# Patent

## Title
Piezoelectric oriented ceramics and method of manufacturing the same

## Abstract

Piezoelectric oriented ceramics containing a Pb(Ti, Zr)O3-based compound having a high degree of orientation not lower than 0.64, which was calculated with the Lotgering method based on an X-ray diffraction pattern in a prescribed cross-section thereof, and having a sintered density not lower than 85% of a theoretical density.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
The present application is a continuation of International application No. PCT/JP2012/080146, filed Nov. 21, 2012, which claims priority to Japanese Patent Application No. 2011-271623, filed Dec. 12, 2011, the entire contents of each of which are incorporated herein by reference.


FIELD OF THE INVENTION
This invention relates to a piezoelectric material, and particularly to crystallographically oriented piezoelectric oriented ceramics and a method of manufacturing the same.
BACKGROUND OF THE INVENTION
Piezoelectric oriented ceramics having a perovskite structure has conventionally been employed as a dielectric material or a piezoelectric material. It has been known that electrical characteristics of the piezoelectric oriented ceramics having such a perovskite structure are improved by orienting crystals thereof.
For example, a technique described in PTD 1 has been proposed as a method of fabricating piezoelectric oriented ceramics having a perovskite structure. With the technique described in PTD 1, piezoelectric oriented ceramics high in crystal orientation is obtained by forming slurry containing a perovskite structure compound mainly composed, for example, of PbTiO3 in magnetic field to thereby fabricate a ceramic compact and firing the fabricated compact.
PTD 1: Japanese Patent Laying-Open No. 2010-090021
SUMMARY OF THE INVENTION
When the manufacturing method described in PTD 1 is applied to fabrication of piezoelectric oriented ceramics containing lead zirconate titanate (hereinafter referred to as a Pb(Ti, Zr)O3-based compound), however, in a sintering process, crystal orientation is lost and hence piezoelectric oriented ceramics containing a Pb(Ti, Zr)O3-based compound could not be obtained. The reason may be because a Pb(Ti, Zr)O3-based compound contains two types of elements occupying a B site of an ABO3-type crystal and hence mutual diffusion of Ti and Zr during a sintering process significantly disturbs a crystal state, which results in loss of crystal orientation.
Therefore, a primary object of this invention is to provide piezoelectric oriented ceramics which is mainly composed of a Pb(Ti, Zr)O3-based compound as a compound having a perovskite structure and has high crystal orientation and a method of manufacturing the same.
Piezoelectric oriented ceramics according to this invention mainly composed of a Pb(Ti, Zr)O3-based compound having a perovskite structure has a degree of orientation not lower than 0.64, which is calculated with the Lotgering method based on an X-ray diffraction pattern in a prescribed cross-section thereof, and has sintered density not lower than 85% of theoretical density.
The piezoelectric oriented ceramics according to this invention is preferably formed of spherical particles.
A method of manufacturing piezoelectric oriented ceramics according to this invention having a degree of orientation not lower than 0.64, which is calculated with the Lotgering method based on an X-ray diffraction pattern in a prescribed cross-section thereof, includes the steps of preparing single crystal powders containing a Pb(Ti, Zr)O3-based compound having a perovskite structure, fabricating slurry containing the single crystal powders as a dispersion phase, obtaining a compact by forming the slurry in magnetic field, and firing the compact, and in the step of firing the compact, the compact is held and fired for 24 hours or longer at a temperature lower by at least 100° C. than a firing temperature lowest among firing temperatures at which sintered density is not lower than 85% of theoretical density in a case of firing under such a condition that a time period for holding a firing temperature is set to 3 hours.
According to the piezoelectric oriented ceramics in this invention, piezoelectric oriented ceramics mainly composed of a Pb(Ti, Zr)O3-based compound and having high crystal orientation and high sintered density can be obtained.
The reason why even piezoelectric oriented ceramics containing a Pb(Ti, Zr)O3-based compound does not lose crystal orientation can be estimated as follows. Namely, it is estimated that, by suppressing a firing temperature and extending a time period for firing in the step of firing the compact containing the Pb(Ti, Zr)O3-based compound, while disturbance of a crystal state due to mutual diffusion of Ti and Zr too abrupt to lose crystal orientation is suppressed, mass transfer sufficient for sintering can be brought about.
The foregoing and other objects, features, and advantages of this invention will become more apparent from the following description of an embodiment for carrying out the invention provided with reference to the drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an SEM image of Pb(Ti0.7Zr0.3)O3 particles according to sample 1 fabricated in an experimental example.
FIG. 2 is a diagram showing sintered density corresponding to each firing temperature of a sintered object of piezoelectric oriented ceramics fired under a condition of holding for 3 hours with a firing temperature being varied, in the step of firing piezoelectric oriented ceramics.
FIG. 3 is a diagram showing specific resistance ρ of the sintered object of piezoelectric oriented ceramics obtained for each firing temperature.
FIG. 4 shows an XRD chart in a prescribed cross-section of the sintered object of the piezoelectric oriented ceramics, with (a) showing an XRD chart of sample 1, (b) showing an XRD chart of sample 2, and (c) showing an XRD chart of sample 3.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
One embodiment of piezoelectric oriented ceramics and a method of manufacturing the same according to the present invention will be described.
(Piezoelectric Oriented Ceramics)
Piezoelectric oriented ceramics according to the present invention is mainly composed of a Pb(Ti, Zr)O3-based compound having a perovskite structure. Particles forming this piezoelectric oriented ceramics are preferably spherical. This is because, when particles forming piezoelectric oriented ceramics are spherical, generation or development of a crack is less likely.
The piezoelectric oriented ceramics according to the present invention has a degree of orientation of a first axis not lower than 0.64, which is calculated with the Lotgering method based on an X-ray Diffraction (XRD) pattern in a prescribed cross-section thereof, and has high crystal orientation. The Lotgering method will be described in detail later.
The piezoelectric oriented ceramics according to the present invention has sintered density not lower than 85% of theoretical density thereof. Theoretical density is calculated, for example, from a size of a unit cell found by analyzing results of measurement with the X-ray diffraction method and an atomic weight. It is noted that this theoretical density ρtheo is represented in the following expression (1):

ρtheo=Wunit/Vunit  (1)

where Wunit represents a weight per unit cell and Vunit represents a volume per unit cell.
Therefore, the piezoelectric oriented ceramics according to the present invention is mainly composed of a Pb(Ti, Zr)O3-based compound high in crystal orientation of one of three crystal axes of ceramic particles.
(Method of Manufacturing Piezoelectric Oriented Ceramics)
An embodiment of a method of manufacturing piezoelectric oriented ceramics according to the present invention will now be described.
In order to manufacture piezoelectric oriented ceramics according to the present invention, powders containing a Pb(Ti, Zr)O3-based compound having a perovskite structure are prepared. In order to prepare the powders containing the Pb(Ti, Zr)O3-based compound, for example, source materials such as PbO, TiO2, and ZrO2 are wet-mixed, followed by drying by calcination, so that a calcined product of the Pb(Ti, Zr)O3-based compound is fabricated. Then, this calcined product is dry-crushed to fabricate calcined powders. In succession, these calcined powders are subjected to heat treatment in flux. Thus, a crystal of a perovskite structure compound is grown, to prepare single crystal powders containing the Pb(Ti, Zr)O3-based compound. It is noted that these single crystal particles are spherical. At least one of KCl and NaCl is advantageously employed as the flux.
In succession, slurry containing the single crystal powders prepared with the method above is fabricated as a dispersion phase. Then, the fabricated slurry is formed in magnetic field, to thereby obtain a compact. By thus forming slurry in magnetic field, an axis of a crystal contained in the compact is oriented in a prescribed direction in accordance with applied magnetic field.
Then, the compact manufactured with the method above is fired to thereby obtain piezoelectric oriented ceramics. Initially, the compact is held and fired for 24 hours or longer at a temperature lower by at least 100° C. than a firing temperature lowest among firing temperatures at which sintered density is not lower than 85% of theoretical density in a case that the compact is fired under such a condition that a time period for holding a firing temperature is set to 3 hours.
Namely, when a compact is fired under such a condition that a time period for holding a firing temperature is set to 3 hours, a firing temperature at which sintered density of 85% of theoretical density is obtained is from 1100 to 1150° C. Therefore, desired piezoelectric oriented ceramics can be fabricated by holding and firing the compact for 24 hours or longer at 1000° C. which is lower by at least 100° C. than the firing temperature. It is noted that the temperature for thus holding for 24 hours or longer is preferably not lower than 950° C. and not higher than 1000° C.
According to the method of manufacturing piezoelectric oriented ceramics in the present invention, a sintered object of piezoelectric oriented ceramics containing a Pb(Ti, Zr)O3-based compound as a compound having a perovskite structure, which has a degree of orientation of the first axis not lower than 0.64, which is calculated with the Lotgering method based on an X-ray diffraction (XRD) pattern in a prescribed cross-section of the piezoelectric oriented ceramics, can be obtained.
An experimental example conducted for confirming an effect of the method of manufacturing piezoelectric oriented ceramics according to the present invention and piezoelectric oriented ceramics fabricated with the manufacturing method will be described below.
1. Fabrication of Sample
(Sample 1)
Sample 1 was fabricated with a fabrication method described below.
PbO, TiO2, and ZrO2 were weighed such that a molar ratio among Pb, Ti, and Zr was set to 1:0.7:0.3 and they were wet-mixed in a ball mill for 15 hours, followed by drying by calcination at 900° C. Thus, a calcined product of Pb(Ti0.7Zr0.3)O3 was obtained.
In succession, the obtained calcined product was dry-crushed and mixed with KCl such that a weight ratio was set to 1:1. This mixture was subjected to heat treatment in an alumina crucible at 1000° C. for 12 hours, followed by cooling to a room temperature. Then, KCl was dissolved in water and removed, followed by drying. Pb(Ti0.7Zr0.3)O3 grown as crystal to particles formed of single crystal was thus obtained. Here, FIG. 1 shows an SEM image of resultant Pb(Ti0.7Zr0.3)O3 crystal particles. As shown in FIG. 1, crystal particles of Pb(Ti0.7Zr0.3)O3 are spherical.
Then, 30 g of Pb(Ti0.7Zr0.3)O3 particles grown as crystal was taken. To 100 parts by weight of these Pb(Ti0.7Zr0.3)O3 particles, 0.5 part by weight of polyvinyl alcohol and 40 parts by weight of pure water were added, and they were mixed in a ball mill for 12 hours, to thereby obtain slurry.
Then, the resultant slurry was molded in magnetic field of 12T, and a compact in which crystals were oriented was obtained. The resultant compact was fired under such a condition that a time period for holding a firing temperature was set to 3 hours, with a firing temperature being varied by 50° C. between 1000° C. and 1200° C. Five sintered objects in total at respective firing temperatures were thus obtained.
Here, sintered density of each sintered object obtained by varying a firing temperature was measured, and results in FIG. 2 were obtained. It is noted that 85% of theoretical density is shown with a dashed line in FIG. 2. FIG. 3 shows specific resistance ρ of each sintered object obtained by varying a firing temperature. Here, though specific resistance ρ is desirably not lower than 1.0×108 Ωm in terms of polarization treatment, it was clear from FIG. 2 that sintered density should be not lower than 85% of theoretical density for a sintered object having necessary specific resistance ρ in FIG. 3. In addition, it was clear from FIG. 2 that a firing temperature at which sintered density of 85% of theoretical density is obtained was between 1100 and 1150° C.
It is noted that sintered density of each sintered object obtained for each firing temperature above was measured with the Archimedean method. Theoretical density was 8.05 g/cm3. Namely, by analyzing results of measurement with the X-ray diffraction method, Vunit representing a volume per unit cell was 6.52×10−23 cm3 and Wunit representing a weight per unit cell was 5.25×10−22 g, and hence theoretical density was calculated from the expression (1) based thereon. Specific resistance ρ of each sintered object was calculated by applying a DC voltage of 100 V to each sintered object for precharging for 15 seconds and thereafter measuring a current which flows through each sintered object.
By holding and firing the compact obtained with the method described above for 24 hours at 1000° C. based on the results in FIGS. 2 and 3, a sintered object (sample 1) was obtained.
(Sample 2)
Sample 2 was fabricated with a fabrication method described below.
PbO, TiO2, and ZrO2 were weighed such that a molar ratio among Pb, Ti, and Zr was set to 1:0.7:0.3 and they were wet-mixed in a ball mill for 15 hours, followed by drying by calcination at 900° C. Thus, a calcined product of Pb(Ti0.7Zr0.3)O3 was obtained.
In succession, the obtained calcined product was dry-crushed and mixed with KCl such that a weight ratio was set to 1:1. This mixture was subjected to heat treatment in an alumina crucible at 1000° C. for 12 hours, followed by cooling to a room temperature. Then, KCl was dissolved in water and removed, followed by drying. Pb(Ti0.7Zr0.3)O3 grown as crystal to single crystal particles was thus obtained.
Then, 30 g of Pb(Ti0.7Zr0.3)O3 particles grown as crystal, which were obtained with the method described above, was taken. To 100 parts by weight of these Pb(Ti0.7Zr0.3)O3 particles, 0.5 part by weight of polyvinyl alcohol and 40 parts by weight of pure water were added and they were mixed in a ball mill for 12 hours, to thereby obtain slurry.
Then, the resultant slurry was molded in magnetic field of 12T, and a compact in which crystals were oriented was obtained. This compact was held and fired at 1150° C. for 3 hours to thereby obtain a sintered object (sample 2).
(Sample 3)
Sample 3 was fabricated with a fabrication method described below.
PbO, TiO2, and ZrO2 were weighed such that a molar ratio among Pb, Ti, and Zr was set to 1:0.7:0.3 and they were wet-mixed in a ball mill for 15 hours, followed by drying by calcination at 900° C. Thus, a calcined product of Pb(Ti0.7Zr0.3)O3 was obtained.
In succession, the obtained calcined product was dry-crushed and mixed with KCl such that a weight ratio was set to 1:1. This mixture was subjected to heat treatment in an alumina crucible at 1000° C. for 12 hours, followed by cooling to a room temperature. Then, KCl was dissolved in water and removed, followed by drying. Pb(Ti0.7Zr0.3)O3 grown as crystal to single crystal particles was thus obtained.
Then, 30 g of Pb(Ti0.7Zr0.3)O3 particles grown as crystal, which were obtained with the method described above, was taken. To 100 parts by weight of these Pb(Ti0.7Zr0.3)O3 particles, 0.5 part by weight of polyvinyl alcohol and 40 parts by weight of pure water were added and they were mixed in a ball mill for 12 hours, to thereby obtain slurry.
Then, the resultant slurry was molded in magnetic field of 12T, and a compact in which crystals were oriented was obtained. This compact was held and fired at 1000° C. for 3 hours, to thereby obtain a sintered object (sample 3).
2. Evaluation
Then, a degree of orientation in a prescribed cross-section of a sintered object of each sample obtained with the fabrication method described above was calculated from the following expression (2) with the Lotgering method. In calculation of the degree of orientation, a sintered object of Pb(Ti, Zr)O3 obtained by firing a compact formed without application of magnetic field was employed as a reference sample.




  
    
      
        
          Degree
          ⁢
          
            
          
          ⁢
          of
          ⁢
          
            
          
          ⁢
          Orientation
          ⁢
          
            
          
          ⁢
          F
        
        =
        
          
            
              
                
                  Σ
                  ⁢
                  
                    
                  
                  ⁢
                  
                    I
                    ⁡
                    
                      (
                      
                        H
                        ⁢
                        
                          
                        
                        ⁢
                        K
                        ⁢
                        
                          
                        
                        ⁢
                        L
                      
                      )
                    
                  
                
                
                  Σ
                  ⁢
                  
                    
                  
                  ⁢
                  
                    I
                    ⁡
                    
                      (
                      hkl
                      )
                    
                  
                
              
              -
              
                
                  Σ
                  ⁢
                  
                    
                  
                  ⁢
                  
                    
                      I
                      0
                    
                    ⁡
                    
                      (
                      
                        H
                        ⁢
                        
                          
                        
                        ⁢
                        K
                        ⁢
                        
                          
                        
                        ⁢
                        L
                      
                      )
                    
                  
                
                
                  Σ
                  ⁢
                  
                    
                  
                  ⁢
                  
                    
                      I
                      0
                    
                    ⁡
                    
                      (
                      hkl
                      )
                    
                  
                
              
            
            
              1
              -
              
                
                  Σ
                  ⁢
                  
                    
                  
                  ⁢
                  
                    
                      I
                      0
                    
                    ⁡
                    
                      (
                      
                        H
                        ⁢
                        
                          
                        
                        ⁢
                        K
                        ⁢
                        
                          
                        
                        ⁢
                        L
                      
                      )
                    
                  
                
                
                  Σ
                  ⁢
                  
                    
                  
                  ⁢
                  
                    
                      I
                      0
                    
                    ⁡
                    
                      (
                      hkl
                      )
                    
                  
                
              
            
          
          ×
          100
        
      
    
    
      
        Expression
        ⁢
        
          
        
        ⁢
        2
      
    
  




Here, ΣI(HKL) represents the total sum of X-ray peak intensities of specific crystal planes (HKL) of a sintered object to be evaluated and ΣI(hkl) is the total sum of X-ray peak intensities of all crystal planes (hkl) of a sintered object to be evaluated. ΣI0(HKL) represents the total sum of X-ray peak intensities of specific crystal planes (HKL) of the reference sample, and ΣI0(hkl) represents the total sum of X-ray peak intensities of all crystal planes (hkl) of the reference sample.
A measurement condition was set to 2θ=20 to 60 deg. Intensities at <100>, <110>, <111>, <200>, <210>, and <211> were employed as intensities of X-ray peaks of all crystal planes (hkl). Intensities at <100> and <200> were employed as specific crystal planes (HKL).
Sintered density of the sintered objects of sample 1 to sample 3 was measured with the method described above.
Table 1 shows results of a degree of orientation, sintered density, and specific resistance ρ of the sintered objects of obtained sample 1 to sample 3, together with a firing condition for each sample. FIG. 4 shows an XRD chart in a prescribed cross-section of a sintered object of piezoelectric oriented ceramics, with (a) showing an XRD chart of sample 1, (b) showing an XRD chart of sample 2, and (c) showing an XRD chart of sample 3. It is noted that specific resistance ρ of each sample was calculated by applying a DC voltage of 100 V to each sample for precharging for 15 seconds and thereafter measuring a current which flowed through the sample.










TABLE 1





Sample
Sample 1
Sample 2*
Sample 3*







Firing
1000° C., 24 hr
1150° C., 3 hr
1000° C., 3 hr


Condition


Degree of
64%
25%
70%


Orientation













Sintered
7.2
g/cm3
7.4
g/cm3
5.6
g/cm3


Density


Specific
8.1 × 108
Ωm
1.6 × 109
Ωm
3.4 × 107
Ωm


Resistance ρ





*in the table indicates out of the range of the present invention.






In Table 1, sample 1 was high in degree of orientation and achieved a high value of sintered density with respect to theoretical density. It can be seen that, though sample 2 achieved a high value of sintered density with respect to theoretical density similarly to sample 1, a degree of orientation of the obtained sintered object was low. It can be seen that, though sample 3 was high in degree of orientation, sintered density was low with respect to theoretical density. Furthermore, although specific resistance ρ not lower than 1.0×108 Ωm is desirable in terms of polarization treatment, it can be seen that sample 3 does not satisfy such a condition.
According to the method of manufacturing piezoelectric oriented ceramics in the present invention, piezoelectric oriented ceramics containing a Pb(Ti, Zr)O3-based compound and having high crystal orientation can be obtained by holding and firing a compact for 24 hours or longer at a temperature lower by at least 100° C. than a firing temperature lowest among firing temperatures at which sintered density is not lower than 85% of theoretical density in a case that the compact is fired under such a condition that a time period for holding a firing temperature is set to 3 hours in the step of firing the compact containing the Pb(Ti, Zr)O3-based compound.
Though the embodiment according to the present invention is directed to piezoelectric oriented ceramics mainly composed of a PZT-based compound which is a Pb(Ti, Zr)O3-based compound, the embodiment is not limited thereto, and the method of manufacturing piezoelectric oriented ceramics according to the present invention may be applied also to fabrication of piezoelectric oriented ceramics containing a Pb{(Ni, Nb), Ti, Zr)O3-based compound containing, in addition to this PZT-based compound, Pb(Ni, Nb)O3 as a third component.

## Claims

1. Piezoelectric oriented ceramics mainly composed of a Pb(Ti,Zr)O3-based compound having a perovskite structure, having a degree of orientation not lower than 0.64, which is calculated with Lotgering method based on an X-ray diffraction pattern in a prescribed cross-section thereof, and having a sintered density not lower than 85% of a theoretical density, wherein single crystal particles forming said piezoelectric oriented ceramics are spherical.

2. The piezoelectric oriented ceramics according to claim 1, wherein said piezoelectric oriented ceramics have a specific resistance not lower than 1.0×108 Ωm.

3. A method of manufacturing piezoelectric oriented ceramics having a degree of orientation not lower than 0.64, which is calculated with Lotgering method based on an X-ray diffraction pattern in a prescribed cross-section thereof, the method comprising:
preparing single crystal powders containing a Pb(Ti,Zr)O3-based compound having a perovskite structure;
fabricating a slurry containing said single crystal powders as a dispersion phase;
obtaining a compact by forming said slurry in a magnetic field; and
firing said compact for 24 hours or longer at a temperature lower by at least 100° C. than a firing temperature at which a sintered density is not lower than 85% of a theoretical density when firing for 3 hours;
wherein single crystal particles forming said piezoelectric oriented ceramics are spherical.

4. The method of manufacturing piezoelectric oriented ceramics according to claim 3, wherein the temperature is not lower than 950° C. and not higher than 1000° C.

5. The method of manufacturing piezoelectric oriented ceramics according to claim 3, wherein the magnetic field is 12T.