The review focuses on the effects of several important additives and templates controlling the calcium carbonate crystals formation and the complexity of the crystal morphologies in vitro. Additives ...include soluble matrices extracted from shells and pearls, amino-acids, magnesium ions and collagen among others. Templates include modified single crystal silicon, natural biominerals among others. Mechanisms proposed to explain the phenomena are not systematic, further studies are necessary to explain how organic matrices mediate calcium carbonate mineralization.
In pyrocarbon materials, the width of the Raman D band (FWHM
D) is very sensitive to low energy structural defects (e.g., disorientations of the graphene layers). The correlation between the two ...parameters, FWHM
D and OA (as derived from selected area electron diffraction: SAED), has allowed to differentiate various pyrocarbons unambiguously. Furthermore, the optical properties of pyrocarbons, i.e., the extinction angle, the optical phase shift and the ordinary and extraordinary reflectance, have been accurately determined at 550
nm by means of the extinction curves method. These results are completed by in-plane and out-of-plane dielectric constant measurements by angular resolved EELS. Moreover, the hybridization degree of the carbon atoms has been assessed by the same technique. About 80% of the carbon atoms of the pyrocarbons have a sp
2 hybridization. The lack of pure sp
2 carbon atoms, as compared to graphite, might be explained by the presence of sp
3-like line defects.
A key to understanding control over mineral formation in mollusk shells is the microenvironment inside the pre-formed 3-dimensional organic matrix framework where mineral forms. Much of what is known ...about nacre formation is from observations of the mature tissue. Although these studies have elucidated several important aspects of this process, the structure of the organic matrix and the microenvironment where the crystal nucleates and grows are very difficult to infer from observations of the mature nacre. Here, we use environmental- and cryo-scanning electron microscopy to investigate the organic matrix structure at the onset of mineralization in the nacre of two mollusk species: the bivalves Atrina rigida and Pinctada margaritifera. These two techniques allow the visualization of hydrated biological materials coupled with the preservation of the organic matrix close to physiological conditions. We identified a hydrated gel-like protein phase filling the space between two interlamellar sheets prior to mineral formation. The results are consistent with this phase being the silk-like proteins, and show that mineral formation does not occur in an aqueous solution, but in a hydrated gel-like medium. As the tablets grow, the silk-fibroin is pushed aside and becomes sandwiched between the mineral and the chitin layer.
Formation of nacre (mother-of-pearl) is a biomineralization process of fundamental scientific as well as industrial importance. However, the dynamics of the formation process is still not understood. ...Here, we use scanning electron microscopy and high spatial resolution ion microprobe depth-profiling to image the full three-dimensional distribution of organic materials around individual tablets in the top-most layer of forming nacre in bivalves. Nacre formation proceeds by lateral, symmetric growth of individual tablets mediated by a growth-ring rich in organics, in which aragonite crystallizes from amorphous precursors. The pivotal role in nacre formation played by the growth-ring structure documented in this study adds further complexity to a highly dynamical biomineralization process.
The need to quantify engineered nanoparticles (ENPs) in the environment is due to the increasing incorporation of these particles in the daily products, which threatens human health and can possibly ...impact natural systems. Ceria NPs (CeO2NPs) and titanium dioxide NPs (TiO2NPs) are two of the most used ENPs in the world. In this study their occurrence was determined in river waters with accurate and relevant techniques such as single particle ICP-MS (spICPMS). In the Loire River (France), the variation of both CeO2NPs and TiO2NPs could be assessed locally, with an increase of the concentrations near a wastewater treatment plant (WWTP) outlet as well as in a lake connected to the river and dedicated to outdoor activities. In the upstream river water, supposedly less impacted by NPs, 6.4 ± 1.2 x 104 part mL-1 Ce-bearing and 13.4 ± 1.8 x 104 part mL-1 Ti-bearing particles were measured. These values increased to 33.9 ± 3.4 x 104 part mL-1 Ce-bearing and 80.3 ± 3.4 x 104 part mL-1 Ti-bearing particles near the WWTP outlet. Equivalent size for sphere distributions ranged from 24 nm to 70 nm for CeO2 and from 80 nm to 500 nm for TiO2 in the river water. In the lake, a raise of the concentrations has been observed with 38.3 ± 2.0 x 104 part mL-1 and 71.6 ± 2.1 x 104 part mL-1 containing Ce and Ti, respectively, with similar size distributions. FEG-SEM imaging confirms the occurrence of Ce- and Ti-bearing particles in the water samples. On the contrary, NPs seem to undergo strong heteroaggregation in the Loire river water. The Ce/La elemental ratios does not evolve from upstream to downstream the WWTP outlet, suggesting that a natural origin cannot be excluded to explain the increase observed in NPs number concentration. On the contrary, the Ce/La ratio increases in the outdoor activities center, which suggests the contribution of NPs potentially related to the cars parked nearby. Besides, elemental ratios Ti/V and Ti/Y have been assessed to highlight an anthropogenic source of Ti in both sampling sites, possibly to the sunscreens used during the summer.
Motivation for detecting engineered nanoparticles (ENPs) in the environment comes from a need to understand fate and behavior of these materials in natural matrices. The difficulty lies in the low ...expected ENP particle number concentration (PNC) and the presence of a large and variable background concentration of natural NPs. We report the PNCs and characteristics of cerium-bearing nanoparticles (Ce-NPs) and titanium-bearing nanoparticles (Ti-NPs) in an aquatic matrix (the Seine River and three of its tributaries) with the use of single particle ICP-MS (spICPMS) and electron microscopy (FEG-SEM). Ce-bearing and Ti-bearing particles were observed in suspended particulate matter collected onto 0.2 μm and 1 kDa filters, using FEG-SEM imaging. At Marnay-sur-Seine, the upstream point, PNCs for Ce-NPs and Ti-NPs were 0.47 ± 0.07 × 10
6
and 1.35 ± 0.17 × 10
6
particles as measured by spICPMS. The maximum PNC for both Ce-NPs and Ti-NPs, 1.59 ± 0.10 × 10
6
particles mL
−1
and 5.89 ± 0.10 × 10
6
particles mL
−1
, respectively, were found in the Marne River, a major tributary to the Seine. It was shown that downstream of each confluence, an increase in the PNC of the Seine is observed, suggesting a significant contribution of the different tributaries. Mass balance of particles flows and elemental ratios of Ce/La showed that in the Marne and the Oise River, a contribution of natural CeO
2
NPs exists. The anthropogenic contribution in TiO
2
ENPs for the Marne River was further assessed with Ti/Al, Ti/V, and Ti/Y elemental ratios. Near constant element ratios in the Seine below the Orge River and Paris city suggest neither contribute significantly to Ce or Ti NP concentrations. The study provides further investigation of the strengths and limitations of the application of spICPMS to natural samples and contributes data to the currently highly-limited dataset on natural NP backgrounds in rivers, information that is key to assessing the potential for quantifying the input of ENPs to surface waters. Of the total mass of Ce and Ti, 83 and 90%, respectively, could be detected as particles by spICPMS.
Shell nacre (mother of pearl) of
Pinctada margaritifera was analyzed by scanning electron microscopy. The originality of this work concerns the sampling performed to observe incipient nacre on the ...mantle side. The whole animal is embedded in methyl methacrylate followed by separation of the shell from the hardened mantle. It is revealed this way how each future nacre layer pre-exists as a film or compartment. Experimental observations also show for the first time, the progressive lateral crystallization inside this film, finishing under the form of a non-periodic pattern of polygonal tablets of bio-aragonite. It is evidenced that nuclei appear in the film in the vicinity of the zone where aragonite tablets of the underlying layer get in contact to each other. A possible explanation is given to show how nucleation is probably launched in time and space by a signal coming from the underlying layer. Finally, it is evidenced that tablets form a Voronoi tiling of the space: this suggests that their growth is controlled by an “aggregation-like” process of “crystallites” and not directly by the aragonite lattice growth.
Many tribological properties and wear mechanisms occurring on the micro-and nanoscale are strongly controlled by the so-called real contact area (
A
r
) which is a small fraction of the nominal or ...apparent contact area (
A
a
). The determination of
A
r
is often based on either (i) a geometrical approach describing the real geometry of contacting surfaces or (ii) a mechanical approach involving contact mechanics and physical-mechanical properties. In addition some experimental methods have also been attempted but they generally do not take into account the presence of third body at the interface—i.e. the wear debris trapped within the contact. In this paper we propose an experimental approach to estimate the dynamic real contact area from the operating parameters (
F
n
,
v,
T) and the tribological responses (
μ,
F
t
) in presence of third body. A scanning thermal microscope (SThM) is used for determining both the thermal conductivity of the third body and the relationship between the contact temperature and the thermal power really dissipated at the micro-asperity level. These results are combined with a thermal model of the macro-tribocontact for computing the real contact area and the real contact pressure. Validation of these results is carried out using a classical Greenwood Williamson model and finite element models built from the real AFM maps.
•New methods are requested for characterizing asbestos fibers in a mineral matrix.•SEM-Raman imaging is efficient for characterizing mineral fibers in-situ.•Confocal Raman imaging makes 3D analysis ...possible.•3D analysis provides information on the aspect ratio and volume fraction of asbestos.•Fibers thinner than 400 nm can be identified by confocal Raman in SEM (λ = 532 nm).
Asbestos consists in natural minerals crystallized in a specific habit and possessing in particular properties. In the case of Naturally Occurring Asbestos, usual methods applied to the identification of mineral fibers and the determination of their possible asbestiform nature seems not efficient, especially in the case of mineral fibers included in mineral matrix.
We present a new in-situ method based on the use of confocal Raman-in-SEM imaging implemented in a Scanning Electron Microscope as an efficient method for in-situ mineralogy. The limitation of conventional methods is discussed. We applied 2D-Raman imaging to the identification of sub-micrometric fibers included in different mineral matrix. We were able to identify actinolite fibers down to 400 nm in diameter, included in feldspar, quartz and/or calcite matrix.
Moreover, Confocal Raman allows the collection of 3D data that would provide access to critical information on the morphology of the amphibole fibers in the volume, such as aspect ratio, fibers distribution and amphibole volume fraction.
We performed this method on various examples of rocks containing actinolite fibers of mean structural formula is: Na0,04-0,12 Mg2,79-3,73 Al0,29-0,58 K0,01 Ca1,79-1,98 Mn0,01-0,09 Fe2+0,99-1,91 Fe3+Si7,64-7,73 O22(OH)2. We demonstrated that coupling confocal Raman imaging and SEM is a new and efficient in-situ method for identification and morphological characterization of amphibole fibers.
Multiscale structure of sheet nacre Rousseau, Marthe; Lopez, Evelyne; Stempflé, Philippe ...
Biomaterials,
11/2005, Letnik:
26, Številka:
31
Journal Article
Recenzirano
Odprti dostop
This work was conducted on
Pinctada maxima nacre (mother of pearl) in order to understand its multiscale ordering and the role of the organic matrix in its structure. Intermittent-contact atomic ...force microscopy with phase detection imaging reveals a nanostructure within the tablet. A
continuous organic framework divides each tablet into nanograins. Their shape is supposed to be flat with a mean extension of 45
nm. TEM performed in the darkfield mode evidences that at least part of the intracrystalline matrix is crystallized and responds like a ‘single crystal’. The tablet is a ‘hybrid composite’. The organic matrix is continuous. The mineral phase is thus finely divided still behaving as a single crystal. It is proposed that each tablet results from the coherent aggregation of nanograins keeping strictly the same crystallographic orientation thanks to a hetero-epitaxy mechanism. Finally, high-resolution TEM performed on bridges from one tablet to the next, in the overlying row, did not permit to evidence a mineral lattice but crystallized organic bridges. The same organic bridges were evidenced by SEM in the interlaminar sequence.
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