Our research group developed a novel nano-pitted (NP) TiO2 surface on grade 2 titanium that showed good mechanical, osteogenic, and antibacterial properties; however, it showed weak hydrophilicity. Our objective was to develop a surface treatment method to enhance the hydrophilicity of the NP TiO2 surface without the destruction of the nano-topography. The effects of dilute and concentrated orthophosphoric (H3PO4) and nitric acids were investigated on wettability using contact angle measurement. Optical profilometry and atomic force microscopy were used for surface roughness measurement. The chemical composition of the TiO2 surface and the oxidation state of Ti was investigated using X-ray photoelectron spectroscopy. The ccH3PO4 treatment significantly increased the wettability of the NP TiO2 surfaces (30°) compared to the untreated control (88°). The quantity of the absorbed phosphorus significantly increased following ccH3PO4 treatment compared to the control and caused the oxidation state of titanium to decrease (Ti4+ → Ti3+). Owing to its simplicity and robustness the presented surface treatment method may be utilized in the industrial-scale manufacturing of titanium implants.

The adsorption technique is widely used in water purification, and its efficiency can be significantly improved by target-specific adsorbent design. Research on iodine and its ion removal from water has attracted a great deal of interest due to increased concentrations in the environment and acute toxic effects, e.g., in human thyroid cells. In this work, the iodide removal performance of two high-surface-area resorcinol–formaldehyde-based carbon aerogels was studied under acidic conditions. The BET surface area was 790 m2/g (RF_ac) and 375 m2/g (RMF-GO), with a corresponding micropore ratio of 36 and 26%, respectively. Both aerogels showed outstanding adsorption capacity, exceeding the reported performance of other carbons and Ag-doped materials. Owing to its basic nature, the RMF-GO carbon aerogel showed higher I− capacity, up to 97 mg/g, than the acidic RF_ac, which reached a capacity of 82 mg/g. The surface chemistry of the aerogels also played a distinct role in the removal. In terms of kinetics, RF_ac removed 60% of the iodide ions and RMF-GO 30% within 8 h. The removal kinetics was of the first order, with a half-life of 1.94 and 1.70 h, respectively.

In this paper we report the synthesis of a N, S co-doped metal free carbon cryogel obtained from a marine biomass derived precursor using urea as nitrogen source. Natural carrageenan intrinsically contains S and inorganic salt. The latter also serves as an activating agent during the pyrolytic step. The overall 11.6 atomic % surface heteroatom concentration comprises 5% O, 4.6% N and 1% S. The purified and annealed final carbon (CA) has a hierarchical pore structure of micro-, meso- and macropores with an apparent surface area of 1070 m2/g. No further treatment was applied. The gas adsorption potential of the samples was probed with H2, CO2 and CH4, while the electrocatalytic properties were tested in an oxygen reduction reaction. The atmospheric CO2 and CH4 storage capacity at 0 °C in the low pressure range is very similar to that of HKUST-1, with the CO2/CH4 selectivity below 20 bar, even exceeding that of the MOF, indicating the potential of CA in biogas separation. The electrocatalytic behavior was assessed in an aqueous KOH medium. The observed specific gravimetric capacitance 377 F/g was exceeded only in B, N dual doped and/or graphene doped carbons from among metal free electrode materials. The CA electrode displays almost the same performance as a commercial 20 wt% Pt/C electrode. The oxygen reduction reaction (ORR) exhibits the 4-electron mechanism. The 500-cycle preliminary stability test showed only a slight increase of the surface charge.

Although hydrogen is considered to be one of the most promising green fuels, its efficient and safe storage and use still raise several technological challenges. Physisorption in porous materials may offer an attractive means of H2 storage, but the state-of-the-art capacity of these kinds of systems is still limited. To overcome the present drawbacks a deeper understanding of the adsorption and surface diffusion mechanism is required along with new types of adsorbents developed and/or optimised for this purpose. In the present study we compare the hydrogen adsorption behaviour of three carbon gels exhibiting different porosity and/or surface chemistry. In addition to standard adsorption characterisation techniques, neutron spin-echo spectroscopy (NSE) has been also applied to explore the surface mobility of the adsorbed hydrogen. Our results reveal that both the porosity and surface chemistry of the adsorbent play a significant role in the adsorption of H2 in these systems.

The occurrence of water sorption hysteresis associated with the filling of micro and narrow mesopores (particularly for pores of widths smaller than ca. 3 nm, where nitrogen and argon isotherms at their boiling temperatures, i.e. 77 K and 87 K, respectively, are known to be reversible) provides additional opportunities for textural characterization. In this work systematic water scanning desorption isotherms within the hysteresis loop were carried out on well-characterized activated carbons with varied textural features and surface chemistry. Accurate micro-mesopore analysis was obtained by means of nitrogen, argon and carbon dioxide adsorption experiments coupled with advanced density functional theory methods (i.e., NLDFT, QSDFT). The obtained results indicated that water adsorption/desorption phenomena for pores of different sizes take place independently from each other. This investigation constitutes a starting point for the interpretation of water adsorption hysteresis by means of scanning desorption measurements. (C) 2015 Elsevier Ltd. All rights reserved.

In case of titanium dental implants, the main goal is to create a surface where the bone cells can attach well, therefore osseointegration can occur. The chemical composition of the surface has an important role, because the surface has a direct contact with the living tissue and induces different reactions for example peri implantitis or osseointegration. In our work titanium sample made from the most commonly used dental implant material (Ti Grade 5) were investigated. The samples were treated by chemical etching in hydrogen-chloride and in phosphoric acid to remove the cut generated burr. After that the samples were anodized in phosphoric acid solution at 10 V, 20 V, 30 V or 40 V. As a result of these treatments, titanium-dioxide layers were created on the surfaces. Phosphorus (originating from the phosphoric acid bath) may also be found on the surfaces. This may promote osseointegration. The surface compositions were investigated with the aid of Secondary Ion Mass Spectrometry (SIMS). Based on these results we can conclude that anodization in phosphoric acid solution increases the phosphorus content of the surface. Approximately to the middle of the titanium-dioxide layer the phosphorus content is constant but lower with one order of magnitude than on the surface. In the deeper layers the phosphorus content continues to decrease until the base material where it significantly reduce.

The catalytic performance of multi-walled carbon nanotubes (MWCNTs) with different surface chemistry was studied in the decomposition reaction of H2O2 at various values of pH and temperature. A comparative analysis of experimental and quantum chemical calculation results is given. It has been shown that both the lowest calculated activation energy (∼18.9 kJ/mol) and the highest rate constant correspond to the N-containing CNT. The calculated chemisorption energy values correlate with the operation stability of MWCNTs. Based on the proposed quantum chemical model it was found that the catalytic activity of carbon materials in electron transfer reactions is controlled by their electron donor capability.

High surface area carbon aerogels with increasing molybdenum content were obtained by carbonization of resorcinol-formaldehyde polymer aerogels after incipient wetness impregnation (IWI). The Mo(VI) form of the impregnant was converted into different molybdenum species during the heat treatment, resulting in samples with substantially different surface and bulk compositions. The samples were tested in the hydroconversion reaction of acetic acid, a model biomass. The reaction pathways and the product distribution were governed by the accessibility of the carbon surface as well as by the amount and form of Mo. The highest selectivity for ethanol was 16%, when 85% of the acetic acid was converted. Post-catalyst analysis of the aerogels revealed that their morphology and chemistry changed substantially during the redox processes. The products of each of the three potential pathways (hydrogenolysis, ketonization and consecutive reduction) oxidized the surface even in the reductive hydrogen flow. (C) 2014 Elsevier Inc. All rights reserved.

The long term effect of the human body on a pyrolytic carbon covered C/C composite maxillofacial implant (CarBulatTm) was investigated by comparing the structure, the surface morphology and composition of an implant retrieved after 8 years to a sterilized, but not implanted one. Although the thickness of the carbon fibres constituting the implants did not change during the 8 year period, the surface of the implant retrieved was covered with a thin surface layer not present on the unimplanted implant. The composition of this layer is identical to the composition of the underlying carbon fibres. Calcium can only be detected on the surface as a trace element implying that the new layer is not formed by bone tissue. Residual soft tissue penetrating the bulk material between the carbon fibre bunches was found on the retrieved implant indicating the importance of the surface morphology in tissue growth and adhering to implants.

Mo-doped carbon aerogels were obtained in the polycondensation reaction of aqueous resorcinol and formaldehyde by adding Mo-salt at two different stages of the synthesis: (i) to the initial sol; (ii) by incipient wetting impregnation of the supercritically dried polymer gel. Molybdenum added during the polymerization yielded a more compact gel structure with practically no mesoporosity. With post-impregnation, by contrast, mesopores of diameter 3–15nm were generated. Carbonization appreciably enhanced the microporous character of both samples, but in the mesopore range their pore size distribution was conserved. The Mo-content of the samples was also different: Mo was lost during the solvent exchange before the supercritical drying (i.e., the Mo failed to bind chemically to the polymer matrix). The residual Mo congregated into 25–60nm bulk clusters of α-Mo2C. In the other carbon aerogel, finely dispersed α-Mo2C and η-Mo3C2 crystals formed, of size 8–20nm. On the surface of both carbons the Mo formed oxides. In the model test reaction (acetic acid hydroconversion) the catalytic activity of both carbon aerogels was enhanced by molybdenum. The more open pore structure, higher concentration and finer Mo distribution, as well as its chemical form, may all be responsible for the greater conversion and higher value products obtained with the post-impregnated sample.

The Do and Do model for water adsorption isotherms of activated carbons has been refined, linking its parameters to the amount of surface oxygenated and nitrogenated complexes on the carbon. As these values can be determined independently, e.g. by X-ray photoelectron spectroscopy, it is possible to predict the water isotherm of an activated carbon or, vice versa, use the water vapour isotherm to characterise its surface functionality. During testing it has been shown that activated carbons that have been heat treated to render them more hydrophobic can be reoxidised by ambient air and become more hydrophilic.

In this study a new permeation measurement equipment is presented which is shown to be capable of measuring low and high gas fluxes through different membranes. The new membrane support system which is introduced here is suitable for thin membranes (>10 mu m) and is expected to provide more accurate results than the design used in earlier permeation measurements.In order to provide a glimpse of the possibilities of the new equipment, hydrogen permeation measurements through a low-density polyethylene (LDPE) and a nickel membrane are presented. The pressure difference dependence of the hydrogen fluxes measured agreed well with the behaviour expected according to Sieverts' law. In case of the LDPE membrane our results can be explained with the molecular diffusion of hydrogen, which agrees with literature data. As for the nickel membrane the results suggest that under our experimental conditions the speed determining step of the permeation is the atomic diffusion. (c) 2013 Published by Elsevier Ltd.

In their previous report, the authors presented observations regarding the long-term application of carbon/carbon implants. After evaluating the good functional and aesthetic results, the effect of the human body on the structure and morphology of the implants was investigated with state of the art methods. An implant retrieved from the body after eight years was compared to implants which were sterilized but not implanted (reference). Carbon and oxygen were the main components of both implants, however, as a result of the interaction with the human body the amount of oxygen increased 3-4 times and phosphorus, sulphur, calcium and iron were detectable as trace elements on the surface. The width of the carbon fibres (5-7 µm) building up the implants was not changed during the interaction with the human body. The surface of the implant retrieved from the human body was covered with a 15-17 µm thick layer, not present on the reference implant, having a similar composition to that of the carbon fibres (high amount of calcium that is typical to bone tissue was not detected). According to these results, the structure and the morphology of the implants were not altered notably by the human body.

N-containing synthetic carbons with narrow porosity were prepared from a chlorinated styrene and divinylbenzene copolymer by a multistep method with a yield of 34 wt%. Surface chemical treatment and thermal carbonization of the starting copolymer was monitored by urea impregnation. Steam activation, oxidation and an additional heat treatment gave the final product. The synthesis route was designed in a cost-effective way. The porosity and the concentration of the introduced nitrogen atoms were determined at each step. The final product has a surface area of 1135 m(2)/g. More than 70% of the pore volume comes from micropores with an average width of 0.7 nm. The 2.3 at.% surface nitrogen atoms are distributed among five detectable species, of which about 44% is quaternary nitrogen. (C) 2011 Elsevier B.V. All rights reserved.

Photomodulated reflectance (PMR) measurement techniques are currently used for the monitoring of ultrashallow junctions. This paper discusses the possibility of applying them to the characterisation of metal layers. A finite element method based computer model has been created to study the dependence of the PMR signal on different sample parameters. We present the results of these simulations and show that the method can be used to establish the thickness of a metal layer (if the material is known) and it can also provide information about the metal/semiconductor interface. This information might be used to characterise the barrier seed layer beneath the metal, by a non-contact and non-destructive way. Simulation results are also supported by actual measurements on test samples. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The present article describes the results and findings explored in the course of the development of the analytically capable prototype of continuous time-of-flight (CTOF) mass spectrometer. Currently marketed pulsed TOF (PTOF) instruments use ion introduction with a 10 ns or so pulse width, followed by a waiting period roughly 100 micros. Accordingly, the sample is under excitation in 10(-4) part of the total measuring time. This very low duty cycle severely limits the sensitivity of the PTOF method. A possible approach to deal with this problem is to use linear sinusoidal dual modulation technique (CTOF) as described in this article. This way the sensitivity of the method is increased, due to the 50% duty cycle of the excitation. All other types of TOF spectrometer use secondary electron multiplier (SEM) for detection, which unfortunately discriminates in amplification in favor of the lighter ions. This discrimination effect is especially undesirable in a mass spectrometric method, which targets high mass range. In CTOF method, SEM is replaced with Faraday cup detector, thus eliminating the mass discrimination effect. Omitting SEM is made possible by the high ion intensity and the very slow ion detection with some hundred hertz detection bandwidth. The electrometer electronics of the Faraday cup detector operates with amplification 10(10) V/A. The primary ion beam is highly monoenergetic due to the construction of the ion gun, which made possible to omit any electrostatic mirror configuration for bunching the ions. The measurement is controlled by a personal computer and the intelligent signal generator Type Tabor WW 2571, which uses the direct digital synthesis technique for making arbitrary wave forms. The data are collected by a Labjack interface board, and the fast Fourier transformation is performed by the software. Noble gas mixture has been used to test the analytical capabilities of the prototype setup. Measurement presented proves the results of the mathematical calculations as well as the future potentiality for use in chemical analysis of gaseous mixtures.

The adsorption of water vapour in a high surface area commercial carbon, as-received and after different surface chemical treatments was investigated as a function of relative humidity by three separate techniques. While gravimetry and small and wide angle X-ray scattering measurements are in reasonable agreement, volumetric observations yielded isotherms with substantially lower values for the water uptake. In each case, the results are sensitive to the surface chemistry of the sample. Several weeks were required to establish equilibrium, with strikingly different results being obtained for measurements carried out on shorter time scales. The slow kinetics of the uptake accounts for most of the discrepancies among the results of the different techniques. Immersion in water caused significant macroscopic swelling of the carbon matrix over a time scale comparable to the adsorption equilibrium time.

Oxide coverage of molybdenum plays an important role in several applications, for example in lighting industry. Surface conditioning procedures were simulated in an XPS instrument by in situ heat treatments while monitoring the surface composition and changes in the chemical states of molybdenum. Heat treatments have been made at different temperatures between 435 and 690°C under vacuum conditions. It has been observed that during heating the molybdenum test samples the native MoO3 layer on the surface dissociates, and a layer of suboxides forms on the surface. This layer hinders the further reduction of the surface, thus reaction speed decreases after the initial phase. It has been established that in the second phase of the heat treatment the activation energy of the process is 1.1±0.2eV. Reduction of MoO3 to elemental molybdenum runs through two intermediate states: Mo6+→Mo5+→Mo4+→Mo0.

Carbon–silica molecular sieves were prepared by carbonization of Scotch fir (Pinus sylvestris) after impregnation with aqueous waterglass (NaxSiyOz, where x, y and z may take a range of values). Compared to Si-free samples, doping significantly modifies the structure that forms during the carbonization process. For carbonization temperatures between 600°C and 1000°C, doped samples shrink less than undoped samples, indicating increased mechanical strength. The specific surface area and pore volume develop in a combined self-activation and chemical vapour deposition (CVD) process. Nevertheless, the presence of the sodium silicates limits self-activation and thus reduces the porosity. Doping drastically reduces the specific surface area, measured both by gas adsorption and small angle X-ray scattering. The latter technique demonstrates that in both doped and undoped samples the specific surface area is isotropic. X-ray photoelectron spectroscopy (XPS) reveals that the spatial distribution of Na and Si atoms within the samples are not identical. The open honeycomb structure, conserved during the heat treatment from the original wood, provides easy access for gas adsorption and separation applications. The ratios of the microporous diffusion time constants of N2 and O2 from frequency response (FR) measurements gave separation factors 3.0, 4.3, 2.7 and 1.3 for samples prepared at 600°C, 700°C, 800°C and 900°C, respectively.