CN110156364A - The method and its application that piezoelectric ceramics surface is modified using Si-Ti-Ca tri compound film - Google Patents
The method and its application that piezoelectric ceramics surface is modified using Si-Ti-Ca tri compound film Download PDFInfo
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- CN110156364A CN110156364A CN201910390276.8A CN201910390276A CN110156364A CN 110156364 A CN110156364 A CN 110156364A CN 201910390276 A CN201910390276 A CN 201910390276A CN 110156364 A CN110156364 A CN 110156364A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/1066—Oxides, Hydroxides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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Abstract
The invention discloses a kind of method and its application being modified using Si-Ti-Ca tri compound film to piezoelectric ceramics surface, for the difference of cement and piezoceramic structures and performance, select Si-Ti-Ca tri compound colloidal sol in piezoelectric ceramics surface pulling film forming, to form uniform, stable, firm Si-Ti-Ca tri compound film on piezoelectric ceramics surface.After adhering to the film, piezoelectric ceramics contact angle becomes smaller, good hydrophilic property, binding force are strong, conducive to the combination in later period and cement；Meanwhile piezoelectric constant and the relative dielectric constant variation of piezoelectric ceramics substrate are smaller, dielectric loss is reduced, and does not influence the normal use of piezoelectric ceramics.
Description
Technical field
The present invention relates to a kind of modified methods in piezoelectric ceramics surface, and in particular to a kind of to use Si-Ti-Ca tri compound
The method that film is modified piezoelectric ceramics surface belongs to piezoelectric ceramics process for modifying surface field.
Background technique
Large scale civil engineering structure and facility involve great expense, scale of investment is big, the military service period is long, and wherein concrete is building
The maximum basic material of engineering field dosage, but make in external loads, environmental factor and the various couplings that not can determine factor
Various damage accumulations are inevitably resulted under, in service phase and degradation resistance destroys, and can also cause calamity under extreme case
The burst accident of difficulty.In order to effectively ensure the safety of life and property, heavy economic losses, averting a calamity property tragedy are reduced
Generation it is necessary to implement health monitoring and lesion assessment to concrete works structure, and the most lacking is and concrete phase at present
Capacitive is good, globality and the high monitoring material of durability.
Cement base piezoelectric composite material is a kind of novel functional composite material, is passed through centainly by piezoelectric ceramics and cement
Mode of communicating is combined.Compared with traditional piezoelectric material, cement base piezoelectric composite material preparation process is simple, at low cost,
The consistency problem between smart material and concrete precursor structure material can be effectively solved simultaneously, such as compatibility of deformation, interface
The problems such as caking property and acoustic impedance match, improves the sensing accuracy and driving force of piezoelectric smart material.Therefore, such composite wood
Material is very suitable to damage, deformation, internal stress and the Strain Distribution etc. of monitoring concrete.In all kinds of buildings to intelligent development
Today, people increasingly pay close attention to cement-base composite material and develop to intelligent direction, keep intelligent building more succinct, reliable and high
The research and development of effect, such composite material have extensive future in engineering applications, cement concrete can be promoted to intelligence
Direction is developed.
Cement base piezoelectric composite material is combined by cement and piezoelectric ceramics, and the composition of the two, structure and property are poor
It is different significant, such as young's modulus, tensile strength, ductility and toughness otherness or discontinuity with height, when cement and pressure
Electroceramics compound tense, interface can not generate chemical action, in conjunction with only relying on physical absorption or mechanical snap power, intensity are low.By
In use in cement base piezoelectric composite material, power, electricity, hot equal excitation and response must be transmitted through interface, be existed in this way
Under stress-electric coupling effect repeatedly, interface is also easy to produce some fine cracks, finally cracks, falls off, and leads to disabler, signal
Distortion, cannot achieve to the permanently effective monitoring of concrete structure engineering.Therefore, for cement base piezoelectric composite material the characteristics of,
Regulate and control to realize the combination of cement and piezoelectric ceramics by interface, improves its interface compatibility, interface bond strength, durability
And overall performance, there is very important realistic meaning to the Long Period Health Monitoring of concrete structure.
Summary of the invention
Stability caused by, interfacial bonding property poor for current cement base piezoelectric composite material interface compatibility difference and durable
Property difference problem, the present invention provides a kind of sides being modified using Si-Ti-Ca tri compound film to piezoelectric ceramics surface
Method, this method are modified piezoelectric ceramics surface using Si-Ti-Ca tri compound film, make piezoelectric ceramics surface contact angle
Become smaller, hydrophily improves, become strong carrying out compound tense interfacial bonding property with cement, conducive to the combination in later period and cement, Ca, Ti and
In the presence of the stability, compatibility and durability for effectively increasing cement base piezoelectric composite material while Si.
The present invention also provides a kind of preparation method of cement base piezoelectric composite material, this method first carries out piezoelectric ceramics
Then Si-Ti-Ca tri compound modified film is carried out with cement compound again.Presence can effectively improve water while Ca, Ti and Si
Globality, interfacial bonding property and the durability of mud base piezoelectric composite material, while the piezoelectric constant of piezoelectric ceramics substrate and opposite
Change in dielectric constant is smaller, and dielectric loss is reduced, and does not influence the normal use of piezoelectric ceramics.
Specific technical solution of the present invention is as follows:
The method that a kind of pair of piezoelectric ceramics surface is modified, this method are: using Si-Ti-Ca tri compound film to piezoelectricity
Ceramic surface is modified, and the Si-Ti-Ca tri compound film is the TiO for mixing calcium2/SiO2Laminated film.Further, institute
It states Si-Ti-Ca tri compound film and overlays on piezoelectric ceramics surface, to increase piezoelectric ceramics subsequent compound with cement or cement base
Compatibility and stability when Material cladding.The cement-base composite material refers to also containing polymerization while containing cement
The composite material of the other compositions such as object, reinforcing fiber.
The present invention is each for the difference and cement base piezoelectric composite material interface of cement and piezoceramic structures and performance
The problem of long durability and stability difference caused by phase poor compatibility, associativity difference, using Si-Ti-Ca tri compound film
It is modified on PZT piezoelectric ceramics surface.Contain Ca in Si-Ti-Ca tri compound film2+、SiO2And TiO2, Ca2+And SiO2
Can respectively with the SiO in cement2、Ca(OH)2Equal ingredients, which effectively combine, forms C-S-H gel, becomes in chemical composition with cement
The entirety of organic unity increases the interfacial bonding property and compatibility of the two so that piezoelectric ceramics be made to combine closely with cement,
Meanwhile TiO2It can enter in reaction system, improve the stability of compound system on a molecular scale, improve the uniform of film
Property, hydrophily and corrosion resistance.Piezoelectric ceramics surface contact angle after the membrane surface modification is small, and good hydrophilic property, binding force is strong,
Conducive to the combination in later period and cement, and the piezoelectric property of piezoelectric ceramics substrate and dielectric properties variation are small, do not influence piezoelectric ceramics
Normal use, improve its globality, compatibility and durability.
Further, method of modifying of the present invention does not require the component of piezoelectric ceramics, may adapt to various piezoelectricity potteries
Porcelain, such as one, two, three, four-component-system piezoelectric ceramics and polynary series piezoelectric ceramic etc..Wherein, binary system PZT piezoelectric ceramics have compared with
High electromechanical coupling factor, good temperature stability and higher Curie temperature (300 DEG C), are used in piezoceramic material
At most most wide one kind is obtained, the prospect with important application value realistic and potential application, therefore preferably PZT piezoelectricity is made pottery
Porcelain.When PZT piezoelectric ceramics and cementitious composite, according to application conditions and demand, need to be cut to required size and shape,
In order to preferably increase the compatibility of piezoelectric ceramics and cement, piezoelectric ceramics is preferably cut into the shape being easy to cementitious composite
Then shape is modified again, such as be cut to the potsherd with certain size.
Further, the Si-Ti-Ca tri compound film is by Si-Ti-Ca tri compound colloidal sol on piezoelectric ceramics surface
Pulling film forming obtains, and the preparation method of Si-Ti-Ca tri compound colloidal sol is: respectively obtaining TiO using sol-gal process2Colloidal sol
And SiO2Colloidal sol, according to titanium: silicon=0.05-0.5:1 molar ratio is by TiO2Colloidal sol and SiO2Colloidal sol is mixed evenly, in 25-
35 DEG C are stirred to react 1-3h, then in 20-40 DEG C of ageing 12-36h, obtain TiO2/SiO2Complex sol；According to calcium: silicon=0.01-
The preferred 0.1-0.4:1 of 0.4:1() molar ratio by Ca (NO3)2It is added to TiO2/SiO2In complex sol, it is stirred to Ca
(NO3)2It is completely dissolved, silane coupling agent is then added, in 25-35 DEG C of ageing 12-36h after adding, it is multiple to obtain Si-Ti-Ca ternary
Close colloidal sol.
Further, the Si-Ti-Ca tri compound film overlays on piezoelectric ceramics surface by way of pulling film forming,
It realizes the modification to piezoelectric ceramics surface, specific method is: obtaining Si-Ti-Ca tri compound colloidal sol in the manner described above, it will
Si-Ti-Ca tri compound colloidal sol in piezoelectric ceramics uniformly pulling film forming, then by piezoelectric ceramics at 80-180 DEG C into
Row low-temperature sintering obtains the modified piezoelectric ceramics of Si-Ti-Ca tri compound film surface.
Further, the piezoelectric ceramics is PZT piezoelectric ceramic piece.
Further, Si-Ti-Ca tri compound colloidal sol is by Best-Effort request membrane formation process in piezoelectric ceramics surface filming.Leaching
When stain pulling film forming, the number of plies of film is 2-6 layer, and first floor dip time is 1-10min, pull rate 10-60mm/min, remaining
Layer dip time is 1-4min, pull rate 10-50mm/min, every layer film natural drying 15min.
Further, the dosage of silane coupling agent is the 1.5-2.5% of silicon mole.Si- can be improved in silane coupling agent
The dispersibility of Ti-Ca tri compound colloidal sol, can also increase the interfacial bonding property of piezoelectric ceramics and film layer.Silane coupling agent has
KH-570(methacryloxypropyl trimethoxy silane), KH-550(γ-aminopropyl triethoxysilane), A151(second
Alkenyl triethoxysilane), A171(vinyltrimethoxysilane), A172(vinyl three (beta-methoxy ethyoxyl) silane) etc.
It is a variety of, preferably KH-570.
Further, low sintering purpose be dispersibility in order to improve ingredient in Si-Ti-Ca tri compound film and
The bond strength of film and piezoelectric ceramics.Sintering uses 80-180 DEG C of low-temperature sintering, and soaking time is generally 1-3h, low-temperature sintering
The probability that film cracking can be reduced also is avoided that the formation of high temperature sintering crystal influences the performance of piezoelectric ceramics.
Further, SiO of the present invention2And TiO2Colloidal sol can be made using method disclosed in the prior art, it is preferred to use
Sol-gel method, respectively with TEOS(tetraethyl orthosilicate) and TBT(butyl titanate) it is raw material, HCl solution and HNO3To urge
Agent, EtOH(ethyl alcohol) it is solvent, hydrolysis preparation SiO2Colloidal sol and TiO2Colloidal sol.Using TiO made from different methods2Colloidal sol
And SiO2Colloidal sol perhaps performance slightly difference, but it is identical as the mechanism of action after cements, it is able to achieve mesh of the invention
's.In a certain specific embodiment of the present invention, a kind of SiO is provided2Colloidal sol and TiO2The specific preparation method of colloidal sol is as follows:
EtOH and TEOS is mixed according to the molar ratio of 3:1, the HCl solution that pH is 2.0 is added dropwise while agitating, is 3- to water silicon ratio
Stop being added dropwise when 5:1,1-3h is stirred to react at 30-50 DEG C, then in 30-50 DEG C of ageing 20-40h, obtains SiO2Colloidal sol；TiO2
Colloidal sol the preparation method comprises the following steps: TBT is added drop-wise in EtOH by EtOH and TBT according to the molar ratio of 0.78:1, be uniformly mixed,
Then the HNO that concentration is 0.2mol/mL is added dropwise again3Solution stops being added dropwise when the volume ratio of water and EtOH are 1:1, after dripping off
It stirs evenly, in 20-35 DEG C of ageing 12-36h, obtains TiO2Colloidal sol.
Preferably, first piezoelectric ceramics is pre-processed, Si-Ti-Ca ternary then is made on piezoelectric ceramics surface again and answers
Close film.Pretreatment, which can be, carries out conventional oil removing ash disposal, cleaning operation to piezoelectric ceramics surface, can also be on this basis
The roughening such as further progress polishing, acid etching operation, to increase the binding force of Si-Ti-Ca tri compound film and piezoelectric ceramics.
Further, piezoelectric ceramics pretreatment mode is: piezoelectric ceramics being carried out oil removing, cleaning treatment, or by piezoelectricity
Then ceramic oil removing, cleaning successively carry out surface polishing with water phase sand paper and abrasive paper for metallograph, then with HF and HNO3Mixed acid solution
Roughening is performed etching, is finally cleaned up.It, can be by the way that piezoelectric ceramics be put into Na when oil removing2CO3The mode impregnated in solution
It carries out, Na2CO3Solution concentration is preferably 10-25wt%.HF concentration is 5-15wt%, HNO in mixed acid solution used3Concentration is
5-15wt%, etch period 10-60s.Cleaning uses distilled water, can first use distilled water flushing, then carries out again ultrasonic clear
It washes, is finally carried out again with the mode of distilled water flushing.
Further, it is multiple to additionally provide a kind of cement/piezoelectric ceramics on the basis of above-mentioned surface modifying method by the present invention
The preparation method of condensation material, this method are: piezoelectric ceramics is carried out according to the above-mentioned method being modified to piezoelectric ceramics surface
Surface is modified, obtains the modified piezoelectric ceramics of Si-Ti-Ca tri compound film surface, then that Si-Ti-Ca tri compound is thin
The piezoelectric ceramics of membrane surface modification carries out compound, obtained cement/piezo-electric ceramic composite material with cement.Piezoelectric ceramics is first carried out
Surface is modified compound with cement progress again, is the Si-Ti-Ca tri compound on piezoelectric ceramics when piezoelectric ceramics is with cements
Directly and cements, which has calcium silicon components product similar with cement composition to film, can respectively with the SiO in cement2、
Ca(OH)2Equal ingredients react to form C-S-H gel, TiO2It can also pass through in the crystal structure of reaction product, improve the uniform of film
Property and hydrophily, and then become with cement the entirety of organic unity, so that piezoelectric ceramics be made to combine closely with cement, compatibility with
Stability greatly improves.
Further, in above-mentioned cement/piezo-electric ceramic composite material preparation method, piezoelectric ceramics is referred to finally and cement
Carry out the piezoelectric ceramics of compound required shape and size.According to actual needs, by piezoelectric ceramics be first cut into required size and
Then shape carries out surface again and is modified, to guarantee that it is modified that all and cements faces carry out surface.
Further, the present invention also provides a kind of cement/piezo-electric ceramic composite material, the composite material is by Si-Ti-Ca
The modified piezoelectric ceramics of tri compound film surface and cementitious composite and obtain.The modified pressure of Si-Ti-Ca tri compound film surface
Electroceramics handles to obtain according to the modified method in above-mentioned piezoelectric ceramics surface.
The present invention is directed to the difference of cement and piezoceramic structures and performance, and Si-Ti-Ca tri compound colloidal sol is selected to press
Electroceramics surface pulling film forming, so that it is thin to form uniform, stable, firm Si-Ti-Ca tri compound on piezoelectric ceramics surface
Film.After adhering to the film, piezoelectric ceramics contact angle becomes smaller (≤30.5 °), good hydrophilic property, binding force are strong, conducive to later period and cement
In conjunction with；Meanwhile the piezoelectric constant and relative dielectric constant of piezoelectric ceramics substrate change smaller (piezoelectric constant d33Change rate≤
2.1%, relative dielectric constant change rate≤2.05%), dielectric loss is reduced (change rate≤2.86%), does not influence piezoelectricity pottery
The normal use of porcelain.Piezoelectric ceramics and cement carry out compound tense, the Ca in laminated film2+And SiO2It can be respectively and in cement
SiO2、Ca(OH)2Equal ingredients react to form C-S-H gel, TiO2It can also pass through in reaction system, improve uniformity, the parent of film
Aqueous and corrosion resistance makes interface form organic whole.Exist while Ca, Ti and Si so that interface bond strength, compatibility
There is apparent improvement with stability, effectively increases the globality and durability of cement base PZT piezo-electricity composite material.
Detailed description of the invention
Fig. 1 is the SiO of comparative example 22Film, the silico-calcium film of comparative example 3, the silicon titanium film of comparative example 4 and embodiment 1 silicon titanium calcium
Piezoelectric ceramics surface contact angle after membrane modifying changes histogram.
Fig. 2 is wetting (contact angle) figure on the PZT piezoelectric ceramics surface of the non-overlay film of comparative example 1.
Fig. 3 is wetting (contact angle) figure on the PZT piezoelectric ceramics surface that embodiment 1 covers silicon titanium calcium film.
Fig. 4 is the SiO of comparative example 22The SEM of film schemes.
Fig. 5 is the SEM figure of the silico-calcium film of comparative example 3.
Fig. 6 is the SEM figure of the silicon titanium film of comparative example 4.
Fig. 7 is the SEM figure of the silicon titanium calcium film of embodiment 1.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention will be further described, and the following instruction is only illustrative, not right
Its content is limited.
In following embodiments, unless otherwise instructed, each concentration is mass percentage concentration.
Embodiment 1
(1) preprepared PZT piezoelectric ceramics block is cut into along polarization direction having a size of 22*15.6* using precision gas cutting machine
The thin slice of 2mm is then placed in the Na that preparatory prepared concentration is 25wt%2CO310min is impregnated in solution, carries out oil removing, is taken out
First distilled water flushing afterwards is finally used distilled water flushing three times then at 40 DEG C of ultrasound 20min, is dried up spare；
(2) the water phase sand paper of 360# is first used to look for along 50 circle of " 8 " word polishing the PZT piezoelectric ceramic thin sheet after oil removing in step (1)
It puts down, then is polished with W40 abrasive paper for metallograph along 50 circle of " 8 " word polishing, then with containing 10wt%HF and 5wt%HNO3Mixed acid solution etching
60s is cleaned by ultrasonic completely after taking-up, dries up spare；
(3) using EtOH and TEOS as raw material, mixing is placed in a beaker by alcohol silicon mol ratio n (EtOH)/n (TEOS)=3 measurement
It is even, the HCl solution of pH=2.0 is added dropwise under magnetic agitation, dripping quantity is controlled in water silicon molar ratio n (H2O)/n (TEOS)=3 is added dropwise
After beaker seal, in 45 DEG C of water-baths stir 2h reaction, be subsequently placed in 40 DEG C of baking ovens and be aged for 24 hours, obtain SiO2It is molten
Glue；
(4) using EtOH and TBT as raw material, by alcohol titanium molar ratio n (EtOH)/n (TBT)=0.78, in anhydrous conditions by TBT drop
It is added in EtOH, is stirred when being added dropwise, the HNO of 0.2mol/mL is then added dropwise thereto again3Solution, dripping quantity are controlled in water alcohol
Volume ratio is 1, stirs 30min after being added dropwise, and is subsequently placed in 25 DEG C of baking ovens and is aged for 24 hours, obtains TiO2Colloidal sol；
(5) by SiO obtained in step (3) and step (4)2Colloidal sol and TiO2Colloidal sol is measured by titanium silicon mol ratio for 0.1
Mixed colloidal sol is reacted 2h in 30 DEG C of magnetic agitations, is then aged for 24 hours at 25 DEG C, obtains TiO by mixing2/SiO2It is compound
Colloidal sol；
(6) with Ca (NO3)2For calcium source, by calcium silicon mol ratio Ca/Si=0.2, by Ca (NO3)2The TiO being added in step (5)2/
SiO2In complex sol, mixing 30min is stirred at room temperature and makes it completely dissolved, the silicon of TEOS mole 2% is then added thereto again
Alkane coupling agent kh-570 is aged at a temperature of 28 DEG C after stirring 30min and obtains final Si-Ti-Ca tri compound colloidal sol for 24 hours；
(7) film balance is used, using the complex sol in step (6) as preparation liquid, is roughened obtained PZT piezoelectricity in step (2)
Pulling film forming is carried out on the surface of ceramic sheet.The membrane number of plies is 3 layers, when first floor film preparation, the PZT piezoelectric ceramic thin sheet of roughening
Dip time in preparation liquid is 5min, pull rate 30mm/min, is spontaneously dried after membrane, drying time 15min,
When prepared by remaining 2 tunic, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 3min, and pull rate is
30mm/min is spontaneously dried after membrane, drying time 15min；
(8) by the PZT piezoelectric ceramic thin sheet after membrane in step (7), low-temperature sintering, soaking time 2h are obtained at 160 DEG C
By the modified PZT piezoceramic material in Si-Ti-Ca tri compound film (abbreviation silicon titanium calcium film) surface.
Embodiment 2
Step (1)-(4) are the same as embodiment 1；
(5) by SiO obtained in step (3) and step (4)2Colloidal sol and TiO2Colloidal sol is measured by titanium silicon mol ratio for 0.2
Mixed colloidal sol is reacted 2.5h in 35 DEG C of magnetic agitations, is then aged 30h at 30 DEG C, obtains TiO by mixing2/SiO2It is multiple
Close colloidal sol；
(6) with Ca (NO3)2For calcium source, by calcium silicon mol ratio Ca/Si=0.3, by Ca (NO3)2The TiO being added in step (5)2/
SiO2In complex sol, mixing 30min is stirred at room temperature and makes it completely dissolved, the silicon of TEOS mole 2% is then added thereto again
Alkane coupling agent kh-570 is aged 27h at a temperature of 30 DEG C after stirring 30min, obtains final Si-Ti-Ca tri compound colloidal sol；
(7) film balance is used, using the complex sol in step (6) as preparation liquid, is roughened obtained PZT piezoelectricity in step (2)
Pulling film forming is carried out on the surface of ceramic sheet.The membrane number of plies is 4 layers, when first floor film preparation, the PZT piezoelectric ceramic thin sheet of roughening
Dip time in preparation liquid is 8min, pull rate 20mm/min, is spontaneously dried after membrane, drying time 15min,
When prepared by remaining 3 tunic, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 4min, and pull rate is
20mm/min is spontaneously dried after membrane, drying time 15min；
(8) by the PZT piezoelectric ceramic thin sheet after membrane in step (7), low-temperature sintering, soaking time 2h are obtained at 120 DEG C
By the modified PZT piezoceramic material in Si-Ti-Ca tri compound film (abbreviation silicon titanium calcium film) surface.
Embodiment 3
Step (1)-(4) are the same as embodiment 1；
(5) by SiO obtained in step (3) and step (4)2Colloidal sol and TiO2Colloidal sol is measured by titanium silicon mol ratio for 0.3
Mixed colloidal sol is reacted 2.5h in 28 DEG C of magnetic agitations, is then aged 33h at 20 DEG C, obtains TiO by mixing2/SiO2It is multiple
Close colloidal sol；
(6) with Ca (NO3)2For calcium source, by calcium silicon mol ratio Ca/Si=0.1, by Ca (NO3)2The TiO being added in step (5)2/
SiO2In complex sol, mixing 30min is stirred at room temperature and makes it completely dissolved, the silicon of TEOS mole 2% is then added thereto again
Alkane coupling agent kh-570 is aged 33h at a temperature of 32 DEG C after stirring 30min, obtains final Si-Ti-Ca tri compound colloidal sol；
(7) film balance is used, using the complex sol in step (6) as preparation liquid, is roughened obtained PZT piezoelectricity in step (2)
Pulling film forming is carried out on the surface of ceramic sheet.The membrane number of plies is 5 layers, when first floor film preparation, the PZT piezoelectric ceramic thin sheet of roughening
Dip time in preparation liquid is 8min, pull rate 15mm/min, is spontaneously dried after membrane, drying time 15min,
When prepared by remaining 4 tunic, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 2min, and pull rate is
15mm/min is spontaneously dried after membrane, drying time 15min；
(8) by the PZT piezoelectric ceramic thin sheet after membrane in step (7), low-temperature sintering, soaking time 2.5h are obtained at 100 DEG C
To the PZT piezoceramic material modified by Si-Ti-Ca tri compound film (abbreviation silicon titanium calcium film) surface.
Embodiment 4
Step (1)-(4) are the same as embodiment 1；
(5) by SiO obtained in step (3) and step (4)2Colloidal sol and TiO2Colloidal sol is measured by titanium silicon mol ratio for 0.4
Mixed colloidal sol is reacted 1.5h in 32 DEG C of magnetic agitations, is then aged 15h at 30 DEG C, obtains TiO by mixing2/SiO2It is multiple
Close colloidal sol；
(6) with Ca (NO3)2For calcium source, by calcium silicon mol ratio Ca/Si=0.2, by Ca (NO3)2The TiO being added in step (5)2/
SiO2In complex sol, mixing 30min is stirred at room temperature and makes it completely dissolved, the silicon of TEOS mole 2% is then added thereto again
Alkane coupling agent kh-570 is aged 15h at a temperature of 30 DEG C after stirring 30min, obtains final Si-Ti-Ca tri compound colloidal sol；
(7) film balance is used, using the complex sol in step (6) as preparation liquid, is roughened obtained PZT piezoelectricity in step (2)
Pulling film forming is carried out on the surface of ceramic sheet.The membrane number of plies is 3 layers, when first floor film preparation, the PZT piezoelectric ceramic thin sheet of roughening
Dip time in preparation liquid is 5min, pull rate 40mm/min, is spontaneously dried after membrane, drying time 15min,
When prepared by remaining 2 tunic, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 3min, and pull rate is
40mm/min is spontaneously dried after membrane, drying time 15min；
(8) by the PZT piezoelectric ceramic thin sheet after membrane in step (7), low-temperature sintering, soaking time 1.5h are obtained at 140 DEG C
To the PZT piezoceramic material modified by Si-Ti-Ca tri compound film (abbreviation silicon titanium calcium film) surface.
Embodiment 5
Step (1)-(4) are the same as embodiment 1；
(5) by SiO obtained in step (3) and step (4)2Colloidal sol and TiO2Colloidal sol is measured by titanium silicon mol ratio for 0.1
Mixed colloidal sol is reacted 2h in 30 DEG C of magnetic agitations, is then aged for 24 hours at 25 DEG C, obtains TiO by mixing2/SiO2It is compound
Colloidal sol；
(6) with Ca (NO3)2For calcium source, by calcium silicon mol ratio Ca/Si=0.3, by Ca (NO3)2The TiO being added in step (5)2/
SiO2In complex sol, mixing 30min is stirred at room temperature and makes it completely dissolved, the silicon of TEOS mole 2% is then added thereto again
Alkane coupling agent kh-570 is aged at a temperature of 30 DEG C after stirring 30min and obtains final Si-Ti-Ca tri compound colloidal sol for 24 hours；
(7) film balance is used, using the complex sol in step (6) as preparation liquid, is roughened obtained PZT piezoelectricity in step (2)
Pulling film forming is carried out on the surface of ceramic sheet.The membrane number of plies is 3 layers, when first floor film preparation, the PZT piezoelectric ceramic thin sheet of roughening
Dip time in preparation liquid is 5min, pull rate 30mm/min, is spontaneously dried after membrane, drying time 15min,
When prepared by remaining 2 tunic, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 3min, and pull rate is
30mm/min is spontaneously dried after membrane, drying time 15min；
(8) by the PZT piezoelectric ceramic thin sheet after membrane in step (7), low-temperature sintering, soaking time 2h are obtained at 160 DEG C
By the modified PZT piezoceramic material in Si-Ti-Ca tri compound film (abbreviation silicon titanium calcium film) surface.
Embodiment 6
Step (1)-(4) are the same as embodiment 1；
(5) by SiO obtained in step (3) and step (4)2Colloidal sol and TiO2Colloidal sol is measured by titanium silicon mol ratio for 0.1
Mixed colloidal sol is reacted 2h in 30 DEG C of magnetic agitations, is then aged for 24 hours at 25 DEG C, obtains TiO by mixing2/SiO2It is compound
Colloidal sol；
(6) with Ca (NO3)2For calcium source, by calcium silicon mol ratio Ca/Si=0.1, by Ca (NO3)2The TiO being added in step (5)2/
SiO2In complex sol, mixing 10min is stirred at room temperature and makes it completely dissolved, the silicon of TEOS mole 2% is then added thereto again
Alkane coupling agent kh-570 is aged at a temperature of 25 DEG C after stirring 30min and obtains final Si-Ti-Ca tri compound colloidal sol for 24 hours；
(7) film balance is used, using the complex sol in step (6) as preparation liquid, is roughened obtained PZT piezoelectricity in step (2)
Pulling film forming is carried out on the surface of ceramic sheet.The membrane number of plies is 3 layers, when first floor film preparation, the PZT piezoelectric ceramic thin sheet of roughening
Dip time in preparation liquid is 5min, pull rate 30mm/min, is spontaneously dried after membrane, drying time 15min,
When prepared by remaining 2 tunic, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 3min, and pull rate is
30mm/min is spontaneously dried after membrane, drying time 15min；
(8) by the PZT piezoelectric ceramic thin sheet after membrane in step (7), low-temperature sintering, soaking time 2h are obtained at 160 DEG C
By the modified PZT piezoceramic material in Si-Ti-Ca tri compound film (abbreviation silicon titanium calcium film) surface.
Embodiment 7
Step (1)-(4) are the same as embodiment 1；
(5) by SiO obtained in step (3) and step (4)2Colloidal sol and TiO2Colloidal sol is measured by titanium silicon mol ratio for 0.1
Mixed colloidal sol is reacted 2h in 30 DEG C of magnetic agitations, is then aged for 24 hours at 25 DEG C, obtains TiO by mixing2/SiO2It is compound
Colloidal sol；
(6) with Ca (NO3)2For calcium source, by calcium silicon mol ratio Ca/Si=0.2, by Ca (NO3)2The TiO being added in step (5)2/
SiO2In complex sol, mixing 30min is stirred at room temperature and makes it completely dissolved, the silicon of TEOS mole 2% is then added thereto again
Alkane coupling agent kh-570 is aged at a temperature of 28 DEG C after stirring 30min and obtains final Si-Ti-Ca tri compound colloidal sol for 24 hours；
(7) film balance is used, using the complex sol in step (6) as preparation liquid, is roughened obtained PZT piezoelectricity in step (2)
Pulling film forming is carried out on the surface of ceramic sheet.The membrane number of plies is 3 layers, when first floor film preparation, the PZT piezoelectric ceramic thin sheet of roughening
Dip time in preparation liquid is 5min, pull rate 30mm/min, is spontaneously dried after membrane, drying time 15min,
When prepared by remaining 2 tunic, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 3min, and pull rate is
30mm/min is spontaneously dried after membrane, drying time 15min；
(8) by the PZT piezoelectric ceramic thin sheet after membrane in step (7) at 80 DEG C low-temperature sintering, soaking time 3h, obtain by
The modified PZT piezoceramic material in Si-Ti-Ca tri compound film (abbreviation silicon titanium calcium film) surface.
Comparative example 1
Step (1)-(2) are the same as embodiment 1；
(3) the PZT piezoelectric ceramic thin sheet in step (2) is subjected to low-temperature sintering, soaking time 2h at 160 DEG C.
Comparative example 2
Step (1)-(3) are the same as embodiment 1；
(4) SiO prepared into step (3)2The Silane coupling reagent KH-570 of TEOS mole 2%, stirring are added in colloidal sol
It is aged for 24 hours at a temperature of 25 DEG C after 30min；
(5) film balance is used, with the SiO in step (4)2Colloidal sol is preparation liquid, the PZT piezoelectricity that roughening obtains in step (2)
Pulling film forming is carried out on the surface of ceramic sheet.The membrane number of plies is 3 layers, when first floor film preparation, the PZT piezoelectric ceramic thin sheet of roughening
Dip time in preparation liquid is 5min, pull rate 30mm/min, is spontaneously dried after membrane, drying time 15min,
When prepared by remaining 2 tunic, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 3min, and pull rate is
30mm/min is spontaneously dried after membrane, drying time 15min；
(6) by the PZT piezoelectric ceramic thin sheet after membrane in step (5), low-temperature sintering, soaking time 2h are obtained at 160 DEG C
By SiO2The modified PZT piezoceramic material of film surface.
Comparative example 3
Step (1)-(3) are the same as embodiment 1；
(4) with Ca (NO3)2For calcium source, by calcium silicon mol ratio Ca/Si=0.2, by Ca (NO3)2The SiO being added in step (3)2
In colloidal sol, mixing 30min is stirred at room temperature and makes it completely dissolved, the silane coupling agent of TEOS mole 2% is then added thereto again
It is aged at a temperature of 25 DEG C after KH-570, stirring 30min and obtains final colloidal sol for 24 hours；
(5) film balance is used, using the colloidal sol in step (4) as preparation liquid, is roughened obtained PZT piezoelectric ceramics in step (2)
Pulling film forming is carried out on the surface of thin slice.The membrane number of plies is 3 layers, when first floor film preparation, and the PZT piezoelectric ceramic thin sheet of roughening is being made
Dip time in film liquid is 5min, pull rate 30mm/min, is spontaneously dried after membrane, drying time 15min, remaining
When prepared by 2 tunics, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 3min, pull rate 30mm/
Min is spontaneously dried after membrane, drying time 15min；
(6) by the PZT piezoelectric ceramic thin sheet after membrane in step (5) at 160 DEG C low-temperature sintering, soaking time be 2h obtain by
The modified PZT piezoceramic material in Si- Ca binary laminated film (abbreviation silico-calcium film) surface.
Comparative example 4
Step (1)-(5) are the same as embodiment 1；
(6) TiO prepared to step (5)2/SiO2The Silane coupling reagent KH-570 of TEOS mole 2% is added in complex sol,
It is aged at a temperature of 25 DEG C after stirring 30min and obtains final colloidal sol for 24 hours；
(7) film balance is used, using the colloidal sol in step (6) as preparation liquid, is roughened obtained PZT piezoelectric ceramics in step (2)
Pulling film forming is carried out on the surface of thin slice.The membrane number of plies is 3 layers, when first floor film preparation, and the PZT piezoelectric ceramic thin sheet of roughening is being made
Dip time in film liquid is 5min, pull rate 30mm/min, is spontaneously dried after membrane, drying time 15min, remaining
When prepared by 2 tunics, dip time of the PZT piezoelectric ceramic thin sheet of roughening in preparation liquid is 3min, pull rate 30mm/
Min is spontaneously dried after membrane, drying time 15min；
(8) by the PZT piezoelectric ceramic thin sheet after membrane in step (7), low-temperature sintering, soaking time 2h are obtained at 160 DEG C
By the modified PZT piezoceramic material in Si-Ti binary laminated film (abbreviation silicon titanium film) surface.
Comparative example 5
Step (1)-(8) are with embodiment 1, the difference is that being added without Silane coupling reagent KH-570 in step (6).It finally obtains by nothing
The modified PZT piezoceramic material in Si-Ti-Ca tri compound film (the abbreviation silicon titanium calcium film) surface of silane coupling agent.
Comparative example 6
It carries out surface to piezoelectric ceramic thin sheet according to the method for embodiment 1 to be modified, the difference is that the PZT in step (8) after membrane
Piezoelectric ceramic thin sheet is sintered at 260 DEG C, soaking time 2h.
Embodiment 1, comparative example 2, comparative example 3, comparative example 4 become by the contact angle of modified PZT piezoelectric ceramic thin sheet
Change as shown in Figure 1, from the graph, it is apparent that the piezoelectric ceramics surface after silico-calcium film, silicon titanium film and silicon titanium calcium membrane modifying connects
Feeler is similar, wetability is preferable, and the interface for being conducive to piezoelectric ceramics and cement-based material regulates and controls.
The Wet Out of PZT piezoelectric ceramic thin sheet after embodiment 1,1 modification of comparative example is tested, as a result such as
Shown in Fig. 2 and 3, it can be seen from the figure that using the piezoelectric ceramics surface hydrophilicity of silicon titanium calcium modified film obviously than not carrying out
The modified good hydrophilic property in surface.
SEM is carried out to the PZT piezoelectric ceramic thin sheet after comparative example 2,1 modification of comparative example 3, comparative example 4 and embodiment
Characterization, as a result as shown in figs. 4-7, it can be seen from the figure that SiO2Film is covered on piezoelectric ceramics surface, and film layer is thicker, covers
Piezoelectric ceramics surface particles pattern has a small amount of crackle to generate since film layer is shunk；Silico-calcium film film layer is very thick, low-temperature sintering caudacoria
The defects of surface hole, generates；All very pettiness, thicknesses of layers become smaller for silicon titanium calcium laminated film and silicon titanium coextruded film crackle, protect
Piezoelectric ceramics surface topography is stayed, roughness is big, increases interface binding power, but silicon titanium calcium laminated film is more evenly, more causes
Close, introducing while Ca and Ti can more efficient improvement interfacial bonding property.
Each PZT piezoelectric ceramic thin sheet made from above-described embodiment and comparative example Jing Guo modification is subjected to performance survey
Examination, specifically: its surface contact angle, quasi-static d are measured in the way of goniometry by contact angle measurement33Measuring instrument measurement
Its piezoelectric constant d33, impedance analyzer measures and calculates its relative dielectric constant and dielectric loss.As a result as shown in table 1 below.
Each performance of above-described embodiment and comparative example 2-6 each PZT piezoelectric ceramic thin sheet obtained Jing Guo modification and
The situation of change that comparative example 1 is compared is as shown in table 2 below.
The PZT piezoelectric ceramic thin sheet is modified through Si-Ti-Ca tri compound film surface it can be seen from Tables 1 and 2
Contact angle becomes smaller (≤30.5 °), while the piezoelectric constant of piezoelectric ceramics substrate and relative dielectric constant change smaller (piezoelectric constant
d33Change rate≤2.10%, relative dielectric constant change rate≤2.05%), dielectric loss is reduced (change rate≤2.86%), no
The normal use for influencing piezoelectric ceramics, has reached under the premise of not influencing PZT piezoelectric ceramics piezoelectric property, makes it have and water
Mud excellent compatibility, and improve cement base PZT piezo-electricity composite material globality, the purpose of stability and durability.In addition, with pure
SiO2The PZT piezoelectric ceramics of membrane surface modification is compared, and hydrophily is more preferable, and Si-Ti-Ca tri compound film has apparent excellent
Gesture.
Claims (10)
1. the method that a kind of pair of piezoelectric ceramics surface is modified, it is characterized in that: using Si-Ti-Ca tri compound film to pressure
Electroceramics surface is modified, and the Si-Ti-Ca tri compound film is the TiO for mixing calcium2/SiO2Laminated film.
2. according to the method described in claim 1, it is characterized in that: the Si-Ti-Ca tri compound film overlays on piezoelectric ceramics table
Face.
3. according to the method described in claim 1, it is characterized in that: the Si-Ti-Ca tri compound film passes through pulling film forming
Mode overlays on piezoelectric ceramics surface, and method is: respectively obtaining TiO using sol-gal process2Colloidal sol and SiO2Colloidal sol, according to titanium: silicon
The molar ratio of=0.05-0.5:1 is by TiO2Colloidal sol and SiO2Colloidal sol is mixed evenly, and 1-3h is stirred to react at 25-35 DEG C, then
In 20-40 DEG C of ageing 12-36h, TiO is obtained2/SiO2Complex sol；According to calcium: silicon=0.01-0.4:1 molar ratio is by Ca
(NO3)2It is added to TiO2/SiO2In complex sol, it is stirred to Ca (NO3)2Be completely dissolved, then be added silane coupling agent into
Row reaction, in 25-35 DEG C of ageing 12-36h after adding, obtains Si-Ti-Ca tri compound colloidal sol；By Si-Ti-Ca tri compound
Then piezoelectric ceramics is carried out at 80-180 DEG C low-temperature sintering, obtained by colloidal sol in piezoelectric ceramics uniformly pulling film forming
The modified piezoelectric ceramics of Si-Ti-Ca tri compound film surface.
4. according to the method described in claim 3, it is characterized in that: the silane coupling agent be KH-570, KH-550, A151,
A171 or A172, the piezoelectric ceramics are PZT piezoelectric ceramic piece.
5. the method according to claim 3 or 4, it is characterized in that: the dosage of silane coupling agent is the 1.5- of silicon mole
2.5%。
6. according to the method described in claim 3, it is characterized in that: the low sintering time is 1-3h.
7. according to the method described in claim 3, it is characterized in that: Si-Ti-Ca tri compound colloidal sol passes through Best-Effort request membrane formation process
In piezoelectric ceramics surface filming, film layer number is 2-6 layer, and first floor dip time is 1-10min, pull rate 10-60mm/min,
Remainder layer dip time is 1-4min, pull rate 10-50mm/min, 15 min of every layer film natural drying.
8. according to the method described in claim 3, it is characterized in that: piezoelectric ceramics lifted in Si-Ti-Ca tri compound colloidal sol at
Before film, by pretreatment, pretreatment mode is: by piezoelectric ceramics carry out oil removing, cleaning treatment, or by piezoelectric ceramics oil removing,
Then cleaning successively carries out surface polishing with water phase sand paper and abrasive paper for metallograph, then with HF and HNO3Mixed acid solution carved
Erosion roughening, finally cleans up.
9. according to the method described in claim 3, it is characterized in that: SiO2Colloidal sol the preparation method comprises the following steps: by EtOH and TEOS according to 3:
1 molar ratio mixing, the HCl solution that pH is 2.0 is added dropwise while agitating, stops when the molar ratio of water and TEOS are 3-5:1
It is only added dropwise, 1-4h is stirred to react at 30-50 DEG C, then in 30-50 DEG C of ageing 20-40h, obtain SiO2Colloidal sol；TiO2The system of colloidal sol
Preparation Method are as follows: according to EtOH: butyl titanate is that butyl titanate is added drop-wise in EtOH by the molar ratio of 0.78:1, is stirred
Uniformly, the HNO that concentration is 0.2mol/mL is then added dropwise again3Solution stops being added dropwise, drop when the volume ratio of water and EtOH are 1:1
It is stirred evenly after complete, in 20-35 DEG C of ageing 12-36h, obtains TiO2Colloidal sol.
10. a kind of preparation method of cement/piezo-electric ceramic composite material, it is characterized in that: by piezoelectric ceramics according to claim 1 institute
The method being modified to piezoelectric ceramics surface stated carries out surface and is modified, and it is modified to obtain Si-Ti-Ca tri compound film surface
Piezoelectric ceramics, then the modified piezoelectric ceramics of Si-Ti-Ca tri compound film surface and cement are carried out to compound, obtained water
Mud/piezo-electric ceramic composite material.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3621960B2 (en) * | 2001-03-30 | 2005-02-23 | 学校法人 関西大学 | Method for forming lead zirconate titanate composite perovskite film |
| DE102004001240A1 (en) * | 2004-01-07 | 2005-08-04 | Jaeckel, Manfred, Dipl.-Ing. | Ceramic- or metal-based moulding material for production of sintered tubes, sheet and other products, comprises ceramic or metallic particles coated with a binder containing polyamide and water |
| CN2760028Y (en) * | 2004-07-26 | 2006-02-22 | 济南大学 | Cement-based piezoelectric composite material |
| CN1775833A (en) * | 2005-11-30 | 2006-05-24 | 华东理工大学 | Method for preparing titanium dioxide functional film from poly ethylene glycol terephthalate substrate surface |
| CN101481117A (en) * | 2009-01-22 | 2009-07-15 | 上海交通大学 | SiO2 sol gel solution and method for preparing piezoelectric particle surface SiO2 coating |
| CN105328751A (en) * | 2015-10-27 | 2016-02-17 | 广西大学 | Method for generating silicon-titanium double-element oxidation film on surface of timber |
| CN106521494A (en) * | 2016-11-06 | 2017-03-22 | 桂林理工大学 | Ni, S codoped TiO2 film, application and preparation method thereof |
| CN107742671A (en) * | 2017-11-27 | 2018-02-27 | 中北大学 | 312 type polymer/cement piezoelectric composite material and preparation method thereof |
-
2019
- 2019-05-10 CN CN201910390276.8A patent/CN110156364B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3621960B2 (en) * | 2001-03-30 | 2005-02-23 | 学校法人 関西大学 | Method for forming lead zirconate titanate composite perovskite film |
| DE102004001240A1 (en) * | 2004-01-07 | 2005-08-04 | Jaeckel, Manfred, Dipl.-Ing. | Ceramic- or metal-based moulding material for production of sintered tubes, sheet and other products, comprises ceramic or metallic particles coated with a binder containing polyamide and water |
| CN2760028Y (en) * | 2004-07-26 | 2006-02-22 | 济南大学 | Cement-based piezoelectric composite material |
| CN1775833A (en) * | 2005-11-30 | 2006-05-24 | 华东理工大学 | Method for preparing titanium dioxide functional film from poly ethylene glycol terephthalate substrate surface |
| CN101481117A (en) * | 2009-01-22 | 2009-07-15 | 上海交通大学 | SiO2 sol gel solution and method for preparing piezoelectric particle surface SiO2 coating |
| CN105328751A (en) * | 2015-10-27 | 2016-02-17 | 广西大学 | Method for generating silicon-titanium double-element oxidation film on surface of timber |
| CN106521494A (en) * | 2016-11-06 | 2017-03-22 | 桂林理工大学 | Ni, S codoped TiO2 film, application and preparation method thereof |
| CN107742671A (en) * | 2017-11-27 | 2018-02-27 | 中北大学 | 312 type polymer/cement piezoelectric composite material and preparation method thereof |
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