In situ investigation of precipitation in aluminium alloys via thermal diffusivity from laser flash analysis

Journal of Thermal Analysis and Calorimetry - In this work, a commercially available laser flash analysis (LFA) device is used for in situ precipitation monitoring in aluminium alloys by following...     

In situ investigation of laser ablation

The complex system of in situ diagnostic methods such as SEM, ballistic microbalance, electric probe and high speed photography is necessary for measurement of basic parameters of laser target interaction. Only the knowledge of these basic parameters allows the discussion of microscopical processes on the target surface by laser irradiation. The results are discussed for our synchronised double laser system and for aluminium target. The mass relation of atoms, ions and droplets emitted by the target was determined. This relation is the base of a complete energy balance of laser target interaction.     

In situ investigation of laser ablation

The complex system of in situ diagnostic methods such as SEM, ballistic microbalance, electric probe and high speed photography is necessary for measurement of basic parameters of laser target interaction. Only the knowledge of these basic parameters allows the discussion of microscopical processes on the target surface by laser irradiation. The results are discussed for our synchronised double laser system and for aluminium target. The mass relation of atoms, ions and droplets emitted by the target was determined. This relation is the base of a complete energy balance of laser target interaction.     

In situ solid-state NMR characterization of pharmaceutical materials: An example of drug-polymer thermal mixing

Pharmaceutical amorphous solid dispersions, a multicomponent system prepared by dispersing drug substances into polymeric matrix via thermal and mechanical processes, represent a major platform to deliver the poorly water-soluble drug. Microscopic properties of drug-polymer contacts play mechanistic roles in manipulating long-term physical stability as well as dissolution profiles. Although solid-state nuclear magnetic resonance has been utilized as an indispensable tool to probe structural details, previous studies are limited to ex situ characterizations. Our work provides likely the first documented example to investigate comelting of ketoconazole and polyacrylic acid, as a model system, in an in situ manner. Their physical mixture is melted and mixed in the solid-state nuclear magnetic resonance rotor under magic angle spinning at up to approximately 400 K. Critical structural events of molecular miscibility and interaction have been successfully identified. These results design and evaluate the instrumental and experimental protocols for real-time characterizations of the comelting of pharmaceutical materials.     

Heterogeneous bulk nucleation and differential thermal analysis

The effect of the addition of Ag₂O on the mechanism of non-isothermal devitrification of Li₂O · 2 SiO₂ glass has been studied by differential thermal analysis. In both bulk and powdered samples, the presence of heterogeneous nuclei lowers the crystallization temperatures but not the value of the crystal growth activation energy.The influence of the catalyst on the crystallization mechanism is not affected by a pre vious heat treatment at the temperature of the maximum nucleation rate.

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Zusammenfassung Die Wirkung des Einflusses von Ag₂O auf den nicht-isothermen Entglasungsmechanismus von Li₂O · 2 SiO₂-Glas wurde durch Differentialthermoanalyse untersucht.Die Gegenwart heterogener Kerne setzt die Kristallisierungstemperaturen herab, jedoch nicht die Werte der Aktivierungsenergien des Kristallwachstums in grob- als auch in feinpulverisierten Proben.Die Wirkung des Katalysators auf den Kristallisationsmechanismus wird durch eine vorhergehende Wärmebehandlung bei der Temperatur der maximalen Keimbildungsgeschwindigkeit nicht beeinflusst.

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Résumé On a étudié, par analyse thermique différentielle, l'effet de l'addition d'Ag₂O sur le mécanisme de dévitrification non-isotherme du verre Li₂O · 2 SiO₂. La présence de noyaux hétérogènes abaisse les températures de cristallisation, mais pas la valeur de l'énergie d'activation de la croissance des cristaux, que les échantillons soient massifs ou pulvérisés.L'influence du catalyseur sur le mécanisme de la cristallisation n'est pas altérée par un traitement thermique préalable à la température de la vitesse maximale de nucléation.

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Li₂O·2SiO₂ , , . .

     

In situ synthesis of hydroxyapatite coating by laser cladding

HA bioceramic coatings were synthesized on titanium substrate by laser cladding using cheap calcium carbonate and calcium hydrogen phosphate. The thermodynamic condition for synthesizing HA was calculated by software Matlab 5.0, the microstructure and phase analysis of laser clad HA bioceramic coatings were studied by electron probe microanalyser (EPMA), X-ray diffractometer (XRD) and transmission electron microscopy (TEM). The theoretical results show that the Gibbs free enthalpy for the synthesis of HA phase is satisfied, and the presence of HA phase in the clad coatings was then further verified by XRD and the selected area diffraction patterns. When the laser power is 600W and the scanning speed is 3.5mm/s, the compact HA bioceramic coatings were obtained, which have cellular dendritic structure and consist of the phases of HA, alpha-Ca(2)P(2)O(7), CaO and CaTiO(3).     

In situ hydrophobized, shape-anisotropic nanoparticles for composite materials

An inverse emulsion technique which allows the anisotropic growth of a broad variety of inorganic nanoparticles, together with an efficient hydrophobization, is described. This method is based upon the combined use of amphiphilic copolymers, which act as emulsifiers as well as compatibilizers, and structure-directing agents that control the crystallization of the inorganic nanoparticles. As a consequence, water-soluble, structure-directing agents can now be applied for the synthesis of hydrophobic, shape-anisotropic nanocrystals. More precisely, spherical, rod-like, and branched CdS as well as Au nanoparticles were prepared. Due to their excellent hydrophobization, these particles were homogeneously incorporated into a poly(2-ethylhexyl methacrylate) matrix. Their shape-dependent properties were transferred to nanocomposites as demonstrated for branched CdS nanocrystals. In comparison to more traditional materials composed of branched CdS nanoparticles, which are stabilized by low molecular weight amphiphiles, our composites show much less scattering. This is due to the homogenous distribution of the nanoparticles in the matrix.     

Certified reference materials for thermal analysis

Eight inorganic substances recommended by ICTA as temperature standard reference materials for DTA and DSC were studied: KNO₃, KClO₄, Ag₂SO₄, K₂CrO₄, quartz, K₂SO₄, BaCO₃ and SrCO₃. The content of pure component in each of these substances was determined by classical chemical analysis. The temperatures and the heats of polymorphic transformations of these substances were measured with a Perkin-Elmer DSC-2 differential scanning calorimeter, and DTA studies were performed on a MOM 1500 D Q-derivatograph. The plot heat of transformation by DSCvs. DTA peak area is advanced as a calibration line for the approximate estimation of quantitative DTA effects. The substances studied will be certified as temperature standard reference materials for use in DTA and DSC.

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Zusammenfassung Acht von der ICTA als Temperaturstandard-Referenzmaterialien für DTA und DSC empfohlene und im Lande verfügbare Substanzen wurden untersucht: KNO₃,KClO₄, Ag₂SO₄, K₂Cr₂O₄, Quarz, K₂SO₄, BaCO₃ und SrCO₃. Der Gehalt der Substanzen an diesen Verbindungen wurde klassisch chemisch-analytisch bestimmt. Temperaturen und Enthalpien der polymorphen Umwandlungen wurden mit dem Gerät DSC 2 (Perkin-Elmer) bestimmt, DTA-Untersuchungen erfolgten mittels Derivatograph Q 1500 D (MOM). Eine Darstellung (Umwandlungsenthalpie aus DSC-Messung) über der DTA-peak-Flä-che wird als Eichgerade für die näherungsweise quantitative Bewertung der DTA-Effekte vorgeschlagen. Die genannten Substanzen sollen als Temperaturstandards für DTA und DSC geprüft werden.

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Automated in situ trace element analysis of silicate materials by laser ablation inductively coupled plasma mass spectrometry

This paper describes the automated in situ trace element analysis of solid materials by laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS). A compact computer-controlled solid state Nd:YAG Merchantek EO UV laser ablation (LA) system has been coupled with the high sensitivity VG PQII S ICP-MS. A two-directional communication was interfaced in-house between the ICP-MS and the LA via serial RS-232 port. Each LA-ICP-MS analysis at a defined point includes a 60 s pre-ablation delay, a 60 s ablation, and a 90 s flush delay. The execution of each defined time setting by LA was corresponding to the ICP-MS data acquisition allowing samples to be run in automated cycle sequences like solution auto-sampler ICP-MS analysis. Each analytical cycle consists of four standards, one control reference material, and 15 samples, and requires about 70 min. Data produced by Time Resolved Analysis (TRA) from ICP-MS were later reduced off-line by in-house written software. Twenty-two trace elements from four reference materials (NIST SRM 613, and fused glass chips of BCR-2, SY-4, and G-2) were determined by the automated LA-ICP-MS method. NIST SRM 610 or NIST SRM 613 was used as an external calibration standard, and Ca as an internal standard to correct for drift, differences in transport efficiency and sampling yield. Except for Zr and Hf in G-2, relative standard deviations for all other elements are less than 10%. Results compare well with the data reported from literature with average limits of detection from 1 ng x g(-1) to 455 ng x g(-1) and less than 100 ng x g(-1) for most trace elements.     

In situ thermo-TOF-SIMS study of thermal decomposition of zinc acetate dihydrate

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used for an in situ thermal decomposition study of Zn(CH₃COO)₂·2H₂O forming ZnO nanoparticles. TOF-SIMS spectra were recorded at regular temperature intervals of 25 °C in positive and negative detection modes in a dynamic thermal process. Controlled heating (5 °C min⁻¹) of Zn(CH₃COO)₂·2H₂O was also carried out using thermogravimetric analysis (TGA) in an oxygen atmosphere (20 ml min⁻¹). Nearly spherical ZnO nanoparticles with no agglomeration and a narrow size distribution (diameter ∼50 nm) were observed, which were characterized using scanning electron microscopy, transmission electron microscopy and x-ray diffraction. In situ thermo-TOF-SIMS was used to monitor the ⁶⁴Zn⁺ and ⁶⁶Zn⁺ ion abundances as a function of temperature, which showed a similar profile to that observed for weight loss in TGA during decomposition. Based on the experimental results, a possible decomposition mechanism for the formation of ZnO is proposed. Copyright © 2004 John Wiley & Sons, Ltd.     

In situ measurement of the thermal expansion behavior of benzocyclobutene films

In situ measurement techniques suitable for determination of the coefficient of thermal expansion (CTE) in thin, spin‐cast polymer films in both the in‐plane and through‐plane directions are presented. An examination of the thermal expansion behavior of cyclotene thin films has been performed. In particular, the effect of film thickness on the in‐plane and through‐plane CTE and in‐plane Young's modulus of spin‐coated cyclotene films was examined. It is shown that the mechanical response of in situ cyclotene films can be adequately described by isotropic film properties. It was also demonstrated that there is no thickness dependence on the free‐standing mechanical properties or on the resulting through‐plane thermal strain in an in situ film. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 311–321, 1999     

Temperature standard reference materials for thermal analysis

The feasibility of the use of potassium nitrate and potassium perchlorate as temperature standards in Differential scanning calorimetry has been studied. The solid-state phase transition temperatures of KNO₃ and KClO₄ were determined by means of DSC. The metrological properties of these salts as calibration materials were examined. The reliability of KNO₃ and KClO₄ calibrations was investigated by twofold determination of the bismuth melting temperature after the apparatus had been calibrated with indium and lead, and with KNO₃ and KCl_O4. Conclusions were drawn concerning the suitability of these salts for use as DSC temperature calibrants.

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Zusammenfassung Es wurde die Möglichkeit der Verwendung von Kaliumnitrat und Kaliumperchlorat als Temperaturstandard für DSC untersucht. Die Bestimmung der Temperaturen für Feststoff-Phasenumwandlungen von Kaliumnitrat und Kaliumperchlorat wurde mittels DSC erreicht. Weiterhin wurden die meßtechnischen Eigenschaften der untersuchten Salze (KNO₃ und KClO₄) als Bezugssubstanzen geprüft. Die Zuverlässigkeit der Kalibrierung mittels KNO₃ und KClO₄ wurde durch eine zweifache Bestimmung der Schmelztemperatur von Wismut überprüft: einmal nach der Kalibrierung des Gerätes mit Indium und Blei und andererseits nach der Kalibrierung mit Kaliumnitrat und Kaliumperchlorat. Angesichts der Resultate kann man feststellen, daß die untersuchten Salze zur Temperaturkalibrierung in der DSC geeignet sind.

     

Literature survey on thermal analysis reference materials

Results of a literature search on thermal analysis reference materials are listed

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Zusammenfassung Vorliegend werden die Ergebnisse einer Literaturrecherche über Referenz-substanzen für die thermische Analyse dargelegt.

     

Effect of nanoparticles on the thermal stability of PMMA nanocomposites prepared by in situ bulk polymerization

Al₂O₃ and ZnO filled poly(methyl methacrylate) nanocomposites were synthesized by free radical (bulk) polymerization. Efficient dispersion was achieved by predispersing the nanoparticles in propylene glycol methyl ether acetate (PGMEA) followed by ultrasonication of nanoparticles into the PMMA syrup. Thermal analysis confirms chemisorption between PGMEA and metal oxide particles. The addition of nanoparticle affects degradation mechanism and consequently improves thermal stability of PMMA. The reduction of polymer chain mobility and the tendency of nanoparticles to eliminate free radicals are the principal effects responsible for these enhancements.     

Characterization of high-technology materials by emanation thermal analysis

The principles of the emanation thermal analysis, based on the measurement of inert gas release from solids, are given. Results of the computer modelling of inert gas release curves during heating of porous and dispersed samples are demonstrated.Examples of the characterization of high-tech ceramic materials and raw materials for their preparation by means of emanation thermal analysis are given, such as the evaluation of reactivity and sinterability of ceramics powders, quality testing of intermediate and final products of advanced technology materials (such as thoria, urania, ferrites, superconducting oxide ceramics, etc.).

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Zusammenfassung Es werden Grundlagen für die Emanationsthermoanalyse /ETA/ auf der Basis der Messung der Inertgasfreisetzung bei Feststoffen gegeben. Ergebnisse von computermodellierten Inertgasfreisetzungskurven bei Erhitzen von porösen und dispersen Proben werden angeführt.Weiterhin werden Beispiele für die mittels ETA durchgeführte Charakterisierung von Spitzentechnologiekeramikmaterialien und den Rohstoffen zu deren Herstellung gegeben: Auswertung von Reaktivität und Sinterbarkeit von Keramikpulver, Qualitätskontrolle der Zwischen- und Endprodukte aus modernen Rohstoffen /wie z. B. Thorerde, Uranerde, Ferrit, supraleitende Oxidkeramiken usw./.

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In situ liquid SIMS analysis of uranium oxide

Trace analysis of nuclear materials in solid particles collected in the environment or particles in liquid slurry generated in nuclear material manufacturing processes can pinpoint elemental, organic, and isotopic signatures of nuclear fuel cycle activities and processes. Such information can support nuclear safeguards programs by increasing our ability to detect undeclared nuclear materials, routine activities for safeguarding at declared facilities, and illicit activities. However, trace radioactive material analysis in liquids and slurries is challenging using bulk approaches. For example, one drawback of sensitive analysis such as inductively coupled plasma mass spectrometry (ICP-MS) is that sample is consumed or destroyed as a result of the technical approach. We developed a vacuum compatible microfluidic interface to enable surface analysis of liquids and solid–liquid interactions using time-of-flight secondary ion mass spectrometry (ToF-SIMS). In this work, we illustrate the initial results from the analysis of liquid uranium oxide standard solutions using in situ liquid SIMS. Because the liquid SIMS analysis is almost nondestructive, the same sample can then be analyzed by other analytical techniques or saved for future reference. Consequently, multimodal analysis is possible. Our results demonstrate that in situ liquid SIMS can be used as a new approach to analyze radioactive materials in liquid and slurry forms of relevance to diverse applications.     

攀矿铁精矿矿浆品位的原位EDXRF分析试验

铁精矿矿浆品位原位EDXRF(能量色散X射线荧光)分析试验在攀钢选矿厂进行,矿浆中水与矿粉体积比在2/5~2/1之间,在(L×W×H=8×2×20cm)的沉淀条件下,经过9 min自然沉淀,静态测量(60 s);从测量结果看出:仪器分析周期约10 min,与化学分析结果的绝对误差小于0.3%,并说明铁精矿矿浆品位在线分析完全可行,这为开发新型在线铁精矿矿浆品位的EDXRF分析仪器提供了依据。     

In situ optical studies of thermal stability of iodine-doped polyazomethine thin films

Chemical vapour deposition (CVD) method, via polycondensation reaction, is used to obtain poly(1,4-phenylene-methylidynitrilo-1,4-phenylenenitrilomethylidyne) (PPI) thin films. The iodine (I₂) doping process of these films is observed in situ, by means of changes of the absorbance spectra. A distinct reduction of the energy gap, being a result of p-type doping, is connected with extracting electrons from π-conjugated system and formation of the polaron states inside the gap. On the basis of UV–Vis–NIR(T) experiments, the heat treatment effect on the absorption coefficient spectra of iodine doped PPI thin films is reported, as a new method, to estimate thermal stability and to obtain the border temperature of doped polymer films. Moreover it is demonstrated that the analysis of absorption bands (shape, level and position) and absorption edge parameters, such as the Urbach energy (E_U) and the energy gap (E_G) can be used to evaluate the changes of polymer chain conformation and conjugation.     

Building materials thermal conductivity measurement and correlation with heat flow meter, laser flash analysis and TCi

The most important factor in the worldwide problem of global warming is the emission of carbon dioxide. The 23% of carbon dioxide emissions generated by building construction must be reduced. Reduction in thermal conductivity, especially via improved insulation, is the most basic factor for decreasing energy consumption. Therefore, accurate and continuous thermal conductivity measurements are important in saving energy. This study presents methods for investigating thermal conductivity measurement and compares three methods: the heat flow meter, laser flash analysis, and thermal conductivity analyzer.