Methods and systems for computing a particle size distribution of small partcles in a process

• US 20090222218A1
• Filed: 04/14/2008
• Published: 09/03/2009
• Est. Priority Date: 03/03/2008
• Status: Active Grant

• Current Assignee: Agilent Technologies, Inc.
• Original Assignee: Agilent Technologies, Inc.
• Inventors: Trutna, William R. JR., Chamberlin, Danielle R., Liu, Maozi
• Granted Patent: US 7,719,682 B2
• Time in Patent Office: Days
• US Class Current: 702/23
• CPC Class Codes: G01J 3/10 Arrangements of light sources specially adapted for spectrometry or colorimetry
• CPC Class Codes: G01N 15/0211 Investigating a scatter or diffraction pattern
• CPC Class Codes: G01N 2015/003 in liquids, e.g. emulsion

Abstract

Methods, systems and computer readable media for computing small particle size distributions of particles in a process stream comprising a sample dilute colloid. A reference matrix of pre-computed reference vectors is provided. Each reference vector represents a discrete particle size or particle size range of a particle size distribution of particles contained in a dilute colloid. Each reference vector represents a reference extinction spectrum over a predetermined wavelength range. A measurement vector representing a measured extinction spectrum of the sample particles in the sample colloid is provided, wherein the measured extinction spectrum has been spectrophotometrically measured over the wavelength range. The particle size distribution and particle concentrations of the particles in the sample colloid are determined using the reference matrix, the measurement vector and linear equations.

Claims

1. A method for computing small particle size distributions of sample particles in a process stream, said sample particles provided in a sample colloid, said method comprising:

providing a reference matrix of pre-computed or pre-measured reference vectors, each reference vector representing a discrete particle size of a particle size distribution of particles contained in a dilute colloid, each the reference vector representing a reference extinction spectrum over a predetermined wavelength range;

providing a measurement vector representing a measured extinction spectrum of the sample particles in the sample colloid, wherein the measured extinction spectrum has been spectrophotometrically measured; and

determining at least one of a particle size, the particle size distribution, and at least one particle concentration of the particles in the sample colloid, using the reference matrix, the measurement vector and linear equations.

2. The method of claim 1, further comprising smoothing the particle size distribution and the particle concentrations.

3. The method of claim 1, wherein said determining comprises applying a non-negative least squares algorithm to the reference matrix and the measurement vector to solve for said particle size distribution and particle concentrations of said sample particles.

4. The method of claim 1, wherein particle sizes of said sample particles are in the range of about 10 nm to about 15 μ

m.

5. The method of claim 1, wherein said reference extinction spectra comprise extinction values determined from Mie scattering spectra.

6. The method of claim 1, wherein said discrete wavelengths are within a range of wavelengths from about 190 nm to about 1100 nm.

7. The method of claim 1, wherein said providing a reference matrix, said providing a measurement vector and said determining the particle size distribution and particle concentrations are performed in real time as a process is being carried out with the process stream.

8. The method of claim 1, wherein said providing a reference matrix, said providing a measurement vector and said determining the particle size distribution and particle concentrations are performed within about five seconds.

9. The method of claim 1, wherein said providing a reference matrix, said providing a measurement vector and said determining the particle size distribution and particle concentrations are performed within about one second.

10. The method of claim 1, wherein said fluid medium comprises a liquid.

11. The method of claim 10, further comprising:

flowing the sample colloid through a flow-through cell and wherein said measured extinction spectrum is measured using the sample particles in the sample colloid in the flow cell.

12. The method of claim 1, wherein said process comprises a batch process and wherein samples are taken from the batch process and measured at line.

13. The method of claim 1, wherein said fluid medium comprises a gas.

14. The method of claim 12, further comprising:

flowing a stream of the sample particles through a sample volume of a spectrophotometer, wherein the measured extinction values are measured from the particles in the sample volume.

15. The method of claim 1, wherein said determining comprises:

calculating a least squared error between said reference matrix and said measurement vector; and

finding a concentration vector that minimizes the least squared error, wherein said concentration vector represents the particle size distribution and particle concentrations of the sample particles flowing in the sample dilute colloid.

16. The method of claim 1, wherein said determining includes iteratively removing from said reference matrix one of said reference vectors that represents a largest discrete particle size or particle size range and each time determining the particle size distribution and particle concentrations in the sample dilute colloid until an error in a fit of said measurement vector to said reference matrix that is greater than a predetermined error tolerance is calculated.

17. The method of claim 1, wherein each said reference vector includes extinction values measured over said discrete wavelengths by the spectrophotometric measurement.

18. The method of claim 1, further comprising:

compensating for forward scattering effects by applying a forward scattering correction factor to values of said reference matrix.

19. The method of claim 1, wherein said providing the measurement vector comprises real time measuring the measurement vector by spectrophotometry at said discrete wavelengths;

and

wherein said determining the particle size distribution and concentrations of the sample particles flowing in the sample dilute colloid is calculated on line.

20. The method of claim 1, further comprising:

outputting said particle size distribution and said particle concentrations of said sample particles flowing in said sample dilute colloid for use by a user.

21. The method of claim 2, wherein said smoothing comprises Gaussian blurring.

22. A method for measuring change of particle size of small particles dispersed in a fluid medium constituting a sample colloid, said method comprising:

providing a reference matrix of pre-computed or pre-measured reference vectors, each said reference vector representing a discrete particle size of a particle size distribution of particles contained in a dilute colloid, each said reference vector representing a reference extinction spectrum over a predetermined wavelength range;

real time measuring a measurement vector representing a measured extinction spectrum of the small particles of the sample colloid, by spectrophotometry over the wavelength range; and

determining at least one of a particle size, the particle size distribution, and at least one particle concentration of the particles in the sample colloid, using said reference matrix, said measurement vector and linear equations.

23. The method of claim 22, wherein said sample dilute colloid is provided in a process stream and said particle size distributions and particle concentrations in the process stream are determined.

24. The method of claim 22, further comprising repeating said real time measuring and said determining at least once during the process, and comparing results of a current round of said determining with at least one previous round of results of said determining.

25. The method of claim 22, further comprising:

comparing the at least one of the determined particle size distribution and the determined particle concentrations with at least one of a predetermined particle size distribution and predetermined particle concentrations; and

generating an alert when said at least one of the determined particle size distribution and the determined particle concentrations differs from said at least one of the predetermined particle size distribution and the predetermined particle concentrations by less than or equal to the absolute value of a predefined difference value.

26. The method of claim 22, wherein said particles are flowing in said fluid medium.

27. A system for measuring small particle size distributions of sample particles in a process stream comprising a sample dilute colloid, said system comprising:

a processor;

a reference matrix of pre-computed or pre-measured reference vectors stored in memory that is accessible by said processor, each reference vector representing a discrete particle size of a particle size distribution of particles in a dilute colloid, each said reference vector representing a reference extinction spectrum over a predetermined wavelength range; and

programming configured to be run by said processor, when the system is provided with a measurement vector representing a measured extinction spectrum of the sample particles in the sample colloid, wherein the measured extinction spectrum has been spectrophotometrically measured, to cause said processor to perform operations comprising;

determining at least one of a particle size, the particle size distribution, and at least one particle concentration of the particles in the sample colloid, using the reference matrix, the measurement vector and linear equations.

28. The system of claim 27, further comprising programming configured to be run by said processor to smooth the particle size distribution and the particle concentrations.

29. The system of claim 27, further comprising programming configured to be run by said processor to pre-compute said reference matrix of pre-computed reference vectors.

30. The system of claim 27, further comprising:

a spectrophotometer configured to measure said extinction values of said sample particles flowing in said sample dilute colloid, said spectrophotometer further being configured to perform at least one of calculating and inputting said measurement vector of said extinction values or inputting said extinction values of said sample particles flowing in said sample dilute colloid to said processor.

31. A computer readable medium carrying one or more sequences of instructions for computing small particle size distributions of sample particles in a process stream, the sample particles provided in a sample colloid, and wherein execution of the one or more sequences of instructions by one or more processors causes the one or more processors to perform a process comprising:

receiving a reference matrix of pre-computed or pre-measured reference vectors, each reference vector representing a discrete particle size or particle size range of a particle size distribution of particles in a dilute colloid, each said reference vector representing a reference extinction spectrum over a predetermined wavelength range;

receiving a measurement vector representing a measured extinction spectrum of the sample particles in the sample colloid, wherein said measured extinction spectrum has been spectrophotometrically measured; and

determining at least one of a particle size, the particle size distribution, and at least one particle concentration of the particles in the sample colloid, using said reference matrix, said measurement vector and linear equations.

32. The computer readable medium of claim 31, further comprising one or more sequences of instructions for outputting, wherein execution of the one or more sequences of instructions for outputting by the one or more processors causes the one or more processors to output said size distribution and concentrations of said sample particles flowing in said sample dilute colloid for use by a user.

33. The computer readable medium of claim 32, further comprising one or more sequences of instructions for smoothing, wherein execution of the one or more sequences of instructions for smoothing by the one or more processors causes the one or more processors to smooth said particle size distribution and said particle concentrations.