Trace-element modeling of the magmatic evolution of rare-earth-rich carbonatite from the Miaoya deposit, Central China

Carbonatites are known to contain the highest concentrations of rare-earth elements (REE) among all igneous rocks. The REE distribution of carbonatites is commonly believed to be controlled by that of the rock forming Ca minerals (i.e., calcite, dolomite, and ankerite) and apatite because of their high modal content and tolerance for the substitution of Ca by light REE (LREE). Contrary to this conjecture, calcite from the Miaoya carbonatite (China), analyzed in situ by laser-ablation inductively-coupled-plasma mass-spectrometry, is characterized by low REE contents (100–260 ppm) and relatively !at chondrite-normalized REE distribution patterns [average (La/Yb)CN=1.6]. The carbonatite contains abundant REE-rich minerals, including monazite and !uorapatite, both precipitated earlier than the REE-poor calcite, and REE-fluorocarbonates that postdated the calcite. Hydrothermal REE-bearing !uorite and barite veins are not observed at Miaoya. The textural and analytical evidence indicates that the initially high concentrations of REE and P in the carbonatitic magma facilitated early precipitation of REE-rich phosphates. Subsequent crystallization of REE-poor calcite led to enrichment of the residual liquid in REE, particularly LREE. This implies that REE are generally incompatible with respect to calcite and the calcite/melt partition coefficients for heavy REE (HREE) are significantly greater than those for LREE. Precipitation of REE-fluorocarbonates late in the evolutionary history resulted in depletion of the residual liquid in LREE, as manifested by the development of HREE-enriched late-stage calcite [(La/Yb)CN=0.7] in syenites associated with the carbonatite. The observed variations of REE distribution between calcite and whole rocks are interpreted to arise from multistage fractional crystallization (phosphates!calcite!REE-!uorocarbonates) from an initially REE-rich carbonatitic liquid.

Non-contact laser-scanning confocal microscopy of the human cornea in vivo

PURPOSE To investigate the utility of using non-contact laser-scanning confocal microscopy (NC-LSCM), compared with the more conventional contact laser-scanning confocal microscopy (C-LSCM), for examining corneal substructures in vivo. METHODS An attempt was made to capture representative images from the tear film and all layers of the cornea of a healthy, 35 year old female, using both NC-LSCM and C-LSCM, on separate days. RESULTS Using NC-LSCM, good quality images were obtained of the tear film, stroma, and a section of endothelium, but the corneal depth of the images of these various substructures could not be ascertained. Using C-LSCM, good quality, full-field images were obtained of the epithelium, subbasal nerve plexus, stroma, and endothelium, and the corneal depth of each of the captured images could be ascertained. CONCLUSIONS NC-LSCM may find general use for clinical examination of the tear film, stroma and endothelium, with the caveat that the depth of stromal images cannot be determined when using this technique. This technique also facilitates image capture of oblique sections of multiple corneal layers. The inability to clearly and consistently image thin corneal substructures - such as the tear film, subbasal nerve plexus and endothelium - is a key limitation of NC-LSCM.

Laser-radar data fusion with Gaussian Process Implicit Surfaces

This work considers the problem of building high-fidelity 3D representations of the environment from sensor data acquired by mobile robots. Multi-sensor data fusion allows for more complete and accurate representations, and for more reliable perception, especially when different sensing modalities are used. In this paper, we propose a thorough experimental analysis of the performance of 3D surface reconstruction from laser and mm-wave radar data using Gaussian Process Implicit Surfaces (GPIS), in a realistic field robotics scenario. We first analyse the performance of GPIS using raw laser data alone and raw radar data alone, respectively, with different choices of covariance matrices and different resolutions of the input data. We then evaluate and compare the performance of two different GPIS fusion approaches. The first, state-of-the-art approach directly fuses raw data from laser and radar. The alternative approach proposed in this paper first computes an initial estimate of the surface from each single source of data, and then fuses these two estimates. We show that this method outperforms the state of the art, especially in situations where the sensors react differently to the targets they perceive.

Using image quality metrics to detect smoke-affected laser data

Field robots often rely on laser range finders (LRFs) to detect obstacles and navigate autonomously. Despite recent progress in sensing technology and perception algorithms, adverse environmental conditions, such as the presence of smoke, remain a challenging issue for these robots. In this paper, we investigate the possibility to improve laser-based perception applications by anticipating situations when laser data are affected by smoke, using supervised learning and state-of-the-art visual image quality analysis. We propose to train a k-nearest-neighbour (kNN) classifier to recognise situations where a laser scan is likely to be affected by smoke, based on visual data quality features. This method is evaluated experimentally using a mobile robot equipped with LRFs and a visual camera. The strengths and limitations of the technique are identified and discussed, and we show that the method is beneficial if conservative decisions are the most appropriate.

Laser-to-radar sensing redundancy for resilient perception in adverse environmental conditions

This paper presents an approach to promote the integrity of perception systems for outdoor unmanned ground vehicles (UGV) operating in challenging environmental conditions (presence of dust or smoke). The proposed technique automatically evaluates the consistency of the data provided by two sensing modalities: a 2D laser range finder and a millimetre-wave radar, allowing for perceptual failure mitigation. Experimental results, obtained with a UGV operating in rural environments, and an error analysis validate the approach.

Reliable automatic camera-laser calibration

Camera-laser calibration is necessary for many robotics and computer vision applications. However, existing calibration toolboxes still require laborious effort from the operator in order to achieve reliable and accurate results. This paper proposes algorithms that augment two existing trustful calibration methods with an automatic extraction of the calibration object from the sensor data. The result is a complete procedure that allows for automatic camera-laser calibration. The first stage of the procedure is automatic camera calibration which is useful in its own right for many applications. The chessboard extraction algorithm it provides is shown to outperform openly available techniques. The second stage completes the procedure by providing automatic camera-laser calibration. The procedure has been verified by extensive experimental tests with the proposed algorithms providing a major reduction in time required from an operator in comparison to manual methods.

Laser-camera data discrepancies and reliable perception in outdoor robotics

This work aims to promote integrity in autonomous perceptual systems, with a focus on outdoor unmanned ground vehicles equipped with a camera and a 2D laser range finder. A method to check for inconsistencies between the data provided by these two heterogeneous sensors is proposed and discussed. First, uncertainties in the estimated transformation between the laser and camera frames are evaluated and propagated up to the projection of the laser points onto the image. Then, for each pair of laser scan-camera image acquired, the information at corners of the laser scan is compared with the content of the image, resulting in a likelihood of correspondence. The result of this process is then used to validate segments of the laser scan that are found to be consistent with the image, while inconsistent segments are rejected. Experimental results illustrate how this technique can improve the reliability of perception in challenging environmental conditions, such as in the presence of airborne dust.

Liquid metal enabled pump

Small-scale pumps will be the heartbeat of many future micro/nanoscale platforms. However, the integration of small-scale pumps is presently hampered by limited flow rate with respect to the input power, and their rather complicated fabrication processes. These issues arise as many conventional pumping effects require intricate moving elements. Here, we demonstrate a system that we call the liquid metal enabled pump, for driving a range of liquids without mechanical moving parts, upon the application of modest electric field. This pump incorporates a droplet of liquid metal, which induces liquid flow at high flow rates, yet with exceptionally low power consumption by electrowetting/deelectrowetting at the metal surface. We present theory explaining this pumping mechanism and show that the operation is fundamentally different from other existing pumps. The presented liquid metal enabled pump is both efficient and simple, and thus has the potential to fundamentally advance the field of microfluidics.

Ambient ionisation mass spectrometry for the characterisation of polymers and polymer additives : A review

The purpose of this review is to showcase the present capabilities of ambient sampling and ionisation technologies for the analysis of polymers and polymer additives by mass spectrometry (MS) while simultaneously highlighting their advantages and limitations in a critical fashion. To qualify as an ambient ionisation technique, the method must be able to probe the surface of solid or liquid samples while operating in an open environment, allowing a variety of sample sizes, shapes, and substrate materials to be analysed. The main sections of this review will be guided by the underlying principle governing the desorption/extraction step of the analysis; liquid extraction, laser ablation, or thermal desorption, and the major component investigated, either the polymer itself or exogenous compounds (additives and contaminants) present within or on the polymer substrate. The review will conclude by summarising some of the challenges these technologies still face and possible directions that would further enhance the utility of ambient ionisation mass spectrometry as a tool for polymer analysis. (C) 2013 Elsevier B. V. All rights reserved.

Characterising in situ activation and degradation of hindered amine light stabilisers using liquid extraction surface analysis-mass spectrometry

Changes in the molecular structure of polymer antioxidants such as hindered amine light stabilisers (HALS) is central to their efficacy in retarding polymer degradation and therefore requires careful monitoring during their in-service lifetime. The HALS, bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (TIN123) and bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (TIN292), were formulated in different polymer systems and then exposed to various curing and ageing treatments to simulate in-service use. Samples of these coatings were then analysed directly using liquid extraction surface analysis (LESA) coupled with a triple quadrupole mass spectrometer. Analysis of TIN123 formulated in a cross-linked polyester revealed that the polymer matrix protected TIN123 from undergoing extensive thermal degradation that would normally occur at 292 degrees C, specifically, changes at the 1- and 4-positions of the piperidine groups. The effect of thermal versus photo-oxidative degradation was also compared for TIN292 formulated in polyacrylate films by monitoring the in situ conversion of N-CH3 substituted piperidines to N-H. The analysis confirmed that UV light was required for the conversion of N-CH3 moieties to N-H - a major pathway in the antioxidant protection of polymers - whereas this conversion was not observed with thermal degradation. The use of tandem mass spectrometric techniques, including precursor-ion scanning, is shown to be highly sensitive and specific for detecting molecular-level changes in HALS compounds and, when coupled with LESA, able to monitor these changes in situ with speed and reproducibility. (C) 2013 Elsevier B. V. All rights reserved.

Stimulation of osteogenic and angiogenic ability of cells on polymers by pulsed laser deposition of uniform akermanite-glass nanolayer

Polymer biomaterials have been widely used for bone replacement/regeneration because of their unique mechanical properties and workability. Their inherent low bioactivity makes them lack osseointegration with host bone tissue. For this reason, bioactive inorganic particles have been always incorporated into the matrix of polymers to improve their bioactivity. However, mixing inorganic particles with polymers always results in inhomogeneity of particle distribution in polymer matrix with limited bioactivity. This study sets out to apply the pulsed laser deposition (PLD) technique to prepare uniform akermanite (Ca2MgSi2O7, AKT) glass nanocoatings on the surface of two polymers (non-degradable polysulfone (PSU) and degradable polylactic acid (PDLLA)) in order to improve their surface osteogenic and angiogenic activity. The results show that a uniform nanolayer composed of amorphous AKT particles (∼30nm) of thickness 130nm forms on the surface of both PSU and PDLLA films with the PLD technique. The prepared AKT-PSU and AKT-PDLLA films significantly improved the surface roughness, hydrophilicity, hardness and apatite mineralization, compared with pure PSU and PDLLA, respectively. The prepared AKT nanocoatings distinctively enhance the alkaline phosphate (ALP) activity and bone-related gene expression (ALP, OCN, OPN and Col I) of bone-forming cells on both PSU and PDLLA films. Furthermore, AKT nanocoatings on two polymers improve the attachment, proliferation, VEGF secretion and expression of proangiogenic factors and their receptors of human umbilical vein endothelial cells (HUVEC). The results suggest that PLD-prepared bioceramic nanocoatings are very useful for enhancing the physicochemical, osteogenic and angiogenic properties of both degradable and non-degradable polymers for application in bone replacement/regeneration.

Direct detection of additives and degradation products from polymers by liquid extraction surface analysis employing chip-based nanospray mass spectrometry

RATIONALE: Polymer-based surface coatings in outdoor applications experience accelerated degradation due to exposure to solar radiation, oxygen and atmospheric pollutants. These deleterious agents cause undesirable changes to the aesthetic and mechanical properties of the polymer, reducing its lifetime. The use of antioxidants such as hindered amine light stabilisers (HALS) retards these degradative processes; however, mechanisms for HALS action and polymer degradation are poorly understood. METHODS: Detection of the HALS TINUVINW123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) and the polymer degradation products directly from a polyester-based coil coating was achieved by liquid extraction surface analysis (LESA) coupled to a triple quadrupole QTRAPW 5500 mass spectrometer. The detection of TINUVINW123 and melamine was confirmed by the characteristic fragmentation pattern observed in LESA-MS/MS spectra that was identical to that reported for authentic samples. RESULTS: Analysis of an unstabilised coil coating by LESA-MS after exposure to 4 years of outdoor field testing revealed the presence of melamine (1,3,5-triazine-2,4,6-triamine) as a polymer degradation product at elevated levels. Changes to the physical appearance of the coil coating, including powder-like deposits on the coating's surface, were observed to coincide with melamine deposits and are indicative of the phenomenon known as polymer ' blooming'. CONCLUSIONS: For the first time, in situ detection of analytes from a thermoset polymer coating was accomplished without any sample preparation, providing advantages over traditional extraction-analysis approaches and some contemporary ambient MS methods. Detection of HALS and polymer degradation products such as melamine provides insight into the mechanisms by which degradation occurs and suggests LESA-MS is a powerful new tool for polymer analysis. Copyright (C) 2012 John Wiley & Sons, Ltd.

Liquid metal/metal oxide frameworks

A new platform described as the liquid metal/metal oxide (LM/MO) framework is introduced. The constituent spherical structures of these frameworks are made of micro- to nanosized liquid metal spheres and nanosized metal oxides, combining the advantages of both materials. It is shown that the diameters of the spheres and the stoichiometry of the structures can be actively controlled. Additionally, the liquid suspension of these spheres demonstrates tuneable plasmon resonances. These spherical structures are assembled to form LM/MO frameworks which are capable of demonstrating high sensitivity towards low concentrations of heavy metal ions, and enhanced solar light driven photocalalytic activities. These demonstrations imply that the LM/MO frameworks are a suitable candidate for the development of future high performance electronic and optical devices.

Hydrodynamic theory of liquid slippage on a solid substrate near a moving contact line

In this Letter a hydrodynamic theory of liquid slippage on a solid substrate near a moving contact line is proposed. A family of spatially varying slip lengths in the Navier slip law recovers the results of past formulations for slip in continuum theories and molecular dynamics simulations and is consistent with well-established experimental observations of complete wetting. This formulation gives a general approach for continuum hydrodynamic theories. New fluid flow behaviors are also predicted yet to be seen in experiment. © 2013 American Physical Society.