EP0578685A1 - Procede et appareil de test par resonance quadripolaire nucleaire (nqr) - Google Patents
Procede et appareil de test par resonance quadripolaire nucleaire (nqr)Info
- Publication number
- EP0578685A1 EP0578685A1 EP92907532A EP92907532A EP0578685A1 EP 0578685 A1 EP0578685 A1 EP 0578685A1 EP 92907532 A EP92907532 A EP 92907532A EP 92907532 A EP92907532 A EP 92907532A EP 0578685 A1 EP0578685 A1 EP 0578685A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nqr
- excitation
- environmental parameter
- sample
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
- G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
- G01R33/441—Nuclear Quadrupole Resonance [NQR] Spectroscopy and Imaging
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
- G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
- G01R33/48—NMR imaging systems
- G01R33/4804—Spatially selective measurement of temperature or pH
Definitions
- This invention relates to a method of, and apparatus for, Nuclear Quadrupole Resonance (NQR) testing a sample having at least one NQR property (particularly NQR resonance frequency or an NQR relaxation time, T lf T 2 , T 2e and T 2 *) which varies with a given environmental parameter, such as pressure, magnetic field or more particularly temperature. It also relates to a method of, and apparatus for, NQR testing for the presence of selected nuclei (particularly nuclei of integral spin quantum number, such as 14 N) in a sample. It also relates to a method of determining the spatial distribution of temperature within a sample.
- NQR Nuclear Quadrupole Resonance
- the invention has application to the detection in the field of 14 N quadrupole resonance signals from the explosive RDX concealed in parcels or luggage or on the person, or deployed in explosive devices.
- it has application to the detection of concealed drugs, for instance at airports.
- NQR measurements have the advantage that they do not require the sample to be placed in a strong magnetic field, and therefore do not require the large, expensive and sample-size limiting magnet structures which are needed for nuclear magnetic resonance (NMR) measurements.
- Nuclear quadrupole resonance response signals are conventionally detected by means of pulsed radiofrequency (rf) radiation of the correct excitation frequency (v 0 ) to excite the selected transition (at a resonance frequency VQ); a pulse of preset width t, rf field amplitude B ⁇ , and flip angle ⁇ generates a decaying signal immediately following the pulse known as a free induction decay (f.i.d.), and two or more pulses of pre-set widths and spacings can generate echoes.
- the pulse width which produces the maximum f.i.d. for a given quadrupolar nucleus in a solid powder is given the symbol t m and the corresponding flip angle the symbol ⁇ m (equivalent, for example, to a "90°" pulse in NMR).
- sensitivity of detection is meant the number of selected nuclei (or amount of material) that can be detected at a given level of probability in a fixed volume of sample over a given test time. This sensitivity may be further improved by Fourier transformation of the accumulated signals to give an absorption spectrum, the area under which is then measured by integration between appropriate limits.
- the present invention seeks to provide an improved method of and apparatus for NQR testing.
- a method of NQR testing a sample having at least one NQR property which varies with a given environmental parameter comprising applying excitation to the sample to excite NQR resonance and detecting the NQR response signal, the excitation being such as to excite an NQR response signal which is detectable during the detection step over a predetermined range of the environmental parameter.
- the invention is based on our discovery that the NQR properties of a sample, such as resonance frequency (or frequencies), spin-lattice relaxation time (T 2 ), spin-spin relaxation time (T 2 ), effective spin-spin relaxation time (T 2e ) or free induction decay relaxation time (T 2 *), may vary considerably with a given environmental parameter, such as temperature, pressure or magnetic field, and that it is therefore necessary to take account of or compensate for these variations when carrying but NQR tests to cover a predetermined range of the environmental parameter. Such compensation can have the unexpected advantage of considerably more sensitive tests than have hitherto been achieved.
- the given predetermined range of the environmental parameter may typically be the range of that parameter likely to be encountered in the field (possibly the national or global average range or maximum range of that parameter). If the parameter is temperature, the predetermined range may be ⁇ 10°C (possibly between 5°C and 25°C) or ⁇ 20°C
- the range may be as much as from -30 C C (corresponding to arctic conditions) to +40°C
- the predetermined range may be, for example, ⁇ 1% ( corresponding to a typical average daily pressure range) or ⁇ 5% ( corresponding to a maximum range).
- the term "detectable” preferably connotes a signal/noise ratio which, within the measurement time of the detection step, is significantly above the actual or expected noise levels, the degree of significance being determined, for example, by standard statistical methods, such as the upper Student's t-distribution.
- the NQR property resonance frequency 1s considered first.
- N 1 VQ (I) 5148 -0.223T -0.000395T 2 N 2 Q ⁇ 2) ⁇ 5277 -0-139T -0.000506T 2 ( 1 )
- N 3 VQ (3) 5332 -0.108T -0.000670T 2 where T is temperature.
- Equation (1) predicts that VQ (I> will vary significantly (between 5041 and 5062 kHz) for a temperature range of -10 to +40 ⁇ C.
- the present invention can, for example, provide that the excitation 1s such as to excite detectable NQR resonance at resonance frequencies between 5041 and 5062 kHz, that is, over a temperature range likely to be experienced with airport luggage.
- a and b vary according to the transition and c is about 70 kJ mol -1 .
- ti . in RDX J. varies, surprisingly, by a factor of approximately 8 between 5 and 25°C.
- ⁇ /T ⁇ For constant ⁇ and at a constant flip angle ⁇ m , a variation in ⁇ /T ⁇ between 1 and 0.1 (an increase in J ⁇ by a factor of ten, corresponding, for N ⁇ in RDX, to a temperature increase near ambient of roughly 20°C) gives rise to an approximately 70% loss in response signal strength. Such a loss may render the response signal undetectable if it is overwhelmed by noise.
- the present invention can accommodate the variation of l ⁇ with an environmental parameter such as temperature.
- T 2 , T 2e and T 2 * may vary with temperature or pressure, although in general it is believed that this variation is less marked than with T-_.
- T 2 and T 2e are spin-spin relaxation times which are relevant to the generation of echoes.
- T 2 * is relevant to the generation of f.i.d.'s.
- One important effect of the variation of the spin-spin relaxation times is on the ratios ⁇ e /T 2 , ⁇ e /T 2e and ⁇ f /T 2 *.
- ⁇ e is the pulse spacing between the pulses used to generate one or more echoes and ⁇ f is the pulse spacing between the pulses (possibly at different frequencies) used to generate f.i.d.'s.
- Variation of these ratios is important because response signal strength is a function of ⁇ e /T 2 , ⁇ e /T 2e and ⁇ fll.* t an exponential being one form of function which is often encountered.
- the present invention can accommodate the variation of such relaxation times with an environmental parameter such as temperature.
- the excitation may be at least one excitation pulse (e.g. a simple or composite pulse) at a single excitation frequency, the or each pulse having a power spectrum sufficient to excite a detectable NQR resonance response signal over the range of resonance frequency corresponding to the range of the environmental parameter.
- excitation pulse e.g. a simple or composite pulse
- all frequencies to be encountered lie within (preferably well within) the power spectrum of the excitation pulse or pulses.
- a disadvantage of this approach is the high rf powers required.
- the excitation is applied at a plurality of different excitation frequencies so that a detectable NQR resonance response signal can be excited over the range of resonance frequency corresponding to the range of the environmental parameter.
- This can be achieved, for instance, by applying separate excitation pulses at different frequencies, or by frequency modulating the fundamental frequency of one or more excitation pulses, or by varying the frequency of each individual pulse.
- ⁇ is the gyromagnetic ratio (1.932 x 10 7 rad s _1 T -1 for
- the number of different frequencies at which the excitation is applied should be as large as possible.
- a conflicting requirement is that the greater the number of frequencies, the longer may be the NQR test.
- the excitation is preferably applied as a series of excitation pulses, at* a plurality of different pulse spacings and/or so as to produce a plurality of different flip angles, so that a detectable NQR resonance response signal can be excited over the range of the relaxation time corresponding to the range of the environmental parameter.
- the pulse spacings in this case the pulse repetition times, t
- the pulse spacings can be chosen according to the principles explained in relation to Figure 1 to excite a detectable NQR response signal over the entire T ⁇ range of interest.
- the relaxation time is T 2 , T 2e or T 2 *
- pulse spacing in this case the spacing referred to as ⁇ e or ⁇
- flip angle may be appropriately adjusted, to excite a detectable NQR response signal over the entire range of interest of the relevant relaxation time.
- the NQR testing takes into account variations both in resonance frequency and J ⁇ caused by variations in the environmental parameter or parameters.
- the excitation is applied as a repetitive series of excitation pulses at each of a plurality of different excitation frequencies, the pulse repetition time being the same for each series, the flip angle being different for each series.
- the pulses associated with the different frequencies can be interleaved without a pulse at one frequency interfering with the response signals generated by pulses at other frequencies.
- the excitation is applied as a series of excitation pulses at each of a plurality of different excitation frequencies, each series including a plurality of pulses for generating echoes
- the spacing between each of the plurality of the pulses ( ⁇ e ) is preferably different for each series (and chosen according to the variation of T 2 or T 2e with the environmental parameter). The variation in T ⁇ can thus still be compensated for by varying flip angle.
- pulses at the different frequencies are preferably applied at staggered spacings ( ⁇ f ) chosen according to the variation of T 2 * with the environmental parameter, ⁇ may be some multiple of (say two or three times ) T 2 *. such as allows a reasonable proportion of the f.i.d. produced by the preceding pulse to be detected before the succeeding pulse is applied, without being so long as to unnecessarily slow down the test.
- the excitation is such that the NQR response signal/noise ratio would be substantially equal at at least two differing values of the environmental parameter. It is preferable that the signal/noise ratio would be substantially equal at as many differing values of the environmental parameter as possible, and that it would be substantially constant between these values (that is, so that it would be substantially constant over the range of the environmental parameter). "Substantially” is to be interpreted in the context of the large variations in signal/noise ratio which may be occasioned by changes in an environmental parameter. Thus by “substantially equal” and
- substantially constant may be meant a minimum signal /noise level within 50%, 60% or preferably 75% of a maximum signal/noise level .
- NQR response signal/noise ratio being substantially equal at at least two differing values of the environmental parameter and preferably substantially constant over the range of the environmental parameter is that it facilitates accurate NQR testing for the presence of selected nuclei in a sample, such as would be required in the example of
- the invention envisages that an alarm signal would be produced if a predetermined threshold of detection were exceeded.
- This threshold might typically be derived from a number of tests carried out on a variety of substances other than the substance of interest in order to determine expected levels of background noise.
- the threshold would typically be set above these expected levels (preferably several standard deviations above these levels ) .
- the effect of the threshold will also be substantially constant. In other words, the sensitivity of detection will be substantially constant. Substantial equality in the signal/noise ratio could be obtained by "post-processing" of the detected NQR response signal by some form of noise filter.
- noise component of the signal/noise ratio need not be specifically measured. It can usually be assumed that noise will be virtually invariant across the range of the environmental parameter. If this is so, then maintaining the signal/noise ratio substantially equal reduces to a requirement to maintain the NQR response signal strength substantially equal. If noise actually varies across the range, then a suitably varying threshold might be appropriate.
- the invention envisages that the NQR response signal/noise ratio may be rendered substantially equal at the at least two differing values of the environmental parameter by compensation for resonance frequency, T ⁇ , T 2 , T 2e or T 2 * variations. Indeed, compensation may be for a combination of or even all of such variations.
- the number and spacing of these frequencies is such that the
- NQR response signal/noise ratio is substantially constant over the range of the environmental parameter.
- VQ ⁇ lies between 5041 and 5062 kHz over a temperature range of -10 to +40°C
- the signal/noise ratio and hence the sensitivity of detection also remains substantially constant.
- the spectrometer in this example is tuned to a mean frequency of 5051.5 kHz, and the probe Q factor and receiver band width are selected so that signal responses at 5041 and 5062 kHz are amplified to the same extent.
- the absorption mode signals from each are then separately integrated between frequency limits pre-set to ensure that the majority of the spectral line lies within the integration limits anywhere in the frequency range from 5041 to 5062 kHz; in this example, integration limits of (say) 2 to 10 kHz will accept a signal from one or other of the excitation frequencies of 5048, 5055 kHz.
- the lower limit of 2 kHz is selected to reduce the effects of changes in the base-line response signal.
- the integrals from both rf sequences are then separately monitored, or added to give the summed output. It will be understood that, in the example described, excitation pulses at different excitation frequencies may in some circumstances excite a single resonance frequency to a significant extent. The summed output of such pulses is not in this experiment nearly as great as if pulses were applied separately in isolation from each other, and their outputs were then summed, because the first pulse saturates subsequent response signals (although clearly this may not always be the case).
- the excitation is applied at n-1 equally spaced frequencies, where n is the nearest integer satisfying the equation n ⁇ ⁇ v 0 / ⁇ v off , where n ⁇ 2, ⁇ v 0 is half of the value of the resonance frequency range corresponding to the range of the environmental parameter, and ⁇ v 0 ff is approximately equal to the precessional frequency (v ⁇ ) (and is therefore a measure of the maximum frequency off-set above which significant reductions in response signal/noise ratio would be observed for a given resonance frequency).
- the lowest frequency may therefore be v 0 - ⁇ v 0 /2+ ⁇ v 0 ff, the next v 0 - ⁇ v 0 /2+2 ⁇ v 0 ff, and so on.
- the integration limits for the Fourier transformed spectrum can then be set between (say) 2 kHz and ⁇ v 0 ⁇ .
- the integrals from all pulse sequences may then be monitored consecutively or summed to obtain the final output.
- the receiver band width and Q-factor of the rf coil would be selected to provide constant sensitivity over the frequency range from v 0 - ⁇ v 0 to v 0 + ⁇ v 0 .
- the pulse spacings and/or flip angles are preferably such that the NQR response signal/noise ratio is substantially constant over the range of the environmental parameter. This can facilitate accurate NQR testing for the presence of selected nuclei in a sample, as discussed previously.
- the pulse spacings and/or flip angles associated with the excitation frequencies preferably are such as to produce an NQR response signal of substantially equal signal/noise ratio at the respective values of the environmental parameter at which the NQR resonance frequency equals the respective excitation frequency. This affords a particularly simple way of compensating for the variation of resonance frequency and relaxation time.
- the flip angles selected will only be correct at the spot frequencies of the excitation pulses, but deviations at intermediate frequencies will be reduced in their effect if integrated signal strengths from consecutive irradiation frequencies are summed.
- inhomogeneities in the. B ⁇ field and varying flip angles caused by temperature shifts between samples and/or temperature variations within a sample will also ensure that the idealised predictions are not followed exactly. It may therefore be necessary in a given case to apply small adjustments to the predicted flip angles to allow for such effects with a given coil .geometry and NQR frequency.
- the excitation might suitably take the form of simple rectangular pulses, it may be preferable that the excitation includes at least one excitation pulse which is so shaped as to produce a response signal whose strength is substantially constant over a limited resonance frequency range.
- Simple rectangular pulses typically have a curved response signal characteristic like that shown in Figure 2; a relatively flat characteristic afforded by a suitably shaped pulse would have the advantage that the sensitivity of detection would be more uniform over the limited resonance frequency range.
- Suitable pulse shapes will be known to the skilled person. One particularly suitable shape is an Her ite pulse (see the paper by M. McCoy and W.S. Warren, 3. Mag.
- the invention extends to apparatus for NQR testing a sample having at least one NQR property which varies with a given environmental parameter, comprising:- storage means in which is stored information on how the or each NQR property varies over a predetermined range of the environmental parameter; means for applying excitation to the sample to excite NQR resonance; means for detecting the NQR response signal; and means, responsive to the information stored in the storage means, for controlling the applying means to excite an NQR response signal which is detectable by the detection means over a predetermined range of the environmental parameter.
- the invention further extends to a method of NQR testing for the presence of selected nuclei in a sample, comprising: deriving an NQR response signal from the sample in such a way that the signal/noise ratio would be substantially equal at at least two differing values of an environmental parameter; and producing an alarm signal from the NQR response signal in dependence on whether a predetermined threshold of detection has been exceeded.
- This aspect of the invention extends to apparatus for NQR testing for the presence of selected nuclei in the sample analogous to the method described immediately above. All the features of the invention as a whole described above apply to this aspect of the invention.
- the invention extends to a method as aforesaid of NQR testing a sample having at least one NQR property which varies with a given environmental parameter, the method being for determining the spatial distribution of temperature within a sample, wherein a relaxation time (T ⁇ , T 2 , T 2e , T 2 *) varies with temperature, and such spatial distribution is determined according to the variation of relaxation time within the sample.
- This method is based on our discovery that relaxation time varies substantially with temperature. It can provide a sensitive technique for temperature distribution imaging.
- the spatial variation distribution of temperature is determined according to the variation of the spin-lattice relaxation time, T ⁇ , within the sample, since we have found that this relaxation time may be most sensitive to temperature.
- T ⁇ spin-lattice relaxation time
- One preferred way of putting this method into practice is to apply a series of excitation pulses to the sample in which the pulse repetition time is varied whilst the flip angle is kept constant. The pulses would be applied, for instance, in the presence of a weak magnetic field to provide spatial encoding of the data. Decoding of the data can be carried out by well-known techniques such as Fourier analysis. T ⁇ data could be converted to temperature data via a look-up table.
- the spatial distribution of temperature may also be determined according to the variation of a spin-spin relaxation time within the sample.
- This method would be put into practice by varying the spacing ( ⁇ e ) between pulses whilst keeping the flip angle constant, in order to encode spatially data relating to the relevant relaxation times. It is thought that this technique may apply to the times T 2 and T 2e but not to the time T 2 *, since in the case of T 2 * there is no relevant pulse spacing which can be varied.
- the invention extends to a method for detecting the presence within a larger article of a specific substance containing quadrupolar atomic nuclei, wherein the irradiation can allow for resonance frequency shifts caused by ⁇ 20°C temperature variations. It also extends to a method for detecting the presence within a larger article of a specific substance containing quadrupolar atomic nuclei, wherein the power spectrum of the irradiation pulses provides substantial power within about 0.1% of any frequency to which NQR resonance may be shifted by any environmental conditions likely to apply to the article.
- the irradiation pulses may be at one or more frequencies equal or close to (maybe within 0.1% of) a resonant frequency of quadrupolar nuclei within the substance to be detected.
- the substance may be drugs, for instance heroin or cocaine, or explosives, for instance HMX, RDX, PETN, or TNT.
- the quadrupolar nuclei in these substances may be 1 N.
- the environmental conditions are such conditions as temperature, pressure or magnetic fields.
- One use for these methods is in the examination of airline baggage or airfreight, where in a typical case ⁇ 10 kHz resonance frequency shifts may be caused by ⁇ 20°C temperature variations.
- a suitable resonance frequency is 5.191 MHz; rf drive signals having a power spectrum of width 18 kHz at half height may be used to allow for the effects of the ⁇ 20°C temperature variation.
- Figure 1 is a plot of the steady-state NQR response signal strength against flip angle for differing values of the ratio ⁇ /T,;
- Figure 2 is a plot of NQR response signal strength against frequency off-set for a 60 ⁇ s excitation pulse (v ⁇ * 9 kHz ) ;
- FIGS 3 are timing diagrams for two embodiments of the invention.
- FIG 4 is a block diagram of NQR apparatus used in the present invention. Referring to the timing diagram of the first embodiment of the invention shown in Figure 3(a), two radio frequency pulses
- the residual oscillations can be made to cancel and only the true NQR response signal is observed. Since t is much longer than either T ⁇ value, no T, compensation is necessary (see Figure
- Signal/noise ratio is proportional to * N, so that it is important to set the pulse repetition time ⁇ so that ⁇ is not significantly longer than 5T,; otherwise information is lost.
- a restriction on the separation, x between the two pulses is that -cf should exceed, say, 2T 2 * or 3T 2 *, in order to allow the f.i.d. from the first pulse to decay substantially before the second pulse is applied. Since T 2 * may vary, for example, with temperature, it may be important to adjust xf in the manner described previously to compensate for this.
- the pulse repetition time ⁇ is made less than 5T, (where T, is now the shorter T, value) and the pulse width and/or rf power adjusted to produce flip angles which are less than ⁇ m and which allow for the variation of ⁇ /T, with temperature, as described earlier in relation to Figure 1. That is, the excitation is such as would produce equal signal strengths at the temperatures at which f, and f 2 are the resonant frequencies. The signals are weaker than when ⁇ /T, » 5, but more can be accumulated in a given time and a lower rf power is required.
- case ( b) series of excitation pulses are applied at two different frequencies f, and f 2 to excite separate echoes at staggered intervals.
- the pulse repetition time ⁇ can be equal to or less than 5T, (as with the two forms of the first embodiment), and the pulse width and/or rf power may be adjusted if necessary to produce flip angles which allow for the variation of ⁇ /T, with NQR resonance frequency, as described earlier in relation to Figure 1.
- the echoes at ⁇ /T, ⁇ 5 are weaker than when ⁇ /T, «5, but more can be accumulated in a given time.
- case (c) (not shown), a long series of short high-power rf pulses at a single frequency and appropriate phases is used with a spacing ⁇ e less than the spin-spin relaxation time T 2 ; the responses are then observed as a train of echoes between each pulse and decay with a time constant T 2e , where in favourable cases T 2e >>T 2 . These echoes are sampled and accumulated to provide the final signal. The whole process is then repeated at one or more different frequencies. This embodiment is particularly advantageous where T 2e is long. It will be appreciated that any temperature variation of the relaxation times, T,, T 2 and T 2e , may need to be allowed for.
- Two radio frequency sources, 1 and 2 provide pulsed rf excitation pulses at frequencies of f, and f 2 , to cover the frequency range produced by differing sample temperatures.
- f, and f 2 are selected according to the output of a storage device 3, in which is stored information on how the NQR resonance frequency, spin-lattice relaxation time, T,, spin-spin relaxation times, T 2 , T 2e and f.i.d. relaxation time, T 2 * of the sample vary with temperature and/or pressure. More frequencies may be necessary if the frequency range is larger than a few tens of kHz.
- a switched frequency synthesizer could be used, provided that the switching time was much less than the f.i.d. time T 2 * (for RDX, this quantity is about 0.8 ms at 298K).
- the rf sources 1 and 2 have normal and phase-shifted outputs
- rf pulse sequences pass to an rf power amplifier 6 of constant output over the frequency range of the rf sources, and thence to an rf probe 7 and rf coil (or coils) 8 surrounding the sample.
- the rf probe receives inputs from the timing circuitry 5 so that the tuning elements can be adjusted to take account of differing excitation frequencies f,, f 2 , etc., which may be necessary for high-Q rf coils.
- the coils produce a uniform field over the working region of the probe.
- the signals generated pass to a pre-amplifier 9 and rf amplifier 10 of sufficient band width to amplify at constant gain all NQR response signal frequencies likely to be encountered.
- the response signals are detected in two separate phase-sensitive detectors lla.b, to generate in-phase and quadrature outputs.
- the output of gates 3a,b, controlling pulses of radio frequency f, (channel 1) is connected as a reference signal to detector 11a and through a 90° phase-shift network 12 to detector lib.
- Outputs from the detectors lla.b are sampled and digitised by analogue-to-digital converters 13a,b under the control of the timing circuitry 5 and then passed to a digital signal processor 14 for display in graphical recorder or video display 15.
- the output of gates 4a,b controlling pulses of radio frequency f 2 (channel 2) is connected as a reference signal to the detector 11a and through the 90°-phase-shift network 12 to the detector lib.
- Outputs from the detectors lla.b are sampled and digitised by the analogue-to-digital convertors 13a,b and stored in a separate memory from the signals in channel 1, this selection being controlled by trigger pulses from the timing circuitry 5.
- both signals are either separately displayed, or summed before display to provide the output of the instrument. An alarm (not shown) may then sound if this signal exceeds a pre-set threshold.
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- Magnetic Resonance Imaging Apparatus (AREA)
- Investigating Or Analyzing Materials By The Use Of Ultrasonic Waves (AREA)
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Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP98121679A EP0928973A3 (fr) | 1991-04-02 | 1992-04-01 | Procédé et appareil d'examen par résonance quadripolaire |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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GB9106789 | 1991-04-02 | ||
GB919106789A GB9106789D0 (en) | 1991-04-02 | 1991-04-02 | Nqr methods and apparatus |
GB9204872 | 1992-03-05 | ||
GB9204872A GB2255830B (en) | 1991-04-02 | 1992-03-05 | Method of and apparatus for NQR testing |
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EP98121679A Division EP0928973A3 (fr) | 1991-04-02 | 1992-04-01 | Procédé et appareil d'examen par résonance quadripolaire |
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EP0578685A1 true EP0578685A1 (fr) | 1994-01-19 |
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EP98121679A Withdrawn EP0928973A3 (fr) | 1991-04-02 | 1992-04-01 | Procédé et appareil d'examen par résonance quadripolaire |
EP92907532A Withdrawn EP0578685A1 (fr) | 1991-04-02 | 1992-04-01 | Procede et appareil de test par resonance quadripolaire nucleaire (nqr) |
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EP98121679A Withdrawn EP0928973A3 (fr) | 1991-04-02 | 1992-04-01 | Procédé et appareil d'examen par résonance quadripolaire |
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EP (2) | EP0928973A3 (fr) |
JP (2) | JPH06507484A (fr) |
FI (1) | FI103923B1 (fr) |
GB (1) | GB2255830B (fr) |
IL (2) | IL101434A (fr) |
WO (1) | WO1992017794A1 (fr) |
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US5365171A (en) * | 1992-11-30 | 1994-11-15 | The United States Of America As Represented By The Secretary Of The Navy | Removing the effects of acoustic ringing and reducing temperature effects in the detection of explosives by NQR |
GB9319875D0 (en) * | 1993-09-27 | 1994-03-09 | British Tech Group | Apparatus for and methods of nuclear resonance testing |
GB9325500D0 (en) * | 1993-12-14 | 1994-09-21 | British Tech Group | Method of and apparatus for detection, and method of configuring such apparatus |
WO1996010193A1 (fr) | 1994-09-29 | 1996-04-04 | British Technology Group Limited | Procede de controle de resonance nucleaire quadripolaire et procede de configuration d'un dispositif de controle de resonance nucleaire quadripolaire |
AU4836396A (en) | 1995-02-24 | 1996-09-11 | British Technology Group Limited | Method of and apparatus for nuclear quadrupole resonance testing a sample, and pulse sequence for exciting nuclear quadrupole resonance |
CA2226263C (fr) * | 1995-07-11 | 2007-08-14 | British Technology Group Limited | Appareil et procede permettant de tester un echantillon par resonance quadripolaire nucleaire |
US5608321A (en) * | 1995-12-28 | 1997-03-04 | The United States Of America As Represented By The Secretary Of The Navy | Method and apparatus for detecting target species having quadropolar muclei by stochastic nuclear quadrupole resonance |
GB9617976D0 (en) | 1996-08-28 | 1996-10-09 | British Tech Group | Method of and apparatus for nuclear quadrupole resonance testing a sample |
AUPQ328299A0 (en) * | 1999-10-06 | 1999-10-28 | Thorlock International Limited | A method and apparatus for detecting a substance using nuclear resonance |
AU781658B2 (en) * | 1999-10-06 | 2005-06-02 | Qr Sciences Limited | A method and apparatus for detecting a substance using nuclear resonance |
AUPS307702A0 (en) | 2002-06-20 | 2002-07-11 | Thorlock International Limited | Pulse sequences for exciting nuclear quadrupole resonance |
AUPS312102A0 (en) * | 2002-06-21 | 2002-07-18 | Thorlock International Limited | Pulse sequences for exciting nuclear quadrupole resonance |
AUPS322802A0 (en) * | 2002-06-26 | 2002-07-18 | Thorlock International Limited | Large volume scanner for nuclear quadrupole resonance measurements (#14) |
AU2003902576A0 (en) * | 2003-05-26 | 2003-06-12 | Qrsciences Technologies Pty Ltd | Method And Apparatus For Detecting Nuclear Quadrupole Resonance Signals In A Sample In The Presence Of Coherent Noise (#10) |
US7332910B2 (en) | 2003-11-24 | 2008-02-19 | E.I. Du Pont De Nemours And Company | Frequency detection system comprising circuitry for adjusting the resonance frequency of a high temperature superconductor self-resonant coil |
US20070245374A1 (en) | 2003-11-24 | 2007-10-18 | Inventec Corporation | Video program subtitle tex recording method and system |
US7301344B2 (en) | 2003-11-24 | 2007-11-27 | E.I. Du Pont De Nemours & Co. | Q-damping circuit including a high temperature superconductor coil for damping a high temperature superconductor self-resonant coil in a nuclear quadrupole resonance detection system |
US7375525B2 (en) | 2003-12-15 | 2008-05-20 | E.I. Du Pont De Nemours And Company | Use of multiple sensors in a nuclear quadropole resonance detection system to improve measurement speed |
US7265549B2 (en) | 2004-04-30 | 2007-09-04 | E. I. Du Pont De Nemours And Company | Scanning a band of frequencies using an array of high temperature superconductor sensors tuned to the same frequency |
EP1740967A2 (fr) * | 2004-04-30 | 2007-01-10 | E.I.Du pont de nemours and company | Procedes et appareil pour balayer une bande de frequences en utilisant un reseau de capteurs supraconducteurs haute temperature |
US7279897B2 (en) * | 2004-04-30 | 2007-10-09 | E. I. Du Pont De Nemours And Company | Scanning a band of frequencies using an array of high temperature superconductor sensors tuned to different frequencies |
WO2006065929A1 (fr) | 2004-12-13 | 2006-06-22 | E. I. Du Pont De Nemours And Company | Alarme aux masques metalliques d'un systeme de detection de la contrebande rqn/rayons x |
WO2006064264A1 (fr) * | 2004-12-16 | 2006-06-22 | King's College London | Procede et appareil pour essai nqr |
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US3681680A (en) * | 1970-05-28 | 1972-08-01 | Varian Associates | Rf spectrometer employing modulation of a dc magnetic field to excite resonance |
GB1329776A (en) * | 1971-10-28 | 1973-09-12 | Sp K Bjuro I Radiotekhnik I El | Spectrometer for investigation of nuclear quadruple resonance in solids |
JPS6024412B2 (ja) * | 1975-09-17 | 1985-06-12 | 株式会社横河電機製作所 | 温度検出装置 |
US4558279A (en) * | 1983-03-07 | 1985-12-10 | University Of Cincinnati | Methods for detecting and imaging a temperature of an object by nuclear magnetic resonance |
US4514691A (en) * | 1983-04-15 | 1985-04-30 | Southwest Research Institute | Baggage inspection apparatus and method for determining presences of explosives |
GB8701695D0 (en) * | 1987-01-27 | 1987-03-04 | Smith J A S | Detecting compounds |
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DE4024834A1 (de) * | 1990-08-04 | 1992-02-27 | Bruker Analytische Messtechnik | Nqr-bildgebungsverfahren |
-
1992
- 1992-03-05 GB GB9204872A patent/GB2255830B/en not_active Expired - Fee Related
- 1992-03-31 IL IL10143496A patent/IL101434A/en active IP Right Grant
- 1992-03-31 IL IL101434A patent/IL101434A0/xx unknown
- 1992-04-01 EP EP98121679A patent/EP0928973A3/fr not_active Withdrawn
- 1992-04-01 EP EP92907532A patent/EP0578685A1/fr not_active Withdrawn
- 1992-04-01 JP JP4506953A patent/JPH06507484A/ja active Pending
- 1992-04-01 WO PCT/GB1992/000580 patent/WO1992017794A1/fr not_active Application Discontinuation
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1993
- 1993-10-01 FI FI934328A patent/FI103923B1/fi not_active IP Right Cessation
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2002
- 2002-12-05 JP JP2002383000A patent/JP3652682B2/ja not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO9217794A1 * |
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IL101434A (en) | 1996-10-16 |
FI103923B (fi) | 1999-10-15 |
GB2255830B (en) | 1995-03-08 |
FI934328A (fi) | 1993-10-01 |
EP0928973A2 (fr) | 1999-07-14 |
WO1992017794A1 (fr) | 1992-10-15 |
GB9204872D0 (en) | 1992-04-22 |
JPH06507484A (ja) | 1994-08-25 |
GB2255830A (en) | 1992-11-18 |
JP3652682B2 (ja) | 2005-05-25 |
EP0928973A3 (fr) | 1999-09-01 |
IL101434A0 (en) | 1992-11-15 |
FI934328A0 (fi) | 1993-10-01 |
JP2003232754A (ja) | 2003-08-22 |
FI103923B1 (fi) | 1999-10-15 |
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