JP2018009981A - Method for quantifying amount of silicon in metal material, method for dissolving metal material including silicon component, and metal material dissolution liquid - Google Patents
Method for quantifying amount of silicon in metal material, method for dissolving metal material including silicon component, and metal material dissolution liquid Download PDFInfo
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- 239000010703 silicon Substances 0.000 title claims abstract description 105
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 105
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000007769 metal material Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004090 dissolution Methods 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 title claims description 35
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 83
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052796 boron Inorganic materials 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 44
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 30
- 239000011707 mineral Substances 0.000 claims abstract description 30
- 239000012488 sample solution Substances 0.000 claims abstract description 30
- -1 fluoride ions Chemical class 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000004458 analytical method Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004993 emission spectroscopy Methods 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 238000004949 mass spectrometry Methods 0.000 claims description 4
- 238000003321 atomic absorption spectrophotometry Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 abstract description 19
- 239000012535 impurity Substances 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000523 sample Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 150000001639 boron compounds Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000009614 chemical analysis method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000005059 solid analysis Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical class [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- RPJKYODNJDVOOO-UHFFFAOYSA-N [B].F Chemical class [B].F RPJKYODNJDVOOO-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
Description
本発明は、金属材料中のケイ素量を定量する方法、ケイ素成分を含む金属材料の溶解方法、および金属材料の溶解液に関する。 The present invention relates to a method for quantifying the amount of silicon in a metal material, a method for dissolving a metal material containing a silicon component, and a solution for dissolving the metal material.
金属材料には、ケイ素成分（例えば、ケイ素やケイ素化合物など）が、特異的な金属性能を発現させる目的で添加物として意図的に添加されたり、もしくは、製造過程で精製されずに不純物として残留したりすることがある。 In metal materials, silicon components (for example, silicon and silicon compounds) are intentionally added as additives for the purpose of expressing specific metal performance, or remain as impurities without being purified in the manufacturing process. Sometimes.
金属材料におけるケイ素の品位評価は、ケイ素の濃度や含有量に応じて、種々の定量方法が適用されている。
例えば、濃度が０．ｎ％程度と高く、金属材料中で均一である場合には、蛍光Ｘ線などに代表される非破壊分析法での定量が可能である。
一方、濃度や含有量が極微量である場合や金属材料中でばらつく場合には、破壊分析法として、発光分光分析法や、化学的な処理によって金属材料を溶液化した後に、目的元素を直接もしくは選択的に分離する化学分析法により定量を行うことが可能である。化学分析法によれば、金属材料を溶液化することで、濃度を均一化できるので、濃度にばらつきのある材料であっても定量することが可能である。
Various quantitative methods are applied to the quality evaluation of silicon in a metal material according to the concentration and content of silicon.
For example, the concentration is 0. When it is as high as about n% and is uniform in the metal material, it can be quantified by a nondestructive analysis method typified by fluorescent X-rays.
On the other hand, when the concentration or content is extremely small or varies in the metal material, as the destructive analysis method, after the metal material is made into a solution by chemical emission, the target element is directly Alternatively, quantification can be performed by a chemical analysis method that selectively separates. According to the chemical analysis method, since the concentration can be made uniform by making the metal material into a solution, it is possible to quantify even a material having a variation in concentration.
一般に、金属材料に不純物として含まれるケイ素成分は極微量であるため、蛍光Ｘ線では定量が困難である。また蛍光Ｘ線以外の固体分析法では、不純物濃度が均一でない場合には、金属材料における代表的な数値として得られないおそれがある。そのため、不純物として混入する極微量のケイ素を定量する場合は、金属材料を溶解させ、その試料溶液を化学分析するのが一般的である。 Generally, since a silicon component contained as an impurity in a metal material is extremely small, it is difficult to determine with a fluorescent X-ray. Further, in solid analysis methods other than fluorescent X-rays, if the impurity concentration is not uniform, there is a possibility that it cannot be obtained as a representative numerical value in a metal material. Therefore, when quantifying a very small amount of silicon mixed as an impurity, it is common to dissolve a metal material and chemically analyze the sample solution.
金属材料を溶解させるときに、不純物がケイ素であれば、鉱酸により比較的容易に溶解できるが、ケイ素化合物として二酸化ケイ素やケイ酸塩などの酸化物であると、溶解させることが困難となる。そこで、溶解させるための助剤としてフッ化水素酸を用いる方法が提案されている（例えば、非特許文献１を参照）。具体的には、鉱酸とフッ化水素酸とを含む処理液に金属材料を添加して加熱することにより、金属成分とともに、ケイ素やケイ素化合物を溶解させて試料溶液を調製することができる。 When the metal material is dissolved, if the impurity is silicon, it can be dissolved relatively easily by a mineral acid, but if the silicon compound is an oxide such as silicon dioxide or silicate, it is difficult to dissolve the metal material. . Then, the method of using hydrofluoric acid as an auxiliary agent for making it melt | dissolve is proposed (for example, refer nonpatent literature 1). Specifically, by adding a metal material to a treatment liquid containing mineral acid and hydrofluoric acid and heating, the sample solution can be prepared by dissolving silicon and the silicon compound together with the metal component.
ただし、フッ化水素酸は、試料溶液の測定装置において、石英からなる部材を腐食させてしまうおそれがある。そのため、フッ化水素酸を用いて溶解させた試料溶液を測定する場合、測定装置において試料溶液が通過する部材を、例えばフッ素樹脂やアルミナなどのフッ化水素酸に耐性を有する材料で構成する必要がある。 However, hydrofluoric acid may corrode a quartz member in a sample solution measuring apparatus. Therefore, when measuring a sample solution dissolved with hydrofluoric acid, the member through which the sample solution passes in the measuring device must be made of a material resistant to hydrofluoric acid such as fluororesin or alumina. There is.
また、フッ化水素酸による腐食を抑制する目的で、フッ化水素酸を用いて溶解させた試料溶液にホウ素化合物を添加する方法が提案されている（例えば、特許文献１を参照）。ホウ素化合物によれば、試料溶液中に残存するフッ化水素酸を不活性化し、その腐食効果を抑制（マスキング）することができる。 For the purpose of suppressing corrosion caused by hydrofluoric acid, a method of adding a boron compound to a sample solution dissolved using hydrofluoric acid has been proposed (see, for example, Patent Document 1). According to the boron compound, hydrofluoric acid remaining in the sample solution can be inactivated, and its corrosion effect can be suppressed (masked).
上述したように、金属材料中のケイ素量を精度よく定量するには、フッ化水素酸を用いてケイ素成分を溶解させる必要があり、フッ化水素酸を含む試料溶液を測定する場合は、フッ化水素酸に耐性を有する部材で構成された特別な測定装置を用いるか、もしくは、試料溶液にホウ素化合物を添加してフッ化水素酸をマスキングする必要がある。 As described above, in order to accurately determine the amount of silicon in the metal material, it is necessary to dissolve the silicon component using hydrofluoric acid. When measuring a sample solution containing hydrofluoric acid, it is necessary to use a fluorocarbon. It is necessary to use a special measuring device composed of a member resistant to hydrofluoric acid, or to mask the hydrofluoric acid by adding a boron compound to the sample solution.
このように、フッ化水素酸を用いる場合、特別な測定装置を用いたり、測定前に試料溶液を前処理したりする必要があるため、工程が複雑となる。 As described above, when hydrofluoric acid is used, it is necessary to use a special measuring device or to pre-process the sample solution before the measurement, which complicates the process.
しかも、本発明者の検討によると、フッ化水素酸をマスキングする目的で添加するホウ素化合物には、その生成過程でケイ素が混入しているため、金属材料中の微量なケイ素量を精度よく定量することが困難であることが分かった。 Moreover, according to the study of the present inventor, the boron compound added for the purpose of masking hydrofluoric acid is mixed with silicon during the formation process, so that a minute amount of silicon in the metal material can be accurately determined. It turned out to be difficult to do.
本発明は、上記課題に鑑みてなされたものであり、鉱酸に溶解させにくいケイ素化合物などのケイ素成分を含む金属材料中のケイ素量を精度よく、かつ簡便に定量する技術を提供することを目的とする。 The present invention has been made in view of the above problems, and provides a technique for accurately and simply quantifying the amount of silicon in a metal material containing a silicon component such as a silicon compound that is difficult to dissolve in mineral acid. Objective.
本発明者は、フッ化水素酸に代わる成分であって、鉱酸に溶解しにくいケイ素化合物を溶解することができ、かつ測定装置を腐食させないような成分について検討を行った。その結果、テトラフルオロホウ酸などの含ホウ素フッ化水素酸誘導体を用いるとよいことが見出された。 This inventor examined the component which can replace the hydrofluoric acid which can melt | dissolve the silicon compound which is hard to melt | dissolve in a mineral acid, and does not corrode a measuring apparatus. As a result, it has been found that a boron-containing hydrofluoric acid derivative such as tetrafluoroboric acid may be used.
この誘導体は、フッ素およびホウ素を含み、酸性条件下で加熱したときにはフッ化物イオンを遊離させ、フッ化水素酸と同様にケイ素化合物を溶解させる一方、常温ではホウ素でフッ化物イオンをマスキングして不活性化させることができる。つまり、この誘導体は、金属材料を処理液中で加熱しながら溶解するときにはフッ化物イオンを発生させるが、金属材料を溶解させた処理液を冷却して分析に供するときにはフッ化物イオンを発生させない。
また、この誘導体は、純度が高いので、金属材料中の微量なケイ素量を精度よく定量することが可能となる。
したがって、鉱酸とともに含ホウ素フッ化水素酸誘導体を併用することにより、ケイ素化合物を溶解させ、金属材料中のケイ素量を精度よく、かつ簡便に定量することができることを見出し、本発明を完成させるに至った。
This derivative contains fluorine and boron. When heated under acidic conditions, this derivative liberates fluoride ions and dissolves the silicon compound in the same way as hydrofluoric acid. Can be activated. That is, this derivative generates fluoride ions when the metal material is dissolved while being heated in the treatment liquid, but does not generate fluoride ions when the treatment liquid in which the metal material is dissolved is cooled and used for analysis.
Further, since this derivative has a high purity, it is possible to accurately quantify a small amount of silicon in the metal material.
Accordingly, it is found that by using a boron-containing hydrofluoric acid derivative together with a mineral acid, the silicon compound can be dissolved, and the amount of silicon in the metal material can be accurately and easily quantified to complete the present invention. It came to.
すなわち、本発明の第１の態様は、
ケイ素成分を含む金属材料中のケイ素量を定量する方法であって、
前記金属材料を含ホウ素フッ化水素酸誘導体と鉱酸とを含む処理液に添加する添加工程と、
前記処理液を加熱することで、前記金属材料の金属成分とともに、前記含ホウ素フッ化水素酸誘導体から遊離するフッ化物イオンにより前記ケイ素成分を溶解させる溶解工程と、
前記溶解工程にて得られた処理液を冷却して試料溶液を調製する調製工程と、
前記試料溶液を分析する分析工程と、を有することを特徴とする、金属材料中のケイ素量を定量する方法が提供される。
That is, the first aspect of the present invention is:
A method for quantifying the amount of silicon in a metal material containing a silicon component,
An addition step of adding the metal material to a treatment liquid containing a boron-containing hydrofluoric acid derivative and a mineral acid;
A dissolution step of dissolving the silicon component by fluoride ions liberated from the boron-containing hydrofluoric acid derivative together with the metal component of the metal material by heating the treatment liquid;
A preparation step of preparing a sample solution by cooling the treatment liquid obtained in the dissolution step;
There is provided an analysis step of analyzing the sample solution, and a method for quantifying the amount of silicon in a metal material is provided.
本発明の第２の態様は、
ケイ素成分を含む金属材料中のケイ素量を定量する方法であって、
前記金属材料を鉱酸に添加し、少なくとも前記金属材料の金属成分を溶解させる第１の溶解工程と、
前記第１の溶解工程にて得られた処理液に含ホウ素フッ化水素酸誘導体を添加し、当該処理液を加熱することで、前記含ホウ素フッ化水素酸誘導体から遊離するフッ化物イオンにより、前記ケイ素成分を溶解させる第２の溶解工程と、
前記第２の溶解工程にて得られた処理液を冷却して試料溶液を調製する調製工程と、
前記試料溶液を分析する分析工程と、を有することを特徴とする、金属材料中のケイ素量を定量する方法が提供される。
The second aspect of the present invention is:
A method for quantifying the amount of silicon in a metal material containing a silicon component,
A first dissolving step of adding the metal material to a mineral acid and dissolving at least a metal component of the metal material;
By adding a boron-containing hydrofluoric acid derivative to the treatment liquid obtained in the first dissolution step and heating the treatment liquid, fluoride ions liberated from the boron-containing hydrofluoric acid derivative, A second dissolving step for dissolving the silicon component;
A preparation step of preparing a sample solution by cooling the treatment liquid obtained in the second dissolution step;
There is provided an analysis step of analyzing the sample solution, and a method for quantifying the amount of silicon in a metal material is provided.
本発明の第３の態様は、第１又は第２の態様の金属材料中のケイ素量を定量する方法において、
前記含ホウ素フッ化水素酸誘導体は、フッ素およびホウ素を含み、酸性条件下で加熱されたときにはフッ化物イオンを遊離させ、常温ではホウ素でフッ化物イオンをマスキングする。
According to a third aspect of the present invention, in the method for quantifying the amount of silicon in the metal material of the first or second aspect,
The boron-containing hydrofluoric acid derivative contains fluorine and boron, liberates fluoride ions when heated under acidic conditions, and masks fluoride ions with boron at room temperature.
本発明の第４の態様は、第１〜第３の態様の金属材料中のケイ素量を定量する方法において、
前記含ホウ素フッ化水素酸誘導体としてテトラフルオロホウ酸を用いる。
According to a fourth aspect of the present invention, in the method for quantifying the amount of silicon in the metal material of the first to third aspects,
Tetrafluoroboric acid is used as the boron-containing hydrofluoric acid derivative.
本発明の第５の態様は、第１〜第４の態様の金属材料中のケイ素量を定量する方法において、
前記分析工程では、ＩＣＰ発光分光分析法、ＩＣＰ質量分析法または原子吸光光度法により測定する。
According to a fifth aspect of the present invention, in the method for quantifying the amount of silicon in the metal material of the first to fourth aspects,
In the analysis step, measurement is performed by ICP emission spectroscopy, ICP mass spectrometry, or atomic absorption spectrophotometry.
本発明の第６の態様は、
ケイ素成分を含む金属材料を溶解する溶解方法であって、
含ホウ素フッ化水素酸誘導体と鉱酸とを含む溶解液に前記金属材料を添加し、加熱することにより、前記金属材料の金属成分とともに、前記含ホウ素フッ化水素酸誘導体から遊離するフッ化物イオンにより前記ケイ素成分を溶解させる、ケイ素成分を含む金属材料の溶解方法が提供される。
The sixth aspect of the present invention is:
A melting method for dissolving a metal material containing a silicon component,
Fluoride ions released from the boron-containing hydrofluoric acid derivative together with the metal component of the metal material by adding the metal material to a solution containing a boron-containing hydrofluoric acid derivative and a mineral acid and heating the solution. Provides a method for dissolving a metal material containing a silicon component, wherein the silicon component is dissolved.
本発明の第７の態様は、
ケイ素成分を含む金属材料を溶解する溶解液であって、
含ホウ素フッ化水素酸誘導体と鉱酸とを含み、
加熱により、前記含ホウ素フッ化水素酸誘導体からフッ化物イオンを遊離させるように構成される、金属材料の溶解液が提供される。
The seventh aspect of the present invention is
A solution for dissolving a metal material containing a silicon component,
A boron-containing hydrofluoric acid derivative and a mineral acid,
A solution of a metal material is provided that is configured to liberate fluoride ions from the boron-containing hydrofluoric acid derivative by heating.
本発明によれば、鉱酸に溶解させにくいケイ素化合物などのケイ素成分を含む金属材料中のケイ素量を精度よく、かつ簡便に定量することができる。 According to the present invention, the amount of silicon in a metal material containing a silicon component such as a silicon compound that is difficult to dissolve in mineral acid can be accurately and easily quantified.
＜第１の実施形態＞
以下、本発明の第１の実施形態について説明をする。
なお、本明細書において、金属材料とは、金属または合金を含む金属成分とケイ素成分とを含有するものである。ケイ素成分とは、特異的な金属性能を発現させるために添加物として意図的に添加されたり、もしくは金属材料の製造過程で生成されずに不純物として残留したりする、ケイ素やケイ素化合物を示す。ケイ素化合物としては、例えば、二酸化ケイ素やケイ酸塩などの酸化物や有機ケイ素化合物（トリメチルシリル基などＳｉを分子構造に有する化合物）を示す。
<First Embodiment>
Hereinafter, a first embodiment of the present invention will be described.
In the present specification, the metal material includes a metal component including a metal or an alloy and a silicon component. The silicon component refers to silicon or a silicon compound that is intentionally added as an additive in order to develop specific metal performance, or remains as an impurity without being generated in the manufacturing process of the metal material. Examples of the silicon compound include oxides such as silicon dioxide and silicate, and organic silicon compounds (compounds having Si in the molecular structure such as trimethylsilyl group).
本実施形態では、金属材料中に不純物として残留する微量なケイ素成分（以下、ケイ素不純物ともいう）を定量する場合を例として説明する。 In the present embodiment, an example will be described in which a trace amount of a silicon component remaining as an impurity in a metal material (hereinafter also referred to as silicon impurity) is quantified.
（準備工程）
まず、分析対象となる金属材料を準備する。金属材料としては、例えば、ケイ素不純物を含むＮｉＣｒ合金などを用いることができる。
(Preparation process)
First, a metal material to be analyzed is prepared. As the metal material, for example, a NiCr alloy containing silicon impurities can be used.
また、金属材料を溶解させるための容器を準備する。この容器としては、ケイ素量を精度よく定量する観点から、密閉型容器を用いることが好ましい。具体的に説明すると、後述するように、金属材料を処理液中で加熱して溶解させるときに、金属材料に含まれるケイ素やケイ素化合物は、フッ化水素酸との反応によりケイフッ化水素酸を形成して処理液に溶解することになる。この際、処理液の温度がケイフッ化水素酸の沸点を超えると、ケイフッ化水素酸が揮散し、ケイ素量が変動してしまうおそれがある。そのため、ケイ素量を精度よく定量するには、ケイフッ化水素酸の揮散を抑制できるような密閉型容器を用いることが好ましい。 In addition, a container for dissolving the metal material is prepared. As this container, it is preferable to use a sealed container from the viewpoint of accurately quantifying the amount of silicon. Specifically, as will be described later, when the metal material is heated and dissolved in the treatment liquid, the silicon or silicon compound contained in the metal material is converted to hydrofluoric acid by reaction with hydrofluoric acid. It will form and dissolve in the processing solution. At this time, if the temperature of the treatment liquid exceeds the boiling point of silicofluoric acid, silicohydrofluoric acid is volatilized and the amount of silicon may fluctuate. Therefore, in order to quantify the silicon amount with high accuracy, it is preferable to use a sealed container that can suppress volatilization of silicofluoric acid.
（添加工程）
次に、密閉型容器に金属材料と金属材料の溶解液を添加して処理液を形成し、容器を密栓する。この溶解液としては、上述したように、含ホウ素フッ化水素酸誘導体および鉱酸を含む溶解液を用いる。
(Addition process)
Next, a metal material and a solution of the metal material are added to the sealed container to form a treatment liquid, and the container is sealed. As this solution, as described above, a solution containing a boron-containing hydrofluoric acid derivative and a mineral acid is used.
鉱酸としては、金属材料の金属成分を溶解可能な成分であればよく、例えば、塩酸、硝酸、過塩素酸、硫酸、およびこれらの混酸などを用いることができる。 The mineral acid may be any component that can dissolve the metal component of the metal material. For example, hydrochloric acid, nitric acid, perchloric acid, sulfuric acid, and mixed acids thereof can be used.
含ホウ素フッ化水素酸誘導体は、フッ素およびホウ素を含み、酸性条件下で加熱したときにはフッ化物イオンを遊離させ、常温ではホウ素でフッ化物イオンをマスキングする化合物である。具体的には、含ホウ素フッ化水素酸誘導体は、鉱酸の存在下で加熱されることにより、フッ化水素酸と同様にフッ化物イオンを遊離させ、ケイ素不純物を溶解させることができる。一方、冷却により例えば常温（２５℃）になると、フッ化物イオンをホウ素との反応によりマスキングしてホウフッ化物イオン（例えばＢＦ４ −）とすることで不活性化させる。このように作用する含ホウ素フッ化水素酸誘導体としては、例えば、テトラフルオロホウ酸などを用いることができる。 A boron-containing hydrofluoric acid derivative is a compound that contains fluorine and boron, liberates fluoride ions when heated under acidic conditions, and masks fluoride ions with boron at room temperature. Specifically, the boron-containing hydrofluoric acid derivative can be heated in the presence of a mineral acid to liberate fluoride ions and dissolve silicon impurities in the same manner as hydrofluoric acid. On the other hand, when the temperature is lowered to, for example, room temperature (25 ° C.), fluoride ions are masked by reaction with boron to be inactivated by forming borofluoride ions (for example, BF 4 − ). As the boron-containing hydrofluoric acid derivative acting in this way, for example, tetrafluoroboric acid can be used.
加熱前の処理液に含まれる含ホウ素フッ化水素酸誘導体は、フッ化物イオンがホウ素でマスキングされて不活性な形態となっている。そのため、処理液では、鉱酸により金属材料の一部、例えば金属成分やケイ素不純物のうちのケイ素などが溶解し始めるが、ケイ素不純物のうちのケイ素化合物（例えば、二酸化ケイ素やケイ酸塩などの酸化物）は溶解せずに、そのままの状態となる。 The boron-containing hydrofluoric acid derivative contained in the treatment liquid before heating is in an inactive form because fluoride ions are masked with boron. Therefore, in the treatment liquid, a part of the metal material, for example, silicon among the metal components and silicon impurities starts to dissolve by the mineral acid, but silicon compounds among the silicon impurities (for example, silicon dioxide and silicates) The oxide is not dissolved and remains as it is.
なお、添加工程において、含ホウ素フッ化水素酸誘導体の添加量は、特に限定されないが、金属材料に対して過剰量とすることが好ましい。 In addition, in the addition step, the addition amount of the boron-containing hydrofluoric acid derivative is not particularly limited, but is preferably excessive with respect to the metal material.
（溶解工程）
次に、添加工程にて得られた処理液を加熱する。これにより、金属成分とともに、ケイ素やケイ素化合物などのケイ素不純物を溶解させる。具体的には、処理液を加熱することで、鉱酸による金属成分の溶解が促される。それと同時に、処理液に含まれる含ホウ素フッ化水素酸誘導体は、鉱酸が存在する酸性条件下で加熱されることとなり、フッ化物イオンを遊離させる。このフッ化物イオンにより、鉱酸では溶解しにくいケイ素化合物が溶解されることになる。その結果、金属成分およびケイ素不純物が溶解する処理液を得る。
(Dissolution process)
Next, the treatment liquid obtained in the addition step is heated. Thereby, silicon impurities such as silicon and silicon compounds are dissolved together with the metal component. Specifically, the metal component is dissolved by the mineral acid by heating the treatment liquid. At the same time, the boron-containing hydrofluoric acid derivative contained in the treatment liquid is heated under acidic conditions in which a mineral acid is present, and liberates fluoride ions. This fluoride ion dissolves a silicon compound that is difficult to dissolve with a mineral acid. As a result, a treatment liquid in which the metal component and silicon impurities are dissolved is obtained.
溶解工程では、含ホウ素フッ化水素酸誘導体がフッ化物イオンを遊離させるように、処理液の温度を１００℃〜２６０℃の範囲内とすることが好ましい。加熱方法としては、特に限定されないが、例えば、ヒーターや高周波加熱装置などを用いて処理液を加熱するとよい。特に、高周波加熱装置を用いて加熱する場合、局所的に加熱できるので、応答性がよくなる。 In the dissolving step, it is preferable that the temperature of the treatment liquid be in the range of 100 ° C. to 260 ° C. so that the boron-containing hydrofluoric acid derivative liberates fluoride ions. Although it does not specifically limit as a heating method, For example, it is good to heat a process liquid using a heater, a high frequency heating apparatus, etc. In particular, when heating is performed using a high-frequency heating device, the responsiveness is improved because the heating can be performed locally.
（調製工程）
次に、溶解工程にて得られた処理液を常温まで冷却し、分析に供する試料溶液を調製する。冷却により、含ホウ素フッ化水素酸誘導体から遊離していたフッ化物イオンがホウ素にマスキングされてホウフッ化物イオン（例えばＢＦ４ −）となり、不活性な状態となる。そのため、本実施形態では、後述の分析工程にて試料溶液を分析装置で測定する際に、フッ化水素酸に耐性を有するフッ素樹脂などからなる試料導入装置を用いる必要がなく、一般的な試料導入装置を用いることができる。
(Preparation process)
Next, the treatment liquid obtained in the dissolution step is cooled to room temperature to prepare a sample solution for analysis. By cooling, the fluoride ions released from the boron-containing hydrofluoric acid derivative are masked by boron to become borofluoride ions (for example, BF 4 − ), and become inactive. Therefore, in this embodiment, it is not necessary to use a sample introduction device made of a fluororesin resistant to hydrofluoric acid when measuring a sample solution with an analyzer in an analysis step described later, and a general sample An introduction device can be used.
（分析工程）
続いて、試料導入装置を用いて試料溶液を分析装置に導入し、試料溶液に含まれるケイ素量を分析する。この分析方法としては、ＩＣＰ発光分光分析法、ＩＣＰ質量分析法または原子吸光光度法が好ましい。より精度よく定量する観点からは、ＩＣＰ発光分光分析法およびＩＣＰ質量分析法においては、マトリックスマッチングを行い、試料溶液の組成の違いを補うようにすることが好ましい。また、分析する際に、好適な内部標準物質を試料溶液に一定量添加し、内部標準補正法を行うことが好ましい。
(Analysis process)
Subsequently, the sample solution is introduced into the analyzer using the sample introduction device, and the amount of silicon contained in the sample solution is analyzed. As this analysis method, ICP emission spectrometry, ICP mass spectrometry or atomic absorption spectrophotometry is preferred. From the viewpoint of quantifying with higher accuracy, in ICP emission spectroscopy and ICP mass spectrometry, it is preferable to perform matrix matching to compensate for the difference in the composition of the sample solution. Moreover, when analyzing, it is preferable to add a certain amount of a suitable internal standard substance to the sample solution and perform the internal standard correction method.
＜第１の実施形態の効果＞
本実施形態によれば、以下に示す１つ又は複数の効果を奏する。
<Effect of the first embodiment>
According to the present embodiment, the following one or more effects are achieved.
本実施形態においては、ケイ素不純物を含む金属材料を溶解させるために、鉱酸とともに、含ホウ素フッ化水素酸誘導体として、例えばテトラフルオロホウ酸を含む溶解液を使用している。この溶解液によれば、金属材料を添加した処理液を加熱したときに、テトラフルオロホウ酸がフッ化物イオンを遊離できるので、ケイ素不純物のうち鉱酸で溶解しにくいケイ素化合物（二酸化ケイ素やケイ酸塩などの酸化物）を溶解させることができる。また、溶解後に得られる処理液を常温まで冷却することにより、遊離するフッ化物イオンをホウ素によりマスキングして不活性な状態に戻すことができる。そのため、冷却した処理液を試料溶液として分析に供する際には、フッ化水素酸に耐性を有する材料からなる試料導入装置などを用いる必要がない。したがって、本実施形態によれば、金属材料を溶解させ、ケイ素不純物に由来するケイ素量を精度よく、かつ簡便に定量することができる。 In this embodiment, in order to dissolve the metal material containing silicon impurities, a solution containing, for example, tetrafluoroboric acid as a boron-containing hydrofluoric acid derivative is used together with a mineral acid. According to this solution, when the treatment liquid to which the metal material is added is heated, tetrafluoroboric acid can liberate fluoride ions, and therefore silicon compounds that are difficult to dissolve with mineral acids among silicon impurities (silicon dioxide and silica). Oxides such as acid salts) can be dissolved. In addition, by cooling the treatment liquid obtained after dissolution to room temperature, the fluoride ions released can be masked with boron and returned to an inactive state. Therefore, when the cooled processing solution is used as a sample solution for analysis, it is not necessary to use a sample introduction device made of a material resistant to hydrofluoric acid. Therefore, according to this embodiment, a metal material can be dissolved and the amount of silicon derived from silicon impurities can be accurately and easily quantified.
また、含ホウ素フッ化水素酸誘導体は、従来、フッ化水素酸を不活性化させるために添加したホウ素化合物のようにケイ素が混入していないので、金属材料に混入する微量なケイ素不純物を精度よく定量することができる。例えば、後述する実施例に示すように、濃度が２０ｐｐｍというような極微量なケイ素を定量することができる。 In addition, boron-containing hydrofluoric acid derivatives do not contain silicon like conventional boron compounds added to inactivate hydrofluoric acid. Can be quantified well. For example, as shown in the examples described later, a very small amount of silicon having a concentration of 20 ppm can be quantified.
また、金属材料を溶解させてケイ素量を分析しているので、ケイ素不純物の含有量もしくは濃度が均一に分布していないような金属材料であっても、ケイ素量をその代表値として精度よく求めることができる。 Moreover, since the silicon content is analyzed by dissolving the metal material, the silicon content is accurately obtained as a representative value even for a metal material in which the content or concentration of silicon impurities is not uniformly distributed. be able to.
＜第２の実施形態＞
上述の第１の実施形態では、溶解工程として、含ホウ素フッ化水素酸誘導体および鉱酸を含む溶解液に金属材料を添加し、金属成分とともにケイ素不純物を同時に溶解させているが、本発明は、これに限定されない。例えば、以下に示すように、金属材料のうち、少なくとも金属成分を溶解させる第１の溶解工程と、ケイ素不純物を溶解させる第２の溶解工程とを設け、金属成分とケイ素不純物を別々に溶解させてもよい。
<Second Embodiment>
In the first embodiment described above, as a dissolving step, a metal material is added to a solution containing a boron-containing hydrofluoric acid derivative and a mineral acid, and silicon impurities are dissolved simultaneously with the metal component. However, the present invention is not limited to this. For example, as shown below, a first dissolving step for dissolving at least a metal component and a second dissolving step for dissolving silicon impurities are provided in the metal material, and the metal components and silicon impurities are separately dissolved. May be.
具体的には、第１の溶解工程として、まず、鉱酸に金属材料を添加し、この処理液を加熱する。これにより、金属材料のうちの金属成分を溶解する。このとき、ケイ素不純物のうち、鉱酸に溶解しやすいケイ素は溶解することもあるが、ケイ素化合物は溶解せず、処理液に残存することになる。 Specifically, as the first dissolution step, first, a metal material is added to the mineral acid, and this treatment liquid is heated. Thereby, the metal component of a metal material is melt | dissolved. At this time, among silicon impurities, silicon that is easily dissolved in the mineral acid may be dissolved, but the silicon compound is not dissolved and remains in the treatment liquid.
続いて、第２の溶解工程として、第１の溶解工程後の処理液に、含ホウ素フッ化水素酸誘導体として例えばテトラフルオロホウ酸を添加し、この処理液を加熱する。これにより、含ホウ素フッ化水素酸からフッ化物イオンを遊離させ、第１の溶解工程で溶け残ったケイ素化合物を溶解させる。 Subsequently, as a second dissolution step, for example, tetrafluoroboric acid is added as a boron hydrofluoric acid derivative to the treatment solution after the first dissolution step, and this treatment solution is heated. Thereby, fluoride ions are liberated from boron-containing hydrofluoric acid, and the silicon compound remaining undissolved in the first dissolution step is dissolved.
その後、第２の溶解工程にて得られた処理液を常温まで冷却し、試料溶液を調製する。その後は、上述の実施形態と同様にケイ素量を分析することができる。 Thereafter, the treatment liquid obtained in the second dissolution step is cooled to room temperature to prepare a sample solution. Thereafter, the silicon content can be analyzed in the same manner as in the above-described embodiment.
＜変形例＞
以上、本発明の実施形態について説明してきたが、本発明は、上述した実施形態に何等限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々に改変することができる。
<Modification>
As mentioned above, although embodiment of this invention has been described, this invention is not limited to the embodiment mentioned above at all, and can be variously modified within the range which does not deviate from the summary of this invention.
上述の実施形態では、微量のケイ素不純物が混入する金属材料における微量なケイ素量を定量する場合について説明したが、本発明では、ケイ素量の定量対象範囲は特に限定されない。例えば、添加物として比較的多量のケイ素成分を含有させた金属材料についてもケイ素量を定量することができる。 In the above-described embodiment, the case of quantifying a trace amount of silicon in a metal material mixed with a trace amount of silicon impurities has been described. However, in the present invention, the quantification target range of the silicon amount is not particularly limited. For example, the amount of silicon can be quantified for a metal material containing a relatively large amount of silicon component as an additive.
以下、本発明をさらに詳細な実施例に基づき説明するが、本発明は、これら実施例に限定されない。 Hereinafter, the present invention will be described based on further detailed examples, but the present invention is not limited to these examples.
（実施例１）
分析対象であるＮｉＣｒ合金材料から、２ｍｍ程度の形状にアロイ片（試験片）を２つ切り出した。これら試験片（サンプル１およびサンプル２）について、図１に示すようにケイ素量の定量を行った。具体的には、試験片を高周波加熱試料分解装置の専用容器に０．５ｇ分、はかり取った。この容器内に、鉱酸として、少量の硝酸および塩酸の混酸を１０ｍＬ、そして、あらかじめ濃度０．１％に調製したテトラフルオロホウ酸を０．１ｍＬ添加した。その後、容器を密閉し、高周波（マイクロ波）によって加熱分解を行い、試験片を溶解した。その後、処理液を常温まで冷却した。
Example 1
Two alloy pieces (test pieces) were cut into a shape of about 2 mm from the NiCr alloy material to be analyzed. For these test pieces (sample 1 and sample 2), the amount of silicon was quantified as shown in FIG. Specifically, 0.5 g of the test piece was weighed out in a dedicated container of the high-frequency heating sample disassembling apparatus. In this container, 10 mL of a mixed acid of a small amount of nitric acid and hydrochloric acid and 0.1 mL of tetrafluoroboric acid prepared in advance to a concentration of 0.1% were added as mineral acids. Thereafter, the container was sealed and subjected to thermal decomposition by high frequency (microwave) to dissolve the test piece. Thereafter, the treatment liquid was cooled to room temperature.
得られた処理液に内部標準物質として濃度１００ｍｇ／Ｌのイットリウム水溶液を０．５ｍＬ添加した後、５０ｍＬの樹脂製の全量フラスコに移し入れ、少量の純水を用いて定容した。これにより分析に供する試料溶液を調製した。 After adding 0.5 mL of an aqueous yttrium solution having a concentration of 100 mg / L as an internal standard substance to the obtained treatment liquid, it was transferred to a 50 mL resin-made whole volume flask, and the volume was adjusted using a small amount of pure water. Thus, a sample solution for analysis was prepared.
試料溶液のそれぞれについて、ＩＣＰ発光分光分析装置を用いて測定し、別途調製した検量線系列を用いて、試験片に含まれるけい素量を測定した。その結果を、下記の表１に示す。 About each sample solution, it measured using the ICP emission-spectral-analysis apparatus, and the amount of silicon contained in a test piece was measured using the analytical curve series prepared separately. The results are shown in Table 1 below.
（参考例１）
また、上記定量値の正確さを評価するために、別の方法として、ＧＤ−ＭＳ（グロー放電質量分析法）により試験片に含まれるケイ素量を測定した。その結果を下記の表１に示す。なお、本実施例で用いるサンプル１およびサンプル２は、不純物濃度が均一であるため、固体分析法でも精度よく定量できることが確認されている。
(Reference Example 1)
Moreover, in order to evaluate the accuracy of the quantitative value, as another method, the amount of silicon contained in the test piece was measured by GD-MS (glow discharge mass spectrometry). The results are shown in Table 1 below. Note that it has been confirmed that Sample 1 and Sample 2 used in this example can be quantified with high accuracy even by solid analysis because the impurity concentration is uniform.
実施例１によれば、サンプル１および２は、いずれもケイ素量が２０ｐｐｍであることが確認された。実施例１の定量結果を参考例１のＧＤ−ＭＳによる定量結果と比較したところ、いずれのサンプルもよく一致することが確認された。つまり、本実施例によれば、ケイ素量を精度よく定量できることが確認された。 According to Example 1, it was confirmed that Samples 1 and 2 both had a silicon content of 20 ppm. When the quantitative result of Example 1 was compared with the quantitative result by GD-MS of Reference Example 1, it was confirmed that all the samples matched well. That is, according to the present Example, it was confirmed that the amount of silicon can be accurately quantified.
以上のように、ケイ素不純物を含む金属材料を鉱酸とともに含ホウ素フッ化水素酸誘導体を併用して溶解することで、ケイ素不純物を良好に溶解させることができ、その溶液に含まれるケイ素量を測定することで、金属材料中のケイ素量を精度よく、かつ簡便に定量できる。 As described above, by dissolving a metal material containing silicon impurities in combination with a mineral acid and a boron-containing hydrofluoric acid derivative, the silicon impurities can be dissolved well, and the amount of silicon contained in the solution can be reduced. By measuring, the amount of silicon in the metal material can be accurately and easily quantified.
Claims (7)
前記金属材料を含ホウ素フッ化水素酸誘導体と鉱酸とを含む処理液に添加する添加工程と、
前記処理液を加熱することで、前記金属材料の金属成分とともに、前記含ホウ素フッ化水素酸誘導体から遊離するフッ化物イオンにより前記ケイ素成分を溶解させる溶解工程と、
前記溶解工程にて得られた処理液を冷却して試料溶液を調製する調製工程と、
前記試料溶液を分析する分析工程と、を有することを特徴とする、金属材料中のケイ素量を定量する方法。 A method for quantifying the amount of silicon in a metal material containing a silicon component,
An addition step of adding the metal material to a treatment liquid containing a boron-containing hydrofluoric acid derivative and a mineral acid;
A dissolution step of dissolving the silicon component by fluoride ions liberated from the boron-containing hydrofluoric acid derivative together with the metal component of the metal material by heating the treatment liquid;
A preparation step of preparing a sample solution by cooling the treatment liquid obtained in the dissolution step;
And an analysis step of analyzing the sample solution. A method for quantifying the amount of silicon in a metal material.
前記金属材料を鉱酸に添加し、少なくとも前記金属材料の金属成分を溶解させる第１の
溶解工程と、
前記第１の溶解工程にて得られた処理液に含ホウ素フッ化水素酸誘導体を添加し、当該処理液を加熱することで、前記含ホウ素フッ化水素酸誘導体から遊離するフッ化物イオンにより、前記ケイ素成分を溶解させる第２の溶解工程と、
前記第２の溶解工程にて得られた処理液を冷却して試料溶液を調製する調製工程と、
前記試料溶液を分析する分析工程と、を有することを特徴とする、金属材料中のケイ素量を定量する方法。 A method for quantifying the amount of silicon in a metal material containing a silicon component,
A first dissolving step of adding the metal material to a mineral acid and dissolving at least a metal component of the metal material;
By adding a boron-containing hydrofluoric acid derivative to the treatment liquid obtained in the first dissolution step and heating the treatment liquid, fluoride ions liberated from the boron-containing hydrofluoric acid derivative, A second dissolving step for dissolving the silicon component;
A preparation step of preparing a sample solution by cooling the treatment liquid obtained in the second dissolution step;
And an analysis step of analyzing the sample solution. A method for quantifying the amount of silicon in a metal material.
含ホウ素フッ化水素酸誘導体と鉱酸とを含む溶解液に前記金属材料を添加し、加熱することにより、前記金属材料の金属成分とともに、前記含ホウ素フッ化水素酸誘導体から遊離するフッ化物イオンにより前記ケイ素成分を溶解させる、ケイ素成分を含む金属材料の溶解方法。 A melting method for dissolving a metal material containing a silicon component,
Fluoride ions released from the boron-containing hydrofluoric acid derivative together with the metal component of the metal material by adding the metal material to a solution containing a boron-containing hydrofluoric acid derivative and a mineral acid and heating the solution. A method for dissolving a metal material containing a silicon component, wherein the silicon component is dissolved by the method.
含ホウ素フッ化水素酸誘導体と鉱酸とを含み、
加熱により、前記含ホウ素フッ化水素酸誘導体からフッ化物イオンを遊離させるように構成される、金属材料の溶解液。
A solution for dissolving a metal material containing a silicon component,
A boron-containing hydrofluoric acid derivative and a mineral acid,
A solution of a metal material configured to liberate fluoride ions from the boron-containing hydrofluoric acid derivative by heating.
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| CN113049671B (en) * | 2021-03-18 | 2023-05-12 | 宁波江丰电子材料股份有限公司 | Method for detecting content of impurity element in cobalt |
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