JP5405218B2 - Sample analysis method, sample carrying member, sample carrying method, and temperature programmed desorption analyzer - Google Patents
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Description
本発明は、分析装置等で分析される試料の試料搬入方法、試料搬入方法で使用される試料搬入部材、これらで搬入された試料の分析を行う試料分析方法および昇温脱離分析装置に関し、特に、電解チャージ等により液体中で調製された試料に対して好適に使用可能な試料分析方法、試料搬入部材、試料搬入方法および昇温脱離分析装置に関する。 The present invention relates to a sample carry-in method for a sample to be analyzed by an analyzer or the like, a sample carry-in member used in the sample carry-in method, a sample analysis method and a temperature-programmed desorption analyzer for analyzing a sample carried in these, In particular, the present invention relates to a sample analysis method, a sample carry-in member, a sample carry-in method, and a temperature programmed desorption analyzer that can be suitably used for a sample prepared in a liquid by electrolytic charging or the like.
図１５は従来の質量分析装置の一例としての昇温脱離分析装置の全体説明図である。
試料の特性を測定、分析する分析装置として、試料から脱離する微量なガスの測定を行う質量分析装置の一例である昇温脱離分析装置（ＴＤＳ：Thermal Desorption Spectrometer）が従来から知られている。
図１５において、従来の昇温脱離分析装置０１では、分析が行われる分析真空室０２には、試料を保持する試料保持部材、いわゆる試料ステージ０３が配置されている。前記試料ステージ０３には、下方から図示しない赤外光が照射され、試料ステージ０３上に保持された試料の昇温が可能な構成となっている。また、前記分析真空室０２は、真空ポンプ（排気装置）０４により真空状態に排気されている。前記分析真空室０２には、前記試料ステージ０３の近傍に質量分析計０６が配置されている。前記質量分析計０６としては、例えば、４重極子質量分析計、いわゆるＱ−ＭＡＳ（quadrupole mass spectrometer）を使用可能である。
FIG. 15 is an overall explanatory view of a temperature-programmed desorption analyzer as an example of a conventional mass spectrometer.
A thermal desorption spectrometer (TDS), which is an example of a mass spectrometer that measures a small amount of gas desorbed from a sample, has been known as an analyzer that measures and analyzes the characteristics of a sample. Yes.
In FIG. 15, in the conventional thermal desorption analyzer 01, a sample holding member for holding a sample, a so-called sample stage 03 is arranged in an analysis vacuum chamber 02 in which analysis is performed. The sample stage 03 is irradiated with infrared light (not shown) from below, so that the temperature of the sample held on the sample stage 03 can be raised. The analysis vacuum chamber 02 is evacuated to a vacuum state by a vacuum pump (exhaust device) 04. In the analysis vacuum chamber 02, a mass spectrometer 06 is disposed in the vicinity of the sample stage 03. As the mass spectrometer 06, for example, a quadrupole mass spectrometer, so-called Q-MAS (quadrupole mass spectrometer) can be used.
前記分析真空室０２には、開閉可能な仕切弁、いわゆるゲートバルブ０１１を介して、搬入室０１２、いわゆるロードロックチャンバが接続されている。前記搬入室０１２には、試料０１４を搬入、搬出可能な試料出入口０１３が形成されている。前記昇温脱離分析装置０１には、ゲート０１１が開いた状態で搬入室０１２と分析真空室０２との間で移動可能な試料移動部材０１５、いわゆるロードロックアームが配置されている。なお、前記搬入室０１２には、真空ポンプ（排気装置）０１６が接続されており、搬入室０１２内部が真空状態に排気可能に構成されている。 The analysis vacuum chamber 02 is connected to a loading chamber 012, a so-called load lock chamber, through a gate valve 011 that can be opened and closed. In the loading chamber 012, a sample inlet / outlet port 013 is formed through which the sample 014 can be loaded and unloaded. In the temperature-programmed desorption analyzer 01, a sample moving member 015 that is movable between the loading chamber 012 and the analysis vacuum chamber 02 with the gate 011 opened, a so-called load lock arm is arranged. A vacuum pump (exhaust device) 016 is connected to the carry-in chamber 012 so that the inside of the carry-in chamber 012 can be evacuated to a vacuum state.
図１５に示す従来の昇温脱離分析装置０１では、昇温脱離分析装置０１の外部で調製された試料０１４が、試料出入口０１３を通じて真空排気前の搬入室０１２の試料移動部材０１５に載せられる。次に、搬入室０１２が真空ポンプ０１６で排気されて真空状態になると、ゲート０１１が開放されて、搬入室０１２から分析真空室０２に試料移動部材０１５を移動させる。そして、試料移動部材０１５上の試料０１４を、図示しないマニュピレータ等を使用して試料移動部材０１５から試料ステージ０３に移動させる。そして、試料ステージ０３上の試料０１４が昇温されることで試料０１４から脱離した成分が、質量分析計０６で測定される。 In the conventional thermal desorption analyzer 01 shown in FIG. 15, the sample 014 prepared outside the thermal desorption analyzer 01 is placed on the sample moving member 015 in the loading chamber 012 before evacuation through the sample inlet / outlet 013. It is done. Next, when the carry-in chamber 012 is evacuated by the vacuum pump 016 to be in a vacuum state, the gate 011 is opened, and the sample moving member 015 is moved from the carry-in chamber 012 to the analysis vacuum chamber 02. Then, the sample 014 on the sample moving member 015 is moved from the sample moving member 015 to the sample stage 03 using a manipulator (not shown) or the like. Then, the component desorbed from the sample 014 due to the temperature rise of the sample 014 on the sample stage 03 is measured by the mass spectrometer 06.
また、このような昇温脱離分析装置に関する技術として、下記の特許文献１記載の技術も公知である。
特許文献１としての特開２００５−９０９８７号公報には、加熱ステージ（１０）上に保持された試料（２１）を昇温した際に、試料（２１）から放出される脱離ガスを質量分析計（２０）で測定し、分析を行う昇温脱離分析装置が記載されている。特許文献１記載の技術では、まず、試料を分析装置に導入する前に、大気中で、試料表面に接着剤を塗布・乾燥させておく。次に、接着剤が塗布された試料を、ロードロックチャンバ（１）内にセットし、真空排気した後、試料搬送機構（５）を使用して、加熱ステージ（１０）上にセットする。そして、加熱ステージ（１０）上の試料表面に対して、銅製の急凍結棒（３４）を使用して液体窒素を注入して冷却し、試料表面の接着剤を収縮硬化させて試料表面の膜を剥離させている。
すなわち、特許文献１記載の技術では、大気中で試料を調製した後、搬入室であるロードロックチャンバ（１）内で真空排気し、その後に、試料を冷却している。
As a technique related to such a temperature programmed desorption analyzer, a technique described in Patent Document 1 below is also known.
Japanese Patent Laid-Open No. 2005-90987 as Patent Document 1 discloses mass spectrometry of desorbed gas released from a sample (21) when the temperature of the sample (21) held on the heating stage (10) is increased. A temperature-programmed desorption analyzer for measuring and analyzing with a meter (20) is described. In the technique described in Patent Document 1, first, an adhesive is applied to the sample surface and dried in the air before the sample is introduced into the analyzer. Next, the sample to which the adhesive has been applied is set in the load lock chamber (1), evacuated, and then set on the heating stage (10) using the sample transport mechanism (5). The sample surface on the heating stage (10) is cooled by injecting liquid nitrogen using a copper quick freezing rod (34) to shrink and harden the adhesive on the sample surface. Is peeling off.
That is, in the technique described in Patent Document 1, after preparing a sample in the atmosphere, it is evacuated in a load lock chamber (1) that is a loading chamber, and then the sample is cooled.
(従来技術の問題点)
特許文献１記載の技術では、常温の試料をステージに載せてから真空排気、冷却による表面膜剥離、昇温の順に行うことによって、昇温時に脱離する成分ガスを測定している。しかし、特許文献１記載の技術では、接着剤を塗布する作業が加わって面倒であったり、接着剤の剥離時に精度良く剥離できない場合には測定結果に悪影響がでる問題もある。
また、前記特許文献１記載の技術や、図１５に示す従来の昇温脱離分析装置０１において、試料を試料ステージ０３に載せてから冷却し、その後に昇温する場合、例えば、鉄鋼材料の水素脆化問題を引き起こす極微量の拡散性水素のように、極微量の成分を測定する場合には、冷却後に比べて脱離しやすい冷却前に真空排気を行うと、排気により極微量の成分が脱離してしまうため、分析の精度、感度が十分でないという問題がある。
(Problems of conventional technology)
In the technique described in Patent Document 1, component gas desorbed at the time of temperature rise is measured by placing a room temperature sample on a stage and then performing evacuation, surface film peeling by cooling, and temperature rise in this order. However, the technique described in Patent Document 1 has a problem that the work of applying the adhesive is added and is troublesome, or the measurement result is adversely affected when the adhesive cannot be removed accurately.
Further, in the technique described in Patent Document 1 and the conventional temperature programmed desorption analyzer 01 shown in FIG. 15, when the sample is cooled after being placed on the sample stage 03 and then heated, for example, When measuring a very small amount of components, such as a very small amount of diffusible hydrogen that causes hydrogen embrittlement problems, if the vacuum is evacuated before cooling, which is easier to desorb than after cooling, a very small amount of components will be generated by the exhaust. Since it is desorbed, there is a problem that the accuracy and sensitivity of the analysis are not sufficient.
さらに、前記従来の昇温脱離分析装置において、昇温脱離分析装置に導入前に、大気中で試料を冷却して、装置に搬入することも考えられるが、冷却時に大気中の成分（主に水）が付着する恐れがある。また、冷却された状態で分析装置まで搬入される途中で大気に曝されたり、排気前の分析装置内の雰囲気ガス中に含まれる成分が試料に吸着されてしまう恐れがあり、極微量の成分の測定に悪影響があり、分析の感度、精度が低下してしまう問題がある。 Furthermore, in the conventional thermal desorption analyzer, it is conceivable that the sample is cooled in the atmosphere and introduced into the apparatus before being introduced into the thermal desorption analyzer. There is a risk of water adhering. In addition, there is a risk of exposure to the air while being transported to the analyzer in a cooled state, or components contained in the atmospheric gas in the analyzer before exhaustion may be adsorbed to the sample. There is a problem that the measurement sensitivity and accuracy are reduced.
前述の事情に鑑み、本発明は、試料に含まれる極微量の成分の分析の感度を高めることを技術的課題とする。 In view of the above circumstances, an object of the present invention is to increase the sensitivity of analysis of a very small amount of components contained in a sample.
前記技術的課題を解決するために、請求項１記載の発明の試料分析方法は、
液体中で試料を調製する試料調製工程と、
調製された前記試料を、試料搬入部材の冷媒液収容部に収容された液体状の冷媒中に沈んだ状態で収容する試料冷却収容工程と、
前記試料が収容された前記試料搬入部材を、真空状態に排気されて分析が行われる分析真空室に接続された搬入室に搬入する試料搬入工程と、
前記搬入室を、真空状態に排気する搬入室排気工程と、
前記搬入室の前記試料搬入部材を前記分析真空室に移動させ、前記試料搬入部材の前記試料を、前記分析真空室の試料保持部材に移動させる試料移動工程と、
前記試料保持部材の試料に対して分析を行う試料分析工程と、
を実行することを特徴とする。
In order to solve the technical problem, the sample analysis method of the invention according to claim 1 comprises:
A sample preparation step of preparing the sample in a liquid;
A sample cooling and storing step for storing the prepared sample in a state where it is submerged in a liquid refrigerant stored in the refrigerant liquid storing portion of the sample carrying-in member;
A sample carrying-in step for carrying the sample carrying-in member containing the sample into a carrying-in chamber connected to an analysis vacuum chamber that is evacuated and analyzed;
A carry-in chamber exhausting step for exhausting the carry-in chamber to a vacuum state;
A sample moving step of moving the sample loading member of the loading chamber to the analysis vacuum chamber and moving the sample of the sample loading member to a sample holding member of the analysis vacuum chamber;
A sample analysis step for analyzing the sample of the sample holding member;
It is characterized by performing.
請求項２に記載の発明は、請求項１に記載の試料分析方法において、
前記液体状の冷媒が収容された冷媒収容槽内に沈められた前記試料搬入部材に対して、前記試料搬入部材の前記冷媒収容部に調製された試料を収容する前記試料冷却収容工程、
を実行することを特徴とする。
The invention according to claim 2 is the sample analysis method according to claim 1,
The sample cooling and storing step of storing the sample prepared in the refrigerant storage portion of the sample loading member with respect to the sample loading member submerged in the refrigerant storage tank in which the liquid refrigerant is stored;
It is characterized by performing.
請求項３に記載の発明は、請求項１または２に記載の試料分析方法において、
液体窒素により構成された前記液体状の冷媒に沈められた試料を収容する前記試料搬入部材が前記搬入室に搬入される前に、前記搬入室を窒素ガスでパージする窒素パージ工程、
を実行することを特徴とする。
The invention according to claim 3 is the sample analysis method according to claim 1 or 2,
A nitrogen purge step of purging the loading chamber with nitrogen gas before the sample loading member containing the sample submerged in the liquid refrigerant composed of liquid nitrogen is loaded into the loading chamber;
It is characterized by performing.
前記技術的課題を解決するために、請求項４に記載の発明の試料搬入部材は、
液体状の冷媒が収容され且つ試料が冷媒中に沈んだ状態で収容可能な凹状に形成されると共に上方が外気に開放された冷媒液収容部を備え、真空状態の真空室を有する分析装置の外部において液体中で調製された試料が搬入され、前記冷媒液収容部の前記冷媒中に前記試料が沈んだ状態で収容されると共に、前記試料を冷媒中に保持した状態で前記分析装置に搬入されることを特徴とする。
In order to solve the technical problem, the sample carry-in member according to claim 4 is:
An analyzer having a vacuum chamber in a vacuum state, which is provided with a refrigerant liquid storage portion that is formed in a concave shape that can store a liquid refrigerant and that can be stored in a state where the sample is submerged in the refrigerant, and that is open to the outside . A sample prepared in a liquid is carried in from outside, and the sample is stored in the refrigerant in the refrigerant liquid storage section while being sinked, and is also carried into the analyzer while the sample is held in the refrigerant. It is characterized by being.
請求項５に記載の発明は、請求項４に記載の試料搬入部材において、
前記分析装置に設けられ且つ分析される試料が保持される試料保持部材に対して、前記試料保持部材の外縁に接触可能に形成され、且つ、前記試料保持部材の外縁に対応する外縁形状を有する試料搬入側縁、
を備えたことを特徴とする。
The invention according to claim 5 is the sample carry-in member according to claim 4,
A sample holding member provided in the analyzer and holding a sample to be analyzed is formed so as to be in contact with the outer edge of the sample holding member and has an outer edge shape corresponding to the outer edge of the sample holding member. Sample loading side edge,
It is provided with.
請求項６に記載の発明は、請求項５に記載の試料搬入部材において、
前記試料保持部材に試料搬入側縁が接触した状態で、前記試料保持部材側に行くに連れて、深さが浅くなるように形成された前記冷媒液収容部、
を備えたことを特徴とする。
The invention described in claim 6 is the sample carrying-in member according to claim 5,
In the state where the sample loading side edge is in contact with the sample holding member, the refrigerant liquid storage portion formed so as to become shallower as it goes to the sample holding member side,
It is provided with.
前記技術的課題を解決するために、請求項７に記載の発明の試料搬入方法は、
液体中で調製された試料を、試料搬入部材の冷媒液収容部に収容された液体状の冷媒中に沈んだ状態で収容する試料冷却収容工程と、
前記試料が収容された前記試料搬入部材を、分析が行われる分析装置に設けられた真空排気される搬入室に搬入する試料搬入工程と、
を実行することを特徴とする。
In order to solve the technical problem, the sample carrying-in method according to claim 7 comprises:
The specimen prepared in a liquid, the sample cooling accommodating step of accommodating in a state sunk into liquid refrigerant contained in the refrigerant liquid storage unit of the sample carrying member,
A sample carrying-in step of carrying the sample carrying-in member containing the sample into a carrying-in chamber that is evacuated and provided in an analyzer in which analysis is performed;
It is characterized by performing.
前記技術的課題を解決するために、請求項８に記載の昇温脱離分析装置は、
搬入室と、
液体状の冷媒が収容され且つ試料が冷媒中に沈んだ状態で収容可能な凹状に形成されると共に上方が外気に開放された冷媒液収容部を備え、前記搬入室の外部において液体中で調製された試料が搬入され、前記冷媒液収容部の前記冷媒中に前記試料が沈んだ状態で収容されると共に、前記試料を冷媒中に保持した状態で前記搬入室に搬入される試料搬入部材と、
前記搬入室を真空状態に排気する排気装置と、
前記搬入室に接続された第１の分析真空室であって、前記搬入室に搬入された前記試料搬入部材の前記冷媒液収容部から移動された試料が保持され且つ試料の昇温を行う試料保持部材が配置されると共に内部が真空に排気される前記第１の分析真空室と、前記第１の分析真空室と接続され且つ試料から脱離したガス成分の質量分析を行う質量分析計が支持されて内部が真空に排気される第２の分析真空室と、を有し、試料の分析が行われる分析真空室と、
前記第１の分析真空室と前記第２の分析真空室との間を接続し、且つ、通過するガスから一部のガス成分を除去するガス除去装置と、
を備えたことを特徴とする。
In order to solve the technical problem, the temperature-programmed desorption analyzer according to claim 8,
A loading room;
Prepared in liquid in the outside of the carry-in chamber, which is provided with a refrigerant liquid storage part that is formed in a concave shape that can store liquid refrigerant and that can be stored in a state where the sample is submerged in the refrigerant, and whose upper part is open to the outside. A sample carrying-in member that is carried in, is contained in the refrigerant in the refrigerant liquid containing portion while the sample is sinked, and is carried into the carry-in chamber while the sample is held in the refrigerant; ,
An exhaust device for exhausting the carry-in chamber to a vacuum state;
A first analysis vacuum chamber connected to the carry-in chamber, in which the sample moved from the refrigerant liquid storage part of the sample carry-in member carried into the carry-in chamber is held and the sample is heated said first analysis vacuum chamber holding member inside is evacuated to a vacuum while being arranged, the first is connected to the analytical vacuum chamber and a mass spectrometer for performing mass analysis of the desorbed gas component from the sample A second analysis vacuum chamber that is supported and evacuated to a vacuum, and an analysis vacuum chamber in which analysis of the sample is performed;
A gas removal device that connects between the first analysis vacuum chamber and the second analysis vacuum chamber and removes a part of gas components from the passing gas;
It is provided with.
請求項９に記載の発明は、請求項８に記載の昇温脱離分析装置において、
前記第１の分析真空室を真空排気する第１の真空ポンプと、
前記第１の分析真空室と前記第１の真空ポンプとを接続する第１の排気路に設けられ、前記第１の分析真空室と前記第１の真空ポンプとの接続、切断を行う第１のバルブと、
を備え、前記質量分析が行われる場合には、前記第１のバルブが閉じられる
ことを特徴とする。
The invention described in claim 9 is the temperature programmed desorption analyzer according to claim 8 ,
A first vacuum pump for evacuating the first analysis vacuum chamber;
A first exhaust passage is provided in a first exhaust path connecting the first analysis vacuum chamber and the first vacuum pump, and connects and disconnects the first analysis vacuum chamber and the first vacuum pump. And the valve
When the mass spectrometry is performed, the first valve is closed.
請求項１に記載の発明によれば、試料が液体状の冷媒中に沈んで冷却された状態で移動されるため、大気に曝されることが低減でき、大気中の成分が試料に付着することを低減できる。また、試料が冷却された状態で真空に排気されるため、真空に排気された後に冷却される場合に比べて、試料の成分の脱離が低減できる。この結果、試料に含まれる極微量の成分の分析の感度を高めることができる。
請求項２に記載の発明によれば、試料搬入部材を冷却することができ、液体状の冷媒が気化しても冷却された試料搬入部材により試料の昇温を低減することが出来る。
請求項３に記載の発明によれば、試料に水分が付着することを低減することができる。
According to the first aspect of the present invention, since the sample is moved in a cooled state after sinking in the liquid refrigerant, exposure to the atmosphere can be reduced, and components in the atmosphere adhere to the sample. Can be reduced. Further, since the sample is evacuated in a cooled state, desorption of the components of the sample can be reduced as compared with the case where the sample is cooled after being evacuated. As a result, it is possible to increase the sensitivity of analysis of a very small amount of components contained in the sample.
According to the second aspect of the present invention, the sample carrying-in member can be cooled, and even if the liquid refrigerant is vaporized, the temperature rise of the sample can be reduced by the cooled sample carrying-in member.
According to invention of Claim 3, it can reduce that a water | moisture content adheres to a sample.
請求項４に記載の発明によれば、試料が液体状の冷媒中に沈んで冷却された状態で移動されるため、大気に曝されることが低減でき、大気中の成分が試料に付着することを低減できる。この結果、試料に含まれる極微量の成分の分析の感度を高めることができる。
請求項５に記載の発明によれば、試料搬入部材から試料保持部材に、試料を容易に移動させることができる。
請求項６に記載の発明によれば、前記冷媒液収容部材の深さが浅くなるように形成された面を通じて、容易に試料を移動させることができる。
According to the fourth aspect of the present invention, since the sample is moved in a cooled state after being submerged in a liquid refrigerant, exposure to the atmosphere can be reduced, and components in the atmosphere adhere to the sample. Can be reduced. As a result, it is possible to increase the sensitivity of analysis of a very small amount of components contained in the sample.
According to the fifth aspect of the present invention, the sample can be easily moved from the sample carry-in member to the sample holding member.
According to the sixth aspect of the present invention, the sample can be easily moved through the surface formed so that the depth of the refrigerant liquid storage member is shallow.
請求項７に記載の発明によれば、試料が液体状の冷媒中に沈んで冷却された状態で移動されるため、大気に曝されることが低減でき、大気中の成分が試料に付着することを低減できる。また、試料が冷却された状態で真空に排気されるため、真空に排気された後に冷却される場合に比べて、試料の成分の脱離が低減できる。この結果、試料に含まれる極微量の成分の分析の感度を高めることができる。
請求項８に記載の発明によれば、試料が液体状の冷媒中に沈んで冷却された状態で移動されるため、大気に曝されることが低減でき、大気中の成分が試料に付着することを低減できる。また、試料が冷却された状態で真空に排気されるため、真空に排気された後に冷却される場合に比べて、試料の成分の脱離が低減できる。この結果、試料に含まれる極微量の成分の分析の感度を高めることができる。また、請求項８に記載の発明によれば、測定結果に悪影響を及ぼす一部のガス成分を除去することができ、試料に含まれる極微量の成分の分析の感度を高めることができる。
According to the seventh aspect of the present invention, since the sample is moved while cooled in the liquid refrigerant, exposure to the atmosphere can be reduced, and components in the atmosphere adhere to the sample. Can be reduced. Further, since the sample is evacuated in a cooled state, desorption of the components of the sample can be reduced as compared with the case where the sample is cooled after being evacuated. As a result, it is possible to increase the sensitivity of analysis of a very small amount of components contained in the sample.
According to the eighth aspect of the invention, since the sample is moved in a cooled state after sinking in the liquid refrigerant, exposure to the atmosphere can be reduced, and components in the atmosphere adhere to the sample. Can be reduced. Further, since the sample is evacuated in a cooled state, desorption of the components of the sample can be reduced as compared with the case where the sample is cooled after being evacuated. As a result, it is possible to increase the sensitivity of analysis of a very small amount of components contained in the sample. In addition, according to the eighth aspect of the present invention, it is possible to remove some gas components that adversely affect the measurement results, and it is possible to increase the sensitivity of analysis of a very small amount of components contained in the sample.
請求項９に記載の発明によれば、質量分析時に第１のバルブが閉じられ、第１の分析真空室において脱離したガスが直接排気されず、第２の分析真空室に移動するため、分析の感度を高めることができる。 According to the invention described in claim 9, the first valves are closed during mass spectrometry, gas desorbed are not exhausted directly in the first analysis vacuum chamber, to move to the second analysis vacuum chamber , Can increase the sensitivity of analysis.
次に図面を参照しながら、本発明の実施の形態の具体例である実施例を説明するが、本発明は以下の実施例に限定されるものではない。
なお、以下の図面を使用した説明において、理解の容易のために説明に必要な部材以外の図示は適宜省略されている。
Next, examples which are specific examples of embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following examples.
In the following description using the drawings, illustrations other than members necessary for the description are omitted as appropriate for easy understanding.
図１は本発明の実施例１の試料分析装置の一例としての昇温脱離分析装置の全体説明図である。
なお、図１において、実施例１の昇温脱離分析装置と、図１５に示した従来の昇温脱離分析装置において、同一の構成については、図１５の各符号から「０」を除いた符号を付し、詳細な説明は省略する。
図１において、本発明の実施例１の試料分析システムＳでは、試料分析装置の一例としての昇温脱離分析装置１の搬入室１２には、搬入室１２内を窒素ガスで充満させる、いわゆる窒素パージするための窒素タンク２０が接続されている。
FIG. 1 is an overall explanatory view of a temperature-programmed desorption analyzer as an example of a sample analyzer of Embodiment 1 of the present invention.
In FIG. 1, in the temperature-programmed desorption analyzer of Example 1 and the conventional temperature-programmed desorption analyzer shown in FIG. 15, “0” is omitted from the reference numerals in FIG. The detailed description is omitted.
In FIG. 1, in the sample analysis system S according to the first embodiment of the present invention, the carry-in chamber 12 of the temperature programmed desorption analyzer 1 as an example of the sample analyzer is filled with nitrogen gas in the carry-in chamber 12. A nitrogen tank 20 for purging with nitrogen is connected.
また、実施例１の試料ステージ３では、図１５に示す構成とは異なり、赤外線が使用されず、クライオスタット（低温恒温装置）が使用されている。なお、このような試料ステージ３は、従来公知の種々のものを使用可能であり、例えば、２０Ｋ程度〜８５０Ｋ程度の温度領域で冷却および昇温が可能なAdvanced Research Systems inc.製のDisplexGM冷凍機式クライオスタットを使用可能である。
また、実施例１の昇温脱離分析装置１では、調製された試料１４は、昇温脱離分析装置１の試料移動部材１５に搬入される際に、試料搬入部材２１に収容された状態で、試料出入口１３を通じて試料移動部材１５に搬入される。
Moreover, in the sample stage 3 of Example 1, unlike the structure shown in FIG. 15, infrared rays are not used, but a cryostat (low temperature constant temperature apparatus) is used. As such a sample stage 3, various conventionally known ones can be used. For example, a Complexplex refrigerator made by Advanced Research Systems Inc. capable of cooling and raising the temperature in a temperature range of about 20K to about 850K. A type cryostat can be used.
Further, in the temperature-programmed desorption analyzer 1 of Example 1, the prepared sample 14 is stored in the sample carry-in member 21 when it is carried into the sample moving member 15 of the temperature-programmed desorption analyzer 1. Then, it is carried into the sample moving member 15 through the sample inlet / outlet 13.
図２は実施例１の試料搬入部材の斜視説明図である。
図３は試料搬入部材に収容された試料を試料ステージに移動させる作業を行う際の説明図である。
図２、図３において、実施例１の試料搬入部材２１は、全体として略直方体状に形成されており、試料ステージ３側の表面である試料搬入側縁２１ａは、円板状の試料ステージ３に対応して、円弧状に凹んだ形状に形成されている。また、前記試料搬入部材２１の上端部には、凹部状の冷媒液収容部２１ｂが形成されている。図２、図３に示すように、前記冷媒液収容部２１ｂは、試料ステージ３に試料搬入側縁２１ａが接触した状態で、試料ステージ３側に行くに連れて、深さが浅くなるように試料移動用傾斜面２１ｃが形成されている。
なお、実施例１の試料保持部材２１は、凹部状の冷媒液収容部２１ｂの大きさに比べて、全体が十分大きな形状のＳＵＳ（Stainless Used Steel）材料で形成されており、全体の熱容量が大きくなっている。
また、実施例１では、前記試料保持部材２１が試料移動部材１５に載せられた状態で、試料移動部材１５の上面の高さが試料ステージ３の上面の高さに一致するように、試料移動部材１５の位置、高さが設定されている。
FIG. 2 is a perspective explanatory view of the sample carry-in member of the first embodiment.
FIG. 3 is an explanatory diagram when the operation of moving the sample accommodated in the sample carrying-in member to the sample stage is performed.
2 and 3, the sample carry-in member 21 of Example 1 is formed in a substantially rectangular parallelepiped shape as a whole, and the sample carry-in side edge 21a, which is the surface on the sample stage 3 side, is a disk-like sample stage 3. Is formed in a shape recessed in an arc shape. Further, a concave-shaped refrigerant liquid storage portion 21 b is formed at the upper end portion of the sample carry-in member 21. As shown in FIGS. 2 and 3, the refrigerant liquid storage portion 21 b is formed such that the depth becomes shallower toward the sample stage 3 side in a state where the sample carry-in side edge 21 a is in contact with the sample stage 3. A sample moving inclined surface 21c is formed.
In addition, the sample holding member 21 of Example 1 is formed of a SUS (Stainless Used Steel) material having a sufficiently large shape as compared with the size of the concave-shaped refrigerant liquid storage portion 21b, and has an overall heat capacity. It is getting bigger.
In the first embodiment, the sample movement is performed so that the height of the upper surface of the sample moving member 15 coincides with the height of the upper surface of the sample stage 3 with the sample holding member 21 placed on the sample moving member 15. The position and height of the member 15 are set.
（実施例１の分析方法の説明）
図４は実施例１の分析方法の説明図であり、図４Ａは試料調製工程の説明図、図４Ｂは試料冷却収容工程の説明図である。
図５は実施例１の分析方法の続きの説明図であり、図５Ａは試料搬入工程の説明図、図５Ｂは試料移動工程の説明図である。
前記実施例１の試料分析システムＳの昇温脱離分析装置１では、金属や非鉄金属の水素脆化の分析、水素吸蔵材料に含まれる水素の分析等を行う場合に、図４Ａに示すように、試料調製工程において、分析対象の試料１４に水素を注入するための電解チャージが行われる。すなわち、電源２６が接続された試料１４を、電解用溶液の一例としての硫酸（Ｈ２ＳＯ４）が収容された電解槽２７内に沈めた状態で電源２６を作動させて、試料１４中に水素を注入する電解チャージを行う。
(Description of Analysis Method of Example 1)
FIG. 4 is an explanatory diagram of an analysis method of Example 1, FIG. 4A is an explanatory diagram of a sample preparation process, and FIG. 4B is an explanatory diagram of a sample cooling and accommodating process.
FIG. 5 is a continuation explanatory diagram of the analysis method of Example 1, FIG. 5A is an explanatory diagram of a sample carrying-in process, and FIG. 5B is an explanatory diagram of a sample moving process.
In the temperature-programmed desorption analyzer 1 of the sample analysis system S of the first embodiment, as shown in FIG. 4A, when performing analysis of hydrogen embrittlement of metals and non-ferrous metals, analysis of hydrogen contained in hydrogen storage materials, and the like. In addition, in the sample preparation process, electrolytic charging for injecting hydrogen into the sample 14 to be analyzed is performed. That is, the power source 26 is operated in a state where the sample 14 connected to the power source 26 is submerged in an electrolytic cell 27 containing sulfuric acid (H 2 SO 4 ) as an example of an electrolysis solution. An electrolytic charge for injecting hydrogen is performed.
次に、図４Ｂにおいて、実施例１の試料冷却収容工程では、まず、試料搬入部材２１を、液体状の冷媒の一例である液体窒素が収容された冷媒収容槽２８内に、試料搬入部材２１を沈めておいて、冷媒液収容部２１ｂに液体窒素を入れると共に、熱容量の大きな試料搬入部材２１を冷却する。そして、電解チャージされて調製された試料１４を、ピンセット等で、電解槽２７から速やかに冷媒収容槽２８内の試料搬入部材２１の冷媒液収容部２１ｂに移動させる。
このとき、昇温脱離分析装置１では、ゲートバルブ１１が閉じられた状態で、搬入室１２内に窒素ガスタンク２０の窒素ガスを充満させておくことで、予め、窒素パージしておく。
Next, in FIG. 4B, in the sample cooling and housing step of Example 1, first, the sample carrying member 21 is placed in the refrigerant containing tank 28 in which liquid nitrogen which is an example of a liquid refrigerant is housed. The sample carrying member 21 having a large heat capacity is cooled while liquid nitrogen is introduced into the refrigerant liquid storage portion 21b. Then, the sample 14 prepared by electrolytic charging is quickly moved from the electrolytic cell 27 to the refrigerant liquid storage part 21b of the sample carrying member 21 in the refrigerant storage tank 28 with tweezers or the like.
At this time, in the temperature-programmed desorption analyzer 1, a nitrogen purge is performed in advance by filling the nitrogen gas in the nitrogen gas tank 20 into the carry-in chamber 12 with the gate valve 11 closed.
次に、図５Ａにおいて、試料搬入工程では、冷媒収容槽２８から試料搬入部材２１を取り出し、試料出入口１３を通じて窒素パージされた搬入室１２に搬入し、試料移動部材（ロードロックアーム）１５に載せる。このとき、冷媒収容槽２８から取り出された試料搬入部材２１の冷媒液収容部２１ｂには、液体窒素が収容されると共に、液体窒素中に試料１４が沈められた状態で移動される。
次に、搬入室排気工程において、搬入室１２の真空ポンプ１６を作動させて、窒素パージされた搬入室１２内を真空状態に排気する。この排気に伴い、搬入室１２内の窒素と、冷媒液収容部２１ｂの液体窒素が気化して排気される。
Next, in FIG. 5A, in the sample loading process, the sample loading member 21 is taken out from the refrigerant storage tank 28, loaded into the loading chamber 12 purged with nitrogen through the sample inlet / outlet 13, and placed on the sample moving member (load lock arm) 15. . At this time, liquid nitrogen is accommodated in the refrigerant liquid accommodating portion 21b of the sample carrying-in member 21 taken out from the refrigerant accommodating tank 28, and the sample 14 is moved while being submerged in the liquid nitrogen.
Next, in the carry-in chamber exhaust process, the vacuum pump 16 in the carry-in chamber 12 is operated, and the inside of the carry-in chamber 12 purged with nitrogen is evacuated to a vacuum state. With this exhaust, the nitrogen in the carry-in chamber 12 and the liquid nitrogen in the refrigerant liquid storage portion 21b are vaporized and exhausted.
前記搬入室１２が、真空排気されて、分析真空室２の真空度に到達すると、図５Ｂに示す試料移動工程において、ゲートバルブ１１が開放され、試料移動部材１５を搬入室１２から分析真空室２に移動させる。すなわち、前記試料移動部材１５を、試料搬入部材２１と共に試料の搬入、搬出が行われる図５Ｂに示す試料交換位置と、試料搬入部材２１が試料ステージ３に接触した図３に示す試料載せ替え位置と、の間で移動させる。前記試料移動部材１５を、図３に示す試料載せ替え位置に移動させると、マニュピレータ２９で試料１４が、掻き出されるように試料ステージ３に移動される。このとき、試料１４は、試料移動用傾斜面２１ｃに沿ってガイドされて試料ステージ３に移動する。なお、実施例１では、冷却された試料１４が温まらないように、前記試料ステージ３は、試料１４が移動される前に、２０［Ｋ］程度に冷却されている。 When the carry-in chamber 12 is evacuated and reaches the vacuum degree of the analysis vacuum chamber 2, the gate valve 11 is opened in the sample moving step shown in FIG. 5B, and the sample moving member 15 is moved from the carry-in chamber 12 to the analysis vacuum chamber. Move to 2. That is, the sample moving member 15 is moved into and out of the sample together with the sample carry-in member 21 and the sample exchange position shown in FIG. 5B and the sample transfer position shown in FIG. 3 where the sample carry-in member 21 is in contact with the sample stage 3. And move between. When the sample moving member 15 is moved to the sample replacement position shown in FIG. 3, the sample 14 is moved to the sample stage 3 by the manipulator 29 so as to be scraped out. At this time, the sample 14 is guided along the sample moving inclined surface 21 c and moves to the sample stage 3. In Example 1, the sample stage 3 is cooled to about 20 [K] before the sample 14 is moved so that the cooled sample 14 is not warmed.
試料１４が試料ステージ３に載せられると、図１に示すように、試料移動部材１５が試料交換位置まで退避する。そして、試料１４が昇温され、試料１４から脱離したガスが、質量分析計６の一例としてのＱ−ＭＡＳにより測定され、試料１４に含まれた極微量の成分の分析が行われる。 When the sample 14 is placed on the sample stage 3, as shown in FIG. 1, the sample moving member 15 is retracted to the sample replacement position. Then, the temperature of the sample 14 is raised, and the gas desorbed from the sample 14 is measured by Q-MAS as an example of the mass spectrometer 6, and the trace amount component contained in the sample 14 is analyzed.
（実施例１の作用）
したがって、前記構成を備えた実施例１の試料分析システムＳでは、調製された試料１４は、大気にほとんど曝されることなく、液体窒素中の試料搬入部材２１に収容されて冷却される。このため、大気に曝された状態で冷却する場合に比べて、冷却時に大気中のガスが付着することが低減されており、分析に悪影響を及ぼすことが低減されている。
また、前記試料搬入部材２１に保持された試料１４は、液体状の冷媒に沈められた状態で保持されており、大気に曝されることなく搬入室１２に収容される。このため、試料１４を昇温脱離分析装置１に移動させる途中や、真空排気前の搬入室１２に搬入後も、試料１４に大気中のガス成分が付着しにくく、付着したガスにより分析に悪影響を及ぼすことが低減されている。
特に、実施例１では、搬入室１２が不活性ガスであり、液体窒素と同成分の窒素でパージされており、大気中の水分が付着することが低減されている。
(Operation of Example 1)
Therefore, in the sample analysis system S of Example 1 having the above-described configuration, the prepared sample 14 is accommodated in the sample carry-in member 21 in liquid nitrogen and cooled while being hardly exposed to the atmosphere. For this reason, compared with the case where it cools in the state exposed to air | atmosphere, the adhesion of the gas in air | atmosphere at the time of cooling is reduced, and it has reduced the bad influence on an analysis.
The sample 14 held by the sample carry-in member 21 is held in a state where it is submerged in a liquid refrigerant and is accommodated in the carry-in chamber 12 without being exposed to the atmosphere. For this reason, gas components in the atmosphere are less likely to adhere to the sample 14 during the movement of the sample 14 to the temperature-programmed desorption analyzer 1 or after loading into the loading chamber 12 before evacuation. The adverse effects have been reduced.
In particular, in Example 1, the carry-in chamber 12 is an inert gas and is purged with nitrogen of the same component as the liquid nitrogen, so that the adhesion of moisture in the atmosphere is reduced.
さらに、実施例１では、試料１４が液体窒素に沈められて、冷却された状態のまま排気が開始され、真空状態に排気される過程で液体窒素が気化、蒸発している。したがって、真空排気後に試料を冷却する場合に比べて、比較的高温で成分が脱離しやすい冷却前の試料から真空排気時に成分が脱離することが低減される。
また、実施例１では、試料搬入部材２１の熱容量が大きな構成となっているため、冷媒収容槽２８で冷却された試料搬入部材２１の温度が上昇しにくく、試料１４が冷却された状態で保持されやすくなっている。したがって、試料１４を試料ステージ３に移動させるまでの間に、試料搬入部材２１が昇温して試料１４の温度が上昇して成分が脱離することが低減されている。
さらに、実施例１では、試料１４が移動される試料ステージ３も２０Ｋ程度に冷却されており、冷却された状態で搬送される試料１４が試料ステージ３に移動した瞬間に温まってしまうことが防止されている。
Further, in Example 1, the sample 14 is submerged in liquid nitrogen, and evacuation is started while being cooled, and liquid nitrogen is vaporized and evaporated in the process of being evacuated to a vacuum state. Therefore, compared with the case where the sample is cooled after evacuation, the component is less desorbed at the time of vacuum evacuation from the sample before cooling, where the component is easily desorbed at a relatively high temperature.
Moreover, in Example 1, since the heat capacity of the sample carrying-in member 21 is large, the temperature of the sample carrying-in member 21 cooled by the refrigerant storage tank 28 is hard to rise, and the sample 14 is held in a cooled state. It is easy to be done. Therefore, before the sample 14 is moved to the sample stage 3, the temperature of the sample carry-in member 21 is increased, the temperature of the sample 14 is increased, and components are desorbed.
Further, in the first embodiment, the sample stage 3 to which the sample 14 is moved is also cooled to about 20K, and the sample 14 conveyed in the cooled state is prevented from being heated at the moment when it is moved to the sample stage 3. Has been.
さらに、実施例１では、試料搬入部材２１の試料搬入側縁２１ａが試料ステージ３の外形に対応して凹んだ形状に形成されると共に、試料移動用傾斜面２１ｃで試料ステージ３側に向かって冷媒液収容部２１ｂの深さが浅くなるように形成され、試料搬入部材２１の上面が試料ステージ３の上面と同じ高さに設定されている。したがって、前記試料搬入部材２１から試料ステージ３に試料を載せ替える際に、試料搬入部材２１の上面と試料ステージ３の上面とが、隙間がほとんどない状態で面一となり、試料１４を容易に移動させることが可能になっている。したがって、試料１４の破損等が低減されており、試料１４の破損による分析への悪影響が低減されている。 Furthermore, in Example 1, the sample carry-in side edge 21a of the sample carry-in member 21 is formed in a concave shape corresponding to the outer shape of the sample stage 3, and the sample moving inclined surface 21c faces the sample stage 3 side. The refrigerant liquid storage portion 21 b is formed to have a shallow depth, and the upper surface of the sample carry-in member 21 is set to the same height as the upper surface of the sample stage 3. Therefore, when the sample is transferred from the sample loading member 21 to the sample stage 3, the upper surface of the sample loading member 21 and the upper surface of the sample stage 3 are flush with each other so that the sample 14 can be easily moved. It is possible to make it. Therefore, the breakage of the sample 14 and the like are reduced, and the adverse effect on the analysis due to the breakage of the sample 14 is reduced.
したがって、実施例１の試料分析システムＳでは、調製された試料１４が試料ステージ３にセットされて分析が行われるまでの間に、試料１４に大気中のガス成分が付着したり、試料１４から成分が脱離することが低減されている。この結果、試料１４が昇温されて脱離ガスを測定、分析する際に、付着したガス成分により分析結果に悪影響が及ぼされたり、試料１４に含まれる極微量の成分が脱離して測定できないといったことが低減され、高感度、高精度の分析を行うことができる。 Therefore, in the sample analysis system S of the first embodiment, the gas component in the atmosphere adheres to the sample 14 or the sample 14 from the sample 14 before the prepared sample 14 is set on the sample stage 3 and analysis is performed. Desorption of components is reduced. As a result, when the sample 14 is heated to measure and analyze the desorbed gas, the analysis result is adversely affected by the attached gas component, or a trace amount component contained in the sample 14 is desorbed and cannot be measured. This makes it possible to perform analysis with high sensitivity and high accuracy.
図６は本発明の実施例２の昇温脱離分析装置の全体説明図であり、実施例１の図１に対応する図である。
次に本発明の実施例２の説明を行うが、この実施例２の説明において、前記実施例１の構成要素に対応する構成要素には同一の符号を付して、その詳細な説明を省略する。この実施例２は、下記の点で前記実施例１と相違しているが、他の点では前記実施例１と同様に構成されている。
FIG. 6 is an overall explanatory view of the temperature-programmed desorption analyzer of Example 2 of the present invention and corresponds to FIG. 1 of Example 1.
Next, a second embodiment of the present invention will be described. In the description of the second embodiment, components corresponding to those of the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. To do. The second embodiment is different from the first embodiment in the following points, but is configured in the same manner as the first embodiment in other points.
図６において、実施例２の昇温脱離分析装置１′では、実施例１と異なり、分析真空室２′が、第１の分析真空室２ａと、第１の分析真空室２ａに配管３１を介して接続された第２の分析真空室２ｂとを有する。そして、前記第１の分析真空室２ａに試料ステージ３が配置され、第２の分析真空室２ｂに質量分析計６が配置されている。なお、前記第２の分析真空室２ｂは、真空ポンプ３３により真空状態に排気されている。
図６において、実施例１の配管３１は、Ｕ字形状に湾曲した形状に構成されており、配管３１の外部には、配管３１を冷却する冷却装置３４が配置されている。したがって、前記配管３１は、通過するガスの一部の成分を吸着して除去するトラップ管としての機能を有する。前記トラップ管３１および冷却装置３４により、実施例２のガス除去装置３１＋３４が構成されている。
In FIG. 6, in the temperature-programmed desorption analyzer 1 ′ of the second embodiment, unlike the first embodiment, the analysis vacuum chamber 2 ′ includes a first analysis vacuum chamber 2 a and a pipe 31 to the first analysis vacuum chamber 2 a. And a second analysis vacuum chamber 2b connected to each other. A sample stage 3 is disposed in the first analysis vacuum chamber 2a, and a mass spectrometer 6 is disposed in the second analysis vacuum chamber 2b. Note that the second analysis vacuum chamber 2 b is evacuated to a vacuum state by a vacuum pump 33.
In FIG. 6, the pipe 31 according to the first embodiment is configured in a U-shaped curve, and a cooling device 34 that cools the pipe 31 is disposed outside the pipe 31. Accordingly, the pipe 31 has a function as a trap pipe that adsorbs and removes a part of the components of the passing gas. The trap tube 31 and the cooling device 34 constitute a gas removal device 31 + 34 of the second embodiment.
（実施例２の作用）
前記実施例１の昇温脱離分析装置１では、試料１４の近傍に質量分析計６が配置されており、感度が高くなっている優位性がある。しかし、例えば、試料１４に吸蔵された水素（Ｈ２）を測定したい場合に、試料１４の電解チャージ時に付着した水分（Ｈ２Ｏ）が液体窒素冷却時に保持されたまま試料ステージ３にセットされることがある。この状態では、極微量の水素に対して、水分が比較的大量になってしまうので、この水分が昇温時に脱離すると、測定結果に悪影響を及ぼすことが考えられる。
これに対して、前記構成を備えた実施例２の昇温脱離分析装置１′では、脱離したガス成分が、Ｕ字形状のトラップ管３１を通過する際に、配管３１の内面に吸着されて除去されやすい水分が除去され、水分に比べて配管３１に吸着されにくい水素成分は、トラップ管３１を通過し、第２の分析真空室２ｂに流入しやすい。したがって、実施例２の昇温脱離分析装置１′は、第２の分析真空室２ｂに配置された質量分析計６により、水分の影響をほとんど受けることなく極微量の水素成分を高感度、高精度に測定することができる。すなわち、実施例２の昇温脱離分析装置１′では、ガス除去装置３１により、不要なガス成分である水分を除去することができ、測定したいガス成分を高感度で測定することができる。
(Operation of Example 2)
In the temperature-programmed desorption analyzer 1 of Example 1, the mass spectrometer 6 is disposed in the vicinity of the sample 14, and there is an advantage that the sensitivity is high. However, for example, when hydrogen (H 2 ) occluded in the sample 14 is to be measured, the moisture (H 2 O) adhering during the electrolytic charging of the sample 14 is set on the sample stage 3 while being held during liquid nitrogen cooling. Sometimes. In this state, since a relatively large amount of water is generated with respect to a very small amount of hydrogen, if this water is desorbed when the temperature is raised, it is considered that the measurement result may be adversely affected.
On the other hand, in the temperature-programmed desorption analyzer 1 ′ having the above-described configuration, the desorbed gas component is adsorbed on the inner surface of the pipe 31 when passing through the U-shaped trap pipe 31. The water component that is easily removed is removed, and the hydrogen component that is less likely to be adsorbed to the pipe 31 than the water easily passes through the trap pipe 31 and flows into the second analysis vacuum chamber 2b. Therefore, the temperature-programmed desorption analyzer 1 ′ of Example 2 is highly sensitive to a very small amount of hydrogen components with almost no influence of moisture by the mass spectrometer 6 disposed in the second analysis vacuum chamber 2 b. It can be measured with high accuracy. That is, in the temperature-programmed desorption analyzer 1 ′ of Example 2, the gas removal device 31 can remove moisture, which is an unnecessary gas component, and can measure the gas component to be measured with high sensitivity.
図７は本発明の実施例３の昇温脱離分析装置の全体説明図であり、実施例２の図６に対応する図である。
次に本発明の実施例３の説明を行うが、この実施例３の説明において、前記実施例１、２の構成要素に対応する構成要素には同一の符号を付して、その詳細な説明を省略する。この実施例３は、下記の点で前記実施例１、２と相違しているが、他の点では前記実施例１、２と同様に構成されている。
FIG. 7 is an overall explanatory view of the temperature programmed desorption analyzer of Example 3 of the present invention, and corresponds to FIG. 6 of Example 2.
Next, a third embodiment of the present invention will be described. In the description of the third embodiment, the same reference numerals are given to the components corresponding to the components of the first and second embodiments, and a detailed description thereof will be given. Is omitted. The third embodiment is different from the first and second embodiments in the following points, but is configured in the same manner as the first and second embodiments in other points.
図７において、実施例３の昇温脱離分析装置１″では、第１の分析真空室２ａには、第１の排気路Ｐ１を介して、第１の真空排気装置の一例としての真空ポンプ４が接続されており、第１の排気路Ｐ１には、第１のバルブＶ１が設けられている。なお、実施例３では、前記真空ポンプ４、３３として、ターボ分子ポンプが使用されており、各分析真空室２ａ，２ｂが１０−８［Ｐａ］程度まで真空排気される。
実施例３では、第１の分析真空室２ａに試料１４を搬入する際に、第１のバルブＶ１が開の状態となって、真空ポンプ４により第１の分析真空室２ａが排気され、且つ、真空ポンプ３３により第２の分析真空室２ｂが排気される。そして、試料Ｓの質量分析が行われる場合には、第１のバルブＶ１が閉の状態となって、第１の真空分析室２ａが、トラップ管３１以外の部分が密閉された状態となる。そして、第２の真空ポンプ３３で引き続き排気を継続した状態で、試料ステージ３が昇温されて、試料１４の質量分析が行われる。
In FIG. 7, in the temperature-programmed desorption analyzer 1 ″ of the third embodiment, a vacuum pump as an example of a first vacuum exhaust device is provided in the first analysis vacuum chamber 2a via the first exhaust passage P1. 4 is connected to the first exhaust passage P1, and a first valve V1 is provided in the first exhaust path P1 In the third embodiment, a turbo molecular pump is used as the vacuum pumps 4 and 33. Each of the analysis vacuum chambers 2a and 2b is evacuated to about 10 −8 [Pa].
In Example 3, when the sample 14 is carried into the first analysis vacuum chamber 2a, the first valve V1 is opened, and the first analysis vacuum chamber 2a is evacuated by the vacuum pump 4, and The second analysis vacuum chamber 2b is evacuated by the vacuum pump 33. When mass analysis of the sample S is performed, the first valve V1 is closed, and the first vacuum analysis chamber 2a is in a state where the portions other than the trap tube 31 are sealed. Then, with the second vacuum pump 33 continuing to be evacuated, the sample stage 3 is heated and mass analysis of the sample 14 is performed.
また、実施例３のトラップ管３１は、第１の分析真空室２ａから延びる上流管３１ａと、第２の分析真空室２ｂから延びる下流管３１ｂと、上流管３１ａの下流端と下流管３１ｂとの間を接続し且つ上流管３１ａおよび下流管３１ｂよりも呼び径が大きなＵ字管３１ｃと、を有する。なお、実施例３では、トラップ管３１の上流管３１ａ、下流管３１ｂ、Ｕ字管３１ｃは、市販の３／８ＳＵＳ３１６管（呼び径が３／８インチのステンレス３１６製の管）を使用している。 The trap tube 31 of the third embodiment includes an upstream tube 31a extending from the first analysis vacuum chamber 2a, a downstream tube 31b extending from the second analysis vacuum chamber 2b, a downstream end of the upstream tube 31a, and a downstream tube 31b. And a U-shaped pipe 31c having a larger nominal diameter than the upstream pipe 31a and the downstream pipe 31b. In Example 3, the upstream pipe 31a, the downstream pipe 31b, and the U-shaped pipe 31c of the trap pipe 31 are commercially available 3/8 SUS316 pipes (made of stainless steel 316 having a nominal diameter of 3/8 inch). Yes.
（コンダクタンスの説明）
第１の真空分析室２ａの圧力をｐ１、第２の真空分析室２ｂの圧力をｐ２とすると、トラップ管３１を流れる気体の流量Ｑ［Ｐａ・ｍ３／ｓ］は、差圧Δｐ［Ｐａ］＝ｐ１−ｐ２により、以下の式（１）で表される。
Ｑ＝Ｃ・Δｐ …式（１）
このときの比例係数Ｃがコンダクタンスである。
(Description of conductance)
Assuming that the pressure in the first vacuum analysis chamber 2a is p1 and the pressure in the second vacuum analysis chamber 2b is p2, the flow rate Q [Pa · m 3 / s] of the gas flowing through the trap tube 31 is the differential pressure Δp [Pa ] = P1-p2 is represented by the following formula (1).
Q = C · Δp (1)
The proportionality coefficient C at this time is conductance.
実施例１〜３のような昇温脱離分析装置１〜１″のように、高真空度（分子流領域）では、気体の平均自由工程が長さＬのパイプの直径Ｄ（断面積Ａ）よりも十分に長く、ｖを気体分子の平均速度とした場合に、コンダクタンスＣは、以下の式（２）で表される。
Ｃ＝（１／４）・ｖ・Ａ・（４Ｄ／３Ｌ）
＝（π／１２）・ｖ（Ｄ３／Ｌ） ［ｍ３／ｓ］ …式（２）
ここで、気体分子の平均速度ｖは、ボルツマン定数をｋ、温度をＴ、気体分子１個の質量をｍ［ｋｇ］、とした場合に、以下の式（３）で表される。
ｖ＝（８ｋＴ／πｍ）１／２ …式（３）
したがって、分子量Ｍの気体については、（分子量Ｍ［ｇ］）＝（気体分子１個の質量ｍ［ｋｇ］）×（アボガドロ数ＮＡ）であるため、式（３）は、以下の式（３′）となる。
ｖ＝｛（８×１．３８×１０−２３×Ｔ）／（３．１４×Ｍ×１０−３／６．０２×１０２３）｝１／２
＝１．４６×１０２×（Ｔ／Ｍ）１／２ …式（３′）
As in the temperature-programmed desorption analyzers 1 to 1 ″ as in Examples 1 to 3, in a high degree of vacuum (molecular flow region), the mean free path of gas is a diameter D (cross-sectional area A) of a pipe having a length L. ), The conductance C is expressed by the following formula (2) where v is the average velocity of gas molecules.
C = (1/4) · v · A · (4D / 3L)
= (Π / 12) · v (D 3 / L) [m 3 / s] Formula (2)
Here, the average velocity v of gas molecules is expressed by the following formula (3), where Boltzmann constant is k, temperature is T, and mass of one gas molecule is m [kg].
v = (8 kT / πm) 1/2 Formula (3)
Therefore, for a gas having a molecular weight M, (molecular weight M [g]) = (mass of one gas molecule m [kg]) × (Avogadro number N A ). Therefore, the equation (3) is expressed by the following equation ( 3 ').
v = {(8 × 1.38 × 10 −23 × T) / (3.14 × M × 10 −3 /6.02×10 23 )} 1/2
= 1.46 × 10 2 × (T / M) 1/2 Formula (3 ′)
したがって、例えば、２０℃の大気（Ｍ＝２９）に対しては、ｖ＝４６４［ｍ／ｓ］となり、式（２）から、Ｃ＝１２１（Ｄ３／Ｌ）［ｍ３／ｓ］となる。Ｕ字形状に湾曲した配管のコンダクタンスは、直管に較べてコンダクタンスが小さくなる。エルボーや直角管などの曲がり配管の場合には、便宜的にまっすぐな配管の長さを１．３倍長い配管として計算して大きな誤差は生じないことが知られている。ここではＵ字管３１ｃに対して同様な取り扱いを行うことにする。したがって、Ｄ＝０．００９５［ｍ］、Ｌ＝０．７５［ｍ］の３／８ＳＵＳ３１６の配管（配管肉厚０．８９ｍｍ）の大気に対するコンダクタンスＣは、Ｃ＝１２１｛（０．００９５−０．０００８９×２）３／１．３×０．７５｝＝０．００００５７１となる。
また、室温（２７℃＝３００Ｋ）の水素（Ｍ＝２）に対しては、ｖ＝１７８８［ｍ／ｓ］となり、Ｃ＝４６８（Ｄ３／Ｌ）［ｍ３／ｓ］となる。したがって、Ｄ＝０．００９５［ｍ］、Ｌ＝０．７５［ｍ］の３／８ＳＵＳＵ３１６のＵ字形状配管（配管肉厚０．８９ｍｍ）の水素に対するコンダクタンスＣは、同様に、Ｃ＝４６８×｛（０．００９５−０．０００８９×２）３／１．３×０．７５｝＝０．０００２２１［ｍ３／ｓ］となる。
Therefore, for example, for the atmosphere at 20 ° C. (M = 29), v = 464 [m / s], and from equation (2), C = 121 (D 3 / L) [m 3 / s] Become. The conductance of a pipe curved in a U shape is smaller than that of a straight pipe. In the case of bent pipes such as elbows and right-angle pipes, it is known that the length of a straight pipe is calculated as a pipe that is 1.3 times longer for the sake of convenience and no large error occurs. Here, the same handling is performed for the U-shaped tube 31c. Therefore, the conductance C with respect to the atmosphere of the 3/8 SUS316 pipe (pipe thickness 0.89 mm) with D = 0.0095 [m] and L = 0.75 [m] is C = 121 {(0.0095-0 .00089 × 2) 3 /1.3×0.75}=0.0000571.
For hydrogen (M = 2) at room temperature (27 ° C. = 300 K), v = 1788 [m / s] and C = 468 (D 3 / L) [m 3 / s]. Accordingly, the conductance C with respect to hydrogen of the U-shaped pipe (pipe thickness 0.89 mm) of 3/8 SUSU 316 with D = 0.0095 [m] and L = 0.75 [m] is similarly C = 468 × {(0.0095−0.00089 × 2) 3 /1.3×0.75}=0.000221 [m 3 / s].
（実施例３の作用）
前記構成を備えた実施例３の試料分析システムＳでは、試料１４に水分や大気の成分等が付着した状態で、試料ステージ３にセットされても、実施例２の試料分析システムと同様に、実施例３の昇温脱離分析装置１″では、トラップ管３１において、内面で吸着され、第２の分析真空室２ｂで水素を高感度、高精度で測定することができる。
特に、大気のガス（窒素や酸素）に比べて、水素は、トラップ管３１におけるコンダクタンスが大きく、流入量が大きくなる。したがって、試料１４に吸蔵された水素を効率的に、第２の分析試料室２ｂに流入させることができる。
(Operation of Example 3)
In the sample analysis system S of the third embodiment having the above-described configuration, even if the sample 14 is set on the sample stage 3 with moisture or atmospheric components attached thereto, the sample analysis system S of the second embodiment, In the temperature-programmed desorption analyzer 1 ″ of Example 3, the trap tube 31 is adsorbed on the inner surface, and hydrogen can be measured with high sensitivity and high accuracy in the second analysis vacuum chamber 2b.
In particular, compared to atmospheric gases (nitrogen and oxygen), hydrogen has a larger conductance in the trap tube 31 and an inflow amount. Therefore, the hydrogen occluded in the sample 14 can efficiently flow into the second analysis sample chamber 2b.
また、実施例３では、第１のバルブＶ１を閉めて第１の分析真空室２ａをトラップ管３１を除いて密閉した状態で、真空ポンプ３３を作動させており、第１の分析真空室２ａの試料１４から脱離したガスが、効率的にトラップ管３１に導かれ、第２の分析真空室２ｂに流入する。したがって、第１のバルブＶ１を開放していたり、真空ポンプ３３を作動させない場合に比べて、脱離したガスを、第２の分析真空室２ｂの質量分析計６で効率的に測定することができる。 In the third embodiment, the vacuum pump 33 is operated in a state where the first valve V1 is closed and the first analysis vacuum chamber 2a is sealed except for the trap tube 31, and the first analysis vacuum chamber 2a is operated. The gas desorbed from the sample 14 is efficiently guided to the trap tube 31 and flows into the second analysis vacuum chamber 2b. Therefore, the desorbed gas can be measured more efficiently by the mass spectrometer 6 in the second analysis vacuum chamber 2b than when the first valve V1 is opened or the vacuum pump 33 is not operated. it can.
（実験例）
次に、コンダクタンスＣや昇温速度と、試料１４からの脱離との関係について、シミュレーション実験を行った。
実験では、実施例３の昇温脱離分析装置１″のモデルを使用し、以下の計算式を使用した。すなわち、第１の分析真空室２ａの体積をＶ１、圧力をｐ１とし、第２の分析真空室２ｂの体積をＶ２、圧力をｐ２とし、真空ポンプ３３の排気速度をＳ、トラップ管３１のコンダクタンスをＣ、試料１４から脱離した気体の量をＱとした場合に、以下の式（５）、（６）が成立する。
Ｖ１・（ｄｐ１／ｄｔ）＝−Ｃ（ｐ１−ｐ２）＋Ｑ …式（５）
Ｖ２・（ｄｐ２／ｄｔ）＝−Ｓ・ｐ２＋Ｃ（ｐ１−ｐ２） …式（６）
(Experimental example)
Next, a simulation experiment was performed on the relationship between the conductance C and the temperature increase rate and the desorption from the sample 14.
In the experiment, the model of the temperature programmed desorption analyzer 1 ″ of Example 3 was used, and the following calculation formula was used. That is, the volume of the first analysis vacuum chamber 2a was V1, the pressure was p1, and the second When the volume of the analysis vacuum chamber 2b is V2, the pressure is p2, the exhaust speed of the vacuum pump 33 is S, the conductance of the trap tube 31 is C, and the amount of gas desorbed from the sample 14 is Q, the following Expressions (5) and (6) are established.
V1 · (dp1 / dt) = − C (p1−p2) + Q (5)
V2 · (dp2 / dt) = − S · p2 + C (p1−p2) Equation (6)
ここで、第２の分析真空室２ｂには真空ポンプ３３が接続されており、排気速度Ｓが大きいため、ｐ２＜＜ｐ１として、ｐ２を除外すると、式（５）は、以下の式（５′）となる。
Ｖ１・（ｄｐ１／ｄｔ）＝−Ｃ・ｐ１）＋Ｑ …式（５′）
また、式（６）において、排気速度Ｓが大きいため、圧力ｐ２の時間変化が非常に小さくなり、（ｄｐ２／ｄｔ）＜＜（Ｓ／Ｖ２）と近似でき、式（６）の左辺を０と近似できる。また、式（５）の場合と同様に、排気速度Ｓが大きいため、Ｃ＜＜Ｓであるため、式（６）は式（６′）に近似できる。
ｐ２＝Ｃ・ｐ１／Ｓ …式（６′）
Here, since the vacuum pump 33 is connected to the second analysis vacuum chamber 2b and the exhaust speed S is high, when p2 is excluded when p2 << p1, the equation (5) is expressed by the following equation (5) ′).
V1 · (dp1 / dt) = − C · p1) + Q (5 ′)
Further, in the equation (6), since the exhaust speed S is large, the time change of the pressure p2 becomes very small, and can be approximated as (dp2 / dt) << (S / V2). Can be approximated. Similarly to the case of Expression (5), since the exhaust velocity S is large and C << S, Expression (6) can be approximated to Expression (6 ′).
p2 = C · p1 / S Equation (6 ′)
以下の実験例では、前記式（５′）、（６′）を使用して、試料１４からのガスの脱離と、コンダクタンスＣ等との関係について、実験を行った。
なお、実験例では、第１の分析真空室２ａの体積Ｖ１を０．００２５［ｍ３］、第２の分析真空室２ｂの体積Ｖ２を０．００７［ｍ３］、真空ポンプ３３の排気速度Ｓを０．２１０［ｍ３／ｓ］とした。
In the following experimental examples, experiments were conducted on the relationship between the desorption of gas from the sample 14, the conductance C, and the like using the equations (5 ') and (6').
In the experimental example, the volume V1 of the first analysis vacuum chamber 2a is 0.0025 [m 3 ], the volume V2 of the second analysis vacuum chamber 2b is 0.007 [m 3 ], and the exhaust speed of the vacuum pump 33 is S was set to 0.210 [m 3 / s].
（実験例１）
実験例１では、脱離する原子の結合エネルギーＥａをＥａ＝５８．６［ｋＪ／ｍｏｌ］＝０．６１［ｅＶ］とし、脱離する気体の数ＮをＮ＝１×１０１５［個］とした。また、試料ステージ３の昇温速度βをβ＝３０［Ｋ／ｍｉｎ］とし、コンダクタンスＣをＣ＝０．０００２［ｍ３／ｓ］とした。なお、気体の温度依存性はないものと仮定した。
（実験例１′）
比較例１では、実施例１のＴＤＳ、すなわち、トラップ管３１や第２の分析真空室２ｂを有しない構成とした以外は、実験例１と同様とした。
実験結果を図８に示す。
(Experimental example 1)
In Experimental Example 1, the bond energy Ea of atoms to be desorbed is Ea = 58.6 [kJ / mol] = 0.61 [eV], and the number N of desorbed gases is N = 1 × 10 15 [pieces]. It was. Further, the temperature increase rate β of the sample stage 3 was set to β = 30 [K / min], and the conductance C was set to C = 0.0002 [m 3 / s]. It was assumed that there was no temperature dependence of the gas.
(Experimental example 1 ')
Comparative Example 1 was the same as Experimental Example 1 except that the TDS of Example 1, that is, the configuration without the trap tube 31 and the second analysis vacuum chamber 2b was used.
The experimental results are shown in FIG.
図８は実験例１および実験例１′の実験結果の説明図であり、図８Ａは横軸に温度を取り縦軸に脱離速度を取った脱離速度の実験結果のグラフ、図８Ｂは横軸に温度を取り縦軸に圧力を取った実験例１′の実験結果のグラフ、図８Ｃは横軸に温度を取り縦軸に圧力を取った実験例１の実験結果のグラフ、図８Ｄは図８Ｃの要部拡大図である。
図８Ａにおいて、試料１４を昇温していくと、２１７［Ｋ］程度で、脱離が発生するものと仮定する。これに対して、図８Ｂに示すように、実験例１′のＴＤＳ（昇温脱離分析システム）では、圧力の変化、すなわち、脱離したガス分子による圧力の上昇が発生し、脱離したガスが測定される。
FIG. 8 is an explanatory diagram of the experimental results of Experimental Example 1 and Experimental Example 1 ′, FIG. 8A is a graph of the experimental result of the desorption rate with the temperature on the horizontal axis and the desorption rate on the vertical axis, and FIG. FIG. 8C is a graph of an experimental result of Experimental Example 1 ′ in which temperature is plotted on the horizontal axis and pressure is plotted on the vertical axis. FIG. 8C is a graph of experimental results of Experimental Example 1 in which temperature is plotted on the horizontal axis and pressure is plotted on the vertical axis. FIG. 8C is an enlarged view of a main part of FIG. 8C.
In FIG. 8A, it is assumed that desorption occurs at about 217 [K] when the temperature of the sample 14 is increased. On the other hand, as shown in FIG. 8B, in the TDS (Temperature Desorption Analysis System) of Experimental Example 1 ′, a pressure change, that is, an increase in pressure due to the desorbed gas molecules occurred and desorbed. Gas is measured.
これに対して、図８Ｃ、図８Ｄに示すように、実験例１のＴＤＳでは、第１の分析真空室２ａの圧力ｐ１（図８Ｃ、図８Ｄの実線参照）においても、第２の分析真空室２ｂの圧力ｐ２（図８Ｃ、図８Ｄの破線参照）でも、圧力上昇が発生し、脱離したガスが測定される。ｐ２の圧力上昇は、図８Ａに示した実験例１′の実験結果と同等であり、第２の分析真空室２ｂにおいて、実験例１′とほぼ同数のガス分子（グラフから０．９７×１０１５［個］）を測定できることが確認された。したがって、第３の実施例では、第２の分析真空室２ｂの水素に対する定量補正係数を修正することなく利用することが可能である。なお、実験例１′では、第１の分析真空室２ａの圧力ｐ１を計測すると、原理的には高感度化を実現できることになるが、検出されたガスの中に含まれる付着物としての水等の影響を排除できないので定量性に乏しくなるなどの問題が残る。 On the other hand, as shown in FIGS. 8C and 8D, in the TDS of Experimental Example 1, the second analysis vacuum is performed even at the pressure p1 in the first analysis vacuum chamber 2a (see the solid line in FIGS. 8C and 8D). Even at the pressure p2 in the chamber 2b (see the broken lines in FIGS. 8C and 8D), the pressure rises and the desorbed gas is measured. The pressure increase of p2 is equivalent to the experimental result of Experimental Example 1 ′ shown in FIG. 8A, and in the second analysis vacuum chamber 2b, approximately the same number of gas molecules (0.97 × 10 15 [pieces]) can be measured. Therefore, in the third embodiment, it is possible to use the second analysis vacuum chamber 2b without correcting the quantitative correction coefficient for hydrogen. In Experimental Example 1 ′, when the pressure p1 in the first analysis vacuum chamber 2a is measured, high sensitivity can be realized in principle, but water as an adhering substance contained in the detected gas is used. Since the influence of the above cannot be excluded, problems such as poor quantitativeness remain.
（実験例２）
実験例２では、コンダクタンスＣの依存性を確認する実験を行った。
実験例２―１では、コンダクタンスＣをＣ＝０．００００２［ｍ３／ｓ］とした以外は、実験例１と同様とした。
実験例２−２では、コンダクタンスＣをＣ＝０．００００５［ｍ３／ｓ］とした以外は、実験例１と同様とした。
実験結果を図９、図１０に示す。
(Experimental example 2)
In Experimental Example 2, an experiment for confirming the dependence of conductance C was performed.
Experimental example 2-1 was the same as experimental example 1 except that the conductance C was C = 0.00002 [m 3 / s].
Experimental Example 2-2 was the same as Experimental Example 1 except that the conductance C was C = 0.00005 [m 3 / s].
The experimental results are shown in FIGS.
図９は実験例２−１の実験結果の説明図であり、図９Ａは図８Ａと同一のグラフ、図９Ｂは図８Ｂと同一のグラフ、図９Ｃは横軸に温度を取り縦軸に圧力を取った実験例２の実験結果のグラフ、図９Ｄは図９Ｃの要部拡大図である。
図９Ｃ、図９Ｄに示すように、実験例２−１では、第１の分析真空室２ａと、第２の分析真空室２ｂとの間のコンダクタンスＣが、実験例１に比べて小さいために、脱離して上昇した圧力ｐ１が低下する速度が小さくなっている。すなわち、第１の分析真空室２ａから第２の分析真空室２ｂに、ガス粒子が少しずつ流入し、第２の分析真空室２ｂで検出されるガス粒子の変化も少しずつになっている。従って、充分に高い温度までの昇温を行う場合でも、測定時間内に全てのガス粒子が第２の分析真空室２ａに導入されない。このため、第２の分析真空室２ｂで検出されるガス粒子の数も、グラフから０．８１×１０１５［個］となった。
9 is an explanatory diagram of the experimental results of Experimental Example 2-1, FIG. 9A is the same graph as FIG. 8A, FIG. 9B is the same graph as FIG. 8B, FIG. 9C is the temperature on the horizontal axis and the pressure on the vertical axis. FIG. 9D is an enlarged view of a main part of FIG. 9C.
As shown in FIGS. 9C and 9D, in Experimental Example 2-1, the conductance C between the first analysis vacuum chamber 2a and the second analysis vacuum chamber 2b is smaller than that in Experimental Example 1. The rate at which the pressure p1 that has been desorbed and increased is reduced. That is, the gas particles gradually flow into the second analysis vacuum chamber 2b from the first analysis vacuum chamber 2a, and the change of the gas particles detected in the second analysis vacuum chamber 2b is also little by little. Therefore, even when the temperature is raised to a sufficiently high temperature, all gas particles are not introduced into the second analysis vacuum chamber 2a within the measurement time. For this reason, the number of gas particles detected in the second analysis vacuum chamber 2b was also 0.81 × 10 15 [pieces] from the graph.
図１０は実験例２の実験結果の説明図であり、図１０Ａは横軸に温度をとり縦軸に第２の圧力変化をとった実験例１、２−１、２−２の実験結果のグラフ、図１０Ｂは図１０Ａの要部拡大図である。
図１０において、実験例２−２では、コンダクタンスＣが、実験例１と実験例２−１の中間程度であるため、第２の分析真空室２ｂにおける圧力ｐ２の変化について、ピークと低下する速度が中間程度になった。なお、実験例２−２では、ガス粒子の数は、０．９１×１０１５［個］であった。したがって、実験例１、２の結果から、コンダクタンスＣが小さすぎると、ガスの定量測定値が低下することが確認された。なお、コンダクタンスＣが１０−１［ｍ３／ｓ］よりも大きくなると、トラップ管３１による吸着、除去性能が小さくなるため、望ましくない。すなわち、実験例では、コンダクタンスＣは、１０−１〜１０−４オーダの範囲が望ましいことが確認された。
FIG. 10 is an explanatory diagram of the experimental results of Experimental Example 2. FIG. 10A shows the experimental results of Experimental Examples 1, 2-1, and 2-2 in which the horizontal axis represents temperature and the vertical axis represents the second pressure change. The graph, FIG. 10B is an enlarged view of the main part of FIG. 10A.
In FIG. 10, in Experiment 2-2, the conductance C is about the middle between Experiment 1 and Experiment 2-1, and therefore the peak and the rate of decrease with respect to the change in the pressure p2 in the second analysis vacuum chamber 2b. Became intermediate. In Experimental Example 2-2, the number of gas particles was 0.91 × 10 15 [pieces]. Therefore, from the results of Experimental Examples 1 and 2, it was confirmed that when the conductance C is too small, the quantitative measurement value of the gas decreases. Note that if the conductance C is larger than 10 −1 [m 3 / s], the adsorption and removal performance by the trap tube 31 is decreased, which is not desirable. That is, in the experimental example, it was confirmed that the conductance C is preferably in the range of 10 −1 to 10 −4 order.
（実験例３）
実験例３では、昇温速度と第２の分析真空室２ｂの圧力変化との関係について実験を行った。
実験例３−１では、実験例１と同様にコンダクタンスＣをＣ＝０．０００２［ｍ３／ｓ］とし、昇温速度βをβ＝６０［Ｋ／ｈ］とした以外は、実験例１と同様とした。
実験例３−２では、実験例２−１と同様にコンダクタンスＣをＣ＝０．０００２［ｍ３／ｓ］とし、昇温速度βをβ＝６０［Ｋ／ｈ］とした以外は、実験例１と同様とした。
実験結果を図１１〜図１３に示す。
(Experimental example 3)
In Experimental Example 3, an experiment was performed on the relationship between the temperature rising rate and the pressure change in the second analysis vacuum chamber 2b.
In Experimental Example 3-1, in the same manner as Experimental Example 1, except that conductance C was C = 0.0002 [m 3 / s] and heating rate β was β = 60 [K / h], Experimental Example 1 And the same.
In Experimental Example 3-2, the experiment was performed except that conductance C was set to C = 0.0002 [m 3 / s] and temperature increase rate β was set to β = 60 [K / h] as in Experimental Example 2-1. Same as Example 1.
Experimental results are shown in FIGS.
図１１は実験例３−１の実験結果の説明図であり、図１１Ａは図８Ａと同様の脱離速度のグラフ、図１１Ｂは図８Ｂと同様の従来の第１の分析真空室の圧力変化のグラフ、図１１Ｃは横軸に温度を取り縦軸に圧力を取った実験例３−１の実験結果のグラフ、図１１Ｄは図１１Ｃの要部拡大図である。
図１１Ａ、図１１Ｂ、図８Ａ、図８Ｂにおいて、実験例３−１では、実験例１に比べて、昇温速度が遅いため、脱離ガス粒子の脱離速度が遅くなっており、脱離速度や圧力変化のピークが下がっている。また、昇温速度が遅いため、脱離が開始する時期が実験例１よりも低温側にシフトしており、ピークは１９７［Ｋ］程度にシフトしている。
図１１Ｃ、図１１Ｄに示すように、実験例３−１では、第２の分析真空室２ｂで検出されるガス粒子の数がグラフから１．０×１０１５［個］であり、実験例１よりも、低い温度で検出が可能となっている。
11 is an explanatory diagram of the experimental results of Experimental Example 3-1, FIG. 11A is a graph of the desorption rate similar to FIG. 8A, and FIG. 11B is the pressure change of the conventional first analysis vacuum chamber similar to FIG. 8B. FIG. 11C is a graph of an experimental result of Experimental Example 3-1, in which the horizontal axis represents temperature and the vertical axis represents pressure, and FIG. 11D is an enlarged view of a main part of FIG. 11C.
In FIG. 11A, FIG. 11B, FIG. 8A, and FIG. 8B, in Experimental Example 3-1, since the temperature rising rate is slower than in Experimental Example 1, the desorption rate of the desorbed gas particles is slow. The peak of speed and pressure change is decreasing. Further, since the rate of temperature rise is slow, the timing at which desorption starts is shifted to a lower temperature side than Experimental Example 1, and the peak is shifted to about 197 [K].
As shown in FIGS. 11C and 11D, in Experimental Example 3-1, the number of gas particles detected in the second analysis vacuum chamber 2b is 1.0 × 10 15 [pieces] from the graph, and Experimental Example 1 It is possible to detect at a lower temperature.
図１２は実験例３−２の実験結果の説明図であり、図１２Ａは図８Ａと同様の脱離速度のグラフ、図１２Ｂは図８Ｂと同様の従来の第１の分析真空室の圧力変化のグラフ、図１２Ｃは横軸に温度を取り縦軸に圧力を取った実験例３−２の実験結果のグラフ、図１２Ｄは図１２Ｃの要部拡大図である。
図１２Ａ、図１２Ｂにおいて、実験例３−２も、実験例３−１と同様に、脱離ガス粒子の脱離速度が遅く、脱離が開始する時期が実験例１よりも低温側にシフトしている。
図１２Ｃ、図１２Ｄに示すように、実験例３−２では、第２の分析真空室２ｂで検出されるガス粒子の数がグラフから０．９９×１０１５［個］であり、実験例３−１とほぼ同様であった。
12 is an explanatory diagram of the experimental results of Experimental Example 3-2, FIG. 12A is a graph of the desorption rate similar to FIG. 8A, and FIG. 12B is the pressure change of the conventional first analysis vacuum chamber similar to FIG. 8B. FIG. 12C is a graph of an experimental result of Experimental Example 3-2 in which the horizontal axis indicates temperature and the vertical axis indicates pressure, and FIG. 12D is an enlarged view of a main part of FIG. 12C.
12A and 12B, Experimental Example 3-2 also has a slow desorption rate of desorbed gas particles, and the timing at which desorption starts is shifted to a lower temperature side than Experimental Example 1 in Experimental Example 3-1. doing.
12C and 12D, in Experimental Example 3-2, the number of gas particles detected in the second analysis vacuum chamber 2b is 0.99 × 10 15 [pieces] from the graph, and Experimental Example 3 It was almost the same as -1.
図１３は実験例３の実験結果のグラフであり、図１３Ａは横軸に温度を取り縦軸に圧力を取った実験例３−１および３−２の第１の分析真空室の圧力変化のグラフ、図１３Ｂは横軸に温度を取り縦軸に圧力を取った実験例３−１および３−２の第２の分析真空室の圧力変化のグラフである。
図１３において、図１３Ａに示すように、実験例３−１、実験例３−２では、コンダクタンスＣの差に伴って、実験例３−１よりも実験例３−２の方が、第２の分析真空室２ｂにガスが移動しにくい、すなわち、第１の分析真空室２ａに残るガスが多く、ピークが大きくなる。よって、実験例３−２では、実験例３−１に比べて、第１の分析真空室２ａと第２の分析真空室２ｂとの圧力差、すなわち、式（１）のΔｐが大きくなる。よって、実験例３−２の方が、コンダクタンスＣが小さいが、Δｐが大きくなるため、実験例３−１、３−２で、式（１）の左辺のＱは、図１３Ｂに示すように、同様となる。
FIG. 13 is a graph of the experimental results of Experimental Example 3. FIG. 13A shows the change in pressure in the first analysis vacuum chambers of Experimental Examples 3-1 and 3-2 in which the horizontal axis represents temperature and the vertical axis represents pressure. FIG. 13B is a graph of pressure change in the second analysis vacuum chambers of Experimental Examples 3-1 and 3-2 in which the horizontal axis represents temperature and the vertical axis represents pressure.
In FIG. 13, as shown in FIG. 13A, in Experimental Example 3-1 and Experimental Example 3-2, with the difference in conductance C, Experimental Example 3-2 is second than Experimental Example 3-1. It is difficult for the gas to move into the analysis vacuum chamber 2b, that is, there is much gas remaining in the first analysis vacuum chamber 2a, and the peak becomes large. Therefore, in Experimental Example 3-2, as compared with Experimental Example 3-1, the pressure difference between the first analysis vacuum chamber 2a and the second analysis vacuum chamber 2b, that is, Δp in Expression (1) is large. Therefore, since the conductance C is smaller in the experimental example 3-2 but Δp is larger, in the experimental examples 3-1, 3-2, the Q on the left side of the expression (1) is as shown in FIG. 13B. The same.
したがって、実験例１、３の実験結果から、昇温速度を遅くすることで、低い温度で測定が可能になると共に、実験例１、２、３の実験結果から、コンダクタンスＣが小さくても、昇温速度を小さくすることで、コンダクタンスＣが大きい場合と同様の結果が得られることが確認された。すなわち、昇温速度を小さくすることで、コンダクタンスＣの大小の影響を小さくすることができることが確認された。
なお、実験例３において、昇温速度を、６０［Ｋ／ｈ］から、１２０［Ｋ／ｈ］、１８０［Ｋ／ｈ］に変更した実験を行ったが、図１３Ｂと同様の結果が得られたため、図示は省略する。
Therefore, from the experimental results of Experimental Examples 1 and 3, it is possible to measure at a low temperature by slowing the temperature rising rate, and from the experimental results of Experimental Examples 1, 2, and 3, even if the conductance C is small, It was confirmed that the same result as that obtained when the conductance C is large can be obtained by reducing the heating rate. That is, it was confirmed that the influence of the conductance C can be reduced by reducing the temperature rising rate.
In Experimental Example 3, an experiment was performed in which the rate of temperature increase was changed from 60 [K / h] to 120 [K / h] and 180 [K / h]. The same result as in FIG. 13B was obtained. Therefore, illustration is omitted.
図１４は実験例１と実験例３−１の比較の説明図であり、図１４Ａは横軸に温度を取り縦軸に圧力を取った実験例１および実験例３−１の第２の分析真空室の圧力変化のグラフ、図１４Ｂは図１４Ａにおいて実験例３−１を縦軸方向に１０倍したグラフと実験例１の要部拡大図である。
図１４に示すように、実験例３−１では、実験例１に比べて低温側にピークがシフトしているが、第２の分析真空室２ｂの圧力ｐ２のピークの値は、オーダーが１０倍以上異なっている。したがって、図１４から、実験例１のように昇温速度を大きくすることで、測定の高感度化に期待できることが確認された。
FIG. 14 is an explanatory diagram for comparison between Experimental Example 1 and Experimental Example 3-1. FIG. 14A is a second analysis of Experimental Example 1 and Experimental Example 3-1, in which the horizontal axis represents temperature and the vertical axis represents pressure. FIG. 14B is a graph of the pressure change in the vacuum chamber, FIG. 14B is a graph in which Experimental Example 3-1 is multiplied by 10 in the vertical axis direction, and FIG.
As shown in FIG. 14, in Experimental Example 3-1, the peak is shifted to a lower temperature side than in Experimental Example 1, but the peak value of the pressure p2 in the second analysis vacuum chamber 2b is 10 in order. It is more than doubled. Therefore, from FIG. 14, it was confirmed that increasing the temperature rising rate as in Experimental Example 1 can be expected to increase the sensitivity of the measurement.
（変更例）
以上、本発明の実施例を詳述したが、本発明は、前記実施例に限定されるものではなく、特許請求の範囲に記載された本発明の要旨の範囲内で、種々の変更を行うことが可能である。本発明の変更例（Ｈ01）〜（Ｈ05）を下記に例示する。
（Ｈ01）前記実施例において、試料分析装置の一例としての昇温脱離分析装置を例示したが、この装置に限定されず、電子顕微鏡等の真空室を有する種々の試料分析装置に適用可能である。また、質量分析計もＱ−ＭＡＳに限定されず、従来公知の質量分析計を使用可能である。
(Example of change)
As mentioned above, although the Example of this invention was explained in full detail, this invention is not limited to the said Example, A various change is performed within the range of the summary of this invention described in the claim. It is possible. Modification examples (H01) to (H05) of the present invention are exemplified below.
(H01) In the above embodiment, the temperature-programmed desorption analyzer is illustrated as an example of the sample analyzer, but is not limited to this device, and can be applied to various sample analyzers having a vacuum chamber such as an electron microscope. is there. Moreover, a mass spectrometer is not limited to Q-MAS, A conventionally well-known mass spectrometer can be used.
（Ｈ02）前記実施例において、試料搬入部材２１の形状、大きさ等は、実施例に例示した構成に限定されず、使用や設計等に応じて適宜変更可能である。例えば、試料搬入部材２１の形状は、試料ステージ３の外形に対応した形状としたが、この構成に限定されず、試料ステージ３の形状とは関係のない外形とすることも可能である。また、熱容量が大きくなくても良い場合には、全体を小型化したり、熱容量が更に大きくしたい場合は全体を大型化したり、熱容量の大きな材料を使用することが可能である。さらに、冷媒液収容部２１ｂの形状も傾斜面を省略したり、四角形の凹部形状を丸形としたり、凹部でなく溝状としたり、あるいは冷媒液収容部２１ｂの上面を塞ぐ蓋を設けたり、任意の形態に変更可能である。 (H02) In the above-described embodiment, the shape, size, and the like of the sample carrying-in member 21 are not limited to the configuration illustrated in the embodiment, and can be appropriately changed according to use, design, and the like. For example, the shape of the sample carry-in member 21 is a shape corresponding to the outer shape of the sample stage 3, but is not limited to this configuration, and may be an outer shape that is not related to the shape of the sample stage 3. If the heat capacity does not have to be large, the whole can be downsized, and if the heat capacity is desired to be further increased, the whole can be enlarged, or a material having a large heat capacity can be used. Furthermore, the shape of the refrigerant liquid storage portion 21b is omitted from the inclined surface, the quadrangular concave portion is rounded, the groove is not a concave portion, or a lid for closing the upper surface of the refrigerant liquid storage portion 21b is provided. It can be changed to any form.
（Ｈ03）前記実施例において、搬入室１２は、試料搬入部材２１を搬入前に窒素パージしておくことが望ましいが、試料１４が大気に曝されない状態で搬入されるので、窒素パージを省略することも可能である。
（Ｈ04）前記実施例において、試料に電解チャージをして、脱離する極微量な水素を測定する分析方法について例示したが、測定対象は水素に限定されず、任意の成分を対象とした分析を行うことができる。また、試料の調製として電解チャージを例示したが、この調整方法に限定されず、液体冷媒に試料を沈めることが可能で、液体冷媒で影響を受けにくい任意の調整方法で調整した試料を使用可能である。
(H03) In the above embodiment, it is desirable that the carry-in chamber 12 is purged with nitrogen before carrying in the sample carry-in member 21, but the sample 14 is carried in without being exposed to the atmosphere, so nitrogen purge is omitted. It is also possible.
(H04) In the above embodiment, an example of an analysis method for measuring a very small amount of desorbed hydrogen by electrolytically charging a sample, but the measurement target is not limited to hydrogen, and analysis for any component It can be performed. In addition, although the electrolytic charge was exemplified as the preparation of the sample, it is not limited to this adjustment method, the sample can be submerged in the liquid refrigerant, and the sample adjusted by any adjustment method that is not easily affected by the liquid refrigerant can be used. It is.
（Ｈ05）前記実施例２において、ガス除去装置３１＋３４に冷却装置３４を設ける構成としたが、冷却しなくても十分に除去できる場合には、冷却装置３４を省略することも可能である。また、配管３１の形状は、Ｕ字管に限定されず、波形形状やＳ字形状等の任意の形状とすることが可能である。
また、実施例２のガス除去装置３１＋３４は、水素ガスに対して水分を除去するためにＵ字管と冷却装置の構成としたが、この構成に限らず、測定したいガス成分が通過し、除去したいガス成分を吸着可能な任意の構成とすることが可能である。例えば、ヘリウム成分を測定したい場合は、ガス除去装置としてクライオポンプを使用することで、ヘリウム成分以外の成分を除去することも不可能ではない。
(H05) Although the cooling device 34 is provided in the gas removal device 31 + 34 in the second embodiment, the cooling device 34 can be omitted if the cooling device 34 can be sufficiently removed without cooling. Moreover, the shape of the piping 31 is not limited to a U-shaped tube, and can be an arbitrary shape such as a waveform shape or an S shape.
In addition, the gas removal device 31 + 34 of the second embodiment has a U-shaped tube and a cooling device for removing moisture from the hydrogen gas. However, the gas removal device 31 + 34 is not limited to this configuration, and a gas component to be measured passes through and is removed. It is possible to adopt an arbitrary configuration capable of adsorbing a desired gas component. For example, when it is desired to measure a helium component, it is not impossible to remove components other than the helium component by using a cryopump as a gas removal device.
本発明の試料分析方法、試料分析装置は、例えば、鉄鋼分野における水素脆化問題の分析や、非鉄金属材料分野における水素脆化問題の分析、燃料電池の水素吸蔵材料の研究開発、半導体、フラットパネルディスプレイの研究開発や故障解析等の分野において好適に使用可能である。 The sample analysis method and sample analyzer of the present invention include, for example, analysis of hydrogen embrittlement problems in the steel field, analysis of hydrogen embrittlement problems in the field of non-ferrous metal materials, research and development of hydrogen storage materials for fuel cells, semiconductors, flats It can be suitably used in the fields of panel display research and development and failure analysis.
１，１′，１″…分析装置、
２，２′…分析真空室、
２ａ…第１の分析真空室、
２ｂ…第２の分析真空室、
３…試料保持部材、
４…第１の真空ポンプ、
６…質量分析計、
１２…搬入室、
１４…試料、
２１…試料搬入部材、
２１ａ…試料搬入側縁、
２１ｂ…冷媒液収容部、
２８…冷媒収容槽、
３１＋３４…ガス除去装置、
Ｐ１…第１の排気路、
Ｖ１…第１のバルブ。
1,1 ', 1 "... analyzer,
2,2 '... Analysis vacuum chamber,
2a ... first analysis vacuum chamber,
2b ... the second analysis vacuum chamber,
3 ... Sample holding member,
4 ... first vacuum pump,
6 ... Mass spectrometer,
12 ... carry-in room,
14 ... sample,
21 ... Sample carrying member,
21a ... Sample loading side edge,
21b ... Refrigerant liquid storage part,
28 ... Refrigerant storage tank,
31 + 34 ... gas removal device,
P1 ... first exhaust passage,
V1 is the first valve.
Claims (9)
調製された前記試料を、試料搬入部材の冷媒液収容部に収容された液体状の冷媒中に沈んだ状態で収容する試料冷却収容工程と、
前記試料が収容された前記試料搬入部材を、真空状態に排気されて分析が行われる分析真空室に接続された搬入室に搬入する試料搬入工程と、
前記搬入室を、真空状態に排気する搬入室排気工程と、
前記搬入室の前記試料搬入部材を前記分析真空室に移動させ、前記試料搬入部材の前記試料を、前記分析真空室の試料保持部材に移動させる試料移動工程と、
前記試料保持部材の試料に対して分析を行う試料分析工程と、
を実行することを特徴とする試料分析方法。 A sample preparation step of preparing the sample in a liquid;
A sample cooling and storing step for storing the prepared sample in a state where it is submerged in a liquid refrigerant stored in the refrigerant liquid storing portion of the sample carrying-in member;
A sample carrying-in step for carrying the sample carrying-in member containing the sample into a carrying-in chamber connected to an analysis vacuum chamber that is evacuated and analyzed;
A carry-in chamber exhausting step for exhausting the carry-in chamber to a vacuum state;
A sample moving step of moving the sample loading member of the loading chamber to the analysis vacuum chamber and moving the sample of the sample loading member to a sample holding member of the analysis vacuum chamber;
A sample analysis step for analyzing the sample of the sample holding member;
The sample analysis method characterized by performing.
を実行することを特徴とする請求項１に記載の試料分析方法。 The sample cooling and storing step of storing the sample prepared in the refrigerant storage portion of the sample loading member with respect to the sample loading member submerged in the refrigerant storage tank in which the liquid refrigerant is stored;
The sample analysis method according to claim 1, wherein:
を実行することを特徴とする請求項１または２に記載の試料分析方法。 A nitrogen purge step of purging the loading chamber with nitrogen gas before the sample loading member containing the sample submerged in the liquid refrigerant composed of liquid nitrogen is loaded into the loading chamber;
The sample analysis method according to claim 1, wherein the sample analysis method is executed.
を備えたことを特徴とする請求項４に記載の試料搬入部材。 A sample holding member provided in the analyzer and holding a sample to be analyzed is formed so as to be in contact with the outer edge of the sample holding member and has an outer edge shape corresponding to the outer edge of the sample holding member. Sample loading side edge,
The sample carrying member according to claim 4, comprising:
を備えたことを特徴とする請求項５に記載の試料搬入部材。 In the state where the sample loading side edge is in contact with the sample holding member, the refrigerant liquid storage portion formed so as to become shallower as it goes to the sample holding member side,
The sample carrying member according to claim 5, comprising:
前記試料が収容された前記試料搬入部材を、分析が行われる分析装置に設けられた真空排気される搬入室に搬入する試料搬入工程と、
を実行することを特徴とする試料搬入方法。 The specimen prepared in a liquid, the sample cooling accommodating step of accommodating in a state sunk into liquid refrigerant contained in the refrigerant liquid storage unit of the sample carrying member,
A sample carrying-in step of carrying the sample carrying-in member containing the sample into a carrying-in chamber that is evacuated and provided in an analyzer in which analysis is performed;
The sample carrying-in method characterized by performing.
液体状の冷媒が収容され且つ試料が冷媒中に沈んだ状態で収容可能な凹状に形成されると共に上方が外気に開放された冷媒液収容部を備え、前記搬入室の外部において液体中で調製された試料が搬入され、前記冷媒液収容部の前記冷媒中に前記試料が沈んだ状態で収容されると共に、前記試料を冷媒中に保持した状態で前記搬入室に搬入される試料搬入部材と、
前記搬入室を真空状態に排気する排気装置と、
前記搬入室に接続された第１の分析真空室であって、前記搬入室に搬入された前記試料搬入部材の前記冷媒液収容部から移動された試料が保持され且つ試料の昇温を行う試料保持部材が配置されると共に内部が真空に排気される前記第１の分析真空室と、前記第１の分析真空室と接続され且つ試料から脱離したガス成分の質量分析を行う質量分析計が支持されて内部が真空に排気される第２の分析真空室と、を有し、試料の分析が行われる分析真空室と、
前記第１の分析真空室と前記第２の分析真空室との間を接続し、且つ、通過するガスから一部のガス成分を除去するガス除去装置と、
を備えたことを特徴とする昇温脱離分析装置。 A loading room;
Prepared in liquid in the outside of the carry-in chamber, which is provided with a refrigerant liquid storage part that is formed in a concave shape that can store liquid refrigerant and that can be stored in a state where the sample is submerged in the refrigerant, and whose upper part is open to the outside. A sample carrying-in member that is carried in, is contained in the refrigerant in the refrigerant liquid containing portion while the sample is sinked, and is carried into the carry-in chamber while the sample is held in the refrigerant; ,
An exhaust device for exhausting the carry-in chamber to a vacuum state;
A first analysis vacuum chamber connected to the carry-in chamber, in which the sample moved from the refrigerant liquid storage part of the sample carry-in member carried into the carry-in chamber is held and the sample is heated said first analysis vacuum chamber holding member inside is evacuated to a vacuum while being arranged, the first is connected to the analytical vacuum chamber and a mass spectrometer for performing mass analysis of the desorbed gas component from the sample A second analysis vacuum chamber that is supported and evacuated to a vacuum, and an analysis vacuum chamber in which analysis of the sample is performed;
A gas removal device that connects between the first analysis vacuum chamber and the second analysis vacuum chamber and removes a part of gas components from the passing gas;
A temperature-programmed desorption analyzer, comprising:
前記第１の分析真空室と前記第１の真空ポンプとを接続する第１の排気路に設けられ、前記第１の分析真空室と前記第１の真空ポンプとの接続、切断を行う第１のバルブと、
を備え、前記質量分析が行われる場合には、前記第１のバルブが閉じられる
ことを特徴とする請求項８に記載の昇温脱離分析装置。 A first vacuum pump for evacuating the first analysis vacuum chamber;
A first exhaust passage is provided in a first exhaust path connecting the first analysis vacuum chamber and the first vacuum pump, and connects and disconnects the first analysis vacuum chamber and the first vacuum pump. And the valve
The temperature programmed desorption analyzer according to claim 8 , wherein the first valve is closed when the mass analysis is performed.
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| FI128645B (en) * | 2018-09-28 | 2020-09-30 | Aalto Univ Foundation Sr | Arrangement and method for thermal desorption measurement |
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| JPS54118164A (en) * | 1978-03-07 | 1979-09-13 | Hitachi Ltd | Frozen sample manufacturing carrier for scanning electronic microscope |
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