WO1992002282A1 - Method and apparatus for analytical sample preparation - Google Patents

Method and apparatus for analytical sample preparation Download PDF

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Publication number
WO1992002282A1
WO1992002282A1 PCT/GB1991/001345 GB9101345W WO9202282A1 WO 1992002282 A1 WO1992002282 A1 WO 1992002282A1 GB 9101345 W GB9101345 W GB 9101345W WO 9202282 A1 WO9202282 A1 WO 9202282A1
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WO
WIPO (PCT)
Prior art keywords
sample
droplets
liquid
subjecting
radiative heating
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.)
Ceased
Application number
PCT/GB1991/001345
Other languages
French (fr)
Inventor
Alan Reuben Eastgate
Wilfried Vogel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Thermo Fisher Scientific Ecublens SARL
Fisons Ltd
Original Assignee
ARL Applied Research Laboratories SA
Fisons Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GB909017446A external-priority patent/GB9017446D0/en
Priority claimed from GB909020315A external-priority patent/GB9020315D0/en
Application filed by ARL Applied Research Laboratories SA, Fisons Ltd filed Critical ARL Applied Research Laboratories SA
Priority to DE69120935T priority Critical patent/DE69120935T2/en
Priority to EP91914547A priority patent/EP0510127B1/en
Priority to US07/969,228 priority patent/US5369035A/en
Publication of WO1992002282A1 publication Critical patent/WO1992002282A1/en
Priority to GB9302664A priority patent/GB2263238B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/16—Evaporating by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/0011—Heating features
    • B01D1/0017—Use of electrical or wave energy
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/24—Nuclear magnetic resonance, electron spin resonance or other spin effects or mass spectrometry
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
    • Y10T436/25125—Digestion or removing interfering materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
    • Y10T436/25875—Gaseous sample or with change of physical state

Definitions

  • Elemental analysis encompasses a variety of techniques which involve the qualitative and/or quantitative determination of the elemental composition of a sample based on the atomic properties of the constituent elements.
  • One such form of elemental analysis is atomic emission spectroscopy (AES) , which involves exciting the chemical elements in a sample to emit light of one or more specific wavelengths (spectral light) .
  • Atomisation and excitation of the sample occurs in a suitable source, for example, an inductively coupled plasma (ICP) .
  • ICP inductively coupled plasma
  • the dispersion may be prepared by various means; spray generators, ther ospray systems, pneumatic nebulisers or ultrasonic nebulisers (USNs) may be used in the case of liquid samples; and electric arc heating or laser ablation used in the case of solid samples.
  • liquid sample any sample for analysis in which the analyte(s) are present in a liquid carrier, for example, solutions, dispersions, suspensions, colloids and slurries.
  • the liquid carrier is evaporated from the dispersed droplets so that the analyte enters the plasma source as an essentially dry aerosol.
  • Evaporation of the liquid is advantageous because it cancels the cooling effect on the plasma caused by the injection of large volumes of liquid, meaning more energy is available for atomisation and excitation; it also reduces other carrier effects such as plasma instability and spectral interferences, for example, oxide interferences when the carrier is water.
  • Conventional methods of evaporation involve passing the dispersed sample, in a flow of carrier gas, through a heated tube, at for example, 130°C, to evaporate the liquid carrier and then through a refrigerated tube to condense and separate the liquid from the analyte aerosol.
  • the sample' is heated, by conduction, to the boiling point of the droplet over a period of about one second, liquid evaporates leaving the analyte contained therein as a single particle.
  • the resulting particle size is therefore defined by the droplet size and the concentration of analyte in the sample.
  • an apparatus for the production of aerosols from liquid samples comprising a) means for generating droplets of the liquid sample, and b) means for subjecting the droplets so formed to rapid radiative heating so as to evaporate liquid from the sample droplets.
  • rapid radiative heating 1 is meant radiative heating of the sample to a temperature above the boiling point of the liquid carrier within a very short time, say between 0.1ms and 0.2s, preferably less than 0.1s and more preferably less than 50ms.
  • the rapid heating may be such as to heat the sample to a temperature of about 200°C within 10ms.
  • a method for the elemental analysis of a liquid sample comprises the steps of a) generating droplets of the liquid sample, b) subjecting the droplets so formed to rapid radiative heating so as to evaporate liquid from the sample droplets, and c) analysing the sample aerosol by an appropriate technique.
  • Appropriate analytical techniques which may be used in the method of the invention include optical emission spectroscopy, atomic absorption spectroscopy, atomic fluorescence spectroscopy and mass spectroscopy.
  • the method of the invention may also be used as a means for coupling liquid chromatography units to any of the aforementioned analytical techniques.
  • a method for the optical emission analysis of a liquid sample comprises the steps of a) generating droplets of the liquid sample, b) subjecting the droplets so formed to rapid radiative heating so as to evaporate liquid from the sample droplets, c) exciting the chemical elements in the sample aerosol to emit light, and d) measuring the intensity of the emitted light at one or more wavelengths.
  • an optical emission spectrometer comprising a) means for generating droplets of a liquid sample, b) means for subjecting the droplets to rapid radiative heating so as to evaporate liquid from the sample droplets, c) means for exciting the chemical elements in the sample aerosol to emit light, and d) means for measuring the intensity of the emitted light at one or more wavelengths.
  • the apparatus and method according to the invention are advantageous in that the rapid radiative heating of the sample droplets prevents or inhibits agglomeration of the droplets into larger droplet. This in turn inhibits the formation, of relatively large particles of the sample under investigation resulting in improved sensitivity.
  • the rapid radiative heating causes the droplets to 'explode* in the boiling process which may result in the partition of the analyte contained therein into smaller particles, rather than 'drying' slowly leaving all the solid material as a single particle.
  • An example of the means by which the rapid radiative heating of the sample droplets can be achieved is to place the dispersed sample at one focus of a reflector or a lens and to heat it with a radiation source placed at the other focus.
  • the heating may be achieved using a reflector, more preferably an ellipsoidal reflector, particularly an ellipsoidal metal reflector.
  • the sample droplets may be heated by intense microwave heating at 22.3GHz (in the case of aqueous liquids).
  • the radiation source to be a heat-bar.
  • the surface of the heat-bar is preferably chosen to be strongly emissive in those regions of the infrared spectrum where the liquid carrier is strongly absorbing.
  • the heat-bar may have a surface of silicon carbide.
  • the sample droplets may be held in a heating chamber, for example, a tube which is transparent to the heating radiation, e.g. a tube of infrared transmissive quartz.
  • the heating chamber may be in the form of a flow-through tube. However, we prefer the heating chamber to be such that re-condensed liquid cannot re-enter the region in which evaporation of the liquid occurs.
  • a suitable form is a vertical tube sealed at one end with both the inlet and the outlet in the other end.
  • the sample aerosol may be separated from the evaporated liquid by one or more liquid removal devices, suitable devices include condensers and gas diffusion cells.
  • Figure 1 is a schematic view of an atomic emission spectrometer.
  • An atomic emission spectrometer comprises a sample conduit upon which are sequentially situated a nebuliser (1) , a sample heating chamber (2) , a condenser (3) and an ICP torch (4) .
  • a liquid sample of the material under investigation is introduced into the nebuliser (1) via a sample inlet port (11) and nebulised i.e. converted to a fine dispersion.
  • the conduit is flushed with argon gas from a pressurised cylinder (not shown) such that the dispersed sample is carried"successively through the heating chamber (2), the condenser (3) and the ICP torch (4) .
  • the heating chamber (2) is located at one focus of an ellipsoidal reflector (22) .
  • the sample is subjected to rapid radiative heating by means of a heat-bar (21) located at the other focus of the reflector (22) .
  • the surface of the heat-bar (21) is chosen to be strongly emissive in those regions of the infrared spectrum at which the liquid carrier of the sample is strongly absorbing.
  • the heating chamber (2) comprises a tube of material which is transparent at these wavelengths, and is in the form of a vertical tube sealed at the top with both the inlet and the outlet in the base.
  • the sample aerosol After heating, and evaporation of liquid from the sample, the sample aerosol passes through the condenser (3) where the sample analyte is separated from the evaporated carrier. The sample aerosol then passes into the ICP torch (4) where it is excited to emission at temperatures of 4,000 to 8,000K.
  • the emitted light is dispersed by a onochromator (5) and its intensity at the wavelength of interest is measured by a detector (6) .
  • the nebuliser (1) , condenser (2) , ICP torch (4) , monochromator (5) and detector (6) may be of conventional design.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

An apparatus for the production of aerosols from liquid samples for elemental analysis comprises means for generating droplets of the liquid sample (1), and means for subjecting the droplets so formed to rapid radiative heating (2, 21, 22) so as to evaporate liquid from the sample droplets. The heating means preferably comprises a heating chamber (2) positioned at one focus of a reflector (22) and a heat-bar (21) positioned at the other focus.

Description

Method and Apparatus for Analytical Sample Preparatio .
This invention relates to apparatus and methods for elemental analysis, in particular to pre-treatment of a sample to be analysed. Elemental analysis encompasses a variety of techniques which involve the qualitative and/or quantitative determination of the elemental composition of a sample based on the atomic properties of the constituent elements. One such form of elemental analysis is atomic emission spectroscopy (AES) , which involves exciting the chemical elements in a sample to emit light of one or more specific wavelengths (spectral light) . Atomisation and excitation of the sample occurs in a suitable source, for example, an inductively coupled plasma (ICP) . The technique is conventionally applied to a fine dispersion of the sample under investigation. The dispersion may be prepared by various means; spray generators, ther ospray systems, pneumatic nebulisers or ultrasonic nebulisers (USNs) may be used in the case of liquid samples; and electric arc heating or laser ablation used in the case of solid samples.
By liquid sample is meant any sample for analysis in which the analyte(s) are present in a liquid carrier, for example, solutions, dispersions, suspensions, colloids and slurries.
In practice it is found that the quality of the analysis depends strongly on the particle size distribution of the dispersion, the presence of larger particles being deleterious in that the atomisation and excitation of such larger particles is less efficient.
In the case of liquid samples it is also desirable that the liquid carrier is evaporated from the dispersed droplets so that the analyte enters the plasma source as an essentially dry aerosol. Evaporation of the liquid is advantageous because it cancels the cooling effect on the plasma caused by the injection of large volumes of liquid, meaning more energy is available for atomisation and excitation; it also reduces other carrier effects such as plasma instability and spectral interferences, for example, oxide interferences when the carrier is water. Conventional methods of evaporation involve passing the dispersed sample, in a flow of carrier gas, through a heated tube, at for example, 130°C, to evaporate the liquid carrier and then through a refrigerated tube to condense and separate the liquid from the analyte aerosol. In such a process the sample' is heated, by conduction, to the boiling point of the droplet over a period of about one second, liquid evaporates leaving the analyte contained therein as a single particle. The resulting particle size is therefore defined by the droplet size and the concentration of analyte in the sample. Thus, even with the fine dispersions produced by, for example, USNs the analyte particles left after evaporation of the liquid may still be larger than is desirable for efficient atomisation and excitation.
We have now found that the atomic emission analysis of liquid samples can be substantially improved by a rapid radiative heating of the dispersion, so as to evaporate liquid from the dispersion, when the atoms to be analysed for are still entrained in small droplets, and that this technique is also valuable in preparing samples for other methods of elemental analysis.
Thus, according to the invention there is provided an apparatus for the production of aerosols from liquid samples comprising a) means for generating droplets of the liquid sample, and b) means for subjecting the droplets so formed to rapid radiative heating so as to evaporate liquid from the sample droplets. By 'rapid radiative heating1 is meant radiative heating of the sample to a temperature above the boiling point of the liquid carrier within a very short time, say between 0.1ms and 0.2s, preferably less than 0.1s and more preferably less than 50ms. Where the carrier is water, for example, the rapid heating may be such as to heat the sample to a temperature of about 200°C within 10ms.
According to a further aspect of the invention there is provided a method for the elemental analysis of a liquid sample, which method comprises the steps of a) generating droplets of the liquid sample, b) subjecting the droplets so formed to rapid radiative heating so as to evaporate liquid from the sample droplets, and c) analysing the sample aerosol by an appropriate technique.
Appropriate analytical techniques which may be used in the method of the invention include optical emission spectroscopy, atomic absorption spectroscopy, atomic fluorescence spectroscopy and mass spectroscopy. The method of the invention may also be used as a means for coupling liquid chromatography units to any of the aforementioned analytical techniques.
According to another specific aspect of the invention, therefore, there is provided a method for the optical emission analysis of a liquid sample, which method comprises the steps of a) generating droplets of the liquid sample, b) subjecting the droplets so formed to rapid radiative heating so as to evaporate liquid from the sample droplets, c) exciting the chemical elements in the sample aerosol to emit light, and d) measuring the intensity of the emitted light at one or more wavelengths. According to another aspect of the invention there is provided an optical emission spectrometer, comprising a) means for generating droplets of a liquid sample, b) means for subjecting the droplets to rapid radiative heating so as to evaporate liquid from the sample droplets, c) means for exciting the chemical elements in the sample aerosol to emit light, and d) means for measuring the intensity of the emitted light at one or more wavelengths.
Similarly, the scope of the invention includes other analytical techniques (examples of which are given above) and corresponding instruments which are appropriately modified.
The apparatus and method according to the invention are advantageous in that the rapid radiative heating of the sample droplets prevents or inhibits agglomeration of the droplets into larger droplet. This in turn inhibits the formation, of relatively large particles of the sample under investigation resulting in improved sensitivity. The rapid radiative heating causes the droplets to 'explode* in the boiling process which may result in the partition of the analyte contained therein into smaller particles, rather than 'drying' slowly leaving all the solid material as a single particle.
An example of the means by which the rapid radiative heating of the sample droplets can be achieved is to place the dispersed sample at one focus of a reflector or a lens and to heat it with a radiation source placed at the other focus.
We prefer the heating to be achieved using a reflector, more preferably an ellipsoidal reflector, particularly an ellipsoidal metal reflector. The sample droplets may be heated by intense microwave heating at 22.3GHz (in the case of aqueous liquids). However, we prefer the radiation source to be a heat-bar.
The surface of the heat-bar is preferably chosen to be strongly emissive in those regions of the infrared spectrum where the liquid carrier is strongly absorbing. For example, where the carrier is water the heat-bar may have a surface of silicon carbide.
During heating, the sample droplets may be held in a heating chamber, for example, a tube which is transparent to the heating radiation, e.g. a tube of infrared transmissive quartz. The heating chamber may be in the form of a flow-through tube. However, we prefer the heating chamber to be such that re-condensed liquid cannot re-enter the region in which evaporation of the liquid occurs. A suitable form is a vertical tube sealed at one end with both the inlet and the outlet in the other end. After heating, the sample aerosol may be separated from the evaporated liquid by one or more liquid removal devices, suitable devices include condensers and gas diffusion cells.
A preferred embodiment of the invention will now be described, by way of illustration only, with reference to the accompanying drawing in which
Figure 1 is a schematic view of an atomic emission spectrometer.
An atomic emission spectrometer comprises a sample conduit upon which are sequentially situated a nebuliser (1) , a sample heating chamber (2) , a condenser (3) and an ICP torch (4) .
A liquid sample of the material under investigation is introduced into the nebuliser (1) via a sample inlet port (11) and nebulised i.e. converted to a fine dispersion. The conduit is flushed with argon gas from a pressurised cylinder (not shown) such that the dispersed sample is carried"successively through the heating chamber (2), the condenser (3) and the ICP torch (4) .
The heating chamber (2) is located at one focus of an ellipsoidal reflector (22) . In the heating chamber (2) the sample is subjected to rapid radiative heating by means of a heat-bar (21) located at the other focus of the reflector (22) . The surface of the heat-bar (21) is chosen to be strongly emissive in those regions of the infrared spectrum at which the liquid carrier of the sample is strongly absorbing. The heating chamber (2) comprises a tube of material which is transparent at these wavelengths, and is in the form of a vertical tube sealed at the top with both the inlet and the outlet in the base.
After heating, and evaporation of liquid from the sample, the sample aerosol passes through the condenser (3) where the sample analyte is separated from the evaporated carrier. The sample aerosol then passes into the ICP torch (4) where it is excited to emission at temperatures of 4,000 to 8,000K.
The emitted light is dispersed by a onochromator (5) and its intensity at the wavelength of interest is measured by a detector (6) .
The nebuliser (1) , condenser (2) , ICP torch (4) , monochromator (5) and detector (6) may be of conventional design.

Claims

Claims :
1. A apparatus for the production of aerosols from liquid samples comprising a) means for generating droplets of the liquid sample, and b) means for subjecting the droplets so formed to rapid radiative heating so as to evaporate liquid from the sample droplets.
2. An apparatus according to Claim 1, further comprising at least one condenser to remove evaporated liquid from the sample aerosol.
3. An apparatus according to Claim 1 or Claim 2, wherein the means for generating droplets of the liquid sample is a nebuliser.
4. An apparatus according to any one of Claim 1 to 3, wherein the means for radiative heating is a radiation source positioned at one focus of a reflector or lens the dispersed sample being positioned at the other focus.
5. An apparatus according to Claim 4, wherein the radiation source is a heat-bar.
6. An apparatus according to Claim 4 or Claim 5, wherein the reflector is an ellipsoidal metal reflector.
7. A method for the elemental analysis of a liquid sample, which method comprises the steps of a) generating droplets of the liquid sample, b) subjecting the droplets so formed to rapid radiative heating so as to evaporate liquid from the sample droplets, and c) analysing the sample aerosol by an appropriate technique.
8. A method for the optical emission analysis of a liquid sample, which method comprises the steps of a) generating droplets of the liquid sample, b) subjecting the droplets so formed to rapid radiative heating so as to evaporate liquid from the sample droplets, c) exciting the chemical elements in the sample aerosol to emit light, and d) measuring the intensity of the emitted light at one or more wavelengths.
9. A method according to Claim 8, wherein excitation of the chemical elements in the sample to emit light occurs in an inductively coupled plasma.
10. An optical emission spectrometer, comprising a) means for generating droplets of a liquid sample, b) means for subjecting the droplets to rapid radiative heating so as to evaporate liquid from the sample droplets, c) means for exciting the chemical elements in the sample aerosol to emit light, and d) means for measuring the intensity of the emitted light at one or more wavelengths.
PCT/GB1991/001345 1990-08-09 1991-08-07 Method and apparatus for analytical sample preparation Ceased WO1992002282A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE69120935T DE69120935T2 (en) 1990-08-09 1991-08-07 METHOD AND DEVICE FOR PREPARING ANALYTICAL SAMPLES
EP91914547A EP0510127B1 (en) 1990-08-09 1991-08-07 Method and apparatus for analytical sample preparation
US07/969,228 US5369035A (en) 1990-08-09 1991-08-07 Method and apparatus for analytical sample preparation
GB9302664A GB2263238B (en) 1990-08-09 1993-02-09 Method and apparatus for analytical sample preparation

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB909017446A GB9017446D0 (en) 1990-08-09 1990-08-09 Spectroscopic method and apparatus
GB9017446.7 1990-08-09
GB909020315A GB9020315D0 (en) 1990-09-18 1990-09-18 Spectroscopic method and apparatus
GB9020315.9 1990-09-18

Publications (1)

Publication Number Publication Date
WO1992002282A1 true WO1992002282A1 (en) 1992-02-20

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US (1) US5369035A (en)
EP (1) EP0510127B1 (en)
JP (1) JPH05502104A (en)
AT (1) ATE140395T1 (en)
AU (1) AU646072B2 (en)
DE (1) DE69120935T2 (en)
WO (1) WO1992002282A1 (en)

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WO1993017320A1 (en) * 1992-02-19 1993-09-02 Fisons Plc Sample nebulizer and evaporation chamber for icp and mip emission or mass spectrometry and spectrometers comprising the same
ES2109159A1 (en) * 1995-04-26 1998-01-01 Univ Alicante Desolvation system, using microwaves, for use in atomic emission spectroscopy

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AUPS245402A0 (en) * 2002-05-21 2002-06-13 Varian Australia Pty Ltd Plasma torch for microwave induced plasmas
US20040002166A1 (en) * 2002-06-27 2004-01-01 Wiederin Daniel R. Remote analysis using aerosol sample transport
WO2005007928A1 (en) * 2003-07-22 2005-01-27 Lg Electronics Inc. Plasma surface processing system and supply device for plasma processing solution therefor
EP1853906A4 (en) * 2005-02-08 2010-03-17 Mds Inc Dbt Mds Sciex Division Method and apparatus for sample deposition
CA2496481A1 (en) * 2005-02-08 2006-08-09 Mds Inc., Doing Business Through It's Mds Sciex Division Method and apparatus for sample deposition
US9997325B2 (en) 2008-07-17 2018-06-12 Verity Instruments, Inc. Electron beam exciter for use in chemical analysis in processing systems
CN106525559A (en) * 2016-09-18 2017-03-22 广西电网有限责任公司电力科学研究院 Petroleum product safe carbonization device

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EP0510127B1 (en) 1996-07-17
US5369035A (en) 1994-11-29
DE69120935D1 (en) 1996-08-22
AU646072B2 (en) 1994-02-03
ATE140395T1 (en) 1996-08-15
JPH05502104A (en) 1993-04-15
DE69120935T2 (en) 1996-12-12
EP0510127A1 (en) 1992-10-28

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