JP2010095404A - Non-lead piezoelectric ceramic and piezoelectric, dielectric and pyroelectric element using the same - Google Patents
Non-lead piezoelectric ceramic and piezoelectric, dielectric and pyroelectric element using the same Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 71
- 239000006104 solid solution Substances 0.000 claims abstract description 23
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 8
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 8
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 8
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 8
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 8
- 229910052788 barium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 4
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 12
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- 238000005245 sintering Methods 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 15
- 230000008878 coupling Effects 0.000 description 8
- 238000010168 coupling process Methods 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 6
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- 150000001875 compounds Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
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- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- -1 Li 2 CO 3 Inorganic materials 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
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- 238000000280 densification Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
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- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
本発明は、ペロブスカイト酸化物であるニオブ酸ナトリウム（NaNbO3）とニオブ酸カリウム（KNbO3）が主体をなし、鉛を含まない圧電セラミックス組成物およびこのものを焼結して得られる圧電セラミックス、並びに当該セラミックスを用いた圧電・誘電素子に関するものである。 The present invention relates to a piezoelectric ceramic composition mainly composed of sodium niobate (NaNbO 3 ) and potassium niobate (KNbO 3 ), which are perovskite oxides, and does not contain lead, and a piezoelectric ceramic obtained by sintering the same, In addition, the present invention relates to a piezoelectric / dielectric element using the ceramic.
圧電セラミックスは、電圧をかけると伸び変形を生じるため、超音波振動子、超音波モーター、精密位置決め素子、圧電トランス等のアクチュエータとして、逆に変形を与えると電圧を発生するため、加速度センサ、カーナビゲーション用圧電ジャイロ、ソナー、超音波診断素子等のセンサとして広範な用途がある。現在、汎用されている圧電セラミックスの主流は、チタン酸ジルコン酸鉛（PZT）を主成分とし、ペロブスカイト構造(ABO3)を呈するものである。 Piezoelectric ceramics cause elongation deformation when a voltage is applied, and as an actuator such as an ultrasonic vibrator, ultrasonic motor, precision positioning element, piezoelectric transformer, etc. There are a wide range of uses as sensors for navigational piezoelectric gyros, sonars, ultrasonic diagnostic elements, and the like. At present, the mainstream of piezoelectric ceramics that are widely used is mainly composed of lead zirconate titanate (PZT) and has a perovskite structure (ABO 3 ).
このPZTセラミックスの圧電性は、菱面晶構造で反強誘電体のジルコン酸鉛（PbZrO3）と正方晶構造で強誘電体のチタン酸鉛（PbTiO3）を組み合わせたことによってもたらされるもので、菱面晶と正方晶の相境界（Morphotropic phase boundary、MPB、PbZrO3/PbTiO3＝52/48付近）付近の組成で最も高い。 Piezoelectricity of the PZT ceramics, those brought about by a combination of ferroelectric lead titanate (PbTiO 3) and lead zirconate antiferroelectric by rhombohedral structure (PbZrO 3) with tetragonal structure The composition is the highest in the vicinity of the phase boundary between rhombohedral and tetragonal crystals (Morphotropic phase boundary, MPB, PbZrO 3 / PbTiO 3 = 52/48).
一方、最近、地球環境汚染の問題から種々の材料から鉛量を低減しようという動きがあり、圧電セラミックスも例外ではない。特には、PZTは鉛を多く含んでいるので、最近では、酸性雨による鉛の溶出など地球環境におよぼす悪影響が問題となっている。
このような事情に鑑みて、PZTの特性に匹敵する非鉛系圧電セラミックス材料の開発が望まれている。
On the other hand, recently, there has been a movement to reduce the amount of lead from various materials due to the problem of global environmental pollution, and piezoelectric ceramics are no exception. In particular, since PZT contains a lot of lead, recently, adverse effects on the global environment such as elution of lead by acid rain have become a problem.
In view of such circumstances, development of a lead-free piezoelectric ceramic material comparable to the characteristics of PZT is desired.
一般式(Na,K)NbO3で表される圧電セラミックス組成物は高いキュリー温度Tcを有するため、近年、PZTを代替する非鉛圧電セラミックスの候補物質として注目されている（特許文献１−8、非特許文献１−８）。更に、最近では、(Na,K)NbO3が主体をなし、PZTと同じ菱面晶―正方晶相境界を形成したものも報告されている（特許文献９）。 Since the piezoelectric ceramic composition represented by the general formula (Na, K) NbO 3 has a high Curie temperature T c , it has recently attracted attention as a candidate material for lead-free piezoelectric ceramics replacing PZT (Patent Document 1- 8, non-patent documents 1-8). Furthermore, recently, it has been reported that (Na, K) NbO 3 is mainly composed of the same rhombohedral-tetragonal phase boundary as PZT (Patent Document 9).
しかしながら、これらの(Na,K)NbO3を主体とした非鉛圧電セラミックスは、PZTの圧電セラミックスに比べて圧電特性がまだ低く、更なる特性の向上が望まれていた。 However, these lead-free piezoelectric ceramics mainly composed of (Na, K) NbO 3 still have lower piezoelectric characteristics than PZT piezoelectric ceramics, and further improvement of the characteristics has been desired.
本発明は、上記問題点に鑑みてなされたものであり、その目的は、(Na,K)NbO3が主体をなし、優れた特性を有する環境に優しい新規なセラミックス組成物およびこのものから得られる圧電セラミックス、並びに当該セラミックスを用いた圧電・誘電素子を提供することにある。 The present invention has been made in view of the above problems, and its object is to obtain a novel environmentally friendly ceramic composition mainly composed of (Na, K) NbO 3 and having excellent characteristics, and from this. It is an object of the present invention to provide a piezoelectric ceramic and a piezoelectric / dielectric element using the ceramic.
本発明者等は、上記課題を解決するために鋭意検討した結果、本発明に到達した。
すなわち、この出願は、以下の発明を提供するものである。
〈１〉一般式{M1aLibNacKdM2e}{Ti1-u-v-q-s-tZruHfvNbsTatWq}O3で表される組成物を主成分とする圧電固溶体組成物。
（式中、M1はBa、 Sr、 Ca、Mg、(Bi0.5K0.5)、(Bi0．5Na0.5)及び(Bi0．5Li0.5)からなる群から選ばれる少なくとも一種の2価或いは2価相当の元素を示す；M2はBi,Yおよびランタノイド元素（La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu）からなる群から選ばれる少なくとも一種の3価の元素を示す。a,b,c,d,e,q,s,t,u,vの範囲がそれぞれ0＜a＜0.3、0≦b≦0.2、0.1≦c≦0.9, 0.1≦d≦0.9、0＜e≦0.10、0≦u≦0.3、0≦v≦0.3、0≦t≦0.2、0＜s≦1、0≦q≦0.10、0.06≦u+v≦0.3、a+b+c+d+e＜1、2a+b+c+d+3e+s+t+2q=2である。）
〈２〉菱面晶―正方晶の相境界を有することを特徴とする〈１〉に記載の圧電固溶体組成物。
〈３〉〈１〉〜〈２〉に記載の圧電固溶体組成物に更にAl, Ba, Bi, Ca, Ce, Cr, Cu, Dy, Er, Eu, Ga, Gd, Ge, Ho, In, Ir, K, La, Lu, Mg, Mn, Na, Nd, Pr, Ru, Sc, Si, Sm, Sn, Sr, Tb, T, V, W, Y及びYbから選ばれた少なくとも１種の金属もしくは金属化合物を添加してなる圧電固溶体組成物。
〈４〉〈１〉〜〈３〉のいずれかに記載の圧電固溶体組成物を焼結して得られる圧電セラミックス。
〈５〉〈１〉〜〈３〉のいずれかに記載の圧電固溶体組成物を焼結して得られる誘電セラミックス。
〈６〉〈１〉〜〈３〉のいずれかに記載の圧電固溶体組成物を焼結して得られる焦電セラミックス。
〈７〉相対密度が95%以上であることを特徴とする〈４〉に記載の圧電セラミックス。
〈８〉相対密度が95%以上であることを特徴とする〈５〉に記載の誘電セラミックス。
〈９〉相対密度が95%以上であることを特徴とする〈６〉に記載の焦電セラミックス。
〈１０〉〈４〉又は〈７〉に記載の圧電セラミックスを含有することを特徴とする圧電素子。
〈１１〉〈５〉又は〈８〉に記載の圧電セラミックスを含有することを特徴とする誘電素子。
〈１２〉〈６〉又は〈９〉に記載の圧電セラミックスを含有することを特徴とする焦電素子。
The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, this application provides the following invention.
<1> formula {M1 a Li b Na c K d M2 e} {Ti 1-uvqst Zr u Hf v Nb s Ta t W q} piezoelectric solid solution composition as a main component represented by the composition by O 3 .
(Wherein M1 is at least one divalent selected from the group consisting of Ba, Sr, Ca, Mg, (Bi 0.5 K 0.5 ), (Bi 0.5 Na 0.5 ) and (Bi 0.5 Li 0.5 ) or M2 is selected from the group consisting of Bi, Y and lanthanoid elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) A, b, c, d, e, q, s, t, u, v ranges 0 <a <0.3, 0 ≦ b ≦ 0.2, 0.1 ≦ c ≦, respectively. 0.9, 0.1 ≦ d ≦ 0.9, 0 <e ≦ 0.10, 0 ≦ u ≦ 0.3, 0 ≦ v ≦ 0.3, 0 ≦ t ≦ 0.2, 0 <s ≦ 1, 0 ≦ q ≦ 0.10, 0.06 ≦ u + v ≦ 0.3, a + b + c + d + e <1, 2a + b + c + d + 3e + s + t + 2q = 2.)
<2> The piezoelectric solid solution composition according to <1>, which has a rhombohedral-tetragonal phase boundary.
<3> The piezoelectric solid solution composition according to <1> to <2> is further added to Al, Ba, Bi, Ca, Ce, Cr, Cu, Dy, Er, Eu, Ga, Gd, Ge, Ho, In, Ir , K, La, Lu, Mg, Mn, Na, Nd, Pr, Ru, Sc, Si, Sm, Sn, Sr, Tb, T, V, W, Y and Yb or at least one metal selected from A piezoelectric solid solution composition obtained by adding a metal compound.
<4> Piezoelectric ceramics obtained by sintering the piezoelectric solid solution composition according to any one of <1> to <3>.
<5> A dielectric ceramic obtained by sintering the piezoelectric solid solution composition according to any one of <1> to <3>.
<6> Pyroelectric ceramics obtained by sintering the piezoelectric solid solution composition according to any one of <1> to <3>.
<7> The piezoelectric ceramic according to <4>, wherein the relative density is 95% or more.
<8> The dielectric ceramic according to <5>, wherein the relative density is 95% or more.
<9> The pyroelectric ceramic according to <6>, wherein the relative density is 95% or more.
<10> A piezoelectric element comprising the piezoelectric ceramic according to <4> or <7>.
<11> A dielectric element comprising the piezoelectric ceramic according to <5> or <8>.
<12> A pyroelectric element comprising the piezoelectric ceramic according to <6> or <9>.
本発明に係る圧電セラミックスは、鉛を含まず環境に優しい高性能圧電セラミック材料である。本発明のセラミックスは、優れた圧電定数d33を示すため、超音波振動子、超音波モーター、精密位置決め素子、圧電トランス等のアクチュエータや、航空機・自動車・鉄道車両・船舶等の振動制御や土木建築物の免振用のアクチュエータとして利用できる。また、本発明のセラミックスは、優れた誘電特性を有するため、静電容量の大きいキャパシタとして利用することが出来る。 The piezoelectric ceramic according to the present invention is a high-performance piezoelectric ceramic material that does not contain lead and is environmentally friendly. Ceramic of the present invention is excellent because of a piezoelectric constant d 33, the ultrasonic transducer, an ultrasonic motor, a precision positioning device, and an actuator such as a piezoelectric transformer, the vibration control and civil engineering, such as aircraft, automobiles, railway vehicles, ships It can be used as an actuator for building vibration isolation. Moreover, since the ceramic of the present invention has excellent dielectric properties, it can be used as a capacitor having a large capacitance.
本発明に係る圧電セラミックス組成物は、一般式{M1aLibNacKdM2e}1-m{Ti1-u-v-q-s-tZruHfvNbsTatWq}O3で表される組成物を主成分とする。
（式中、M1はBa、 Sr、 Ca、Mg、(Bi0.5K0.5)、(Bi0．5Na0.5)及び(Bi0．5Li0.5)からなる群から選ばれる少なくとも一種2価或いは2価相当の元素を示す；M2はBi,Yおよびランタノイド元素（La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu）からなる群から選ばれる少なくとも一種3価の元素を示す。a,b,c,d,e,q,s,t,u,vの範囲がそれぞれ0＜a＜0.3、0≦b≦0.2、0.1≦c≦0.9, 0.1≦d≦0.9、0＜e≦0.10、0.06＜u≦0.3、0≦u≦0.3、0≦v≦0.3、0≦t≦0.2、0＜s≦1、0≦q≦0.10、0.06≦u+v≦0.3、a+b+c+d+e＜1、2a+b+c+d+3e+s+t+2q=2である。）
The piezoelectric ceramic composition according to the present invention has a composition represented by the general formula {M1 a Li b Na c K d M2 e } 1-m {Ti 1-uvqst Zr u Hf v Nb s Ta t W q } O 3 The main component.
Wherein M1 is at least one divalent or 2 selected from the group consisting of Ba, Sr, Ca, Mg, (Bi 0.5 K 0.5 ), (Bi 0.5 Na 0.5 ) and (Bi 0.5 Li 0.5 ). M2 is selected from the group consisting of Bi, Y and lanthanoid elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) Represents at least one trivalent element, and ranges of a, b, c, d, e, q, s, t, u, v are 0 <a <0.3, 0 ≦ b ≦ 0.2, 0.1 ≦ c ≦ 0.9, 0.1 ≦ d ≦ 0.9, 0 <e ≦ 0.10, 0.06 <u ≦ 0.3, 0 ≦ u ≦ 0.3, 0 ≦ v ≦ 0.3, 0 ≦ t ≦ 0.2, 0 <s ≦ 1, 0 ≦ q ≦ 0.10, 0.06 ≦ u + v ≦ 0.3, a + b + c + d + e <1, 2a + b + c + d + 3e + s + t + 2q = 2)
本発明に係る組成物の第一の特徴は、組成物中に有害な鉛を含有していない点ある。そのため、製造プロセスにおける鉛成分の揮発および廃棄物などからの鉛の流出がなく安全であり、また、鉛を外部環境に排出させないための環境対策が不要となるので、コストの面からも有利な点である。 The first feature of the composition according to the present invention is that no harmful lead is contained in the composition. Therefore, it is safe because there is no volatilization of the lead component in the manufacturing process and no outflow of lead from waste, and environmental measures are not required to prevent lead from being discharged into the external environment, which is also advantageous from a cost standpoint. Is a point.
本発明に係る組成物の第二の特徴は、a+b+c+d+e＜1、2a+b+c+d+3e+s+t+2q=2である点である。
いわゆるペロブスカイトのＡ−サイト及び/又はＢ−サイトに価数の高い元素（例えばＡ−サイトにLa、Ｂ−サイトにW）で価数の低い元素（例えばＡ−サイトのLi, Na, K、Ｂ−サイトのTi, Nb）を置換することによって、電気的中性を保ちながら、Ａ−サイトに空孔を作ることである。Ａ−サイトに空孔があれば、強誘電ドメインが動きやすくなり、圧電特性が向上できると考えられる。
The second feature of the composition according to the present invention is that a + b + c + d + e <1, 2a + b + c + d + 3e + s + t + 2q = 2.
Elements having a high valence at the A-site and / or B-site of the so-called perovskite (for example, La at the A-site and W at the B-site) (for example, Li, Na, K at the A-site, By substituting (Ti, Nb) of the B-site, vacancies are created in the A-site while maintaining electrical neutrality. If there is a hole in the A-site, the ferroelectric domain is likely to move and the piezoelectric characteristics can be improved.
本発明に係る組成物の第三の特徴は、0.06≦u+v≦0.3である点である。特許文献９に示されるように、本発明の基本組成である、一般式{Mx(NayLizK1-y-z)1-x}1-m{(Ti1-u-vZruHfv)x(Nb1-wTaw)1-x}O3で表される組成物を主成分とする圧電固溶体組成物は、0.06≦u+vの組成で菱面晶―正方晶の相境界を形成し、誘電・圧電及び焦電特性が特に高い。本発明は、菱面晶―正方晶相境界付近の組成を基本組成にし、Ａ−サイトに空孔を作ることである。そのため、圧電特性の更なる向上が期待できる。 A third feature of the composition according to the present invention is that 0.06 ≦ u + v ≦ 0.3. As shown in Patent Document 9, the general formula {M x (Na y Li z K 1-yz ) 1-x } 1-m {(Ti 1-uv Zr u Hf v ), which is the basic composition of the present invention. A piezoelectric solid solution composition composed mainly of a composition represented by x (Nb 1-w Ta w ) 1-x } O 3 has a rhombohedral-tetragonal phase boundary with a composition of 0.06 ≦ u + v. Formed and has particularly high dielectric / piezoelectric and pyroelectric properties. In the present invention, the composition near the rhombohedral-tetragonal phase boundary is used as a basic composition, and vacancies are formed at the A-site. Therefore, further improvement in piezoelectric characteristics can be expected.
本発明に係るペロブスカイト固溶体組成物は、所望の各種金属塩、例えば炭酸塩、シュウ酸塩、硝酸塩、水酸化物、酸化物等、種々の形態のものを原料として用い、これらの原料を所定の組成に混合し、最終的に前記一般式で示される組成になるように調製することによって得ることができる。
また、その圧電セラミックスは、上記組成物を所望の組成になるように配合し、たとえばエタノールなどの溶媒中でボールミル等により混合し、この混合物を乾燥し、大気中で好ましくは仮焼する。仮焼条件は、原料の種類及び組成により異なるが、通常、温度は850〜1000℃、時間は2〜10時間である。こうして得られた仮焼後の混合物をボールミル等で粉砕し、バインダーを添加し、1軸圧力で成形した。この成形体をたとえば電気炉で高温（たとえば1000〜1300℃）にて焼成することにより得ることができる。
The perovskite solid solution composition according to the present invention uses various kinds of desired metal salts such as carbonates, oxalates, nitrates, hydroxides, oxides, and the like as raw materials. It can be obtained by mixing the composition and finally preparing it to have the composition represented by the above general formula.
The piezoelectric ceramic is blended with the above composition so as to have a desired composition, mixed with a ball mill or the like in a solvent such as ethanol, the mixture is dried, and preferably calcined in the air. Although the calcination conditions vary depending on the type and composition of the raw material, the temperature is usually 850 to 1000 ° C. and the time is 2 to 10 hours. The calcined mixture thus obtained was pulverized with a ball mill or the like, added with a binder, and molded with uniaxial pressure. This molded body can be obtained, for example, by firing at a high temperature (for example, 1000 to 1300 ° C.) in an electric furnace.
また、上記のペロブスカイト構造（ABO3）の組成式においては、Ａ-サイトを構成する原子とＢ-サイトを構成する原子が１：１となる化学量論比となることが最も好ましい。
しかし、原料秤量工程や混合工程や造粒工程や焼結工程などにおいて構成元素が化学量論比から数ｍｏｌ％程度、例えば５ｍｏｌ％以下変動することがある。また、上記のように組成比の変動により、結晶構造が単一なペロブスカイト構造ではなく数ｍｏｌ％の不純物相が生じる場合があるが、本発明の圧電固溶体組成物においては、上記のように組成比を化学量論比から数ｍｏｌ％変動しても、数ｍｏｌ％の不純物が生じる場合であっても、圧電特性などの電気的特性は大きく変化しない。
In the composition formula of the perovskite structure (ABO 3 ), it is most preferable that the stoichiometric ratio is 1: 1 so that the atoms constituting the A-site and the atoms constituting the B-site are 1: 1.
However, in the raw material weighing process, the mixing process, the granulating process, the sintering process, and the like, the constituent elements may vary from the stoichiometric ratio by about several mol%, for example, 5 mol% or less. In addition, as described above, due to the change in the composition ratio, an impurity phase of several mol% may be generated instead of a single perovskite structure. However, in the piezoelectric solid solution composition of the present invention, the composition is as described above. Even when the ratio is changed by several mol% from the stoichiometric ratio, even when several mol% of impurities are generated, the electrical characteristics such as piezoelectric characteristics do not change greatly.
また、本発明においては、上記一般式で示される圧電固溶体組成物だけではなく、該組成物に更にAl, Ba, Bi, Ca, Ce, Cr, Cu, Dy, Er, Eu, Ga, Gd, Ge, Ho, In, Ir, K, La, Lu, Mg, Mn, Na, Nd, Pr, Ru, Sc, Si, Sm, Sn, Sr, Tb, T, V, W, Y及びYbから選ばれた少なくとも１種の金属もしくは金属を含む化合物を添加した圧電固溶体組成物とすることもできる。金属の含有量は特に制約されないが、組成物全体の１５重量％以下、好ましくは１０重量％以下更に好ましくは５重量％以下である。
上記金属を含む化合物としては、所望の各種金属塩、例えば炭酸塩、シュウ酸塩、硝酸塩、水酸化物、酸化物等、種々の形態のものを原料として用いることができる。
In the present invention, not only the piezoelectric solid solution composition represented by the above general formula, but also the composition further contains Al, Ba, Bi, Ca, Ce, Cr, Cu, Dy, Er, Eu, Ga, Gd, Ge, Ho, In, Ir, K, La, Lu, Mg, Mn, Na, Nd, Pr, Ru, Sc, Si, Sm, Sn, Sr, Tb, T, V, W, Y and Yb In addition, a piezoelectric solid solution composition to which at least one metal or a compound containing a metal is added may be used. The metal content is not particularly limited, but is 15% by weight or less of the total composition, preferably 10% by weight or less, more preferably 5% by weight or less.
As the compound containing the metal, various desired metal salts such as carbonates, oxalates, nitrates, hydroxides and oxides can be used as raw materials.
この圧電固溶体組成物は、上記一般式で表される組成物を主成分とし、上記添加金属を補助成分として所定量含有するものである。そのため、上記一般式で表される組成物は燒結するとき、上記添加元素が燒結助剤として働き、緻密化しやすくなる。その結果、常圧下の燒結で98%以上という高い相対密度を有する、機械強度の優れた圧電セラミックスが得られる。
また、上記一部の添加元素（例えばMn, Al）はこれを所定の範囲内で上記一般式で表される組成物に添加し燒結することにより、緻密化および粒子の成長を促進し、これを添加していない圧電セラミックスよりも更に圧電特性・誘電特性が向上される。そのため、鉛を含有せず、優れた特性を有する環境に優しい新規な圧電セラミックス、並びに当該セラミックスを用いた圧電・誘電素子として利用することができる。
This piezoelectric solid solution composition contains a composition represented by the above general formula as a main component and a predetermined amount of the additive metal as an auxiliary component. For this reason, when the composition represented by the above general formula is sintered, the additive element functions as a sintering aid and is easily densified. As a result, a piezoelectric ceramic having excellent mechanical strength and having a high relative density of 98% or more by sintering under normal pressure can be obtained.
Further, the above-mentioned part of the additive elements (for example, Mn, Al) is added to the composition represented by the above general formula within a predetermined range and sintered to promote densification and particle growth. Piezoelectric and dielectric properties are further improved as compared with piezoelectric ceramics to which no is added. Therefore, it can be used as a new environmentally friendly piezoelectric ceramic that does not contain lead and has excellent characteristics, and a piezoelectric / dielectric element using the ceramic.
このような圧電固溶体組成物は、前記一般式で示される組成物を好ましくは仮焼させた後、Al, Ba, Bi, Ca, Ce, Cr, Cu, Dy, Er, Eu, Ga, Gd, Ge, Ho, In, Ir, K, La, Lu, Mg, Mn, Na, Nd, Pr, Ru, Sc, Si, Sm, Sn, Sr, Tb, T, V, W, Y及びYbから選ばれた少なくとも１種の金属もしくは金属を含む化合物を所望の組成になるように配合することにより得られる。
またこの圧電固溶体組成物の焼結体はこの組成物をボールミルで混合し、好ましくはバインダーを添加し、1軸圧力で成形した。この成形体を電気炉で高温たとえば1000〜1300℃にて焼成することにより得ることができる。
また、上記焼成後に得られる上記圧電セラミックスにおいては、上記添加物として添加される金属元素がペロブスカイト構造のＡ−サイト及び/又はＢ−サイトに入っても良いし、粒内或いは粒界に含有されても良い。
Such a piezoelectric solid solution composition is preferably obtained by calcining the composition represented by the above general formula, and then Al, Ba, Bi, Ca, Ce, Cr, Cu, Dy, Er, Eu, Ga, Gd, Ge, Ho, In, Ir, K, La, Lu, Mg, Mn, Na, Nd, Pr, Ru, Sc, Si, Sm, Sn, Sr, Tb, T, V, W, Y and Yb Further, it is obtained by blending at least one metal or a compound containing a metal so as to have a desired composition.
The sintered body of the piezoelectric solid solution composition was formed by mixing the composition with a ball mill, preferably adding a binder, and uniaxial pressure. This molded body can be obtained by firing at a high temperature, for example, 1000 to 1300 ° C. in an electric furnace.
Further, in the piezoelectric ceramic obtained after the firing, the metal element added as the additive may enter the A-site and / or B-site of the perovskite structure, and is contained in the grain or grain boundary. May be.
以下、本発明を実施例により更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
実施例１〜３
まず、化学的に高純度のK2CO3、Na2CO3、BaCO3、SrCO3、CaCO3、MgO、Bi2O3、Li2CO3、La2O3、Ce2O3、Pr2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Tm2O3、Yb2O3、Lu2O3、Y2O3、Nb2O5、Ta2O5、TiO2、ZrO2、HfO2及びWO3を原料として用い、所望の組成になるように配合し、エタノール中でボールミルにより混合した。次に、この混合物を乾燥し、大気中で仮焼した。仮焼条件は、原料の種類及び組成により異なるが、通常、温度は850〜1000℃、時間は2〜10時間である。こうして得られた仮焼後の混合物をボールミルで粉砕し、バインダーを添加し、1軸圧力で成形した。この成形体を電気炉で1000〜1300℃にて焼成し、緻密な圧電セラミックスペレットを得た。
Examples 1-3
First, chemically high purity K 2 CO 3 , Na 2 CO 3 , BaCO 3 , SrCO 3 , CaCO 3 , MgO, Bi 2 O 3 , Li 2 CO 3 , La 2 O 3 , Ce 2 O 3 , Pr 2 O 3 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 2 O 3 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , Lu 2 O 3 , Y 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , TiO 2 , ZrO 2 , HfO 2 and WO 3 are used as raw materials and blended to have a desired composition, Mix in a ball mill in ethanol. Next, this mixture was dried and calcined in the air. Although the calcination conditions vary depending on the type and composition of the raw material, the temperature is usually 850 to 1000 ° C. and the time is 2 to 10 hours. The calcined mixture thus obtained was pulverized with a ball mill, a binder was added, and the mixture was molded at a uniaxial pressure. The compact was fired at 1000 to 1300 ° C. in an electric furnace to obtain dense piezoelectric ceramic pellets.
得られた緻密な圧電セラミックスについては、圧電特性を評価するため、両面を鏡面研磨した後、金スパッタ膜を付け、電極とした。次に、100-180℃のシリコーンオイル中で20-50kV/cmの条件で分極処理を行った。これにより、本発明の圧電セラミックスを用いた圧電素子を得た。 The obtained dense piezoelectric ceramic was subjected to mirror polishing on both sides to evaluate piezoelectric characteristics, and then a gold sputtered film was attached to form an electrode. Next, polarization treatment was performed in 100-180 ° C. silicone oil at 20-50 kV / cm. Thereby, a piezoelectric element using the piezoelectric ceramic of the present invention was obtained.
得られた上記圧電素子について、24時間放置した後、比誘電率εr、電気機械結合係数kp、圧電d33定数を測定した。比誘電率εrの測定にはインピーダンスアナライザーを用い、測定周波数は1kHzとした。電気機械結合係数kpは、インピーダンスアナライザーを用い、共振−反共振法により測定した。圧電定数 d33の測定には、d33メータ（YE2730A、APC）を用いた。また、比誘電率ピークの温度をキュリー温度Tcとした。 The obtained piezoelectric element was allowed to stand for 24 hours, and then the relative dielectric constant ε r , electromechanical coupling coefficient k p , and piezoelectric d 33 constant were measured. An impedance analyzer was used to measure the relative dielectric constant ε r and the measurement frequency was 1 kHz. The electromechanical coupling coefficient k p was measured by a resonance-antiresonance method using an impedance analyzer. A d 33 meter (YE2730A, APC) was used to measure the piezoelectric constant d 33 . Further, the temperature of the relative dielectric constant peak was defined as the Curie temperature Tc .
本発明の実施例１〜３の圧電セラミックスの化学組成及びキュリー温度Tc、比誘電率εr、電気機械結合係数kp及び圧電定数d33を表1に示す。得られたセラミックスの相対密度は、組成及び製造法によって多少の差はあるが、ほとんどの試料において98%以上であった。
なお、比較例１は無添加試料である。
Table 1 shows the chemical composition, Curie temperature T c , relative dielectric constant ε r , electromechanical coupling coefficient k p, and piezoelectric constant d 33 of the piezoelectric ceramics of Examples 1 to 3 of the present invention. The relative density of the obtained ceramics was 98% or more in most samples, although there were some differences depending on the composition and production method.
Comparative Example 1 is an additive-free sample.
［考察］
実施例１〜３は、上記一般式{M1aLibNacKdM2e}{Ti1-u-v-q-s-tZruHfvNbsTatWq}O3において、M1として（Bi0.5K0.5）とBaとを組み合わせ、M2としてLa, a=0.08, c=0.50, d=0.50, s=0.92, u=0.06, b=q=t=v=0としつつ、M2の添加量を変化させた場合の圧電セラミックスである。
これらの圧電セラミックスは高い比誘電率εr、高いキュリー温度、50%以上の高い電気機械結合係数kp及び310pC/N以上の高い圧電定数d33を同時に有するため、アクチュエータ部品として利用することが出来る。
[Discussion]
In Examples 1 to 3, the general formula {M1 a Li b Na c K d M2 e } {Ti 1 -uvqst Zr u Hf v Nb s Ta t W q } O 3 represents (Bi 0.5 K 0.5 ) as M1. And Ba were combined, and M2 was added as La, a = 0.08, c = 0.50, d = 0.50, s = 0.92, u = 0.06, b = q = t = v = 0 In the case of piezoelectric ceramics.
These piezoelectric ceramics have high dielectric constant ε r , high Curie temperature, high electromechanical coupling coefficient k p of 50% or more and high piezoelectric constant d 33 of 310 pC / N or more, so they can be used as actuator parts I can do it.
実施例４〜５
実施例３において、仮焼後の混合物にAl化合物（Al(OH)3）或いはMn化合物（MnO2）を添加し、ボールミルで粉砕し、バインダーを添加し、1軸圧力で成形した。この成形体を電気炉で1000〜1300℃にて焼成し、緻密な圧電セラミックスペレットを得た。
得られた緻密な圧電セラミックスについては、圧電特性を評価するため、両面を鏡面研磨した後、金スパッタ膜を付け、電極とした。次に、100-180℃のシリコーンオイル中で20-50kV/cmの条件で分極処理を行った。これにより、本発明の圧電セラミックスを用いた圧電素子を得た。
得られた上記圧電素子について、24時間放置した後、比誘電率εr、電気機械結合係数kp、圧電d33定数を測定した。比誘電率εrの測定にはインピーダンスアナライザーを用い、測定周波数は1kHzとした。電気機械結合係数kpは、インピーダンスアナライザーを用い、共振−反共振法により測定した。圧電定数 d33の測定には、d33メータ（YE2730A、APC）を用いた。また、比誘電率ピークの温度をキュリー温度Tcとした。
Examples 4-5
In Example 3, an Al compound (Al (OH) 3 ) or Mn compound (MnO 2 ) was added to the mixture after calcination, pulverized with a ball mill, a binder was added, and molding was performed with uniaxial pressure. The compact was fired at 1000 to 1300 ° C. in an electric furnace to obtain dense piezoelectric ceramic pellets.
The obtained dense piezoelectric ceramic was subjected to mirror polishing on both sides to evaluate piezoelectric characteristics, and then a gold sputtered film was attached to form an electrode. Next, polarization treatment was performed in 100-180 ° C. silicone oil at 20-50 kV / cm. Thereby, a piezoelectric element using the piezoelectric ceramic of the present invention was obtained.
The obtained piezoelectric element was allowed to stand for 24 hours, and then the relative dielectric constant ε r , electromechanical coupling coefficient k p , and piezoelectric d 33 constant were measured. Ratio using an impedance analyzer for the measurement of the dielectric constant epsilon r, measurement frequency was 1 kHz. The electromechanical coupling coefficient k p was measured by a resonance-antiresonance method using an impedance analyzer. A d 33 meter (YE2730A, APC) was used to measure the piezoelectric constant d 33 . Further, the temperature of the relative dielectric constant peak was defined as the Curie temperature Tc .
本発明の実施例４の圧電セラミックスの化学組成及びキュリー温度Tc、比誘電率εr、電気機械結合係数kp及び圧電定数d33を表２に示す。得られたセラミックスの相対密度は、組成及び製造法によって多少の差はあるが、ほとんどの試料において98%以上であった。 Table 2 shows the chemical composition, Curie temperature T c , relative dielectric constant ε r , electromechanical coupling coefficient k p, and piezoelectric constant d 33 of the piezoelectric ceramic of Example 4 of the present invention. The relative density of the obtained ceramics was 98% or more in most samples, although there were some differences depending on the composition and production method.
［考察］
実施例４〜５の圧電セラミックスは、実施例３のそれに比し、更に高い比誘電率εr、50%以上の高い電気機械結合係数kp及び370pC/N以上の高い圧電定数d33を同時に有することが判る。
[Discussion]
The piezoelectric ceramics of Examples 4 to 5 simultaneously have a higher relative dielectric constant ε r , a higher electromechanical coupling coefficient k p of 50% or higher and a higher piezoelectric constant d 33 of 370 pC / N or higher than those of Example 3. It turns out that it has.
Claims (12)
（式中、M1はBa, Sr, Ca, Mg, (Bi0.5K0.5) , (Bi0．5Na0.5)及び(Bi0．5Li0.5)からなる群から選ばれる少なくとも一種の2価或いは2価相当の元素を示す；M2はBi,Yおよびランタノイド元素（La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu）からなる群から選ばれる少なくとも一種の3価の元素を示す。a,b,c,d,e,q,s,t,u,vの範囲がそれぞれ0＜a＜0.3、0≦b≦0.2、0.1≦c≦0.9, 0.1≦d≦0.9、0＜e≦0.10、0≦u≦0.3、0≦v≦0.3、0≦t≦0.2、0＜s≦1、0≦q≦0.10、0.06≦u+v≦0.3、a+b+c+d+e＜1、2a+b+c+d+3e+s+t+2q=2である。） Formula {M1 a Li b Na c K d M2 e} {Ti 1-uvqst Zr u Hf v Nb s Ta t W q} O 3 piezoelectric solid solution composition as a main component a composition represented by.
(Wherein M1 is at least one divalent selected from the group consisting of Ba, Sr, Ca, Mg, (Bi 0.5 K 0.5 ), (Bi 0.5 Na 0.5 ) and (Bi 0.5 Li 0.5 ) or M2 is selected from the group consisting of Bi, Y and lanthanoid elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) A, b, c, d, e, q, s, t, u, v ranges 0 <a <0.3, 0 ≦ b ≦ 0.2, 0.1 ≦ c ≦, respectively. 0.9, 0.1 ≦ d ≦ 0.9, 0 <e ≦ 0.10, 0 ≦ u ≦ 0.3, 0 ≦ v ≦ 0.3, 0 ≦ t ≦ 0.2, 0 <s ≦ 1, 0 ≦ q ≦ 0.10, 0.06 ≦ u + v ≦ 0.3, a + b + c + d + e <1, 2a + b + c + d + 3e + s + t + 2q = 2.)
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| WO2015033685A1 (en) * | 2013-09-06 | 2015-03-12 | 株式会社村田製作所 | Dielectric porcelain composition, and capacitor manufactured using same |
| WO2015046434A1 (en) * | 2013-09-30 | 2015-04-02 | 株式会社村田製作所 | Multilayer piezoelectric ceramic electronic component and method for manufacturing multilayer piezoelectric ceramic electronic component |
| JP2016025193A (en) * | 2014-07-18 | 2016-02-08 | 国立研究開発法人産業技術総合研究所 | Broadband high-sensitivity ae sensor |
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| CN114315350A (en) * | 2022-01-24 | 2022-04-12 | 武汉理工大学 | Sodium bismuth titanate-barium zirconate titanate lead-free wide-temperature energy storage ceramic and preparation method thereof |
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| WO2015033685A1 (en) * | 2013-09-06 | 2015-03-12 | 株式会社村田製作所 | Dielectric porcelain composition, and capacitor manufactured using same |
| WO2015046434A1 (en) * | 2013-09-30 | 2015-04-02 | 株式会社村田製作所 | Multilayer piezoelectric ceramic electronic component and method for manufacturing multilayer piezoelectric ceramic electronic component |
| JPWO2015046434A1 (en) * | 2013-09-30 | 2017-03-09 | 株式会社村田製作所 | Multilayer piezoelectric ceramic electronic component and method for manufacturing multilayer piezoelectric ceramic electronic component |
| US10014463B2 (en) | 2013-09-30 | 2018-07-03 | Murata Manufacturing Co., Ltd. | Multilayer piezoelectric ceramic electronic component and method for manufacturing multilayer piezoelectric ceramic electronic component |
| JP2016025193A (en) * | 2014-07-18 | 2016-02-08 | 国立研究開発法人産業技術総合研究所 | Broadband high-sensitivity ae sensor |
| CN110981467B (en) * | 2019-12-09 | 2020-12-29 | 华中科技大学 | Lead-free pyroelectric composite ceramic material and preparation method thereof |
| CN110981467A (en) * | 2019-12-09 | 2020-04-10 | 华中科技大学 | Lead-free pyroelectric composite ceramic material and preparation method thereof |
| CN111302798A (en) * | 2020-02-25 | 2020-06-19 | 西安工业大学 | Lanthanum oxide doped modified potassium-sodium niobate-based transparent ceramic and preparation method thereof |
| CN111302798B (en) * | 2020-02-25 | 2022-02-22 | 西安工业大学 | Lanthanum oxide doped modified potassium-sodium niobate-based transparent ceramic and preparation method thereof |
| CN114315350A (en) * | 2022-01-24 | 2022-04-12 | 武汉理工大学 | Sodium bismuth titanate-barium zirconate titanate lead-free wide-temperature energy storage ceramic and preparation method thereof |
| CN114315350B (en) * | 2022-01-24 | 2023-05-23 | 武汉理工大学 | Bismuth sodium titanate-barium zirconate titanate leadless wide-temperature energy storage ceramic and preparation method thereof |
| CN116803949A (en) * | 2023-06-27 | 2023-09-26 | 清华大学 | Sodium niobate-based antiferroelectric ceramic material, preparation method thereof and capacitor |
| CN116803949B (en) * | 2023-06-27 | 2024-05-28 | 清华大学 | Sodium niobate-based antiferroelectric ceramic material, preparation method thereof and capacitor |
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