Boron doped M-phase VO2 nanoparticles with low metal-insulator phase transition temperature for smart windows

Vanadium dioxide (VO₂) is considered to be a promising candidate for energy-efficient smart windows because of its special reversible Metal-Insulator Transition (MIT) near the ambient temperature. However, its use is constrained by its high transition temperature (T_C) relative to the room temperature. In this paper, VO₂ doped by boron, could achieve an outstanding metal-insulator phase transition property with a low T_C (28.1 °C) close to the room temperature. This enhancement strongly contributes to the studies of the VO₂-based smart windows. A limit doping level of around 9.0 at% is observed for the boron-doped VO₂. Moreover, the particle size is getting smaller and more uniform and the particle distribution becomes more equal and compact with the continued increase in the doping content. Such uniform grain size and grain boundary conditions suppress the extension of the hysteresis loop (ΔT decreases from 25 °C to 7 °C). In addition, the T_C first declines with the increase in the boron content and it starts to increase after reaching its minima of 28.1 °C at 6.0 at% doping level. This feature is the consequence of the competition between the inhibition on the phase transition caused by the V⁵⁺ and the promotion on the phase transition caused by the heterogeneous defect-nucleation sites. VO₂ doped with 6.0 at% boron exhibits a favorable thermochromic performance with ΔT_sol of 12.5% and T_lum up to 54.3%, which is promising for the smart windows.     

Design criterion based on the cohesive energy and defect patterns of VO2 thermally induced phase transition materials

Vanadium dioxide (VO₂) is one of the most widely used thermally induced phase transition materials. However, the phase transition regulation mechanism and specific modulation relationship of VO₂ materials are still not entirely clear. Here, we propose a comprehensive and precise phase transition material design criterion based on the cohesive energy and defect patterns. The results revealed that the associated regulation mechanism, including the size, strain, vacancy as well as crystal plane and shape, of these materials can be determined via design criteria and first principles calculations. Moreover, the specific modulation relationship of the thickness-induced phase transition can also be confirmed by means of experiments. These findings show that our design criterion provides an effective approach for the design of VO₂ thermally induced phase transition materials.     

Infrared radiation and thermal properties of Al-doped SrZrO3 perovskites for potential infrared stealth coating materials in the high-temperature environment

The Al-doped SrZrO₃ perovskite powder with low infrared emissivity at high temperatures was prepared. The infrared radiation performance and thermophysical properties of the perovskites at high temperatures were discussed. As a result, the infrared emissivity of the Al-doped SrZrO₃ perovskite powder is associated with Al³⁺-doping content, phase composition and particle morphology. The flaky particles SrZr_0.85Al_0.15O_2.925 formed by heat treatment at 1000 °C for 6 h have the lowest infrared emissivity of 0.245 in 3–5 μm wavebands at 590 °C. The perovskite powder's infrared emissivity is positively correlated with its electrical resistivity and has no apparent change after heating over 800 °C for long-term. The SrZr_0.85Al_0.15O_2.925 perovskite ceramic formed by pressureless sintering still maintains ideal heat insulation performance with the thermal conductivity from 1.17 to 2.21 W m^?1 K^?1 below 1400 °C. The Al-doped SrZrO₃ perovskite tablet exhibits significant weak radiation intensity due to its characteristics of both low infrared emissivity and thermal conductivity at high temperatures.     

Enhanced radar and infrared compatible stealth properties in hierarchical SnO2@ZnO nanostructures

Hierarchical SnO₂@ZnO nanostructures are successfully synthesized in a large scale by using a simple hydrothermal method. The SnO₂ nanowires epitaxially grow on the non-polarized plane of ZnO nanorods with a six-fold symmetry. The radar wave absorbing and infrared emissivity properties of hierarchical SnO₂@ZnO nanostructures are studied. Such hybrid hierarchical SnO₂@ZnO nanostructures show enhanced radar and infrared compatible stealth properties than ZnO or SnO₂. The minimum reflection loss (RL) is −23.51 dB at 9.2 GHz with a bandwidth (RL<−10 dB) of 3.5 GHz and the average infrared emissivity in middle-infrared band and far-infrared band are around 0.65 and 0.89, respectively.     

Photoluminescence response of colloidal quantum dots on VO2 film across metal to insulator transition

We have proposed a method to probe metal to insulator transition in VO₂ measuring photoluminescence response of colloidal quantum dots deposited on the VO₂ film. In addition to linear luminescence intensity decrease with temperature that is well known for quantum dots, temperature ranges with enhanced photoluminescence changes have been found during phase transition in the oxide. Corresponding temperature derived from luminescence dependence on temperature closely correlates with that from resistance measurement during heating. The supporting reflectance data point out that photoluminescence response mimics a reflectance change in VO₂ across metal to insulator transition. Time-resolved photoluminescence study did not reveal any significant change of luminescence lifetime of deposited quantum dots under metal to insulator transition. It is a strong argument in favor of the proposed explanation based on the reflectance data.

PACS

71.30. + h; 73.21.La; 78.47.jd     

Metal-to-insulator transition and its effective manipulation studied from investigations in V1-xNbxO2 bulks

Nb doping effects on crystalline structure, transport transition and magnetic properties are investigated for V_1-xNb_xO₂ (0 $\le$x$\le$ 5%) bulks. At room temperature, doping does not change structure of monoclinic phase but causes an increase in lattice parameters for the range of x$\le$ 3%, further doping leads to a structure transition to rutile tetragonal phase. Each sample simultaneously displays a transition to insulating behavior and a sharp decrease in susceptibility below an almost same critical temperature (T_c). The T_c is shown to shift from ~ 340 K at x = 0 to ~ 277 K at x = 5% at a rate of ~ ?13 K/at%. It is argued that the observed sharp decrease in susceptibility originates from the formation of V-V dimers with spins in anti-parallel, while the insulating behavior below T_c is due to the electron movement from one dimerized state to another with the help of Variable-Range-Hopping mechanism. Furthermore, it is proposed that doping by larger cations, which would suppress the formation of dimers, can be used to manipulate the metal-insulator transition to lower temperatures.     

Preparation and characterization of HfO2/VO2/HfO2 sandwich structures with low phase transition temperature,excellent thermochromic properties,and superior durability

In the last few decades, smart windows made from VO₂-based thermochromic films have attracted extensive attention, but their actual commercial applications are limited by low luminous transmittance (T_lum), low solar modulation ability (ΔT_sol), high phase transition temperature (T_c), and poor durability. In this study, glass/HfO₂/VO₂/HfO₂ tri-layer films were designed and deposited on glass substrates by pulse laser deposition. Crystal structures, surface morphology, surface roughness, electrical properties, and optical properties of as-prepared sandwich structure films were analyzed. Results showed that both HfO₂ buffer layer and antireflection layer (ARL) were monoclinic phase and grew along the (020) and (?111) crystal planes, respectively. HfO₂ buffer layer not only reduced T_c of VO₂ film by about 20 °C, but also played an important role in regulating crystal quality and surface morphology of VO₂ films. More importantly, by covering films with HfO₂ ARL, T_lum and ΔT_sol of VO₂ film were greatly improved. In particular, when the thicknesses of HfO₂ buffer layer and ARL were 80 nm and 120 nm, the obtained HfO₂/VO₂/HfO₂ tri-layer film reached a balance between high T_lum (～47.2%), high ΔT_sol (～9.1%) and low T_c (～49.1 °C). In addition, after 216 h of boiling water treatment, T_lum and ΔT_sol of HfO₂/VO₂/HfO₂ film covered with 120 nm thick ARL still remained at 49.3% and 7.0%, showing excellent durability. This research provides a new strategy for designing VO₂-based smart windows with high performance and good durability.     

Simultaneous low reflection in near-infrared range and low emission in long-wave infrared properties of Al/Bi2O3 composites

In this work, flaky aluminum was coated with bismuth oxide to obtain low reflection in near-infrared range and low emission in long-wave infrared stealth material. The composites were prepared through coprecipitation method, characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), and measured by ultraviolet spectrophotometer and dual band infrared emissometer. The morphology and microstructure show that the flaky aluminum was coated by bismuth oxide nanoparticles. The optimal reaction temperature was 50 °C, and the optimized amount of Al was 20 wt%. Meanwhile, the infrared emissivity in 8–14 μm infrared waveband range was 0.462 and the reflectivity was 39.1% at wavelength of 1.064 μm. In addition, it could also achieve good thermal insulation in a thinner thickness. When the temperature of heating platform reached 100 °C, the temperature of the disk with 0.30 mm thickness was 26.9 °C which was only 2.7 °C higher than that of the disk with 0.94 mm thickness. It may shed light on a new material design orientation to obtain high performance infrared and laser compatible stealth materials.     

二氧化钛相变研究现状

综述了二氧化钛由锐钛矿型向金红石型转变的影响因素,重点研究了温度调控与添加剂调控对二氧化钛锐钛矿型向金红石型转变的影响和作用机理。结果表明：温度调控能直接有效地促进二氧化钛锐钛矿型向金红石型转变;掺杂熔点低于TiO2的金属氧化物V2O5、SnO2等,离子半径与Ti4+半径相近的Fe3+、V4+、Ce4+等,以及体积小的低价阴离子Cl-、F-等都能促进TiO2由锐钛矿型向金红石型转变。     

VO2相变温度及性能的影响因素与应用研究进展

二氧化钒（VO2）作为一种相变金属氧化物,相变温度为68℃。在68℃以下VO2呈绝缘单斜相,在68℃以上呈金红石相,由于这种晶体结构的变化导致VO2在光性能和电性能方面表现出可逆的突变,从而成为光电开关领域的宠儿。基于此,本文对VO2的制备方法及其调控VO2相变温度与性能所采取的主要手段进行了综述,并归纳了不同制备方法的优缺点及调控VO2相变温度与性能的因素,总结了近年来VO2的应用进展,最后对VO2今后的发展趋势进行了展望,期望对相关领域的研究者具有指导作用。     

Citrate-assisted hydrothermal synthesis of vanadium dioxide textured films with metal-insulator transition and infrared thermochromic properties

The present study reports the fast synthesis of VO₂ (М₁) oriented films on the r-Al₂O₃(012) substrates by the hydrothermal method using citric acid and vanadium (V) oxide as precursors with post deposition annealing in inert atmosphere. The effects of synthesis parameters (solution concentration and autoclave filling factor) on the films composition, morphology and electric properties are considered using XRD, Raman spectroscopy, AFM and SEM. The obtaining VO₂(M₁)/r-Al₂O₃ films show a metal-insulator transition with resistivity change of ~3.5 orders of magnitude and excellent thermochromic properties in the long-wavelength IR region. This work demonstrates a promising technique to promote the commercial implementation of VO₂ as material for design of infrared (IR) switch devices.     

Statistical and electrical properties of the conduction electrons of a metal nanosphere in the region of metal-insulator transition

Statistical and electrical properties of the conduction electrons of a silver or gold sphere with a radius from 1 to 2 nm are shown to differ drastically from the properties of electrons in a bulk metal sample. If the radius of a noble metal sphere decreases from 10 to 1 nm, its conductivity oscillates around the bulk metal value with increasing amplitude and drops at the ''magic’ numbers of electrons. These numbers are equal to 186, 198, 254, 338, 440, 556, 676, 832, 912, 1,284, 1,502, and 1,760, in agreement with various experimental data. We show that the conductivity and capacitance of a metal nanosphere can be changed by several orders of magnitude by adding or removing just a few electrons.     

非晶态粉体玻璃化转变温度的测量方法与装置

为了研究非晶态高分子粉体玻璃化转变与结块特性,需要建立一种实用有效的玻璃化转变温度的测定方法。基于非晶态高分子粉体的体膨胀系数在玻璃化转变时发生突变的原理,采用热膨胀计技术,提出了一种用膨胀计测量非晶态高分子粉体玻璃化转变温度的新方法——膨胀计法,并建立了相应的测量装置。以聚苯乙烯为例,详细介绍了用该方法进行测量及数据处理的过程,并考察了测量结果的有效性。以谷物及含水淀粉体为例,考察了该方法在食品粉体玻璃化转变温度测量中的应用。结果表明,膨胀计法测量非晶态高分子粉体玻璃化转变温度,实用、有效,为非晶态高分子粉体的玻璃化转变温度测量提供了一种新途径。     

Volume phase transition temperature tuning and investigation of the swelling–deswelling oscillation of responsive microgels

Temperature‐ and pH‐responsive polyampholyte microgels were prepared by an aqueous dispersion polymerization. Scanning electron microscopy and dynamic laser light scattering (DLS) were employed for the characterization of the morphology and size distribution of the microgels. Temperature‐ and pH‐dependent volume phase transitions of the polyampholyte microgels were also investigated using DLS. The microgels showed an interesting swelling–deswelling oscillatory behavior when the pH was varied. An interpretation was proposed for the phenomenon in terms of Coulombic repulsion and hydrophobic hydration. It is of great interest that the volume phase transition temperature (VPTT) of the polyampholyte microgels can be varied by changing the pH. This could be a convenient approach for tuning the VPTT of N‐isopropylacrylamide‐based hydrogels. Copyright © 2007 Society of Chemical Industry     

HAN-TEAN-H_2O 三元体系的相变及其相图

用ＤＳＣ研究了ＨＡＮ－ＴＥＡＮ－Ｈ２Ｏ三元体系的低温热行为，建立了该体系低温下相变与组分关系的相图。考察了玻璃化转化温度随ＨＡＮ／ＴＥＡＮ比例的变化规律。发现了三元体系的溶液性质在ＨＡＮ－ＴＥＡＮ比率较大时，与ＨＡＮ－Ｈ２Ｏ二元体系相似，而在ＨＡＮ／ＴＥＡＮ比率较小时，则与ＴＥＡＮ－Ｈ２Ｏ二元体系相似。     

Sc- and W-substitution and tuning of phase transition in the Al2Mo3O12

Al₂Mo₃O₁₂ is a typical negative thermal expansion (NTE) material, whose thermal expansion behavior depends on its crystal phase. The thermal shock caused by temperature-induced phase transition limits its wide application. The two series of Al_{2. x}Sc_xMo₃O₁₂ (0 ≤ x ≤ 1) and Al₂Mo_3-xW_xO₁₂ (0 ≤ x ≤ 2.5) solid solutions with controllable phase transition temperature were synthesized via single cation substitution at the A or B position. The problem of thermal shock caused by the change of temperature is effectively solved in the synthesized Al_1.6Sc_0.4Mo₃O₁₂ and Al₂Mo_0.5W_2.5O₁₂, showing stable NTE performance above room temperature, and the coefficients of thermal expansion of which are ?2.19 × 10^?6 °C^?1 in 100–550 °C and ?4.25 × 10^?6 °C^?1 in 85–500 °C, respectively. A-site cation substitution is a more effective way to tune the thermal expansion properties of Al₂Mo₃O₁₂, which is attributed to the fact that the bond strength of A-O is weaker than that of B–O in the compound.     

Effect of post-cure on the glass transition temperature and mechanical properties of epoxy adhesives

The effects of post-curing and cure temperature on the glass transition temperature, T _g, and the mechanical properties of epoxy adhesives were studied. T _g was measured by a dynamic mechanical analysis apparatus developed in-house and the mechanical properties of the adhesives (yield strength, Young’s modulus and failure strain) were measured by a tensile machine. The relationships between T _g and mechanical performance under various post-cure conditions were investigated. The curing process was the same for all tests, consisting of an initial stage performed at different temperatures followed by cooling at room temperature. Three sets of specimens were considered, sharing the same initial cure process, but with a different post-curing procedure. In the first set, the specimens were only subjected to a curing process; in the second set, the specimens were subjected to a curing process followed by a post-cure performed at a temperature below the T _g of the fully cured network, T _g∞; and in the third set, the specimens were subjected to a curing process followed by a post-cure performed at a temperature above the T _g∞. When post-cured at a temperature above T _g∞, the mechanical and physical properties tend to have a constant value for any cure temperature.     

Thermoelectric properties and phase transition of doped single crystals and polycrystals of Bi2Te3

The temperature dependences of the electrical conductivity , Seebeck coefficient , and heat capacity C_p(T) of polycrystalline samples of Bi₂Te₃, Bi₂Te₃+1%CuI, and Bi₂Te₃+1%(CuI+1/2Pb) are investigated in the temperature range below room temperature. Based on the temperature dependences of all investigated physical properties, it is discovered that phase transition occurs at 120–200 K. Investigation of single crystals shows that anomalies in the electrical resistivity occur only across the crystal growth axis (across the well-conducting Bi–Te plane). Investigation of the low-temperature dependence of electrical conductivity shows that all polycrystalline samples exhibit quasi-two-dimensional electron transport. Additionally, quasi-two-dimensional transport is detected in single crystals based on anisotropy analysis (where is the resistivity along the crystal growth axis, and is resistivity across the crystal growth axis) and temperature dependence below 50 K. The Fermi energy is estimated using the temperature dependence of . It is discovered that an increase in at T > 200 K is associated with the phase transition. For single-crystal samples, the maximum thermoelectric figure of merit ZT, as observed along the crystal growth axis, increases with doping. A maximum ZT value of ∼1.1 is observed for the Bi₂Te₃+1%(CuI+1/2Pb) sample at room temperature ().     

Fabrication and characterization of Pr6O11-HfO2 ultra-high temperature infrared radiation coating

In this study, pure HfO₂ and Pr₆O₁₁-HfO₂ coatings were prepared by atmospheric plasma spraying. The chemical compositions, morphologies, infrared radiation performances and thermal resistances of the coatings were characterized. The results showed that doping Pr₆O₁₁ could effectively improve the infrared emittance of the HfO₂ coating. The HfO₂ coating doping with 10 wt. % Pr₆O₁₁ exhibited the highest infrared emittance, which was 0.859 at room temperature and 0.883 at 1600 °C, correspondingly. This was mainly attributed to the oxygen vacancies, which created by the substitution of Hf⁴⁺ by Pr³⁺, could introduce localized energy states within the HfO₂ band gap and increase the lattice distortion, producing lower symmetry vibrations. In addition, the Pr₆O₁₁-HfO₂ infrared radiation coating possessed high tensile adhesive strength and good thermal resistance, which could withstand a high temperature treatment at 1700 °C for at least 50 h without exfoliation, and there was only a slight reduction in emittance.     

VO2薄膜相变及其温度滞后

以攀钢产V2O5为原料，采用无机胶体法制备电阻突变VO2薄膜，研究了VO2薄膜的电阻突变温度、突变数量级及其突变温度滞后. 结果表明，VO2薄膜相变温度为35℃，制备方法和衬底材质对VO2薄膜的电阻突变数量级有较大影响. 以普通玻璃和石英玻璃作衬底、用H2还原法，可使VO2薄膜的电阻突变达到2~3个数量级，用N2热分解法仅能达到1.5~2个数量级；普通玻璃衬底上VO2薄膜的电阻突变数量级小于石英玻璃衬底上的VO2薄膜的电阻突变数量级. VO2薄膜的电阻突变温度滞后为1~6℃，电阻突变数量级、衬底材质和制备方法对其有较大影响.