Polycrystalline Grains Research Articles

A synergistic effect of the ion beam sputtered NiO x hole transport layer and MXene doping on inverted perovskite solar cells

The synergistic effect of high-quality NiO x hole transport layers (HTLs) deposited by ion beam sputtering on ITO substrates and the Ti3C2T x MXene doping of CH3NH3PbI3 (MAPI) perovskite layers is investigated in order to improve the power conversion efficiency (PCE) of p-i-n perovskite solar cells (PSCs). The 18 nm thick NiO x layers are pinhole-free and exhibit large-scale homogeneous surface morphology as revealed by the atomic force microscopy (AFM). The grazing-incidence x-ray diffraction showed a 0.75% expansion of the face-centered cubic lattice, suggesting an excess of oxygen as is typical for non-stoichiometric NiO x . The HTLs were used to fabricate the PSCs with MXene-doped MAPI layers. A PSC with undoped MAPI layer served as a control. The size of MAPI polycrystalline grains increased from 430 ± 80 nm to 620 ± 190 nm on the doping, as revealed by AFM. The 0.15 wt% MXene doping showed a 14.3% enhancement in PCE as compared to the PSC with undoped MAPI. The energy-resolved electrochemical impedance spectroscopy revealed one order of magnitude higher density of defect states in the band gap of MXene-doped MAPI layer, which eliminated beneficial effect of reduced total area of larger MAPI grain boundaries, decreasing short-circuit current. The PCE improvement is attributed to a decrease of the work function from −5.26 eV to −5.32 eV on the MXene doping, which increased open-circuit voltage and fill factor.

Thermal Preprocessing of Rapidly Solidified Al 6061 Feedstock for Tunable Cold Spray Additive Manufacturing

In this work, the influence of thermal pre-processing upon the microstructure and hardness of Al 6061 feedstock powder is considered through the lens of cold spray processing and additive manufacturing. Since solid-state cold spray processes refine and retain microstructural constituents following impact-driven and high-strain rate severe plastic deformation and bonding, thermal pre-processing enables application-driven tuning of the resultant consolidation achieved via microstructural and, therefore, mechanical manipulation of the feedstock prior to use. Microstructural analysis was achieved via X-ray diffraction, scanning electron microscopy, transmission electron microscopy, electron backscatter diffraction, energy dispersive spectroscopy, and differential thermal calorimetry. On the other hand, nanoindentation testing and analysis were relied upon to quantify pre-processing effects and microstructural evolution influences on the resultant hardness as a function of time at 540 °C. In the case of the as-atomized powder, β-Mg2Si-, Al-Fe-, and Mg-Si-type phases were observed along polycrystalline grain boundaries. Furthermore, after a 60 min hold time at 540 °C, Al-Fe-Si-Cr-Mn- and Mg-Si-type intermetallic phases were also observed along grain boundaries. Furthermore, the as-atomized hardness at 250 nm of indentation depth was 1.26 GPa and continuously decreased as a function of hold time until reaching 0.88 GPa after 240 min at 540 °C. Finally, contextualization of the observations with tuning cold spray additive manufacturing part performance via powder pre-processing is presented for through-process and application-minded design.

Entropy-driven microstructure evolution predicted with the steepest-entropy-ascent quantum thermodynamic framework

A Potts model and the Replica Exchange Wang–Landau algorithm is used to construct an energy landscape for a crystalline solid containing surfaces and grain boundaries. The energy landscape is used by an equation of motion from the steepest-entropy-ascent quantum thermodynamic (SEAQT) framework to explore the kinetics of three distinct kinds of microstructural evolution: polycrystalline sintering, precipitate coarsening, and grain growth. The steepest-entropy-ascent postulate predicts unique kinetic paths for these non-equilibrium processes without needing any detailed information about the underlying physical mechanisms of the processes. A method is also proposed for associating the kinetic path in state space to a set of smoothly evolving microstructural descriptors. The SEAQT-predicted kinetics agree well with available experimental kinetics for ZrO2 sintering, Al3Li precipitate coarsening, and grain growth in nanocrystalline Pd. The computational cost associated with calculating the energy landscape needed by the approach is comparable to a Monte Carlo simulation. However, the subsequent kinetic calculations from the SEAQT equation of motion are quite modest and save considerable computational resources by obviating the need for averaging multiple kinetic Monte Carlo runs.

Photoinduced large polaron transport and dynamics in organic–inorganic hybrid lead halide perovskite with terahertz probes

Organic-inorganic hybrid metal halide perovskites (MHPs) have attracted tremendous attention for optoelectronic applications. The long photocarrier lifetime and moderate carrier mobility have been proposed as results of the large polaron formation in MHPs. However, it is challenging to measure the effective mass and carrier scattering parameters of the photogenerated large polarons in the ultrafast carrier recombination dynamics. Here, we show, in a one-step spectroscopic method, that the optical-pump and terahertz-electromagnetic probe (OPTP) technique allows us to access the nature of interplay of photoexcited unbound charge carriers and optical phonons in polycrystalline CH3NH3PbI3 (MAPbI3) of about 10 μm grain size. Firstly, we demonstrate a direct spectral evidence of the large polarons in polycrystalline MAPbI3. Using the Drude–Smith–Lorentz model along with the Frӧhlich-type electron-phonon (e-ph) coupling, we determine the effective mass and scattering parameters of photogenerated polaronic carriers. We discover that the resulting moderate polaronic carrier mobility is mainly influenced by the enhanced carrier scattering, rather than the polaron mass enhancement. While, the formation of large polarons in MAPbI3 polycrystalline grains results in a long charge carrier lifetime at room temperature. Our results provide crucial information about the photo-physics of MAPbI3 and are indispensable for optoelectronic device development with better performance.

Chemical vapor deposition of sp2-boron nitride on mechanically polished pyrolytic boron nitride substrates

Nanocrystalline sp2-boron nitride (BN) thin films have been grown for 2 and 4.5 h on mechanically polished polycrystalline pyrolytic boron nitride substrates at 1060 °C via chemical vapor deposition using diborane (B2H6) and ammonia (NH3) as the B- and N sources, respectively. The use of an N/B gas phase ratio of 200 resulted in sp2-BN thin films having a stoichiometric surface chemistry, as determined by x-ray photoelectron spectroscopy. Cross-sectional transmission electron microscopy revealed the initial growth of ∼4 nm thick partially ordered [0001] sp2-BN layers regardless of the crystallographic orientation of the sets of layers in the substrate. A transition zone then formed within the deposited films that contained randomly oriented polycrystalline grains and that culminated in the formation of protrusions. Atomic force microscopy verified an increase in roughening of the surfaces of the films with an increase in growth time and the associated thickness.

Nanocrystalline Yttria-Stabilized Zirconia Ceramics for Cranial Window Applications.

Transparent yttria-stabilized zirconia (YSZ) ceramics are promising for cranial window applications because of their good mechanical and optical properties as well as biocompatibility. YSZ discs with different yttria concentrations were either processed via current-activated pressure-assisted densification (CAPAD) using commercial nanoparticles or densified via spark plasma sintering (SPS) using pyrolysis-synthesized nanoparticles in-house. This study provided critical results to screen composition, processing, microstructure, and cytocompatibility of transparent YSZ discs for cranial window applications. CAPAD-processed YSZ discs with 6 or 8 mol % yttria (6YSZ and 8YSZ) and SPS-densified YSZ discs with 4 mol % yttria (4YSZ_P) showed 200-350 nm polycrystalline grains containing 20-30 nm crystallite domains. SPS-densified YSZ discs with 8 mol % yttria (8YSZ_P) showed larger polycrystalline grains of 819 ± 155 nm with 29 ± 5 nm crystallite domains. CAPAD-processed YSZ discs with 3 mol % yttria (3YSZ) showed 39 ± 9 nm grains. Bone-marrow-derived stem cells (BMSCs) on the polished YSZ discs showed statistically higher spreading areas than those on the unpolished YSZ discs of the same compositions. Generally, polished 8YSZ, 4YSZ_P, and 8YSZ_P discs and unpolished 8YSZ_R, 4YSZ_PR, and 8YSZ_PR discs had lower average cell adhesion densities than other YSZ discs under direct contact conditions. Under indirect contact conditions, all the YSZ disc groups showed similar average cell adhesion densities to the Cell-only control. The groups of polished 4YSZ_P and 8YSZ_P discs, unpolished 4YSZ_PR and 8YSZ_PR discs, and particle control of 8YSZ_Pnp showed higher Y3+ ion concentrations than other groups. No mineral deposition was detected on the polished YSZ discs after cell culture. Considering multiple factors such as cytocompatibility, cell adhesion density, Y3+ ion release, mineral deposition, and optical transparency collectively, 8YSZ may be the best candidate for the cranial window applications. Further studies are needed to evaluate the long-term transparency and biocompatibility of YSZ discs.

Mechanical Performance and Deformation Behavior of CoCrNi Medium-Entropy Alloy at the Atomic Scale

CoCrNi medium-entropy alloy has superior cryogenic properties with simultaneous growth of strength and plasticity at low temperatures. In order to observe the microstructure and deformation behavior of the alloy at the atomic scale, its mechanical properties and deformation mechanism at different temperatures and strain rates were investigated using molecular dynamics. It is indicated that the alloy’s strength was enhanced at low temperatures and high strain rates due to the production of high dislocation density. The introduction of grain boundaries significantly decreased the dislocation density during the alloy’s deformation and correspondingly reduced the crystal strength. However, the introduction of twin boundaries in polycrystalline grains obviously enhanced the strength of the polycrystal, especially at the twin boundary spacing of 3.08 nm. The strength’s enhancement was attributed to the increasing dislocation density produced by the interaction between twin boundaries and dislocations during deformation.

The Role of Grain Boundaries in the Corrosion Process of Fe Surface: Insights from ReaxFF Molecular Dynamic Simulations

Intergranular corrosion is the most common corrosion phenomenon in Fe-based alloys. To better understand the mechanism of intergranular corrosion, the influence of grain boundaries on Fe-H2O interfacial corrosion was studied using molecular dynamics simulation based on a new Fe-H2O reaction force field potential. It is found that the corrosion rate at the polycrystalline grain boundary is significantly faster than that of twin crystals and single crystals. By the analysis of stress, it can be found that the stress at the polycrystalline grain boundary and the sigma5 twin grain boundary decreases sharply during the corrosion process. We believe that the extreme stress released at the grain boundary will promote the dissolution of Fe atoms. The formation of vacancies on the Fe matrix surface will accelerate the diffusion of oxygen atoms. This leads to the occurrence of intergranular corrosion.

Crystallographic orientation mapping of lizardite serpentinite by Raman spectroscopy

Abstract. The serpentine mineral lizardite displays strong Raman anisotropy in the OH-stretching region, resulting in significant wavenumber shifts (up to ca. 14.5 cm−1) that depend on the orientation of the impinging excitation laser relative to the crystallographic axes. We quantified the relationship between crystallographic orientation and Raman wavenumber using well-characterised samples of Monte Fico lizardite by applying Raman spectroscopy and electron backscatter diffraction (EBSD) mapping on thin sections of polycrystalline samples and grain mounts of selected single crystals, as well as by a spindle stage Raman study of an oriented cylinder drilled from a single crystal. We demonstrate that the main band in the OH-stretching region undergoes a systematic shift that depends on the inclination of the c-axis of the lizardite crystal. The data are used to derive an empirical relationship between the position of this main band and the c-axis inclination of a measured lizardite crystal: y=14.5cos 4 (0.013x+0.02)+(3670±1), where y is the inclination of the c-axis with respect to the normal vector (in degrees), and x is the main band position (wavenumber in cm −1) in the OH-stretching region. This new method provides a simple and cost-effective technique for measuring and quantifying the crystallographic orientation of lizardite-bearing serpentinite fault rocks, which can be difficult to achieve using EBSD alone. In addition to the samples used to determine the above empirical relationship, we demonstrate the applicability of the technique by mapping the orientations of lizardite in a more complex sample of deformed serpentinite from Elba Island, Italy.

Manipulation of the In Situ Nitrogen‐Vacancy Doping Efficiency in CVD‐Grown Diamond

Herein, the in situ generation of nitrogen‐vacancy (NV) centers in diamond during chemical vapor deposition (CVD) is investigated depending on the electric‐field strength at the sample position. The alteration of the electric‐field strength is induced by changing the resonance conditions within the resonator cavity while keeping the growth input variables constant. The electric‐field strength distribution is obtained by simulation results. During the growth experiments, optical‐emission spectroscopy data is collected, which shows the impact of the electric‐field strength on the radical concentrations within the plasma and the gas temperature. Through the reduction of the electric‐field strength, the synthesis of thick, high‐quality, nitrogen‐doped diamond without the formation of a polycrystalline rim around the sample edges and the twinning‐induced growth of polycrystalline grains was accomplished. Therefore, a reduced internal and more homogeneous stress distribution is achieved. Furthermore, significant influences on the in situ NV doping are discovered. In addition to a considerable gain of the in situ NV generation, also a major enhancement of the in situ incorporation efficiency of NV centers in comparison to centers up to almost 3% is observed. Depending on the application, this makes posttreatment processes for additional NV generation dispensable.

Disentangling Magnetic and Grain Contrast in Polycrystalline FeGe Thin Films Using Four-Dimensional Lorentz Scanning Transmission Electron Microscopy

The study of nanoscale chiral magnetic order in polycrystalline materials with a strong Dzyaloshinskii-Moriya interaction is interesting for the observation of magnetic phenomena at grain boundaries and interfaces. This is especially true for polycrystalline materials, which can be grown using scalable techniques, the scalability of which is promising for future device applications. One such material is sputter-deposited B20 $\mathrm{Fe}\mathrm{Ge}$ on $\mathrm{Si}$, which is actively investigated as the basis for low-power high-density magnetic memory technology in a scalable material platform. Although conventional Lorentz electron microscopy provides the requisite spatial resolution to probe chiral magnetic textures in single-crystal $\mathrm{Fe}\mathrm{Ge}$, probing the magnetism of sputtered B20 $\mathrm{Fe}\mathrm{Ge}$ is more challenging because the submicron crystal grains add confounding contrast. This is a more general problem for polycrystalline magnetic devices, where scattering from grain boundaries tends to hide comparably weaker signals from magnetism. We address the challenge of disentangling magnetic and grain contrast by applying four-dimensional Lorentz scanning transmission electron microscopy using an electron-microscope pixel-array detector. Supported by analytical and numerical models, we find that the most important parameter for imaging magnetic materials with polycrystalline grains is the ability for the detector to sustain large electron doses, where having a high-dynamic-range detector becomes extremely important. Despite the small grain size in sputtered B20 $\mathrm{Fe}\mathrm{Ge}$ on $\mathrm{Si}$, using this approach, we are still able to observe helicity switching of skyrmions and magnetic helices across two adjacent grains, as they thread through neighboring grains. We reproduce this effect using micromagnetic simulations by assuming that the grains have distinct orientation and magnetic chirality and find that magnetic helicity couples to crystal chirality. Our methodology for imaging magnetic textures is applicable to other thin-film magnets used for spintronics and memory applications, where an understanding of how magnetic order is accommodated in polycrystalline materials is important.

Holocene fluvial depositional regimes of the Huab River, Skeleton Coast, Namibia

AbstractDryland fluvial systems respond to hydroclimate changes on Quaternary timescales, yet deciphering the palaeoenvironmental histories they preserve is often complex. Whilst hydrological signals are preserved in sediment stores as variations in sediment amount, character, and composition, studies in dryland settings such as Namibia that link sedimentological and compositional changes to palaeoflow are limited. Focusing on the Huab River, Skeleton Coast, this paper presents the first integrated study of textural, compositional, and stratigraphic features from a Namibian fluvial archive. Petrographic and heavy mineral assemblages from Raman laser spectroscopy are combined with lithostratigraphic and particle size analysis. Together with a chronology established through 42 optically stimulated luminescence ages, we reconstruct provenance, changes in river style, and fluvial response to climate.The Huab lithostratigraphic record details periods of flashy ephemeral flow interbedded with flow within well‐defined channels. Compositional assemblages indicate that humid conditions during the early to mid‐Holocene resulted in activation of sediment stores across the catchment. Episodic discharge within an ephemeral river from 12 to 9 ka was followed by a more sustained river flow in a channelized system from 7 to 5 ka. During the late Holocene, better hydraulic sorting, increased mechanical breakdown of polycrystalline grains, and flash flood lithofacies suggest that flow occurred within a more arid climate. This fine‐scaled analysis of an ephemeral fluvial system indicates the utility of assessing compositional changes to distinguish between depositional regimes. This is an important approach for reconstructing fluvial response to climate and for obtaining palaeoenvironmental records from complex sedimentary archives in dryland river settings.

Theoretical basis for phase field modeling of polycrystalline grain growth using a spherical-Gaussian-based 5-D computational approach

Using a previously developed phase field modeling method, where interface energies are described by spherical gaussians that allow the modeling of complex anisotropies, a new phase field model was developed to model 5-D anisotropy in polycrystalline grain growth. We present the use of quaternions, assigned to individual grains as orientations and misorientations for grain boundaries, as a means of simulating the ongoing mesoscale changes during anisotropic polycrystalline grain growth. The full 5-D landscape is scanned in MATLAB, and the grain boundary (GB) energy of each grain boundary is calculated from the continuous function developed by Bulatov et al. MATLAB is then used to find all local minima in the GB energy which are stored for use in the phase field model. The methodology of including these minima in the phase field model involves using 2-D gaussian switches, which match the misorientation between grains with misorientations for the GB energy minima. Within a threshold range of the minima misorientation, the switch activates a spherical Gaussian to set the GB energy to the desired value creating in combination a full 5D GB energy space. This creates a GB energy that morphs in real time and space as the GB plane or grain orientations change. Implementation methods of the model are outlined for the Multiphysics Object Oriented Simulation Environment (MOOSE), where reduced order parameters still retain individual grain identification useful for individually assigned quaternions.

Flow-modulated deposition of sp2-boron nitride using diborane and ammonia on chemomechanically polished (0001) 4H-SiC substrates

Nanocrystalline sp2-BN thin films have been grown on (0001) 4H-SiC substrates at 1030 °C via continuous flow and discontinuous flow-modulated chemical vapor deposition techniques using diborane (B2H6) and ammonia (NH3) as the B and N sources, respectively. The latter technique enabled observations of both the effect of hydrogen purge steps between precursor injections and the length of injection times for B2H6 on the stoichiometry and microstructure of the films. Stoichiometric BN was achieved in all films grown continuously within the N/B gas phase ratio range of 20–200; this was not observed for the discontinuously grown films unless both the B2H6 flow rate and the injection time were minimized. Cross-sectional transmission electron microscopy of films grown both continuously and discontinuously at N/B = 200 and using short B2H6 injection times relative to that of NH3 for the latter process route revealed the initial growth of ∼4 nm thick partially ordered sp2-BN layers. A transition zone then formed containing randomly oriented polycrystalline grains. Excess B incorporated into the discontinuously grown films during long B2H6 injection times resulted in single layer mixtures of amorphous and sp2-BN without any observed ordering.

A molecular dynamics study on the cyclic plastic deformation mechanism of Al–Mg alloys

The deformation mechanism and hardening law of single-crystal and polycrystalline Al–Mg alloy materials during the cyclic loading deformation process of different paths are studied herein according to the principle of molecular dynamics. An analysis of the single-crystal simulation results indicates that the Bauschinger effect decreases with the increase of strain. The cyclic loading leads to dislocation locking and other obstacles, which, in turn, lead to hardening of the material. After that, the force generated by the accumulated strain moves the dislocation obstacle and causes the material to soften. Based on the Voronoi polygon method, polycrystalline models with different grain sizes are established, and the plastic deformation mechanism of these models under cyclic loading is analyzed. The results show that the critical grain size of the direct and inverse Hall–Petch relationship exists in the Al–Mg alloy. When the grain size is below this value, grain rotation and grain boundary sliding become the main deformation mechanisms of the small polycrystalline grains. Dislocation blockage remains an important factor in the hardening of polycrystalline materials, while the aggregation of solute atoms at the grain boundaries is another contributing factor.

Non-melt selective enhancement of crystalline structure in molybdenum thin films using femtosecond laser pulses

It is challenging to crystalize a thin film of higher melting temperature when deposited on a substrate with comparatively lower melting point. Trading such disparities in thermal properties between a thin film and its substrate can significantly impede material processing. We report a novel solid-state crystallization process for annealing of high melting point molybdenum thin films. A systematic investigation of laser induced annealing from single pulse to high pulse overlapping is reported upon scanning at fluences lower than the threshold required for the damage/ablation of molybdenum thin films. The approach allows better control of the grain size by changing the applied laser fluence. Atomic force microscopy surface morphology and x-ray diffraction (XRD) analysis reveal significant improvements in the average polycrystalline grain size after laser annealing; the sheet resistance was reduced by 19% of the initial value measured by a Four-point probe system. XRD confirms the enlargement of the single crystal grain size. No melting was evident, although a change in the close packing, shape and size of nanoscale polycrystalline grains is observed. Ultrashort laser induced crystallinity greatly enhances the electrical properties; Hall measurements reinforced that the overall carrier concentration increases after scanning at different laser fluences. The proposed method, based on the aggregation and subsequent growth of polycrystalline and single crystal-grains, leading to enhanced crystallization, has potential to be applicable in thin film processing industry for their wide applications.

Efficient Fitting of 3D Tessellations to Curved Polycrystalline Grain Boundaries

The curvature of grain boundaries in polycrystalline materials is an important characteristic, since it plays a key role in phenomena like grain growth. However, most traditional tessellation models that are used for modeling the microstructure morphology of these materials, e.g., Voronoi or Laguerre tessellations, have flat faces and thus fail to incorporate the curvature of the latter. For this reason, we consider generalizations of Laguerre tessellations—variations of so-called generalized balanced power diagrams (GBPDs)—that exhibit non-convex cells. With as many as ten parameters for each cell, it is computationally demanding to fit GBPDs to three-dimensional image data containing hundreds of grains. We therefore propose a modification of the traditional definition of GBDPs that allows gradient-based optimization methods to be employed. The resulting reduction in runtime makes it feasible to find approximations to real experimental datasets. We demonstrate this on a three-dimensional x-ray diffraction (3DXRD) mapping of an AlCu alloy, but we also evaluate the modeling errors for simulated data. Furthermore, we investigate the effect of noisy image data and whether the smoothing of image data prior to the fitting step is advantageous.

Pulsed laser deposited and sulfurized Cu2ZnSnS4 thin film for efficient solar cell

Kesterite quaternary material Cu2ZnSnS4, (CZTS)-based thin-film solar cells have attracted intensive attention owing to their earth-abundant nature, stable thermodynamic structure, and large potential for high power conversion efficiency (PCE) defined by their suitable optoelectronic properties. As a widely used thin film preparation method, pulsed laser deposition (PLD) has not been fully studied in CZTS thin-film solar cell. Herein, a promising route based on PLD from a quaternary target and post-sulphuration for CZTS thin film was achieved. Through systematical investigation and optimization of substrate temperature, laser pulse energy, and sulfurization temperature, the CZTS thin films showed single kesterite structure, high (112) orientation, and dense polycrystalline grains with controlled composition. The CZTS thin-film solar cell exhibited a record PCE of 6.62%, the highest reported value when using pulsed laser deposited and sulfurized process, due to its lower series resistance, reduced grain boundary effects, superior interface quality, and a suitable depletion width. This research offers a facile and robust preparation method for CZTS films with enhanced photovoltaic properties and increased efficiency.

Microstructure of IN738LC Fabricated Using Laser Powder Bed Fusion Additive Manufacturing

Abstract Nickel-base superalloys are extensively used in the production of gas turbine hot-section components as they offer exceptional creep strength and superior fatigue resistance at high temperatures. Such improved properties are due to the presence of precipitate-strengthening phases such as Ni3Ti or Ni3Al (γ′ phases) in the normally face-centered cubic (FCC) structure of the solidified nickel. Although this second phase is the main reason for the improvements in properties, the presence of such phases also results in increased processing difficulties as these alloys are prone to crack formation. In this work, specimens of IN738LC are fabricated on a Coherent Creator laser powder bed fusion (L-PBF) additive manufacturing (AM) equipment. Optical microscopy (OM), scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and X-ray diffraction (XRD) are carried out to characterize the deposit region. Metallurgical continuity is achieved in the entire deposit region and the specimens do not show any warpage. However, the specimens show voids (e.g., pores and cracks) in the deposit region. The results show that the percentage void area decreases along the build height direction. The deposited IN738LC shows polycrystalline grains in the entire deposit region as confirmed by XRD and EBSD. The grain size also shows variations along the build direction. In summary, the results open opportunities for academic researchers and small-scale businesses in fabricating high-γ′ nickel-base superalloys on a desktop laser powder bed fusion AM equipment.

Petrogenesis of Kaapvaal lamproites (aka orangeites) constrained by the composition of olivine and similarities with kimberlites and other diamondiferous lamproites

Kaapvaal lamproites, also known as orangeites, are H2O-rich, diamondiferous, highly micaceous, ultrapotassic rocks. Olivines in kimberlites have been shown to be extremely useful in tracking melt evolution, highlighting the importance of the chemical effects of SCLM assimilation on asthenosphere-derived melts. Kaapvaal lamproites are derived from melting metasomatised SCLM and may be expected to form an endmember to the asthenosphere melt-SCLM trend defined by kimberlites. In this contribution, we use olivine composition in Kaapvaal lamproites to further understand melt evolution in the SCLM and assess the similarity between Kaapvaal lamproite, other diamondiferous lamproites, and kimberlite petrogenesis in cratonic regions.We present olivine composition for representative on- and off-craton Kaapvaal lamproites from Finsch and Melton Wold, respectively. Olivines from these Kaapvaal lamproites are characterized by distinct core and rim zones, regardless of the size of individual grains. Polycrystalline grains are abundant at Finsch but relatively rare at Melton Wold. The olivine cores from both occurrences are predominantly Mg-rich (Fo>89) whereas Fe-rich cores (Fo<89) are rare. Mg-rich cores are interpreted to be derived from the disaggregation of mantle peridotites, including sheared peridotites, whereas Fe-rich cores are derived from olivines of the Cr-poor megacryst suite. The average Fo and NiO concentrations of the Melton Wold cores are lower than Finsch cores, likely related to less refractory off-craton mantle. The olivine rims at Finsch and Melton Wold are characterized by reverse zoning with ranges of Fo89-92 and Fo90-91, respectively. The rims are interpreted to represent crystallisation related to a complex interplay between increasing oxidation, assimilation of orthopyroxene, and increasing alkali content of the melt during evolution.The average core and rim compositions of Finsch and Melton Wold, in conjunction with data from diamondiferous lamproites of other cratonic regions, define a broad positive correlation. Kaapvaal lamproites have Mg-rich core and rim compositions, similar to that of Lac de Gras kimberlites, and interpreted to reflect sampling and equilibration of low volume Kaapvaal lamproite melt with refractory mantle. In contrast to Lac de Gras kimberlites, Kaapvaal lamproites have high abundances of groundmass phlogopite that reflect metasomatic material in the SCLM source, likely present as veins within refractory peridotite. This suggests that increasing proportions of melt-metasomatised SCLM interactions are not always linked with increasing Fe content of melts.We show that the petrogenesis of Kaapvaal lamproites is similar to that of kimberlites and lamproites from other cratonic regions, however, the high abundance of phlogopite and Fo-rich olivine rims suggest a distinct metasomatic lithology in the source and that olivine composition; i.e., a proxy for melt composition, may be strongly controlled by melt volume during melt-SCLM interactions.