Interrogation of pressurized samples

Abstract

Methods and apparatus for interrogating samples under static high pressure. In one example, an apparatus includes a first anvil having a culet and a hole in a middle portion of the culet. The apparatus also includes a second anvil having a second culet positioned along the first culet. The apparatus further includes a gasket sandwiched between the first and second culets. The first and second anvils are configured to apply a compressive force to the gasket to cause a portion the gasket adjacent to the hole to plastically deform and enter the hole to pressurize a sample contained therein.

Description

INTERROGATION OF PRESSURIZED SAMPLESCROSS-REFERENCE TO RELATED APPLICATION(S)

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 635,880, filed on April 18, 2024, and entitled “A Novel Means to Generate High Pressure,” the contents of which are incorporated herein by reference.FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with Government support under Grant No. DE-SC0023248 awarded by the Department of Energy. The government has certain rights in the invention.FIELD OF THE DISCLOSURE

[0003] Various example embodiments relate to high-pressure equipment and, more specifically but not exclusively, to interrogation of samples under static high-pressure loading.BACKGROUND

[0004] High pressure experiments can reveal information about materials’ properties, phase transitions, and reactions that are not observable under normal (e.g., 1 atm) pressure conditions. Example pressures achievable with modern high-pressure equipment are in the range of up to about 200 GPa. Example applications of high-pressure equipment include, but are not limited to, material science, geophysics, shock physics, and certain industrial processes.BRIEF SUMMARY OF SOME SPECIFIC EMBODIMENTS

[0005] Various examples provide methods and apparatus for interrogating samples under static high pressure. One example provides a diamond anvil cell (DAC) having a perforated diamond anvil. When a blank piece of metal is placed between the two diamond anvils of the DAC and subjected to a compressive force thereby, the metal flows into the perforation to seal and pressurize the sample contained therein. The disclosed DAC can beneficially be used, e.g., for implementing various high-pressure sample-interrogation techniques, such as X-ray diffraction, various X-ray absorption spectroscopies, X-ray and optical Raman, etc., by enabling improved coupling of electromagnetic radiation into and out of the sample.

[0006] In one example, an apparatus comprises: a first anvil having a first culet and further having a hole in a middle portion of the first culet; a second anvil having a second culet positioned along the first culet; and a gasket sandwiched between the first and second culets, wherein the first and second anvils are configured to apply a compressive force to the gasket to cause a portion of the gasket adjacent to the hole to plastically deform and enter the hole to pressurize a sample contained therein.

[0007] In another example, a method of interrogating a sample comprises: placing a sample into a hole located in a middle portion of a first culet of a first anvil; sandwiching a gasket between the first culet and a second culet positioned along the first culet, the second culet belonging to a second anvil; and applying a compressive force to the gasket with the first and second anvils to cause a portion of the gasket adjacent to the hole to plastically deform and enter the hole to pressurize the sample contained therein.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Other aspects, features, and benefits of various disclosed embodiments will become more fully apparent, by way of example, from the following detailed description and the accompanying drawings, in which:

[0009] FIG. 1 is a schematic diagram illustrating a diamond anvil cell (DAC) according to some examples.

[0010] FIGS. 2A-2B pictorially illustrate a diamond anvil that can be used in the DAC of FIG. 1 according to some examples.

[0011] FIG. 3 is a schematic diagram illustrating a cross-sectional side view of an anvil assembly that can be used in the DAC of FIG. 1 according to some examples.

[0012] FIG. 4 is a schematic diagram illustrating a system for interrogating a pressurized sample according to some examples.

[0013] FIG. 5 graphically shows a Raman spectrum measured with the system of FIG. 4 according to one example.

[0014] FIG. 6 graphically shows ruby fluorescence spectra measured with the system of FIG. 4 according to some examples.

[0015] FIGS. 7A-7B graphically illustrate X-ray scans of the anvil assembly shown in FIG. 3 obtained with the system of FIG. 4 according to some examples.

[0016] FIG. 8 graphically illustrates an X-ray diffraction pattern measured with the system of FIG. 4 according to one example.

[0017] FIG. 9 shows a post-experiment photograph of a recovered gasket used in the anvil assembly of FIG. 3 according to one example.DETAILED DESCRIPTION

[0018] Diamond anvil cells (DACs) are devices capable of generating static high pressures, e.g., in the range of around 1 GPa to 200 GPa. In some examples, a DAC has two opposed diamond anvils with a metallic gasket in between them that has a hole drilled in the center. A sample is placed in the hole, and as a mechanical screw force is applied between the anvils, pushing them toward one another, the anvils squeeze the gasket laden with a sample. Contact between the anvil flat surfaces and the metallic gasket allows the sample to be sealed and pressurized.

[0019] Various experimental techniques, such as X-ray diffraction, X-ray absorption, X-ray Raman, optical Raman, infrared, and nuclear magnetic resonance (NMR) spectroscopies can be employed to interrogate the properties of pressurized samples, and various DAC designs are used to accommodate these experimental methods. However, at least some of these designs suffer from a common limitation: the sample is largely confined by a metallic (e.g., rhenium or stainless steel) gasket and the two diamond windows. For some interrogation methods, this configuration may present a significant challenge. For example, in typical X-ray absorption measurements, the signal is collected perpendicular to the probe beam direction, which may cause the transmitted and / or scattered X-ray beams to pass through approximately 2 mm of X-ray attenuating metal. Some designs use low-Z Be gaskets, which are toxic and not as ductile or strong as rhenium or stainless- steel gaskets. Some designs use a small, e.g., 1 * 6 mm2Re gasket to reduce attenuation of X rays going to and from the sample, but this approach still results in a reduced collection solid angle of the detectable radiation.

[0020] In the case of NMR, the metallic gasket typically chokes the radio-frequency (RF) signal, restricting the coupling between the sample and the RF coil(s). In some examples, an RF coil can be coupled to the sample using a split gasket resonator, where the gasket is created with an empty slot that is filled with electrically insulating diamond and NaCl powders to allow RF signals into and out of the pressurized volume. In some other examples, the RF coils are positioned as closely as possible to the sample to allow the RF field lines to “dip” into the sample region. However, in at least some use cases, such designs may suffer from relatively poor filling factors, making NMR at high pressures rather challenging. Some additional designs use composite high-pressure gaskets with embedded NMR coils employing powders, such as corundum sealed with epoxy, which may perform relatively well in27Al NMR up to about 30 GPa. However, such gaskets may be rather challenging to use for 'H NMR due to the interfering proton signals from the epoxy and the water from corundum.

[0021] At least some of the above-indicated challenges can beneficially be addressed using various embodiments disclosed herein. An example embodiment provides a design that pushes the sample “out” of the gasket plane to enable the sample so pushed to be exposed to less-attenuated probe beam while still being under high pressure, thereby improving RF, X-ray, and optical access to the sample.

[0022] In one example, a DAC-cell design features a hole laser-drilled in the center of one of the diamond tips. This hole contains the sample under study. A blank gasket placed adjacent to the diamond-anvil tip covers the hole containing the sample, and a second opposing diamond anvil (with no hole) is brought toward the first diamond anvil and the blank gasket (also with no hole). As load is applied to both opposing anvils, pressure applied to the gasket causes the gasket metal to flow into the hole in the diamond anvil containing the sample. This reflowed metal pressurizes the sample like a movable piston pressurizes gas inside a cylinder used for gas compression.

[0023] FIG. 1 is a schematic diagram illustrating a diamond anvil cell (DAC) 100 according to some examples. The DAC 100 includes first and second opposing diamond anvils 120, 140. Smaller horizontal facets 122, 142 of the diamond anvils 120, 140 are typically referred to as culets. Larger horizontal facets 126, 146 of the diamond anvils 120, 140 are typically referred to as tables. A gasket 130 is positioned between the culets 122 and 142. In the example shown, the gasket 130 has a small cylindrical hole 132 near the center thereof. In some other examples, the employedgasket may not have a hole, as described in more detail below, e.g., in reference to FIGS. 2-4. In such examples, the gasket may be a solid metal piece (e.g., a disk) and may be referred to as the “blank gasket.”

[0024] Backing plates 110, 150 are used to transfer an external force F to the tables 126, 146 as indicated in FIG. 1. The applied force is transferred through the anvil body to the culets 122, 142 and is applied to the gasket 130. When the force F is sufficiently large, the gasket 130 is plastically deformed, which causes the hole 132 to be compressed accordingly. In a typical example, the hole 132 contains a sample, a pressure -transmitting medium, and a pressure sensor. The gasket’s compression causes the pressure acting upon the sample to increase as metal plastically flows into the hole. Although the hole may deform slightly during this process in some cases, this deformation is small compared to the deformation of the metallic gasket due to the fact that diamond has a far higher yield strength than the gasket material. The pressure-transmitting medium operates to transform the uniaxial pressure supplied by the diamond anvils 120, 140 into substantially uniform hydrostatic pressure inside the sealed hole 132. In various examples, the pressure-transmitting medium may be argon, xenon, hydrogen, or helium gas, paraffin oil, a salt, such as NaCl, or a mixture of alcohols, such as methanol and ethanol. The pressure sensor typically comprises a reference material whose behavior under pressure is known. In various examples, the reference material can be a ruby crystal, a13C chip, NaCl, or one of structurally simple metals, such as copper or platinum.

[0025] In some examples, the sample can be viewed through the diamond anvils 120, 140 and illuminated by X-rays and / or visible light (also see FIG. 4). In this manner, various sampleinterrogation techniques can be implemented. In some examples, such interrogation techniques may include one or more of the following: diffraction; fluorescence; absorption; Nuclear Forward Scattering, Mossbauer, Raman, or Brillouin scattering; nuclear magnetic resonance; and electron paramagnetic resonance (EPR). In some examples, with electrodes attached to the sample, electrical and magnetoelectrical measurements can be performed, as well as resistive heating of the sample, e.g., to over 1000 K. Even higher temperatures can be achieved with laser-induced heating.

[0026] FIGS. 2A-2B pictorially illustrate a diamond anvil 220 that can be used in the DAC 100 according to some examples. More specifically, FIG. 2A is a sketch showing a three-dimensional (3D) perspective view of the diamond anvil 220. FIG. 2B shows a photograph of the diamond anvil220. In some examples, the diamond anvil 220 is used instead of the diamond anvil 120 in the DAC 100.

[0027] In the example shown, the diamond anvil 220 is produced by “drilling” a hole 224 in the culet 122 of the diamond anvil 120 either via laser drilling or mechanical diamond drilling. In some examples, the drilling is performed using a pulsed Nd-YAG laser having an output wavelength of 532 nm, output power of 7 W, and a pulse repetition rate between 1 kHz and 60 kHz. Hereafter, the diamond anvil 220 or a functional equivalent thereof may be referred to as the “perforated anvil.” In one example, the diamond anvil 220 comprises a Type la diamond, with the culet diameter of ~350 pm. The hole 224 is located approximately in the center of the culet 122 and has a diameter (or a transverse size) of ~ 130 pm and a depth (longitudinal size) of ~60 pm.

[0028] FIG. 3 is a schematic diagram illustrating a cross-sectional side view of an anvil assembly 300 that can be used in the DAC 100 according to some examples. The assembly 300 includes diamond anvils 140 and 220 and a blank gasket 330 positioned therebetween. The blank gasket 330 is a contiguous metal piece that does not have any holes in the area corresponding to the culets 122 and 142 or to the hole 224. A sample 302, together with a ruby sensor and a pressuretransmitting medium (not explicitly shown in FIG. 3), may be loaded into the hole 224 and sealed therein by the gasket 330 when external compression forces are applied to the assembly 300 as indicated in FIG. 1.

[0029] FIG. 4 is a schematic diagram illustrating a system 400 for interrogating a pressurized sample 302 according to some examples. The system 400 includes a modified DAC 100, which uses the anvil assembly 300. For clarity of depiction, only the diamond anvil 220 of the modified DAC 100 and the sample 302 loaded therein are explicitly shown in FIG. 4. Based on the description of FIG. 4 provided below and further based on the above description of FIGS. 1-3, a person of ordinary skill in the pertinent art will readily understand how to make and use the system 400 without any undue experimentation.

[0030] In the example shown, the system 400 also includes excitation sources 401 , 402 and detectors 411, 412. The excitation source 401 is configured to generate an electromagnetic (EM) probe beam 403 and direct the generated beam to the sample 302 such that the beam is substantially (e.g., to within ±10°) parallel to the culet 122 and to a main plain of the gasket 330 (also see FIG. 3).The excitation source 402 is configured to generate an electromagnetic probe beam 404 and direct the generated beam to the sample 302 such that the beam is substantially (e.g., to within ±10°) orthogonal to the culet 122 and to the main plain of the blank gasket 330 (also see FIG. 3). The detector 411 is configured to detect an electromagnetic signal 413 produced in the sample 302 in response to either the probe beam 403 or the probe beam 404. The detected signal 413 has a propagation direction that is substantially (e.g., to within ±10°) parallel to the culet 122 and to the main plain of the gasket 330 (also see FIG. 3). The detector 412 is configured to detect an electromagnetic signal 414 produced in the sample 302 in response to either the probe beam 403 or the probe beam 404. The detected signal 414 has a propagation direction that is substantially (e.g., to within ±10°) orthogonal to the culet 122 and to the main plain of the gasket 330 (also see FIG. 3).

[0031] Herein, the term “vertical” refers to a direction that is approximately orthogonal to a main plane of the blank gasket 330 or to the planes of the culets 122, 142. The term “horizontal” refers to a direction that is approximately parallel to the main plane of the blank gasket 330 or to the planes of the culets 122, 142. Herein, a “main plane” of an object, such as a gasket, a substrate, a chip, or a board is a plane parallel to a substantially planar surface thereof that has about the largest area among exterior surfaces of the object. This substantially planar surface may be referred to as a main surface. The exterior surfaces of the object that have one relatively large size, e.g., length, but are of much smaller area, e.g., less than one quarter of the main-surface area, are referred to as the edges of the object.

[0032] In various examples, either of the probe beams 403, 404 may include one or more EM components selected from the group consisting of X-ray radiation, RF waves, infrared light, visible light, UV light, gamma rays, terahertz radiation, and microwave radiation. Similarly, either of the response signals 413, 414 may include one or more EM components selected from the group consisting of X-ray radiation, RF waves, infrared light, visible light, U V light, gamma rays, terahertz radiation, and microwave radiation. Beneficially neither of the probe beams 403 and 404 and neither of the detected response signals 413 and 414 pass through the gasket 330 (also see FIG. 3), thereby enabling more efficient electromagnetic excitation of the sample 302 loaded into the modified DAC 100 and / or more efficient detection of the corresponding electromagnetic response signals compared to those in at least some conventional systems. Example measurements performed with the system 400 are described in more detail below in reference to FIGS. 5-9.Example 1

[0033] A 10-pm ruby sphere was first inserted into the hole 224 (for pressure monitoring), and then the sample 302 comprising SnC2O4 powder (Sigma-Aldrich, 99% purity) was also placed into the hole 224. The gasket 330 comprised a layered composite of copper and stainless steel. Copper, being a soft metal, tends to provide less stress to the hole edges. The copper layer in the gasket 330 was approximately 20 pm thick and was on top of a 250 pm thick stainless-steel piece. Copper also tends to flow relatively easily into the hole 224 when pressure is applied, thereby pressurizing the sample 302 therein. The use of copper may also be beneficial for NMR measurements as copper has a low current resistivity as a conduit for RF currents. The layered composite gasket 330 was compressed using the external forces F to pressurize the sample (also see FIG. 1). Thereafter, Raman spectroscopy and ruby fluorescence measurements were performed using the corresponding configuration of the system 400. The laser light (532 nm) from a LASOS® laser illuminated the sample 302 through the back of the diamond anvil 220, thereby exciting the ruby sphere. Ruby fluorescence was collected using a Jobin Yvon U1000® spectrometer, which had a Spectrum One CCD® detector, and then displayed on a desktop computer. The same laser and spectrometer were used to measure Raman spectra of the sample 302 at various pressures.

[0034] FIG. 5 graphically shows a Raman spectrum 502 measured with the system 400 as described above. The sample 302 comprising SnC2O4 in the modified DAC 100 was gradually pressurized in the modified DAC 100 to about 20 GPa. The Raman spectrum 502 is an ambient pressure spectrum. The two strongest peaks in the spectrum 512 are: (i) peak A representing the v(SnO) + Sung mode near 508 cm1and (ii) peak B representing the v(CO) mode observed near 1463 cm1.

[0035] FIG. 6 graphically shows ruby fluorescence spectra measured with the system 400 as described above. For pressures below 10 GPa, both R1 and R2 lines are present, indicating a low shear stress. However, above 10 GPa, the R2 line diminishes, and the spectrum broadens significantly, indicating departure from hydrostatic conditions. Better polishing of the walls of the hole 224 is expected to reduce nonhydrostatic stress.Example 2

[0036] The diamond anvils 220, 140 were ultrasonically cleaned from any residual sample and other contamination. One ruby crystal was placed at the blind end of the empty hole 224. Seleno- DL-cystine (Sigma- Aldrich, 99% pure) powder was then manually added into the hole 224, and a blank stainless-steel gasket 330 (250 pm thick) was used to cover the hole 224. The opposing diamond anvil 140 was brought into contact with the gasket 330, as indicated in FIG. 3, to seal and pressurize the sample 302 as described above.

[0037] The resulting sealed DAC 100 was brought to the Brockhouse IVU beamline at the Canadian Light Source for interrogation. The DAC 100 was installed such that the vertical diamond-diamond axis was perpendicular to the probe X-ray beam 404. In this example, the X-ray beam 404 had the following dimensions: 130 pm (horizontal) x 83 pm (vertical). The X-ray beam 404 was aligned such that it skimmed just above the main plane of the blank gasket 330 and into the side wall of the hole 224. X-ray diffraction patterns were captured using monochromatic X rays of 19.8 keV collected with a Rayonix® image plate camera.

[0038] FIGS. 7A-7B graphically illustrate X-ray scans of the assembly 300 with the abovedescribed configuration of the system 400 according to some examples. The sample 302 was properly positioned for X-ray diffraction measurements by scanning the position of the assembly 300 relative to the probe X-ray beam 404 in the (vertical) Z-axis direction and the (horizontal) X- axis direction, both perpendicular to the longitudinal axis of the X-ray beam 404. FIG. 7A graphically shows an intensity profile 710 of the response signal 413 during the vertical scan. FIG. 7B similarly graphically shows an intensity profile 720 of the response signal 413 during the horizontal scan. The abscissas in FIGS. 7A-7B represent readouts of the corresponding dials of the scan table on which the DAC 100 was mounted.

[0039] A dip 712 in the intensity profile 710 (FIG. 7A) corresponds to the positions around 52.5 mm in which the blank gasket 330 intercepts the probe beam 404. As the sample 302 was located just above the gasket along the Z-axis, the Z-axis position of the probe X-ray beam 404 was set to 52 mm for X-ray diffraction measurements. The X-axis position of the probe X-ray beam 404 was set to 28.6 mm, which approximately corresponded to the center of the intensity profile 720 (FIG. 7B).

[0040] FIG. 8 graphically illustrates an X-ray diffraction pattern 800 of the seleno-DL-cystine sample 302 measured with the system 400 according to one example. The diffraction pattern 800 was captured with the probe X-ray beam 404 being in the XZ position set as described above in reference to FIGS. 7A-7B. The sample 302 was pressurized to 2.5 GPa. The X-ray energy was 19.8 keV.

[0041] FIG. 9 shows a post-experiment photograph 900 of a recovered gasket 330 according to one example. The recovered gasket 330 has an indentation 902 made by the diamond anvil 220. A small vertical protrusion 904 is evident in the center of the indentation 902. The protrusion 904 demonstres that the metal from the gasket 330 was plastically deformed when a compressive force was applied to the anvil assembly 330 and entered the hole 224 to pressurize the sample contained therein.

[0042] Although example embodiments are described above in reference to diamond anvils and DACs in general, various embodiments are not so limited. Based on the provided description, a person of ordinary skill in the pertinent art will be able to make and use additional embodiments with high-pressure cells employing other (than diamond) anvil materials without any undue experimentation. For example, at least some the following anvil materials may be used in various additional embodiments: (i) tungsten carbide, WC; (ii) WC with Ni or Co binders; (iii) hard metals, such as Mo and W; (iv) sapphire, AI2O3; (v) cubic zirconia, ZrCh; and (vi) refractory and wide bandgap materials, such as alumina, SiC, GaN, BN, AIN, and hard ceramics.

[0043] According to an example embodiment disclosed above, e.g., in the summary section and / or in reference to any one or any combination of some or all of FIGS. 1-9, provided is an apparatus comprising: a first anvil having a first culet and further having a hole in a middle portion of the first culet; a second anvil having a second culet positioned along the first culet; and a gasket sandwiched between the first and second culets, wherein the first and second anvils are configured to apply a compressive force to the gasket to cause a portion of the gasket adjacent to the hole to plastically deform and enter the hole to pressurize a sample contained therein.

[0044] In some embodiments of the above apparatus, the first culet has a size smaller than 1 mm.

[0045] In some embodiments of any of the above apparatus, the hole has a transverse size smaller than 50% of the culet size.

[0046] In some embodiments of any of the above apparatus, the hole has a depth greater than 10% of the culet size.

[0047] In some embodiments of any of the above apparatus, the hole has a substantially cylindrical shape with a depth-to-diameter ratio greater than 0.3.

[0048] In some embodiments of any of the above apparatus, the gasket comprises a metal selected from the group consisting of copper, steel, nickel, aluminum, brass, Inconel, tantalum, silver, lead, chromium.

[0049] In some embodiments of any of the above apparatus, the gasket comprises a first layer made of a first metal and a second layer made of a second metal, the first layer facing the first culet, the second layer facing the second culet, the first metal being softer than the second metal which will more easily flow into the sample hole.

[0050] In some embodiments of any of the above apparatus, each of the first and second anvils is made of a respective material selected from the group consisting of: diamond; tungsten carbide; molybdenum; tungsten; sapphire; cubic zirconia; alumina; silicon carbide; gallium nitride; boron nitride; aluminum nitride; and a ceramic material.

[0051] In some embodiments of any of the above apparatus, the sample is pressurized to a pressure greater than 1 GPa.

[0052] In some embodiments of any of the above apparatus, the apparatus further comprises an excitation source configured to generate an electromagnetic (EM) probe beam directed at the sample substantially parallel to the first culet.

[0053] In some embodiments of any of the above apparatus, the apparatus further comprises a detector configured to detect an EM signal emitted from the sample in response to the EM probe beam, wherein the emitted EM signal has a propagation direction that is substantially parallel to the first culet.

[0054] In some embodiments of any of the above apparatus, the apparatus further comprises a detector configured to detect an EM signal emitted from the sample in response to the EM probe beam, wherein the emitted EM signal has a propagation direction that is substantially orthogonal to the first culet.

[0055] In some embodiments of any of the above apparatus, the apparatus further comprises an excitation source configured to generate an electromagnetic (EM) probe beam directed at the sample substantially perpendicular to the first culet.

[0056] In some embodiments of any of the above apparatus, the apparatus further comprises a detector configured to detect an EM signal emitted from the sample in response to the EM probe beam, wherein the emitted EM signal has a propagation direction that is substantially parallel to the first culet.

[0057] In some embodiments of any of the above apparatus, the apparatus further comprises a detector configured to detect an EM signal emitted from the sample in response to the EM probe beam, wherein the emitted EM signal has a propagation direction that is substantially perpendicular to the first culet.

[0058] According to another example embodiment disclosed above, e.g., in the summary section and / or in reference to any one or any combination of some or all of FIGS. 1-9, provided is a method of interrogating a sample, comprising: placing a sample into a hole located in a middle portion of a first culet of a first anvil; sandwiching a gasket between the first culet and a second culet positioned along the first culet, the second culet belonging to a second anvil; and applying a compressive force to the gasket with the first and second anvils to cause a portion of the gasket adjacent to the hole to plastically deform and enter the hole to pressurize the sample contained therein.

[0059] In some embodiments of the above method, the method further comprises directing, substantially parallel to the first culet, an electromagnetic (EM) probe beam generated with an excitation source.

[0060] In some embodiments of any of the above methods, the method further comprises detecting, with a detector, an EM signal emitted from the sample in response to the EM probe beam,wherein the emitted EM signal has a propagation direction that is substantially parallel or substantially orthogonal to the first culet.

[0061] In some embodiments of any of the above methods, the excitation source and the detector are configured to implement a sample-interrogation technique selected from the group consisting of: diffraction; fluorescence; absorption; Raman scattering; nuclear magnetic resonance; electron paramagnetic resonance; X-ray Raman scattering; and nuclear forward scattering.

[0062] In some embodiments of any of the above methods, the sample is pressurized to a pressure greater than 1 GPa.

[0063] With regard to the processes, systems, methods, heuristics, etc. described herein, it should be understood that, although the steps of such processes, etc. have been described as occurring according to a certain ordered sequence, such processes could be practiced with the described steps performed in an order other than the order described herein. It further should be understood that certain steps could be performed simultaneously, that other steps could be added, or that certain steps described herein could be omitted. In other words, the descriptions of processes herein are provided for the purpose of illustrating certain embodiments and should in no way be construed so as to limit the claims.

[0064] Accordingly, it is to be understood that the above description is intended to be illustrative and not restrictive. Many embodiments and applications other than the examples provided would be apparent upon reading the above description. The scope should be determined, not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. It is anticipated and intended that future developments will occur in the technologies discussed herein, and that the disclosed systems and methods will be incorporated into such future embodiments. In sum, it should be understood that the application is capable of modification and variation.

[0065] All terms used in the claims are intended to be given their broadest reasonable constructions and their ordinary meanings as understood by those knowledgeable in the technologies described herein unless an explicit indication to the contrary is made herein. In particular, use of the singular articles such as “a,” “the,” “said,” etc. should be read to recite one or more of the indicated elements unless a claim recites an explicit limitation to the contrary.

[0066] The Abstract of the Disclosure is provided to allow the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the foregoing Detailed Description, it can be seen that various features are grouped together in various embodiments for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments incorporate more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter lies in fewer than all features of a single disclosed embodiment. Thus, the following claims are hereby incorporated into the Detailed Description, with each claim standing on its own as a separately claimed subject matter.

[0067] While this disclosure includes references to illustrative embodiments, this specification is not intended to be construed in a limiting sense. Various modifications of the described embodiments, as well as other embodiments within the scope of the disclosure, which are apparent to persons skilled in the art to which the disclosure pertains are deemed to lie within the principle and scope of the disclosure, e.g., as expressed in the following claims.

[0068] Unless explicitly stated otherwise, each numerical value and range should be interpreted as being approximate as if the word “about” or “approximately” preceded the value or range.

[0069] Although the elements in the following method claims, if any, are recited in a particular sequence with corresponding labeling, unless the claim recitations otherwise imply a particular sequence for implementing some or all of those elements, those elements are not necessarily intended to be limited to being implemented in that particular sequence.

[0070] Reference herein to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the disclosure. The appearances of the phrase “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive of other embodiments. The same applies to the term “implementation.”

[0071] Unless otherwise specified herein, the use of the ordinal adjectives “first,” “second,” “third,” etc., to refer to an object of a plurality of like objects merely indicates that differentinstances of such like objects are being referred to, and is not intended to imply that the like objects so referred-to have to be in a corresponding order or sequence, either temporally, spatially, in ranking, or in any other manner.

[0072] Unless otherwise specified herein, in addition to its plain meaning, the conjunction “if’ may also or alternatively be construed to mean “when” or “upon” or “in response to determining” or “in response to detecting,” which construal may depend on the corresponding specific context. For example, the phrase “if it is determined” or “if [a stated condition] is detected” may be construed to mean “upon determining” or “in response to determining” or “upon detecting [the stated condition or event]” or “in response to detecting [the stated condition or event].”

[0073] Also, for purposes of this description, the terms “couple,” “coupling,” “coupled,” “connect,” “connecting,” or “connected” refer to any manner known in the art or later developed in which energy is allowed to be transferred between two or more elements, and the interposition of one or more additional elements is contemplated, although not required. Conversely, the terms “directly coupled,” “directly connected,” etc., imply the absence of such additional elements.

[0074] Any numerical range recited herein includes all values from the lower value to the upper value. For example, if a range is stated as 1% to 50%, it is intended that the narrower ranges thereof, such as 2% to 40%, 10% to 30%, 1% to 3%, etc., are expressly enumerated by said statement. These specific examples represent only a limited subset of what is intended to be covered, and all possible combinations of numerical values between and including the lowest value and the highest value of the enumerated range are to be considered to be expressly stated in this application.

[0075] The modifier “about” or “approximately” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (for example, it includes at least the degree of error associated with the measurement of the particular quantity). The modifier “about” or “approximately” should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4” also discloses the range “from 2 to 4.” The term “about” may refer to plus or minus 10% of the indicated number. For example, “about 10%” may indicate a range of 9% to 11%, and “about 1” may mean from 0.9-1.1.Other meanings of “about” may be apparent from the context, such as rounding off, so that, for example, “about 1” may also mean from 0.5 to 1.4.

[0076] For purposes of this disclosure, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, the present disclosure relies on general principles of organic chemistry, inorganic chemistry, and material science, as accepted in the pertinent arts. For example, specific functional moieties and reactivity in accordance with some of such principles are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March, March's Advanced Organic Chemistry, 5th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modem Methods of Organic Synthesis, 3rd Edition, Cambridge University Press, Cambridge, 1987, the entire contents of each of which are incorporated herein by reference.

[0077] “BRIEF SUMMARY OF SOME SPECIFIC EMBODIMENTS” in this specification is intended to introduce some example embodiments, with additional embodiments being described in “DETAILED DESCRIPTION” and / or in reference to one or more drawings. “BRIEF SUMMARY OF SOME SPECIFIC EMBODIMENTS” is not intended to identify essential elements or features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

Claims

CLAIMSWhat is claimed is:

1. An apparatus, comprising: a first anvil having a first culet and further having a hole in a middle portion of the first culet; a second anvil having a second culet positioned along the first culet; and a gasket sandwiched between the first and second culets, wherein the first and second anvils are configured to apply a compressive force to the gasket to cause a portion of the gasket adjacent to the hole to plastically deform and enter the hole to pressurize a sample contained therein.

2. The apparatus of claim 1, wherein the first culet has a size smaller than 1 mm.

3. The apparatus of claim 2, wherein the hole has a transverse size smaller than 50% of the culet size.

4. The apparatus of claim 2, wherein the hole has a depth greater than 10% of the culet size.

5. The apparatus of claim 1, wherein the hole has a substantially cylindrical shape with a depth- to-diameter ratio greater than 0.3.

6. The apparatus of claim 1, wherein the gasket comprises a metal selected from the group consisting of copper, steel, nickel, aluminum, brass, Inconel, tantalum, silver, lead, chromium.

7. The apparatus of claim 1, wherein the gasket comprises a first layer made of a first metal and a second layer made of a second metal, the first layer facing the first culet, the second layer facing the second culet, the first metal being softer than the second metal.

8. The apparatus of claim 1, wherein each of the first and second anvils is made of a respective material selected from the group consisting of: diamond;tungsten carbide; molybdenum; tungsten; sapphire; cubic zirconia; alumina; silicon carbide; gallium nitride; boron nitride; aluminum nitride;BeCu; and a ceramic material.

9. The apparatus of claim 1 , wherein the sample is pressurized to a pressure greater than 1 GPa.

10. The apparatus of claim 1, further comprising an excitation source configured to generate an electromagnetic (EM) probe beam directed at the sample substantially parallel to the first culet.

11. The apparatus of claim 10, further comprising a detector configured to detect an EM signal emitted from the sample in response to the EM probe beam, wherein the emitted EM signal has a propagation direction that is substantially parallel to the first culet.

12. The apparatus of claim 10, further comprising a detector configured to detect an EM signal emitted from the sample in response to the EM probe beam, wherein the emitted EM signal has a propagation direction that is substantially orthogonal to the first culet.

13. The apparatus of claim 1, further comprising an excitation source configured to generate an electromagnetic (EM) probe beam directed at the sample substantially perpendicular to the first culet.

14. The apparatus of claim 13, further comprising a detector configured to detect an EM signal emitted from the sample in response to the EM probe beam, wherein the emitted EM signal has a propagation direction that is substantially parallel to the first culet.

15. The apparatus of claim 13, further comprising a detector configured to detect an EM signal emitted from the sample in response to the EM probe beam, wherein the emitted EM signal has a propagation direction that is substantially perpendicular to the first culet.

16. A method of interrogating a sample, comprising: placing a sample into a hole located in a middle portion of a first culet of a first anvil; sandwiching a gasket between the first culet and a second culet positioned along the first culet, the second culet belonging to a second anvil; and applying a compressive force to the gasket with the first and second anvils to cause a portion of the gasket adjacent to the hole to plastically deform and enter the hole to pressurize the sample contained therein.

17. The method of claim 16, further comprising directing, substantially parallel to the first culet, an electromagnetic (EM) probe beam generated with an excitation source.

18. The method of claim 17, further comprising detecting, with a detector, an EM signal emitted from the sample in response to the EM probe beam, wherein the emitted EM signal has a propagation direction that is substantially parallel or substantially orthogonal to the first culet.

19. The method of claim 19, wherein the excitation source and the detector are configured to implement a sample-interrogation technique selected from the group consisting of diffraction; fluorescence;X-ray absorption; optical Raman scattering;nuclear forward scattering;X-ray Raman scattering; nuclear magnetic resonance; and electron paramagnetic resonance.

20. The method of claim 16, wherein the sample is pressurized to a pressure greater than 1 GPa.

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