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Multiscale Modeling of Intergranular Fracture in Aluminum: Constitutive Relation For Interface Debonding

Intergranular fracture is a dominant mode of failure in ultrafine grained materials. In the present study, the atomistic mechanisms of grain-boundary debonding during intergranular fracture in aluminum are modeled using a coupled molecular dynamics finite element simulation. Using a statistical mechanics approach, a cohesive-zone law in the form of a traction-displacement constitutive relationship, characterizing the load transfer across the plane of a growing edge crack, is extracted from atomistic simulations and then recast in a form suitable for inclusion within a continuum finite element model. The cohesive-zone law derived by the presented technique is free of finite size effects and is statistically representative for describing the interfacial debonding of a grain boundary (GB) interface examined at atomic length scales. By incorporating the cohesive-zone law in cohesive-zone finite elements, the debonding of a GB interface can be simulated in a coupled continuum-atomistic model, in which a crack starts in the continuum environment, smoothly penetrates the continuum-atomistic interface, and continues its propagation in the atomistic environment. This study is a step towards relating atomistically derived decohesion laws to macroscopic predictions of fracture and constructing multiscale models for nanocrystalline and ultrafine grained materials.

Yamakov, V.↗

Deformation processes in forging ceramics

The deformation processes involved in the forging of refractory ceramic oxides were investigated. A combination of mechanical testing and forging was utilized to investigate both the flow and fracture processes involved. Deformation studies of very fine grain Al203 revealed an apparent transition in behavior, characterized by a shift in the strain rate sensitivity from 0.5 at low stresses to near unity at higher stresses. The behavior is indicative of a shift in control between two dependent mechanisms, one of which is indicated to be cation limited diffusional creep with significant boundary enhancement. The possible contributions of slip, indicated by crystallographic texture, interface control of the diffusional creep and inhomogeneous boundary sliding are also discussed. Additional experiments indicated an independence of deformation behavior on MgO doping and retained hot pressing impurities, at least for ultrafine grained material, and also an independence of test atmosphere.

Cannon, R. M.↗

Superhard Nanocrystalline Homometallic Stainless Steel on Steel for Seamless Coatings

The objective of this work is to deposit nanocrystalline stainless steel onto steel substrates (homometallic) for enhanced wear and corrosion resistance. Homometallic coatings provide superior adhesion, and it has been shown that ultrafine-grained materials exhibit the increased hardness and decreased permeability desired for protective coatings. Nanocrystals will be produced by controlling nucleation and growth and use of an ion beam during deposition by e-beam evaporation or sputtering. Phase I is depositing 31 6L nanocrystalline stainless steel onto 31 6L stainless steel substrates. These coatings exhibit hardnesses comparable to those normally obtained for ceramic coatings such ZrO2, and possess the superior adhesion of seamless, homometallic coatings. Hardening the surface with a similar material also enhances adhesion, by avoiding problems associated with thermal and lattice mismatch. So far we have deposited nanocrystalline homometallic 316L stainless steel coatings by varying the ions and the current density of the ion beams. For all deposition conditions we have produced smooth, uniform, superhard coatings. All coatings exhibit hardness of at least 200% harder than that of bulk materials. Our measurements indicate that there is a direct relationship between nanohardness and the current density of the ion beam. Stress measurements indicate that stress in the films is increasingly proportional to current density of the ion beam. TEM, XPS, and XRD results indicate that the coated layers consist of FCC structure nanocrystallites with a dimension of about 10 to 20 nm. The Ni and Mo concentration of these coating are lower than those of bulk 316L but the concentration of Cr is higher.

Tobin, Eric J.↗

Atomistic Cohesive Zone Models for Interface Decohesion in Metals

Using a statistical mechanics approach, a cohesive-zone law in the form of a traction-displacement constitutive relationship characterizing the load transfer across the plane of a growing edge crack is extracted from atomistic simulations for use within a continuum finite element model. The methodology for the atomistic derivation of a cohesive-zone law is presented. This procedure can be implemented to build cohesive-zone finite element models for simulating fracture in nanocrystalline or ultrafine grained materials.

Yamakov, Vesselin I.↗

High-strength silicon carbides by hot isostatic pressing

Silicon carbide has strong potential for heat engine hardware and other high-temperature applications because of its low density, good strength, high oxidation resistance, and good high-temperature creep resistance. Hot isostatic pressing (HIP) was used for producing alpha and beta silicon carbide (SiC) bodies with near-theoretical density, ultrafine grain size, and high strength at processing temperatures of 1900 to 2000 C. The HIPed materials exhibited ultrafine grain size. Furthermore, no phase transformation from beta to alpha was observed in HIPed beta-SiC. Both materials exhibited very high average flexural strength. It was also shown that alpha-SiC bodies without any sintering aids, when HIPed to high final density, can exhibit very high strength. Fracture toughness K (sub C) values were determined to be 3.6 to 4.0 MPa m (sup 1/2) for HIPed alpha-SiC and 3.7 to 4.1 MPa m (sup 1/2) for HIPed beta-SiC. In the HIPed specimens strength-controlling flaws were typically surface related. In spite of improvements in material properties such as strength and fracture toughness by elimination of the larger strength-limiting flaws and by grain size refinement, HIPing has no effect on the Weibull modulus.

Dutta, Sunil↗

High-strength silicon carbides by hot isostatic pressing

Silicon carbide has strong potential for heat engine hardware and other high-temperature applications because of its low density, good strength, high oxidation resistance, and good high-temperature creep resistance. Hot isostatic pressing (HIP) was used for producing alpha and beta silicon carbide (SiC) bodies with near-theoretical density, ultrafine grain size, and high strength at processing temperatures of 1900 to 2000 C. The HIPed materials exhibited ultrafine grain size. Furthermore, no phase transformation from beta to alpha was observed in HIPed beta-SiC. Both materials exhibited very high average flexural strength. It was also shown that alpha-SiC bodies without any sintering aids, when HIPed to high final density, can exhibit very high strength. Fracture toughness K (sub C) values were determined to be 3.6 to 4.0 MPa m (sup 1/2) for HIPed alpha-SiC and 3.7 to 4.1 MPa m (sup 1/2) for HIPed beta-SiC. In the HIPed specimens strength-controlling flaws were typically surface related. In spite of improvements in material properties such as strength and fracture toughness by elimination of the larger strength-limiting flaws and by grain size refinement, HIPing has no effect on the Weibull modulus.

Dutta, Sunil↗

Carbon petrology in cometary dust

Chondritic porous (CP) interplanetary dust particles (IDP's) are collected in the Earth's stratosphere. There exists an extensive database on major and minor element chemistry, stable isotopes, noble gas abundances and mineralogy of many CP IDP's, as well as infrared and Raman spectroscopic properties. For details on the mineralogy, chemistry and physical properties of IDP's, I refer to the reviews by Mackinnon and Rietmeijer (1987), Bradley et al. (1988) and Sandford (1987). Texture, mineralogy (Mackinnon and Rietmeijer, 1987) and chemistry (Schramm et al., 1989; Flynn and Sutton, 1991) support the notion that CP IDP's are a unique group of ultrafine-grained extraterrestiral materials that are distinct from any known meteorite class. Their fluffy, or porous, morphology suggests that CP IDP's probably endured minimal alteration by protoplanetary processes since their formation. It is generally accepted that CP IDP's are solid debris from short-period comets. The evidence is mostly circumstantial but this notion gained significant support based on the comet Halley dust data (Brownlee, 1990). In this paper, I will accept that CP IDP's are indeed cometary dust. The C/Si ratio in CP IDP's is 3.3 times higher than in CI carbonaceous chondrites (Schramm et al. 1989). The intraparticle carbon distribution is heteorogeneous (Rietmeijer and McKay, 1986). Carbon occurs both in oxidized and reduced forms. Analytical electron microscope (AEM) and Raman spectroscopic analyses have shown the presence of several carbon forms in CP IDP's but the data are scattered in the literature. Carbons in cometary CP IDP's are among the most pristine Solar System carbons available for laboratory study. Similar to a recently developed petrological model for the diversity of layer silicates in CP IDP's (Zolensky, 1991) that is useful to constrain in situ aqueous alteration in comets (Rietmeijer and Mackinnon, 1987a), I here present the first effort to develop a petrological concept of carbons in CP IDP's. This concept is useful to constrain comet evolution. I also present the philosophical constraint facing Earth Scientists in studies of protoplanets that require a new approach to cometary dust studies.

Rietmeijer, Frans J. M.↗

Ultrafine-grained mineralogy and matrix chemistry of olivine-rich chondritic interplanetary dust particles

Olivine-rich chondritic interplanetary dust particles (IDPs) are an important subset of fluffy chondritic IDPs collected in the earth's stratosphere. Particles in this subset are characterized by a matrix of nonporous, ultrafine-grained granular units. Euhedral single crystals, crystals fragments, and platey single crystals occur dispersed in the matrix. Analytical electron microscopy of granular units reveals predominant magnesium-rich olivines and FeNi-sulfides embedded in amorphous carbonaceous matrix material. The variable ratio of ultrafine-grained minerals vs. carbonaceous matrix material in granular units support variable C/Si ratios, and some fraction of sulfur is associated with carbonaceous matrix material. The high Mg/(Mg+Fe) ratios in granular units is similar to this distribution in P/Comet Halley dust. The chondritic composition of fine-grained, polycrystalline IDPs gradually breaks down into nonchondritic, and ultimately, single mineral compositions as a function of decreased particle mass. The relationship between particle mass and composition in the matrix of olivine-rich chondritic IDPs is comparable with the relationship inferred for P/Comet Halley dust.

Rietmeijer, F. J. M.↗

Nature and origin of matrix in the unique type 3 chondrite, Kakangari

The characteristics of the matrix of the Kakangari type-3 chondrite were investigated using high-resolution TEM and AEM. It was found that the textural and mineralogical characteristics of the fine-grained matrix of Kakangari are different from those of the other chondrite groups. Unlike the matrix phases present in the CV3 and CO3 chondrites, the matrix mineralogy of Kakangari contains clear information regarding its possible origin and thermal history. Data obtained are most consistent with an origin of Kakangari by annealing, without melting at high temperature (possibly during a chondrule-forming thermal event), of clusters or aggregates of ultrafine-grained amorphous or crystalline phases. The precursor materials were most likely to have been a mixture of nebula and presolar dust. Chondrules in Kakangari were probably formed from identical precursors to the matrix, but reached temperatures sufficiently high to produce melting.

Brearley, Adrian J.↗

Characterization and properties of controlled nucleation thermochemical deposited /CNTD/ silicon carbide

Results are presented for an investigation designed to characterize the microstructure of controlled nucleation thermomechanical deposition (CNTD) produced SiC material with respect to grain structure, stoichiometry, phase analysis, etc., and to evaluate the room-temperature and high-temperature fracture and oxidation behavior. By using the CNTD process, ultrafine-grained SiC is deposited on tungsten wires as substrates, with superior surface smoothness and without the macrocolumnar growth commonly observed in conventional CVD materials. The results suggest that the high-purity, fully dense, and stable grain size SiC material produced by CNTD shows potential for high-temperature structural applications, provided that pertinent problems are resolved.

Dutta, S.↗

Characterization and properties of controlled nucleation thermochemical deposited (CNTD) silicon carbide

The microstructure of controlled nucleation thermochemical deposition (CNTD) - SiC material was studied and the room temperature and high temperature bend strength and oxidation resistance was evaluated. Utilizing the CNTD process, ultrafine grained (0.01-0.1 mm) SiC was deposited on W - wires (0.5 mm diameter by 20 cm long) as substrates. The deposited SiC rods had superior surface smoothness and were without any macrocolumnar growth commonly found in conventional CVD material. At both room and high temperature (1200 - 1380 C), the CNTD - SiC exhibited bend strength approximately 200,000 psi (1380 MPa), several times higher than that of hot pressed, sintered, or CVD SiC. The excellent retention of strength at high temperature was attributed to the high purity and fine grain size of the SiC deposit and the apparent absence of grain growth at elevated temperatures. The rates of weight change for CNTD - SiC during oxidation were lower than for NC-203 (hot pressed SiC), higher than for GE's CVD - SiC, and considerably below those for HS-130 (hot pressed Si3N4). The high purity, fully dense, and stable grain size CNTD - SiC material shows potential for high temperature structural applications; however problem areas might include: scaling the process to make larger parts, deposition on removable substrates, and the possible residual tensile stress.

Dutta, S.↗

Possible Gems and Ultra-Fine Grained Polyphase Units in Comet Wild 2.

GEMS and ultrafine grained polyphase units (UFG-PU) in anhydrous IDPs are probably some of the most primitive materials in the solar system. UFG-PUs contain nanocrystalline silicates, oxides, metals and sulfides. GEMS are rounded approximately 100 nm across amorphous silicates containing embedded iron-nickel metal grains and sulfides. GEMS are one of the most abundant constituents in some anhydrous CPIDPs, often accounting for half the material or more. When NASA's Stardust mission returned with samples from comet Wild 2 in 2006, it was thought that UFG-PUs and GEMS would be among the most abundant materials found. However, possibly because of heating during the capture process in aerogel, neither GEMS nor UFG-PUs have been clearly found.

Gainsforth, Z.↗

A proposition for the classification of carbonaceous chondritic micrometeorites

Classification of interplanetary dust particles (IDP's) should be unambiguous and, if possible, provide an opportunity to interrelate these ultrafine IDP's with the matrices of undifferentiated meteorites. I prefer a scheme of chemical groupings and petrologic classes that is based on primary IDP properties that can be determined without prejudice by individual investigators. For IDP's of 2-50 microns these properties are bulk elemental chemistry, morphology, shape, and optical properties. The two major chemical groups are readily determined by energy dispersive spectroscopic analysis using the scanning or analytical electron microscope. Refinement of chondritic IDP classification is possible using the dominant mineral species, e.g. olivine, pyroxene, and layer silicates, and is readily inferred from FTIR, and automated chemical analysis. Petrographic analysis of phyllosilicate-rich IDP's will identify smectite-rich and serpentine-rich particles. Chondritic IDP's are also classified according to morphology, viz., CP and CF IDP's are aggregate particles that differ significantly in porosity, while the dense CS IDP's have a smooth surface. The CP IDP's are characterized by an anhydrous silicate mineralogy, but small amounts of layer silicates may be present. Distinction between the CP and CF IDP's is somewhat ambiguous, but the unique CP IDP's are fluffy, or porous, ultrafine-grained aggregates. The CP IDP's, which may contain silicate whiskers, are the most carbon-rich extraterrestrial material presently known. The CF IDP's are much less porous that CP IDP's. Using particle type definitions, CP IDP's in the NASA JSC Cosmic Dust Catalogs are approx. 15 percent of all IDP's that include nonchondritic spheres. Most aggregate particles are of the CF type.

Rietmeijer, Frans J. M.↗

The origin of magnemite on Mars

An explanation for the magnetic properties of Martian surface material is discussed, specifically that the surface particles were composed primarily of smectite clay (nontronite) pigmented throughout by a red magnetic phase. The thermal treatment of nontronite in air, for long periods at 700 deg C or short periods at 900 deg C, results in destruction of the nontronite structure, a distinct reddening in color, and a spectacular increase in magnetic susceptibility and saturation magnetization (up to 4.4 Am squared/kg). Magnetic property measurements suggest that the magnetism is due to the presence of ultrafine particles of alpha or gamma Fe2O3; the precise identify was not resolved. Thermally treated nontronite has chemical, color and magnetic properties akin to those found by Viking on Mars. These results favor an origin for the fine grained Martian surface material by repeated impacts into an Fe-rich smectite-charged regolith, the smectite having resulted from hydrothermal alteration of volcanic or impact generated glass, the magnetic phase having resulted from the pressure or thermal shocked nontronite.

Hargraves, R. B.↗

Effect of processing on fracture toughness of silicon carbide as determined by Vickers indentations

Several alpha-SiC materials were processed by hot isostatic pressing (HIPing) and by sintering an alpha-SiC powder containing boron and carbon. Several beta-SiC materials were processed by HIPing a beta-SiC powder with boron and carbon additions. The fracture toughnesses K(sub 1c) of these beta- and alpha-SiC materials were estimated from measurements of Vickers indentations. The three formulas used to estimate K(sub 1c) from the indentation fracture patterns resulted in three ranges of K(sub 1c) estimates. Furthermore, each formula measured the effects of processing differently. All three estimates indicated that fine-grained HIPed alpha-SiC has a higher K(sub 1c) than coarsed-grained sintered alpha-SiC. Hot isostatically pressed beta-SiC, which had an ultrafine grain structure, exhibited a K(sub 1c) comparable to that of HIPed alpha-SiC.

Dannels, Christine M.↗

Magnetic changes accompanying the thermal decomposition of nontronite /in air/ and its relevance to Martian mineralogy

It is found that the thermal treatment of nontronite in air, for long periods at 700 C or short periods at 900 C, results in the destruction of the nontronite structure, a distinct reddening in color, and a large increase in magnetic susceptibility and saturation magnetization. Measurements and calculations of the magnetic properties suggest that the magnetism is due to the presence of ultrafine particles of alpha or gamma Fe2O3. The highly magnetic thermally treated nontronite is amorphous to X-rays consistent with an ultrafine grain size. Prolonged heating results in the growth of alpha Fe2O3, while reflectivity spectra of a sample heated for 1 hr at 900 C indicate the presence of an opaque, magnetite-like phase in addition to alpha Fe2O3. It is found that the thermally treated nontronite has chemical, color, and magnetic properties similar to those found by Viking on Mars. It is concluded that these results indicate an origin for the fine grained Martian surface material by repeated impacts into an Fe-rich smectite-charged regolith (Weldon et al., 1980).

Moskowitz, B. M.↗

Chemically anomalous, pre-accretionally irradiated grains in interplanetary dust -- interstellar grains?

Ultrafine-grained matrix is a unique and fundamental building block of chondritic porous (CP) interplanetary dust particles. Most IDPs so far determined to be of cometary origin belong to the CP class. The matrix in CP IDPs is not homogeneous but rather a loose mixture of discrete single crystals (e.g., olivine, pyroxene, Fe sulfides) and polyphase grains. The petrographic diversity observed among the polyphase grains suggest that they were formed under variable physiochemical conditions. One particular class of polyphase grains are a dominant component in cometary IDPs. Although their occurrence is well documented, the terminology used to describe them is confused. They have been called many names. Here they are simply called GEMS (Glass with Embedded Metal and Sulfides). The bulk compositions of GEMS are within a factor of 3 chondritic (solar) for all major elements except C. Quantitative thin-film X-ray (EDS) analyses have shown that GEMS are systematically depleted in Mg and Si, enriched in S, Fe, and Ni, and stoichiometrically enriched in O. Electron energy-loss spectroscopy (EELS) suggests that the excess O is present as hydroxyl (-OH) groups. These same chemical 'anomalies' were observed in solar-wind-irradiated amorphous rims on the surfaces of IDPs, suggesting that the compositions of GEMS reflect prior exposure to ionizing radiation. In order to test this hypothesis, a sample of Allende (CV3) matrix was exposed to proton flux. Radiation-damaged amorphous rims on olivine and pyroxene crystals in the Allende sample were found to be depleted in Mg and Ca, enriched in S, Fe, and Ni, and stoichiometrically enriched in O. Thus, the compositions of GEMS are indeed consistent with exposure to ionizing radiation. This study suggests that chemical as well as isotopic anomalies may be used to identify presolar interstellar grains in primitive meteoritic materials.

Bradley, J. P.↗