JPS62188919A - Method and instrument for direct emission analysis by multistage laser excitation - Google Patents
Method and instrument for direct emission analysis by multistage laser excitationInfo
- Publication number
- JPS62188919A JPS62188919A JP22576485A JP22576485A JPS62188919A JP S62188919 A JPS62188919 A JP S62188919A JP 22576485 A JP22576485 A JP 22576485A JP 22576485 A JP22576485 A JP 22576485A JP S62188919 A JPS62188919 A JP S62188919A
- Authority
- JP
- Japan
- Prior art keywords
- laser
- light
- test sample
- pulse
- oscillator
- 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.)
- Granted
Links
- 230000005284 excitation Effects 0.000 title claims description 29
- 238000004458 analytical method Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 21
- 239000013307 optical fiber Substances 0.000 claims abstract description 16
- 238000012360 testing method Methods 0.000 claims description 56
- 238000001228 spectrum Methods 0.000 claims description 31
- 230000003287 optical effect Effects 0.000 claims description 26
- 238000004611 spectroscopical analysis Methods 0.000 claims description 9
- 238000005452 bending Methods 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 6
- 230000003595 spectral effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000010183 spectrum analysis Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 54
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000012937 correction Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009529 body temperature measurement Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic 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
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、レーザ多段励起直接発光分析方法及び装置に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method and apparatus for laser multi-stage excitation direct emission analysis.
従来の技術及び発明が解決しようとする問題点従来の発
光分光分析方法は、Ｃ，Ｐ、Ｓ、Ａ、ｓ。PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Conventional emission spectroscopy methods include C, P, S, A, and s.
Ｓｎ等の分析をする場合、真空分光器を用いて、波長が
２００ｎｍ以下の真空紫外域の発光スペクトル金光検出
器でとらえていた。真空紫外域の光は空気等のガスによ
って吸収される。それがため従来の発光分析装置では、
励起発光装置と分光分析装置とを一体化しなければ々ら
なかった。一般に分光分析装置では、分析の精度を上昇
させるために清浄な室内に設置しなければならない。そ
のため励起発光装置と分光分析装置とが一体となってい
る従来の発光分析装置を作業現場等に設置してリアルタ
イムでその場分析を行なうことはできなかった。When analyzing Sn, etc., a vacuum spectrometer is used to capture the emission spectrum in the vacuum ultraviolet region with a wavelength of 200 nm or less using a gold photodetector. Light in the vacuum ultraviolet region is absorbed by gases such as air. Therefore, in conventional emission spectrometers,
It was necessary to integrate the excitation luminescence device and the spectroscopic analysis device. In general, spectroscopic analyzers must be installed in a clean room to improve the accuracy of analysis. For this reason, it has not been possible to install a conventional emission spectrometer in which an excitation luminescence device and a spectroscopic analysis device are integrated at a work site or the like to perform on-site analysis in real time.
このため、本発明者は広範な研究をおこない、レーザパ
ルスの多段励起によって、被検試料を蒸発・励起すれば
、標的分析元素の発光線スペクトル光のうち２００ ｎ
ｍ以上の長波長成分を特に強く発光させることができる
ことを発見し、本発明に至った。For this reason, the present inventor has conducted extensive research and found that if the test sample is evaporated and excited by multistage excitation of laser pulses, 200 nm of the emission line spectrum light of the target analyte element can be evaporated and excited.
It was discovered that long wavelength components of m or more can be particularly strongly emitted, leading to the present invention.
本発明の構成
本発明の第１番目の発明は、第１のレーザ発振器からの
第１のレーザパルスを被検試料上に集光して被検試料を
励起し、次いでＱ、１ｎｓから１゜μθ後に第２発振器
からの第２のレーザパルスを第１のレーザパルスと同一
光軸で被検試料の同一位置に集光するか又は第１のレー
ザパルスの光軸と平行又はほぼ平行な光軸で第１のレー
ザ光パルスの被検試料上への集光位置の極近傍の位置に
集光し、さらに被検試料を励起し、波長２００ｎｍ以上
の発光線スペクトル光を反射鏡、レンズ、および／また
は光ファイバー等の手段により分光分析器に導き、分光
分析することからなるレーザ多段励起直接発光分析方法
に関する。Structure of the Present Invention The first aspect of the present invention focuses a first laser pulse from a first laser oscillator onto a test sample to excite the test sample, and then Q, from 1 ns to 1°. After μθ, the second laser pulse from the second oscillator is focused on the same position of the test sample with the same optical axis as the first laser pulse, or the light is parallel or almost parallel to the optical axis of the first laser pulse. The axis focuses the first laser light pulse on a position very close to the focusing position on the test sample, further excites the test sample, and reflects the emission line spectrum light with a wavelength of 200 nm or more using a mirror, lens, And/or relates to a laser multistage excitation direct emission analysis method, which comprises guiding the invention to a spectrometer using means such as an optical fiber for spectroscopic analysis.
本発明の第２番目の発明は分光分析器、第１のレーザ発
振器電気的遅延装置に連結した第２のレーザ発振器を固
定し、前記第１のレーザ発振器の出射口近傍に必要に応
じて光路変更のためのプリズムおよび／または誘電体多
層膜鏡を固定し７．２つのレーザ発振器からのレーザビ
ームを重ねるため第１のレーザビーム上に波長板および
第２のレーザビームを曲げるだめの偏光ビームスプリッ
タ−を設けるか、又は２つのレーザビームを近接してイ
行又はほぼ平行になるように第２のレーザビーム用のレ
ーザ光反射鏡を設け、２つのレーザビーム中に集光レン
ズを固定し、被検試料からの発光線スペクトルを分光分
析器に伝送するための反射鏡、レンズおよび／または光
ファイバー等の手段を設けたレーザ多段励起直接発光分
析装置に関する。A second aspect of the present invention is to fix a second laser oscillator connected to a spectroscopic analyzer and a first laser oscillator electrical delay device, and to set an optical path near the emission port of the first laser oscillator as necessary. 7. Fix a prism and/or dielectric multilayer mirror for modification; 7. Polarize the wave plate and bend the second laser beam onto the first laser beam to overlap the laser beams from the two laser oscillators; Either a splitter is provided, or a laser beam reflector is provided for the second laser beam so that the two laser beams are aligned closely or almost parallel, and a condenser lens is fixed in the two laser beams. The present invention relates to a laser multistage excitation direct emission analyzer equipped with means such as a reflecting mirror, a lens, and/or an optical fiber for transmitting an emission line spectrum from a test sample to a spectroscopic analyzer.
本発明の第３番目の発明は、第２番目の発明において第
１のレーザ発振器と電気的遅延装置に連結しまた第２の
レーザ発振器とを位置的に逆にした場合の態様である。A third invention of the present invention is an embodiment in which the first laser oscillator and the second laser oscillator are connected to an electrical delay device in the second invention, and the positions of the second laser oscillator and the second laser oscillator are reversed.
本発明の発光装置の原理について説明する。The principle of the light emitting device of the present invention will be explained.
本発明のレーザ多段励起直接発光分析装置は、被検試料
にレーザ光パルスを二発集光し目的分析元素種類に対応
した２００ ｎｍ以上の長波長の固有線スペクトル光の
光強度を従来より強め、検出感度及び精度を向上させる
方法を用いている。The laser multi-stage excitation direct emission spectrometer of the present invention focuses two laser light pulses on a test sample and increases the light intensity of the characteristic line spectrum light with a long wavelength of 200 nm or more corresponding to the target analysis element type compared to conventional methods. , using methods to improve detection sensitivity and accuracy.
被検試料を発光させるために、捷ずｔ・−ザパルスを１
発、被検試料上に集光する。すると、被検試料」、にプ
ラズマができる。このプラズマは、レーザパルスのエネ
ルギーによ！フ被検試料の含有元素の原子が励起されて
できたものであり、レーザパルスが被検試料に集光され
てから数ｎθから数十ｎｅの時間をおいて各々の元素固
有の線スペクトル光を発光する。その発光の時間的変化
を第１図に示す。第１図は、横軸に時間をとり縦軸に発
光強度をとったものである。この図は、本発明にかかる
研究過程で得られたものであり、鉄（Ｆｅ）の線スペク
トル光の位置である２５９．３ｎｍの波長で１００ ｍ
ＪのＱスイッチＲＵＢＹレーザ光を焦点距離５０龍の溶
融石英製のレンズによシ低炭素鋼に集光し、てできたプ
ラズマを分光分析したものを模式的にあられしたもので
ある。To make the test sample emit light, apply 1 pulse of t.
The light is emitted and focused on the test sample. Then, plasma is formed on the test sample. This plasma is generated by the energy of the laser pulse! It is created when the atoms of the elements contained in the test sample are excited, and after a few nθ to several tens of ne after the laser pulse is focused on the test sample, the line spectrum light unique to each element is emitted. emits light. Figure 1 shows the temporal changes in the luminescence. In FIG. 1, the horizontal axis represents time and the vertical axis represents luminescence intensity. This figure was obtained during the research process related to the present invention, and is 100 m at a wavelength of 259.3 nm, which is the position of the iron (Fe) line spectrum light.
This is a schematic representation of the spectroscopic analysis of the plasma produced by concentrating J's Q-switch RUBY laser light onto low carbon steel using a fused silica lens with a focal length of 50 mm.
発光の過程は、レーザ光パルスが被検試料にあたってか
ら、３０ｎ６から４μｓ程度の時間、連続スペクトル光
を放射する。固有線スペクトル光は、数十ｎ８の時間を
おいてから放射される。固有線スペクトル光の発光時間
は、元素の種類及び元素の含有量および個々の固有線ス
ペクトル光によって異る。通常のレーザ励起の発光分析
では、測光装置、例えば光電子増倍管によりこの固有線
スペクトル光強度を測光し、元素の濃度を分析する。こ
の発光過程から本発明者らは、レーザ光が被検試料に当
ってから固有線スペクトル光が出てくるまでの時間に原
子がどのように励起されていくのか、広範な研究を、お
こない、各々の元素の固有線スペクトル光のうち長波長
成分の強度を強める方法を発明した。In the process of light emission, continuous spectrum light is emitted for a period of about 30n6 to 4 μs after the laser light pulse hits the test sample. The characteristic line spectrum light is emitted after a time interval of several tens n8. The emission time of the characteristic line spectrum light varies depending on the type of element, the content of the element, and the individual characteristic line spectrum light. In ordinary laser-excited emission analysis, the light intensity of this characteristic line spectrum is measured using a photometer, such as a photomultiplier tube, and the concentration of the element is analyzed. From this light emission process, the present inventors conducted extensive research on how atoms are excited during the time from when the laser light hits the test sample until the characteristic line spectrum light is emitted. We have invented a method to enhance the intensity of long wavelength components of the characteristic line spectrum light of each element.
固有線スペクトル光の発光現象は、励起された原子のエ
ネルギー状態の変化によっておこり、電子の軌道間の遷
移の確率の高いものが、そのエネルギ一単位間の差に相
当する波長の光を放出する。The emission phenomenon of eigenline spectrum light occurs due to changes in the energy state of excited atoms, and those with a high probability of transition between electron orbits emit light with a wavelength corresponding to the one-unit difference in energy. .
また、固有線スペクトル光の強度は個々のエネルギー準
位間にある原子の数に比例し、当該準位により多くの原
子を励起できれば、発光強度は強くなる。Furthermore, the intensity of light with an eigenline spectrum is proportional to the number of atoms between individual energy levels, and the more atoms that can be excited at that level, the stronger the emission intensity will be.
本発明は、この理論にのつとシレーザ光、６ルスを１発
被検試料に集光し、できた試料雲にもう一度レーザ光パ
ルスを集光し効率の良い励起を行ない長波長にある固有
線スペクトル光に対応する励起状態の原子の存在確率を
増加せしめより発光しやすい条件をつくり、また、より
多くの原子を励起し発光強度を強め、検出感度、精度を
向上させた。Based on this theory, the present invention focuses one laser laser beam, 6 LS, on the test sample, and then focuses another laser light pulse on the sample cloud to perform efficient excitation. This increases the probability of the existence of atoms in an excited state corresponding to the light spectrum, creating conditions that make it easier to emit light, and also excites more atoms to increase the intensity of light emission, improving detection sensitivity and accuracy.
本発明のレーザ多段励起直接発光分析装置において、分
光分析器は従来公知のものを使用する。In the laser multistage excitation direct emission spectrometer of the present invention, a conventionally known spectroscopic analyzer is used.
分光分析器は光検出器例えば光電子増倍管および／また
はホトダイオード９アレイなどの多チャンネル光検出器
を備えている分光器と例えば光検出器からの電気信号の
増幅器、電気信号処理装置、光検出器からのデータを計
算処理し、濃度値を出力するコンピュータを備えている
ものを含む。しかし分光分析器は２００ ｎｍ以上の波
長の発光スイクトルを分析するものであればどのような
ものでも使用できる。本発明では２００ ｎｍ以上の長
波長の光を分析するため、分光器は、真空装置を備えて
いなくてもよく、光検出器も従来より長波長に感度のあ
るものを使用できる。A spectrometer comprises a multi-channel photodetector, e.g. a photomultiplier tube and/or a photodiode array. This includes those equipped with a computer that calculates and processes data from the device and outputs concentration values. However, any spectrometer can be used as long as it analyzes emission spectral wavelengths of 200 nm or more. In the present invention, since light with a long wavelength of 200 nm or more is analyzed, the spectroscope does not need to be equipped with a vacuum device, and a photodetector that is more sensitive to longer wavelengths than conventional ones can be used.
レーザ発振器は、レーザ光の発振部分であり、レーザに
電力を供給する電源部分は、外部に備えつけ、電気ケー
ブルによってレーザ発振器に供給してもよい。発振周期
は１発／分〜１００ Ｋｐｐｓである。レーザ光パルス
は、半値半幅で１μθｅｃ以下、 １０ ｍＪ／ ｐｕ
ｌｓｅ以上のエネルギーが必要であり、波長はなるべく
固有線スにクトル光の波長から離れているものを使用す
る。２台のレーザ装置は、同じ波長のものでなくてもよ
い。またレーザ光パルスのエネルギーもおなしでなくて
もよい。A laser oscillator is a part that oscillates laser light, and a power supply part that supplies power to the laser may be provided externally and supplied to the laser oscillator through an electric cable. The oscillation cycle is 1 shot/min to 100 Kpps. The laser light pulse has a half-width at half maximum of 1 μθec or less, 10 mJ/pu
Energy greater than lse is required, and a wavelength that is as far away from the wavelength of the characteristic light as possible is used. The two laser devices do not need to have the same wavelength. Furthermore, the energy of the laser light pulse does not have to be constant.
電気的遅延回路は、０．１ｎｓから１０ｎ８程度まで、
任意にレーザの発振を遅らせ、励起する効率を目的分析
元素によって変化させ、より効率を向上させる。Electrical delay circuits range from 0.1ns to about 10n8,
Optimally, the laser oscillation is delayed and the excitation efficiency is changed depending on the target analyte element to further improve the efficiency.
２台のレーザ発振器からのレーザ光パルスｔ［−の被検
試料の同−箇所又はほぼ同一箇所に集光させるためには
、どちらか一方のレーザ光光軸にもう一方のレーザ光・
々ルスの光軸を合わせる方法と２つの光軸を近接平行に
し、被検試料に集光する２方法がある。前者の方法の一
例として、直線偏波のレーザ光パルスを１／２波長板に
入射させ偏波方向を変更し、２方向からの直線偏波のレ
ーザ光パルスを同一光軸上を通過するように、２方向か
らの光軸の交点に偏光ビームスプリッタ−をおき、一方
のレーザ光パルスを透過し、もう一方のレーザ光パルス
を反射させて光軸を合わせる方法がある。後者の方法と
して、２つの光軸のレーザ光パルスをレーザ反射鏡を用
いて、殆ど同軸とみなせるくらい近接、平行させ、被検
試料上に集光する方法がある。レーザ光パルスの反射鏡
、およびレンズは、レーザ光パルスの波長、単一パルス
あたりの光エネルギー量を考え、材質等を決めなくては
ならない。In order to focus the laser beam pulses t[- from two laser oscillators on the same or almost the same place on the test sample, the optical axis of one of the laser beams must be aligned with the other laser beam.
There are two methods: one method is to align the optical axes of the laser beams, and the other method is to make the two optical axes close to each other in parallel and focus the light on the test sample. As an example of the former method, a linearly polarized laser light pulse is incident on a 1/2 wavelength plate, the polarization direction is changed, and the linearly polarized laser light pulses from two directions are passed on the same optical axis. Another method is to align the optical axes by placing a polarizing beam splitter at the intersection of the optical axes from two directions, transmitting one laser beam pulse, and reflecting the other laser beam pulse. As the latter method, there is a method in which laser light pulses of two optical axes are brought close and parallel to each other so that they can be considered to be almost coaxial using a laser reflector, and the light is focused on the test sample. The material of the laser light pulse reflecting mirror and lens must be determined in consideration of the wavelength of the laser light pulse and the amount of light energy per single pulse.
励起されてできたプラズマからの光を分光分析器まで導
くのは、紫外域に高い透過効率を有する光ファイバーを
用いてもよい。An optical fiber having high transmission efficiency in the ultraviolet region may be used to guide the light from the excited plasma to the spectroscopic analyzer.
このレーザ多段励起直接発光分析装置を例えば、鉄鋼精
練現場の工程管理分析に応用する場合、従来、溶融被検
試料をサンプリング・冷却固化し、分析室へ搬送し、ス
パーク放電励起により固有線スペクトル光を分析してい
た方法に代わり、鉄鋼精練現場にレーザ発振器を備え励
起・発光を鉄鋼精練現場でおこない得られるプラズマ光
を光ファイバーにより分析室に伝送し分析室で清浄状態
で保持されている分光分析器によって目的元素の濃度を
算出し現場の精練処理を行なうことができる。For example, when applying this laser multi-stage excitation direct emission spectrometer to process control analysis at a steel refining site, conventionally, a molten test sample is sampled, cooled and solidified, transported to an analysis laboratory, and then excited by spark discharge to produce characteristic line spectra. In place of the conventional method of analyzing steel, a laser oscillator is installed at the steel smelting site, excitation and emission are performed at the steel smelting site, and the resulting plasma light is transmitted to the analysis laboratory via optical fiber, where it is maintained in a clean state. The concentration of the target element can be calculated using the device and the on-site refining process can be carried out.
連続分析の可能性も非常に高いと考えられる。It is thought that the possibility of continuous analysis is also very high.
また、非接触で分析ができること、および遠距離から分
析をおこなえることが非常に重要なことである。又各現
場に励起発光装置を数台を設置し、その数台の励起発光
装置からの発光スペクトルを清浄な室内に設置し１台の
分光分析器で分析できる。Also, it is very important to be able to conduct analysis without contact and from a distance. Furthermore, several excitation/emission devices are installed at each site, and the emission spectra from the several excitation/emission devices can be installed in a clean room and analyzed with a single spectrometer.
本発明ではさらに１台又は数台のレーザ発振器を設置し
て、第２のレーザパルスで集光後、０］ｎｓ〜１０μｓ
後にさらに１又は２以上のレーザパルスを被検試料の同
一位置に集光させてもよい。In the present invention, one or more laser oscillators are further installed, and after focusing the light with the second laser pulse, 0]ns to 10μs
Later, one or more laser pulses may be further focused on the same position on the test sample.
本発明の装置を図面により説明する。The apparatus of the present invention will be explained with reference to the drawings.
第２図は、レーザ多段励起直接発光分析装置のフローシ
ートである。FIG. 2 is a flow sheet of a laser multistage excitation direct emission spectrometer.
ｌは、第１のレーザ発振器、１′は第２のレーザ発振器
、２は分光器、３は光検出器、４は増幅器、５は電気信
号処理装置、６は電子制御器、７はレーザのコントロー
ラ、８は電気的遅延装置、９はプリズム、１０は１／２
波長板、１１は偏光ビームスプリッタ−１１２は集光レ
ンズ、１３は被検試料、１４は光ファイバー、１５は光
フアイバー集光レンズ、１６はレーザ電源、１８はレー
ザ発振器である。1 is a first laser oscillator, 1' is a second laser oscillator, 2 is a spectrometer, 3 is a photodetector, 4 is an amplifier, 5 is an electric signal processing device, 6 is an electronic controller, and 7 is a laser oscillator. controller, 8 is an electrical delay device, 9 is a prism, 10 is 1/2
11 is a polarizing beam splitter, 112 is a condenser lens, 13 is a test sample, 14 is an optical fiber, 15 is an optical fiber condenser lens, 16 is a laser power source, and 18 is a laser oscillator.
このうち、２の分光器、３の光検出器、４の増幅器、５
の電気信号処理装置、６の電子制御器が分光分析器を構
成している。分光分析器としてこのような５つの部分か
ら構成されることは必要の要件ではなく、他の分光分析
器も使用できる。Of these, 2 spectrometers, 3 photodetectors, 4 amplifiers, 5
An electric signal processing device 6 and an electronic controller 6 constitute a spectroscopic analyzer. It is not necessary for the spectrometer to consist of five parts; other spectrometers can also be used.
第２図において第１のレーザ発振器の位置に電気的遅延
装置８に連結した第２のレーザ発振器を設け、第２のレ
ーザ発振器の位置に第１のレーザ発振器を設け、第２の
レーザ発振器からの第２のレーザパルスを１／２波長板
１０を通し、第１のレーザ発振器からの第１のレーザパ
ルスを偏光ビームスプリッタ−１１により、屈曲させて
もよい。In FIG. 2, a second laser oscillator connected to an electrical delay device 8 is provided at the position of the first laser oscillator, a first laser oscillator is provided at the position of the second laser oscillator, and a second laser oscillator is connected to the second laser oscillator. The second laser pulse may be passed through a half-wave plate 10, and the first laser pulse from the first laser oscillator may be bent by a polarizing beam splitter 11.
横型のレーザ発振器を図示したが縦型レーザ発振器を使
用できる。このような装置で発光分析を行なう場合、２
つのレーザパルスの焦点位置に被検試料１３を置き、２
つのレーザ発振器からのレーザパルスを時間的間隔を置
いて被検試料１３上に集光させ、その試料を励起させ、
その発光スペクトルを光ファイバー１４で分光分析器に
導き、分析を行なう。Although a horizontal laser oscillator is illustrated, a vertical laser oscillator can also be used. When performing emission analysis with such a device, 2
Place the test sample 13 at the focus position of two laser pulses,
Laser pulses from two laser oscillators are focused on the test sample 13 at time intervals to excite the sample,
The emission spectrum is guided to a spectroscopic analyzer via an optical fiber 14 and analyzed.
第３図は、レーザ多段励起直接発光分析装置の別の態様
例である。１７はレーザ光反射鏡である。FIG. 3 shows another embodiment of the laser multistage excitation direct emission spectrometer. 17 is a laser beam reflecting mirror.
この第３図に示す態様では２つのレーザ光の光軸を近接
して平行又はほぼ平行になるように第２のレーザ用のレ
ーザ光反射光を設けた例である。The embodiment shown in FIG. 3 is an example in which the reflected laser beam for the second laser is provided so that the optical axes of the two laser beams are close to each other and are parallel or substantially parallel.
第４図は、レーザ多段励起直接発光分析装置の別の態様
例である。１９は現場、２０は光学台である。FIG. 4 shows another embodiment of the laser multistage excitation direct emission spectrometer. 19 is the site, and 20 is an optical bench.
第４図において点線から左側の部分は現場に設置し、点
線から右側の部分は清浄な室に設置できる。In Fig. 4, the part to the left of the dotted line can be installed on site, and the part to the right of the dotted line can be installed in a clean room.
第２図において６のコンピューターから１のレーザ発振
器のコントローラーと１８のレーザ発振器に発射の信号
゛が伝送される。すると、１のレーザ発振器からレーザ
光パルスが発射される。１８のレーザ発振器は８の遅延
回路により所定の時間遅延された後発射される。１のレ
ーザ発振器から発射されたレーザ光パルスによって１３
の被検試料は励起されプラズマ状態となる。その瞬間、
あるいは、蒸気状態の瞬間、１８のレーザ発振器から発
射され７’ｃ Ｌ／ −サ光パルスが蒸気状あるいはプ
ラズマ状の試料に集光され、より高密度なプラズマが被
検試料上にできる。In FIG. 2, a firing signal is transmitted from 6 computers to 1 laser oscillator controller and 18 laser oscillators. Then, a laser light pulse is emitted from one laser oscillator. Eighteen laser oscillators are emitted after being delayed for a predetermined time by eight delay circuits. 13 by the laser light pulse emitted from the laser oscillator 1
The test sample is excited and enters a plasma state. that moment,
Alternatively, at the moment of the vapor state, 7'c L/- laser light pulses emitted from the 18 laser oscillators are focused on the vapor or plasma sample, creating a higher density plasma on the test sample.
プラズマから放射される光は、１５の光フアイバー集光
レンズによって効率よ＜１４の光ファイバーに取り込め
られ、２の分光器まで伝送される。その後、２の分光器
によシ波長別に分光され長波長の固有線スペクトル光の
位置に精密におかれた３の光検出器によって線ス深りト
ル光が検出され、光電変換され４の増幅器を経由し、５
の電気信号処理装置によってサンプルホールド、アナロ
グ−デジタル変換をおこない、６のコンピュータとのデ
ータ転送のための制御をおこない、６のコンピュータに
取シ込まれる。６のコンピュータでは、とりこまれたデ
ータの演算処理が行なわれ、濃度計算値が出力される。The light emitted from the plasma is efficiently captured into <14 optical fibers by 15 optical fiber condensing lenses and transmitted to two spectrometers. After that, the spectrometer 2 separates the light into wavelengths, and the photodetector 3, which is placed precisely at the position of the long-wavelength characteristic line spectrum light, detects the line depth light, which is photoelectrically converted and sent to the amplifier 4. via 5
The electrical signal processing device performs sample hold and analog-to-digital conversion, controls data transfer with computer 6, and is input to computer 6. The computer No. 6 performs arithmetic processing on the captured data and outputs a calculated concentration value.
また、第１図の態様例では２台のレーザ発振器からのレ
ーザ光パルスを１３０被検試料上の同一箇所に集光する
ために１のレーザ発振器は直線偏波のレーザ光パルスを
出力するものとし、この偏波面を１／２波長板によって
回転し偏光ビームスプリッタ−を透過させ、１８のレー
ザ発振器からのレーザ光パルスは、偏光ビームスプリッ
タ−によシ反射され、光軸を同一として被検試料に集光
させる構造である。In addition, in the embodiment shown in Fig. 1, one laser oscillator outputs linearly polarized laser light pulses in order to focus the laser light pulses from two laser oscillators on the same spot on the 130 test sample. The plane of polarization is rotated by a 1/2 wavelength plate and transmitted through a polarizing beam splitter, and the laser light pulses from the 18 laser oscillators are reflected by the polarizing beam splitter, and the optical axis is set to be the same as that of the polarizing beam splitter. It has a structure that focuses light on the sample.
第３図は、２台のレーザ発振器からのレーザ光パルスを
１３の被検試料上の同一箇所に集光するために１８のレ
ーザ発振器からのレーザ光パルスを１７のレーザ反射鏡
によって反射させ、１のレーザ発振器の光軸に近接平行
させて１３の被検試料に集光させる構造である。FIG. 3 shows that in order to focus the laser light pulses from two laser oscillators on the same spot on 13 test samples, the laser light pulses from 18 laser oscillators are reflected by 17 laser reflecting mirrors. It has a structure in which the light is focused on 13 test samples in close parallel to the optical axis of 1 laser oscillator.
第４図は、現場の工程管理分析にレーザ多段励起発光分
析装置を使用するときの態様例である。FIG. 4 shows an example of a mode in which a laser multistage excitation emission spectrometer is used for on-site process control analysis.
ｌおよび１８のレーザ発振器、９のプリズム、１０の１
／２波長板および１１の偏光ビームスプリッタ−を、現
場の環境に対応した構造の２０の光学台に固定し、従来
の分析室には、７のレーザのコントローラー、１６のレ
ーザ電源、２，３，４．６．８からなる分光分析器を備
え、１３の被検試料および２０の光学台は、現場に備え
つけておく。固有線スペクトル光の２の分光器までの伝
送は１４の光ファイバーによっておこ力い、高精度な分
光分析を容易に行なうことができる。l and 18 laser oscillators, 9 prisms, 1 of 10
A /2 wavelength plate and 11 polarizing beam splitters are fixed to 20 optical benches with a structure suitable for the on-site environment, and in a conventional analysis room, there are 7 laser controllers, 16 laser power supplies, , 4.6.8, and 13 test samples and 20 optical benches are provided on site. Transmission of the characteristic line spectrum light to the two spectrometers is carried out by 14 optical fibers, making it possible to easily perform highly accurate spectroscopic analysis.
本発明における被検試料は固体、液体または気体の状態
であっても良い。又被検試料が溶融金属である場合第５
〜６図に示すような消耗型サンプリングプローブを用い
る。そのサンプリングプローブは、下端閉鎖型の筒状を
々しており、それの下端又は下端近くの壁面に溶融金属
取入口を設け、そのプローブが測定すべき溶融金属のス
ラグ層を通過する間、その溶融スラグが、その取入口か
らプローブの中に入らないような構成を有している。The test sample in the present invention may be in a solid, liquid, or gaseous state. In addition, if the test sample is molten metal, the fifth
~Use a consumable sampling probe as shown in Figure 6. The sampling probe has a cylindrical shape with a closed bottom end, and has a molten metal inlet at or near the bottom end of the sampling probe. The structure is such that molten slag does not enter the probe through its intake port.
第５図は消耗型サンプリングプローブの一態様例を示す
。FIG. 5 shows an example embodiment of a consumable sampling probe.
１１３は紙管、１２５は溶融金属取出口、１３１はその
取出口に取付けた溶融金属の温度で溶融又は燃焼する金
属板、１３０は鉄、セラミック又はシェルモールド製の
鋳型、１２８は溶融金属温度測定センサー、溶融金属中
の含有酸素量測定センサー又は測温と酸素量測定を兼ね
るセンサー、１２９はり−）’線、１２６はメス型のコ
ネクター、１１４はレベルセンサーである。113 is a paper tube, 125 is a molten metal outlet, 131 is a metal plate that melts or burns at the temperature of the molten metal attached to the outlet, 130 is a mold made of iron, ceramic or shell mold, 128 is a molten metal temperature measurement Sensor, a sensor for measuring the amount of oxygen contained in the molten metal or a sensor for both temperature measurement and oxygen amount measurement, 129 beam -)' wire, 126 a female connector, 114 a level sensor.
第６図Ｋ、消耗型サンプリングプローブの構造の別の態
様例を示す。FIG. 6K shows another example of a consumable sampling probe structure.
第６図は、外側に材質を紙製または鉄製の円筒管１１３
を配置し、その内部に砂あるいは鉄の型１３０を固定し
、型の表面の下部に、金属のコーティングをほどこし、
鋳型下部側面に、溶融金属取入口１２５を有し、スラグ
遮蔽板１３１を取入口に取シ付け、型上部に１メス型コ
ネクタを有し、その下部、壁面にガス排出口１３５を有
し、下端部は、耐火セメント１３６によって閉鎖してい
る。Figure 6 shows a cylindrical tube 113 whose outer material is made of paper or iron.
A sand or iron mold 130 is fixed inside the mold, and a metal coating is applied to the lower part of the surface of the mold.
It has a molten metal intake port 125 on the side surface of the lower part of the mold, a slag shielding plate 131 is attached to the entrance, a 1-female connector on the upper part of the mold, and a gas discharge port 135 on the wall surface below it, The lower end is closed with refractory cement 136.
発明の効果
第１表にレーザ多段励起直接発光分析装置及び方法によ
る実験結果を記載する。この表は、固有線メイクトル光
（以下、Ｓとする）の時間積分強度を分子に、連続光成
分（以下、Ｂとする）の時間積分強度を分母にとり、レ
ーザ光パルス単発の場合とレーザ光、２ルスが二元の場
合について値Ｓ／Ｂにより波長３００ｎｍｙの線スペク
トルの検出感度の違いを比較したものである。値Ｓ／Ｂ
は、大きいほど検出感度が高いことになり、検出感度を
比較するときの目安となる。Effects of the Invention Table 1 lists experimental results using a laser multistage excitation direct emission spectrometer and method. This table takes the time-integrated intensity of the eigenline Meiktor light (hereinafter referred to as S) as the numerator and the time-integrated intensity of the continuous light component (hereinafter referred to as B) as the denominator, and shows the case of a single laser beam pulse and the case of a single laser beam pulse. , 2. Differences in detection sensitivity of a line spectrum at a wavelength of 300 nm are compared based on the value S/B in the case where the Lus is binary. Value S/B
The larger is, the higher the detection sensitivity is, and serves as a guideline when comparing detection sensitivities.
第５図から、レーザ光パルス単発の時のＳ／Ｂとレーザ
光パルスが二元の時のＳ／Ｂを比較するとレーザ光・ξ
ルスが二元の時の方が３倍から１０倍はどＳ／Ｂが大き
い。これは、すなわち、従来のレーザ光パルス単発の方
法よりレーザ光パルス二元の方法が分析感度の改善に効
果があることを表すものである。From Figure 5, comparing the S/B when a single laser beam pulse is used and the S/B when the laser beam pulse is two-dimensional, the laser beam ξ
When the Luz is binary, the S/B is 3 to 10 times larger. This means that the method using two laser light pulses is more effective in improving the analysis sensitivity than the conventional method using a single laser light pulse.
このように、レーザ多段励起直接発光分析装置及び方法
を利用すれば、発光量の少なかった長波長の固有線スペ
クトル光を強めて分析に供することができる。In this way, by using the laser multistage excitation direct emission spectrometry apparatus and method, it is possible to intensify the long-wavelength characteristic line spectrum light, which has a small amount of light emission, and use it for analysis.
第５図の実験結果は、波長１．０６μｍ、パルス幅１２
ｎ日、パルスエネルギー８５０ ｍＪの直線偏波のＮａ
：ＹＡＧ レーザ発振器を第１段目のレーザ発振器とし
、波長１０６μｍ、パルス幅１５ ｎ Ｂｂ ’ξルス
エネルギー５００ ｍＪの直線偏波のＮａ：ＹＡＧレー
ザ発振器を第２段目のレーザ発振器とｌ〜、低炭素鋼、
溶融はんだ、ニッケル系ステンレス鋼、全被検試料とし
、第１段目のレーザ光パルスを被検試料上に集光してか
ら４０ｎθ後に第２段目のレーザ光パルスを被検試料上
に集光し、集光してできだプラズマからの光を紫外光用
光ファイバーで、Ｃｚｅｒｎｙ−Ｔｕｒｎｅｒ型の１ｍ
常圧分光器に伝送、分光した後、光検出器である光電子
増倍管にて光電変換し、増幅し電気的処理装置にて積分
操作などをしたのち、コンぎユータにより演算し出力し
たものである。The experimental results shown in Figure 5 show a wavelength of 1.06 μm and a pulse width of 12
n days, linearly polarized Na with pulse energy 850 mJ
A :YAG laser oscillator is used as the first stage laser oscillator, and a linearly polarized Na:YAG laser oscillator with a wavelength of 106 μm and a pulse width of 15 n Bb 'ξ las energy of 500 mJ is used as the second stage laser oscillator. low carbon steel,
All test samples are molten solder, nickel-based stainless steel, and the first stage laser light pulse is focused on the test sample, and 40nθ later, the second stage laser light pulse is focused on the test sample. The light from the resulting plasma is transmitted through a Czerny-Turner type 1m optical fiber.
After being transmitted to an atmospheric pressure spectrometer and subjected to spectroscopy, it is photoelectrically converted by a photomultiplier tube, which is a photodetector, amplified, and integrated by an electrical processing device, and then calculated and output by a computer. It is.
固有線スはりトル光の値Ｓは、固有線スＲりトル光のあ
る波長の光の強度から、固有線スペクトル光のない波長
の光の強度を差し引いたものであり、連続光の値Ｂは、
固有線スペクトル光のない波長におけるの光の強度とし
て求めたものである１、但、分光器の出射スリット幅を
一定と考えている。The value S of the characteristic line spectrum light is obtained by subtracting the intensity of light at a wavelength where there is no characteristic line spectrum light from the intensity of the light at a wavelength with the characteristic line spectrum light, and the value S of the continuous light is teeth,
It is determined as the intensity of light at a wavelength where there is no light in the characteristic line spectrum.However, the output slit width of the spectrometer is assumed to be constant.
以上のことから、本発明のレーザ多段励起直接発光分析
装置によυ３００ ｎｍ以上の長波長の固有線メイクト
ル光を強く発光させ、長波長の固有線スハクトル光によ
る分光分析を可能にした。これにより、分光分析器の光
学系装置の簡略化および、メンテナンスの簡略化をはか
り１分析時間をほとんど極限まで短くすることができた
。From the above, the laser multi-stage excitation direct emission spectrometer of the present invention strongly emits characteristic line Meiktol light with a long wavelength of υ300 nm or more, making spectroscopic analysis using long wavelength characteristic line Meiktl light possible. As a result, it was possible to simplify the optical system of the spectroscopic analyzer, simplify maintenance, and shorten the time per analysis to almost the minimum.
第 １ 表Table 1
第１図はレーザパルスが被検試料に集光された際のその
発光量の時間的変化を示すグラフである。
第２図乃至第４図は本発明の好ましい装置のフローシー
トである。
第５図乃至第６図はサンプリングプローブの概略図であ
る。
（外５名）
時間［μＳ］
第２図
第３図
第４図
手続補正書
昭和６０年１１月／を日
２、発明の名称
レーザ多段励起直接発光分析方法及び装置６、補正をす
る者
事件との関係 特許出願人
住所
名称 岡山大学長
住所
名称 大阪酸累工業株式会社
４、代理人
５、補正の対象
明細書の〔特許請求の範囲〕と〔発明の詳細な説明〕の
欄（別 紙）
（１） 特許請求の範囲を次のように訂正する。
「（１）第１のレーザ発振器からの第１のレーザパルス
を被検試料上に集光して被検試料乞励起し。
次いでＱ、１ｎｓかも１０μｓ後に第２発振器からの第
２のレーザパルスを第１のレーザパルスト同一元軸で被
検試料の同一位置に集光するか又は第１のレーザパルス
の光軸と平行又はほぼ平行な光軸で第１のレーザパルス
の被検試料上への集光位置の極近傍の位置に集光し、さ
らに被検試料を励起し。
波長２００ｎｍ以上の発光線スペクトル九ン反射鏡。
レンズ、および／また哄光ファイバー等の手段により分
光分析器に導き１分光分析することからなるレーザ多段
励起直接発光分析方法。
（２） 第２のレーザパルスによる被検試料上への集
光後さらに１又は２以上のレーザパルスを時間的間隔装
置いて被検試料の同一位置又はそれの極近傍位置に集光
することからなる特許請求の範囲第１項記載の方法。
（５） 分光分析器、第１のレーザ発振器電気的遅延
装置に連結し１こ第２のレーザ発振器を固定し、前記第
１のレーザ発振器の出射口近傍に必要に応じて光路変更
のためのプリズムおよび／または誘電体多層膜鏡を固定
し、２つのレーザ発振器からのレーザビームラ重ねるた
め第１のレーザビーム上に波長板および第２のレーザビ
ームを曲げるための偏光ビームスプリッタ−乞設けるか
。
又は２つのレーザビーム乞近接して平行又ははば平行に
なるように第２のレーザビーム用のレーザ光反射鏡を設
け、２つのレーザビーム中に集光レンズを固定し、被検
試料からの発光線スペクトルを分光分析器に伝送するた
めの反射鏡、レンズおよび／または元ファイバー等の手
段２設けたレーザ多段励起直接発光分析装置。
（４） 分光分析器、第１のレーザ発振器、電気的遅
延装置に連結した第２のレーザ発振器を固定し。
前記第２のレーザ発振器の出射口近傍に必要に応じて光
路変更のためのプリズムおよび／または誘電体多層膜鏡
を固定し、２つのレーザ発振器からのレーザビームを重
ねるため第２のレーザビーム上に波長板および第１０Ｖ
−ザビームを曲けるための偏光ビームスプリッタ−を設
けるか、又は２つのレーザビームを近接して平行又はほ
ぼ平行になるように第１のレーザビーム用のレーザ光反
射鏡を設け、２つのレーザビーム中に集光レンズヶ固定
し、被検試料からの発光線スペクトルを分光分析器に伝
送するための反射鏡、レンズおよび／または元ファイバ
ー等の手段を設けたレーザ多段励起直接発光分析装置。
」
（２）明細書を次のように訂正する。
頁 行 訂正前 訂正後
４ １ ルを ル光強度５ １２ 発
振器 発振器。
９ １５ ルを ル元を１２ ２０ ７
はし ７は１のし１４ １０ 反射光
反射鋭頁 行 訂正前 訂正後
１４ １６ と１８のレーザ発録器 （削除する）
１４ １８ １８ １′１５ ５
＠
１６ ５−波長板 １０の一波長板１６
４ し偏光 ・ 子１１の偏光１６ ４
１８ １’１６ ５ 偏光ビーム
１１の偏光ビーム１６ １０ １８
７’１６ ２０ １６ ８
の電気的遅延回路、１６１６ ２０ ４．６，８
４，５．６１７ ５ ２の分光器 分
光器２１７ １７ 取出口 取入ロア
１Ｂ
１８ ９ 表面の下ｆＡ 表面１８ １０
インク インク１２フ頁 行 訂正前
訂正後
１８ １１ 取入口 取入口１２５１８
１２ コネクタ コネクタ１２６１９ ６
第５図 第１表
２１ 下４ 溶融はんだ中 ステンレス鋼中２
１ 下２ ステンレス鋼中 溶融はんだ中（３１
図面第２図、第５図、第４図、第５図及び第６図を添附
のものに訂正する。
第２図
第３図FIG. 1 is a graph showing temporal changes in the amount of light emitted when a laser pulse is focused on a test sample. FIGS. 2-4 are flow sheets of a preferred apparatus of the present invention. Figures 5 and 6 are schematic diagrams of the sampling probe. (Other 5 people) Time [μS] Figure 2 Figure 3 Figure 4 Procedural amendment November 1985 / Day 2, Name of invention Laser multi-stage excitation direct emission analysis method and apparatus 6, Case of person making amendment Relationship with Patent Applicant Address Name Okayama University President Address Name Osaka Sanku Kogyo Co., Ltd. 4, Agent 5, [Claims] and [Detailed Description of the Invention] columns of the specification to be amended (attachment) ) (1) The scope of claims is amended as follows. (1) Focus the first laser pulse from the first laser oscillator onto the test sample to excite the test sample. Then, after Q, 1ns or 10μs, the second laser pulse from the second oscillator is applied. The first laser pulse is focused on the same position on the test sample with the same axis of the first laser pulse, or the first laser pulse is focused onto the test sample with the optical axis parallel or almost parallel to the optical axis of the first laser pulse. The light is focused at a position very close to the light collection position and further excites the test sample.Emission line with a wavelength of 200 nm or more is reflected by a mirror.The light is guided to a spectroscopic analyzer by means such as a lens and/or an optical fiber. A laser multi-stage excitation direct emission analysis method comprising spectroscopic analysis. (2) After the second laser pulse focuses light onto the test sample, one or more laser pulses are applied at time intervals to the test sample. The method according to claim 1, which comprises focusing the light at the same position or a position very close to it. A laser oscillator is fixed, a prism and/or a dielectric multilayer mirror for changing the optical path is fixed as necessary near the emission aperture of the first laser oscillator, and a second laser beam ray from the two laser oscillators is overlapped. Either a wave plate on one laser beam and a polarizing beam splitter for bending the second laser beam are required. Alternatively, a polarizing beam splitter for bending the second laser beam may be provided on the first laser beam. A means such as a reflector, a lens, and/or a source fiber for transmitting the emission line spectrum from the test sample to the spectrometer by fixing a condensing lens in the two laser beams and transmitting the emission line spectrum from the test sample to the spectrometer. 2. A laser multistage excitation direct emission analysis device provided with 2. (4) A spectroscopic analyzer, a first laser oscillator, and a second laser oscillator connected to an electrical delay device are fixed. Near the exit of the second laser oscillator. If necessary, a prism and/or a dielectric multilayer mirror is fixed for changing the optical path, and a wave plate and a 10V laser beam are placed on the second laser beam to overlap the laser beams from the two laser oscillators.
- Provide a polarizing beam splitter for bending the laser beam, or provide a laser beam reflector for the first laser beam so that the two laser beams are closely parallel or nearly parallel, and the two laser beams are A laser multistage excitation direct emission spectrometer, which has a condenser lens fixed therein and is equipped with means such as a reflector, a lens, and/or a source fiber for transmitting the emission line spectrum from a test sample to a spectrometer. (2) The description is amended as follows. Page Line Before correction After correction 4 1 Le light intensity 5 12 Oscillator Oscillator. 9 15 le ru yuan 12 20 7
Chopsticks 7 is 1 14 10 Reflected light
Reflection sharp page line Before correction After correction 14 Laser recorder of 16 and 18 (Delete)
14 18 18 1'15 5
@16 5-wave plate 10 one-wave plate 16
4 Polarized light ・ Polarized light of child 11 16 4
18 1'16 5 Polarized beam
11 polarized beams 16 10 18
7'16 20 16 8
electrical delay circuit, 1616 20 4.6,8
4,5.617 5 Spectrometer 2 Spectrometer 217 17 Outlet Intake lower
1B 18 9 Below surface fA Surface 18 10
Ink Ink 12th page line Before correction After correction 18 11 Intake port Intake port 12518
12 Connector Connector 12619 6
Figure 5 Table 1 21 Lower 4 Molten solder medium Stainless steel medium 2
1 Lower 2 In stainless steel In molten solder (31
Figures 2, 5, 4, 5, and 6 of the drawings are corrected to the attached ones. Figure 2 Figure 3
Claims (4)
被検試料上に集光して被検試料を励起し、次いで０．１
ｎｓから１０μｓ後に第２発振器からの第２のレーザパ
ルスを第１のレーザパルスと同一光軸で被検試料の同一
位置に集光するか又は第１のレーザパルスの光軸と平行
又はほぼ平行な光軸で第１のレーザ光パルスの被検試料
上への集光位置の極近傍の位置に集光し、さらに被検試
料を励起し、波長２００ｎｍ以上の発光線スペクトル光
を反射鏡、レンズ、および／または光ファイバー等の手
段により分光分析器に導き、分光分析することからなる
レーザ多段励起直接発光分析方法。(1) The first laser pulse from the first laser oscillator is focused onto the test sample to excite the test sample, and then 0.1
10 μs after ns, the second laser pulse from the second oscillator is focused on the same position on the test sample with the same optical axis as the first laser pulse, or parallel or almost parallel to the optical axis of the first laser pulse. The first laser beam pulse is focused on the test sample at a position very close to the focus position on the test sample with the optical axis, and the test sample is further excited, and the emission line spectrum light with a wavelength of 200 nm or more is reflected by a mirror, A laser multistage excitation direct emission analysis method comprising guiding the laser to a spectroscopic analyzer using means such as a lens and/or an optical fiber for spectroscopic analysis.
さらに１又は２以上のレーザパルスを時間的間隔を置い
て被検試料の同一位置又はそれの極近傍位置に集光する
からなる特許請求の範囲第１項記載の方法。(2) After the light is focused on the test sample by the second laser pulse, one or more laser pulses are further focused at the same position on the test sample or at a position very close to it at a time interval. The method according to claim 1.
、前記第１のレーザ発振器の出射口近傍に必要に応じて
光路変更のためのプリズムおよび／または誘電体多層膜
鏡を固定し、２つのレーザ発振器からのレーザビームを
重ねるため第１のレーザビーム上に波長板および第２の
レーザビームを曲げるための偏光ビームスプリッターを
設けるか、又は２つのレーザビームを近接して平行又は
ほぼ平行になるように第２のレーザビーム用のレーザ光
反射鏡を設け、２つのレーザビーム中に集光レンズを固
定し、被検試料からの発光線スペクトルを分光分析器に
伝送するための反射鏡、レンズおよび／または光ファイ
バー等の手段を設けたレーザ多段励起直接発光分析装置
。(3) Spectroscopic analyzer, first laser oscillator. fixing a second laser oscillator connected to an electrical delay device; fixing a prism and/or a dielectric multilayer mirror for changing the optical path as necessary near the emission aperture of the first laser oscillator; A wave plate may be provided on the first laser beam to overlap the laser beams from two laser oscillators and a polarizing beam splitter may be provided to bend the second laser beam, or the two laser beams may be placed in close parallel or nearly parallel alignment. A laser light reflecting mirror for the second laser beam is provided, a condensing lens is fixed in the two laser beams, and a reflecting mirror for transmitting the emission line spectrum from the test sample to the spectroscopic analyzer; Laser multistage excitation direct emission spectrometer equipped with means such as lenses and/or optical fibers.
に連結した第２のレーザ発振器を固定し、前記第２のレ
ーザ発振器の出射口近傍に必要に応じて光路変更のため
のプリズムおよび／または誘電体多層膜鏡を固定し、２
つのレーザ発振器からのレーザビームを重ねるため第２
のレーザビーム上に波長板および第１のレーザビームを
曲げるための偏光ビームスプリッターを設けるか、又は
２つのレーザビームを近接して平行又はほぼ平行になる
ように第１のレーザビーム用のレーザ光反射鏡を設け、
２つのレーザビーム中に集光レンズを固定し、被検試料
からの発光線スペクトルを分光分析器に伝送するための
反射鏡、レンズおよび／または光ファイバー等の手段を
設けたレーザ多段励起直接発光分析装置。(4) A second laser oscillator connected to a spectrometer and a first laser oscillator electrical delay device is fixed, and a prism for changing the optical path and a /or fix the dielectric multilayer mirror,
A second laser beam is used to overlap the laser beams from two laser oscillators.
A wavelength plate and a polarizing beam splitter for bending the first laser beam are provided on the laser beam of the first laser beam, or the laser beam for the first laser beam is arranged so that the two laser beams are brought close to each other so that they become parallel or nearly parallel. Install a reflector,
Laser multistage excitation direct emission analysis in which a condensing lens is fixed in two laser beams and means such as a reflector, lens, and/or optical fiber are provided to transmit the emission line spectrum from the test sample to a spectrometer. Device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22576485A JPS62188919A (en) | 1985-10-09 | 1985-10-09 | Method and instrument for direct emission analysis by multistage laser excitation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22576485A JPS62188919A (en) | 1985-10-09 | 1985-10-09 | Method and instrument for direct emission analysis by multistage laser excitation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62188919A true JPS62188919A (en) | 1987-08-18 |
| JPH055301B2 JPH055301B2 (en) | 1993-01-22 |
Family
ID=16834439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22576485A Granted JPS62188919A (en) | 1985-10-09 | 1985-10-09 | Method and instrument for direct emission analysis by multistage laser excitation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62188919A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02134545A (en) * | 1988-11-16 | 1990-05-23 | Nkk Corp | Laser-light emitting spectrochemical analysis method |
| JPH04507136A (en) * | 1989-04-21 | 1992-12-10 | リーハイ ユニヴァースティ | Transient spectrophotometry and equipment for in-process analysis of molten metals |
| US6008897A (en) * | 1999-01-19 | 1999-12-28 | National Research Council Of Canada | Method and apparatus for materials analysis by enhanced laser induced plasma spectroscopy |
| US6661511B2 (en) | 2001-01-16 | 2003-12-09 | National Research Council Of Canada | Method and apparatus for enhanced laser-induced plasma spectroscopy using mixed-wavelength laser pulses |
| JP2006266792A (en) * | 2005-03-23 | 2006-10-05 | Jfe Steel Kk | Emission spectrochemical analyzer of molten metal |
| JP2011007640A (en) * | 2009-06-26 | 2011-01-13 | Shikoku Electric Power Co Inc | Continuous concentration measuring apparatus and method |
-
1985
- 1985-10-09 JP JP22576485A patent/JPS62188919A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02134545A (en) * | 1988-11-16 | 1990-05-23 | Nkk Corp | Laser-light emitting spectrochemical analysis method |
| JPH04507136A (en) * | 1989-04-21 | 1992-12-10 | リーハイ ユニヴァースティ | Transient spectrophotometry and equipment for in-process analysis of molten metals |
| US6008897A (en) * | 1999-01-19 | 1999-12-28 | National Research Council Of Canada | Method and apparatus for materials analysis by enhanced laser induced plasma spectroscopy |
| US6661511B2 (en) | 2001-01-16 | 2003-12-09 | National Research Council Of Canada | Method and apparatus for enhanced laser-induced plasma spectroscopy using mixed-wavelength laser pulses |
| JP2006266792A (en) * | 2005-03-23 | 2006-10-05 | Jfe Steel Kk | Emission spectrochemical analyzer of molten metal |
| JP2011007640A (en) * | 2009-06-26 | 2011-01-13 | Shikoku Electric Power Co Inc | Continuous concentration measuring apparatus and method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH055301B2 (en) | 1993-01-22 |
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