JP2010223721A - Method for analysis of impurities in fluorine compound - Google Patents
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本発明は、フッ素化合物中の不純物分析方法に関する。 The present invention relates to a method for analyzing impurities in a fluorine compound.
従来より、フッ素化合物中の不純物を分析する方法が開発されている。不純物の含有量を測定するには、原子吸光分析装置、誘導結合プラズマ（ＩＣＰ）発光分光分析装置又はＩＣＰ質量分析装置などが用いられるが、これらの装置を用いて不純物を測定するには、試料を溶液にして装置に供する必要がある。分析しようとするフッ素化合物を溶液にする（「前処理」と称されている）には、（１）乾式灰化法、（２）湿式灰化法、（３）アルカリあるいは酸融解法、（４）酸素フラスコ燃焼法、（５）燃焼ガス吸収法、（６）燃焼ガス吸収法溶液などがある（例えば特許文献１参照）。 Conventionally, methods for analyzing impurities in fluorine compounds have been developed. In order to measure the impurity content, an atomic absorption spectrometer, an inductively coupled plasma (ICP) emission spectrometer, or an ICP mass spectrometer is used. To measure impurities using these apparatuses, a sample is used. It is necessary to make the solution into a device. In order to make the fluorine compound to be analyzed into a solution (referred to as “pretreatment”), (1) dry ashing method, (2) wet ashing method, (3) alkali or acid melting method, ( 4) Oxygen flask combustion method, (5) Combustion gas absorption method, (6) Combustion gas absorption method solution, etc. (see, for example, Patent Document 1).
このうち、アルカリ融解法は、フッ化物として揮発する成分も簡便な操作で高精度且つ低濃度まで分析可能である。例えば、非特許文献１には、フッ素樹脂中のフッ素を簡易に定量するにあたり、アルカリ融解法を採用している。具体的には、ポリテトラフルオロエチレン（ＰＴＦＥ）を試料として使用する場合、まず、炭酸カリウム製のカプセルを作製し、そのカプセルの中空部分（穴）に試料を正確に量り取る。続いて、予め粉砕乾燥した炭酸カリウム粉末をその中空部分の上部まで詰め込む。そして、電気炉で３００℃から１時間で６００℃まで昇温し、６００℃で１時間分解させたのち、カプセルを電気炉から取り出して放冷する。その後、カプセルを１Ｌのメスフラスコに入れ、水で溶解し、次いで塩酸を加えて中性とし、水で定容にする。 Among these, the alkali melting method can analyze a component that volatilizes as a fluoride with high accuracy and low concentration by a simple operation. For example, Non-Patent Document 1 employs an alkali melting method for easily quantifying fluorine in a fluororesin. Specifically, when polytetrafluoroethylene (PTFE) is used as a sample, first, a capsule made of potassium carbonate is prepared, and the sample is accurately weighed into a hollow portion (hole) of the capsule. Subsequently, potassium carbonate powder that has been pulverized and dried in advance is packed to the top of the hollow portion. Then, the temperature is raised from 300 ° C. to 600 ° C. in one hour in an electric furnace and decomposed at 600 ° C. for one hour, and then the capsule is taken out of the electric furnace and allowed to cool. The capsule is then placed in a 1 L volumetric flask, dissolved in water, then neutralized with hydrochloric acid and made up to volume with water.
しかしながら、フッ素化合物中の不純物成分の分析を行うにあたり、非特許文献１の手法を採用して前処理を施したあとＩＣＰ発光分光分析装置で分析したところ、満足した結果が得られなかった。その原因は、炭酸カリウム製のカプセルの中空部分に試料を量り取ったあと炭酸カリウム粉末をその中空部分の上部まで詰め込み６００℃でフッ素化合物を熱処理するが、６００℃という高温で熱処理するため不純物成分の一部が揮発性のフッ化物となり、そのフッ化物が炭酸カリウム粉末の粉粒同士の間に存在する微小隙間を通じてカプセル外に放散したことにあると考えられる。 However, when analyzing the impurity component in the fluorine compound, when the pretreatment was performed using the method of Non-Patent Document 1 and the analysis was performed with an ICP emission spectroscopic analyzer, a satisfactory result was not obtained. The cause is that after weighing the sample in the hollow portion of the capsule made of potassium carbonate, the potassium carbonate powder is packed up to the top of the hollow portion and the fluorine compound is heat-treated at 600 ° C. It is considered that a part of the volatile fluoride became a volatile fluoride, and the fluoride was diffused out of the capsule through a minute gap existing between the powders of the potassium carbonate powder.
本発明はこのような課題を解決するためになされたものであり、フッ素化合物中の不純物成分を高精度で且つ低濃度まで分析可能にすることを主目的とする。 The present invention has been made to solve such problems, and has as its main object to make it possible to analyze an impurity component in a fluorine compound to a low concentration with high accuracy.
本発明者らは、炭酸カリウムのカプセルの中空部分（穴）にフッ素化合物を量り取ったあとこの中空部分を炭酸カリウムの塊状の蓋で覆い、比較的低温（４００℃以下）で熱処理してフッ素化合物を溶融させたあと溶液化したところ、フッ素化合物中の不純物を高精度で且つ低濃度まで定量分析を行うことができることを見いだし、本発明を完成するに至った。 The inventors measured the fluorine compound in the hollow portion (hole) of the capsule of potassium carbonate, and then covered the hollow portion with a bulky lid of potassium carbonate, and heat-treated at a relatively low temperature (400 ° C. or lower). When the compound was melted and then made into a solution, it was found that impurities in the fluorine compound could be quantitatively analyzed with high accuracy and low concentration, and the present invention was completed.
本発明のフッ素化合物中の不純物の分析方法は、コップ状に形成されたアルカリ金属塩のカプセルの中空部分にフッ素化合物の試料を量り取り、その中空部分の開口をアルカリ金属塩の塊状の蓋で密閉し、前記フッ素化合物の融点以上４００℃以下に設定された熱処理温度まで昇温して前記試料を融解させたあと溶液化し、その溶液中の不純物を定量分析するものである。 According to the method for analyzing impurities in a fluorine compound of the present invention, a sample of a fluorine compound is weighed into a hollow portion of a cup-shaped alkali metal salt capsule, and the opening of the hollow portion is covered with a lump of alkali metal salt. The sample is sealed, heated to a heat treatment temperature set to a melting point of the fluorine compound and not higher than 400 ° C., and the sample is melted to form a solution, and impurities in the solution are quantitatively analyzed.
本発明の分析方法では、熱処理温度を低温（フッ素化合物の融点以上４００℃以下）に設定するため、従来のように高温（６００℃）まで加熱する場合と比べて、フッ素化合物中の不純物が例えばフッ化物などの揮発成分に変わるのではなく、不純物成分とアルカリ金属との不揮発性の酸化物に変わる。また、従来のようにカプセルの開口をアルカリ金属塩の粉末で覆うのではなく、アルカリ金属塩の塊状の蓋で覆うため、カプセルの中空部分がしっかりと密閉される。こうしたことから、不純物成分の一部が揮発成分となってカプセル外に放散してしまうのを有効に防止することができ、ひいては不純物を高精度で且つ低濃度まで分析することが可能となる。 In the analysis method of the present invention, since the heat treatment temperature is set to a low temperature (from the melting point of the fluorine compound to 400 ° C. or less), the impurities in the fluorine compound are, for example, less than that in the conventional heating to a high temperature (600 ° C.). Instead of a volatile component such as fluoride, it changes to a non-volatile oxide of an impurity component and an alkali metal. Further, since the opening of the capsule is not covered with an alkali metal salt powder as in the prior art, but is covered with an alkali metal salt lump, the hollow portion of the capsule is tightly sealed. For this reason, it is possible to effectively prevent a part of the impurity component from becoming a volatile component and dissipating out of the capsule. As a result, the impurity can be analyzed with high accuracy and to a low concentration.
本発明の不純物分析方法において、フッ素化合物としては、例えばポリテトラフルオロエチレン（ＰＴＦＥ、融点３２７℃）、ポリフッ化ビニリデン（ＰＶＤＦ、融点１７１℃）、テトラフルオロエチレン−ペルフルオロアルキルビニルエーテル共重合体（ＰＦＡ、融点３１０℃）、テトラフルオロエチレン−エチレン共重合体（ＥＴＦＥ、融点２７０℃）などのフッ素樹脂のほか、パーフルオロアルカンスルホン酸やパーフルオロカルボン酸などが挙げられる。 In the impurity analysis method of the present invention, examples of the fluorine compound include polytetrafluoroethylene (PTFE, melting point 327 ° C.), polyvinylidene fluoride (PVDF, melting point 171 ° C.), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA, In addition to fluorine resins such as a melting point of 310 ° C. and a tetrafluoroethylene-ethylene copolymer (ETFE, melting point of 270 ° C.), perfluoroalkanesulfonic acid, perfluorocarboxylic acid, and the like can be given.
本発明の不純物分析方法において、不純物としては、特に限定するものではないが、例えば、ケイ素化合物、ホウ素化合物、硫黄化合物、ハロゲン化合物などが挙げられる。このうち、ケイ素化合物やホウ素化合物は、従来、分析中に揮発性のフッ化物となりやすく精度よく分析するのが困難とされていた化合物であるため、本発明を適用する意義が高い。 In the impurity analysis method of the present invention, the impurities are not particularly limited, and examples thereof include silicon compounds, boron compounds, sulfur compounds, and halogen compounds. Among these compounds, silicon compounds and boron compounds are compounds that have been conventionally considered to be volatile fluorides during analysis and difficult to analyze with high precision, and therefore, the significance of applying the present invention is high.
本発明の不純物分析方法において、カプセルの原料となるアルカリ金属塩のアルカリ金属成分としては、リチウム、ナトリウム、カリウムなどが挙げられ、アルカリ金属と塩を形成する酸成分としては炭酸塩、硫酸塩、硝酸塩、塩酸塩などが挙げられる。アルカリ金属塩としては、炭酸ナトリウムや炭酸カリウムが好ましく、炭酸カリウムがより好ましい。 In the impurity analysis method of the present invention, examples of the alkali metal component of the alkali metal salt used as the raw material of the capsule include lithium, sodium, potassium, etc., and the acid component that forms a salt with the alkali metal includes carbonate, sulfate, Examples thereof include nitrates and hydrochlorides. As an alkali metal salt, sodium carbonate and potassium carbonate are preferable, and potassium carbonate is more preferable.
本発明の不純物分析方法において、アルカリ金属塩のカプセルとその蓋を作製するには、例えば、三次元形状のアルカリ金属塩の中実体（中身が詰まっている形態）を作製し、その中実体にコルクボーラー又はその類似器具で穴を開け、くり抜いた部分を蓋として用いることができる。あるいは、アルカリ金属塩のカプセルと蓋とをそれぞれ金型を利用して精度よく作製してもよい。 In the impurity analysis method of the present invention, in order to produce an alkali metal salt capsule and its lid, for example, a solid body of an alkali metal salt having a three-dimensional shape (a form in which the contents are packed) is produced, A hole can be made with a cork borer or similar device, and the hollowed portion can be used as a lid. Alternatively, each of the alkali metal salt capsule and the lid may be prepared with high precision using a mold.
本発明の不純物分析方法において、熱処理温度は、測定対象の不純物が不揮発性の成分になるようにフッ素化合物の融点以上４００℃以下で適宜設定すればよい。例えば、不純物としてホウ素化合物が含まれている場合には、熱処理により不揮発性のホウ素とアルカリ金属との酸化物（例えばアルカリ金属がカリウムの場合にはＫ2ＳｉＯ3 など）になり、不純物としてケイ素化合物が含まれている場合には、熱処理により不揮発性のケイ素とアルカリ金属との酸化物（例えばアルカリ金属がカリウムの場合にはＫ2Ｂ4Ｏ7 など）になる。なお、熱処理温度としてフッ素化合物の融点を採用した場合には、４００℃近辺の温度を採用した場合に比べて、フッ素化合物が融解しきるまでに時間を要したり不純物が不揮発性の成分に変わるのに時間を要したりするものの、本発明の効果すなわち不純物を高精度で且つ低濃度まで分析することができるという効果を奏する。また、不純物のほぼ全量を不揮発性の成分に変換させるためには、熱処理温度まで昇温したあと該熱処理温度で保持することが好ましい。こうすれば、分析精度がより高くなる。ここで、熱処理温度で保持する時間は、測定対象の不純物に応じて適宜設定すればよいが、例えば１０〜１２０分の間で設定すればよい。熱処理温度まで昇温する場合には、その昇温速度を１〜２℃／ｍｉｎの低速とするのが好ましい。急激に昇温すると不純物が不揮発成分に変わるほかに不純物の一部がフッ素化して揮発成分に変わるおそれがあり、その場合にはカプセルが蓋で密閉されているとはいえ、揮発成分がカプセル外に放散する可能性があるからである。 In the impurity analysis method of the present invention, the heat treatment temperature may be appropriately set between the melting point of the fluorine compound and 400 ° C. or less so that the impurity to be measured becomes a non-volatile component. For example, when a boron compound is included as an impurity, it becomes a non-volatile boron and alkali metal oxide (for example, K 2 SiO 3 when the alkali metal is potassium) by heat treatment, and silicon as the impurity. When the compound is contained, it becomes non-volatile silicon and alkali metal oxide (for example, K 2 B 4 O 7 when the alkali metal is potassium) by heat treatment. Note that when the melting point of the fluorine compound is adopted as the heat treatment temperature, it takes time until the fluorine compound is completely melted or the impurities are changed to non-volatile components as compared with the case where a temperature around 400 ° C. is adopted. However, the effect of the present invention, that is, the effect that impurities can be analyzed with high accuracy and low concentration is obtained. In order to convert almost the entire amount of impurities into a non-volatile component, it is preferable that the temperature is raised to the heat treatment temperature and then maintained at the heat treatment temperature. In this way, the analysis accuracy becomes higher. Here, the holding time at the heat treatment temperature may be appropriately set according to the impurity to be measured, but may be set, for example, for 10 to 120 minutes. When the temperature is raised to the heat treatment temperature, the rate of temperature rise is preferably a low rate of 1 to 2 ° C./min. If the temperature rises suddenly, impurities may turn into non-volatile components, and some of the impurities may be fluorinated to turn into volatile components. In this case, the volatile components are outside the capsule, even though the capsule is sealed with a lid. This is because there is a possibility of being dissipated.
本発明の不純物分析方法において、熱処理したあと溶液化するには、熱処理温度からそのまま放冷したあと純水に溶解して溶液化してもよいが、その場合には、熱処理温度が４００℃以下のため、試料中に未燃成分（煤など）が残っていることがある。こうした未燃成分が溶液中に混入すると、分析装置に悪影響を及ぼすことがある。例えば、ＩＣＰ発光分光分析装置などのように分析時にノズルから溶液を噴霧する装置の場合には、ノズルが未燃成分によって詰まるおそれがある。こうしたことから、試料を熱処理温度で処理したあと、アルカリ金属塩の融点以上（例えば９００℃以上）に加熱してカプセル及び蓋を融解させ、その後放冷して純水に溶解して溶液化することが好ましい。こうすれば、試料中のフッ素化合物は完全に燃焼するため、未燃成分による分析装置への悪影響を防止することができる。このようにアルカリ金属塩の融点以上になるように昇温する場合には、昇温速度を１０℃／ｍｉｎ以上、例えば１５〜２０℃／ｍｉｎの高速としてもよい。こうすれば、分析時間を短くすることができる。 In the impurity analysis method of the present invention, in order to form a solution after heat treatment, the solution may be left to cool as it is from the heat treatment temperature and then dissolved in pure water to form a solution. In this case, the heat treatment temperature is 400 ° C. or lower. Therefore, unburned components (such as soot) may remain in the sample. If such unburned components are mixed in the solution, the analyzer may be adversely affected. For example, in the case of an apparatus that sprays a solution from a nozzle at the time of analysis, such as an ICP emission spectroscopic analysis apparatus, the nozzle may be clogged with unburned components. For this reason, after the sample is treated at the heat treatment temperature, it is heated to a temperature higher than the melting point of the alkali metal salt (for example, 900 ° C. or higher) to melt the capsule and lid, and then left to cool and dissolve in pure water to form a solution. It is preferable. By doing so, the fluorine compound in the sample is completely combusted, so that it is possible to prevent the unburned component from adversely affecting the analyzer. Thus, when raising the temperature to be equal to or higher than the melting point of the alkali metal salt, the rate of temperature rise may be 10 ° C./min or higher, for example, 15 to 20 ° C./min. By doing so, the analysis time can be shortened.
本発明の不純物分析方法において、溶液化したあとの分析は、従来と同様、原子吸光分析装置、ＩＣＰ発光分析装置、ＩＣＰ質量分析装置などを利用して行うことができる。 In the impurity analysis method of the present invention, the analysis after the solution is made can be performed using an atomic absorption analyzer, an ICP emission analyzer, an ICP mass spectrometer, or the like, as in the past.
［実施例］
まず、炭酸カリウム製のカプセルとその蓋を作製した。カプセル作製手順を図１に示す。白金ルツボに炭酸カリウム粉末を入れ、加熱溶融した。溶融した炭酸カリウムを有底筒型の黒鉛ルツボに入れて放冷し、外径１０ｍｍ、高さ１８ｍｍで中実の炭酸カリウム円柱体を取り出した。この炭酸カリウム円柱体をコルクボーラーで加工して直径６ｍｍ、深さ１５ｍｍの穴を開け、カプセルが完成した。このとき、コルクボーラーの中空筒状の差込部には、抜き取った炭酸カリウムの塊が残っているため、この塊を加工してカプセルの穴の蓋とした。なお、蓋は、穴の直径よりもやや大きめのコルクボーラーを用いて別の炭酸カリウム円柱体から塊を抜き取り、その塊を加工して作製してもよい。
[Example]
First, a capsule made of potassium carbonate and its lid were prepared. The capsule manufacturing procedure is shown in FIG. Potassium carbonate powder was placed in a platinum crucible and melted by heating. The molten potassium carbonate was put into a bottomed cylindrical graphite crucible and allowed to cool, and a solid potassium carbonate cylinder having an outer diameter of 10 mm and a height of 18 mm was taken out. This potassium carbonate cylinder was processed with a cork borer to make a hole with a diameter of 6 mm and a depth of 15 mm, thereby completing a capsule. At this time, since the extracted potassium carbonate lump remains in the hollow cylindrical insertion part of the cork borer, this lump was processed to form a lid for the capsule hole. The lid may be produced by extracting a lump from another potassium carbonate cylinder using a cork borer slightly larger than the diameter of the hole and processing the lump.
次に、試料中のケイ素及びホウ素の定量分析を行った。試料として、市販されているフッ素樹脂（試料Ａという）を用意した。また、試料Ａに所定量のケイ素とホウ素を加えたものを用意し、これを試料Ａ+とした。具体的には、試料Ａ+は、ケイ素標準溶液（例えばＳＰＥＸ社製ＰＬＳＩ９−２Ｙ Ｓｉ１０００ｍｇ／Ｌ）とホウ素標準溶液（例えばＳＰＥＸ社製ＰＬＢ９−２Ｙ Ｂ１０００ｍｇ／Ｌ）を、試料Ａに対してケイ素及びホウ素がそれぞれ１００μｇ／ｇとなるように添加して調製した。そして試料Ａ及び試料Ａ+について、以下の手順にしたがってケイ素及びホウ素の定量分析を行った。なお、以下には試料Ａについて説明するが、試料Ａ+についても同様である。
Next, quantitative analysis of silicon and boron in the sample was performed. A commercially available fluororesin (referred to as sample A) was prepared as a sample. Also, providing a plus silicon and boron a predetermined amount of the sample A, which was used as a sample A +. Specifically, a sample A + is obtained by using a silicon standard solution (for example, PLSI9-
まず、０．２ｇの試料Ａをカプセルの穴に量り取り、その穴の開口を蓋で密閉した。次いで、そのカプセルごと白金ルツボに入れて電気炉で熱処理温度４００℃まで徐々に昇温し、４００℃で３０分保持した。これにより、試料Ａは融解した。このときの昇温速度は１時間あたり１００℃（約１．７℃／ｍｉｎ）とした。その後、９００℃まで急激に昇温し、９００℃で３０分保持した。これにより、白金ルツボ内で炭酸カリウム製のカプセル及び蓋が融解した。このときの昇温速度は３０分で５００℃（約１７℃／ｍｉｎ）とした。なお、熱処理工程での時間と加熱温度との関係を図２に示す。放冷後、白金ルツボごとテフロンビーカーに入れて純水を加え、白金ルツボの内容物を純水に溶かして溶液とした。白金ルツボを純水で洗いながら取り出し、その洗浄液も先の溶液に合わせ、そこに塩酸７ｍＬを加えた。塩酸を加えた溶液を８０〜９０℃に加熱して炭酸ガスを抜いた後、ＰＭＰ（ポリメチルペンテン）製メスフラスコ（１００ｍＬ）に移し、純水で定容にした。得られた溶液を用いてＩＣＰ発光分光分析法により、ケイ素およびホウ素を定量した。試料Ａ及び試料Ａ+の定量分析の結果を表１に示す。 First, 0.2 g of sample A was weighed into a capsule hole, and the opening of the hole was sealed with a lid. Next, the capsules were placed in a platinum crucible, gradually heated to a heat treatment temperature of 400 ° C. in an electric furnace, and held at 400 ° C. for 30 minutes. Thereby, sample A melted. The heating rate at this time was 100 ° C. per hour (about 1.7 ° C./min). Then, it heated up rapidly to 900 degreeC and hold | maintained at 900 degreeC for 30 minutes. This melted the capsule and lid made of potassium carbonate in the platinum crucible. The heating rate at this time was 500 ° C. (about 17 ° C./min) in 30 minutes. Note that the relationship between the time in the heat treatment step and the heating temperature is shown in FIG. After allowing to cool, the platinum crucible was placed in a Teflon beaker and pure water was added, and the contents of the platinum crucible were dissolved in pure water to obtain a solution. The platinum crucible was taken out while washing with pure water, the washing solution was also combined with the previous solution, and 7 mL of hydrochloric acid was added thereto. The solution to which hydrochloric acid was added was heated to 80 to 90 ° C. to remove carbon dioxide, and then transferred to a volumetric flask (100 mL) made of PMP (polymethylpentene) and made up to volume with pure water. Silicon and boron were quantified by ICP emission spectrometry using the obtained solution. Table 1 shows the results of quantitative analysis of sample A and sample A + .
表１に示す添加回収率は、試料Ａ+を調製する際に試料Ａに添加した所定量のケイ素とホウ素の回収率を表し、表１の欄外に示す式により算出したものである。この添加回収率が１００％に近いほど精度が高いことになるが、ここではケイ素及びホウ素の添加回収率はともに９６％であったため、高精度な分析結果が得られたと判断した。また、別途、定量下限を求めた。定量下限は、ブランク試験を４回繰り返し行い、その標準偏差の１０倍とした。なお、ブランク試験とは、空試験値を得るために試料を用いないで、試料を用いたときと同様の操作を行う試験をいう。その結果、ケイ素は９．７μｇ／ｇ、ホウ素は２．３μｇ／ｇであった。つまり、定量下限は、０．０００３〜０．００１重量％であり、低濃度の不純物の定量分析が可能なことがわかった。これらの結果から、試料Ａのホウ素及びケイ素の定量結果も、高精度で低濃度まで分析された結果であるといえる。なお、試料Ａとは異なる市販のフッ素樹脂からなる試料Ｂについても定量分析を行った。その結果を表２に示す。 The addition recovery rate shown in Table 1 represents the recovery rate of a predetermined amount of silicon and boron added to Sample A when preparing Sample A +, and was calculated by the formula shown in the margin of Table 1. The closer this addition recovery rate is to 100%, the higher the accuracy. However, since the addition recovery rates of silicon and boron were both 96%, it was judged that a highly accurate analysis result was obtained. Separately, the lower limit of quantification was determined. The lower limit of quantification was set to 10 times the standard deviation by repeating the blank test four times. In addition, a blank test means the test which does not use a sample in order to obtain a blank test value, but performs the same operation as when a sample is used. As a result, silicon was 9.7 μg / g and boron was 2.3 μg / g. That is, the lower limit of quantification is 0.0003 to 0.001% by weight, and it was found that quantitative analysis of low concentration impurities is possible. From these results, it can be said that the results of quantitative determination of boron and silicon in Sample A were also analyzed to a low concentration with high accuracy. In addition, the quantitative analysis was performed also about the sample B which consists of a commercially available fluororesin different from the sample A. FIG. The results are shown in Table 2.
［比較例］
試料Ａ及び試料Ａ+について、非特許文献１の手順にしたがってケイ素及びホウ素の定量分析を行った。なお、以下には試料Ａについて説明するが、試料Ａ+についても同様である。まず、炭酸カリウム製のカプセルの穴に試料Ａを入れ、予め粉砕乾燥した炭酸カリウム粉末を穴の上部まで詰め込んだ。そして、電気炉で３００℃から１時間で６００℃まで昇温し、６００℃で１時間保持したのち、カプセルを電気炉から取り出して放冷した。その後、カプセルをメスフラスコに入れ、純水で溶解し、次いで塩酸を加えて中性とし、純水で定容にした。この溶液を用いてＩＣＰ発行分光分析法により、ケイ素及びホウ素を定量分析した。そして、試料Ａと試料Ａ+の分析結果から実施例と同様にして添加回収率を求めたところ、９０％未満であった。これは、熱処理温度が６００℃という高温のため、ケイ素化合物は熱処理時にケイ酸カリウムのほかに揮発性のフッ化ケイ素（ＳｉＦ4）となり、ホウ素化合物は熱処理時にホウ酸カリウムのほかに揮発性のフッ化ホウ素（ＢＦ3）となって、試料を覆っている炭酸カリウム粉末の微小な隙間からカプセル外へ放散したことが原因と考えられる。また、実施例と同様にして定量下限を求めたところ、０．０１重量％以下となった。このことから、実施例は、比較例に比べて、高精度で且つ低濃度まで定量分析が可能なことがわかった。
[Comparative example]
Sample A and sample A + were subjected to quantitative analysis of silicon and boron according to the procedure of Non-Patent Document 1. Note that the following will be described for Sample A, same is true for samples A +. First, sample A was put into a hole of a capsule made of potassium carbonate, and potassium carbonate powder that had been crushed and dried in advance was packed up to the top of the hole. Then, the temperature was raised from 300 ° C. to 600 ° C. in 1 hour in an electric furnace and held at 600 ° C. for 1 hour, and then the capsule was taken out of the electric furnace and allowed to cool. Thereafter, the capsule was put into a measuring flask, dissolved with pure water, then neutralized by adding hydrochloric acid, and made up to volume with pure water. Using this solution, silicon and boron were quantitatively analyzed by ICP emission spectroscopy. And when the addition recovery rate was calculated | required like the Example from the analysis result of sample A and sample A + , it was less than 90%. This is because the heat treatment temperature is 600 ° C., the silicon compound becomes volatile silicon fluoride (SiF 4 ) in addition to potassium silicate during heat treatment, and the boron compound is volatile in addition to potassium borate during heat treatment. The cause is considered to be boron fluoride (BF 3 ), which was released out of the capsule through a minute gap of the potassium carbonate powder covering the sample. Further, when the lower limit of quantification was determined in the same manner as in the example, it was 0.01% by weight or less. From this, it was found that the example can be quantitatively analyzed with higher accuracy and lower concentration than the comparative example.
本発明は、フッ素樹脂などのフッ素化合物中の不純物を分析するために用いられる。 The present invention is used for analyzing impurities in a fluorine compound such as a fluororesin.
Claims (5)
コップ状に形成されたアルカリ金属塩のカプセルの中空部分にフッ素化合物の試料を量り取り、その中空部分の開口をアルカリ金属塩の塊状の蓋で密閉し、前記フッ素化合物の融点以上４００℃以下に設定された熱処理温度まで昇温して前記試料を融解させたあと溶液化し、その溶液中の不純物を定量分析する、
フッ素化合物中の不純物分析方法。 A method for analyzing impurities in a fluorine compound,
A sample of the fluorine compound is weighed in the hollow portion of the capsule of the alkali metal salt formed in a cup shape, and the opening of the hollow portion is sealed with an alkali metal salt lump so that the melting point of the fluorine compound is not lower than 400 ° C. Raise the temperature to the set heat treatment temperature and melt the sample, then turn it into a solution and quantitatively analyze the impurities in the solution.
Method for analyzing impurities in fluorine compounds.
請求項１に記載の不純物分析方法。 After melting the sample, the capsule and the lid are melted by heating above the melting point of the alkali metal salt, and then allowed to cool and dissolved in pure water to form a solution.
The impurity analysis method according to claim 1.
請求項１又は２記載の不純物分析方法。 After raising the temperature to the heat treatment temperature, hold at the heat treatment temperature for 10 to 120 minutes.
The impurity analysis method according to claim 1 or 2.
請求項１〜３のいずれか１項に記載の不純物分析方法。 The fluorine compound includes a silicon compound or a boron compound as impurities.
The impurity analysis method according to claim 1.
請求項１〜４のいずれか１項に記載の不純物分析方法。 The alkali metal salt is potassium carbonate.
The impurity analysis method according to claim 1.
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| CN103728288A (en) * | 2014-01-10 | 2014-04-16 | 福建医科大学 | Method for oxidizing terephthalic acid to enhance fluorescence by employing nanometer copper oxide to catalyze hydrogen peroxide |
| CN106198394A (en) * | 2016-06-29 | 2016-12-07 | 中国电建集团贵阳勘测设计研究院有限公司 | A kind of microcosmic judges the method for aggregate basic active |
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| CN103728288A (en) * | 2014-01-10 | 2014-04-16 | 福建医科大学 | Method for oxidizing terephthalic acid to enhance fluorescence by employing nanometer copper oxide to catalyze hydrogen peroxide |
| CN106198394A (en) * | 2016-06-29 | 2016-12-07 | 中国电建集团贵阳勘测设计研究院有限公司 | A kind of microcosmic judges the method for aggregate basic active |
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