JP2002179412A - Method of isolating and refining cubic spinel-type silicon nitride - Google Patents
Method of isolating and refining cubic spinel-type silicon nitrideInfo
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- JP2002179412A JP2002179412A JP2000379336A JP2000379336A JP2002179412A JP 2002179412 A JP2002179412 A JP 2002179412A JP 2000379336 A JP2000379336 A JP 2000379336A JP 2000379336 A JP2000379336 A JP 2000379336A JP 2002179412 A JP2002179412 A JP 2002179412A
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- silicon nitride
- cubic spinel
- type silicon
- pressure phase
- low
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、立方晶スピネル型
窒化ケイ素中における未反応の低圧相窒化ケイ素を分離
して精製するための立方晶スピネル型窒化ケイ素の分
離、精製方法に関するものである。The present invention relates to a method for separating and purifying cubic spinel silicon nitride for separating and purifying unreacted low-pressure phase silicon nitride in cubic spinel silicon nitride.
【０００２】[0002]
【従来の技術】立方晶スピネル型窒化ケイ素は、極最近
になって合成方法が開発された。すなわち、ケイ素（Ｓ
ｉ）と窒素（Ｎ2）を反応させたり、低圧相窒化ケイ素
（α−Ｓｉ3Ｎ4、β−Ｓｉ3Ｎ4、アモルファスＳｉ3Ｎ4
など）を衝撃圧縮法を含む１５ＧＰａ、２０００Ｋ以上
の高温高圧で処理したりすることにより、立方晶スピネ
ル型窒化ケイ素が得られる。このようにして得られた立
方晶スピネル型窒化ケイ素を工業的に応用するために
は、立方晶スピネル型窒化ケイ素の純度を高める必要が
あった。2. Description of the Related Art A method of synthesizing cubic spinel silicon nitride has been developed very recently. That is, silicon (S
i) and nitrogen (N 2 ), or low pressure phase silicon nitride (α-Si 3 N 4 , β-Si 3 N 4 , amorphous Si 3 N 4
Or the like is treated at a high temperature and a high pressure of 2,000 K or more, including a shock compression method, to obtain cubic spinel silicon nitride. In order to industrially apply the cubic spinel silicon nitride thus obtained, it is necessary to increase the purity of the cubic spinel silicon nitride.
【０００３】[0003]
【発明が解決しようとする課題】ところが、低圧相窒化
ケイ素の高温高圧処理で立方晶スピネル型窒化ケイ素へ
の転換率を１００％に近づけるためには、５０万気圧以
上の超高圧の条件が要求される。このような超高圧の条
件は大掛かりな装置を必要とし、そのコストも嵩むこと
から、工業的に採用することは困難である。従って、低
圧相窒化ケイ素の高温高圧処理は、５０万気圧よりかな
り低い圧力で行われることになる。その場合、高温高圧
処理による生成物は、立方晶スピネル型窒化ケイ素のほ
かに不純物として未反応の低圧相窒化ケイ素を含むこと
となり、その低圧相窒化ケイ素を分離し、精製する必要
がある。However, in order to bring the conversion of low-pressure phase silicon nitride into cubic spinel-type silicon nitride by high-temperature and high-pressure treatment close to 100%, ultrahigh pressure conditions of 500,000 atmospheres or more are required. Is done. Such ultra-high pressure conditions require a large-scale device and increase the cost, so that it is difficult to industrially adopt it. Therefore, the high-temperature and high-pressure treatment of the low-pressure phase silicon nitride is performed at a pressure considerably lower than 500,000 atmosphere. In that case, the product obtained by the high-temperature and high-pressure treatment contains unreacted low-pressure phase silicon nitride as impurities in addition to the cubic spinel-type silicon nitride, and it is necessary to separate and purify the low-pressure phase silicon nitride.
【０００４】本発明は、上記のような従来技術に存在す
る問題点に着目してなされたものである。その目的とす
るところは、立方晶スピネル型窒化ケイ素中に含まれる
不純物としての未反応の低圧相窒化ケイ素を効率良く分
離、精製して純度を高めることができる立方晶スピネル
型窒化ケイ素の分離、精製方法を提供することにある。The present invention has been made by focusing on the problems existing in the prior art as described above. Its purpose is to efficiently separate and purify the unreacted low-pressure phase silicon nitride as an impurity contained in the cubic spinel silicon nitride, and to separate the cubic spinel silicon nitride, which can increase the purity, It is to provide a purification method.
【０００５】[0005]
【課題を解決するための手段】上記の目的を達成するた
めに、第１の発明の立方晶スピネル型窒化ケイ素の分
離、精製方法は、低圧相窒化ケイ素を高温高圧処理する
ことによって得られ、未反応の低圧相窒化ケイ素を含有
する立方晶スピネル型窒化ケイ素に、フッ化水素酸と硝
酸又は硫酸との混酸溶液を加熱状態で作用させ、立方晶
スピネル型窒化ケイ素中における低圧相窒化ケイ素を分
離して精製することを特徴とするものである。In order to achieve the above object, a method for separating and purifying cubic spinel-type silicon nitride according to the first invention is obtained by subjecting low-pressure phase silicon nitride to high-temperature and high-pressure treatment, A mixed acid solution of hydrofluoric acid and nitric acid or sulfuric acid is allowed to act on the cubic spinel-type silicon nitride containing unreacted low-pressure phase silicon nitride in a heated state, and the low-pressure phase silicon nitride in the cubic spinel-type silicon nitride is converted into It is characterized by being separated and purified.
【０００６】第２の発明の立方晶スピネル型窒化ケイ素
の分離、精製方法は、第１の発明において、前記混酸溶
液を１１０〜１６０℃の温度条件下で作用させるもので
ある。The method for separating and purifying cubic spinel-type silicon nitride according to a second aspect of the present invention is the method according to the first aspect, wherein the mixed acid solution is operated at a temperature of 110 to 160 ° C.
【０００７】第３の発明の立方晶スピネル型窒化ケイ素
の分離、精製方法は、第１又は第２の発明において、前
記立方晶スピネル型窒化ケイ素と未反応の低圧相窒化ケ
イ素とは粉末であって、各粉末の粒子径が１０μｍ以下
であるものである。According to a third aspect of the present invention, there is provided a method for separating and purifying cubic spinel-type silicon nitride according to the first or second aspect, wherein the cubic spinel-type silicon nitride and the unreacted low-pressure phase silicon nitride are powdered. The particle diameter of each powder is 10 μm or less.
【０００８】[0008]
【発明の実施の形態】以下、本発明の実施形態について
詳細に説明する。立方晶スピネル型窒化ケイ素（高圧相
窒化ケイ素）の分離、精製方法は、低圧相窒化ケイ素を
高圧処理することによって得られ、未反応の低圧相窒化
ケイ素を含有する立方晶スピネル型窒化ケイ素に、フッ
化水素酸と硝酸又は硫酸との混酸溶液を加熱状態で作用
させ、立方晶スピネル型窒化ケイ素中における低圧相窒
化ケイ素を分離して精製するものである。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. A method for separating and purifying cubic spinel-type silicon nitride (high-pressure phase silicon nitride) is obtained by subjecting low-pressure phase silicon nitride to high-pressure treatment, and comprising cubic spinel-type silicon nitride containing unreacted low-pressure phase silicon nitride. A mixed acid solution of hydrofluoric acid and nitric acid or sulfuric acid is applied in a heated state to separate and purify low-pressure phase silicon nitride in cubic spinel-type silicon nitride.
【０００９】立方晶スピネル型窒化ケイ素は高圧相窒化
ケイ素であって、低圧相窒化ケイ素を高圧処理すること
によって得られる。この場合の圧力は２０〜８０ＧＰａ
の範囲内で適宜設定される。高圧になれば不純物として
の低圧相窒化ケイ素は減少するが、工業的に採用するこ
とは困難であるため、通常は上記範囲のうち低い圧力で
実施される。圧力が２０ＧＰａ未満の場合には立方晶ス
ピネル型窒化ケイ素を収率良く得ることができず、８０
ＧＰａを越える場合には装置が大掛かりなものとなり、
そのコストも嵩むこととなり好ましくない。[0009] Cubic spinel silicon nitride is high-pressure phase silicon nitride, and is obtained by high-pressure processing of low-pressure phase silicon nitride. The pressure in this case is 20-80 GPa
Is set as appropriate within the range. When the pressure becomes high, the low-pressure phase silicon nitride as an impurity is reduced, but it is difficult to industrially adopt the silicon nitride. When the pressure is less than 20 GPa, cubic spinel-type silicon nitride cannot be obtained with a high yield.
If it exceeds GPa, the equipment becomes large-scale,
The cost is undesirably increased.
【００１０】上記の圧力で高圧処理することにより数千
度の高温に達し、低圧相窒化ケイ素が高圧相である立方
晶スピネル型窒化ケイ素に転移する。このようにして得
られた立方晶スピネル型窒化ケイ素には、未反応の低圧
相窒化ケイ素が含まれる。従って、得られる立方晶スピ
ネル型窒化ケイ素の粉末は、低圧相窒化ケイ素の粉末と
の混合粉末となる。The high-pressure treatment at the above pressure reaches a high temperature of several thousand degrees, and the low-pressure phase silicon nitride is transformed into a cubic spinel-type silicon nitride, which is a high-pressure phase. The cubic spinel silicon nitride thus obtained contains unreacted low-pressure phase silicon nitride. Therefore, the obtained cubic spinel-type silicon nitride powder is a mixed powder with the low-pressure phase silicon nitride powder.
【００１１】次に、立方晶スピネル型窒化ケイ素中に含
まれる低圧相窒化ケイ素の分離、精製方法について説明
する。分離、精製の対象となる立方晶スピネル型窒化ケ
イ素と低圧相窒化ケイ素との混合粉末は、微粉末、具体
的には粒子径が１０μｍ以下の粉末であることが好まし
く、１μｍ以下の粉末であることがさらに好ましい。し
かも、それらの粒子径の分布ができるだけ均一であるこ
とが望ましい。１０μｍを越える大きな粒子が存在した
り、粒子径に不揃いがあると、立方晶スピネル型窒化ケ
イ素粉末に覆われた低圧相窒化ケイ素粉末が存在した
り、大きな粒子径の低圧相窒化ケイ素粉末が混在して溶
解が進まなかったり、溶解に時間を要したりして好まし
くない。また、立方晶スピネル型窒化ケイ素と低圧相窒
化ケイ素との混合粉末の比表面積、水分等も、後述する
フッ化水素酸との反応に影響があるため、考慮すること
が望ましい。Next, a method for separating and purifying low-pressure phase silicon nitride contained in the cubic spinel silicon nitride will be described. The mixed powder of the cubic spinel silicon nitride and the low-pressure phase silicon nitride to be separated and purified is a fine powder, specifically, a powder having a particle diameter of 10 μm or less, and preferably a powder of 1 μm or less. Is more preferable. Moreover, it is desirable that the distribution of the particle diameters is as uniform as possible. If large particles exceeding 10 μm are present or the particle size is irregular, low-pressure phase silicon nitride powder covered with cubic spinel-type silicon nitride powder exists, or low-pressure phase silicon nitride powder with a large particle size is mixed. Dissolution does not proceed, or dissolution takes time, which is not preferable. It is also desirable to consider the specific surface area, moisture, and the like of the mixed powder of the cubic spinel-type silicon nitride and the low-pressure phase silicon nitride, since they affect the reaction with hydrofluoric acid described below.
【００１２】立方晶スピネル型窒化ケイ素の分離、精製
は、立方晶スピネル型窒化ケイ素中に含まれる低圧相窒
化ケイ素とフッ化水素酸（フッ酸）との次のような
（１）式に示す反応に基づいて行われる。The separation and purification of the cubic spinel-type silicon nitride are represented by the following formula (1) of low-pressure phase silicon nitride and hydrofluoric acid (hydrofluoric acid) contained in the cubic spinel-type silicon nitride. It is based on the reaction.
【００１３】 Ｓｉ3Ｎ4 ＋ １２ＨＦ ＝ ４ＮＨ3 ＋ ３ＳｉＦ4 ・・・（１） この反応では、１モルの低圧相窒化ケイ素に対して１２
モルのフッ化水素が反応する。従って、１回で処理でき
る立方晶スピネル型窒化ケイ素と低圧相窒化ケイ素との
混合粉末の量は、この粉末中の立方晶スピネル型窒化ケ
イ素の濃度とフッ化水素量で規定される。ルシャトリエ
の法則に従って、この化学反応は圧力が高くなると右に
優先的に進行する。圧力は１〜２００気圧の範囲である
ことが好ましい。１気圧未満では反応の進行が十分では
なく、２００気圧を越えると耐用圧力の高い反応容器の
製作は技術的に困難になるとともに、高価なものとなる
ため、好ましくない。この圧力は１０〜１００気圧の範
囲がさらに好ましい。Si 3 N 4 + 12HF = 4NH 3 + 3SiF 4 (1) In this reaction, 12 moles per mole of low-pressure silicon nitride is used.
Molar hydrogen fluoride reacts. Therefore, the amount of the mixed powder of the cubic spinel silicon nitride and the low-pressure phase silicon nitride that can be treated in one operation is determined by the concentration of the cubic spinel silicon nitride and the amount of hydrogen fluoride in the powder. According to Le Chatelier's law, this chemical reaction proceeds preferentially to the right at higher pressures. The pressure preferably ranges from 1 to 200 atmospheres. If the pressure is less than 1 atm, the reaction does not proceed sufficiently. If the pressure exceeds 200 atm, the production of a reaction vessel having a high working pressure becomes technically difficult and expensive, which is not preferable. This pressure is more preferably in the range of 10 to 100 atm.
【００１４】上記の反応後には低圧相窒化ケイ素（Ｓｉ
3Ｎ4）が分解して窒素がアンモニアになり、ケイ素が四
フッ化ケイ素になるので、その量を考慮して必要なフッ
化水素酸を加える。After the above reaction, low pressure phase silicon nitride (Si
3 N 4) is a nitrogen becomes ammonia decomposition, because silicon is silicon tetrafluoride, adding hydrofluoric acid required in consideration of the amount.
【００１５】立方晶スピネル型窒化ケイ素の分離、精製
のために使用される酸は、フッ化水素酸と硝酸又は硫酸
との混酸溶液である。すなわち、混酸溶液としては、フ
ッ化水素酸と硝酸の溶液、フッ化水素酸と硝酸と硫酸の
溶液及びフッ化水素酸と硫酸の溶液がある。硝酸又は硫
酸は、前記低圧相窒化ケイ素とフッ化水素酸の反応の触
媒として作用する。反応を促進させるために、フッ化水
素酸の量はモル比で低圧相窒化ケイ素の２０〜２００倍
であることが望ましい。このモル比が２０倍未満では反
応を促進させる効果が少なく、２００倍を越えても反応
促進の効果はそれ以上望めず、かえって未反応のフッ化
水素酸が残存して好ましくない。The acid used for separation and purification of the cubic spinel silicon nitride is a mixed acid solution of hydrofluoric acid and nitric acid or sulfuric acid. That is, the mixed acid solution includes a solution of hydrofluoric acid and nitric acid, a solution of hydrofluoric acid, nitric acid and sulfuric acid, and a solution of hydrofluoric acid and sulfuric acid. Nitric acid or sulfuric acid acts as a catalyst for the reaction between the low-pressure phase silicon nitride and hydrofluoric acid. To promote the reaction, the amount of hydrofluoric acid is desirably 20 to 200 times the molar ratio of the low pressure phase silicon nitride. If the molar ratio is less than 20 times, the effect of promoting the reaction is small, and if it exceeds 200 times, the effect of promoting the reaction cannot be expected any more, and unreacted hydrofluoric acid remains unpreferably.
【００１６】分離、精製は、加熱、加圧状態で所定時間
処理することにより行われる。その場合の加熱温度と時
間の関係は、１６０℃では１時間以内、１５０℃で２時
間、１４０℃で４時間、１３０℃では８時間である。つ
まり、反応温度が１０℃下がると、反応時間はおよそ２
倍となる。さらに、低圧相窒化ケイ素の量や粒子径が大
きくなれば、それらに比例して反応時間を要することと
なる。反応温度は、１１０〜１６０℃が好ましい。反応
温度が１１０℃未満では反応時間が長くなり過ぎて工業
的な条件としては不適当であり、１６０℃を越えると低
圧相窒化ケイ素とフッ化水素酸とを選択的に反応させる
効果が低下する。Separation and purification are carried out by heating and pressurizing for a predetermined time. In this case, the relationship between the heating temperature and time is within 1 hour at 160 ° C, 2 hours at 150 ° C, 4 hours at 140 ° C, and 8 hours at 130 ° C. In other words, when the reaction temperature drops by 10 ° C., the reaction time becomes about 2 hours.
Double. Furthermore, if the amount and the particle diameter of the low-pressure phase silicon nitride are increased, the reaction time is required in proportion thereto. The reaction temperature is preferably from 110 to 160 ° C. If the reaction temperature is lower than 110 ° C., the reaction time becomes too long, which is unsuitable for industrial conditions. If the temperature exceeds 160 ° C., the effect of selectively reacting low-pressure phase silicon nitride with hydrofluoric acid is reduced. .
【００１７】処理時間に関しては、０．１μｍ以下の立
方晶スピネル型窒化ケイ素粉末と低圧相窒化ケイ素の粉
末の混合粉末の場合、１６０℃の温度で加熱時間や放冷
時間を除いた反応時間は１時間で十分である。以上のよ
うな化学的処理後の立方晶スピネル型窒化ケイ素粉末
は、濾過などの固液分離手段によって混酸溶液から分離
される。これにより、精製された純度の高い立方晶スピ
ネル型窒化ケイ素粉末が得られる。Regarding the treatment time, in the case of a mixed powder of cubic spinel-type silicon nitride powder and low-pressure phase silicon nitride powder of 0.1 μm or less, the reaction time excluding the heating time and the cooling time at 160 ° C. is as follows. One hour is enough. The cubic spinel silicon nitride powder after the above chemical treatment is separated from the mixed acid solution by solid-liquid separation means such as filtration. Thereby, a purified cubic spinel-type silicon nitride powder having a high purity can be obtained.
【００１８】なお、化学的処理に関する装置及び操作方
法の具体的条件は、日本工業規格ＪＩＳ Ｒ １６０３
−１９９４「ファインセラミックス用窒化ケイ素微粉末
の化学的分析法」（平成６年４月１日改正）や学術誌An
alytical Chemistry １９６８年４０巻 １６８２〜
１６８６頁掲載のB.Bernas著「A new method for decom
position and comprehensive analysis of silicates b
y atomic absorptionspectrometry」等を参考にして決
定される。ちなみに、後者の学術誌AnalyticalChemistr
yには、ケイ酸塩（酸化物）をフッ化水素酸などの酸で
処理する方法が記載されている。The specific conditions of the apparatus and the operation method relating to the chemical treatment are described in Japanese Industrial Standard JIS R 1603.
-1994 “Chemical Analysis of Silicon Nitride Fine Powder for Fine Ceramics” (revised on April 1, 1994) and the journal An
alytical Chemistry 1968 Vol. 40 1682-
"A new method for decom" by B. Bernas on page 1686
position and comprehensive analysis of silicates b
y atomic absorption spectrometry "and the like. By the way, the latter journal AnalyticalChemistr
In y, a method of treating a silicate (oxide) with an acid such as hydrofluoric acid is described.
【００１９】上記の実施形態により発揮される効果を以
下にまとめて説明する。 ・ 実施形態で説明した立方晶スピネル型窒化ケイ素の
分離、精製方法によれば、フッ化水素酸は硝酸又は硫酸
の存在下で加熱状態にて、立方晶スピネル型窒化ケイ素
と反応することなく、ほとんど低圧相窒化ケイ素と反応
する。このため、立方晶スピネル型窒化ケイ素中に含ま
れる不純物としての未反応の低圧相窒化ケイ素が効率良
く分離、精製される。従って、立方晶スピネル型窒化ケ
イ素の純度を高めることができる ・ 混酸溶液を１１０〜１６０℃の温度条件にて作用さ
せることにより、低圧相窒化ケイ素とフッ化水素酸との
反応を効率良く進行させることができる。例えば、１６
０℃で作用させることにより、低圧相窒化ケイ素とフッ
化水素酸とを選択的に１時間以内の短時間のうちに反応
させることができる。The effects exerted by the above embodiment will be described below. According to the method for separating and refining cubic spinel silicon nitride described in the embodiment, hydrofluoric acid is heated in the presence of nitric acid or sulfuric acid, without reacting with cubic spinel silicon nitride. Reacts mostly with low pressure phase silicon nitride. For this reason, unreacted low-pressure phase silicon nitride as an impurity contained in the cubic spinel-type silicon nitride is efficiently separated and purified. Therefore, the purity of the cubic spinel-type silicon nitride can be increased. The reaction between the low-pressure phase silicon nitride and hydrofluoric acid proceeds efficiently by operating the mixed acid solution at a temperature of 110 to 160 ° C. be able to. For example, 16
By acting at 0 ° C., the low-pressure phase silicon nitride and hydrofluoric acid can be selectively reacted within a short time of one hour or less.
【００２０】・ 立方晶スピネル型窒化ケイ素と未反応
の低圧相窒化ケイ素とが粉末であって、各粉末の粒子径
が１０μｍ以下であることにより、低圧相窒化ケイ素の
粉末を容易に混酸溶液に溶解させることができ、低圧相
窒化ケイ素とフッ化水素酸との反応を効率良く進行させ
ることができる。The cubic spinel-type silicon nitride and the unreacted low-pressure phase silicon nitride are powders, and the particle diameter of each powder is 10 μm or less, so that the low-pressure phase silicon nitride powder can be easily converted into a mixed acid solution. It can be dissolved, and the reaction between low-pressure phase silicon nitride and hydrofluoric acid can proceed efficiently.
【００２１】[0021]
【実施例】以下、実施例及び比較例を挙げて前記実施形
態をさらに具体的に説明する。 （実施例１）図１は本発明を実施するための反応容器を
例示したものである。すなわち、反応容器１を構成する
外壁２は有底円筒状に形成され、その開口部には第１フ
ランジ３が突出形成されている。この外壁２はステンレ
ス鋼製で、１８０℃の温度で８０気圧の圧力に耐え得る
強度を有している。フランジ３の外周面には雄ねじ４が
螺刻されている。外壁２の内部には有底円筒状の内壁５
が嵌合されている。この内壁５はフッ素樹脂製で、高温
の酸に対する耐久性を備えている。内壁５の開口部には
第２フランジ６が突設され、その第２フランジ６には段
差状に形成された環状係合部７が突出形成されている。The above embodiment will be described more specifically with reference to examples and comparative examples. (Example 1) FIG. 1 illustrates a reaction vessel for carrying out the present invention. That is, the outer wall 2 constituting the reaction vessel 1 is formed in a cylindrical shape with a bottom, and the first flange 3 is formed to project from the opening. The outer wall 2 is made of stainless steel and has a strength that can withstand a pressure of 80 atm at a temperature of 180 ° C. A male screw 4 is threaded on the outer peripheral surface of the flange 3. Inside the outer wall 2 is a cylindrical inner wall 5 having a bottom.
Are fitted. The inner wall 5 is made of a fluororesin and has durability against a high-temperature acid. A second flange 6 protrudes from the opening of the inner wall 5, and an annular engaging portion 7 formed in a step shape protrudes from the second flange 6.
【００２２】反応容器１の蓋体８は有蓋円筒状に形成さ
れ、その内周面には雌ねじ９が螺刻されている。この蓋
体８の雌ねじ９が外壁２の雄ねじ４に螺合され、内圧に
対する耐久性を発揮できるようになっている。蓋体８の
内奥部には蓋内壁１０が嵌合され、その中心部には前記
内壁５の環状係合部７に係合する係合凹部１１が凹設さ
れている。そして、内壁５の内部には立方晶スピネル型
窒化ケイ素粉末５０重量％と低圧相窒化ケイ素（β型窒
化ケイ素）の粉末５０重量％の混合粉末１２が収容され
るとともに、フッ化水素酸と硝酸又は硫酸との混酸溶液
１３が注入されるようになっている。The lid 8 of the reaction vessel 1 is formed in a closed cylindrical shape, and a female screw 9 is threaded on an inner peripheral surface thereof. The female screw 9 of the lid 8 is screwed to the male screw 4 of the outer wall 2 so as to exhibit durability against internal pressure. A lid inner wall 10 is fitted into the inner part of the lid 8, and an engagement recess 11 that engages with the annular engagement part 7 of the inner wall 5 is formed in the center of the lid inner wall 10. A mixed powder 12 of 50% by weight of cubic spinel silicon nitride powder and 50% by weight of low-pressure phase silicon nitride (β-type silicon nitride) powder is accommodated in the inner wall 5, and hydrofluoric acid and nitric acid are mixed. Alternatively, a mixed acid solution 13 with sulfuric acid is injected.
【００２３】さて、試料粉末量約２００ｍｇの混合粉末
１２と、濃度４６重量％のフッ化水素酸（低圧相窒化ケ
イ素に対して１００倍モル）５ｍｌと、濃度６９重量％
の硝酸１ｍｌとの混酸溶液１３を反応容器１の内壁５内
部（内容積２３ｍｌ）に注入した。そして、温度１６０
℃、圧力２０気圧で１、２、４，８及び１６時間化学処
理を行った。反応容器１の温度が室温に冷却した後、溶
解しなかった試料は反応容器１から取り出し、水洗し乾
燥した。得られた窒化ケイ素の回収率は約４５％から約
２９％であり、それらをＸ線回折にて同定した。その結
果を図２に示した。The mixed powder 12 having a sample powder amount of about 200 mg, hydrofluoric acid having a concentration of 46% by weight (100 times the mol of the low-pressure phase silicon nitride), and a concentration of 69% by weight were used.
A mixed acid solution 13 with 1 ml of nitric acid was poured into the inner wall 5 (inner volume 23 ml) of the reaction vessel 1. And the temperature 160
Chemical treatment was carried out at a temperature of 20 ° C. and a pressure of 20 atm for 1, 2, 4, 8 and 16 hours. After the temperature of the reaction vessel 1 was cooled to room temperature, the undissolved sample was taken out of the reaction vessel 1, washed with water and dried. The recovery of the obtained silicon nitride was about 45% to about 29%, and they were identified by X-ray diffraction. The result is shown in FIG.
【００２４】図２において、Aは処理前の立方晶スピネ
ル型窒化ケイ素粉末５０重量％と低圧相窒化ケイ素の粉
末５０重量％の混合粉末で、BからFは順に反応時間１、
２、４，８及び１６時間処理後の試料についてのＸ線回
折図である。その結果、BからFのいずれの試料も１００
％立方晶スピネル型窒化ケイ素であることが明らかにな
った。従って、１６０℃、１時間の化学処理で低圧相窒
化ケイ素粉末は完全にフッ化水素酸と反応し、室温に放
冷後溶液中にあり、立方晶スピネル型窒化ケイ素は極わ
ずかに反応するものの、大部分は反応せず、固体のまま
である。よって、この固体を採取することで立方晶スピ
ネル型窒化ケイ素を分離、精製することができた。In FIG. 2, A is a mixed powder of 50% by weight of the cubic spinel type silicon nitride powder before treatment and 50% by weight of the low-pressure phase silicon nitride powder.
FIG. 4 is an X-ray diffraction diagram for the samples after 2, 4, 8 and 16 hours of treatment. As a result, all samples from B to F
% Cubic spinel silicon nitride. Therefore, the low-pressure phase silicon nitride powder completely reacts with hydrofluoric acid by the chemical treatment at 160 ° C. for 1 hour, and is left in the solution after cooling to room temperature. Although cubic spinel silicon nitride reacts very little, , Mostly unreacted and remain solid. Therefore, cubic spinel-type silicon nitride could be separated and purified by collecting this solid.
【００２５】なお、前記実施形態を次のように変更して
具体化することもできる。 ・ 内壁５及び蓋内壁１０を省略したり、第１フランジ
３を省略したりした構成の反応容器１を用いてもよい。The above embodiment can be embodied with the following modifications. A reaction vessel 1 having a configuration in which the inner wall 5 and the lid inner wall 10 are omitted, or in which the first flange 3 is omitted may be used.
【００２６】・ 反応容器１の形状を球形状、角筒状等
となるように構成してもよい。さらに、実施形態より把
握される技術的思想について以下に記載する。 ・ 前記混酸溶液を加圧状態で作用させる請求項１から
請求項３のいずれか一項に記載の立方晶スピネル型窒化
ケイ素の分離、精製方法。この製造方法によれば、低圧
相窒化ケイ素とフッ化水素酸との反応を促進させること
ができる。The shape of the reaction vessel 1 may be spherical, rectangular, or the like. Further, technical ideas grasped from the embodiments will be described below. The method for separating and purifying cubic spinel-type silicon nitride according to any one of claims 1 to 3, wherein the mixed acid solution is operated in a pressurized state. According to this production method, the reaction between low-pressure phase silicon nitride and hydrofluoric acid can be promoted.
【００２７】・ 前記低圧相窒化ケイ素に対するフッ化
水素酸のモル比は２０〜２００倍である請求項1から請
求項３のいずれか一項に記載の立方晶スピネル型窒化ケ
イ素の分離、精製方法。この製造方法によれば、低圧相
窒化ケイ素とフッ化水素酸の反応を促進させることがで
きる。The method for separating and purifying cubic spinel-type silicon nitride according to any one of claims 1 to 3, wherein the molar ratio of hydrofluoric acid to the low-pressure phase silicon nitride is 20 to 200 times. . According to this production method, the reaction between low-pressure phase silicon nitride and hydrofluoric acid can be promoted.
【００２８】[0028]
【発明の効果】以上、詳述したように、本発明によれば
次のような効果を奏する。第１の発明の立方晶スピネル
型窒化ケイ素の分離、精製方法によれば、立方晶スピネ
ル型窒化ケイ素中に含まれる不純物としての未反応の低
圧相窒化ケイ素を効率良く分離、精製し、立方晶スピネ
ル型窒化ケイ素の純度を高めることができる。As described above, according to the present invention, the following effects can be obtained. According to the method for separating and purifying cubic spinel-type silicon nitride of the first invention, unreacted low-pressure phase silicon nitride as an impurity contained in the cubic spinel-type silicon nitride is efficiently separated and purified, and The purity of the spinel silicon nitride can be increased.
【００２９】第２の発明の立方晶スピネル型窒化ケイ素
の分離、精製方法によれば、第１の発明の効果に加え、
低圧相窒化ケイ素とフッ化水素酸との反応を効率良く進
行させることができる。According to the method for separating and purifying cubic spinel silicon nitride of the second invention, in addition to the effects of the first invention,
The reaction between low-pressure phase silicon nitride and hydrofluoric acid can proceed efficiently.
【００３０】第３の発明の立方晶スピネル型窒化ケイ素
の分離、精製方法によれば、第１又は第２の発明の効果
に加え、低圧相窒化ケイ素の粉末を容易に溶解させて、
低圧相窒化ケイ素とフッ化水素酸との反応を効率良く進
行させることができる。According to the method for separating and purifying cubic spinel-type silicon nitride of the third invention, in addition to the effects of the first or second invention, the powder of low-pressure phase silicon nitride is easily dissolved,
The reaction between low-pressure phase silicon nitride and hydrofluoric acid can proceed efficiently.
【図１】 立方晶スピネル型窒化ケイ素の分離、精製装
置を分解して示す縦断面図。FIG. 1 is an exploded longitudinal sectional view showing a cubic spinel type silicon nitride separation and purification device.
【図２】 実施例の立方晶スピネル型窒化ケイ素を示す
Ｘ線回折図。FIG. 2 is an X-ray diffraction diagram showing the cubic spinel-type silicon nitride of the example.
１…立方晶スピネル型窒化ケイ素の分離、精製するため
の反応容器。1. A reaction vessel for separating and purifying cubic spinel silicon nitride.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 矢島 祥行 茨城県つくば市並木１丁目１番地 科学技 術庁 無機材質研究所 内 (72)発明者 高橋 勝彦 愛知県知多郡美浜町美浜緑苑３−３−13 (72)発明者 伊藤 憲治 愛知県知多郡武豊町字熊野21−１−21 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor: Yoshiyuki Yajima 1-1-1, Namiki, Tsukuba, Ibaraki Science and Technology Agency Inorganic Materials Research Laboratory (72) Inventor: Katsuhiko Takahashi 3-3 Mihama Ryoen, Mihama-cho, Chita-gun, Aichi Prefecture −13 (72) Inventor Kenji Ito 21-1-21 Kumano, Taketoyo-cho, Chita-gun, Aichi
Claims (3)
よって得られ、未反応の低圧相窒化ケイ素を含有する立
方晶スピネル型窒化ケイ素に、フッ化水素酸と硝酸又は
硫酸との混酸溶液を加熱状態で作用させ、立方晶スピネ
ル型窒化ケイ素中における低圧相窒化ケイ素を分離して
精製することを特徴とする立方晶スピネル型窒化ケイ素
の分離、精製方法。1. A mixed acid solution of hydrofluoric acid and nitric acid or sulfuric acid is heated to cubic spinel-type silicon nitride obtained by subjecting low-pressure phase silicon nitride to high-pressure treatment and containing unreacted low-pressure phase silicon nitride. A method for separating and purifying cubic spinel-type silicon nitride, characterized in that the cubic spinel-type silicon nitride is allowed to act in a state to separate and purify low-pressure phase silicon nitride in cubic spinel-type silicon nitride.
条件下で作用させる請求項１に記載の立方晶スピネル型
窒化ケイ素の分離、精製方法。2. The method for separating and purifying cubic spinel silicon nitride according to claim 1, wherein the mixed acid solution is allowed to act under a temperature condition of 110 to 160 ° C.
応の低圧相窒化ケイ素とは粉末であって、各粉末の粒子
径が１０μｍ以下である請求項１又は請求項２に記載の
立方晶スピネル型窒化ケイ素の分離、精製方法。3. The cubic spinel according to claim 1, wherein the cubic spinel-type silicon nitride and the unreacted low-pressure phase silicon nitride are powders, and each powder has a particle size of 10 μm or less. Method for separation and purification of silicon nitride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6589899B2 (en) * | 2000-10-12 | 2003-07-08 | National Institute For Research In Inorganic Materials | Spinel type sialon, spinel type silicon oxynitride and methods for producing their powders |
| US7438883B2 (en) * | 2003-04-23 | 2008-10-21 | Nof Corporation | High-pressure phase silicon nitride having a cubic spinel structure and the manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6589899B2 (en) * | 2000-10-12 | 2003-07-08 | National Institute For Research In Inorganic Materials | Spinel type sialon, spinel type silicon oxynitride and methods for producing their powders |
| US7438883B2 (en) * | 2003-04-23 | 2008-10-21 | Nof Corporation | High-pressure phase silicon nitride having a cubic spinel structure and the manufacturing method |
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