This work was supported by the Slovak Research and Development Agency under the contracts No. APVV-16-0079 and APVV-15-0621, grants VEGA 1/0182/16 and VEGA 2/0082/17, and the internal IGA grant of Palack&#253; University (IGA_PrF_2018_002). We are grateful to R. R&#252;ffer (ESRF, Grenoble) for assistance with the synchrotron experiments.

1. Preparation of a MG
NOTE: To demonstrate a broad range of diagnostic capabilities of NFS in combination with M&#246;ssbauer spectrometry, an appropriate MG composition was designed, namely (Fe3Co1)76Mo8Cu1B15 (at.%). This system shows the magnetic transition from the ferromagnetic to paramagnetic state below the onset of crystallization. Moreover, crystallites that emerge during the first crystallization step form bcc-Fe,Co phase. Because cobalt replaces iron in some atomic positions of the bcc lattice, deviations&#160;in the respective hyperfine interactions occur.
<ol>
	<li>Preparation of the melt 
	NOTE: M&#246;ssbauer spectrometry and NFS scan the local atomic arrangements via hyperfine interactions of 57Fe nuclei that are present in the investigated samples. Natural abundance of this stable nuclide among all Fe isotopes is, however only 2.19%. To decrease the acquisition time of in situ NFS experiments, the relative content of the 57Fe isotope should be increased to about 50%.
	<ol>
		<li>Take a quartz glass crucible (cylindrical shape with a diameter of 15 mm), cover its inner walls with boron nitride to avoid possible contamination of the content by Si from the walls, and insert 0.4050 g of highly enriched 57Fe (~ 95%) and 0.5267 g of standard electrolytic pure iron (purity 99.95%) to this crucible. The total mass of the mixture is of 0.9317 g and ensures isotopic enrichment of ca. 50% 57Fe. 
		NOTE: Because of the high price of the stable 57Fe isotope, optimize its amount to the lowest possible mass. Approximately 500 mg of 57Fe should be enough to ensure the overall weight of the melt to approximately 1.5 g. This is the low technological limit of the preparation equipment.</li>
		<li>Add 0.3245 g of electrolytic Co (99.85%), 0.0184g of Cu (99.8%), 0.2222 g of Mo (99.95%) and 0.0470 g of crystalline B (99.95%) into the same quartz glass crucible. The total mass of the mixture is of 1.5438 g and the intended composition of the powder is (Fe3Co1)76Mo8Cu1B15.</li>
		<li>Melt the obtained mixture of standard electrolytic materials by inductive heating in a quartz glass crucible under protective Argon (4N8) atmosphere to avoid oxidation, and use a radiofrequency field of 90-120 kHz. 
		NOTE: The radio frequency field ensures mixing of the individual components in the crucible. Their mixing proceeds further by the help of eddy currents when a melt is formed. Allow sufficient time to melt the powder mixture and form a liquid. Visual inspection is sufficient, there is no need to measure the temperature of the resulting liquid.</li>
		<li>Remove the obtained small ingot from the crucible. Visually check the occurrence of any traces of slag spots on its surface. If present, remove them by mechanical polishing.</li>
	</ol>
	</li>
	<li>Preparation of the ribbon-shaped sample
	<ol>
		<li>Use an apparatus for planar flow casting. An example of such a device is shown in Figure 1. 
		NOTE: The melt inside a quartz tube is expelled by Ar flow onto a quenching wheel which rotates in the air. There is no need for special atmospheric conditions under which the quenching wheel is operated (e.g., vacuum or inert gas environment) for this composition of the melt.</li>
		<li>Because of small weight of the ingot (~1.5 g), choose a quartz tube with a nozzle that has a round orifice of 0.8 mm in diameter. Put the ingot inside and melt it using inductive heating. Keep the temperature of the melt at 1,280-1,295 &#176;C.</li>
		<li>Adjust the surface speed of the cooling wheel to 40 m/s.</li>
		<li>Cast the melt upon the rotating quenching wheel under ambient conditions, i.e., in the air. 
		NOTE: The resulting ribbon is about 1.5-2 mm wide, 25-27 &#181;m thick, and 5 m long. The air side of the ribbon, which was exposed during the production to the surrounding air atmosphere, is optically shiny (glossy) while the opposite wheel side, which was in direct contact with the quenching wheel, is mat (dull). These subtle ribbon qualities result from the low mass of the melt. Thus, it is important to verify the final chemical composition of the produced as-quenched ribbon because of the low input masses of the individual elements.</li>
	</ol>
	</li>
	<li>Verification of the final chemical composition of the ribbon
	<ol>
		<li>Prepare several (up to five) short pieces of the ribbon, each having a mass of about 0.70 mg. Chose them from different parts of the produced ribbon along its length.</li>
		<li>Dissolve every single piece of ribbon in 1 mL of concentrated (67%) HNO3 acid and fill with water to reach 50 mL total volume of the solution.</li>
		<li>Determine the content of Mo and B by optical emission spectrometry with inductively coupled plasma (OES-ICP). Use the method of external calibration as provided in the instrument&#39;s manual. Record the signals at the following wavelengths: Mo at 203.844 nm and 204.598 nm, and B at 249.773 nm.</li>
		<li>Determine the content of Fe, Co, and Cu by flame atomic absorption spectrometry (F-AAS). Use the method of external calibration as provided in the instrument&#39;s manual, and select these wavelengths: Fe at 248.3 nm, Co at 240.7 nm, and Cu at 324.7 nm.</li>
	</ol>
	</li>
	<li>Structural characterization of the produced ribbons
	<ol>
		<li>Check the amorphous nature of the produced ribbons by performing X-ray diffraction (XRD) in Bragg-Brentano geometry; use the Cu anode with a wavelength of 0.154056 nm, record the diffraction pattern from 20-100&#176; of 2&#920; with an angular step of 0.05&#176; and acquisition time of 20 s for one point. 
		NOTE: The XRD diffractogram of an amorphous sample is characterized by broad reflection peaks like those shown in Figure 2. No narrow lines that indicate the presence of crystallites should be present.</li>
		<li>Prepare small pieces of the produced ribbons with a total mass of about 3-5 mg and place them into a graphite crucible of a DSC equipment. 
		NOTE: Small pieces of about 2 mm in length can be cut off from the ribbon by scissors.</li>
		<li>Perform the DSC experiment with a temperature ramp of 10 K/min in a temperature range of 50-700 &#176;C under Ar atmosphere.</li>
		<li>Determine the temperature of the onset of crystallization Tx1, which is taken at the kink of the most pronounced peak on the DSC curve. 
		NOTE: The temperature of the onset of crystallization Tx1 is indicated in Figure 3 by an arrow.</li>
		<li>Chose five temperatures of annealing that cover both the pre-crystallization and crystallization regions on the DSC for further ex situ annealing. 
		NOTE: In our case, appropriate temperatures are 370, 410, 450, 510, and 550 &#176;C as shown in Figure 3.</li>
	</ol>
	</li>
	<li>Ex situ annealing
	<ol>
		<li>Prepare five groups of ~ 7 cm long pieces (the total length) of the as-quenched ribbon. The individual ribbons should be at least 1 cm long.</li>
		<li>For ex situ annealing, use a furnace (Figure 4). Set up the destination temperature and wait for 15 min for its stabilization. 
		NOTE: The furnace design ensures minimal onset times for isothermal annealing. This furnace consists of two parts: upper and lower round massive nickel-plated copper blocks that act as a temperature homogenizer. Kanthal A strips heat up the blocks with high dynamics of temperature regulation and stabilization. The destination temperature is that determined in step 1.4.5.</li>
		<li>Insert pieces of the ribbon into the evacuated and thermally stabilized zone. To do this, open a 7-10 mm gap between the two blocks and slide the ribbons directly into the center of the heated zone.</li>
		<li>Close the gap immediately. In this way, the temperature of the sample achieves the furnace temperature in less than 5 s within a 0.1 K difference.</li>
		<li>Perform the annealing at 370, 410, 450, 510, and 550 &#176;C for 30 min under vacuum to prevent surface oxidation.</li>
		<li>After annealing, remove the heated ribbons and place them on a cold substrate inside the vacuum system. This ensures fast cooling of the samples to room temperature. 
		NOTE: Thermal treatment of the as-quenched ribbons induces structural changes that eventually lead to crystallization of the originally amorphous material.</li>
	</ol>
	</li>
</ol>
2. Methods of Investigation
<ol>
	<li>M&#246;ssbauer spectrometry 
	NOTE: The use of iron enriched to about 50% in 57Fe for production of the studied MG ensures sufficiently short acquisition times for in situ NFS experiments. On the other hand, the effective thickness of the ribbons is significantly increased. This poses issues related to extremely high broadening of the absorption M&#246;ssbauer spectral lines recorded in a conventional transmission geometry experiment. That is why surface sensitive techniques of M&#246;ssbauer spectrometry should be considered. Namely, Conversion Electron M&#246;ssbauer Spectrometry (CEMS) and Conversion X-ray M&#246;ssbauer Spectrometry (CXMS) can be applied. While CEMS scans subsurface regions to the depth of about 200 nm, CXMS provides information from deeper areas that extend down to about 5-10 &#181;m.
	<ol>
		<li>Prepare the samples for CEMS/CXMS experiments; use 6-8 pieces of ~ 1 cm long ribbons for one sample.</li>
		<li>Attach the ribbons side-by-side to an aluminum holder to form a compact area of about 1 x 1 cm2; use adhesive tape over the ends of the ribbons; all ribbons must be placed with their air sides upwards. 
		NOTE: Ensure that there is an electric contact between the ribbons and the holder and that the central part of the sample (about 8 x 10 mm2) is clean from any surface contamination, e.g., remains of the adhesive tape.</li>
		<li>Insert the aluminum holder with the sample into the CEMS/CXMS detector.</li>
		<li>Prior to the measurement, thoroughly wash the inner detector volume with a stream of the detection gas to expel all residual air. Allow 10-15 min to accomplish this procedure.</li>
		<li>Adjust the gas flow through the detector by a needle valve to 3 mL/min.</li>
		<li>Connect a high voltage to the detector: a typical value is about 1.2 kV for CEMS and about 200 V higher for CXMS.</li>
		<li>Record the CEMS and CXMS M&#246;ssbauer spectra using a constant acceleration spectrometer equipped with a 57Co/Rh radioactive source. Operate the spectrometer with a gas detector at room temperature according to the manual.</li>
		<li>Accomplish the detection of conversion electrons and X-rays by a gas detector filled with a He+CH4 and Ar+CH4 gas mixture, respectively. Keep the amount of CH4 at 10% in both cases.</li>
		<li>Repeat steps 2.1.2 to 2.1.8 for the wheel side of the investigated ribbons.</li>
		<li>Perform velocity calibration14 of the apparatus by using a thin (12.5 &#181;m) &#945;-Fe foil.</li>
		<li>Evaluate the CEMS/CXMS spectra; quote the obtained isomer shift values with respect to a room temperature M&#246;ssbauer spectrum of the calibration &#945;-Fe foil. 
		NOTE: The obtained M&#246;ssbauer spectra can be evaluated by any suitable fitting code, for example by the Confit software24.</li>
	</ol>
	</li>
	<li>NFS
	<ol>
		<li>Accomplish the NFS experiments using a suitable nuclear resonance beamline at a synchrotron. A possible option: ID 18 at the European Synchrotron Radiation Facility (ESRF) in Grenoble, France.25</li>
		<li>Tune the energy of the photon beam to 14.413 keV with a bandwidth of ~ 1 meV.</li>
		<li>Place an approximately 6 mm long ribbon of the investigated MG in a vacuum furnace.</li>
		<li>Record the NFS time-domain patterns during continuous heating of the sample to a temperature of up to 700 &#176;C with a ramp of 10 K/min. Use 1-min time intervals for acquisition of experimental data during the entire in situ annealing process. 
		NOTE: The transmission geometry of the NFS experiment ensures that information on hyperfine interactions is obtained from the sample&#39;s bulk.</li>
		<li>Evaluate the NFS experimental data using a suitable software (e.g., www.nrixs.com). 
		NOTE: During one in situ experiment, typically up to 100 NFS time-domain patterns are recorded. During their evaluation by the CONUSS software package26,27, consider the application of a special free software called Hubert that can evaluate such enormous data quantities in a semi-automatic mode28.</li>
	</ol>
	</li>
</ol>

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Physique. 9 (5-6), 595-607 (2008).</li><li>Seto, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Condensed+matter+physics+using+nuclear+resonant+scattering.">Condensed matter physics using nuclear resonant scattering.</a> J. Phys. Soc. Jpn. 82 (2), 021016 (2013).</li><li>Machala, L., Proch&#225;zka, V., Miglierini, M., Sharma, V. K., Maru&#353;&#225;k, Z., Wille, H. -. C. h., Zbo&#345;il, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+Evidence+of+Fe(V)+and+Fe(IV)+Intermediates+during+Reduction+of+Fe(VI)+to+Fe(III):+A+Nuclear+Forward+Scattering+of+Synchrotron+Radiation+Approach.">Direct Evidence of Fe(V) and Fe(IV) Intermediates during Reduction of Fe(VI) to Fe(III): A Nuclear Forward Scattering of Synchrotron Radiation Approach.</a> Phys. Chem. Chem. Phys. 17 (34), 21787-21790 (2015).</li></ol>

The authors have nothing to disclose.

Ex situ M&#246;ssbauer effect experiments describe a steady situation which is encountered in the investigated MG after the applied heat treatment. Each spectrum was collected for a duration of several hours at room temperature. Thus, the evolution of the originally amorphous structure was followed as a function of annealing conditions. Because M&#246;ssbauer spectrometry is sensitive to hyperfine interactions acting upon the resonant nuclei, faint details of structural and/or magnetic modifications induced by e...

Iron-based MGs prepared by rapid quenching of a melt represent industrially attractive materials with numerous practical applications1. Especially since their magnetic properties are often superior to conventional (poly)crystalline alloys2,3. To better benefit from their advantageous parameters, their response to elevated temperatures should be known. With increasing temperature, the amorphous structure relaxes and, finally, the crystallization starts. In some types of MGs, this can lead to the deterioration of their magnetic parameters and, consequently, poorer performance. There are, however, several families of iron-based MGs with special compositions4,5,6,7 in which the newly formed crystalline grains are very fine, typically below about 30 nm in size. The nanocrystals stabilize the structure and thus, preserve acceptable magnetic parameters over a wide temperature range8,9. These are the so-called nanocrystalline alloys (NCA).
The long-term performance reliability of MGs, especially under elevated temperatures and/or tough conditions (ionizing radiation, corrosion, etc.) demands thorough knowledge of their behavior and individual physical parameters. Because MGs are amorphous, the assortment of analytical techniques that are suitable for their characterization is rather limited. For example, diffraction methods provide broad and featureless reflections that can be used only for the verification of amorphicity.
It is noteworthy that several, usually indirect methods exist that provide fast and non-destructive characterization of MGs (e.g., magnetostrictive delay line sensing principle). This method provides fast characterization of structural and stress states including the presence of inhomogeneities. It was advantageously applied to fast and non-destructive characterization along the whole length of MG ribbons10,11.
More detailed insight into disordered structural arrangement can be achieved via hyperfine interactions that sensitively reflect the local atomic arrangement of the resonant atoms. Moreover, variations in topological and chemical short-range order can be revealed. In this respect, the methods like nuclear magnetic resonance (NMR) spectrometry and/or M&#246;ssbauer spectrometry, both performed on 57Fe nuclei, should be considered12,13. While the former method provides response exclusively to magnetic dipole hyperfine interactions, the latter is sensitive also to the electric quadrupole interactions. Thus, M&#246;ssbauer spectrometry makes simultaneously available information on both the structural arrangement and magnetic states of the resonant iron nuclei14.
Nevertheless, to achieve reasonable statistics, the acquisition of a M&#246;ssbauer spectrum usually takes several hours. This restriction should be considered especially when temperature-dependent experiments are envisaged. Elevated temperature that is applied during the experiment causes structural modifications in the investigated MGs15. Consequently, only ex situ experiments performed at room temperature upon samples that were first annealed at certain temperature and then returned to ambient conditions provide reliable results.
The evolution of MG structures during heat treatment is routinely studied by analytical techniques which enable rapid data acquisition as for example X-ray diffraction of synchrotron radiation (DSR), differential scanning calorimetry (DSC), or magnetic measurements. Though in situ experiments are possible, the obtained information concerns either structural (DSR, DSC) or magnetic (magnetic data) features. However, in the case of DSC (and magnetic measurements) the identification of the type of (nano)grains that emerge during the crystallization is not possible. On the other hand, DSR data do not indicate the magnetic states of the investigated system. A solution to this situation is a technique that makes use of hyperfine interactions: NFS of synchrotron radiation16. It belongs to a group of methods that exploits nuclear resonant scattering processes17. Due to extremely high brilliance of radiation obtained from the third generation of synchrotrons, temperature NFS experiments under in situ conditions became feasible18,19,20,21,22,23.
Both M&#246;ssbauer spectrometry and NFS are governed by the same physical principles related to nuclear resonance among energy levels of 57Fe nuclei. Nevertheless, while the former scans hyperfine interactions in the energy domain, the latter provides interferograms in the time domain. In this way, the results obtained from both methods are equivalent and complementary. To evaluate the NFS data, a reasonable physical model must be established. This challenging task can be accomplished by the help of M&#246;ssbauer spectrometry which provides the first estimate. Complementarity between these two methods means that in situ NFS inspects transient states and M&#246;ssbauer spectrometry reflects the stable states, viz. the initial and/or the final state of a material studied ex situ.
This article describes in detail selected applications of these two less common methods of nuclear resonances: here, we apply them to the investigation of structural modifications that occur in a (Fe2.85Co1)77Mo8Cu1B14 MG exposed to heat treatment. We hope that this article attracts the interest of researchers to use these techniques for the investigation of similar phenomena and eventually with different types of materials.

<table><tbody><tr><td>stable isotope, &lt;sup&gt;57&lt;/sup&gt;Fe</td><td>Isoflex USA</td><td>iron-57</td><td>metallic form</td></tr><tr><td>standard eletrolytic Fe, 99.95 %</td><td>Sigma Aldrich (Merck)</td><td>1.03819</td><td>fine powder</td></tr><tr><td>electrolytic Co, 99.85 %</td><td>Sigma Aldrich (Merck)</td><td>1.12211</td><td>fine powder</td></tr><tr><td>electrolytic Cu, 99.8 %</td><td>Sigma Aldrich (Merck)</td><td>1.02703</td><td>fine powder</td></tr><tr><td>electrolytic Mo, 99.95 %</td><td>Sigma Aldrich (Merck)</td><td>1.12254</td><td>fine powder</td></tr><tr><td>crystalline B, 99.95 %</td><td>Sigma Aldrich (Merck)</td><td>266620</td><td>crystalline</td></tr><tr><td>calibration foil for M&amp;ouml;ssbauer spectrometry, bcc-Fe</td><td>GoodFellow</td><td>564-385-23</td><td>foil 0.0125 mm, purity 99.85 %</td></tr><tr><td>HNO&lt;sub&gt;3&lt;/sub&gt; acid, ANALPURE Ultra</td><td>Analytika Praha, Czech Republic</td><td>UAc0061a</td><td>concentration 67 %, volume 500 mL</td></tr><tr><td>spectrometer for atomic absorption spectrometry</td><td>Perkin Elmer 1100, Germany</td><td></td><td></td></tr><tr><td>spectrometer for optical emmission spectrometry with inductively coupled plasma</td><td>Jobin Yvon 70 Plus, France</td><td></td><td></td></tr><tr><td>X-ray diffractometer</td><td>Bruker D8 Advance, USA</td><td></td><td></td></tr><tr><td>differential scanning calorimeter</td><td>Perkin Elmer DSC 7, Germany</td><td></td><td></td></tr></tbody></table>

methods of ex situ and in situ investigations of structural transformations: the case of crystallization of metallic glasses

We demonstrate the use of two nuclear-based analytical methods that can follow the modifications of microstructural arrangement of iron-based metallic glasses (MGs). Despite their amorphous nature, the identification of hyperfine interactions unveils faint structural modifications. For this purpose, we have employed two techniques that utilize nuclear resonance among nuclear levels of a stable 57Fe isotope, namely M&#246;ssbauer spectrometry and nuclear forward scattering (NFS) of synchrotron radiation. The effects of heat treatment upon (Fe2.85Co1)77Mo8Cu1B14 MG are discussed using the results of ex situ and in situ experiments, respectively. As both methods are sensitive to hyperfine interactions, information on structural arrangement as well as on magnetic microstructure is readily available. M&#246;ssbauer spectrometry performed ex situ describes how the structural arrangement and magnetic microstructure appears at room temperature after the annealing under certain conditions (temperature, time), and thus this technique inspects steady states. On the other hand, NFS data are recorded in situ during dynamically changing temperature and NFS examines transient states. The use of both techniques provides complementary information. In general, they can be applied to any suitable system in which it is important to know its steady state but also transient states.

The XRD pattern in Figure 2 exhibits broad featureless diffraction peaks. The observed reflections demonstrate that the produced ribbon of the (Fe2.85Co1)77Mo8Cu1B14 MG is XRD amorphous.
Due to its sensitivity, XRD has some limitations in unveiling surface crystallization. The presence of crystallites amounting to less than about 2-3%...

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Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

Here, we present a protocol to describe ex situ and in situ investigations of structural transformations in metallic glasses. We employed nuclear-based analytical methods which inspect hyperfine interactions. We demonstrate the applicability of M&#246;ssbauer spectrometry and nuclear forward scattering of synchrotron radiation during temperature-driven experiments.

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

We demonstrate the use of two nuclear-based analytical methods that can follow the modifications of microstructural arrangement of iron-based metallic ...

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Research

JoVE Journal

Engineering

8.5K Views.  Slovak University of Technology in Bratislava, Slovakia. Hier presenteren we een protocol om te beschrijven van ex situ en in situ onderzoeken van structurele transformaties in metalen bril. Wij dienst nucleaire gebaseerde analysemethoden die hyperfine interacties keuren. We tonen de toepasselijkheid van Mössbauer spectrometrie en nucleaire voorwaartse verstrooiing van synchrotronstraling tijdens temperatuur gestuurde experimenten.

Video: Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

Simulation of the Planetary Interior Differentiation Processes in the Laboratory

A planetary interior is under high-pressure and high-temperature conditions and it has a layered structure. There are two important processes that led to that layered structure, (1) percolation of liquid metal in a solid silicate matrix by planet differentiation, and (2) inner core crystallization by subsequent planet cooling. We conduct high-pressure and high-temperature experiments to simulate both processes in the laboratory. Formation of percolative planetary core depends on the efficiency of melt percolation, which is controlled by the dihedral (wetting) angle. The percolation simulation includes heating the sample at high pressure to a target temperature at which iron-sulfur alloy is molten while the silicate remains solid, and then determining the true dihedral angle to evaluate the style of liquid migration in a crystalline matrix by 3D visualization. The 3D volume rendering is achieved by slicing the recovered sample with a focused ion beam (FIB) and taking SEM image of each slice with a FIB/SEM crossbeam instrument. The second set of experiments is designed to understand the inner core crystallization and element distribution between the liquid outer core and solid inner core by determining the melting temperature and element partitioning at high pressure. The melting experiments are conducted in the multi-anvil apparatus up to 27 GPa and extended to higher pressure in the diamond-anvil cell with laser-heating. We have developed techniques to recover small heated samples by precision FIB milling and obtain high-resolution images of the laser-heated spot that show melting texture at high pressure. By analyzing the chemical compositions of the coexisting liquid and solid phases, we precisely determine the liquidus curve, providing necessary data to understand the inner core crystallization process.

The high-pressure and high-temperature experiments described here mimic planet interior differentiation processes. The processes are visualized and better understood by high-resolution 3D imaging and quantitative chemical analysis.

A planetary interior is under high-pressure and high-temperature conditions and it has a layered structure. There are two important processes that led to ...

Production of Synthetic Nuclear Melt Glass

Realistic surrogate nuclear debris is needed within the nuclear forensics community to test and validate post-detonation analysis techniques. Here we outline a novel process for producing bulk surface debris using a high temperature furnace. The material developed in this study is physically and chemically similar to trinitite (the melt glass produced by the first nuclear test). This synthetic nuclear melt glass is assumed to be similar to the vitrified material produced near the epicenter (ground zero) of any surface nuclear detonation in a desert environment. The process outlined here can be applied to produce other types of nuclear melt glass including that likely to be formed in an urban environment. This can be accomplished by simply modifying the precursor matrix to which this production process is applied. The melt glass produced in this study has been analyzed and compared to trinitite, revealing a comparable crystalline morphology, physical structure, void fraction, and chemical composition.

A protocol for the production of synthetic nuclear melt glass, similar to trinitite, is presented.

Realistic surrogate nuclear debris is needed within the nuclear forensics community to test and validate post-detonation analysis techniques. Here we ...

X-ray Powder Diffraction in Conservation Science: Towards Routine Crystal Structure Determination of Corrosion Products on Heritage Art Objects

The crystal structure determination and refinement process of corrosion products on historic art objects using laboratory high-resolution X-ray powder diffraction (XRPD) is presented in detail via two case studies.
The first material under investigation was sodium copper formate hydroxide oxide hydrate, Cu4Na4O(HCOO)8(OH)2&#8729;4H2O (sample 1) which forms on soda glass/copper alloy composite historic objects (e.g., enamels) in museum collections, exposed to formaldehyde and formic acid emitted from wooden storage cabinets, adhesives, etc. This degradation phenomenon has recently been characterized as &#34;glass induced metal corrosion&#34;.
For the second case study, thecotrichite, Ca3(CH3COO)3Cl(NO3)2&#8729;6H2O (sample 2), was chosen, which is an efflorescent salt forming needlelike crystallites on tiles and limestone objects which are stored in wooden cabinets and display cases. In this case, the wood acts as source for acetic acid which reacts with soluble chloride and nitrate salts from the artifact or its environment.
The knowledge of the geometrical structure helps conservation science to better understand production and decay reactions and to allow for full quantitative analysis in the frequent case of mixtures.

Modern high resolution X-ray powder diffraction (XRPD) in the laboratory is used as an efficient tool to determine crystal structures of long-known corrosion products on historic objects.

The crystal structure determination and refinement process of corrosion products on historic art objects using laboratory high-resolution X-ray powder ...

Chemistry

A Novel Method for In Situ Electromechanical Characterization of Nanoscale Specimens

Electrically assisted deformation (EAD) is increasingly being used to improve the formability of metals during processes such as sheet metal rolling and forging. Adoption of this technique is proceeding despite disagreement concerning the underlying mechanism responsible for EAD. The experimental procedure described herein enables a more explicit study compared to previous EAD research by removing thermal effects, which are responsible for disagreement in interpreting previous EAD results. Furthermore, as the procedure described here enables EAD observation in situ and in real time in a transmission electron microscope (TEM), it is superior to existing post-mortem methods that observe EAD effects post-test. Test samples consist of a single crystal copper (SCC) foil having a free-standing tensile test section of nanoscale thickness, fabricated using a combination of laser and ion beam milling. The SCC is mounted to an etched silicon base that provides mechanical support and electrical isolation while serving as a heat sink. Using this geometry, even at high current density (~3,500 A/mm2), the test section experiences a negligible temperature increase (&#60;0.02 &#176;C), thus eliminating Joule heating effects. Monitoring material deformation and identifying the corresponding changes to microstructures, e.g. dislocations, are accomplished by acquiring and analyzing a series of TEM images. Our sample preparation and in situ experiment procedures are robust and versatile as they can be readily utilized to test materials with different microstructures, e.g., single and polycrystalline copper.

A Novel Method for In Situ Electromechanical Characterization of Nanoscale Specimens

Isolating electrical and thermal effects on electrically assisted deformation (EAD) is very difficult using macroscopic samples. Metallic sample micro- and nanostructures together with a custom test procedure have been developed to evaluate the impact of applied current on the formation without joule heating and evolution of dislocations on these samples.

Electrically assisted deformation (EAD) is increasingly being used to improve the formability of metals during processes such as sheet metal rolling and ...

Optimized Sealing Process and Real-Time Monitoring of Glass-to-Metal Seal Structures

Residual stress is an essential factor to keeping the hermeticity and robustness of a glass-to-metal seal structure. The purpose of this report is to demonstrate a novel protocol to characterize and measure residual stress in a glass-to-metal seal structure without destroying the insulation and hermeticity of sealing materials. In this research, a femto-laser inscribed fiber Bragg grating sensor is used. The glass-to-metal seal structure that is measured consists of a metal shell, sealing glass, and Kovar conductor. To make the measurements worthwhile, the specific heat treatment of metal-to-glass seal (MTGS) structure is explored to obtain the model with best hermeticity. Then, the FBG sensor is embedded into the path of sealing glass and becomes well-fused with the glass as the temperature cools to RT. The Bragg wavelength of FBG shifts with the residual stress generated in sealing the glass. To calculate the residual stress, the relationship between Bragg wavelength shift and strain is applied, and the finite element method is also used to make the results reliable. The online monitoring experiments of residual stress in sealing glass are carried out at different loads, such as high temperature and high pressure, to broaden functions of this protocol in harsh environments.

Key procedures to optimize the sealing process and achieve real-time monitoring of the metal-to-glass seal (MTGS) structure are described in detail. The embedded fiber Bragg grating (FBG) sensor is designed to achieve online monitoring of temperature and high-level residual stress in the MTGS with simultaneous environmental pressure monitoring.

Residual stress is an essential factor to keeping the hermeticity and robustness of a glass-to-metal seal structure. The purpose of this report is to ...

Sample Preparation and Experimental Design for In Situ Multi-Beam Transmission Electron Microscopy Irradiation Experiments

There is a need to understand materials exposed to overlapping extreme environments such as high temperature, radiation, or mechanical stress. When these stressors are combined there may be synergistic effects that enable unique microstructural evolution mechanisms to activate. Understanding of these mechanisms is necessary for the input and refinement of predictive models and critical for engineering of next generation materials. The basic physics and underlying mechanisms require advanced tools to be investigated. The in situ ion irradiation transmission electron microscope (I&#179;TEM) is designed to explore these principles.
To quantitatively probe the complex dynamic interactions in materials, careful preparation of samples and consideration of experimental design is required. Particular handling or preparation of samples can easily introduce damage or features that obfuscate the measurements. There is no one correct way to prepare a sample; however, many mistakes can be made. The most common errors and things to consider are highlighted within. The I&#179;TEM has many adjustable variables and a large potential experimental space, therefore it is best to design experiments with a specific scientific question or questions in mind.
Experiments have been performed on large number of sample geometries, material classes, and with many irradiation conditions. The following are a subset of examples that demonstrate unique in situ capabilities utilizing the I3TEM. Au nanoparticles prepared by drop casting have been used to investigate the effects of single ion strikes. Au thin films have been used in studies on the effects of multibeam irradiation on microstructure evolution. Zr films have been exposed to irradiation and mechanical tension to examine creep. Ag nanopillars were subjected to simultaneous high temperature, mechanical compression, and ion irradiation to study irradiation induced creep as well. These results impact fields including: structural materials, nuclear energy, energy storage, catalysis, and microelectronics in space environments.

Sample preparation techniques are outlined with specific considerations for in situ ion irradiation TEM experiments. Ion species, energy, and fluence are discussed with methods for how to select and compute them. Finally, procedures for conducting an experiment are described and accompanied by the representative results.

There is a need to understand materials exposed to overlapping extreme environments such as high temperature, radiation, or mechanical stress. When these ...

Crystallization of Proteins on Chip by Microdialysis for In Situ X-ray Diffraction Studies

This protocol describes the manufacturing of reproducible and inexpensive microfluidic devices covering the whole pipeline for crystallizing proteins on-chip with the dialysis method and allowing in situ single-crystal or serial crystallography experiments at room temperature. The protocol details the fabrication process of the microchips, the manipulation of the on-chip crystallization experiments and the treatment of the in situ collected X-ray diffraction data for the structural elucidation of the protein sample. The main feature of this microfabrication procedure lies on the integration of a commercially available, semipermeable regenerated cellulose dialysis membrane in between two layers of the chip. The molecular weight cut-off of the embedded membrane varies depending on the molecular weight of the macromolecule and the precipitants. The device exploits the advantages of microfluidic technology, such as the use of minute volumes of samples (&#60;1 &#181;L) and fine tuning over transport phenomena. The chip coupled them with the dialysis method, providing precise and reversible control over the crystallization process and can be used for investigating phase diagrams of proteins at the microliter scale. The device is patterned using a photocurable thiolene-based resin with soft imprint lithography on an optically transparent polymeric substrate. Moreover, the background scattering of the materials composing the microchips and generating background noise was evaluated rendering the chip compatible for in situ X-ray diffraction experiments. Once protein crystals are grown on-chip up to an adequate size and population uniformity, the microchips can be directly mounted in front of the X-ray beam with the aid of a 3D printed holder. This approach addresses the challenges rising from the use of cryoprotectants and manual harvesting in conventional protein crystallography experiments through an easy and inexpensive manner. Complete X-ray diffraction data sets from multiple, isomorphous lysozyme crystals grown on-chip were collected at room temperature for structure determination.

Crystallization of Proteins on Chip by Microdialysis for In Situ X-ray Diffraction Studies

This paper details the fabrication protocol of microfluidic chips developed for on-chip protein crystallization with the dialysis method and in situ X-ray diffraction experiments. The microfabrication process makes it possible to integrate a semipermeable regenerated cellulose dialysis membrane with any molecular weight cut-off, between two layers of the chip.

This protocol describes the manufacturing of reproducible and inexpensive microfluidic devices covering the whole pipeline for crystallizing proteins ...

Synthesis of High-ZT Thermoelectric Materials via Mechanochemical Methods

Demonstrating the Simplicity and In Situ Temperature Monitoring of the Mechanochemical Synthesis of Metal Chalcogenides Suitable for Thermoelectrics

Mechanochemical synthesis is an extremely useful strategy to reach thermoelectric materials due to its solvent-free one-step character, as the targeted thermoelectricity (TE) materials in a nanocrystalline format can be prepared by mere high-energy milling of elemental precursors. Nevertheless, the subsequent densification method (e.g., spark plasma sintering or hot pressing) is required afterward, similarly to other synthetic methodologies. In this study, the simplicity of mechanochemical synthesis is&#160;presented for two selected metal chalcogenides, namely copper sulfide (Cu1.8S, digenite) and tin selenide (SnSe, svetlanaite), which are known for high ZT values. These compounds can be prepared via a mechanically induced self-propagating reaction (MSR), which is a combustion-like process instantly yielding the products in a very short timeframe (within 1 min). The occurrence of MSR can be well-tracked by in situ temperature monitoring since an abrupt temperature increase occurs at the moment of MSR. We have developed a device which is capable of monitoring the temperature inside the milling jar every 80 ms during planetary ball milling, and it is therefore possible to very precisely track the moment of MSR ignition. The developed device presents an improvement in the monitoring capabilities in comparison with commercially available analogs. This contribution aims to provide a visual insight into all steps, with simple high-energy ball milling of elements to reach TE materials and in situ temperature monitoring being the central points.

Here, we present a protocol to synthesize two metal chalcogenides (Cu1.8S and SnSe) suitable for thermoelectrics via an ultrafast (second-range), solvent-free, and one-step mechanochemical synthesis using elemental precursors. Simultaneously, we demonstrate the monitoring of the temperature in the jar during planetary ball milling in situ by the newly developed device.

Mechanochemical synthesis is an extremely useful strategy to reach thermoelectric materials due to its solvent-free one-step character, as the targeted ...

Automated Protein Crystallization and Real-Time Data Collection

Crystallization and In Situ Room Temperature Data Collection Using the Crystallization Facility at Harwell and Beamline VMXi, Diamond Light Source

Protocols for robotic protein crystallization using the Crystallization Facility at Harwell and in situ room temperature data collection from crystallization plates at Diamond Light Source beamline VMXi are described. This approach enables high-quality room-temperature crystal structures to be determined from multiple crystals in a straightforward manner and provides very rapid feedback on the results of crystallization trials as well as enabling serial crystallography. The value of room temperature structures in understanding protein structure, ligand binding, and dynamics is becoming increasingly recognized in the structural biology community. This pipeline is accessible to users from all over the world with several available modes of access. Crystallization experiments that are set up can be imaged and viewed remotely with crystals identified automatically using a machine learning tool. Data are measured in a queue-based system with up to 60&#176; rotation datasets from user-selected crystals in a plate. Data from all the crystals within a particular well or sample group are automatically merged using xia2.multiplex with the outputs straightforwardly accessed via a web browser interface.

Author Spotlight: Advancing Protein Structure Analysis for Drug Development 

We present a protocol for the crystallization of proteins using the crystallization facility in the Research Complex at Harwell and subsequent in situ X-ray crystallographic data collection from crystals within the plates at Diamond&#39;s Versatile Macromolecular Crystallography in situ (VMXi) beamline. We describe sample requirements, crystallization protocols, and data collection guidelines.

Protocols for robotic protein crystallization using the Crystallization Facility at Harwell and in situ room temperature data collection from ...

Biochemistry

Fluid-cell Raman Spectroscopy for operando Studies of Reaction and Transport Phenomena during Silicate Glass Corrosion

Fluid-cell Raman Spectroscopy (FCRS) enables the real-time and space-resolved (operando) study of reaction mechanisms, kinetics, and their mutual interactions with transport processes during silicate glass corrosion at the micrometer scale and at elevated temperatures. This manuscript provides a detailed protocol for setting up an FCRS experiment, exemplified by a corrosion experiment with a ternary Na borosilicate glass and a 0.5 M NaHCO3 solution at a temperature of 86 &#177; 1 &#176;C. The protocol involves (i) sample preparation, (ii) assembly of the fluid cell, and (iii) setting of Raman measurement parameters for collecting Raman spectra across the sample/solution interface in regular time intervals. The results from the experiment show the formation of a water-rich zone between a silica-based surface alteration layer (SAL) and the pristine glass, which is an intrinsic feature of an interface-coupled dissolution-precipitation model for the formation of a SAL during silicate glass corrosion. The ability to track the reaction and transport processes during the corrosion of silicate glasses and potentially of other transparent materials, spatially resolved and in real-time, represents a unique strength of this technique, overcoming the disadvantages of conventional analysis of multi-step quenching experiments. The corrosion of the top side of the glass sample represents a current issue, reducing spatial resolution at depth due to precipitation within the laser pathway. This is caused by a solution-filled gap between the sapphire window of the fluid cell lid and the top side of the monolith, which is difficult to avoid during the experimental setup. This must be taken into account when choosing the depth at which the measurement should be made. In a few cases, the formation of air bubbles was observed, which disrupted or even led to the termination of the experiment. However, this can be avoided by carefully setting up the experiment, which requires little practice.

Fluid-cell Raman Spectroscopy (FCRS) enables in operando observations of reaction and transport phenomena during the aqueous corrosion of silicate glasses at a microscopic level, at elevated temperatures, and in real-time. Without interrupting ongoing processes, FCRS provides information about reaction mechanisms, kinetics, and transport processes.

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

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