Method of and apparatus for in-situ measurement of changes in fluid composition by electron spin resonance (ESR) spectrometry

• US 7,868,616 B2
• Filed: 11/08/2007
• Issued: 01/11/2011
• Est. Priority Date: 10/31/2006
• Status: Active Grant

• Current Assignee: Active Spectrum, Inc. (Bruker Corporation)
• Original Assignee: Active Spectrum, Inc. (Bruker Corporation)
• Inventors: White, James, White, Christopher
• Primary Examiner(s): Arana; Louis M
• Application Number:
  US11/983,393
• Publication Number:
  US 20080164874A1
• Time in Patent Office: 1,160 Days
• Field of Search: 324/316
• US Class Current: 324/316
• CPC Class Codes: G01N 24/08 by using nuclear magnetic resonance G01N24/12 takes precedence
• CPC Class Codes: G01N 24/10 by using electron paramagnetic resonance G01N24/12 takes precedence
• CPC Class Codes: G01R 33/307 specially adapted for moving the sample relative to the MR system, e.g. spinning mechanisms, flow cells or means for positioning the sample inside a spectrometer
• CPC Class Codes: G01R 33/34 Constructional details, e.g. resonators , specially adapted to MR
• CPC Class Codes: G01R 33/343 of slotted-tube or loop-gap type
• CPC Class Codes: G01R 33/345 of waveguide type G01R33/343 takes precedence
• CPC Class Codes: G01R 33/60 using electron paramagnetic resonance G01R33/24, G01R33/62 take precedence
• CPC Class Codes: H01P 7/06 Cavity resonators

Abstract

A miniaturized instrument and method of using electron spin resonance spectrometry for measuring the degradation of lubricating fluids, and the like, that includes continuously passing a sample of such fluid through a resonating RF microwave cavity resonator during the application therethrough of a uniform slowly varying uniform magnetic field that is rapidly modulated and measuring the resulting phase modulation or amplitude modulation thereof to derive an electron spin resonance signal that directly senses the molecular changes in the fluid sample resulting from fluid degradation during operation of the vehicle, such as peroxy radicals in vehicle engine oil and the like.

Claims

1. A method of using electron spin resonance spectrometry for in situ measuring of a degradation of operating machinery fluids, the method comprising acts of:

passing a sample of a fluid through a resonating RF microwave cavity resonator during the application therethrough of a swept uniform magnetic field;

wherein the fluid sample has a magnetic susceptibility and application of the swept uniform magnetic field causes a magnetic resonance that effects changes in the magnetic susceptibility of the sample at a RF frequency depending on a Zeeman field at the sample,

modulating a modulation magnetic field, correspondingly to vary the magnetic susceptibility and the magnetic resonance in the fluid sample, which results in at least one of an RF phase modulation and an amplitude modulation; and

measuring at least one of the resulting RF phase modulation or amplitude modulation thereof to derive an electron spin resonance signal, whereby the electron spin resonance signal is indicative of molecular changes in the fluid sample resulting from fluid degradation during operation of the machinery.

2. The method of claim 1 wherein in modulating the modulation magnetic field to vary the magnetic susceptibility, the magnetic susceptibility varies the Zeeman field at the sample and therefore the frequency of said magnetic resonance and varies the RF frequency of the cavity resonator and a quality factor of the cavity resonator.

3. The method of claim 2 wherein in modulating the modulation magnetic field, the magnetic field modulation is of audio frequency, and wherein application of the swept uniform magnetic field is of the order of 100 HZ and less.

4. The method of claim 2 wherein said measuring is effected by demodulating said phase modulation by frequency discrimination in a frequency servo-loop that integrates discrimination output and supports the RF frequency of said cavity resonator.

5. An electron spin resonance spectrometer for in situ measuring of the degradation of operating machinery fluids, comprising:

an RF microwave cavity resonator having inlet and outlet passages for continually passing a sample of such fluid through the RF microwave cavity resonator during microwave resonating thereof and during the application therethrough of a swept uniform magnetic field;

wherein the fluid sample has a magnetic susceptibility and application of the swept uniform magnetic field causes a magnetic resonance that effects changes in the magnetic susceptibility of the sample at a RF frequency depending on a Zeeman field at the sample,

means for modulating a modulation magnetic field, correspondingly to vary the resonant magnetic susceptibility and said magnetic resonance in the fluid sample, which results in at least one of an RF phase modulation and an amplitude modulation; and

means for measuring the resulting RF phase modulation or amplitude modulation thereof to derive an electron spin resonance signal, whereby the electron spin resonance signal is indicative of molecular changes in the fluid sample resulting from fluid degradation during operation of the machinery.

6. The spectrometer of claim 5 wherein the means for modulating the modulation magnetic field varies the Zeeman field at the sample and therefore the frequency of said magnetic resonance and varies the RF frequency of the cavity resonator and a quality factor of the cavity resonator.

7. The spectrometer of claim 5 wherein the means for modulating the modulation magnetic field provides a modulation of audio frequency, and wherein application of the swept uniform magnetic field is of the order of 100 HZ and less.

8. The spectrometer of claim 7 wherein said measuring means comprises a frequency discriminator for demodulating said phase modulation in a frequency servo-loop containing a VCO and that integrates discriminator output and sets the VCO at the RF frequency of said cavity resonator.

9. The spectrometer as claimed in claim 5 further comprising means for detecting a concentration of soot in the fluid sample through broad carbon resonance.

10. The spectrometer as claimed in claim 5 further comprising means for inferring the dielectric constant and water content of the sample by measurement of the cavity resonator frequency and insertion loss indicated by changes in the RF power output.

11. The spectrometer as claimed in claim 5 further comprising a single permanent magnet and a modulating coil structure and a magnetc permittivity yoke, wherein the cavity resonator is of a form that is stacked and sandwiched between the single permanent magnet and the modulating coil structure and the magnetic permittivity yoke, with the spectrometer being adapted to be mounted onboard in situ with the operating machinery.

12. The spectrometer of claim 5 wherein the spectrometer is mounted onboard in situ with operating machinery such that a pump drives fluid from a engine through a filter into said inlet and through said resonant cavity, exiting at said outlet, such that the sample of the fluid is continuously introduced into and withdrawn from the cavity resonator in a controlled and continuous pass-through during the microwave resonating within the cavity resonator and the application of the swept uniform magnetic field therewithin.

13. A method of using electron spin resonance spectrometry for measuring a degradation of lubricating fluids during operation of a vehicle, the method comprising acts of:

continuously passing a sample of such fluid through a resonating RF microwave cavity resonator during the application therethrough of a swept uniform magnetic field that is modulated, and

measuring a resulting phase modulation or amplitude modulation thereof to derive an electron spin resonance signal that is indicative of molecular changes in the fluid sample resulting from fluid degradation during operation of the vehicle.