Ubiquitous transmissive raman spectroscopy for stand-off detection

• US 10,436,716 B2
• Filed: 09/24/2014
• Issued: 10/08/2019
• Est. Priority Date: 09/24/2014
• Status: Active Grant

• Current Assignee: Smiths Detection (Smiths Group International Holdings Ltd.)
• Original Assignee: Smiths Detection (Smiths Group International Holdings Ltd.)
• Inventors: Lee, Vincent Yuan-Hsiang
• Primary Examiner(s): Amara, Mohamed K
• Application Number:
  US14/495,295
• Publication Number:
  US 20160084765A1
• Time in Patent Office: 1,840 Days
• CPC Class Codes: G01J 3/0291 Housings; Spectrometer accessories; Spatial arrangement of elements, e.g. folded path arrangements
• CPC Class Codes: G01J 3/44 Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
• CPC Class Codes: G01N 21/65 Raman scattering

Abstract

A substance analysis system and method are provided, the system disposable a variable stand-off distance from a substance in situ, including an emitter disposed to emit radiation onto the substance in situ, and a detector disposed the variable stand-off distance from the substance in situ, the detector comprising a receiver defining a substantially collimated collection path over the variable stand-off distance.

Claims

1. A substance analysis system disposable a variable stand-off distance from a substance in situ, the system comprising:

an emitter disposed to emit radiation onto a first region of the substance in a container in situ; and

a detector disposed the variable stand-off distance from the substance in situ, the detector comprising a receiver defining a substantially collimated collection path over the variable stand-off distance, where the collection path is unfocused on any distinct substance region within the container so that the detector receives radiation from a second region of the substance, wherein the second region is larger than the first region and the angular distance between the first region and the second region is equal to or greater than 90 degrees and less than 180 degrees,

wherein the received radiation is representative of the entire substance, and

wherein;

the emitter emits radiation into the first region of the substance in the container along an emission direction,

the detector receives radiation from the second region of the substance along a radiation collection direction, and

the angular distance between the first region and the second region is defined as an angle between the emission direction and the radiation collection direction.

2. The system of claim 1 wherein the receiver is configured to receive a transmission Raman signal from a substantially columnar portion of the substance.

3. The system of claim 1, wherein the system is configured to analyze substances within at least one of a container that is substantially opaque to visible light and a container substantially transparent to visible light.

4. The system of claim 1, further comprising a sensor configured to determine when a container is configured relative to the system such that a substance within the container may be analyzed by the system.

5. The system of claim 1, further comprising a processor configured to indicate the presence of predetermined components within the substance based on the output of a comparator.

6. The system of claim 1, further comprising a comparator configured to compare the wavelength of the received Raman signal with the wavelength of the emitted radiation.

7. A method of transmission Raman analysis comprising:

emitting radiation towards a first wall portion of a container in situ onto a first region of a sample in the container, wherein emitted radiation becomes a diffusive light source within the sample in the container without formation of a distinct substance region; and

receiving a transmission Raman signal through a second wall portion of the container, the received signal including Raman radiation reflected from multiple portions of the sample within the container, the received signal including Raman radiation collected from a second region of the sample in the container, wherein the second region is larger than the first region and the angular distance between the first region and the second region is equal to or greater than 90 degrees and less than 180 degrees,

wherein the receiver is disposable a stand-off distance from the container in situ, and

wherein the Raman signal is received through a collection path that is substantially collimated and unfocused on any distinct substance region within the container, the Raman signal being representative of the sample, and

wherein;

emitting radiation onto the first region of the sample in the container comprises emitting radiation onto the first region along an emitter initial transmission axis,

receiving the Raman radiation collected from the second region of the sample in the container comprises collecting the Raman radiation along the detector collection axis, and

the angular distance between the first region and the second region being defined as an angle between the emitter initial transmission axis and the detector collection axis.

8. The method of claim 7, further comprising comparing the transmission Raman signal with the emitted radiation.

9. The method of claim 7, wherein no reference beam is used, the method further comprising:

receiving a Raman signal including container background information;

looking up matching container background information; and

subtracting the looked-up container background information from the received Raman signal.

10. The method of claim 9, wherein the matching container background information is selected from a table comprising entries for a plurality of glass types and a plurality of plastic types.

11. The method of claim 7, wherein at least one of the emitted radiation or Raman radiation illuminates the entire contents of the container by the internal reflection of radiation between the inner walls of the container.

12. The method of claim 7, wherein a Raman signal is generated from multi-path excitation of a whole liquid substance within the container.

13. The method of claim 7, wherein the Raman signal is at least one of omni-directional or ubiquitous.

14. The method of claim 7, wherein the container is generally opaque to visible light.

15. The method of claim 7, wherein said first wall portion is defined by an outer surface of the container, and said second wall portion is defined by an inner surface of the container directly interior to said outer surface.

16. A method of analyzing a substance in a container in situ a variable stand-off distance from a substance analysis system, the container having an interior surface and an exterior surface, the method comprising:

directing a beam of radiation at the container onto a first region of a sample in the container such that at least a portion of the radiation passes through the container and is scattered in the substance and at least a portion of the scattered radiation reflects off of the interior surface of the container, the radiation in the substance resulting in emission of a Raman signal representative of the entire substance;

detecting the Raman signal representative of the entire substance, wherein the emitted Raman signal is collected from a second region of the sample in the container, wherein the second region is larger than the first region and the angular distance between the first region and the second region is equal to or greater than 90 degrees and less than 180 degrees, and the Raman signal is detected through a collection path that is substantially collimated and unfocused on any distinct substance region within the container; and

comparing the Raman signal to the radiation of the radiation source, and

wherein;

directing the beam of radiation onto the first region of a sample in the container comprises emitting the beam of radiation along an emission path having a first direction,

collecting the emitted Raman signal from the second region of the sample in the container comprises collecting the emitted Raman signal along the collection path having a second direction and

the angular distance between the first region and the second region is defined as an angle between the emission path having the first direction and the collection path having the second direction.

17. The method of claim 16, further comprising:

wherein the directing comprises at least one of;

directing a beam of radiation at a container generally opaque to visible light and detecting the Raman signal representative of the contents of a substance contained in the generally opaque container;

or

directing a beam of radiation at a non-opaque container and detecting the Raman signal representative of the contents of a substance contained in the non-opaque container.

18. The method of claim 16, wherein the substance comprises a liquid substance.

19. The method of claim 16, wherein the radiation source is configured to emit a beam of radiation such that a substance contained in a generally opaque container will emit a transmission Raman signal for detecting the Raman signal.

20. The method of claim 16, wherein the radiation in the substance is reflected in the container;

and

wherein the radiation travels in the substance resulting in emission of Raman radiation at various angular orientations with respect to each other, respectively.

21. A method of analyzing liquid substances in both generally opaque to visible light containers and generally transparent containers, respectively, using a substance analysis system disposable a variable stand-off distance from the liquid substances in situ, comprising:

directing a beam of radiation at a first location on a container containing a liquid substance, wherein the beam of radiation is directed into a first region of the liquid substance in the container;

directing a detector at a second location on the container, the second location being different from the first location;

wherein the beam of radiation and the detector are configured so that radiation from the beam passes through the container and into the substance to produce a transmission Raman signal including Raman radiation from a plurality of locations in the substance so the detector can detect the transmission Raman signal, wherein the transmission Raman signal is collected from a second region of the liquid substance in the container, wherein the second region is larger than the first region and the angular distance between the first region and the second region is equal to or greater than 90 degrees and less than 180 degrees, and wherein the transmission Raman signal is received through a collection path that is substantially collimated and unfocused on any distinct substance region within the container, the transmission Raman signal being indicative of the entire composition of the substance;

comparing the transmission Raman signal with the radiation emitted by the emitter;

determining based on a library of characteristics of components of interest whether the transmission Raman signal indicates that the substance contains a component of interest; and

outputting whether or not the substance contains a component of interest, and

wherein;

directing the beam of radiation into the first region of the liquid substance in the container comprises directing the beam of radiation along an emission path direction,

collecting the transmission Raman signal from the second region of the liquid substance in the container comprises collecting the transmission Raman signal along the collection path direction, and

the angular distance between the first region and the second region is defined as an angle between the emission path direction and the collection path direction.

22. The method of claim 21, wherein detection of the transmission Raman signal from the substance in the container is angularly independent of the beam of radiation when the beam of radiation is directed at a generally opaque container that is opaque to visible wavelengths of light.

23. The method of claim 21, further comprising determining whether the transmission Raman signal indicates that the substance contains at least one of acetone, cyclohexane, ethanol, ethylene glycol, or H₂O₂ and outputting a warning if it is determined that the transmission Raman signal indicates that the substance contains at least one of acetone, cyclohexane, ethanol, ethylene glycol, or H₂O₂.

24. The method of claim 21, wherein the first location is approximately 135°

from the second location.

25. A substance analysis system disposable a variable stand-off distance from a container in situ, the system comprising:

an emitter configured to emit radiation directed at a first location on the container, at least a portion of the radiation passing through the container and into a substance in the container onto a first region of the substance in the container, with at least a portion of the radiation in the substance being reflected within the container; and

a detector with a receiving portion directed at a second location on the container, the detector being configured to receive a transmission Raman signal including Raman radiation from multiple portions of the substance, wherein the transmission Raman signal is collected from a second region of the sample in the container, wherein the second region is larger than the first region and the angular distance between the first region and the second region is equal to or greater than 90 degrees and less than 180 degrees, the Raman signal being representative of the entire substance, wherein the Raman signal is received through a collection path that is substantially collimated and unfocused on any distinct substance region within the container,

wherein the radiation directed at a first location on the container and the Raman radiation are substantially co-axial, and

wherein;

an emission path is defined as extending between the emitter and the first region of the substance in the container and along an emitter initial transmission axis,

the collection path is defined as extending between the second region and the detector and along a detector collection axis, and

the angular distance between the first region and the second region is defined as an angle between the emitter initial transmission axis and the detector collection axis.

26. The system of claim 25, wherein the emitter is configured to emit focused radiation.

27. The system of claim 25, wherein the emitter is configured to emit non-focused radiation.

28. The system of claim 25, wherein the emitter is a stationary laser.

29. A substance analysis system disposable a variable stand-off distance from a container in situ, the system comprising:

a detector with a receiving portion directed at the container, the detector being configured to receive a reflected radiation signal from multiple portions of a substance in the container, wherein the reflected radiation signal is based on a beam of radiation signal directed onto a first region of a sample within the container, the detector a stand-off distance from the container, where the receiving portion of the detector includes a collection aperture configured to receive a substantially collimated beam of radiation reflected from the substance in the container, wherein the beam of radiation is unfocused on any distinct substance region within the container, and wherein the reflected radiation signal is representative of the entire substance, and wherein the reflected radiation signal is collected from a second region of the sample in the container, the second region being larger than the first region and the angular distance between the first region and the second region is equal to or greater than 90 degrees and less than 180 degrees and

wherein;

the beam of radiation directed onto the first region of a sample within the container comprises emitting the beam of radiation along an emission path having a first direction,

collecting the reflected radiation signal from the second region of the sample in the container comprises collecting the reflected radiation signal along a collection path having a second direction and

the angular distance between the first region and the second region is defined as an angle between the emission path having the first direction and the collection path having the second direction.

30. The substance analysis system of claim 29, where the collection aperture is approximately five mm in diameter.

31. The substance analysis system of claim 29, where the container is substantially opaque to visible wavelengths.