JP3327052B2 - Method and apparatus for measuring impurity element in polymer material - Google Patents
Method and apparatus for measuring impurity element in polymer materialInfo
- Publication number
- JP3327052B2 JP3327052B2 JP13296595A JP13296595A JP3327052B2 JP 3327052 B2 JP3327052 B2 JP 3327052B2 JP 13296595 A JP13296595 A JP 13296595A JP 13296595 A JP13296595 A JP 13296595A JP 3327052 B2 JP3327052 B2 JP 3327052B2
- Authority
- JP
- Japan
- Prior art keywords
- soft
- ray
- rays
- wavelength
- measured
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002861 polymer material Substances 0.000 title claims description 28
- 239000012535 impurity Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 10
- 239000000463 material Substances 0.000 claims description 42
- 229920000642 polymer Polymers 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 22
- 229910052717 sulfur Inorganic materials 0.000 description 22
- 239000011593 sulfur Substances 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000010409 thin film Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002083 X-ray spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Analysing Materials By The Use Of Radiation (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高分子体中の不純物元
素、例えば、硫黄、ナトリウムやカルシウム等を測定す
るための測定方法および装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for measuring impurity elements in a polymer, for example, sulfur, sodium and calcium.
【０００２】[0002]
【従来の技術】近年、生体観察を目的として、特開平３
−２４６５００号公報、篠原邦夫：レーザー研究第１８
巻第１１号等に見られるように、軟Ｘ線領域の波長の軟
Ｘ線を用いた軟Ｘ線顕微鏡の開発が行われている。この
軟Ｘ線顕微鏡は、光源から発した軟Ｘ線を物体に照射
し、この物体を透過した光を軟Ｘ線検出器で検出するこ
とにより、物体内部の組成の違いによる軟Ｘ線透過率の
違いを利用して物体の内部組織等の観察を行うものであ
る。2. Description of the Related Art Recently, Japanese Patent Laid-Open Publication No.
-246500, Kunio Shinohara: Laser Research 18th
As described in Vol. 11, etc., a soft X-ray microscope using soft X-rays having a wavelength in the soft X-ray region has been developed. This soft X-ray microscope irradiates an object with soft X-rays emitted from a light source, and detects light transmitted through the object with a soft X-ray detector, thereby obtaining a soft X-ray transmittance due to a difference in composition inside the object. Is used to observe the internal structure of an object or the like using the difference.
【０００３】軟Ｘ線の光源としては放射光（シンクロト
ロン光）とレーザープラズマ軟Ｘ線光源があるが、レー
ザープラズマ軟Ｘ線は輝度の高いパルス軟Ｘ線光源であ
るため生体の動的観察が可能であると期待されている。
このようなレーザープラズマ軟Ｘ線を用いる軟Ｘ線顕微
鏡システムとしては、主として、２次元軟Ｘ線検出器と
被測定材を密着させ、この被測定材に軟Ｘ線を照射し、
検出された軟Ｘ線像を光学顕微鏡、電子顕微鏡、原子間
力顕微鏡等で拡大観察する密着型の軟Ｘ線顕微鏡があ
る。[0003] As soft X-ray light sources, there are synchrotron radiation and laser plasma soft X-ray light source. However, laser plasma soft X-ray is a pulse soft X-ray light source with high brightness, so that dynamic observation of a living body is possible. Is expected to be possible.
As a soft X-ray microscope system using such a laser plasma soft X-ray, mainly, a two-dimensional soft X-ray detector is brought into close contact with a material to be measured, and the material to be measured is irradiated with soft X-rays.
There is a contact-type soft X-ray microscope in which a detected soft X-ray image is observed under magnification by an optical microscope, an electron microscope, an atomic force microscope, or the like.
【０００４】この軟Ｘ線顕微鏡は、現在、生体観察に利
用するべく検討されている。生体観察に利用するために
は、いわゆる「水の窓」波長域（２．５〜４．３ｎｍ）
の軟Ｘ線を用いる必要があり、その波長域の選択窓を得
るために回折格子、フィルター、多層膜およびゾーンプ
レート等が検討され、これらの幾つかを組合せることに
より「水の窓」波長域の軟Ｘ線を得てきた。この波長域
の軟Ｘ線を用いることにより水分と水分以外の物質の軟
Ｘ線透過率の違いを利用して水溶液中で活動するバクテ
リア、細胞等の観察や生体内に多く含まれる水分以外の
構造物、組織の観察が可能になる。[0004] This soft X-ray microscope is currently being studied for use in living body observation. For use in living body observation, the so-called “water window” wavelength range (2.5 to 4.3 nm)
It is necessary to use soft X-rays, and a diffraction grating, a filter, a multilayer film, a zone plate, etc. are studied in order to obtain a selection window of the wavelength range. Soft X-rays in the region. The use of soft X-rays in this wavelength range allows observation of bacteria and cells that are active in an aqueous solution by utilizing the difference in soft X-ray transmittance between water and substances other than water, and other than water that is often contained in a living body. Observation of structures and tissues becomes possible.
【０００５】[0005]
【発明が解決しようとする課題】高分子材料や高分子膜
の改良・開発、特性評価には高分子材料の内部組織や構
成元素の分布状況を把握することが重要となる。しか
し、水分をあまり含まない高分子材料に対しては高分子
を形成する元素によるコントラストが必要となり、前記
「水の窓」波長域（２．５〜４．３ｎｍ）の軟Ｘ線によ
る観察は効果的でない。In order to improve, develop, and evaluate the properties of a polymer material and a polymer film, it is important to understand the internal structure of the polymer material and the distribution of constituent elements. However, for a polymer material that does not contain much water, contrast by the element forming the polymer is necessary, and observation with soft X-rays in the above-mentioned “water window” wavelength range (2.5 to 4.3 nm) is difficult. Not effective.
【０００６】また、近年、酸性雨等により高分子材料の
劣化が問題となっている。高分子材料内に侵入した不純
物、特に降雨によって高分子材料内に侵入する酸、アル
カリ等を観察する手段として光学顕微鏡、ＥＰＭＡ、Ｓ
ＥＭによる観察が行われている。光学顕微鏡では、高分
子材料自体に形状変化（表面）や大きな屈折率変化およ
び吸収率変化（内部）がない場合には侵入物の分布や存
在を確認することは困難である。In recent years, deterioration of polymer materials due to acid rain or the like has become a problem. Optical microscopy, EPMA, S
Observation by EM is performed. With an optical microscope, it is difficult to confirm the distribution and presence of an intruder if the polymer material itself does not have a shape change (surface) or a large change in refractive index and change in absorption (inside).
【０００７】また、ＥＰＭＡ、ＳＥＭでは、高真空中で
高分子材料に電子ビームを照射するため測定時に組成変
化や形状変化を起こし同じ高分子材料の経時変化を観察
できない。また、特定元素の分布を調べるには多くの時
間と労力が必要となる。本発明は、上記問題を解決する
もので、高分子膜等の高分子材料中の不純物元素、例え
ば、硫黄、ナトリウムやカルシウム等を分析するための
高分子材料中の不純物元素の測定方法および装置を提供
することを目的とする。Further, in EPMA and SEM, since a polymer material is irradiated with an electron beam in a high vacuum, a change in composition or a change in shape occurs at the time of measurement, so that a change over time of the same polymer material cannot be observed. In addition, much time and effort are required to examine the distribution of a specific element. The present invention solves the above problems, and a method and apparatus for measuring an impurity element in a polymer material for analyzing a polymer element such as a polymer film, for example, sulfur, sodium, and calcium. The purpose is to provide.
【０００８】[0008]
【課題を解決するための手段】発明者は、上記問題を解
決するために、従来の光学顕微鏡とは異なる波長の光で
ある軟Ｘ線光源となるレーザープラズマ軟Ｘ線を用いた
軟Ｘ線顕微鏡に注目した。しかし、従来の軟Ｘ線顕微鏡
では、特に「水の窓」波長域（２．５〜４．３ｎｍ）に
注目されている。この波長の軟Ｘ線は水に対して透明で
炭素を含む生体には透明でないため、水中の生体を観察
するには適している。しかし、この「水の窓」波長域の
軟Ｘ線は生体を含む高分子材料中の硫黄、ナトリウム、
カルシウム、ケイ素、アルミニウム等はほとんど炭素と
同程度に不透明である。このため高分子材料中の硫黄、
ナトリウム、カルシウム等の分布を観察することはでき
ない。In order to solve the above-mentioned problems, the present inventor has proposed a soft X-ray using a laser plasma soft X-ray which is a soft X-ray light source having a wavelength different from that of a conventional optical microscope. Attention was paid to the microscope. However, in the conventional soft X-ray microscope, attention is particularly paid to the wavelength range of “water window” (2.5 to 4.3 nm). Since soft X-rays of this wavelength are transparent to water and not transparent to living bodies containing carbon, they are suitable for observing living bodies in water. However, soft X-rays in this “water window” wavelength range are produced by sulfur, sodium,
Calcium, silicon, aluminum, etc. are almost as opaque as carbon. Therefore, sulfur in the polymer material,
The distribution of sodium, calcium, etc. cannot be observed.
【０００９】そこで高分子を構成する元素である炭素、
水素、窒素、酸素に対しては透明で、硫黄、ナトリウ
ム、カルシウム等には不透明な軟Ｘ線を用いて高分子材
料中の硫黄、ナトリウム、カルシウム等の観察を行うこ
とを思いついた。そしてこれら高分子材料を構成する元
素および不純物元素の原子散乱因子から各波長の軟Ｘ線
に対する吸収係数を算出し、高分子の構成元素を含む硫
黄、ナトリウム、カルシウム等の各波長毎の吸収率を比
較することにより波長４．４〜６ｎｍの軟Ｘ線を光源と
して用いることが最適であることを見出した。Therefore, carbon, which is an element constituting a polymer,
The inventors came up with the idea of observing sulfur, sodium, calcium and the like in a polymer material using soft X-rays which are transparent to hydrogen, nitrogen and oxygen and opaque to sulfur, sodium and calcium. Then, the absorption coefficient for each wavelength of soft X-rays is calculated from the atomic scattering factors of the elements and impurity elements constituting these polymer materials, and the absorptance for each wavelength of sulfur, sodium, calcium, etc. containing the constituent elements of the polymer is calculated. Was found to be optimal to use a soft X-ray having a wavelength of 4.4 to 6 nm as a light source.
【００１０】そして、波長４．４〜６ｎｍの軟Ｘ線を光
源として用いることにより高分子を構成する炭素の透過
率が高くなることと酸性雨等を構成する硫黄、ナトリウ
ムやカルシウム等の透過率が低くなること、すなわち透
過率の違いによって硫黄、ナトリウム、カルシウム等を
含有する高分子材料を軟Ｘ線が透過したときに高分子材
料中の硫黄、ナトリウムやカルシウム等の分布が像とし
て観察できる高分子材料中の不純物元素の測定方法およ
び装置を創出した。By using soft X-rays having a wavelength of 4.4 to 6 nm as a light source, the transmittance of carbon constituting the polymer is increased, and the transmittance of sulfur, sodium, calcium and the like constituting acid rain and the like is increased. That is, the distribution of sulfur, sodium, calcium, etc. in the polymer material can be observed as an image when soft X-rays pass through the polymer material containing sulfur, sodium, calcium, etc. due to the difference in transmittance. A method and apparatus for measuring impurity elements in polymer materials have been created.
【００１１】即ち、本発明の高分子材料中の不純物元素
の測定方法は、高分子材料よりなる被測定材に４．４〜
６ｎｍの波長の軟Ｘ線を照射する照射工程と、該被測定
材を透過した４．４〜６ｎｍの波長の軟Ｘ線を検出する
ための軟Ｘ線検出工程とからなり、該被測定材中の原子
番号１１〜３０の不純物を測定することを特徴とする。
また、本発明の高分子材料中の不純物元素の測定装置
は、レーザー発生手段と、軟Ｘ線を発生させるためのタ
ーゲットと、この軟Ｘ線から４．４〜６ｎｍの波長を選
択するためのフィルタと、高分子材料よりなる被測定材
を透過した４．４〜６ｎｍの波長の軟Ｘ線を検出するた
めの軟Ｘ線検出手段と、を有し、該被測定材中の原子番
号１１〜３０の不純物を測定することを特徴とする。That is, the method for measuring an impurity element in a polymer material according to the present invention employs a method for measuring an impurity element in a polymer material in a range of 4.4 to 4.0.
An irradiation step of irradiating the soft X-ray of 6nm wavelength, Ri Do from the soft X-ray detection step for detecting the soft X-ray wavelength of 4.4~6nm transmitted through the該被measuring material,該被measurement Atoms in wood
It is characterized in that impurities of numbers 11 to 30 are measured .
Further, the apparatus for measuring an impurity element in a polymer material according to the present invention includes a laser generating means, a target for generating soft X-rays, and a wavelength for selecting a wavelength of 4.4 to 6 nm from the soft X-rays. filter and, possess a soft X-ray detecting means for detecting the soft X-ray wavelength of 4.4~6nm transmitted through the measured material made of polymer material, the atomic number of該被measured material in
It is characterized in that impurities of Nos. 11 to 30 are measured .
【００１２】本発明の照射工程は、高分子材料よりなる
被測定材に４．４〜６ｎｍの波長の軟Ｘ線を照射する工
程である。被測定材となる高分子材料としては、通常の
炭化水素よりなる有機高分子をマトリックスとする材料
である。炭化水素に、酸素、窒素を含むものでもよい。
例えば、ＡＢＳ樹脂や塩化ビニル等の構造用プラスチッ
ク、塗膜等が対象となる。被測定材の厚さは、サブミク
ロン〜数１０ミクロンがよい。サブミクロンより薄いと
組織（元素の種類や密度）の差によるコントラストが得
にくく、逆に、数１０μｍより厚いと軟Ｘ線の透過量が
全体的に少なくなるため組織が見えにくくなるという問
題がある。The irradiation step of the present invention is a step of irradiating a soft X-ray having a wavelength of 4.4 to 6 nm to a material to be measured made of a polymer material. The polymer material to be measured is a material having an organic polymer made of a normal hydrocarbon as a matrix. The hydrocarbon may contain oxygen and nitrogen.
For example, structural plastics such as ABS resin and vinyl chloride, and coating films are applicable. The thickness of the material to be measured is preferably from submicron to several tens of microns. If the thickness is smaller than submicron, it is difficult to obtain contrast due to the difference in the structure (the type and density of elements). On the other hand, if the thickness is larger than several tens of μm, the amount of transmitted soft X-rays is reduced as a whole. is there.
【００１３】照射工程には、軟Ｘ線発生手段と、この軟
Ｘ線から４．４〜６ｎｍの波長を選択するためのフィル
タを使用する。軟Ｘ線発生手段としては、従来と同様
に、放射光（シンクロトロン光）を発生するシンクロト
ロン、レーザープラズマ軟Ｘ線発生装置を使用できる。
特にレーザープラズマ軟Ｘ線発生装置はレーザー発生手
段と、軟Ｘ線を発生させるためのターゲットとで構成で
き、簡易である。さらにレーザープラズマ軟Ｘ線発生装
置では、輝度の高いパルス軟Ｘ線光を発生でき、被測定
材の動的観察が可能となる。In the irradiation step, a soft X-ray generating means and a filter for selecting a wavelength of 4.4 to 6 nm from the soft X-ray are used. As the soft X-ray generating means, a synchrotron for generating radiation light (synchrotron light) and a laser plasma soft X-ray generator can be used as in the conventional case.
Particularly, the laser plasma soft X-ray generator can be constituted by a laser generating means and a target for generating soft X-rays, and is simple. Furthermore, the laser plasma soft X-ray generator can generate pulsed soft X-ray light with high luminance, and enables dynamic observation of the material to be measured.
【００１４】レーザー発生手段としては、１０9 Ｗ／ｃ
ｍ2 以上の照射強度を達成できるという条件を充足する
装置ならば特に限定はなく、例えば、ＹＡＧレーザー、
ガスレーザー、エキシマレーザー、炭酸ガスレーザーを
用いることができる。また、ターゲットとしては、原子
番号が６〜４０の元素を主成分とするものを用いること
ができる。その理由は、照射強度１０9 〜１０13Ｗ／ｃ
ｍ2 以上において少なくとも波長４ｎｍ以上において充
分な光量を有する軟Ｘ線を発生させることが可能である
ためである。なお、ターゲツトとしては、充分な光量を
必要とするため、常温下で密度が大きい固体状態のもの
がよい。具体的には、グラファイト、マグネシウム、ア
ルミニウム、シリコン、チタン、マンガン、鉄、ニッケ
ル、コバルト、銅、亜鉛、ゲルマニウム、が適してい
る。As a laser generating means, 10 9 W / c
There is no particular limitation as long as the device satisfies the condition that an irradiation intensity of at least m 2 can be achieved .
Gas lasers, excimer lasers, can be used carbon dioxide gas laser. As the target, a target containing an element having an atomic number of 6 to 40 as a main component can be used. The reason is that the irradiation intensity is 10 9 to 10 13 W / c.
This is because it is possible to generate a soft X-ray having a sufficient light amount at least at a wavelength of 4 nm or more at m 2 or more. Since a sufficient amount of light is required as the target, a solid state having a high density at room temperature is preferable. Specifically, graphite, magnesium, aluminum, silicon, titanium, manganese, iron, nickel, cobalt, copper, zinc, and germanium are suitable.
【００１５】また、フィルターとしては、４．４〜６ｎ
ｍの波長を選択可能な材料から構成されるものであれば
限定はない。その理由は、フィルターとして使用可能な
材料は、その波長選択の特性だけで選ばれているからで
ある。具体的には、少なくとも炭素を含有する高分子、
グラファイト、ダイヤモンド等から構成されているもの
を使用することができる。また、フィルターの厚さは、
０．１〜２０μｍがよい。この範囲の厚さであれば、高
分子の観察に必要とする軟Ｘ線の波長に対する透過率を
１０-1〜１０-20 程度に調整できるからである。また、
フィルターは２種類組み合わせて用いてもよい。さら
に、被測定材が可視光に対し透明な場合は、可視光をカ
ットするフィルター、例えばアルミニウム等を用いるこ
とが好ましい。Further, as a filter, 4.4-6n
There is no limitation as long as it is made of a material capable of selecting a wavelength of m. The reason for this is that the material that can be used as a filter is selected solely based on its wavelength selection characteristics. Specifically, a polymer containing at least carbon,
Those composed of graphite, diamond and the like can be used. Also, the thickness of the filter is
0.1-20 μm is preferred. This is because if the thickness is in this range, the transmittance for the wavelength of the soft X-ray required for observing the polymer can be adjusted to about 10 -1 to 10 -20 . Also,
The filters may be used in combination of two types. Further, when the material to be measured is transparent to visible light, it is preferable to use a filter for cutting visible light, for example, aluminum or the like.
【００１６】軟Ｘ線検出工程は被測定材を透過した４．
４〜６ｎｍの波長の軟Ｘ線を検出する工程である。この
軟Ｘ線検出手段としては、数十ミクロン以下の空間分解
能を有し、波長４．４〜６ｎｍの軟Ｘ線に感度を有する
装置ならば特に限定はなく、例えば、マイクロチャンネ
ルプレート（ＭＣＰ）、ＣＣＤカメラ等の固体検出器や
イメージプレートやレジスト、軟Ｘ線乾板あるいはフィ
ルムを用いることができる。なお、軟Ｘ線検出工程で
４．４〜６ｎｍの波長の軟Ｘ線を検出するため、軟Ｘ線
検出手段の前で４．４〜６ｎｍ以外の波長を取り除く必
要がある。従って、これら不要の波長の軟Ｘ線を取り除
くフィルターは被測定材と軟Ｘ線検出手段の間に配置す
ることもできる。In the soft X-ray detecting step, the light transmitted through the material to be measured.
This is a step of detecting soft X-rays having a wavelength of 4 to 6 nm. The soft X-ray detecting means is not particularly limited as long as it has a spatial resolution of several tens of microns or less and is sensitive to soft X-rays having a wavelength of 4.4 to 6 nm. For example, a microchannel plate (MCP) , it can be used CC D camera etc. solid state detector or an image plate or a resist, the soft X-ray dry plate or film. In order to detect soft X-rays having a wavelength of 4.4 to 6 nm in the soft X-ray detecting step, it is necessary to remove wavelengths other than 4.4 to 6 nm before the soft X-ray detecting means. Therefore, a filter for removing soft X-rays of these unnecessary wavelengths can be arranged between the material to be measured and the soft X-ray detecting means.
【００１７】[0017]
【作用・効果】高分子材料よりなる被測定材に４．４〜
６ｎｍの波長の軟Ｘ線を照射する。この４．４〜６ｎｍ
の波長の軟Ｘ線は、被測定材の主構成元素である、炭
素、水素、酸素により吸収されない、そして被測定材中
の原子番号が１１〜３０の不純物元素により吸収され
る。従って被測定材を透過した４．４〜６ｎｍの波長の
軟Ｘ線は被測定材中の原子番号が１１〜３０の不純物元
素の存在位置および量により濃度が異なりコントラスト
ができる。このコントラストを軟Ｘ線検出工程で検出す
る。これにより被測定材中の不純物元素の存在位置と存
在量が測定できる。[Function / Effect] 4.4 ~
Irradiate soft X-rays with a wavelength of 6 nm. This 4.4 to 6 nm
Is not absorbed by the main constituent elements of the material to be measured, carbon, hydrogen and oxygen, and is absorbed by the impurity element having an atomic number of 11 to 30 in the material to be measured. Therefore, the soft X-rays having a wavelength of 4.4 to 6 nm transmitted through the material to be measured have different concentrations depending on the locations and amounts of the impurity elements having atomic numbers of 11 to 30 in the material to be measured, and a contrast can be obtained. This contrast is detected in a soft X-ray detection step. As a result, the position and amount of the impurity element in the material to be measured can be measured.
【００１８】照射工程で使用するレーザー発生手段はレ
ーザーをターゲット上に照射する。これによりターゲッ
トが加熱され軟Ｘ線を発生する。この軟Ｘ線はフイルタ
ーを通過することにより４．４〜６ｎｍの波長の軟Ｘ線
となる。この軟Ｘ線が被測定材を通過し、被測定材中の
原子番号が１１〜３０の不純物元素の存在位置および量
に応じて吸収され軟Ｘ線にコントラストが生ずる。この
コントラストが軟Ｘ線検出工程で検出され、これにより
被測定材中の不純物元素の存在位置と存在量が測定され
る。[0018] The laser generating means to be used in the irradiation process Les
The irradiated on the target Za. As a result, the target is heated to generate soft X-rays. This soft X-ray passes through a filter and becomes a soft X-ray having a wavelength of 4.4 to 6 nm. The soft X-rays pass through the material to be measured, and are absorbed in accordance with the position and amount of the impurity element having an atomic number of 11 to 30 in the material to be measured, and contrast is generated in the soft X-rays. This contrast is detected in the soft X-ray detection step, whereby the position and amount of the impurity element in the material to be measured are measured.
【００１９】フイルターとして炭素を含有する高分子、
グラファイト、ダイヤモンドを用いると容易に４．４〜
６ｎｍの波長の軟Ｘ線を得ることができる。すなわち、
炭素を透過する軟Ｘ線は、炭素により４．４〜６ｎｍの
波長の軟Ｘ線以外の波長の軟Ｘ線が効率的に吸収され、
４．４〜６ｎｍの波長の軟Ｘ線が透過できるからであ
る。A polymer containing carbon as a filter,
4.4 or more easily when using graphite and diamond
Soft X-rays having a wavelength of 6 nm can be obtained. That is,
As for soft X-rays that pass through carbon, soft X-rays having wavelengths other than soft X-rays having a wavelength of 4.4 to 6 nm are efficiently absorbed by carbon,
This is because soft X-rays having a wavelength of 4.4 to 6 nm can be transmitted.
【００２０】本発明の高分子材料中の不純物元素の測定
方法および装置は、サブミクロンから数１０ミクロン厚
さの高分子材料や高分子膜等の高分子体の主成分である
炭素を比較的良く透過する波長４．４〜６ｎｍの軟Ｘ線
を用いているので、高分子体にダメージを与えることな
く高分子体中の原子番号が１１〜３０の硫黄、カルシウ
ム、ナトリウム等の高分子体の成分でない元素の分布お
よびその濃度測定を可能とする。その結果、例えば高分
子体への酸性雨成分元素の浸透し易さ、凝集し易さ等の
評価手段等に利用することができる。The method and apparatus for measuring an impurity element in a polymer material according to the present invention uses a relatively large amount of carbon, which is a main component of a polymer such as a polymer material or a polymer film having a thickness of submicron to several tens of microns. Since soft X-rays having a wavelength of 4.4 to 6 nm that transmit well are used, a polymer such as sulfur, calcium, or sodium having an atomic number of 11 to 30 in the polymer without damaging the polymer. Enables the measurement of the distribution of the element that is not a component and the concentration of the element. As a result, for example, it can be used as a means for evaluating the ease of infiltration and aggregation of the acid rain component element into the polymer.
【００２１】[0021]
【実施例】以下、実施例に基づき本発明を詳細に説明す
る。 （実施例１）図１は本発明の高分子材料中の不純物元素
の測定装置の概略構成を示した図である。この装置はＹ
ＡＧレーザー装置１、集光レンズ２、真空窓４をもつ真
空容器９、この真空容器９内に保持されたターゲット３
および試料台１０とからなる。この試料台１０には被測
定材である高分子薄膜６が載置され、その高分子薄膜６
の上にフイルターを構成する薄膜５が配置されている。
また、真空容器９内は真空ポンプ（図示せず）によって
減圧されている。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments. (Embodiment 1) FIG. 1 is a view showing a schematic configuration of an apparatus for measuring an impurity element in a polymer material according to the present invention. This device is Y
An AG laser device 1, a condenser lens 2, a vacuum container 9 having a vacuum window 4, and a target 3 held in the vacuum container 9.
And a sample table 10. A polymer thin film 6 which is a material to be measured is placed on the sample stage 10, and the polymer thin film 6
The thin film 5 constituting the filter is disposed on the filter.
The pressure inside the vacuum vessel 9 is reduced by a vacuum pump (not shown).
【００２２】この装置では、ＹＡＧレーザー装置１から
のレーザー光をレンズ２で集光し、鉄で構成されたター
ゲット３に照射する。このターゲット３上の集光径（直
径）は４０〜３０μｍ以下になるようにした。したがっ
て、レンズ２や真空窓４による表面反射を考慮すると鉄
ターゲット３上でのレーザー光の照射強度は１０11〜１
０13Ｗ／ｃｍ2 となる。これにより鉄ターゲット２にレ
ーザープラズマ軟Ｘ線を発生させることができる。鉄タ
ーゲット２から発生したレーザープラズマ軟Ｘ線はフィ
ルターである厚さ３μｍのポリプロピレン膜に０．１μ
ｍのアルミニウムを蒸着した薄膜５に照射し、透過させ
る。これにより波長４．４〜６ｎｍの軟Ｘ線８のみが薄
膜５を透過する。この薄膜５を透過した軟Ｘ線８が被測
定材である高分子薄膜６を照射し、高分子薄膜６を透過
し軟Ｘ線検出手段７を構成する軟Ｘ線用乾板もしくは軟
Ｘ線用フィルム、レジスト材等に露光する。In this apparatus, laser light from a YAG laser apparatus 1 is condensed by a lens 2 and irradiated on a target 3 made of iron. The condensing diameter (diameter) on the target 3 was set to 40 to 30 μm or less. Therefore, in consideration of the surface reflection by the lens 2 and the vacuum window 4, the irradiation intensity of the laser beam on the iron target 3 is 10 11 to 1
0 13 W / cm 2 . As a result, laser plasma soft X-rays can be generated on the iron target 2. The laser plasma soft X-rays generated from the iron target 2 are applied to a 3 μm thick polypropylene film as a filter by 0.1 μm.
The thin film 5 on which m of aluminum is deposited is irradiated and transmitted. Thereby, only the soft X-rays 8 having a wavelength of 4.4 to 6 nm pass through the thin film 5. The soft X-rays 8 transmitted through the thin film 5 irradiate a polymer thin film 6 as a material to be measured, and pass through the polymer thin film 6 to form a soft X-ray dry plate or a soft X-ray. Exposure to film, resist material, etc.
【００２３】波長４．４〜６ｎｍの軟Ｘ線８が、高分子
薄膜６を透過する過程で高分子薄膜６の内部組織に含ま
れる原子番号が１１〜３０の不純物元素の存在位置およ
び量に応じて吸収され、軟Ｘ線にコントラストが生ず
る。このコントラストが軟Ｘ線像として軟Ｘ線検出手段
７に撮影される。これにより高分子薄膜６の内部組織が
観察できる。When the soft X-rays 8 having a wavelength of 4.4 to 6 nm pass through the polymer thin film 6, the positions and amounts of impurity elements having atomic numbers 11 to 30 contained in the internal structure of the polymer thin film 6 are determined. Accordingly, contrast is generated in the soft X-ray. This contrast is captured by the soft X-ray detecting means 7 as a soft X-ray image. Thereby, the internal structure of the polymer thin film 6 can be observed.
【００２４】この装置の鉄ターゲット２から発生した軟
Ｘ線のスペクトルを斜入射型回折格子分光器を用いて測
定した結果を図２に示す。このスペクトルからわかるよ
うに、波長４〜１２ｎｍの輝度の高い軟Ｘ線スペクトル
となっている。この軟Ｘ線スペクトルは、鉄ターゲット
２に対する照射強度を１０11〜１０13Ｗ／ｃｍ2 として
いるため、主として鉄の５価から１２価のイオンからの
軟Ｘ線スペクトルとなったものと思われる。FIG. 2 shows the result of measuring the spectrum of soft X-rays generated from the iron target 2 of this apparatus using a grazing incidence type diffraction grating spectroscope. As can be seen from this spectrum, the soft X-ray spectrum has a high luminance at a wavelength of 4 to 12 nm. The soft X-ray spectrum is believed for the illumination intensity to iron target 2 is set to 10 11 ~10 13 W / cm 2 , which mainly consisted of pentavalent iron soft X-ray spectra from 12-valent ions .
【００２５】この軟Ｘ線をフィルターを構成する薄膜５
に照射し、薄膜５を透過した軟Ｘ線スペクトルを図３に
示す。本実施例で使用したアルミニウムを蒸着したポリ
プロピレンの薄膜からなるフイルターは、図３に示すよ
うに、波長４．４〜６ｎｍの軟Ｘ線のみとなっている。
この装置を用い、被測定材として膜厚１０μｍのポリエ
チレンテレフタレート（ＰＥＴ）に８５重量％の硫酸水
を３０秒付着させ、水洗して表面の硫酸を除去した試料
を用いて実験を行った。レーザーの照射回数は１０００
回、軟Ｘ線検出器としてホロテストフィルム（レジスト
材）を使用した。また、光源から被測定材までの距離は
１１ｃｍとした。これにより図４に示すＸ線写真像を得
た。このＸ線写真像は被測定材に残存する硫酸中の硫黄
元素の存在位置と濃度とを見ているもので、硫黄元素が
波長４．５ｎｍ付近に高い吸収係数を持つため、硫黄を
介して被測定材の組織観察が可能となるものである。This soft X-ray is applied to a thin film 5 constituting a filter.
FIG. 3 shows a soft X-ray spectrum transmitted through the thin film 5. As shown in FIG. 3, the filter made of a thin film of polypropylene deposited with aluminum used in the present example is only soft X-rays having a wavelength of 4.4 to 6 nm.
Using this apparatus, an experiment was performed using a sample in which 85% by weight of sulfuric acid was adhered to polyethylene terephthalate (PET) having a film thickness of 10 μm as a material to be measured for 30 seconds and washed with water to remove sulfuric acid on the surface. Laser irradiation frequency is 1000
A holotest film (resist material) was used as a soft X-ray detector. The distance from the light source to the material to be measured was 11 cm. As a result, an X-ray photographic image shown in FIG. 4 was obtained. This X-ray photograph looks at the position and concentration of sulfur element in the sulfuric acid remaining in the material to be measured. Since the sulfur element has a high absorption coefficient at a wavelength of about 4.5 nm, the X-ray image passes through sulfur. The structure of the material to be measured can be observed.
【００２６】なお、図４のＸ線写真像と比較のために、
可視光による光学顕微鏡像を図５に示す。この図５の可
視光の像では、表面のエッチングだけが観察されてい
る。これに対して図４の軟Ｘ線像には硫黄の分布が明瞭
に観察される。次に、被測定材として膜厚７．５μｍの
ポリイミド中の硫黄の分布の経時変化の観察を行なっ
た。図６は、ポリイミドに硫黄を付着させ、水洗した直
後に前記したのと同じ条件で軟Ｘ線によるＸ線写真像を
得たものである。図７は図６の被測定材をさらに室内で
１０日間放置した後、同じ部分を前記したのと同じ条件
で軟Ｘ線によるＸ線写真像を得たものである。図６およ
び図７の白っぽい部分が硫黄の存在を示している。図７
の１０日間放置後の像では硫黄が凝集し、その部分を起
点として割れが発生しているのがわかる。これによりポ
リイミドの割れの原因が明瞭に硫黄の凝集によるもので
あると結論づけることができる。For comparison with the X-ray image shown in FIG.
An optical microscope image using visible light is shown in FIG. In the visible light image of FIG. 5, only surface etching is observed. On the other hand, the distribution of sulfur is clearly observed in the soft X-ray image of FIG. Next, a time-dependent change in the distribution of sulfur in a 7.5 μm-thick polyimide as a material to be measured was observed. FIG. 6 shows an X-ray photographic image obtained by soft X-rays under the same conditions as described above immediately after sulfur was attached to polyimide and washed with water. FIG. 7 shows an X-ray photographic image of soft X-rays on the same portion under the same conditions as described above after the material to be measured of FIG. 6 was further left indoors for 10 days. The whitish portions in FIGS. 6 and 7 indicate the presence of sulfur. FIG.
In the image after standing for 10 days, it can be seen that sulfur has agglomerated and cracks have occurred starting from that portion. Thus, it can be concluded that the cause of the polyimide crack is clearly due to sulfur aggregation.
【図１】本発明の実施例の高分子材料中の不純物元素の
測定装置の概略構成を示す概略図である。FIG. 1 is a schematic diagram showing a schematic configuration of an apparatus for measuring an impurity element in a polymer material according to an embodiment of the present invention.
【図２】実施例の鉄ターゲットから発生した軟Ｘ線のス
ペクトルを示す図である。FIG. 2 is a diagram showing a spectrum of soft X-rays generated from an iron target of an example.
【図３】実施例のフィルターを透過した軟Ｘ線のスペク
トルを示す図である。FIG. 3 is a diagram showing a spectrum of a soft X-ray transmitted through a filter of an example.
【図４】実施例で測定された被測定材の軟Ｘ線写真像で
ある。FIG. 4 is a soft X-ray photographic image of a material to be measured measured in an example.
【図５】図４のＸ線写真像と同じ部分を撮影した可視光
写真像である。FIG. 5 is a visible light photographic image of the same part as the X-ray photographic image of FIG.
【図６】実施例で測定されたポリイミドに硫黄を付着さ
せ、水洗した直後の被測定材の軟Ｘ線写真像である。FIG. 6 is a soft X-ray photographic image of a material to be measured immediately after sulfur was attached to the polyimide measured in the example and washed with water.
【図７】実施例で測定されたポリイミドに硫黄を付着さ
せ、水洗した後さらに１０日間放置した後の図６と同じ
部分の被測定材の軟Ｘ線写真像である。7 is a soft X-ray photographic image of the same part as that of FIG. 6 after sulfur was attached to the polyimide measured in the example, washed with water, and left for 10 days.
１…ＹＡＧレーザー装置 ２…集光レンズ ３…ターゲット ４…真空窓 ５…フイルターを構成する薄膜 ６…被測定材で
ある高分子薄膜 ７…軟Ｘ線検出手段 ８…波長４．４
〜６ｎｍの軟Ｘ線 ９…真空容器 １０…試料台DESCRIPTION OF SYMBOLS 1 ... YAG laser apparatus 2 ... Condensing lens 3 ... Target 4 ... Vacuum window 5 ... Thin film which comprises a filter 6 ... Polymer thin film which is a material to be measured 7 ... Soft X-ray detection means 8 ... Wavelength 4.4
~ 6 nm soft X-ray 9 ... Vacuum container 10 ... Sample stand
───────────────────────────────────────────────────── フロントページの続き (72)発明者 舘 和幸 愛知県愛知郡長久手町大字長湫字横道41 番地の１ 株式会社豊田中央研究所内 (72)発明者 水野 隆教 愛知県愛知郡長久手町大字長湫字横道41 番地の１ 株式会社豊田中央研究所内 (56)参考文献 特開 平３−246500（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 23/22 G21K 3/00 G21K 7/00 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazuyuki Tachi 41-Cho, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside Toyota Central Research Laboratory Co., Ltd. 41, Yokomichi, Toyoda Central Research Institute, Inc. (56) References JP-A-3-246500 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) G01N 23/22 G21K 3 / 00 G21K 7/00
Claims (3)
ｎｍの波長の軟Ｘ線を照射する照射工程と、該被測定材
を透過した４．４〜６ｎｍの波長の軟Ｘ線を検出するた
めの軟Ｘ線検出工程とからなり、該被測定材中の原子番
号が１１〜３０の不純物元素を測定することを特徴とす
る高分子材料中の不純物元素の測定方法。The present invention relates to a method for measuring a material to be measured comprising a polymer material.
an irradiation step of irradiating the soft X-ray wavelength of nm, Ri Do from the soft X-ray detection step for detecting the soft X-ray wavelength of 4.4~6nm transmitted through the該被measuring material,該被measurement Atomic number in material
Method of measuring the impurity element of the polymeric material in which No. is characterized that you measure the impurity elements 11 to 30.
ためのターゲットと、この軟Ｘ線から４．４〜６ｎｍの
波長を選択するためのフィルタと、高分子材料からなる
被測定材を透過した４．４〜６ｎｍの波長の軟Ｘ線を検
出するための軟Ｘ線検出手段と、を有し、該被測定材中
の原子番号が１１〜３０の不純物元素を測定することを
特徴とする高分子材料中の不純物元素の測定装置。2. A laser generating means, a target for generating soft X-rays, a filter for selecting a wavelength of 4.4 to 6 nm from the soft X-rays, and a material to be measured comprising a polymer material. anda soft X-ray detecting means for detecting the soft X-ray wavelength of the transmitted 4.4～6Nm, 該被measured material in
Measuring device of an impurity element polymeric material which atomic number is characterized that you measure the impurity elements 11 to 30.
子、グラファイト、ダイヤモンド等から構成されている
請求項２記載の高分子材料中の不純物元素の測定装置。3. The apparatus for measuring an impurity element in a polymer material according to claim 2, wherein the filter is made of a polymer containing at least carbon, graphite, diamond or the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13296595A JP3327052B2 (en) | 1995-05-02 | 1995-05-02 | Method and apparatus for measuring impurity element in polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13296595A JP3327052B2 (en) | 1995-05-02 | 1995-05-02 | Method and apparatus for measuring impurity element in polymer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08304311A JPH08304311A (en) | 1996-11-22 |
| JP3327052B2 true JP3327052B2 (en) | 2002-09-24 |
Family
ID=15093650
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13296595A Expired - Fee Related JP3327052B2 (en) | 1995-05-02 | 1995-05-02 | Method and apparatus for measuring impurity element in polymer material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3327052B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010286405A (en) * | 2009-06-12 | 2010-12-24 | Sii Nanotechnology Inc | X-ray transmission inspection apparatus and X-ray transmission inspection method |
| JP2010286406A (en) * | 2009-06-12 | 2010-12-24 | Sii Nanotechnology Inc | X-ray transmission inspection apparatus and X-ray transmission inspection method |
| JP2013221882A (en) * | 2012-04-18 | 2013-10-28 | Hitachi Ltd | Measuring apparatus |
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1995
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH08304311A (en) | 1996-11-22 |
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