Application of indium tin oxide (ITO) thin film as a low emissivity film on Ni-based alloy at high temperature

Indium tin oxide (ITO) films as the low emissivity coatings of Ni-based alloy at high temperature were studies. ITO films were deposited on the polished surface of alloy K424 by direct current magnetron sputtering. These ITO-coated samples were heat-treated in air at 600–900 °C for 150 h to explore the effect of high temperature environment on the emissivity. The samples were analyzed by X-ray diffraction (XRD), SEM and EDS. The results show that the surface of sample is integrity after heat processing at 700 °C and below it. A small amount of fine crack is observed on the surface of sample heated at 800 °C and Ti oxide appears. There are lots of fine cracks on the sample annealed at 900 °C and a large number of various oxides are detected. The average infrared emissivities at 3–5 μm and 8–14 μm wavebands were tested by an infrared emissivity measurement instrument. The results show the emissivity of the sample after annealed at 600 and 700 °C is still kept at a low value as the sample before annealed. The ITO film can be used as a low emissivity coating of super alloy K424 up to 700 °C.     

A self-method for resolving the problem of apparent LWIR emissivity for quantitative thermography up to 130 °C

In a previous work, we succeeded in connecting normal LWIR apparent emissivity to the spectral one of an aluminum nitride ceramic plate. The key problem was the knowledge of the effective spectral bandwidth in use in the system. Hence we have developed an analyzer which permits to identify the spectral bandwidth of IR system using only its raw data. It proceeds by minimizing the dispersion from linearity of the characteristic thermosignals/integrated radiance over a temperature range of the IR system. The capacities of the analyzer are tested for five commercial cameras. Each of these systems exhibits a similar formatting process implemented during the thermogram recording. The effective spectral bandwidth shows plausible values. It varies significantly from one model to the other and the residual non-linearity is connected to the NETD of the IR system. The robustness of the apparent emissivity measurements is also tested with the aid of emissivity reference of 0.5. The overall accuracy of the method is less than 1%, depending on the specular or diffuse part of the reflected irradiation. Applied in field situation, the method is suitable to detect absolute variation of emissivity of less than 6 ⋅ 10⁻³. We use the analyzer to determine the spectral bandwidth of a commercial 320 × 240 microbolometer uncooled IRFPA camera which had already served to characterize the normal LWIR apparent emissivity of the aluminum nitride ceramic plate. By using the spectral response of the two major microbolometer sensor technologies, the general formulation of apparent emissivity matches our apparent emissivity measurements. An agreement better than 0.6% in absolute value and a less than 6 ⋅ 10⁻³%/°C dispersion are found over the entire temperature range [40–130 °C].     

A preliminary study on a new LiBOB/acetamide solid phase transition electrolyte

New solid electrolytes containing acetamide and lithium bioxalato borate (LiBOB) with different molar ratios have been investigated. Their melting points (T_m) are around 42 °C. The ionic conductivities and activation energies vary drastically below and above T_m, indicating a typical feature of phase transition electrolyte. The ionic conductivity of the LiBOB/acetamide electrolyte with a molar ratio of 1:8 is 5 × 10^? 8 S cm^? 1 at 25 °C but increases to 4 × 10^? 3 S cm^? 1 at 60 °C. It was found that anode materials, such as graphite and Li₄Ti₅O₁₂, could not discharge and charge properly in this electrolyte at 60 °C due to the difficulty in forming a stable passivating layer on the anodes. However, a Li/LiFePO₄ cell with this electrolyte can be charged properly after heating to 60 °C, but cannot be charged at room temperature. Although the LiBOB/acetamide electrolytes are not suitable for Li-ion batteries due to poor electrode compatibility, the current results indicate that a solid electrolyte with a slightly higher phase transition temperature than room temperature may find potential application in stationary battery for energy storage where the electrolyte is at high conductive liquid state at elevated temperature and low conductive solid state at low temperature. The interaction between acetamide and LiBOB in the electrolyte is also studied by Raman and FTIR spectroscopy.     

Preparation and characterization of solid polymer electrolytes based on PHEMO and PVDF-HFP

Polymer electrolyte membranes consisting of a novel hyperbranched polyether PHEMO (poly(3-{2-[2-(2-hydroxyethoxy) ethoxy] ethoxy}methyl-3′-methyloxetane)), PVDF-HFP (poly(vinylidene fluoride-hexafluoropropylene)) and LiTFSI have been prepared by solution casting technique. X-ray diffraction of the PHEMO/PVDF-HFP polymer matrix and pure PVDF-HFP revealed the difference in crystallinity between them. The effect of different amounts of PVDF-HFP and lithium salts on the conductivity of the polymer electrolytes was studied. The ionic conductivity of the prepared polymer electrolytes can reach 1.64 × 10^? 4 S·cm^? 1 at 30 °C and 1.75 × 10^? 3 S·cm^? 1 at 80 °C. Thermogravimetric analysis informed that the PHEMO/PVDF-HFP matrix exhibited good thermal stability with a decomposition temperature higher than 400 °C. The electrochemical experiments showed that the electrochemical window of the polymer electrolyte was around 4.2 V vs. Li⁺/Li. The PHEMO/PVDF-HFP polymer electrolyte, which has good electrochemical stability and thermal stability, could be a promising solid polymer electrolyte for polymer lithium ion batteries.     

Study on ionic conductivity of polymer electrolyte plasticized with PEG–aluminate ester for rechargeable lithium ion battery

We have synthesized poly(ethylene glycol) (PEG)-aluminate ester as a plasticizer for solid polymer electrolytes. The thermal stability, ionic conductivity and electrochemical stability of the polymer electrolyte which consist of poly(ethylene oxide) (PEO)-based copolymer, PEG–aluminate ester and lithium bis-trifluoromethanesulfonimide (LiTFSI) were investigated. Addition of PEG–aluminate ester increased the ionic conductivity of the polymer electrolyte, showing greater than 10^− 4 S cm^− 1 at 30 °C. The polymer electrolyte containing PEG–aluminate ester retained thermal stability of the non-additive polymer electrolyte and exhibited electrochemical stability up to 4.5 V vs. Li⁺/Li at 30 °C.     

The synthesis and characterization of Al/Co3O4 magnetic composite pigments with low infrared emissivity and low lightness

The main challenge of low infrared emissivity coatings based on aluminum flake lies in finding an efficient method to synthesize the composite pigment with low infrared emissivity and low lightness simultaneously. In this work, we overcome this constraint to some extent, synthesizing a novel Al/Co₃O₄ magnetic composite pigments with low infrared emissivity and low lightness by thermal cracking and hot flowing method. The results show that the covering area of Co₃O₄ on the aluminum flake can be tuned by the amount of CoCO₃ adding in precursor and the reaction temperature of hot flowing, both of which pay a key factor on the VIS and IR spectral reflectance and magnetic properties. The magnetic Al/Co₃O₄ composite pigments with low lightness and low infrared emissivity can be obtained at 130 °C for 24 h in hot flowing liquid. The lightness L¹ can be decreased to 69.2, however the infrared emissivity (8–14 μm) is also low to 0.45. Compared with the single Al flakes, Al/Co₃O₄ magnetic composite pigments present stronger magnetic properties. Therefore, the Al/Co₃O₄ magnetic composite pigments have offered new choice for the pigments of low infrared emissivity coatings.     

Sintering kinetics and oxide ion conduction in Sr-doped apatite-type lanthanum silicates,La9Sr1Si6O26.5

These last past years, a major interest has been devoted to decrease the working temperature of solid oxide fuel cells (SOFCs) down to about 700 °C.Apatite materials (La_10 ? xSr_xSi₆O_27?x/2) are attractive candidates for solid electrolytes, with a high ionic conductivity at these intermediate temperatures. An apatite powder (x = 1) with a 0.75 µm mean particle size, produced by solid state reaction, was tape cast to obtain green sheets with a thickness of about 260 µm.On one hand, the densification mechanism of the apatite ceramic during the intermediate solid state sintering has been approached. It appeared from the kinetical tests performed under isothermal conditions between 1250 and 1550 °C, that densification could be controlled by the diffusion at grain boundaries of the rare-earth element, La, with an activation energy of 470 kJ/mol.On the other hand, conductivity measurements were performed on apatite samples sintered at 1400 and 1500 °C. The ionic conductivity was mainly sensitive to the presence of secondary phases at 1400 °C. The ionic conductivity of the apatite sintered at 1500 °C (mean grain size = 3.9 µm) is equal to 1.2 × 10^? 2 S/cm at 700 °C.     

Polymer electrolytes based on poly(vinylidene fluoride-co-hexafluoropropylene) with crosslinked poly(ethylene glycol) for lithium batteries

The combination of a poly(ethylene glycol) (PEG) network and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) copolymer chains is one of the most efficient means for modifying PVDF-HFP gel electrolytes. Previous preparations tend to introduce contamination into the polymer gel electrolyte because of irradiation, high temperature or the initiator needed for crosslinking which might result in the electrochemical degradation. In order to overcome the above disadvantages, a new method has been developed to successfully prepare the semi-interpenetrating polymer networks of PVDF-HFP based electrolytes with crosslinked diepoxy polyethylene glycol (DIEPEG). In this process, impurities are avoided because of a moderate reaction temperature at 50 °C and poly(ethylenimine) (PEI) as the crosslinking agent. Microporous films with various compositions are prepared and characterized. Thermal, mechanical, swelling and electrochemical properties, as well as microstructures of the prepared polymer electrolytes have been investigated using thermogravimetric analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and scanning electron microscopy. The results show that the blend polymer electrolyte with PVDF-HFP/PEI + DIEPEG (60:40 w/w) has an ionic conductivity of 2.3 mS cm^? 1 at room temperature in the presence of 1 M LiPF₆ in EC and DMC (1:1 w/w). All the blend electrolytes are electrochemically stable up to 4.8 V versus Li/Li⁺. The results reveal that this new method may be very promising for improving PVDF-HFP based electrolytes.     

Development of dry polymer electrolyte based on polyethylene oxide with co-bridging agent crosslinked by electron beam

Polyethylene oxide (PEO)-based electrolytes were crosslinked using electron beam (EB) irradiation. The gel contents of a polymer film were increased after irradiation doses of 0, 140, 280, and 420 kGy, with ionic conductivities of 0.831, 1.55, 6.08, and 7.95 (× 10^? 5) S cm^? 1 at 40 °C, respectively. The slight decrease in conductivity at higher temperatures after irradiation is due to the retardation of polymer motion by crosslinking. The electrolyte with higher EB dose amount exhibits higher conductivity due to stabilization of the amorphous state. The EB crosslinking with a co-bridging agent shows enhanced conductivities of 4.71, 6.59, and 7.18 (× 10^? 5) S cm^? 1 at 40 °C, after irradiation with 140, 280, and 420 kGy. Addition of the co-bridging agent is effective for developing a crosslinked structure with a smaller EB dose. Tensile strength becomes two to three times higher with irradiation compared to the non-treated polymer. Combination of the EB technique with a co-bridging agent is a simple and effective method to prepare strong dry polymer electrolyte films with improved room temperature conductivity.     

Improving the visible transmittance of low-e titanium nitride based coatings for solar thermal applications

Low-emissivity (low-e) coatings on glass are nowadays extensively used for energy saving applications in architectural windows and on solar thermal collectors. In this work the feasibility of TiN-based layers as low-e coatings has been studied. TiN samples were deposited by reactive magnetron sputtering and, in order to improve their optical properties (transmission in the visible range, T and emissivity, ?), we have investigated the changes in optical response following three different approaches: (i) post-deposition annealing treatments up to 500 °C, (ii) doping the TiN layers with aluminium (target composition: Ti/Al = 90/10, 75/25 and 50/50) and (iii) deposition of antireflective coatings of TiO₂ in multilayers structures. The crystalline structure and chemical composition of the multilayers were studied by X-Ray Diffraction and Rutherford Backscattering Spectroscopy, respectively. Spectroscopic Ellipsometry, Fourier Transform Infrared Spectroscopy and direct emissivity measurements were employed to determine the optical properties T and ?. We have concluded that the most noticeable improvement has been obtained by the deposition of multilayers structures increasing in a 30% the original transmittance of the single TiN coatings.     

Effect of amphiphilic hyperbranched-star polymer on the structure and properties of PVDF based porous polymer electrolytes

An amphiphilic hyperbranched-star polymer (HPE-g-MPEG) was synthesized by grafting methoxy poly(ethylene glycol) to the end of the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent. The synthesized amphiphilic hyperbranched-star polymer was blended with poly(vinylidene fluoride) (PVDF) to fabricate porous membranes via typical phase inversion process, and then the membranes were filled and swollen by a liquid electrolyte solution to form polymer electrolytes. The influences of HPE-g-MPEG on the morphology, crystallinity, liquid electrolyte uptake, mechanical properties of the porous membranes and the electrochemical properties of the activated membranes were investigated. It was found that the addition of HPE-g-MPEG resulted in a significant increase in porosity and a considerable reduction in crystallinity of the blend membranes, which favored the liquid electrolyte uptake and, consequently, led to a remarkable increase in ion conductivity at ambient temperature. The maximum ion conductivity observed in this study was 1.76 × 10^? 3 S/cm at 20 °C for the blend membrane with a HPE-g-MPEG/PVDF ratio of 3/10 (w/w).     

Effect of thermal history and characterization of plasticized,composite polymer electrolyte based on PEO and tetrapropylammonium iodide salt (Pr4N+I-)

The search for anionic conductors based on solid polymer electrolytes is important for the development of photo-electrochemical (PEC) solar cells due to their many favourable chemical and physical properties. Although solid polymer electrolytes have been extensively studied as cation, mainly lithium ion, conductors for applications in secondary batteries, their use as anionic conductors have not been studied in greater detail. In a previous paper we reported the application of a PEO based iodide ion conducting electrolyte in a PEC solar cell. This electrolyte had the composition PEO: Pr₄N⁺I^? = 9:1 with 50 wt.% ethylene carbonate (EC). In this work we have studied the effect of incorporating alumina filler on the properties of this electrolyte. The investigation was extended to electrical and dielectric measurements including high frequency impedance spectroscopy and thermal analysis.In the DSC themograms two endothermic peaks have been observed on heating, one of these peaks is attributed with the melting of the PEO crystallites, while the other peak with a melting temperature ~ 30 °C is attributed to the melting of the EC rich phase. The melting temperature of both these peaks shows a marked variation with alumina content in the electrolyte. The temperature dependence of the conductivity shows that there is an abrupt conductivity increase in the first heating run evidently due to the melting of the EC rich phase. High conductivity values are retained at lower temperatures in the second heating. Conductivity isotherms show the existence of two maxima, one at ~ 5% Al₂O₃ content and the other at ~ 15%. The occurrence of these two maxima has been explained in terms of the interactions caused by alumina grains, the crystallinity and melting of the PEO rich phase. As seen from latent heat of melting, the crystallinity of the electrolyte has reduced considerably during the first heating run. In contrast to the conductivity enhancement caused by ceramic fillers in PEO-based cation containing electrolytes, no conductivity enhancement has been observed in the present PEO based anionic conducting materials by adding alumina except at low temperatures.     

Surface temperature measurement of the plasma facing components with the multi-spectral infrared thermography diagnostics in tokamaks

For the long-pulse high-confinement discharges in tokamaks, the equilibrium of plasma requires a contact with the first wall materials. The heat flux resulting from this interaction is of the order of 10 MW/m² for steady state conditions and up to 20 MW/m² for transient phases. The monitoring on surface temperatures of the plasma facing components (PFCs) is a major concern to ensure safe operation and to optimize performances of experimental operations on large fusion facilities. Furthermore, this measurement is also required to study the physics associated to the plasma material interactions and the heat flux deposition process. In tokamaks, infrared (IR) thermography systems are routinely used to monitor the surface temperature of the PFCs. This measurement requires an accurate knowledge of the surface emissivity. However, and particularly for metallic materials such as tungsten, this emissivity value can vary over a wide range with both the surface condition and the temperature itself, which makes instantaneous measurement challenging. In this context, the multi-spectral infrared method appears as a very promising alternative solution. Indeed, the system has the advantage to carry out a non-intrusive measurement on thermal radiation while evaluating surface temperature without requiring a mandatory surface emissivity measurement.In this paper, a conceptual design for the multi-spectral infrared thermography is proposed. The numerical study of the multi-channel system based on the Levenberg-Marquardt (LM) nonlinear curve fitting is applied. The numerical results presented in this paper demonstrate the design allows for measurements over a large temperature range with a relative error of less than 10%. Furthermore, laboratory experiments have been performed from 200 °C to 740 °C to confirm the feasibility for temperature measurements on stainless steel and tungsten. In these experiments, the unfolding results from the multi-channel detection provide good performance on temperature measurement, which supports our numerical evaluation and demonstrates the potential feasibility for metallic surface high temperature measurement with this method.     

Studies on the percolation limit of Ce0.9Gd0.1O1.95 in La0.6Sr0.4Co0.2Fe0.8O3−δ–Ce0.9Gd0.1O1.95 nanocomposites for solid oxide fuel cells application

A large difference in thermal expansion coefficient of electrode and electrolyte leads to imperfect electrode/electrolyte interface and hence significant polarization losses in solid oxide fuel cells. To overcome the difficulties associated with electrode and electrode/electrolyte interface, there is need to fabricate the composite cathode. Thus the present paper deals with study of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ(LSCF)–Ce_0.9Gd_0.1O_1.95(GDC) nanocomposite with different fractions of GDC obtained by physical mixing of combustion synthesized nanopowders. No secondary phases were observed upon sintering at 1100 °C for 2 h affirming the chemical compatibility between LSCF and GDC. The composites with relatively high GDC% have higher density as a consequence of rapid grain growth and less conductivity. The nanocomposite with 50% of GDC showed electric conductivity of 30 Scm⁻¹ at 500 °C and low area specific resistance of 106 Ω cm² with 10 μs relaxation time at 200 °C.     

Investigation of the effects of Ni-based alloy K465 on the normal spectral emissivity during oxidation

The normal spectral emissivity of Ni-based alloy K465 during oxidation is experimentally measured at 810, 914 and 998 °C for 12 h in air over the wavelength from 1.3 to 2.4 μm. The combined standard uncertainty of the normal spectral emissivity is less than 3%. The oscillations of the emissivity and the effects of oxidation temperature, heating time and wavelength on the emissivity are investigated. The oscillations of the emissivity are formed by the interference effect between the radiation from the surfaces of the substrate and the oxidation film. The oscillation extremums of the emissivity shift towards larger wavelengths as the oxidation process proceeds. The results show that the normal spectral emissivity increases as the temperature increases at the initial time. The normal spectral emissivity decreases as wavelength increases except for the occurrence of the oscillations of the emissivity. The normal spectral emissivity increases rapidly at the initial heating time, and the change of emissivity becomes slow when the oxidation tends to be saturated gradually. Besides, the emissivity fitting models versus heating time and wavelength are established, which fit the experimental results very well. The emissivity relative errors of the fitting models are less than 4%.     

Multispectral pyrometry for surface temperature measurement of oxidized Zircaloy claddings

Non-contact temperature measurement in a nuclear reactor is still a huge challenge because of the numerous constraints to consider, such as the high temperature, the steam atmosphere, and irradiation. A device is currently developed at CEA to study the nuclear fuel claddings behavior during a Loss-of-Coolant Accident. As a first step of development, we designed and tested an optical pyrometry procedure to measure the surface temperature of nuclear fuel claddings without any contact, under air, in the temperature range 700–850 °C. The temperature of Zircaloy-4 cladding samples was retrieved at various temperature levels. We used Multispectral Radiation Thermometry with the hypothesis of a constant emissivity profile in the spectral ranges 1–1.3 µm and 1.45–1.6 µm. To allow for comparisons, a reference temperature was provided by a thermocouple welded on the cladding surface. Because of thermal losses induced by the presence of the thermocouple, a heat transfer simulation was also performed to estimate the bias. We found a good agreement between the pyrometry measurement and the temperature reference, validating the constant emissivity profile hypothesis used in the MRT estimation. The expanded measurement uncertainty (k = 2) of the temperature obtained by the pyrometry method was ±4 °C, for temperatures between 700 and 850 °C. Emissivity values, between 0.86 and 0.91 were obtained.     

Synthesis,ionic conductivity,and thermal properties of proton conducting polymer electrolyte for high temperature fuel cell

Hyperbranched polymer (poly-1a) with sulfonic acid groups at the end of chains was successfully synthesized. Interpenetration reaction of poly-1a with a hyperbranched polymer with acryloyl groups at the end of chains (poly-1b) as a cross-linker afforded a tough electrolyte membrane. The poly-1a and the resulting electrolyte membrane showed the ionic conductivities of 7 × 10^− 4 and 8 × 10^− 5 S/cm, respectively, at 150 °C under dry condition. The ionic conductivities of the poly-1a and the electrolyte membrane exhibited the VTF type temperature dependence. And also, both poly-1a and the resulting electrolyte membrane were thermally stable up to 200 °C.     

Synthesis and properties of a new class of fluorine-containing dilithium salts for lithium-ion batteries

A facile synthetic route for the development of a new class of dilithium salts is described. Because of the presence of two lithium ions per molecule, these salts require lower concentrations than commonly used salts to achieve comparable ionic conductivities at ambient temperatures. An ionic conductivity of 3.55 × 10^− 3 S/cm at 30 °C was obtained using 0.5 M salt solution in 1:1 wt/wt ethylene carbonate:dimethyl carbonate. The salts exhibit excellent thermal stabilities to at least 350 °C and are electrochemically stable below 4.2 V versus lithium metal. The best salt was tested with a polymer electrolyte system. Incorporation of a polyethylene glycol-based borate ester plasticizer improved the ionic conductivity of the solid polymer electrolyte film up to 1.36 × 10^− 5 S/cm at 30 °C, which is 10 times higher than that of un-plasticized electrolyte films.     

High mobility I− / I3− redox couple in a molecular plastic crystal: A potential new generation of electrolyte for solid-state photoelectrochemical cells

A series of new electrolyte materials based on a molecular plastic crystal doped by different iodide salts together with iodine have been prepared and characterized by thermal analysis, ionic conductivity, electrochemical and solid-state NMR diffusion measurements. In these materials, the plastic crystal phase of succinonitrile acts as a good matrix for the quaternary ammonium based iodides and iodine and appears to act in some cases as a solid-state “solvent” for the binary dopants. The materials were prepared by mixing the components in the molten state with subsequent cooling into the plastic crystalline state. This resulted in waxy-solid electrolytes in the temperature range from − 40 to 60 °C. The combination of structural variation of the cations, and fast redox couple diffusion (comparable with liquid-based electrolytes), as well as a high ionic conductivity of up to 3 × 10^− 3 S cm^− 1 at ambient temperature, make these materials very attractive for potential use in solid-state photoelectrochemical cells.     

Ionic conductivity of polymer electrolyte membranes based on polyphosphazene with oligo(propylene oxide) side chains

A polyphosphazene [NP(NHR)₂]_n with oligo[propylene oxide] side chains − R = –[CH(CH₃)–CH₂O]_m–CH₃ (m = 6 – 10) was synthesized by living cationic polymerisation and polymer-analogue substitution of chlorine from the intermediate precursor [NPCl₂]_n using the corresponding primary amine RNH₂. The polymer had an average molecular weight of 3.3 × 10⁵ D. Polymer electrolytes with different concentrations of dissolved lithium triflate (LiCF₃SO₃) were prepared. Mechanically stable polymer electrolyte membranes were formed using UV radiation induced crosslinking of the polymer salt mixture in the presence of benzophenone as photoinitiator. The glass transition temperature of the parent polymer was found to be − 75 °C before cross linking. It increases after crosslinking and with increasing amounts of salt to a maximum of − 55 °C for 20 wt.% LiCF₃SO₃. The ionic conductivity was determined by impedance spectroscopy in the temperature range 0–80 °C. The highest conductivity was found for a salt concentration of 20 wt.% LiCF₃SO₃: 6.5 × 10^− 6 S·cm^− 1 at 20 °C and 2.8 × 10^− 4 S cm^− 1 at 80 °C. The temperature dependence of the conductivities was well described by the MIGRATION concept.