Metallic thin-film thermocouple for thermoelectric microgenerators

A new metallic thin-film thermocouple orientated towards thermoelectric microgenerators has been developed. It consists of a 3 μm thick NiCr/SiO₂/Sb multilayer structure sputter deposited onto a thermally oxidized silicon substrate. A relative Seebeck coefficient of _ab = 76 μV K⁻¹ and an optimal figure of merit of z_ab = 0.08 × 10⁻³ K⁻¹ have been measured for this material combination. Both parameters are very close to the theoretical values.     

Simultaneous determination of lead and cadmium at a glassy carbon electrode modified with Langmuir–Blodgett film of p-tert-butylthiacalix[4]arene

A glassy carbon electrode (GCE) modified with a Langmuir–Blodgett (LB) film of p-tert-butylthiacalix[4]arene (TCA) has been investigated as a disposable sensor for measuring the trace levels of lead and cadmium. The possibility of determining lead and cadmium at trace levels was examined with differential pulse stripping voltammetry in the measurement step. The electrochemical response was characterized with respect to supporting electrolyte, pH of solution, accumulation time, accumulation potential, layers of the LB films, and possible interferences. Calibration plots were found to be linear in the range 2 × 10⁻⁷ to 5 × 10⁻⁵ mol l⁻¹ (Cd²⁺) and 1 × 10⁻⁷ to 2.5 × 10⁻⁵ mol l⁻¹ (Pb²⁺); the detection limits were 2 × 10⁻⁸ mol l⁻¹ (Cd²⁺) and 8 × 10⁻⁹ mol l⁻¹ (Pb²⁺). Possible recognition mechanism was also discussed. From the analysis of real samples (river, lake and tap water) it can be concluded that the method is sensitive and reproducible in determining of these elements and can be used in the analysis of natural water samples.     

Fabrication of improved piezoresistive silicon cantilever probes for the atomic force microscope

This paper describes an improved design for a monolithic silicon atomic force microscope (AFM) probe using piezoresistive sensing. The probe is V shaped, with a sharp tip at the free end and two piezoresistors at the root, and is fabricated using silicon-on-insulator (SOI) starting material. The maximum sensitivity of the AFM probe is measured to be 4.0(± 0.1) × 10⁻⁷ Å⁻¹, which is larger than that of the previous parallel-arm piezoresistive AFM probe. The measured results are in reasonable agreement with the values predicted by theory. The minimum detectable force and minimum detectable deflection of the AFM probes are predicted to be 1.0 × 10⁻¹⁰ N and 0.29 Å_r.m.s., respectively, using a Wheatstone bridge arrangement biased at a voltage of ± 5 V and bandwidth of 10 Hz–1 kHz.     

Adsorptive voltammetry of Hg(II) ions at a glassy carbon electrode coated with electropolymerized methyl-red film

The glassy carbon electrode coated with electropolymerized methyl-red film, 1.2 × 10⁻⁶ m in thickness, (PMRE) showed high sensitivity towards Hg(II) ions. PMREs were adopted to accumulate and detect Hg(II) ions in a pH 2.56 Britton–Robinson buffer solution. Cyclic voltammogram of the accumulated Hg species on PMREs exhibited an anodic wave at 0.64 V and a cathodic wave at 0.13 V, due to the oxidation of accumulated Hg species on PMREs and the reduction of Hg(II) ions in the solution, respectively. For this heterogeneous adsorption of Hg(II) ions onto PMREs, the maximum surface concentration, adsorption equilibrium, and Gibbs energy change were evaluated to be 5.12 × 10⁻⁶ mol m⁻², 3.7 × 10⁵ l mol⁻¹, and −30.1 kJ mol⁻¹, respectively. The anodic peak current at 0.64 V was linear with the concentration of Hg(II) ions in the range of 1.1 × 10⁻¹⁰ to 1.1 × 10⁻⁷ M with a detection limit of 4.4 × 10⁻¹¹ M. The proposed method was utilized successfully for the detection of Hg(II) ions in the lake water.     

Simulation and fabrication of piezoresistive membrane type MEMS strain sensors

Two piezoresistive (n-polysilicon) strain sensors on a thin Si₃N₄/SiO₂ membrane with improved sensitivity were successfully fabricated by using MEMS technology. The primary difference between the two designs was the number of strips of the polysilicon patterns. For each design, a doped n-polysilicon sensing element was patterned over a thin 3 μm Si₃N₄/SiO₂ membrane. A 1000×1000 μm² window in the silicon wafer was etched to free the thin membrane from the silicon wafer. The intent of this design was to fabricate a flexible MEMS strain sensor similar in function to a commercial metal foil strain gage. A finite element model of this geometry indicates that strains in the membrane will be higher than strains in the surrounding silicon. The values of nominal resistance of the single strip sensor and the multi-strip sensor were 4.6 and 8.6 kΩ, respectively. To evaluate thermal stability and sensing characteristics, the temperature coefficient of resistance [TCR=(ΔR/R₀)/ΔT] and the gage factor [GF=(ΔR/R₀)/] for each design were evaluated. The sensors were heated on a hot plate to measure the TCR. The sensors were embedded in a vinyl ester epoxy plate to determine the sensor sensitivity. The TCR was 7.5×10⁻⁴ and 9.5×10⁻⁴/°C for the single strip and the multi-strip pattern sensors. The gage factor was as high as 15 (bending) and 13 (tension) for the single strip sensor, and 4 (bending) and 21 (tension) for the multi-strip sensor. The sensitivity of these MEMS sensors is much higher than the sensitivity of commercial metal foil strain gages and strain gage alloys.     

Determination of reduced glutathione using an amperometric carbon paste electrode chemically modified with TTF–TCNQ

The development of an amperometric sensor for the determination of reduced glutathione (GSH) is described. The sensor is based on tetrathiafulvalene–tetracyanoquinodimethane (TTF–TCNQ) incorporated into the graphite powder/Nujol oil matrix. The electrooxidation of GSH was monitored amperometrically at 200 mV versus SCE (saturated calomel electrode). The amperometric response of the sensor was linearly proportional to the GSH concentration between 20 and 300 μmol l⁻¹, in 0.1 mol l⁻¹ phosphate buffer (pH 8.0), containing 0.1 mol l⁻¹ KCl and 0.5 mmol l⁻¹ Na₂H₂EDTA, as supporting electrolyte.

The detection limit, considering signal/noise ratio equal three, was 4.2 μmol l⁻¹ for GSH and the repeatability obtained as relative standard deviation was of 5.1% for a series of 10 successive measurements.     

Perchlorate selective membrane electrodes based on synthesized platinum(II) complexes for low-level concentration measurements

Three synthesized platinum(II) complexes, [PtR₂(NN)] (R = Me, p-MeC₆H₄ and p-MeOC₆H₄; NN = 2,2′-bipyridyl), were studied to characterize their ability as an anion carrier in a PVC membrane electrode. The polymeric membrane electrodes (PME) and also coated glassy carbon electrodes (CGCE) prepared with [Pt(p-MeOC₆H₄)₂(NN)] showed excellent response characteristics to perchlorate ions. The electrodes exhibited Nernstian responses to ClO₄⁻ ions over a wide concentration range from 5 × 10⁻⁷ to 4.0 × 10⁻¹ M for PME and 1.5 × 10⁻⁷ to 2.7 × 10⁻¹ M for CGCE with low detection limits (4.0 × 10⁻⁷ M for PME and 1.0 × 10⁻⁷ M for CGCE). The electrodes possess fast response time, satisfactory reproducibility, appropriate lifetime and, most importantly, good selectivity toward ClO₄⁻ relative to a variety of other common anions. The potentiometric response of the electrodes is independent of the pH of the test solution in the pH range 2.5–9.5. The proposed sensors were used in potentiometric determination of perchlorate ions in mineral water, urine samples and also samples containing interfering anions. The interaction of the ionophore with perchlorate ions was shown by UV–vis spectroscopy.     

Gasochromic effect of palladium doped peroxopolytungstic acid films prepared by the sol-gel route

Gasochromic palladium doped peroxopolytungstic acid (Pd:P-PTA) films have been prepared using dip-coating deposition from peroxopolytungstic acid (P-PTA) sols into which PdCl₂ was added in molar ratios Pd:W=1:125, 1:100, 1:53, and 1:40. These films exhibit reversible colouring/bleaching changes when exposed to hydrogen or hydrogen/argon mixture (4%) and air, alternatively. Gasochromically coloured and bleached films were characterised using in-situ Fourier transform infrared (FT-IR) spectroscopy. The vibrational modes of as-deposited, coloured and bleached films were assigned and the polaron absorption, which characterises the IR spectra of coloured films, was detected. Colouring/bleaching kinetics of films exposed to H₂ and H₂/Ar mixture as a function of the concentration of the catalyst and temperature of heat-treatment is reported. Proton (σ_pr) and electronic (σ_el) conductivities determined from impedance spectra revealed an increase in σ_el from 10⁻⁵ S cm⁻¹ in bleached state, to 10⁻³ S cm⁻¹ in coloured state, while σ_pr remained constant (10⁻² S cm⁻¹).     

Study of the potentiometric response towards sodium ions of Na0.44−xMnO2 for the development of selective sodium ion sensors

Single phase Na_0.44MnO₂ powder was synthetized by a classical solid-state reaction. Using a plastic technology, we studied the potentiometric response versus Na⁺ ions in aqueous medium. A Nernstian-like response (55 mV/dec) was obtained for concentrations ranging from 1 M to 2 × 10⁻⁴ M with a quite good selectivity towards Li⁺, K⁺, Mg²⁺ and Ca²⁺. Through an ageing study of this material in aqueous solution, we clearly identified the sensing material as being the Na_0.33MnO₂ phase. Furthermore, we proved that the sensing activity of this compound is routed in its ability to reversibly insert/de-insert Na⁺ ions.     

Development of a highly sensitive and selective optical chemical sensor for batch and flow-through determination of mercury ion

A very sensitive, highly selective and reversible optical chemical sensor (optode) for mercury ion is described. The sensor is based on the interaction of Hg²⁺ with 2-mercapto-2-thiazoline (MTZ) in plasticized PVC membrane incorporating a proton-selective chromoionophore (ETH5294) and lipophilic anionic sites (sodium tetraphenylborate, NaTPB). The membranes were cast onto glass substrates and used for the determination of mercury ion in aqueous solutions by batch and flow-through methods. The sensor could be used in the range 2.0 × 10⁻¹⁰ to 1.5 × 10⁻⁵ M (0.04 ng mL⁻¹ to 3 μg mL⁻¹) Hg²⁺ with a detection limit of 5.0 × 10⁻¹¹ M and a response time of <40 s. It can be easily and completely regenerated by dilute nitric acid solution. The sensor has been incorporated into a home-made flow-through cell for determination of mercury ion in flowing streams with improved sensitivity, precision and detection limit. The sensor showed excellent selectivity for Hg²⁺ with respect to several common alkali, alkaline earth and transition metal ions. The results obtained for the determination of mercury ion in river water samples using the proposed optode was found to be comparable with the well-established cold-vapor atomic absorption method.     

Trace detection of nitroaromatic compounds with layer-by-layer assembled {SBA/PSS}n/PDDA modified electrode

The {SBA/PSS}_n/PDDA films modified electrode was prepared by layer-by-layer (LBL) assembly with mesoporous SiO₂ (SBA), poly(sodium 4-styrene-sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDDA) in this paper. SBA is a large pore-size mesoporous material with highly ordered hexagonally arranged mesochannels and high thermal stability etc. The electrochemical characteristics of the {SBA/PSS}_n/PDDA films have been studied by electrochemical impedance spectroscopy in 0.1 M KCl solution containing 5.0 mM Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ at the formal potential of 0.230 V. The ultratrace nitroaromatic compounds (NACs) such as TNT, TNB, DNT and DNB were determined by differential pulse voltammetry (DPV) measurement. The sensitivities for NACs determination with {SBA/PSS}_n/PDDA modified electrode were dependent on the number of layers, pH and ionic strength of electrolyte, based on which a set of optimized conditions for film fabrication was inferred. The current responses were linear with NACs ranging from 10⁻⁹ to 10⁻⁷ mol/l. The results showed that the {SBA/PSS}_n/PDDA modified electrode established a new way for fast, simple and sensitive analysis of NACs.     

Application of the independent molecule model to elucidate the dynamics of structure I methane hydrate: a second report

Two model systems of methane hydrate are constructed. One has a small cage surrounded by 12 large cages. The other has a large cage surrounded by four small cages and ten large cages. Three different H-bonding network patterns between waters are formed, and three random configurations of methane in each cage are chosen. A new method called the surface water fixed model is presented in which the energy minimum conformations for both model systems are preserved close to the X-ray crystallized structure. With normal mode analysis, we calculated frequencies of 2916.6 cm⁻¹ for a small cage at a centre, 2915.9 cm⁻¹ not at a centre, and 2911.7 cm⁻¹ for a large cage at a centre, and 2911.3 cm⁻¹ not at a centre. These frequencies are in moderate agreement with the corresponding Raman spectra, though not adequate. With our new method, however, it should be possible to improve agreement with the Raman spectra, if a model system vastly larger than the present model systems were constructed.     

Construction of a highly selective PVC-based membrane sensor for Ce(III) ions

A highly Ce(III) ion-selective poly vinyl chloride (PVC) membrane sensor based on N′-[(2-hydroxyphenyl)methylidene]-2-furohydrazide (NHMF) as an excellent sensing material is successfully developed. The electrode shows a good selectivity for Ce(III) ions with respect to most common cations including alkali, alkaline earth, transition and heavy metal ions. The proposed sensor exhibits a wide linear response with a slope of 19.4 ± 0.3 mV/decade over the concentration range of 1.0 × 10⁻⁵ to 1.0 × 10⁻¹ M, and a detection limit of 7.6 × 10⁻⁶ M of Ce(III) ions. The sensor response is independent of pH in the range of 3.5–10.0. The proposed electrode was applied as an indicator electrode in potentiometric titration of Ce(III) ions with EDTA and C₂O₄². It was also successfully applied in the determination of cerium ions in aqueous samples.     

Perchlorate-selective membrane sensors based on two nickel-hexaazamacrocycle complexes

The perchlorate salts of nickel(II) complexes of 1,3,5,8,10,13-hexaazacyclotetradecane (1) and 1,8-tert-butyl-1,3,5,8,10,13-hexaazacyclotetradecane (2) were used in construction of PVC based membrane electrodes. These sensors show very good selectivity for ClO₄⁻ ions over a wide variety of anions. These electrodes exhibit Nernstian behavior with the slopes of 59.5 and 59.3 mV per decade for (1) and (2), respectively. The working concentration ranges of the sensors are 1.0 × 10⁻¹–9.0 × 10⁻⁷ M (1) and 1.0 × 10⁻¹–5.0 × 10⁻⁷ M (2) with the detection limits of 6.0 × 10⁻⁷ and 2.0 × 10⁻⁷ M, respectively. The response time of the both sensors is very fast, and can be used for 2 (I) and 12 (II) weeks in a pH range of 3.0–11.0. These electrodes were applied to the determination of perchlorate ions in wastewater and cattle urine samples.     

Evaluation of the selective detection of 4,6-dinitro-o-cresol by a molecularly imprinted polymer based microsensor electrosynthesized in a semiorganic media

A carbon fiber microelectrode (CFME) was coated with a polymeric film, in order to synthesize an MIP based voltammetric microsensor for the selective determination of DNOC. The polymeric synthesis was carried out by electrocopolymerization of aniline and o-phenylenediamine (o-PD) in a water:methanol (1:1) media. The response of the MIP-sensor synthesized to the target analyte, was linear in a range from 8 × 10⁻⁷ to 10⁻⁴ M with a sensitivity of 1.6 × 10³ nA M⁻¹ and good stability and repeatability (<14%). Different rebinding experiments were carried out in order to evaluate the binding properties of the MIP-sensor. The experimental adsorption isotherms were fitted to Langmuir, Bi-Langmuir and Freundlich–Langmuir isotherms and the Langmuir model was chosen as the best fitting model. Under the optimized experimental conditions, the voltammetric microsensor was able to differentiate between DNOC and other closely related compounds such as other dinitrophenolic pesticides like binapacryl or dinobuton.     

LTCC compatible PLZT thick-films for piezoelectric devices

The production of PLZT thick-films for piezoelectric devices prepared from perovskite-type (Pb, La)(Zr, Ti)O₃ powders is described. The powder manufacture, paste preparation and thick-film production compatible with the low temperature co-fired ceramics (LTCC) process are detailed. The maximum firing temperature of applied technology is 850 °C. Measurements of the dielectric and piezoelectric properties of the produced films are carried out. The low dielectric loss (0.022) and high d₃₃ and d₃₁ piezoelectric coefficients (85.7×10⁻¹² and −34.6×10⁻¹² m/V, respectively) of the material, together with a relatively low sintering temperature, make it suitable for various applications, e.g. ultrasonics.     

DNA hybridization measurement by self-sensing piezoresistive microcantilevers in CMOS biosensor

Understanding the mechanism of how biological reactions produce mechanical loadings is fundamental to biomedical developments. A CMOS biosensor chip is developed to measure in situ the induced surface stress change by DNA hybridization. For 20-mer thiol-modified single stranded DNA (ssDNA), the mechanism of ssDNA attached to gold surface via a sulfur–gold linkage can be investigated by using the Langmuir adsorption model. Experimental results indicate that the immobilization response is less than 1 s, the total number of ssDNA molecules on the cantilever is about 3 × 10¹¹, and the induced surface stress is 0.15 N/m. The surface stress sensitivity of the sensor is about 3.5 × 10⁻⁵ m/N. The estimated adsorption rate of the ssDNA is 0.005 s⁻¹. The biosensor is capable of discriminating complimentary molecular targets and thus may provide a powerful platform for high throughput real-time analysis of DNA.     

Thermal expansion of Chromium (Cr) to melting temperature

In situ x-ray data on molar volumes of chromium have been collected over the temperature range from 300 K to melting. The sample was heated to melting by passing an electrical current through the sample (the technique of electrical resistance wire heating). The sample consists of a tungsten wire as a heater and a mixture of Cr and W powder, which is placed in a hole of 250 μm diameter. Tungsten was used as an internal standard for temperature determination. In order to prevent the specimen from oxidation, the experiments were carried out in an argon flow. Unit cell parameters of Cr at different temperatures were calculated using (110), (200), (211), and (220) reflections. Precision of determination of lattice parameter is 10⁻⁴ A at 300 K and 5 10⁻⁴ A at 2000 K. Thermal expansion of Cr increases rapidly at temperatures higher than 1200 K. The linear thermal expansion () of chromium between 300 and 2130 K is given by: = 1.220(5) 10⁻⁵ − 1.150(6) 10⁻⁸ T + 1.132(8) 10⁻⁶ T² − 0.507(7)/T² (T, K). In our experiments, Cr melted between 2120 and 2150 K.     

Manganese(II)-selective PVC membrane electrode based on a pentaazamacrocyclic manganese complex

Manganese(II) complex of 14,16-dimethyl-1,4,7,10,13-pentaazacyclohexadeca-13,16-diene [Me₂(16)dieneN₅] (I) was synthesized and used in the fabrication of Mn²⁺-selective ISE membrane in PVC matrix. The membrane having Mn(II) macrocyclic complex as electroactive material along with sodium tetraphenylborate (NaTPB) as anion discriminator and dioctylphthalate (DOP) as plasticizer in poly(vinylchloride) (PVC) matrix was prepared for the determination of Mn²⁺. The best performance was observed by the membrane having Mn(II) complex–PVC–NaTPB–DOP in the ratio 1:5:1:3. The sensor worked well over a concentration range of 1.25 × 10⁻⁵ to 1.0 × 10⁻¹ M between pH 3.0 and 8.0 and had a fast response time of 20 s with a lifetime of 4 months. Their performance in partially non-aqueous medium was found satisfactory up to 30% (v/v) alcoholic content. Electrodes exhibited excellent selectivity for Mn²⁺ ion over other mono-, di-, trivalent cations. It can also be used as indicator electrode in the potentiometric titration of Mn²⁺ against EDTA.     

Thin-film thermocouples of Ge doped with Au and B

High thermoelectric power (S300 μV K⁻¹;ρ10⁻⁴ Ω m) has been achieved for germanium layers doped with gold deposited by evaporation. The relative simplicity and good reproducibility of the method seems to be promising for thermopiles in some types of microsensors.