Solid-State Transformation of an Additive Manufactured Inconel 625 Alloy at 700 °C

Inconel 625, a nickel-based superalloy, has drawn much attention in the emerging field of additive manufacturing (AM) because of its excellent weldability and resistance to hot cracking. The extreme processing condition of AM often introduces enormous residual stress (hundreds of MPa to GPa) in the as-fabricated parts, which requires stress-relief heat treatment to remove or reduce the internal stresses. Typical residual stress heat treatment for AM Inconel 625, conducted at 800 °C or 870 °C, introduces a substantial precipitation of the δ phase, a deleterious intermetallic phase. In this work, we used synchrotron-based in situ scattering and diffraction methods and ex situ electron microscopy to investigate the solid-state transformation of an AM Inconel 625 at 700 °C. Our results show that while the δ phase still precipitates from the matrix at this temperature, its precipitation rate and size at a given time are both smaller when compared with their counterparts during typical heat treatment temperatures of 800 °C and 870 °C. A comparison with thermodynamic modeling predictions elucidates these experimental findings. Our work provides the rigorous microstructural kinetics data required to explore the feasibility of a promising lower-temperature stress-relief heat treatment for AM Inconel 625. The combined methodology is readily extendable to investigate the solid-state transformation of other AM alloys.

Formation mechanisms of ringwoodite: clues from the Martian meteorite Northwest Africa 8705

Ringwoodite and wadsleyite are the high-pressure polymorphs of olivine, which are common in shocked meteorites. They are the major constituent minerals in the terrestrial mantle. NWA 8705, an olivine-phyric shergottite, was heavily shocked, producing shock-induced melt veins and pockets associated with four occurrences of ringwoodite: (1) the lamellae intergrown with the host olivine adjacent to a shock-induced melt pocket; (2) polycrystalline assemblages preserving the shapes and compositions of the pre-existing olivine within a shock-induced melt vein (60 μm in width); (3) the rod-like grains coexisting with wadsleyite and clinopyroxene within a shock-induced melt vein; (4) the microlite clusters embedded in silicate glass within a very thin shock-induced melt vein (20 μm in width). The first two occurrences of ringwoodite likely formed via solid-state transformation from olivine, supported by their morphological features and homogeneous compositions (Mg# 64–62) similar to the host olivine (Mg# 66–64). The third occurrence of ringwoodite might fractionally crystallize from the shock-induced melt, based on its heterogeneous and more FeO-enriched compositions (Mg# 76–51) than those of the coexisting wadsleyite (Mg# 77–67) and the host olivine (Mg# 66–64) of this meteorite. The coexistence of ringwoodite, wadsleyite, and clinopyroxene suggests a post-shock pressure of 14–16 GPa and a temperature of 1650–1750 °C. The fourth occurrence of ringwoodite with compositional variation (Mg# 72–58) likely crystallized from melt at 16–18 GPa and 1750–1850 °C. The presence of the four occurrences of ringwoodite was probably due to their very fast cooling rates in and/or adjacent to the thin shock-induced melt veins and small pockets. In addition, the higher Fa-contents of the host olivine (Fa35–39) in NWA 8705 than those in ordinary chondrites (Fa16–32) makes the olivine–ringwoodite transformation prolong to a lower pressure.

Kaolinite-to-Chlorite Conversion from Si,Al-Rich Fluid-Origin Veins/Fe-Rich Carboniferous Shale Interaction

The kaolinite-to-chlorite conversion is one of the chloritization processes that occurs in low temperature diagenetic and hydrothermal systems. The mechanism of this mineralogical transformation is still under discussion, since direct transformation, conversion via berthierine as intermediate phase or direct formation of berthierine/chlorite mix, either by dissolution-crystallization or by solid state transformation (or a combination of both), are all hypotheses put forward. In this context, each description of a kaolinite-to-chlorite conversion occurrence becomes an opportunity to shed new light and to renew this debate. Studying Carboniferous shale–crosscut by large quartz-kaolinite veins–from the mining basin of the North of France, we report therefore an uncommon kaolinite-Fe-rich chlorite assemblage. This assemblage appears as a chlorite fringe 20 µm wide along the interfaces between the shale and the quartz-kaolinite veins. All petrographical, mineralogical and chemical data suggest that the Fe-chlorite results from the interaction between the shale, providing the Fe,Mg supply, and the Si,Al-rich veins, leading to the chloritization of the kaolinite at a small scale via at least one dissolution-recrystallisation step. High-resolution observations highlight that neoformed Fe-rich chlorite contains some 7Å isochemical layers, as relict of berthierine. Therefore, we advance that the conversion takes place either through the precipitation of berthierine following by a second step involving solid state berthierine-chlorite conversion, or through the direct precipitation of a chlorite-rich/berthierine-poor mix driven by the Fe/(Fe + Mg) ratio, at low temperature and in reducing conditions. The comparison of our data with the recent literature allows to prefer the second hypothesis.

Jadeite and its relatives: fake news or a real tool to constrain shock conditions?

Jadeite is frequently reported in shocked meteorites, displaying a variety of textures and grain sizes that suggest formation by either solid-state transformation or by crystallization from a melt. Sometimes, jadeite has been identified solely on the basis of Raman spectra. Here we argue that additional characterization is needed to confidently identify jadeite and distinguish it from related species. Based on chemical and spectral analysis of three new occurrences, complemented by first-principles calculations, we show that related pyroxenes in the chemical space (Na)M2(Al)M1(Si2)TO6 – (Ca)M2(Al)M1(AlSi)TO6 – (□)M2(Si)M1(Si2)TO6 with up to 2.25 atoms Si per formula unit have spectral features similar to jadeite. However, their distinct stability fields and synthesis pathways, considered together with textural constraints, have specific implications for precursor phases and estimates of impactor size, encounter velocity, and crater diameter. A reassessment of reported jadeite occurrences puts in a new light many previous conclusions about the shock histories preserved in particular meteorites.

Relationships Between Fat Crystal Characteristics and Emulsion Stability in Water in Oil Systems

Investigations were made into the stabilization of water in oil emulsions using crystalline particles of paraffin wax and fully hydrogenated canola and cottonseed oils. A model system was studied to develop a methodology of study and provide a benchmark for a subsequent study of a real-world system. The model system involved the use of light mineral oil, purified water, paraffin wax and glycerol monooleate emulsifier. The wax was crystallized prior to and following emulsification. Prepared emulsion samples were monitored for sedimentation and flocculation behaviour. Measurements of coalescence were obtained by pulsed field gradient NMR. Formation of the solid crystalline wax phase following emulsification resulted in emulsions more stable to flocculation and coalescence than samples containing the same amount of wax crystallized prior to emulsification. Analysis of emulsion samples with polarized light microscopy showed the wax crystals were associated with the water droplet interfaces rather than dispersed freely within the continuous oil phase. Another investigation employed similar experimental protocols but incorporated food-grade materials. Two different solid fats were used, chosen for their differing polymorphic (crystal habit) behaviour. Solid crystals of canola stearine (ß-tending) and cottonseed stearine (ß-tending) were compared in their abilities to stabilize emulsions at levels of addition between 0 and 2%. Each type of fat was incorporated into the emulsion in a pre-crystallized state, or while melted and crystallized following emulsification. Cottonseed stearine was found to be in the ß polymorph when quickly crystallized following emulsification from 45⁰ to 5⁰C over 6 minutes. Further calorimetric and X-ray diffraction investigations revealed this crystallization behaviour was a result of a solid-state transformation via an imperfectly formed ß̕ intermediate. With respect to the post-crystallized emulsions, where the polymorphism of the two fats were both in the ß-form, the canola stearine provided better stabilization against coalescence than the cottonseed stearine. This observation coincided with a stronger energy of interfacial attachment for crystallized canola than for cottonseed as calculated from measurements of contact angle and interfacial tension. With the pre-crystallized system, incorporation of cottonseed stearine resulted in reduced sedimentation and coalescence compared to samples containing pre-crystallized canola stearine. This difference was attributed to the presence of fine shards of ß̕-form crystals. The system that imparted the highest degree of overall stability incorporated the use of canola stearine srystallized following emulsification.

Relationships Between Fat Crystal Characteristics and Emulsion Stability in Water in Oil Systems

Investigations were made into the stabilization of water in oil emulsions using crystalline particles of paraffin wax and fully hydrogenated canola and cottonseed oils. A model system was studied to develop a methodology of study and provide a benchmark for a subsequent study of a real-world system. The model system involved the use of light mineral oil, purified water, paraffin wax and glycerol monooleate emulsifier. The wax was crystallized prior to and following emulsification. Prepared emulsion samples were monitored for sedimentation and flocculation behaviour. Measurements of coalescence were obtained by pulsed field gradient NMR. Formation of the solid crystalline wax phase following emulsification resulted in emulsions more stable to flocculation and coalescence than samples containing the same amount of wax crystallized prior to emulsification. Analysis of emulsion samples with polarized light microscopy showed the wax crystals were associated with the water droplet interfaces rather than dispersed freely within the continuous oil phase. Another investigation employed similar experimental protocols but incorporated food-grade materials. Two different solid fats were used, chosen for their differing polymorphic (crystal habit) behaviour. Solid crystals of canola stearine (ß-tending) and cottonseed stearine (ß-tending) were compared in their abilities to stabilize emulsions at levels of addition between 0 and 2%. Each type of fat was incorporated into the emulsion in a pre-crystallized state, or while melted and crystallized following emulsification. Cottonseed stearine was found to be in the ß polymorph when quickly crystallized following emulsification from 45⁰ to 5⁰C over 6 minutes. Further calorimetric and X-ray diffraction investigations revealed this crystallization behaviour was a result of a solid-state transformation via an imperfectly formed ß̕ intermediate. With respect to the post-crystallized emulsions, where the polymorphism of the two fats were both in the ß-form, the canola stearine provided better stabilization against coalescence than the cottonseed stearine. This observation coincided with a stronger energy of interfacial attachment for crystallized canola than for cottonseed as calculated from measurements of contact angle and interfacial tension. With the pre-crystallized system, incorporation of cottonseed stearine resulted in reduced sedimentation and coalescence compared to samples containing pre-crystallized canola stearine. This difference was attributed to the presence of fine shards of ß̕-form crystals. The system that imparted the highest degree of overall stability incorporated the use of canola stearine srystallized following emulsification.

Structure Homogeneity and Thermal Stability of Austempered Ductile Iron

Solid-state transformation during heat treatment is of great practical importance because it significantly affects the final structure, properties, and thermal stability of cast components. The present study highlights the issue of structure formation and its effect on the thermal stability of high-quality cast iron, namely, austempered ductile iron (ADI). In this study, experiments were carried out for castings with a 25-mm-walled thickness and under variable heat treatment conditions, i.e., austenitization and austempering within ranges of 850 °C to 925 °C and 250 °C to 380 °C, respectively. The X-ray diffraction (XRD) investigations were carried out within a range of − 260 °C to + 450 °C to study the structure parameters related to the XRD tests, which provided information related to the phase participation, lattice parameters, and stresses in the microstructure as well as with an expansion of the crystal lattice. The results also provide insight into the role of the structure and its homogeneity on the thermal stability of ADI cast iron. The present work also aims to develop strategies to suppress the formation of blocky-shaped austenite in the ADI structure to maintain a homogeneous microstructure and high thermal stability.

Experimental study of chlorite authigenesis and influence on porosity maintenance in sandstones

ABSTRACT Chlorite is recognized as a key mineral for preserving reservoir quality in deeply buried sandstones, as chlorite coatings inhibit the nucleation of quartz overgrowths. A limited understanding of the mechanisms and conditions under which these authigenic chlorite coatings form prevents the accurate forward modeling of diagenesis and limits reservoir quality models critical to a wide range of geoscience applications. We present experimental data that show how authigenic chlorite grain coatings preserve porosity in deeply buried sandstone reservoirs, using a series of hydrothermal reactor experiments to simulate quartz cementation and capture the evolving porosity. To simulate reservoir evolution, berthierine-bearing sandstone samples (Lower Jurassic Cook Formation, Oseberg Field, 30/6-17R, Norway) were exposed to a silica-supersaturated Na2CO3 (0.1 M) solution for 72 hours at temperatures of between 100 and 250 °C. Quantification of the temperature-dependent changes in the volume of authigenic chlorite, the thickness and coverage of the clay coatings, and the sample porosity shows increases in chlorite volume (from ∼ 2% to ∼ 14%). This occurs by the transformation, of patchy amorphous berthierine into grain-coating Fe-chlorite cements through a mixture of the solid-state transformation and dissolution–precipitation mechanisms, siderite replacement, and direct precipitation on clay-free surfaces. With increasing temperature, the chlorite coatings increase from ∼ 3.8 μm to ∼ 5.4 μm thick and expand their grain surface coverage from ∼ 28% to ∼ 50%. The face-to-edge and face-to-face foliaceous structure of the clay coatings produced are morphologically similar to those observed in deeply buried sandstones. Only above temperatures of 175 °C is porosity preserved as a consequence of inhibition of quartz overgrowths and the generation of secondary porosity. Our quantitative approach enhances our knowledge regarding the temperature and mineral precursor influence on chlorite-coating authigenesis and therefore provides key insight for chlorite grain coatings for reservoir potential in sedimentary sequences greater than 2.5 km.