WO2016031617A1 - ガスクロマトグラフィー質量分析用試料サンプリング材 - Google Patents

ガスクロマトグラフィー質量分析用試料サンプリング材 Download PDF

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WO2016031617A1
WO2016031617A1 PCT/JP2015/073085 JP2015073085W WO2016031617A1 WO 2016031617 A1 WO2016031617 A1 WO 2016031617A1 JP 2015073085 W JP2015073085 W JP 2015073085W WO 2016031617 A1 WO2016031617 A1 WO 2016031617A1
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gas chromatography
mass spectrometry
carbon nanotubes
carbon nanotube
chromatography mass
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PCT/JP2015/073085
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English (en)
French (fr)
Japanese (ja)
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前野　洋平
佳奈 後藤
卓哉 湯峯
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日東電工株式会社
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/622—Ion mobility spectrometry
    • G01N27/623—Ion mobility spectrometry combined with mass spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86

Definitions

  • the present invention relates to a sample sampling material for gas chromatography mass spectrometry.
  • Gas chromatography is an analysis that uses a mobile phase as a gas, flows a measurement sample through the column together with the mobile phase, and performs high-performance separation and detection using the interaction (adsorption, distribution, etc.) of the stationary phase. Is the method.
  • An analysis method for measuring the mass spectrum of a single component separated by gas chromatography and performing qualitative analysis after performing gas chromatography is called gas chromatography mass spectrometry (GC / MS). .
  • An object of the present invention is a sample sampling material for gas chromatography mass spectrometry in which a sample is sampled by a stamp, and a peak derived from a contaminant in a mass spectrum obtained by gas chromatography mass spectrometry measurement is reduced, and accurate qualitative analysis is performed. It is an object of the present invention to provide a sample sampling material for gas chromatography mass spectrometry that can perform analysis.
  • Sample sampling material for gas chromatography mass spectrometry of the present invention A sampling material for sampling a sample of gas chromatography mass spectrometry with a stamp, Including a base material and a fibrous columnar structure,
  • the fibrous columnar structure is a fibrous columnar structure including a plurality of fibrous columnar objects,
  • the fibrous columnar material is oriented in a substantially vertical direction with respect to the substrate.
  • the fibrous columnar structure is a carbon nanotube aggregate including a plurality of carbon nanotubes.
  • the carbon nanotube has a plurality of layers, the distribution width of the number distribution of the carbon nanotubes is 10 or more, and the relative frequency of the mode value of the number distribution of the carbon nanotubes is 25% or less. .
  • the carbon nanotube has a length of 300 ⁇ m or more.
  • the carbon nanotube has a plurality of layers, the mode value of the number distribution of the carbon nanotubes is present in 10 or less layers, and the relative frequency of the mode value is 30% or more. .
  • the carbon nanotube has a length of 300 ⁇ m or more.
  • a sample sampling material for gas chromatography mass spectrometry that samples a sample by a stamp, and a peak derived from a contaminant in a mass spectrum obtained by gas chromatography mass spectrometry measurement is reduced, and accurate qualitative analysis is performed.
  • a sample sampling material for gas chromatography mass spectrometry capable of performing analysis can be provided.
  • the sample sampling material for gas chromatography mass spectrometry of the present invention is a sampling material for sampling a sample for gas chromatography mass spectrometry with a stamp.
  • the sample sampling material for gas chromatography mass spectrometry of the present invention is a sampling material for collecting a sample necessary for measuring gas chromatography mass spectrometry by stamping the sample (pressing of the sampling material). .
  • any appropriate sample that can be analyzed by gas chromatography or gas chromatography mass spectrometry can be adopted.
  • the sample sampling material for gas chromatography mass spectrometry of the present invention includes a base material and a fibrous columnar structure.
  • the sample sampling material for gas chromatography mass spectrometry of the present invention is derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement by including a base material and a specific fibrous columnar structure as described later. Therefore, it is possible to provide a sample sampling material for gas chromatography / mass spectrometry that can perform accurate qualitative analysis.
  • sample sampling material for gas chromatography mass spectrometry of the present invention includes a base material and a fibrous columnar structure
  • sample sampling material has any other appropriate member as long as the effects of the present invention are not impaired. Also good.
  • any appropriate base material can be adopted as the base material as long as the effects of the present invention are not impaired.
  • Examples of such a base material include aluminum, copper, gold, nickel, stainless steel, and carbon.
  • the thickness of the substrate can be set to any appropriate value depending on the purpose.
  • the surface of the substrate is subjected to conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, etc. in order to improve adhesion, retention, etc.
  • Coating treatment with a primer for example, the above-mentioned adhesive substance may be performed.
  • the base material may be a single layer or a multilayer body.
  • the fibrous columnar structure is a fibrous columnar structure including a plurality of fibrous columnar objects.
  • the size of the fibrous columnar structure is such that a sample necessary for measuring gas chromatography mass spectrometry can be collected by stamping (pressing a sampling material) on the sample, and gas chromatography mass spectrometry can be performed. Any suitable size can be adopted. As such a size, the size when viewed from the upper surface (the surface side opposite to the substrate of the fibrous columnar structure) is preferably 1 mm 2 to 1000 mm 2 , more preferably 10 mm 2 to 700 mm 2 , more preferably 20 mm 2 to 500 mm 2 , particularly preferably 30 mm 2 to 300 mm 2 , and most preferably 50 mm 2 to 100 mm 2 . When the size falls within the above range, the contaminant-derived peak in the mass spectrum obtained by gas chromatography mass spectrometry measurement is further reduced, and more accurate qualitative analysis can be performed.
  • a sample sampling material can be provided.
  • the length of the fibrous columnar material is preferably 50 ⁇ m to 3000 ⁇ m, more preferably 200 ⁇ m to 2000 ⁇ m, still more preferably 300 ⁇ m to 1500 ⁇ m, particularly preferably 400 ⁇ m to 1000 ⁇ m, and most preferably 500 ⁇ m to 1000 ⁇ m. It is. When the length of the fibrous columnar body is within the above range, the contaminant-derived peak in the mass spectrum obtained by gas chromatography mass spectrometry measurement is further reduced, and more accurate qualitative analysis can be performed. A sample sampling material for gas chromatography mass spectrometry can be provided.
  • FIG. 1 shows a schematic cross-sectional view of an example of a sample sampling material for gas chromatography mass spectrometry in a preferred embodiment of the present invention.
  • a sample sampling material 1000 for gas chromatography mass spectrometry has a base material 100 and a fibrous columnar structure 10.
  • the fibrous columnar structure 10 includes a plurality of fibrous columnar objects 2. One end of the fibrous columnar object 2 is fixed to the substrate 100.
  • the fibrous columnar body 2 is oriented in the direction of the length L.
  • the fibrous columnar body 2 is oriented in a substantially vertical direction with respect to the substrate 100.
  • the “substantially perpendicular direction” means that the angle with respect to the surface of the substrate 100 is preferably 90 ° ⁇ 20 °, more preferably 90 ° ⁇ 15 °, and further preferably 90 ° ⁇ 10 °. And particularly preferably 90 ° ⁇ 5 °.
  • any appropriate material can be adopted as the material for the fibrous columnar material.
  • examples thereof include metals such as aluminum and iron; inorganic materials such as silicon; carbon materials such as carbon nanofibers and carbon nanotubes (CNT); and high modulus resins such as engineering plastics and super engineering plastics.
  • the resin include polystyrene, polyethylene, polypropylene, polyethylene terephthalate, acetyl cellulose, polycarbonate, polyimide, polyamide, and the like.
  • Any appropriate physical properties can be adopted as the physical properties such as the molecular weight of the resin as long as the object of the present invention can be achieved.
  • the diameter of the fibrous columnar material is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, still more preferably 2 nm to 500 nm, particularly preferably 2 nm to 200 nm, and most preferably 2 nm to 100 nm.
  • the diameter of the fibrous columnar body is within the above range, so that the peak derived from the contaminant in the mass spectrum obtained by gas chromatography mass spectrometry measurement is further reduced, and a more accurate qualitative analysis can be performed.
  • a sample sampling material for chromatography mass spectrometry can be provided.
  • the fibrous columnar structure is preferably a carbon nanotube aggregate including a plurality of carbon nanotubes.
  • the fibrous columnar product is preferably a carbon nanotube.
  • the fibrous columnar structure is an aggregate of carbon nanotubes including a plurality of carbon nanotubes, so that contaminant-derived peaks in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced and more accurate qualitative analysis. It is possible to provide a sample sampling material for gas chromatography mass spectrometry that can perform the above.
  • One preferred embodiment of the aggregate of carbon nanotubes includes a plurality of carbon nanotubes, the carbon nanotubes having a plurality of layers, and the carbon nanotube layer.
  • the distribution width of the number distribution is 10 layers or more, and the relative frequency of the mode value of the layer number distribution is 25% or less.
  • the distribution width of the number distribution of the carbon nanotubes is preferably 10 or more, more preferably 10 to 30 layers, still more preferably 10 to 25 layers, particularly The number of layers is preferably 10 to 20 layers.
  • the “distribution width” of the number distribution of carbon nanotubes refers to the difference between the maximum number and the minimum number of carbon nanotube layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and further, the carbon nanotubes have excellent adhesive properties. It can be the carbon nanotube aggregate shown. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the number of layers and the number distribution of carbon nanotubes may be measured by any appropriate apparatus. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes may be taken out from the aggregate of carbon nanotubes and measured by SEM or TEM to evaluate the number of layers and the number distribution of the layers.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the maximum number of carbon nanotube layers is preferably 5 to 30 layers, more preferably 10 to 30 layers, and even more preferably 15 to 30 layers. Particularly preferred are 15 to 25 layers.
  • the minimum number of carbon nanotube layers is preferably 1 to 10 layers, and more preferably 1 to 5 layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, Furthermore, the carbon nanotube can be a carbon nanotube aggregate exhibiting excellent adhesive properties. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the relative frequency of the mode value of the number distribution of carbon nanotubes is preferably 25% or less, more preferably 1% to 25%, and even more preferably 5% to 25%. Particularly preferred is 10% to 25%, and most preferred is 15% to 25%.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area. It can be an aggregate of carbon nanotubes exhibiting excellent adhesive properties. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the mode of the number distribution of the carbon nanotubes is preferably present from 2 layers to 10 layers, more preferably from 3 layers to 10 layers. .
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and the carbon nanotubes have excellent adhesive properties. It can become the carbon nanotube aggregate which shows. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the carbon nanotubes may have any appropriate shape in cross section.
  • the cross section may be substantially circular, elliptical, n-gonal (n is an integer of 3 or more), and the like.
  • the length of the carbon nanotube is preferably 50 ⁇ m or more, more preferably 100 ⁇ m to 3000 ⁇ m, still more preferably 300 ⁇ m to 1500 ⁇ m, still more preferably 400 ⁇ m to 1000 ⁇ m, particularly
  • the thickness is preferably 500 ⁇ m to 1000 ⁇ m.
  • the diameter of the carbon nanotube is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, and further preferably 2 nm to 500 nm.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area.
  • the carbon nanotube aggregates exhibit excellent adhesive properties. Can be. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the specific surface area and density of the carbon nanotubes can be set to any appropriate values.
  • Another preferred embodiment of the aggregate of carbon nanotubes includes a plurality of carbon nanotubes, the carbon nanotubes having a plurality of layers, and the carbon nanotubes.
  • the mode value of the number distribution of layers exists in 10 layers or less, and the relative frequency of the mode value is 30% or more.
  • the distribution width of the number distribution of the carbon nanotubes is preferably 9 or less, more preferably 1 to 9 layers, further preferably 2 to 8 layers, particularly Three to eight layers are preferred.
  • the “distribution width” of the number distribution of carbon nanotubes refers to the difference between the maximum number and the minimum number of carbon nanotube layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and furthermore, the carbon nanotubes have excellent adhesive properties. It can be the carbon nanotube aggregate shown. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the number of layers and the number distribution of carbon nanotubes may be measured by any appropriate apparatus. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes may be taken out from the aggregate of carbon nanotubes and measured by SEM or TEM to evaluate the number of layers and the number distribution of the layers.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the maximum number of carbon nanotube layers is preferably 1 to 20 layers, more preferably 2 to 15 layers, and further preferably 3 to 10 layers. .
  • the maximum number of carbon nanotube layers is preferably 1 to 20 layers, more preferably 2 to 15 layers, and further preferably 3 to 10 layers.
  • the minimum number of carbon nanotube layers is preferably 1 to 10 layers, more preferably 1 to 5 layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, Furthermore, the carbon nanotube can be a carbon nanotube aggregate exhibiting excellent adhesive properties. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the relative frequency of the mode value of the number distribution of the carbon nanotubes is preferably 30% or more, more preferably 30% to 100%, and further preferably 30% to 90%. Particularly preferred is 30% to 80%, and most preferred is 30% to 70%.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area. It can be an aggregate of carbon nanotubes exhibiting excellent adhesive properties. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the mode value of the number distribution of the carbon nanotubes is preferably present in the number of layers of 10 or less, more preferably in the number of layers from 1 to 10, and more preferably The number of layers is from 2 to 8 and particularly preferably from 2 to 6 layers.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and the carbon nanotubes have excellent adhesive properties. It can become the carbon nanotube aggregate which shows. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the shape of the carbon nanotube it is sufficient that its cross section has any appropriate shape.
  • the cross section may be substantially circular, elliptical, n-gonal (n is an integer of 3 or more), and the like.
  • the length of the carbon nanotube is preferably 50 ⁇ m or more, more preferably 100 ⁇ m to 3000 ⁇ m, still more preferably 300 ⁇ m to 1500 ⁇ m, still more preferably 400 ⁇ m to 1000 ⁇ m, and particularly
  • the thickness is preferably 500 ⁇ m to 1000 ⁇ m.
  • the diameter of the carbon nanotube is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, and further preferably 2 nm to 500 nm.
  • the carbon nanotubes can have excellent mechanical properties and a high specific surface area.
  • the carbon nanotube aggregates exhibit excellent adhesive properties. Can be. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • the specific surface area and density of the carbon nanotubes can be set to any appropriate values.
  • Any appropriate method can be adopted as a method for producing a carbon nanotube aggregate.
  • a method for producing a carbon nanotube aggregate for example, a catalyst layer is formed on a smooth substrate, a carbon source is filled in a state where the catalyst is activated by heat, plasma, etc., and carbon nanotubes are grown.
  • a method of producing an aggregate of carbon nanotubes oriented almost vertically from a substrate by a vapor deposition method (Chemical Vapor Deposition: CVD method).
  • CVD method Chemical Vapor Deposition: CVD method
  • any appropriate substrate can be adopted as the substrate that can be used in the method for producing a carbon nanotube aggregate.
  • the material which has smoothness and the high temperature heat resistance which can endure manufacture of a carbon nanotube is mentioned.
  • examples of such materials include quartz glass, silicon (such as a silicon wafer), and a metal plate such as aluminum.
  • any appropriate apparatus can be adopted as an apparatus for producing the carbon nanotube aggregate.
  • a thermal CVD apparatus as shown in FIG. 2, a hot wall type configured by surrounding a cylindrical reaction vessel with a resistance heating type electric tubular furnace can be cited.
  • a heat-resistant quartz tube is preferably used as the reaction vessel.
  • Any suitable catalyst can be used as a catalyst (catalyst layer material) that can be used in the production of the carbon nanotube aggregate.
  • metal catalysts such as iron, cobalt, nickel, gold, platinum, silver, copper, are mentioned.
  • an alumina / hydrophilic film may be provided between the substrate and the catalyst layer as necessary.
  • any appropriate method can be adopted as a method for producing the alumina / hydrophilic film.
  • it can be obtained by forming a SiO 2 film on a substrate, depositing Al, and then oxidizing it by raising the temperature to 450 ° C.
  • Al 2 O 3 interacts with the SiO 2 film hydrophilic, different Al 2 O 3 surface particle diameters than those deposited Al 2 O 3 directly formed.
  • Al is deposited and heated to 450 ° C. and oxidized without forming a hydrophilic film on the substrate, Al 2 O 3 surfaces having different particle diameters may not be formed easily.
  • a hydrophilic film is prepared on a substrate and Al 2 O 3 is directly deposited, it is difficult to form Al 2 O 3 surfaces having different particle diameters.
  • the thickness of the catalyst layer that can be used in the production of the carbon nanotube aggregate is preferably 0.01 nm to 20 nm, more preferably 0.1 nm to 10 nm in order to form fine particles.
  • the formed carbon nanotubes can have both excellent mechanical properties and a high specific surface area. It can be a carbon nanotube aggregate exhibiting excellent adhesive properties. Therefore, if a sample sampling material for gas chromatography mass spectrometry having such an aggregate of carbon nanotubes is used, the peaks derived from contaminants in the mass spectrum obtained by gas chromatography mass spectrometry measurement are further reduced, and more accurate. Qualitative analysis can be performed.
  • Any appropriate method can be adopted as a method for forming the catalyst layer.
  • a method of depositing a metal catalyst by EB (electron beam), sputtering, or the like, a method of applying a suspension of metal catalyst fine particles on a substrate, and the like can be mentioned.
  • any appropriate carbon source can be used as the carbon source that can be used for the production of the carbon nanotube aggregate.
  • hydrocarbons such as methane, ethylene, acetylene, and benzene
  • alcohols such as methanol and ethanol
  • Arbitrary appropriate temperature can be employ
  • the temperature is preferably 400 ° C to 1000 ° C, more preferably 500 ° C to 900 ° C, and further preferably 600 ° C to 800 ° C. .
  • ⁇ Evaluation of the number and distribution of carbon nanotubes in a carbon nanotube aggregate The number of carbon nanotube layers and the number distribution of carbon nanotubes in the aggregate of carbon nanotubes were measured by a scanning electron microscope (SEM) and / or a transmission electron microscope (TEM). From the obtained carbon nanotube aggregate, at least 10 or more, preferably 20 or more carbon nanotubes were observed by SEM and / or TEM, the number of layers of each carbon nanotube was examined, and a layer number distribution was created.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • sample sampling method The end face of the carbon nanotube aggregate was pressure-bonded and adsorbed on the surface to which the sample was attached.
  • ⁇ Method of gas chromatography mass spectrometry> The aggregate of carbon nanotubes with the sample attached to the growth end face is peeled off from the silicon substrate or base material, cut or compressed to a size that fits into the sample cup, put into the sample cup, and then put into the pyrolyzer.
  • the gas generated in the sample was concentrated and collected on a part of the GC column with liquid nitrogen using a microjet cryotrap, and then GC / MS measurement was performed.
  • ⁇ Evaluation based on measurement results of gas chromatography mass spectrometry> Collect 50 ⁇ g of liquid paraffin with known ingredients in advance, put it in the sample cup, put the sample cup in the pyrolyzer, and use the microjet cryotrap to evacuate the gas generated at that time with liquid nitrogen. After concentration and collection in the part, GC / MS measurement was performed. Contamination was evaluated by comparing the obtained liquid paraffin peak with a foreign substance peak appearing as noise.
  • Example 1 An Al thin film (thickness 10 nm) was formed on a silicon wafer (manufactured by Silicon Technology) as a substrate by a sputtering apparatus (manufactured by ULVAC, RFS-200). On this Al thin film, an Fe thin film (thickness 1 nm) was further vapor-deposited by a sputtering apparatus (ULVAC, RFS-200). Thereafter, this substrate was placed in a 30 mm ⁇ quartz tube, and a mixed gas of helium / hydrogen (90/50 sccm) maintained at 600 ppm in water was allowed to flow through the quartz tube for 30 minutes to replace the inside of the tube.
  • a mixed gas of helium / hydrogen 90/50 sccm
  • the inside of the tube was heated to 765 ° C. using an electric tubular furnace and stabilized at 765 ° C. While maintaining the temperature at 765 ° C., the tube was filled with a mixed gas of helium / hydrogen / ethylene (85/50/5 sccm, moisture content 600 ppm) and left for 5 minutes to grow carbon nanotubes on the substrate.
  • a mixed gas of helium / hydrogen / ethylene 85/50/5 sccm, moisture content 600 ppm
  • the carbon nanotube aggregate (1) formed on the silicon substrate is peeled off from the silicon substrate, and the end face of the carbon nanotube aggregate on the silicon substrate side is pressure-bonded and fixed to the aluminum base material, so that the thickness is made of aluminum.
  • Example 2 In Example 1, except that the thickness of the Fe thin film was changed to 2 nm and the standing time was changed to 15 minutes, the same procedure as in Example 1 was performed to obtain the carbon nanotube aggregate (2) in which the carbon nanotubes were oriented in the length direction. Obtained.
  • the carbon nanotubes included in the carbon nanotube aggregate (2) had a length of 300 ⁇ m.
  • the mode value was present in three layers, and the relative frequency was 72%.
  • the carbon nanotube aggregate (2) formed on the silicon substrate is peeled off from the silicon substrate, and the end face of the carbon nanotube aggregate on the silicon substrate side is pressure-bonded and fixed to a copper base material, so that the thickness is made of copper.
  • the evaluation results are shown in Table 1.
  • Example 3 A carbon nanotube aggregate (3) in which the carbon nanotubes were oriented in the length direction was obtained in the same manner as in Example 1, except that the standing time was changed to 25 minutes.
  • the length of the carbon nanotube with which the carbon nanotube aggregate (3) is provided was 500 ⁇ m.
  • the mode value was present in two layers, and the relative frequency was 75%.
  • the carbon nanotube aggregate (3) formed on the silicon substrate is peeled off from the silicon substrate, and the end face of the carbon nanotube aggregate on the silicon substrate side is pressure-bonded to a brass SEM sample stand (Nisshin EM, ⁇ 10mm ⁇ 10mm).
  • Example 4 In Example 1, except that the thickness of the Fe thin film was changed to 2 nm and the standing time was changed to 35 minutes, the same procedure as in Example 1 was performed to obtain a carbon nanotube aggregate (4) in which the carbon nanotubes were oriented in the length direction. Obtained.
  • the carbon nanotubes included in the carbon nanotube aggregate (4) had a length of 700 ⁇ m.
  • the mode value was present in three layers, and the relative frequency was 72%.
  • the carbon nanotube aggregate (4) formed on the silicon substrate is peeled off from the silicon substrate, and the end surface of the carbon nanotube aggregate on the silicon substrate side is pressure-bonded and fixed to a SUS plate (0.5 mm), thereby fixing the SUS.
  • a sample sampling material (4) for gas chromatography mass spectrometry was obtained, in which a carbon nanotube aggregate having a length of 10 mm, a width of 10 mm, and a length of 700 ⁇ m was placed on a 0.5 mm-thick base material.
  • the evaluation results are shown in Table 1.
  • Example 5 An Al thin film (thickness 10 nm) was formed on a silicon substrate (made by KST, wafer with thermal oxide film, thickness 1000 ⁇ m) using a vacuum deposition apparatus (made by JEOL, JEE-4X Vacuum Evaporator), and then oxidized at 450 ° C. for 1 hour. Treated. In this way, an Al 2 O 3 film was formed on the silicon substrate. On this Al 2 O 3 film, an Fe thin film (thickness 2 nm) was further deposited by a sputtering apparatus (manufactured by ULVAC, RFS-200) to form a catalyst layer.
  • a sputtering apparatus manufactured by ULVAC, RFS-200
  • the obtained silicon substrate with a catalyst layer was cut and placed in a 30 mm ⁇ quartz tube, and a helium / hydrogen (120/80 sccm) mixed gas maintained at a moisture content of 350 ppm was allowed to flow into the quartz tube for 30 minutes. Was replaced. Thereafter, the inside of the tube was gradually raised to 765 ° C. in 35 minutes using an electric tubular furnace, and stabilized at 765 ° C. While maintaining the temperature at 765 ° C., a mixed gas of helium / hydrogen / ethylene (105/80/15 sccm, moisture content 350 ppm) is filled in the tube, and left for 5 minutes to grow carbon nanotubes on the substrate.
  • the carbon nanotube aggregate (5) formed on the silicon substrate is peeled off from the silicon substrate, and the end face of the carbon nanotube aggregate on the silicon substrate side is pressure-bonded to an aluminum SEM sample stage (Nisshin EM, ⁇ 10mm ⁇ 5mm).
  • Example 6 A carbon nanotube aggregate (6) in which the carbon nanotubes were oriented in the length direction was obtained in the same manner as in Example 5, except that the standing time was changed to 15 minutes.
  • the carbon nanotubes included in the carbon nanotube aggregate (6) had a length of 300 ⁇ m.
  • the distribution width of the number distribution is 17 layers (4 to 20 layers), and the mode values are present in the 4th and 8th layers.
  • the frequencies were 20% and 20%, respectively.
  • the carbon nanotube aggregate (6) formed on the silicon substrate is peeled off from the silicon substrate, and the end surface of the carbon nanotube aggregate on the silicon substrate side is pressure-bonded to a carbon SEM sample stand (Nisshin EM, ⁇ 10mm ⁇ 5mm).
  • a sample sampling material (6) for gas chromatography mass spectrometry in which a carbon nanotube aggregate having a length of 7 mm, a width of 7 mm, and a length of 300 ⁇ m is placed on a 5 mm thick base material made of carbon is used. Obtained.
  • the evaluation results are shown in Table 1.
  • Example 7 In Example 4, a carbon nanotube aggregate (7) in which the carbon nanotubes were aligned in the length direction was obtained in the same manner as in Example 4 except that the standing time was changed to 25 minutes.
  • the length of the carbon nanotube with which the carbon nanotube aggregate (7) is provided was 500 ⁇ m.
  • the distribution width of the number distribution is 17 layers (4 to 20 layers), and the mode values are present in the 4th and 8th layers.
  • the frequencies were 20% and 20%, respectively.
  • the carbon nanotube aggregate (7) formed on the silicon substrate is peeled off from the silicon substrate, and the end face of the carbon nanotube aggregate on the silicon substrate side is pressure-bonded to an aluminum SEM sample stage (Nisshin EM, ⁇ 10mm ⁇ 5mm).
  • an aluminum SEM sample stage Nishin EM, ⁇ 10mm ⁇ 5mm.
  • the sample sampling material for gas chromatography mass spectrometry of the present invention can be used for gas chromatography mass spectrometry.

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Publication number Priority date Publication date Assignee Title
WO2019151129A1 (ja) * 2018-02-02 2019-08-08 パナソニック株式会社 吸着器、濃縮器及び検出装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08501228A (ja) * 1992-08-07 1996-02-13 ジェンザイム・コーポレイション 非液体細胞試料の採取方法
JP2014126470A (ja) * 2012-12-27 2014-07-07 Nitto Denko Corp オージェ電子分光分析装置用試料固定部材

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08501228A (ja) * 1992-08-07 1996-02-13 ジェンザイム・コーポレイション 非液体細胞試料の採取方法
JP2014126470A (ja) * 2012-12-27 2014-07-07 Nitto Denko Corp オージェ電子分光分析装置用試料固定部材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019151129A1 (ja) * 2018-02-02 2019-08-08 パナソニック株式会社 吸着器、濃縮器及び検出装置

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