JPS6257594B2 - - Google Patents
Info
- Publication number
- JPS6257594B2 JPS6257594B2 JP55042611A JP4261180A JPS6257594B2 JP S6257594 B2 JPS6257594 B2 JP S6257594B2 JP 55042611 A JP55042611 A JP 55042611A JP 4261180 A JP4261180 A JP 4261180A JP S6257594 B2 JPS6257594 B2 JP S6257594B2
- Authority
- JP
- Japan
- Prior art keywords
- porcelain
- sintering
- powder
- pbf
- lead
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052573 porcelain Inorganic materials 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- -1 alkali metal salt Chemical class 0.000 claims description 4
- 238000003746 solid phase reaction Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims 2
- 238000000034 method Methods 0.000 description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 9
- 230000008878 coupling Effects 0.000 description 8
- 238000010168 coupling process Methods 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 5
- 229910052845 zircon Inorganic materials 0.000 description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】
本発明はジルコン・チタン酸鉛系圧電性磁器の
ごとき含鉛系磁器の製造方法にかかる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing lead-containing porcelain such as zircon-lead titanate-based piezoelectric porcelain.
ジルコン・チタン酸鉛を主成分とする磁器は誘
電率が高く、圧電性も大きい。そして諸特性の温
度や時間に対する信頼性も高いので、今日各種超
音波振動子やコンデンサ材料として広く実用され
ている。 Porcelain whose main ingredients are zircon and lead titanate have a high dielectric constant and high piezoelectricity. Since it has high reliability with respect to temperature and time, it is widely used today as a material for various ultrasonic transducers and capacitors.
これらの磁器は通常次の様な方法で製造されて
いる。まず、酸化鉛（PbO），酸化ジルコン
（ZrO2），酸化チタン（TiO2）及び主成分となる他
の金属酸化物粉末を化学量論的に所定量を秤量
し、ボールミル等を用いて混合する。混合粉末を
800℃程度の温度で数時間仮焼した後、所定の寸
法、形状にプレン成型する。そして1200〜1300℃
の高温で数時間焼結してはじめて磁器化する。 These porcelains are usually manufactured by the following method. First, predetermined amounts of lead oxide (PbO), zircon oxide (ZrO 2 ), titanium oxide (TiO 2 ), and other metal oxide powders as the main components are weighed stoichiometrically and mixed using a ball mill, etc. do. mixed powder
After calcining at a temperature of about 800°C for several hours, it is pre-molded into a predetermined size and shape. and 1200~1300℃
It becomes porcelain only after being sintered at high temperatures for several hours.
ところで、主成分の一つであるPbOはその融点
が1000℃以下にあるため、これ以上の温度の大気
中で焼結するとPb成分の一部が蒸発してしま
う。 By the way, since PbO, which is one of the main components, has a melting point of 1000° C. or lower, if it is sintered in the atmosphere at a temperature higher than this, part of the Pb component will evaporate.
そこで、焼結中にPbOの蒸発を防止し、化学量
論的なジルコン・チタン酸鉛系鉛器を得るために
各種の工夫がこらされている。 Therefore, various efforts have been made to prevent PbO from evaporating during sintering and to obtain stoichiometric zircon/lead titanate-based lead ware.
例えば上述した仮焼粉末のプレス成型体を
PbZrO3磁器粉末と共に白金ルツボ中に密封して
焼結する方法や、あるいはPbZrO3磁器で造られ
た容器の中へプレス成型体を入れて焼結する等の
方法がとられている。 For example, if the press-molded body of the above-mentioned calcined powder is
Methods have been used, such as sealing it in a platinum crucible with PbZrO 3 porcelain powder and sintering it, or placing a press molded body in a container made of PbZrO 3 porcelain and sintering it.
従つて白金ルツボやPbZrO3磁器粉末あるいは
PbZrO3磁器容器等を準備せねばならず、またこ
れら容器に密封する作業等は量産処理の大きな障
害となつている。 Therefore, platinum crucible, PbZrO 3 porcelain powder or
PbZrO 3 porcelain containers and the like must be prepared, and the work of sealing these containers is a major hindrance to mass production.
また、PbOの蒸気は人体に有害であるため焼結
中に発生するPbO蒸気を特殊な装置により大気中
に拡散する事を防がねばならない。従つて市販さ
れている電気炉をそのまま使用することが出来
ず、高価な特殊装置の取付けが必要である。 Furthermore, since PbO vapor is harmful to the human body, special equipment must be used to prevent the PbO vapor generated during sintering from dispersing into the atmosphere. Therefore, commercially available electric furnaces cannot be used as they are, and expensive special equipment must be installed.
以上の様な理由でジルコン・チタン酸鉛系磁器
のような含鉛系磁器は鉛を含まない他の磁器と比
較して高価なものになつている。 For the reasons mentioned above, lead-containing porcelains such as zircon-lead titanate-based porcelains are more expensive than other lead-free porcelains.
上記従来の製造法における欠点を改良した方法
として、前述のような磁器の製造工程で成分原料
あるいは仮焼粉末にアルカリ金属塩とPbF2との
混合粉末を焼結温度低下剤として添加して焼結を
行なうことにより、焼結温度をPbOの融点以下に
下げる製造法が提案されている。この方法に従え
ば700℃程度の低温で充分焼結した磁器が得ら
れ、その結果
(1)大気中で裸の状態での焼結が可能となり、焼
結工程が簡潔化されると同時に所要工数が大巾に
削減される。(2)PbO蒸気の発生に対する公害防止
設備が不要となる。(3)積層セラミツクコンデンサ
の様に磁器内部に電極を有する用途に対しては、
従来は電極材料として白金やパラジウム等の耐熱
性に優れた高価な貴金属しか用いることが出来な
かつたが本発明の方法を採用すれば内部電極材料
としてニツケルや銀等の安価な金属材料の使用が
可能となり、原料費が大巾に削減出来る。 As a method to improve the shortcomings of the conventional manufacturing methods described above, a mixed powder of alkali metal salt and PbF 2 is added as a sintering temperature lowering agent to the component raw materials or calcined powder in the porcelain manufacturing process as described above. A production method has been proposed in which the sintering temperature is lowered to below the melting point of PbO by performing sintering. If this method is followed, it is possible to obtain porcelain that is sufficiently sintered at a low temperature of about 700℃, and as a result: (1) sintering can be performed in the bare state in the atmosphere, which simplifies the sintering process and at the same time Man-hours are drastically reduced. (2) No pollution prevention equipment is required for the generation of PbO vapor. (3) For applications with electrodes inside the ceramic, such as multilayer ceramic capacitors,
Conventionally, only expensive noble metals with excellent heat resistance such as platinum and palladium could be used as electrode materials, but by adopting the method of the present invention, inexpensive metal materials such as nickel and silver can be used as internal electrode materials. This makes it possible to significantly reduce raw material costs.
ところで、アルカリ金属塩とPbF2とを組み合
せた焼結温度低下剤を使用して製造したPb
（Zr0.52Ti0.52）O3磁器の径方向振動における電気
機械結合係数Ｋrの値はその最高値が例えば特開
昭54−25909「含鉛系磁器の製造方法」によれば
Ｋr＝46％にすぎない。電気機械結合係数は圧電
材料の電気エネルギと機械エネルギの変換効率を
示す定数で、この値が大きいほど圧電材料として
は優れている。そして例えば圧電材料を超音波の
送受波用変換子として用いる場合には電気機械結
合係数の値が大きいほど送受波感度が上がる。ま
た圧力センサーとして使用する場合も、電気機械
結合係数が大きい程感度が高い。更にセラミツ
ク・フイルタやメカニカルフアルタに使用する場
合には電気機械結合係数が大きい程通過域の帯域
巾が広がる。以上の様な理由で電気機械結合係数
が大きい材料が望まれているにもかかわららず、
前述のごとくアルカリ金属とPbF2とを組み合せ
た焼結温度低下剤を用いた場合にはｋrはたかだ
か46％にすぎない。 By the way, Pb produced using a sintering temperature lowering agent that combines an alkali metal salt and PbF2
(Zr 0 . 52 Ti 0 . 52 ) O 3 The maximum value of the electromechanical coupling coefficient K r in radial vibration of porcelain is, for example, according to JP-A-54-25909 "Method for manufacturing lead-containing porcelain". K r = only 46%. The electromechanical coupling coefficient is a constant indicating the conversion efficiency between electrical energy and mechanical energy of a piezoelectric material, and the larger this value, the better the piezoelectric material. For example, when a piezoelectric material is used as a transducer for transmitting and receiving ultrasonic waves, the larger the value of the electromechanical coupling coefficient, the higher the sensitivity for transmitting and receiving waves. Also, when used as a pressure sensor, the larger the electromechanical coupling coefficient, the higher the sensitivity. Furthermore, when used in ceramic filters or mechanical filters, the larger the electromechanical coupling coefficient, the wider the pass band width. Despite the desire for materials with a large electromechanical coupling coefficient for the reasons mentioned above,
As mentioned above, when a sintering temperature lowering agent combining an alkali metal and PbF 2 is used, k r is only 46% at most.
本発明はアルカリ金属塩とPbF2とをあらかじ
め固相反応せしめ、その粉末を磁器の主成分原料
の仮焼粉末に添加して焼結する事を特徴としてお
り、その目的は低温で焼結出来る利点を維持した
まま、従来法より更に大きな圧電性を示す磁器を
得ることにある。 The present invention is characterized in that an alkali metal salt and PbF 2 are subjected to a solid phase reaction in advance, and the resulting powder is added to the calcined powder, which is the main component raw material for porcelain, and sintered. The object of the present invention is to obtain porcelain that exhibits even greater piezoelectricity than conventional methods while maintaining its advantages.
以下実施例に沿つて本発明の詳細な説明を行な
う。 The present invention will be described in detail below with reference to Examples.
実施例
成分原料として酸化鉛（PbO），酸化ジルコン
（ZrO2）及び酸化チタン（TiO2）の粉末を準備し
た。これらをPb（Zr0.52Ti0.48）O3になる様な割
合で秤量した後ボールミルを用いて24時間混合し
た。そして800℃の温度で２時間仮焼した。Example Powders of lead oxide (PbO), zircon oxide (ZrO 2 ), and titanium oxide (TiO 2 ) were prepared as component raw materials. These were weighed in such a proportion as to give Pb(Zr 0 . 52 Ti 0 . 48 ) O 3 and mixed for 24 hours using a ball mill. Then, it was calcined at a temperature of 800°C for 2 hours.
一方、弗化ナトリウム（NaF）と弗化鉛
（PbF2）の粉末を１対２のモル比でボールミル混
合し、450℃の温度で１時間仮焼した後擂かい機
で粉砕した粉末を用意した。この粉末を先に準備
したジルコン・チタン酸鉛仮焼粉に３〜60mol％
の範囲で添加し、ボールミルで混合した後、直径
20mm、厚さ１mmの円板にプレス成型した。この成
型体を700℃の大気中で２時間焼結し、得られた
磁器円板の上、下面を研磨後全電極を蒸着した。
最後に4KV／mmの直流電界を１時間印加して分極
処理を施し、径方向振動における電気機械結合係
数ｋrの測定を行なつた。本発明の結果を図に曲
線１で示す。 On the other hand, powders of sodium fluoride (NaF) and lead fluoride (PbF 2 ) were mixed in a ball mill at a molar ratio of 1:2, calcined at a temperature of 450°C for 1 hour, and then ground using a grinder. did. Add this powder to the previously prepared zircon/lead titanate calcined powder by 3 to 60 mol%.
After adding in the range of and mixing in a ball mill, the diameter
It was press-molded into a disc of 20 mm and 1 mm thick. This molded body was sintered in the atmosphere at 700°C for 2 hours, and after polishing the top and bottom surfaces of the resulting porcelain disk, all electrodes were deposited.
Finally, a DC electric field of 4 KV/mm was applied for 1 hour to perform polarization treatment, and the electromechanical coupling coefficient k r in radial vibration was measured. The results of the present invention are shown by curve 1 in the figure.
なお、同図にはNaFとPbF2の原料粉末をPb
（Zr0.52Ti0.48）O3の仮焼粉末に添加して得られた
結果も曲線２として同時に示されている。 In addition, the same figure shows raw material powders of NaF and PbF 2 as Pb
The results obtained by adding (Zr 0 . 52 Ti 0 . 48 ) O 3 to the calcined powder are also shown as curve 2 at the same time.
本図から明らかな様にNaFとPbF2とはあらか
じめ固相反応せしめた粉末を用いる方が従来の原
料粉末のまま添加する場合より磁器の圧電性が改
善される事は明白である。 As is clear from this figure, it is clear that the piezoelectricity of the porcelain is improved by using a powder that has undergone a solid phase reaction with NaF and PbF 2 in comparison to adding it as a conventional raw material powder.
これはNaFあるいはPbF2単独では低温で液相
を形成しないばかりか、Pb（Zr0.52Ti0.48）O3と
個々の混入物とが液相を形成する前に反応する可
能性が強いのに対し、NaFとPbF2をあらかじめ
反応させておいた場合には上記の様に単独でPb
（Zr0.52Ti0.48）O3と反応してしまう心配が皆無
で、確実に低温度で液相を形成するためと考えら
れる。従つて２成分以上からなる焼結温度低下剤
を用いる場合には、これらをあらかじめ固相反応
させた粉末を使用する方が低温度で磁器化が進
み、圧電性も大きくなる。 This is not only because NaF or PbF 2 alone does not form a liquid phase at low temperatures, but also because Pb(Zr 0 . 52 Ti 0 . 48 ) O 3 and individual contaminants may react before forming a liquid phase. On the other hand, if NaF and PbF 2 are reacted in advance, Pb alone will react as shown above.
(Zr 0 . 52 Ti 0 . 48 ) This is thought to be because there is no fear of it reacting with O 3 and it reliably forms a liquid phase at a low temperature. Therefore, when using a sintering temperature lowering agent consisting of two or more components, it is better to use a powder obtained by subjecting these components to a solid phase reaction in advance, so that porcelain formation progresses at a lower temperature and piezoelectricity increases.
図は本発明の製造法及び従来の製造法に従つて
圧電性磁器を製造した場合に得られた電気機械結
合係数ｋrの値を示している。
１は本発明の方法によつて得られた圧電性磁器
の特性、２は従来方法によつて得られた圧電性磁
器の特性を示す。
The figure shows the values of the electromechanical coupling coefficient k r obtained when piezoelectric porcelain was manufactured according to the manufacturing method of the present invention and the conventional manufacturing method. 1 shows the characteristics of piezoelectric porcelain obtained by the method of the present invention, and 2 shows the characteristics of piezoelectric porcelain obtained by the conventional method.
Claims (1)
て焼結することによりジルコン・チタン酸鉛系磁
器を製造する方法において、前記焼結温度低下剤
としてアルカリ金属塩とPbF2とをあらかじめ固
相反応せしめたものを使用することを特徴とする
圧電性磁器の製造方法。1 In a method for producing zircon-lead titanate-based porcelain by adding a sintering temperature reducing agent to calcined raw material powder and sintering it, an alkali metal salt and PbF 2 are added in advance as the sintering temperature reducing agent. A method for producing piezoelectric porcelain characterized by using a material subjected to solid phase reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4261180A JPS56140074A (en) | 1980-04-01 | 1980-04-01 | Manufacture of piezoelectric ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4261180A JPS56140074A (en) | 1980-04-01 | 1980-04-01 | Manufacture of piezoelectric ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56140074A JPS56140074A (en) | 1981-11-02 |
| JPS6257594B2 true JPS6257594B2 (en) | 1987-12-01 |
Family
ID=12640818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4261180A Granted JPS56140074A (en) | 1980-04-01 | 1980-04-01 | Manufacture of piezoelectric ceramic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56140074A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0719485B2 (en) * | 1987-12-16 | 1995-03-06 | 住友金属鉱山株式会社 | Dielectric porcelain and method for manufacturing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5425909A (en) * | 1977-07-29 | 1979-02-27 | Nippon Electric Co | Method of making leaddcontaining ceramic |
-
1980
- 1980-04-01 JP JP4261180A patent/JPS56140074A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5425909A (en) * | 1977-07-29 | 1979-02-27 | Nippon Electric Co | Method of making leaddcontaining ceramic |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56140074A (en) | 1981-11-02 |
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