Determining the effects of vapor sorption in polymers with the quartz crystal microbalance/heat conduction calorimeter

The quartz crystal microbalance/heat conduction calorimeter (QCM/HCC) is a versatile instrument coupling both gravimetric and calorimetric techniques. The QCM/HCC is used to probe vapor sorption in thin films. Three parameters are measured simultaneously as a thin film undergoes vapor sorption, namely: mass changes in the film (±10 ng), corresponding thermal effects upon vapor sorption (±100 nW), and motional resistance (±0.5Ω) changes within the film. A range of film thicknesses (0.75 to 8.5 μm) of the polymer, Tecoflex? are cast on QCMs and the interaction of each film with ethanol and water is determined. From the direct calorimetric measurements, sorption enthalpies (Δ_sorptionH kJ/mol) are determined for the film–vapor interactions. Sorption isotherms are then analyzed for each film. The isotherms shown here generally display a linear Henry's Law dissolution relationship between the vapor pressure and the amount of vapor sorbed into the film. Motional resistance data provides a window to view viscoelastic effects of the polymer films upon vapor sorption. Motional resistance data are compared for ethanol sorption in a relatively thin (0.75 μm) and thicker (8.5 μm) Tecoflex? film. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3893–3906, 2004     

A simple,rapid method for the generation of ligand binding isotherms

Using the protonation of tris(hydroxymethyl)aminomethane (Tris) as a standard reaction, a technique is established for the generation of reaction isotherms by continuous titration in a flow microcalorimeter. The procedure uses an exponential dilution device of simple design that provides a constant internal volume, efficient mixing of the contents and is a closed system. The method has considerable advantages over conventional calorimetric procedures and the precision of enthalpy measurements is estimated to be within ± 2%.     

Push-Button Electrochemical Analyser

Abstract

The design of a new instrument for routine analysis of electroactive substances is presented. The instrument is a potentiostat in which potential control is maintained by varying the rate of delivery of current pulses of uniform charge content to a small electrochemical cell. Digital readout of the concentration in desired units is obtained by counting and displaying the number of current impulses. The entire analysis consists of introducing a sample, pressing the potentiostat button and reading the result within 3–5 seconds - hence the name, “push-button analyser”. A block diagram, schematic diagrams and parts list are included.     

简易示差扫描量热计的研制

<正> 示差扫描量热计(DSC)是在示差热分析仪(DTA)基础上发展起来的新型热分析仪,它在高分子方面已取得广泛应用.我们自1975年起研制了适合有机、高分子应用的DSC,取得一些经验,简介如后. 图1是DSC的结构示意图.DSC独有的单元是量热部.它由一对小加热器组成的试料部(量热部Ⅰ)和由热量补偿回路等组成的热量补偿部(量热部Ⅱ)构成.我们研制以此单元为主,其它部分均以商品仪器配用.     

Effect of Cathode Nozzle Geometry and Process Parameters on the Energy Distribution for an Argon Transferred Arc

The influence of two nozzle geometries and three process parameters (arc current, arc length and plasma sheath gas flow rate) on the energy distribution for an argon transferred arc is investigated. Measurements are reported for a straight bore cylindrical and for a convergent nozzle, with arc currents of 100 A and 200 A and electrode gaps of 10 mm and 20 mm. These correspond to typical operating parameters generally used in plasma transferred arc cutting and welding operations. The experimental set up consisted of three principal components: the cathode-torch assembly, the external, water-cooled anode, and the reactor chamber. For each set of measurements the power delivered to each system component was measured through calorimetric means, as function of the arc’s operating conditions. The results obtained from this study show that the shape of the cathode torch nozzle has an important influence on arc behaviour and on the energy distribution between the different system components. A convergent nozzle results in higher arc voltages, and consequently, in higher powers being generated in the discharge for the same applied arc current, when compared to the case of a straight bore nozzle. This effect is attributed to the fluidynamic constriction of the arc root attachment, and the consequential increase in the arc voltage and thus, in the Joule heating. The experimental data so obtained is compared with the predictions of a numerical model for the electric arc, based on the solution of the Navier–Stokes and Maxwell equations, using the commercial code FLUENT©. The original code was enhanced with dedicated subroutines to account for the strong temperature dependence of the thermodynamic and transport properties under plasma conditions. The computational domain includes the heat conduction within the solid electrodes and the arc-electrode interactions, in order to be able to calculate the heat distribution in the overall system. The level of agreement achieved between the experimental data and the model predictions confirms the suitability of the proposed, “relatively simple” model as a tool to use for the design and optimization of transferred arc processes and related devices. This conclusion was further supported by spectroscopic measurements of the temperature profiles present in the arc column and image analysis of the intensity distribution within the arc, under the same operating conditions.     

Calorimetry under Stress A Preliminary Study in Single Crystalline Cu-Zn-Al Shape Memory Alloys

A non-differential calorimetric analyzer was developed for an INSTRON 1123 machine (a stress-strain-temperature analyzer) with a temperature chamber INSTRON 1110. The study was performed using the Joule effect and pseudoelastic martensitic transformations in single crystals of Cu-Zn-Al alloys. The analysis of the system establishes that: the sensitivity of calorimetric measurements after a filter of two poles and two zeros is 166 mV W^-1 (at 297 K), the noise is near 1.5 μV and the drift is close to 30 μV in 6 h. The reproducibility of the sensitivity working with one sample is better than ±0.3%, and the change to a new sample keeps the value below ±0.5%. The uncertainty in reproducibility in the martensitic transformation (including repositioning) does not overcome ±1.6%. The used calorimetric sensors limit the temperature to 373 K. The furnace control originated fluctuations on the base line (near ±20 μV), which by means of an auxiliary signal processing were reduced to 50% (less than ±10 μV). This revised version was published online in July 2006 with corrections to the Cover Date.     

Calorimetric investigation of order–disorder transition in Cu0.6Pd0.4 and Cu0.85Pd0.15 alloys

Order–disorder phase transitions in Cu_0.6Pd_0.4 and Cu_0.85Pd_0.15 alloys have been investigated using differential scanning calorimetry and drop calorimetry. The differential scanning calorimetry measurements show that the transition in both these alloys are reversible in nature and the enthalpy increment measurements reveal that these transitions are first order in nature. The transition temperature of first-order phase transition in Cu_0.6Pd_0.4 and Cu_0.85Pd_0.15 alloys have been evaluated to be 884(±2) and 799(±2) K, respectively, from drop calorimetric measurements. The latent heat of first-order phase transition in Cu_0.6Pd_0.4 alloy were evaluated to be 31.2(±0.6) and 28.9(±0.5) J g^?1, by enthalpy increment and differential scanning calorimetry measurements, respectively. Similarly, the latent heat of first-order phase transition in Cu_0.85Pd_0.15 alloy were evaluated to be 23.1(±0.6) and 21.3(±0.5) J g^?1, by enthalpy increment and differential scanning calorimetry measurements, respectively. The solidus temperatures of Cu_0.6Pd_0.4 and Cu_0.85Pd_0.15 alloys were found to be 1,457(±2) and 1,360 K, respectively.     

A calorimetric study of the enthalpy of micelle formation by a polystyrene-b-polyisoprene block copolymer in n-hexadecane

A calorimetric study was made of micelle formation by a polystyrene-b-polyisoprene block copolymer in n-hexadecane which is a selectively bad solvent for polystyrene. A value of −44.0 ± 4.0 kJ mol⁻¹ was obtained for the enthalpy of micellisation, in good agreement with a value of −40.7 ± 2.2 kJ mol⁻¹ determined for this system in an earlier study from measurements of the temperature dependence of the critical micelle concentration. The agreement between the results supports the use of a simple mass-action model in accounting for the thermodynamics of micellisation of block copolymers in organic solvents.     

Thermochemical Properties of the Lattice Oxygen in W,Mn-Containing Mixed Oxide Catalysts for the Oxidative Coupling of Methane

Mixed NaWMn/SiO₂ oxide, samples containing individual components (Na, W, Mn) and their double combinations (Na–W, Na–Mn, W–Mn) supported on silica were studied by temperature programmed reduction (TPR) and desorption (TPD), and heat flow calorimetry during their reoxidation with molecular oxygen in pulse mode. The NaWMn/SiO₂ mixed oxide was shown to contain two different types of reactive lattice oxygen. The weakly-bonded oxygen can be reversibly released from the oxide in a flow of inert gas in the temperature range of 575?900°C, while the strongly-bonded oxygen can be removed during the reduction of the sample with hydrogen at 700–900°C. The measured thermal effect of oxygen consumption for these two oxygen forms are 185 and 350 kJ/mol, respectively. The amount of oxygen removed at reduction (~443 μmol/g) considerably exceeded the amount desorbed in an inert gas flow (~56 μmol/g). The obtained results suggest that the reversible oxygen desorption is due to the redox process in which manganese ions are involved, while during the temperature programmed reduction, mainly oxygen bonded with tungsten is removed.     

Low-temperature heat capacities and derived thermodynamic functions of cyclohexane

The low-temperature heat capacities of cyclohexane were measured in the temperature range from 78 to 350 K by means of an automatic adiabatic calorimeter equipped with a new sample container adapted to measure heat capacities of liquids. The sample container was described in detail. The performance of this calorimetric apparatus was evaluated by heat capacity measurements on water. The deviations of experimental heat capacities from the corresponding smoothed values lie within ±0.3%, while the inaccuracy is within ±0.4%, compared with the reference data in the whole experimental temperature range. Two kinds of phase transitions were found at 186.065 and 279.684 K corresponding solid-solid and solid-liquid phase transitions, respectively. The entropy and enthalpy of the phase transition, as well as the thermodynamic functions {H_(T)-H _{298.15 K}} and {S _(T)-S_{298.15 K}}, were derived from the heat capacity data. The mass fraction purity of cyclohexane sample used in the present calorimetric study was determined to be 99.9965% by fraction melting approach. This revised version was published online in July 2006 with corrections to the Cover Date.     

iR correction: Part I. A computerised interrupt method

A microprocessor-controlled potentiostat is used with an optically isolated switch to measure uncompensated iR drop to within ±0.1 mV using the current-interrupt method. The iR drop is calculated at the instant of interruption after back extrapolation of the potential decay. Added uncompensated resistance is measured for both dummy and electrochemical cells and good agreement is obtained between added and found values.     

A swept-potential electrochemical detector for flow streams

An instrument has been designed, constructed, and evaluated for electrochemical measurements in flow streams. The instrument is basically a computer-controlled potentiostat with features which are necessary for measurements in flow streams. These features include real-time graphics display, rapid transfer of data to disk storage, automated compensation for IR drop, and automated d.c. current offset. The instrument can be programmed to operate in several modes, but the primary mode of operation is rapid-sweep square-wave voltammetry. Programs are available for post-run processing of the data and display of any desired voltammogram or current vs. time plot. Any alphanumeric or display of any desired can be copied on a dot-matrix printer. Performance evaluations in unstirred solutions indicate limits of detection of less than 1 × 10^?9 M in favorable cases.     

A Practical Approach for the Detection of Protein Tau with a Portable Potentiostat

Along with many factors, the change in protein tau isoforms, which has an obvious role in the function of microtubules, is an important biomarker of Alzheimer's disease. The aim of this study is to determine the protein Tau-441 with a portable potentiostat using a practical approach. For this purpose, screen printed electrodes (SPCEs) were first hydroxylated and then functional self-assembled monolayers were formed on the surface with 3-aminopropyltriethoxysilane (APTES). Evidence of anti-Tau being immobilized on to the surface was followed by techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Fourier transform infrared spectroscopy (FTIR). The constructed immunosensor showed a linear response within the concentration range of 0.0064–0.8 ng/mL for the target analyte Tau-441 and the limit of detection was found to be 0.0053 ng/mL. In addition, analytical behaviors such as reproducible measurements and storage life of the developed immunosensor with a portable potentiostat were also investigated. It has been demonstrated that Tau-441 can be captured with the help of portable device with sensitivity in CSF environment.     

A calorimetric setup for measuring heat effects of processes in solutions

A calorimetric setup was developed to determine the heat effects of chemical processes in solutions with a sensitivity of ～10^?5 K and an accuracy of temperature control in the thermostat of better than ±0.001 K. The performance of the calorimeter was tested by measuring the heat effects of solution of 1-propanol (m = 0.02–0.08 mol/kg), potassium chloride (m = 0.01–0.73 mol/kg), and L-phenylalanine (m = 0.0008–0.03 mol/kg) in water at 25°C.     

Development of a new contactless dielectrophoresis system for active particle manipulation using movable liquid electrodes

This study presents a new DEP manipulation technique using a movable liquid electrode, which allows manipulation of particles by actively controlling the locations of electrodes and applying on–off electric input signals. This DEP system consists of mercury as a movable liquid electrode, indium tin oxide (ITO)‐coated glass, SU‐8‐based microchannels for electrode passages, and a PDMS medium chamber. A simple squeezing method was introduced to build a thin PDMS layer at the bottom of the medium chamber to create a contactless DEP system. To determine the operating conditions, the DEP force and the friction force were analytically compared for a single cell. In addition, an appropriate frequency range for effective DEP manipulation was chosen based on an estimation of the Clausius–Mossotti factor and the effective complex permittivity of the yeast cell using the concentric shell model. With this system, we demonstrated the active manipulation of yeast cells, and measured the collection efficiency and the dielectrophoretic velocity of cells for different AC electric field strengths and applied frequencies. The experimental results showed that the maximum collection efficiency reached was approximately 90%, and the dielectrophoretic velocity increased with increasing frequency and attained the maximum value of 10.85 ± 0.95 μm/s at 100 kHz, above which it decreased.     

Studying dispersoid systems

Summary Measurements of energy transformation in mitochondria are done on a capillary differential titration calorimeter CTD2156. It is important to mention that a sediment is quickly formed by the mitochondria suspension without mixing by means of a vibrating needle. During the measurements, the vibrating needle is located inside the working volume of the chamber. The design of the calorimeter is substantiated theoretically. It provides a new mode of a reagent input in the measuring volume of the calorimetric chambers. It expands the spectrum of tasks that can be solved using this instrument. In the capillary calorimeter the calorimetric chambers unit is simple and small in size. These advantages of capillary chambers provide an opportunity to unite 20 capillary calorimetric chambers in one calorimetric block. It allows designing a multi-channel titration calorimeter. There are obvious advantages of such a calorimeter over other instruments in screening researches and in researches of objects maintaining stability only for a short time.     

Eine Methode zur Bestimmung der spezifischen Radioaktivität der „freien Aminosäuren“ in Gewebeextrakten von Säugetieren

Some experiences are given with a measuring device for the determination of the specific radioactivity of ¹⁴C-labelled brain amino-acids. The apparatus consists of an automatic amino-acid analyzer combined with a flow cell filled with anthracene. The reproducibility of the method is ±5% to ±1% m.e. in the range of 1×10^?3 μCi to 5×10^?2 μCi. A quantitative determination of 3×10^?4 μCi/ml eluant is still possible.     

Nickel oxide Nanoparticles/Carbon Nanotubes Nanocomposite for Non-enzymatic Determination of Hydrogen Peroxide

In this work, nickel oxide nanoparticles-modified multi-walled carbon nanotubes (CNTs) were prepared and used for H2O2 sensing application. Firstly, ex situ NiO nanoparticles (NPs) were prepared and further used to decorate polyethylenimine (PEI)-modified carboxylated CNTs. The obtained nanocomposite and its precursors were identified by using X-ray diffraction, thermal analysis, Raman spectroscopy and SEM and TEM images, N2 adsorption-desorption isotherms, and electrochemical techniques. The sensing properties of the NiO-modified nanocomposite toward H2O2 were studied by electrochemical techniques using glassy carbon electrodes (GCEs) as support material. After optimizing the sensor construction, the sensor sensitivity was about of 0.83±0.01 A M⁻¹ cm⁻² with a LOD of about 1.0 μM. In addition, it showed excellent anti-interference properties, reproducibility, and stability (over 4 months). Finally, such sensors were coupled to a flow injection device and the H2O2 concentration of some commercial antiseptic solutions were successfully obtained (with recovery ratios between 96.3–102.4 %).     

Improved conditions for measurement of the specific heat capacities of pure triglycerides by differential scanning calorimetry

Reproducible specific heat capacities (C _p) of triglycerides can be obtained by using heat-flux DSC under improved operating conditions. The improved operating parameters, such as the scanning rate, the sample mass and the atmosphere within the DSC chamber, were established via statistical analysis of the experimental data with trilaurin as a sample. The specific heat capacity results on trilaurin were compared with the values calculated by using estimation methods. The precision of the specific heat capacity measured for trilaurin under these conditions was within ±1%.     

LC–MS/MS method for simultaneous determination of ramelteon and its metabolite M‐II in human plasma: Application to a clinical pharmacokinetic study in healthy Chinese volunteers

A sensitive liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) method was developed and validated for the simultaneous determination of ramelteon and its active metabolite M‐II in human plasma. After extraction from 200 μL of plasma by protein precipitation, the analytes and internal standard (IS) diazepam were separated on a Hedera ODS‐2 (5 μm, 150 × 2.1 mm) column with a mobile phase consisted of methanol–0.1% formic acid in 10 mm ammonium acetate solution (85:15, v/v) delivered at a flow rate of 0.5 mL/min. Mass spectrometric detection was operated in positive multiple reaction monitoring mode. The calibration curves were linear over the concentration range of 0.0500–30.0 ng/mL for ramelteon and 1.00–250 ng/mL for M‐II, respectively. This method was successfully applied to a clinical pharmacokinetic study in healthy Chinese volunteers after a single oral administration of ramelteon. The maximum plasma concentration (C_max), the time to the C_max and the elimination half‐life for ramelteon were 4.50 ± 4.64ng/mL, 0.8 ± 0.4h and 1.0 ± 0.9 h, respectively, and for M‐II were 136 ± 36 ng/mL, 1.1 ± 0.5 h, 2.1 ± 0.4 h, respectively.