Hall-petch relationship and strain rate sensitivity of nanocrystalline Mg - 5wt% A1 alloy

This study investigated the grain size dependence of mechanical properties and deformation mechanisms of microcrystalline (mc) and nanocrystalline (nc: grain size below 100 nm) Mg-5wt% Al alloys. The Hall-Petch relationship was investigated by both instrumented indentation tests and compression tests. The test results from the indentation tests and compression tests match well with each other. The breakdown of Hall-Petch relationship and the elevated strain rate sensitivity (SRS) of present Mg-5wt% Al alloys when the grain size was reduced below 58nm indicated the more significant role of GB mediated mechanisms in plastic deformation process. However, the relatively smaller SRS values compared to GB sliding and coble creep process suggested the plastic deformation in the current study is still dislocation mediated mechanism dominant.

Raman microscopy of haidingerite Ca(AsO3OH)•H2O and brassite Mg(AsO3OH)•4H2O

Raman spectroscopy has been used to study the arsenate minerals haidingerite Ca(AsO3OH)•H2O and brassite Mg(AsO3OH)•4H2O. Intense Raman bands in haidingerite spectrum observed at 745 and 855 cm-1 are assigned to the (AsO3OH)2- ν3 antisymmetric stretching and ν1 symmetric stretching vibrational modes. For brassite two similarly assigned intense bands are found at 809 and 862 cm-1. The observation of multiple Raman bands in the (AsO3OH)2- stretching and bending regions suggests that the arsenate tetrahedrons in the crystal structures of both minerals studied are strongly distorted. Broad Raman bands observed at 2842 cm-1 for haidingerite and 3035 cm-1 for brassite indicate strong hydrogen bonding of water molecules in the structure of these minerals. OH…O hydrogen bond lengths were calculated from the Raman spectra based on empiric relations.

Is the mineral borickyite (Ca,Mg)(Fe3+,Al)4(PO4,SO4,CO3)(OH)8•3-7.5H2O the same as delvauxite CaFe3+4(PO4,SO4)2(OH)8•4-6H2O?

The two minerals borickyite and delvauxite CaFe3+4(PO4,SO4)2(OH)8•4-6H2O have the same formula. Are the minerals identical or different? The minerals borickyite and delvauxite have been characterised by Raman spectroscopy. The minerals are related to the minerals diadochite and destinezite. Both minerals are amorphous. Delvauxite appears to vary in crystallinity from amorphous to semi-crystalline. The minerals are often X-ray non-diffracting. The minerals are found in soils and may be described as ‘colloidal’ minerals. Vibrational spectroscopy enables an assessment of the molecular structure of borickyite and delvauxite. Bands are assigned to phosphate and sulphate stretching and bending modes. Multiple water bending and stretching modes imply that non-equivalent water molecules in the structure exist with different hydrogen bond strengths. The two minerals show differing spectra and must be considered as different minerals.

RF magnetron sputtering deposition of bioactive Ca-P-based coatings on Ti-6Al-4V alloy

RF magnetron concurrent sputtering of Hydroxyapatite and Ti forming functionally graded calcium phosphate-based composite bioactive films on Ti-6Al-4V orthopedic alloy is reported. Calcium oxide phosphate (4CaO•P2O5) is the main crystalline phase. In vitro cell culturing tests suggest outstanding biocompatibility of the Ca-P-Ti films. Images of the plasma-enhanced sputtering processes and cell culturing are presented and discussed.

Indentation size effect and strain rate sensitivity of nanocrystalline Mg-Al alloys

Deformation Behaviour of microcrystalline (mc) and nanocrystalline (nc) Mg-5%Al alloys produced by hot extrusion of ball-milled powders were investigated using instrumented indentation tests. The hardness values of the mc and nc metals exhibited indentation size effect (ISE), with nc alloys showing weaker ISE. The highly localized dislocation activities resulted in a small activation volume, hence enhanced strain rate sensitivity. Relative higher strain rate sensitivity and the negative Hall-Petch Relationship suggested the increasingly important role of grain boundary mediated mechanisms when the grain size decreased to nanometer region.

Compressive behaviour of nanocrystallilne Mg-5%Al alloys

Magnesium alloys are attracting increasing research interests due to their low density, high specific strength and good mechineability and availability as compared to other structural materials. However, the deformation and failure mechanisms of nanocrystalline Mg alloys have not been well understood. In this work, the deformation behavior of nanocrystalline Mg-5% Al alloys was investigated using compression test, with a focus on the effects of grain size. The average grain size of the Mg-Al alloy was changed from 13 µm to 50 nm via mechanical milling. The results showed that grain size had a significant influence on the yield stress and ductility of the Mg alloys, and the materials exhibited increased strain rate sensitivity with decrease of grain size. The deformation mechanisms were also strongly dependent with the grain sizes.

Deformation behaviours of coarse-grained and nanocrystalline Mg-5wt% Al alloys

Magnesium alloys have been of growing interest to various engineering applications, such as the automobile, aerospace, communication and computer industries due to their low density, high specific strength, good machineability and availability as compared with other structural materials. However, most Mg alloys suffer from poor plasticity due to their Hexagonal Close Packed structure. Grain refinement has been proved to be an effective method to enhance the strength and alter the ductility of the materials. Several methods have been proposed to produce materials with nanocrystalline grain structures. So far, most of the research work on nanocrystalline materials has been carried out on Face-Centered Cubic and Body-Centered Cubic metals. However, there has been little investigation of nanocrystalline Mg alloys. In this study, bulk coarse-grained and nanocrystalline Mg alloys were fabricated by a mechanical alloying method. The mixed powder of Mg chips and Al powder was mechanically milled under argon atmosphere for different durations of 0 hours (MA0), 10 hours (MA10), 20 hours (MA20), 30 hours (MA30) and 40 hours (MA40), followed by compaction and sintering. Then the sintered billets were hot-extruded into metallic rods with a 7 mm diameter. The obtained Mg alloys have a nominal composition of Mg–5wt% Al, with grain sizes ranging from 13 μm down to 50 nm, depending on the milling durations. The microstructure characterization and evolution after deformation were carried out by means of Optical microscopy, X-Ray Diffraction, Scanning Electron Microscopy, Transmission Electron Microscopy, Scanning Probe Microscopy and Neutron Diffraction techniques. Nanoindentaion, compression and micro-compression tests on micro-pillars were used to study the size effects on the mechanical behaviour of the Mg alloys. Two kinds of size effects on the mechanical behaviours and deformation mechanisms were investigated: grain size effect and sample size effect. The nanoindentation tests were composed of constant strain rate, constant loading rate and indentation creep tests. The normally reported indentation size effect in single crystal and coarse-grained crystals was observed in both the coarse-grained and nanocrystalline Mg alloys. Since the indentation size effect is correlated to the Geometrically Necessary Dislocations under the indenter to accommodate the plastic deformation, the good agreement between the experimental results and the Indentation Size Effect model indicated that, in the current nanocrystalline MA20 and MA30, the dislocation plasticity was still the dominant deformation mechanism. Significant hardness enhancement with decreasing grain size, down to 58 nm, was found in the nanocrystalline Mg alloys. Further reduction of grain size would lead to a drop in the hardness values. The failure of grain refinement strengthening with the relatively high strain rate sensitivity of nanocrystalline Mg alloys suggested a change in the deformation mechanism. Indentation creep tests showed that the stress exponent was dependent on the loading rate during the loading section of the indentation, which was related to the dislocation structures before the creep starts. The influence of grain size on the mechanical behaviour and strength of extruded coarse-grained and nanocrystalline Mg alloys were investigated using uniaxial compression tests. The macroscopic response of the Mg alloys transited from strain hardening to strain softening behaviour, with grain size reduced from 13 ìm to 50 nm. The strain hardening was related to the twinning induced hardening and dislocation hardening effect, while the strain softening was attributed to the localized deformation in the nanocrystalline grains. The tension–compression yield asymmetry was noticed in the nanocrystalline region, demonstrating the twinning effect in the ultra-fine-grained and nanocrystalline region. The relationship k tensions < k compression failed in the nanocrystalline Mg alloys; this was attributed to the twofold effect of grain size on twinning. The nanocrystalline Mg alloys were found to exhibit increased strain rate sensitivity with decreasing grain size, with strain rate ranging from 0.0001/s to 0.01/s. Strain rate sensitivity of coarse-grained MA0 was increased by more than 10 times in MA40. The Hall-Petch relationship broke down at a critical grain size in the nanocrystalline region. The breakdown of the Hall-Petch relationship and the increased strain rate sensitivity were due to the localized dislocation activities (generalization and annihilation at grain boundaries) and the more significant contribution from grain boundary mediated mechanisms. In the micro-compression tests, the sample size effects on the mechanical behaviours were studied on MA0, MA20 and MA40 micro-pillars. In contrast to the bulk samples under compression, the stress-strain curves of MA0 and MA20 micro-pillars were characterized with a number of discrete strain burst events separated by nearly elastic strain segments. Unlike MA0 and MA20, the stress-strain curves of MA40 micro-pillars were smooth, without obvious strain bursts. The deformation mechanisms of the MA0 and MA20 micro-pillars under micro-compression tests were considered to be initially dominated by deformation twinning, followed by dislocation mechanisms. For MA40 pillars, the deformation mechanisms were believed to be localized dislocation activities and grain boundary related mechanisms. The strain hardening behaviours of the micro-pillars suggested that the grain boundaries in the nanocrystalline micro-pillars would reduce the source (nucleation sources for twins/dislocations) starvation hardening effect. The power law relationship of the yield strength on pillar dimensions in MA0, MA20 supported the fact that the twinning mechanism was correlated to the pre-existing defects, which can promote the nucleation of the twins. Then, we provided a latitudinal comparison of the results and conclusions derived from the different techniques used for testing the coarse-grained and nanocrystalline Mg alloy; this helps to better understand the deformation mechanisms of the Mg alloys as a whole. At the end, we summarized the thesis and highlighted the conclusions, contributions, innovations and outcomes of the research. Finally, it outlined recommendations for future work.

Compressive behaviour of nanocrystalline Mg-5Al alloys

Magnesium alloys are attracting increasing research interests due to their low density, high specific strength, good machinability and availability as compared to other structural materials. However, the deformation and failure mechanisms of nanocrystalline (nc) Mg alloys have not been well understood. In this work, the deformation behaviour of nc Mg-5Al alloys was investigated using compression test, with focus on the effects of grain size. The average grain size of the Mg- Al alloy was changed from 13 to 50 nm via mechanical milling. The results showed that grain size had a significant influence on the yield stress and ductility of the Mg alloys, and the materials exhibited increased strain rate sensitivity with a decrease in grain size. The deformation mechanisms were also strongly dependent on the grain sizes.

Vibrational spectroscopy of the phosphate mineral lazulite – (Mg, Fe)Al2(PO4)2·(OH)2 found in the Minas Gerais, Brazil

This research was done on lazulite samples from the Gentil mine, a lithium bearing pegmatite located in the municipality of Mendes Pimentel, Minas Gerais, Brazil. Chemical analysis was carried out by electron microprobe analysis and indicated a magnesium rich phase with partial substitution of iron. Traces of Ca and Mn, (which partially replaced Mg) were found. The calculated chemical formula of the studied sample is: (Mg0.88, Fe0.11)Al1.87(PO4)2.08(OH)2.02. The Raman spectrum of lazulite is dominated by an intense sharp band at 1060 cm-1 assigned to PO stretching vibrations of of tetrahedral [PO4] clusters presents into the HPO2/4- units. Two Raman bands at 1102 and 1137 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The two infrared bands at 997 and 1007 cm-1 are attributed to the m1 PO3/4- symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm-1 are assigned to the v3PO3/4- antisymmetric stretching modes from both the HOP and tetrahedral [PO4] clusters. A set of Raman bands at 605, 613, 633 and 648 cm-1 are assigned to the m4 out of plane bending modes of the PO4, HPO4 and H2PO4 units. Raman bands observed at 414, 425, 460, and 479 cm-1 are attributed to the m2 tetrahedral PO4 clusters, HPO4 and H2PO4 bending modes. The intense Raman band at 3402 and the infrared band at 3403 cm-1 are assigned to the stretching vibration of the OH units. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral lazulite to be understood.

Removal of bisphenol A from wastewater by Ca-montmorillonite modified with selected surfactants

Organo Arizona SAz-2 Ca-montmorillonite was prepared with different surfactant (DDTMA and HDTMA) loadings through direct ion exchange. The structural properties of the prepared organoclays were characterized by XRD and BET instruments. Batch experiments were carried out on the adsorption of bisphenol A (BPA) under different experimental conditions of pH and temperature to determine the optimum adsorption conditions. The hydrophobic phase and positively charged surface created by the loaded surfactant molecules are responsible for the adsorption of BPA. The adsorption of BPA onto organoclays is well described by pseudo-second order kinetic model and the Langmuir isotherm. The maximum adsorption capacity of the organoclays for BPA obtained from a Langmuir isotherm was 151.52 mg/g at 297 K. This value is among the highest values for BPA adsorption compared with other adsorbents. In addition, the adsorption process was spontaneous and exothermic based on the adsorption thermodynamics study. The organoclays intercalated with longer chain surfactant molecules possessed a greater adsorption capacity for BPA even under alkaline conditions. This process provides a pathway for the removal of BPA from contaminated waters.

Nanostructured high strength Mg-5%Al-x%Nd alloys prepared by mechanical alloying

Nanostructured high strength Mg-5%Al-x%Nd alloys were prepared by mechanical alloying. Microstructural characterization reveled average crystalline size to be about 30 nm after mechanical alloying while it increased to about 90 nm after sintering and extrusion. Mechanical properties showed increase in 0.2% yield stress, ultimate tensile strength was attributed to reduction in gain size as well as to the enhanced diffusion after mechanical activation. Although ultra high yield stress was observed from the specimen with 5% Nd, its ductility was reduced to about 1.6%.

Fabrication and microstructure of mechanically alloyed Mg-Al-Nd alloys

In this work, nanocrystalline Mg-Al-Nd alloys were fabricated using mechanical alloying method. Phase structure of the extrided rods was examined using X-ray diffraction (XRD) and the microstructures were observed using transmission electronic microscopy (TEM). High yield strength was obtained in the alloys with a high Nd content due to grain refinement and Nd rich precipitate phase.

A vibrational spectroscopic study of the phosphate mineral rimkorolgite (Mg,Mn2+)5(Ba, Sr)(PO4)4·8H2O from Kovdor massif, Kola Peninsula, Russia

We have studied aspect of the molecular structure of the phosphate mineral rimkorolgite from Zheleznyi iron mine, Kovdor massif, Kola Peninsula, Russia, using SEM with EDX and vibrational spectroscopy. Qualitative chemical analysis shows a homogeneous phase, composed by P, Mg, Ba, Mn and Ca. Small amounts of Si were also observed. An intense Raman peak at 975 cm−1 is assigned to the PO43− ν1 symmetric stretching mode. The Raman band at 964 cm−1 is attributed to the HPO42− ν1 symmetric stretching vibration. Raman bands observed at 1016, 1035, 1052, 1073, 1105 and 1135 cm−1 are attributed to the ν3 antisymmetric stretching vibrations of the HPO42− and PO43− units. Complexity in the spectra of the phosphate bending region is observed. The broad Raman band at 3272 cm−1 is assigned to the water stretching vibration. Vibrational spectroscopy enables aspects on the molecular structure of rimkorolgite to be undertaken.

A new period of volcanogenic massive sulfide formation in the Yilgarn: A volcanological study of the ca 2.76 Ga Hollandaire VMS deposit, Yilgarn Craton, Western Australia

The Archean Hollandaire volcanogenic massive sulfide deposit is a felsic–siliciclastic VMS deposit located in the Murchison Domain of the Youanmi Terrane, Yilgarn Craton, Western Australia. It is hosted in a succession of turbidites, mudstones and coherent rhyodacite sills and has been metamorphosed to upper greenschist/lower amphibolite facies and includes a pervasive S1 deformational fabric. The coherent rhyodacitic sills are interpreted as syndepositional based on geochemical similarities with well-known VMS-associated felsic rocks and similar foliations to the metasediments. We offer several explanations for the absence of textural evidence (e.g. breccias) for syn-depositional origins: 1) the subaqueous sediments were dehydrated by long-lived magmatism such that no pore-water remained to drive quench fragmentation; 2) pore-space occlusion by burial and/or, 3) alteration overprinting and obscuring of primary breccias at contact margins. Mineralisation occurs by sub-seafloor replacement of original host rocks in two ore bodies, Hollandaire Main (~125 x >500 m and ~8 m thick) and Hollandaire West (~100 x 470 m and ~5 m thick), and occurs in three main textural styles, massive sulfides, which are exclusively hosted in turbidites and mudstones, and stringer and disseminated sulfides, which are also hosted in coherent rhyodacite. Most sulfides have textures consistent with remobilisation and recrystallisation. Hydrothermal metamorphism has altered the hangingwall and footwall to similar degrees, with significant gains in Mg, Mn and K and losses in Na, Ca and Sr. Garnet and staurolite porphyryoblasts also exhibit a footprint around mineralisation, extending up to 30 m both above and below the ore zone. High precision thermal ionisation mass spectrometry of zircons extracted from the coherent rhyodacite yield an age of 2759.5 ± 0.9 Ma, which along with geochemical comparisons, places the succession within the 2760–2735 Ma Greensleeves Formation of the Polelle Group of the Murchison Supergroup. Geochemical and geochronological evidence link the coherent rhyodacite sills to the Peter Well Granodiorite pluton ~2 km to the W, which acted as the heat engine driving hydrothermal circulation during VMS mineralisation. This study highlights the importance of both: detailed physical volcanological studies from which an accurate assessment of timing relationships, particularly the possibility of intrusions dismembering ore horizons, can be made; and identifying synvolcanic plutons and other similar suites, for VMS exploration targets in the Youanmi Terrane and worldwide.