JP7240128B2 - Ca2Si5N8 single crystal - Google Patents
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Description
本発明は、Ｃａ2Ｓｉ5Ｎ8単晶に関する。 The present invention relates to Ca2Si5N8 single crystals.
Ｃａ2Ｓｉ5Ｎ8単晶は、蛍光体原料として用いられている。例えば、Ｃａ2Ｓｉ5Ｎ8単晶とユーロピウム化合物とを混合し、高温加熱炉の炉内を窒素ガスなどで加圧して炉内圧力を維持しながら、１６００℃以上で焼成することにより、蛍光体を製造することができる（特許文献１～３）。 Ca 2 Si 5 N 8 single crystal is used as a phosphor material. For example, a single crystal of Ca 2 Si 5 N 8 and a europium compound are mixed, and the inside of a high-temperature heating furnace is pressurized with nitrogen gas or the like to maintain the pressure in the furnace, and is fired at 1600° C. or higher to obtain fluorescence. body can be manufactured (Patent Documents 1 to 3).
Ｃａ2Ｓｉ5Ｎ8単晶は、大気中の僅かな水分で酸化してしまう。酸化したＣａ2Ｓｉ5Ｎ8単晶は、蛍光体用原料として適さないうえ、厳密な割合で原料調合を行うことが困難になる。そのため、当該技術分野では酸素が忌避物質として認識されており、蛍光体を製造する際には、大気との接触を完全に遮断した環境下で行うことが必要となる。
本発明の課題は、大気中の酸素や水分に対する安定性が高いＣａ2Ｓｉ5Ｎ8単晶を提供することにある。
A single crystal of Ca 2 Si 5 N 8 is oxidized by a small amount of moisture in the air. Oxidized Ca 2 Si 5 N 8 single crystal is not suitable as a raw material for phosphors, and it becomes difficult to mix the raw materials in strict proportions. Therefore, in the technical field, oxygen is recognized as a repellent substance, and when producing phosphors, it is necessary to carry out in an environment in which contact with the atmosphere is completely cut off.
An object of the present invention is to provide a Ca 2 Si 5 N 8 single crystal that is highly stable against atmospheric oxygen and moisture.
本発明者らは、Ｘ線回折スペクトルにおいて特定の回折角２θに位置するピークの半値幅が特定値以下であるＣａ2Ｓｉ5Ｎ8単晶が、大気中の酸素や水分に対する安定性が高いことを見出した。 The present inventors have found that a Ca 2 Si 5 N 8 single crystal in which the half width of the peak located at a specific diffraction angle 2θ in the X-ray diffraction spectrum is a specific value or less has high stability against oxygen and moisture in the atmosphere. I found out.
すなわち、本発明は、次の〔１〕～〔３〕を提供するものである。
〔１〕Ｘ線回折スペクトルにおいて２θ＝３６．０°に位置するピークの半値幅が０．１９５°以下である、Ｃａ2Ｓｉ5Ｎ8単晶。
〔２〕平均粒子径が５～５０μｍであるＳｉ3Ｎ4を原料として含む、〔１〕記載のＣａ2Ｓｉ5Ｎ8単晶。
〔３〕大気暴露１時間後の酸素増加率が１０％以下である、〔１〕又は〔２〕記載のＣａ2Ｓｉ5Ｎ8単晶。
That is, the present invention provides the following [1] to [3].
[1] A Ca 2 Si 5 N 8 single crystal in which the half width of the peak located at 2θ=36.0° in the X-ray diffraction spectrum is 0.195° or less.
[2] The Ca 2 Si 5 N 8 single crystal according to [1], containing Si 3 N 4 having an average particle size of 5 to 50 μm as a raw material.
[3] The Ca 2 Si 5 N 8 single crystal according to [1] or [2], which has an oxygen increase rate of 10% or less after one hour exposure to the atmosphere.
本発明によれば、大気中の酸素や水分に対する安定性が高いＣａ2Ｓｉ5Ｎ8単晶を提供することができる。 According to the present invention, it is possible to provide a Ca 2 Si 5 N 8 single crystal that is highly stable against atmospheric oxygen and moisture.
本発明のＣａ2Ｓｉ5Ｎ8単晶は、Ｘ線回折スペクトルにおいて２θ＝３６．０°に位置するピークの半値幅が０．１９５°以下であることを特徴とするものである。
ここで、本明細書において、Ｘ線回折スペクトルは、粉末Ｘ線回折測定法に準拠し、以下の条件により測定することができる。なお、Ｘ線回折測定装置として、例えば、Ｄ８ ＡＤＶＡＮＣＥ（Ｂｒｕｋｅｒ社製）を使用することができる。
The Ca 2 Si 5 N 8 single crystal of the present invention is characterized in that the half width of the peak located at 2θ=36.0° in the X-ray diffraction spectrum is 0.195° or less.
Here, in this specification, the X-ray diffraction spectrum can be measured according to the powder X-ray diffraction measurement method under the following conditions. As an X-ray diffraction measurement device, for example, D8 ADVANCE (manufactured by Bruker) can be used.
Ｘ線源 Ｃｕｋα
測定範囲 ２θ＝５～６５°
測定間隔 ０．０２３４°
走査速度 ７．８°／ｍｉｎ
測定電圧 ３５ｋＶ
測定電流 ３５０ｍＡ
X-ray source Cukα
Measuring range 2θ=5～65°
Measurement interval 0.0234°
Scanning speed 7.8°/min
Measuring voltage 35kV
Measurement current 350mA
粉末Ｘ線回折測定法により得られたＸ線回折スペクトルに基づいて、２θ＝３６．０°に位置するピークの半値幅（ＦＷＨＭ）を読み取る。ここで、２θ＝３６．０°に位置するピークは、図１に示すように、Ｘ線回折スペクトルの中で相対強度が高く、かつ他のピークと重ならないため、Ｃａ2Ｓｉ5Ｎ8単晶に特異的なものである。 Based on the X-ray diffraction spectrum obtained by powder X-ray diffractometry, the half width (FWHM) of the peak located at 2θ=36.0° is read. Here, as shown in FIG . 1, the peak located at 2θ=36.0° has a high relative intensity in the X - ray diffraction spectrum and does not overlap with other peaks. It is crystal-specific.
Ｘ線回折スペクトルにおいて２θ＝３６．０°に位置するピークの半値幅は０．１９５°以下であるが、大気中の酸素や水分に対する安定性（以下、単に「安定性」とも称する）のより一層の向上の観点から、０．１９０°以下が好ましく、０．１８５°以下が更に好ましい。 The half width of the peak located at 2θ = 36.0° in the X-ray diffraction spectrum is 0.195° or less, but the stability against oxygen and moisture in the atmosphere (hereinafter simply referred to as “stability”) From the viewpoint of further improvement, it is preferably 0.190° or less, more preferably 0.185° or less.
また、本発明のＣａ2Ｓｉ5Ｎ8単晶は、安定性向上の観点から、平均粒子径が５～５０μｍであるＳｉ3Ｎ4を原料として含むことが好ましい。Ｓｉ3Ｎ4の平均粒子径は、より一層の安定性向上の観点から、５～４０μｍが好ましく、５～３０μｍが更に好ましい。ここで、本明細書において「平均粒子径」とは、ＪＩＳ Ｒ １６２９「ファインセラミックス原料のレーザ回折・散乱法による粒子径分布測定方法」に準拠して試料の粒度分布を体積基準で作成したときに積算分布曲線の５０％に相当する粒子径（ｄ50）を意味する。なお、レーザ回折・散乱法による粒子径分布測定装置として、例えば、マイクロトラックＭＴ３３００ＥＸ II（マイクロトラック・ベル社製）を使用することができる。 From the viewpoint of improving stability, the Ca 2 Si 5 N 8 single crystal of the present invention preferably contains Si 3 N 4 having an average particle size of 5 to 50 μm as a raw material. The average particle size of Si 3 N 4 is preferably 5 to 40 μm, more preferably 5 to 30 μm, from the viewpoint of further improving stability. Here, the "average particle size" in this specification refers to the particle size distribution of a sample in accordance with JIS R 1629 "Method for measuring particle size distribution of fine ceramic raw materials by laser diffraction/scattering method". means the particle diameter (d 50 ) corresponding to 50% of the cumulative distribution curve. For example, Microtrac MT3300EX II (manufactured by Microtrac Bell) can be used as a particle size distribution measuring device using a laser diffraction/scattering method.
本発明のＣａ2Ｓｉ5Ｎ8単晶は、このような特性を具備するため、大気中の酸素や水分に対する安定性に優れている。例えば、本発明のＣａ2Ｓｉ5Ｎ8単晶を、室温（２０～２５℃）、相対湿度３０～４０％の環境下で、１時間大気暴露したときの酸素増加率を通常１０％以下、好ましくは８％以下、より好ましくは７％以下、更に好ましくは６．５％以下に抑えることができる。なお、下限値は特に限定されず、０％であっても構わない。具体的な評価方法は、後掲の実施例に記載に方法により行うことができる。 Since the Ca 2 Si 5 N 8 single crystal of the present invention has such characteristics, it has excellent stability against oxygen and moisture in the atmosphere. For example, when the Ca 2 Si 5 N 8 single crystal of the present invention is exposed to the atmosphere for 1 hour at room temperature (20 to 25° C.) and relative humidity of 30 to 40%, the oxygen increase rate is usually 10% or less, It can be suppressed to preferably 8% or less, more preferably 7% or less, still more preferably 6.5% or less. The lower limit is not particularly limited, and may be 0%. A specific evaluation method can be carried out according to the method described in Examples below.
このように、本発明のＣａ2Ｓｉ5Ｎ8単晶は、大気中の酸素や水分に対する安定性に優れるため、例えば、蛍光体の原料として極めて有用である。 As described above, the Ca 2 Si 5 N 8 single crystal of the present invention has excellent stability against oxygen and moisture in the air, and is therefore extremely useful as a raw material for phosphors, for example.
本発明のＣａ2Ｓｉ5Ｎ8単晶は、粉末Ｘ線回折測定において上記特性を具備すれば、適宜の方法により製造することが可能であり、特に限定されない。例えば、炉内で窒化ケイ素と、窒化カルシウムとの混合物を、酸素非含有雰囲気下、１３００～１５００℃で焼成することにより製造することができる。 The Ca 2 Si 5 N 8 single crystal of the present invention is not particularly limited, and can be produced by an appropriate method as long as it has the above characteristics in powder X-ray diffraction measurement. For example, it can be produced by firing a mixture of silicon nitride and calcium nitride in a furnace at 1300 to 1500° C. in an oxygen-free atmosphere.
窒化ケイ素としては、窒化ケイ素の安定性や取り扱い性等の観点から、Ｓｉ3Ｎ4を用いることが好ましい。Ｓｉ3Ｎ4には、α型とβ型の結晶形が存在するが、より一層の安定性向上の観点から、β型が好ましい。
窒化ケイ素としてＳｉ3Ｎ4を用いる場合、Ｓｉ3Ｎ4の平均粒子径は、より一層の安定性向上の観点から、５～５０μｍが好ましく、５～４０μｍがより好ましく、５～３０μｍが更に好ましい。
As the silicon nitride, it is preferable to use Si 3 N 4 from the viewpoint of the stability and handleability of silicon nitride. Si 3 N 4 has α-type and β-type crystal forms, and the β-type is preferred from the viewpoint of further improving stability.
When Si 3 N 4 is used as silicon nitride, the average particle size of Si 3 N 4 is preferably 5 to 50 μm, more preferably 5 to 40 μm, even more preferably 5 to 30 μm, from the viewpoint of further improving stability. .
窒化カルシウムとしては、例えば、Ｃａ3Ｎ2、ＣａＮ、Ｃａ2Ｎが挙げられ、１種又は２種以上を使用することができる。中でも、より一層の安定性向上の観点から、Ｃａ3Ｎ2好ましい。 Calcium nitride includes, for example, Ca 3 N 2 , CaN, and Ca 2 N, and one or more of them can be used. Among them, Ca 3 N 2 is preferable from the viewpoint of further improving stability.
窒化ケイ素及び窒化カルシウムは、Ｃａ2Ｓｉ5Ｎ8となる量を混合すればよく、窒化ケイ素と窒化カルシウムの種類に応じて化学量論組成を満たすように使用量を適宜決定することができる。
Ｓｉ3Ｎ4と、窒化カルシウムとの混合は、乳鉢、ボールミル等を用いることができる。
Silicon nitride and calcium nitride may be mixed in amounts to form Ca 2 Si 5 N 8 , and the amount used can be appropriately determined so as to satisfy the stoichiometric composition according to the types of silicon nitride and calcium nitride.
A mortar, a ball mill, or the like can be used to mix Si 3 N 4 and calcium nitride.
焼成炉は、炉内の雰囲気を調整できる炉であればよく、高温加熱炉のような特殊な焼成炉でなくてもよい。炉内圧は、常圧でよく、高圧にする必要がない。 The firing furnace may be any furnace capable of adjusting the atmosphere in the furnace, and does not have to be a special firing furnace such as a high-temperature heating furnace. The furnace internal pressure may be normal pressure, and does not need to be high pressure.
炉内の雰囲気としては、酸素非含有雰囲気下であれば特に限定されず、例えば、不活性ガス雰囲気下であればよい。より具体的には、窒素ガス雰囲気下、アルゴンガス雰囲気下、窒素水素混合ガス雰囲気下、アルゴン水素混合ガス雰囲気下を挙げることができる。中でも、アルゴンガス雰囲気下、窒素ガス雰囲気下が好ましい。なお、窒素水素混合ガス又はアルゴン水素混合ガスを用いる場合は、水素を３～５体積％とすることが好ましい。 The atmosphere in the furnace is not particularly limited as long as it is an oxygen-free atmosphere, and may be, for example, an inert gas atmosphere. More specifically, a nitrogen gas atmosphere, an argon gas atmosphere, a nitrogen-hydrogen mixed gas atmosphere, and an argon-hydrogen mixed gas atmosphere can be mentioned. Among them, an argon gas atmosphere and a nitrogen gas atmosphere are preferable. When using a nitrogen-hydrogen mixed gas or an argon-hydrogen mixed gas, it is preferable that the hydrogen content is 3 to 5% by volume.
焼成温度は１３００～１５００℃であり、かかる範囲内とすることで、Ｃａ2Ｓｉ5Ｎ8を単晶として得ることができる。焼成温度は、より一層の安定性向上の観点から、１３５０～１５００℃が好ましく、１４００～１５００℃が更に好ましい。
焼成時間は、より一層の安定性向上の観点から、０．５～１２時間が好ましく、２～１０時間がより好ましく、４～８時間が更に好ましい。
The sintering temperature is 1300 to 1500° C. By setting the temperature within this range, Ca 2 Si 5 N 8 can be obtained as a single crystal. The firing temperature is preferably 1,350 to 1,500° C., more preferably 1,400 to 1,500° C., from the viewpoint of further improving stability.
The firing time is preferably 0.5 to 12 hours, more preferably 2 to 10 hours, and even more preferably 4 to 8 hours, from the viewpoint of further improving stability.
以下、実施例を挙げて、本発明の実施の形態を更に具体的に説明する。但し、本発明は、下記の実施例に限定されるものではない。 EXAMPLES The embodiments of the present invention will now be described more specifically with reference to Examples. However, the present invention is not limited to the following examples.
１．平均粒子径の測定
原料として使用したＳｉ3Ｎ4の粒度分布を、ＪＩＳ Ｒ １６２９「ファインセラミックス原料のレーザ回折・散乱法による粒子径分布測定方法」に準拠して体積基準で作成した。そして、積算分布曲線の５０％に相当する粒子径（ｄ50）を求めた。なお、レーザ回折・散乱法による粒子径分布測定装置として、マイクロトラックＭＴ３３００ＥＸ II（マイクロトラック・ベル社製）を使用した。
1. Measurement of Average Particle Size The particle size distribution of Si 3 N 4 used as a raw material was prepared on a volume basis in accordance with JIS R 1629 “Method for measuring particle size distribution of fine ceramic raw materials by laser diffraction/scattering method”. Then, the particle diameter (d 50 ) corresponding to 50% of the integrated distribution curve was obtained. Microtrac MT3300EX II (manufactured by Microtrac Bell) was used as a particle size distribution measuring device by a laser diffraction/scattering method.
２．半値幅の測定
Ｘ線回折装置（Ｄ８ ＡＤＶＡＮＣＥ、Ｂｒｕｋｅｒ社製）を用いてＸ線回折スペクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行った。Ｃａ2Ｓｉ5Ｎ8単晶と判断した場合には、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。なお、Ｘ線回折測定装置として、Ｄ８ ＡＤＶＡＮＣＥ（Ｂｒｕｋｅｒ社製）を使用し、測定条件は上記において説明したとおりである。
2. Measurement of half-value width An X-ray diffraction spectrum was measured using an X-ray diffractometer (D8 ADVANCE, manufactured by Bruker), and mineral phases were identified from the X-ray diffraction pattern. When it was judged to be a Ca 2 Si 5 N 8 single crystal, the half width of 2θ=36.0° (Cukα) was read. D8 ADVANCE (manufactured by Bruker) was used as an X-ray diffraction measurement device, and the measurement conditions were as described above.
３．大気暴露試験
各実施例及び比較例で得られたＣａ2Ｓｉ5Ｎ8単晶について、グローブボックス内で、試料カプセルに充填して、酸素窒素同時分析装置（ＴＣＨ－６００、ＬＥＣＯジャパン社製）を用いて酸素濃度を測定した。次いで、グローブボックス内でＣａ2Ｓｉ5Ｎ8単晶０．３ｇをスクリュー管に量り取り、密栓し大気中に取り出した。次いで、温度２０℃、相対湿度４０％の大気下でスクリュー管を開放状態で１時間静置した後、密栓し再びグローブボックス内に戻し、試料カプセルに充填して、酸素窒素同時分析装置により酸素濃度を測定した。次いで、大気暴露試験後における酸素増加率を下記式（１）により算出した。そして、酸素増加率が１０質量％以下であるものを「〇」、酸素増加率が１０質量％超であるものを「×」として評価した。
3. Atmospheric exposure test Ca 2 Si 5 N 8 single crystals obtained in each example and comparative example were filled in a sample capsule in a glove box and analyzed by an oxygen and nitrogen simultaneous analyzer (TCH-600, manufactured by LECO Japan). was used to measure the oxygen concentration. Next, 0.3 g of Ca 2 Si 5 N 8 single crystal was weighed into a screw tube in a glove box, sealed tightly, and taken out into the atmosphere. Then, after leaving the screw tube in an open state for 1 hour in an atmosphere with a temperature of 20° C. and a relative humidity of 40%, it is sealed and returned to the glove box, filled into a sample capsule, and oxygen is analyzed by an oxygen-nitrogen simultaneous analyzer. Concentration was measured. Next, the oxygen increase rate after the atmospheric exposure test was calculated by the following formula (1). A sample with an oxygen increase rate of 10% by mass or less was evaluated as "O", and a sample with an oxygen increase rate of more than 10% by mass was evaluated as "x".
酸素増加率（％）＝（Ｘ－Ｙ）／Ｙ×１００ （１） Oxygen increase rate (%) = (XY)/Y x 100 (1)
〔式中、Ｘは大気暴露試験後のＣａ2Ｓｉ5Ｎ8単晶の酸素濃度（質量％）を示し、Ｙは大気暴露試験前のＣａ2Ｓｉ5Ｎ8単晶の酸素濃度（質量％）を示す。〕 [In the formula, X represents the oxygen concentration (% by mass) of the Ca 2 Si 5 N 8 single crystal after the atmospheric exposure test, and Y represents the oxygen concentration (% by mass) of the Ca 2 Si 5 N 8 single crystal before the atmospheric exposure test. ). ]
実施例１
原料の取扱いは、露点を－９０℃以下に保っているグローブボックス内で行った。先ず、平均粒子径が２８．２μｍであるＳｉ3Ｎ4（信越化学社製）と、Ｃａ3Ｎ2（太平洋セメント社製）とをＣａ：Ｓｉのモル比で２：５になるように秤量した。秤量後、メノウ乳鉢と乳棒を用いて１０分間混合した。混合した原料を管状炉に仕込み、Ｎ2ガスを１Ｌ／ｍｉｎの速度で流通させ、１４５０℃まで５℃／ｍｉｎで昇温し、６時間保持して焼成を行った。焼成後、管状炉から取り出し、鉱物を得た。得られた鉱物について、Ｘ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Example 1
Raw materials were handled in a glove box with a dew point kept below -90°C. First, Si 3 N 4 (manufactured by Shin-Etsu Chemical Co., Ltd.) having an average particle size of 28.2 μm and Ca 3 N 2 (manufactured by Taiheiyo Cement Co., Ltd.) were weighed so that the Ca:Si molar ratio was 2:5. bottom. After weighing, they were mixed for 10 minutes using an agate mortar and pestle. The mixed raw material was put into a tubular furnace, N 2 gas was passed at a rate of 1 L/min, the temperature was raised to 1450° C. at a rate of 5° C./min, and the mixture was held for 6 hours for firing. After firing, it was removed from the tubular furnace to obtain minerals. The X-ray diffraction spectrum of the obtained mineral was measured with an X-ray diffraction device, the mineral phase was identified from the X-ray diffraction pattern, and the half width at 2θ=36.0° (Cukα) was read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
実施例２
焼成温度を１５００℃に変更したこと以外は、実施例１と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Example 2
A mineral was obtained by the same operation as in Example 1, except that the sintering temperature was changed to 1500°C. Regarding the obtained mineral, the X-ray diffraction spectrum was measured with an X-ray diffraction device in the same manner as in Example 1, the mineral phase was identified from the X-ray diffraction pattern, and the half width of 2θ = 36.0 ° (Cukα) read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
実施例３
平均粒子径が１５．３μｍであるＳｉ3Ｎ4（信越化学社製）を用い、焼成温度を１３００℃に変更したこと以外は、実施例１と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Example 3
A mineral was obtained in the same manner as in Example 1 except that Si 3 N 4 (manufactured by Shin-Etsu Chemical Co., Ltd.) having an average particle size of 15.3 μm was used and the firing temperature was changed to 1300°C. Regarding the obtained mineral, the X-ray diffraction spectrum was measured with an X-ray diffraction device in the same manner as in Example 1, the mineral phase was identified from the X-ray diffraction pattern, and the half width of 2θ = 36.0 ° (Cukα) read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
実施例４
焼成温度を１４５０℃に変更したこと以外は、実施例３と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Example 4
A mineral was obtained by the same operation as in Example 3, except that the firing temperature was changed to 1450°C. Regarding the obtained mineral, the X-ray diffraction spectrum was measured with an X-ray diffraction device in the same manner as in Example 1, the mineral phase was identified from the X-ray diffraction pattern, and the half width of 2θ = 36.0 ° (Cukα) read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
実施例５
焼成温度を１５００℃に変更したこと以外は、実施例３と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Example 5
A mineral was obtained by the same operation as in Example 3, except that the firing temperature was changed to 1500°C. Regarding the obtained mineral, the X-ray diffraction spectrum was measured with an X-ray diffraction device in the same manner as in Example 1, the mineral phase was identified from the X-ray diffraction pattern, and the half width of 2θ = 36.0 ° (Cukα) read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
実施例６
平均粒子径が６．６μｍであるＳｉ3Ｎ4（信越化学社製）を用い、焼成温度を１４５０℃に変更したこと以外は、実施例１と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Example 6
A mineral was obtained in the same manner as in Example 1, except that Si 3 N 4 (manufactured by Shin-Etsu Chemical Co., Ltd.) having an average particle size of 6.6 μm was used and the firing temperature was changed to 1450°C. Regarding the obtained mineral, the X-ray diffraction spectrum was measured with an X-ray diffraction device in the same manner as in Example 1, the mineral phase was identified from the X-ray diffraction pattern, and the half width of 2θ = 36.0 ° (Cukα) read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
実施例７
焼成温度を１５００℃に変更したこと以外は、実施例６と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Example 7
A mineral was obtained by the same operation as in Example 6, except that the sintering temperature was changed to 1500°C. Regarding the obtained mineral, the X-ray diffraction spectrum was measured with an X-ray diffraction device in the same manner as in Example 1, the mineral phase was identified from the X-ray diffraction pattern, and the half width of 2θ = 36.0 ° (Cukα) read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
比較例１
平均粒子径が５４．２μｍであるＳｉ3Ｎ4（信越化学社製）を用い、焼成温度を１５００℃に変更したこと以外は、実施例１と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相を同定したところ、Ｃａ2Ｓｉ5Ｎ8とＣａＳｉＮ2との混晶であることが確認された。そのため、２θ＝３６．０°（Ｃｕｋα）の半値幅の測定及び大気暴露試験を断念した。
Comparative example 1
A mineral was obtained in the same manner as in Example 1 except that Si 3 N 4 (manufactured by Shin-Etsu Chemical Co., Ltd.) having an average particle size of 54.2 μm was used and the firing temperature was changed to 1500°C. The X-ray diffraction spectrum of the obtained mineral was measured with an X-ray diffraction device in the same manner as in Example 1, and the mineral phase was identified from the X -ray diffraction pattern. It was confirmed to be crystal. Therefore, the measurement of the half width at 2θ=36.0° (Cukα) and the atmospheric exposure test were abandoned.
比較例２
焼成温度を１３００℃に変更したこと以外は、実施例６と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Comparative example 2
A mineral was obtained by the same operation as in Example 6, except that the firing temperature was changed to 1300°C. Regarding the obtained mineral, the X-ray diffraction spectrum was measured with an X-ray diffraction device in the same manner as in Example 1, the mineral phase was identified from the X-ray diffraction pattern, and the half width of 2θ = 36.0 ° (Cukα) read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
比較例３
平均粒子径が３．８μｍであるＳｉ3Ｎ4（信越化学社製）を用い、焼成温度を１５００℃に変更した以外は、実施例１と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Comparative example 3
A mineral was obtained in the same manner as in Example 1 except that Si 3 N 4 (manufactured by Shin-Etsu Chemical Co., Ltd.) having an average particle size of 3.8 μm was used and the firing temperature was changed to 1500°C. Regarding the obtained mineral, the X-ray diffraction spectrum was measured with an X-ray diffraction device in the same manner as in Example 1, the mineral phase was identified from the X-ray diffraction pattern, and the half width of 2θ = 36.0 ° (Cukα) read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
比較例４
焼成温度を１４５０℃に変更したこと以外は、比較例３と同様の操作により鉱物を得た。得られた鉱物について、実施例１と同様にＸ線回折装置によりＸ線回折スベクトルを測定し、Ｘ線回折パターンから鉱物相の同定を行い、２θ＝３６．０°（Ｃｕｋα）の半値幅を読み取った。次いで、大気暴露試験を行い、評価した。その結果を表１に示す。
Comparative example 4
A mineral was obtained in the same manner as in Comparative Example 3, except that the firing temperature was changed to 1450°C. Regarding the obtained mineral, the X-ray diffraction spectrum was measured with an X-ray diffraction device in the same manner as in Example 1, the mineral phase was identified from the X-ray diffraction pattern, and the half width of 2θ = 36.0 ° (Cukα) read. An atmospheric exposure test was then performed and evaluated. Table 1 shows the results.
表１から、Ｘ線回折スペクトルにおいて２θ＝３６．０°に位置するピークの半値幅が０．１９５°以下であるＣａ2Ｓｉ5Ｎ8単晶は、大気暴露試験後の酸素増加率が１０％以下に抑えられており、大気中の酸素や水分に対する安定性が高いことがわかる。 From Table 1, the Ca 2 Si 5 N 8 single crystal having a half width of 0.195° or less of the peak located at 2θ = 36.0° in the X-ray diffraction spectrum has an oxygen increase rate of 10 after the atmospheric exposure test. % or less, indicating high stability against atmospheric oxygen and moisture.
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