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US2418029A - Electron probe analysis employing X-ray spectrography - Google Patents

Electron probe analysis employing X-ray spectrography Download PDF

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US2418029A
US2418029A US505573A US50557343A US2418029A US 2418029 A US2418029 A US 2418029A US 505573 A US505573 A US 505573A US 50557343 A US50557343 A US 50557343A US 2418029 A US2418029 A US 2418029A
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electron
ray
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electron probe
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Hillier James
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RCA Corp
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions
    • G01N23/2076—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions for spectrometry, i.e. using an analysing crystal, e.g. for measuring X-ray fluorescence spectrum of a sample with wavelength-dispersion, i.e. WDXFS
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/252—Tubes for spot-analysing by electron or ion beams; Microanalysers

Definitions

  • This invention relates generally to electron optics and more particularly. to X-ray spectrographic means for analyzing materials irradiated by an electron beam having minute cross-sectional area,
  • theinstant invention contemplates a unique improvement upon existing methods of X-ray analysis wherein a minute cross-sectional area of the surface of the material under observation is subjected ⁇ to irradiation by an extremely ne beam of high velocity electrons.
  • the X-rays generated by the impingement otthe high velocity electrons uponthe minute electron irradiated material surface area are A.analyzed by means of any conventional photcgraphicor electrical X-ray spectrographic apparatus. From the wavelengths of thepcharacteristic radiation of the material, the ⁇ elements thereof may be determined., hence a point analysis of the specimen is desirab'l ⁇ e.
  • X-ray spectroscopes of the type described in X-rays in Theory and Experiment by Compton and Allison, may be employed to Vanalyze the X-ray radiation derived from the material under observation.
  • the Von Laue type spectrometer employing a zinc blonde crystal for forming a ⁇ diffraction pattern of the X-ray radiationupon a photographic plate, provides a satisfactory permanent record of the X-ray spectrographic characteristics of the material.
  • the Bragg type spectrometer also described in 'the reference mentioned heretofore, employs an ionizationV chamber for indicating the X-ray refractionTi-rom a zinc blende crystal the angular relation of which is adjustable with respect to the axis of the derived X-ray radiation.
  • Various other types of X-ray spectroscopes or X-ray spectrometers may be employed toequal advantage.
  • the instant invention is related to apnlicants copending U S. application, Ser. No. 505,572, led October 8, .1.943, which describes several methods of and means for electron irradiating extremely minute areas of either electron permeable or electron opaque substances.
  • This copending application describes several methods oi and means for making a velocity analysis of electrons transmitted by or reiiected from said electron irradiated area.
  • the instant invention contemplates means for spectrcanalyzing X-ray radiation de rived from a minute electron irradiated area of substances which may or may not be substantially opaque to electrons.
  • ⁇ Another object of .the invention is to provide an improved method of and means for microscopically analyzingnia- ⁇ terals substantially opaqueto ⁇ irradiating elec- 5 trons.
  • a further object of the invention is to provide animproved method of and means for microscopically analyzing materials by subjecting minute' areas of' said materials to high velocity electron irradiation, and spectroanalyzing X-rays generated in the vicinity of said electronic irradiation.
  • Anadditional object of the invention is to provide an improved means for electron irradiating a* minute area of a material to generate Xfrays therefrom and electrical means for spec,- trcanalyzing said Xf-ray radiation.
  • the invention will be further described ⁇ by ref-V erence to the accompanying drawing of which the single iigure is a schematic, diagram of a typical embodiment thereof.,
  • an electron source I which may comprise, for example, a thermionic cathode and an apertured anode having high 3 electron accelerating potentials therebetween, is focused by a conventional electron lens 2 toform a greatly" reduced image 3 of the electron source llj ⁇
  • the ⁇ image 3 is ⁇ further vfocused by means of a second electron lens 4 to form substantially a point image of the electron source l at thepoint ⁇ 5 ⁇ o ⁇ n ⁇ the surfacel of ⁇ a ⁇ material 6 tcV be spectroanalyzed.
  • the rst and second electron lenses 2, il, respectively may be of either the conventional electromagnetic or electrostatic types employed in electron microscopes and similar apparatus.
  • the electron lenses may be energized by any means known in the art.
  • the electron irradiation of the point 5 on the surface of the electron opaque material 6 provides X-ray radiation in the vicinity of the point 5 due to the energy released by the high velocity electrons comprising the electron beam. A portion of this X-ray radiation is intercepted. by an X-ray spectroscope 8 of any known type which will provide the desired X-ray spectroanalysis.
  • the X-ray spectroscope 8 shown in the drawing comprises ⁇ a pair of lead collimating apertures 9, I0 for selecting an extremely minute X-ray beam for spectroanalysis.
  • the selected X-ray radiation is applied to a crystal II, which may be composed, ⁇
  • the crystal I I is arranged to be oriented with respect to the X-ray beam, in order that the X-rays may either be transmitted by the crystal or reflected therefrom.
  • the Velocity of lthe X-rays impinging upon the crystals II will determine the refraction of the X-rays derived from the crystal.
  • the X-ray radiation derived from the crystal may be applied to a photographic plate I2, to obtain a spectroscopic pattern characteristic of the material under observation.
  • a photographic plate in an X-ray spectroscope of the type described, it is customary to orient the crystal so that it transmits the applied X-rays to the photographic plate.
  • an ionization chamber not shown in the drawing, is substituted for the photographic plate I2.
  • the X-rays are reflected from the crystal II, and the current derived from the ionization chamber is indicated in terms of the angular orientation of the crystal with respect to the axis of the applied X-rays.
  • the invention described comprises a novel method of and means for spectroanalyzing eX- tremely minute surface areas of materials by focusing a high Velocity electron beam upon a minute area of the materialsurface, and spectroscopically analyzing X-rays generated by said electron bombardment.
  • the ⁇ method of microscopically analyzing the atomic composition of amaterial comprising electron irradiating a minute cross-sectional area of said material,generating X-rays in the vicinity of said area in response to said irradiation, and spectroanalyzing said generated X-rays.
  • a 2 The method of microscopically analyzing the atomic composition of a material comprising generating an electron probe of minute cross-sectional area, electron irradiating said material by said electron probe, generating X-rays in the vicinity of said area in respons to vsaid irradiation, and spectroanalyzing said generated X-rays.
  • a spectroscope for analyzing the atomic composition of a material including means for supporting said material, means for electron irradiating a predetermined minute cross-sectional surface area of said material to generate X-rays in the vicinity of said irradiation,-and means for spectroanalyzing said generated X-rays.
  • A4 ing an electron probe of minute cross-sectional area, means for supporting an object, means for irradiating substantially only a minute surface area of said object by said electron probe to gene Y ating an electron probe of minute cross-section- 4.
  • a spectroscope including means for generatal area., means for supporting an object, means for irradiating substantially only a minute surface area of said object by said electron probe to generate X-rays in the vicinity of said electron irradiation, and photographic means for spectroanalyzing said generated X-rays.
  • a spectroscope including means for generating an electron probe of minute cross-sectional area, means for supporting an object, means for irradiatingsaid object by said electron probe to generate X-rays in the Vicinity of said electron irradiation, and photographic means and an X-ray refracting crystal disposed intermediate said object and said photographic means for spectroanalyzing said generated X-rays.
  • a spectrometer for analyzing the atomic composition of a material including means for supporting said material, means for electron .irradiating s-ubstantially only a predetermined minute cross-sectional surface area of said material to generate X-rays in the vicinity of said irradiation, and electrical means for spectroanalyzing said generated X-rays.

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Description

ELECTRON PROBE ANALYSIS EMPLOYING X-RAY SPECTROGRAPHY Filed oct. 8, 19.43
Patented Mar. 25, 1947 ELao'raoN PROBE ANALYSIS EMPLoYiNG X-RAY SPECTROGRAPHY .I ames Hillier, Granbury, N. J assignor` to Radio Corporation of America, a
Ware
corporation of Dela- .appucaaon ottenere, 1943, serial No.5o5,573
7 Claims. (CL 25d-49.5)
This invention relates generally to electron optics and more particularly. to X-ray spectrographic means for analyzing materials irradiated by an electron beam having minute cross-sectional area,
Investigation of the characteristics of various materials by X-ray analysis is Well known. However', theinstant invention contemplates a unique improvement upon existing methods of X-ray analysis wherein a minute cross-sectional area of the surface of the material under observation is subjected `to irradiation by an extremely ne beam of high velocity electrons. The X-rays generated by the impingement otthe high velocity electrons uponthe minute electron irradiated material surface area are A.analyzed by means of any conventional photcgraphicor electrical X-ray spectrographic apparatus. From the wavelengths of thepcharacteristic radiation of the material, the` elements thereof may be determined., hence a point analysis of the specimen is desirab'l`e.
X-ray spectroscopes of the type described in X-rays in Theory and Experiment by Compton and Allison, may be employed to Vanalyze the X-ray radiation derived from the material under observation. The Von Laue type spectrometer, employing a zinc blonde crystal for forming a` diffraction pattern of the X-ray radiationupon a photographic plate, provides a satisfactory permanent record of the X-ray spectrographic characteristics of the material. Similarly, the Bragg type spectrometer, also described in 'the reference mentioned heretofore, employs an ionizationV chamber for indicating the X-ray refractionTi-rom a zinc blende crystal the angular relation of which is adjustable with respect to the axis of the derived X-ray radiation. Various other types of X-ray spectroscopes or X-ray spectrometers may be employed toequal advantage.
The instant invention is related to apnlicants copending U S. application, Ser. No. 505,572, led October 8, .1.943, which describes several methods of and means for electron irradiating extremely minute areas of either electron permeable or electron opaque substances. This copending application describes several methods oi and means for making a velocity analysis of electrons transmitted by or reiiected from said electron irradiated area. The instant invention contemplates means for spectrcanalyzing X-ray radiation de rived from a minute electron irradiated area of substances which may or may not be substantially opaque to electrons.
Among the objects of the invention are to provide an improved method of and means for micro- 2 scopically analyzing materials. `Another object of .the invention is to provide an improved method of and means for microscopically analyzingnia-` terals substantially opaqueto `irradiating elec- 5 trons. A further object of the invention is to provide animproved method of and means for microscopically analyzing materials by subjecting minute' areas of' said materials to high velocity electron irradiation, and spectroanalyzing X-rays generated in the vicinity of said electronic irradiation. A Further objects of theinventionjinclude improved means for electron'v irradiating minute areas of a substance to generate X-rays there.-` from and photographic X-ray spectrographic means for providing al permanentl record of the X-ray spectrographic characteristics of the said material'. Anadditional object of the invention is to provide an improved means for electron irradiating a* minute area of a material to generate Xfrays therefrom and electrical means for spec,- trcanalyzing said Xf-ray radiation. The invention will be further described` by ref-V erence to the accompanying drawing of which the single iigure is a schematic, diagram of a typical embodiment thereof.,
Referring to the drawing, an electron source I, which may comprise, for example, a thermionic cathode and an apertured anode having high 3 electron accelerating potentials therebetween, is focused by a conventional electron lens 2 toform a greatly" reduced image 3 of the electron source llj `The `image 3 is` further vfocused by means of a second electron lens 4 to form substantially a point image of the electron source l at thepoint `5 `o`n` the surfacel of `a` material 6 tcV be spectroanalyzed. It should be understood that the rst and second electron lenses 2, il, respectively, may be of either the conventional electromagnetic or electrostatic types employed in electron microscopes and similar apparatus. The electron lenses may be energized by any means known in the art.
The electron irradiation of the point 5 on the surface of the electron opaque material 6 provides X-ray radiation in the vicinity of the point 5 due to the energy released by the high velocity electrons comprising the electron beam. A portion of this X-ray radiation is intercepted. by an X-ray spectroscope 8 of any known type which will provide the desired X-ray spectroanalysis.
For the purpose of illustration, the X-ray spectroscope 8 shown in the drawing, comprises `a pair of lead collimating apertures 9, I0 for selecting an extremely minute X-ray beam for spectroanalysis. The selected X-ray radiation is applied to a crystal II, which may be composed,`
for example, of zinc blende. The crystal I I is arranged to be oriented with respect to the X-ray beam, in order that the X-rays may either be transmitted by the crystal or reflected therefrom.-
The Velocity of lthe X-rays impinging upon the crystals II will determine the refraction of the X-rays derived from the crystal. The X-ray radiation derived from the crystal may be applied to a photographic plate I2, to obtain a spectroscopic pattern characteristic of the material under observation. When employing a photographic plate in an X-ray spectroscope, of the type described, it is customary to orient the crystal so that it transmits the applied X-rays to the photographic plate.
However, if electrical indication of the X-ray characteristics is desired, an ionization chamber, not shown in the drawing, is substituted for the photographic plate I2. The X-rays are reflected from the crystal II, and the current derived from the ionization chamber is indicated in terms of the angular orientation of the crystal with respect to the axis of the applied X-rays.
Thus the invention described comprises a novel method of and means for spectroanalyzing eX- tremely minute surface areas of materials by focusing a high Velocity electron beam upon a minute area of the materialsurface, and spectroscopically analyzing X-rays generated by said electron bombardment.
I claimV as my invention:
y1. The `method of microscopically analyzing the atomic composition of amaterial comprising electron irradiating a minute cross-sectional area of said material,generating X-rays in the vicinity of said area in response to said irradiation, and spectroanalyzing said generated X-rays.
A 2. The method of microscopically analyzing the atomic composition of a material comprising generating an electron probe of minute cross-sectional area, electron irradiating said material by said electron probe, generating X-rays in the vicinity of said area in respons to vsaid irradiation, and spectroanalyzing said generated X-rays.
3. A spectroscope for analyzing the atomic composition of a material including means for supporting said material, means for electron irradiating a predetermined minute cross-sectional surface area of said material to generate X-rays in the vicinity of said irradiation,-and means for spectroanalyzing said generated X-rays.
A4 ing an electron probe of minute cross-sectional area, means for supporting an object, means for irradiating substantially only a minute surface area of said object by said electron probe to gene Y ating an electron probe of minute cross-section- 4. A spectroscope including means for generatal area., means for supporting an object, means for irradiating substantially only a minute surface area of said object by said electron probe to generate X-rays in the vicinity of said electron irradiation, and photographic means for spectroanalyzing said generated X-rays.
6. A spectroscope including means for generating an electron probe of minute cross-sectional area, means for supporting an object, means for irradiatingsaid object by said electron probe to generate X-rays in the Vicinity of said electron irradiation, and photographic means and an X-ray refracting crystal disposed intermediate said object and said photographic means for spectroanalyzing said generated X-rays.
7. A spectrometer for analyzing the atomic composition of a material including means for supporting said material, means for electron .irradiating s-ubstantially only a predetermined minute cross-sectional surface area of said material to generate X-rays in the vicinity of said irradiation, and electrical means for spectroanalyzing said generated X-rays.
. JAMES HILLIER..
REFERENCES CITED The following references are of lrecord in the iile of this paten Y UNITED STATES PATENTSV Number Name Date 2,079,900 Cohn May 11, 1937 2,131,536 Knoll et al Sept. 27,1938 2,281,325 Ramo Apr. 28, 1942 1,971,277 Rupp Aug. 21, 1934 2,341,108 McLachlan Feb. 8, 1944 2,025,488 Yap Dec. 24, 1935 2,257,774 Von Ardenne Oct. 7, 1941 1,596,305 Rentschler Aug. 17, 1926 1,997,356 Bryant Apr. 9,1935 2,197,033 Diels Apr. 16,1940 2,274,215 Ruska Feb. 24,1942
FOREIGN PATENTS Number Country Date 86,274 Swiss Aug. 16, 1920
US505573A 1943-10-08 1943-10-08 Electron probe analysis employing X-ray spectrography Expired - Lifetime US2418029A (en)

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2557662A (en) * 1948-11-29 1951-06-19 Research Corp Short-wave electromagnetic radiation catoptrics
US2711480A (en) * 1948-06-29 1955-06-21 Friedman Herbert Method of measuring thickness of thin layers
US2877353A (en) * 1954-07-14 1959-03-10 Gen Electric X-ray microscope
US2908821A (en) * 1955-05-06 1959-10-13 Ontario Research Foundation Apparatus for spectrochemical analysis and structural analysis of solids, fluids andgases by means of x-rays
US2916621A (en) * 1958-04-24 1959-12-08 California Inst Res Found Electron probe microanalyzer
US2982814A (en) * 1958-02-14 1961-05-02 Philips Corp Apparatus for determining the composition and condition of a specimen of material
US3005098A (en) * 1958-03-31 1961-10-17 Gen Electric X-ray emission analysis
US3049618A (en) * 1959-05-13 1962-08-14 Commissariat Energie Atomique Methods and devices for performing spectrum analysis, in particular in the far ultraviolet region
US3086114A (en) * 1959-05-26 1963-04-16 Siemens Ag Electron microscope diaphragm arrangement with auxiliary device for X-ray spectroscopy of irradiated specimen
US3107297A (en) * 1960-08-29 1963-10-15 Applied Res Lab Inc Electron probe X-ray analyzer wherein the emitted X-radiation passes through the objective lens
US3149258A (en) * 1954-09-09 1964-09-15 Sheldon Edward Emanuel Electron microscope with an X-ray target
US3204095A (en) * 1960-12-21 1965-08-31 Hitachi Ltd Electron probe microanalyzer with means to eliminate the effect of surface irregularities
US3223837A (en) * 1961-07-10 1965-12-14 First Pennsylvania Banking And Beam probe system and apparatus
US3229087A (en) * 1961-09-25 1966-01-11 First Pennsylvania Banking And Electron microanalyzer and monitoring system
US3235727A (en) * 1961-03-02 1966-02-15 First Pennsylvania Banking And Electron probe system
US3246146A (en) * 1963-07-11 1966-04-12 Ass Elect Ind Apparatus for the X-ray analysis of a liquid suspension of specimen material
US3597577A (en) * 1967-09-07 1971-08-03 Combustible Nucleaire X-ray examination of welds
US4182959A (en) * 1978-07-27 1980-01-08 SEA Investigation Division, Inc. Methods for use in fire investigation
US4320298A (en) * 1962-04-27 1982-03-16 The Marquardt Corporation Warhead detector
US4697080A (en) * 1986-01-06 1987-09-29 The United States Of America As Represented By The United States Department Of Energy Analysis with electron microscope of multielement samples using pure element standards

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH86274A (en) * 1916-02-25 1920-08-16 Reiniger Gebbert & Schall Akti Method and device for examining secondary radiation, particularly X-rays.
US1596305A (en) * 1921-02-14 1926-08-17 Westinghouse Lamp Co X-ray tube
US1971277A (en) * 1931-06-26 1934-08-21 Gen Electric Device for analyzing the structure of matter
US1997356A (en) * 1931-02-04 1935-04-09 Beryl B Bryant Invisible radiation, detection, and utilization
US2025488A (en) * 1933-03-29 1935-12-24 Yap Chu-Phay X-ray diffraction apparatus
US2079900A (en) * 1933-11-01 1937-05-11 Willi M Cohn Method of testing materials
US2131536A (en) * 1932-03-16 1938-09-27 Knoll Max Electron microscope
US2197033A (en) * 1937-06-10 1940-04-16 Telefunken Gmbh Electron device
US2257774A (en) * 1937-02-18 1941-10-07 Ardenne Manfred Von Electronic-optical device
US2274215A (en) * 1939-07-22 1942-02-24 Fides Gmbh Electronic microscope
US2281325A (en) * 1941-08-20 1942-04-28 Gen Electric Electron microscope
US2341108A (en) * 1942-03-05 1944-02-08 American Cyanamid Co X-ray technique

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH86274A (en) * 1916-02-25 1920-08-16 Reiniger Gebbert & Schall Akti Method and device for examining secondary radiation, particularly X-rays.
US1596305A (en) * 1921-02-14 1926-08-17 Westinghouse Lamp Co X-ray tube
US1997356A (en) * 1931-02-04 1935-04-09 Beryl B Bryant Invisible radiation, detection, and utilization
US1971277A (en) * 1931-06-26 1934-08-21 Gen Electric Device for analyzing the structure of matter
US2131536A (en) * 1932-03-16 1938-09-27 Knoll Max Electron microscope
US2025488A (en) * 1933-03-29 1935-12-24 Yap Chu-Phay X-ray diffraction apparatus
US2079900A (en) * 1933-11-01 1937-05-11 Willi M Cohn Method of testing materials
US2257774A (en) * 1937-02-18 1941-10-07 Ardenne Manfred Von Electronic-optical device
US2197033A (en) * 1937-06-10 1940-04-16 Telefunken Gmbh Electron device
US2274215A (en) * 1939-07-22 1942-02-24 Fides Gmbh Electronic microscope
US2281325A (en) * 1941-08-20 1942-04-28 Gen Electric Electron microscope
US2341108A (en) * 1942-03-05 1944-02-08 American Cyanamid Co X-ray technique

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711480A (en) * 1948-06-29 1955-06-21 Friedman Herbert Method of measuring thickness of thin layers
US2557662A (en) * 1948-11-29 1951-06-19 Research Corp Short-wave electromagnetic radiation catoptrics
US2877353A (en) * 1954-07-14 1959-03-10 Gen Electric X-ray microscope
US3149258A (en) * 1954-09-09 1964-09-15 Sheldon Edward Emanuel Electron microscope with an X-ray target
US2908821A (en) * 1955-05-06 1959-10-13 Ontario Research Foundation Apparatus for spectrochemical analysis and structural analysis of solids, fluids andgases by means of x-rays
US2982814A (en) * 1958-02-14 1961-05-02 Philips Corp Apparatus for determining the composition and condition of a specimen of material
US3005098A (en) * 1958-03-31 1961-10-17 Gen Electric X-ray emission analysis
US2916621A (en) * 1958-04-24 1959-12-08 California Inst Res Found Electron probe microanalyzer
US3049618A (en) * 1959-05-13 1962-08-14 Commissariat Energie Atomique Methods and devices for performing spectrum analysis, in particular in the far ultraviolet region
US3086114A (en) * 1959-05-26 1963-04-16 Siemens Ag Electron microscope diaphragm arrangement with auxiliary device for X-ray spectroscopy of irradiated specimen
US3107297A (en) * 1960-08-29 1963-10-15 Applied Res Lab Inc Electron probe X-ray analyzer wherein the emitted X-radiation passes through the objective lens
US3204095A (en) * 1960-12-21 1965-08-31 Hitachi Ltd Electron probe microanalyzer with means to eliminate the effect of surface irregularities
US3235727A (en) * 1961-03-02 1966-02-15 First Pennsylvania Banking And Electron probe system
US3223837A (en) * 1961-07-10 1965-12-14 First Pennsylvania Banking And Beam probe system and apparatus
US3229087A (en) * 1961-09-25 1966-01-11 First Pennsylvania Banking And Electron microanalyzer and monitoring system
US4320298A (en) * 1962-04-27 1982-03-16 The Marquardt Corporation Warhead detector
US3246146A (en) * 1963-07-11 1966-04-12 Ass Elect Ind Apparatus for the X-ray analysis of a liquid suspension of specimen material
US3597577A (en) * 1967-09-07 1971-08-03 Combustible Nucleaire X-ray examination of welds
US4182959A (en) * 1978-07-27 1980-01-08 SEA Investigation Division, Inc. Methods for use in fire investigation
US4697080A (en) * 1986-01-06 1987-09-29 The United States Of America As Represented By The United States Department Of Energy Analysis with electron microscope of multielement samples using pure element standards

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