Graphite Growth Research Articles

Effects of impurities on graphite shape during solidification of spheroidal graphite cast ions

Since the discovery that magnesium and cerium (and more generally rare earths) added at low level to cast iron melts lead to spherodized graphite, it is known that some other elements are detrimental even when present as traces. In all practicality, it has soon been recognized that adding rare earths to the melt helps counteracting the effect of these detrimental elements. Accordingly, only few works have been devoted to studying the effect of trace elements in melts without any rare earths. This is the first aim of the present work to review those studies as they contain the material to understand the mechanism for spheroidal graphite degeneracy.From this review, three types of degeneracy have been defined which show up when the critical level of any particular element is exceeded. These results are then discussed to show that all degeneracies certainly proceed in the same way. To substantiate this discussion, the growth of compacted graphite as obtained by low level treatment of cast iron melt with magnesium is also presented. Finally, a mechanism is suggested for describing the action of trace elements on spheroidal graphite degeneracy. This mechanism is partly substantiated by first-principles calculations which showed that all elements can strongly adsorb on the prismatic planes which are the planes on which carbon atoms add on during graphite growth.

Experimental Modeling of Silicate and Carbonate Sulfidation under Lithospheric Mantle P,T-Parameters

Interactions of mantle silicates with subducted carbonates, sulfides, and sulfur-rich fluids are experimentally simulated in the olivine-ankerite-sulfur and olivine-ankerite-pyrite systems using a multi-anvil high-pressure split-sphere apparatus at 6.3 GPa and range of 1050–1550 °C. Recrystallization of Fe,Ni-bearing olivine and ankerite in a sulfur melt was found to be accompanied by sulfidation of olivine and carbonate, involving partial extraction of metals, carbon, and oxygen into the melt, followed by the formation of pyrite (±pyrrhotite), diopside, and Fe-free carbonates. The main features of metasomatic alteration of Fe,Ni-olivine by a reduced sulfur fluid include: (i) a zonal structure of crystals (Fe-rich core, Mg-rich rim); (ii) inclusions of pyrite and pyrrhotite in olivine; (iii) certain Raman spectral characteristics of olivine. At T > 1350 °C, two immiscible melts, a predominantly sulfur melt with dissolved components (or a Fe–Ni–S–O melt) and a predominantly carbonate one, are generated. The redox interaction of these melts leads to the formation of metastable graphite (1350–1550 °C) and diamond growth (1550 °C). The studied olivine-ankerite-sulfur and olivine-ankerite-pyrite interactions may be considered as the basis for simulation of metasomatic processes accompanied by the formation of mantle sulfides during subduction of crustal material to the silicate mantle.

Enhanced thermal resistance of carbon/phenolic composites by addition of novel nano-g-C3N4

Effects of a novel carbon/phenolic (CF/PR) ablator filled with acidified graphitic carbon nitride (ag-C3N4) on ablative resistance were evaluated. Ablative properties of CF/PR composites were significantly enhanced by 69.23% with incorporating 0.2 wt% ag-C3N4, ascribing to the formation of the dense carbon layer over the fibers, increased graphitization degree and more pyrolysis gases. Molecular dynamics simulations of ag-C3N4 inside the matrix confirm the origins of improved ablation resistance arising from the fact that ag-C3N4 alters the breaking patterns and spatial distribution of the polymer fragments, and reduces the graphitic growth temperature by 400 K. And the decomposition of ag-C3N4 and phenolic at the fiber-matrix interface collides the fibers' surfaces to undermine the structural integrity, which induces the phase transformation from short-range to long-range order of the matrix carbon because of the templating effect (transverse) and the interlayer π-π stacking (longitudinal) of the fibers at extremely high temperature.

Study on Carbon Particle Inclusions during 4H-SiC Growth by Using Physical Vapor Transport System

A study on carbon particle inclusions during 4H-SiC bulk growth is presented. Special attentions were paid to design of graphite growth compartment, size of SiC source materials, and process of seed crystal handling. It was found that common carbon inclusions with size of 30μm or less were attributed to carbon particles from graphitized SiC source. Less common carbon inclusions with size of over 100μm were also found and were attributed to poor seed crystal mounting process. In order to reduce carbon inclusions, several experiments were designed by using a NAURA Advanced Physical Vapor Transport (PVT) System APS130G. A graphite plate separator was inserted into the growth compartment to prevent the carbon particles from transporting to the growth surface. SiC powder materials with larger diameters were selected to reduce source graphitization. Additional clean process was performed to remove carbon particle residuals on graphite parts during seed mounting. The results showed significant improvement of carbon inclusion problems in SiC ingots and thus high-quality SiC wafers were made successfully.

An effect of reduced S-rich fluids on diamond formation under mantle-slab interaction

Experimental study, dedicated to understanding the effect of S-rich reduced fluids on the diamond-forming processes under subduction settings, was performed using a multi-anvil high-pressure split-sphere apparatus in Fe3C-(Mg,Ca)CO3-S and Fe0-(Mg,Ca)CO3-S systems at the pressure of 6.3 GPa, temperatures in the range of 900–1600 °C and run time of 18–60 h. At the temperatures of 900 and 1000 °C in the carbide-carbonate-sulfur system, extraction of carbon from cohenite through the interaction with S-rich reduced fluid, as well as C0-producing redox reactions of carbonate with carbide were realized. As a result, graphite formation in assemblage with magnesiowüstite, cohenite and pyrrhotite (±aragonite) was established. At higher temperatures (≥1100 °C) formation of assemblage of Fe3+-magnesiowüstite and graphite was accompanied by generation of fO2-contrasting melts - metal-sulfide with dissolved carbon (Fe-S-C) and sulfide-oxide (Fe-S-O). In the temperature range of 1400–1600 °C spontaneous diamond nucleation was found to occur via redox interactions of carbide or iron with carbonate. It was established, that interactions of Fe-S-C and Fe-S-O melts as well as of Fe-S-C melt and magnesiowüstite, were С0-forming processes, accompanied by disproportionation of Fe. These resulted in the crystallization of Fe3+-magnesiowüstite+graphite assemblage and growth of diamond. We show that a participation of sulfur in subduction-related elemental carbon-forming processes results in sharp decrease of partial melting temperatures (~300 °C), reducting the reactivity of the Fe-S-C melt relatively to FeC melt with respect to graphite and diamond crystallization and decrease of diamond growth rate.

Experimental carbonatite/graphite carbon isotope fractionation and carbonate/graphite geothermometry

Abstract Carbon isotope exchange between carbon-bearing high temperature phases records the carbon (re-) processing in the Earth's interior, where the vast majority of global carbon is stored. Redox reactions between carbonate phases and elemental carbon govern the mobility of carbon, which then can be traced by its isotopes. We determined the carbon isotope fractionation factor between graphite and a Na2CO3-CaCO3 melt at 900–1500 °C and 1 GPa; The failure to isotopically equilibrate preexisting graphite led us to synthesize graphite anew from organic material during the melting of the carbonate mixture. Graphite growth proceeds by (1) decomposition of organic material into globular amorphous carbon, (2) restructuring into nano-crystalline graphite, and (3) recrystallization into hexagonal graphite flakes. Each transition is accompanied by carbon isotope exchange with the carbonate melt. High-temperature (1200–1500 °C) equilibrium isotope fractionation with type (3) graphite can be described by Δ 13 C c a r b o n a t e - g r a p h i t e = 3.17 ( ± 0.07 ) · 10 6 T 2 (temperature T in K). As the experiments do not yield equilibrated bulk graphite at lower temperatures, we combined the ≥1200 °C experimental data with those derived from upper amphibolite and lower granulite facies carbonate-graphite pairs (Kitchen and Valley, 1995; Valley and O'Neil, 1981). This yields the general fractionation function Δ 13 C c a r b o n a t e - g r a p h i t e = 3.37 ± 0.04 · 10 6 T 2 usable as a geothermometer for solid or liquid carbonate at ≥600 °C. Similar to previous observations, lower-temperature experiments (≤1100 °C) deviate from equilibrium. By comparing our results to diffusion and growth rates in graphite, we show that at ≤1100 °C carbon diffusion is slower than graphite growth, hence equilibrium surface isotope effects govern isotope fractionation between graphite and carbonate melt and determine the isotopic composition of newly formed graphite. The competition between diffusive isotope exchange and growth rates requires a more careful interpretation of isotope zoning in graphite and diamond. Based on graphite crystallization rates and bulk isotope equilibration, a minimum diffusivity of Dgraphite = 2 × 10−17 m2s−1 for T > 1150 °C is required. This value is significantly higher than calculated from experimental carbon self-diffusion constants (∼1.6 × 10−29 m2 s−1) but in good agreement with the value calculated for mono-vacancy migration (∼2.8 × 10−16 m2 s−1).

Natural Graphite Cuboids

Graphite cuboids are abundant in ultrahigh-pressure metamorphic rocks and are generally interpreted as products of partial or complete graphitization of pre-existing diamonds. The understanding of the graphite cuboid structure and its formation mechanisms is still very limited compared to nanotubes, cones, and other carbon morphologies. This paper is devoted to the natural occurrences of graphite cuboids in several metamorphic and magmatic rocks, including diamondiferous metamorphic assemblages. The studied cuboids are polycrystalline aggregates composed either of numerous smaller graphite cuboids with smooth surfaces or graphite flakes radiating from a common center. Silicates, oxides, and sulphides are abundant in all the samples studied, testifying that the presence of oxygen, sulfur, or sulphides in natural systems does not prevent the spherulitic growth of graphite. The surface topography and internal morphology of graphite cuboids combined with petrological data suggest that graphite cuboids originated from a magmatic or metamorphic fluid/melt and do not represent products of diamond-graphite transformation processes, even in diamond-bearing rocks.

Growth of Spheroidal Graphite on Nitride Nuclei: Disregistry and Crystallinity During Early Growth

The graphite phase resulting from the stable solidification of iron-carbon-silicon alloys can have a variety of morphologies, from lamellar to spheroidal, including undesired degenerated morphologies. Spheroidal graphite is preferred when high strength and ductility are required. Understanding the nucleation and growth mechanism of graphite will improve control of its morphology during industrial processing. The crystalline structure of spheroidal graphite in iron-carbon-silicon alloys exhibits a multi-regions substructure. Literature opinions on the degree of crystallinity of the core of the spheroid are divergent. Unconvincing explanations are offered. The ability of nitrides to serve as graphite nuclei is questioned because of the high linear disregistry. To bring some clarity into the early crystallization of graphite in iron melts, interrupted solidification samples were examined through scanning electron microscopy. Disregistry calculations and thermodynamic analysis demonstrated that certain nitrides are favorable for graphite nucleation. Some unique pictures showing graphite platelets growing out of the nucleus were obtained from deep-etched samples. They bring evidence of the disorientation of graphite platelets growing around the graphite nuclei for the particular case of Mg-Al-Si nitrides. It is suggested that the low crystallinity observed in the core of some graphite spheroids is the result of this random orientation of the graphite platelets growing on nucleating inclusions during early solidification and of subsequent curved-circumferential growth.

PIP process greatly influencing the microstructure and electrical conductivity of polymer-derived SiCN ceramics

Precursor infiltration and pyrolysis (PIP) technique is widely used to densify porous ceramics. In this paper, PIP technique was used to fabricate dense polymer-derived SiCN ceramic bulks from porous SiCN preforms. Electrical conductivity and microstructure of dense SiCNs and the evolution with pyrolysis temperature were studied. Results were compared with that of porous SiCNs which were prepared by powder consolidation route without PIP process. Raman analysis showed that graphitization level of free-carbon in dense SiCNs is higher than that in porous SiCNs. As a consequence, the electrical conductivity of dense SiCNs was much higher than that of porous SiCNs. Free-carbon in porous SiCNs underwent a sp3-to-sp2 transition with increasing pyrolysis temperature throughout the temperature range of 1000 °C–1400 °C, whereas the sp3-to-sp2 transition was completed before 1200 °C in dense SiCNs. Main structural evolution of free-carbon in dense SiCNs was the growth of nanocrystalline graphite (nc-graphite) into ordered graphite when pyrolyzed at temperatures higher than 1200 °C. The growth activation energy of sp2 cluster size vs. pyrolysis temperature in the nc-graphite growth stage was found to be higher than that in the sp3-to-sp2 transition stage. The activation energy of conductivity increasing vs. pyrolysis temperature of the porous SiCNs was higher than that of the dense SiCNs, indicating that the electrical conductivity is more sensitive to the sp3-to-sp2 transition process than the sp2 cluster growth. This paper indicates that processing route can have great influence on the microstructure and electrical property of PDCs.

Analyses of Nucleation and Growth of Graphite for Spheroidal Graphite Cast Iron

Analyses of Nucleation and Growth of Graphite for Spheroidal Graphite Cast Iron

A graphite nodule growth model validated by in situ synchrotron x-ray tomography

An accurate prediction of ductile cast iron (DCI) microstructures is crucial for a science-based optimisation of cast component design. The number density and distribution of graphite nodules critically influence the mechanical performance of a component in service. Although models predicting nodule growth have been researched for many years, recent improvements have been impeded by lack of detailed experimental data on nodule growth kinetics for validation. This data has now been made available through in situ observations of the solidification of DCI using synchrotron x-ray tomography in combination with a high temperature environmental cell. In the present investigation, a new sphere of influence (SoI) model for spheroidal graphite growth is proposed. It inherently incorporates the competition for carbon between neighbouring nodules and the depletion of carbon in the matrix. Comparing simulation results to the in situ observations of graphite growth, the SoI model successfully predicts both growth of individual nodules as well as the size distribution of a large nodule population during solidification.

Graphite and Diamond Formation in the Carbide–Oxide–Carbonate Interactions (Experimental Modeling under Mantle P,T-Conditions)

Experimental modeling of the formation of graphite and diamond as a result of carbide–fluid interactions was performed in the Fe3C–SiO2–Al2O3–(Mg,Ca)CO3 systems at 6.3 and 7.5 GPa and 1100–1650 °C. In the experiments with ƒO2-gradient (7.5 GPa, 1250–1350 °C), graphite + magnesiowüstite + garnet ± cohenite assemblage was formed. Graphite was produced through the redox interactions of carbide with carbonate or CO2 (reducing conditions), and redox reactions of magnesiowüstite and CO2 (oxidizing conditions). At 1450–1650 °C, crystallization of graphite, garnet, magnesiowüstite and ferrospinel, as well as generation of Fe2+,3+-rich carbonate–silicate melt occurred. This melt, saturated with carbon, acted as a medium of graphite crystallization and diamond growth on seeds. In the experiments without ƒO2-gradient (6.3 GPa), decarbonation reactions with the formation of CO2-fluid and Fe,Mg,Ca-silicates, as well as C0-producing redox reactions of CO2-fluid with cohenite were simultaneously realized. As a result, graphite (± diamond growth) was formed in assemblage with Fe2+,Fe3+,Mg-silicates and magnetite (1100–1200 °C), or with Fe3+-rich garnet and orthopyroxene (1300–1500 °C). It has been established that a potential mechanism for the crystallization of graphite or diamond growth is the oxidation of cohenite by CO2-fluid to FeO and Fe3O4, accompanied by the extraction of carbon from Fe3C and the corresponding reduction of CO2 to C0.

Some paradoxical observations about spheroidal graphite degeneracy

Differential thermal analysis experiments have been performed on samples machined from Y2-blocks cast with different high-silicon spheroidal graphite irons. Depending on magnesium, silicon, cerium and antimony content, the as-cast microstructure showed various levels of chunky graphite in the central part of the blocks. In contrast, the microstructure of the materials after remelting and resolidification during differential thermal analysis consisted of lamellar or compacted graphite. The formation of chunky graphite in the as-cast microstructure is rationalized using an index or silicon equivalent that has been recently suggested. The differences in the microstructures after differential thermal analysis are discussed in terms of available free magnesium. Emphasis is finally put on the striking differences in characteristic size of the microstructures made of compacted graphite as compared to lamellar graphite and chunky graphite. This leads to tentative conclusions about growth of compacted and chunky graphite which would be worthy of further experimental investigations.

Analysis of Local Conditions on Graphite Growth and Shape During Solidification of Ductile Cast Iron

3D X-ray tomography recordings have been used to study graphite growth during solidification of ductile cast iron. Using data from such recordings, it is shown how local growth conditions influence growth rate and morphology of nodules during solidification. Experiments show that it is common for nodules to gradually change shape during solidification so that sphericity decreases. It is also found that different shaped nodules can evolve in direct contact with liquid iron and also after they are encapsulated in austenite. It is observed that a significant proportion of originally complete spherical nodules become less spherical via formation of protrusions on the surface; these new surfaces are observed to grow relatively faster. It is shown that encapsulation of the graphite nodule by austenite may be incomplete and that at the end of solidification, partial encapsulation and the effect of the number of nearest graphite nodules play a crucial role in determining the final graphite morphology.

A Multi-phase-field Approach for Solidification with Non-negligible Volumetric Expansion—Application to Graphite Growth in Nodular Cast Iron

Multi-phase field models have become powerful tools for prediction of microstructure evolution in technical alloys. Coupling to CALPHAD databases provides complex multicomponent multiphase thermodynamic data and diffusion matrices. Although many thermodynamic databases contain volume data, this information is by now hardly used for solidification, since a comprehensive modelling of volumetric expansion based on solid- and fluid-mechanics exceeds present computational capacities. A novel multicomponent multi-phase-field approach is presented which handles volumetric expansion in a simplified way. It assumes that temporary pressure caused by local expansion is instantaneously released by matter transport on a time scale much faster than diffusion. The new approach neglects any mechanical and kinetic aspects of expansion, but allows for a change in total volume and for thermodynamically consistent volume fractions. Moreover, expansion-driven matter fluxes and associated advective solute transport are considered. Application is illustrated by the example of spheroidal graphite growth in a hypoeutectic cast iron alloy.

Surface Carbon as a Reactive Intermediate in Dry Reforming of Methane to Syngas on a 5% Ni/MnO Catalyst

A 5% Ni/MnO catalyst has been tested for the dry reforming of methane at different temperatures and reactant partial pressures. Changing the reactant ratio with time on stream results in a decrease in the deactivation rate of the catalyst. Graphitic carbon growth and metal particle sintering have been observed by applying in situ transmission XRD using synchrotron radiation under actual reaction conditions. Both methane and carbon monoxide separately result in graphitic surface carbon, which can then be oxidized by carbon dioxide. The morphology of the surface carbon has been analyzed by TEM, and the reactions of both methane and carbon monoxide result in the same graphitic multiwalled carbon nanotubes. The present combination of catalytic experiments and in situ techniques suggests that surface carbon acts as an intermediate in the formation of CO and that catalyst deactivation happens via metallic particle sintering. These results enable a more rational choice of reaction conditions to ensure high catal...

Metastable Eutectoid Transformation in Spheroidal Graphite Cast Iron: Modeling and Validation

This paper presents a new microstructural model of the metastable eutectoid transformation in spheroidal graphite cast irons. The model takes into account the nucleation and growth of pearlite nodules. The nucleation is assumed to be continuous and dependent on the metastable undercooling associated with the upper limit of the three-phase field, while the growth rate is considered to be ruled by the silicon partitioning between ferrite and cementite at the pearlite/austenite front. The initial conditions for the metastable transformation are obtained from a microstructural simulation of solidification, graphite growth, and stable eutectoid transformation. These microstructural models are coupled with the thermal balance solved at a macroscopic level via the finite element method. The experimental validation of the metastable eutectoid model achieved by comparison with measured values of ferrite, graphite, and pearlite fractions at the end of the cooling process demonstrates the sound predictive capabilities of the proposed model.

Synchrotron quantification of graphite nodule evolution during the solidification of cast iron

In cast iron, graphite develops in conjunction with the metallic matrix during solidification. The morphology and distribution of the embedded graphite is pivotal for mechanical properties from yield strength to fatigue. A novel high temperature environmental cell was developed and combined with in situ synchrotron tomography to investigate and quantify microstructural evolution, including graphite nodule nucleation and growth rates in ductile cast iron. The mechanisms of degenerate graphite nodule formation were also revealed. The formation of a coherent primary gamma phase dendritic network before the graphite nucleation is demonstrated. The graphite nodule nucleation rate, mobility and growth rates are compared to classical models, highlighting the limitations in these models. The results provide unique insights to tune the temperature pathways during cast iron solidification to achieve desired uniform rounded graphite morphologies and size distributions.

Revisiting Models for Spheroidal Graphite Growth

Recent experiments resolved nucleation and growth of graphite during solidification of ductile cast iron in 4D using synchrotron X-ray tomography. A numerical model for microstructure formation during solidification is compared with the experiments. Despite very good overall agreement between observations of spheroidal graphite growth and model results, significant deviations exist towards the end of solidification. We use the experimental observations to analyse the relation between graphite growth rate and the state of the particle neighbourhood to pinpoint possible links between growth rate of individual graphite spheres and the overall solidification state. With this insight we revisit existing models for growth of spheroidal graphite and discuss possible modifications in order to correctly describe the critical final stage of solidification.

The Structure of Cast Irons

There appear to be two main growth mechanisms for graphite in cast iron i) Coupled eutectic growth forms of gray irons which are classical growth modes of simultaneous parallel growth of graphite and austenite, not reliant on a bifilm mechanism. These are necessarily fine structures as a result of their control by the rate of diffusion of carbon in the liquid. These structures are well understood. (ii) Uncoupled eutectic mechanisms which appear to be much less well understood, including (a) growth of graphite on silica bifilm substrates floating freely in the melt, forming such structures as A-type graphite flakes. This prediction appears to have now been confirmed by direct observation. The transition to (b) nodular morphology occurs by Mg eliminating the silica bifilms by an exchange reaction. In this way the substrates for flake growth are instantly removed, and graphite can now wrap completely around nuclei, thereby growing as a nodule. Graphite structures in heavy sections such as chunky graphite may now be understandable in terms of the reorganisation by flotation of bifilms and/or nuclei.