AC/DC Thermal Nano-Analyzer Compatible with Bulk Liquid Measurements.

Nanocalorimetry, or thermal nano-analysis, is a powerful tool for fast thermal processing and thermodynamic analysis of materials at the nanoscale. Despite multiple reports of successful applications in the material sciences to study phase transitions in metals and polymers, thermodynamic analysis of biological systems in their natural microenvironment has not been achieved yet. Simply scaling down traditional calorimetric techniques, although beneficial for material sciences, is not always appropriate for biological objects, which cannot be removed out of their native biological environment or be miniaturized to suit instrument limitations. Thermal analysis at micro- or nano-scale immersed in bulk liquid media has not yet been possible. Here, we report an AC/DC modulated thermal nano-analyzer capable of detecting nanogram quantities of material in bulk liquids. The detection principle used in our custom-build instrument utilizes localized heat waves, which under certain conditions confine the measurement area to the surface layer of the sample in the close vicinity of the sensing element. To illustrate the sensitivity and quantitative capabilities of the instrument we used model materials with detectable phase transitions. Here, we report ca. 106 improvement in the thermal analysis sensitivity over a traditional DSC instrument. Interestingly, fundamental thermal properties of the material can be determined independently from heat flow in DC (direct current) mode, by using the AC (alternating current) component of the modulated heat in AC/DC mode. The thermal high-frequency AC modulation mode might be especially useful for investigating thermal transitions on the surface of material, because of the ability to control the depth of penetration of AC-modulated heat and hence the depth of thermal sensing. The high-frequency AC mode might potentially expand the range of applications to the surface analysis of bulk materials or liquid-solid interfaces.

Influence of Post Processing on Thermal Conductivity of ITO Thin Films.

This work presents the influence of post processing on morphology, thermal and electrical properties of indium tin oxide (ITO) thin films annealed at 400 °C in different atmospheres. The commercially available 170 nm thick ITO layers deposited on glass were used as a starting material. The X-ray diffraction measurements revealed polycrystalline structure with dominant signal from (222) plane for all samples. The annealing reduces the intensity of this peak and causes increase of (221) and (440) peaks. Atomic force microscopy images showed that the surface morphology is typical for polycrystalline layers with roughness not exceeding few nm. Annealing in the oxygen and the nitrogen-hydrogen mixture (NHM) changes shapes of grains. The electrical conductivity decreases after annealing except the one of layer annealed in NHM. Thermal conductivities of annealed ITO thin films were in range from 6.4 to 10.6 W·m-1·K-1, and they were higher than the one for starting material-5.1 W·m-1·K-1. Present work showed that annealing can be used to modify properties of ITO layers to make them useful for specific applications e.g., in ITO based solar cells.

Microscopic investigations of morphology and thermal properties of ZnO thin films grown by atomic layer deposition method.

This work presents the study of morphology and thermal properties of thin ZnO films fabricated by atomic layer deposition. The layers were deposited on n-Si(100) wafers at 200 °C. X-ray diffraction measurements showed the polycrystalline structure of the thin films with preferred (100) orientation. The thinner ZnO layers were fine grained, while the thicker films were formed with larger, elongated grains. Surface morphology parameters and the thermal conductivities were obtained from microscopic measurements. Thermal properties correlated with surface roughness of the ZnO thin films. Variations in thermal conductivity followed the changes in morphology of the layers. The mean surface roughness depended on the number of deposition cycles and varied from 1.1-2.6 nm. Thermal conductivity varied from 0.28 to 4.29 Wm-1K-1 and increased also with an increase of average crystallite size. The possible correlations between electrical conductivity and thermal conductivity were also analyzed. The phonon contribution to total thermal conductivity dominates over the electron thermal conductivity.

Influence of doping on thermal diffusivity of single crystals used in photonics: measurements based on thermal wave methods.

Three crystals used in solid-state lasers, namely, yttrium aluminum garnet (YAG), yttrium orthovanadate (YVO(4)), and gadolinium calcium oxoborate (GdCOB), were investigated to determine the influence of dopants on their thermal diffusivity. The thermal diffusivity was measured by thermal wave method with a signal detection based on mirage effect. The YAG crystals were doped with Yb or V, the YVO(4) with Nd or Ca and Tm, and the GdCOB crystals contained Nd or Yb. In all cases, the doping caused a decrease in thermal diffusivity. The analysis of complementary measurements of ultrasound velocity changes caused by dopants leads to the conclusion that impurities create phonon scattering centers. This additional scattering reduces the phonon mean free path and accordingly results in the decrease of the thermal diffusivity of the crystal. The influence of doping on lattice parameters was investigated, additionally.

Determination of thermal conductivity of thin layers used as transparent contacts and antireflection coatings with a photothermal method.

A photothermal experiment with mirage detection was used to determine the thermal conductivity of various thin films deposited on semiconductor substrates. The first type consisted of conducting oxide films: ZnO and CdO deposited on GaSb:Te, while the other contained high dielectric constant HfO(2) layers on Si. All films were fabricated using a magnetron sputtering technique. Experimental results showed that the value of the thermal conductivity of ZnO and CdO films is lower than the value obtained for HfO(2). Thermal conductivities of investigated thin films are about 2 orders of magnitude lower than those corresponding to bulk materials.

Photodeflection signal formation in photothermal measurements: comparison of the complex ray theory, the ray theory, the wave theory, and experimental results.

A comparison is made of three methods for modeling the interaction of a laser probe beam with the temperature field of a thermal wave. The three methods include: (1) a new method based on complex ray theory, which allows us to take into account the disturbance of the amplitude and phase of the electric field of the probe beam, (2) the ray deflection averaging theory of Aamodt and Murphy, and (3) the wave theory (WT) of Glazov and Muratikov. To carry out this comparison, it is necessary to reformulate the description of the photodeflection signal in either the WT or the ray deflection averaging theory. It is shown that the differences between calculated signals using the different theories are most pronounced when the radius of the probe beam is comparable with the length of the thermal wave in the region of their interaction. Predictions of the theories are compared with experimental results. A few parameters of the experimental setup are determined through multiparameter fitting of the theoretical curves to the experimental data. A least-squares procedure was chosen as a fitting method. The conclusion is that the calculation of the photodeflection signal in the framework of the complex ray theory is a more accurate approach than the ray deflection averaging theory or the wave one.

Measurement of the thermal diffusivity of dental filling materials using modified Angström's method.

OBJECTIVES: A new measuring technique for the determination of thermal diffusivity is proposed. Using this technique, the thermal properties of a few different dental filling materials were measured. METHODS: The proposed method for measurement of thermal diffusivity is based on the classical Angström's method. The method exploits the propagation of a plane thermal wave generated by a Peltier's device in a cylindrical sample along its axis. The thermal diffusivity of the sample is calculated from the phase difference between harmonic components of temperatures measured at sample surfaces, perpendicular to the direction of thermal wave propagation. The estimated accuracy of measurement is typically about 10% for samples with low thermal diffusivity. The proposed method was used for the determination of thermal diffusivities of Achatit Bichromatic, Charisma and Dentimet dental filling materials. RESULTS: The measured thermal diffusivities were: 0.295(0.020)x10(-6)m(2)s(-1) for Achatit Bichromatic, 0.321(0.015)x10(-6)m(2)s(-1) for Charisma and 1.70(0.12)x10(-6)m(2)s(-1) for Dentimet. The thermal conductivities of these materials were also estimated. The results were compared with values obtained from independent constant flux measurements with marble as a reference material. SIGNIFICANCE: There are no standard techniques for the determination of the thermal properties of dental filling materials. Moreover, it is difficult to find the thermal diffusivity and the thermal conductivity of many of them. The method proposed in this paper allows the simple and accurate measurement of thermal diffusivity. Thermal parameters of dental filling materials should be compatible with the parameters of human teeth. Lack of thermal compatibility can cause not only patient discomfort but also mechanical stresses leading to microcracks.

A new FTIR-ATR cell for drug diffusion studies.

The drug diffusion of most compounds, particularly hydrophilic molecules through the skin is limited by the permeation of the outermost cell layers of the epidermis, the stratum corneum(SC). For this reason it is of interest to characterize drug diffusion processes through this skin layer. A new FTIR-ATR cell was developed for non-invasive real time measurements of drug diffusion. The diffusion of water through an artificial polyethyleneglycol-polydimethylsiloxane membrane was studied. Additionally the diffusion of urea in human SC was analyzed. Based on a mathematical model the diffusion coefficients were derived. We could reveal that this cell associates the advantages of the Franz diffusion cell and the FTIR-ATR spectroscopy as a new powerful method for determining drug diffusion through biological membranes.