Method and apparatus for in-process liquid analysis by laser induced plasma spectroscopy

• US 6,700,660 B2
• Filed: 02/08/2002
• Issued: 03/02/2004
• Est. Priority Date: 02/08/2001
• Status: Expired due to Fees

• Current Assignee: Noranda, Inc. (Glencore Plc), National Research Council Canada
• Original Assignee: Noranda, Inc. (Glencore Plc), National Research Council Canada
• Inventors: Heon, Rene, Lucas, John M., Sabsabi, Mohamad
• Primary Examiner(s): Nguyen, Thong
• Assistant Examiner(s): Lavarias, Arnel C.
• Application Number:
  US10/071,529
• Publication Number:
  US 20020159059A1
• Time in Patent Office: 753 Days
• Field of Search: 356/318, 356/311, 356/313, 356/317, 356/51, 356/36, 250/428, 250/430, 250/432.R, 250/435, 250/438, 250/573, 250/576
• US Class Current: 356/318
• CPC Class Codes: G01N 21/15 Preventing contamination of the components of the optical system or obstruction of the light path
• CPC Class Codes: G01N 21/718 Laser microanalysis, i.e. with formation of sample plasma
• CPC Class Codes: G01N 21/85 Investigating moving fluids or granular solids

Abstract

A method and apparatus for spectrochemical analysis of liquids, including molten materials, using laser-induced plasma spectroscopy. The apparatus preferably comprises a high power pulsed laser focused on the surface of a liquid stream flowing in a measurement cell, and an optical spectrometer-detector assembly, which receives, detects and analyzes the radiation emitted by the high temperature plasma thereby excited. The measurement cell, and optional pump, establish a steady flow of liquid, thereby permitting the laser to repeatedly sample a fresh unperturbed surface, representative of the liquid volume, while also ensuring that bubbles and waves formed in the liquid are removed from the focal volume. Gas (usually air) blown above the liquid prevents aerosols and matter ejected from the sample responsive to the incident energy from interacting with subsequent laser pulses, and from accumulating on the optics.

Claims

1. A laser-induced plasma spectroscopy apparatus for the analysis of the composition of liquid and molten materials comprising:

a laser emitting pulses at given repetition rate and along a given beam path;

an optical means to direct the laser pulses to a location at a surface of the liquid to generate a plasma that emits elemental radiation that corresponds to at least one compositional element of the liquid;

a probe structure, which detects the emitted elemental radiation along a detection path, said probe structure including an optical window, a spectrometer for analyzing the spectra of the emitted radiation, a detector to detect the light diffracted by the spectrometer, a data processor which determines a concentration of the predetermined element; and

a flow cell assembly which establishes a substantially steady flow of the liquid past the said location at the surface of the liquid, the flowing liquid at this location being truly representative of the liquid bulk flown into the cell, said flow sufficient to prevent said pulses from perturbing said surface at said location, said cell assembly including a controller to control the liquid surface level and the flow speed.

2. An apparatus according to claim 1, wherein the controller comprises a pump to circulate the liquid in a closed loop.

3. An apparatus according to claim 1, wherein the controller includes a liquid vessel set above the probed liquid surface in the cell assembly and filled at a substantially constant level.

4. An apparatus according to claim 1 that includes further a liquid mixing means.

5. An apparatus according to claim 4 wherein the liquid mixing means is a perforated plate.

6. An apparatus according to claim 1, wherein the cell assembly is configured in such a way that the liquid overflows from all sides.

7. An apparatus according to claim 6 that includes further a liquid mixing means.

8. An apparatus according to claim 7 wherein the liquid mixing means is a perforated plate.

9. An apparatus according to claim 1, wherein said probe structure further comprises an optical structure configured so that the incident laser beam and the light collected from the plasma are substantially collinear.

10. An apparatus according to claim 1, further comprising fiber optic means to convey the elemental radiation emitted by the plasma to said spectrometer of said probe structure.

11. An apparatus according to claim 1, wherein the laser generates multiple pulses at the same wavelength separated by a short time interval, to produce and excite the plasma at the surface of the liquid.

12. An apparatus according to claim 1, wherein the laser generates multiple pulses at different wavelengths simultaneously or separated by a short time interval, to produce and excite the plasma at the surface of the liquid.

13. An apparatus according to claim 1, wherein said probe structure comprises an intensified photodiode array detector.

14. An apparatus according to claim 1, wherein said probe structure comprises a CCD camera.

15. An apparatus according to claim 1, wherein said probe structure comprises an intensified CCD camera.

16. An apparatus according to claim 1, wherein said probe structure comprises a plurality of photomultipliers positioned to detect both (i) emissions from the predetermined element and (ii) background radiation.

17. An apparatus according to claim 1, wherein the determination of concentration of a predetermined element is made by comparison with a predetermined calibration curve.

33. The apparatus of claim 1 wherein said flow is sufficient to prevent waves being induced at said location on said surface by said laser pulses.

34. The apparatus of claim 1 wherein said flow is sufficient to prevent bubbles induced in the liquid by said laser pulses from reaching said surface at said location.

37. The apparatus of claim 1, which further comprises a gas flow generator to substantially prevent liquid drops, which are ejected from the liquid in response to the incident laser pulses, from accumulating on said optical window of said probe structure and along the laser beam path and the detection path.

18. A method of laser-induced plasma spectroscopy analysis for liquid and molten materials, comprising the steps of:

directing laser pulses at a given repetition rate and along a given beam path onto a location at the liquid surface to generate a plasma that emits elemental radiation that corresponds to at least one compositional element of the liquid;

detecting the emitted elemental radiation along a detection path and analyzing its spectra with a spectrometer;

processing the spectra to determine a concentration of the predetermined element; and

establishing a substantially steady flow of liquid past the said location at the liquid surface, said flow sufficient to prevent said pulses from perturbing said surface at said location, the flowing liquid at this location being truly representative of the bulk of the liquid to analyze; and

controlling the liquid surface level and the flow speed.

19. A method according to claim 18, wherein the step of controlling consists in establishing a substantially constant liquid level.

20. A method according to claim 19 wherein controlling is performed with a pump that circulates the liquid in a closed loop.

21. A method according to claim 19 wherein controlling is performed with a liquid vessel set above the probed liquid surface and maintained at a substantially constant level.

22. A method according to claim 18 wherein the step of establishing a flowing liquid at the said location substantially representative of the liquid bulk is obtained by mixing the liquid.

23. A method according to claim 18 wherein the liquid after passing through said location at the liquid surface flows in all directions before being discharged.

24. A method according to claim 18 wherein said laser beam path and detection path are substantially superimposed.

25. A method according to claim 18, further comprising the step of conveying the elemental radiation emitted by the plasma to the spectrometer in said detecting step using optical fiber optics.

26. A method according to claim 18 wherein the laser generates multiple pulses at the same wavelength separated by a short time interval to produce and excite the plasma at the surface of the liquid.

27. A method according to claim 18 wherein the laser generates multiple pulses at different wavelengths simultaneously or separated by a short time interval to produce and excite the plasma at the surface of the liquid.

28. A method according to claim 18, wherein said detecting step includes using a photodiode array detector.

29. A method according to claim 18, wherein said detecting step includes using a CCD camera.

30. A method according to claim 18, wherein said detecting step includes using an intensified CCD camera.

31. A method according to claim 18, wherein said detecting step includes using a plurality of photomultipliers positioned to detect both (i) emissions from the predetermined element and (ii) background radiation.

32. A method according to claim 18, wherein the step of processing the spectra to determine a concentration of the predetermined element is made by comparison with a predetermined calibration curve.

35. The method of claim 18 wherein said flow is sufficient to prevent waves being induced at said location by said laser pulses.

36. The method of claim 18 wherein said flow is sufficient to prevent bubbles induced in the liquid by said laser pulses from reaching said surface at said location.

38. The method of claim 18, which further comprises blowing gas above the liquid surface to substantially prevent liquid drops, which are ejected from the liquid in response to the incident laser pulses, from accumulating anywhere along the laser beam path and the detection path.