JP2016070870A - QUANTIFICATION METHOD OF AlN CONTAINED IN Al OR Al ALLOY - Google Patents
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本発明は、Al金属材(本発明において「Al」と記載する場合がある。)またはAl合金材(本発明において「Al合金」と記載する場合がある。)中に含有されるAlNの定量方法に関するものである。 In the present invention, determination of AlN contained in an Al metal material (may be described as “Al” in the present invention) or an Al alloy material (may be described as “Al alloy” in the present invention). It is about the method.
AlやAl合金は、アルミ缶や自転車のフレーム材等の構造材として汎用的に用いられている。さらに、最近では、半導体素子の電極や電気配線材としても利用されている。そして、AlやAl合金の製造は、窒素雰囲気中における融解工程を経て製造される場合がある。
当該窒素雰囲気中における融解工程を経て製造されたAlやAl合金においては、微量のAlNが生成し不純物として含有されることがある。ところが、AlNを含有するAlやAl合金を、例えば半導体素子の電極や電気配線材として使用すると、当該半導体素子の電気特性等に悪影響を与える可能性がある為、AlやAl合金中におけるAlNの含有量を把握することは極めて重要である。
Al and Al alloys are widely used as structural materials such as aluminum cans and bicycle frame materials. Furthermore, recently, it is also used as an electrode of an semiconductor element or an electric wiring material. And manufacture of Al and Al alloy may be manufactured through the melting process in nitrogen atmosphere.
In Al and Al alloys manufactured through the melting step in the nitrogen atmosphere, a trace amount of AlN may be generated and contained as impurities. However, if Al or Al alloy containing AlN is used, for example, as an electrode or electrical wiring material of a semiconductor element, it may adversely affect the electrical characteristics of the semiconductor element. Therefore, AlN in Al or Al alloy It is extremely important to know the content.
従来、AlNの定量方法としては、非特許文献1に、X線回折法(XRD法)を利用した定量例が記載されている。
当該非特許文献1に記載されたXRD法は、被測定対象の試料へX線を照射し、得られたAlN由来のX線回折ピークの強度を基にAlN濃度を定量する方法である。当該方法は、AlNが被測定対象の試料において主成分であり、且つ、数10質量%のオーダーにて含有されている場合には有効な方法である。
Conventionally, as a quantification method of AlN, Non-Patent Document 1 describes a quantification example using an X-ray diffraction method (XRD method).
The XRD method described in Non-Patent Document 1 is a method of irradiating a sample to be measured with X-rays and quantifying the AlN concentration based on the intensity of the obtained X-ray diffraction peak derived from AlN. This method is an effective method when AlN is a main component in the sample to be measured and is contained in the order of several tens of mass%.
また、非特許文献2に、ファインセラミックス用AlNの微粉末の化学分析法が記載されている。
当該非特許文献2に記載された化学分析法は、粉末試料に硫酸や塩酸を添加して加圧容器で分解したのち、誘導結合プラズマ発光分光分析法(ICP−OES法)でAlNを定量する方法である。
Non-Patent Document 2 describes a chemical analysis method for AlN fine powder for fine ceramics.
In the chemical analysis method described in Non-Patent Document 2, AlN is quantified by inductively coupled plasma emission spectrometry (ICP-OES method) after adding sulfuric acid or hydrochloric acid to a powder sample and decomposing it in a pressurized container. Is the method.
本発明者は、AlまたはAl合金中に含有されるAlNの定量方法へ、非特許文献1、2に記載された定量方法の適用を検討した。しかしながら、AlまたはAl合金中に含有されるAlNの定量方法へ、非特許文献1、2に記載された定量方法を適用しても、AlN濃度を上手く定量できないことが判明した。 This inventor examined application of the quantification method described in nonpatent literatures 1 and 2 to the quantification method of AlN contained in Al or Al alloy. However, it has been found that the AlN concentration cannot be quantified well even when the quantification methods described in Non-Patent Documents 1 and 2 are applied to the quantification method of AlN contained in Al or Al alloy.
まず、非特許文献1に記載された定量方法を適用した場合、AlNの検出感度が低く、本発明に係るAlまたはAl合金中に含有されるAlN濃度のように、1質量%以下の微量のAlNの場合は定量が困難である。 First, when the quantification method described in Non-Patent Document 1 is applied, the detection sensitivity of AlN is low, and a trace amount of 1% by mass or less such as the AlN concentration contained in Al or Al alloy according to the present invention is used. In the case of AlN, quantification is difficult.
一方、非特許文献2に記載されたファインセラミックス用AlNの微粉末の化学分析法を適用した場合、当該化学分析法は、AlNのみならず、AlまたはAl合金中のAlメタルをも溶解してしまうため、AlNのみを選択的に定量できないという問題がある。 On the other hand, when the chemical analysis method of fine powder of AlN for fine ceramics described in Non-Patent Document 2 is applied, the chemical analysis method dissolves not only AlN but also Al metal in Al or Al alloy. Therefore, there is a problem that only AlN cannot be selectively quantified.
本発明は、上述の状況の下で為されたものであり、その解決しようとする課題は、AlまたはAl合金中に含有された、例えば1質量%以下である微量のAlNを検出でき、且つ、これを定量できる方法を提供することである。 The present invention has been made under the above-mentioned circumstances, and the problem to be solved is to detect a trace amount of AlN contained in Al or an Al alloy, for example, 1% by mass or less, and It is to provide a method by which this can be quantified.
上述の課題を解決する為、本発明者は研究を行い、被測定対象であるAlまたはAl合金を所定の酸で処理することにより、AlまたはAl合金のメタル分を溶解し、AlNを残渣に残すことにより、AlNとメタル分とを分離できることを知見した。ここで本発明者らはさらに研究を行い、得られた残渣を、硫酸根を有する硫酸系の融剤で溶解して溶液化し、当該溶液に含有されるAl濃度を測定することで、AlNを定量分析する方法に想到した。
そして、上述した、AlまたはAl合金からAlNを残渣として分離する方法、および、残渣中のAlNを定量分析する方法を組み合わせることで、被測定対象であるAlまたはAl合金中に含有された、例えば1質量%以下である微量のAlまたはAl合金を検出でき、且つ、それを定量できる方法を見出し本発明に至ったものである。
In order to solve the above-mentioned problems, the present inventor conducted research and treated Al or Al alloy to be measured with a predetermined acid to dissolve the metal content of Al or Al alloy, and to convert AlN into a residue. It was found that AlN and the metal component can be separated by leaving. Here, the present inventors conducted further research and dissolved the obtained residue with a sulfuric acid-based flux having sulfate radicals to measure the concentration of Al contained in the solution. I came up with a method for quantitative analysis.
And, by combining the above-described method of separating AlN from Al or Al alloy as a residue and the method of quantitatively analyzing AlN in the residue, contained in Al or Al alloy to be measured, for example, The present inventors have found a method capable of detecting a trace amount of Al or an Al alloy of 1% by mass or less and quantifying it, and have reached the present invention.
すなわち、本発明に係る第1の発明は、
AlNを含有するAl金属材またはAl合金材を溶解容器に秤量したのち、酸を加えてメタル分を溶解除去し、残渣を捕集材により捕集する工程と、
前記残渣を捕集した捕集材を灰化する工程と、
前記捕集材を灰化して得られた残渣へ、融剤を添加し加熱して融解塩とする工程と、
前記融解塩を酸性溶液により溶解し、融解塩の酸性溶液とする工程と、
前記融解塩の酸性溶液に含有されるAl濃度を測定し、前記AlNを含有するAl金属材またはAl合金材におけるAlNの含有率を算出する工程とを有する、ことを特長とするAlまたはAl合金中に含有されるAlNの定量方法である。
第2の発明は、
前記AlNを含有するAl金属材またはAl合金材へ加える酸として、酸化力のある酸を用いることを特長とする第1の発明に記載のAlまたはAl合金中に含有されるAlNの定量方法である。
第3の発明は、
前記融剤として、硫酸系融剤を用いることを特長とする第1または第2の発明に記載のAlまたはAl合金中に含有されるAlNの定量方法である。
第4の発明は、
前記融解塩の酸性溶液に含有されるAl濃度の測定方法としてICP−OES法を用いることを特長とする第1から第3の発明のいずれかに記載のAlまたはAl合金中に含有されるAlNの定量方法である。
That is, the first invention according to the present invention is:
A step of weighing an Al metal material or Al alloy material containing AlN in a dissolution vessel, adding an acid to dissolve and remove the metal, and collecting the residue with a collection material;
Ashing the collection material that collected the residue;
To the residue obtained by ashing the collection material, adding a flux and heating to a molten salt;
Dissolving the molten salt with an acidic solution to obtain an acidic solution of the molten salt;
Measuring the Al concentration contained in the acidic solution of the molten salt, and calculating the content of AlN in the Al metal material or Al alloy material containing the AlN. This is a method for quantifying AlN contained therein.
The second invention is
The method for quantifying AlN contained in Al or Al alloy according to the first invention, wherein an acid having an oxidizing power is used as the acid added to the Al metal material or Al alloy material containing AlN. is there.
The third invention is
The method for quantifying AlN contained in Al or an Al alloy according to the first or second invention, wherein a sulfuric acid-based flux is used as the flux.
The fourth invention is:
The AlP contained in the Al or Al alloy according to any one of the first to third inventions, wherein an ICP-OES method is used as a method for measuring the Al concentration contained in the molten salt acidic solution. This is a quantitative method.
本発明に係るAlまたはAl合金に含有されるAlNの定量方法に拠れば、AlまたはAl合金中に含有された1質量%以下のAlNを選択的に検出でき、且つ、定量分析可能となった。 According to the method for quantifying AlN contained in Al or Al alloy according to the present invention, 1% by mass or less of AlN contained in Al or Al alloy can be selectively detected and quantitative analysis can be performed. .
本発明に係るAlまたはAl合金中に含有されるAlNの定量方法は、当該AlまたはAl合金中に含有されるAlN以外のメタル分を選択的に溶解する酸を用いて、AlNのみを残渣として分離、回収する方法である。そして、当該AlまたはAl合金中に含有される1質量%以下のAlNを、選択的且つ高感度で検出でき、且つ、精度良く定量分析することを可能とするものである。以下に本発明に係るAlまたはAl合金中に含有されるAlNの定量方法について説明する。 The method for quantifying AlN contained in Al or Al alloy according to the present invention uses an acid that selectively dissolves a metal component other than AlN contained in the Al or Al alloy, and uses only AlN as a residue. It is a method of separation and recovery. Then, 1% by mass or less of AlN contained in the Al or Al alloy can be detected selectively and with high sensitivity, and quantitative analysis can be performed with high accuracy. The method for quantifying AlN contained in Al or an Al alloy according to the present invention will be described below.
(1)AlまたはAl合金の秤量工程
AlまたはAl合金試料を、天秤を用いて溶解容器へ秤量し、蓋をする。当該溶解容器はガラス製または石英製のものが適用可能であり、容量は200ml〜300mlのビーカーが好ましい。尚、AlまたはAl合金試料の秤量には、0.1mgまで秤量可能な電子天秤を用いることが好ましい。
(1) Weighing step of Al or Al alloy An Al or Al alloy sample is weighed into a melting container using a balance and covered. The melting container can be made of glass or quartz, and preferably has a capacity of 200 ml to 300 ml beaker. For weighing Al or Al alloy samples, it is preferable to use an electronic balance capable of weighing up to 0.1 mg.
(2)AlまたはAl合金の溶解工程
AlまたはAl合金を酸により溶解し、含有されるAlNを残渣に残して分離する工程である。
1)AlまたはAl合金を溶解する酸
まず、AlまたはAl合金を溶解する酸について説明する。
当該酸としては、AlまたはAl合金を含むメタル分を溶解可能な酸化性の酸であれば、特に限定することはないが、硝酸と塩酸との混酸や、硫酸と硝酸の混酸を使用することが出来る。例えば、塩酸と硝酸との混酸であれば、12mol/Lの塩酸(10〜30ml)と、14mol/Lの硝酸(10〜30ml)と、純水(20〜30ml)との混合物である混酸を用いることが出来、硫酸と硝酸との混酸であれば、9mol/Lの硫酸(20〜30ml)と、14mol/Lの硝酸(10〜20ml)と、純水(10〜20ml)との混合物である混酸を用いることが出来る。
尚、本発明において、「塩酸」とは12mol/Lの塩酸であり、「硝酸」とは14mol/Lの硝酸であり、「硫酸」とは9mol/Lの硫酸である。
(2) Step of dissolving Al or Al alloy In this step, the Al or Al alloy is dissolved with an acid, and the contained AlN is left as a residue and separated.
1) Acid that dissolves Al or Al alloy First, an acid that dissolves Al or Al alloy will be described.
The acid is not particularly limited as long as it is an oxidizing acid capable of dissolving a metal component including Al or Al alloy, but a mixed acid of nitric acid and hydrochloric acid or a mixed acid of sulfuric acid and nitric acid should be used. I can do it. For example, in the case of a mixed acid of hydrochloric acid and nitric acid, a mixed acid that is a mixture of 12 mol / L hydrochloric acid (10 to 30 ml), 14 mol / L nitric acid (10 to 30 ml), and pure water (20 to 30 ml) is used. If it is a mixed acid of sulfuric acid and nitric acid, it is a mixture of 9 mol / L sulfuric acid (20-30 ml), 14 mol / L nitric acid (10-20 ml), and pure water (10-20 ml). A certain mixed acid can be used.
In the present invention, “hydrochloric acid” is 12 mol / L hydrochloric acid, “nitric acid” is 14 mol / L nitric acid, and “sulfuric acid” is 9 mol / L sulfuric acid.
2)AlまたはAl合金の溶解
被測定対象であるAlまたはAl合金試料へ、上述した混酸を添加し、十分に撹拌後200℃程度の温度で加温し、当該試料中のメタル分が完全に溶解するまで加温し、AlまたはAl合金の溶解液を得る。
当該溶解の際、AlまたはAl合金試料への混酸の添加量は、AlまたはAl合金試料を十分に溶解できる量であれば良い。例えば、塩酸(20ml)と、硝酸(20ml)と、純水(20ml)との混合物である混酸で良い。また加熱には、サンドバスやホットプレート等の使用が便宜である。
2) Dissolution of Al or Al alloy Add the above-mentioned mixed acid to the Al or Al alloy sample to be measured, sufficiently stir and heat at a temperature of about 200 ° C, and the metal content in the sample is completely Heat until dissolved to obtain a solution of Al or Al alloy.
At the time of dissolution, the amount of mixed acid added to the Al or Al alloy sample may be an amount that can sufficiently dissolve the Al or Al alloy sample. For example, a mixed acid that is a mixture of hydrochloric acid (20 ml), nitric acid (20 ml), and pure water (20 ml) may be used. For the heating, it is convenient to use a sand bath or a hot plate.
(3)濾過工程
得られたAlまたはAl合金の溶解液を室温まで放冷したのち、捕集材である定量濾紙等を用いて当該試料溶液を濾過し、AlN由来の残渣を捕集する。引き続き、濾紙と残渣を純水で十分に洗浄する。
当該濾過工程において、定量濾紙としては、5B以上の定量濾紙であれば特に限定することはなく、5Cの定量濾紙等も使用可能である。
(3) Filtration step After the obtained Al or Al alloy solution is allowed to cool to room temperature, the sample solution is filtered using a quantitative filter paper or the like, which is a collection material, to collect AlN-derived residues. Subsequently, the filter paper and the residue are thoroughly washed with pure water.
In the filtration step, the quantitative filter paper is not particularly limited as long as it is a 5B or higher quantitative filter paper, and 5C quantitative filter paper or the like can also be used.
(4)灰化工程
AlN由来の残渣を捕集した定量濾紙を坩堝に移入したのち、当該濾紙が黒く炭化するまで加熱する。引き続き坩堝を強熱し、濾紙が完全に燃焼し灰化するまで加熱する。
当該灰化工程において、坩堝はAlが含まれていないものであれば使用可能であるが、Pt製坩堝を使用することが好ましい。
(4) Ashing process After the quantitative filter paper which collected the residue derived from AlN is transferred to the crucible, it is heated until the filter paper is carbonized black. Subsequently, the crucible is ignited and heated until the filter paper is completely burned and ashed.
In the ashing step, the crucible can be used as long as it does not contain Al, but it is preferable to use a Pt crucible.
(5)融解工程
前記濾紙が完全に燃焼し灰化したら、残渣を含む坩堝を放冷する。その後、坩堝へ融剤を添加し、当該融剤から白煙が出なくなるまで加熱する。引き続き、坩堝を強熱しながら残渣を撹拌し、当該残渣が融剤へ完全に融解して、融解塩となるまで加熱する。
ここで、融剤としては硫酸系融剤である二硫酸カリウムを用いることが好ましいが、同じ硫酸系融剤として二硫酸ナトリウムを使用しても良い。
また、当該工程で硫酸系融剤を用いた融解を行う為、当該観点からも、坩堝として当該硫酸系融剤に不溶なPt製坩堝を使用することは、好ましい構成である。
(5) Melting step When the filter paper is completely burned and incinerated, the crucible containing the residue is allowed to cool. Then, a flux is added to the crucible and heated until no white smoke is emitted from the flux. Subsequently, the residue is stirred while igniting the crucible, and heated until the residue is completely melted into the flux and becomes a molten salt.
Here, it is preferable to use potassium disulfate which is a sulfuric acid-based flux as the flux, but sodium disulfate may be used as the same sulfuric acid-based flux.
In addition, since melting using a sulfuric acid-based flux is performed in this step, it is preferable to use a Pt crucible that is insoluble in the sulfuric acid-based flux as the crucible from this viewpoint.
(6)融解塩の溶解工程
融解塩が生成した坩堝を室温まで放冷したのち、当該坩堝を酸水溶液の入ったビーカー中に浸漬し、当該ビーカーへ蓋をする。そして、坩堝を浸漬した酸水溶液を加熱し、生成した融解塩を酸水溶液中へ完全に溶解し室温まで放冷する。放冷後、酸水溶液をメスフラスコに移入し、さらにビーカーと蓋とを純水で洗浄し、当該洗浄液も加えて定容して試料溶液を得る。
酸水溶液は、塩酸水溶液や硝酸水溶液が好ましく使用できる。例えば、塩酸水溶液であれば、純水(20〜40ml)と、塩酸(5〜20ml)との混合溶液を使用することが出来る。
酸水溶液の加熱には、サンドバスやホットプレート等が便宜である。
(6) Molten salt dissolution step After the crucible where the molten salt is formed is allowed to cool to room temperature, the crucible is immersed in a beaker containing an aqueous acid solution, and the beaker is covered. Then, the aqueous acid solution in which the crucible is immersed is heated, and the generated molten salt is completely dissolved in the aqueous acid solution and allowed to cool to room temperature. After allowing to cool, the acid aqueous solution is transferred into a volumetric flask, and the beaker and the lid are washed with pure water, and the washing solution is added and the volume is adjusted to obtain a sample solution.
As the acid aqueous solution, a hydrochloric acid aqueous solution or a nitric acid aqueous solution can be preferably used. For example, in the case of an aqueous hydrochloric acid solution, a mixed solution of pure water (20 to 40 ml) and hydrochloric acid (5 to 20 ml) can be used.
A sand bath or a hot plate is convenient for heating the acid aqueous solution.
(7)Alの含有量の測定工程
測定試料溶液のAl濃度測定には、ICP−OES装置を用いるのが便宜である。そこで以下、ICP−OES装置を用いた、測定試料溶液中のAl濃度の測定を例として説明する。
(7) Measurement step of Al content It is convenient to use an ICP-OES apparatus for measuring the Al concentration of the measurement sample solution. Therefore, hereinafter, measurement of Al concentration in a measurement sample solution using an ICP-OES apparatus will be described as an example.
1)測定試料溶液とAl測定標準試料溶液との調製
得られた試料溶液を、当該溶液中のAlN濃度に応じて、適宜希釈して測定試料溶液を調製する。
一方、測定試料溶液中のAl濃度に応じて、Al測定標準試料溶液を調製する。このとき、測定試料溶液とAl測定標準試料溶液とに含有される、酸濃度や二硫酸カリウム濃度は同程度の濃度になるように調製することが好ましい。また、Al測定標準試料溶液としては、市販の1g/Lの標準試料溶液を適宜希釈して調製することが便宜である。希釈濃度範囲は0.1〜100mg/Lの範囲で、複数の濃度水準で調製することが好ましい。
1) Preparation of measurement sample solution and Al measurement standard sample solution The obtained sample solution is appropriately diluted according to the AlN concentration in the solution to prepare a measurement sample solution.
On the other hand, an Al measurement standard sample solution is prepared according to the Al concentration in the measurement sample solution. At this time, it is preferable that the acid concentration and the potassium disulfate concentration contained in the measurement sample solution and the Al measurement standard sample solution are adjusted so as to be approximately the same. Moreover, as an Al measurement standard sample solution, it is convenient to dilute a commercially available standard sample solution of 1 g / L as appropriate. The dilution concentration range is in the range of 0.1 to 100 mg / L, and it is preferable to prepare at a plurality of concentration levels.
2)ICP−OES装置によるAl濃度の測定
ICP−OES装置によるAl濃度の測定波長は、共存元素の妨害がなければ、特に限定することはないが、最も感度の良い167.079nmの波長を用いることが好ましい。また、その他の測定条件については、メーカー推奨の条件を使用することが望ましい。当該ICP−OES装置を用いて測定試料溶液とAl測定標準試料溶液とのAl濃度を測定し、当該測定値から試料溶液中のAlの含有量(g)を算出する。
尚、測定試料溶液中に含有されるAlの含有量測定に使用するICP−OES装置は、特に限定することはないが、例えば(株)日立ハイテクサイエンス社製のSPS3520UVや(株)島津製作所製のICPE−9000等が適用可能である。
本法の定量下限は、測定試料溶液中のAlNの含有率が0.01質量%程度まで定量可能である。
2) Measurement of Al concentration by ICP-OES device The wavelength of Al concentration measurement by ICP-OES device is not particularly limited as long as there is no interference with coexisting elements, but the most sensitive wavelength of 167.079 nm is used. It is preferable. For other measurement conditions, it is desirable to use the conditions recommended by the manufacturer. The Al concentration of the measurement sample solution and the Al measurement standard sample solution is measured using the ICP-OES apparatus, and the Al content (g) in the sample solution is calculated from the measurement value.
The ICP-OES apparatus used for measuring the content of Al contained in the measurement sample solution is not particularly limited. For example, SPS3520UV manufactured by Hitachi High-Tech Science Co., Ltd. or Shimadzu Corporation ICPE-9000 or the like can be applied.
The lower limit of quantification of this method can be quantified to a content of AlN in the measurement sample solution of about 0.01% by mass.
3)測定試料溶液中におけるAlNの含有率(質量%)を算出する工程
ICP−OESで測定したAlの含有量(g)を元に以下の式1を用いて、当該試料中のAlNの含有率を算出する。
A1=(A2/W)×F×100・・・式1
但し、A1:測定試料溶液中におけるAlNの含有率、
A2:測定試料溶液中におけるAl含有量(g)、
W:測定試料の試料採取量(g)、
F:Alの窒化係数(1.5191)
3) Step of calculating the AlN content (% by mass) in the measurement sample solution Using the following formula 1 based on the Al content (g) measured by ICP-OES, the content of AlN in the sample Calculate the rate.
A1 = (A2 / W) × F × 100 Formula 1
However, A1: Content rate of AlN in the measurement sample solution,
A2: Al content (g) in the measurement sample solution,
W: Sample collection amount of measurement sample (g),
F: Ni nitride coefficient of Al (1.5191)
(8)まとめ
以上説明したように、本発明に係るAl合金中のAlNの定量方法を用いれば、AlまたはAl合金材中に含有される1質量%以下のAlNを、選択的に高感度で検出でき、且つ、精度良く定量可能である。したがって、本発明は、金属加工分野や半導体分野等で使用されるAlまたはAl合金中のAlN濃度のモニター方法として、好適に用いることが出来る。
(8) Summary As described above, if the method for quantifying AlN in an Al alloy according to the present invention is used, 1% by mass or less of AlN contained in Al or an Al alloy material is selectively and highly sensitive. It can be detected and quantified with high accuracy. Therefore, the present invention can be suitably used as a method for monitoring the AlN concentration in Al or Al alloys used in the metal processing field, the semiconductor field, and the like.
以下、実施例を参照しながら本発明をより具体的に説明する。但し、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
(実施例1)
実施例1に係るAl合金試料としてAlCu合金(Al90質量%、Cu10質量%)0.5gを準備し、300mlビーカーへ投入した。分析精度を確認するために当該試料の秤量は3個ずつ秤量して以下の操作を実施した。尚、当該実施例1に係るAl合金試料は1.0質量%のAlNを含有するものである。
一方、AlCu合金を投入したビーカーへ、純水20mlと硝酸20mlと塩酸20mlとをそれぞれ注入したのち、当該混酸を注入したビーカーへ時計皿で蓋をしてよく撹拌した。
Example 1
As an Al alloy sample according to Example 1, 0.5 g of an AlCu alloy (Al 90 mass%, Cu 10 mass%) was prepared and charged into a 300 ml beaker. In order to confirm the analysis accuracy, the samples were weighed three by three and the following operations were performed. The Al alloy sample according to Example 1 contains 1.0% by mass of AlN.
On the other hand, 20 ml of pure water, 20 ml of nitric acid, and 20 ml of hydrochloric acid were poured into a beaker charged with an AlCu alloy, and then the beaker into which the mixed acid had been poured was covered with a watch glass and stirred well.
次に、当該混酸を注入したビーカーを、サンドバスを用い200℃の温度で加熱し30分間保持して、Al合金試料中のメタル分を混酸に溶解させた。その後、当該混酸を注入したビーカーを放冷した。
当該ビーカーを室温まで放冷した後、5Bの定量濾紙を用いてビーカーの内容物を濾過し、さらにビーカーの内壁等に付着したAlN由来の残渣を純水で洗い流しながら、5Bの定量濾紙に捕集した。そして引き続き、当該5Bの定量濾紙と捕集された残渣とを、純水で十分に洗浄した。
Next, the beaker into which the mixed acid was injected was heated at a temperature of 200 ° C. using a sand bath and held for 30 minutes, so that the metal content in the Al alloy sample was dissolved in the mixed acid. Thereafter, the beaker into which the mixed acid was injected was allowed to cool.
After the beaker is allowed to cool to room temperature, the content of the beaker is filtered using a 5B quantitative filter paper, and the AlN-derived residue adhering to the inner wall of the beaker is washed off with pure water and trapped on the 5B quantitative filter paper. Gathered. Subsequently, the 5B quantitative filter paper and the collected residue were sufficiently washed with pure water.
前記残渣を捕集した5Bの定量濾紙を、Pt製の坩堝内に移入した。そして当該Pt製の坩堝をセラミックス製の網の上に載せ、ブンゼンバーナーを用いて5Bの定量濾紙が黒く炭化するまで加熱した。引き続き、当該Pt製の坩堝を三角架の上に乗せ換えて、ブンゼンバーナーを用いて強熱し、5Bの定量濾紙が完全に燃焼するまで加熱した。 The 5B quantitative filter paper that collected the residue was transferred into a crucible made of Pt. The Pt crucible was placed on a ceramic net and heated using a Bunsen burner until the 5B quantitative filter paper was carbonized black. Subsequently, the Pt crucible was placed on a triangular frame, ignited using a Bunsen burner, and heated until the 5B quantitative filter paper was completely burned.
当該Pt製の坩堝を室温まで放冷したのち、二硫酸カリウム融剤を1g添加した。そして、当該Pt製の坩堝をセラミックスの製の網の上に載せて、添加した二硫酸カリウムから白煙が出なくなるまで、ブンゼンバーナーで加熱した。引き続き、当該Pt製の坩堝を三角架の上に乗せ換えて、ブンゼンバーナーで強熱しながらPt製の坩堝の内容物を撹拌し、前記残渣が完全に融解するまで加熱した。 After allowing the Pt crucible to cool to room temperature, 1 g of potassium disulfate flux was added. Then, the Pt crucible was placed on a ceramic net and heated with a Bunsen burner until no white smoke was produced from the added potassium disulfate. Subsequently, the Pt crucible was placed on a triangular frame, the contents of the Pt crucible were stirred while ignited with a Bunsen burner, and heated until the residue was completely melted.
前記残渣が完全に融解したら、Pt製の坩堝を室温まで放冷し前記残渣の融解塩を得た。
当該室温まで放冷された融解塩が入ったPt製の坩堝を、純水40mlと塩酸10mlとの混酸を注入した200mlビーカーに投入し、時計皿で蓋をした。引き続き、当該ビーカーをサンドバスによりサンドバスで加温し、融解塩を完全に混酸中へ溶解した。そして、得られた融解塩を溶解した混酸を、100mlのメスフラスコへ移入し、さらにビーカーと時計皿とを純水で洗浄したものも加えて定容し、実施例1に係る試料溶液を得た。尚、空試験においても、(0027)〜(0031)段落に記載の操作を同様に実施した。
When the residue was completely melted, the Pt crucible was allowed to cool to room temperature to obtain a molten salt of the residue.
The crucible made of Pt containing the molten salt allowed to cool to room temperature was put into a 200 ml beaker into which a mixed acid of 40 ml of pure water and 10 ml of hydrochloric acid was poured, and the lid was covered with a watch glass. Subsequently, the beaker was heated with a sand bath in a sand bath, and the molten salt was completely dissolved in the mixed acid. Then, the mixed acid obtained by dissolving the obtained molten salt was transferred to a 100 ml volumetric flask, and a beaker and a watch glass washed with pure water were added and the volume was adjusted to obtain a sample solution according to Example 1. It was. In the blank test, the operations described in paragraphs (0027) to (0031) were similarly performed.
得られた試料溶液を2ml分取し、10mlのメスフラスコへ移入したのち、塩酸を1ml添加し、純水で10mlに定容して測定試料溶液を得た。
一方、標準試料溶液は、市販のAl標準試料溶液(1g/L)を、Al濃度で1.0mg/Lと、5.0mg/Lと、10mg/Lとになるように、10mlのメスフラスコに添加したのち、塩酸1mlと空試験溶液2mlとをそれぞれ添加し、純水で10mlに定容して調製した。
尚、試料溶液と空試験溶液の分取は、分取精度が相対標準偏差で1%程度のピペットを用いることが好ましい。
2 ml of the obtained sample solution was collected and transferred to a 10 ml volumetric flask, 1 ml of hydrochloric acid was added, and the volume was adjusted to 10 ml with pure water to obtain a measurement sample solution.
On the other hand, as the standard sample solution, a commercially available Al standard sample solution (1 g / L) is prepared in a 10 ml volumetric flask so that the Al concentration is 1.0 mg / L, 5.0 mg / L, and 10 mg / L. Then, 1 ml of hydrochloric acid and 2 ml of the blank test solution were added, and the volume was adjusted to 10 ml with pure water.
In addition, it is preferable to use a pipette having a relative standard deviation of about 1% for the separation of the sample solution and the blank test solution.
得られた実施例1に係る測定試料溶液、および、実施例1に係るAlの標準試料溶液中のAl濃度をICP−OES法に拠り測定し、測定結果から実施例1に係るAl合金試料中のAlN含有率の定量値を算出した。当該定量値を「定量値−1」として表1に記載した。
尚、ICP−OES測定装置は、(株)日立ハイテクサイエンス社製のSPS3520UVを用いた。そして、当該ICP−OES測定装置の測定条件を表2に記載した。
The Al concentration in the obtained measurement sample solution according to Example 1 and the standard sample solution of Al according to Example 1 was measured based on the ICP-OES method, and the Al results in the Al alloy sample according to Example 1 were measured. The quantitative value of the AlN content was calculated. The quantitative value is shown in Table 1 as “quantitative value-1”.
As the ICP-OES measuring apparatus, SPS3520UV manufactured by Hitachi High-Tech Science Co., Ltd. was used. And the measurement conditions of the said ICP-OES measuring apparatus were described in Table 2.
実施例1に係るAlまたはAl合金中に含有されるAlNの定量方法の精度を確認する為、実施例1に係るAl合金試料中のAlN含有率の定量値の分析を3個併行で実施し、「定量値−2」「定量値−3」を得たので、これらの値、「定量値−1〜3」の平均値、RSD〔(相対標準偏差(%)=(標準偏差/平均値)×100〕も表1に記載した。 In order to confirm the accuracy of the determination method of AlN contained in Al or Al alloy according to Example 1, analysis of the quantitative value of AlN content in the Al alloy sample according to Example 1 was performed in parallel. Since “quantitative value-2” and “quantitative value-3” were obtained, the average value of these values, “quantitative value-1 to 3”, RSD [(relative standard deviation (%) = (standard deviation / average value) ) × 100] is also shown in Table 1.
(実施例2)
実施例2に係るAl合金試料として0.1質量%のAlNを含有するAlCu合金を準備した。そして、実施例2に係るAlの標準試料溶液は、Al濃度で0.1mg/Lと、0.5mg/Lと、1.0mg/Lとになるように調製した。それ以外は、実施例1と同様にして、実施例2に係るAl合金試料中のAlN含有率の定量値を測定した。これらの値、「定量値−1〜3」の平均値、RSD〔(相対標準偏差(%)=(標準偏差/平均値)×100〕も表1に記載した。
(Example 2)
An AlCu alloy containing 0.1% by mass of AlN was prepared as an Al alloy sample according to Example 2. The Al standard sample solution according to Example 2 was prepared so that the Al concentration was 0.1 mg / L, 0.5 mg / L, and 1.0 mg / L. Other than that was carried out similarly to Example 1, and measured the quantitative value of the AlN content rate in the Al alloy sample which concerns on Example 2. FIG. These values, the average value of “quantitative values—1 to 3”, and RSD [(relative standard deviation (%) = (standard deviation / average value) × 100)] are also shown in Table 1.
(実施例3)
実施例3に係るAl合金試料として1.0質量%のAlNを含有するAlGa合金(Al75質量%、Ga25質量%)を準備し、実施例1と同様に実施した。実施例3に係るAl合金試料中のAlN含有率の定量値を測定した。これらの値、「定量値−1〜3」の平均値、RSD〔(相対標準偏差(%)=(標準偏差/平均値)×100〕も表1に記載した。
(Example 3)
As an Al alloy sample according to Example 3, an AlGa alloy (Al 75% by mass, Ga 25% by mass) containing 1.0% by mass of AlN was prepared and carried out in the same manner as in Example 1. The quantitative value of the AlN content in the Al alloy sample according to Example 3 was measured. These values, the average value of “quantitative values—1 to 3”, and RSD [(relative standard deviation (%) = (standard deviation / average value) × 100)] are also shown in Table 1.
(実施例4)
実施例4に係るAl合金試料として0.1質量%のAlNを含有するAlGa合金を準備した。そして、実施例4に係るAlの標準試料溶液は、Al濃度で0.1mg/Lと、0.5mg/Lと、1.0mg/Lとになるように調製した。それ以外は、実施例1と同様にして、実施例4に係るAl合金試料中のAlN含有率の定量値を測定した。これらの値、「定量値−1〜3」の平均値、RSD〔(相対標準偏差(%)=(標準偏差/平均値)×100〕も表1に記載した。
Example 4
As an Al alloy sample according to Example 4, an AlGa alloy containing 0.1% by mass of AlN was prepared. The Al standard sample solution according to Example 4 was prepared so that the Al concentration was 0.1 mg / L, 0.5 mg / L, and 1.0 mg / L. Other than that was carried out similarly to Example 1, and measured the quantitative value of the AlN content rate in the Al alloy sample which concerns on Example 4. FIG. These values, the average value of “quantitative values—1 to 3”, and RSD [(relative standard deviation (%) = (standard deviation / average value) × 100)] are also shown in Table 1.
(評価)
表1に示す結果から、実施例1から4において、AlN含有率の各「定量値−1〜3」の値、およびその平均値は、定量精度の範囲で、AlN含有率の仕込み値と良く一致しており、正確に定量できることが理解出来る。また、定量精度もRSD(相対標準偏差)の値で1.2〜5.4%であり、精度良く定量できることが理解出来る。
(Evaluation)
From the results shown in Table 1, in Examples 1 to 4, the value of each “quantitative value—1 to 3” of the AlN content rate and the average value thereof are well within the range of quantitative accuracy, and the preparation value of the AlN content rate is good. It can be understood that they are consistent and can be accurately quantified. In addition, the quantitative accuracy is 1.2 to 5.4% in terms of RSD (relative standard deviation), and it can be understood that the quantitative accuracy can be achieved.
以上から明らかなように、本発明に係るAlまたはAl合金に含有されるAlNの定量方法に拠れば、Al合金中に含有された1質量%以下のAlNを選択的に高感度で検出でき、且つ、精度良く定量分析可能となった。従って、本発明は例えば、半導体分野や金属加工分野等で使用するAlまたはAl合金中のAlN濃度を、モニターする方法として有効である。また、本発明は、各種合金中の窒化物の定量にも応用可能である。 As is clear from the above, according to the method for quantifying AlN contained in Al or Al alloy according to the present invention, 1% by mass or less of AlN contained in the Al alloy can be selectively detected with high sensitivity, In addition, quantitative analysis can be performed with high accuracy. Therefore, the present invention is effective, for example, as a method for monitoring the AlN concentration in Al or Al alloy used in the semiconductor field, metal working field, and the like. The present invention can also be applied to the determination of nitrides in various alloys.
Claims (4)
前記残渣を捕集した捕集材を灰化する工程と、
前記捕集材を灰化して得られた残渣へ、融剤を添加し加熱して融解塩とする工程と、
前記融解塩を酸性溶液により溶解し、融解塩の酸性溶液とする工程と、
前記融解塩の酸性溶液に含有されるAl濃度を測定し、前記AlNを含有するAl金属材またはAl合金材におけるAlNの含有率を算出する工程とを有する、ことを特長とするAlまたはAl合金中に含有されるAlNの定量方法。 A step of weighing an Al metal material or Al alloy material containing AlN in a dissolution vessel, adding an acid to dissolve and remove the metal, and collecting the residue with a collection material;
Ashing the collection material that collected the residue;
To the residue obtained by ashing the collection material, adding a flux and heating to a molten salt;
Dissolving the molten salt with an acidic solution to obtain an acidic solution of the molten salt;
Measuring the Al concentration contained in the acidic solution of the molten salt, and calculating the content of AlN in the Al metal material or Al alloy material containing the AlN. A method for quantifying AlN contained therein.
4. The determination of AlN contained in Al or Al alloy according to claim 1, wherein an ICP-OES method is used as a method for measuring the Al concentration contained in the acidic solution of the molten salt. 5. Method.
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