JP6371174B2 - How to determine the chemical state of sulfur - Google Patents
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- 229910052717 sulfur Inorganic materials 0.000 title claims description 84
- 239000011593 sulfur Substances 0.000 title claims description 84
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 82
- 239000000126 substance Substances 0.000 title claims description 32
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- 238000010521 absorption reaction Methods 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 48
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- 238000002834 transmittance Methods 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 description 20
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- 238000005259 measurement Methods 0.000 description 15
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- 238000000862 absorption spectrum Methods 0.000 description 13
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- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 10
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000002795 fluorescence method Methods 0.000 description 8
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- 238000004073 vulcanization Methods 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 4
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- 238000000691 measurement method Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920005683 SIBR Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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Description
本発明は、硫黄含有高分子複合材料における硫黄の化学状態を調べる方法に関する。 The present invention relates to a method for examining the chemical state of sulfur in a sulfur-containing polymer composite material.
ＸＡＦＳ（Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ）法は、Ｘ線を照射し、狙った原子におけるＸ線吸収量を測定する方法であり、化学状態（結合）の違いによって吸収できるＸ線エネルギーが異なるため、詳細な化学状態を調べる方法として有効である。 The XAFS (X-ray Absorption Fine Structure) method is a method of irradiating X-rays and measuring the amount of X-ray absorption in a target atom, and the X-ray energy that can be absorbed varies depending on the difference in chemical state (bonding). It is effective as a method for examining a detailed chemical state.
しかし、ゴム中の硫黄架橋の硫黄の結合の長さは、硫黄含有化合物中に内在するモノスルフィド結合、ジスルフィド結合、ポリスルフィド結合等の結合の長さと異なっているものの、スペクトルで検出されるピークエネルギーは近い。また、酸化亜鉛が配合されている硫黄と反応し、硫化亜鉛も生成される。 However, although the sulfur bond length of sulfur bridges in rubber is different from the bond length of monosulfide bonds, disulfide bonds, polysulfide bonds, etc. inherent in sulfur-containing compounds, the peak energy detected in the spectrum Is close. Moreover, it reacts with sulfur in which zinc oxide is blended to produce zinc sulfide.
このようにゴム中の硫黄の化学状態は複雑であり、硫黄含有化合物や硫化亜鉛等の他の硫黄含有成分を含まない組成物のＸＡＦＳスペクトルと比較すると、ブロードなスペクトルになってしまうため、高精度な硫黄の化学状態を調べる測定方法が求められている。 In this way, the chemical state of sulfur in the rubber is complicated, and it becomes a broad spectrum compared to the XAFS spectrum of a composition not containing other sulfur-containing components such as sulfur-containing compounds and zinc sulfide. There is a need for a measurement method that accurately examines the chemical state of sulfur.
更に特許文献１には、高分子材料に照射したＸ線の吸収量を測定し、高分子の劣化状態を解析する劣化解析方法として、酸素原子のＫ殻吸収端の全ピーク面積から、高分子材料に酸素やオゾンなどが結合した量を求める手法が提案されている。しかし、この手法でも、硫黄架橋部分のみを評価することは難しい。
Further, in
本発明は、前記課題を解決し、硫黄含有高分子複合材料中の化学状態について、精度の高い情報が得られる評価方法を提供することを目的とする。 This invention solves the said subject and aims at providing the evaluation method from which highly accurate information is obtained about the chemical state in a sulfur containing polymer composite material.
本発明は、硫黄含有高分子複合材料に、薄膜を介してＸ線を照射し、Ｘ線のエネルギーを変えながらＸ線吸収量を測定する際、入射Ｘ線強度として前記薄膜からのシグナルと、前記硫黄含有高分子複合材料からのシグナルとを同種類の検出器を用いて同時に計測することにより、硫黄の化学状態を調べる方法に関する。 When the present invention irradiates a sulfur-containing polymer composite material with X-rays through a thin film and measures the X-ray absorption amount while changing the energy of the X-ray, the signal from the thin film as the incident X-ray intensity, The present invention relates to a method for examining the chemical state of sulfur by simultaneously measuring signals from the sulfur-containing polymer composite material using the same type of detector.
上記薄膜のＸ線透過率が０．５以上であることが好ましい。 The X-ray transmittance of the thin film is preferably 0.5 or more.
上記Ｘ線を用いて走査するエネルギー範囲を２３００〜４０００ｅＶ及び／又は１００〜２８０ｅＶとすることで、硫黄Ｋ殻吸収端付近及び／又は硫黄Ｌ殻吸収端付近の硫黄のＸ線吸収量を測定することが好ましい。 By setting the energy range scanned using the X-ray to 2300 to 4000 eV and / or 100 to 280 eV, the X-ray absorption amount of sulfur near the sulfur K shell absorption edge and / or sulfur L shell absorption edge is measured. It is preferable.
前記薄膜は、２３００〜４０００ｅＶ及び／又は１００〜２８０ｅＶのエネルギー領域にＸ線吸収を持たないことが好ましい。 The thin film preferably has no X-ray absorption in the energy region of 2300 to 4000 eV and / or 100 to 280 eV.
上記Ｘ線は、光子数が１０７ｐｈｏｔｏｎｓ／ｓ以上、輝度が１０１０ｐｈｏｔｏｎｓ／ｓ／ｍｒａｄ２／ｍｍ２／０．１％ｂｗ以上であることが好ましい。 The X-ray preferably has a photon number of 10 7 photons / s or higher and a luminance of 10 10 photons / s / mrad 2 / mm 2 /0.1% bw or higher.
本発明によれば、硫黄含有高分子複合材料に、薄膜を介してＸ線を照射し、Ｘ線のエネルギーを変えながらＸ線吸収量を測定する際、入射Ｘ線強度として前記薄膜からのシグナルと、前記硫黄含有高分子複合材料からのシグナルとを同種類の検出器を用いて同時に計測することにより、硫黄の化学状態を調べる方法であるので、当該材料中の硫黄の化学状態について、精度の高い情報を得ることが可能となる。 According to the present invention, when a sulfur-containing polymer composite material is irradiated with X-rays through a thin film and the X-ray absorption is measured while changing the energy of the X-rays, the signal from the thin film is obtained as the incident X-ray intensity. And the signal from the sulfur-containing polymer composite material by simultaneously measuring the sulfur chemical state by using the same type of detector, the accuracy of the chemical state of sulfur in the material is determined. High information can be obtained.
本発明は、硫黄含有高分子複合材料（以下、単に「試料」ともいう。）に、薄膜を介してＸ線を照射し、Ｘ線のエネルギーを変えながらＸ線吸収量を測定する際、入射Ｘ線強度として前記薄膜からのシグナルと、前記硫黄含有高分子複合材料からのシグナルとを同種類の検出器を用いて同時に計測することにより、硫黄の化学状態を調べる方法である。 In the present invention, when a X-ray absorption amount is measured while irradiating a sulfur-containing polymer composite material (hereinafter, also simply referred to as “sample”) with X-rays through a thin film and changing X-ray energy, This is a method for examining the chemical state of sulfur by simultaneously measuring the signal from the thin film and the signal from the sulfur-containing polymer composite material as the X-ray intensity using the same type of detector.
硫黄含有高分子複合材料にＸ線を照射し、Ｘ線のエネルギーを変えながらＸ線吸収量を測定して硫黄の化学状態を調べる方法において、（１）同一光源のＸ線を薄膜を介して試料に照射し、入射Ｘ線を薄膜に、該薄膜を透過したＸ線を試料に同時に照射すること、（２）入射Ｘ線を薄膜に照射することにより得られるシグナルと、該薄膜を透過したＸ線を試料に照射することにより得られるシグナルとを、同種類の検出器を用いて同時に計測すること、により、正確な化学状態が調べられる。従って、例えば、前記方法を用いたＸＡＦＳ法で試料のＸ線吸収量を測定すると、ＸＡＮＥＳ領域だけでなく、精密な測定が困難なＥＸＡＦＳ領域でも精度良く計測できる。 In a method of examining the chemical state of sulfur by irradiating a sulfur-containing polymer composite material with X-rays and measuring the X-ray absorption while changing the energy of the X-rays, (1) X-rays from the same light source are passed through a thin film. Irradiating the sample, irradiating the sample with incident X-rays, and simultaneously irradiating the sample with X-rays transmitted through the thin film; (2) signals transmitted by irradiating the thin film with incident X-rays and transmitted through the thin film By measuring simultaneously the signals obtained by irradiating the sample with X-rays using the same type of detector, the exact chemical state can be examined. Therefore, for example, when the X-ray absorption amount of a sample is measured by the XAFS method using the above method, it is possible to measure not only in the XANES region but also in the EXAFS region where precise measurement is difficult.
硫黄含有高分子複合材料としては、硫黄を含む高分子材料であれば特に限定されず、例えば、従来公知の硫黄含有ゴム組成物を使用でき、例えば、硫黄加硫剤等の硫黄含有化合物、ゴム成分、他の配合材料を含むゴム組成物などが挙げられる。 The sulfur-containing polymer composite material is not particularly limited as long as it is a polymer material containing sulfur. For example, a conventionally known sulfur-containing rubber composition can be used. For example, a sulfur-containing compound such as a sulfur vulcanizing agent, rubber Examples thereof include rubber compositions containing components and other compounding materials.
硫黄含有化合物としては、例えば、粉末硫黄、沈降硫黄、コロイド硫黄、不溶性硫黄、高分散性硫黄などの硫黄加硫剤等が挙げられる。 Examples of the sulfur-containing compound include sulfur vulcanizing agents such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur.
ゴム成分としては、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、ブチルゴム（ＩＩＲ）、ハロゲン化ブチルゴム（Ｘ−ＩＩＲ）、スチレンイソプレンブタジエンゴム（ＳＩＢＲ）などのジエン系ゴムなどが挙げられる。また、ゴム成分は、水酸基、アミノ基などの変性基を１つ以上含むものでもよい。 As rubber components, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), halogenated Examples thereof include diene rubbers such as butyl rubber (X-IIR) and styrene isoprene butadiene rubber (SIBR). The rubber component may contain one or more modifying groups such as hydroxyl groups and amino groups.
更にゴム成分としては、前記ゴム成分と１種類以上の樹脂とが複合された複合材料も使用できる。上記樹脂としては特に限定されず、例えば、ゴム工業分野で汎用されているものが挙げられ、例えば、Ｃ５系脂肪族石油樹脂、シクロペンタジエン系石油樹脂などの石油樹脂が挙げられる。 Furthermore, as the rubber component, a composite material in which the rubber component and one or more kinds of resins are combined can also be used. The resin is not particularly limited, and examples thereof include those widely used in the rubber industry field, and examples thereof include petroleum resins such as C5 aliphatic petroleum resins and cyclopentadiene petroleum resins.
硫黄含有高分子複合材料には、カーボンブラック、シリカなどの充填剤、シランカップリング剤、酸化亜鉛、ステアリン酸、老化防止剤、ワックス、オイル、硫黄以外の加硫剤、加硫促進剤等、従来公知のゴム分野の配合物を適宜配合してもよい。このようなゴム材料（ゴム組成物）は、公知の混練方法などを用いて製造できる。このようなゴム材料としては、例えば、タイヤ用ゴム材料（タイヤ用ゴム組成物）などが挙げられる。 Sulfur-containing polymer composite materials include carbon black, silica and other fillers, silane coupling agents, zinc oxide, stearic acid, anti-aging agents, waxes, oils, vulcanizing agents other than sulfur, vulcanization accelerators, etc. A conventionally known compound in the rubber field may be appropriately compounded. Such a rubber material (rubber composition) can be produced using a known kneading method or the like. Examples of such rubber materials include tire rubber materials (tire rubber compositions).
本発明の方法に供される薄膜としては、金属薄膜、窒化ケイ素の薄膜、コロジオン等のポリマー薄膜等が挙げられ、なかでも、本発明の効果が充分に得られる点で、金属薄膜が好ましい。 Examples of the thin film used in the method of the present invention include a metal thin film, a silicon nitride thin film, a polymer thin film such as collodion, and the like. Among these, a metal thin film is preferable in that the effect of the present invention can be sufficiently obtained.
上記薄膜としては、測定するエネルギー範囲にＸ線吸収を持たない薄膜であることが好ましい。例えば、硫黄Ｋ殻吸収端付近（２３００〜４０００ｅＶ）、硫黄Ｌ殻吸収端付近（１００〜２８０ｅＶ）の測定を行う場合、このエネルギー領域に吸収を持たない薄膜を好適に使用できる。金属薄膜であれば、アルミニウム（Ａｌ）を好適に使用できる。 The thin film is preferably a thin film having no X-ray absorption in the energy range to be measured. For example, when measuring near the sulfur K shell absorption edge (2300 to 4000 eV) and near the sulfur L shell absorption edge (100 to 280 eV), a thin film having no absorption in this energy region can be suitably used. If it is a metal thin film, aluminum (Al) can be used conveniently.
上記薄膜のＸ線透過率は０．５以上であることが好ましく、０．７以上であることがより好ましい。Ｘ線透過率は、薄膜の種類や厚みによって異なるため、適宜適当な種類を選定し、上記Ｘ線透過率となるように、厚み等を調整する必要がある。例えば、アルミニウム箔の厚みであれば、図３に示すＸ線透過率から、厚み１μｍ以下であることが好ましい。 The X-ray transmittance of the thin film is preferably 0.5 or more, and more preferably 0.7 or more. Since the X-ray transmittance varies depending on the type and thickness of the thin film, it is necessary to appropriately select an appropriate type and adjust the thickness and the like so that the X-ray transmittance is obtained. For example, if it is the thickness of an aluminum foil, it is preferable that it is 1 micrometer or less in thickness from the X-ray transmittance shown in FIG.
上記金属薄膜としては、上記のように、任意の金属を任意の厚みに調整した薄膜を用いることができるが、上記のような金属箔が存在しない場合や作製が困難な場合は、窒化ケイ素の薄膜などの自立膜に金属の蒸着を施した金属蒸着膜を金属薄膜として用いても構わない。金属蒸着を施す方法としては、真空蒸着法、スパッタリング法等の公知の方法を挙げることができる。 As the metal thin film, as described above, a thin film prepared by adjusting an arbitrary metal to an arbitrary thickness can be used. However, when the metal foil as described above is not present or difficult to produce, silicon nitride is used. A metal vapor-deposited film obtained by depositing metal on a free-standing film such as a thin film may be used as the metal thin film. Examples of a method for performing metal vapor deposition include known methods such as vacuum vapor deposition and sputtering.
前記のとおり、本発明は、前記硫黄含有高分子複合材料に、前記薄膜を介してＸ線を照射し、Ｘ線のエネルギーを変えながらＸ線吸収量を測定する際、入射Ｘ線強度として前記薄膜からのシグナルと、前記硫黄含有高分子複合材料からのシグナルとを同種類の検出器を用いて同時に計測することにより、硫黄の化学状態を調べる方法であり、例えば、ＸＡＦＳ（Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ：吸収端近傍Ｘ線吸収微細構造）測定の実施により、Ｘ線吸収量を測定できる。 As described above, in the present invention, when the X-ray absorption amount is measured while irradiating the sulfur-containing polymer composite material with X-rays through the thin film and changing the energy of the X-rays, This is a method for examining the chemical state of sulfur by simultaneously measuring a signal from a thin film and a signal from the sulfur-containing polymer composite material using the same type of detector. For example, XAFS (X-ray Absorption) By performing Fine Structure (X-ray absorption fine structure near absorption edge) measurement, the X-ray absorption amount can be measured.
ＸＡＦＳは、一般的に、吸収端（吸収が立ち上がるエネルギー）から５０ｅＶ位までのピークが出現する領域をＸＡＮＥＳ（Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｎｅａｒ Ｅｄｇｅ Ｓｔｒｕｃｔｕｒｅ）領域、それよりも高エネルギーの緩やかな振動成分が出現する領域をＥＸＡＦＳ（Ｅｘｔｅｎｄｅｄ Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ）領域と呼ぶ。ＥＸＡＦＳ領域における該振動はＥＸＡＦＳ振動と呼ばれるが、硫黄などの軽元素は隣接する原子との吸収端のエネルギーが近いため、従来の方法ではＥＸＡＦＳ振動を検出することは困難であった。 In XAFS, generally, the region where the peak from the absorption edge (energy at which absorption rises) to about 50 eV appears is the XANES (X-ray Absorption Near Edge Structure) region, and a gentle vibration component with higher energy appears. The area to be called is called an EXAFS (Extended X-ray Absorption Fine Structure) area. The vibration in the EXAFS region is called EXAFS vibration. However, since light elements such as sulfur have close energy at the absorption edge with adjacent atoms, it is difficult to detect the EXAFS vibration with the conventional method.
ＸＡＮＥＳ領域は、試料に狙った原子の吸収端近傍のＸ線を照射した際、内殻準位にいた電子が励起状態に遷移するため、狙った原子がどのような原子と結合しているか（化学状態）がわかる。一方、ＥＸＡＦＳ領域は、内殻電子が原子核の束縛を離れ、光電子として飛び出す。その際、光電子は波として表されるため、近くに他の原子がいる場合には、波が干渉して返ってくる。そのため、中心原子の周囲の原子数、原子種、原子間距離等の情報が得られる。一般にＸＡＮＥＳ領域では、各結合に対応するピークを分離することで、測定した物質において、どの結合がどの程度かを知ることができる。なお、本発明は、ＸＡＮＥＳ領域、ＥＸＡＦＳ領域共に有効である。 In the XANES region, when the sample is irradiated with X-rays near the absorption edge of the target atom, electrons in the core level transition to an excited state, so what kind of atom the target atom is bonded to ( Chemical state). On the other hand, in the EXAFS region, inner-shell electrons leave the nucleus and are ejected as photoelectrons. At that time, since photoelectrons are represented as waves, if there are other atoms nearby, the waves interfere and return. Therefore, information such as the number of atoms around the central atom, atomic species, and interatomic distance can be obtained. In general, in the XANES region, by separating the peaks corresponding to each bond, it is possible to know which bond and how much in the measured substance. The present invention is effective for both the XANES region and the EXAFS region.
硫黄加硫剤等の硫黄含有化合物を用いたゴム材料をはじめとする硫黄を含有する高分子複合材料の化学状態を調べる方法として、硫黄Ｋ殻吸収端付近におけるＸＡＦＳ法が挙げられるが、以下のような透過法、蛍光法、電子収量法などが汎用されている。 As a method for examining the chemical state of a polymer composite material containing sulfur such as a rubber material using a sulfur-containing compound such as a sulfur vulcanizing agent, there is the XAFS method in the vicinity of the sulfur K-shell absorption edge. Such transmission method, fluorescence method, electron yield method and the like are widely used.
（透過法）
試料を透過してきたＸ線強度を検出する方法である。透過光強度測定には、フォトダイオードアレイ検出器などが用いられる。
(Transmission method)
This is a method for detecting the X-ray intensity transmitted through a sample. For measurement of transmitted light intensity, a photodiode array detector or the like is used.
（蛍光法）
試料にＸ線を照射した際に発生する蛍光Ｘ線を検出する方法である。検出器は、Ｌｙｔｌｅ検出器、半導体検出器などがある。前記透過法の場合、試料中の含有量が少ない元素のＸ線吸収測定を行うと、シグナルが小さい上に含有量の多い元素のＸ線吸収によりバックグラウンドが高くなるためＳ／Ｂ比の悪いスペクトルとなる。それに対し蛍光法（特にエネルギー分散型検出器などを用いた場合）では、目的とする元素からの蛍光Ｘ線のみを測定することが可能であるため、含有量が多い元素の影響が少ない。そのため、含有量が少ない元素のＸ線吸収スペクトル測定を行う場合に有効的である。また、蛍光Ｘ線は透過力が強い（物質との相互作用が小さい）ため、試料内部で発生した蛍光Ｘ線を検出することが可能となる。そのため、本手法は透過法に次いでバルク情報を得る方法として最適である。
(Fluorescence method)
This is a method for detecting fluorescent X-rays generated when a sample is irradiated with X-rays. Examples of the detector include a Lytle detector and a semiconductor detector. In the case of the transmission method, when X-ray absorption measurement of an element having a small content in a sample is performed, the background is increased due to the X-ray absorption of an element having a small content and a large content, so that the S / B ratio is poor. It becomes a spectrum. On the other hand, in the fluorescence method (especially when an energy dispersive detector or the like is used), it is possible to measure only the fluorescent X-rays from the target element, so that the influence of the element having a large content is small. Therefore, it is effective when measuring an X-ray absorption spectrum of an element having a small content. In addition, since fluorescent X-rays have strong penetrating power (low interaction with substances), it is possible to detect fluorescent X-rays generated inside the sample. Therefore, this method is the most suitable method for obtaining bulk information after the transmission method.
（電子収量法）
試料にＸ線を照射した際に流れる電流を検出する方法である。そのため試料が導電物質である必要がある。また、表面敏感（試料表面の数ｎｍ程度の情報）であるという特徴もある。試料にＸ線を照射すると元素から電子が脱出するが、電子は物質との相互作用が強いため、物質中での平均自由行程が短い。
(Electron yield method)
This is a method for detecting a current flowing when a sample is irradiated with X-rays. Therefore, the sample needs to be a conductive material. In addition, there is a feature that the surface is sensitive (information about several nm on the sample surface). When the sample is irradiated with X-rays, electrons escape from the element, but electrons have a strong interaction with the substance, so that the mean free path in the substance is short.
このように、透過法は、ＸＡＦＳの基本的な測定方法で、入射光強度と試料を透過したＸ線強度を検出してＸ線吸収量を測定する方法であるため、試料のバルク情報が得られ、対象化合物が一定以上の濃度（例えば、数ｗｔ％以上）でなければ測定が困難という特徴がある。また、高分子材料中の硫黄に対する炭素の割合が大きいため、炭素の吸収が大きくバックグラウンドとして検出されるため、Ｓ／Ｎ比が悪く、硫黄の感度が下がってしまう問題がある。電子収量法は、表面敏感な方法であり、試料表面の数十ｎｍ程度の情報が得られる。しかし、比較的エネルギーが高いため、Ｘ線の侵入深さが大きくなると同時に表面へ電子が流れにくくなり、シグナルが弱くなる問題がある。一方、蛍光法は、電子収量法に比べて表面からある程度深い部分からの情報が得られるという特徴と、対象化合物濃度が低くても測定できるという特徴がある。本発明では、蛍光法が好適に用いられる。 As described above, the transmission method is a basic measurement method of XAFS, and is a method of detecting the incident light intensity and the X-ray intensity transmitted through the sample and measuring the X-ray absorption amount. In other words, it is difficult to measure unless the target compound has a certain concentration (eg, several wt% or more). In addition, since the ratio of carbon to sulfur in the polymer material is large, carbon absorption is large and detected as a background, so that there is a problem that the S / N ratio is poor and the sensitivity of sulfur is lowered. The electron yield method is a surface-sensitive method, and information on the surface of a sample of about several tens of nanometers can be obtained. However, since the energy is relatively high, there is a problem that the X-ray penetration depth increases and at the same time, electrons do not easily flow to the surface and the signal becomes weak. On the other hand, the fluorescence method has the characteristics that information from a part deeper than the surface can be obtained compared to the electron yield method, and the measurement can be performed even when the concentration of the target compound is low. In the present invention, the fluorescence method is preferably used.
ここで、蛍光法について、具体的に以下説明する。
蛍光法とは、試料にＸ線を照射した際に発生する蛍光Ｘ線をモニタリングする方法であり、Ｘ線吸収量と蛍光Ｘ線の強度に比例関係があることを用いて、蛍光Ｘ線の強度からＸ線吸収量を間接的に求める方法となる。蛍光法を行う場合、電離箱を用いた方法とＳＤＤ（シリコンドリフト検出器）やＳＳＤ（シリコンストリップ検出器）などの半導体検出器を用いることが多い。電離箱では比較的簡便に測定ができるが、エネルギー分別が困難なことと、試料からの散乱Ｘ線や対象元素以外の蛍光Ｘ線が入ってしまうためバックグランドを上げてしまうことがあり、試料と検出器間にソーラースリットやフィルターを設置する必要がある。ＳＤＤやＳＳＤを用いた場合、好感度でかつ、エネルギー分別が可能であるため、目的元素からの蛍光Ｘ線のみを取り出すことができ、Ｓ／Ｂ比よく測定することが可能となる。
Here, the fluorescence method will be specifically described below.
The fluorescence method is a method for monitoring fluorescent X-rays generated when a sample is irradiated with X-rays, and uses the fact that there is a proportional relationship between the amount of X-ray absorption and the intensity of fluorescent X-rays. This is a method of indirectly obtaining the X-ray absorption amount from the intensity. When performing the fluorescence method, a method using an ionization chamber and a semiconductor detector such as an SDD (silicon drift detector) or an SSD (silicon strip detector) are often used. The ionization chamber can be measured relatively easily, but the background may be raised due to the difficulty of energy separation and scattered X-rays from the sample and fluorescent X-rays other than the target element. It is necessary to install a solar slit or filter between the detector and the detector. When SDD or SSD is used, the sensitivity is good and the energy can be separated, so that only fluorescent X-rays from the target element can be taken out and measurement can be performed with a high S / B ratio.
しかし、例えば、ＸＡＦＳ測定を用いる場合、測定時刻によって入射Ｘ線強度が変化するため、それに起因するバラつきを抑えるには、同一光源のＸ線を用いて同時に測定することが望ましい。このような手法として、入射Ｘ線強度をＡｕメッシュや集光ミラーに流れた電流量を用いて測定するとともに、試料の蛍光Ｘ線強度をフォトダイオードやＳＤＤ（シリコンドリフト検出器）を用いて測定する方法が検討されているが、別々の検出器で測定すると、図１のように、検出器の違いによる検出効率の差が生じ、精度の高い化学状態を得ることが困難である。 However, for example, when XAFS measurement is used, since the incident X-ray intensity changes depending on the measurement time, it is desirable to simultaneously measure using X-rays of the same light source in order to suppress variations caused by the measurement. As such a method, the incident X-ray intensity is measured using the amount of current flowing through the Au mesh or the collecting mirror, and the fluorescent X-ray intensity of the sample is measured using a photodiode or an SDD (silicon drift detector). However, when measuring with separate detectors, a difference in detection efficiency due to the difference in detectors occurs as shown in FIG. 1, making it difficult to obtain a highly accurate chemical state.
これに対し、本発明は、図２の概念図に示すとおり、光源（入射Ｘ線）と試料との間に薄膜を介させて測定することで、該薄膜からのシグナル（蛍光Ｘ線強度等）と、試料からのシグナル（蛍光Ｘ線強度等）とを同種類の検出器を用いて同時に計測することが可能となる。従って、硫黄含有高分子複合材料中の硫黄の化学状態について、より精度の高い情報が得られるものである。 On the other hand, as shown in the conceptual diagram of FIG. 2, the present invention measures the signal (fluorescent X-ray intensity, etc.) from the thin film by measuring through a thin film between the light source (incident X-ray) and the sample. ) And signals from the sample (fluorescent X-ray intensity, etc.) can be simultaneously measured using the same type of detector. Therefore, more accurate information can be obtained about the chemical state of sulfur in the sulfur-containing polymer composite material.
なお、ＸＡＦＳ法は、Ｘ線エネルギーで走査するため光源には連続Ｘ線発生装置が必要であり、詳細な化学状態を解析するには高いＳ／Ｎ比及びＳ／Ｂ比のＸ線吸収スペクトルを測定する必要がある。そのため、シンクロトロンから放射されるＸ線は、少なくとも１０１０（ｐｈｏｔｏｎｓ／ｓ／ｍｒａｄ２／ｍｍ２／０．１％ｂｗ）以上の輝度を有し、且つ連続Ｘ線源であるため、ＸＡＦＳ測定には最適である。尚、ｂｗはシンクロトロンから放射されるＸ線のｂａｎｄ ｗｉｄｔｈを示す。 In the XAFS method, a continuous X-ray generator is required for the light source to scan with X-ray energy, and an X-ray absorption spectrum with a high S / N ratio and S / B ratio is required to analyze a detailed chemical state. Need to be measured. Therefore, the X-ray emitted from the synchrotron has a luminance of at least 10 10 (photons / s / mrad 2 / mm 2 /0.1% bw) or more and is a continuous X-ray source. Ideal for. Note that bw represents the band width of X-rays emitted from the synchrotron.
上記Ｘ線の輝度（ｐｈｏｔｏｎｓ／ｓ／ｍｒａｄ２／ｍｍ２／０．１％ｂｗ）は、好ましくは１０１０以上、より好ましくは１０１１以上である。上限は特に限定されないが、放射線ダメージがない程度以下のＸ線強度を用いることが好ましい。 The X-ray luminance (photons / s / mrad 2 / mm 2 /0.1% bw) is preferably 10 10 or more, more preferably 10 11 or more. Although an upper limit is not specifically limited, It is preferable to use the X-ray intensity below the extent that there is no radiation damage.
また、上記Ｘ線の光子数（ｐｈｏｔｏｎｓ／ｓ）は、好ましくは１０７以上、より好ましくは１０９以上である。上限は特に限定されないが、放射線ダメージがない程度以下のＸ線強度を用いることが好ましい。 Further, the number of photons (photons / s) of the X-ray is preferably 10 7 or more, more preferably 10 9 or more. Although an upper limit is not specifically limited, It is preferable to use the X-ray intensity below the extent that there is no radiation damage.
上記Ｘ線を用いて走査するエネルギー範囲としては、（１）２３００〜４０００ｅＶ、（２）１００〜２８０ｅＶの範囲が好適である。上記範囲を走査することで、それぞれ、硫黄Ｋ殻吸収端付近、硫黄Ｌ殻吸収端付近の硫黄のＸ線吸収量を測定でき、材料中の硫黄の化学状態の情報が得られる。（１）の範囲の場合、より好ましくは２３５０〜３５００ｅＶであり、（２）の範囲の場合、より好ましくは１５０〜２６０ｅＶである。 The energy range scanned using the X-ray is preferably (1) 2300 to 4000 eV and (2) 100 to 280 eV. By scanning the above ranges, the X-ray absorption amount of sulfur near the sulfur K shell absorption edge and the sulfur L shell absorption edge can be measured, respectively, and information on the chemical state of sulfur in the material can be obtained. In the case of (1), it is more preferably 2350-3500 eV, and in the case of (2), more preferably 150-260 eV.
本発明は、入射Ｘ線強度を照射した薄膜から得られるシグナル、該薄膜を透過したＸ線を試料に照射して得られるシグナルを同種類の検出器を用いて同時に計測する方法であるが、検出器としては特に限定されず、フォトダイオード、ＳＤＤ等、公知のものを使用可能である。本発明では、同種類の検出器を用いて同種類のシグナルが測定され、例えば、薄膜からのシグナルとして蛍光Ｘ線を測定する場合、試料からのシグナルとしても蛍光Ｘ線を測定する。 The present invention is a method of simultaneously measuring a signal obtained from a thin film irradiated with incident X-ray intensity and a signal obtained by irradiating a sample with X-rays transmitted through the thin film using the same type of detector, The detector is not particularly limited, and a known one such as a photodiode or SDD can be used. In the present invention, the same type of signal is measured using the same type of detector. For example, when fluorescent X-ray is measured as a signal from a thin film, the fluorescent X-ray is also measured as a signal from a sample.
前記のとおり、硫黄含有高分子複合材料に、薄膜を介してＸ線を照射し、Ｘ線のエネルギーを変えながらＸ線吸収量を測定する際、入射Ｘ線強度として前記薄膜からのシグナルと、前記硫黄含有高分子複合材料からのシグナルとを同種類の検出器を用いて同時に計測することで、試料中の硫黄の正確な化学状態を解析できるものであるが、以下、更に具体的に説明する。 As described above, when the X-ray absorption amount is measured while irradiating the sulfur-containing polymer composite material through the thin film and changing the energy of the X-ray, the signal from the thin film as the incident X-ray intensity, By simultaneously measuring the signal from the sulfur-containing polymer composite material using the same type of detector, the exact chemical state of sulfur in the sample can be analyzed. To do.
図４は、後述する実施例、比較例１〜２の試料をＸＡＦＳ測定して得られた硫黄原子のＫ殻吸収端付近におけるＸ線吸収スペクトル、図５は、そのＸ線吸収スペクトルを拡大したスペクトルを示す。 4 shows an X-ray absorption spectrum in the vicinity of the K-shell absorption edge of sulfur atoms obtained by XAFS measurement of the samples of Examples and Comparative Examples 1 and 2 described later, and FIG. 5 shows an enlarged X-ray absorption spectrum. The spectrum is shown.
実施例については、図２の概略図に示す装置を用いて、（１）同一光源のＸ線を薄膜を介して試料に照射し、入射Ｘ線を薄膜に、該薄膜を透過したＸ線を試料に同時に照射すること、（２）入射Ｘ線を薄膜に照射することにより得られる蛍光Ｘ線（シグナル）と、該薄膜を透過したＸ線を試料に照射することにより得られる蛍光Ｘ線（シグナル）とを、ＳＤＤ等の同種類の検出器を用いて同時に計測すること、により、Ｘ線吸収スペクトルを得る。具体的には、薄膜のシグナルから得られる入射Ｘ線強度及び該薄膜のＸ線透過率を用いて得られる薄膜を透過したＸ線の強度と、それを照射して得られる試料のシグナルとをもとに、図４〜５の実施例のＸ線吸収スペクトルが得られる。 For the embodiment, using the apparatus shown in the schematic diagram of FIG. 2, (1) the sample is irradiated with X-rays from the same light source through a thin film, incident X-rays are turned into a thin film, and X-rays transmitted through the thin film are (2) X-ray fluorescence (signal) obtained by irradiating a thin film with incident X-rays and X-ray fluorescence obtained by irradiating the specimen with X-rays transmitted through the thin film ( Signal) is simultaneously measured using the same type of detector such as SDD to obtain an X-ray absorption spectrum. Specifically, the incident X-ray intensity obtained from the signal of the thin film and the intensity of the X-ray transmitted through the thin film obtained using the X-ray transmittance of the thin film, and the signal of the sample obtained by irradiating the X-ray Based on the X-ray absorption spectra of the examples of FIGS.
一方、比較例１のＸ線吸収スペクトルは、Ｘ線をアルミニウム板に照射してシグナルを計測し、入射Ｘ線強度を測定すること、Ｘ線を試料に照射してシグナルを計測すること、を別途実施し、得られた入射Ｘ線強度、試料のシグナルをもとにして作製される。比較例２のＸ線吸収スペクトルは、図２の装置において、薄膜に代えてアルミニウムのメッシュを用い、該メッシュのシグナルから得られる入射Ｘ線強度、試料のシグナルをもとにして作製される。 On the other hand, the X-ray absorption spectrum of Comparative Example 1 is to measure the signal by irradiating the aluminum plate with X-ray, measure the incident X-ray intensity, and measure the signal by irradiating the sample with X-ray. Separately, it is produced based on the incident X-ray intensity and the sample signal obtained. The X-ray absorption spectrum of Comparative Example 2 is prepared based on the incident X-ray intensity obtained from the mesh signal and the sample signal, using an aluminum mesh instead of the thin film in the apparatus of FIG.
図５のＸＡＮＥＳ領域を比較すると、実施例に比べ、比較例１、２は、共に２４７２ｅＶ付近に見られるピークが小さくつぶれたようになっていることが分かる。また、図４の実施例のスペクトルでは、２５７０ｅＶ以降に、うねうねとしたＥＸＡＦＳ振動が見られるが、比較例１、２は、共にＥＸＡＦＳ振動がはっきり見られない。このように、本発明の実施例の方法を用いることで、比較例１、２に比べ、精度良く測定できる。これは、比較例では、同時計測できないことで生じた時間による入射Ｘ線強度の変化由来の誤差、ドレイン電流とＳＤＤ検出器の検出感度の違い由来の誤差、がスペクトルに追加されているのに対し、実施例では、そのような誤差が存在しないため、より正確なスペクトルが得られているものと推察される。 Comparing the XANES region of FIG. 5, it can be seen that the peaks seen in the vicinity of 2472 eV are smaller in both Comparative Examples 1 and 2 than in the Example. In addition, in the spectrum of the example of FIG. 4, the undulating EXAFS vibration is seen after 2570 eV, but the EXAFS vibration is not clearly seen in both Comparative Examples 1 and 2. Thus, by using the method of the example of the present invention, it is possible to measure with higher accuracy than in Comparative Examples 1 and 2. This is because, in the comparative example, an error due to a change in incident X-ray intensity due to time that cannot be simultaneously measured, an error due to a difference in drain current and detection sensitivity of the SDD detector, are added to the spectrum. On the other hand, in the embodiment, since such an error does not exist, it is assumed that a more accurate spectrum is obtained.
以上のとおり、本発明の方法を採用することにより、硫黄含有高分子複合材料中の硫黄の化学状態に関する情報を精度よく得ることが可能となる。 As described above, by adopting the method of the present invention, it becomes possible to accurately obtain information on the chemical state of sulfur in the sulfur-containing polymer composite material.
実施例に基づいて、本発明を具体的に説明するが、本発明はこれらのみに限定されるものではない。 The present invention will be specifically described based on examples, but the present invention is not limited to these examples.
＜実施例及び比較例＞
（ゴム材料）
以下の配合内容に従い、硫黄及び加硫促進剤以外の材料を充填率が５８％になるように（株）神戸製鋼所製の１．７Ｌバンバリーミキサーに充填し、８０ｒｐｍで１４０℃に到達するまで混練した（工程１）。工程１で得られた混練物に、硫黄及び加硫促進剤を以下の配合にて添加し、１６０℃で２０分間加硫することでゴム材料を得た（工程２）。
<Examples and Comparative Examples>
(Rubber material)
In accordance with the following blending contents, materials other than sulfur and vulcanization accelerator were charged into a 1.7 L Banbury mixer manufactured by Kobe Steel Co., Ltd. so that the filling rate was 58%, and until reaching 140 ° C. at 80 rpm. Kneaded (Step 1). Sulfur and a vulcanization accelerator were added to the kneaded material obtained in
（配合）
天然ゴム５０質量部、ブタジエンゴム５０質量部、カーボンブラック６０質量部、オイル５質量部、老化防止剤２質量部、ワックス２．５質量部、酸化亜鉛３質量部、ステアリン酸２質量部、粉末硫黄１．２質量部、及び加硫促進剤１質量部。
なお、使用材料は以下のとおりである。
天然ゴム：ＴＳＲ２０
ブタジエンゴム：宇部興産（株）製ＢＲ１５０Ｂ
カーボンブラック：キャボットジャパン（株）製のショウブラックＮ３５１
オイル：（株）ジャパンエナジー製のプロセスＸ−１４０
老化防止剤：大内新興化学工業（株）製のノクラック６Ｃ（Ｎ−１，３−ジメチルブチル−Ｎ’−フェニル−ｐ−フェニレンジアミン）
ワックス：日本精蝋（株）製のオゾエース０３５５
酸化亜鉛：東邦亜鉛（株）製の銀嶺Ｒ
ステアリン酸：日油（株）製の椿
粉末硫黄（５％オイル含有）：鶴見化学工業（株）製の５％オイル処理粉末硫黄（オイル分５質量％含む可溶性硫黄）
加硫促進剤：大内新興化学工業（株）製のノクセラーＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド）
(Combination)
Natural rubber 50 parts by mass, butadiene rubber 50 parts by mass, carbon black 60 parts by mass, oil 5 parts by mass, anti-aging agent 2 parts by mass, wax 2.5 parts by mass, zinc oxide 3 parts by mass, stearic acid 2 parts by mass, powder 1.2 parts by mass of sulfur and 1 part by mass of vulcanization accelerator.
The materials used are as follows.
Natural rubber: TSR20
Butadiene rubber: BR150B manufactured by Ube Industries, Ltd.
Carbon Black: Show Black N351 manufactured by Cabot Japan
Oil: Process X-140 manufactured by Japan Energy Co., Ltd.
Anti-aging agent: NOCRACK 6C (N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Wax: Ozoace 0355 manufactured by Nippon Seiwa Co., Ltd.
Zinc oxide: Silver candy R made by Toho Zinc Co., Ltd.
Stearic acid: Koji powder sulfur manufactured by NOF Corporation (containing 5% oil): 5% oil-treated powder sulfur manufactured by Tsurumi Chemical Co., Ltd. (soluble sulfur containing 5% by mass of oil)
Vulcanization accelerator: Noxeller CZ (N-cyclohexyl-2-benzothiazylsulfenamide) manufactured by Ouchi Shinsei Chemical Co., Ltd.
以下の実施例、比較例１、２において、作製したゴム材料の硫黄Ｋ殻吸収端近傍におけるＸＡＦＳ測定を実施し、ＸＡＦＳスペクトルを得た。なお、薄膜には、厚み２００ｎｍの窒化ケイ素製のメンブレンの上に２００ｎｍのアルミニウムを蒸着した金属蒸着膜を用いた。 In the following examples and comparative examples 1 and 2, XAFS measurement was performed in the vicinity of the sulfur K-shell absorption edge of the produced rubber material, and an XAFS spectrum was obtained. In addition, the metal vapor deposition film which vapor-deposited 200 nm aluminum on the 200-nm-thick silicon nitride membrane was used for the thin film.
＜ＸＡＦＳ測定＞
各試料について、ＸＡＦＳを使用して、Ｘ線吸収スペクトルを得た。
（使用装置）
ＸＡＦＳ：ＳＰｒｉｎｇ−８ ＢＬ２７ＳＵのＢブランチのＸＡＦＳ測定装置
（測定条件）
輝度：１×１０１６ｐｈｏｔｏｎｓ／ｓ／ｍｒａｄ２／ｍｍ２／０．１％ｂｗ
光子数：５×１０１０ｐｈｏｔｏｎｓ／ｓ
分光器：結晶分光器
エネルギー範囲：２３６０〜３５００ｅＶ
<XAFS measurement>
For each sample, an X-ray absorption spectrum was obtained using XAFS.
(Device used)
XAFS: SPring-8 BL27SU B-branch XAFS measurement system (measurement conditions)
Luminance: 1 × 10 16 photons / s / mrad 2 / mm 2 /0.1% bw
Number of photons: 5 × 10 10 photons / s
Spectrometer: Crystal spectrometer Energy range: 2360-3500 eV
（実施例）
図２の装置構成に従って、上記薄膜を試料の上流側に設置して、ＸＡＦＳ測定を実施した。具体的には、上記エネルギー範囲の同一光源のＸ線を薄膜を介して試料に照射し、入射Ｘ線を薄膜に、該薄膜を透過したＸ線を試料に同時に照射することで、入射Ｘ線を薄膜に照射することにより得られる蛍光Ｘ線と、該薄膜を透過したＸ線を試料に照射することにより得られる蛍光Ｘ線とを、ＳＤＤ（シリコンドリフト検出器）を用いて同時に測定し、得られた入射Ｘ線強度及び試料から得られる蛍光Ｘ線強度をもとに、試料のＸ線吸収スペクトルを得た。
(Example)
According to the apparatus configuration of FIG. 2, the thin film was placed on the upstream side of the sample, and XAFS measurement was performed. Specifically, the sample is irradiated with X-rays of the same light source in the above energy range through a thin film, incident X-rays are irradiated onto the thin film, and X-rays transmitted through the thin film are simultaneously irradiated onto the sample. X-ray fluorescence obtained by irradiating a thin film with X-rays and X-ray fluorescence obtained by irradiating the sample with X-rays transmitted through the thin film are simultaneously measured using an SDD (silicon drift detector), An X-ray absorption spectrum of the sample was obtained based on the obtained incident X-ray intensity and the fluorescent X-ray intensity obtained from the sample.
（比較例１）
Ｘ線を１ｍｍのアルミニウム板に照射して蛍光Ｘ線を計測し、入射Ｘ線強度を測定すること、Ｘ線を試料に照射して蛍光Ｘ線を計測すること、を別途実施し、得られた入射Ｘ線強度、試料から得られる蛍光Ｘ線強度をもとに、試料のＸ線吸収スペクトルを得た。上記２つの蛍光Ｘ線の強度は共にＳＤＤにより計測した。
(Comparative Example 1)
It is obtained by separately performing irradiation of X-rays onto a 1 mm aluminum plate to measure fluorescent X-rays, measuring incident X-ray intensity, and irradiating the sample with X-rays to measure fluorescent X-rays. Based on the incident X-ray intensity and the fluorescent X-ray intensity obtained from the sample, an X-ray absorption spectrum of the sample was obtained. Both intensities of the two fluorescent X-rays were measured by SDD.
（比較例２）
上記薄膜の代わりに、アルミニウムのメッシュを用いて、該メッシュに流れた電流をＡＤＣＭＴデジタルエレクトロメータ８２４０（（株）エーディーシー製）で計測して、入射Ｘ線強度を測定した以外は、上記実施例と同様の方法で、試料のＸ線吸収スペクトルを得た。
(Comparative Example 2)
The above implementation was performed except that an aluminum mesh was used instead of the thin film, and the current flowing through the mesh was measured with an ADMT digital electrometer 8240 (manufactured by ADC Corporation) to measure the incident X-ray intensity. An X-ray absorption spectrum of the sample was obtained in the same manner as in the example.
図４、５に示されているように、入射Ｘ線強度と試料からのシグナルとを、薄膜を用いて同種類の検出器により同時に測定した実施例、同種類の検出器により別途測定した比較例１、及び別々の検出器により同時に測定した比較例２の硫黄Ｋ殻ＸＡＦＳスペクトルを対比すると、薄膜を用いて同種類の検出器により同時に測定した場合、スペクトルがシャープで、精度が高められた。従って、薄膜を用いて、入射Ｘ線強度と試料からのシグナルとを、同種類の検出器により同時に測定することで、硫黄の化学状態を精度よく測定でき、本発明の評価法の有効性が立証された。 As shown in FIGS. 4 and 5, an example in which the incident X-ray intensity and the signal from the sample were simultaneously measured by the same type of detector using a thin film, and a comparison separately measured by the same type of detector. When comparing the sulfur K-shell XAFS spectrum of Example 1 and Comparative Example 2 measured simultaneously with separate detectors, the spectrum was sharp and the accuracy was improved when measured simultaneously with the same type of detector using a thin film. . Therefore, by using a thin film and simultaneously measuring the incident X-ray intensity and the signal from the sample with the same type of detector, the chemical state of sulfur can be measured with high accuracy, and the effectiveness of the evaluation method of the present invention is improved. Proven.
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