Search

Calcium silicate hydrate (C-S-H), is the principal hydration product of Portland cement that mainly contributes to the physical and mechanical properties of concrete. This paper aims to investigate the three-dimensional structure of C-S-H with Ca/Si ratios of 1.0 and 1.6 at the nanoscale using electron tomography. The 3D reconstructions and selected region of interest analysis confirm that the morphology of both C-S-H materials are foil-like structures. The difference between the two materials is the density of elongated structures. C-S-H with Ca/Si ratio 1.6 is clearly composed of denser particles compared to the other C-S-H material due to overlapping of the foil-like structure. Pore analysis shows that C-S-H 1.0 and C-S-H 1.6 have porosities 69.2% and 49.8% respectively. Pore size distribution also reveals that C-S-H 1.0 has pore size range between 0-250 nm and C-S-H 1.6 between 0-100 nm. The pore network's size of C-S-H 1.0 is significantly larger than 1.6. This study illustrates the capability of using electron tomography to determine the 3D nanoscale structure of cementitious products and to distinguish between C-S-H 1.0 and 1.6.

The introduction of multigrain crystallography (MGC) applied in a laser-heated diamond anvil cell (LH-DAC) using synchrotron X-rays has provided a new path to investigate the microstruc-tural evolution of materials at extreme conditions, allowing for simultaneous investigations of phase identification, strain state determination, and orientation relations across phase transitions in a single experiment. Here, we applied this method to a sample of San Carlos olivine beginning at ambient conditions and through the α olivine → γ-ringwoodite phase transition. At ambient temperatures, by measuring the evolution of individual Bragg reflections, olivine shows profuse angular streaking consistent with the onset of yielding at a measured stress of ~1.5 GPa, considerably lower than previously reported, which may have implications for mantle evolution. Furthermore, γ-ringwoodite phase was found to nucleate as micron to sub-micron grains imbedded with small amounts of a secondary phase at 15 GPa and 1000◦C. Using MGC, we were able to extract and refine individual crystallites of the secondary unknown phase where it was found to have a structure consistent with the ε-phase previously described in chondritic meteorites.

If a crystal lattice is subjected to a stress, it becomes distorted and no longer represents the ideal crystal symmetry, and if the stress introduces defects such as dislocations, some of this distortion is preserved after the applied stress is removed. In this study, we investigate lattice distortion in quartz at the micron scale with synchrotron X-ray Laue diffraction. From Laue images the local deviatoric strain tensor is derived and corresponding stresses are calculated based on elastic properties. The method is applied to metasedimentary quartzites from the Bergell Alps that were deformed at conditions of greenschist facies metamorphism. The residual palaeostrain is represented in maps of the deviatoric strain tensor components and with deviatoric strain axis pole figures. Data suggest overall shortening perpendicular to the schistosity plane but with considerable asymmetry relative to foliation and lineation, probably attributed to simple shear. Crystallographic pole figures from Laue diffraction agree with neutron diffraction and EBSD measurements and display quartz c-axes girdle distributions with maxima also perpendicular to schistosity. The method shows promise to be used as a palaeo-piezometer to unravel the stress field during tectonic deformation.

© 2020. XtalCAMP is a software package based on the MATLAB platform, which is suitable for, but not limited to, the analysis and visualization of scanning Laue X-ray micro-/nanodiffraction data. The main objective of the software is to provide complementary functionalities to the Laue indexing software packages used at several synchrotron beamlines. The graphical user interfaces allow the easy analysis of characteristic microstructure features, including real-time intensity mapping for a quick examination of phase, grain and defect distribution, 2D color-coded mapping of microstructural properties from the output of other Laue indexing software, crystal orientation visualization, grain boundary characterization based on orientation/misorientation calculation, principal strain/stress analysis, and strain ellipsoid representation, as well as a series of additional toolkits. As an example, XtalCAMP is applied to the microstructural investigation of a solution-heat-treated Ni-based superalloy manufactured using a laser 3D-printing technique, and a deformed natural quartzite from Val Bregaglia in the Central Alps.

Slates are low-grade metamorphic argillaceous rocks which have developed an intense tectonic fabric, referred to as slaty cleavage. Due to their unique properties they have long been used as building materials, especially tiles for roofs and floors. The fabric, characterized by strong alignment of platy phyllosilicate crystals, produces extreme anisotropy that has been of great interest in structural geology: What different fabric types are observed? How do they form? Here we review crystal preferred orientation (CPO) and add new information to establish a comprehensive base for future studies. Slates are composed of fine-grained phyllosilicates (dominantly white mica and chlorite, sometimes chloritoid), quartz and accessories. Texture analyses of these polyphase rocks with high energy synchrotron X-ray diffraction and high resolution EBSD reveal strong alignment of mica and chlorite, in some cases exceeding any previously reported texture strength, including metals. Interestingly, the CPO of quartz, with highly flattened grains (shape preferred orientation or SPO), is practically random. Recrystallization microstructures observed by scanning electron microscopy suggest that the phyllosilicate preferred orientation is largely caused by crystal growth under stress, and that quartz was subject to pressure solution and reprecipitation, producing an anisotropic shape. While phyllosilicates preferred orientation in slates is much higher than reports for shale, schists and gneiss, elastic seismic anisotropy for slates is similar to shales where a significant component is due to aligned porosity.

Slags fromthe remoteMota Farun locality above Casaccia (Val Bregaglia, Swiss Alps) have been analyzed with scanning electron microscopy, X-ray powder diffraction and microfocus synchrotron X-ray diffraction to determine mineralogical composition and microstructures. Non-magnetic slag samples are largely composed of euhedral and dendritic iron-rich olivine in a glassy matrix. Locally there are zones with globular inclusions rich in bornite ((Cu5Fe)S4) and locally metallic copper. Some regions display dendritic pentlandite ((Fe,Ni)9S8). Magnetic samples are mainly composed of fayalite (Fe2SiO4) and wüstite (FeO), with minor magnetite (Fe3O4). The mineralogical composition indicates that slags were the product of copper smelting. The slag compositions andmorphologies are analogous to slags described from the Oberhalbstein (Graubünden, Switzerland) and the Trentino Alps (Italy) which are attributed to metallurgical exploitations of the Late Bronze Age. While the origin of the ore could not be determined, it may be related to ore deposits of chalcopyrite in greenschists and serpentinites in the vicinity, such as Alp Tgavretga (Septimer Pass) and Val Perossa (Val Bregaglia).

A complex association of millimeter-sized, aerodynamically-shaped debris, including glass spherules, glass filaments, and composite-fused melt particles was recovered from beach sands on the shores of the Motoujina Peninsula in Hiroshima Bay, Japan. Based on optical microscopy, this debris comprises six morphological groups ranging from clear glasses to rubber-like constituents. Scanning electron microscopy and synchrotron X-ray microdiffraction revealed dominant aluminum, silicon and calcium (Al-Si-Ca) elemental composition with some iron, mainly in glass, associated with precipitates of mullite and anorthite microcrystals, hematite dendrites and iron-chromium globules, indicative of original temperature conditions >1800 °C. Aerodynamically-shaped fallout debris, including glass spherules described in this study, are generally produced by single high-energy catastrophic events, such as an extraterrestrial body impacting Earth or a nuclear explosion. This study interprets the large volumes of fallout debris generated under extreme temperature conditions as products of the Hiroshima August 6th, 1945 atomic bomb aerial detonation. The chemical composition of the melt debris provides clues to their origin, particularly with regard to city building materials. This study is the first published record and description of fallout resulting from the destruction of an urban environment by atomic bombing.

Clinopyroxene and plagioclase (andesine) microlites in an obsidian flow from Glass Mountain (NE California, USA) display strong alignment. Synchrotron X-ray diffraction, coupled with Rietveld analysis, was used to quantify crystallographic-preferred orientation (CPO). Clinopyroxene, with a rod-shaped morphology, shows a strong alignment of [001] in the flow direction and (010) aligned parallel to the inferred flow plane. Andesine, with a platy morphology, displays an alignment of (010) platelets in the flow plane. Some pole densities exceed 90 multiples of random distribution. Applying a model of rigid ellipsoidal inclusions in a viscous matrix, the local pure shear strains are between 2 and 3.

In the geologic record, the quartz c-axis patterns are widely adopted in the investigation of crystallographic preferred orientations (CPO) of naturally deformed rocks. To this aim, in the present work, four different methods for measuring quartz c-axis orientations in naturally sheared rocks were applied and compared: the classical universal stage technique, the computer-integrated polarization microscopy method (CIP), the time-of-flight (TOF) neutron diffraction analysis , and the electron backscatter diffraction (EBSD). Microstructural analysis and CPO patterns of quartz, together with the ones obtained for feldspars and micas in mylonitic granitoid rocks, have been then considered to solve structural and geological questions related to the Montalto crustal scale shear zone (Calabria, southern Italy). Results obtained by applying the different techniques are discussed, and the advantages as well as limitations of each method are highlighted. Importantly, our findings suggest that patterns obtained by means of different techniques are quite similar. In particular, for such mylonites, a subsimple shear (40% simple shear vs 60% pure shear) by shape analysis of porphyroclasts was inferred. A general tendency of an asymmetric c-maximum near to the Z direction (normal to foliation) suggesting dominant basal slip, consistent with fabric patterns related to dynamically recrystallization under greenschist facies, is recognized. Rhombohedral slip was likely active as documented by pole figures of positive and negative rhombs (TOF), which reveal also potential mechanical Dauphiné twinning. Results showed that the most complete CPO characterization on deformed rocks is given by the TOF (from which also other quartz crystallographic axes can be obtained as well as various mineral phases may be investigated). However, this use is restricted by the fact that (a) there are very few TOF facilities around the world and (b) there is loss of any domainal reference, since TOF is a bulk type analysis. EBSD is a widely used technique, which allows an excellent microstructural control of the user covering a good amount of investigated grains. CIP and US are not expensive techniques with respect the other kind of investigations and even if they might be considered obsolete and/or time-consuming, they have the advantage to provide a fine and grain by grain “first round” inspection on the investigated rock fabric.

We became aware of uncertainties about lattice parameters for osmium in Table 1 and B.K. Godwal (with the Department of Earth and Planetary Science at UC Berkeley) has reanalyzed the radial diamond anvil cell diffraction data, measured in situ at high pressure and compressive stress, with the Moment Pole Stress model in an advanced MAUD Rietveld technique (Wenk et al., 2014), taking into account lattice distortion under stress. [Table presented] The new results compare much better with data from hydrostatic experiments (Godwal et al., 2012). Since the emphasis of the paper was on mechanical twinning, we did not pay much attention to lattice distortion. Note that standard deviations are based on the Rietveld fit.

Seismic anisotropy has been found in many regions of the Earth's interior. Its presence in the Earth's crust has been known since the 19th century, and is due in part to the alignment of anisotropic crystals in rocks, and in part to patterns in the distribution of fractures and pores. In the upper mantle, seismic anisotropy was discovered 50 years ago, and can be attributed for the most part, to the alignment of intrinsically anisotropic olivine crystals during large scale deformation associated with convection. There is some indication for anisotropy in the transition zone, particularly in the vicinity of subducted slabs. Here we focus on the deep Earth – the lower mantle and core, where anisotropy is not yet mapped in detail, nor is there consensus on its origin. Most of the lower mantle appears largely isotropic, except in the last 200–300 km, in the D″ region, where evidence for seismic anisotropy has been accumulating since the late 1980s, mostly from shear wave splitting measurements. Recently, a picture has been emerging, where strong anisotropy is associated with high shear velocities at the edges of the large low shear velocity provinces (LLSVPs) in the central Pacific and under Africa. These observations are consistent with being due to the presence of highly anisotropic MgSiO3 post-perovskite crystals, aligned during the deformation of slabs impinging on the core-mantle boundary, and upwelling flow within the LLSVPs. We also discuss mineral physics aspects such as ultrahigh pressure deformation experiments, first principles calculations to obtain information about elastic properties, and derivation of dislocation activity based on bonding characteristics. Polycrystal plasticity simulations can predict anisotropy but models are still highly idealized and neglect the complex microstructure of polyphase aggregates with strong and weak components. A promising direction for future progress in understanding the origin of seismic anisotropy in the deep mantle and its relation to global mantle circulation, is to link macroscopic information from seismology and microscopic information mineral physics through geodynamics modeling. Anisotropy in the inner core was proposed 30 years ago to explain faster P wave propagation along the direction of the Earth's axis of rotation as well as anomalous splitting of core sensitive free oscillations. There is still uncertainty about the origin of this anisotropy. In particular, it is difficult to explain its strength, based on known elastic properties of iron, as it would require almost perfect alignment of iron crystals. Indeed, the strongly anomalous P travel times observed on paths from the South Sandwich Islands to Alaska may or may not be due to inner core anisotropy, and will need to be explained before consensus can be reached on the strength of anisotropy in the inner core and its origin.

Pozzolanic reaction of volcanic ash with hydrated lime is thought to dominate the cementing fabric and durability of 2000-year-old Roman harbor concrete. Pliny the Elder, however, in first century CE emphasized rock-like cementitious processes involving volcanic ash (pulvis) "that as soon as it comes into contact with the waves of the sea and is submerged becomes a single stone mass (fierem unum lapidem), impregnable to the waves and every day stronger" (Naturalis Historia 35.166). Pozzolanic crystallization of Al-tobermorite, a rare, hydrothermal, calcium-silicate-hydrate mineral with cation exchange capabilities, has been previously recognized in relict lime clasts of the concrete. Synchrotron-based X-ray microdiffraction maps of cementitious microstructures in Baianus Sinus and Portus Neronis submarine breakwaters and a Portus Cosanus subaerial pier now reveal that Al-tobermorite also occurs in the leached perimeters of feldspar fragments, zeolitized pumice vesicles, and in situ phillipsite fabrics in relict pores. Production of alkaline pore fluids through dissolution-precipitation, cation-exchange and/or carbonation reactions with Campi Flegrei ash components, similar to processes in altered trachytic and basaltic tuffs, created multiple pathways to post-pozzolanic phillipsite and Al-tobermorite crystallization at ambient seawater and surface temperatures. Long-term chemical resilience of the concrete evidently relied on water-rock interactions, as Pliny the Elder inferred. Raman spectroscopic analyses of Baianus Sinus Al-tobermorite in diverse microstructural environments indicate a cross-linked structure with Al3+ substitution for Si4+ in Q3 tetrahedral sites, and suggest coupled [Al3++Na+] substitution and potential for cation exchange. The mineral fabrics provide a geoarchaeological prototype for developing cementitious processes through low-temperature rock-fluid interactions, subsequent to an initial phase of reaction with lime that defines the activity of natural pozzolans. These processes have relevance to carbonation reactions in storage reservoirs for CO2 in pyroclastic rocks, production of alkali-activated mineral cements in maritime concretes, and regenerative cementitious resilience in waste encapsulations using natural volcanic pozzolans.

Felsic and mafic gneisses constitute large proportions of the upper and lower continental crust. Gneisses often display high anisotropy of elastic properties associated with preferred orientations of sheet silicates. Here we study the elastic anisotropy of a sample of Tambo gneiss from Promontogno in the Central Alps. We apply optical microscopy, time-of-flight neutron diffraction, neutron and X-ray tomography to quantify mineral composition and microstructures and use them to construct self-consistent models of elastic properties. They are compared to results of ultrasonic measurements on a cube sample in a multi-anvil apparatus and on a spherical sample in an apparatus that can measure velocities in multiple directions. Both methods provide similar results. It is shown that models of microstructure-derived elastic properties provide a good match with ultrasonic experiment results at pressures above 100 MPa. At a pressure of 0.1 MPa the correspondence between the model and the experiment is worse. This may be caused by an oversimplification of the model with respect to microfractures or uncertainties in the experimental determination of S-wave velocities and elastic tensor inversion. The study provides a basis to determine anisotropic elastic properties of rocks either by ultrasonic experiments or quantitative models based on microstructures. This information can then be used for interpretation of seismic data of the crust.

The lower mantle is estimated to be composed of mostly bridgmanite and a smaller percentage of ferropericlase, yet very little information exists for two-phase deformation of these minerals. To better understand the rheology and active deformation mechanisms of these lower mantle minerals, especially dislocation slip and the development of crystallographic preferred orientation (CPO), we deformed mineral analogs neighborite (NaMgF3, iso-structural with bridgmanite) and halite (NaCl, iso-structural with ferropericlase) together in the deformation-DIA at the Advanced Photon Source up to 51% axial shortening. Development of CPO was recorded in situ with X-ray diffraction, and information on microstructural evolution was collected using X-ray microtomography. Results show that when present in as little as 15% volume, the weak phase (NaCl) controls the deformation. Compared to single phase NaMgF3 samples, samples with just 15% volume NaCl show a reduction of CPO in NaMgF3 and weakening of the aggregate. Microtomography shows both NaMgF3 and NaCl form highly interconnected networks of grains. Polycrystal plasticity simulations were carried out to gain insight into slip activity, CPO evolution, and strain and stress partitioning between phases for different synthetic two-phase microstructures. The results suggest that ferropericlase may control deformation in the lower mantle and reduce CPO in bridgmanite, which implies a less viscous lower mantle and helps to explain why the lower mantle is fairly isotropic.

The evolution of the elastic properties of organic-rich shale as a function of thermal maturity remains poorly constrained. This understanding is pivotal to the characterization of source rocks and unconventional reservoirs. To better constrain the evolution of the elastic properties and microstructure of organic- rich shale, we have studied the acoustic velocities and elastic anisotropy of samples from two microstructurally different organic-rich shales before and after pyrolysis-induced thermal maturation. To more physically imitate in situ thermal maturation, we performed the pyrolysis experiments on intact core plugs under applied reservoir-magnitude confining pressures. Iterative characterization of the elastic properties of a clay-rich, laminar Barnett Shale sample documents the development of subparallel to bedding cracks by an increase in velocity sensitivity to pressure perpendicular to the bedding. These cracks, however, are not visible through time-lapse scanning electron microscope imaging, indicating either submicrometer crack apertures or predominant development within the core of the sample. At elevated confining pressures, in the absence of pore pressure, these induced cracks close, at which point, the sample is acoustically indistinguishable from the prepyrolysis sample. Conversely, a micritic Green River sample does not exhibit the formation of aligned compliant features. Rather, the sample exhibits a largely directionally independent decrease in velocity as load-bearing, pore-filling kerogen is removed from the sample. Due to the weak alignment of minerals, there is comparatively little intrinsic anisotropy; further, due to the relatively directionally independent evolution of velocity, the evolution of the anisotropy as a function of thermal maturity is not indicative of aligned compliant features. Our results have indicated that horizons of greater thermal maturity may be acoustically detectable in situ through increases in the elastic anisotropy of laminar shales or decreases in the acoustic velocities of nonlaminar shales, micritic rocks, or siltstones.

Lattice distortions in crystals can be mapped at the micron scale using synchrotron X-ray Laue microdiffraction (μXRD). From lattice distortions the shape and orientation of the elastic strain tensor can be derived and interpreted in terms of residual stress. Here we apply the new method to vein quartz from the original boudinage locality at Bastogne, Belgium. A long-standing debate surrounds the kinematics of the Bastogne boudins. The μXRD measurements reveal a shortening residual elastic strain, perpendicular to the vein wall, corroborating the model that the Bastogne boudins formed by layer-parallel shortening and not by layer-parallel extension, as is in the geological community generally inferred by the process of boudinage.

The significance of shales for unconventional hydrocarbon reservoirs, nuclear waste repositories, and geologic carbon stor- age has opened new research frontiers in geophysics. Among many of its unique physical properties, elastic anisotropy had long been investigated by experimental and computational ap- proaches. Here, we calculated elastic properties of Cretaceous Muderong Shale from Australia with a self-consistent averaging method based on microstructural information. The volume frac- tion and crystallographic preferred orientation distributions of constituent minerals were based on synchrotron x-ray diffrac- tion experiments. Aspect ratios of minerals and pores, deter- mined from scanning electron microscopy, were introduced in the self-consistent averaging. Our analysis suggested that phyllosilicates (i.e., illite-mica, illite-smectite, kaolinite, and chlorite) were dominant with ~70 vol:%. The shape of clay platelets displayed an average aspect ratio of 0.05. These plate- lets were aligned parallel to the bedding plane with a high degree of preferred orientation. The estimated porosity at am- bient pressure was ~17 vol:% and was divided into equiaxial pores and flat pores with an average aspect ratio of 0.01. Our model gave results that compared satisfactorily with values derived from ultrasonic velocity measurements, confirming the validity and reliability of our approximations and averaging approach.

Although the crystal structure of the high-pressure SiO2 polymorph stishovite has been studied in detail, little is known about the development of crystallographic preferred orientation (CPO) during deformation in stishovite. Insight into CPO and associated deformation mechanics of stishovite would provide important information for understanding subduction of quartz-bearing crustal rocks into the mantle. To study CPO development, we converted a natural sample of flint to stishovite in a laser-heated diamond anvil cell and compressed the stishovite aggregate up to 38 GPa. We collected diffraction patterns in radial geometry to examine in situ development of crystallographic preferred orientation and find that (001) poles preferentially align with the compression direction. Viscoplastic self-consistent modeling suggests the most likely slip systems at high pressure and ambient temperature are pyramidal and basal slip.

Opal has long fascinated scientists. It is one of the few minerals with an amorphous structure, and yet, compared to silica glass, it is highly organized on the mesoscale. By means of inelastic neutron scattering (INS), we could document that in four samples of opal at low temperature an ice-like structure of water is present, with details depending on microstructural characteristics. While FTIR spectra for all samples are nearly identical and thus not very informative, INS shows clear differences, highlighting the significance of microstructures. Neutron diffraction at 100 K on one of the opal samples provides evidence for crystalline cubic ice.

We report on measurements of residual stress up to 300 MPa with a microfocused synchrotron X-ray beam in quartz fragments in a cataclasite from the damage zone of the San Andreas fault, California (USA). Samples were extracted from the San Andreas Fault Observatory at Depth drill core at a depth of 2.7 km. Stresses were derived from lattice distortions observed on Laue diffraction images. These stresses are distributed nonhomogeneously at the micron scale and are much higher than bulk-rock strengths of fault gouge, suggesting different processes at the microscopic and macroscopic scales. Our results indicate that residual lattice strain in quartz is a potential paleopiezometer to estimate stress in deformed rocks.

A regional analysis of the anisotropy of the magnetic susceptibility on low-grade metamorphic, chloritoid-bearing slates of the Paleozoic in Central Armorica (Brittany, France) revealed very high values for the degree of anisotropy (up to 1.43). Nonetheless, high-field torque magnetometry indicates that the magnetic fabric is dominantly paramagnetic. Chloritoid's intrinsic degree of anisotropy of 1.47±0.06, suggests that chloritoid-bearing slates can have a high degree of anisotropy without the need of invoking a significant contribution of strongly anisotropic ferromagnetic (s.l.) minerals. To validate this assumption we performed a texture analysis on a representative sample of the chloritoid-bearing slates using hard X-ray synchrotron diffraction. The preferred orientation patterns of both muscovite and chloritoid are extremely strong (~38.6m.r.d. for muscovite, 20.9m.r.d. for chloritoid) and display roughly axial symmetry about the minimum magnetic susceptibility axis, indeed suggesting that chloritoid may have a profound impact on the magnetic fabric of chloritoid-bearing rocks. However, modeling the anisotropy of magnetic susceptibility by averaging single crystal properties indicates that the CPO of chloritoid only partially explains the slate's anisotropy.

A sample of anorthosite from the granulite facies Morin Shear Zone (Quebec, Canada) was investigated for crystal preferred orientation and elastic anisotropy. Time-of-flight neutron diffraction data obtained with the HIPPO diffractometer at LANSCE were analyzed with the Rietveld method to obtain orientation distribution functions of the principal phases (plagioclase, clinopyroxene and orthopyroxene). Texture and microstructures are compatible with the plastic deformation of the aggregate under high-T conditions. All mineral phases depict a significant preferred orientation that could be related to the general top-to-the north shearing history of the Morin Shear Zone. Texture patterns suggest that (010)[001] in plagioclase and (110)[001] in clinopyroxene are likely dominant slip systems. Using preferred orientation data P- and S-waves velocities and elastic anisotropy were calculated and compared with previous studies to explore elastic properties of rocks with different pyroxene-plagioclase mixtures. P-wave velocity, S-wave splitting and anisotropy increase with clinopyroxene content. Seismic anisotropy is linked to the texture symmetry which can lead to large deviations between actual anisotropy and that measured along Cartesian XYZ sample directions (lineation/foliation reference frame). This is significant for the prediction and interpretation of seismic data, particularly for monoclinic or triclinic texture symmetries.

Serpentinites, deformed in mantle subduction zones, are thought to contribute significantly to seismic anisotropy of the upper mantle and have therefore been of great interest with studies on deformation, preferred orientation, and elastic properties. Here we present a combined study of a classical sample from Val Malenco, Italy, investigating the microstructure and texture with state-of-the art synchrotron X-ray and neutron diffraction methods and measuring ultrasonic velocities both with a multi-anvil apparatus and a novel instrument to measure 3-D velocities on spheres. Both, results from diffraction methods and velocity measurements are compared, discussing advantages and disadvantages. From spherical velocities, elastic tensor properties can be derived by inversion. Also from quantitative texture measurements, elastic properties can be modeled by self-consistent averaging. Good agreement between the velocity and microstructural models is observed.

The mineralogy and spatial distribution of nano-crystalline corrosion products that form in the steel/concrete interface were characterized using synchrotron X-ray micro-diffraction (μ-XRD). Two types of low-nickel high-chromium reinforcing steels embedded into mortar and exposed to NaCl solution were investigated. Corrosion in the samples was confirmed by electrochemical impedance spectroscopy (EIS). μ-XRD revealed that goethite (α-FeOOH) and akaganeite (β-FeOOH) are the main iron oxide-hydroxides formed during the chloride-induced corrosion of stainless steel in concrete. Goethite is formed closer to the surface of the steel due to the presence of chromium in the steel, while akaganeite is formed further away from the surface due to the presence of chloride ions. Detailed microstructural analysis is shown and discussed on one sample of each type of steel.

The magnetic structure of two natural samples of goethite (α-FeOOH) with varying crystallinity was analyzed at 15 and 300 K by neutron diffraction. The well crystallized sample has the Pb′nm color space group and remained antiferromagnetic up to 300 K, with spins aligned parallel to the c axis. The purely magnetic 100 peak, identifying this color space group, was clearly resolved. The nanocrystalline sample shows a phase transition to the paramagnetic state at a temperature below 300 K. This lowering of the Néel temperature may be explained by the interaction of magnetic clusters within particles. The nuclear structure, refined with the Rietveld and pair distribution function methods, is consistent with reports in the literature.

With in situ nanocompression experiments in a transmission electron microscope, we investigated plastic deformation in natural quartz crystals and observed both dislocation plasticity as well as mechanical twinning. Through this experimental method, we are able to provide direct evidence of Dauphiné twin nucleation and could measure the intrinsic twinning stress. The twinning phenomena appear to include a memory effect, where the same twin can reappear upon successive loading and unloading events. The data provide insight into this twin generation mechanism and can be used as a benchmark for the use of twins in quartz for paleopiezometry. Together, the observation of room-temperature dislocation plasticity and reversible twinning adds new insight into the extensive field of quartz plasticity and demonstrates the usefulness of small-scale testing techniques for mineral physics.

Plagioclase feldspars comprise a large portion of the Earth's crust and are very anisotropic, making accurate knowledge of their elastic properties important for understanding the crust's anisotropic seismic signature. However, except for albite, existing elastic constants for plagioclase feldspars are derived from measurements that cannot resolve the triclinic symmetry. We calculate elastic constants for plagioclase end-members albite NaAlSi3O8 and anorthite CaAl2Si2O8 and intermediate andesine/ labradorite NaCaAl3Si5O16 using density functional theory to compare with and improve existing elastic constants and to study trends in elasticity with changing composition. We obtain elastic constants similar to measured elastic constants and find that anisotropy decreases with anorthite content.

Elastic anisotropy of sheet-silicate-rich rocks such as shalesand slates strongly depends on the orientation distribution ofplatelet-shaped minerals, as well as shape and orientation ofpores. Bulk elastic anisotropy of the rock results in the anisotropywith respect to the propagation of elastic waves, and consequently,the fastest P-waves can travel with velocities exceedingthe slowest velocities by a factor of two or even greater. An importantfactor is the sheet-silicate's grain shapes.We approacheda model system of biotite platelets in an isotropic matrix withdifferent methods: A mean-field self-consistent method thatconsidered ellipsoidal particles in an effective anisotropic matrix,and a full-field method based on fast Fourier transformsthat considered the microstructure, the topology of the polycrystal,and local interactions. Both methods provided numericallyvery close results. Using these results, we predicted that the aggregatewith more oblate grain shape (thinner platelets) waselastically more anisotropic than the material with grains of lessoblate shape, but only for small volume fractions of orientedplatelets. For large fractions of platelets, the opposite was true.This switchover in the elastic anisotropy depended on texturestrength, platelet shape, and elastic properties of the isotropicmatrix.

The lowermost few hundreds of kilometres of the Earth's mantle are elastically anisotropic; seismic velocities vary with direction of propagation and polarization. Observations of strong seismic anisotropy correlate with regions where subducted slab material is expected. In this study, we evaluate the hypothesis that crystal preferred orientation (CPO) in a slab, as it impinges on the core-mantle boundary, is the cause of the observed anisotropy. Next, we determine if fast polarization directions seen by shear waves can be mapped to directions of geodynamic flow. This approach is similar to our previous study performed for a 2-D geodynamic model. In this study, we employ a 3-D geodynamic model with temperaturedependent viscosity and kinematic velocity boundary conditions defined at the surface of the Earth to create a broad downwelling slab. Tracers track the deformation that we assume to be accommodated by dislocation creep. We evaluate the models for the presence of perovskite or post-perovskite and for different main slip systems along which dislocation creep may occur in post-perovskite [(100),(010) and (001)]-resulting in four different mineralogical models of CPO. Combining the crystal pole orientations with single crystal elastic constants results in seismically distinguishable models of seismic anisotropy. The models are evaluated against published seismic observations by analysing different anisotropic components: the radial anisotropy, the splitting for (sub-)vertical phases (i.e. azimuthal anisotropy), and the splitting for subhorizontal phases. The patterns in radial anisotropy confirm our earlier results in 2-D. Observations of radial anisotropy and splitting in subhorizontal phases are mostly consistent with our models of post-perovskite with (010)-slip and (001)-slip. Our model of (001)-slip predicts stronger splitting than for (010)-slip for horizontally propagating phases in all directions. The strongest seismic anisotropy in this model occurs where the slab impinges on the core-mantle boundary. The azimuthal anisotropy pattern for (001)-slip shows fast axis directions at the edges of the slab (sub-)parallel to flow directions, suggesting horizontal flows may be mapped out in the lowermost mantle using seismic observations. © The Authors 2014. Published by Oxford University Press on behalf of The Royal Astronomical Society.

Foliated antigorite serpentinites are contributing to seismic anisotropy in subduction zones. However, uncertainty remains regarding the development of antigorite crystal preferred orientations (CPO). This study analyzes the CPOs of antigorite and olivine in variably serpentinized samples of antigorite serpentinite from three localities in Southwest Japan, using U-stage, EBSD, and synchrotron X-rays. In all samples (010) poles show a maximum parallel to the lineation, and (001) poles concentrate normal to the foliation with a partial girdle about the lineation. (100) poles are less distinct and scatter widely. The three measurement methods give similar results, though orientation distributions from X-ray analysis which averages over larger sample volumes are more regular and weaker than U-stage and EBSD which focuses on local well-crystallized grains. In olivine-bearing serpentinite, the olivine CPO does not appear to control the antigorite CPO, though there are some topotactic relationships. The antigorite CPO formed contemporaneously with serpentinization and shear deformation. Based on our analyses, in a subduction zone mantle wedge, the (010) pole of antigorite is parallel to the direction of the subduction, and (001) lattice planes are parallel to the interface of the subducting oceanic plate. By averaging single crystal elastic properties over orientation distributions wave velocities have been calculated. Fast P velocities are parallel to the subduction direction and slow velocities are perpendicular to the subducting plate with an anisotropy of 10-15%. © 2013 Elsevier B.V.

Synchrotron X-ray diffraction images are increasingly used to characterize not only structural and microstructural features of polycrystalline materials, but also crystal preferred orientation distributions. Diffraction data can be analyzed quantitatively and efficiently with the Rietveld method and here the detailed procedure is reported from the experiment to the calibration of the two-dimensional detector and full analysis of the sample. In particular, we emphasize the advantage of doing the calibration inside the Rietveld least-squares fitting instead of a preliminary graphical calibration. Then the procedure is described to quantify crystal preferred orientations with the Rietveld method implemented in software Materials Analysis Using Diffraction. The process is illustrated for a US nickel coin, a 75 at.% copper 25 at.% nickel alloy with face-centered cubic structure and a strong cube texture. © 2014 International Centre for Diffraction Data.

Synchrotron X-ray diffraction images are increasingly used to characterize crystallographic preferred orientation distributions (texture) of fine-grained polyphase materials. Diffraction images can be analyzed quantitatively with the Rietveld method as implemented in the software package Materials Analysis Using Diffraction. Here we describe the analysis procedure for diffraction images collected with high energy X-rays for a complex, multiphase shale, and for those collected in situ in diamond anvil cells at high pressure and anisotropic stress.

The microstructures, mineralogy and chemistry of representative samples collected from the cores of the San Andreas Fault drill hole (SAFOD) and the Taiwan Chelungpu-Fault Drilling project (TCDP) have been studied using optical microscopy, TEM, SEM, XRD and XRF analyses. SAFOD samples provide a transect across undeformed host rock, the fault damage zone and currently active deforming zones of the San Andreas Fault. TCDP samples are retrieved from the principal slip zone (PSZ) and from the surrounding damage zone of the Chelungpu Fault. Substantial differences exist in the clay mineralogy of SAFOD and TCDP fault gouge samples. Amorphous material has been observed in SAFOD as well as TCDP samples. In line with previous publications, we propose that melt, observed in TCDP black gouge samples, was produced by seismic slip (melt origin) whereas amorphous material in SAFOD samples was formed by comminution of grains (crush origin) rather than by melting. Dauphiné twins in quartz grains of SAFOD and TCDP samples may indicate high seismic stress. The differences in the crystallographic preferred orientation of calcite between SAFOD and TCDP samples are significant. Microstructures resulting from dissolution-precipitation processes were observed in both faults but are more frequently found in SAFOD samples than in TCDP fault rocks. As already described for many other fault zones clay-gouge fabrics are quite weak in SAFOD and TCDP samples. Clay-clast aggregates (CCAs), proposed to indicate frictional heating and thermal pressurization, occur in material taken from the PSZ of the Chelungpu Fault, as well as within and outside of the SAFOD deforming zones, indicating that these microstructures were formed over a wide range of slip rates. © 2014 Elsevier Ltd.

Anisotropy of elastic properties in clay-rich sedimentary rocks has been of long-standing interest. These rocks are cap rocks of oil and gas reservoirs, as well as seals for carbon sequestration. Elasticity of shales has been approached by direct velocity measurements and by models based on microstructures. Here we are revisiting the classical Kimmeridge shale studied by Hornby (1998) by first quantifying microstructural features such as phase volume fractions, grain shapes and grain orientations, and pore distributions with advanced analytical methods and then using this information in different models to explain bulk elastic properties. It is shown that by application of a self-consistent algorithm based on Eshelby's (1957) model of inclusions in a homogeneous medium, it is possible to explain most experimental elastic constants, though some discrepancies remain which may be due to the interpretation of experimental data. Using a differential effective medium approach, an almost perfect agreement with experimental stiffness coefficients can be obtained, though the physical basis of this method may be questionable. The influence of single crystal elastic properties, grain shapes, preferred orientation, and volume and shapes of pores on elastic properties of shale is explored. © 2013. American Geophysical Union. All Rights Reserved.

Understanding dynamics across phase transformations and the spatial distribution of minerals in the lower mantle is crucial for a comprehensive model of the evolution of the Earth's interior. Using the multigrain crystallography technique (MGC) with synchrotron x-rays at pressures of 30 GPa in a laser-heated diamond anvil cell to study the formation of bridgmanite [(Mg,Fe)SiO 3 ] and ferropericlase [(Mg,Fe)O], we report an interconnected network of a smaller grained ferropericlase, a configuration that has been implicated in slab stagnation and plume deflection in the upper part of the lower mantle. Furthermore, we isolated individual crystal orientations with grain-scale resolution, provide estimates on stress evolutions on the grain scale, and report {110} twinning in an iron-depleted bridgmanite, a mechanism that appears to aid stress relaxation during grain growth and likely contributes to the lack of any appreciable seismic anisotropy in the upper portion of the lower mantle., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

The study of orientation variant selection helps to reveal the mechanism and dynamic process of martensitic transformations driven by temperature or pressure/stress. This is challenging due to the multiple variants which may coexist. While effects of temperature and microstructure in many martensitic transformations have been studied in detail, effects of stress and pressure are much less understood. Here, an in situ variant selection study of Mn 2 O 3 across the cubic-to-orthorhombic martensitic transformation explores orientation variants at pressures up to 51.5 GPa and stresses up to 5.5 GPa, using diamond anvil cells in radial geometry with synchrotron X-ray diffraction. The diamonds not only exert pressure but also impose stress and cause plastic deformation and texture development. The crystal orientation changes were followed in situ and a {110} c 〈001〉 c // (100) o 〈010〉 o relationship was observed. Only the {110} c plane perpendicular to the stress direction was selected to become (100) o , resulting in a very strong texture of the orthorhombic phase. Contrary to most other martensitic transformations, this study reveals a clear and simple variant selection that is attributed to structural distortions under pressure and stress., Competing Interests: The authors declare no conflict of interest.

Crystallographic preferred orientation (CPO) of post-perovskite (Mg,Fe)SiO 3 (pPv) has been believed to be one potential source of the seismic anisotropic layer at the bottom of the lower mantle (D″ layer). However, the natural CPO of pPv remains ambiguous in the D″ layer. Here we have carried out the deformation experiments of pPv-(Mg 0.75 ,Fe 0.25 )SiO 3 using synchrotron radial X-ray diffraction in a membrane-driven laser-heated diamond anvil cell from 135 GPa and 2,500 K to 154 GPa and 3,000 K. Our results show that the intrinsic texture of pPv-(Mg 0.75 ,Fe 0.25 )SiO 3 should be (001) at realistic P-T conditions of the D″ layer, which can produce a shear wave splitting anisotropy of ∼3.7% with V SH >V SV . Considering the combined effect of both pPv and ferropericlase, we suggest that 50% or less of deformation is sufficient to explain the origin of the shear wave anisotropy observed seismically in the D″ layer beneath the circum-Pacific rim.

The pyroclastic aggregate concrete of Trajan's Markets (110 CE), now Museo Fori Imperiali in Rome, has absorbed energy from seismic ground shaking and long-term foundation settlement for nearly two millenia while remaining largely intact at the structural scale. The scientific basis of this exceptional service record is explored through computed tomography of fracture surfaces and synchroton X-ray microdiffraction analyses of a reproduction of the standardized hydrated lime-volcanic ash mortar that binds decimeter-sized tuff and brick aggregate in the conglomeratic concrete. The mortar reproduction gains fracture toughness over 180 d through progressive coalescence of calcium-aluminum-silicate-hydrate (C-A-S-H) cementing binder with Ca/(Si+Al) ≈ 0.8-0.9 and crystallization of strätlingite and siliceous hydrogarnet (katoite) at ≥ 90 d, after pozzolanic consumption of hydrated lime was complete. Platey strätlingite crystals toughen interfacial zones along scoria perimeters and impede macroscale propagation of crack segments. In the 1,900-y-old mortar, C-A-S-H has low Ca/(Si+Al) ≈ 0.45-0.75. Dense clusters of 2- to 30-µm strätlingite plates further reinforce interfacial zones, the weakest link of modern cement-based concrete, and the cementitious matrix. These crystals formed during long-term autogeneous reaction of dissolved calcite from lime and the alkali-rich scoriae groundmass, clay mineral (halloysite), and zeolite (phillipsite and chabazite) surface textures from the Pozzolane Rosse pyroclastic flow, erupted from the nearby Alban Hills volcano. The clast-supported conglomeratic fabric of the concrete presents further resistance to fracture propagation at the structural scale.

Transition metals Ti, Zr, and Hf have a hexagonal close-packed structure (α) at ambient conditions, but undergo phase transformations with increasing temperature and pressure. Of particular significance is the high-pressure hexagonal ω phase which is brittle compared to the α phase. There has been a long debate about transformation mechanisms and orientation relations between the two crystal structures. Here we present the first high pressure experiments with in situ synchrotron x-ray diffraction texture studies on polycrystalline aggregates. We follow crystal orientation changes in Zr, confirming the original suggestion by Silcock for an α→ω martensitic transition for Ti, with (0001)(α)||(1120)(ω), and a remarkable orientation memory when ω reverts back to α.

To extend the range of high-temperature, high-pressure studies within the diamond anvil cell, a Liermann-type diamond anvil cell with radial diffraction geometry (rDAC) was redesigned and developed for synchrotron X-ray diffraction experiments at beamline 12.2.2 of the Advanced Light Source. The rDAC, equipped with graphite heating arrays, allows simultaneous resistive and laser heating while the material is subjected to high pressure. The goals are both to extend the temperature range of external (resistive) heating and to produce environments with lower temperature gradients in a simultaneously resistive- and laser-heated rDAC. Three different geomaterials were used as pilot samples to calibrate and optimize conditions for combined resistive and laser heating. For example, in Run#1, FeO was loaded in a boron-mica gasket and compressed to 11 GPa then gradually resistively heated to 1007 K (1073 K at the diamond side). The laser heating was further applied to FeO to raise temperature to 2273 K. In Run#2, Fe-Ni alloy was compressed to 18 GPa and resistively heated to 1785 K (1973 K at the diamond side). The combined resistive and laser heating was successfully performed again on (Mg0.9Fe0.1)O in Run#3. In this instance, the sample was loaded in a boron-kapton gasket, compressed to 29 GPa, resistive-heated up to 1007 K (1073 K at the diamond side), and further simultaneously laser-heated to achieve a temperature in excess of 2273 K at the sample position. Diffraction patterns obtained from the experiments were deconvoluted using the Rietveld method and quantified for lattice preferred orientation of each material under extreme conditions and during phase transformation.

Synchrotron radiation X-ray tomographic microscopy (SRXTM) was used to characterize the three-dimensional microstructure, geometry and distribution of different phases in two shale samples obtained from the North Sea (sample N1) and the Upper Barnett Formation in Texas (sample B1). Shale is a challenging material because of its multiphase composition, small grain size, low but significant amount of porosity, as well as strong shape- and lattice-preferred orientation. The goals of this round-robin project were to (i) characterize microstructures and porosity on the micrometer scale, (ii) compare results measured at three synchrotron facilities, and (iii) identify optimal experimental conditions of high-resolution SRXTM for fine-grained materials. SRXTM data of these shales were acquired under similar conditions at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory, USA, the Advanced Photon Source (APS) of Argonne National Laboratory, USA, and the Swiss Light Source (SLS) of the Paul Scherrer Institut, Switzerland. The data reconstruction of all datasets was handled under the same procedures in order to compare the data quality and determine phase proportions and microstructures. With a 10× objective lens the spatial resolution is approximately 2 µm. The sharpness of phase boundaries in the reconstructed data collected from the APS and SLS was comparable and slightly more refined than in the data obtained from the ALS. Important internal features, such as pyrite (high-absorbing), and low-density features, including pores, fractures and organic matter or kerogen (low-absorbing), were adequately segmented on the same basis. The average volume fractions of low-density features for sample N1 and B1 were estimated at 6.3 (6)% and 4.5 (4)%, while those of pyrite were calculated to be 5.6 (6)% and 2.0 (3)%, respectively. The discrepancy of data quality and volume fractions were mainly due to different types of optical instruments and varying technical set-ups at the ALS, APS and SLS.

The size of nanocrystals provides a limitation on dislocation activity and associated stress-induced deformation. Dislocation-mediated plastic deformation is expected to become inactive below a critical particle size, which has been proposed to be between 10 and 30 nanometers according to computer simulations and transmission electron microscopy analysis. However, deformation experiments at high pressure on polycrystalline nickel suggest that dislocation activity is still operative in 3-nanometer crystals. Substantial texturing is observed at pressures above 3.0 gigapascals for 500-nanometer nickel and at greater than 11.0 gigapascals for 20-nanometer nickel. Surprisingly, texturing is also seen in 3-nanometer nickel when compressed above 18.5 gigapascals. The observations of pressure-promoted texturing indicate that under high external pressures, dislocation activity can be extended down to a few-nanometers-length scale.

Understanding deformation of mineral phases in the lowermost mantle is important for interpreting seismic anisotropy in Earth's interior. Recently, there has been considerable controversy regarding deformation-induced slip in MgSiO(3) post-perovskite. Here, we observe that (001) lattice planes are oriented at high angles to the compression direction immediately after transformation and before deformation. Upon compression from 148 gigapascals (GPa) to 185 GPa, this preferred orientation more than doubles in strength, implying slip on (001) lattice planes. This contrasts with a previous experiment that recorded preferred orientation likely generated during the phase transformation rather than deformation. If we use our results to model deformation and anisotropy development in the D'' region of the lower mantle, shear-wave splitting (characterized by fast horizontally polarized shear waves) is consistent with seismic observations.

Calcium silicate hydrate (CSH) is the major volume phase in the matrix of Portland cement concrete. Total x-ray scattering measurements with synchrotron x rays on synthetic CSH(I) shows nanocrystalline ordering with a particle diameter of 3.5(5) nm, similar to a size-broadened 1.1 nm tobermorite crystal structure. The CSH component in hydrated tricalcium silicate is found to be similar to CSH(I). Only a slight bend and additional disorder within the CaO sheets is required to explain its nanocrystalline structure.