CN103755958A - Preparation method of polyimide/copper calcium titanate coated silver nanoparticle composite material - Google Patents
Preparation method of polyimide/copper calcium titanate coated silver nanoparticle composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of polyimide/CCTO@Ag nanoparticle composite material with high dielectric and low loss. According to the method, polyimide is used as matrix, the prepared CCTO@Ag nanoparticles are ultrasonically dispersed in absolute ethyl alcohol, then is blended with polyimide monomer in solvent, then in situ polymerization reaction is carried out on the monomer at room temperature to simultaneously realize copolymerization of polyimide and intercalation recombination with the CCTO@Ag nanoparticles, obtained stock solution is subjected to gradient annealing according to a coating method to finally obtain the polyimide/CCTO@Ag nanoparticle composite film. Compared with pure polyimide, the polyimide/CCTO@Ag nanoparticle composite material prepared according to the preparation method has the dielectric constant (103) increased by 30 times, also has low dielectric loss (0.006) and can be widely applied in fields of high energy storage capacitors, artificial organs, high speed integrated circuits, and the like.
Description
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Technical field
The preparation method who the present invention relates to a kind of high dielectric, low-loss polyimide/CaCu 3 Ti 4 O (CCTO) coated with silver (Ag) Core-shell Structure Nanoparticles matrix material, belongs to technical field of electronic materials.
Background technology
Polymkeric substance is because its good electricity, heat and ductility have a wide range of applications in electrical condenser, unicircuit and High-Voltage Insulation field, however the low characteristic limitations of specific inductivity its further develop.Along with the integrated and microminiaturized development of current electronic applications device, need to provide the novel material that simultaneously possesses high-k and low dielectric loss to meet the demands.
In order to obtain required high performance material, generally employing method is that polymer materials is carried out to doping vario-property at present, and conventional adulterating method mainly contains two kinds.One is take polymkeric substance as substrate, by compound with it the ferroelectric ceramic grain with high-k, prepares polymkeric substance/ferroelectric ceramic(s) matrix material.But there are some problems in the method, the one, its specific inductivity of synthetic matrix material not high enough (being conventionally less than 50), does not reach the demand of practical application.The specific inductivity of matrix material can increase along with the increase of the doping of ceramic particle, but too high doping can cause again the reduction of matrix material snappiness and other mechanical propertys, the increase that has also brought dielectric loss simultaneously.In order to obtain the matrix material that various aspects of performance is good under lower doping, need searching to there is the more material of high-k; The 2nd, ferroelectric material has electrostrictive effect, and use can bring Composites Fatigue for a long time, reduces the life-span of device; The 3rd, pottery used is mostly a leaded class material, and this has inevitably brought pollution to environment, therefore needs to find unleaded high dielectric constant material and is used as substituting; The 4th, ceramic particle size used is mostly in micron level, there is the problem of intercalation difficulty with polymer macromolecule compound tense, make in compound system the interaction zone of two-phase little, consistency is poor, has fundamentally caused the dielectric properties room for promotion of material limited.
Another method is that the nano material (metal nanoparticle or carbon nano fiber etc.) of mixing high conductivity is prepared nanometer dielectric composite; this matrix material is due to its good performance; also a lot of achievements have been obtained having obtained nearly ten years widely paying close attention to; but the problem existing is to ooze theoretical impact owing to exceeding; near percolation threshold, can there is the phase transformation from isolator to conductor in material; thereby cause its dielectric loss significantly to increase, to practical application, brought difficulty.
Thereby improve nanometer dielectric topmost problem and be present in the dielectric loss of finding suitable method and reduce material, dielectric loss that there are some researches show matrix material is higher, it is compound that topmost reason is that polymkeric substance and particles of inorganic material two are compared difficulty, the dielectric constant values of two-phase differs greatly and has caused composite inner organic phase to bear larger field intensity simultaneously, limited the further raising of specific inductivity, therefore needed to find new method and solve this problem.Inorganic particle surface is processed and well solved this problem with the compound preparation nanometer of organism dielectric medium, and the surface treatment of inorganic particle is mainly divided into increase polar group, Coated with Organic Matter, inorganic particle is coated etc. this several method.
Leadless environment-friendly material CaCu 3 Ti 4 O (CCTO), due to its unusual huge dielectric constant and low-loss, is more and more paid close attention in recent years, and its preparation method comprises traditional solid state reaction and wet chemical method.Polyimide is one of organic polymer material of over-all properties the best, high temperature resistant reaching more than 400 ℃, life-time service temperature range-200 ℃～300 ℃, are particularly suitable for the use of working in harsh environment, at engineering field, microelectronic has a wide range of applications.Little for the report of polyimide and CaCu 3 Ti 4 O (CCTO) matrix material at present, known polyimide/micron CCTO matrix material that is reported as, it is at lower still very low (49) and the dielectric loss higher (0.24) of specific inductivity of higher doping ratio (40vol% CCTO), the CCTO its preparation method of micron level used adopts traditional solid reaction process, the method needs higher temperature (being greater than 1000 ℃) and consuming timely grows (being greater than 24 hours), prepared its dispersiveness of micron CCTO is poor in addition, and macromole intercalation is difficulty comparatively.
Summary of the invention
The present invention is directed to the problem that in prior art, matrix material two-phase consistency is poor He specific inductivity is low and dielectric loss is high, a kind of preparation method of polyimide/CCTO@Ag nano particle composite material with high-k and low dielectric loss is provided.CCTO@Ag nano particle is due to the high electroconductibility of the silver-colored particle in surface and lower specific inductivity, can effectively reduce percolation threshold, solve the poor problem with macromole intercalation difficulty of consistency that polymkeric substance and large-size particle compound tense exist, improve the consistency between polyimide and CCTO@Ag nano particle, promote the combination of polyimide macromole and CCTO@Ag nano particle, thereby obtain the polyimide/CCTO@Ag nano particle composite material that possesses premium properties.
First the present invention adopts wet chemistry method and crystal seed method to prepare the CCTO@Ag nano particle of good dispersity, then utilizes CCTO@Ag nano particle to adulterate to Kapton, improves its specific inductivity.
The preparation method who the invention provides a kind of polyimide/CCTO@Ag nano particle composite material, as shown in Figure 1, the method completes by following steps:
(1) with wet chemical method, prepare CCTO nano particle, and at CCTO particle outside coated with silver nano particle, form the nano particle of CCTO@Ag nucleocapsid structure;
(2) after a kind of monomer of CCTO@Ag nano particle and polyimide is uniformly dispersed in solvent, add again the monomer of another kind of polyimide, at starvation, under 20～40 ℃ of conditions, home position polymerization reaction 4-16 hour obtains the stoste of polyimide/CCTO@Ag nano particle composite material, and wherein the ratio of the cumulative volume of two kinds of monomers of CCTO@Ag nano particle and polyimide is 1.5～5%;
(3) by (2) gained stoste film in substrate, in the inherent vacuum chambers of 60 ℃～300 ℃ scopes, carry out Gradient annealing, after cleaning, drying, obtain polyimide/CCTO@Ag nanoparticle composite film.
In step (1), the crystal seed method after the coated with silver nano particle employing improvement of CCTO particle outside is at the peripheral coated with silver nano particle of nanometer CCTO particle, and the method specifically comprises the following steps:
(1) sodium hydroxide that takes the nanometer CCTO particle powder of 0.1 gram and 1.0204 grams is dissolved in the distilled water of 50 milliliters, ultrasonic 30 minutes, by its centrifugal oven dry, obtains powders A.The tin chloride of 0.5980 gram is joined in the solution of 25 ml methanol and the mixing of 25 ml distilled waters, and add the vitriol oil (98wt%) of 1 milliliter to obtain solution B, powders A is joined in solution B, stir after 1 hour, through centrifugal washing and drying repeatedly, obtain powder C.
(2) ammoniacal liquor of the Silver Nitrate of 2.2932 grams and 1 milliliter is dissolved in the distilled water of 50 milliliters, obtain the ammoniated silver nitrate solution D (0.27mol/L) of high density, in addition the ammoniacal liquor of the Silver Nitrate of 0.4247 gram and 0.2 milliliter is dissolved in the distilled water of 50 milliliters, obtains the ammoniated silver nitrate solution E (0.05mol/L) of lower concentration.
(3) powder C is joined in solution D and reacted 30 minutes, after centrifugal, again the powder obtaining is joined in solution E, the CCTO@Ag nanoparticulate dispersion that fully stirring reaction 17-24 hour obtains being coated, obtains required CCTO@Ag powder of nanometric particles through centrifugal oven dry.
In one embodiment of the invention, the diameter of the CCTO nano particle that the described wet chemical method of step (1) is prepared is 80 nanometers, and coated silver nano-grain diameter is 35 nanometers.
In step (2), specifically comprise the following steps:
(1) take a certain amount of CCTO@Ag powder of nanometric particles and be placed in Glass Containers, then pour a certain amount of N into, (DMAC) solution stirring in N-N,N-DIMETHYLACETAMIDE, then add a certain amount of diaminodiphenyl oxide (ODA) to be uniformly mixed, and Glass Containers is placed in to ultrasonic decollator processes 0.5 hour～2 hours.
(2) take a certain amount of equal benzene four hydroxy acid dianhydrides (PMDA) and add in above-mentioned mixed solution, under starvation condition, stirring reaction for some time obtains the stoste of polyimide/CCTO@Ag nano particle composite material.
Described response hierarchy can be selected first CCTO Ag nano particle to be mixed with diaminodiphenyl oxide (ODA), after ultrasonic 0.5 hour～2 hours, mix with equal benzene four hydroxy acid dianhydrides (PMDA) again, or first CCTO@Ag nano particle is mixed with equal benzene four hydroxy acid dianhydrides (PMDA), after ultrasonic 0.5 hour～2 hours, mix with diaminodiphenyl oxide (ODA) again.Different proportionings are specially, first the mol ratio that is equal benzene four hydroxy acid dianhydrides (PMDA) and diaminodiphenyl oxide (ODA) is 1:1～1.2:1, and secondly CCTO@Ag nano particle is controlled at 1.5vol%～5vol% with the ratio of the cumulative volume of two kinds of monomers of polyimide.Suitable temperature of reaction for to keep 20 ℃～40 ℃ in water-bath or oil bath.Starvation condition can be selected nitrogen, rare gas element or vacuum condition.
In step (3), specifically comprise the following steps:
(1) sheet glass, silicon chip or other materials with higher melt of selecting smooth surface and even thickness are used as substrate.
(2) stoste is poured on this substrate, makes it to launch to pave.
(3) substrate is placed in to container annealing reaction under starvation condition and also through post-processed, obtains polyimide/CCTO@Ag nanoparticle composite film.
Described container can provide the container of comparatively high temps environment for baking oven or retort furnace or other, and starvation condition can be selected nitrogen, rare gas element or vacuum condition.Annealing temperature is preferably chosen several values respectively within the scope of 60 ℃～300 ℃, and 60 ℃, 100 ℃, 200 ℃, be incubated respectively 1 hour at 300 ℃, temperature rise rate remains on 0.5 ℃/min～2 ℃/min, then cooling naturally.Post-processed preferably immerses sheet glass with laminated film in distilled water 10 minutes～60 minutes, then with tweezers, take laminated film off, after clean with distilled water flushing, put into baking oven, at 50 ℃～90 ℃, be incubated 2 hours～within 5 hours, dry and obtain polyimide/CCTO@Ag nanoparticle composite film.
The structural representation of the matrix material finally making is referring to Fig. 4.
The present invention utilizes CCTO@Ag nano particle to mix with two kinds of monomers of polyimide, monomer and nano particle composite on the one hand, two kinds of monomers carry out in-situ polymerization and obtain polyimide molecule long-chain on the other hand, after CCTO nano grain surface is processed with silver is coated, can effectively improve compound in interface of polyimide and CCTO, CCTO@Ag nano particle and polymeric matrix are formed evenly and be firmly combined and effectively reduce percolation threshold, promote the polarization at interface, improve the electric field distribution of composite inner, thereby improve the specific inductivity of polyimide/CCTO@Ag matrix material, reduce its dielectric loss.The dielectric properties of prepared polyimide/CCTO@Ag nano particle composite material are significantly improved.
Polyimide/CCTO@Ag nanoparticle composite film material that the present invention produces, compared with the Kapton of pure phase, under extremely low doping ratio (3vol%), the value of the high-k obtaining has improved approximately 30 times (103), and keeps low dielectric loss (0.006) simultaneously.This matrix material is conducive to meet the integrated demand of current electrical condenser and electron device, for the preparation of later portable equipment has brought new prospect, will store in high density energy simultaneously, obtain application widely in a series of high-technology fields such as High Performance Insulation interlayer and thin-film device, and can promote the progress of two-phase composites interfacial interaction theoretical investigation.
Compared with prior art, the preparation method of polyimide/CCTO@Ag nano particle composite material provided by the invention has the following advantages: one, because being synthesizes CCTO nano particle with wet chemistry method, its synthetic method is relatively simple, short (2 hours) consuming time and sintering temperature (700 ℃) are lower than traditional solid state reaction (1000 ℃), thereby energy consumption has significantly and to reduce, human and material resources and the energy have been saved.With the coated with silver nano particle outside CCTO particle of the crystal seed method after improvement, make its formation CCTO@Ag have the nano particle of nucleocapsid structure, with respect to solid state reaction, it is more even that reactant mixes in solution, and reaction is at room temperature carried out, be easier to operation.Evenly and good dispersity, its transmission electron microscope picture is shown in Fig. 2 to the CCTO@Ag nano particle size distribution generating, its two, unleaded CCTO nano particle environmentally safe, and do not have electrostrictive effect, mixes the laminated film of preparing in polymkeric substance, uses for a long time the mechanical fatigue that also can not cause material, its three, CCTO nano particle has higher specific inductivity, therefore, can make matrix material have high specific inductivity in the situation that doping is low, has kept the snappiness of material, they are four years old, coated with silver nano-grain to CCTO surface is to have utilized electroconductibility that surperficial silver-colored particle is higher and lower specific inductivity, and then improve compound in interface of polyimide and CCTO, CCTO@Ag nano particle and polymeric matrix are formed evenly and be firmly combined and effectively reduce percolation threshold, promote the polarization at interface, improve the electric field distribution of composite inner, thereby improve the specific inductivity of polyimide/CCTO@Ag matrix material, reduce its dielectric loss and good mechanical property, and then significantly improve the performance of matrix material, reach the object of practical application.Adopt situ aggregation method by compound to CCTO@Ag nano particle and polyimide, the method cost is lower, and preparation technology is simple, and film-forming properties is better and size is controlled, can realize continuous, large-scale production.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of polyimide/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 (b) of the CCTO nano particle prepared, and the transmission electron microscope diffractogram (c) of CCTO@Ag nano particle and EDX ultimate analysis figure (d).
Fig. 3 is the XRD figure of CCTO@Ag nano particle and the contrast of CCTO standard card (ICDD Card 70-0609) and Ag standard card (JCPDS No.4-0783) of preparing.
Fig. 4 is the structural representation of polyimide/CCTO@Ag nano particle composite material of preparing of the technical program.
Fig. 5 comprises the XRD figure of matrix material that embodiment 1, embodiment 2 and embodiment 3 make and original polyimide and the contrast of CCTO@Ag nano particle.
Fig. 6 comprises matrix material and original polyimide specific inductivity at room temperature and the graph of a relation of frequency that embodiment 1, embodiment 2 and embodiment 3 make.
Fig. 7 comprises matrix material and original polyimide dielectric loss value at room temperature and the graph of a relation of frequency that embodiment 1, embodiment 2 and embodiment 3 make.
Embodiment
Below with reference to accompanying drawing, describe the preparation method of polyimide/CCTO@Ag nano particle composite material of the present invention in detail.
First, adopt the dispersed nanometer CCTO particle preferably of oxalic acid presoma reaction method preparation, the method specifically comprises the following steps:
(1) by titanium tetrachloride (TiCl
4) (18.2093 grams) add hydrolysis in frozen water (distilled water of 0 ℃) (1920 milliliters), utilizes ammoniacal liquor (NH simultaneously
4while OH) regulating PH to be in solution to certain numerical value that white floss precipitation output is maximum (regulating PH to be about at 8 o'clock), make it to generate dichloro oxygen titanium (TiOCl
2).
(2) said mixture is placed in Büchner funnel through repeatedly washing suction filtration, obtains the precipitation of white floss.
(3) white floss precipitation is transferred in beaker, added two appropriate oxalic acid hydrate (C
2h
2o
4.2H
2o) (24.2054 grams) mix, and at 25 ℃～45 ℃, fully stirring reaction a few hours to solution is clarified.
(4) in above-mentioned settled solution, add calcium carbonate (2.4022 grams) stoichiometric number hour, meanwhile, Gerhardite (17.3952 grams) is dissolved in the mixed solution of acetone and distilled water (volume ratio 4:1), and above-mentioned two kinds of solution hybrid reaction a few hours are obtained to light blue precipitation, through washing suction filtration at high temperature anneal a few hours (generally choosing 700 ℃, 2 hours), obtain the pure phase of nano barium titanate copper calcium (CCTO).
(5) the nanometer CCTO making is disperseed, can use mechanical dispersion or ultra-sonic dispersion method or both combinations, finally dry and obtain dispersed nanometer CCTO particle preferably.
This nanometer CCTO particle is that particle size dispersion is between 60～80 nanometers, and become crystallinity better, be uniformly dispersed, by controlling the ratio of reactant, the nanometer CCTO particle generating is free from foreign meter, as titanium dioxide or unreacted cupric oxide etc. completely, the solution that in the present embodiment, suction filtration cleans can be selected distilled water, deionized water or acetone etc., dispersion treatment can adopt mechanical dispersion or ultra-sonic dispersion method, preferably, the present embodiment adopts and first by mechanical dispersion process, in mortar, pulverizes 0.5 hour～2 hours, then powder is dissolved in and in dehydrated alcohol or other solvents not reacting with it, is placed in ultrasonic decollator and processes 1 hour～2 hours.Oven dry can adopt processes 2 hours～5 hours in baking oven.
Be understandable that the nanometer CCTO particle that the present embodiment provides is not limited to above-mentioned preparation method.
Follow the crystal seed method of using again after improvement at the peripheral coated with silver nano particle of nanometer CCTO particle, the method specifically comprises the following steps:
(6) sodium hydroxide that takes the nanometer CCTO particle powder of 0.1 gram and 1.0204 grams is dissolved in the distilled water of 50 milliliters, ultrasonic 30 minutes, by its centrifugal oven dry, obtains powders A.The tin chloride of 0.5980 gram is joined in the solution that the distilled water of 25 ml methanol and 25 milliliters mixes, and add the vitriol oil of 1 milliliter to obtain solution B, powders A is joined in solution B, stir after 1 hour, through centrifugal washing and drying repeatedly, obtain powder C.
(7) ammoniacal liquor of the Silver Nitrate of 2.2932 grams and 1 milliliter is dissolved in the distilled water of 50 milliliters, obtain the ammoniated silver nitrate solution D (0.27mol/L) of high density, in addition the ammoniacal liquor of the Silver Nitrate of 0.4247 gram and 0.2 milliliter is dissolved in the distilled water of 50 milliliters, obtains the ammoniated silver nitrate solution E (0.05mol/L) of lower concentration.
(8) powder C is joined in solution D and reacted 30 minutes, after centrifugal, again the powder obtaining is joined in solution E, the CCTO@Ag nanoparticulate dispersion that fully stirring reaction 17-24 hour obtains being coated, obtains required CCTO@Ag powder of nanometric particles through centrifugal oven dry.
The coated silver nano-grain diameter of CCTO nano grain surface is about 35 nanometers.Be understandable that the CCTO@Ag nano particle that the present embodiment provides is not limited to above-mentioned preparation method.
A) press the flow process in Fig. 1, the diaminodiphenyl oxide (ODA) that takes 2.554 grams adds in the three-necked bottle that fills (DMAC) solution in 7.4 milliliters of N,N-dimethylacetamide.
B) take the CCTO@Ag powder of nanometric particles (volume fraction is 1.5vol%) of 0.1955 gram and add in above-mentioned mixed solution, limit edged carries out magnetic agitation.
C) b) solution of gained is put into ultrasonic decollator 2 hours, solution is mixed.
D) take the equal benzene four hydroxy acid dianhydrides (PMDA) of 2.835 grams and add in mixed solution, limit edged carries out magnetic agitation, then, in the environment of logical nitrogen protection, reacts the stoste that obtains polyimide/CCTO@Ag nano particle composite material for 8 hours at 30 ℃.
E) stoste of matrix material is poured on glass substrate, makes it to launch to pave, put into retort furnace, in the annealing of vacuum environment Gradient, at 60 ℃, 100 ℃, 200 ℃ and 300 ℃, be incubated 1 hour successively, then cooling naturally, temperature rise rate is 2 ℃/min.
F) glass substrate with matrix material is immersed in distilled water to 30 minutes, then with tweezers, take film off, put into baking oven after clean with distilled water flushing, at 60 ℃, be incubated 2 hours and dry and obtain polyimide/CCTO@Ag nanoparticle composite film.
Fig. 2 is the CCTO nano particle of preparation and the transmission electron microscope picture of CCTO@Ag nano particle, the diameter of CCTO nano particle is about 80 nanometers (a) as seen from the figure, the diameter Distribution of the silver-colored particle of CCTO@Ag nano particle periphery is in 35 nanometer left and right (b), and without agglomeration generation on a large scale, disperse comparatively even between nano particle.CCTO@Ag nano particle diffractogram structure is shown as the stack of CCTO and Ag two-phase, and wherein red mark is the diffraction phase of Ag, and what white marked is the diffraction phase (c) of CCTO.In EDX analysis chart, show that this material is only containing Ca, Cu, Ti and Ag element, without other dephasigns (d).Above-mentioned experimental result shows that prepared particle is the nucleocapsid structure of the coated Ag particle in CCTO surface.
Fig. 3 is the XRD figure of the CCTO@Ag nano particle prepared with wet chemical method and the contrast of standard card, from collection of illustrative plates, can find out that CCTO@Ag nano particle and CCTO and Ag standard card meet fine, do not have other impurity peaks to occur, shown that prepared CCTO@Ag nano particle is the nucleocapsid structure of the coated CCTO particle of silver-colored particle.
In Fig. 5, be the XRD figure of prepared matrix material, from collection of illustrative plates, can find out, it is fine that CCTO Ag nano particle and polyimide two combine, and do not have other impurity peaks to occur.
In Fig. 6, be prepared matrix material dielectric constant values at room temperature, as can be seen from Figure, laminated film specific inductivity increases compared with original polyimide, when 100Hz, from 3.5, has brought up to 15.9.
In Fig. 7, be prepared matrix material dielectric loss value at room temperature, as can be seen from Figure, during 100Hz, dielectric loss is 0.024, increases to some extent, but still remain on lower level compared with original polyimide.
embodiment 2
A) press the flow process in Fig. 1, the diaminodiphenyl oxide (ODA) that takes 2.554 grams adds in the three-necked bottle that fills (DMAC) solution in 74 milliliters of N,N-dimethylacetamide.
B) take the CCTO@Ag powder of nanometric particles (volume fraction is 3vol%) of 0.393 gram making and add in above-mentioned mixed solution, limit edged carries out magnetic agitation.
C) b) solution of gained is put into ultrasonic decollator 2 hours, solution is mixed.
D) take the equal benzene four hydroxy acid dianhydrides (PMDA) of 2.835 grams and add in mixed solution, limit edged carries out magnetic agitation, then, in the environment of logical nitrogen protection, at room temperature reacts the stoste that obtains polyimide/CCTO@Ag nano particle composite material for 4 hours.
E) stoste of matrix material is poured on glass substrate, makes it to launch to pave, put into retort furnace, in the annealing of vacuum environment Gradient, at 60 ℃, 100 ℃, 200 ℃ and 300 ℃, be incubated 1 hour successively, then cooling naturally, temperature rise rate is 2 ℃/min.
F) glass substrate with matrix material is immersed in distilled water to 30 minutes, then with tweezers, take film off, put into baking oven after clean with distilled water flushing, at 60 ℃, be incubated 2 hours and dry and obtain polyimide/CCTO@Ag nanoparticle composite film.
In Fig. 5, be the XRD figure of prepared matrix material, from collection of illustrative plates, can find out, it is fine that CCTO Ag nano particle and polyimide two combine, and do not have other impurity peaks to occur.
In Fig. 6, be prepared matrix material dielectric constant values at room temperature, as can be seen from Figure, specific inductivity has increased significantly compared with original polyimide, during 100Hz, from 3.5, has brought up to 103.
It in Fig. 7, is prepared matrix material dielectric loss value at room temperature, as can be seen from Figure, during 100Hz, dielectric loss is 0.006, increase to some extent compared with original polyimide, but still remain on lower level, the specific inductivity in this embodiment and dielectric loss all meet the demand of practical application.
embodiment 3
A) press the flow process in Fig. 1, the diaminodiphenyl oxide (ODA) that takes 2.554 grams adds in the three-necked bottle that fills (DMAC) solution in 74 milliliters of N,N-dimethylacetamide.
B) take the CCTO@Ag powder of nanometric particles (volume fraction is 5vol%) of 0.669 gram making and add in above-mentioned mixed solution, limit edged carries out magnetic agitation.
C) b) solution of gained is put into ultrasonic decollator 2 hours, solution is mixed.
D) take the equal benzene four hydroxy acid dianhydrides (PMDA) of 2.835 grams and add in mixed solution, limit edged carries out magnetic agitation, then, in the environment of logical nitrogen protection, reacts the stoste that obtains polyimide/CCTO@Ag nano particle composite material for 16 hours at 40 ℃.
E) stoste of matrix material is poured on glass substrate, makes it to launch to pave, put into retort furnace, in the annealing of vacuum environment Gradient, at 60 ℃, 100 ℃, 200 ℃ and 300 ℃, be incubated 1 hour successively, then cooling naturally, temperature rise rate is 2 ℃/min.
F) glass substrate with matrix material is immersed in distilled water to 30 minutes, then with tweezers, take film off, put into baking oven after clean with distilled water flushing, at 60 ℃, be incubated 2 hours and dry and obtain polyimide/CCTO@Ag nanoparticle composite film.
In Fig. 5, be the XRD figure of prepared matrix material, from collection of illustrative plates, can find out, it is fine that CCTO Ag nano particle and polyimide two combine, and do not have other impurity peaks to occur.
In Fig. 6, be prepared matrix material dielectric constant values at room temperature, as can be seen from Figure, specific inductivity has increased significantly compared with original polyimide, during 100Hz, from 3.5, has brought up to 38.5.
In Fig. 7, be prepared matrix material dielectric loss value at room temperature, as can be seen from Figure, during 100Hz, dielectric loss is 0.047, increases to some extent compared with original polyimide.
Claims (5)
1. a preparation method for polyimide/CaCu 3 Ti 4 O coated with silver nano particle composite material, is characterized in that, comprises the steps:
(1) with wet chemical method, prepare CCTO nano particle, and at CCTO particle outside coated with silver nano particle, form the nano particle of CCTO@Ag nucleocapsid structure;
(2) after a kind of monomer of CCTO@Ag nano particle and polyimide is uniformly dispersed in solvent, add again the monomer of another kind of polyimide, at starvation, under 20～40 ℃ of conditions, home position polymerization reaction 4-16 hour obtains the stoste of polyimide/CCTO@Ag nano particle composite material, and wherein the ratio of the cumulative volume of two kinds of monomers of CCTO@Ag nano particle and polyimide is 1.5～5%;
(3) by (2) gained stoste film in substrate, in the inherent vacuum chambers of 60 ℃～300 ℃ scopes, carry out Gradient annealing, after cleaning, drying, obtain polyimide/CCTO@Ag nanoparticle composite film.
2. preparation method according to claim 1, is characterized in that, in step (1), at CCTO particle outside coated with silver nano particle, comprises following process:
(1) sodium hydroxide that takes the nanometer CCTO particle powder of 0.1 gram and 1.0204 grams is dissolved in the distilled water of 50 milliliters, ultrasonic 30 minutes, by its centrifugal oven dry, obtains powders A; The tin chloride of 0.5980 gram is joined in the solution that the distilled water of 25 ml methanol and 25 milliliters mixes, and add the vitriol oil of 1 milliliter to obtain solution B, powders A is joined in solution B, stir after 1 hour, washing and drying obtains powder C;
(2) ammoniacal liquor of the Silver Nitrate of 2.2932 grams and 1 milliliter is dissolved in the distilled water of 50 milliliters, obtain the ammoniated silver nitrate solution D of high density, in addition the ammoniacal liquor of the Silver Nitrate of 0.4247 gram and 0.2 milliliter is dissolved in the distilled water of 50 milliliters, obtains the ammoniated silver nitrate solution E of lower concentration;
(3) powder C is joined in solution D and reacted 30 minutes, after centrifugal, again the powder obtaining is joined in solution E, the CCTO@Ag nanoparticulate dispersion that fully stirring reaction 17-24 hour obtains being coated, obtains required CCTO@Ag powder of nanometric particles through centrifugal oven dry.
3. preparation method according to claim 1, is characterized in that, the diameter of the CCTO nano particle that the described wet chemical method of step (1) is prepared is 80 nanometers, and coated silver nano-grain diameter is 35 nanometers.
4. preparation method according to claim 1, it is characterized in that, in step (2), first CCTO@Ag powder of nanometric particles is mixed with diaminodiphenyl oxide, after ultrasonic 0.5 hour, mix with equal benzene four hydroxy acid dianhydrides again, or first CCTO@Ag nano particle is mixed with equal benzene four hydroxy acid dianhydrides, after ultrasonic 0.5 hour, mix with diaminodiphenyl oxide again.
5. preparation method according to claim 1, is characterized in that, in step (3), annealing process is at 60 ℃, 100 ℃, and 200 ℃, be incubated respectively 1 hour at 300 ℃, temperature rise rate remains on 0.5 ℃/min～2 ℃/min, then cooling naturally.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103951976A (en) * | 2014-05-22 | 2014-07-30 | 哈尔滨理工大学 | Nano core-shell particle/polyimide (PI) composite film, and preparation method and application thereof |
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| CN112143038A (en) * | 2020-10-21 | 2020-12-29 | 北京中科纳清科技股份有限公司 | Triboelectric nano material, preparation method thereof and triboelectric composite material |
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| CN115124837A (en) * | 2021-12-28 | 2022-09-30 | 苏州太湖电工新材料股份有限公司 | Polyimide composite film |
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