Method and apparatus for spectroscopic analysis of heterogeneous materials

• US 6,008,896 A
• Filed: 07/01/1998
• Issued: 12/28/1999
• Est. Priority Date: 07/01/1998
• Status: Expired due to Fees

• Current Assignee: National Research Council Canada
• Original Assignee: National Research Council Canada
• Inventors: Sabsabi, Mohamad, Cielo, Paolo
• Primary Examiner(s): EVANS, FANNIE L
• Application Number:
  US09/108,210
• Time in Patent Office: 545 Days
• Field of Search: 356/317, 356/318
• US Class Current: 356/318
• CPC Class Codes: G01N 21/718 Laser microanalysis, i.e. with formation of sample plasma

Abstract

A method and apparatus for rapid in-situ spectroscopic analysis of unknown heterogeneous materials is disclosed. The apparatus uses a high power pulsed laser whose beam is focused on the material, typically a porous compound of unknown composition such as an amalgamated powder or a mineral sample. The pulsed laser beam vaporizes a small volume of the material and produces a plasma having an elemental composition which is representative of the material composition. The optical emission of the plasma is analyzed with an optical spectrometer. The pulsed spectrum is detected by a gated photodiode array detector or by an array of individually positioned photomultipliers, to detect a background emission and a line emission representative of a given element present in the material. Because such measurements may fluctuate considerably for porous materials due to unpredictable variations of the plasma temperature and the amount of vaporized mass, the signals are normalized by establishing a ratio of the intensity of the signals to that of the background plasma emission.

Claims

1. A method for in-situ analysis of an unknown heterogeneous material, the method comprising:

emitting laser pulses from a laser energy emitter,

focusing said pulses on a sample of said heterogeneous material to generate a plasma emitting a broad continuum radiation as well as elemental radiation derived from a separate compositional element or elements of said heterogeneous material,

measuring both the continuum radiation and a net elemental radiation of a specific line emission which is representative of a selected element present in said heterogeneous material,

obtaining at least one normalized signal by establishing a ratio of said net elemental radiation of a specific line emission, and the continuum radiation, and

determining the concentration of said element as a function of said at least one normalized signal.

2. The method of claim 1 wherein said concentration is determined from a calibration curve obtained by plotting a number of said normalized signals corresponding to samples with different elemental concentrations against the corresponding concentrations as independently measured.

3. The method of claim 1 wherein said radiation intensity of a specific line emission is measured at a time slot which corresponds to a substantially complete atomization of the plasma.

4. The method of claim 3 where both said continuum radiation and said specific line emissions are measured at a time slot which corresponds to a substantially complete atomization of the plasma.

5. The method of claim 1 where both said continuum radiation and said specific line emissions are measured using an array of individually positioned photomultipliers.

6. The method of claim 4 where both said continuum radiation and said specific line emissions are measured during the same time period after the laser pulse.

7. The method of claim 1 where said continuum radiation is measured during a different time slot than the radiation of said specific line emission.

8. The method of claim 1 where said continuum radiation is measured by integrating the full spectrum including the continuum background as well as the line emissions.

9. The method of claim 1 where said continuum radiation is combined with other lines representative of elements whose concentration affects the continuum level.

10. An apparatus for in-situ spectroscopic analysis of an unknown heterogeneous material, the apparatus comprising:

a laser energy emitter,

means for focusing energy emitted from said laser emitter on a sample of said heterogeneous material, thereby generating a plasma emitting a broad continuum radiation as well as elemental radiation derived from separate compositional elements of said heterogeneous material,

detecting means for detecting said continuum radiation and for detecting said elemental radiation,

analyzing means for spectrally and temporally analyzing said continuum radiation as well as said elemental radiation,

processing means for obtaining normalized signals by establishing a ratio of said elemental radiation of specific line emissions which are representative of selected elements present in said heterogeneous material and the continuum radiation, and

delay means for gating off a phase in plasma development wherein atomization of said plasma is not substantially complete.

11. The apparatus according to claim 10 comprising separate delay means for detecting said continuum radiation and separate delay means for detecting said elemental radiation derived from separate compositional elements of said heterogeneous material.

12. The apparatus according to claim 10 wherein said detecting means is a gated photodiode array of detectors.

13. The apparatus according to claim 10 wherein said detecting means is an array of individual photomultipliers.