A continuous and scalable method for the wet spinning of cellulose nanofibrils (CNFs) is introduced in a core/shell configuration. Control on the interfacial interactions was possible by the choice ...of the shell material and coagulant, as demonstrated here with guar gum (GG) and cellulose acetate (CA). Upon coagulation in acetone, ethanol, or water, GG and CA formed supporting polymer shells that interacted to different degrees with the CNF core. Coagulation rate was shown to markedly influence the CNF orientation in the filament and, as a result, its mechanical strength. The fastest coagulation noted for the CNF/GG core/shell system in acetone led to an orientation index of ∼0.55 (Herman’s orientation parameter of 0.40), Young’s modulus of ∼2.1 GPa, a tensile strength of ∼70 MPa, and a tenacity of ∼8 cN/tex. The system that underwent the slowest coagulation rate (CNF/GG in ethanol) displayed a limited CNF orientation but achieved an intermediate level of mechanical resistance, owing to the strong core/shell interfacial affinity. By using CA as the supporting shell, it was possible to spin CNF into filaments with high water absorption capacity (43 g water/g dry filament). This was explained by the fact that water (used as the coagulant for CA) limited the densification of the CNF core structure, yielding filaments with high accessible area and pore density.
We demonstrated that low-cost and environmentally friendly filaments of native cellulose can be prepared by dry spinning an aqueous suspension of cellulose nanofibers (CNF). The CNF were extracted ...from banana rachis, a bioresidue from banana cultivation. The relationship between spinning rate, CNF concentration, and the mechanical properties of the filaments were investigated and the results showed that the modulus of the filaments was increased from 7.8 to 12.6 GPa and the strength increased from 131 to 222 MPa when the lowest concentration and highest speed was used. This improvement is believed to be due to an increased orientation of the CNF in the filament. A minimum concentration of 6.5 wt % was required for continuous filament spinning using the current setup. However, this relatively high concentration is thought to limit the orientation of the CNF in the filament. The process used in this study has a good potential for upscaling providing a continuous filament production with well-controlled speed, but further work is required to increase the orientation and subsequently the mechanical properties.
Matrix-matched calibration by natural zircon standards and analysis of natural materials as a reference are the principle methods for achieving accurate results in microbeam U–Pb dating and Hf ...isotopic analysis. We describe a new potential zircon reference material for laser ablation ICP-MS that was extracted from a potassic granulite facies rock collected in the southern part of the Bohemian Massif (Plešovice, Czech Republic).
Data from different techniques (ID-TIMS, SIMS and LA ICP-MS) and several laboratories suggest that this zircon has a concordant U–Pb age with a weighted mean
206Pb/
238U date of 337.13
±
0.37 Ma (ID-TIMS, 95% confidence limits, including tracer calibration uncertainty) and U–Pb age homogeneity on the scale used in LA ICP-MS dating. Inhomogeneities in trace element composition due to primary growth zoning prevent its use as a calibration standard for trace element analysis. The content of U varies from 465 ppm in pristine parts of the grains to ~
3000 ppm in actinide-rich sectors that correspond to pyramidal faces with a high degree of metamictization (present in ca. 30% of the grains). These domains are easily recognized from high intensities on BSE images and should be avoided during the analysis. Hf isotopic composition of the Plešovice zircon (>
0.9 wt.% Hf) is homogenous within and between the grains with a mean
176Hf/
177Hf value of 0.282482
±
0.000013 (2SD). The age and Hf isotopic homogeneity of the Plešovice zircon together with its relatively high U and Pb contents make it an ideal calibration and reference material for laser ablation ICP-MS measurements, especially when using low laser energies and/or small diameters of laser beam required for improved spatial resolution.
Crystals of K-feldspar (
C
2/
m
), in contact with highly concentrated aqueous NaCl solutions at 500°C and 200 MPa, are pseudomorphically replaced by high albite
as a result of an interface-coupled ...dissolution/reprecipitation process. The reaction occurs at an extremely sharp reaction front (<10 nm) and involves the complete breakdown of the initial framework structure. This results in the release of tetrahedrally incorporated elements such as Fe
3+
and Ti
4+
and a significant increase in Si/Al disorder across the reaction interface. The evolving microstructure is controlled by crystallographic relations between the phases. This leads to highly anisotropic, sawtooth-shaped intergrowths of albite and initial K-feldspar, resulting in the least structural misfit between the two framework structures. As a result, the newly formed interfaces appear to be semicoherent, and cracks across the reaction fronts even indicate elastic strain. The reaction produces 2 distinctive albite types (
albite
-
1
and
albite
-
2
). Both are polycrystalline, with
albite
-2 showing significantly larger subgrain sizes. This indicates a secondary coarsening step driven by the reduction in interfacial energy within the polycrystalline replacement product. The reaction also produces a highly porous rim. However, the porosity is not evenly distributed resulting in a porous
albite
-
1
and a non-porous
albite
-
2
that mostly surrounds large, euhedral pores. Despite the substantial volume fraction of porosity in
albite
-
1
, no significant 3D interconnectivity could be detected, making the presence of a pervasive porosity unlikely. However, the result of coarsening is the continuous modification of the 3D porosity distribution. This could potentially provide a mechanism for fluid transport through the replacement rim until textural and chemical equilibration is achieved.
We introduce and propose zircon M257 as a future reference material for the determination of zircon U‐Pb ages by means of secondary ion mass spectrometry. This light brownish, flawless, cut gemstone ...specimen from Sri Lanka weighed 5.14 g (25.7 carats). Zircon M257 has TIMS‐determined, mean isotopic ratios (2s uncertainties) of 0.09100 ± 0.00003 for 206pb/238U and 0.7392 ± 0.0003 for 207pb/235U. Its 206pb/238U age is 561.3 ± 0.3 Ma (unweighted mean, uncertainty quoted at the 95% confidence level); the U‐Pb system is concordant within uncertainty of decay constants. Zircon M257 contains ∼ 840 μg g−1 U (Th/U ∼ 0.27). The material exhibits remarkably low heterogeneity, with a virtual absence of any internal textures even in cathodoluminescence images. The uniform, moderate degree of radiation damage (estimated from the expansion of unit‐cell parameters, broadening of Raman spectral parameters and density) corresponds well, within the “Sri Lankan trends”, with actinide concentrations, U‐Pb age, and the calculated alpha fluence of 1.66 × 1018 g−1. This, and a (U+Th)/He age of 419 ± 9 Ma (2s), enables us to exclude any unusual thermal history or heat treatment, which could potentially have affected the retention of radiogenic Pb. The oxygen isotope ratio of this zircon is 13.9%o VSMOW suggesting a metamorphic genesis in a marble or calc‐silicate skarn.
Nous présentons et proposons à la communauté le zircon M257 qui pourrait devenir un matériau de référence pour la détermination des âges U‐Pb sur zircon par spectrométrie de masse à ions secondaires (SIMS). Ce spécimen scié d'une gemme brun clair, sans defauts, provenant du Sri Lanka, pèse 5.14 g (25.7 carats). Les moyennes des rapports isotopiques (et les incertitudes associées 2s) mesurées par TIMS sur ce zircon M257 sont 0.09100 ± 0.00003 en 206pb/238U et 0.7392 ± 0.0003 en 207pb/235U. Son âge 206pb/238U est de 561.3 ± 0.3 Ma (moyenne non pondérée, incertitude: 95% intervalle de confiance); le système U‐Pb y est concordant, aux erreurs sur les constantes de désintégration près. Le zircon M257 contient ∼ 840 μg g−1 U (Th/U ∼ 0.27). Ce matériel montre de très faibles hétérogénéités, avec une quasi absence de textures internes, même a I'examen par cathodoluminescence. Le degrê de dommage lié aux radiations (estimé par I'expansion des paramètres de la cellule unitaire, I'élargissement des paramètres des spectres Raman et la densité) est modéré et uniforme. II se corrèle bien, (sur I'alignement “Sri Lanka”) avec les concentrations en actinides, I'âge U‐Pb et la fluence calculée de 1.66 × 1018 g−1 Ceci, coupléà son âge (U+Th)/He de 419 ± 9 Ma (2s), nous permet d'exclure I'existence d'événement thermique passé, ou de traitement par la chaleur, qui aurait potentiellement pu affecter le processus de rétention de Pb radiogénique. Le rapport isotopique de I'oxygène de ce zircon est 13.9%o VSMOW, suggérant une génèse par métamorphisme, au sein d'un marbre ou d'un skarn calco‐silicaté.
An essential operation in the mineral processing of copper ores into concentrates is blending, as it guarantees a constant feed for the flotation cells, increases metal recovery rate and reduces ...tailings. In this study, copper ores from Huelva province (Spain) were investigated by quantitative XRD (X-ray diffraction) methods to optimize blending and detect penalty minerals, which can affect flotation and concentrate quality. The Rietveld method in combination with cluster analysis, PLSR and more traditional chemical analysis provide a more complete and in-depth characterization of the ore and the whole process. The mineralogical monitoring can be fully automated to enable real-time decision making.
The use of high-speed detectors made X-ray diffraction (XRD) become an important tool for process control in mining and metal industries. Decreasing ore qualities and increasing prices for raw ...materials require a better control of processed ore and a more efficient use of energy. Traditionally quality control of iron ore sinter has relied on time-consuming wet chemistry. The mineralogical composition that defines the physical properties such as hardness or reducibility is not monitored. XRD analysis in combination with Rietveld quantification and statistical data evaluation using partial least-squares regression (PLSR) has been successfully established to determine the mineralogical composition and the Fe2+ content of iron ore sinter within an analysis time of less than 10 min per sample. A total of 35 iron ore sinter samples were measured and evaluated using PLSR and the Rietveld method. The results were compared with wet chemistry data. PLSR results show accuracy for the Fe2+ content of ±0.14%. No pure phases, crystal structures, or complex modeling of peak shapes are required. The Rietveld method was used to quantify the total phase composition of the samples. The Fe2+ content could be calculated from all phases present. Both methods take the full XRD pattern into account and can be simultaneously applied on the same measurement. PLSR was found to be the more robust method if only Fe2+ results are required. The Rietveld method helps predict other parameters such as the compressional strength of the sinter by monitoring all existing phases (e.g., larnite, C2S, or silico-ferrite of calcium and aluminum phases).
We report the synthesis of colloidal Mn(2+)-doped ZnO (Mn(2+):ZnO) quantum dots and the preparation of room-temperature ferromagnetic nanocrystalline thin films. Mn(2+):ZnO nanocrystals were prepared ...by a hydrolysis and condensation reaction in DMSO under atmospheric conditions. Synthesis was monitored by electronic absorption and electron paramagnetic resonance (EPR) spectroscopies. Zn(OAc)(2) was found to strongly inhibit oxidation of Mn(2+) by O(2), allowing the synthesis of Mn(2+):ZnO to be performed aerobically. Mn(2+) ions were removed from the surfaces of as-prepared nanocrystals using dodecylamine to yield high-quality internally doped Mn(2+):ZnO colloids of nearly spherical shape and uniform diameter (6.1 +/- 0.7 nm). Simulations of the highly resolved X- and Q-band nanocrystal EPR spectra, combined with quantitative analysis of magnetic susceptibilities, confirmed that the manganese is substitutionally incorporated into the ZnO nanocrystals as Mn(2+) with very homogeneous speciation, differing from bulk Mn(2+):ZnO only in the magnitude of D-strain. Robust ferromagnetism was observed in spin-coated thin films of the nanocrystals, with 300 K saturation moments as large as 1.35 micro(B)/Mn(2+) and T(C) > 350 K. A distinct ferromagnetic resonance signal was observed in the EPR spectra of the ferromagnetic films. The occurrence of ferromagnetism in Mn(2+):ZnO and its dependence on synthetic variables are discussed in the context of these and previous theoretical and experimental results.
In this paper, we will report about the implementation of the self-consistent Kröner–Eshelby model for the calculation of X-ray elastic constants for general, triclinic crystal symmetry. With ...applying appropriate symmetry relations, the point groups of higher crystal symmetries are covered as well. This simplifies the implementation effort to cover the calculations for any crystal symmetry. In the literature, several models can be found to estimate the polycrystalline elastic properties from single crystal elastic constants. In general, this is an intermediate step toward the calculation of the polycrystalline response to different techniques using X-rays, neutrons, or ultrasonic waves. In the case of X-ray residual stress analysis, the final goal is the calculation of X-ray Elastic constants. Contrary to the models of Reuss, Voigt, and Hill, the Kröner–Eshelby model has the benefit that, because of the implementation of the Eshelby inclusion model, it can be expanded to cover more complicated systems that exhibit multiple phases, inclusions or pores and that these can be optionally combined with a polycrystalline matrix that is anisotropic, i.e., contains texture. We will discuss a recent theoretical development where the approaches of calculating bounds of Reuss and Voigt, the tighter bounds of Hashin–Shtrikman and Dederichs–Zeller are brought together in one unifying model that converges to the self-consistent solution of Kröner–Eshelby. For the implementation of the Kröner–Eshelby model the well-known Voigt notation is adopted. The 4-rank tensor operations have been rewritten into 2-rank matrix operations. The practical difficulties of the Voigt notation, as usually concealed in the scientific literature, will be discussed. Last, we will show a practical X-ray example in which the various models are applied and compared.
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