Temperature-dependent Phase Change Research Articles

Thermoresponsive poly (N-vinylcaprolactam)-g-galactosylated chitosan hydrogel: synthesis, characterization, and controlled release properties

A dual (thermo- and pH-) responsive hybrid copolymer, poly(N-vinylcaprolactam) grafted galactosylated chitosan (PNVCL-g-GC) was synthesized by EDC/NHS crosslinking. PNVCL-g-GC exhibited a temperature-dependent phase change (LCST) at 32 °C in aqueous solutions. PNVCL-g-GC hydrogel scaffold was fabricated by freeze-drying, and evaluated as a delivery vehicle dependent on environmental pH and temperature. PNVCL-g-GC was characterized using ATR-FTIR, 1H-NMR, DSC, TGA, rheometry, and SEM. The swelling degree increased by the decrease both in temperature and pH. A faster BSA release was observed at 40 °C and at pH 7.2 from the cytocompatible and hemocompatible copolymer.

Structural and spectroscopic characterization of irreversible phase changes in rapidly heated precursors of europium-doped titania nanoparticles

We observe temperature-dependent phase changes in a precursor of europium-doped titania (p-Eu:TiO2) that is prepared via precipitation and is laser-heated to temperatures between 473K and 1246K within sub-second heating durations. The phase changes are characterized using X-ray diffraction and site-selective photoluminescence spectroscopy. We find that upon heating, the initially amorphous p-Eu:TiO2 first transforms into the anatase phase and then into a mixed anatase/rutile phase. These phase transformations change the local environment of the dopant Eu3+ ions resulting in modifications to the Eu3+ ions spectroscopic properties, with the modifications occurring for calcination temperatures above approximately 573K following sub-second durations. These results demonstrate the temperature sensing ability of p-Eu:TiO2 nanoparticles for use in sub-second heating events. Moreover, at 573K this temperature is lower than other host materials that we have evaluated (i.e., La2O3, ZrO2 and Y2O3).

Functional Versatility of a Series of Zr Metal-Organic Frameworks Probed by Solid-State Photoluminescence Spectroscopy.

Many of the desirable properties of metal-organic frameworks (MOFs) can be tuned by chemical functionalization of the organic ligands that connect their metal clusters into multidimensional network solids. When these linker molecules are intrinsically fluorescent, they can pass on this property to the resultant MOF, potentially generating solid-state sensors, as analytes can be bound within their porous interiors. Herein, we report the synthesis of a series of 14 interpenetrated Zr and Hf MOFs linked by functionalized 4,4'-[1,4-phenylene-bis(ethyne-2,1-diyl)]-dibenzoate (peb2-) ligands, and we analyze the effect of functional group incorporation on their structures and properties. Addition of methyl, fluoro, naphthyl, and benzothiadiazolyl units does not affect the underlying topology, but induces subtle structural changes, such as ligand rotation, and mediates host-guest interactions. Further, we demonstrate that solid-state photoluminescence spectroscopy can be used to probe these effects. For instance, introduction of naphthyl and benzothiadiazolyl units yields MOFs that can act as stable fluorescent water sensors, a dimethyl modified MOF exhibits a temperature dependent phase change controlled by steric clashes between interpenetrated nets, and a tetrafluorinated analogue is found to be superhydrophobic despite only partial fluorination of its organic backbone. These subtle changes in ligand structure coupled with the consistent framework topology give rise to a series of MOFs with a remarkable range of physical properties that are not observed with the ligands alone.

Two-Dimensional SiO2/VO2 Photonic Crystals with Statically Visible and Dynamically Infrared Modulated for Smart Window Deployment.

Two-dimensional (2D) photonic structures, widely used for generating photonic band gaps (PBG) in a variety of materials, are for the first time integrated with the temperature-dependent phase change of vanadium dioxide (VO2). VO2 possesses thermochromic properties, whose potential remains unrealized due to an undesirable yellow-brown color. Here, a SiO2/VO2 core/shell 2D photonic crystal is demonstrated to exhibit static visible light tunability and dynamic near-infrared (NIR) modulation. Three-dimensional (3D) finite difference time domain (FDTD) simulations predict that the transmittance can be tuned across the visible spectrum, while maintaining good solar regulation efficiency (ΔTsol = 11.0%) and high solar transmittance (Tlum = 49.6%). Experiments show that the color changes of VO2 films are accompanied by NIR modulation. This work presents a novel way to manipulate VO2 photonic structures to modulate light transmission as a function of wavelength at different temperatures.

Optical temperature sensor with enhanced sensitivity by employing hybrid waveguides in a silicon Mach-Zehnder interferometer.

We report on a novel design of an on-chip optical temperature sensor based on a Mach-Zehnder interferometer configuration where the two arms consist of hybrid waveguides providing opposite temperature-dependent phase changes to enhance the temperature sensitivity of the sensor. The sensitivity of the fabricated sensor with silicon/polymer hybrid waveguides is measured to be 172 pm/°C, which is two times larger than a conventional all-silicon optical temperature sensor (~80 pm/°C). Moreover, a design with silicon/titanium dioxide hybrid waveguides is by calculation expected to have a sensitivity as high as 775 pm/°C. The proposed design is found to be design-flexible and robust to fabrication errors.

Location, Partitioning Behavior, and Interaction of Capsaicin with Lipid Bilayer Membrane: Study Using Its Intrinsic Fluorescence.

Capsaicin is an ingredient of a wide variety of red peppers, and it has various pharmacological and biological applications. The present study explores the interaction of capsaicin with dimyristoylphosphatidylcholine (DMPC) lipid bilayer membrane by monitoring various photophysical parameters using its intrinsic fluorescence. In order to have a clearer understanding of the photophysical responses of capsaicin, studies involving (i) its solvation behavior in different solvents, (ii) the partition coefficient of capsaicin in different thermotropic phase states of lipid bilayer membrane, and (iii) its location inside lipid bilayer membrane have been carried out. Capsaicin has a reasonably high partition coefficient for DMPC liposome membrane, in both solid gel (2.8 ± 0.1 × 10(5)) and liquid crystalline (2.6 ± 0.1 × 10(5)) phases. Fluorescence quenching study using cetylpyridinium chloride (CPC) as quencher suggests that the phenolic group of capsaicin molecule is generally present near the headgroup region and hydrophobic tail present inside hydrophobic core region of the lipid bilayer membrane. The intrinsic fluorescence intensity and lifetime of capsaicin sensitively respond to the temperature dependent phase changes of liposome membrane. Above 15 mol %, capsaicin in the aqueous liposome suspension medium lowers the thermotropic phase transition temperature by about 3 °C, and above 30 mol %, the integrity of the membrane is significantly lost.

Numerical studies of the effects of phase transitions on Venusian mantle convection

This paper presents a study on the effects of phase transitions on the mantle convection of Venus in a three-dimensional (3D) spherical shell domain. Our model includes strong depth- and temperature-dependent viscosity and exothermic phase change from olivine to spinel as well as endothermic phase change from spinel to perovskite. From extensive numerical simulations of the effects of Rayleigh number (Ra), and the Clapeyron slopes and depths of phase changes, we found the following: (1) The endothermic phase change prevents mass flow through the interface. Increasing the absolute value of the Clapeyron slopes decreases radial mass flux and normalized radial mass flux at the endothermic phase boundary, and decreases the number of mantle plumes. In other words, mass flow through the phase boundary decreases. The inhibition influence of phase changes increases, as do convective wavelengths. (2) Increasing Ra also increases the convective wavelength and decreases the number of mantle plumes, but it has less influence on the mass exchange. As Ra increases, the convective vigor increases along with the radial mass flux and the mass flow through the phase boundary; however, the normalized mass flux through the phase boundary varies little with Ra, which is different from the conclusion that increasing Ra will greatly increase the inhibition of mass flow through the phase boundary based on two-dimensional (2D) modeling. (3) Increasing the depth of endothermic phase change will slightly decrease the number of mantle plumes, but has little effect on the mass flow through the phase boundary. Consistent with previous studies, our results show that the phase change from spinel to perovskite could inhibit the mass flow through the phase boundary, but they also show that the buildup of hot materials under the endothermic phase boundary in the 3D model could not be so large as to cause strong episodic overturns of mantle materials, which is quite different from previous 2D studies. Our results suggest that it is difficult for phase changes to cause significant magmatism on Venus; in other words, phase changes may not be the primary cause of catastrophic resurfacing on Venus.

Influence of temperature on phase stability and thermal conductivity of single- and double-ceramic-layer EB–PVD TBC top coats consisting of 7YSZ, Gd2Zr2O7 and La2Zr2O7

Yttria Stabilized Zirconia (YSZ) is usually used as ceramic top coat for gas turbine blades and vanes. Investigations have shown the accelerated phase transformation and the intensified sinter effects of the YSZ top coat at temperatures between 1200°C and 1300°C, leading to changes of microstructure. Such modifications of the microstructure lead to higher thermal stresses and consequently reduce the lifetime. Furthermore, thermal conductivity λ of the top coat increases. For this reason lanthanum zirconate (La2Zr2O7) and gadolinium zirconate (Gd2Zr2O7) as top coat get into focus because of their high phase stability up to their melting points and the lower thermal conductivity compared to YSZ.Within this work single- (SCL) and double-ceramic-layer (DCL) top coats consisting of 7wt.% yttria stabilized zirconia (7YSZ), La2Zr2O7 or Gd2Zr2O7 are deposited by means of Electron Beam–Physical Vapor Deposition (EB–PVD). Aim of this work is on the one hand the investigation of temperature-dependent phase behavior and change of thermal conductivity of SCL and DCL top coats. On the other hand the influence of different top coat materials and architectures on the growth of thermally grown oxide (TGO) is of key interest. In a first step morphology and coating thickness were determined using scanning electron microscopy (SEM). The SCL and DCL systems show a columnar microstructure with a coating thickness of about 150μm. In a second step thermal conductivity of SCL and DCL systems was measured between 400°C and 1300°C by means of laser flash technique. The third step contained X-ray diffraction measurements of SCL and DCL systems after atmospherical isothermal oxidation at 1300°C. Finally, the TGO at the interface was analyzed. The TGO composition was determined by means of energy dispersive X-ray spectroscopy (EDX). The TGO phase was identified by using X-ray diffraction. Thus, by a correlation between morphology, architecture, coating material and TGO behavior information about oxygen diffusion processes have been obtained.

Prediction of hole characteristics and hole productivity during pulsed Nd:YAG laser beam percussion drilling

A thermal finite element model is proposed to simulate and predict hole taper ( Ta), heat-affected zone and material removal rate during laser beam percussion drilling in two difficult-to-laser-drill materials having wide difference in their thermophysical and optical properties. The developed model incorporates temperature-dependent thermal properties, optical properties and phase change phenomena of the sheet materials to predict the hole profile through the isotherm generated along the depth of the hole due to repeated laser pulses. Hole characteristics and hole productivity parameters are compared for both the sheet materials. The predicted values of hole taper with respect to pulse width have been compared with the experimentally obtained values. It is observed that hole characteristics are mainly affected by pulse width in the Aluminium alloy sheet and pulse frequency in the Inconel sheet, whereas peak power has prominent effect on material removal rate for both the sheet materials.

Modeling and optimization of laser beam percussion drilling of nickel-based superalloy sheet using Nd: YAG laser

The creation of small diameter holes in thin sheets (<3mm) of superalloys using a laser beam is a challenging task. Knowledge of the effect of laser related process variables on hole related responses with respect to variation of sheet thickness is essential to obtain a hole of requisite quality. Therefore, in this paper a coupled methodology comprising of Finite Element Method (FEM) and Artificial Neural Network (ANN) has been used to develop a prediction model for the Laser Beam Percussion Drilling (LBPD) process. First, a 2D axisymmetric FEM-based thermal model for LBPD has been developed incorporating temperature-dependent thermal properties, optical properties and phase change phenomena of the sheet material. The developed FEM-based thermal model is validated with self-conducted experimental results in terms of hole taper which is further used to generate adequate input and output data for training and testing of the ANN model. Gray Relational Analysis (GRA) coupled with Principal Component Analysis (PCA) has been effectively used for the multi-objective optimization of the LBPD process utilizing the data predicted by the trained ANN model. The developed ANN model has been used to predict the performance characteristics of the LBPD process. The results predicted by the ANN model show that with the increase in pulse width and peak power the hole taper, material removal rate (MRR) and heat-affected zone (HAZ) increases. The acquired combination of optimal process variables produce a hole with good integral quality, i.e., a reduction of hole taper by 32.1%, increase of material removal rate by 28.9% and reduction of extent of HAZ by 4.5%.

Characteristics of amorphous complex formed between indomethacin and lidocaine hydrochloride

Indomethacin (IM) easily forms an amorphous complex with lidocaine (LC) by heat treatment. To know the mechanism involved in the formation of this complex, we studied temperature-dependent phase changes in mixtures of IM and lidocaine hydrochloride (LH), in which the cationic form of LC forms a salt with Cl−, in various molar ratios by using DSC and NMR. Although heating of the mixture of IM and LC (IM+LC), formed a eutectic mixture, that of IM and LH (IM+LH) did not, and IM in the IM+LH mixture was dissolved into fused LH. Cooling of the fused IM+LH showed the glass transition in all of the samples containing various amounts of IM, suggesting that fused IM+LH took a homogenous amorphous state (IM/LH) below its glass transition temperature, in contrast to the fused IM+LC, which formed the rubber state and/or glass state depending on the molar content of IM. The results of the NMR study showed that IM in IM/LH caused the electronic structure of LH to change in such a way as to become similar to that of LC, but this effect was limited. Hence, mode of interaction of LH with IM is different from that of LC with IM.

Modeling and optimization of laser beam percussion drilling of thin aluminum sheet

Modeling and optimization of machining processes using coupled methodology has been an area of interest for manufacturing engineers in recent times. The present paper deals with the development of a prediction model for Laser Beam Percussion Drilling (LBPD) using the coupled methodology of Finite Element Method (FEM) and Artificial Neural Network (ANN). First, 2D axisymmetric FEM based thermal models for LBPD have been developed, incorporating the temperature-dependent thermal properties, optical properties, and phase change phenomena of aluminum. The model is validated after comparing the results obtained using the FEM model with self-conducted experimental results in terms of hole taper. Secondly, sufficient input and output data generated using the FEM model is used for the training and testing of the ANN model. Further, Grey Relational Analysis (GRA) coupled with Principal Component Analysis (PCA) has been effectively used for the multi-objective optimization of the LBPD process using data predicted by the trained ANN model. The developed ANN model predicts that hole taper and material removal rates are highly affected by pulse width, whereas the pulse frequency plays the most significant role in determining the extent of HAZ. The optimal process parameter setting shows a reduction of hole taper by 67.5%, increase of material removal rate by 605%, and reduction of extent of HAZ by 3.24%.

Features of heat-induced amorphous complex between indomethacin and lidocaine

We studied temperature-dependent phase changes in the mixture of indomethacin (IM) and lidocaine (LC) in various molar ratios by differential scanning calorimetry (DSC). DSC studies were carried out between −40°C and 180°C heating/cooling/heating cycle at a rate of 10°C/min under a nitrogen gas flow. Although LC in the liquid state was crystallized, fused IM showed a glass transition signal upon cooling. Hence, cooling of fused IM caused it to assume the amorphous state below its glass transition temperature. Heating of the mixture of IM and LC resulted in formation of a eutectic mixture between them, and cooling of the fused mixture caused formation of the amorphous state at any molar ratio examined. It is noteworthy that the amorphous solid of the fused complex of IM and LC was in the rubber state and glass state in the mixtures containing IM between 20% and 40%, whereas there was only the glass state in the samples containing 50% IM and higher. In addition, crystallization of LC took place by cooling the fused sample containing 10% IM.

An experimentally based thermo-kinetic phase transformation model for multi-pass laser heat treatment by using high power direct diode laser

Laser-based phase transformation hardening (LPTH), based on rapid heating and cooling cycles produces hard and wear-resistant layers only at the selective region of the components. However, the bulk mass of the material's core property is retained. The advantages of high power direct diode laser in comparison with other high power lasers (CO2 and Nd:YAG) have put this type of laser as a main heat source for localized heat treatment. However, a tempered zone is formed in overlapping regions of a large heat-treated area during multi-pass laser heat treatment (MPLHT) that affects the uniformity of heat-treated depth of material. This study is focused on the development of a uniform hardness distribution model to minimize the tem- pering effect during the MPLHT process. A tool steel AISI S7 is heat treated by using different levels of laser power (1,400-1,800 W) and scanning speeds (15-25 mm/s). An experimentally based finite element (FE) thermal model is developed to predict the cross-sectional as well as surface temperature history of the MPLHT process. The temperature-dependent material properties and phase change kinetics are taken into account in the model. The laser beam is considered as a moving rectangular-shaped heat source (12 mm×1 mm) with a uniform distribution (top-hat) of laser power. The temperature history acquired from the FE thermal model is coupled with thermo-kinetic (TK) equations to determine the corresponding phase trans- formations and hardness. The tempering effect of MPLHT is studied for different sizes of overlap (1 mm- 3m m) and lengths of scan (10 mm-35 mm). The TK model results are verified with experimental ones to optimize the process- ing parameters. The optimized processing parameters, in- cluding laser power, scanning speed, size of overlap, and the length of scan are used to achieve a uniform hardness distribution and an even depth of heat treatment in the MPLHT area.

An experimentally based thermo-kinetic hardening model for high power direct diode laser cladding

High power direct diode laser (HPDDL) based cladding is found to be an economical process for repairing or building valued components and tools that are used in the automotive, aerospace, nuclear and defense industries. In this study, a 2-kW HPDDL of 808 nm in wavelength, rectangular-shaped laser spot of 12 mm × 1 mm with uniform distribution (top-hat) of laser power is used to carry out the experiments. An off-axis powder injection system is used to deposit tool steel H13 on the AISI 4140 steel substrate. A number of experiments are carried out by changing the laser power and scanning speeds while keeping a constant powder feed rate to produce different sizes of clad. An experimentally based finite element (FE) thermal model is developed to predict the cross-sectional temperature history of the cladding process. The temperature-dependent material properties and phase change kinetics are taken into account in this model. As-used experimental boundary conditions are adopted in this model. The acquired temperature history from the FE model is used to predict the temperature gradient, rates of heating and cooling cycles, and the solidification of the clad to the substrate. The FE thermal model results are coupled with thermo-kinetic (TK) equations to predict the hardness of the clad to the substrate. Metallurgical characterization and hardness measurements are performed to quantify the effect of processing parameters on the variation of clad geometry, microstructure, and the change of hardness of the clad to the substrate. The results show that a good metallurgically bonded clad of hardness uniformity is achieved.

In-situ investigation of the kesterite formation from binary and ternary sulphides

The formation of kesterite (Cu 2ZnSnS 4) from different stoichiometric mixtures of binary and ternary sulphides was investigated by in-situ high temperature synchrotron X-ray diffraction. The data were collected during the heating, the annealing and the cooling cycle. The Rietveld analysis of the diffractograms led us to determine temperature dependent phase changes qualitatively and quantitatively as well as the lattice constants of the different phases. Showing exemplarily with the mixture 2CuS + SnS + ZnS the formation of Cu 2ZnSnS 4 starts just below 300 °C. The volume size of the fcc anion substructure of the newly formed kesterite at 300 °C corresponds to the one of the ZnS phase. The lattice parameter of Cu 2ZnSnS 4 increases nonlinearly with increasing temperature showing possibly the trend of different formation stages. Comparing the lattice constants a and c of the several synthesized kesterites at 700 °C among each other and with a pre-synthesized kesterite, remarkable variations were obtained, whereas the ratio of the lattice parameter ( c/2 a) is comparable. These features led to the assumption that the cation distribution may vary in dependence on temperature and on the phase mixture used as starting material.

Temperature and pressure effects on structural and conformational properties of POPC/SM/cholesterol model raft mixtures—a FT-IR, SAXS, DSC, PPC and Laurdan fluorescence spectroscopy study

We report on the effects of temperature and pressure on the structure, conformation and phase behavior of aqueous dispersions of the model lipid “raft” mixture palmitoyloleoylphosphatidylcholine (POPC)/bovine brain sphingomyelin (SM)/cholesterol (Chol) (1:1:1). We investigated interchain interactions, hydrogen bonding, conformational and structural properties as well as phase transformations of this system using Fourier transform-infrared (FT-IR) spectroscopy, small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC) coupled with pressure perturbation calorimetry (PPC), and Laurdan fluorescence spectroscopy. The IR spectral parameters in combination with the scattering patterns from the SAXS measurements were used to detect structural and conformational transformations upon changes of pressure up to 7–9 kbar and temperature in the range from 1 to about 80 °C. The generalized polarization function ( GP) values, obtained from the Laurdan fluorescence spectroscopy studies also reveal temperature and pressure dependent phase changes. DSC and PPC were used to detect thermodynamic properties accompanying the temperature-dependent phase changes. In combination with literature fluorescence spectroscopy and microscopy data, a tentative p, T stability diagram of the mixture has been established. The data reveal a broad liquid-order/solid-ordered (l o + s o) two-phase coexistence region below 8 ± 2 °C at ambient pressure. With increasing temperature, a l o + l d + s o three-phase region is formed, which extends up to ∼27 °C, where a liquid-ordered/liquid-disordered (l o + l d) immiscibility region is formed. Finally, above 48 ± 2 °C, the POPC/SM/Chol (1:1:1) mixture becomes completely fluid-like (liquid-disordered, l d). With increasing pressure, all phase transition lines shift to higher temperatures. Notably, the l o + l d (+s o) phase coexistence region, mimicking raft-like lateral phase separation in natural membranes, extends over a rather wide temperature range of about 40 °C, and a pressure range, which extends up to about 2 kbar for T = 37 °C. Interestingly, in this pressure range, ceasing of membrane protein function in natural membrane environments has been observed for a variety of systems.

Phase control of an exciton-polariton in a quantum well waveguide and its application to optical devices

Electric-field-induced phase change of an exciton-polariton transmitted along the GaAs quantum well waveguide was measured as a function of temperature. Large phase changes up to 120 K were obtained. These phase changes explain the highly-efficient operation of Mach-Zehnder-type modulators and directional-coupler-type switches up to 77 K. These results are not explainable simply in terms of polariton stability, which indicates that the temperature-dependent phase change under the electric field is affected by more complex factors related to the polariton effect.

Effect of laser cladding on fatigue strength of an alloy steel : Chen, J.Q., Takezono, S., Li, G.X. and Tanaka, T. J. Soc. Mater. Sci., Jpn. (1995) 44 (498), 343–347

High power direct diode laser (HPDDL) based cladding is found to be an economical process for repairing or building valued components and tools that are used in the automotive, aerospace, nuclear and defense industries. In this study, a 2-kW HPDDL of 808 nm in wavelength, rectangular-shaped laser spot of 12 mm × 1 mm with uniform distribution (top-hat) of laser power is used to carry out the experiments. An off-axis powder injection system is used to deposit tool steel H13 on the AISI 4140 steel substrate. A number of experiments are carried out by changing the laser power and scanning speeds while keeping a constant powder feed rate to produce different sizes of clad. An experimentally based finite element (FE) thermal model is developed to predict the cross-sectional temperature history of the cladding process. The temperature-dependent material properties and phase change kinetics are taken into account in this model. As-used experimental boundary conditions are adopted in this model. The acquired temperature history from the FE model is used to predict the temperature gradient, rates of heating and cooling cycles, and the solidification of the clad to the substrate. The FE thermal model results are coupled with thermo-kinetic (TK) equations to predict the hardness of the clad to the substrate. Metallurgical characterization and hardness measurements are performed to quantify the effect of processing parameters on the variation of clad geometry, microstructure, and the change of hardness of the clad to the substrate. The results show that a good metallurgically bonded clad of hardness uniformity is achieved.

Formgedächtnislegierungen als Federn einsetzen

Shape memory alloys are able to change the external shape as a result of a temperature dependent phase change. This effect can be used to generate motion in actuators. There are partly complex connections between compound, heat treatment and the resultant properties. Today many actuators running with shape memory springs are used in highly advanced cars, most of them to control and supervise motors und cooling units. Shape memory actuators could fulfill the task of control especially advantageous when they use the ambient heat as an independent part and at the same time take on the tasks of a sensor and actuator.