Optimisation of an integrated optical evanescent wave absorbance sensor for the determination of chlorinated hydrocarbons in water

The suitability of an integrated optical chemical sensor for the determination of highly volatile chlorinated hydrocarbons in aqueous solutions has been proven. The analytes are detected by NIR absorption spectrometry in the evanescent field of an integrated optical strip waveguide generated in a BGG31 (Schott, Germany) glass substrate, which is coated with a hydrophobic polymer superstrate as sensing layer. It has been shown that the sensitivity increases when the refractive index of the superstrate is increased from 1.333 up to 1.46. Different UV-cured polysiloxanes with low cross sensitivity to water have been prepared. Due to the good light transmission properties of the IO-sensors prepared by this method, quantitative measurements have been performed with the model system trichloroethene (TCE) in water. A detection limit of 22 ppm has been found and the sensor response times (t(90)-value) are between five and fourteen minutes for a coating thickness of around 30 microm. The sensor response is totally reversible. The analyte desorbes in air within 2 min. The enrichment of trichloroethene in the polysiloxane coating can be described by film diffusion through the aqueous boundary layer as rate determining step.     

Optimisation of an integrated optical evanescent wave absorbance sensor for the determination of chlorinated hydrocarbons in water

The suitability of an integrated optical chemical sensor for the determination of highly volatile chlorinated hydrocarbons in aqueous solutions has been proven. The analytes are detected by NIR absorption spectrometry in the evanescent field of an integrated optical strip waveguide generated in a BGG31 (Schott, Germany) glass substrate, which is coated with a hydrophobic polymer superstrate as sensing layer. It has been shown that the sensitivity increases when the refractive index of the superstrate is increased from 1.333 up to 1.46. Different UV-cured polysiloxanes with low cross sensitivity to water have been prepared. Due to the good light transmission properties of the IO-sensors prepared by this method, quantitative measurements have been performed with the model system trichloroethene (TCE) in water. A detection limit of 22 ppm has been found and the sensor response times (t₉₀-value) are between five and fourteen minutes for a coating thickness of around 30 m. The sensor response is totally reversible. The analyte desorbes in air within 2 min. The enrichment of trichloroethene in the polysiloxane coating can be described by film diffusion through the aqueous boundary layer as rate determining step.     

Fabrication and Properties of Doped Porous Polysiloxane Sol-Gel Layers on Optical Fibers

Polysiloxane porous layers doped with TiO- and phenyl-groups were fabricated by the sol-gel method. Starting sols were prepared from alkoxides using catalysis by HCl or HF. Stable SiO-TiO-sols were obtained by using HF. Porous gel layers with thicknesses of 0.3–1.1 m were coated on fiber surfaces or silicon wafers. Layers with the refractive index of 1.38–1.48 were prepared. The fractional porosity of the layers was estimated to be 0.1–0.35. The interactions of the layers with vapor or liquid chlorinated hydrocarbons, alcohols or aromatic hydrocarbons have been studied in immersing experiments by measuring the output light intensity from the fibers. The observed changes of the output intensity could be correlated to changes of the refractive index of the layer caused by the penetration of the tested chemicals into the layer pores.     

Comparison of Different High and Low Index Materials in the Manufacture of High Laser Damage Threshold Mirrors at the 351 nm Wavelength

Sol-gel material based mirrors have been produced by forming alternate layers of high refractive index and low refractive index thin films. These mirrors have proven to have a high laser induced damage threshold [LIDT]. Using nitric acid stabilized zirconia derived from zirconium-n-propoxide and base catalyzed silica, a 16 layer mirror with a reflectivity of better than 94% at 351 nm and 45° angle of incidence was fabricated. This had an LIDT of 7.7 J/cm2 at 351 nm with a 0.7 ns pulse width. Crazing prevented further layers being deposited. Both spin and dip coating were attempted with dip coating yielding the best results.The coating structure has been analyzed using XPS depth profiling and AES. The bulk materials have been investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD) and TGA. High refractive index layers using Hafnia with nitric or acetic acid have also been investigated as prospective high LIDT mirrors.Alternative acidic routes to silica have been studied as a possible low index material and a route to preventing crazing.     

Sol–gel preparation of double-layer tri-wavelength antireflective coating

Double-layer tri-wavelength antireflective (AR) coating effective simultaneously at 351, 527 and 1,053?nm has been designed and prepared by the sol?Cgel process. The refractive index and film thickness of bottom layer and up layer are 1.27 and 113?nm, and 1.17 and 245?nm, respectively. The bottom layer with refractive index of 1.27 was prepared from a mixture of acid-catalyzed and base-catalyzed silica sols, and the up layer with refractive index of 1.17 was prepared from polypropylene oxide modified silica sol. It was found that the addition of polypropylene oxide into the sol significantly decreased the refractive index and increased the hydrophobicity of the AR coating. The obtained tri-wavelength AR coating gives very high transmittance of 99.7, 99.1 and 98.0?% at 351, 527 and 1,053?nm, simultaneously.     

Controlling Factors for the Conversion of Trifluoroacetate Sols into Thin Metal Fluoride Coatings

Metal fluoride films were prepared from trifluoroacetate sols by a spin-coating method. Effects of preparation conditions on the deposition of fluoride films have been examined in order to control the thickness and the refractive index of the films. It was suggested that the fluoride was formed by the thermal decomposition of the trifluoroacetate sols generating gaseous phases such as (CF₃CO)₂O, CO and CO₂. This reaction mechanism seemed to largely effect the deposition of the fluoride films in terms of the formation of pores. Characteristics of the fluoride films could be changed by varying the heat treatment. The refractive index of the MgF₂ films decreased with increasing heating temperature, which might result from the increased porosity of the films. Drying the film before the heat treatments was effective in the control of the refractive index.     

Thin film composite optical waveguides for sensor applications: a review

We review the design and fabrication of thin-film composite optical waveguides (OWG) with high refractive index for sensor applications. A highly sensitive optical sensor device has been developed on the basis of thin-film, composite OWG. The thin-film OWG was deposited onto the surface of a potassium-ion-exchanged (K⁺) glass OWG by sputtering or spin coating (5–9 mm wide, and with tapers at both ends). By allowing an adiabatic transition of the guided light from the secondary OWG to the thin-film OWG, the electric field of the evanescent wave at the thin film was enhanced. The attenuation of the guided light in the thin film layer was small, and the guided light intensity changed sensitively with the refractive index of the cladding layer. Our experimental results demonstrate that thin-film, composite OWG gas sensors or immunosensors are much more sensitive than sensors based on other technologies.     

在激光下几种磷酸盐溶液的折光规律

研究了KH₂PO₄、KD₂PO₄、NH₄H₂PO₄溶液、H₂和D₂O对激光的折光性。测定了它们对He-Ne激光和钠光的折光率温度系数及色散能力。确定了不同溶液折光指数与浓度的关系。单独给出了几种饱和溶液的折光规律,并用激光纹影法精确测定了相应溶液的饱和度数据。     

Fe—Silicalite—2催化剂表面CO2加氢反应性能的研究

研究了Ｆｅ／Ｓｉｌｉｃａｌｉｔｅ－２催化剂ＣＯ２加氢低碳烯烃反应性能，利用ＣＯ２－ＴＰＤ，ＣＯ２／Ｈ２－ＴＰＳＲ和ＣＯ／Ｈ２－ＴＰＳＲ表征手段，考察了铁含量及ＭｎＯ助剂对Ｆｅ／Ｓｉｌｉｃａｌｉｔｅ－２催化剂ＣＯ２吸附脱附及加氢反应性能的影响，表明随铁含量增加可提高催化剂对ＣＯ２的吸附能力，有利于提高ＣＯ２加氢反应的转化率。     

Room-Temperature Mirror Preparation Using Sol-Gel Chemistry and Laminar-Flow Coating Technique

The CEA/DAM megajoule-class pulsed Nd:glass laser devoted to Inertial Confinement Fusion (ICF) research will require 240 cavity-end mirrors. The approved laser design necessitates 42-cm × 46-cm × 9-cm highly-reflective (HR)-coated substrates representing more than 50 m² of coated area. Prototypes of these dielectric mirrors were prepared with interference quaterwave stacks of SiO₂ and ZrO₂-PVP (PolyVinylPyrrolidone) thin films starting from sol-gel colloidal suspensions (sols). Low refractive index material was based on nanosized silica particles and high refractive index coating solution was made of a composite system. The colloidal/polymeric ratio in the composite system has been optimized regarding refractive index value, laser damage threshold and chemical interactions have been studied using FT-IR spectroscopy. A deposition technique so-called Laminar Flow Coating (LFC) has been associated to sol-gel chemistry for HR laser damage-resistant sol-gel coating development. This novel coating method confirmed its main advantages compared to dipping or spinning processes: coating large flat square substrates at room temperature with small solution consumption, good thickness uniformity, weak edge-effects, induced stress-free coating, good optical properties and laser damage resistance fulfilling.     

Procedure for and results of simultaneous determination of aromatic hydrocarbons and fatty acid methyl esters in diesel fuels by high performance liquid chromatography

The content of aromatic hydrocarbons in diesel fuels is regulated by appropriate standards, and a further reduction in the allowed concentration of these hazardous substances in these fuels is expected. The content of aromatic hydrocarbons in diesel fuels is most often determined using standard methods EN-12916 or ASTM D-6591. The content of polycyclic aromatic hydrocarbons (PAHs) is determined from a single peak obtained using normal phase high-performance liquid chromatography (NP-HPLC), a column of the NH2 type, n-heptane as the eluent, refractive index detector (RID) and backflushing of the eluent. However, the methods mentioned above cannot be applied when the fuel contains fatty acid methyl esters (FAME), which lately has become more common. The content of FAME in diesel oils is determined using mid-IR spectrophotometry based on the absorption of carbonyl group. However, no standard procedure for the determination of classes of aromatic hydrocarbons in diesel fuels containing FAME is yet available. The present work describes such a modification of methods EN-12916/ASTM D-6591 that provides a simultaneous determination of individual groups of aromatic hydrocarbons, total content of polycyclic aromatic hydrocarbons and the FAME content in diesel fuels. The refractive index detector (RID) and n-heptane as the mobile phase are still used, but backflushing of the eluent is applied after the elution of all polycyclic aromatic hydrocarbons. Additionally, ultraviolet diode array detection is used for the exact determination of low contents of polycyclic aromatic hydrocarbons and to confirm the presence of FAME in the analyzed fuel.     

PRODUCTION OF LIGHT ALKENES FROM CO AND/OR CO_2 HYDROGENATION OVER K-Fe-MnO/SILICALITE-2 CATALYST

High selectivity to light alkenes can be achieved from CO and CO_2hydrogenation over K-Fe-MnO/Si-2 catalyst.The alkene selectivity isinsensitive to reaction temperature for CO hydrogenation,while apparentlyincreases for CO_2 hydrogenation with raising reaction temperature.An increasein alkene selectivity is observed for both CO and CO_2 hydrogenation with GHSVrising,While a decrease with the elevation of reaction pressure for both CO/H_2and CO_2/H_2 reaction.A two-step mechanism is suggested forCO_2 hydrogenation to form hydrocarbons,by which the variations incontributions of CO and HC as products of CO_2/H_2 reaction with change ofreaction temperature,GHSV and pressure are explained.Moreover,thecatalyst is favorable for selective production of light olefins,which can alsoconcern the slightly secondary reactions of light olefins to some extent.     

不同温度下α-氨基酸在CTAB溶液中的体积及折光率的变化

Densities(ρ)and refractive indices(nD)of glycine(Gly),DL-alanine(Ala),DL-valine(Val)(0.02,0.04,0.06,0.08,and 0.10 mol·L-1)in 0.005 and 0.008 mol·L-1 aqueous cetyltrimethylammonium bromide(CTAB)have been measured at 298.15,303.15,308.15,and 313.15 K.The density data have been utilized to calculate apparent molar volumes(φv),partial molar volumes(φ0v),at infinite dilution and partial molar volumes of transfer φ0v(tr)of amino acids.The refractive index data have been used to calculate molar refractivity(RD)of amino acids in aqueous cetyltrimethylammonium bromide.It has been observed that φ0v varies linearly with increasing number of carbon atoms in the alkyl chain of amino acids,and hence,was split to get contributions from the zwitterionic end groups(NH 3,COO-)and methylene group(CH2)of the amino acids.The behaviour of these parameters has been used to investigate the solute-solute,solute-solvent interactions and the effect of cetyltrimethylammonium cation on these interactions.     

PRODUCTION OF LIGHT OLEFINS FROM CO2 HYDROGENATION OVER Fe/SILICALITE-2 CATALYST. I.CATALYTIC REACTIVI-FY AND REACTION MECHANISM

K-Fe-MnO/Silicalite-2 is a desirable catalyst for the production of light olefins from CO2 hydrogenation The activity can be improved greatly with increasing the Fe loading, and the selectivities to hydrocarbons rise with Fe loading increase However, an ambiguous effect of Fe loading on the selectivity of light olefin in hydrocarbon products is observed. The CO2 hydrogenation containing a two-step mechanism CO2+H2=CO+H2O, a reversible water gas shift reaction, and CO+(m/2n+1)H2 =1/nCnHm+H2O2, a Frscher-Tropsch reaction, is suggested by the results of CO2-TPD and CO2/H2-TPSR as well as CO/H2-TPSR characterizations.     

Structural, optical and photoelectric properties of ZnO:In and Mg x Zn1 −x O nanofilms prepared by sol-gel method

The photochromic sol-gel hybrid materials containing cyanoazobenzene chromophores were described. These materials were obtained by copolycondensation of the functionalized triethoxysilane and tetraethoxysilane precursor. They were deposited on glass substrates via spin coating and casting techniques to provide thin transparent films. The UV-vis spectroscopy showed reversibility of the trans-cis photoisomerization of the chromophoric fragments. The reversible change of refractive index of the films on illumination with white light was determined by ellipsometry. The difference of real part of the refractive index of the sample was in the range 0.0053–0.0075. Formation of diffraction grating was achieved by two beam coupling arrangement using a 532 nm laser. The diffraction efficiency for the first order diffraction was in the range of 2–3.5%. The kinetics of photochromic grating recording and erasing was described by biexponential function approach.     

Understanding Refractive Index Changes in Homologous Series of Unbranched Organic Compounds Based on Beer's Law

Changes of the refractive index for homologous series of hydrocarbons are usually plotted versus the density. While there is a clear linear dependence for alkanes and alkenes, the linearity deteriorates for homologous series with functional groups involving heteroatoms. The slope can even become negative, e. g., for carboxylic acids. For gaining a deeper understanding and to establish a more general correlation, we reinvestigate the corresponding theories starting with the Newton-Laplace, Gladstone-Dale and the Lorentz-Lorenz rules. We revisit the concept of molar refractivity pioneered by Landolt and Brühl and show that it is closely connected with a twin of Beer's law. We conclude that the refractive index of homologues series should better be plotted versus the molar concentration of the main UV-chromophore, the C−H bond, which actually causes the refractive index changes. This new approach is not limited to alkanes and alkenes but holds for homologous series with functional groups including heteroatoms.     

化学接枝改进ZnO-有机硅纳米复合材料的光学性能

采用N-(三甲氧基硅丙基)-4-叠氮-2,3,5,6-四氟苯甲酰胺(PFPA-silane)改性纳米氧化锌,并将PFPA-silane接枝在有机硅聚合物链上.接枝反应改变了纳米复合物的折光指数,并使ZnO纳米粒子与有机硅基体的折光指数更加匹配.这减少了纳米氧化锌粒子对光的散射作用,增加了纳米ZnO-有机硅纳米复合物的透明性.所制备的复合物通过接枝改性后透光率最多可提高50%.研究结果表明无机物和聚合物的折光指数的匹配程度可以通过偶联剂与聚合物基体的反应来进行调控.     

In-situ characterization of thin polymer films for applications in chemical sensing of volatile organic compounds by spectroscopic ellipsometry

Polymer coatings are applied in many kinds of chemical sensors. The interaction with organic vapours changes the physical properties of the coating material. For optical sensors, changes in the coating volume and the complex refractive index are most important. Spectroscopic ellipsometry has been applied for the first time to the in-situ characterization of thin poly(dimethylsiloxane) films in contact with tetrachloroethene, toluene and cyclohexane vapours. The differences in bulk refractive index between organic solvent and polymer are large for toluene and tetrachloroethene and both effects were studied separately. Cyclohexane has a bulk refractive index very close to the investigated poly(dimethylsiloxane) films. Therefore the calculation of the volume fraction of the analyte in the mixture phase with the polymer is subject to large errors for vapour concentrations below 5000 ppm. Paper presented at the ANAKON ’95, Schliersee, München, Germany     

Solution properties of polymers of pyridinium and ammonium methacrylates

Solution properties of poly[1(2-hydroxyethyl)pyridiniumbenzene sulfonate methacrylate] and poly[1(2-hydroxyethyl)trimethylammoniumbenzene sulfonate methacrylate] were studied. Within a certain concentration range of some added low molecular weight electrolytes, phase separation occurs. The dependence of intrinsic viscosity on molecular weight was determined and the steric factor estimated for both polymers. For nonaqueous solvents, an extrapolation of the dependence of the refractive index increment of the polymer on the refractive index increment of the polymer on the refractive index of the solvent leads to an apparent refractive index of the polymer, different from the refractive index determined directly by the immersion method. Some peculiarities of light scattering in solutions with no electrolyte added are mentioned.     

Concentration and temperature dependence of the refractive index increment of a polystyrene sample in trans-decalin

The refractive index increment of macromolecules in solution has been observed to be a function of concentration, temperature, molecular weight, wavelength of light, and solvent. Most of the studies have been performed in dilute or semidilute solutions, and therefore the concentration dependence of the refractive index increment was too small to be accurately observed. This study was performed on solutions of polystyrene in trans-decalin at mass fractions, w₂, from 0.01 to 0.11 and at 436 and 546 nm wavelengths. The concentration and temperature dependence of the refractive index increment were measured, and comparisons were made with previous theories.