Handling Nanoparticle Content in Nanocomposite Thin Films Deposited by Misty Plasma Processes through Controlled Flash Boiling Atomization.

Misty plasma processes based on colloidal solutions sprayed into low-pressure plasmas have recently shown great potential for multifunctional thin film deposition. In such processes, nanoparticle accumulation in ring-shaped structures remains the main obstacle to the synthesis of high-quality coatings containing abundant, small-scale, and evenly dispersed nanoparticles. These local buildups appear after a colloidal droplet evaporates from a substrate. Accordingly, controlling the droplets' size in the spray is of key importance to ensure a uniform nanoparticle content in the plasma-deposited nanocomposite film. In this work, it is shown that the use of more volatile solvents produces finer droplets on the substrate, thereby improving nanoparticle dispersion in the matrix. A one-dimensional evaporation model is further developed and used to show that, contrary to what one might expect, this result cannot be attributed to faster evaporation during droplet transport in the low-pressure plasma. Instead, a so-called "flash" boiling atomization mechanism is discussed to support the experimental findings.

Anatase TiO2 deposited at low temperature by pulsing an electron cyclotron wave resonance plasma source.

Photocatalytic surfaces have the potentiality to respond to many of nowadays societal concerns such as clean H2 generation, CO2 conversion, organic pollutant removal or virus inactivation. Despite its numerous superior properties, the wide development of TiO2 photocatalytic surfaces suffers from important drawbacks. Hence, the high temperature usually required (> 450 °C) for the synthesis of anatase TiO2 is still a challenge to outreach. In this article, we report the development and optimisation of an ECWR-PECVD process enabling the deposition of anatase TiO2 thin films at low substrate temperature. Scanning of experimental parameters such as RF power and deposition time was achieved in order to maximise photocatalytic activity. The careful selection of the deposition parameters (RF power, deposition time and plasma gas composition) enabled the synthesis of coatings exhibiting photocatalytic activity comparable to industrial references such as P25 Degussa and Pilkington Activ at a substrate temperature below 200 °C. In addition, to further decrease the substrate temperature, the interest of pulsing the plasma RF source was investigated. Using a duty cycle of 50%, it is thus possible to synthesise photocatalytic anatase TiO2 thin films at a substrate temperature below 115 °C with a deposition rate around 10 nm/min.

Fabrication of a nickel nanowire mesh electrode suspended on polymer substrate.

We report on an efficient strategy for the fabrication of an ultra-long suspended nanowire mesh suitable for nanodevice architectures on a polymer surface. First, nickel nanowires are synthesized directly on a template substrate by magnetron sputtering. Laser interference lithography followed by deep reactive ion etching is used to create the nanograted template substrate constituted of one-dimensional line pattern arrays of 240 nm in periodicity. Ordered alignment of ultra-long nanowires (∼180 nm in diameter) with high fidelity to the template pattern is observed by scanning electron microscopy. The transfer of the pre-defined parallel nanowire array from the template surface to a target polymer substrate for electrical characterization of the system is demonstrated. The electrical behaviour of the nanowire mesh, suspended between two electrodes, was found to be linear, stable, and reproducible. This result suggests that this nanofabrication process will open an efficient way to the design and construction of novel nanodevices.

Hierarchical carbon nanostructure design: ultra-long carbon nanofibers decorated with carbon nanotubes.

Hierarchical carbon nanostructures based on ultra-long carbon nanofibers (CNF) decorated with carbon nanotubes (CNT) have been prepared using plasma processes. The nickel/carbon composite nanofibers, used as a support for the growth of CNT, were deposited on nanopatterned silicon substrate by a hybrid plasma process, combining magnetron sputtering and plasma-enhanced chemical vapor deposition (PECVD). Transmission electron microscopy revealed the presence of spherical nanoparticles randomly dispersed within the carbon nanofibers. The nickel nanoparticles have been used as a catalyst to initiate the growth of CNT by PECVD at 600°C. After the growth of CNT onto the ultra-long CNF, SEM imaging revealed the formation of hierarchical carbon nanostructures which consist of CNF sheathed with CNTs. Furthermore, we demonstrate that reducing the growth temperature of CNT to less than 500°C leads to the formation of carbon nanowalls on the CNF instead of CNT. This simple fabrication method allows an easy preparation of hierarchical carbon nanostructures over a large surface area, as well as a simple manipulation of such material in order to integrate it into nanodevices.

Titanium carbide/carbon composite nanofibers prepared by a plasma process.

The incorporation of metal or metal carbide nanoparticles into carbon nanofibers modifies their properties and enlarges their field of application. The purpose of this work is to report a new non-catalytic and easy method to prepare organized metal carbide-carbon composite nanofibers on nanopatterned silicon substrates prepared by laser interference lithography coupled with deep reactive ion etching. Titanium carbide-carbon composite nanofibers were grown on the top of the silicon lines parallel to the substrate by a hybrid plasma process combining physical vapor deposition and plasma enhanced chemical vapor deposition. The prepared nanofibers were analyzed by scanning electron microscopy, x-ray photoelectron spectroscopy, Raman spectroscopy and transmission electron microscopy. We demonstrate that the shape, microstructure and the chemical composition of the as-grown nanofibers can be tuned by changing the plasma conditions.

Integration of a carbon nanotube based electrode in silicon microtechnology to fabricate electrochemical transducers.

An original approach was developed and validated for the fabrication of a carbon nanotube (CNT) electrode synthesized directly onto a carbon buffer thin film deposited on a highly doped monocrystalline silicon surface. The buffer layer of amorphous carbon thin film was deposited by physical vapour deposition on the silicon substrate before CNT synthesis. For this purpose, nickel was deposited on the carbon buffer layer by an electrochemical procedure and used as a catalyst for the CNT growth. The CNT synthesis was achieved by plasma enhanced chemical vapour deposition (PECVD) in an electron cyclotron resonance (ECR) plasma chamber using a C(2)H(2)/NH(3) gas mixture. In order to evaluate the electrochemical behaviour of the CNT-based electrode, the carbon layer and the silicon/carbon interface were studied. The resulting buffer layer enhanced the electronic transport from the doped silicon to the CNTs. The electrode surface was studied by XPS and characterized by both SEM and TEM. The electrochemical response exhibited by the resulting electrodes modified with CNTs was also examined by cyclic voltammetry. The whole process was found to be compatible with silicon microtechnology and could be envisaged for the direct integration of microsensors on silicon chips.

Single- and few-walled carbon nanotubes grown at temperatures as low as 450 degrees c: electrical and field emission characterization.

Single-wall (SW-) and few-walled (FW-) carbon nanotubes (CNTs) were synthesized on aluminum/ cobalt coated silicon at temperatures as low as 450 degrees C by plasma enhanced chemical vapor deposition technique (PECVD). The SWCNTs and FWCNTs grow vertically oriented and well separated from each other. The cold field emission studies of as-grown SWCNTs and FWCNTs showed low turn-on field emission threshold voltages, strongly dependent of the nanotubes morphology. Current-voltage curves of individual CNTs, measured by conductive atomic force microscopy (CAFM), showed an electrical resistance of about 90 Komega, that is attributed mainly to the resistance of the contact between the CNTs and the conductive CAFM tip (Au and Pt).

Plasticity in hydraulic architecture of Scots pine across Eurasia.

Widespread tree species must show physiological and structural plasticity to deal with contrasting water balance conditions. To investigate these plasticity mechanisms, a meta-analysis of Pinus sylvestris L. sap flow and its response to environmental variables was conducted using datasets from across its whole geographical range. For each site, a Jarvis-type, multiplicative model was used to fit the relationship between sap flow and photosynthetically active radiation, vapour pressure deficit (D) and soil moisture deficit (SMD); and a logarithmic function was used to characterize the response of stomatal conductance (G(s)) to D. The fitted parameters of those models were regressed against climatic variables to study the acclimation of Scots pine to dry/warm conditions. The absolute value of sap flow and its sensitivity to D and SMD increased with the average summer evaporative demand. However, relative sensitivity of G(s) to D (m/G (s,ref), where m is the slope and G(s,ref) is reference G(s) at D = 1 kPa) did not increase with evaporative demand across populations, and transpiration per unit leaf area at a given D increased accordingly in drier/warmer climates. This physiological plasticity was linked to the previously reported climate- and size-related structural acclimation of leaf to sapwood area ratios. G (s,ref), and its absolute sensitivity to D(m), tended to decrease with age/height of the trees as previously reported for other pine species. It is unclear why Scots pines have higher transpiration rates at drier/warmer sites, at the expense of lower water-use efficiency. In any case, our results suggest that these structural adjustments may not be enough to prevent lower xylem tensions at the driest sites.

MRI evaluation of bulky tumor masses in the mesentery and bladder involvement in peritoneal carcinomatosis.

AIM: Peritonectomy procedures with intraperitoneal chemohyperthermia are an effective but costly treatment for peritoneal carcinomatosis (PC). Consequently a proper selection of patients is necessary. We evaluated the benefit of MRI prior to surgery, in the detection of two of the main surgery contraindications: bulky mesenteric tumors and bladder implants. METHODS: Three experts retrospectively reviewed abdominal and pelvic MRI from 19 cases of surgically proved PC (ovary: 7; colorectal: 7; gastric: 2; pseudomyxoma peritonei: 2; appendix: 1). RESULTS: Mesenteric tumors were always identified as hypersignal masses on axial and coronal fat suppression gadolinium-enhanced T1 images (n=3). Three out of five bladder implants were detected. The two cases of bladder implants that were not detected on MRI were missed because the bladder was not filled. The best sequence for the detection of bladder involvement was axial T2-weighted images with bladder filling. CONCLUSIONS: Evaluating the preoperative resectability of PC is crucial for patient management. MRI seems to reliably detect bulky mesenteric tumors and bladder implants on condition the bladder is filled and appropriate sequences are used.

Europe-wide reduction in primary productivity caused by the heat and drought in 2003.

Future climate warming is expected to enhance plant growth in temperate ecosystems and to increase carbon sequestration. But although severe regional heatwaves may become more frequent in a changing climate, their impact on terrestrial carbon cycling is unclear. Here we report measurements of ecosystem carbon dioxide fluxes, remotely sensed radiation absorbed by plants, and country-level crop yields taken during the European heatwave in 2003. We use a terrestrial biosphere simulation model to assess continental-scale changes in primary productivity during 2003, and their consequences for the net carbon balance. We estimate a 30 per cent reduction in gross primary productivity over Europe, which resulted in a strong anomalous net source of carbon dioxide (0.5 Pg C yr(-1)) to the atmosphere and reversed the effect of four years of net ecosystem carbon sequestration. Our results suggest that productivity reduction in eastern and western Europe can be explained by rainfall deficit and extreme summer heat, respectively. We also find that ecosystem respiration decreased together with gross primary productivity, rather than accelerating with the temperature rise. Model results, corroborated by historical records of crop yields, suggest that such a reduction in Europe's primary productivity is unprecedented during the last century. An increase in future drought events could turn temperate ecosystems into carbon sources, contributing to positive carbon-climate feedbacks already anticipated in the tropics and at high latitudes.

Predicting the onset of net carbon uptake by deciduous forests with soil temperature and climate data: a synthesis of FLUXNET data.

We tested the hypothesis that the date of the onset of net carbon uptake by temperate deciduous forest canopies corresponds with the time when the mean daily soil temperature equals the mean annual air temperature. The hypothesis was tested using over 30 site-years of data from 12 field sites where CO(2) exchange is being measured continuously with the eddy covariance method. The sites spanned the geographic range of Europe, North America and Asia and spanned a climate space of 16 degrees C in mean annual temperature. The tested phenology rule was robust and worked well over a 75 day range of the initiation of carbon uptake, starting as early as day 88 near Ione, California to as late as day 147 near Takayama, Japan. Overall, we observed that 64% of variance in the timing when net carbon uptake started was explained by the date when soil temperature matched the mean annual air temperature. We also observed a strong correlation between mean annual air temperature and the day that a deciduous forest starts to be a carbon sink. Consequently we are able to provide a simple phenological rule that can be implemented in regional carbon balance models and be assessed with soil and temperature outputs produced by climate and weather models.

Seasonal dynamics of soil carbon dioxide efflux and simulated rhizosphere respiration in a beech forest.

Respiration of the rhizosphere in a beech (Fagus sylvatica L.) forest was calculated by subtracting microbial respiration associated with organic matter decomposition from daily mean soil CO2 efflux. We used a semi-mechanistic soil organic matter model to simulate microbial respiration, which was validated against "no roots" data from trenched subplots. Rhizosphere respiration exhibited pronounced seasonal variation from 0.2 g C m(-2) day(-1) in January to 2.3 g C m(-2) day(-1) in July. Rhizosphere respiration accounted for 30 to 60% of total soil CO2 efflux, with an annual mean of 52%. The high Q10 (3.9) for in situ rhizosphere respiration was ascribed to the confounding effects of temperature and changes in root biomass and root and shoot activities. When data were normalized to the same soil temperature based on a physiologically relevant Q10 value of 2.2, the lowest values of temperature-normalized rhizosphere respiration were observed from January to March, whereas the highest value was observed in early July when fine root growth is thought to be maximal.

Mechanisms of xylem recovery from winter embolism in Fagus sylvatica.

Hydraulic conductivity in the terminal branches of mature beech trees (Fagus sylvatica L.) decreased progressively during winter and recovered in the spring. The objective of this study was to determine the mechanisms involved in recovery. Two periods of recovery were identified. The first recovery of hydraulic conductivity occurred early in the spring, before bud break, and was correlated with the occurrence of positive xylem pressure at the base of the tree trunk. Active refilling of the embolized vessels caused the recovery. The second recovery of hydraulic conductivity occurred after bud break and was correlated with the onset of cambial activity. Formation of new functional vessels, leading to an increase in xylem diameter, was largely responsible for the increase in xylem conductivity. The two mechanisms were complementary: active refilling of embolized vessels occurred mostly in the root and the trunk, whereas formation of new functional vessels occurred mainly in young terminal shoots.

Respiration as the main determinant of carbon balance in European forests.

Carbon exchange between the terrestrial biosphere and the atmosphere is one of the key processes that need to be assessed in the context of the Kyoto Protocol. Several studies suggest that the terrestrial biosphere is gaining carbon, but these estimates are obtained primarily by indirect methods, and the factors that control terrestrial carbon exchange, its magnitude and primary locations, are under debate. Here we present data of net ecosystem carbon exchange, collected between 1996 and 1998 from 15 European forests, which confirm that many European forest ecosystems act as carbon sinks. The annual carbon balances range from an uptake of 6.6 tonnes of carbon per hectare per year to a release of nearly 1 t C ha(-1) yr(-1), with a large variability between forests. The data show a significant increase of carbon uptake with decreasing latitude, whereas the gross primary production seems to be largely independent of latitude. Our observations indicate that, in general, ecosystem respiration determines net ecosystem carbon exchange. Also, for an accurate assessment of the carbon balance in a particular forest ecosystem, remote sensing of the normalized difference vegetation index or estimates based on forest inventories may not be sufficient.

Stomatal conductance, growth and root signaling in Betula pendula seedlings subjected to partial soil drying.

Seedlings of Betula pendula Roth were grown with their root systems separated between two soil compartments. Four treatments were imposed: (i) adequate irrigation in both compartments (WW, controls); (ii) adequate irrigation in one compartment and drought in the other compartment (WD); (iii) drought in both compartments (DD); and (iv) half of the root system severed and the remainder kept well-watered (root excision, RE). Predawn leaf water potential, stomatal conductance, soil-to-leaf specific hydraulic conductance, and root and leaf growth decreased in DD-treated seedlings, which also displayed severe leaf shedding (30% loss in leaf area). The DD treatment also resulted in increased concentrations of abscisic acid (ABA) and its glucose ester in the xylem sap of roots and shoots compared to concentrations in control seedlings (about 200 versus 20 nM). Despite the difference in xylem sap concentrations, total ABA flux to the shoots was similar in the two treatments (1-2 pmol ABA m(-2) leaf area s(-1)) as a result of reduced transpiration in the DD-treated seedlings. Compared with root growth in control plants, root growth increased in the RE-treated plants and decreased in the drying compartment of the WD treatment; however, the RE and WD treatments only slightly reduced leaf expansion, and had no detectable effects on shoot water relations or ABA concentrations of the root and shoot xylem sap. We conclude that short-term soil water depletion affecting only 50% of the root system does not cause a measurable stress response in birch shoots, despite root growth cessation in the fraction of drying soil.

Transpiration of a boreal pine forest measured by branch bag, sap flow and micrometeorological methods.

Three independent methods were used to evaluate transpiration of a boreal forest: the branch bag, sap flow and eddy covariance methods. The branch bag method encloses several thousand needles and gives a continuous record of branch transpiration. The sap flow method provides a continuous record of sap velocity and an estimate of tree transpiration. The eddy covariance method typically measures evaporation rates between a forest and the atmosphere. We deployed an extra eddy covariance system below the forest to estimate canopy transpiration by difference. The three systems detected small water vapor fluxes despite a plentiful supply of energy to drive evaporation. We also observed that transpiration rates were low even when the soil was well supplied with water. Low rates of transpiration were attributed to the canopy's low leaf area index and the marked reduction in stomatal conductance as vapor pressure deficits increased. Water vapor fluxes, derived from the sap flow method, lagged behind those derived by the branch bag method by 1 to 2 h. The sap flow method also suffered from sampling errors caused by the non-uniformity of flow across the sapwood and the spatial variability of sapwood cross section throughout the forest. Despite technical difficulties associated with hourly measurements, daily totals of transpiration agreed well with values derived from micrometeorological systems.

Stomatal conductance, growth and root signaling in young oak seedlings subjected to partial soil drying.

Leaf conductance, water relations, growth, and abscisic acid (ABA) concentrations in xylem sap, root apices and leaves were assessed in oak seedlings (Quercus robur L.) grown with a root system divided between two compartments and subjected to one of four treatments: (a) well watered, WW; (b) half of root system exposed to soil drying and half kept well watered, WD; (c) whole root system exposed to drought, DD; and (d) half of root system severed, RE. Sharp decreases in plant stomatal conductance, leaf water potential, hydraulic conductance and leaf growth were observed during DD treatment. No significant differences in plant leaf water potential and stomatal conductance were detected between the WW and WD treatments. Nevertheless, the WD treatment resulted in inhibition of leaf expansion and stimulation of root elongation only in the well-watered compartment. Abscisic acid concentrations did not change in leaves, root tips, or xylem sap of WD- compared to WW-treated plants. Increased concentrations of ABA were observed in xylem sap from DD-treated plant roots, but the total flux of ABA to shoots was reduced compared to that in WW-treated plants, because of decreases in transpiration flux. Similar plant responses to the WD and RE treatments indicate that the responses observed in the WD-treated plants were probably not triggered by a positive signal originating from drying roots.