JP5050263B2 - Dielectric manufacturing method and precursor composition manufacturing method thereof - Google Patents
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Description
本発明は、マイクロ波誘電体の製造方法、及びその前駆体組成物とその製造方法に関する。 The present invention relates to a method for producing a microwave dielectric, a precursor composition thereof, and a method for producing the same.
近年、移動体通信や衛星通信等の利用の拡大に伴い、各種のマイクロ波及びミリ波帯域を利用した通信システムが急速に発展しつつある。 In recent years, with the expansion of the use of mobile communication, satellite communication, and the like, communication systems using various microwave and millimeter wave bands are rapidly developing.
マイクロ波帯域を利用する機器においては、マイクロ波誘電体材料が広く利用されている。既知のこのような材料の一つとして、ＳｎＴｉＯ４系酸化物誘電体が挙げられるが、この材料は結晶中への不純物の混入等で、比誘電率εｒや無負荷品質係数Ｑ（Ｑｕ）、共振周波数の温度係数τｆといった特性が著しく低下するという問題がある。 Microwave dielectric materials are widely used in devices that use the microwave band. As one of such known materials, SnTiO 4 oxide dielectrics can be cited. This material is mixed with impurities in the crystal, and the like, and thus the relative dielectric constant ε r and the no-load quality factor Q (Q u ), The characteristic such as the temperature coefficient τ f of the resonance frequency is remarkably deteriorated.
ＳｎＴｉＯ４系酸化物誘電体の製造方法として、例えば、非特許文献１には、９９．９％以上の純度を有する酸化チタン及び酸化スズを原料として用いることが開示されている。その製造工程は、上記の原料を所定量秤量して６時間湿式混合し、１１００℃での仮焼を施した後、１４５０℃の温度で２４時間焼成し急冷して焼結させる、というものである。 As a method for producing a SnTiO 4 -based oxide dielectric, for example, Non-Patent Document 1 discloses using titanium oxide and tin oxide having a purity of 99.9% or more as raw materials. The manufacturing process involves weighing a predetermined amount of the above raw materials, wet mixing for 6 hours, calcining at 1100 ° C., firing at 1450 ° C. for 24 hours, quenching and sintering. is there.
しかしながら、この工程においては、湿式粉砕混合であるため、例えばボールミルを用いる場合には、ボールを構成するジルコニアやアルミナなどの不純物が混入するおそれがある。さらに、粉砕、混合に６時間もの長時間を要すること、１１００℃での仮焼を要すること、仮焼後に微粉砕工程を要すること、焼結温度に１４５０℃の高温を要することなどから、設備コスト、ランニングコストの低減が困難である。このように不純物混入の抑制による材料特性の改善及びコスト低減が、課題となっている。 However, since this process is wet pulverized and mixed, for example, when a ball mill is used, impurities such as zirconia and alumina constituting the ball may be mixed. Furthermore, it takes 6 hours to pulverize and mix, requires calcination at 1100 ° C., requires a fine pulverization step after calcination, requires a high sintering temperature of 1450 ° C., etc. It is difficult to reduce costs and running costs. Thus, improvement of material properties and cost reduction due to suppression of impurity contamination are problems.
一般的に、高純度の金属酸化物を得る方法として、ゾル・ゲル法等の溶液中での合成方法が挙げられる。これを誘電体に応用した技術が、多数開示されているものの、ＳｎＴｉＯ４合成については実施例がない。 In general, a method for obtaining a high-purity metal oxide includes a synthesis method in a solution such as a sol-gel method. Although many technologies that apply this to dielectrics have been disclosed, there is no example of SnTiO 4 synthesis.
特許文献１には、パイロクロア型Ｓｎ２Ｔｉ２Ｏ７を前駆体としてそれを酸素ガスまたは酸素ガスと不活性ガスの混合ガス中で熱処理することによりＳｎＴｉＯ４を生成する方法が開示されている。 Patent Document 1 discloses a method for producing SnTiO 4 by heat treating it in oxygen gas or a mixed gas of an oxygen gas and an inert gas using pyrochlore type Sn 2 Ti 2 O 7 as a precursor.
しかしながら、上記前駆体Ｓｎ２Ｔｉ２Ｏ７を得るためには、９００℃〜１０００℃で５〜２０時間の焼成を要し、焼成試料中に不純物として金属Ｓｎが含まれてしまうといった問題点がある。 However, in order to obtain the precursor Sn 2 Ti 2 O 7 , firing at 900 ° C. to 1000 ° C. for 5 to 20 hours is required, and the fired sample contains metal Sn as an impurity. is there.
従って、本発明の技術的課題は、ＳｎＴｉＯ４系の酸化物誘電体の製造方法において、高純度で均一な前駆体組成物の製造方法を提供することと、該前駆体組成物を従来の方法よりも低温で熱処理することにより低コストで生成でき、かつ比誘電率εｒ及び品質係数Ｑｕ値が高く、温度安定性に優れた誘電体の製造方法を提供することにある。 Accordingly, the technical problem of the present invention is to provide a method for producing a highly pure and uniform precursor composition in a method for producing a SnTiO 4 -based oxide dielectric, and to apply the precursor composition to a conventional method. can be generated at low cost by a heat treatment at a temperature lower than, and the relative dielectric constant epsilon r and the quality factor Q u value is high, it is to provide a method for producing a temperature stability better Yuden body.
本発明は、水または有機溶媒中に原料を溶融させ高温高圧下での反応を利用することにより合成された化合物を前駆体とし、それを焼成に供することを検討した結果なされたものである。 The present invention has been made as a result of investigating using a compound synthesized by melting a raw material in water or an organic solvent and utilizing a reaction under high temperature and pressure as a precursor, and subjecting it to firing.
即ち、本発明は、誘電体粉末を製造するために用いられるＳｎ及びＴｉを構成元素とするパイロクロア型酸化物からなり、その化学式がＳｎ ２ Ｔｉ ２ Ｏ ６ で表される前駆体組成物を製造する方法であって、スズ塩化物又はフッ化物とチタン塩化物又はアルコキシドとをアンモニア水あるいは水酸化カリウム溶液の溶媒中で混合し、反応させた後乾燥・焼成することを特徴とする前駆体組成物の製造方法である。 That is , the present invention produces a precursor composition comprising a pyrochlore type oxide having Sn and Ti as constituent elements used for producing dielectric powder, the chemical formula of which is represented by Sn 2 Ti 2 O 6. A precursor composition characterized in that tin chloride or fluoride and titanium chloride or alkoxide are mixed in a solvent of aqueous ammonia or potassium hydroxide solution, reacted, dried and fired. It is a manufacturing method of a thing.
また、本発明は、化学式ＳｎＴｉＯ４で表される誘電体の製造方法において、Ｓｎ及びＴｉを構成元素とするパイロクロア型酸化物からなり、その化学式がＳｎ ２ Ｔｉ ２ Ｏ ６ で表される前駆体組成物を用い、その前駆体組成物を３００℃以上の温度で熱処理することにより誘電体粉末を生成することを特徴とする誘電体の製造方法である。 The present invention also relates to a method for producing a dielectric represented by the chemical formula SnTiO 4 , comprising a pyrochlore type oxide having Sn and Ti as constituent elements, the precursor of which the chemical formula is represented by Sn 2 Ti 2 O 6. A dielectric manufacturing method characterized in that a dielectric powder is produced by using a composition and heat-treating the precursor composition at a temperature of 300 ° C. or higher.
さらに、本発明によれば、前記誘電体の製造方法において、前記誘電体粉末を成形して焼結することを特徴とする誘電体の製造方法が得られる。 Furthermore, according to the present invention, in the method for manufacturing a dielectric, the method for manufacturing a dielectric is characterized in that the dielectric powder is molded and sintered.
本発明では、従来方法である、出発原料の仮焼及び焼結による固相拡散で粒成長する反応と異なり、溶液中の均一系反応により酸化物が生成でき、高純度で均一な粒成長の抑制されたＳｎＴｉ系酸化物誘電体粉末が得られる。高純度で粒度分布が狭い微粉末が得られることから、従来の方法に比較して低い焼成温度でも十分に緻密化し、製造コストを低減することができる。また、このようにして得られた焼結体は、均一な組織を有し、高特性発現に繋がる、と言える。 In the present invention, unlike the conventional method in which grain growth is caused by solid phase diffusion by calcination and sintering of a starting material, an oxide can be generated by a homogeneous reaction in a solution, and high-purity and uniform grain growth is achieved. A suppressed SnTi-based oxide dielectric powder is obtained. Since a fine powder having a high purity and a narrow particle size distribution can be obtained, it can be sufficiently densified even at a lower firing temperature compared to the conventional method, and the production cost can be reduced. Moreover, it can be said that the sintered body obtained in this way has a uniform structure and leads to the expression of high characteristics.
本発明によれば、スズ塩化物又はフッ化物及びチタン塩化物又はアルコキシドをアンモニア水又は水酸化カリウム溶液の溶媒中で混合し、高温高圧下での反応を利用することにより合成された化合物を前駆体とし、それを熱処理して生成した酸化物粉末を用いることで、従来と比べて極めて低温での焼結においても十分に緻密化し、比誘電率εｒ、Ｑｕ、共振周波数の温度係数τｆといった特性が優れたマイクロ波誘電体ＳｎＴｉＯ４の製造が可能となる。 According to the present invention, a compound synthesized by mixing tin chloride or fluoride and titanium chloride or alkoxide in a solvent of aqueous ammonia or potassium hydroxide solution and utilizing a reaction under high temperature and high pressure is used as a precursor. By using an oxide powder produced by heat-treating the body, it is sufficiently densified even in sintering at a very low temperature compared to the conventional case, and the relative permittivity ε r , Q u , the temperature coefficient τ of the resonance frequency A microwave dielectric SnTiO 4 having excellent characteristics such as f can be manufactured.
本発明についてさらに詳しく説明する。 The present invention will be described in more detail.
本発明の前駆体動組成物は、Ｓｎ及びＴｉを構成元素とするパイロクロア型酸化物からなり、その化学式がＳｎ２Ｔｉ２Ｏ６で表される構成である。この前駆体組成物を製造するには、スズ塩化物又はフッ化物とチタン塩化物又はアルコキシドとをアンモニア水あるいは水酸化カリウム溶液の溶媒中で混合し、反応させた後乾燥することによる。この方法は、溶液中の均一系反応により酸化物が生成でき、高純度で均一な粒成長の抑制されたＳｎＴｉ系酸化物誘電体粉末からなる前駆体動組成物が得られる。 The precursor dynamic composition of the present invention is composed of a pyrochlore oxide having Sn and Ti as constituent elements, and the chemical formula thereof is represented by Sn 2 Ti 2 O 6 . In order to produce this precursor composition, tin chloride or fluoride and titanium chloride or alkoxide are mixed in a solvent of aqueous ammonia or potassium hydroxide solution, reacted, and then dried. In this method, an oxide can be generated by a homogeneous reaction in a solution, and a precursor dynamic composition comprising a SnTi-based oxide dielectric powder with high purity and uniform grain growth is obtained.
さらに、本発明の誘電体の製造方法は、この前駆体組成物を用いて、３００℃以上の温度で熱処理することによって、化学式ＳｎＴｉＯ４で表される誘電体粉末を製造する方法である。 Furthermore, the dielectric production method of the present invention is a method for producing a dielectric powder represented by the chemical formula SnTiO 4 by heat-treating the precursor composition at a temperature of 300 ° C. or higher.
さらに、この誘電体粉末を成形して焼結して酸化物誘電体として用いても良い。その場合、前駆体組成物を３００℃で熱処理したＳｎＴｉＯ４粉末を用いることにより、８００℃での焼結が可能であり、従来の方法に比較して低温で十分に緻密化したＳｎＴｉＯ４焼結体が得られる。 Further, the dielectric powder may be molded and sintered to be used as an oxide dielectric. In that case, by using SnTiO 4 powder obtained by heat-treating the precursor composition at 300 ° C., sintering at 800 ° C. is possible, and SnTiO 4 sintering sufficiently densified at a low temperature as compared with the conventional method. The body is obtained.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically by way of examples.
（実施例１）
１ｍｏｌ／ｌのＳｎＦ２水溶液１０ｍｌと、１ｍｏｌ／ｌのＴｉ（ｉ−Ｃ３Ｈ７Ｏ）４エタノール溶液１０ｍｌとを混合し充分に攪拌した。この混合溶液にアンモニア水を溶媒として加えたものをオートクレーブへ移し、１８０℃で１時間のマイクロ波加熱を伴うソルボサーマル合成を行った後、ろ過・水洗を行い、１０５℃で一昼夜乾燥することにより、本発明の前駆体組成物Ｓｎ２Ｔｉ２Ｏ６を得た。この粉末のＸ線回折測定結果を図１に示す。
Example 1
10 ml of 1 mol / l SnF 2 aqueous solution and 10 ml of 1 mol / l Ti (i-C 3 H 7 O) 4 ethanol solution were mixed and sufficiently stirred. A solution obtained by adding ammonia water as a solvent to this mixed solution is transferred to an autoclave, subjected to solvothermal synthesis with microwave heating at 180 ° C. for 1 hour, filtered, washed with water, and dried at 105 ° C. overnight. The precursor composition Sn 2 Ti 2 O 6 of the present invention was obtained. The X-ray diffraction measurement result of this powder is shown in FIG.
得られた前駆体組成物をアルミナ坩堝に投入し、大気雰囲気中３００℃で２時間かけて熱処理を行った。熱処理後の粉末についてＸ線回折装置（ＣｕＫα線を使用）を用いて構造同定を行った結果、ＳｎＴｉＯ４であることが確認された。またこの粉末の粒度分布を測定したところ、Ｄ５０値が０．１０μｍであり、粒度形状は非常に小さく、分布も極めて狭いものであった。続いてこの酸化物粉末を、バインダー混合、成形し、８００℃で２時間焼結した。 The obtained precursor composition was put into an alumina crucible and heat-treated at 300 ° C. for 2 hours in an air atmosphere. As a result of structural identification of the powder after heat treatment using an X-ray diffractometer (using CuKα rays), it was confirmed to be SnTiO 4 . When the particle size distribution of the powder was measured, the D50 value was 0.10 μm, the particle size shape was very small, and the distribution was extremely narrow. Subsequently, the oxide powder was mixed with a binder, formed, and sintered at 800 ° C. for 2 hours.
（実施例２）
１ｍｏｌ／ｌのＳｎＣｌ２・２Ｈ２Ｏ水溶液１０ｍｌと、１ｍｏｌ／ｌのＴｉ（ｉ−Ｃ３Ｈ７Ｏ）４エタノール溶液１０ｍｌとを混合し充分に攪拌した。この混合溶液に水酸化カリウム溶液を溶媒として加えたものをオートクレーブへ移し、２００℃で１時間のマイクロ波加熱を伴うソルボサーマル合成を行った後、ろ過・水洗を行い、１０５℃で一昼夜乾燥することにより、本発明の前駆体組成物Ｓｎ２Ｔｉ２Ｏ６を得た。
(Example 2)
10 ml of 1 mol / l SnCl 2 .2H 2 O aqueous solution and 10 ml of 1 mol / l Ti (i-C 3 H 7 O) 4 ethanol solution were mixed and sufficiently stirred. A solution obtained by adding a potassium hydroxide solution as a solvent to this mixed solution is transferred to an autoclave, subjected to solvothermal synthesis with microwave heating at 200 ° C. for 1 hour, filtered and washed, and dried at 105 ° C. overnight. Thus, the precursor composition Sn 2 Ti 2 O 6 of the present invention was obtained.
得られた前駆体組成物をアルミナ坩堝に投入し、実施例１と同様に大気雰囲気中３００℃で２時間かけて熱処理を行った。熱処理後の粉末についてＸ線回折装置を用いて構造同定を行った結果、ＳｎＴｉＯ４であることが確認された。この粉末の粒度分布を測定したところ、Ｄ５０値が０．１１μｍであり、粒度形状は非常に小さく、分布も極めて狭いものであった。続いてこの酸化物粉末を、バインダー混合、成形し、８００℃で２時間焼結した。 The obtained precursor composition was put into an alumina crucible and heat-treated at 300 ° C. for 2 hours in the air atmosphere in the same manner as in Example 1. As a result of structural identification of the powder after the heat treatment using an X-ray diffractometer, it was confirmed to be SnTiO 4 . When the particle size distribution of the powder was measured, the D50 value was 0.11 μm, the particle size shape was very small, and the distribution was extremely narrow. Subsequently, the oxide powder was mixed with a binder, formed, and sintered at 800 ° C. for 2 hours.
（比較例１）
純度が９９．９％以上のＳｎＯ２、ＴｉＯ２をＳｎＴｉＯ４の組成となるように秤量し、ボールミルを用いて２０時間混合し、１１００℃で仮焼を施した。続いて、仮焼粉をボールミルで２４時間粉砕し、平均粒径が１．２μｍの酸化物粉末を得た。この酸化物粉末を、実施例と同様に、バインダー混合、成形し、１４５０℃の温度で５時間焼成した。なお、焼結工程において、１４５０℃に満たない温度での焼成では単相ＳｎＴｉＯ４焼結体を得ることはできなかった。
(Comparative Example 1)
SnO 2 and TiO 2 having a purity of 99.9% or more were weighed so as to have a composition of SnTiO 4 , mixed for 20 hours using a ball mill, and calcined at 1100 ° C. Subsequently, the calcined powder was pulverized with a ball mill for 24 hours to obtain an oxide powder having an average particle diameter of 1.2 μm. This oxide powder was mixed with a binder, formed, and fired at a temperature of 1450 ° C. for 5 hours in the same manner as in the Examples. In the sintering step, it was not possible to obtain a single-phase SnTiO 4 sintered body by firing at a temperature lower than 1450 ° C.
（比較例２）
純度が９９．９％以上のＳｎＯ２、ＴｉＯ２をＳｎＴｉＯ４の組成となるように秤量し、ボールミルを用いて２０時間混合し、１１００℃で仮焼を施した。続いて、仮焼粉をボールミルで３６時間粉砕し、平均粒径が１．０μｍの酸化物粉末を得た。比較例１と同様にして、酸化物誘電体を作製した。なお、この場合においても、１４５０℃に満たない温度での焼成では単相ＳｎＴｉＯ４焼結体を得ることはできなかった。
(Comparative Example 2)
SnO 2 and TiO 2 having a purity of 99.9% or more were weighed so as to have a composition of SnTiO 4 , mixed for 20 hours using a ball mill, and calcined at 1100 ° C. Subsequently, the calcined powder was pulverized by a ball mill for 36 hours to obtain an oxide powder having an average particle size of 1.0 μm. In the same manner as in Comparative Example 1, an oxide dielectric was produced. Even in this case, it was not possible to obtain a single-phase SnTiO 4 sintered body by firing at a temperature lower than 1450 ° C.
このようにして得られた、実施例、比較例の各酸化物誘電体について、焼結温度、及び、焼結体の平均の結晶粒径、比誘電率εｒ、品質係数Ｑｕ、共振周波数の温度係数τｆをそれぞれ評価した。焼結密度はアルキメデス法により測定した。また、τｆは２３〜８０℃の温度領域で測定し、τｆ＝（ｆ８０−ｆ２３）／（ｆ２３×ΔＴ）、ΔＴ＝８０℃−２３℃＝５７℃にて算出した。これらの結果を次の表１に示す。 For each of the oxide dielectrics of Examples and Comparative Examples thus obtained, the sintering temperature, the average crystal grain size of the sintered body, the relative dielectric constant ε r , the quality factor Q u , the resonance frequency The temperature coefficient τ f was evaluated. The sintered density was measured by the Archimedes method. Moreover, (tau) f was measured in the temperature range of 23-80 degreeC, and computed at (tau) f = (f80-f23) / (f23 * (DELTA) T) and (DELTA) T = 80 degreeC-23 degreeC = 57 degreeC. These results are shown in Table 1 below.
上記表１の結果によれば、本発明の製造方法を用いることによって結晶粒径の増加が抑制されるとともに、焼結密度の向上が認められる。また、εｒ、Ｑｕ、τｆのいずれの特性についても比較例よりも優れた特性を発現していることが明らかである。 According to the results in Table 1 above, the use of the production method of the present invention suppresses an increase in crystal grain size and an improvement in the sintered density. In addition, it is clear that all the characteristics of ε r , Q u , and τ f are more excellent than the comparative example.
以上の説明の通り、本発明の前駆体組成物、その製造方法、それを用いた誘電体の製造方法は、マイクロ波誘電体の製造に適用される。 As described above, the precursor composition of the present invention, the method for producing the same, and the method for producing a dielectric using the same are applied to the production of a microwave dielectric.
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| JP2003034573A (en) * | 2000-11-20 | 2003-02-07 | Kyocera Corp | Dielectric porcelain and dielectric resonator using the same |
| JP2002371074A (en) * | 2001-04-13 | 2002-12-26 | Mitsubishi Chemicals Corp | Process for producing oxirane compounds |
| JP4462850B2 (en) * | 2003-05-30 | 2010-05-12 | 独立行政法人物質・材料研究機構 | Method for producing Sn-based oxide having perovskite structure |
| US7460958B2 (en) * | 2004-10-07 | 2008-12-02 | E.I. Du Pont De Nemours And Company | Computer-implemented system and method for analyzing mixtures of gases |
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