Grazing Incidence Synchrotron X-ray Diffraction Research Articles

Delayed parabolic oxidation via transient thermal exposures on a polycrystalline nickel-based superalloy

Multiple oxides were observed during the transient oxidation stage of the polycrystalline Ni-based superalloy, RR1000, before a protective Cr2O3 scale formed. Thermogravimetric analysis, synchrotron grazing incidence X-ray diffraction, and electron microscopy were performed on samples subjected to isothermal exposures at 800 °C for up to 100 h. Transient effects governed the early stages up to 40 h. NiO, spinels (NiCr2O4, (Ni,Co)(Cr,Co)2O4), Cr2O3/(Cr0.88Ti0.12)2O3, NiTiO3, and CrTaO4 formed during the initial stage with pseudo-linear kinetics. At the onset of parabolic kinetics, extensive Cr2O3 and TiO2 growth dominated scale formation with the former emerging as the major passivating oxide.

Modulating Polymer Ultrathin Film Crystalline Fraction and Orientation with Nanoscale Curvature.

We investigated the effect of nanoscale curvature on the structure of thermally equilibrated poly-3-hexylthiophene (P3HT) ultrathin films. The curvature-induced effects were investigated with synchrotron grazing incidence X-ray diffraction (GIXRD) and atomic force microscopy (AFM). Our results demonstrate that nanoscale curvature reduces the polymer crystalline fraction and the crystal length. The first effect is strongest for the lowest curvature and results in a decrease in the out-of-plane thickness of the polymer crystals. On the other hand, the crystal in-plane length decreases with the increase in substrate curvature. Finally, the semi-quantitative analysis of crystal anisotropy shows a marked dependence on the substrate curvature characterized by a minimum at curvatures between 0.00851 nm-1 and 0.0140 nm-1. The results are discussed in terms of a curvature-dependent polymer fraction, which fills the interstices between neighboring particles and cannot crystallize due to extreme space confinement. This fraction, whose thickness is highest at the lowest curvatures, inhibits the crystal nucleation and the out-of-plane crystal growth. Moreover, because of the adhesion to the curved portion of the substrates, crystals adopt a random orientation. By increasing the substrate curvature, the amorphous fraction is reduced, leading to polymer films with higher crystallinity. Finally, when the thickness of the film exceeds the particle diameter, the curvature no longer affects the crystal orientation, which, similarly to the flat case, is predominantly edge on.

Development of a versatile electrochemical cell for in situ grazing-incidence X-ray diffraction during non-aqueous electrochemical nitrogen reduction.

In situ techniques are essential to understanding the behavior of electrocatalysts under operating conditions. When employed, in situ synchrotron grazing-incidence X-ray diffraction (GI-XRD) can provide time-resolved structural information of materials formed at the electrode surface. In situ cells, however, often require epoxy resins to secure electrodes, do not enable electrolyte flow, or exhibit limited chemical compatibility, hindering the study of non-aqueous electrochemical systems. Here, a versatile electrochemical cell for air-free in situ synchrotron GI-XRD during non-aqueous Li-mediated electrochemical N2 reduction (Li-N2R) has been designed. This cell not only fulfills the stringent material requirements necessary to study this system but is also readily extendable to other electrochemical systems. Under conditions relevant to non-aqueous Li-N2R, the formation of Li metal, LiOH and Li2O as well as a peak consistent with the α-phase of Li3N was observed, thus demonstrating the functionality of this cell toward developing a mechanistic understanding of complicated electrochemical systems.

Ex‐situ synchrotron X‐ray diffraction study of CO2 corrosion‐induced surface scales developed in low‐alloy steel with different initial microstructure

The CO2 corrosion-induced scale developed in the surface region of the low-grade carbon steel is thoroughly investigated to understand the corrosion mechanisms involved during exposure to CO2-saturated aqueous environments. In this work, in addition to the electron microscopy and lab-source X-ray diffraction (XRD) methods, ex-situ depth-resolved phase identification of the corrosion scales developed on steel with different initial microstructures is performed using synchrotron grazing incidence XRD at different incidence angles. The CO2 corrosion mechanism is discussed considering the observed distribution of the corrosion products formed at a different depth relative to the time of electrochemical exposure of the steels.

On High-Temperature Thermal Cleaning of Li7La3Zr2O12 Solid-State Electrolytes

The deployment of Li7La3Zr2O12 (LLZO) garnets as solid-state electrolytes for Li-metal solid-state batteries faces challenges due to their reactivity with water and carbon dioxide, resulting in the formation of a Li2CO3/LiOH contamination layer on the LLZO surface. This contamination layer contributes to high Li/LLZO interfacial resistance, voltage polarization at the Li anode, and the formation of Li dendrites. In this work, we study the feasibility of high temperature annealing (600–900 °C) as a thermal cleaning method for LLZO. By conducting a comprehensive analysis of the LLZO surface using X-ray photoelectron spectroscopy, hard X-ray photoelectron spectroscopy, in situ grazing incidence synchrotron X-ray diffraction, and Raman spectroscopy, an inherent issue related to high-temperature thermal cleaning is identified. While heat-treatment effectively reduces the Li2CO3/LiOH contamination, it also leads to the formation of the La2Zr2O7 phase on the LLZO surface due to Li losses. The impact of these factors on the voltage polarization, interfacial resistance, and critical current density of Li/LLZO/Li symmetrical cells was assessed by electrochemical impedance spectroscopy and galvanostatic cycling measurements.

Change in the gas sensing mechanism and improved sensing response on ion-irradiated palladium-graphene oxide nanocomposite

In this study, we synthesized Pd-graphene oxide (Pd-GO) nanocomposite layers on SiO2/Si substrates using chemical method. Pd-GO layers were treated with swift heavy ion irradiation (100 MeV Ag ions, 1013 ions/cm2). The structural properties of the pristine as well as the ion irradiated samples were investigated using synchrotron grazing incidence x-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) techniques. XRD shows peaks corresponding to Pd (FCC, space group-Fd-3m), GO and synthetic graphite. The relative graphite peak intensities increased after ion irradiation, indicating reduction of GO. The sensor responses of nanocomposite layers towards exposure of 35 ppm H2 at 100 °C, were measured for several cycles. Ion-irradiated Pd-GO samples show enhancement in the sensing response of H2 gas by about 24% and with lower recovery times (25%), as compared to pristine Pd-GO nanocomposite samples. The change in type of conductivity from p-type gas sensing layer in pristine nanocomposite to n-type conductivity, along with an increase in conductivity (about 500 times) in ion irradiated samples were observed. The change in type of conductivity on ion-irradiation is attributed to the reduction of GO layer and the changes in conductivity on hydrogen exposure is explained due to hydrogen spill-over effect in the two-component system. The improvement in sensitivity upon ion-irradiation was due to the increase in concentration of structural defects due to electronic energy loss, as studied by SRIM simulation. This study points towards using ion induced electronic energy loss as a new tool for varying the gas sensing properties of GO based sensors.

Superstructures, Commensurations, and Rotation of Single-Layer TaS2 on Au(111) Induced by Cs Intercalation/Deintercalation

We use in situ synchrotron grazing incidence X-ray diffraction and X-ray reflectivity to investigate with high resolution the structure of a two-dimensional single layer of tantalum sulfide grown on a Au(111) surface and its evolution during intercalation by Cs atoms and deintercalation, which decouples and recouples the two materials, respectively. The grown single layer consists of a mixture of TaS2 and its S-depleted version, TaS, both aligned with gold, and forming moirés where 7 (respectively 13) lattice constants of the 2D layer almost perfectly match 8 (respectively 15) substrate lattice constants. Intercalation fully decouples the system by lifting the single layer by ∼370 pm and induces an increase of its lattice parameter by 1-2 picometers. The system gradually evolves, during cycles of intercalation/deintercalation assisted by an H2S atmosphere, toward a final coupled state consisting of the fully stoichiometric TaS2 dichalcogenide whose moiré is found very close to the 7/8 commensurability. The reactive H2S atmosphere appears necessary to achieve full deintercalation, presumably by preventing S depletion and the concomitant strong bonding with the intercalant. The structural quality of the layer improves during the cyclic treatment. In parallel, because they are decoupled from the substrate by the intercalation of cesium, some of the TaS2 flakes rotate by 30°. These produce two additional superlattices with characteristic diffraction patterns of different origins. The first is aligned with gold's high symmetry crystallographic directions and is a commensurate moiré ((6 × 6)-Au(111) coinciding with (3√3 × 3√3)R30°-TaS2). The second is incommensurate and corresponds to a near coincidence of (6 × 6) unit cells of 30°-rotated TaS2 with (4√3 × 4√3)Au(111) surface ones. This structure, which is less coupled to gold, might be related to the ∼(3× 3) charge density wave previously reported even at room temperature in TaS2 grown on noninteracting substrates. A (3 × 3) superstructure of 30°-rotated TaS2 islands is indeed revealed by complementary scanning tunneling microscopy.

Cu interfaced Fe/Pt multilayer with improved (001) texture, enhanced L10 transformation kinetics and high magnetic anisotropy

In the present work, enhanced L10 ordering kinetics with improved crystallographic texturing in [001] direction and high magnetic coercivity of about 6 kOe is observed in L10 ordered Fe(1-x)CuxPt films, after successive isochronal vacuum annealing of multilayer structure [(Fe(1-x)/Cux)/Pt]x10. Synchrotron grazing incidence x-ray diffraction (GIXRD) measurements, performed using area detector confirms the onset of L10 ordering at 200 °C and presence of high degree of ordering at 300 °C. In-plane and out-of-plane GIXRD measurements validates texturing of magnetic easy axis [001] in out of film plane direction. Enormous increase in magnetic coercivity is observed from MOKE measurements in L10 ordered state. Lower ordering temperature with enhance (001) texturing and high magnetic coercivity is desirable for potential device applications of FePt. Effect of Cu and annealing temperature on structural and magnetic properties is investigated systematically in Fe(1-x)CuxPt films. Structural investigation discloses that lattice distortion in L10 ordered state caused by Cu addition and high interfacial energy associated with initial multilayer structure drives faster interdiffusion. Both of these aspects collectively work for FCC to FCT transformation, hence results in enhanced kinetics and texturing effects of L10 FePt.

Strain Profile in the Subsurface of He-Ion-Irradiated Tungsten Accessed by S-GIXRD

The strain profile in the subsurface of He-ion-irradiated W was figured out by unfolding the synchrotron-grazing incidence X-ray diffraction (S-GIXRD) patterns at different incidence angles. The results show that for 2 × 1021 ions/m2 He2+-irradiated W, in addition to a compressive strain exists in the depths of 0–100 nm due to mechanical polishing, an expansion strain appears in the depth beyond 100 nm owing to irradiation-induced lattice swelling. This work provides a reference for the study of irradiation damage in the subsurface by S-GIXRD.

Templated electrodeposition as a scalable and surfactant-free approach to the synthesis of Au nanoparticles with tunable aspect ratios.

A high-throughput method for the fabrication of ordered arrays of Au nanoparticles is presented. It is based on pulsed electrodeposition into porous anodic alumina templates. In contrast to many synthesis routes, it is cyanide-free, prior separation of the alumina template from the aluminium substrate is not required, and the use of contaminating surfactants/capping agents often found in colloidal synthesis is avoided. The aspect ratio of the nanoparticles can also be tuned by selecting an appropriate electrodeposition time. We show how to fabricate arrays of nanoparticles, both with branched bases and with hemispherical bases. Furthermore, we compare the different morphologies produced with electron microscopies and grazing-incidence synchrotron X-ray diffraction. We find the nanoparticles are polycrystalline in nature and are compressively strained perpendicular to the direction of growth, and expansively strained along the direction of growth. We discuss how this can produce dislocations and twinning defects that could be beneficial for catalysis.

Aggregate formation in crystalline blends of α-sexithiophene and para-sexiphenyl

Earlier reports on rod-like conjugated molecules of similar shape and size such as α-sexithiophene (6T) and para-sexiphenyl (6P) indicated mixed crystal growth in equimolar blends. The spectral overlap between the 6P fluorescence and 6T absorption might there give rise to resonant energy transfer between the two species. In marked contrast to H-type aggregation found for 6T bulk crystals, isolated monolayers of 6T as well as 6T monolayers sandwiched between 6P multilayers have been reported to show pronounced green (instead of red) fluorescence, which has been attributed to J-type aggregation. Here, we investigate whether these altered optical properties of 6T translate from the monolayer to a bulk equimolar blend with 6P. Insight into the mixed crystal structure for vacuum co-deposited films of 6T + 6P is provided by using synchrotron grazing-incidence x-ray diffraction on different substrates. By correlating the optical properties of the pure and the mixed systems using absorption and photoluminescence spectroscopy we identify the green emission known from 6T monolayers to prevail in the blend. Our analysis indicates the formation of aggregates which are promoted by the molecular arrangement in the mixed crystal structure highlighting that the remarkable optical properties of 6T/6P heterostacks translate into mixed crystalline films. This study underlines that tuning the opto-electronic properties of organic semiconductors by blending species of similar shape but distinct opto-electronic properties is a promising pathway to achieve altered material properties.

Tuning the randomization of lamellar orientation in poly(3-hexylthiophene) thin films with substrate nano-curvature

We report the effect of substrates with uniform nanocurvature on the structure of deposited thin films of high molecular weight regio-regular poly(3-hexylthiophene) (P3HT). The curvature-induced effects on the in-plane and out-of-plane crystalline structure and the lamellae orientation were investigated using synchrotron Grazing Incidence X-ray Diffraction (GIXRD) and Atomic Force Microscopy (AFM).It was found that the substrate curvature influences both the lamellar persistence length and the 3D orientation. In particular, AFM results showed that the lamellar persistence length is reduced as the surface nano-curvature increases. GIXRD experiments showed a diffraction ring for the (100) peak for regio-regular P3HT thin films onto all the nano-curved surfaces with respect to the flat one, corresponding to an overall random lamellar orientation for nano-curved films. Semi-quantitative determinations of the degree of randomization show that it increases with the substrate nano-curvature. Finally, dark conductivity measurements of regio-regular P3HT thin films showed again an increase of about one order of magnitude with curvature, with a threshold value of 0.014 nm−1, closely following the same changing trend of the lamellar orientational and morphological parameters. This last effect, which indeed was not observed for amorphous regio-random P3HT thin films deposited onto substrates with the same nanocurvature, suggests the strong correlation of the dark conductivity increase to the peculiar curvature-induced lamellar features (i.e., reduced persistence length and increased orientation randomness) arrangement in regio-regular P3HT thin films. A phenomenological model is proposed to account for the observed structural and electrical effects of nano-curved substrates.

In-Operando Diffraction and Spectroscopic Evaluation of Pure, Zr-, and Ce-Doped Vanadium Dioxide Thermochromic Films Derived via Glycolate Synthesis.

Pure and doped vanadia (VO2, V0.98Zr0.02O2, V0.98Ce0.02O2) samples were prepared by wet chemistry synthesis from vanadyl glycolate intermediate phase and tape casted into films. Combining in-operando grazing incidence synchrotron X-ray diffraction and Raman spectroscopy, we studied the structural evolution of the films under isothermal conditions. The setup allowed assessment of the thermochromic functionality with continuous monitoring of the monoclinic to tetragonal transition in pure and doped vanadia phases, responsible for the transmission and reflection of light in the infrared part of the solar spectrum. The materials characterisation by X-ray diffraction beamline (MCX) goniometer demonstrated ideal performance, combining flexible geometry, high resolution, and the potential to accommodate the multi-channel equipment for in-operando characterisation. This method proved viable for evaluating the relevant structural and physical, and thereof functional properties of these systems. We revealed that dopants reduce the transition temperature by 5 °C on average. The synthetic route of the films was held responsible for the observed phase separation. The more favourable behaviour of cerium-doped sample was attributed to cerium alkoxide behaviour. In addition, structural, microstructural, thermal, and spectroscopic characterisation on powder samples was performed to gain more insight into the development of the phases that are responsible for thermochromic features in a broader range of doping ratios. The influence of the dopants on the extent of the thermochromic transition (transmission to reflection hysteresis) was also evaluated using (micro) structural, thermal and spectroscopic methods of powder samples. Characterisations showed that zirconium doping in 2, 4, and 6 mol% significantly influenced the phase composition and morphology of the precursor. Vanadium oxides other than VO2 can easily crystallise; however, a thermal treatment regime that allowed crystallisation of VO2 as a single phase was established.

Microstructure evolution of pure tungsten after low-energy and high-fluence He+ implantation assessed by synchrotron grazing incidence X-ray diffraction

A clear understanding on the H/He plasma implantation behavior in the plasma facing materials is a key issue to manage the implanted H/He in a future nuclear fusion reactor. In this work, the microstructure evolution of pure tungsten after low-energy (100 eV) and high-fluence (1023~1024 /m2) helium ion implantation was investigated by the synchrotron grazing incidence X-ray diffraction (S-GIXRD) and nanoindentation. Benefiting from the depth dependence of S-GIXRD and nanoindentation, it was found that the unimplanted W surface layer was composed of two zones: the compressed zone with a thickness of ~56 ± 2 nm under the top surface, which was introduced by the mechanical polishing, and the unaffected matrix. The helium implanted W surface layer was composed of four zones along the direction from the top surface to deep depth: the compressed zone with a thickness of ~46 ± 10 nm, transition zone with a thickness of ~146 ± 14 nm, expanded zone, and the matrix. The compressed zone becomes thinner after He implantation possibly owing to the formation of He-complexes. The expanded zone resulted from the helium atoms entering into the tungsten lattice, while the transition zone is a result of competition between the expanding and compressing effects.

Synthesis of epitaxial monolayer Janus SPtSe

Janus single-layer transition metal dichalcogenides, in which the two chalcogen layers have a different chemical nature, push chemical composition control beyond what is usually achievable with van der Waals heterostructures. Here, we report such a Janus compound, SPtSe, which is predicted to exhibit strong Rashba spin–orbit coupling. We synthetized it by conversion of a single-layer of PtSe2 on Pt(111) via sulfurization under H2S atmosphere. Our in situ and operando structural analysis with grazing incidence synchrotron X-ray diffraction reveals the process by which the Janus alloy forms. The crystalline long-range order of the as-grown PtSe2 monolayer is first lost due to thermal annealing. A subsequent recrystallization in presence of a source of sulfur yields a highly ordered SPtSe alloy, which is isostructural to the pristine PtSe2. The chemical composition is resolved, layer-by-layer, using angle-resolved X-ray photoelectron spectroscopy, demonstrating that Se-by-S substitution occurs selectively in the topmost chalcogen layer.

Lipid membrane templated misfolding and self-assembly of intrinsically disordered tau protein

The aggregation of the intrinsically disordered tau protein into highly ordered β-sheet-rich fibrils is implicated in the pathogenesis of a range of neurodegenerative disorders. The mechanism of tau fibrillogenesis remains unresolved, particularly early events that trigger the misfolding and assembly of the otherwise soluble and stable tau. We investigated the role the lipid membrane plays in modulating the aggregation of three tau variants, the largest isoform hTau40, the truncated construct K18, and a hyperphosphorylation-mimicking mutant hTau40/3Epi. Despite being charged and soluble, the tau proteins were also highly surface active and favorably interacted with anionic lipid monolayers at the air/water interface. Membrane binding of tau also led to the formation of a macroscopic, gelatinous layer at the air/water interface, possibly related to tau phase separation. At the molecular level, tau assembled into oligomers composed of ~ 40 proteins misfolded in a β-sheet conformation at the membrane surface, as detected by in situ synchrotron grazing-incidence X-ray diffraction. Concomitantly, membrane morphology and lipid packing became disrupted. Our findings support a general tau aggregation mechanism wherein tau’s inherent surface activity and favorable interactions with anionic lipids drive tau-membrane association, inducing misfolding and self-assembly of the disordered tau into β-sheet-rich oligomers that subsequently seed fibrillation and deposition into diseased tissues.

Titania-Coated Alumina Foam Photocatalyst for Memantine Degradation Derived by Replica Method and Sol-Gel Reaction.

In the present work, alumina (Al2O3) foam was prepared by the replica method where a polyurethane (PU) foam (30 pores per inch (ppi)) template was impregnated with a 60 wt.% Al2O3 suspension. Sintered Al2O3 foam was used as substrate for the deposition of sol-gel derived titania (TiO2) film using dip coating. For the preparation of TiO2 sol, titanium(IV) isopropoxide (Ti-iPrOH) was used as the precursor. The common problem of qualification and quantification of a crystalline coating on a highly porous 3D substrate with an uneven surface was addressed using a combination of different structural characterization methods. Using Powder X-ray Diffraction (PXRD) and synchrotron Grazing Incidence X-ray Diffraction (GIXRD) on bulk and powdered Al2O3 foam and TiO2-coated Al2O3 foam samples, it was determined Al2O3 foam crystallizes to corundum and coating to anatase, which was also confirmed by Fourier Transformed Infrared Spectroscopy (FTIR). Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM/EDS) revealed the structural and microstructural properties of the substrate and coating. Differential Thermal Analysis (DTA) and Thermogravimetric Analysis (TGA) were used to clarify the evolution of the porous microstructure. The Al2O3-TiO2 composite was evaluated as a photocatalyst candidate for the degradation of the micropollutant medication memantine. The degradation rate was monitored using a light-emitting diode (LED) lamp operating at electromagnetic (EM) wavelength of 365 nm. The photocatalytic activity of sol-gel-derived TiO2 film immobilized on the Al2O3 foam was compared with commercially available TiO2 nanoparticles, P25-Degussa, in the form of a suspension. The levels of memantine were monitored by High-Performance Liquid Chromatography–Tandem Mass Spectrometry (HPLC–MS/MS). The efficiency and rate of the memantine photodegradation by suspended TiO2 nanoparticles is higher than the TiO2-coated Al2O3 foam. But, from the practical point of view, TiO2-coated Al2O3 foam is more appropriate as a valuable photocatalytic composite material.

Identifying heating rate dependent oxidation reactions on a nickel-based superalloy using synchrotron diffraction

Synchrotron grazing incidence X-ray diffraction has been used to newly reveal the heating rate dependent oxidation reactions that develop on a polycrystalline nickel-based superalloy. A continuous layer of precursor oxide was shown to form during the heating stage. Their approximate growth rates, their effect on local surface compositions of the alloy substrate, and their degree of interface planarity are considered critical in determining subsequent oxidation reactions when held for extended thermal exposures. The precursor oxides were predominantly nickel or cobalt based (NiO/CoO and Co3O4/NiCo2O4). Following the fastest heating rates (40 °C min−1 and above), the stable Cr2O3 phase formed, inhibiting Ni or Co diffusion to the surface. At slower heating rates (10–20 °C min−1), no evidence of the stable Cr2O3 was found, even after 200 h at elevated thermal exposure, instead continued growth of the precursor oxides was observed. Heating at 5 °C min−1 gave rise to an intriguing zone where sufficient precursor and favourable kinetics enabled the formation of a spinel, NiCr2O4, surface layer. Cross sections observed with electron microscopy confirmed this to be planar and continuous. Heating at the slowest tested 2 °C min−1 contrarily gives a non-protective surface layer comprising an outwardly growing NiO/CoO precursor oxide on top of an inwardly growing mixed oxide. The quantities, interfacial morphologies of oxides of the precursor oxide grown and the possible thermodynamic reactions that lead to their formation are discussed.

Influence of Iodine Doping on the Structure, Morphology, and Physical Properties of Manganese Phthalocyanine Thin Films

Doping with halide ions is a popular method to alter the properties of metal phthalocyanines (MPcs), particularly magnetic and electrical nature of organic semiconductors for applications in spintronic or electronic devices. Doping can cause a structural rearrangement in MPc packing, and the physical properties may be correlated with molecular packing. Films of a planar and magnetic MPc, manganese(II)phthalocyanine (MnPc), are chosen for iodine doping study. The optical, magnetic, and electrical properties of pristine- and iodine-doped MnPc thin films are investigated and can be directly associated with their molecular structure. Two-dimensional grazing incidence synchrotron X-ray diffraction reveals structural disorder in MnPc films upon iodine infusion induced by the reorientation of ordered, edge-on molecular configuration to tilted and face-on configurations in a random fashion. The film morphology changes accordingly, where in the uniform crystallites reorganize in a disordered manner. The ferromagne...

Active-Phase Formation and Stability of Gd/Pt(111) Electrocatalysts for Oxygen Reduction: An In Situ Grazing Incidence X-Ray Diffraction Study.

Alloys of platinum and gadolinium present significant activity enhancement over pure Pt for the oxygen reduction reaction (ORR), both in the form of extended electrode surfaces and nanoparticulate catalysts. The active phase consists of a compressed Pt overlayer formed on Pt5 Gd electrodes upon exposure to the electrolyte by acid leaching. Here, we investigate the formation, strain and correlation lengths of the active Pt overlayer by using in situ synchrotron grazing incidence X-ray diffraction on Gd/Pt(111) single-crystalline electrodes. The overlayer forms upon exposure to electrolyte under open circuit conditions; the compressive strain relaxes slightly upon repeated electrochemical cycling in the potential range 0.6 to 1.0 V versus the reversible hydrogen electrode (RHE). In addition, the strain relaxes strongly when exposing the electrode to 1.2 V versus RHE, and the thickness of the crystalline portion of the overlayer increases with potential above 1.3 V versus RHE.