CN109320241A - A kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics - Google Patents

A kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics Download PDF

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CN109320241A
CN109320241A CN201811231239.4A CN201811231239A CN109320241A CN 109320241 A CN109320241 A CN 109320241A CN 201811231239 A CN201811231239 A CN 201811231239A CN 109320241 A CN109320241 A CN 109320241A
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powder
ball
crucible
idiosome
calcining
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李智敏
闫养希
刘治宏
张东岩
张茂林
郝跃
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Xidian University
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Abstract

The invention discloses a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics, specifically comprise the following steps: to prepare prefabricated presoma niobic acid nickel powder material；Basis material is prepared again, then weighs Al2O3Powder and Li2CO3Powder and basis material, which are added together in ball grinder, carries out ball-milling treatment, obtains mixed powder；Then mixed powder successively dried, calcined and cooling treatment, obtain pre-synthesis powder；Obtained pre-synthesis powder is successively ground, ball milling and drying and processing, obtain prefabricated mixed powder material, the PVA solution for adding preparation is granulated, and then the powder made is sieved, the powder obtained after filtering is finally pressed into idiosome；Dumping, natural cooling processing and calcination processing are successively carried out to idiosome is obtained；The potsherd that calcining obtains is polished, is handled by silver；Potsherd after obtained silver ink firing is polarised.

Description

A kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics
Technical field
The invention belongs to ceramic materials preparation technology fields, are related to a kind of lithium aluminium codope hafnium lead titanates-lead nickle niobate pressure The preparation method of electroceramics.
Background technique
With electronic information technology, aerospace and the high speed development of national defense industry, in high-tech area using especially Sound source driver, efficient transmission underwater acoustic transducer and it is medical in terms of piezoelectric material is proposed more High request.High performance piezoelectric material research at present be concentrated mainly on relaxation Ferroelectric monocrystal material and polynary series piezoelectric ceramic this Two aspects.
It is lead magnesium niobate-lead titanate (1-x) Pb (MgNb) O that relaxation Ferroelectric monocrystal material, which is studied more,3- xPbTiO3(PMN-PT) monocrystalline, piezoelectric property are much higher than traditional PZT piezoelectric ceramics, piezoelectric constant d33It can achieve 2200pC/N.It can be very good to be applied to sound source driving aspect, such as: the underwater acoustic transducer of efficient transmission, medical ultrasound pass The Ultrasonic NDT etc. of sensor and NEW TYPE OF COMPOSITE plate armour.Although relaxation Ferroelectric monocrystal material has very excellent piezoelectricity Performance, but its preparation process is relative complex, at high cost, long preparation period, and Curie temperature is low, temperature stability is poor etc. lacks Point greatly limits its batch production and industrial applications.
Polynary series piezoelectric ceramic research is mainly based upon Pb (Zr, Ti) O3System develops improved ternary system, quaternary system pressure Electroceramics, including Pb (Zr, Ti) O3-Pb (Mn, Nb) O3, Pb (Zr, Ti) O3-Pb(Zn,Nb)O3、Pb(Zr,Ti)O3-Pb(Ni, Nb)O3And Pb (Zr, Ti) O3-Pb(Zn,Nb)O3-Pb(Ni,Nb)O3Deng.Compared to low one-component system piezoelectric ceramics, polynary system piezoelectricity Ceramics can make up for it the single defect of its performance, be provided simultaneously with good piezoelectricity, dielectric and mechanical performance, and application field is wider It is general.As one of piezoceramic material area research hot spot in recent years.But their preparation process is complicated at present, sintering condition It is higher, and piezoelectric modulus is difficult to break through 800pC/N.In recent years studies have shown that: Pb (Hf, Ti) O3-Pb(Nb,Ni)O3Piezoelectricity pottery Porcelain has excellent piezoelectric property, and piezoelectric modulus is expected to break through 800pC/N.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics, The piezoelectric ceramics obtained using the preparation method, piezoelectric constant are greater than 800pC/N.
The technical scheme adopted by the invention is that a kind of system of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics Preparation Method specifically comprises the following steps:
Step 1, by NiCO3-2Ni(OH)2-4H2O and Nb2O5Powder mixing, successively passes through ball milling, drying, calcining and cooling Processing, obtains prefabricated presoma niobic acid nickel (NiNb2O6) powder；
Step 2, according to 0.51Pb (Ti0.7Hf0.3)O3-0.49Pb(Ni1/3Nb1/3)O3Stoichiometric ratio weighs Pb3O4Powder Body, TiO2Powder, HfO2NiNb obtained in powder and step 12O6Powder forms basis material, then weighs Al2O3Powder and Li2CO3Powder, Al2O3Powder and Li2CO3The mole of powder is hafnium lead titanates-lead nickle niobate Pb (Ti, Hf) O3-Pb(Ni, Nb)O3The 0.1~3.0% of mole；
Step 3, by Pb weighed in step 23O4Powder, TiO2Powder, HfO2Powder, NiNb2O6Powder and Al2O3Powder Body and Li2CO3Powder is added in ball grinder and carries out ball-milling treatment, obtains mixed powder；Then mixed powder is successively dried Dry, calcining and cooling treatment, obtain pre-synthesis powder；
Step 4, the pre-synthesis powder obtained through step 3 is successively ground, ball milling and drying and processing, is obtained prefabricated mixed Dry mash is closed, the PVA solution for adding preparation is granulated, and then the powder made is sieved；It will finally obtain after filtering Powder is pressed into idiosome；
Step 5, idiosome is obtained to step 4 and successively carries out dumping, natural cooling processing and calcination processing, obtain three oxidations two The hafnium of aluminium and carbonic acid lithium doping lead titanates-lead nickle niobate piezoelectric ceramics；
Step 6, the potsherd that step 5 calcining obtains polished, handled by silver；
Step 7, the potsherd after the silver ink firing obtained in the step 6 is polarised.
The features of the present invention also characterized in that
Detailed process is as follows for step 1:
Step 1.1, by NiCO3-2Ni(OH)2-4H2O powder and Nb2O5Powder is weighed and is mixed according to molar ratio 1:3 It closes, forms mixed powder；
Step 1.2, mixed powder and abrading-ball that step 1.1 obtains are added to together in ball grinder and are added into ball grinder Enter dehydrated alcohol as ball-milling medium, carries out ball-milling treatment, obtain uniform mixed powder；
Step 1.3, it step 1.2 is obtained mixed powder is placed in baking oven to carry out drying and processing, obtain mixed powder material, dry Dry temperature control are as follows: 80 DEG C~100 DEG C；
Step 1.4, the resulting mixed powder material of step 1.3 is put into crucible, and mixed powder material is pressed in crucible It is real, lid is then covered on crucible, is made to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere And the mixed powder material under the conditions of 1050 DEG C~1150 DEG C temperature in calcining at constant temperature crucible, heating rate control 3~5 DEG C/ Min, calcination time control are as follows: 1.5h~2.5h；
Step 1.5, after the completion of step 1.4 calcining, crucible is taken out from Muffle furnace, crucible is made to naturally cool to room Temperature, crucible is interior to form presoma NiNb2O6Powder.
Detailed process is as follows for step 3:
Step 3.1, weighed Al in the basis material and step 2 step 2 obtained2O3Powder and Li2CO3Powder mixing It is formed to ball milling powder, will be added in ball grinder together to ball milling powder and abrading-ball, and dehydrated alcohol is added into ball grinder As ball-milling medium, ball-milling treatment is carried out, mixed powder is obtained；
Step 3.2, mixed powder step 3.1 obtained, which is placed in baking oven, carries out drying and processing, obtains mixed powder material； The temperature of drying controls are as follows: 80 DEG C~100 DEG C；
The resulting mixed powder material of step 3.2 is put into crucible, and mixed powder material is pressed in crucible by step 3.3 It is real, lid is then covered on crucible, is made to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere And the mixed powder material under the conditions of 800~950 DEG C of temperature in calcining at constant temperature crucible, heating rate are controlled in 3~5 DEG C/min, are forged Burn time control are as follows: 1.5h~2.5h；
Step 3.4, after the completion of the calcining in step 3.3, crucible is taken out from Muffle furnace, naturally cools to crucible Room temperature, crucible is interior to form pre-synthesis powder.
Detailed process is as follows for step 4:
Step 4.1, the pre-synthesis powder that step 3 obtains is poured into mortar and is ground, obtain pre-synthesis powder A；
Step 4.2, pre-synthesis powder A and abrading-ball that step 4.1 obtains are put into togerther in ball grinder and carry out ball-milling treatment, And dehydrated alcohol is added during ball-milling treatment as ball-milling medium, obtain prefabricated mixed powder B；
Step 4.3, the pre-synthesis powder material B obtained through step 4.2 is dried, obtains pre-synthesis dry mash；
It in step 4.3, is dried during the drying process using baking oven, and drying temperature controls are as follows: 80 DEG C~100 DEG C；
Step 4.4, it weighs PVA to be dissolved in the water, makes the PVA solution that mass percent concentration is 4%~7%；
Step 4.5, PVA solution step 4.4 made is added to the step 4.3 obtained through step 4.3, will be through step 4.2 obtained pre-synthesis powder material B drying, obtain carrying out granulation processing in pre-synthesis dry mash, obtain powder；Every gram of pre-synthesis is dry The PVA solution of 0.1ml~0.2ml to be added in powder；
Step 4.6, after step 4.5 completes granulation processing, the powder of forming is subjected to sieving processing using sieve；
Step 4.7, the powder obtained after step 4.6 sieving is pressed into idiosome under the pressure of 90Mpa~110Mpa.
Detailed process is as follows for step 5:
Step 5.1, under the conditions of 600 DEG C~700 DEG C, idiosome is obtained to step 4 and carries out dumping, is naturally cooled to again later Room temperature；
Step 5.2, will through step 5.1, treated that idiosome is put into Muffle furnace, under air atmosphere, with 2.5 DEG C/min Muffle furnace is warming up to 1250 DEG C~1350 DEG C by the rate of~3.5 DEG C/min, and calcining at constant temperature idiosome 1.5h~2.5h is to get to three The hafnium of Al 2 O and carbonic acid lithium doping lead titanates-lead nickle niobate piezoelectric ceramics.
Detailed process is as follows for dumping in step 5.1:
Under air atmosphere, Muffle furnace is warming up to 120 DEG C with 2.5 DEG C/min~3.5 DEG C/min rate, calcining at constant temperature Then idiosome 0.5h is continuously heating to 600 DEG C~700 DEG C with 2.5 DEG C/min~3.5 DEG C/min rate, calcining at constant temperature idiosome 2h is to get to the idiosome after dumping.
Detailed process is as follows for step 6:
Step 6.1, obtained idiosome will be handled through step 5.2 to throw using the sand paper of 600-1000 mesh in polishing machine Light；
Step 6.2, obtained idiosome will be handled through step 6.1 to be placed in beaker, dehydrated alcohol is added, it is clear in ultrasonic wave Wash ultrasound 20min in device；
Step 6.3, obtained idiosome will be handled through step 6.2 to carry out applying silver, put baking oven drying after being painted with into immediately, and Oven temperature control is 80-100 DEG C；
Step 6.4, obtained idiosome will be handled through step 6.3 to be put into Muffle furnace, under air atmosphere, with 2.5 DEG C/ Muffle furnace is warming up to 120 DEG C, calcining at constant temperature idiosome 10min by min~3.5 DEG C/min rate, later with 2.5 DEG C/min~ The rate of 3.5 DEG C/min is continuously heating to 320 DEG C, calcining at constant temperature idiosome 0.5h, then with 3.5 DEG C/min~4.5 DEG C/min Rate is continuously heating to 650 DEG C, and calcining at constant temperature idiosome 2h is to get to the potsherd after silver ink firing.
Detailed process is as follows for step 7:
Potsherd after the silver ink firing obtained in the step 6 is polarized under the conditions of room temperature~200 DEG C；Polarization time For 10~30min, polarized electric field is 2~3kV/cm.
Beneficial effects of the present invention are as follows:
(1) hafnium lead titanates-lead nickle niobate piezoelectric ceramics preparation method of lithium carbonate and aluminum oxide doping of the present invention, institute It uses material to be easy to get, preparation process is simple, and manufacturing cost is low, favorable repeatability, is conducive to produce in batches；
(2) hafnium lead titanates-lead nickle niobate piezoelectric ceramics preparation method of lithium carbonate and aluminum oxide doping of the present invention, is adopted With building Li+-Al3+The method of ion pair is distorted piezoelectric ceramics lattice structure, reduces its symmetry, thus significantly Improve the piezoelectric property of ceramics.By being formulated the adjustment improvement with technique, its piezoelectric constant, d are significantly improved33=680~ 810pC/N；
(3) the hafnium lead titanates-lead nickle niobate piezoelectric ceramics preparation side adulterated using lithium carbonate of the present invention and aluminum oxide The piezoelectric ceramics that method is prepared can be applied to novel big displacement driver, the underwater acoustic transducer of efficient transmission, medical supersonic The device that sensor etc. has higher requirements to piezoelectric property.
Specific embodiment
The present invention is described in detail With reference to embodiment.
A kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics of the present invention, specifically includes as follows Step:
Step 1, by NiCO3-2Ni(OH)2-4H2O and Nb2O5Powder mixing, successively passes through ball milling, drying, calcining and cooling Processing, obtains prefabricated presoma niobic acid nickel (NiNb2O6) powder；
Detailed process is as follows for step 1:
Step 1.1, by NiCO3-2Ni(OH)2-4H2O powder and Nb2O5Powder is weighed and is mixed according to molar ratio 1:3 It closes, forms mixed powder；NiCO3-2Ni(OH)2-4H2The purity of O powder is 99.9%；Nb2O5The purity of powder is 99.9%；
Step 1.2, mixed powder and abrading-ball that step 1.1 obtains are added to together in ball grinder and are added into ball grinder Enter dehydrated alcohol as ball-milling medium, carries out ball-milling treatment, obtain uniform mixed powder.
During ball-milling treatment, the dosage of ball-milling medium dehydrated alcohol are as follows: every gram to ball milling powder will be added 0.6ml The dehydrated alcohol of~1.2ml；Zirconia ball of the abrading-ball using diameter 3mm~5mm, and ball material mass ratio are as follows: (1.5~3): 1 (ball material mass ratio refers to the mass ratio to ball milling powder and zirconia ball)；Ball-milling Time is 10h~14h.
Step 1.3, it step 1.2 is obtained mixed powder is placed in baking oven to carry out drying and processing, obtain mixed powder material；It dries Dry temperature control are as follows: 80 DEG C~100 DEG C, drying time 2h.
Step 1.4, the resulting mixed powder material of step 1.3 is put into crucible, and mixed powder material is pressed in crucible It is real, lid is then covered on crucible, is made to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere And the mixed powder material under the conditions of 1050 DEG C~1150 DEG C temperature in calcining at constant temperature crucible, heating rate control 3~5 DEG C/ Min, calcination time control are as follows: 1.5h~2.5h；
Step 1.5, after the completion of step 1.4 calcining, crucible is taken out from Muffle furnace, crucible is made to naturally cool to room Temperature, crucible is interior to form presoma NiNb2O6Powder.
Step 2, according to 0.51Pb (Ti0.7Hf0.3)O3-0.49Pb(Ni1/3Nb1/3)O3Stoichiometric ratio weighs Pb3O4Powder Body, TiO2Powder, HfO2NiNb obtained in powder and step 12O6Powder forms basis material, then weighs Al2O3Powder and Li2CO3Powder, Al2O3Powder and Li2CO3The mole of powder is hafnium lead titanates-lead nickle niobate Pb (Ti, Hf) O3-Pb(Ni, Nb)O3The 0.1~3.0% of mole；
Wherein Pb3O4The purity of powder is 99.9%；TiO2The purity of powder is 99.9%；HfO2The purity of powder is 99.9%；Al2O3The purity of powder is 99.9%；Li2CO3The purity of powder is 99.9%.
Step 3, by Pb weighed in step 23O4Powder, TiO2Powder, HfO2Powder, NiNb2O6Powder and Al2O3Powder Body and Li2CO3Powder is added in ball grinder and carries out ball-milling treatment, obtains mixed powder；Then mixed powder is successively dried Dry, calcining and cooling treatment, obtain pre-synthesis powder；
Detailed process is as follows for step 3:
Step 3.1, weighed Al in the basis material and step 2 step 2 obtained2O3Powder and Li2CO3Powder mixing It is formed to ball milling powder, will be added in ball grinder together to ball milling powder and abrading-ball, and dehydrated alcohol is added into ball grinder As ball-milling medium, ball-milling treatment is carried out, mixed powder is obtained；
In step 3.1, during ball-milling treatment, the dosage of ball-milling medium dehydrated alcohol are as follows: every gram to ball milling powder The dehydrated alcohol of 0.6ml~1.2ml is added；Zirconia ball of the abrading-ball using diameter 3mm~5mm, and ball material mass ratio Are as follows: (1.5~3): 1 (ball material mass ratio refers to the mass ratio to ball milling powder and zirconia ball)；Ball-milling Time be 10h~ 14h。
Step 3.2, mixed powder step 3.1 obtained, which is placed in baking oven, carries out drying and processing, obtains mixed powder material； The temperature of drying controls are as follows: 80 DEG C~100 DEG C, dries 2h.
The resulting mixed powder material of step 3.2 is put into crucible, and mixed powder material is pressed in crucible by step 3.3 It is real, lid is then covered on crucible, is made to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere And the mixed powder material under the conditions of 800~950 DEG C of temperature in calcining at constant temperature crucible, heating rate are controlled in 3~5 DEG C/min, are forged Burn time control are as follows: 1.5h~2.5h；
Step 3.4, after the completion of the calcining in step 3.3, crucible is taken out from Muffle furnace, naturally cools to crucible Room temperature, crucible is interior to form pre-synthesis powder.
Step 4, the pre-synthesis powder obtained through step 3 is successively ground, ball milling and drying and processing, is obtained prefabricated mixed Dry mash is closed, PVA (polyvinyl alcohol) solution for adding preparation is granulated, and then the powder made is sieved, rejects big powder Grain；The powder obtained after filtering is finally pressed into idiosome；
Step 4 is specifically implemented according to the following steps:
Step 4.1, the pre-synthesis powder that step 3 obtains is poured into mortar and is ground, (be ground to pre-synthesis powder Grain is evenly dispersed) obtain pre-synthesis powder A；
Step 4.2, pre-synthesis powder A and abrading-ball that step 4.1 obtains are put into togerther in ball grinder and carry out ball-milling treatment, And dehydrated alcohol is added during ball-milling treatment as ball-milling medium, obtain prefabricated mixed powder B；
Zirconia ball of the abrading-ball using diameter 3mm~5mm, and ball material mass ratio in step 4.2 are as follows: (1.5~3): 1 (ball material mass ratio refers to the mass ratio to ball milling powder and zirconia ball)；The dosage of ball-milling medium dehydrated alcohol are as follows: every gram Prefabricated mixed powder A the dehydrated alcohol of 0.6ml~1.2ml, Ball-milling Time control are as follows: 10h~14h is added；
Step 4.3, the pre-synthesis powder material B obtained through step 4.2 is dried, obtains pre-synthesis dry mash；
It in step 4.3, is dried during the drying process using baking oven, and drying temperature controls are as follows: 80 DEG C~100 DEG C, drying 2h。
Step 4.4, it weighs PVA to be dissolved in the water, makes the PVA solution that mass percent concentration is 4%~7%；
Step 4.5, PVA solution step 4.4 made is added to the step 4.3 obtained through step 4.3, will be through step 4.2 obtained pre-synthesis powder material B drying, obtain carrying out granulation processing in pre-synthesis dry mash, obtain powder；Every gram of pre-synthesis is dry The PVA solution of 0.1ml~0.2ml to be added in powder；
Step 4.6, after step 4.5 completes granulation processing, the powder of forming is subjected to sieving processing using sieve, is rejected The wherein biggish powder of partial size；
In step 4.6, the specification of sieve are as follows: average pore size is 60 mesh~100 mesh；
Step 4.7, the powder obtained after step 4.6 sieving is pressed into idiosome under the pressure of 90Mpa~110Mpa；
The idiosome that step 4.7 obtains is that cross-sectional diameter is 10mm, the cylindrical type idiosome of height 0.5mm~1.5mm.
Step 5, idiosome is obtained to step 4 and successively carries out dumping, natural cooling processing and calcination processing, obtain three oxidations two The hafnium of aluminium and carbonic acid lithium doping lead titanates-lead nickle niobate piezoelectric ceramics；
Step 5 is specifically implemented according to the following steps:
Step 5.1, under the conditions of 600 DEG C~700 DEG C, idiosome is obtained to step 4 and carries out dumping, is naturally cooled to again later Room temperature；
The specific process of dumping: under air atmosphere, Muffle furnace is heated up with 2.5 DEG C/min~3.5 DEG C/min rate To 120 DEG C, then calcining at constant temperature idiosome 0.5h is continuously heating to 600 DEG C~700 with 2.5 DEG C/min~3.5 DEG C/min rate DEG C, calcining at constant temperature idiosome 2h is to get to the idiosome after dumping；
Step 5.2, will through step 5.1, treated that idiosome is put into Muffle furnace, under air atmosphere, with 2.5 DEG C/min Muffle furnace is warming up to 1250 DEG C~1350 DEG C by the rate of~3.5 DEG C/min, and calcining at constant temperature idiosome 1.5h~2.5h is to get to three The hafnium of Al 2 O and carbonic acid lithium doping lead titanates-lead nickle niobate piezoelectric ceramics.
The potsherd that step 5 calcining obtains is polished, is handled by silver by step 6；Detailed process is as follows for step 6:
Step 6.1, obtained idiosome will be handled through step 5.2 to throw using the sand paper of 600-1000 mesh in polishing machine Light；
Step 6.2, obtained idiosome will be handled through step 6.1 to be placed in beaker, dehydrated alcohol is added, it is clear in ultrasonic wave Wash ultrasound 20min in device；
Step 6.3, obtained idiosome will be handled through step 6.2 to carry out applying silver, put baking oven drying after being painted with into immediately, and Oven temperature control is 80-100 DEG C；Dry 10min.
Step 6.4, obtained idiosome will be handled through step 6.3 to be put into Muffle furnace, under air atmosphere, with 2.5 DEG C/ Muffle furnace is warming up to 120 DEG C, calcining at constant temperature idiosome 10min by min~3.5 DEG C/min rate, later with 2.5 DEG C/min~ The rate of 3.5 DEG C/min is continuously heating to 320 DEG C, calcining at constant temperature idiosome 0.5h, then with 3.5 DEG C/min~4.5 DEG C/min Rate is continuously heating to 650 DEG C, and calcining at constant temperature idiosome 2h is to get to the potsherd after silver ink firing.
Potsherd after the silver ink firing obtained in the step 6 is polarised by step 7；
Step 7 is specifically implemented according to the following steps:
Potsherd after the silver ink firing obtained in the step 6 is polarized under the conditions of room temperature~200 DEG C；Polarization time For 10~30min, polarized electric field is 2~3kV/cm.
The piezoelectric ceramic piece that will be handled through step 7 stands test its piezoelectric property afterwards for 24 hours at room temperature.The present invention is implemented Example is using commercially available chemical pure raw material, Pb3O4The purity of powder is 99.9%；TiO2The purity of powder is 99.9%；HfO2Powder Purity be 99.9%；Al2O3The purity of powder is 99.9%；Li2CO3The purity of powder is 99.9%；NiCO3-2Ni(OH)2- 4H2The purity of O powder is 99.9%；Nb2O5The purity of powder is 99.9%.
Embodiment 1
Step 1, by NiCO3-2Ni(OH)2-4H2O and Nb2O5Powder mixing, successively passes through ball milling, drying, calcining and cooling Processing, obtains prefabricated presoma niobic acid nickel (NiNb2O6) powder；
Step 1.1, by NiCO3-2Ni(OH)2-4H2O powder and Nb2O5Powder is weighed and is mixed according to molar ratio 1:3 It closes, forms mixed powder；
Step 1.2, by through step 1.1 mixed powder and abrading-ball be added in ball grinder together and be added into ball grinder Dehydrated alcohol carries out ball-milling treatment, obtains uniform mixed powder as ball-milling medium；
During ball-milling treatment, the dosage of ball-milling medium dehydrated alcohol are as follows: every gram to ball milling powder will be added 0.8ml Dehydrated alcohol；Zirconia ball of the abrading-ball using diameter 4mm, and ball material mass ratio are as follows: 1.5:1；Ball-milling Time is 10h.
Step 1.3, the uniform mixed powder through step 1.2 is placed in baking oven and carries out drying and processing, obtain mixed powder Material；The temperature of drying controls are as follows: 90 DEG C, dries 2h.
Step 1.4, the mixed powder material through step 1.3 is put into crucible, and by mixed powder material in crucible and compacting, Lid is covered in crucible again, makes to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere and 1050 DEG C Mixed powder material under the conditions of temperature in calcining at constant temperature crucible, heating rate control is in 4 DEG C/min, calcination time control are as follows: 1.5h；
Step 1.5, after the completion of the calcining in step 1.4, crucible is taken out from Muffle furnace, naturally cools to crucible Room temperature, crucible is interior to form presoma NiNb2O6Powder.
Step 2, according to 0.51Pb (Ti0.7Hf0.3)O3-0.49Pb(Ni1/3Nb1/3)O3Stoichiometric ratio weighs Pb3O4Powder Body, TiO2Powder, HfO2NiNb obtained in powder and step 12O6Powder, then weigh Al2O3Powder and Li2CO3Powder, Al2O3Powder and Li2CO3The mole of powder is respectively hafnium lead titanates-lead nickle niobate Pb (TiHf) O3-Pb(NiNb)O3Mole 0.1%；
Step 3, by Pb weighed in step 23O4Powder, TiO2Powder, HfO2Powder, NiNb2O6Powder and Al2O3Powder Body and Li2CO3Powder is added in ball grinder and carries out ball-milling treatment, obtains mixed powder；Then mixed powder is successively dried Dry, calcining and cooling treatment, obtain pre-synthesis powder；
Step 3.1, weighed Al in the basis material and step 2 step 2 obtained2O3Powder and Li2CO3Powder mixing It is formed to ball milling powder, will be added in ball grinder together to ball milling powder and abrading-ball, and dehydrated alcohol is added into ball grinder As ball-milling medium, ball-milling treatment is carried out, mixed powder is obtained；
In step 3.1, during ball-milling treatment, the dosage of ball-milling medium dehydrated alcohol are as follows: every gram to ball milling powder The dehydrated alcohol of 1.0ml is added；Zirconia ball of the abrading-ball using diameter 4mm, and ball material mass ratio are as follows: 1.5:1；Ball milling Time is 14h；
Step 3.2, the uniform mixed powder through step 3.1 is placed in baking oven and carries out drying and processing, obtain mixed powder Material；The temperature of drying controls are as follows: 90 DEG C；
Step 3.3, the mixed powder material through step 3.2 is put into crucible, and by mixed powder material in crucible and compacting, Lid is covered in crucible again, makes to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere and 800 DEG C Mixed powder material under the conditions of temperature in calcining at constant temperature crucible, heating rate control is in 4 DEG C/min, calcination time control are as follows: 1.5h；
Step 3.4, after the completion of the calcining in step 3.3, crucible is taken out from Muffle furnace, naturally cools to crucible Room temperature, crucible is interior to form pre-synthesis powder.
Step 4 is successively ground the pre-synthesis powder obtained through step 3, ball milling and drying and processing, is obtained prefabricated mixed Dry mash is closed, the PVA solution for adding preparation is granulated, and the powder made is sieved later, rejects big powder；Finally incited somebody to action The powder obtained after filter is pressed into idiosome, is specifically implemented according to the following steps:
The pre-synthesis powder obtained through step 3 is poured into mortar and is ground by step 4.1, obtains pre-synthesis powder A；
The pre-synthesis powder A and abrading-ball that obtain through step 4.1 are put into togerther in ball grinder at progress ball milling by step 4.2 Reason, and dehydrated alcohol is added as ball-milling medium during ball-milling treatment, obtain prefabricated mixed powder B；
Zirconia ball of the abrading-ball using diameter 4mm, and ball material mass ratio in step 4.2 are as follows: 1.5:1；Ball-milling medium The dosage of dehydrated alcohol are as follows: the dehydrated alcohol of 0.8ml will be added in every gram of prefabricated mixed powder A, and Ball-milling Time control is 10h；
Step 4.3 dries the pre-synthesis powder material B obtained through step 4.2, obtains pre-synthesis dry mash.
It in step 4.3, is dried during the drying process using baking oven, and drying temperature controls are as follows: 90 DEG C.
Step 4.4 weighs PVA and is dissolved in the water, and makes the PVA solution that mass percent concentration is 4%；
The PVA solution made through step 4.4 is added in the pre-synthesis dry mash obtained through step 4.3 by step 4.5 Granulation processing is carried out, powder is obtained；The PVA solution of 0.1ml to be added in every gram of prefabricated mixed powder material；
Step 4.6, through step 4.5 complete granulation processing after, the powder of forming is sifted out, reject wherein partial size it is biggish Powder；
In step 4.6, the specification of sieve are as follows: average pore size is 60 mesh；
The powder obtained after step 4.6 sieving is pressed into idiosome under the pressure of 110Mpa by step 4.7.
The idiosome that step 4.7 obtains is that cross-sectional diameter is 10mm, the cylindrical type idiosome of height 0.5mm.
Step 5, to through step 4 obtain idiosome successively carry out dumping, natural cooling processing and calcination processing, obtain three oxidations The hafnium of two aluminium and carbonic acid lithium doping lead titanates-lead nickle niobate piezoelectric ceramics, is specifically implemented according to the following steps:
Step 5.1, under the conditions of 600 DEG C, dumping is carried out to idiosome is obtained through step 4, later cooled to room temperature again；
The specific process of dumping: under air atmosphere, Muffle furnace is warming up to 120 DEG C with the rate of 2.5 DEG C/min, constant temperature Idiosome 0.5h is calcined, is continuously heating to 600 DEG C later with the rate of 2.5 DEG C/min, calcining at constant temperature idiosome 2h is to get to after dumping Idiosome；
Step 5.2, will through step 5.1, treated that idiosome is put into Muffle furnace, under air atmosphere, with 2.5 DEG C/min Rate Muffle furnace is warming up to 1250 DEG C, calcining at constant temperature idiosome 1.5h is to get the hafnium for arriving aluminum oxide and carbonic acid lithium doping Lead titanates-lead nickle niobate piezoelectric ceramics.
Step 6, the potsherd that step 5 calcining obtains polished, handled by silver, is specifically implemented according to the following steps:
Step 6.1, obtained idiosome will be handled through step 5.2 to polish using the sand paper of 600 mesh in polishing machine；
Step 6.2, obtained idiosome will be handled through step 6.1 to be placed in beaker, dehydrated alcohol is added, it is clear in ultrasonic wave Wash ultrasound 20min in device；
Step 6.3 carries out the idiosome obtained through step 6.2 processing to apply silver, puts baking oven drying after being painted with into immediately, and Oven temperature control is 90 DEG C；
Step 6.4, obtained idiosome will be handled through step 6.3 to be put into Muffle furnace, under air atmosphere, with 2.5 DEG C/ Muffle furnace is warming up to 120 DEG C by the rate of min, and calcining at constant temperature idiosome 10min continues to heat up with the rate of 2.5 DEG C/min later To 320 DEG C, calcining at constant temperature idiosome 0.5h, 650 DEG C, calcining at constant temperature idiosome 2h then are continuously heating to the rate of 3.5 DEG C/min, Obtain sample after silver ink firing.
Step 7, the sample after the silver ink firing obtained in the step 6 is polarized under the conditions of 180 DEG C；Polarization time is 10min, polarized electric field 3kV/cm.
Embodiment 2
Step 1, by NiCO3-2Ni(OH)2-4H2O and Nb2O5Powder mixing, successively passes through ball milling, drying, calcining and cooling Processing, obtains prefabricated presoma niobic acid nickel (NiNb2O6) powder；
Step 1.1, by NiCO3-2Ni(OH)2-4H2O powder and Nb2O5Powder is weighed and is mixed according to molar ratio 1:3 It closes, forms mixed powder；
Step 1.2, by through step 1.1 mixed powder and abrading-ball be added in ball grinder together and be added into ball grinder Dehydrated alcohol carries out ball-milling treatment, obtains uniform mixed powder as ball-milling medium；
During ball-milling treatment, the dosage of ball-milling medium dehydrated alcohol are as follows: every gram to ball milling powder will be added 1.2ml Dehydrated alcohol；Zirconia ball of the abrading-ball using diameter 5mm, and ball material mass ratio are as follows: 3:1；Ball-milling Time is 14h.
Step 1.3, the uniform mixed powder through step 1.2 is placed in baking oven and carries out drying and processing, obtain mixed powder Material；The temperature of drying controls are as follows: 100 DEG C, dries 2h.
Step 1.4, the mixed powder material through step 1.3 is put into crucible, and by mixed powder material in crucible and compacting, Lid is covered in crucible again, makes to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere and 1150 DEG C Mixed powder material under the conditions of temperature in calcining at constant temperature crucible, heating rate control is in 5 DEG C/min, calcination time control are as follows: 2.5h；
Step 1.5, after the completion of the calcining in step 1.4, crucible is taken out from Muffle furnace, naturally cools to crucible Room temperature, crucible is interior to form presoma NiNb2O6Powder.
Step 2, according to 0.51Pb (Ti0.7Hf0.3)O3-0.49Pb(Ni1/3Nb1/3)O3Stoichiometric ratio weighs Pb3O4Powder Body, TiO2Powder, HfO2NiNb obtained in powder and step 12O6Powder, then weigh Al2O3Powder and Li2CO3Powder, Al2O3Powder and Li2CO3The mole of powder is respectively hafnium lead titanates-lead nickle niobate Pb (TiHf) O3-Pb(NiNb)O3Mole 3.0%；
Step 3, by Pb weighed in step 23O4Powder, TiO2Powder, HfO2Powder, NiNb2O6Powder and Al2O3Powder Body and Li2CO3Powder is added in ball grinder and carries out ball-milling treatment, obtains mixed powder；Then mixed powder is successively dried Dry, calcining and cooling treatment, obtain pre-synthesis powder；
Step 3.1, weighed Al in the basis material and step 2 step 2 obtained2O3Powder and Li2CO3Powder mixing It is formed to ball milling powder, will be added in ball grinder together to ball milling powder and abrading-ball, and dehydrated alcohol is added into ball grinder As ball-milling medium, ball-milling treatment is carried out, mixed powder is obtained；
In step 3.1, during ball-milling treatment, the dosage of ball-milling medium dehydrated alcohol are as follows: every gram to ball milling powder The dehydrated alcohol of 1.2ml is added；Zirconia ball of the abrading-ball using diameter 5mm, and ball material mass ratio are as follows: 3:1；When ball milling Between be 10h；
Step 3.2, the uniform mixed powder through step 3.1 is placed in baking oven and carries out drying and processing, obtain mixed powder Material；The temperature of drying controls are as follows: 100 DEG C；
Step 3.3, the mixed powder material through step 3.2 is put into crucible, and by mixed powder material in crucible and compacting, Lid is covered in crucible again, makes to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere and 950 DEG C Mixed powder material under the conditions of temperature in calcining at constant temperature crucible, heating rate control is in 5 DEG C/min, calcination time control are as follows: 2.5h；
Step 3.4, after the completion of the calcining in step 3.3, crucible is taken out from Muffle furnace, naturally cools to crucible Room temperature, crucible is interior to form pre-synthesis powder.
Step 4, the pre-synthesis powder obtained through step 3 is successively ground, ball milling and drying and processing, is obtained prefabricated mixed Dry mash is closed, the PVA solution for adding preparation is granulated, and the powder made is sieved later, rejects big powder；Finally incited somebody to action The powder obtained after filter is pressed into idiosome, is specifically implemented according to the following steps:
Step 4.1, the pre-synthesis powder obtained through step 3 is poured into mortar and is ground, obtain pre-synthesis powder A；
The pre-synthesis powder A and abrading-ball that obtain through step 4.1 are put into togerther in ball grinder at progress ball milling by step 4.2 Reason, and dehydrated alcohol is added as ball-milling medium during ball-milling treatment, obtain prefabricated mixed powder B；
Zirconia ball of the abrading-ball using diameter 5mm, and ball material mass ratio in step 4.2 are as follows: 3:1；Ball-milling medium without The dosage of water-ethanol are as follows: the dehydrated alcohol of 1.2ml will be added in every gram of prefabricated mixed powder A, and Ball-milling Time control is 14h；
Step 4.3 dries the pre-synthesis powder material B obtained through step 4.2, obtains pre-synthesis dry mash.
It in step 4.3, is dried during the drying process using baking oven, and drying temperature controls are as follows: 100 DEG C, dry 2h.
Step 4.4 weighs PVA and is dissolved in the water, and makes the PVA solution that mass percent concentration is 5%；
The PVA solution made through step 4.4 is added in the pre-synthesis dry mash obtained through step 4.3 by step 4.5 Granulation processing is carried out, powder is obtained；The PVA solution of 0.15ml to be added in every gram of prefabricated mixed powder material；
Step 4.6, through step 4.5 complete granulation processing after, the powder of forming is sifted out, reject wherein partial size it is biggish Powder；
In step 4.6, the specification of sieve are as follows: average pore size is 80 mesh；
Step 4.7, the powder obtained after step 4.6 sieving is pressed into idiosome under the pressure of 90Mpa.
The idiosome that step 4.7 obtains is that cross-sectional diameter is 10mm, the cylindrical type idiosome of height 1.0mm.
Step 5, to through step 4 obtain idiosome successively carry out dumping, natural cooling processing and calcination processing, obtain three oxidations The hafnium of two aluminium and carbonic acid lithium doping lead titanates-lead nickle niobate piezoelectric ceramics, is specifically implemented according to the following steps:
Step 5.1, under the conditions of 700 DEG C, dumping is carried out to idiosome is obtained through step 4, later cooled to room temperature again；
The specific process of dumping: under air atmosphere, Muffle furnace is warming up to 120 DEG C with the rate of 3.5 DEG C/min, constant temperature Idiosome 0.5h is calcined, is continuously heating to 700 DEG C later with the rate of 3.5 DEG C/min, calcining at constant temperature idiosome 2h is to get to after dumping Idiosome；
Step 5.2, will through step 5.1, treated that idiosome is put into Muffle furnace, under air atmosphere, with 3.5 DEG C/min Rate Muffle furnace is warming up to 1350 DEG C, calcining at constant temperature idiosome 2.5h is to get the hafnium for arriving aluminum oxide and carbonic acid lithium doping Lead titanates-lead nickle niobate piezoelectric ceramics.
Step 6, the potsherd that step 5 calcining obtains polished, handled by silver, is specifically implemented according to the following steps:
Step 6.1, obtained idiosome will be handled through step 5.2 to polish using the sand paper of 800 mesh in polishing machine；
Step 6.2, obtained idiosome will be handled through step 6.1 to be placed in beaker, dehydrated alcohol is added, it is clear in ultrasonic wave Wash ultrasound 20min in device；
Step 6.3 carries out the idiosome obtained through step 6.2 processing to apply silver, puts baking oven drying after being painted with into immediately, and Oven temperature control is 100 DEG C；
Step 6.4 will handle obtained idiosome through step 6.3 and be put into Muffle furnace, under air atmosphere, with 3.5 DEG C/ Muffle furnace is warming up to 120 DEG C by the rate of min, and calcining at constant temperature idiosome 10min continues to heat up with the rate of 3.5 DEG C/min later To 320 DEG C, calcining at constant temperature idiosome 0.5h, 650 DEG C, calcining at constant temperature idiosome 2h then are continuously heating to the rate of 4.5 DEG C/min, Obtain sample after silver ink firing.
Step 7, the sample after the silver ink firing obtained in the step 6 is polarized under the conditions of 200 DEG C；Polarization time is 30min, polarized electric field 2.5kV/cm.
Embodiment 3
Step 1, preparation is by NiCO3-2Ni(OH)2-4H2O and Nb2O51:3 is mixed powder in molar ratio, by ball milling, is dried Dry, calcining and cooling treatment, obtained prefabricated presoma niobic acid nickel (NiNb2O6) powder, it is specifically implemented according to the following steps:
Step 1.1, by NiCO3-2Ni(OH)2-4H2O powder and Nb2O5Powder is weighed and is mixed according to molar ratio 1:3 It closes, forms mixed powder.
Step 1.2, by through step 1.1 mixed powder and abrading-ball be added in ball grinder together and be added into ball grinder Dehydrated alcohol carries out ball-milling treatment, obtains uniform mixed powder as ball-milling medium.
During ball-milling treatment, the dosage of ball-milling medium dehydrated alcohol are as follows: every gram to ball milling powder will be added 0.6ml Dehydrated alcohol；Abrading-ball using diameter 3mm zirconia ball, and ball material mass ratio be 2:1；Ball-milling Time is 12h.
Step 1.3, the uniform mixed powder through step 1.2 is placed in baking oven and carries out drying and processing, obtain mixed powder Material；The temperature of drying controls are as follows: 80 DEG C；Dry 2h.
Step 1.4, the mixed powder material through step 1.3 is put into crucible, and by mixed powder material in crucible and compacting, Lid is covered in crucible again, makes to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere and 1100 DEG C Mixed powder material under the conditions of temperature in calcining at constant temperature crucible, heating rate control is in 3 DEG C/min, calcination time control are as follows: 2h；
Step 1.5, after the completion of the calcining in step 1.4, crucible is taken out from Muffle furnace, naturally cools to crucible Room temperature, crucible is interior to form presoma NiNb2O6Powder.
Step 2, according to 0.51Pb (Ti0.7Hf0.3)O3-0.49Pb(Ni1/3Nb1/3)O3Stoichiometric ratio weighs Pb3O4Powder Body, TiO2Powder, HfO2NiNb obtained in powder and step 12O6Powder, then weigh Al2O3Powder and Li2CO3Powder, Al2O3Powder and Li2CO3The mole of powder is respectively hafnium lead titanates-lead nickle niobate Pb (TiHf) O3-Pb(NiNb)O3Mole 0.2%；
Step 3, by Pb weighed in step 23O4Powder, TiO2Powder, HfO2Powder, NiNb2O6Powder and Al2O3Powder Body and Li2CO3Powder is added in ball grinder and carries out ball-milling treatment, obtains mixed powder；Then mixed powder is successively dried Dry, calcining and cooling treatment, obtain pre-synthesis powder, are specifically implemented according to the following steps:
Step 3.1, by weighed Al in the basis material obtained through step 2 and step 22O3Powder and Li2CO3Powder is mixed It closes and is formed to ball milling powder, will be added in ball grinder together to ball milling powder and abrading-ball, and anhydrous second is added into ball grinder Alcohol carries out ball-milling treatment, obtains mixed powder as ball-milling medium.
During ball-milling treatment, the dosage of ball-milling medium dehydrated alcohol are as follows: every gram to ball milling powder will be added 0.6ml Dehydrated alcohol；Zirconia ball of the abrading-ball using diameter 3mm, and ball material mass ratio are as follows: 2:1；Ball-milling Time is 12h.
Step 3.2, the uniform mixed powder through step 3.1 is placed in baking oven and carries out drying and processing, obtain mixed powder Material；The temperature of drying controls are as follows: 80 DEG C；
Step 3.3, the mixed powder material through step 3.2 is put into crucible, and by mixed powder material in crucible and compacting, Lid is covered in crucible again, makes to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere and 850 DEG C Mixed powder material under the conditions of temperature in calcining at constant temperature crucible, heating rate control is in 3 DEG C/min, calcination time control are as follows: 2h；
Step 3.4, after the completion of the calcining in step 3.3, crucible is taken out from Muffle furnace, naturally cools to crucible Room temperature, crucible is interior to form pre-synthesis powder.
Step 4, the pre-synthesis powder obtained through step 3 is successively ground, ball milling and drying and processing, is obtained prefabricated mixed Dry mash is closed, the PVA solution for adding preparation is granulated, and the powder made is sieved later, rejects big powder；Finally incited somebody to action The powder obtained after filter is pressed into idiosome, is specifically implemented according to the following steps:
Step 4.1, the pre-synthesis powder obtained through step 3 is poured into mortar and is ground, obtain pre-synthesis powder A；
Step 4.2, the pre-synthesis powder A and abrading-ball that obtain through step 4.1 are put into togerther in ball grinder and are carried out at ball milling Reason, and dehydrated alcohol is added as ball-milling medium during ball-milling treatment, obtain prefabricated mixed powder B；
Zirconia ball of the abrading-ball using diameter 3mm, and ball material mass ratio in step 4.2 are as follows: 2:1；Ball-milling medium without The dosage of water-ethanol are as follows: the dehydrated alcohol of 0.6ml, Ball-milling Time control are as follows: 12h will be added in every gram of prefabricated mixed powder A；
Step 4.3, the pre-synthesis powder material B obtained through step 4.2 is dried, obtains pre-synthesis dry mash.
It in step 4.3, is dried during the drying process using baking oven, and drying temperature controls are as follows: 80 DEG C, dry 2h；
Step 4.4, it weighs PVA to be dissolved in the water, makes the PVA solution that mass percent concentration is 7%；
Step 4.5, the PVA solution made through step 4.4 is added in the pre-synthesis dry mash obtained through step 4.3 Granulation processing is carried out, powder is obtained；The PVA solution of 0.2ml to be added in every gram of prefabricated mixed powder material；
Step 4.6, after step 4.5 completes granulation processing, the powder of forming is sifted out, it is biggish to reject wherein partial size Powder；
In step 4.6, the specification of sieve are as follows: average pore size is 100 mesh；
Step 4.7, the powder obtained after step 4.6 sieving is pressed into idiosome under the pressure of 100Mpa.
The idiosome that step 4.7 obtains is that cross-sectional diameter is 10mm, the cylindrical type idiosome of height 1.5mm.
Step 5, to through step 4 obtain idiosome successively carry out dumping, natural cooling processing and calcination processing, obtain three oxidations The hafnium of two aluminium and carbonic acid lithium doping lead titanates-lead nickle niobate piezoelectric ceramics, is specifically implemented according to the following steps:
Step 5.1, under the conditions of 650 DEG C, dumping is carried out to idiosome is obtained through step 4, later cooled to room temperature again；
The specific process of dumping: under air atmosphere, Muffle furnace is warming up to 120 DEG C with the rate of 3 DEG C/min, constant temperature is forged Idiosome 0.5h is burnt, is continuously heating to 650 DEG C later with the rate of 3 DEG C/min, calcining at constant temperature idiosome 2h is to get to the embryo after dumping Body；
Step 5.2, will through step 5.1, treated that idiosome is put into Muffle furnace, under air atmosphere, with 3 DEG C/min's Muffle furnace is warming up to 1300 DEG C by rate, and calcining at constant temperature idiosome 2h is to get the hafnium metatitanic acid for arriving aluminum oxide and carbonic acid lithium doping Lead-lead nickle niobate piezoelectric ceramics.
Step 6, the potsherd that step 5 calcining obtains polished, handled by silver, is specifically implemented according to the following steps:
Step 6.1, obtained idiosome will be handled through step 5.2 to polish using the sand paper of 1000 mesh in polishing machine；
Step 6.2, obtained idiosome will be handled through step 6.1 to be placed in beaker, dehydrated alcohol is added, it is clear in ultrasonic wave Wash ultrasound 20min in device；
Step 6.3, obtained idiosome will be handled through step 6.2 to carry out applying silver, put baking oven drying after being painted with into immediately, and Oven temperature control is 80 DEG C；
Step 6.4, obtained idiosome will be handled through step 6.3 to be put into Muffle furnace, under air atmosphere, with 3 DEG C/min Rate Muffle furnace is warming up to 120 DEG C, calcining at constant temperature idiosome 10min is continuously heating to 320 later with the rate of 3 DEG C/min DEG C, calcining at constant temperature idiosome 0.5h is then continuously heating to 650 DEG C with the rate of 4 DEG C/min, and calcining at constant temperature idiosome 2h is to get arriving Sample after silver ink firing.
Step 7, the sample after the silver ink firing obtained in the step 6 is polarized at room temperature；Polarization time is 20min, polarized electric field 2kV/cm.
Embodiment 4
Process as described in Example 3, wherein Al in step 22O3Powder and Li2CO3The mole of powder is respectively hafnium metatitanic acid Lead-lead nickle niobate Pb (TiHf) O3-Pb(NiNb)O3The 0.4% of mole.
Embodiment 5
Process as described in Example 3, wherein Al in step 22O3Powder and Li2CO3The mole of powder is respectively hafnium metatitanic acid Lead-lead nickle niobate Pb (TiHf) O3-Pb(NiNb)O3The 0.5% of mole.
Embodiment 6
Process as described in Example 3, wherein Al in step 22O3Powder and Li2CO3The mole of powder is respectively hafnium metatitanic acid Lead-lead nickle niobate Pb (TiHf) O3-Pb(NiNb)O3The 1.0% of mole.
Embodiment 7
Process as described in Example 3, wherein Al in step 22O3Powder and Li2CO3The mole of powder is respectively hafnium metatitanic acid Lead-lead nickle niobate Pb (TiHf) O3-Pb(NiNb)O3The 1.5% of mole.
Embodiment 8
Process as described in Example 3, wherein Al in step 22O3Powder and Li2CO3The mole of powder is respectively hafnium metatitanic acid Lead-lead nickle niobate Pb (TiHf) O3-Pb(NiNb)O3The 2.0% of mole.
By the resulting piezoelectric ceramic piece of embodiment 3~8, stands at room temperature test its piezoelectric property afterwards for 24 hours respectively, specifically See Table 1 for details for test result
Table 1
In a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics of the present invention, with .49Pb (Ni1/3Nb2/3)O3-0.51Pb(Ti0.7Hf0.3)O3It, will be high-purity using traditional solid reaction process based on system piezoelectric ceramics Pb3O4Powder, TiO2Powder, HfO2Powder, NiO powder, Nb2O5Powder is as basis material, with high-purity 99.99%Al2O3Powder And Li2CO3Powder can prepare the hafnium metatitanic acid of high piezoelectric constant by simple, technique that is being easily achieved as dopant material Lead-lead nickle niobate piezoelectric ceramics.
As shown in table 1, using a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics of the present invention Its piezoelectric property of the piezoelectric ceramics prepared is excellent and repeated strong, and piezoelectric constant is 680~810pC/N.
Utilize a kind of pressure that the preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics is prepared of the present invention Electroceramics can be used for novel big displacement driver, the underwater acoustic transducer of efficient transmission, medical ultrasonic sensor etc. to piezoelectricity The device that can be had higher requirements.
A kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics of the present invention, by Pb (Hf, Ti)O3-Pb(Nb,Ni)O3In ceramic systems, a small amount of donor and acceptor's ion (Li is adulterated+And Al3+), replace Pb (Hf, Ti) O3-Pb(Nb,Ni)O3The position A ion in crystal structure, constructs Li in crystal+-Al3+Defect ion pair, to increase substantially The piezoelectric property of ceramics obtains the high performance piezoelectric ceramic material that piezoelectric modulus is more than or equal to 800pC/N.

Claims (8)

1. a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics, it is characterised in that: specifically include as Lower step:
Step 1, by NiCO3-2Ni(OH)2-4H2O and Nb2O5Powder mixing is successively passed through at ball milling, drying, calcining and cooling Reason, obtains prefabricated presoma niobic acid nickel powder material；
Step 2, according to 0.51Pb (Ti0.7Hf0.3)O3-0.49Pb(Ni1/3Nb1/3)O3Stoichiometric ratio weighs Pb3O4Powder, TiO2 Powder, HfO2NiNb obtained in powder and step 12O6Powder forms basis material, then weighs Al2O3Powder and Li2CO3 Powder, Al2O3Powder and Li2CO3The mole of powder is hafnium lead titanates-lead nickle niobate Pb (Ti, Hf) O3-Pb(Ni,Nb)O3It rubs The 0.1~3.0% of that amount；
Step 3, by Pb weighed in step 23O4Powder, TiO2Powder, HfO2Powder, NiNb2O6Powder and Al2O3Powder and Li2CO3Powder is added in ball grinder and carries out ball-milling treatment, obtains mixed powder；Then mixed powder successively dried, forged Burning and cooling treatment, obtain pre-synthesis powder；
Step 4, the pre-synthesis powder obtained through step 3 is successively ground, ball milling and drying and processing, it is dry obtains prefabricated mixing Powder, the PVA solution for adding preparation are granulated, and then the powder made is sieved；The powder that will finally be obtained after filtering It is pressed into idiosome；
Step 5, to step 4 obtain idiosome successively carry out dumping, natural cooling processing and calcination processing, obtain aluminum oxide and Hafnium lead titanates-lead nickle niobate piezoelectric ceramics of carbonic acid lithium doping；
The potsherd that step 5 calcining obtains is polished, is handled by silver by step 6；
Potsherd after the silver ink firing obtained in the step 6 is polarised by step 7.
2. a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics according to claim 1, Be characterized in that: detailed process is as follows for the step 1:
Step 1.1, by NiCO3-2Ni(OH)2-4H2O powder and Nb2O5Powder is weighed and is mixed according to molar ratio 1:3, shape At mixed powder；
Step 1.2, mixed powder and abrading-ball that step 1.1 obtains are added to together in ball grinder and nothing is added into ball grinder Water-ethanol carries out ball-milling treatment, obtains uniform mixed powder as ball-milling medium；
Step 1.3, it step 1.2 is obtained mixed powder is placed in baking oven to carry out drying and processing, obtain mixed powder material, drying Temperature control are as follows: 80 DEG C~100 DEG C；
Step 1.4, the resulting mixed powder material of step 1.3 is put into crucible, and by mixed powder material in crucible and compacting, so Lid is covered on crucible afterwards, makes to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere and 1050 DEG C~1150 DEG C of temperature under the conditions of mixed powder material in calcining at constant temperature crucible, heating rate control is in 3~5 DEG C/min, calcining Time control are as follows: 1.5h~2.5h；
Step 1.5, after the completion of step 1.4 calcining, crucible is taken out from Muffle furnace, crucible is made to naturally cool to room temperature, earthenware Presoma NiNb is formed in crucible2O6Powder.
3. a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics according to claim 2, Be characterized in that: detailed process is as follows for the step 3:
Step 3.1, weighed Al in the basis material and step 2 step 2 obtained2O3Powder and Li2CO3Powder be mixed to form to Ball milling powder will be added in ball grinder together to ball milling powder and abrading-ball, and dehydrated alcohol is added as ball into ball grinder Grinding media carries out ball-milling treatment, obtains mixed powder；
Step 3.2, mixed powder step 3.1 obtained, which is placed in baking oven, carries out drying and processing, obtains mixed powder material；Drying Temperature control are as follows: 80 DEG C~100 DEG C；
The resulting mixed powder material of step 3.2 is put into crucible by step 3.3, and by mixed powder material in crucible and compacting, so Lid is covered on crucible afterwards, makes to form confined space in crucible, crucible is placed in Muffle furnace, in air atmosphere and 800 Mixed powder material under the conditions of~950 DEG C of temperature in calcining at constant temperature crucible, heating rate are controlled in 3~5 DEG C/min, calcination time Control are as follows: 1.5h~2.5h；
Step 3.4, after the completion of the calcining in step 3.3, crucible is taken out from Muffle furnace, crucible is made to naturally cool to room Temperature, crucible is interior to form pre-synthesis powder.
4. a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics according to claim 3, Be characterized in that: detailed process is as follows for the step 4:
Step 4.1, the pre-synthesis powder that step 3 obtains is poured into mortar and is ground, obtain pre-synthesis powder A；
Step 4.2, pre-synthesis powder A and abrading-ball that step 4.1 obtains are put into togerther in ball grinder and carry out ball-milling treatment, and Dehydrated alcohol is added during ball-milling treatment as ball-milling medium, obtains prefabricated mixed powder B；
Step 4.3, the pre-synthesis powder material B obtained through step 4.2 is dried, obtains pre-synthesis dry mash；
It in step 4.3, is dried during the drying process using baking oven, and drying temperature controls are as follows: 80 DEG C~100 DEG C；
Step 4.4, it weighs PVA to be dissolved in the water, makes the PVA solution that mass percent concentration is 4%~7%；
Step 4.5, PVA solution step 4.4 made is added to the step 4.3 obtained through step 4.3, will be through step 4.2 Obtained pre-synthesis powder material B drying, obtains carrying out granulation processing in pre-synthesis dry mash, obtains powder；Every gram of pre-synthesis dry powder The PVA solution of 0.1ml~0.2ml to be added in material；
Step 4.6, after step 4.5 completes granulation processing, the powder of forming is subjected to sieving processing using sieve；
Step 4.7, the powder obtained after step 4.6 sieving is pressed into idiosome under the pressure of 90Mpa~110Mpa.
5. a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics according to claim 4, Be characterized in that: detailed process is as follows for the step 5:
Step 5.1, under the conditions of 600 DEG C~700 DEG C, idiosome is obtained to step 4 and carries out dumping, naturally cools to room again later Temperature；
Step 5.2, will through step 5.1, treated that idiosome is put into Muffle furnace, under air atmosphere, with 2.5 DEG C/min~3.5 DEG C/Muffle furnace is warming up to 1250 DEG C~1350 DEG C by the rate of min, calcining at constant temperature idiosome 1.5h~2.5h is to get to three oxidations The hafnium of two aluminium and carbonic acid lithium doping lead titanates-lead nickle niobate piezoelectric ceramics.
6. a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics according to claim 5, Be characterized in that: detailed process is as follows for dumping in the step 5.1:
Under air atmosphere, Muffle furnace is warming up to 120 DEG C with 2.5 DEG C/min~3.5 DEG C/min rate, calcining at constant temperature idiosome Then 0.5h is continuously heating to 600 DEG C~700 DEG C, calcining at constant temperature idiosome 2h with 2.5 DEG C/min~3.5 DEG C/min rate, i.e., Idiosome after obtaining dumping.
7. a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics according to claim 5, Be characterized in that: detailed process is as follows for the step 6:
Step 6.1, obtained idiosome will be handled through step 5.2 to polish using the sand paper of 600-1000 mesh in polishing machine；
Step 6.2, obtained idiosome will be handled through step 6.1 to be placed in beaker, dehydrated alcohol is added, in ultrasonic cleaner Middle ultrasound 20min；
Step 6.3, obtained idiosome will be handled through step 6.2 to carry out applying silver, put baking oven drying, and baking oven after being painted with into immediately Temperature control is 80-100 DEG C；
Step 6.4, obtained idiosome will be handled through step 6.3 to be put into Muffle furnace, under air atmosphere, with 2.5 DEG C/min~ Muffle furnace is warming up to 120 DEG C, calcining at constant temperature idiosome 10min by the rate of 3.5 DEG C/min, later with 2.5 DEG C/min~3.5 DEG C/ The rate of min is continuously heating to 320 DEG C, calcining at constant temperature idiosome 0.5h, then with 3.5 DEG C/min~4.5 DEG C/min rate after Continuous to be warming up to 650 DEG C, calcining at constant temperature idiosome 2h is to get to the potsherd after silver ink firing.
8. a kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics according to claim 7, Be characterized in that: detailed process is as follows for the step 7:
Potsherd after the silver ink firing obtained in the step 6 is polarized under the conditions of room temperature~200 DEG C；Polarization time is 10 ~30min, polarized electric field are 2~3kV/cm.
CN201811231239.4A 2018-10-22 2018-10-22 A kind of preparation method of lithium aluminium codope hafnium lead titanates-lead nickle niobate piezoelectric ceramics Pending CN109320241A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110498683A (en) * 2019-08-16 2019-11-26 西安电子科技大学 A kind of low-temperature sintering prepares hafnium lead titanates-lead nickle niobate piezoelectric ceramics method
CN110642621A (en) * 2019-10-21 2020-01-03 湖南云天雾化科技有限公司 High-performance piezoelectric ceramic and manufacturing method thereof
CN110818410A (en) * 2019-11-12 2020-02-21 西安电子科技大学 High-temperature PIN-PHT piezoelectric ceramic and preparation method thereof
CN113149644A (en) * 2021-03-24 2021-07-23 哈尔滨工业大学 Low-temperature sintered lead antimonate manganese-lead zirconate titanate low-dielectric-loss piezoelectric ceramic and preparation method thereof
CN113185289A (en) * 2021-03-31 2021-07-30 哈尔滨工业大学 Lead manganous niobate-lead nickelate-lead zirconate titanate high-voltage electric ferroelectric ceramic with ultralow dielectric loss and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102020464A (en) * 2009-09-16 2011-04-20 罗伯特.博世有限公司 Ceramic material for piezoelectric type actuator device and/or sensor device and preparation method thereof
CN103979955A (en) * 2014-05-13 2014-08-13 哈尔滨工业大学 Barium titanate based leadless piezoceramic material doped and modified by lithium-aluminum ion pair and preparing method thereof
CN105948736A (en) * 2016-05-03 2016-09-21 哈尔滨工业大学 Lithium oxide-trivalent oxide co-doped ABO3 structure-based high-temperature stability piezoelectric ceramic material and preparation method thereof
CN107056293A (en) * 2017-06-06 2017-08-18 西安电子科技大学 Fe2O3The preparation method of doping PHT PNN piezoelectric ceramics
CN107216130A (en) * 2017-06-06 2017-09-29 西安电子科技大学 A kind of preparation method of PHT PNN piezoceramic materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102020464A (en) * 2009-09-16 2011-04-20 罗伯特.博世有限公司 Ceramic material for piezoelectric type actuator device and/or sensor device and preparation method thereof
CN103979955A (en) * 2014-05-13 2014-08-13 哈尔滨工业大学 Barium titanate based leadless piezoceramic material doped and modified by lithium-aluminum ion pair and preparing method thereof
CN105948736A (en) * 2016-05-03 2016-09-21 哈尔滨工业大学 Lithium oxide-trivalent oxide co-doped ABO3 structure-based high-temperature stability piezoelectric ceramic material and preparation method thereof
CN107056293A (en) * 2017-06-06 2017-08-18 西安电子科技大学 Fe2O3The preparation method of doping PHT PNN piezoelectric ceramics
CN107216130A (en) * 2017-06-06 2017-09-29 西安电子科技大学 A kind of preparation method of PHT PNN piezoceramic materials

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
H.TANG ETAL.: "Investigation of dielectric and piezoelectric properties in Pb(Ni1/3Nb2/3)O3–PbHfO3–PbTiO3 ternary system", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 *
Y FENG ETAL.: "Enhanced piezoelectric properties and constricted hysteresis behaviour in PZT ceramics induced by Li+–Al3+ ionic pairs", 《ROYAL SOCIETY OF CHEMISTRY ADVANCES》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110498683A (en) * 2019-08-16 2019-11-26 西安电子科技大学 A kind of low-temperature sintering prepares hafnium lead titanates-lead nickle niobate piezoelectric ceramics method
CN110642621A (en) * 2019-10-21 2020-01-03 湖南云天雾化科技有限公司 High-performance piezoelectric ceramic and manufacturing method thereof
CN110642621B (en) * 2019-10-21 2021-12-21 湖南云天雾化科技有限公司 High-performance piezoelectric ceramic for electronic cigarette oil atomization and manufacturing method thereof
CN110818410A (en) * 2019-11-12 2020-02-21 西安电子科技大学 High-temperature PIN-PHT piezoelectric ceramic and preparation method thereof
CN110818410B (en) * 2019-11-12 2021-09-21 西安电子科技大学 High-temperature PIN-PHT piezoelectric ceramic and preparation method thereof
CN113149644A (en) * 2021-03-24 2021-07-23 哈尔滨工业大学 Low-temperature sintered lead antimonate manganese-lead zirconate titanate low-dielectric-loss piezoelectric ceramic and preparation method thereof
CN113185289A (en) * 2021-03-31 2021-07-30 哈尔滨工业大学 Lead manganous niobate-lead nickelate-lead zirconate titanate high-voltage electric ferroelectric ceramic with ultralow dielectric loss and preparation method thereof
CN113185289B (en) * 2021-03-31 2022-06-03 哈尔滨工业大学 Lead manganous niobate-lead nickelate-lead zirconate titanate high-voltage electric ferroelectric ceramic with ultralow dielectric loss and preparation method thereof

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Application publication date: 20190212