Laser Sintering of SnO2 : Sb Sol-Gel Coatings

Sb doped sol-gel SnO2 single layers (thickness 100 nm) were prepared from alcoholic solution and deposited via a dip coating process on fused silica substrates. The coatings have been sintered at a typical rate of 10–15 cm2/s by CO2 laser irradiation. The laser spot was scanned in one direction at a speed of 15,000 cm/s and the sample was moved in a perpendicular one at a speed up to 250 mm/s. The temperature of the topmost 10 m layer was monitored by a fast pyrometer (s resolution). The following properties of the coatings have been determined: the electrical resistivity , the carrier density n, and mobility , the structure, the thickness, the mesoscopic and micromorphology and the density. The sintering by CO2 laser radiation is mainly a thermal driven process. At T 500°C it allows to obtain coatings with a smaller resistivity (6.8×10–3 cm) than those produced by conventional furnace firing (el2.9×10–2 cm). The results are discussed in terms of particle size and packing density.     

Estimation of distribution of vinyl groups in micron-sized monodisperse polymer microspheres by bromine titration method

The distribution of vinyl groups in polystyrene/poly(styrene-divinylbenzene) (PS/P(S-DVB)) composite microspheres produced by seeded copolymerization of S and DVB in the presence of 2.1-m monodisperse PS seed particles was estimated from the amount detected with bromine titration method as a function of the reaction time under various conditions.Part CXXIII of the series Studies on Suspension and Emulsion.     

Effect of Surfactants on the Immobilization of 4-(2-Pyridylazo)resorcinol on Silochroms

The effect of cationic surfactants (cetyltrimethylammonium bromide, cetylpyridinium bromide, and tetrabutylammonium perchlorate) and a nonionic surfactant (OP-7) on the conditions of the immobilization of 4-(2-pyridylazo)resorcinol (PAR) on three types of silica gel (Silochrom S-120 (200–350 m), Silochrom S-120 (315–500 m), and Silochrom S-80 (200–350 m)) was studied. It was found that OP-7 does not affect the adsorption of surfactants. The effect of cationic surfactants increases in the order tetrabutylammonium perchlorate < cetyltrimethylammonium bromide < cetylpyridinium bromide. The adsorption activity of silica gels increases in the order Silochrom S-120 (315–500 m) < Silochrom S-80 (200–350 m) < Silochrom S-120 (200–350 m). Cetylpyridinium bromide provides full immobilization of PAR on silica gel Silochrom S-120 (200–350 m) in the pH range 2–9.     

Preparation of micron-size monodisperse polymer particles by seeded polymerization utilizing the dynamic monomer swelling method

Utilizing a new type of monomer swelling method, 6.1 m-size monodisperse polymer particles were prepared by seeded polymerization. 1.8 m-size monodisperse polystyrene (PS) seed particles (1.8 m in size) were prepared by dispersion polymerization in ethanol-water (80/20, v/v) medium in the presence of poly(acrylic acid) as stabilizer with 2,2-azobisisobutyronitrile as initiator. The PS seed dispersion was mixed with ethanol-water (60/40, v/v) solution dissolving styrene (S) monomer, benzoyl peroxide as initiator, and poly(vinyl alcohol) as stabilizer. By slow, continuous, dropwise addition of water with a micro feeder into the mixture, the PS particles absorbed the many S monomers, which were separated from the medium and swelled from 1.8 m to 8.4 m while keeping the monodispersity high. We named this procedure the dynamic swelling method. Then, the seeded polymerization of the absorbed S monomer was carried out in the presence of NaNO₂ as water-solube inhibitor.Part CXXII of the series Studies on Suspension and Emulsion.     

Diffusion of water in gelatin studied by a new refractometric method

Summary A refractometric method designed to study the diffusive behaviour of low molecular compounds in solid macromolecular substances in the form of thin layers is described. The layer thickness is determined interferometrically in the apparatus. The system gelatin-water is studied at three different thicknesses, 31 , 40 and 82 , at 25°C. The diffusion process is found to be characterized by a diffusion coefficient which is dependent on concentration only, i. e. independent of time. Also, the concentration at the surface of the layer is found to change instantly from the initial concentration to the equilibrium concentration at the beginning of a diffusion experiment.

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Zusammenfassung Es wird eine refraktometrische Methode zur Untersuchung der Diffusion von niedermolekularen Verbindungen in festen makromolekularen Substanzen in Form dünner Schichten beschrieben. Die Schichtdicke wird im Gerät interferometrisch bestimmt. Das System Gelatine-Wasser ist bei drei verschiedenen Dicken (31 , 40 und 82 ) bei 25°C gemessen. Es zeigt sich, daß der Diffusionskoeffizient allein von der Konzentration, also z. B. u. a. unabhängig von der Zeit ist. Auch wechselt die Konzentration an der Oberflächenschicht augenblicklich von der anfänglichen zur Gleichgewichtskonzentration bei Beginn eines Diffusions-experimentes.

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With 13 figures and 2 tables     

Study of traffic pollution by metals in Seville (Spain) by physical and chemical speciation methods

Eighty-three samples of atmospheric particles were collected at a representative traffic site in the Mediterranean city of Seville during a period of one year. Urban particles were collected on quartz filters with a high-volume sampler coupled with a cascade impactor which separates particles into six size ranges: >10, 10–4.9, 4.9–2.7, 2.7–1.3, 1.3–0.6, and <0.6 m. The total metal content, its distribution by size (physical speciation), and the concentrations of different chemical forms (chemical speciation) in particles less than 0.6 m were determined. The chemical speciation scheme furnished four fractions: soluble and exchangeable metals; carbonates, oxides, and reducible metals; oxidisable and sulfidic metals bound to organic matter; and residual metals. The samples were analysed by ICP–OES for Pb, Ni, Cd, S, Fe, Zn, Cu, Ba, Mn, and V. Gaseous pollutants, traffic intensities, and primary meteorological data provided by the atmospheric and traffic networks were statistically related to the analytical data. Analytical and statistical results from physical and chemical speciation singled out Ba as a valid tracer of vehicular traffic, instead of Pb, in cities with high traffic density. Another important relationship was found between Pb and Cu. Physical speciation of lead showed that the major risk for health was from fine particles less than 2.7 m, because particles between 2.7 and 0.6 m were the size fractions of the total suspended particles with the major mass abundance of lead (mainly particles between 2.7 and 1.3 m) and because particles less than 0.6 m were the fraction of airborne particles most abundant in the urban air. Chemical speciation results showed that special attention must be taken with Ni and Cd concentrations, because of their high potential bioavailability, mainly a result of the high solubility of the chemical forms of Ni in the finest particles.     

A technique for capillary joining in capillary electrophoresis

Summary Aspects of cracking and joining capillaries have been investigated. Capillary coupling was achieved using various methods. The most successful used hydrofluoric acid-etched capillaries to form male and female ends which were then joined together. This type of joint was used to connect sections of capillary of similar and different internal diameters with minimal loss in resolution, peak width and number of theoretical plates. (Uridine and hypoxanthine was used as a test mixture). For hypoxanthine on a 50 m/50 m etched joined capillary 10 cm from the detector window the number of theoretical plates was 96.6% of that for hypoxanthine on an unbroken capillary. Following the relative success of capillary joining, a coupled capillary flowcell (50 m/200 m) was produced and evaluated.     

Depth profile studies of ZrTiN coatings by laser ablation inductively coupled plasma mass spectrometry

The feasibility of depth profiling was studied by using a 193-nm ArF* excimer laser ablation system (GeoLas, MicroLas, Goettingen, Germany) with a lens array-based beam homogenizer in combination with an ICP-QMS Agilent 7500. Two ablation cells (20 and 1.5 cm³) were compared at the laser repetition rate of 1 Hz, laser beam energy of 135 mJ and the carrier gas flow rate 1.5 L min^–1 He + 0.78 L min^–1 Ar. The ablation cell dimensions are important parameters for signal tailing; however, very small cell volumes (e.g. 1.5 cm³) may cause memory effects, which can be probably explained by dominant inertial losses of aerosol on cell walls with its delayed mobilization. The 20-cm³ ablation cell seems to be appropriate for depth profiling by continuous single-hole drilling. The study of the influence of the pit diameter magnitude on the waning and emerging signals under small crater depth/diameter aspect ratios, which range between 0.75 and 0.0375 for the 3-m-thick coatings and pit diameters 4–80 m, revealed that the steady-state signals of pure coating and pure substrate (out of interface) were obtained at crater diameters between 20 and 40 m. Depth resolution defined by means of slopes of tangents in the layer interface region depend on the pit diameter and has an optimum value between 20 and 40 m and gives 0.6 m for the 20-m pit. In-depth variation of concentration of coating constituent (Ti) was proved to be almost identical with two different laser/ICP systems.Viktor Kanický performed this work while on leave at ETH Zurich     

Accurate reflectance measurements in the infrared spectral range using an integrating sphere

An integrating sphere is used together with a Fourier transform spectrometer for directional-hemispherical reflectance measurements in the spectral range from 1m to 15m. Comparisons with PTB's fundamental sphere reflectometer around 1m show that the uncertainty of the infrared measurements is ±0.01.     

A two-ply artificial blood vessel of polyurethane and poly(L-lactide)

A biodegradable microporous small-caliber vascular prosthesis has been developed that consists of two layers. The inner layer has been made highly antithrombogenic by cross-linking of a mixture of linoleic acid and an aliphatic polyetherurethane with dicumylperoxide. Microporosity was introduced by adding sodiumfluoride crystals of about 5 m in diameter prior to cross-linking and leaching them out afterwards.The outer ply has been constructed by precipitating a (95/5) physical mixture of polyesterurethane and poly(L-lactide) from solution in the presence of sugar crystals with dimensions in the range 30–90 m which were removed by exposing the graft to water.The two-ply grafts were tested in vivo by replacing 1 cm of the abdominal aorta of rats. All the grafts remained patent at least up to 1 year and did not exhibit any aneurismal formation. The inner layer was covered with endothelial cells and several layers of smooth muscle cells.     

1D Polymeric copper(II) azido complexes. Synthesis,spectral and structural studies of [Cu(ethyl isonicotinate)2(N3)2]n and [Cu(methyl isonicotinate)2(NO3)(N3)]n complexes

Two new 1:2 polymeric complexes of copper(II) azide with ethyl isonicotinate (1) and methyl isonicotinate (2) have been synthesized and characterized by spectroscopic and crystallographic methods. The polymeric structure of complex (1) features six coordinated copper centers, a pair of trans-coordinated ligand molecules, and asymmetric ₂-1,1 and ₂-1,3-azido bridges resulting in a 1D chain structure. In complex (2), each copper atom which is located at an inversion center, is coordinated to a pair of trans ligand molecules, to the nitrogen atom of two -1,1-azido ligand and to an oxygen atom of a bridging (-O,O) nitrogen group. The i.r., electronic and e.s.r. spectra of the complexes are reported.     

Determination of traces of sodium alkylbenzenesulphonate by high-performance liquid chromatography. Application to water

Summary For the trace determination of sodium alkylbenzenesulphonate (ABS) by HPLC the following conditions were employed: Shimadzu ZORBAX SIL Column (5 m, 4.6 mm i.d. x 150 mm) as stationary phase, 0.2% ammoniaethanol (v/v) as mobile phase, UV detector at 225 nm, injection volume 12 l. The chromatograms of ABS were simple and sharp (detection limit of ABS 0.02 g in 12 l of ethanol). The calibration curves of ABS were linear in a concentration range of 0.03 0.3 g in 12 l of ethanol. In the case of linear sodium dodecylbenzenesulphonate positive errors of 1 4% were caused by non-ionic surfactants or laurylsulphate (6 times excess), 10 50% positive errors were caused by 2 6 times excess of household detergents.Standard water samples containing ABS were treated with a weak base anion-exchange resin, the adsorbed ABS were eluted, and then determined either by HPLC or by the methylene blue spectrophotometric method. Recoveries of ABS in water were about 92 107% by HPLC.

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Bestimmung von Spuren Natriumalkylbenzolsulfonat mit Hilfe der HPLC. Anwendung auf Wasser

Zusammenfassung Für die Spurenbestimmung von Natriumalkylbenzolsulfonat (ABS) durch HPLC werden die folgenden Bedingungen empfohlen:Shimadzu ZORBAX SIL (5 m, 4,6 mm x 150 mm) als stationäre Phase, 0,2% Ammoniak/Ethanol als mobile Phase, UV-Detektor bei 225 nm, Injektionsvolumen 12 l. Die erhaltenen Chromatogramme sind einfach und scharf (Nachweisgrenze 0,02 g in 12 ml Ethanol). Die Eichkurven sind im Konzentrationsbereich von 0,03–0,3 g in 12 l Ethanol linear. Im Falle des linearen Natriumdodecylbenzolsulfonats werden bei Anwesenheit von nicht-ionischen oberflächenaktiven Substanzen oder von Laurylsulfat in 6fachem Überschuß positiver Fehler von 1–4% erhalten; bei 2–6fachem Überschuß von Haushaltswaschmitteln ergeben sich positive Fehler von 10–50%.Standard-Wasserproben werden zunächst einer Behandlung mit einem Anionenaustauscher unterzogen, die adsorbierten ABS eluiert und durch HPLC oder nach der Methylenblaumethode analysiert. Wiederfindungsraten liegen bei 92–107%.

     

A toxic reagent-free method for normal-phase matrix solid-phase dispersion extraction and reversed-phase liquid chromatographic determination of aldrin,dieldrin, and DDTs in animal fats

A method for the determination of aldrin, dieldrin, DDT, DDE, and DDD contamination in animal fats (beef tallow, lard, and chicken fat) without using toxic reagents is developed, that uses high-performance liquid chromatography after the sample has been prepared by matrix solid-phase dispersion (MSPD) with acidic alumina oxide. A reversed-phase C₁-silica column with a mobile phase of 50% (v/v) ethanol solution (in water) and a photo-diode array detector were used for the determination. Average recoveries of the target compounds (0.2–5.0 g g^–1) ranged from 84–98%, with coefficients of variation of <5%. The limits of quantitation were 0.16 g g^–1 for AD, 0.10 g g^–1 for DD, 0.06 g g^–1 for DDT, 0.07 g g^–1 for DDE, and 0.05 g g^–1 for DDD. No toxic reagents were used at all.     

Changes of cellulose fiber wall structure during drying investigated using NMR self-diffusion and relaxation experiments

The self-diffusion of water sorbed in cellulose fibers was investigatedby means of NMR during slow drying in order to follow changes in the celluloseporous structure. In pulp fibers pores with at least one dimension on them scale were observed at high amounts of sorbed water and nm-scale pores atlow amounts. Beating affected the m-scale pores. Regenerated cellulosefibers had nm-scale pores up to high amounts of water. Bulk water was observedas a second component with long T ₂ in a CPMGexperiment. The sequence of water removal for kraft pulp fibers is: (1) bulkwater, (2) water in m-scale pores and (3) water in nm-scale pores.     

Oxygen evolution on electrodes of different roughness: an electrochemical noise study

Rough and porous Ni layers have been obtained by cathodic deposition from a NiCl₂, NH₄Cl solution, at high current density. Characterisation by SEM has shown that they consisted of micro-dendrites separated by pores with a typical diameter of 1 m. In addition, circular hollows (10–100 m in diameter) were found on the deposit surface; their density varied with the deposition current density and deposition charge. The surface roughness of the Ni deposits, measured by EIS, was found to increase roughly linearly with the deposition charge, and to be little dependent on current density, provided a threshold value was exceeded. The oxygen evolution reaction has been studied on these electrodes by simultaneous real-time measurements of potential and electrolyte resistance fluctuations. The analysis of the electrochemical noise indicated that the dimensions of oxygen bubbles detaching from the electrodes slightly increased with the deposit surface roughness. It is not clear, however, whether or not this increase was associated with the effect of the small (1 m) or the large (10–100 m) features on the electrode-bubble interactions.     

Synthesis,characterization and crystal structures of heterometallic trinuclear carbonyl sulfido clusters (η5-Cp)MoFeCo- (CO)8(μ3-S) and [(η5-Cp)Mo]2Fe(CO)7(μ3-S)

HFe2Co(CO)9(3-S) reacts with (5-Cp)Mo(CO)3Cl in refluxing THF to give heterometallic trinuclear clusters (5-Cp)MoFeCo(CO)8(3-S) and [(5-Cp)Mo]2Fe(CO)7-(3-S), which have been characterized by elemental analyses, i.r., 1H- and 13C-n.m.r. and X-ray crystal structure determination. An electrophilic addition–elimination sequence is proposed for their formation.     

High-performance liquid chromatographic determination of saponins fromHedera helix L. using a light-scattering detector

Summary A high-performance liquid chromatographic method for the simultaneous determination of bidesmosidic and monodesmosidic saponins from the leaves ofHedera helix L. using a light-scattering detector is proposed.A satisfactory separation of the bidesmosidic and monodesmosidic saponins is obtained in 25 min on a reversed phase RP18 using an acetonitrile-water mixture as eluant. Hederasaponin C and -hederin were found to be the major saponins of the leaves. The linearity of response, repeatability and reproducibility of the proposed method were tested. The detection limits for hederasaponin C and -hederin were 0,1 and 0.05 g/20 l respectively.     

Preparation of micron-size monodisperse polymer microspheres having crosslinked structures and vinyl groups

Micron-size monodisperse polymer microspheres having crosslinked structures therein and vinyl groups thereon were prepared by seeded copolymerization of styrene and divinylbenzene with 2,2-azobisisobutyronitrile as initiator in ethanolwater medium in the presence of 2.1-m monodisperse polystyrene seed particles produced by dispersion polymerization. The optimum conditions of the seeded copolymerization for producing the microspheres with good monodispersity and colloidal stability were determined.Part CXXI of the series Studies on Suspension and Emulsion.     

Flow injection analysis at μl/min flow rates

The characteristics of knitted open tube (KOT) figure eight reactors and coil reactors at l/min flow rates were compared using plate height (H) calculations and peak height measurements. Peak broadening independent of flow rate was seen for the figure eight KOT but not the coil at flow rates of 150–300 l/min. Below 150 /min, the plate height values of both reactors were inversely proportional to flow rate. It was concluded that a 0.5-m KOT figure eight reactor is the most effective way to introduce delay time for a 1 1 injection size and tubing of 0.3 mm I.D. Enhancement of peak height response was particularly pronounced at flow rates less than 100 l/min.     

Polarographische Bestimmung von ?thylen-bis-thiurammonosulfid

Zusammenfassung Das polarographische Verhalten von Äthylen-bis-thiurammonosulfid, das als fungitoxisches Abbauprodukt der Pflanzenschutzmittel Maneb, Zineb und Nabam auftritt, wird beschrieben. Zur Bestimmung wird M Acetatpuffer pH 4,7 als Grundlösung empfohlen. Es erscheint eine gut ausgebildete Reduktionsstufe mit dem Halbstufen potential –1,085 V (GKE). Die untere Bestimmungsgrenze liegt bei etwa 0,5 g/ml. Bei Anwendung der Impulsmethode (single-sweep-Technik) lassen sich in 0,8 N HCl noch 0,05 g/ml bestimmen.

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Polarographic determination of ethylene-bis-thiuram-monosulphide

The polarographic properties of ethylene-bis thiuram-monosulphide, a fungitoxic degradation product of the fungicides Maneb, Zineb, and Nabani have been described. For analytical purposes the recommended supporting electrolyte is M acetate buffer (pH 4,7) in which a well-defined reduction wave is produced at a half wave potential of –1.085 V (SCE). The lower limit of detection is near 0.5 g/ml for classical DC-polarography whereas it is still possible to determine 0.05 g/ml 0.8 N HCl using the single sweep method.