JP2013250061A - Element analyzer - Google Patents
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- JP2013250061A JP2013250061A JP2012122719A JP2012122719A JP2013250061A JP 2013250061 A JP2013250061 A JP 2013250061A JP 2012122719 A JP2012122719 A JP 2012122719A JP 2012122719 A JP2012122719 A JP 2012122719A JP 2013250061 A JP2013250061 A JP 2013250061A
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- 238000000605 extraction Methods 0.000 claims abstract description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 36
- 239000000284 extract Substances 0.000 claims abstract description 4
- 238000004458 analytical method Methods 0.000 claims description 13
- 238000000921 elemental analysis Methods 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 239000010439 graphite Substances 0.000 description 21
- 229910002804 graphite Inorganic materials 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 150000002431 hydrogen Chemical class 0.000 description 14
- 238000001514 detection method Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000012629 conventional elemental analysis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
本発明は、例えば鉄鋼や非鉄金属、セラミックスなどの測定試料中に含まれる酸素（Ｏ）、窒素（Ｎ）、水素（Ｈ）、等の元素を分析する元素分析装置に関するものである。 The present invention relates to an element analyzer for analyzing elements such as oxygen (O), nitrogen (N), and hydrogen (H) contained in measurement samples such as steel, non-ferrous metals, and ceramics.
従来の元素分析装置としては、特許文献１に示すように、インパルス電流を流してジュール発熱させた黒鉛るつぼに試料を入れて当該試料を加熱融解し、試料中の酸素（Ｏ）、窒素（Ｎ）、水素（Ｈ）を黒鉛るつぼにより還元分解して、一酸化炭素（ＣＯ）、窒素（Ｎ２）、水素（Ｈ２）等のガスを発生させるものがある。そして、この元素分析装置は、試料中の酸素（Ｏ）を一酸化炭素（ＣＯ）として（低濃度の酸素（Ｏ）を高精度に分析する場合には、後段の酸化器により一酸化炭素（ＣＯ）を二酸化炭素（ＣＯ２）に酸化して二酸化炭素（ＣＯ２）として）、窒素（Ｎ）を窒素（Ｎ２）として、水素（Ｈ）を後段の酸化器にて水素（Ｈ２）をＨ２Ｏに酸化してＨ２Ｏとして検出する。 As a conventional elemental analyzer, as shown in Patent Document 1, a sample is placed in a graphite crucible that is heated by Joule heating by passing an impulse current, the sample is heated and melted, and oxygen (O), nitrogen (N ) And hydrogen (H) are reduced and decomposed with a graphite crucible to generate gas such as carbon monoxide (CO), nitrogen (N 2 ), hydrogen (H 2 ). This elemental analyzer uses oxygen (O) in the sample as carbon monoxide (CO) (when analyzing low-concentration oxygen (O) with high accuracy, carbon monoxide ( the CO) is oxidized to carbon dioxide (CO 2) carbon dioxide (as CO 2)), nitrogen (N) and nitrogen (as N 2), hydrogen (hydrogen H) at the subsequent stage of oxidizer (H 2) is oxidized in H 2 O is detected as the H 2 O.
この元素分析装置においては、図４に示すように、酸素（Ｏ）や水素（Ｈ）の分析精度は、黒鉛るつぼの温度が高くなるに連れて低下し、一方で、窒素（Ｎ）の分析精度は、黒鉛るつぼの温度が高くなるに連れて向上する。つまり、酸素（Ｏ）や水素（Ｈ）の分析精度と窒素（Ｎ）の分析精度とは、黒鉛るつぼの加熱温度に対して逆の挙動を示す。 In this elemental analyzer, as shown in FIG. 4, the analysis accuracy of oxygen (O) and hydrogen (H) decreases as the temperature of the graphite crucible increases, while the analysis of nitrogen (N). The accuracy improves as the temperature of the graphite crucible increases. That is, the analysis accuracy of oxygen (O) and hydrogen (H) and the analysis accuracy of nitrogen (N) show opposite behaviors with respect to the heating temperature of the graphite crucible.
ここで、従来の元素分析装置では、図５に示すように、試料に含まれている元素をガス成分として抽出する際のるつぼの加熱温度は一定とされている。そうすると、黒鉛るつぼの加熱温度を、酸素（Ｏ）や水素（Ｈ）をガス成分として抽出するのに最適な温度に設定すると、窒素（Ｎ）が窒素（Ｎ２）として十分に抽出されずに分析精度が悪くなってしまう。一方で、黒鉛るつぼの加熱温度を、窒素（Ｎ）をガス成分として抽出するのに最適な温度に設定すると、試料に含まれている酸素（Ｏ）の他、黒鉛るつぼ自体に含まれている酸素（Ｏ）が抽出されてしまい分析精度が悪くなってしまう。このように、単一の試料を用いて同時分析すると、酸素（Ｏ）、窒素（Ｎ）及び水素（Ｈ）の全てを高精度に分析することが極めて困難である。 Here, in the conventional elemental analyzer, as shown in FIG. 5, the heating temperature of the crucible when extracting the element contained in the sample as a gas component is constant. Then, when the heating temperature of the graphite crucible is set to an optimum temperature for extracting oxygen (O) and hydrogen (H) as gas components, nitrogen (N) is not sufficiently extracted as nitrogen (N 2 ). Analysis accuracy will deteriorate. On the other hand, when the heating temperature of the graphite crucible is set to an optimum temperature for extracting nitrogen (N) as a gas component, it is contained in the graphite crucible itself in addition to oxygen (O) contained in the sample. Oxygen (O) is extracted, resulting in poor analytical accuracy. Thus, when simultaneous analysis is performed using a single sample, it is extremely difficult to analyze all of oxygen (O), nitrogen (N), and hydrogen (H) with high accuracy.
ここで、酸素（Ｏ）、窒素（Ｎ）及び水素（Ｈ）の各元素を高精度に分析する場合には、同じ試料を複数用意し、試料毎に、黒鉛るつぼの加熱温度を、各元素をガス成分として抽出するのに最適な温度に加熱して、各元素をそれぞれ分析する必要がある。 Here, when analyzing each element of oxygen (O), nitrogen (N), and hydrogen (H) with high accuracy, a plurality of the same samples are prepared, and the heating temperature of the graphite crucible is set for each sample. It is necessary to analyze each element by heating to an optimum temperature for extraction as a gas component.
ところが、このような手法では、酸素（Ｏ）や水素（Ｈ）を高精度に分析するための分析及び窒素（Ｎ）を高精度に分析するための分析の少なくとも２つの元素分析が必要となり、全ての元素を高精度に分析するために要する分析時間が長時間に亘ってしまうという問題がある。また、各元素を高精度に分析するためには、例えば黒鉛るつぼ、Ｈｅガス等のキャリアガス、又は試薬といった消耗品を元素分析毎に用意する必要があり、コスト増大を招いてしまう問題もある。 However, such a method requires at least two elemental analyzes, ie, an analysis for analyzing oxygen (O) and hydrogen (H) with high accuracy and an analysis for analyzing nitrogen (N) with high accuracy. There is a problem that the analysis time required for analyzing all the elements with high accuracy takes a long time. In addition, in order to analyze each element with high accuracy, it is necessary to prepare consumables such as a graphite crucible, a carrier gas such as He gas, or a reagent for each elemental analysis, resulting in an increase in cost. .
そこで本発明は、上記問題点を一挙に解決すべくなされたものであり、試料に含まれている各元素を単一の試料を用いて同時に且つ高精度に分析することをその主たる所期課題とするものである。 Therefore, the present invention has been made to solve the above-mentioned problems all at once, and its main intended problem is to analyze each element contained in a sample simultaneously and with high accuracy using a single sample. It is what.
すなわち本発明に係る元素分析装置は、るつぼに入れた試料を加熱炉内で加熱し、当該試料に含まれている元素をガス成分として抽出して定量分析する元素分析装置であって、前記試料に含まれている第１元素をガス成分として抽出する第１元素抽出最適温度で加熱炉を加熱する第１抽出モードと、前記試料に含まれている前記第１元素とは異なる第２元素をガス成分として抽出するものであり、前記第１抽出最適温度よりも高温である第２元素抽出最適温度で加熱炉を加熱する第２抽出モードと組み合わせて実行することを特徴とする。 That is, the elemental analysis apparatus according to the present invention is an elemental analysis apparatus that heats a sample put in a crucible in a heating furnace, extracts an element contained in the sample as a gas component, and quantitatively analyzes the sample. A first extraction mode for heating the heating furnace at a first element extraction optimum temperature for extracting the first element contained in the gas as a gas component, and a second element different from the first element contained in the sample The extraction is performed as a gas component, and is performed in combination with a second extraction mode in which the heating furnace is heated at a second element extraction optimum temperature that is higher than the first extraction optimum temperature.
このようなものであれば、第１元素を抽出するのに最適な第１元素抽出最適温度で加熱炉を加熱する第１抽出モード及び第２元素を抽出するのに最適な第２元素抽出最適温度で加熱炉を加熱する第２抽出モードを組み合わせることによって、各モードで第１元素及び第２元素を最適な条件で抽出することができるので、単一の試料を用いて各元素を高精度に同時分析することができる。また、各元素を高精度に分析するために複数の試料を準備して、それぞれ各元素に最適な加熱温度で加熱するという複数の分析を行う必要が無いため、各元素を高精度に分析するための分析時間を短縮することができる。さらに、各元素を高精度に分析するために用いる例えば黒鉛るつぼ、Ｈｅガス等のキャリアガス、又は試薬といった消耗品の消費量を低減することができ、ランニングコストを削減することができる。 In such a case, the first extraction mode for heating the heating furnace at the optimum first element extraction temperature for extracting the first element and the second element extraction optimum for extracting the second element are optimal. By combining the second extraction mode in which the heating furnace is heated at a temperature, the first element and the second element can be extracted under optimum conditions in each mode, so that each element can be accurately obtained using a single sample. Can be analyzed simultaneously. In addition, it is not necessary to prepare multiple samples to analyze each element with high accuracy, and to perform each analysis at the optimum heating temperature for each element, so each element is analyzed with high accuracy. Analysis time can be reduced. Furthermore, consumption of consumables such as a graphite crucible, a carrier gas such as He gas, or a reagent used for analyzing each element with high accuracy can be reduced, and a running cost can be reduced.
第１元素抽出最適温度よりも高温な第２元素抽出最適温度である第２抽出モードを先に行うと、黒鉛るつぼ自体に含まれる第１元素が第１抽出モードにおいて抽出されてしまう、或いは、第１元素の抽出が不十分となる恐れがある。このため、前記第１抽出モードを行った後に前記第２抽出モードを行うものであることが望ましい。例えば、第１元素が酸素（Ｏ）であり、第２元素が窒素（Ｎ）の場合には、先に窒素抽出最適温度で加熱すると、後の酸素抽出最適温度で加熱した場合に、黒鉛るつぼ自体に含まれる酸素まで抽出されて、酸素の測定誤差となってしまうといった問題を解決することができる。 If the second extraction mode that is the second element extraction optimum temperature that is higher than the first element extraction optimum temperature is performed first, the first element contained in the graphite crucible itself is extracted in the first extraction mode, or The extraction of the first element may be insufficient. For this reason, it is desirable to perform the second extraction mode after performing the first extraction mode. For example, when the first element is oxygen (O) and the second element is nitrogen (N), the graphite crucible is heated when heated at the optimum temperature for nitrogen extraction first and then heated at the optimum temperature for subsequent oxygen extraction. It is possible to solve the problem that oxygen contained in itself is extracted to cause an oxygen measurement error.
前記第１抽出モードが、前記試料に含まれている酸素をガス成分として抽出する酸素抽出最適温度で加熱炉を加熱するものであり、前記第２抽出モードが、前記試料に含まれている窒素をガス成分として抽出する窒素抽出最適温度で加熱炉を加熱するものであれば、本発明の効果が一層優れたものとなる。 The first extraction mode is for heating the heating furnace at an oxygen extraction optimum temperature for extracting oxygen contained in the sample as a gas component, and the second extraction mode is nitrogen contained in the sample. If the heating furnace is heated at a nitrogen extraction optimum temperature for extracting as a gas component, the effect of the present invention will be further improved.
このように構成した本発明によれば、試料に含まれる複数の元素を単一の試料を用いて同時に且つ高精度に分析することができる。 According to the present invention configured as described above, a plurality of elements contained in a sample can be analyzed simultaneously and with high accuracy using a single sample.
以下に本発明に係る元素分析装置１００について図面を参照して説明する。 Hereinafter, an elemental analysis apparatus 100 according to the present invention will be described with reference to the drawings.
本実施形態の元素分析装置１００は、るつぼＲ内に収容された金属試料又はセラミック試料（以下、単に試料ともいう。）を加熱溶融し、その際に発生するガス成分を分析することによって、当該試料内部に含まれている元素を測定するものである。 The elemental analysis apparatus 100 of the present embodiment heats and melts a metal sample or a ceramic sample (hereinafter also simply referred to as a sample) accommodated in the crucible R, and analyzes the gas component generated at that time, thereby The element contained in the sample is measured.
具体的にこのものは、図１に示すように、加熱炉１内に発生した試料ガスをキャリアガス（例えばＨｅガス等）とともに流通させる単一ガス流路２を形成する流通管を有し、当該流通管上に、ＣＯ検出部３、酸化部４、ＣＯ２検出部５、Ｈ２Ｏ検出部６、ＣＯ２除去部７、Ｈ２Ｏ除去部８及びＮ２検出部９が、この順に直列に設けられている。 Specifically, as shown in FIG. 1, this has a flow pipe that forms a single gas flow path 2 through which a sample gas generated in the heating furnace 1 flows along with a carrier gas (for example, He gas), On the distribution pipe, the CO detection unit 3, the oxidation unit 4, the CO 2 detection unit 5, the H 2 O detection unit 6, the CO 2 removal unit 7, the H 2 O removal unit 8 and the N 2 detection unit 9 are arranged in this order. It is provided in series.
ＣＯ検出部３は、試料ガスに含まれる一酸化炭素（ＣＯ）を検出してその濃度を測定（検出）するものであり、非分散型赤外線ガス分析計（ＮＤＩＲ）により構成されている。 The CO detector 3 detects carbon monoxide (CO) contained in the sample gas and measures (detects) the concentration thereof, and is configured by a non-dispersive infrared gas analyzer (NDIR).
酸化部４は、ＣＯ検出部３の下流側に設けられ、試料ガスに含まれる一酸化炭素（ＣＯ）を二酸化炭素（ＣＯ２）に酸化するとともに、水素（Ｈ）を水（Ｈ２Ｏ）に酸化して水蒸気を生成するものである。本実施形態の酸化部４は、例えば酸化銅（ＣｕＯ）を用いて構成されており、具体的には、石英管内に酸化銅（ＣｕＯ）を充填することにより構成され、その酸化銅（ＣｕＯ）は、約６００度程度に加熱されている。この酸化銅（ＣｕＯ）の加熱方法は、発熱抵抗体により加熱する方法等が考えられる。 The oxidation unit 4 is provided on the downstream side of the CO detection unit 3 and oxidizes carbon monoxide (CO) contained in the sample gas into carbon dioxide (CO 2 ) and hydrogen (H) into water (H 2 O). It is oxidized to produce water vapor. The oxidation unit 4 of the present embodiment is configured by using, for example, copper oxide (CuO), specifically, by filling the quartz tube with copper oxide (CuO), and the copper oxide (CuO). Is heated to about 600 degrees. As a heating method of the copper oxide (CuO), a method of heating with a heating resistor, etc. can be considered.
ＣＯ２検出部５は、試料ガスに含まれる二酸化炭素（ＣＯ２）を検出してその濃度を測定するものであり、非分散型赤外線ガス分析計（ＮＤＩＲ）により構成されている。このＣＯ２検出部５は、その測定精度から試料内部に含まれる酸素（Ｏ）が低濃度（例えば２００ｐｐｍ未満）の場合に有効である。 The CO 2 detection unit 5 detects carbon dioxide (CO 2 ) contained in the sample gas and measures its concentration, and is constituted by a non-dispersive infrared gas analyzer (NDIR). This CO 2 detection unit 5 is effective when oxygen (O) contained in the sample has a low concentration (for example, less than 200 ppm) because of its measurement accuracy.
Ｈ２Ｏ検出部６は、試料ガスに含まれる水（水蒸気）を検出してその濃度を測定するものであり、非分散型赤外線ガス分析計（ＮＤＩＲ）により構成されている。 The H 2 O detection unit 6 detects water (water vapor) contained in the sample gas and measures the concentration thereof, and is configured by a non-dispersive infrared gas analyzer (NDIR).
なお、酸化部４、ＣＯ２検出部５及びＨ２Ｏ検出部６を接続するガス流路を形成する流通管は、１００℃以上に加熱されている。具体的には、流通管の外周面には、発熱抵抗体等からなる加熱機構が設けられている。これにより、酸化部４により生成された水蒸気が、Ｈ２Ｏ検出部６に到達するまでに結露して減少して生じるＨ２Ｏ検出部６の測定誤差を防止することができる。さらに、結露した水によって流通管が錆びてしまうことを防止することもできる。 Incidentally, a flow pipe forming the gas passage which connects the oxidation unit 4, CO 2 detector 5 and H 2 O detection unit 6 is heated above 100 ° C.. Specifically, a heating mechanism made of a heating resistor or the like is provided on the outer peripheral surface of the flow pipe. Thus, the water vapor generated by oxidation unit 4 can be prevented measurement error of H 2 O detection unit 6 caused by decreased condensation to reach in H 2 O detection unit 6. Furthermore, it is possible to prevent the flow pipe from being rusted by condensed water.
ＣＯ２除去部７は、酸化部６を通過した試料ガスから二酸化炭素（ＣＯ２）を吸着して除去するものであり、試料ガスに含まれる窒素（Ｎ２）に対して反応及び吸着等しないものであり、例えば、アスカライト又はゼオライト系モレキュラーシーブ等を用いることができる。 The CO 2 removal unit 7 adsorbs and removes carbon dioxide (CO 2 ) from the sample gas that has passed through the oxidation unit 6, and does not react, adsorb, or the like with respect to nitrogen (N 2 ) contained in the sample gas. For example, ascarite or zeolite molecular sieve can be used.
Ｈ２Ｏ除去部８は、酸化部６を通過した試料ガスから水（水蒸気）を吸着して除去するものであり、試料ガスに含まれる窒素（Ｎ２）に対して反応及び吸着等しないものであり、例えば、過塩素酸マグネシウム又は塩化カルシウム等を用いることができる。 The H 2 O removal unit 8 adsorbs and removes water (water vapor) from the sample gas that has passed through the oxidation unit 6 and does not react or adsorb to nitrogen (N 2 ) contained in the sample gas. For example, magnesium perchlorate or calcium chloride can be used.
Ｎ２検出部９は、試料ガスに含まれる窒素（Ｎ２）を検出してその濃度を測定するものであり、熱伝導度型分析計（ＴＣＤ）により構成されている。 The N 2 detector 9 detects nitrogen (N 2 ) contained in the sample gas and measures the concentration thereof, and is constituted by a thermal conductivity analyzer (TCD).
なお、各検出部により得られた測定信号（各ガス成分の濃度を示す測定値）は、演算部１０に出力される。測定信号を取得した演算部１０は、各測定信号に基づいて、試料内部に含まれる酸素（Ｏ）、水素（Ｈ）及び窒素（Ｎ）の濃度を演算する。そして、演算部１０は、演算結果である酸素（Ｏ）、水素（Ｈ）及び窒素（Ｎ）の濃度を図示しない出力部（モニタ）に出力する。なお、演算部１０の具体的な構成は、例えばＣＰＵ、内部メモリ、入出力インタフェース、ＡＤ変換器等からなる汎用又は専用のコンピュータであり、前記内部メモリの所定領域に格納してあるプログラムに基づいてＣＰＵやその周辺機器等が作動することにより、酸素（Ｏ）、水素（Ｈ）及び窒素（Ｎ）の濃度を演算する。なお、演算部１０は、コンピュータによることなくバッファや増幅器、比較器等を用いたディスクリートアナログ回路を用いて構成しても構わない。 The measurement signal (measured value indicating the concentration of each gas component) obtained by each detection unit is output to the calculation unit 10. The calculation unit 10 that has acquired the measurement signal calculates the concentrations of oxygen (O), hydrogen (H), and nitrogen (N) contained in the sample based on each measurement signal. And the calculating part 10 outputs the density | concentration of oxygen (O), hydrogen (H), and nitrogen (N) which is a calculation result to the output part (monitor) which is not shown in figure. The specific configuration of the arithmetic unit 10 is, for example, a general-purpose or dedicated computer including a CPU, an internal memory, an input / output interface, an AD converter, and the like, and is based on a program stored in a predetermined area of the internal memory. When the CPU and its peripheral devices are operated, the concentrations of oxygen (O), hydrogen (H), and nitrogen (N) are calculated. The arithmetic unit 10 may be configured using a discrete analog circuit using a buffer, an amplifier, a comparator, or the like without using a computer.
しかして本実施形態の元素分析装置１００は、図２に示すように、試料に含まれている第１元素である酸素（Ｏ）をガス成分として抽出する酸素抽出最適温度Ｔ１で加熱炉１を加熱する第１抽出モードと、試料に含まれている第２元素である窒素（Ｎ）をガス成分として抽出する酸素抽出最適温度Ｔ１よりも高温である第２元素抽出最適温度Ｔ２で加熱炉１を加熱する第２抽出モードとを組み合わせて実行する。なお、図２には、第1抽出モード及び第２抽出モードを実行した場合に得られる酸素（Ｏ）、窒素（Ｎ）及び水素（Ｈ）の濃度測定値の経時変化も示している。 Thus elemental analyzer 100 of the present embodiment, as shown in FIG. 2, the furnace 1 oxygen (O) is the first element contained in the sample with oxygen extraction optimum temperatures T 1 to be extracted as a gas component And a second element extraction optimum temperature T 2 that is higher than the oxygen extraction optimum temperature T 1 for extracting nitrogen (N), which is the second element contained in the sample, as a gas component. The second extraction mode for heating the heating furnace 1 is executed in combination. FIG. 2 also shows changes with time in measured concentration values of oxygen (O), nitrogen (N), and hydrogen (H) obtained when the first extraction mode and the second extraction mode are executed.
具体的には、加熱炉１に設けられた加熱機構（不図示）を制御する制御装置１１が、前記加熱機構を制御することより、第１抽出モード及び第２抽出モードを組み合わせて連続的に実行させる。つまり、制御装置１１は、第１抽出モードを行った後に第２抽出モードを実行させる。なお、本実施形態の加熱機構は、黒鉛るつぼＲを上下から挟持する上部電極及び下部電極と、これら電極にインパルス電流を印加させる電源とを有するものである。そして、制御装置１１は、加熱機構の電源を制御することにより、前記第１抽出モード及び第２抽出モードを実行させる。 Specifically, the control device 11 that controls a heating mechanism (not shown) provided in the heating furnace 1 continuously controls the heating mechanism by combining the first extraction mode and the second extraction mode. Let it run. That is, the control device 11 executes the second extraction mode after performing the first extraction mode. In addition, the heating mechanism of this embodiment has an upper electrode and a lower electrode that sandwich the graphite crucible R from above and below, and a power source that applies an impulse current to these electrodes. And the control apparatus 11 performs the said 1st extraction mode and 2nd extraction mode by controlling the power supply of a heating mechanism.
第１抽出モードは、試料に含まれている酸素（Ｏ）を抽出するのに最適な加熱温度Ｔ１（例えば２０００℃）及び加熱時間Ｓ１（例えば２０秒）で黒鉛るつぼＲを加熱するモードである。この第１抽出モードにおいては、試料に含まれている酸素（Ｏ）が一酸化炭素（ＣＯ）として抽出され、試料に含まれている水素（Ｈ）が水（Ｈ２Ｏ）として抽出されるとともに、試料に含まれている窒素（Ｎ）が窒素（Ｎ２）として抽出される。 The first extraction mode is a mode in which the graphite crucible R is heated at a heating temperature T 1 (for example, 2000 ° C.) and a heating time S 1 (for example, 20 seconds) optimal for extracting oxygen (O) contained in the sample. It is. In the first extraction mode, oxygen (O) contained in the sample is extracted as carbon monoxide (CO), and hydrogen (H) contained in the sample is extracted as water (H 2 O). At the same time, nitrogen (N) contained in the sample is extracted as nitrogen (N 2 ).
第２抽出モードは、試料に含まれている窒素（Ｎ）を抽出するのに最適な加熱温度Ｔ２（例えば２５００℃）及び加熱時間Ｓ２（例えば２０秒）で黒鉛るつぼＲを加熱するモードである。この第２抽出モードにおいては、前記第１抽出モードにおいて試料から抽出できなかった窒素（Ｎ）が窒素（Ｎ２）として抽出される（図２の斜線部分）。なお、図２の斜線部分は、従来の元素分析装置により酸素最適温度Ｔ１で一定加熱した場合には抽出されない部分である。一方で、従来の元素分析装置により窒素最適温度Ｔ２で一定加熱した場合には黒鉛るつぼ自体に含まれている酸素が抽出されてしまい測定誤差となる。 In the second extraction mode, the graphite crucible R is heated at a heating temperature T 2 (for example, 2500 ° C.) and a heating time S 2 (for example, 20 seconds) that are optimal for extracting nitrogen (N) contained in the sample. It is. In the second extraction mode, nitrogen (N) that could not be extracted from the sample in the first extraction mode is extracted as nitrogen (N 2 ) (shaded area in FIG. 2). Incidentally, the hatched portion in FIG. 2, in the case of constant heating at an oxygen optimum temperatures T 1 by conventional elemental analysis device is a part which is not extracted. On the other hand, the measurement error will be extracted oxygen contained in the graphite crucible itself when certain heated in a nitrogen optimum temperature T 2 by a conventional elemental analysis device.
このように構成した本実施形態に係る元素分析装置１００によれば、酸素（Ｏ）を抽出するのに最適な酸素抽出最適温度Ｔ１で加熱炉１を加熱する第１抽出モード及び窒素（Ｎ）を抽出するのに最適な窒素抽出最適温度Ｔ２で加熱炉１を加熱する第２抽出モードを組み合わせることによって、各モードで酸素（Ｏ）及び窒素（Ｎ）を最適な条件で抽出することができるので、単一の試料を用いて各元素（酸素及び窒素）を高精度に同時分析することができる。また、酸素及び窒素を高精度に分析するために複数の試料を準備して、それぞれ各元素に最適な加熱温度で加熱するという複数の分析を行う必要が無いため、各元素を高精度に分析するための分析時間を短縮することができる。さらに、各元素を高精度に分析するために用いる例えば黒鉛るつぼＲ、Ｈｅガス等のキャリアガス、又は試薬といった消耗品の消費量を低減することができ、ランニングコストを削減することができる。 According to the elemental analysis device 100 according to this embodiment configured as described above, oxygen (O) the first extraction mode and nitrogen to heat the furnace 1 at the optimum oxygen extraction optimum temperatures T 1 to extract the (N ) by combining the second extraction mode for heating the heating furnace 1 at the optimum nitrogen extracted optimum temperature T 2 for extracting, extracting oxygen (O) and nitrogen (N) at the optimum conditions in each mode Therefore, each element (oxygen and nitrogen) can be simultaneously analyzed with high accuracy using a single sample. In addition, it is not necessary to prepare multiple samples to analyze oxygen and nitrogen with high precision, and to perform multiple analyzes of heating at the optimal heating temperature for each element. Analyzing time can be shortened. Furthermore, the consumption of consumables such as graphite crucible R, a carrier gas such as He gas, or a reagent used for analyzing each element with high accuracy can be reduced, and the running cost can be reduced.
なお、本発明は前記実施形態に限られるものではない。例えば、前記実施形態では、元素に含まれる酸素及び水素の両方を定量分析するものであったが、酸素又は水素の一方のみを定量分析するものであっても良い。 The present invention is not limited to the above embodiment. For example, in the above embodiment, both oxygen and hydrogen contained in the element are quantitatively analyzed, but only one of oxygen and hydrogen may be quantitatively analyzed.
また、試料の種類に応じて、第１抽出モード又は第２抽出モードの何れか一方のみを実行するように構成しても良い。例えば、試料の種類に応じて、第１抽出モード及び第２抽出モードを１つの分析工程で実行するパターンと、第１抽出モード又は第２抽出モードの一方のみを実行するパターンとを切り替え可能に構成しても良い。 Further, only one of the first extraction mode and the second extraction mode may be executed according to the type of sample. For example, it is possible to switch between a pattern in which the first extraction mode and the second extraction mode are executed in one analysis step and a pattern in which only one of the first extraction mode or the second extraction mode is executed according to the type of sample. It may be configured.
さらに前記実施形態では、第１抽出モード及び第２抽出モードを各１回ずつ行うものであったが、それらを複数回交互に繰り返して行うものであっても良い。 Furthermore, in the said embodiment, although 1st extraction mode and 2nd extraction mode were each performed once, you may perform by repeating them alternately several times.
その上、前記実施形態では、第１抽出モードの酸素抽出最適温度Ｔ１から第２抽出モードの窒素抽出最適温度Ｔ２にステップ状（階段状）に変化するものであったが、図３に示すように、第１抽出モード及び第２抽出モードの間に黒鉛るつぼの加熱温度を滑らかに連続的に変化させる移行モードを有するものであっても良い。 Moreover, in the embodiment, in a thing that changes from oxygen abstraction optimum temperature T 1 of the first extraction mode to the second extraction mode nitrogen extracted optimum temperature T 2 stepwise (stepwise) in FIG. 3 As shown, it may have a transition mode in which the heating temperature of the graphite crucible is smoothly and continuously changed between the first extraction mode and the second extraction mode.
黒鉛るつぼの他に、セラミックるつぼを用いるものであっても良い。この場合、元素分析装置が高周波加熱炉を備えるものであり、試料中に存在する炭素や硫黄などを分析するものであっても良い。 In addition to the graphite crucible, a ceramic crucible may be used. In this case, the elemental analysis apparatus includes a high-frequency heating furnace, and may analyze carbon, sulfur, etc. present in the sample.
また、測定試料中に含まれる測定対象元素をユーザが指定することで、抽出モードの組み合わせ、温度又は順序が自動的に制御部１１により制御されるものであっても良い。 Moreover, the combination of extraction modes, temperature, or order may be automatically controlled by the control unit 11 by designating a measurement target element included in a measurement sample.
その他、本発明は前記実施形態に限られず、その趣旨を逸脱しない範囲で種々の変形が可能であるのは言うまでもない。 In addition, it goes without saying that the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.
１００・・・元素分析装置
Ｒ・・・るつぼ
１・・・加熱炉
Ｔ１・・・第１元素抽出最適温度（酸素抽出最適温度）
Ｔ２・・・第２元素抽出最適温度（窒素抽出最適温度）
100 ... elemental analyzer R ... crucible 1 ... furnace T 1 ... first element extraction optimum temperature (oxygen extraction optimum temperature)
T 2 ... second element extraction optimum temperature (nitrogen extraction optimum temperature)
Claims (3)
前記試料に含まれている第１元素をガス成分として抽出する第１元素抽出最適温度で加熱炉を加熱する第１抽出モードと、前記試料に含まれている前記第１元素とは異なる第２元素をガス成分として抽出するものであり、前記第１元素抽出最適温度よりも高温である第２元素抽出最適温度で加熱炉を加熱する第２抽出モードとを組み合わせて実行することを特徴とする元素分析装置。 An element analysis device that heats a sample put in a crucible in a heating furnace, extracts an element contained in the sample as a gas component, and quantitatively analyzes the element,
A first extraction mode in which the heating furnace is heated at a first element extraction optimum temperature for extracting the first element contained in the sample as a gas component, and a second different from the first element contained in the sample. An element is extracted as a gas component, and is executed in combination with a second extraction mode in which the heating furnace is heated at a second element extraction optimum temperature that is higher than the first element extraction optimum temperature. Elemental analyzer.
前記第２抽出モードが、前記試料に含まれている窒素をガス成分として抽出する窒素抽出最適温度で加熱炉を加熱するものである請求項１又は２記載の元素分析装置。 The first extraction mode is for heating the heating furnace at an oxygen extraction optimum temperature for extracting oxygen contained in the sample as a gas component,
The elemental analysis apparatus according to claim 1 or 2, wherein the second extraction mode is for heating the heating furnace at a nitrogen extraction optimum temperature for extracting nitrogen contained in the sample as a gas component.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020137147A1 (en) * | 2018-12-26 | 2020-07-02 | 株式会社堀場製作所 | Elemental analysis device, program for elemental analysis device, and elemental analysis method |
| WO2022091748A1 (en) * | 2020-11-02 | 2022-05-05 | 株式会社堀場製作所 | Element analysis method, element analysis device, and program for element analysis device |
| WO2022190466A1 (en) | 2021-03-12 | 2022-09-15 | 株式会社堀場製作所 | Element analysis device, operation method for element analysis device, and work program for element analysis device |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5610252A (en) * | 1979-07-04 | 1981-02-02 | Nippon Steel Corp | Method for determining sulfur in metal |
| JPS61194359A (en) * | 1985-02-23 | 1986-08-28 | Horiba Ltd | Method for analysis of element in specimen by using crucible |
| JPH0427838A (en) * | 1990-05-22 | 1992-01-30 | Kobe Steel Ltd | Gas analyzing method and ni capsule for gas analysis |
| JPH06148170A (en) * | 1992-11-13 | 1994-05-27 | Nkk Corp | Analyzing method for trace oxygen of iron and steel |
| JPH1183841A (en) * | 1997-09-08 | 1999-03-26 | Sanyo Special Steel Co Ltd | Classified analysis of oxide inclusion oxygen in metal |
| JPH11166923A (en) * | 1997-12-06 | 1999-06-22 | Horiba Ltd | Element analyzing method |
| JP2000193657A (en) * | 1998-12-25 | 2000-07-14 | Horiba Ltd | Oxygen analysis method in sample and device |
| JP2001124675A (en) * | 1999-10-25 | 2001-05-11 | Horiba Ltd | Element analyzer |
| JP2004219364A (en) * | 2003-01-17 | 2004-08-05 | Daido Steel Co Ltd | Method for analyzing oxygen in si sample |
-
2012
- 2012-05-30 JP JP2012122719A patent/JP5968083B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5610252A (en) * | 1979-07-04 | 1981-02-02 | Nippon Steel Corp | Method for determining sulfur in metal |
| JPS61194359A (en) * | 1985-02-23 | 1986-08-28 | Horiba Ltd | Method for analysis of element in specimen by using crucible |
| JPH0427838A (en) * | 1990-05-22 | 1992-01-30 | Kobe Steel Ltd | Gas analyzing method and ni capsule for gas analysis |
| JPH06148170A (en) * | 1992-11-13 | 1994-05-27 | Nkk Corp | Analyzing method for trace oxygen of iron and steel |
| JPH1183841A (en) * | 1997-09-08 | 1999-03-26 | Sanyo Special Steel Co Ltd | Classified analysis of oxide inclusion oxygen in metal |
| JPH11166923A (en) * | 1997-12-06 | 1999-06-22 | Horiba Ltd | Element analyzing method |
| JP2000193657A (en) * | 1998-12-25 | 2000-07-14 | Horiba Ltd | Oxygen analysis method in sample and device |
| JP2001124675A (en) * | 1999-10-25 | 2001-05-11 | Horiba Ltd | Element analyzer |
| JP2004219364A (en) * | 2003-01-17 | 2004-08-05 | Daido Steel Co Ltd | Method for analyzing oxygen in si sample |
Non-Patent Citations (1)
| Title |
|---|
| JPN6016008155; 知惠賢二郎: '金属材料等における元素分析（ガス成分）方法' ＩＩＣ ＲＥＶＩＥＷ Ｎｏ．４１, 200904, 第３１-３６頁 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020137147A1 (en) * | 2018-12-26 | 2020-07-02 | 株式会社堀場製作所 | Elemental analysis device, program for elemental analysis device, and elemental analysis method |
| WO2022091748A1 (en) * | 2020-11-02 | 2022-05-05 | 株式会社堀場製作所 | Element analysis method, element analysis device, and program for element analysis device |
| WO2022190466A1 (en) | 2021-03-12 | 2022-09-15 | 株式会社堀場製作所 | Element analysis device, operation method for element analysis device, and work program for element analysis device |
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|---|---|
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