CN101820569B - Formula of multilayer piezoelectric ceramic for loudspeaker drive and production method thereof - Google Patents
Formula of multilayer piezoelectric ceramic for loudspeaker drive and production method thereof Download PDFInfo
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Abstract
The invention discloses a multilayer piezoelectric ceramic with ultralow sintering temperature and lower production cost for a loudspeaker drive and a production method thereof. The formula of the multilayer piezoelectric ceramic for the loudspeaker drive has the stoichiometric general formula of Pb1-xSrx(Zn1/3Nb2/3)y(Ni1/3Nb2/3)z(Li1/2Sb1/2)(0.25-y-z)Zr0.375Ti0.375O3+tLi2CO3+muMnCO3, wherein x is more than 0.000mol and less than 0.100mol; y is more than 0.000mol and less than 0.150mol; z is more than 0.000mol and less than 0.100mol; t is more than 0.00 percent by weight and less than 0.200 percent by weight; and mu is more than 0.00 percent by weight and less than 0.200 percent by weight.
Description
Technical field
The present invention relates to a kind of loudspeaker drive, relate in particular to a kind of multilayer piezoelectric ceramic for loudspeaker drive and manufacture method thereof.
Background technology
Piezoceramic material is a kind of can with the functionality ceramic material of mechanical energy and the mutual conversion of electric energy, because it has high piezoelectric property, being widely used in all kinds of electronic devices.Multilayer piezoelectric ceramic for loudspeaker is exactly a kind of novel electro-acoustic element, it is compared with traditional coil-moving speaker has following advantage: do not need magnet in (1) piezoelectric speaker structure, do not disturb and impact thereby also can not exist any magnetic field that circuit is on every side produced; (2) thickness ultrathin of piezoelectric speaker, the thickness of at present made piezoelectric speaker itself only has 0.7mm, and the thickness of coil-moving speaker is general all more than 3mm, by contrast, piezoelectric speaker can be installed on more that (3) piezoelectric speaker has light characteristics in the narrow space, weight is generally all less than 1g, and is lighter by 30%～50% than traditional moving-coil speaker; (4) piezoelectric speaker is low in energy consumption, is generally less than 15mW, is 1/5～1/2 of coil-moving speaker consumed power, and this has prolonged the battery life of device greatly; (5) acoustic design of piezoelectric speaker is simple, and the back side only needs little room.Just because of these advantages of piezoelectric speaker, under the trend of current device miniaturization, has extremely wide application prospect.Be mainly used in the consumer electronics industrial field, such as mobile phone, digital camera, Digital Video, MP3, MP4, portable digital-video product, handheld electronic game machine etc.
Multilayer piezoelectric speaker is comprised of two parts, and a part is the multilayer piezoelectric ceramic driver that has polarized at thickness direction, and a part is metal substrate (also claiming vibrating diaphragm), and the multilayer piezoelectric ceramic driver then is the core of piezoelectric speaker.
We know that piezoceramic material mostly is the lead base oxide, and when high temperature sintering, because the volatilization of lead oxide will cause stoichiometry to depart from, hydraulic performance decline and to the pollution of environment simultaneously, also wastes energy; The another one aspect, the driver of piezoelectric speaker must adopt sandwich construction, during the sintering of multilayer structures device, need in the silver slurry, to add part precious metal palladium (Pd) as interior electrode sintering, generally speaking, sintering temperature is higher, and it is larger to contain the palladium amount in the electrode slurry, and so that the used slurry price of interior electrode is higher.Therefore, reduce the volatilization that sintering temperature not only is conducive to reduce lead oxide (PbO), and can reduce in the slurry palladium content or need not add palladium and with the fine silver slurry, the cost of electrode in reducing is conducive to the production of multilayer piezoelectric ceramic for loudspeaker drive industrialization.
At present, generally about 1150 ℃, used interior electrode is that palladium content surpasses silver-palladium electrode of 35% to the sintering temperature of external multilayer piezoelectric ceramic material, and is expensive, cost is high, and the distortion of ceramic diaphragm sintering is large, qualification rate is low.Although and some domestic producers use the low-temperature sintering technology at 980～1050 ℃, used interior electrode still is 10～15% palladium slurry for content, and price is still more expensive.Therefore, work of the present invention is intended to find out a kind of prescription of suitable piezoceramic material and manufacture method thereof to reduce sintering temperature, thereby use the inner electrode of fine silver slurry, can take into account again the desired high planar electromechanical coupling factor of multilayer piezoelectric ceramic for loudspeaker drive, low mechanical quality factor and low dynamo-electric loss simultaneously.
Summary of the invention
A technical problem to be solved by this invention is: a kind of have ultra-low sintering temperature, multilayer piezoelectric ceramic for loudspeaker drive that manufacturing cost is lower are provided.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: described loudspeaker drive with the stoichiometry general formula of the prescription of multilayer piezoelectric ceramic is: Pb
1-xSr
x(Zn
1/3Nb
2/3)
y(Ni
1/3Nb
2/3)
z(Li
1/2Sb
1/2)
(025-y-z)Zr
0.375Ti
0.375O
3+ tLi
2CO
3+ u MnCO
3
Wherein:
0.000mol＜x＜0.100mol；0.000mol＜y＜0.150mol；0.000mol＜z＜0.100mol；
0.00wt%＜t＜0.200wt%; 0.00wt%＜u＜0.200wt%, the wt% percentage by weight.
Another technical problem to be solved by this invention is: a kind of manufacture method with ultra-low sintering temperature, multilayer piezoelectric ceramic for loudspeaker drive that manufacturing cost is lower is provided.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: a kind of manufacture method of multilayer piezoelectric ceramic for loudspeaker drive claimed in claim 1 comprises the steps:
(1) batching, stirring ball-milling, sand milling
Stoichiometric proportion by the prescription general formula takes by weighing: Pb
3O
4, SrCO
3, ZnO, Nb
2O
5, NiO, Sb
2O
5, ZrO
2, TiO
2, MnCO
3, Li
2CO
3Mix, then it is joined in the agitating ball mill, adding deionized water in the agitating ball mill is dispersant, adding zirconia ball in the agitating ball mill is ball-milling medium, the weight ratio of deionized water and raw material is 1: 1.5～2, with agitating ball mill ball milling 3～5 hours, the set of frequency of agitating ball mill upconverter is 40～45HZ, separation of oxygenated zirconium ball joins sand mill in the lump with compound, grinds 1～2 hour with sand mill, the rotating speed of sand mill is 2000～2200 rev/mins, use particle size analyzer determination, its granularity should meet d (50)=0.1～0.2um, discharging, put into thermostatic drying chamber 90～120 degree temperature dryings 8～12 hours, material is put in the Universalpulverizer again and ground, discharging is by 80 purpose standard screens;
(2) pre-burning
Material after pulverizing is placed in the alumina crucible, and compacting adds a cover, in box resistance furnace, with 800～820 degree pre-burnings insulations 2～4 hours, naturally cool to room temperature, come out of the stove;
(3) sand milling and oven dry
Smashing and put into the pre-burning powder to pieces Universalpulverizer grinds, discharging, by 80 purpose standard screens, pack into the powder after grinding in the Stainless steel basin and add deionized water, be moved in the lump in the sand mill after stirring, the weight ratio of deionized water and powder is 1: 1.5～2, ground 1～2 hour with sand mill, the rotating speed of sand mill is 2000～2200 rev/mins, discharging is put into clean stainless steel drip pan with compound and is transplanted on thermostatic drying chamber 80～120 degree oven dry 8～12 hours, material is joined in the Universalpulverizer to grind again, discharging is by 100 purpose standard screens;
(4) preparation of curtain coating slurry
Above-mentioned porcelain powder and solvent are joined in the ball grinder by a certain percentage, and to add zirconia ball be ball-milling medium that ball milling disperseed 5～10 hours, added afterwards adhesive and continued ball milling 10～15 hours, filtered discharging.Wherein: solvent is toluene or dimethylbenzene and absolute alcohol, and the ratio of itself and porcelain powder is: 0.30～0.35: 1; Adhesive (26%PVB toluene solution) with the ratio of porcelain powder is: 0.25～0.35: 1; The ratio of zirconia ball and porcelain powder is: 1.5～2.0: 1;
(5) casting film-forming
Be deaeration 1～2 hour under the condition of 0.050～0.065MPa in vacuum degree with the curtain coating of above-mentioned filtration discharging slurry, left standstill 10～12 hours, carry out casting film-forming with casting machine afterwards, belt speed is controlled at 500～1200rpm, and the baking temperature of each temperature province of casting machine is: 60～90,90～100,90～110 degree; Simultaneously, also must regulate the size of the exhausting amount of diaphragm drying; The THICKNESS CONTROL of diaphragm is at 20～50um, and is certain, different thickness, the temperature and the exhausting amount that need to regulate dry section; Casting machine automatically is cut into diaphragm and sets the diaphragm that needs size;
(6) printing lamination
Adjust automatic charging printing lamination machine, mainly comprise adjusting and process pressing base, net, adjustment scraper plate and drying baker are transferred to the temperature of setting; With the printing material of fine silver slurry as electrode, spread the above-mentioned diaphragm of one deck on the printing support plate, by the web plate seal one deck that designs, oven dry, temperature is 60～80 degree; Repave one deck diaphragm, pressing, its pressing pressure is 15～25MPa, printing; So repeat, by the requirement of multilayer piezoelectric speaker driver, be laminated to 3～5 layers to diaphragm, diaphragm is taken off and diaphragm is encapsulated in the special plastic bag of PE with vacuum packing machine from the printing support plate, palpus guarantees air tight, and the diaphragm after the justifying printing has comprised a plurality of blanks;
(7) lamination
The above-mentioned packaging bag that the good diaphragm of printing lamination is housed is put into the balancer such as Intelligent hot and carry out lamination, make its each interlayer finer and close under certain temperature and pressure; The temperature of lamination is 55～70 degree, and pressure is 20～50Mpa;
(8) cutting
After lamination is complete, carefully cut off plastic packaging bag, take out to give birth to diaphragm, the line of cut that gets on by printing cuts into the blank of single multilayer piezoelectric ceramic for loudspeaker drive; This blank is carefully dipped in upper silver slurry with writing brush carry out end-blocking by polarity;
(9) binder removal
The blank that above-mentioned end-blocking is good is put into chamber type electric resistance furnace or continuous tunnel furnace, and temperature 280～350 degree are incubated 25～50 hours and carry out the organic substance eliminating, are warmed up to 500～700 degree again, and are last, naturally cool to room temperature with stove;
(10) sintering
The blank of above-mentioned binder removal is put in box sintering furnace or the tunnel sintering furnace, and tipped upside down on the blank with square alumina crucible and to seal, 2～5 degrees/mins of programming rates 900～920 degree sintered heat insulatings 2～4 hours, naturally cool to room temperature with stove;
(11) polarization
The device that sinters is placed in the special-purpose anchor clamps, with the anchor clamps of integral body put into be heated in the baking oven 180～260 the degree, under this temperature, apply the direct voltage of 25～38V to device, continue 15～30 minutes, be prepared into the multilayer piezoelectric ceramic for loudspeaker driver.
In order to solve better another technical problem of the present invention, the further technical scheme that the present invention adopts is: in described batching, stirring ball-milling, sand milling processing step (1), compound is joined sand mill in the lump, ground 1.5 hours with sand mill, the rotating speed of sand mill is 2000 rev/mins, use particle size analyzer determination, its granularity should meet d (50)=0.1～0.15um.
In order to solve better another technical problem of the present invention, the further technical scheme that the present invention adopts is: in described pre-sinter process step (2), material after pulverizing is placed in the alumina crucible, and compacting adds a cover, and 800～820 degree pre-burnings insulations are 2～3 hours in box resistance furnace.
In order to solve better another technical problem of the present invention, the further technical scheme that the present invention adopts is: in described sintering process step (10), the blank of above-mentioned binder removal is put in box sintering furnace or the tunnel sintering furnace, and tip upside down on the blank with square alumina crucible and to seal, 2～3 degrees/mins of programming rates are spent sintered heat insulatings 2～3 hours 900～920.
Advantage of the present invention is: multilayer piezoelectric ceramic for loudspeaker drive of the present invention and manufacture method thereof, by the optimization to prescription, under the condition that satisfies all kinds of performances of multilayer piezoelectric ceramic driver, make sintering temperature be controlled at the ultralow temperature of 900-930 degree, compare with traditional high temperature sintering 1050-1150 degree and low-temperature sintering 980-1050 degree and have following advantage:
1, can save in a large number electric energy, and prolong the useful life of high-temperature sintering apparatus, greatly reduce lead oxide (PbO) volatilization, reduce the pollution to environment.
2, because piezoelectric ceramic piece only has the thickness about 0.1mm, especially easily distortion in high temperature sintering, the present invention adopts sintered at ultra low temperature technique, can reduce deformation of products in the sintering process, can greatly improve the yields of product, for industrialization facilitates, reduce cost.
3, can use the fine silver slurry to be inner electrode, replaced the used expensive silver of high temperature sintering-palladium slurry inner electrode, therefore, make its cost of making the multilayer piezoelectric ceramic driver use silver-palladium to starch the low cost of manufacture 60%～150% of product than like product, this point has very strong competitiveness.
Embodiment
Describe particular content of the present invention in detail below by specific embodiment.
Embodiment one:
The present invention replaces part Pb with Sr, can reduce plumbous volatilization sintering is become easily, simultaneously, introduces a certain amount of antimony lithium lead plumbate, can reduce the Qm value, adds an amount of Li
2CO
3As the low temperature additive, an amount of MnCO
3Can improve the temperature stability of material, improve the intensity of potsherd, but can only add trace.
Therefore take the multilayer piezoelectric ceramic for loudspeaker drive of fine silver as interior electrode sintered at ultra low temperature, its stoichiometry general formula is:
Pb
1-xSr
x(Zn
1/3Nb
2/3)
y(Ni
1/3Nb
2/3)
z(Li
1/2Sb
1/2)
(0.25-y-z)Zr
0.375Ti
0.375O
3+tLi
2CO
3+u?MnCO
3
Wherein:
0.000mol＜x＜0.100mol；0.000mol＜y＜0.150mol；0.000mol＜z＜0.100mol；
0.00wt%＜t＜0.200wt%; 0.00wt%＜u＜0.200wt%, the wt% percentage by weight.
Choose x=0.02,0.04,0.08,0.10 y=0.10 z=0.08 t=0.10 u=0.05 is a prescription as an example.
Its manufacturing technology steps is as follows:
1, batching, stirring ball-milling, sand milling
Press x=0.02,0.04,0.08,0.08 y=0.12, z=0.08, t=0.10, u=0.05 stoichiometric take by weighing Pb
3O
4, SrCO
3, ZnO, Nb
2O
5, NiO, Sb
2O
5, ZrO
2, TiO
2, MnCO
3, Li
2CO
3Mix, then it is joined in the agitating ball mill, adding deionized water in the agitating ball mill is dispersant, adding zirconia ball in the agitating ball mill is ball-milling medium, the weight ratio of deionized water and raw material is 1: 1.5, with agitating ball mill ball milling 3 hours, the set of frequency of agitating ball mill upconverter is 40HZ, and separation of oxygenated zirconium ball joins sand mill in the lump with compound, ground 1.5 hours with sand mill, the rotating speed of sand mill is 2000 rev/mins, uses particle size analyzer determination, and its granularity should meet d (50)=0.114um, discharging, put into thermostatic drying chamber 90 degree temperature dry 2 hours, and again with dry 8 hours of Temperature Setting to 120, material was put in the Universalpulverizer ground again, discharging is by 80 purpose standard screens.
In the processing step 1 of the manufacture method of multilayer piezoelectric ceramic for loudspeaker drive of the present invention, adopted first ball milling again sand milling method with powder handling ultra-fine, compare with the like product manufacturing process, its powder dispersity is good, uniform doping, specific area is large, the reactivity advantages of higher is also for realizing that low temperature presintering and low-temperature sintering play a role.
(2) pre-burning
Material after pulverizing is placed in the alumina crucible, and compacting adds a cover, in box resistance furnace, with 800 degree pre-burnings insulations 2 hours, naturally cool to room temperature, come out of the stove.
(3) sand milling and oven dry
Smashing and put into the pre-burning powder to pieces Universalpulverizer grinds, discharging, by 80 purpose standard screens, pack into the powder after grinding in the Stainless steel basin and add deionized water, be moved in the lump in the sand mill after stirring, the weight ratio of deionized water and powder is 1: 1.5, ground 1.5 hours with sand mill, the rotating speed of sand mill is 2000 rev/mins, and discharging is put into clean stainless steel drip pan with compound and is transplanted on dry 2 hours of thermostatic drying chamber 90 degree temperature, again with dry 8 hours of Temperature Setting to 120, material is joined in the Universalpulverizer again and grind, discharging is by 100 purpose standard screens.
(4) preparation of curtain coating slurry
Above-mentioned porcelain powder and solvent are joined in the ball grinder by a certain percentage, and to add zirconia ball be ball-milling medium that ball milling disperseed 6 hours, added afterwards adhesive and continued ball milling 12 hours, filtered discharging.Wherein: solvent is toluene or dimethylbenzene and absolute alcohol, and the ratio of itself and porcelain powder is: 0.30～: 1; Adhesive (26%PVB toluene solution) with the ratio of porcelain powder is: 0.35: 1; The ratio of zirconia ball and porcelain powder is: 1.5～: 1.
(5) casting film-forming
Be deaeration 1 hour under the condition of 0.050MPa in vacuum degree with the curtain coating of above-mentioned filtration discharging slurry, left standstill 12 hours that carry out casting film-forming with casting machine afterwards, belt speed is controlled at 800rpm, the baking temperature of each temperature province of casting machine is: 90,100,110 degree; Simultaneously, also must regulate the size of the exhausting amount of diaphragm drying; The THICKNESS CONTROL of diaphragm is at 35um, and is certain, different thickness, the temperature and the exhausting amount that need to regulate dry section; Casting machine automatically is cut into diaphragm and sets the diaphragm that needs size.
(6) printing lamination
Adjust automatic charging printing lamination machine, mainly comprise adjusting and process pressing base, net, adjustment scraper plate and drying baker are transferred to the temperature of setting; With the printing material of fine silver slurry as electrode, spread the above-mentioned diaphragm of one deck on the printing support plate, by the web plate seal one deck that designs, oven dry, temperature is 80 degree; Repave one deck diaphragm, pressing, its pressing pressure is 20MPa, printing; So repeat, by the requirement of multilayer piezoelectric speaker driver, be laminated to 3 layers to diaphragm, diaphragm is taken off and diaphragm is encapsulated in the special plastic bag of PE with vacuum packing machine from the printing support plate, palpus guarantees air tight, and the diaphragm after the justifying printing has comprised a plurality of blanks.
(7) lamination
The above-mentioned packaging bag that the good diaphragm of printing lamination is housed is put into the balancer such as Intelligent hot and carry out lamination, make its each interlayer finer and close under certain temperature and pressure; The temperature of lamination is 55～70 degree, and pressure is 20～50Mpa.
(8) cutting
After lamination is complete, carefully cut off plastic packaging bag, take out to give birth to diaphragm, the line of cut that gets on by printing cuts into the blank of single multilayer piezoelectric ceramic for loudspeaker drive; This blank is carefully dipped in upper silver slurry with writing brush carry out end-blocking by polarity.
(9) binder removal
The blank that above-mentioned end-blocking is good is put into chamber type electric resistance furnace or continuous tunnel furnace, and temperature 340 degree are incubated 45 hours and carry out the organic substance eliminating, are warmed up to 700 degree again, and are last, naturally cool to room temperature with stove.
(10) sintering
The blank of above-mentioned binder removal is put in box sintering furnace or the tunnel sintering furnace, and tip upside down on the blank with square alumina crucible and to seal, 2～5 degrees/mins of programming rates, two kinds of material are spent sintered heat insulatings 2 hours 880,900,920,940,960,980 respectively, naturally cool to room temperature with stove.
(11) polarization
The device that sinters is placed in the special-purpose anchor clamps, with the anchor clamps of integral body put into be heated in the baking oven 180～260 the degree, under this temperature, apply the direct voltage of 25～38V to device, continue 15～30 minutes, be prepared into the multilayer piezoelectric ceramic for loudspeaker driver.
The multilayer piezoelectric ceramic for loudspeaker drive of preparation is placed and was tested its piezoelectric property in 12 hours as stated above, the test instrument: accurate LCR digital electric bridge TH2818 automatic component analyzer, produced with the sub-Co., Ltd that sends us by cable by Changzhou.
Under the different sintering temperatures of table 1, different content of strontium are on the impact of material piezoelectric property
Can be drawn by table 1, the relevant performance parameter of multilayer piezoelectric speaker driver is when the sintering temperature of 900-920 degree, and its performance is best.Simultaneously, when X=0.06, piezoelectric ceramic devices Kp value is the highest, and Qm is minimum, and dynamo-electric loss is minimum, and direct capacitance is maximum; Piezoelectric property is best.
Embodiment two:
Take the multilayer piezoelectric ceramic for loudspeaker drive of fine silver as interior electrode sintered at ultra low temperature, its stoichiometry general formula is:
Pb
1-xSr
x(Zn
1/3Nb
2/3)
y(Ni
1/3Nb
2/3)
z(Li
1/2Sb
1/2)
(0.25-y-z)Zr
0.375Ti
0.375O
3+tLi
2CO
3+u?MnCO
3
Wherein:
0.000mol＜x＜0.100mol; 0.000mol＜y＜0.150mol; 0.000mol＜z＜0.100mol; 0.00wt%＜t＜0.200wt%; 0.00wt%＜u＜0.200wt%, the wt% percentage by weight.
We choose as an example two prescriptions of x=0.06 y=0.05,0.10,0.12,0.15 z=0.08, t=0.10, u=0.05,
The method of manufacturing technology step of embodiment two is identical with example one manufacturing technology steps, only in the manufacturing technology steps 10 of example 1, change into: the blank of above-mentioned binder removal is put in box sintering furnace or the tunnel sintering furnace, and tip upside down on the blank with square alumina crucible and to seal, programming rate 2-5 degrees/min, two kinds of material naturally cool to room temperature respectively at 880,900,920,940,960 degree sintered heat insulating 2h with stove.
Place 12h by the driver of the multilayer piezoelectric ceramic for loudspeaker of above-mentioned process preparation and test its piezoelectric property, the test instrument: accurate LCR digital electric bridge TH2818 automatic component analyzer, produced with the sub-Co., Ltd that sends us by cable by Changzhou;
Under table 2, the different sintering temperature, different (Zn
1/3Nb
2/3) content is on the impact of material piezoelectric property
Can be drawn by table 2, the relevant performance parameter of multilayer piezoelectric speaker driver is when the sintering temperature of 900-920 degree, and its performance is best.Simultaneously, when y=0.12, the Kp value of multilayer piezoelectric ceramic for loudspeaker drive is the highest, and Qm is minimum, and dynamo-electric loss is minimum, and direct capacitance is maximum; Piezoelectric property is best.
Embodiment three
Take the multilayer piezoelectric ceramic for loudspeaker drive of fine silver as interior electrode sintered at ultra low temperature, with following general formula Pb
1-xSr
x(Zn
1/3Nb
2/3)
y(Ni
1/3Nb
2/3)
z(Li
1/2Sb
1/2)
(0.25-y-z)Zr
0.375Ti
0.375O
3+ tLi
2CO
3+ uMnCO
3The composition of expression material is in the formula
0.000mol＜x＜0.100mol；0.000mol＜y＜0.150mol；0.000mol＜z＜0.100mol；0.00wt％＜t＜0.200wt％；0.00wt％＜u＜0.200wt％。
We choose x=0.06, and y=0.12, z=0.04,0.06,0.08,0.10, t=0.10, u=0.05 be two prescriptions as an example,
The method of manufacturing technology step of embodiment three is identical with example two manufacturing technology steps.
Place 12h by the driver of the multilayer piezoelectric ceramic for loudspeaker of above-mentioned process preparation and test its piezoelectric property, the test instrument: accurate LCR digital electric bridge TH2818 automatic component analyzer, produced with the sub-Co., Ltd that sends us by cable by Changzhou.
Under table 3, the different sintering temperature, different (Ni
1/3Nb
2/3) content is on the impact of material piezoelectric property
Can be drawn by table 3, the relevant performance parameter of multilayer piezoelectric speaker driver is when the sintering temperature of 900-920 degree, and its performance is best.Simultaneously, when Z=0.08, the Kp value of multilayer piezoelectric ceramic for loudspeaker drive is the highest, and Qm is minimum, and dynamo-electric loss is minimum, and direct capacitance is maximum; Piezoelectric property is best.
Embodiment four
Take the multilayer piezoelectric ceramic for loudspeaker drive of fine silver as interior electrode sintered at ultra low temperature, with following general formula Pb
1-xSr
x(Zn
1/3Nb
2/3)
y(Ni
1/3Nb
2/3)
z(Li
1/2Sb
1/2)
(0.25-y-z)Zr
0.375Ti
0.375O
3+ tLi
2CO
3+ uMnCO
3The composition of expression material is in the formula
0.000mol＜x＜0.100mol；0.000mol＜y＜0.150mol；0.000mol＜z＜0.100mol；0.00wt％＜t＜0.200wt％；0.00wt％＜u＜0.200wt％。
We choose x=0.06, and y=0.12, z=0.08, t=0.03,0.06,0.08,0.10, u=0.05 be two prescriptions as an example,
The method of manufacturing technology step of embodiment four is identical with example two manufacturing technology steps.
Place 12h by the driver of the multilayer piezoelectric ceramic for loudspeaker of above-mentioned process preparation and test its piezoelectric property, the test instrument: accurate LCR digital electric bridge TH2818 automatic component analyzer, produced with the sub-Co., Ltd that sends us by cable by Changzhou.
Under table 4, the different sintering temperature, Different L i2CO3 content is on the impact of material piezoelectric property
Can be drawn by table 4, along with Li
2CO
3The minimizing of content, sintering temperature is higher, and the relevant performance parameter of its multilayer piezoelectric speaker driver turns for the better.When content is less than 0.03%, also do not detect the piezoelectric property of device in sintering temperature when following at 920 degree, and when content reaches 0.1%, when sintering temperature was spent at 900-920, the Kp value of its multilayer piezoelectric ceramic for loudspeaker drive was the highest, and Qm is minimum, dynamo-electric loss is minimum, and direct capacitance is maximum.
To sum up, the present invention uses following general formula take the multilayer piezoelectric ceramic for loudspeaker drive of fine silver as interior electrode sintered at ultra low temperature
Pb
1-xSr
x(Zn
1/3Nb
2/3)
y(Ni
1/3Nb
2/3)
z(Li
1/2Sb
1/2)
(0.25-y-z)Zr
0.375Ti
0.375O
3+ tLi
2CO
3+ uMnCO
3The composition of expression material is in the formula
0.000mol＜x＜0.100mol；0.000mol＜y＜0.150mol；0.000mol＜z＜0.100mol；0.00wt％＜t＜0.200wt％；0.00wt％＜u＜0.200wt％。
We choose X=0.06, y=0.12, z=0.08, t=0.10, u=0.05 is as the prescription stoichiometry, and the manufacturing technology steps by the embodiment of the invention has produced take fine silver as inner electrode, the multilayer piezoelectric ceramic for loudspeaker drive of sintering temperature under the condition of 900 or 920 degree, its performance meets the requirements.The present invention proves by a large amount of experimental datas: its calcined temperature is controlled at 800～820 degree, is incubated 2～4 hours; Its firing temperature is at the 900-920 degree, be incubated 2～4 hours, inner electrode uses the fine silver slurry, the performance parameter of its piezoelectric ceramic actuator: with three-decker, tape casting diaphragm thickness is 35～37um, piezoelectric actuator is of a size of 18*18 (L*W) and (annotates: because the various performance parameters of multilayer piezoelectric ceramic driver is different because of the difference of physical dimension for example, therefore among the present invention when not specifying, it all refers to " three-decker; tape casting diaphragm thickness is 35～37um, and piezoelectric actuator is of a size of L*W=18*18):
Planar electromechanical coupling factor K
P＞0.50 Static Electro capacity C
0＞650nF,
Mechanic quality factor＜50 dynamo-electric loss Tg δ＜3.0%
Can reach the performance requirement of multilayer piezoelectric ceramic for loudspeaker drive fully.
Claims (5)
1. multilayer piezoelectric ceramic for loudspeaker drive, it is characterized in that: described loudspeaker drive with the stoichiometry general formula of the prescription of multilayer piezoelectric ceramic is:
Pb
1-xSr
x(Zn
1/3Nb
2/3)
y(Ni
1/3Nb
2/3)
z(Li
1/2Sb
1/2)
(0.25-y-z)Zr
0.375Ti
0.375O
3+tLi
2CO
3+u?MnCO
3
Wherein:
0.000mol<x<0.100mol?；0.000mol<y<0.150mol；0.000mol<z<0.100mol?；
0.00wt%＜t＜0.200wt%; 0.00wt%＜u＜0.200wt%, the wt% percentage by weight.
2. the manufacture method of a multilayer piezoelectric ceramic for loudspeaker drive claimed in claim 1 is characterized in that: comprise the steps:
(1) batching, stirring ball-milling, sand milling
Stoichiometric proportion by the prescription general formula takes by weighing: Pb
3O
4, SrCO
3, ZnO, Nb
2O
5, NiO, Sb
2O
5, ZrO
2, TiO
2, MnCO
3, Li
2CO
3Mix, then it is joined in the agitating ball mill, adding deionized water in the agitating ball mill is dispersant, adding zirconia ball in the agitating ball mill is ball-milling medium, the weight ratio of deionized water and raw material is 1:1.5～2, with agitating ball mill ball milling 3～5 hours, the set of frequency of agitating ball mill upconverter is 40～45HZ, separation of oxygenated zirconium ball joins sand mill in the lump with compound, grinds 1～2 hour with sand mill, the rotating speed of sand mill is 2000～2200 rev/mins, use particle size analyzer determination, its granularity should meet d(50)=0.1～0.2um, discharging, put into thermostatic drying chamber 90～120 degree temperature dryings 8～12 hours, material is put in the Universalpulverizer again and ground, discharging is by 80 purpose standard screens;
(2) pre-burning
Material after pulverizing is placed in the alumina crucible, and compacting adds a cover, in box resistance furnace, with 800～820 degree pre-burnings insulations 2～4 hours, naturally cool to room temperature, come out of the stove;
(3) sand milling and oven dry
Smashing and put into the pre-burning powder to pieces Universalpulverizer grinds, discharging, by 80 purpose standard screens, pack into the powder after grinding in the Stainless steel basin and add deionized water, be moved in the lump in the sand mill after stirring, the weight ratio of deionized water and powder is 1:1.5～2, ground 1～2 hour with sand mill, the rotating speed of sand mill is 2000～2200 rev/mins, discharging is put into clean stainless steel drip pan with compound and is transplanted on thermostatic drying chamber 80～120 degree oven dry 8～12 hours, material is joined in the Universalpulverizer to grind again, discharging is by 100 purpose standard screens;
(4) preparation of curtain coating slurry
Porcelain powder and solvent are joined in the ball grinder by a certain percentage, and to add zirconia ball be ball-milling medium that ball milling disperseed 5～10 hours, added afterwards adhesive and continued ball milling 10～15 hours, filtered discharging,
Wherein: solvent is toluene or dimethylbenzene and absolute alcohol, and the ratio of itself and porcelain powder is: 0.30～0.35:1;
The 26%PVB toluene solution as the ratio of adhesive and porcelain powder is: 0.25～0.35:1; The ratio of zirconia ball and porcelain powder is: 1.5～2.0:1;
(5) casting film-forming
Be deaeration 1～2 hour under the condition of 0.050～0.065MPa in vacuum degree with the curtain coating of above-mentioned filtration discharging slurry, left standstill 10～12 hours, carry out casting film-forming with casting machine afterwards, belt speed is controlled at 500～1200rpm, and the baking temperature of each temperature province of casting machine is: 60～90,90～100,90～110 degree; Simultaneously, also must regulate the size of the exhausting amount of diaphragm drying; The THICKNESS CONTROL of diaphragm is at 20～50um, and is certain, different thickness, the temperature and the exhausting amount that need to regulate dry section; Casting machine automatically is cut into diaphragm and sets the diaphragm that needs size;
(6) printing lamination
Adjust automatic charging printing lamination machine, mainly comprise adjusting and process pressing base, net, adjustment scraper plate and drying baker are transferred to the temperature of setting; With the printing material of fine silver slurry as electrode, spread the above-mentioned diaphragm of one deck on the printing support plate, by the web plate seal one deck that designs, oven dry, temperature is 60～80 degree; Repave one deck diaphragm, pressing, its pressing pressure is 15～25MPa, printing; So repeat, by the requirement of multilayer piezoelectric speaker driver, be laminated to 3～5 layers to diaphragm, diaphragm is taken off and diaphragm is encapsulated in the special plastic bag of PE with vacuum packing machine from the printing support plate, palpus guarantees air tight, and the diaphragm after the justifying printing has comprised a plurality of blanks;
(7) lamination
The above-mentioned packaging bag that the good diaphragm of printing lamination is housed is put into the balancer such as Intelligent hot and carry out lamination, make its each interlayer finer and close under certain temperature and pressure; The temperature of lamination is 55～70 degree, and pressure is 20～50Mpa;
(8) cutting
After lamination is complete, carefully cut off plastic packaging bag, take out to give birth to diaphragm, the line of cut that gets on by printing cuts into the blank of single multilayer piezoelectric ceramic for loudspeaker drive; This blank is carefully dipped in upper silver slurry with writing brush carry out end-blocking by polarity;
(9) binder removal
The blank that above-mentioned end-blocking is good is put into chamber type electric resistance furnace or continuous tunnel furnace, and temperature 280～350 degree are incubated 25～50 hours and carry out the organic substance eliminating, are warmed up to 500～700 degree again, and are last, naturally cool to room temperature with stove;
(10) sintering
The blank of above-mentioned binder removal is put in box sintering furnace or the tunnel sintering furnace, and tipped upside down on the blank with square alumina crucible and to seal, 2～5 degrees/mins of programming rates 900～920 degree sintered heat insulatings 2～4 hours, naturally cool to room temperature with stove;
(11) polarization
The device that sinters is placed in the special-purpose anchor clamps, with the anchor clamps of integral body put into be heated in the baking oven 180～260 the degree, under this temperature, apply the direct voltage of 25～38V to device, continue 15～30 minutes, be prepared into the multilayer piezoelectric ceramic for loudspeaker driver.
3. according to the manufacture method of multilayer piezoelectric ceramic for loudspeaker drive claimed in claim 2, it is characterized in that: in described batching, stirring ball-milling, sand milling processing step (1), compound is joined sand mill in the lump, ground 1.5 hours with sand mill, the rotating speed of sand mill is 2000 rev/mins, use particle size analyzer determination, its granularity should meet d(50)=0.1～0.15um.
4. according to the manufacture method of multilayer piezoelectric ceramic for loudspeaker drive claimed in claim 2, it is characterized in that: in described pre-sinter process step (2), material after pulverizing is placed in the alumina crucible, and compacting adds a cover, and 800～820 degree pre-burnings insulations are 2～3 hours in box resistance furnace.
5. according to the manufacture method of multilayer piezoelectric ceramic for loudspeaker drive claimed in claim 2, it is characterized in that: in described sintering process step (10), the blank of above-mentioned binder removal is put in box sintering furnace or the tunnel sintering furnace, and tip upside down on the blank with square alumina crucible and to seal, 2～3 degrees/mins of programming rates are spent sintered heat insulatings 2～3 hours 900～920.
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| CN108358629A (en) * | 2018-01-27 | 2018-08-03 | 天津大学 | The preparation of low temperature co-fired self-supporting PZT bases multi-layer piezoelectric thick film |
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| CN103200507B (en) * | 2012-01-10 | 2017-05-17 | 广东捷成科创电子股份有限公司 | Manufacturing method of multi-layer piezoelectric loudspeaker oscillator and multi-layer piezoelectric loudspeaker oscillator |
| CN103424065A (en) * | 2013-07-29 | 2013-12-04 | 中国原子能科学研究院 | Small distance measuring method |
| CN104525942B (en) * | 2014-12-19 | 2017-05-31 | 深圳顺络电子股份有限公司 | Preparation method, slice component of soft magnetic metal composite and preparation method thereof |
| CN108882130B (en) * | 2018-07-24 | 2020-07-14 | 西安创联电气科技（集团）有限责任公司 | Piezoelectric automobile loudspeaker |
| CN110950658A (en) * | 2018-09-27 | 2020-04-03 | 湖南嘉业达电子有限公司 | Preparation method of power type piezoelectric ceramic capable of being sintered at low temperature |
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| CN1839487A (en) * | 2003-08-21 | 2006-09-27 | 日本碍子株式会社 | Piezoelectric/electrostrictive device |
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