JP2009075038A - Pressure sensitive material - Google Patents
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本発明は、圧力を印加すると電気抵抗率が変化する感圧材料に関する。 The present invention relates to a pressure-sensitive material whose electrical resistivity changes when pressure is applied.
従来から、金属または半導体素子を用いた圧力または感圧材料が一般的に使用されており、中でもシリコン単結晶からなる半導体感圧材料は、金属歪ゲージと比較し、加圧時の電気抵抗変化が大きく圧力感度が数桁優れることから幅広い応用がなされている。しかしながら、従来の半導体感圧材料は機械的強度が弱く、高圧下では単体で使用することが出来ないため耐圧容器に組み込んで測定を行っており、検出装置の構成が複雑になるとともにコスト高となる問題があった。また、１５０℃を超える高温下ではその電気特性から圧力を検出することができなくなるという問題があった。 Conventionally, pressure or pressure-sensitive materials using metals or semiconductor elements have been generally used. Among them, semiconductor pressure-sensitive materials made of silicon single crystal have a change in electrical resistance when pressurized compared to metal strain gauges. Is widely used because of its large pressure sensitivity and several orders of magnitude. However, conventional semiconductor pressure-sensitive materials have low mechanical strength and cannot be used alone under high pressure, so measurements are incorporated into pressure-resistant containers, making the configuration of the detection device complicated and costly. There was a problem. In addition, there is a problem that the pressure cannot be detected from the electrical characteristics at a high temperature exceeding 150 ° C.
この問題を解決するため高温・高圧下で使用できる感圧材料に関する研究が種々なされており、その一例が特許文献１に開示されている。特許文献１の感圧材料は、Ｓｉ３Ｎ４とＣを反応させ、ＳｉＣを析出させた、Ｓｉ３Ｎ４を主成分とする多結晶セラミックス材料であり、Ｓｉ３Ｎ４を主成分とする多結晶セラミックス材料に析出させたＳｉＣの有するピエゾ抵抗効果、すなわち、材料に圧力を加えると電気抵抗が変化する現象を利用して圧力を検出するものであり、主成分であるＳｉ３Ｎ４が高強度であるため耐圧容器等で感圧材料を保護しなくても高圧下で使用可能となり、耐熱性にも優れたＳｉ３Ｎ４とＳｉＣから構成されているので高温下での圧力検出が可能となる。 In order to solve this problem, various researches have been made on pressure-sensitive materials that can be used under high temperature and high pressure, and an example thereof is disclosed in Patent Document 1. The pressure-sensitive material of Patent Document 1 is a polycrystalline ceramic material containing Si 3 N 4 as a main component in which Si 3 N 4 and C are reacted to precipitate SiC, and Si 3 N 4 is the main component. The pressure is detected by utilizing the piezoresistance effect of SiC deposited on the polycrystalline ceramic material, that is, the phenomenon that the electrical resistance changes when pressure is applied to the material. The main component Si 3 N 4 is Because it is high strength, it can be used under high pressure without protecting the pressure sensitive material with a pressure vessel, etc., and it is composed of Si 3 N 4 and SiC with excellent heat resistance, so pressure detection at high temperature is possible. It becomes possible.
また、特許文献１と類似した構成の耐放電性複合材料が特許文献２に開示されている。特許文献２の耐放電性複合材料は、例えばＳｉ３Ｎ４等からなる絶縁性セルの中にカーボン等からなる導電性粒子を分散させ、所定の電気抵抗値を発現させたものであり、絶縁性セルに導電性粒子を３次元網目状に分散させる事により導電パスが形成され、この導電性粒子の添加量によって電気抵抗値が制御される。
本発明は、従来の感圧材料で利用されるピエゾ抵抗効果ではない別原理に基づく新規な感圧材料を提供すること、特に、高温・高圧下でも使用可能な優れた圧力感度を有する感圧材料を提供することを目的としている。 The present invention provides a novel pressure-sensitive material based on another principle that is not a piezoresistive effect used in conventional pressure-sensitive materials, in particular, pressure-sensitive material having excellent pressure sensitivity that can be used even under high temperature and high pressure. The purpose is to provide materials.
本発明は、第１の粒子を主体とした母材中に前記第１の粒子とは導電性が異なる第２の粒子が空隙を有した凝集粉として分散した感圧材料であって、前記第２の粒子の凝集粉の空隙率が２５ｖｏｌ％以上、５５ｖｏｌ％以下であり、前記第２の粒子同士の加圧による接触状態の変化により電気抵抗が変化する特性を有する感圧材料である。ここで空隙率は下記の式により算出される。
空隙率＝Ｖｖａｃ／（Ｖｖａｃ＋Ｖ２）・・・（数式１）
感圧材料の密度＝（（Ｖ１×ｄ１）＋（Ｖ２×ｄ２））／（Ｖｖａｃ＋Ｖ１＋Ｖ２）・・・（数式２）
Ｖｖａｃ：第２の粒子中の空隙の体積
Ｖ１：第１の粒子の体積
Ｖ２：第２の粒子の体積
ｄ１：第１の粒子の密度
ｄ２：第２の粒子の密度
The present invention is a pressure-sensitive material in which a second particle having a different conductivity from the first particle is dispersed in a base material mainly composed of the first particle as an agglomerated powder having a void. 2 is a pressure-sensitive material having a characteristic that the porosity of the agglomerated powder of the particles 2 is 25 vol% or more and 55 vol% or less, and the electric resistance is changed by the change of the contact state due to the pressurization of the second particles. Here, the porosity is calculated by the following equation.
Porosity = V vac / (V vac + V 2 ) (Equation 1)
Density of pressure-sensitive material = ((V 1 × d 1 ) + (V 2 × d 2 )) / (V vac + V 1 + V 2 ) (Equation 2)
V vac : volume of voids in the second particle V 1 : volume of the first particle V 2 : volume of the second particle
d 1 : density of the first particles d 2 : density of the second particles
本発明の感圧材料１は図１（a）に示すように、第１の粒子から構成される母材１１の中に第２の粒子が凝集粉１２として分散している。第２の粒子の凝集粉１２の一部を拡大して模式的に示したのが図１（ｂ）と（ｃ）である。それぞれに空隙２３，３３が存在しているのが特徴である。かかる感圧材料によれば、図1（ｂ）に示す感圧材料に圧力が作用していない又は圧力が低い状態に対し、同図（ｃ）に示す作用する圧力が増加した状態では、第２の粒子３４から構成される凝集粉１２内の空隙３３がつぶれて第２の粒子３４同士の接触面積が増加するなど両者の接触状態が変化する。この作用する圧力に応じた接触状態の変化により第２の粒子２４（３４）同士の界面の接触抵抗が変化し、その結果、作用する圧力に応じて感圧材料の電気抵抗が変化する。この時、前記第２の粒子２４からなる凝集粉１２内の空隙率が２５ｖｏｌ％以上であることで加圧時の第２の粒子同士の接触面積変化が大きくなるため高い圧力感度を有した感圧材料を得ることができる。また、この空隙率が５５ｖｏｌ％より高いと加圧時に凝集体が変形しすぎて、加圧を解除しても加圧前の状態に戻らなくなってしまい、初期抵抗値が変わってゼロ点がずれたり、材料が破壊してしまうなどの問題が生じる。 In the pressure-sensitive material 1 of the present invention, as shown in FIG. 1A, second particles are dispersed as agglomerated powder 12 in a base material 11 composed of first particles. FIGS. 1B and 1C schematically show an enlarged part of the aggregated powder 12 of the second particles. The feature is that the air gaps 23 and 33 exist respectively. According to such a pressure-sensitive material, in the state where the pressure acting on the pressure-sensitive material shown in FIG. 1 (b) is not acting or the pressure is low, The contact state between the two particles 34 changes, for example, the gap 33 in the agglomerated powder 12 composed of the two particles 34 is crushed and the contact area between the second particles 34 increases. The contact resistance at the interface between the second particles 24 (34) changes due to the change in the contact state according to the acting pressure, and as a result, the electrical resistance of the pressure-sensitive material changes according to the acting pressure. At this time, since the change in the contact area between the second particles at the time of pressurization is increased because the porosity in the aggregated powder 12 made of the second particles 24 is 25 vol% or more, a feeling having high pressure sensitivity. A pressure material can be obtained. Also, if this porosity is higher than 55 vol%, the agglomerates will be deformed too much at the time of pressurization and will not return to the state before pressurization even when the pressurization is released, the initial resistance value will change and the zero point will shift. Or the material is destroyed.
このように、上記感圧材料では導電性粒子等のピエゾ抵抗効果を利用するのではなく、第２の導電性粒子同士の接触界面における接触状態の変化、具体的に言えば接触抵抗の変化を利用して圧力を検出するので、従来のピエゾ抵抗効果を利用する感圧材料に比べて第１の粒子又は第２の粒子を広い範囲から選択することができ、工業生産上有利である。 As described above, the pressure-sensitive material does not use the piezoresistance effect of the conductive particles or the like, but changes the contact state at the contact interface between the second conductive particles, specifically, changes in the contact resistance. Since the pressure is detected by using, the first particle or the second particle can be selected from a wide range as compared with the conventional pressure-sensitive material using the piezoresistance effect, which is advantageous in industrial production.
さらに上記感圧材料において、前記第２の粒子の結晶粒径が１０ｎｍ以上、１００ｎｍ未満であることが好ましい。この粒子径の計測方法はＴＥＭ写真より結晶粒子の径を１００個測定し、その平均値より算出される値である。結晶粒径の測定方法は、粒子における最も長いところを測定した値を長軸径とし、最も短いところを測定した値を短軸径とし、その２つの値の平均値を１つの粒子の結晶粒径とした。そして得られた１００個の数値の個数平均値を結晶粒径とした。第２の粒子の結晶粒径を１００ｎｍ未満とすることで単位体積当たりの結晶粒子の数が増えると共に比表面積も増加し、第２の粒子２４同士による加圧時の接触面積変化が大きくなることで電気抵抗変化も大きくなり、より圧力感度の高い感圧材料を得ることができる。また、結晶粒径が小さいと焼結を阻害するため、第２の粒子内の空隙率も高くなり、高い圧力感度が得られる。結晶粒径が１０ｎｍよりも小さい粒子は製造が難しく、実質的に入手困難であり高コストになるために好ましくない。 Furthermore, in the pressure-sensitive material, it is preferable that the second particles have a crystal grain size of 10 nm or more and less than 100 nm. This particle diameter measurement method is a value calculated from an average value obtained by measuring 100 crystal particle diameters from a TEM photograph. The crystal grain size is measured by measuring the longest part of the particle as the major axis diameter, and measuring the shortest part as the minor axis diameter. The average of the two values is the crystal grain of one particle. The diameter. The number average value of the 100 numerical values obtained was taken as the crystal grain size. By making the crystal grain size of the second particles less than 100 nm, the number of crystal particles per unit volume increases and the specific surface area also increases, and the change in contact area during pressurization between the second particles 24 increases. As a result, the electrical resistance change also increases, and a pressure-sensitive material with higher pressure sensitivity can be obtained. Moreover, since sintering is inhibited when the crystal grain size is small, the porosity in the second particles is also increased, and high pressure sensitivity is obtained. Particles having a crystal grain size smaller than 10 nm are not preferable because they are difficult to produce, are substantially difficult to obtain, and are expensive.
さらに加えて上記感圧材料において、前記第２の粒子の粒度分布から算出される体積平均粒径が０．０５μｍ以上、５．２μｍ以下であることが好ましい。この粒度分布測定はレーザー回折・散乱式測定装置（例えば堀場製作所製、型番ＬＡ−９２０）を用いて行い、ここでの平均粒径とは粒度分布における累積５０体積％径のｄ５０のことである。これら粒度分布から算出される平均粒径の値は第２の粒子が凝集してなる凝集粉の大きさである。すなわち、粒径の小さな第２の粒子の１次粒子が凝集して大きな２次粒子として存在していることを示している。この測定は原料の段階で行うものであるが、第２の粒子は空隙を有した凝集粉の状態で母材中に分散させるために、主に難焼結材料から構成され、凝集粉は焼結の過程ではほとんど焼結されずに、焼結体中でも原料の状態とほぼ同じ状態で分散されている。この凝集粉の大きさが０．０５μｍよりも小さいと凝集粉内に存在する第２の粒子の数が少なく、第２の粒子同士の界面の面積が小さくなるために、加圧時の第２の粒子同士の接触面積変化が少なくなり高い圧力感度が得られない。また、凝集粉の平均粒径が５．２μｍよりも大きいと、凝集粉の分布が偏在し易く、材料の均質性が悪くなったり機械強度の低下が起こりやすいため好ましくない。凝集粉の平均粒径の上限は好ましくは５．０μｍである。 In addition, in the pressure-sensitive material, the volume average particle size calculated from the particle size distribution of the second particles is preferably 0.05 μm or more and 5.2 μm or less. This particle size distribution measurement is performed using a laser diffraction / scattering type measuring device (for example, model number LA-920, manufactured by Horiba, Ltd.), and the average particle size here is d50 having a cumulative 50 volume% diameter in the particle size distribution. . The value of the average particle diameter calculated from these particle size distributions is the size of the agglomerated powder obtained by aggregating the second particles. That is, the primary particles of the second particles having a small particle diameter are aggregated to exist as large secondary particles. This measurement is performed at the raw material stage, but the second particles are mainly composed of a hardly sintered material in order to disperse in the base material in the form of agglomerated powder having voids. In the sintering process, it is hardly sintered and is dispersed in the sintered body in almost the same state as the raw material. If the size of the aggregated powder is smaller than 0.05 μm, the number of second particles present in the aggregated powder is small, and the area of the interface between the second particles is small. The change in the contact area between the particles is reduced, and high pressure sensitivity cannot be obtained. In addition, if the average particle size of the aggregated powder is larger than 5.2 μm, the distribution of the aggregated powder tends to be unevenly distributed, and the homogeneity of the material tends to deteriorate or the mechanical strength tends to decrease. The upper limit of the average particle diameter of the aggregated powder is preferably 5.0 μm.
さらに加えて上記感圧材料において、前記第２の粒子がカーボン、炭化珪素及びこれらの複合物で構成される複合化合物の一種またはそれらの二種以上を含むことが望ましい。第２の粒子を難焼結性のカーボンや炭化珪素から選定することで容易に第２の導電性粒子中に空隙を導入することができる。 In addition, in the pressure-sensitive material, it is desirable that the second particles include one or more of composite compounds composed of carbon, silicon carbide, and a composite thereof. By selecting the second particles from hardly sinterable carbon or silicon carbide, voids can be easily introduced into the second conductive particles.
さらに加えて上記感圧材料において、前記第１の粒子が、炭化珪素、窒化珪素、炭化チタン、サイアロン、窒化アルミニウム、アルミナ、ムライト、ジルコニア、マグネシア、コージェライト、アルミニウムチタネートのいずれか一種またはそれらの二種以上を含むことが好ましい。これら機械強度が高く、高温においても化学的に安定している材料からなる粒子を選択することにより、高温・高圧に対する抵抗力は母材が負担するので、より高圧・高温にも耐えうる感圧材料が構成される。 In addition, in the pressure-sensitive material, the first particles may be any one of silicon carbide, silicon nitride, titanium carbide, sialon, aluminum nitride, alumina, mullite, zirconia, magnesia, cordierite, aluminum titanate, or a combination thereof. It is preferable that 2 or more types are included. By selecting particles made of materials that have high mechanical strength and are chemically stable even at high temperatures, the base material bears the resistance to high temperatures and high pressures. The material is composed.
さらに加えて前記第１の粒子が窒化珪素、前記第２の粒子がカーボンであることが好ましい。母材を構成する第１の粒子を、高温下における機械的強度、および化学的安定性の極めて高い窒化珪素とし、第２の粒子を難焼結性で空隙を導入しやすいカーボンとすることにより、特に高温・高圧下において高い耐久性と、高い圧力感度を具現可能な感圧材料が構成される。 In addition, it is preferable that the first particles are silicon nitride and the second particles are carbon. By making the first particles constituting the base material silicon nitride having extremely high mechanical strength and chemical stability at high temperatures, and making the second particles carbon that hardly sinters and easily introduces voids. In particular, a pressure-sensitive material capable of realizing high durability and high pressure sensitivity at high temperatures and high pressures is constructed.
本発明によれば、第１の粒子を主体とした母材中に前記第１の粒子とは導電性が異なる第２の粒子が空隙を有した凝集粉として分散した感圧材料であって、前記第２の粒子の凝集粉の空隙率が２５ｖｏｌ％以上、５５ｖｏｌ％以下であり、前記第２の粒子同士の加圧による接触状態の変化により電気抵抗が変化する特性を有する新規な感圧材料を提供できる。この新規な感圧材料は、広い範囲から材料を選定できること、また第２の粒子の凝集粉の空隙率を２５ｖｏｌ％以上、５５ｖｏｌ％以下として第２の粒子同士の接触面積変化を大きくすることで高い圧力感度を有した感圧材料を得ることができる。また、上記態様の感圧材料によれば、第１の粒子を耐熱性に優れた所定の機械的強度を有する材料から選定することで、高温・高圧下において高い圧力感度を備えた感圧材料を提供できる。 According to the present invention, a pressure sensitive material in which a second particle having a different conductivity from the first particle is dispersed as an aggregated powder having voids in a base material mainly composed of the first particle, Novel pressure-sensitive material having a characteristic that the porosity of the aggregated powder of the second particles is 25 vol% or more and 55 vol% or less, and the electric resistance is changed by the change of the contact state due to the pressurization of the second particles. Can provide. This new pressure-sensitive material can be selected from a wide range, and the porosity of the agglomerated powder of the second particles is set to 25 vol% or more and 55 vol% or less to increase the contact area change between the second particles. A pressure-sensitive material having high pressure sensitivity can be obtained. Moreover, according to the pressure sensitive material of the said aspect, the pressure sensitive material provided with the high pressure sensitivity under high temperature and high pressure by selecting the 1st particle | grains from the material which has the predetermined mechanical strength excellent in heat resistance. Can provide.
本発明をその実施例によって具体的に説明するが、これら実施例により本発明が限定されるものではない。 The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
(実施例１)
実施例１は第１の粒子に絶縁性の窒化珪素、第２の粒子に炭化珪素を用いた例である。α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、β-ＳｉＣ粉末（住友大阪セメント製、結晶粒径３０ｎｍ）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９４．０：６．０である。第２の粒子となるβ−ＳｉＣ粉末は、ＴＥＭによる結晶粒径観察では３０ｎｍ、凝集粉の平均粒径はレーザー回折・散乱式粒度分布測定装置（堀場製作所製、型番ＬＡ−９２０）で測定したところ１．２μｍの値が得られた。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作製した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力２０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体を電気抵抗率評価用として３ｍｍ角、長さ１２ｍｍの試験片に加工した。電気抵抗率評価用試料には、３ｍｍ角の面に厚さ１ｍｍのＣｕ電極をロー付けし、該Ｃｕ電極にΦ０．６ｍｍのＣｕリード線をハンダ付けした。
［評価方法］
密度測定は東洋精機製作所製の密度測定装置（型番Ｄ−Ｈ）を用いて行い、（１）（２）式より空隙率を算出した。電気抵抗変化率の測定は、３ｍｍ×１２ｍｍの面を１００ＭＰａの圧力で加圧しながら日置電機製の抵抗計３５４１を用いて２５℃、２００℃の条件で電気抵抗測定を行った。また、１００ＭＰaの印加後、外観に異常がないかを目視にて確認した。なお、以下の実施例２〜１７及び比較例１〜２でも同様な方法で評価した。
［測定結果］
測定結果を表1に示す。空隙率は２７vol.％、電気抵抗変化率はそれぞれ０．０１０％/ＭＰａ（２５℃）、０．０１１％/ＭＰa（２００℃）であった。
(Example 1)
Example 1 is an example in which insulating silicon nitride is used for the first particles and silicon carbide is used for the second particles. 38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of β-SiC powder (manufactured by Sumitomo Osaka Cement, crystal particle size 30 nm), sintered Weighed 6.0 g of Al 2 O 3 (manufactured by Koyo Chemical Co., model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by Koyo Chemical Co., model number: YYO01PA) as auxiliary agents, and performed ball mill mixing in ethanol. It was. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 94.0: 6.0. The β-SiC powder as the second particles was 30 nm in the crystal particle size observation by TEM, and the average particle size of the agglomerated powder was measured with a laser diffraction / scattering type particle size distribution analyzer (manufactured by Horiba, model number LA-920). However, a value of 1.2 μm was obtained. After drying the mixed powder, a compact having a diameter of 36 mm and a thickness of 10 mm was produced at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 20 MPa. The obtained sintered body was processed into a 3 mm square test piece having a length of 12 mm for evaluation of electrical resistivity. A 1 mm thick Cu electrode was brazed to a 3 mm square surface of the electrical resistivity evaluation sample, and a Φ 0.6 mm Cu lead wire was soldered to the Cu electrode.
[Evaluation methods]
Density measurement was performed using a density measuring device (model number DH) manufactured by Toyo Seiki Seisakusho, and the porosity was calculated from equations (1) and (2). The rate of change in electrical resistance was measured under conditions of 25 ° C. and 200 ° C. using a resistance meter 3541 made by Hioki Electric while pressing a 3 mm × 12 mm surface with a pressure of 100 MPa. Further, after applying 100 MPa, it was visually confirmed whether there was any abnormality in the appearance. In addition, the following methods 2-17 and Comparative Examples 1-2 were also evaluated in the same manner.
[Measurement result]
Table 1 shows the measurement results. The porosity was 27 vol.%, And the electric resistance change rates were 0.010% / MPa (25 ° C.) and 0.011% / MPa (200 ° C.), respectively.
実施例２〜７は第１の粒子に絶縁性の窒化珪素、第２の粒子にカーボンを用い、ＴＥＭで算出されるカーボンの結晶粒径を１５〜１２２ｎｍまで変化させた例である。
（実施例２）
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：＃３８８５）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Examples 2 to 7 are examples in which insulating silicon nitride is used for the first particles, carbon is used for the second particles, and the crystal grain size of carbon calculated by TEM is changed from 15 to 122 nm.
(Example 2)
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (Tokai Black, model number: # 3885), sintering aid As agents, 6.0 g of Al 2 O 3 (manufactured by Koyo Chemical Co., model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by Koyo Chemical Co., model number: YYO01PA) were weighed and ball milled in ethanol. . Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例３)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：＃３８４５）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Example 3
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (Tokai Black, model number: # 3845), sintering aid As agents, 6.0 g of Al 2 O 3 (manufactured by Koyo Chemical Co., model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by Koyo Chemical Co., model number: YYO01PA) were weighed and ball milled in ethanol. . Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例４)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：＃３８００）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Example 4
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (Tokai Black, model number: # 3800), sintering aid As agents, 6.0 g of Al 2 O 3 (manufactured by Koyo Chemical Co., model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by Koyo Chemical Co., model number: YYO01PA) were weighed and ball milled in ethanol. . Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例５)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製カーボンブラック、型番：Ｇ−ＳＨＰ）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
(Example 5)
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (carbon black manufactured by Tokai Carbon, model number: G-SHP), sintered As an auxiliary agent, weighed 6.0 g of Al 2 O 3 (manufactured by high purity chemical, model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by high purity chemical, model number: YYO01PA), and performed ball mill mixing in ethanol. It was. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例６)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製アクアブラック、型番：１６２）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Example 6
α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm) 38.0 g, C powder (Tokai Carbon Aqua Black, model number: 162), 3.0 g, sintering aid As a result, 6.0 g of Al 2 O 3 (manufactured by Koyo Chemical Co., model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by Koyo Chemical Co., model number: YYO01PA) were weighed and mixed in a ball mill in ethanol. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例７)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：ＴＡ）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
(Example 7)
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (Tokai Black, model number: TA), sintering aid As a result, 6.0 g of Al 2 O 3 (manufactured by high purity chemical, model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by high purity chemical, model number: YYO01PA) were weighed and mixed in a ball mill in ethanol. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
実施例８は第１の粒子にＳｉ３Ｎ４、第２の粒子にＣを用い、焼結圧力を下げて空隙率を高くした例である。
(実施例８)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製アクアブラック、型番：＃３８００）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力１０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Example 8 is an example in which Si 3 N 4 is used for the first particles and C is used for the second particles, and the porosity is increased by lowering the sintering pressure.
(Example 8)
α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm) 38.0 g, C powder (Tokai Carbon Aqua Black, model number: # 3800) 3.0 g, sintering aid As agents, 6.0 g of Al 2 O 3 (manufactured by Koyo Chemical Co., model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by Koyo Chemical Co., model number: YYO01PA) were weighed and ball milled in ethanol. . Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The compact was sintered in a nitrogen atmosphere in a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 10 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
実施例９は第１の粒子にＳｉＣ、第２の粒子にＣを用いた例である。
(実施例９)
α-ＳｉＣ粉末（屋久島電工製、型番：ＳＨ−７、）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：＃３８００）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Example 9 is an example in which SiC is used for the first particles and C is used for the second particles.
Example 9
38.0 g of α-SiC powder (manufactured by Yakushima Denko, model number: SH-7), 3.0 g of C powder (Tokai Black, model number: # 3800), Al 2 O 3 (sintering aid) 6.0 g of high-purity chemicals, model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by high-purity chemicals, model number: YYO01PA) were weighed and mixed in a ball mill in ethanol. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
実施例１０〜１１は、母材となる第１の粒子に導電性の窒化珪素、第二の粒子に凝集しにくいカーボンを用いた例である。
（実施例１０）
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：＃８５００/Ｆ）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Examples 10 to 11 are examples in which conductive silicon nitride is used for the first particles serving as the base material and carbon that hardly aggregates is used for the second particles.
(Example 10)
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (Tokai Black, model number: # 8500 / F) As a binder, weigh 6.0 g of Al 2 O 3 (manufactured by high purity chemical, model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by high purity chemical, model number: YYO01PA), and mix in a ball mill in ethanol. went. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例１１)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：＃７５５０ＳＢ/Ｆ）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Example 11
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (Tokai Black, model number: # 7550SB / F) As a binder, weigh 6.0 g of Al 2 O 3 (manufactured by high purity chemical, model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by high purity chemical, model number: YYO01PA), and mix in a ball mill in ethanol. went. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
実施例１２から１４は、母材となる第１の粒子に導電性の窒化珪素、第二の粒子に凝集しやすいカーボンを用いた例である。
(実施例１２)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：ＳＨＲ）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Examples 12 to 14 are examples in which conductive silicon nitride is used for the first particles as the base material and carbon that easily aggregates is used for the second particles.
(Example 12)
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (Tokai Black, model number: SHR), sintering aid As a result, 6.0 g of Al 2 O 3 (manufactured by high purity chemical, model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by high purity chemical, model number: YYO01PA) were weighed and mixed in a ball mill in ethanol. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例１３)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：Ｇ−ＳＨＹ）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
(Example 13)
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (Tokai carbon-made Toka Black, model number: G-SHY), sintered Weighed 6.0 g of Al 2 O 3 (manufactured by Koyo Chemical Co., model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by Koyo Chemical Co., model number: YYO01PA) as auxiliary agents, and performed ball mill mixing in ethanol. It was. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例１４)
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：Ｇ−ＳＨＰ）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。今回の測定には影響は無かったが、測定後の外観検査で試料に微小なクラックが見られ、これを超える高圧での使用は困難であることが分かった。
(Example 14)
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (Tokai Black, model number: G-SHP), sintered As an auxiliary agent, weighed 6.0 g of Al 2 O 3 (manufactured by high purity chemical, model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by high purity chemical, model number: YYO01PA), and performed ball mill mixing in ethanol. It was. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results. Although there was no effect on this measurement, it was found that the appearance inspection after the measurement showed minute cracks in the sample, making it difficult to use at higher pressures.
実施例１５〜１７は第１の粒子を変えて第２の粒子にＣを用いた例である。
(実施例１５)
Ａｌ２Ｏ３粉末（住友大阪セメント製、型番：ＡＫＰ−５０）を４４．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：＃３８００）を３．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Examples 15 to 17 are examples in which C is used as the second particle by changing the first particle.
(Example 15)
44.0 g of Al 2 O 3 powder (manufactured by Sumitomo Osaka Cement, model number: AKP-50), 3.0 g of C powder (Tokai Black, model number: # 3800), Y 2 O 3 (manufactured by High Purity Chemical) , Model number: YYO01PA) was weighed and ball milled in ethanol. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例１６)
ＺｒＯ２粉末（東ソー製、型番：ＴＺ−３ＹＥ）を７２．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：＃３８００）を８．０ｇ、エタノール中でボールミル混合を行った。ここで第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
Example 16
Ball mill mixing was performed in 72.0 g of ZrO 2 powder (manufactured by Tosoh, model number: TZ-3YE), 8.0 g of C powder (Tokai Carbon, model number: # 3800), and ethanol in ethanol. Here, the volume ratio of the first particles to the second particles is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
(実施例１７)
ＴｉＣ粉末（高純度化学製）を３８．０ｇ、Ｃ粉末（東海カーボン製トーカブラック、型番：＃３８００）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。
(Example 17)
38.0 g of TiC powder (manufactured by high purity chemical), 3.0 g of C powder (Tokai Black made by Tokai Carbon, model number: # 3800), Al 2 O 3 (manufactured by high purity chemical, model number: ALO05PA) as a sintering aid ), 3.0 g of Y 2 O 3 (manufactured by Koyo Chemical Co., Ltd., model number: YYO01PA) was weighed and mixed in a ball mill in ethanol. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results.
比較例１は、母材となる第１の粒子に導電性の窒化珪素、第二の粒子に結晶粒径の大きなカーボンを用いた例である。
（比較例１）
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（日本黒鉛製、型番：ＡＣＢ−１５０）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力３０ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。結晶粒径が５０μｍと大きいため、凝集体の空隙率が２２．９ｖｏｌ％と低く、第２の粒子同士の接触面積変化も小さくなり、電気抵抗変化率は０．００７％/ＭＰaと低い値となった。
Comparative Example 1 is an example in which conductive silicon nitride is used for the first particles as the base material and carbon having a large crystal grain size is used for the second particles.
(Comparative Example 1)
α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm) 38.0 g, C powder (manufactured by Nippon Graphite, model number: ACB-150), 3.0 g, sintering aid As a result, 6.0 g of Al 2 O 3 (manufactured by Koyo Chemical Co., model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by Koyo Chemical Co., model number: YYO01PA) were weighed and mixed in a ball mill in ethanol. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 30 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results. Since the crystal grain size is as large as 50 μm, the porosity of the aggregate is as low as 22.9 vol%, the change in contact area between the second particles is small, and the rate of change in electrical resistance is as low as 0.007% / MPa. became.
比較例２は第１の粒子に絶縁性の窒化珪素、第２の粒子にカーボンを使用し、焼結圧力を下げて第２の粒子の空隙率を高くした例である。
（比較例２）
α-Ｓｉ３Ｎ４粉末（宇部興産製、型番：Ｅ１０、平均粒径０．５μｍ）を３８．０ｇ、Ｃ粉末（東海カーボン製、型番：＃３８００）を３．０ｇ、焼結助剤としてＡｌ２Ｏ３（高純度化学製、型番：ＡＬＯ０５ＰＡ）を６．０ｇ、Ｙ２Ｏ３（高純度化学製、型番：ＹＹＯ０１ＰＡ）を３．０ｇ秤量し、エタノール中でボールミル混合を行った。ここで助材を含む第１の粒子と第２の粒子の体積比率は９１．４：８．６である。第２の粒子となるＣ粉末は、ＴＥＭによる結晶粒径観察、およびレーザー回折・散乱式粒度分布測定装置で得られた凝集粉の平均粒径を表１に示した。混合粉を乾燥した後、１００ＭＰaの圧力でΦ３６ｍｍ、厚さ１０ｍｍの成形体を作成した。その成形体を、ホットプレスにて、焼結温度１６５０℃、保持時間２時間、加圧力５ＭＰａ、窒素雰囲気中で焼結した。得られた焼結体から実施例１と同一寸法の試験片を加工し、同一方法で評価した。測定結果を表1に示す。凝集体の空隙率が５８．０ｖｏｌ％と高く、材料の強度が弱くなり測定後に試料が破損してしまった。
Comparative Example 2 is an example in which insulating silicon nitride is used for the first particles and carbon is used for the second particles, and the porosity of the second particles is increased by lowering the sintering pressure.
(Comparative Example 2)
38.0 g of α-Si 3 N 4 powder (manufactured by Ube Industries, model number: E10, average particle size 0.5 μm), 3.0 g of C powder (manufactured by Tokai Carbon, model number: # 3800), as a sintering aid 6.0 g of Al 2 O 3 (manufactured by high purity chemical, model number: ALO05PA) and 3.0 g of Y 2 O 3 (manufactured by high purity chemical, model number: YYO01PA) were weighed and ball mill mixed in ethanol. Here, the volume ratio of the first particles and the second particles containing the auxiliary material is 91.4: 8.6. Table 1 shows the average particle size of the agglomerated powder obtained by observing the crystal particle size by TEM and the laser diffraction / scattering particle size distribution analyzer. After the mixed powder was dried, a molded body having a diameter of 36 mm and a thickness of 10 mm was prepared at a pressure of 100 MPa. The molded body was sintered in a nitrogen atmosphere by a hot press at a sintering temperature of 1650 ° C., a holding time of 2 hours, a pressing force of 5 MPa. A test piece having the same dimensions as in Example 1 was processed from the obtained sintered body and evaluated by the same method. Table 1 shows the measurement results. The porosity of the aggregate was as high as 58.0 vol%, the strength of the material was weakened, and the sample was damaged after the measurement.
本発明の実施例によればいずれの構成であっても、電気抵抗変化率が０．０１０％/ＭＰａ以上と圧力感度が高く、２００℃の高温、１００ＭＰaの高圧下でも圧力検知可能な感圧材料が実現された。また、実施例１〜１７及び比較例１，２より、第２の粒子の凝集粉の空隙率が２５〜５５ｖｏｌ％の範囲以外のときは０．０１０％／ＭＰａ以上の高い電気抵抗変化率が得られなかったり、機械強度不足で材料にクラックが入って使用できなくなることを示した。さらに実施例２〜７では、ＴＥＭにより算出される第２の粒子の結晶粒径が１０ｎｍ以上、１００ｎｍ以下であれば０．０１５％/ＭＰa以上の高い電気抵抗変化率が得られることを示した。さらに実施例１０〜１４では、粒度分布から算出される平均粒径が０．０５μｍ以上、５μｍ以下であれば０．０１５％/ＭＰａ以上の高い電気抵抗変化率が得られることを示した。 According to the embodiment of the present invention, even in any configuration, the pressure sensitivity is as high as 0.010% / MPa or more, and the pressure sensitivity is capable of detecting pressure even at a high temperature of 200 ° C. and a high pressure of 100 MPa. The material was realized. Further, from Examples 1 to 17 and Comparative Examples 1 and 2, when the porosity of the aggregated powder of the second particles is outside the range of 25 to 55 vol%, a high electric resistance change rate of 0.010% / MPa or more is obtained. It was not obtained or it was shown that the material could not be used due to cracks in the mechanical strength. Furthermore, in Examples 2 to 7, it was shown that a high electric resistance change rate of 0.015% / MPa or more can be obtained if the crystal grain size of the second particles calculated by TEM is 10 nm or more and 100 nm or less. . Further, in Examples 10 to 14, it was shown that when the average particle size calculated from the particle size distribution is 0.05 μm or more and 5 μm or less, a high electric resistance change rate of 0.015% / MPa or more can be obtained.
本発明の感圧材料は静水圧の計測や高温・高圧下での圧力検知が可能である。また、自動車のエンジン内の圧力計測（筒内圧力センサ）、ディーゼルエンジンのインジェクターに燃料を供給するコモンレールの圧力計測に適用可能であり、さらに、高圧タンクや高圧ボンベの静水圧計測にも利用できる。 The pressure-sensitive material of the present invention can measure hydrostatic pressure and detect pressure under high temperature and high pressure. It can also be used for pressure measurement in automobile engines (in-cylinder pressure sensor), pressure measurement on common rails that supply fuel to diesel engine injectors, and also for hydrostatic pressure measurement in high-pressure tanks and cylinders. .
１ 感圧材料
１１ 第１の粒子から構成される母材
１２ 第２の粒子の凝集粉
２３，３３ 空隙
２４，３４ 第２の粒子
DESCRIPTION OF SYMBOLS 1 Pressure sensitive material 11 Base material comprised from 1st particle | grain 12 Aggregate powder 23,33 of 2nd particle | grains 24,34 2nd particle | grain
Claims (6)
The pressure-sensitive material according to claim 5, wherein the first particles are silicon nitride and the second particles are carbon.
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| JP2012052864A (en) * | 2010-08-31 | 2012-03-15 | Chiba Univ | High-sensitivity distortion sensor with metal surface treatment applied nano filler |
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