Demand, brings new prospect for the preparation of later portable equipment, will store in high density energy simultaneously, High Performance Insulation every
A series of high-technology fields such as layer and thin-film device obtain and is widely applied, and two-phase composites interface phase can be promoted
Interaction Theory progress of research.
Compared with prior art, the preparation method of polyimides/CCTO@Ag nano particle composite material that the present invention provides
Having the advantage that one, owing to being to use wet chemistry method to synthesize CCTO nano-particle, its synthetic method is relatively easy, consumption
Time short (2 hours) and sintering temperature (700 DEG C) lower than traditional solid state reaction (1000 DEG C), thus energy consumption has and significantly drops
Low, save human and material resources and the energy.With the crystal seed method coated with silver nano-particle outside CCTO granule after improvement so that it is
Forming CCTO@Ag and have the nano-particle of nucleocapsid structure, relative to solid state reaction, it is the most equal that reactant mixes in the solution
Even, and reaction at room temperature carry out, it is easier to operation.The CCTO@Ag nano-particle size distribution generated uniformly and good dispersion,
Its transmission electron microscope picture is shown in Fig. 2；Its two, unleaded CCTO nano-particle environmentally safe, and not there is electrostriction effect, mix
The laminated film of preparation in polymer, long use is also not result in the mechanical fatigue of material；Its three, CCTO nano-particle
There is higher dielectric constant, therefore, so that composite has high dielectric constant in the case of doping is low, protect
Hold the pliability of material；Its four, to CCTO surface silver nano-grain cladding be the conduction that make use of surface Argent grain higher
Property and relatively low dielectric constant, and then improve compound in interface of polyimides and CCTO so that CCTO@Ag nano-particle
Formed with polymeric matrix and uniformly and be firmly combined and effectively reduce percolation threshold, promote the polarization at interface, improve compound
The Electric Field Distribution of material internal, thus improve the dielectric constant of polyimides/CCTO@Ag composite, reduce its dielectric loss
With good mechanical performance, and then the performance of composite is greatly improved, reaches the purpose of actual application.Use the most poly-
Legal being combined with polyimides by CCTO@Ag nano-particle, the method cost is relatively low, and preparation technology is simple, film property preferably and
Size is controlled, can realize continuous, large-scale production.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the polyimides/CCTO@Ag nanoparticle composite film preparation process of the technical program.
Fig. 2 is transmission electron microscope picture (a) and the CCTO@Ag nano-particle transmission electron microscope picture of the CCTO nano-particle prepared
(b), and transmission electron microscope diffraction pattern (c) of CCTO@Ag nano-particle and EDX elementary analysis figure (d).
Fig. 3 is XRD figure and the CCTO standard card (ICDD Card 70-0609) of the CCTO@Ag nano-particle prepared
Contrast with Ag standard card (JCPDS No.4-0783).
Fig. 4 is the structural representation of polyimides/CCTO@Ag nano particle composite material that the technical program is prepared.
Fig. 5 includes embodiment 1, embodiment 2 and the prepared composite of embodiment 3 and original polyimides and CCTO@Ag
The XRD figure of nano-particle contrast.
Fig. 6 includes embodiment 1, embodiment 2 and the prepared composite of embodiment 3 and original polyimides at room temperature
The graph of a relation of dielectric constant and frequency.
Fig. 7 includes embodiment 1, embodiment 2 and the prepared composite of embodiment 3 and original polyimides at room temperature
The graph of a relation of dielectric loss value and frequency.
Detailed description of the invention
The preparation of the polyimides/CCTO@Ag nano particle composite material of the present invention is described in detail below with reference to accompanying drawing
Method.
Embodiment 0, prepares the CCTO@Ag nano-particle of good dispersion
First, using oxalic acid presoma reaction method to prepare dispersibility preferable nanometer CCTO granule, the method specifically includes
Following steps:
(1) by titanium tetrachloride (TiCl4) (18.2093 grams) add water in frozen water (distilled water of 0 DEG C) (1920 milliliters)
Solve, utilize ammonia (NH simultaneously4OH) regulate when PH is that in solution, White Flocculus precipitation yields is most to certain numerical value, and (adjust
When joint PH is about 8), it is allowed to generate dichloro oxygen titanium (TiOCl2).
(2) said mixture is placed in buchner funnel through repeatedly washing sucking filtration, obtains the precipitation of White Flocculus.
(3) White Flocculus precipitation is transferred in beaker, add two appropriate oxalic acid hydrate (C2H2O4.2H2O)
(24.2054 grams) mix, and be sufficiently stirred for stoichiometric number hour and clarify to solution at 25 DEG C～45 DEG C.
(4) in above-mentioned settled solution, add calcium carbonate (2.4022 grams) stoichiometric number hour, meanwhile, be hydrated three
Copper nitrate (17.3952 grams) is dissolved in the mixed liquor of acetone and distilled water (volume ratio 4:1), and by anti-for the mixing of above two solution
Light blue precipitation should be obtained a few hours, through washing sucking filtration at high temperature anneal a few hours (typically choosing 700 DEG C, 2 hours)
Obtain the pure phase of nano barium titanate copper calcium (CCTO).
(5) by prepared nanometer CCTO dispersion, it is possible to use mechanical dispersion or ultra-sonic dispersion method or both knots
Close, finally dry and obtain dispersibility preferable nanometer CCTO granule.
This nanometer CCTO granule be particle size distribution between 60～80 nanometers, and become crystalline substance preferably, be uniformly dispersed, logical
Crossing the ratio controlling reactant, the nanometer CCTO granule of generation is free from foreign meter, as titanium dioxide or unreacted aoxidize completely
Copper etc., the solution that in the present embodiment, sucking filtration cleans can be selected for distilled water, deionized water or acetone etc., and dispersion processes and can use
Mechanical dispersion or ultra-sonic dispersion method, it is preferable that first the present embodiment uses pulverizes 0.5 by mechanical dispersion process in mortar
Hour～2 hours, then powder is dissolved in dehydrated alcohol or other solvents not reacted and is placed in ultrasonic disperse
Device processes 1 hour～2 hours.Drying can use and process 2 hours～5 hours in an oven.
It is understandable that the nanometer CCTO granule that the present embodiment provides is not limited to above-mentioned preparation method.
The most again by the crystal seed method after improvement at nanometer CCTO granule periphery coated with silver nano-particle, the method is specifically wrapped
Include following steps:
(6) weigh the nanometer CCTO particle powder of 0.1 gram and the sodium hydroxide of 1.0204 grams is dissolved in the distilled water of 50 milliliters
In, ultrasonic 30 minutes, it is centrifuged drying, is obtained powders A.The stannic chloride of 0.5980 gram is joined 25 ml methanol and 25 millis
In the solution of the distilled water mixing risen, and the concentrated sulphuric acid adding 1 milliliter obtains solution B, powders A is joined in solution B, stirring
After 1 hour, it is dried to obtain powder C through being repeatedly centrifuged washing.
(7) silver nitrate of 2.2932 grams and the ammonia of 1 milliliter are dissolved in the distilled water of 50 milliliters, obtain high concentration
Ammoniated silver nitrate solution D (0.27mol/L), is additionally dissolved in 50 milliliters by the silver nitrate of 0.4247 gram and the ammonia of 0.2 milliliter
In distilled water, obtain the ammoniated silver nitrate solution E (0.05mol/L) of low concentration.
(8) powder C is joined in solution D and react 30 minutes, after being centrifuged, again the powder obtained is joined solution E
In, it is sufficiently stirred for the CCTO@Ag nanoparticulate dispersion that reaction obtains being coated with for 17-24 hour, obtains institute through centrifugal drying
The CCTO@Ag powder of nanometric particles needed.
The silver nano-grain diameter of CCTO nano grain surface cladding is about 35 nanometers.It is understandable that the present embodiment carries
The CCTO@Ag nano-particle of confession is not limited to above-mentioned preparation method.
Embodiment 1
A) pressing the flow process in Fig. 1, diaminodiphenyl ether (ODA) addition weighing 2.554 grams fills 7.4 milliliters of N, N-diformazans
In yl acetamide in the three-necked bottle of (DMAC) solution.
B) the CCTO@Ag powder of nanometric particles (volume fraction is 1.5vol%) weighing 0.1955 gram adds above-mentioned mixed liquor
In, limit edged carries out magnetic agitation.
C) solution of b) gained is put in ultrasonic dispersers 2 hours, make solution mix homogeneously.
D) weighing in pyromellitic acid anhydride (PMDA) the addition mixed liquor of 2.835 grams, limit edged carries out magnetic agitation, so
After in the environment that logical nitrogen is protected, at 30 DEG C reaction within 8 hours, obtain polyimides/CCTO@Ag nano particle composite material
Stock solution.
E) by the stock solution of composite on the glass substrate, it is allowed to expansion and paves, put in Muffle furnace, in vacuum environment
Gradient is annealed, and is incubated 1 hour successively at 60 DEG C, 100 DEG C, 200 DEG C and 300 DEG C, and then Temperature fall, heating rate is 2
℃/min。
F) by the glass substrate immersion distilled water with composite 30 minutes, then thin film is taken off with tweezers, with steaming
Distilled water puts into baking oven after rinsing well, is incubated drying in 2 hours and obtains polyimides/CCTO@Ag nano-particle again at 60 DEG C
Close thin film.
Fig. 2 is CCTO nano-particle and the transmission electron microscope picture of CCTO@Ag nano-particle, the CCTO as seen from the figure of preparation
The diameter of nano-particle is about 80 nanometers (a), and the diameter Distribution of the Argent grain that CCTO@Ag nano-particle is peripheral is at 35 ran
Occur without large-scale agglomeration between (b), and nano-particle, disperse the most uniform.CCTO@Ag nano-particle diffraction pattern is tied
Structure is shown as the superposition that CCTO and Ag is biphase, wherein the diffraction phase for Ag of red mark, the diffraction for CCTO of white mark
Phase (c).EDX analysis chart shows this material containing only Ca, Cu, Ti and Ag element, without other dephasigns (d).Above-mentioned experimental result table
The bright prepared nucleocapsid structure that granule is CCTO Surface coating Ag granule.
Fig. 3 is the XRD figure contrast with standard card of the CCTO@Ag nano-particle prepared with wet chemical method, from collection of illustrative plates
On can be seen that CCTO@Ag nano-particle is fine with what CCTO and Ag standard card met, do not have other impurity peaks to occur, table
Understand the nucleocapsid structure that prepared CCTO@Ag nano-particle is Argent grain cladding CCTO granule.
Fig. 5 is the XRD figure of prepared composite, from collection of illustrative plates it can be seen that CCTO@Ag nano-particle and polyamides are sub-
It is fine that amine two combines, and does not has other impurity peaks to occur.
Being prepared composite dielectric constant values at room temperature in Fig. 6, as can be seen from Figure, laminated film is situated between
Electric constant increases compared with original polyimides, has brought up to 15.9 when 100Hz from 3.5.
Fig. 7 is prepared composite dielectric loss value at room temperature, as can be seen from Figure, is situated between during 100Hz
Matter loss is 0.024, increased, but remain at relatively low level compared with original polyimides.
Embodiment 2
A) pressing the flow process in Fig. 1, diaminodiphenyl ether (ODA) addition weighing 2.554 grams fills 74 milliliters of N, N-diformazans
In yl acetamide in the three-necked bottle of (DMAC) solution.
B) the CCTO@Ag powder of nanometric particles (volume fraction is 3vol%) weighing prepared 0.393 gram adds above-mentioned mixing
In liquid, limit edged carries out magnetic agitation.
C) solution of b) gained is put in ultrasonic dispersers 2 hours, make solution mix homogeneously.
D) weighing in pyromellitic acid anhydride (PMDA) the addition mixed liquor of 2.835 grams, limit edged carries out magnetic agitation, so
After in the environment that logical nitrogen is protected, at room temperature reaction within 4 hours, obtain polyimides/CCTO@Ag nano particle composite material
Stock solution.
E) by the stock solution of composite on the glass substrate, it is allowed to expansion and paves, put in Muffle furnace, in vacuum environment
Gradient is annealed, and is incubated 1 hour successively at 60 DEG C, 100 DEG C, 200 DEG C and 300 DEG C, and then Temperature fall, heating rate is 2
℃/min。
F) by the glass substrate immersion distilled water with composite 30 minutes, then thin film is taken off with tweezers, with steaming
Distilled water puts into baking oven after rinsing well, is incubated drying in 2 hours and obtains polyimides/CCTO@Ag nano-particle again at 60 DEG C
Close thin film.
Fig. 5 is the XRD figure of prepared composite, from collection of illustrative plates it can be seen that CCTO@Ag nano-particle and polyamides are sub-
It is fine that amine two combines, and does not has other impurity peaks to occur.
Fig. 6 is prepared composite dielectric constant values at room temperature, as can be seen from Figure, dielectric constant with
Original polyimides is compared and is had increased significantly, and has brought up to 103 from 3.5 during 100Hz.
Fig. 7 is prepared composite dielectric loss value at room temperature, as can be seen from Figure, is situated between during 100Hz
Matter loss is 0.006, increased, but remains at relatively low level, in this embodiment compared with original polyimides
Dielectric constant and dielectric loss are satisfied by the demand of actual application.
Embodiment 3
A) pressing the flow process in Fig. 1, diaminodiphenyl ether (ODA) addition weighing 2.554 grams fills 74 milliliters of N, N-diformazans
In yl acetamide in the three-necked bottle of (DMAC) solution.
B) the CCTO@Ag powder of nanometric particles (volume fraction is 5vol%) weighing prepared 0.669 gram adds above-mentioned mixing
In liquid, limit edged carries out magnetic agitation.
C) solution of b) gained is put in ultrasonic dispersers 2 hours, make solution mix homogeneously.
D) weighing in pyromellitic acid anhydride (PMDA) the addition mixed liquor of 2.835 grams, limit edged carries out magnetic agitation, so
After in the environment that logical nitrogen is protected, at 40 DEG C reaction within 16 hours, obtain polyimides/CCTO@Ag nano particle composite material
Stock solution.
E) by the stock solution of composite on the glass substrate, it is allowed to expansion and paves, put in Muffle furnace, in vacuum environment
Gradient is annealed, and is incubated 1 hour successively at 60 DEG C, 100 DEG C, 200 DEG C and 300 DEG C, and then Temperature fall, heating rate is 2
℃/min。
F) by the glass substrate immersion distilled water with composite 30 minutes, then thin film is taken off with tweezers, with steaming
Distilled water puts into baking oven after rinsing well, is incubated drying in 2 hours and obtains polyimides/CCTO@Ag nano-particle again at 60 DEG C
Close thin film.
Fig. 5 is the XRD figure of prepared composite, from collection of illustrative plates it can be seen that CCTO@Ag nano-particle and polyamides are sub-
It is fine that amine two combines, and does not has other impurity peaks to occur.
Fig. 6 is prepared composite dielectric constant values at room temperature, as can be seen from Figure, dielectric constant with
Original polyimides is compared and is had increased significantly, and has brought up to 38.5 from 3.5 during 100Hz.
Fig. 7 is prepared composite dielectric loss value at room temperature, as can be seen from Figure, is situated between during 100Hz
Matter loss is 0.047, increased compared with original polyimides.
Claims (5)
1. the preparation method of polyimides/CaCu 3 Ti 4 O coated with silver nano particle composite material, it is characterised in that include as
Lower step:
(1) prepare CCTO nano-particle, and coated with silver nano-particle outside CCTO granule with wet chemical method, form CCTO@
The nano-particle of Ag nucleocapsid structure；
(2), after being uniformly dispersed in solvent by a kind of monomer of CCTO@Ag nano-particle Yu polyimides, another kind is added
The monomer of polyimides, at starvation, under the conditions of 20～40 DEG C home position polymerization reaction 4-16 hour obtain polyimides/
The stock solution of CCTO@Ag nano particle composite material, wherein the cumulative volume of CCTO@Ag nano-particle and two kinds of monomers of polyimides it
Ratio is 1.5～5%；
(3) by (2) gained stock solution film in substrate, in the range of 60 DEG C～300 DEG C, in vacuum tank, carry out Gradient annealing, clean
Polyimides/CCTO@Ag nanoparticle composite film is obtained after drying.
Preparation method the most according to claim 1, it is characterised in that in step (1), coated with silver is received outside CCTO granule
Rice grain, including following process:
(1) weigh the nanometer CCTO particle powder of 0.1 gram and the sodium hydroxide of 1.0204 grams be dissolved in the distilled water of 50 milliliters,
Ultrasonic 30 minutes, it is centrifuged drying, is obtained powders A；The stannic chloride of 0.5980 gram is joined 25 ml methanol and 25 milliliters
Distilled water mixing solution in, and the concentrated sulphuric acid adding 1 milliliter obtains solution B, powders A is joined in solution B, stirs 1
After hour, washing and drying obtains powder C；
(2) silver nitrate of 2.2932 grams and the ammonia of 1 milliliter are dissolved in the distilled water of 50 milliliters, obtain the ammonification of high concentration
Silver nitrate solution D, is additionally dissolved in the silver nitrate of 0.4247 gram and the ammonia of 0.2 milliliter in the distilled water of 50 milliliters, obtains low
The ammoniated silver nitrate solution E of concentration；
(3) powder C is joined in solution D and react 30 minutes, again the powder obtained is joined in solution E after being centrifuged, fill
Divide stirring reaction within 17-24 hour, to obtain the CCTO@Ag nanoparticulate dispersion being coated with, obtain required through centrifugal drying
CCTO@Ag powder of nanometric particles.
Preparation method the most according to claim 1, it is characterised in that step (1) described wet chemical method is prepared
A diameter of 80 nanometers of CCTO nano-particle, a diameter of 35 nanometers of silver nano-grain of cladding.
Preparation method the most according to claim 1, it is characterised in that in step (2), first by CCTO@Ag nanoparticle powder
End mix with diaminodiphenyl ether, within ultrasonic 0.5 hour, mixes with PMDA more afterwards, or first by CCTO@Ag nano-particle and
PMDA mixes, and mixes with diaminodiphenyl ether after ultrasonic 0.5 hour again.
Preparation method the most according to claim 1, it is characterised in that in step (3), annealing process at 60 DEG C, 100 DEG C,
200 DEG C, being incubated 1 hour at 300 DEG C respectively, heating rate is maintained at 0.5 DEG C/min～2 DEG C/min, then Temperature fall.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101712784A (en) * | 2009-10-29 | 2010-05-26 | 西安交通大学 | Nuclear shell structured packing/polymer-based composite material and preparation method thereof |
| CN102875827A (en) * | 2012-10-24 | 2013-01-16 | 哈尔滨理工大学 | Preparation method of ceramic/polyimide composite film high in dielectric constant at high temperature |
| CN102924920A (en) * | 2012-11-23 | 2013-02-13 | 哈尔滨理工大学 | Amorphous calcium-copper-titanium-oxygen ceramic/polyimide composite film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102875827A (en) * | 2012-10-24 | 2013-01-16 | 哈尔滨理工大学 | Preparation method of ceramic/polyimide composite film high in dielectric constant at high temperature |
| CN102924920A (en) * | 2012-11-23 | 2013-02-13 | 哈尔滨理工大学 | Amorphous calcium-copper-titanium-oxygen ceramic/polyimide composite film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 溶胶-凝胶法制备巨介电常数材料CaCu3Ti4O12;杨昌辉等;《硅酸盐学报》;20060630;第34卷(第6期);753-756 * |
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