Geologic formations are used for many purposes such as hydrocarbon production, geothermal production and carbon dioxide sequestration. In general, formations are characterized in order to determine if the formations are suitable for their intended purpose.
One way to characterize a formation is to convey a downhole tool through a borehole penetrating the formation. The tool is configured to perform measurements of one or more properties of the formation at various depths in the borehole to create a measurement log.
Many types of logs can be used to characterize a formation. In one type of log referred to as a neutron log, a neutron source and a neutron detector are disposed in a downhole tool. The neutron source is used to irradiate the formation and the neutrons resulting from interactions with atoms of the formation are detected with the neutron detector. A formation property such as density or porosity can be determined from the detected neutrons. It can be appreciated that improving the sensitivity of the neutron detector can improve the accuracy of the formation characterization.
Disclosed is an apparatus for detecting a neutron. The apparatus includes: a neutron interaction material configured to emit a charged particle upon absorbing a neutron; a plurality of nanoparticles distributed in the neutron interaction material, each nanoparticle in the plurality being configured to scintillate upon interacting with the charged particle to emit a pulse of light; a photodetector coupled to the neutron interaction material and configured to receive the pulse of light and generate a signal based on the received pulse of light; and a processor configured to receive the signal in order to detect the neutron.
Also disclosed is an apparatus for estimating a property of an earth formation penetrated by a borehole. The apparatus includes: a carrier configured to be conveyed through the borehole; a neutron source disposed at the carrier and configured to irradiate the formation with neutrons; a neutron detector disposed at the carrier and configured to detect a neutron resulting from one or more interactions between the neutrons emitted from the neutron source and the formation, the neutron detector having a neutron interaction material configured to emit a charged particle upon absorbing a neutron and a plurality of nanoparticles distributed in the neutron interaction material, each nanoparticle in the plurality being configured to scintillate upon interacting with the charged particle to emit a pulse of light; and a photodetector coupled to the neutron interaction material and configured to detect the pulse of light and generate a signal upon detecting the pulse of light; wherein the signal is used to estimate the property.
Further disclosed is a method for estimating a property of an earth formation penetrated by a borehole. The method includes: conveying a carrier through the borehole; irradiating the formation with neutrons emitted from a neutron source; receiving neutrons resulting from interactions of the emitted neutrons with the formation using a neutron detector, the neutron detector having a neutron interaction material configured to emit a charged particle upon absorbing a neutron and a plurality of nanoparticles distributed in the neutron interaction material, each nanoparticle in the plurality being configured to scintillate upon interacting with the charged particle to emit a pulse of light; receiving the pulse of light with a photodetector to produce a signal; and estimating the property using the signal.
The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
Disclosed are apparatus and method for detecting neutrons in a downhole tool with improved sensitivity and, hence, accuracy. In one or more embodiments, neutrons detected during neutron well logging operations are used to estimate a property of an earth formation such as density or porosity using processing techniques known in the art.
A detailed description of one or more embodiments of the disclosed apparatus and method presented herein by way of exemplification and not limitation with reference to the Figures.
Still referring to
Still referring to
Reference may now be had to
Shown here are values of the reaction cross-section a for thermal neutrons with energy En=0.025 eV.
The second stage is based on a scintillation process that occurs based on the charged particle(s) interacting with a scintillation material 21. Moving through the scintillation material, the charged particle(s) experience losses of the energy due to ionization. Part of the lost energy is transferred into visible light emitted when excitons (i.e., electron-hole pairs) are relaxed at luminescent centers of scintillation. The emitted visible light is collected at an optical window 22 of a photodetector 23 such as photomultiplier tube (PMT), which converts the emitted visible light signal into the pulse of voltage/current.
The scintillation process depends on the relaxation of the electronic excited states formed when the charged particle(s) interacts with the scintillation material 21. The average path of such particle(s) can be several microns long and multiple “hot” carriers are created along the charged particle trajectory due to ionization losses of its energy. The term “hot” relates to a particle or hole having an increase in its energy. The scheme illustrating relaxation of such “hot” carriers when the scintillation material is doped (or activated) with Ce (referred to as scintillator atoms) is shown in
The overall efficiency of the relaxation process defining the light yield (LY) of the scintillation process is determined as the conversion rate of the energy deposited by charged particles in the scintillation material into visible light photons. It is defined by the mechanisms of different phases of “hot” electron and hole relaxation. Parameters of these mechanisms depend on the electronic structure of the scintillation material, particularly, on the location of the 5d electronic energy levels of Ce3+ ions relatively to top and bottom of valence and conduction bands of the matrix material containing the scintillator atoms. Also, the concentration of different structural defects in the matrix material is important because such defects create local distortions of the electronic structure in the vicinity of Ce3+ ions which could decrease the efficiency of exciton formation and their radiative recombination decreasing the overall relaxation process efficiency.
The atomic structural properties of glass scintillation materials are different from the properties of crystalline scintillation materials. Because of the absence of long range ordering in the atomic structure of the glass, which is an amorphous material, the ability for the fast and efficient transport of exciton energy to radiating centers is limited. Moreover, a localization site of the activator's ion in the glass atomic structure is not very well defined. The dispersion of Ce3+ ion site structures in the glass appears due to their localization in slightly different chemical environments (several closest coordination shells formed by glass matrix atoms could have little bit different atomic structure). This splits energies of 5d states of Ce3+ ions which are very sensitive to a crystalline field depending on the localization site and, as the result, much wider and more disperse 5d radiating band is formed in the electronic structure of the glass scintillator in comparison with 5d band formed by Ce dopant in single crystal scintillation material. This fact and also a much higher probability of the structural defect presence in the vicinity of the Ce3+ ions which could trap thermalized charge carries and excitons and cause their nonradiative recombination in the case of glass explains why a typical value of LY for glass scintillation materials is much lower than typical value of LY for single crystal scintillators.
It should be pointed out that the relaxation of “hot” carriers created in the process of the interaction of charge particle with scintillation material is localized in an area extending approximately 100 nm from the trajectories of charges particles formed at the first stage of the neutron detection process. This localization of the relaxation process provides the opportunity to improve the performance of glass scintillators through the impregnation of the nano-sized single crystal scintillators (referred to as nanocrystals) into a glass matrix. In this case, for those “hot” electrons formed along the charged particle trajectory, the relaxation and light emission take place in the nanocrystals and are defined by the properties of the nanocrystals as illustrated in
It should be pointed out that the above disclosure is very different from the idea behind composite neutron sensitive scintillators made of the mechanical mixture of B2O3 and ZnS:Ag particles of micron size. In the case of the mechanical mixture, the 10B enriched boron oxide works as neutron absorber and the ZnS:Ag particles convert Li+ and alpha particle (He+) species emitted in a neutron absorption reaction into visible light. The size of B2O3 and ZnS:Ag particles is chosen to be smaller than mean free path of alpha particle in these materials, which is about 2.5 um. As the result, the B2O3—ZnS:Ag composite scintillator has very low transparency due to light scattering at the boundaries of the material grains. Therefore this composite scintillator can be used only in the form of thin layer deposited at the surface of the PMT optical window.
The scintillation material based on scintillator nanocrystals impregnated into glass matrix does not suffer from this problem if the size of the nanocrystals is at least four times smaller than the wavelength of the light emitted in the scintillation process (approximately 400 nm (nanometer) for Ce3+ activated scintillators). Also, if the scintillator nanocrystal size is approximately 100 nm instead of 1 um (micron), much more uniform distribution of scintillation material inside of neutron absorption material (i.e., the glass matrix) can be reached and better performance parameters of the scintillation material can be obtained. Another benefit from the use of scintillation nanocrystals is related to the following nanoscale effect: scintillation material in the form of nanocrystals can be doped with higher amounts of Ce in comparison with the same scintillation material in the form of a single crystal volume due to the modification of the atomic structure of nanocrystals caused by the surface tension. The higher concentration of Ce in the scintillator increases the density of the 5d band in its electronic structure that increases the efficiency of the capture of thermalized charged carriers by Ce3+ ions. Moreover, isolation of nano-particles in the glass matrix from each other prevents migration quenching of the activator luminescence, which is one of the factors limiting scintillation light yield in single crystals.
In general, scintillation material with the structure illustrated in
Another approach to synthesize the glass with the desired nanocrystal structure is to use a mixture of the scintillator nanocrystals and glass matrix material as a raw material for the glass synthesis. In order for the glass matrix material to be sensitive to neutron detection/absorption and have a high neutron detection efficiency, the glass matrix material contains relatively high concentrations of Lithium-6 and/or Boron-10 in one or more embodiments. The glass itself is synthesized by heating the raw materials according to the temperature program illustrated in
Referring to
The main goal of Stage 2 of the synthesis process is to reconstruct scintillation nanocrystals in the glass matrix by annealing the glass obtained in Stage 1 at temperature Tc, which slightly below the vitrification temperature Tg. The temperature of glass sample is slowly increased during time period t5. Then, the glass is annealed (or “recrystallized”) at constant temperature Tc during time period t6. Also, the temperature Tc can be slowly increased during the recrystallization depending on the material. After annealing, the glass is slowly cooled down. If nanocrystals are not dissolved completely in the glass melt at Stage 1 (Requirement 1) and their fragments, which could contain only few crystal unit cells, are still present in the glass matrix, they (i.e., the fragments) start to play a role of seeds for crystallization during Stage 2 if (Requirement 2) chemical composition of the glass matrix surrounding such seeds allows the crystallization (i.e., the glass matrix in close proximity of nanocrystal seeds contains elements in necessary concentrations required for the crystallization or nanocrystal growth). Requirements 1 and 2 are crucial for the successful synthesis of the scintillation glass with impregnated scintillation nano crystals.
One approach to increase the probability of the successful nanocrystal recovery during Stage 2 of the synthesis process is to increase the concentration of nanocrystals in the initial mixture used to produce glass. But, too high of a concentration of nanocrystals in the mixture with the glass matrix material can cause avalanche recrystallization during the fast cooling step of Stage 1 of the synthesis process when almost all matter of the mixture is converted into the aggregation of crystallites with sizes exceeding 100 nm. As a result, instead of transparent glass, non transparent glass ceramics is produced. Another approach is to use the glass matrix material which constitutes the glass matrix with the elemental composition close to the composition of desired nanocrystals. This will help to meet Requirement 2 and as a result increase the probability of the successful recrystallization of nanocrystals at Stage 2 of the glass synthesis process. However, if glass matrix contains too much raw material for nanocrystal growth or temperature TC is above the optimal value for a given glass composition, again the avalanche recrystallization occurs with the same consequences.
If Stage 1 of neutron detection uses nuclear reaction (2), then the glass matrix containing the nanostructured scintillation material is a boron-based glass containing substantial concentrations of Boron-10 isotope. In one or more embodiments, the general composition of the boron-based glass is M1O2—B2O3—M22O3—MgO, where M1=Si, Ge, M2=Y, La or rare earth metal ion from Pr to Lu. In this case, nanocrystals of garnet (Y3Al5O12 or YAG) doped with Ce or Eu can be used as scintillator nanocrystals for the synthesis.
One method to synthesize nanocrystals of scintillators includes a two-step process. Step 1 includes precipitation of raw material to produce nanoparticles with desired chemical composition. Step 2 includes calcinations of the obtained precipitates.
For Step 1, NH4HCO3 was used as a precipitation agent in one embodiment. Solutions of Y and Al nitrates with the concentration of 1 mol per liter were mixed in appropriate proportion and combined with NH4HCO3 to obtain a stoichiometric composition of the defined chemical compound of the desired scintillator material. To dope nanoparticles with Ce, ions of corresponding chemical compounds were added into solutions used in the precipitation. YAG:Ce nanoparticles were obtained from the precipitation in Step 1. In this case, no hard agglomerates of garnet nanoparticles were observed and their average size was approximately 100 nm.
For Step 2, the material obtained at Step 1 is annealed at temperature in the range between 700° C. and 1300° C. depending on the material and required structure of the scintillator nanocrystals.
Radioluminescence spectra measured for synthesized nanocrystals of garnet material with different concentrations of Ce are illustrated in
To synthesize nanostructured scintillation material under consideration, nanocrystals of YAG:Ce scintillator are mixed with the glass matrix material with the general composition SiO2 (20-30%)-B2O3 (25-50%)-Al2O3 (0-10%)-Y2O3 (20-30%)-MgO (12-15%)-CeO2 (3-5%). The synthesis is performed according to the temperature program shown in
From the data presented above, it is demonstrated that it is possible to synthesize nanostructured glass scintillation material which would consist of scintillator nanocrystals impregnated into a glass matrix having a neutron interaction material such as Boron-10. Considered glass is synthesized at Tp=1450° C. in one or more embodiments. In spite of the melting point of YAG:Ce being Tm=1870° C., even such a large difference between and Tp=1450° C. and Tm=1870° C. could not prevent the dissolution of nanocrystals in molten glass matrix during Stage 1 of material synthesis. Ce3+ ions used as an activator in scintillator nanocrystals also migrate away from the nanocrystals deep into the glass matrix and as a result it is difficult to restore high Ce3+ concentration in nanocrystals during their recrystallization at Stage 2 of the glass synthesis. These phenomena are due to different solubilities of activator material in nanocrystals and glass matrix at Tp and Tc. Different materials such as YAl3(BO3)4, Y(Al—Sc)3(BO3)4 and (Al—Sc)3(BO3)4 doped with Ce have melting points near 1350° C., which is closer to the Tp temperature for boron-based glass in comparison with the crystallization temperature of garnets. As a result, two opposite processes of dissolving of nanocrystals and their recrystallization will take place in parallel at Stage 1 of the synthesis. Thus, a larger fraction of nanocrystals will be preserved in the glass matrix during the glass melting and that will provide better scintillation properties to the synthesized nanostructured glass.
An alternative way to improve the performance of nanostructured glass is to replace Y2O3 in the glass matrix material with Gd2O3. High concentration of Gd3+ ions causes the formation of a subzone in the forbidden zone in the electronic structure of the matrix and this subzone promotes the transfer of low energy excitation to luminescent Ce3+ ions. Light yield of the glass obtained from the mixture of glass matrix material SiO2(25%)-B2O3(30%)-Gd2O3(30%)-MgO (15%) with 10 weight % of Y3Al5O12:Ce nanocrystals (Sample 3) is six times larger than the LY observed for Samples 1 and 2 discussed above. At the same time, it should be pointed out that natural Gd has a very high neutron absorption cross section due to neutron absorption without emission of a high energy charged particle by the 157Gd isotope. Thus, for nanostructured scintillation glass with Gd in the glass matrix used for neutron detection, purified Gd with very low concentration of 157Gd isotope is used for its synthesis.
If Stage 1 of neutron detection uses reaction (1), then the glass matrix should be made of a glass matrix having a substantial concentration of lithium such as a lithium-magnesium glass. In one or more embodiments, the lithium-magnesium glass has the general formula of Li2O—Al2O3—MgO with addition of CeO2 or Eu2O3. The choice of scintillator nanocrystals should be defined by the compatibility of the nanocrystals with the glass matrix according to the material synthesis process such as described in
It can be appreciated that crystals are just one type of a nanoparticle and that nanoparticles having scintillation properties can also be impregnated or distributed throughout the neutron absorber matrix material. One skilled in the art will know that nanoparticles are very small objects that are measured in nanometers. Nanoparticles can range in diameter from one nanometer to a hundred or more nanometers, but are generally less than one micron for purposes of this disclosure. It can be appreciated that while the neutron absorber material disclosed above is in the embodiment of a glass matrix, other embodiments of material transparent to light other than glass can also be used.
In support of the teachings herein, various analysis components may be used, including a digital and/or an analog system. For example, the downhole electronics 11 or the surface computer processing 12 may include the digital and/or analog system. The system may have components such as a processor, storage media, memory, input, output, communications link (wired, wireless, pulsed mud, optical or other), user interfaces, software programs, signal processors (digital or analog) and other such components (such as resistors, capacitors, inductors and others) to provide for operation and analyses of the apparatus and methods disclosed herein in any of several manners well-appreciated in the art. It is considered that these teachings may be, but need not be, implemented in conjunction with a set of computer executable instructions stored on a computer readable medium, including memory (ROMs, RAMs), optical (CD-ROMs), or magnetic (disks, hard drives), or any other type that when executed causes a computer to implement the method of the present invention. These instructions may provide for equipment operation, control, data collection and analysis and other functions deemed relevant by a system designer, owner, user or other such personnel, in addition to the functions described in this disclosure.
Further, various other components may be included and called upon for providing for aspects of the teachings herein. For example, a power supply (e.g., at least one of a generator, a remote supply and a battery), cooling component, heating component, magnet, electromagnet, sensor, electrode, transmitter, receiver, transceiver, antenna, controller, optical unit, electrical unit or electromechanical unit may be included in support of the various aspects discussed herein or in support of other functions beyond this disclosure.
The term “carrier” as used herein means any device, device component, combination of devices, media and/or member that may be used to convey, house, support or otherwise facilitate the use of another device, device component, combination of devices, media and/or member. Other exemplary non-limiting carriers include drill strings of the coiled tube type, of the jointed pipe type and any combination or portion thereof. Other carrier examples include casing pipes, wirelines, wireline sondes, slickline sondes, drop shots, bottom-hole-assemblies, drill string inserts, modules, internal housings and substrate portions thereof.
Elements of the embodiments have been introduced with either the articles “a” or “an.” The articles are intended to mean that there are one or more of the elements. The terms “including” and “having” are intended to be inclusive such that there may be additional elements other than the elements listed. The conjunction “or” when used with a list of at least two terms is intended to mean any term or combination of terms. The terms “first” and “second” are used to distinguish elements and are not used to denote a particular order. The term “couple” relates to coupling a first component to a second component either directly or indirectly through an intermediate component.
It will be recognized that the various components or technologies may provide certain necessary or beneficial functionality or features. Accordingly, these functions and features as may be needed in support of the appended claims and variations thereof, are recognized as being inherently included as a part of the teachings herein and a part of the invention disclosed.
While the invention has been described with reference to exemplary embodiments, it will be understood that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications will be appreciated to adapt a particular instrument, situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.