SE544674C2 - A beam path component for use in neutron scattering equipment and method of producing such - Google Patents
A beam path component for use in neutron scattering equipment and method of producing suchInfo
- Publication number
- SE544674C2 SE544674C2 SE2051446A SE2051446A SE544674C2 SE 544674 C2 SE544674 C2 SE 544674C2 SE 2051446 A SE2051446 A SE 2051446A SE 2051446 A SE2051446 A SE 2051446A SE 544674 C2 SE544674 C2 SE 544674C2
- Authority
- SE
- Sweden
- Prior art keywords
- beam path
- path component
- sample
- sample holder
- balance
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000001956 neutron scattering Methods 0.000 title claims abstract description 24
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 49
- 239000000956 alloy Substances 0.000 claims abstract description 49
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 18
- 238000002474 experimental method Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 241001012508 Carpiodes cyprinus Species 0.000 claims description 5
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- 238000010894 electron beam technology Methods 0.000 claims description 4
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- 230000001678 irradiating effect Effects 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 13
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- 239000000523 sample Substances 0.000 description 107
- 239000010955 niobium Substances 0.000 description 19
- 238000005259 measurement Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007769 metal material Substances 0.000 description 5
- 239000005300 metallic glass Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
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- 238000012546 transfer Methods 0.000 description 4
- ABEXEQSGABRUHS-UHFFFAOYSA-N 16-methylheptadecyl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC(C)C ABEXEQSGABRUHS-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 241000764238 Isis Species 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001998 small-angle neutron scattering Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001093 Zr alloy Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000005417 image-selected in vivo spectroscopy Methods 0.000 description 2
- 238000001427 incoherent neutron scattering Methods 0.000 description 2
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- 229910052726 zirconium Inorganic materials 0.000 description 2
- -1 AL7049A Chemical compound 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910008651 TiZr Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
- G01N23/20025—Sample holders or supports therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The present invention relates to a beam path component, for example a sample holder, for use in neutron scattering equipment and a method of producing such. The beam path component is formed from a Zr-based alloy comprising: Cu: 19 - 26 wt%; a combination of Al and Nb: 2-6.3 wt%; Hf: 0-7% wt%; unavoidable impurities; and balance Zr. The Zr-based metallic alloy is chemically homogenous and X-ray amorphous and thereby exhibiting low scattering and high transmission. The method according to the invention is an additive manufacturing method.
Description
A beam path component for use in neutron scattering equipment and method of producing such Field of the invention The present invention relates to a beam path component for use in neutronscattering equipment, the beam path component being adapted to be at least partlyplaced in a neutron beam path and exhibiting low scattering and hightransmission. In particular the present invention relates to a sample holder for usein neutron scattering experiments. The invention further relates to producing a beam path component of a metallic material.
Background of the invention Neutron scattering based techniques are used for studying various materialproperties. Neutron diffraction (elastic scattering) techniques are used for analyzingstructures; where inelastic neutron scattering is used in studying atomic vibrationsand other atomic and molecular motion. Although extremely useful, neutronscattering based techniques are still expensive and access to research facilitiesoffering these techniques are limited. This is due to that the neutrons are producedin research reactors or spallation neutron sources and the experimental equipmentis large, complex and expensive to run. In such scenarios it is of vital importancethat the experimental equipment is reliable and does not disturb themeasurements. Even failure of individual small parts may be hazardous and/ or result in loss of valuable beam time.
Common to the various neutron scattering based techniques is a neutron beamthat is directed to a sample and through the scattering events interact with thesample. For nearly all neutron scattering measurements, there is a container orsample holder for holding the sample in the neutron beam. In addition tocontaining for example a powder or liquid sample, the sample holder may also becritical for providing a specific sample environment. Specific sample environmentsinclude, but are not limited to high and low temperatures, high and low pressure,presences of solvents, gases and other substances. Also providing mechanicalforces such as shear and electrical and magnetic fields are examples of conditions in the sample environments. The sample environment may be static or dynamic. Inorder to provide the desired sample environment the sample holder may comprise,or be in connection with for example, but not limited to a furnace, a pressure-cell, amagnet, a cryostat, a shearing cell, a rheometer, an extrusion nozzle or a combination thereof.
The sample holder and sample environment may also scatter neutrons andcontribute to the measured scattering intensity during an experiment. It may bepossible to measure the scattering intensity of an empty sample holder and use thisas a measure of the background for the measurement. However, calibrationmeasurements of this type do not account for the absorption of the sample ormultiple scattering events between the sample and the sample holder or other partsin the sample environment. If the scattering intensities from the empty sampleholder and parts in the sample environment are large, then the subtractiontechnique will deteriorate the ratio of signal to noise. The unwanted scattering hashere been described as occurring mainly in close proximity to the sample, i.e. fromthe sample holder or other parts in the sample environment. However, unwantedscattering may occur in other places in the experimental equipment, basically in allinstances wherein the neutron beam passes through a material, for example by parts such as windows, filters, collimators and monochromators.
A preferred way to improve the measurement is to reduce the scattering of thesample holder through a proper choice of materials and reducing the amount ofthese materials at least in the portions of the sample holder, or other parts, that issubjected directly to the neutron beam. However, the chosen material must alsohave mechanical properties, and in some cases chemical properties, that is suitablefor the application. As exemplif1ed above a sample holder may have a complexdesign and/ or should function in extreme temperatures or pressures, for example.To provide a material that combines low scattering and the mechanical propertiesand/ or chemical properties required for more advanced sample holders or other parts remains a challenge.
Amorphous quartz (quartz glass or fused quartz) has commonly been used insample holders and windows in neutron scattering equipment. Amorphous quartzfulfils the requirements of low scattering (low scattering cross section om) andhaving low absorption (low absorption cross section oa). However, amorphousquartz is a brittle material and is difficult to machine in any but the simplest geometries. The brittleness is also a risk and a limitation in the handling of theequipment at the experimental sites. Therefore, the use of amorphous quartz is limited to windows or other simple sample holders or parts of sample holders.
As an alternative to amorphous quartz metal materials are used, for examplevanadium, aluminium and aluminium alloys such as AL7049A, AL7075A, NiCrAl,and TAV6. Other alloys such as MP35N, CuBe and TiZr have also been suggested.Although selected to give low scattering sample holders in these materials will showa considerably higher scattering than amorphous quartz. In order to be a viablealternative, the parts that are subjected to the neutron beam must be made thin,typically with a thickness less than 0.5 mm. This forms a contradiction, at least insome applications, with the purpose of choosing a metallic material to be able toprovide more complex geometries by utilizing the more suitable mechanicalproperties of the metallic material. Further, even as the machinability typically ismuch better with the metallic alloys than the amorphous glass, the requirement tokeep any part subjected to the neutron beam as thin as possible puts severe limitations to the design.
“Ultrathin aluminum sample cans for single crystal inelastic neutron scattering”, M.B. Stone et al, Review of Scientific Instruments 82, 055117 (201 1) discloses a thinAl container, in principle a standard beverage can without the top portion, as asample container. The walls can be made very thin, a typical value of 0.076 mmwas reported. The sample container is considered as low scattering. However, onlyvery simple geometries are relevant due to the very thin walls andholders/containers being subjected to a large mechanical forces or pressure, for example, cannot be produced in accordance with the described method.
Summary of the invention Although advances have been made in providing materials and designs suitable forneutron scattering experiments there is still a need for improvements, especiallyregarding complex sample holders and sample environments suitable for studying dynamic processes.
This is achieved by the beam path component according to claim 1, the method as defined in claim 12, and the sample holder as defined in claimAccording to one aspect of the invention a beam path component is provided. The beam path component intended for use in neutron scattering equipment is adaptedto be at least partly placed in a neutron beam path of the neutron scatteringequipment. The material of the beam path component is a Zr-based alloycomprising: Cu: 19-26 Wt%; a combination of Al and Nb: 2-6.3 Wt%; Hf: 0-7 Wt%; unavoidable impurities; and balance Zr. The Zr-based metallic alloy is chemically homogenous and X-ray amorphous.
According to one embodiment of the invention the material of the beam pathcomponent is a ZrCuAlNb-alloy comprising: Cu: 19-26 Wt%; Al 1-4 Wt%; Nb: 1-2.3 Wt%; Hf: 0-7 Wt%; unavoidable impurities;and balance Zr.
According to one embodiment of the invention the material of the beam pathcomponent is a ZrCuAlNb-alloy comprising: Cu: 23-26 Wt%; Al 2-4 Wt%; Nb: 1-2.Wt%; Hf: 0-7 Wt%; unavoidable impurities; and balance Zr.
According to one embodiment of the invention the material of the beam pathcomponent is a ZrCuAlNb-alloy comprising: Cu: 23-25 Wt%; Al 3-5 Wt%; Nb: 1-Wt%; Hf: 0-7 Wt%; unavoidable impurities; and balance Z.
According to one embodiment of the invention the material of the beam pathcomponent is a ZrCuAlNb-alloy comprising: Cu: 23.9 Wt%; Al 3.7 Wt%; Nb: 1.8 Wt%; Hf: 0-7 Wt%; unavoidable impurities; and balance Zr.
According to one aspect of the invention the beam path component is a sampleholder or a part of a sample holder, the sample holder arranged to accommodate a sample to be investigated in the neutron scattering equipment.
According to one embodiment of the invention the sample holder comprises at leastone internal channel arranged to accommodate a sample in liquid form or in gas form in Which sample is caused to flow Within the sample holder.
According to one embodiment of the invention the sample holder is an extrusion nozzle.
According to one aspect of the invention a complex sample holder is providedcomprising a plurality of separate parts, Wherein at least one separate part is abeam path component according to the above specification. According to one embodiment of the invention the sample holder is a Couette cell comprising anouter cylinder and an inner cylinder, wherein at least one of the outer and inner cylinders are made of the Zr-based alloy.
According to aspects of the invention the properties associated to a metal areutilized in the beam path component, including mechanical properties, electricalproperties and thermal properties. According to one embodiment of the invention atleast a part of the beam path component forms a temperature controlling deviceand is arranged to heat or cool the sample through thermal conductivity. Accordingto one embodiment the beam path component forms a transmitter of electrical current and/ or electrical field to the sample.
Thanks to the superior mechanical properties as compared to for exampleamorphous quartz, the sample holder may form a vacuum chamber or being part ofa vacuum chamber. Similarly, a beam path component, for example in the form of a window may be a part of a vacuum system or chamber.
According to one aspect of the invention a method of producing a beam pathcomponent for neutron scattering experiments is provided. The method comprisesthe steps of: -providing a starting metal powder suitable for additive manufacturing, wherein themetal powder comprises particles with the composition: Cu: 19-26 Wt%; a combination of Al and Nb: 2-63 wt%; Hf: O-7wt%; unavoidable impurities; andbalance Zr; -providing a representation of the beam path component; -performing the additive manufacturing according to the representation of the beampath component, wherein the additive manufacturing comprises the steps of:-arranging the metal powder in a step-wise layer-by-layer process in the direction ofa predetermined production axis; -irradiating with a laser or electron beam each metal powder layer based on therepresentation of the beam path component wherein portions of the metal powderlayer is at least partly melted and re-solidified, and wherein the melting and re-solidified is controlled so that the formed beam path component is chemically homogenous and X-ray amorphous.
According to one embodiment of the invention the starting metal powder is aZrCuAlNb-alloy comprising: Cu: 23-25 Wt%; Al 3-5 wt%; Nb: 1-3 wt%; Hf: 0-7 wt%; unavoidable impurities; and balance Z.According to one embodiment of the invention the starting metal powder is aZrCuAlNb-alloy comprising: Cu: 23.9 Wt%; Al 3.7 wt%; Nb: 1.8 Wt%; Hf: 0-7 Wt%; unavoidable impurities; and balance Zr.
According to one aspect of the invention a sample holder is provided which hasbeen produced with the above described method. The sample holder may compriseat least one internal channel or have a geometrical complex form. The sample holder produced by the method may be an extrusion nozzle.
Thanks to the invention a beam path component and in particular a sample holdersuitable for neutron scattering experiments may be provided that exhibits theproperties of a metal and still may be considered as having low scattering and low absorption.
One advantage afforded by the invention is that geometrical complex beam pathcomponents can be produced more cost effectively than with prior art materials.Some geometries may not even be possible to produce vvith the prior art materials, at least not having low scattering and low absorption.
A further advantage is that a beam path component according to the invention willbe less fragile as compared to for example amorphous quartz, which will make the beam path component safer to handle.
A further advantage is that a beam path component or a sample holder according tothe present invention easily can be designed to withstand the mechanical loads in a vacuum application.
The beam path component is preferably produced by additive manufacturing, forexample SLM 3D-printing. The ability to use additive manufacturing (AM) for theproduction makes it easier to provide complex shapes, in particular complex internal shapes such as internal channels.
A further advantage of the beam path component according to the invention is thatthe materials thermal properties makes it suitable to be a part of a temperaturecontrolling arrangement. The electrical properties make it suitable to form a conductor or transmitter of electrical current or electrical field.
In the following, the invention will be described in more detail, by way of exampleonly, with regard to non-limiting embodiments thereof, reference being made to the accompanying dravvings.
Brief description of the drawingsFigures la-b illustrates embodiments of the sample holder according to the invention; Figures 2a-b illustrates an extrusion nozzle according to the invention;Figure 3 illustrates a Couette cell according to the invention; Figure 4 is a flowchart of the method according to the invention; Figures 5 is a graph of transmission data for the slab samples of the Zr-based material according to the invention; Figure 6 is a graph of scattering data for a slab sample of the Zr-based material according to the invention, wherein Q; and Figure 7 is a graph of scattering data of a slab sample of the Zr-based material according to the invention and the nozzle according to the invention.
Detailed description Terms such as ”top”, “bottom”, upper”, lower”, “below”, “above” etc are used merelywith reference to the geometry of the embodiment of the invention shown in thedrawings and/ or during normal operation of the beam path component and are not intended to limit the invention in any manner.
The term “beam path component” is used herein to denote a component of aneutron scattering equipment, which is directly inserted in the neutron beam, i.e.in the beam path. Examples or embodiments of beam path components include,but are not limited to, a sample holder, a component or part of the component usedto form a specific sample environment in the proximity to the sample, a window in the beam path.
The characterization “low scattering” used herein refers to scattering that iscommonly recognized as sufficiently low for neutron scattering experiments, inparticular small angle neutron scattering experiments (SANS). A differentialscattering cross-section in the range of 4.0 to 0.20 cm-1 sterad-l in the range ofmomentum transfer vectors 0.009 to 0.017 Ä-l and a differential scattering cross-section of less than 0.02 cm-1 sterad-l in the range of momentum transfer vectors 0.1 to 0.4 Ä-l is considered to be low scattering for the purposes discussed herein.The characterization “low absorption” or “high transmission” used herein refers toabsorption that is commonly recognized as sufficiently low, or respectivelytransmission that is sufficiently high, for neutron scattering experiments, inparticular small-angle neutron scattering experiments (SANS). A neutrontransmission per 2.2 mm thickness that is higher than 0.88 for a Wavelength of 1 Äand 0.80 for 15 Ä is considered to be high transmission for the purposes discussed herein.
The characterization “chemically homogenous” used herein means that a sample ischemically the same, no matter Where in the volume of the investigated piece thatsample is taken. Thus, there are no chemical gradients in the sample, and the composition is equal in all sub-volumes.
The characterization “X-ray amorphous” used herein means that no crystallinitycan be detected in X-ray diffraction patterns using regular and commerciallyavailable X-ray diffraction (XRD) instruments such as a Bruker D8 AdvanceDiffractometer With CuKd radiation and a Bragg-Brentano experimental setup. Thatno crystallinity can be detected is defined as the absence of sharp diffraction peaks.The term “X-ray amorphous” is used Within the research community to classify amorphous materials.
The denotation “N: X Wt%” means the content X in Weight % of element N in thealloy, exemplified With “Cu: 26 Wt%” meaning an alloy comprising 26 % Cu byWeight.
Thermal stability and Crystallization for a Zr-based alloy are investigated in“Thermal stability and Crystallization of a Zr-based metallic glass produced by SuctionCasting and selective laser melting”, Victor Pacheco et al, Journal of Alloys and Compounds 825 (2020) 153995, Which is hereby incorporated by references. 3D printing parameters influences on the final properties of a Zr-based alloy areinvestigated in “Development of process parameters for selective laser melting of a Zr-based bulk metallic glass”, Jithin James Marattukalam et al, AdditiveManufacturing 33 (2020) 101 124, Which is hereby incorporated by references.
According to the present invention a beam path component is provided Whichcomprises a material that, With regards to neutron scattering properties, fulf1ls the criteria of being:-chemically homogenous, to avoid areas / phases With different scattering length densities.- an alloy With elements that have a low scattering and high transmission.
With regards to mechanical properties the beam path component comprises amaterial With mechanical properties generally associated With a construction metalor a construction metal alloy such as Al or Al alloys such as AL7049A, AL7075A,NiCrAl, and TAV6. The hardness of the material should be Within 5-10 GPa, and theYoung's modulus 100-150 GPa, as measured With nanoindentation. The thermal conductivity of the alloy is around 5 W m-ï K-ï at room temperature (300 K) and the electrical conductivity around 0.5 uQ-l m-ï.
According to the invention the beam path component is formed of a material that isa metallic glass and Wherein the material is an alloy based on Zirconium (Zr), Withone of, or a combination of the alloying elements: Cupper (Cu), Aluminium (Al),Niobium (Nb) and Hafnium (H1) and unavoidable impurities. The Zr-based alloy ischemically homogenous and X-ray amorphous. The unavoidable impurities aresuch that commonly occur in producing alloys at an industrial scale and include,but are not limited to: nitrogen (H), oxygen (O), carbon (C), iron (Fe) and chromium (Co), Wherein the content of the impurity metals should be kept below 2%.
According to one embodiment of the invention the beam path component is formedof a X-ray amorphous and chemically homogenous Zr-based alloy comprising: Cu: 19-26 Wt%; Al or Nb or a combination of Al and Nb: 2-53 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr.
According to one embodiment of the invention the material of the X-ray amorphousand chemically homogenous beam path component is a ZrCuAlNb-alloy comprising:Cu: 19-26 Wt%; A1 1-4 Wt%; Nb: 1-2.3 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr.
According to one embodiment of the invention the ZrCuA1Nb-alloy comprises:Cu: 23-26 Wt%; Al 2-4 Wt%; Nb: 1-2.3 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr.
According to one embodiment of the invention the ZrCuA1Nb-alloy comprises:Cu: 23-25 Wt%; Al 3-5 Wt%; Nb: 1-3 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr.
According to one embodiment of the invention the ZrCuA1Nb-alloy comprises:Cu: 23.9 Wt%; Al 3.7 Wt%; Nb: 1.8 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr.
According to one embodiment of the invention the beam path component is asample holder arranged to accommodate a sample to be investigated in the neutronscattering equipment and during use provided at least partly Within the neutronbeam path. Figure la illustrates schematically, in a cross-sectional view, a sampleholder assembly 100 according to one embodiment of the invention, Wherein thesample holder 105 is formed from the Zr-based alloy described above. The sampleholder 105 is in the form of a container accommodating the sample 1 10, hereexemplified by a powder sample and is during use provided at least partly in theneutron beam 120. The sample holder 105 may be provided in a large variety ofshapes, including but not limited to cylindrical (depicted in Figure la) and cuboidaland annular. The sample holder 105 is typically attached to a fiXture 130 Which in turn is attached to a frame (not shown) of a measurement equipment. The fiXture ll 130 may serve as a lid to the sample holder 105, as depicted, or be attached inother ways. The fixture 130 is typically kept away from the neutron beam path and does not need to be formed of the above described Zr-based alloy.
According to one embodiment of the invention the beam path component is awindow which during use is arranged for the neutron beam path to pass through.The window may be provided in close proximity of the sample, for example as a partof a sample container or in another part of the neutron scattering equipment.Figure lb illustrates schematically, in a cross-sectional view, a sample holderassembly 150 according to one embodiment of the invention, wherein the sampleholder l 15 is in the form of a container, for example in form of a cuboid, of a firstmaterial. The sample holder l 15 is provided with at least one window 140 which isformed of the Zr-based alloy described above. The sample l 10 to be contained inthe sample holder assemblies 100, 150 may for example be in form of a powder, aliquid or a gas or combinations thereof. The sample holder assemblies are typicallyarranged to provide sample spaces that are between 0.5 to 10 mm in the direction of the neutron beam.
According to one embodiment of the invention the beam path component is awindow which constitute a part of a beam delivery system, such as for collimators and guides or a part in a detector assembly such as in a detector vessel.
According to one embodiment of the invention the beam path component is formedof the above described Zr-based alloy and comprises at least one internal channelarranged to accommodate a sample, typically in liquid or gas form, wherein thesample flows through the sample holder during the neutron measurements.Alternatively, the sample holder is arranged to provide an internal compartmentfacilitating a motion of, or within, the sample, for example for rheological studies.Figure 2 a-b schematically illustrates an extrusion nozzle 200 in a) a side view andb) a cross-section along the marking A-A. The extrusion nozzle 200 is intended forstudies of a polymeric material that is feed through the extrusion nozzle 200 andextrudes on leaving the nozzle head. The extrusion nozzle may for example be madeto correspond to a nozzle commonly used for fused f1lament fabrication with 3Dprinters. To study the extrusion process by neutron scattering the extrusion nozzlemust be placed within the neutron beam path, and hence the extrusion nozzle musthave the above described properties with regards to scattering. In addition, which is apparent for the skilled in the art, an extrusion nozzle must withstand considerablemechanical force and also be chemically stable since the polymeric material may bechemically aggressive. The extrusion nozzle 200 comprises an internal channel 210forming a through hole extending from a first end 220 of the extrusion nozzle 200 toa second end 230 of the extrusion nozzle 200. The first end 220 is adapted to beattached to a feeding structure (not shown) for providing the polymeric materialthat is to be extruded. Typically, the internal channel has a first diameter at thefirst end 220 and a second smaller diameter 230 at the second end. The nozzle 200according to the invention may typically be 10-20 mm long and 5-10 mm wide andwith an internal channel 210 that has a diameter of 1-4 mm in the first end and a diameter of less than 0.5 mm in the second end.
According to one aspect of the invention a complex sample holder is provided,which comprises a plurality of parts wherein at least one part is a beam pathcomponent according to the invention. One example of a complex sample holderand one embodiment of the invention is a Couette cell 300 for rheological studiesschematically illustrated in figure 3. The Couette cell 300 according to the inventioncomprises an outer cylinder 310 and an inner cylinder 320 wherein a liquid sampleis to be accommodated in the sample space 330 formed by the gap between theouter cylinder 310 and inner cylinder 320. The gap is typically in the order of 0.5mm. At least one of the outer cylinder 310 and inner cylinder 320 of the Couettecell 300 are formed of the above described Zr-alloy in order to allow for undisturbedmeasurements of the contained liquid. According to the illustrated embodiment theinner cylinder 320 is the part made to rotate and may be provided with means forproviding heat or cold and/ or electrical current or fields and the inner cylinder 320is preferably formed in the described Zr-alloy, taking advantage of the mechanicaland/ or the electrical and/ or the thermal conductive properties of the metal material.
According to one embodiment of the invention the beam path component or a partof the beam path component forms a temperature controlling arrangement and isarranged to heat or cool the sample. The thermal conductivity of the material ishence utilized to for example transfer heat from a portion of sample holder notwithin the beam path and comprising a heater, for example a resistive heater, to aportion of the sample holder being in contact with the sample and within the beam path. Alternatively, contactless heating, for example with a laser or with an IR-source may also be implemented, in Which case all of the sample holder may be within the beam path.
According to one embodiment of the invention the beam path component or a partof the beam path component forms a transmitter of electrical current and/ orelectrical field to the sample. The sample holder may be connected to a currentand/ or voltage source by electrical leads and utilizing the high electricalconductivity, at least compared to a highly isolating material as amorphous quartz, of the metal a current and/ or an electrical field may be provided to the sample.
The ability to provide a beam path component and in particular a sample holderwith the mechanical, electrical, and thermal properties associated with a metal isan important advantage in many applications and opens up new possibilities for measurements and/ or increases the speed and/ or reduces risks and costs.
The beam path component and in particular the sample holder according to theinvention has herein been described as being formed in only the described Zr-basedalloy. As apparent for the skilled person a beam path component may comprise ofseveral parts and in particular, parts that are not intended to be in within the beampath. Such parts could be formed in other materials than the described Zr-basedalloy. However, great care must be taken in joining the different parts of the beampath component in order not to destroy the X-ray amorphous properties of the parts made of the described Zr-based alloy and intended to be within the beam path.
The beam path component according to the invention is preferably produced byadditive manufacturing in order to provide a final product with the describedmetallic glass properties, i.e. chemically homogenous and X-ray amorphous.Suitable additive manufacturing techniques include, but are not limited to metal3D-printing such as Selective Laser Melting, SLM, and Electron Beam Melting, EBM. Suitable equipment is commercially available.
The method according to the invention of producing a beam path component forneutron scattering experiments is illustrated in the flowchart of Figure 4 and comprises the steps of: - 410: providing a starting metal powder suitable for additive manufacturing, the metal powder being particles of the above described Zr-based alloy;- 420: providing a representation of the beam path component; - 430: performing the additive manufacturing according to the representation of the beam path component, wherein the additive manufacturing comprises the steps of: - 440 arranging the metal powder in a step-wise layer-by-layer process in the direction of a predetermined production axis; - 450 irradiating with a laser or electron beam each metal powder layer based onthe representation of the beam path component wherein portions of the metalpowder layer is at least partly melted and re-solidified and 460 wherein the melting and re-solidification is controlled so that the formed beam path component is chemically homogenous and X-ray amorphous.
All of the above described variations of the Zr-based alloy may be used in the AMmethod according to the invention. Suitable starting metal powder is commerciallyavailable, for example the alloy sold under the name AMZ4 from Heraeus AdditiveManufacturing GmbH. The industrial grade alloy AMZ4 consists ofZr70560_gCu20_sAl10_4 (at%) where Cu and Al are high purity elements (>99.9%) andZr705 denotes the industrial grade pre-alloy Zr R60705. The pre-alloy is composedof 95.5 at% Zr and Hf, 3.0 at% Nb, 1.0 at% oXygen as well as other impurities (0.45at% hydrogen, 0.38 at% carbon, 0.32 at% iron and chromium, 0.16 at% nitrogen.
The alloy is typically provided as a powder metal of spherical particles with a sizedistribution between 10 and 45 pm. According to the specification for AMZ4 thecomposition may vary according to: Cu: 23-25 wt%; Al 3-5 wt%; Nb: 1-3 wt%; Hf: 0- 7 wt%; unavoidable impurities; and balance Zr.
The representation of the beam path component may for example be generated froma set of CAD drawings of the object to be produced. Methods for generating arepresentation of an object suitable for a specific AM equipment or a type of AMequipment are known in the art. Typically, programs / tools therefore are provided by the equipment manufacturer or third-party suppliers.
According to one embodiment the representation of the beam path component is arepresentation of a sample holder, or part of a sample holder and the produced item is a sample holder or part of a sample holder.
According to one embodiment representation of the beam path component is arepresentation of a sample holder with an internal structure such as an internal channel and the produced item is a sample holder with an internal structure.
According to one embodiment of the method the AM method is SLM. The meltingand re-solidification may be controlled by controlling the SLM printing parameterslaser power, laser beam diameter, scan speed, hatch spacing, overlap, strip width,and layer thickness. Suitable parameters are investigated and established in“Development of process parameters for selective laser melting of a Zr-based bulkmetallic glass”, Jithin James Marattukalam et al, Additive Manufacturing 33 (2020)101 124, incorporated by references. According to one embodiment the beam pathcomponent were processed using a remelting scan strategy (each layer melted twice)with 67° rotations between each layer. The layer thickness was 20 um. Titaniummay be used as the build plate material. The laser powers should be in the range of55 W to 85 W and most preferably at or below 75 W with laser spot diameter in theorder of 40 um with a wavelength of the laser between 900 and 1200 nm. A scanspeed in the order of 2000 mm / s, a hatch spacing 100 um and an overlay between0 to 0.05 mm are suitable. EOS M100 SLM from EOS GmbH is a suitablecommercially available AM equipment. With the instructions from the methodaccording the invention and with the above parameter settings as reasonablestarting points, the skilled person will, without undue burden, be able to producechemically homogenous and X-ray amorphous beam path components using otherequipment and/ or with variations in some of the above described parameters. Theskilled person will also realize that the parameters indicated above may be balancedin a plurality of ways to provide sufficient heat energy to achieve the local meltingand a rapid enough cooling for the re-solidification to occur to form a beam path component that is chemically homogenous and X-ray amorphous.
Production of beam path components of Alloy AMZ4A study of AMZ4 (an alloy of Zr, Cu, AI, and Nb marketed by Heraeus Additive Manufacturing GmbH) has been performed. Samples were prepared to verify the use of the Zr-based alloy and investigate the effect of different parameters inprinting process. An example product Was also prepared of a complex sample holderand neutron scattering measurements performed to evaluate the performance of thesamples and example product. The samples Were made With an EOS M100 SLM.For this study the best laser power parameter from [“Development of processparameters for selective laser melting of a Zr-based bulk metallic glass”, JithinJames Marattukalam et al, Additive Manufacturing 33 (2020) 101124] Was selected(75 W) to make X-ray amorphous AMZ4 samples. Previous Work had a range oflaser process powers from 55 W to 105 W. The only parameter that Was tuned inthis experiment Was the overlap. The samples Were processed With the same laserpower, scan speed, and hatch spacing, etc. as previously reported in the referenced publication. in TableParameter Value Unit:Laser Povifer ?'5 N'Scan Speed ÉÜÛÜ mm s*Batch Spacšng Chi mmDveršap Ü to 0.85 mmStršpe “Wkšth j' Hateh Length 5 mmScan Strategy XY re-meíšt smith å? degree mtation: åeachíayer is) double meitedï) Laser Beam Bèemzevter 40 pmLager Thšckness 20 pm Table 1 parameters for Additive Manufacturing process In order to retain commercial confidentiality of results, an allocation of beam time(12 hours access) Was purchased from the STFC ISIS Pulsed Neutron and MuonFacility. Measurements Were made on the Larmor instrument configured for small-angle neutron scattering measurements. SANS measurements Were made using abeam 8 mm high by 6 mm Wide beam. Samples Were mounted on a purpose-builtholder made of absorbing polymer composite (Addbor N25) that fitted on theinstrument sample changer. Apart from the AMZ4 samples, the direct beam Wasmeasured With no sample in order to determine transmissions and backgroundscattering from air. Calibration checks Were made using the RTl polymer reference sample maintained at the ISIS facility and a NIST glassy carbon reference material.
The sample transmissions Were recorded as a function of Wavelength on the monitor detector. Typical measuring times for scattering Were about % hour persample for scattering (corresponding to 20 uA hrs beam on target) and about 8minutes for transmissions (5 uA hrs). Data were reduced using the ISIS SANSinterface in the Mantid software package to correct for background scattering(empty beam), sample transmission, integrated incident flux and the instrument detector homogeneity.
Apart from slab like samples that may represent a beam path component in theform of “windows' one sample fabricated as an extrusion nozzle for fused f1lament manufacturing was prepared and measured.
Measurements were made of transmission of the incident beam through eachsample. Figure 5 is a graph of transmission vs wavelength for each slab sample.The transmission was observed to be similar for each of the slab samples, whichindicates that the investigated ranges of AM process parameters give materials thatfulfil the requirements With regards to transmission / absorption. Figures 6 and 7are graphs, intensity vs momentum transfer (Q), of scattering data of a sample ofthe Zr-based material according to the invention. Figure 6 shows the samples madewith different overlaps and the scattering result are well within the requirements of “low scattering”.
The nozzle was investigated by the same method and the result presented in Figure7 wherein the scattering for one sample slab (0.01 mm overlap) are plotted inabsolute units (filled circles) and compared With the data for the nozzle (continuousline) which is scaled to an effective mean thickness in the beam direction of 4.15mm. The result shows that also a complex beam path component, such as anextrusion nozzle may be fabricated in the described Zr-based alloy with the described AM-method.
The slab samples and the fabricated nozzle all showed high (good) neutrontransmission. The possibility to make complex shapes such as the extrusion nozzleusing additive manufacturing provides the opportunity to prepare devices andcontainers for various in-situ or in-operando studies. Measurements made ondifferent sample are reproducible. In particular, the scattering from the nozzle,when scaled appropriately, overlaps well with data measured for simple rectangular slabs.
It is possible that for a number of applications thinner sample windows could be used. If extra rigidity or better mechanical strength is required, reinforcedstructures With ridges to increase the second moment of area in appropriate directions could easily be fabricated using additive manufacturing.
The present invention is not limited to the above-described embodiments orexamples. Various alternatives, modif1cations and equivalents may be used. Inparticular the skilled person may envisage other beam part components than thehere described, Wherein the mechanical, electrical and thermal properties of the Zr-based amorphous metal is utilized. Therefore, the above embodiments should notbe taken as limiting the scope of the invention, Which is defined by the appending claims.
Claims (20)
1. ClaimsA beam path component (105, 140, 200, 310, 320) for use in neutronscattering equipment, the beam path component (105, 140, 200, 310, 320)being adapted to be at least partly placed in a neutron beam path (120) of theneutron scattering equipment, the beam path component (105, 140, 200,310, 320) characterized in that the material of the beam path component(105, 140, 200, 310, 320) is a Zr-based alloy comprising: Cu: 19 -26 Wt%; a combination of Al and Nb: 2-6.3 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr; and Wherein the Zr-based metallic alloy is chemically homogenous and X-ray amorphous. The beam path component (105, 140, 200, 310, 320) according to claim 1,wherein the Zr-based alloy is a ZrCuAlNb-alloy comprising: Cu: 19-26 Wt%; Al 1-4 Wt%; Nb: 1-2.3 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr. The beam path component (105, 140, 200, 310, 320) according to claim 2,wherein the Zr-based alloy comprises: Cu: 23-26 Wt%; Al 2-4 Wt%; Nb: 1-2.3 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr. 4. The beam path component (105, 140, 200, 310, 320) according to claim 21, wherein the Zr-based alloy comprises:Cu: 23-25 Wt%; Al 3-5 Wt%; Nb: 1-3 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr. . The beam path component (105, 140, 200, 310, 320) according to claim 3, wherein the Zr-based alloy comprises:Cu: 23.9 Wt%; Al 3.7 Wt%; Nb: 1.8 Wt%; Hf: 0-7% Wt%; unavoidable impurities; and balance Zr. . The beam path component (105, 200) according to any of claims 1-5, characterized in that the beam path component is a sample holder (105,200), or a part of a sample holder, the sample holder arranged toaccommodate a sample to be investigated in the neutron scattering equipment. . The beam path component (200) according to claim 6, wherein the sample holder (200) comprises at least one internal channel (210) arranged toaccommodate a sample in liquid form or in gas form in Which sample is caused to flow Within the sample holder. . The beam path component (200) according to claim 7, wherein the sample holder is an extrusion nozzle (200). . The beam path component (310, 320) according to claim 1, wherein the beam path component (310, 320) is arranged in a Couette cell (300) comprising an outer cylinder (310) and an inner cylinder (320) and a samplespace 330 is formed between the outer cylinder (310) and the inner cylinder(320), wherein at least one of the outer (310) and inner (320) cylinders are made of the Zr-based alloy. 10.The beam path component (140) according to any of claims 1-5,characterized in that the beam path component is window (140) arranged in a sample holder, a beam delivery system or in a detector assembly. 1 1.The beam path component according to any of claims 6-10, Wherein at leasta part of the beam path component (105, 140, 200, 310/320) forms atemperature controlling arrangement and is arranged to heat or cool the sample through thermal conductivity. 12.The beam path component according to any of claims 6-10, wherein at leasta part of the beam path component (105, 140, 200, 310/320) forms a transmitter of electrical current and/ or electrical field to the sample. 13.A method of producing a beam path component for neutron scattering experiments, the method comprising the steps of:-(410) providing a starting metal powder suitable for additive manufacturing,the metal powder comprising particles of a Zr-based alloy comprising: Cu: 19 - 26 Wt%; a combination of Al and Nb: 2-6.3 wt%; Hf: 0-7 wt%; unavoidable impurities; and balance Zr;- (420) providing a representation of the beam path component;- (430) performing the additive manufacturing according to therepresentation of the beam path component, wherein the additivemanufacturing comprises the steps of:- (440) arranging the metal powder in a step-wise layer-by-layer process inthe direction of a predetermined production axis;- (450) irradiating with a laser or electron beam each metal powder layerbased on the representation of the beam path component wherein portions of the metal powder layer is at least partly melted and re-solidified, andWherein (460) the melting and re-solidified is controlled so that the formed beam path component is chemically homogenous and X-ray amorphous. 14.The method according to claim 13, Wherein the starting metal powder is a ZrCuAlNb-alloy comprising: Cu: 23-25 Wt%; Al 3-5 Wt%; Nb: 1-3 Wt%; Hf: O-7% Wt%; unavoidable impurities; and balance Zr. 15.The method according to claim 14, Wherein the Zr-based alloy comprises: Cu: 23.9 Wt%; Al 3.7 Wt%; Nb: 1.8 Wt%; Hf: O-7% Wt%; unavoidable impurities; and balance Zr. 16.The method according to any of claims 13-15, Wherein the beam path component is a sample holder. 17.The method according to claim 16, Wherein the sample holder comprises at least one internal channel. 18.A beam path component according to claim 1 produced With the method according to claim19.A sample holder according to claim 6 produced With the method according to claim20.A Window according to claim J-ÅQ produced With the method according to claim 13.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101386933A (en) * | 2008-11-06 | 2009-03-18 | 中国原子能科学研究院 | Neutron diffraction sample chamber |
EP2944401A1 (en) * | 2014-05-15 | 2015-11-18 | Heraeus Deutschland GmbH & Co. KG | Method for producing a component from a metallic alloy containing an amorphous phase |
CN106198584A (en) * | 2016-07-13 | 2016-12-07 | 东莞中子科学中心 | For preparing neutron scattering experiment without the titanium-zirconium alloy of magnetic sample box and application thereof |
US20170197246A1 (en) * | 2014-07-15 | 2017-07-13 | Heraeus Holding Gmbh | Method for producing a component from a metal alloy with an amorphous phase |
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CN101386933A (en) * | 2008-11-06 | 2009-03-18 | 中国原子能科学研究院 | Neutron diffraction sample chamber |
EP2944401A1 (en) * | 2014-05-15 | 2015-11-18 | Heraeus Deutschland GmbH & Co. KG | Method for producing a component from a metallic alloy containing an amorphous phase |
US20170197246A1 (en) * | 2014-07-15 | 2017-07-13 | Heraeus Holding Gmbh | Method for producing a component from a metal alloy with an amorphous phase |
CN106198584A (en) * | 2016-07-13 | 2016-12-07 | 东莞中子科学中心 | For preparing neutron scattering experiment without the titanium-zirconium alloy of magnetic sample box and application thereof |
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