CN107141763A - Flexible high dielectric thin film of a kind of Inorganic whisker and preparation method thereof - Google Patents
Flexible high dielectric thin film of a kind of Inorganic whisker and preparation method thereof Download PDFInfo
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Abstract
Flexible high dielectric thin film of a kind of Inorganic whisker and preparation method thereof, comprises the following steps：Polyurethane elastomer is kneaded with CaCu 3 Ti 4 O powder, vulcanizing agent and coupling agent, compound rubber is obtained；Vulcanization and coupling reaction are occurred into for the compound rubber and film is made, the flexible high dielectric thin film of the Inorganic whisker is obtained.The preparation method, each component is kneaded to form compound rubber, the ripe glue of polyurethane of vulcanization reaction formation space network occurs each other in the presence of vulcanizing agent for the continuous phase polyurethane elastomer in compound rubber, it is filled in the dispersed phase CaCu 3 Ti 4 O powder in polyurethane elastomer and occurs coupling reaction with polyurethane elastomer in the presence of coupling agent, and then obtain using the ripe glue of the polyurethane of space network as primary structure, the flexible high dielectric thin film of the powder filled Inorganic whisker in the space network of CaCu 3 Ti 4 O.The thin-film dielectric constant is high, dielectric loss is low, tensile resistance is strong, flexibility is excellent, good processability.
Description
Technical field
The present invention relates to dielectric material technical field, more particularly to a kind of flexible high dielectric thin film of Inorganic whisker and
Its preparation method.
Background technology
With developing rapidly for information and microelectronics industry, semiconductor device miniature, integrated, intelligent, high frequency
Application demand quickly increase.It is increasing electronic component, such as medium substrate, diectric antenna, dynamic RAM, embedding
Enter formula thin-film capacitor etc., both required that dielectric material possesses excellent dielectric properties, require again it possess good mechanical property and
Processing characteristics.
Traditional inorganic piezoelectric ceramics have high-k and higher stability, but its fragility is big, processing temperature compared with
Height, limits its application the shortcomings of with current circuit integrated process technology poor compatibility.
In recent years, the CaCu 3 Ti 4 O (CaCu of perovskite-like structure3Ti4O12, CCTO) and material receives the wide of researchers
General concern.CCTO is a kind of oxide with body-centered cubic perovskite-like structure.CCTO have superelevation dielectric constant (~
104), and its dielectric constant has good frequency stability and temperature stability.It is different from BaTiO in addition3Exist Deng ferroelectric material
There is phase transformation in curie point, within the temperature range of 100~600K, and any phase transformation is not observed in CCTO.In addition, CCTO is also
There is good nonlinear current-voltage.The so many excellent characteristics of CCTO allow it to apply in capacitor, detection of gas
The numerous areas such as device, photo luminescent devices, resistance-variable storing device.
It is the synthesis technique of CCTO powders and the performance improvement of CCTO ceramic materials to study at present more.But actually should
In, dielectric film is particularly suited for preparing various electricity devices.Successfully given birth to although epitaxy single-crystal CCTO films have been reported
Length is in MgO, LaAlO3Deng on oxide monocrystal substrate, polycrystalline CCTO films are also reported successful growth on the silicon chip of platinum plating,
And the dielectric constant of purely inorganic CCTO films is high.But the dielectric loss of purely inorganic CCTO films is higher, breakdown potential is forced down, and crisp
Property it is big, structural strength is relatively low, and this causes its machinability poor, and from practical application, also there is a big difference.
The content of the invention
Based on this, it is necessary to provide the Inorganic whisker that a kind of dielectric constant is high, dielectric loss is low, flexible flexible high
Dielectric film and preparation method thereof.
A kind of preparation method of the flexible high dielectric thin film of Inorganic whisker, including following preparation process：
Polyurethane elastomer is kneaded with CaCu 3 Ti 4 O powder, vulcanizing agent and coupling agent, compound rubber is obtained；
Vulcanization and coupling reaction are occurred into for the compound rubber and film is made, the Inorganic whisker is obtained flexible high
Dielectric film.
In the preparation method of the flexible high dielectric thin film of above-mentioned Inorganic whisker, by polyurethane elastomer and CaCu 3 Ti 4 O
Powder, vulcanizing agent and coupling agent knead to form compound rubber, are combined the continuous phase polyurethane elastomer in rubber in vulcanizing agent
Occur the ripe glue of polyurethane of vulcanization reaction formation space network under effect each other, be filled in polyurethane elastomer
In the presence of coupling agent with polyurethane elastomer coupling reaction occurs for dispersed phase CaCu 3 Ti 4 O powder, and then obtains with stereoscopic graticule
The ripe glue of polyurethane of shape structure is primary structure, the powder filled Inorganic whisker in the space network of CaCu 3 Ti 4 O
Flexible high dielectric thin film.Inorganic whisker flexibility high dielectric thin film compares existing purely inorganic CCTO films, not only has
Dielectric constant height and the low advantage of dielectric loss, but also have the advantages that tensile resistance is strong, flexible excellent, and then cause it
Good processability.
In one of the embodiments, the mass ratio of the CaCu 3 Ti 4 O powder and the polyurethane elastomer is 1~5：
1。
In one of the embodiments, the coupling agent is selected from coupling agent KH550, coupling agent KH560 and coupling agent A151
At least one of；The mass ratio of the coupling agent and the polyurethane elastomer is 0.01~0.1：1.
In one of the embodiments, the vulcanizing agent in double two or five vulcanizing agents and cumyl peroxide at least
It is a kind of；The mass ratio of the vulcanizing agent and the polyurethane elastomer is 0.01~0.05：1.
In one of the embodiments, the condition of the mixing is that 20~120min is kneaded in opening rubber mixing machine.
In one of the embodiments, the condition of the vulcanization and coupling reaction is：Heating pressurization, the temperature of the heating
For 150~200 DEG C, the pressure of the pressurization is 2~6Mpa.
In one of the embodiments, it is described that method that film uses is made for mould pressing, it is described will be described compound
Rubber occurs vulcanization and coupling reaction and is specially the step of film is made：The compound rubber is placed in thickness for 50~200 μ
In m mould in vulcanizer 5~20min of heat-insulation pressure keeping, obtain the flexible high dielectric thin film of the Inorganic whisker.
In one of the embodiments, the preparation method of the flexible high dielectric thin film of the Inorganic whisker also includes metatitanic acid
The preparation process of copper calcium powder body：
Calcium carbonate powder, cupric oxide powder, titanium dioxide powder, inorganic salts and solvent are well mixed, mixing slurry is obtained
Material, wherein the calcium carbonate powder, the cupric oxide powder and the titanium dioxide powder are according to CaCu3Ti4O12Chemistry meter
Amount is than adding, and the mass ratio of the inorganic salts and the calcium carbonate powder is 15~25：1, the solvent and the Paris white
The volume mass ratio of body is 15~25mL：1g；
The mixed slurry is dried, in calcining 1~7h at 700~900 DEG C, obtained in the CaCu 3 Ti 4 O containing inorganic salts
Between powder；
Powder washing in the middle of the CaCu 3 Ti 4 O containing inorganic salts is removed into inorganic salts, drying obtains the copper titanate
Calcium powder body.
In one of the embodiments, it is described by calcium carbonate powder, cupric oxide powder, titanium dioxide powder, inorganic salts and
Solvent is well mixed, and the step of obtaining mixed slurry includes：
First the calcium carbonate powder, the cupric oxide powder, the titanium dioxide powder and the solvent are well mixed,
Then the inorganic salts are added and continue well mixed, the mixed slurry is obtained.
Additionally provide that a kind of preparation method by the flexible high dielectric thin film of above-mentioned Inorganic whisker prepares is inorganic
Organic composite flexibility high dielectric thin film.
Brief description of the drawings
Fig. 1 is the load-deformation curve for the flexible high dielectric thin film of Inorganic whisker that embodiment 3 is obtained；
Fig. 2 is the stereoscan photograph of the section for the flexible high dielectric thin film of Inorganic whisker that embodiment 3 is obtained.
Embodiment
For the ease of understanding the present invention, the present invention is carried out more fully below with reference to relevant drawings and specific embodiment
Description.Presently preferred embodiments of the present invention is given in accompanying drawing.But, the present invention can be realized in many different forms, and
It is not limited to embodiment described herein.On the contrary, the purpose for providing these embodiments makes to the disclosure
Understand more thorough comprehensive.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
The arbitrary and all combination of the Listed Items of pass.
The preparation method of the flexible high dielectric thin film of the Inorganic whisker of an embodiment in the present invention, including following step
Rapid S1~S2.
Step S1：Polyurethane elastomer is kneaded with CaCu 3 Ti 4 O powder, vulcanizing agent and coupling agent, compound life is obtained
Glue.
CCTO has the dielectric constant (~10 of superelevation4), and its dielectric constant has good frequency stability and temperature
Stability.Polyurethane elastomer has standby good tack, wide tolerable temperature (- 50 DEG C~150 DEG C), excellent processability
Can, relatively low processing temperature, relatively low dielectric loss, excellent insulating properties, flexible and high-breakdown-voltage, but its dielectric constant is logical
It is often relatively low, it is difficult to meet the performance requirement of microelectronic component.Therefore the application selects polyurethane elastomer and titanium by research
Sour copper calcium powder body formation Inorganic whisker film.
Step S1 is mixed polyurethane elastomer with CaCu 3 Ti 4 O powder, vulcanizing agent and coupling agent using the method for mixing
It is even, make CaCu 3 Ti 4 O powder filled into polyurethane elastomer, wherein polyurethane elastomer is continuous phase, CaCu 3 Ti 4 O powder is
Dispersed phase, and the compound rubber with mobility and plasticity is formed, mixing is conducive to vulcanizing in subsequent step S2 and coupling is anti-
The processing of the techniques such as film and should be made.
In embodiment, the condition of mixing is that 20~120min is kneaded in opening rubber mixing machine.
In embodiment, the mass ratio of CaCu 3 Ti 4 O powder and polyurethane elastomer is 1~5：1.The proportioning of each component
Affect step S2 vulcanization and coupling reaction.In the proportion CaCu 3 Ti 4 O powder can be filled into greatest extent poly-
In urethane elastomer, and CaCu 3 Ti 4 O powder can be combined with the performance of polyurethane elastomer best.
Preferably, the mass ratio of CaCu 3 Ti 4 O powder and polyurethane elastomer is 2~4：1.It is highly preferred that copper titanate calcium powder
The mass ratio of body and polyurethane elastomer is 3：1.
In embodiment, polyurethane elastomer is blending-type polyurethane elastomer, and its obtained Inorganic whisker is flexible
The flexibility of high dielectric thin film is preferably.
In embodiment, coupling agent is selected from coupling agent KH550 (chemical names：Gamma-aminopropyl-triethoxy-silane), coupling agent
KH560 (chemical names：γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane) and coupling agent A151 (chemical names：The second of vinyl three
At least one of TMOS).In embodiment, the mass ratio of coupling agent and polyurethane elastomer is 0.01~0.1：1.It is even
Join agent simultaneously containing close inorganic group and organic-philic group, close inorganic group can be acted on CaCu 3 Ti 4 O powder, organic-philic group
It can be acted on polyurethane elastomer, coupling agent can be combined CaCu 3 Ti 4 O powder with polyurethane elastomer.
Preferably, the mass ratio of coupling agent and polyurethane elastomer is 0.04~0.08：1.It is highly preferred that coupling agent is with gathering
The mass ratio of urethane elastomer is 0.06：1.
In embodiment, vulcanizing agent is selected from double two or five vulcanizing agents (double 2,5 vulcanizing agents) and cumyl peroxide extremely
Few one kind.The mass ratio of vulcanizing agent and polyurethane elastomer is 0.01~0.05：1.Vulcanizing agent causes between polyurethane elastomer
Generation vulcanization reaction, generates the ripe glue of polyurethane of space network.
Preferably, the mass ratio of vulcanizing agent and polyurethane elastomer is 0.03：1.
In embodiment, CaCu 3 Ti 4 O powder can CaCu 3 Ti 4 O powder be commercially produced by being commercially available, but at present
It is less, it is general using self-control.
In embodiment, CaCu 3 Ti 4 O powder is synthesized by molten-salt growth method.It is situated between using the inorganic salts of low melting point as reaction
Matter, reactant has certain solubility in fused salt, greatly accelerates the diffusion rate of ion, reactant is realized in the liquid phase
Atomic scale is mixed, and reaction is just converted into solid-liquid reaction by solid-solid reaction.The method is for conventional solid method, with technique
Simply, synthesis temperature is low, soaking time is short, the powder chemical composition of synthesis is uniform, crystal morphology is good, thing phase purity height etc. is excellent
Point.In addition, the method for preparing CaCu 3 Ti 4 O powder also has inorganic salts easily separated and reusable advantage.
Specifically, the preparation process of CaCu 3 Ti 4 O powder comprises the following steps：
Calcium carbonate powder, cupric oxide powder, titanium dioxide powder, inorganic salts and solvent are well mixed, mixing slurry is obtained
Material, wherein calcium carbonate powder, cupric oxide powder and titanium dioxide powder are according to CaCu3Ti4O12Stoichiometric proportion add, it is inorganic
The mass ratio of salt and calcium carbonate powder is 15~25：1, the volume mass ratio of solvent and calcium carbonate powder is 15~25mL：1g；Will
Mixed slurry is dried, and in calcining 1~7h at 700~900 DEG C, obtains powder in the middle of the CaCu 3 Ti 4 O containing inorganic salts；It will contain
Powder washing removes inorganic salts in the middle of the CaCu 3 Ti 4 O of inorganic salts, and drying obtains CaCu 3 Ti 4 O powder.
In the preparation process of above-mentioned CaCu 3 Ti 4 O powder, by the ratio for controlling inorganic salts and solvent and calcium carbonate powder
Example so that the crystal morphology of the CaCu 3 Ti 4 O powder of preparation is good, thing phase purity is high, and then be conducive to improving Inorganic whisker soft
The dielectric properties and tensile resistance of property high dielectric thin film.
Preferably, the temperature of powder drying is 60~100 in the middle of the CaCu 3 Ti 4 O of mixed slurry drying and removing inorganic salts
℃。
Further, calcium carbonate powder, cupric oxide powder, titanium dioxide powder, inorganic salts and solvent are well mixed, obtained
The step of to mixed slurry, includes：First calcium carbonate powder, cupric oxide powder, titanium dioxide powder and solvent are well mixed, so
Inorganic salts are added afterwards and continue well mixed, obtain mixed slurry.
Further, well mixed step uses ball-milling method, and the rotating speed of ball milling is 160rpm~230rpm, first will
Calcium carbonate powder, cupric oxide powder, titanium dioxide powder and the solvent well mixed time are 1~6h；Inorganic salts are added to continue
The well mixed time is 0.5~3h.
Preferably, inorganic salts are at least one of sodium chloride and potassium chloride.Preferably, solvent is absolute ethyl alcohol.
Preferably, the step of powder in the middle of the CaCu 3 Ti 4 O containing inorganic salts being washed is using hot deionized water washing, heat
The temperature of deionized water is 60~90 DEG C.
Step S2：Vulcanization and coupling reaction are occurred into for compound rubber and film is made, Inorganic whisker is obtained flexible high
Dielectric film.
In compound rubber so after mixing, continuous phase polyurethane elastomer occurs each other in the presence of vulcanizing agent
The ripe glue of polyurethane of vulcanization reaction formation space network, is filled in the dispersed phase CaCu 3 Ti 4 O powder in polyurethane elastomer
Occur coupling reaction with polyurethane elastomer in the presence of coupling agent, and then obtain with the ripe glue of the polyurethane of space network
For primary structure, the flexible high dielectric thin film of the powder filled Inorganic whisker in the space network of CaCu 3 Ti 4 O.That is,
Inorganic whisker flexibility high dielectric thin film is CaCu 3 Ti 4 O-polyurethane compound dielectric film.
Compared to existing purely inorganic CCTO films, CCTO/ composite polyimide materials, CCTO/ epoxy resin laminated films
And CCTO/ polyvinylidene fluoride composite films, Inorganic whisker flexibility high dielectric thin film, not only with dielectric constant height and Jie
The low advantage of electrical loss, but also have the advantages that tensile resistance is strong, flexible excellent, and then cause its good processability.
Tested at room temperature in frequency for 100Hz, the flexible high dielectric thin film of the obtained Inorganic whisker, its dielectric is normal
Number up to 41, dielectric loss is below 0.05, and the tension fracture elongation rate of film reaches as high as 308.9% more than 150%.
In addition, Inorganic whisker flexibility high dielectric thin film also has high intensity, high tenacity, ageing-resistant, anti-wear performance
Excellent, oil resistant and acid-proof alkaline is excellent, good tack and the advantages of tolerable temperature wide (- 50 DEG C~150 DEG C).
In embodiment, the condition of vulcanization and coupling reaction is：Heating pressurization, the temperature of heating is 150~200 DEG C, plus
The pressure of pressure is 2~6Mpa.
In embodiment, method that film uses is made for mould pressing, it is 50~200 that compound rubber is placed in into thickness
μm mould in vulcanizer 5~20min of heat-insulation pressure keeping, obtain the flexible high dielectric thin film of Inorganic whisker.Thus by
The thickness for the flexible high dielectric thin film of Inorganic whisker that the thickness control of mould is obtained, in the present embodiment, what is obtained is inorganic
The thickness of organic composite flexibility high dielectric thin film is 50~200 μm.
The preparation method of the flexible high dielectric thin film of above-mentioned Inorganic whisker, preparation method is simple, and what is obtained is inorganic organic
Composite and flexible high dielectric thin film dielectric constant is higher, dielectric loss is low, flexible and tensile resistance is excellent, is expected to as thin-film electro
Dielectric material is applied in the electronic components such as dynamic RAM, embedded capacitor.
Present invention also offers the preparation method of the flexible high dielectric thin film of above-mentioned Inorganic whisker prepare it is inorganic
Organic composite flexibility high dielectric thin film.
It is specific embodiment below.
Embodiment 1
By 10.11g Paris whites, 24.10g cupric oxide powders, 32.27g titanium dioxide powders, 190mL absolute ethyl alcohols, 266g oxygen
Change zirconium mill ball to add in grinding pot, with 200rpm rotating speed ball milling 1.5h in planetary ball mill, then add
199gNaCl continues ball milling 1.5h with 200rpm rotating speed and obtains mixed slurry；Above-mentioned mixed slurry is placed in baking in 75 DEG C of dryings
It is dry, it is placed in after being fitted into alumina crucible in high temperature furnace and obtains powder in the middle of the CCTO of saliferous in 850 DEG C of roasting 2h.With 85 DEG C
Powder in the middle of the CCTO of the above-mentioned saliferous of deionization cyclic washing with silver nitrate solution detection supernatant liquor until be not observed bright
Untill whitening color is precipitated, by the CCTO slurries drying obtained after washing to CCTO powders.
Take CCTO powders 58.88g, polyurethane elastomer 30.00g, double 2,5 vulcanizing agent 0.90g, the coupling agent of above-mentioned synthesis
KH550 1.18g are placed in opening rubber mixing machine kneads the obtained compound rubbers of 30min repeatedly.The compound rubber is placed in into thickness
Spend in the mould for 80 μm and thickness is obtained about with the temperature pressurize 10min of 3MPa pressure and 160 DEG C in vulcanizer
For the flexible high dielectric thin film of 80 μm of Inorganic whiskers.
Embodiment 2
By 10.11g Paris whites, 24.10g cupric oxide powders, 32.27g titanium dioxide powders, 190mL absolute ethyl alcohols, 266g oxygen
Change zirconium mill ball to add in grinding pot, with 160rpm rotating speed ball milling 6h in planetary ball mill, then add 199gKCl with
160rpm rotating speed continues ball milling 3h and obtains mixed slurry；Above-mentioned mixed slurry is placed in drying in 75 DEG C of dryings, loads oxidation
It is placed in after in aluminium crucible in high temperature furnace and obtains powder in the middle of the CCTO of saliferous in 750 DEG C of roasting 5h.With 75 DEG C of deionizations repeatedly
Powder in the middle of the CCTO of above-mentioned saliferous is washed until obvious white precipitate is not observed with silver nitrate solution detection supernatant liquor
Untill, by the CCTO slurries drying obtained after washing to CCTO powders.
Take CCTO powders 34.35g, polyurethane elastomer 30.00g, double 2,5 vulcanizing agent 0.90g, the coupling agent of above-mentioned synthesis
KH560 0.68g are placed in opening rubber mixing machine kneads the obtained compound rubbers of 30min repeatedly.The compound rubber is placed in into thickness
Spend in the mould for 50 μm and thickness is obtained about with the temperature pressurize 10min of 2MPa pressure and 180 DEG C in vulcanizer
For the flexible high dielectric thin film of 50 μm of Inorganic whiskers.
Embodiment 3
By 20.22g Paris whites, 48.20g cupric oxide powders, 64.54g titanium dioxide powders, 380mL absolute ethyl alcohols, 532g oxygen
Change zirconium mill ball to add in grinding pot, with 180rpm rotating speed ball milling 2h in planetary ball mill, then add 398gNaCl
Ball milling 2h is continued with 180rpm rotating speed and obtains mixed slurry；Above-mentioned mixed slurry is placed in drying in 75 DEG C of dryings, loads oxygen
It is placed in after changing in aluminium crucible in high temperature furnace and obtains powder in the middle of the CCTO of saliferous in 800 DEG C of roasting 4h.Deionization with 80 DEG C is anti-
It is heavy up to substantially white is not observed with silver nitrate solution detection supernatant liquor that powder in the middle of the CCTO of above-mentioned saliferous is washed in after backwashing
Untill shallow lake, by the CCTO slurries drying obtained after washing to CCTO powders.
Take CCTO powders 91.59g, polyurethane elastomer 30.00g, double 2,5 vulcanizing agent 0.90g, the coupling agent of above-mentioned synthesis
KH550 1.83g are placed in opening rubber mixing machine kneads the obtained compound rubbers of 30min repeatedly.The compound rubber is placed in into thickness
Spend in the mould for 100 μm and thickness is obtained about with the temperature pressurize 10min of 4MPa pressure and 160 DEG C in vulcanizer
For the flexible high dielectric thin film of 100 μm of Inorganic whiskers.
Embodiment 4
By 20.22g Paris whites, 48.20g cupric oxide powders, 64.54g titanium dioxide powders, 380mL absolute ethyl alcohols, 532g oxygen
Change zirconium mill ball to add in grinding pot, with 230rpm rotating speed ball milling 1h in planetary ball mill, then add 265gNaCl,
133gKCl continues ball milling 0.5h with 230rpm rotating speed and obtains mixed slurry；Above-mentioned mixed slurry is placed in baking in 75 DEG C of dryings
It is dry, it is placed in after being fitted into alumina crucible in high temperature furnace and obtains powder in the middle of the CCTO of saliferous in 700 DEG C of roasting 7h.With 65 DEG C
Powder in the middle of the CCTO of the above-mentioned saliferous of deionization cyclic washing with silver nitrate solution detection supernatant liquor until be not observed bright
Untill whitening color is precipitated, by the CCTO slurries drying obtained after washing to CCTO powders.
Take the CCTO powders 91.59g of above-mentioned synthesis, polyurethane elastomer 30.00g, cumyl peroxide 0.90g, idol
Connection agent A151 1.83g are placed in opening rubber mixing machine kneads the obtained compound rubbers of 30min repeatedly.The compound rubber is placed in into
Film thickness is in vulcanizer with the temperature pressurize 10min of 5MPa pressure and 180 DEG C is to obtain thickness in 150 μm of mould
The flexible high dielectric thin film of Inorganic whisker that about 150 μm of degree.
Embodiment 5
By 20.22g Paris whites, 48.20g cupric oxide powders, 64.54g titanium dioxide powders, 380mL absolute ethyl alcohols, 532g oxygen
Change zirconium mill ball to add in grinding pot, with 160rpm rotating speed ball milling 4h in planetary ball mill, then add 398gNaCl
Ball milling 2h is continued with 160rpm rotating speed and obtains mixed slurry.Above-mentioned mixed slurry is placed in drying in 75 DEG C of dryings, loads oxygen
It is placed in after changing in aluminium crucible in high temperature furnace and obtains powder in the middle of the CCTO of saliferous in 900 DEG C of roasting 1h.Deionization with 90 DEG C is anti-
It is heavy up to substantially white is not observed with silver nitrate solution detection supernatant liquor that powder in the middle of the CCTO of above-mentioned saliferous is washed in after backwashing
Untill shallow lake, by the CCTO slurries drying obtained after washing to CCTO powders.
Take the CCTO powders 91.59g, polyurethane elastomer 30.00g, double 2,5 vulcanizing agent 0.90g, KH550 of above-mentioned synthesis
Coupling agent 1.83g is placed in opening rubber mixing machine kneads the obtained compound rubbers of 30min repeatedly.The compound rubber is placed in into thickness
Spend in the mould for 200 μm in vulcanizer with 6MPa pressure and 200 DEG C of temperature pressurize 10min, obtain thickness about
For the flexible high dielectric thin film of 200 μm of Inorganic whiskers.
Embodiment 6
Embodiment 6 is substantially the same manner as Example 3, and difference is：In the step of preparing CCTO powders, absolute ethyl alcohol
Volume is 303mL, and NaCl quality is 505g；In the step of preparing Inorganic whisker flexibility high dielectric thin film, above-mentioned synthesis
CCTO powder 91.59g, polyurethane elastomer 18.00g, double 2,5 vulcanizing agent 0.18g, coupling agent KH550 0.18g, mixing
Time is 20min.
Embodiment 7
Embodiment 7 is substantially the same manner as Example 3, and difference is：In the step of preparing CCTO powders, absolute ethyl alcohol
Volume is 500mL, and NaCl quality is 400g, and mixed slurry is calcined the CCTO that 2h obtains saliferous at 800 DEG C after being dried at 60 DEG C
Middle powder, washing uses 60 DEG C of deionization；In the step of preparing Inorganic whisker flexibility high dielectric thin film, coupling agent
KH550 quality be 2.4g, the quality of double 2,5 vulcanizing agents be 1.5g, the time of mixing be 1h.
Embodiment 8
Embodiment 8 is substantially the same manner as Example 3, and difference is：In the step of preparing CCTO powders, absolute ethyl alcohol
Volume is 505mL, and NaCl quality is 303g；In the step of preparing Inorganic whisker flexibility high dielectric thin film, coupling agent
KH550 quality be 3.0g, mixing time be 2h.
Comparative example 1
Reference《Function hybridized film with high-k》(Dang Z.M.,Zhou T.,Yao S.H.,Yuan
J.J., Zha J.W., Song H.T., Li J.Y., Chen Q., Yang W.T., Bai J.B., advanced material, 2009,21,
2077-2082.)：The continuous phase filled using polyimides as CCTO.
Comparative example 2
The reference of comparative example 2《" there is the Kynoar/CaCu 3 Ti 4 O and Kynoar/La of high dielectric and mechanical performance
Doped titanic acid copper calcium composite》(A.Srivastava, K.K.Jana, P.Maiti, D.Kumar., investigation of materials bulletin,
2015,70,735-742.)：The continuous phase filled using Kynoar as CCTO.
It is inorganic that the flexible high dielectric thin film of Inorganic whisker and comparative example 1~2 that embodiment 1~8 is obtained are obtained
Organic composite dielectric film, tests its dielectric constant, dielectric loss in the case where room temperature, frequency are 100Hz and carries out extension test, obtain
The elongation at break of the dielectric constant, dielectric loss and the extension test that arrive, as shown in table 1.
Table 1
As shown in Table 1, the flexible high dielectric thin film of the Inorganic whisker of embodiment 1~8, its dielectric constant is 19~41,
Its dielectric loss is well below comparative example 1~2, and elongation at break is much higher than comparative example 1~2.The nothing that wherein embodiment 3 is obtained
Stress (Tensile stress)-strain (Strain) curve of machine organic composite flexibility high dielectric thin film, as shown in figure 1, its
Tension fracture elongation rate is about 160%, illustrates flexible, the good processability of the flexible high dielectric thin film of Inorganic whisker.
The section for the flexible high dielectric thin film of Inorganic whisker that embodiment 3 is obtained is scanned electronic microscope photos, obtains
Stereoscan photograph is as shown in Fig. 2 CCTO particles distribute very evenly in polyurethane matrix, and then improve inorganic organic multiple
Close the mechanical property and dielectric properties of flexible high dielectric thin film.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. the preparation method of the flexible high dielectric thin film of a kind of Inorganic whisker, it is characterised in that including following preparation process：
Polyurethane elastomer is kneaded with CaCu 3 Ti 4 O powder, vulcanizing agent and coupling agent, compound rubber is obtained；
Vulcanization and coupling reaction are occurred into for the compound rubber and film is made, the flexible high dielectric of the Inorganic whisker is obtained
Film.
2. a kind of preparation method of the flexible high dielectric thin film of Inorganic whisker as claimed in claim 1, it is characterised in that institute
The mass ratio for stating CaCu 3 Ti 4 O powder and the polyurethane elastomer is 1~5：1.
3. a kind of preparation method of the flexible high dielectric thin film of Inorganic whisker as claimed in claim 1, it is characterised in that institute
State coupling agent and be selected from least one of coupling agent KH550, coupling agent KH560 and coupling agent A151；The coupling agent with it is described
The mass ratio of polyurethane elastomer is 0.01~0.1：1.
4. a kind of preparation method of the flexible high dielectric thin film of Inorganic whisker as claimed in claim 1, it is characterised in that institute
State vulcanizing agent and be selected from double at least one of two or five vulcanizing agents and cumyl peroxide；The vulcanizing agent and the polyurethane bullet
Property body mass ratio be 0.01~0.05：1.
5. a kind of preparation method of the flexible high dielectric thin film of Inorganic whisker as claimed in claim 1, it is characterised in that institute
The condition for stating mixing is that 20~120min is kneaded in opening rubber mixing machine.
6. a kind of preparation method of the flexible high dielectric thin film of Inorganic whisker as claimed in claim 1, it is characterised in that institute
State vulcanization and the condition of coupling reaction is：Heating pressurization, the temperature of the heating is 150~200 DEG C, and the pressure of the pressurization is
2~6Mpa.
7. a kind of preparation method of the flexible high dielectric thin film of Inorganic whisker as claimed in claim 1, it is characterised in that institute
State and method that film uses is made for mould pressing, it is described that vulcanization and coupling reaction are occurred into for the compound rubber and are made thin
The step of film is specially：By the compound rubber be placed in thickness be in 50~200 μm of mould in vulcanizer heat-insulation pressure keeping 5~
20min, obtains the flexible high dielectric thin film of the Inorganic whisker.
8. a kind of preparation method of the flexible high dielectric thin film of Inorganic whisker as described in any one of claim 1~7, it is special
Levy and be, include the preparation process of CaCu 3 Ti 4 O powder：
Calcium carbonate powder, cupric oxide powder, titanium dioxide powder, inorganic salts and solvent are well mixed, mixed slurry is obtained, its
Described in calcium carbonate powder, the cupric oxide powder and the titanium dioxide powder according to CaCu3Ti4O12Stoichiometric proportion add
Enter, the mass ratio of the inorganic salts and the calcium carbonate powder is 15~25：1, the body of the solvent and the calcium carbonate powder
Product mass ratio is 15~25mL：1g；
The mixed slurry is dried, in calcining 1~7h at 700~900 DEG C, powder in the middle of the CaCu 3 Ti 4 O containing inorganic salts is obtained
Body；
Powder washing in the middle of the CaCu 3 Ti 4 O containing inorganic salts is removed into inorganic salts, drying obtains the copper titanate calcium powder
Body.
9. a kind of preparation method of the flexible high dielectric thin film of Inorganic whisker as claimed in claim 8, it is characterised in that institute
State and be well mixed calcium carbonate powder, cupric oxide powder, titanium dioxide powder, inorganic salts and solvent, obtain the step of mixed slurry
Suddenly include：
First the calcium carbonate powder, the cupric oxide powder, the titanium dioxide powder and the solvent are well mixed, then
Add the inorganic salts and continue well mixed, obtain the mixed slurry.
10. a kind of preparation method of the flexible high dielectric thin film of Inorganic whisker as described in claim 1~9 is prepared
Inorganic whisker flexibility high dielectric thin film.
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| CN107722604A (en) * | 2017-10-20 | 2018-02-23 | 南京大学 | A kind of missile wing wave absorbing patch and preparation method thereof |
| CN107722605A (en) * | 2017-10-20 | 2018-02-23 | 南京南大波平电子信息有限公司 | A kind of rubber-based low frequency wave absorbing patch and preparation method thereof |
| CN109553903A (en) * | 2018-12-06 | 2019-04-02 | 怀化学院 | CaCu 3 Ti 4 O composite mortar, CaCu 3 Ti 4 O composite film material and preparation method thereof |
| CN115157735A (en) * | 2022-08-12 | 2022-10-11 | 华中科技大学鄂州工业技术研究院 | Preparation method of composite thick film |
| CN115260623A (en) * | 2022-08-26 | 2022-11-01 | 石家庄安耐普电缆附件有限公司 | Flexible high-dielectric material and production method thereof |
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| CN107722604A (en) * | 2017-10-20 | 2018-02-23 | 南京大学 | A kind of missile wing wave absorbing patch and preparation method thereof |
| CN107722605A (en) * | 2017-10-20 | 2018-02-23 | 南京南大波平电子信息有限公司 | A kind of rubber-based low frequency wave absorbing patch and preparation method thereof |
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| CN115260623A (en) * | 2022-08-26 | 2022-11-01 | 石家庄安耐普电缆附件有限公司 | Flexible high-dielectric material and production method thereof |
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