Influence of Temperature and Time on the Stability of Silver in Silica Sol-Gel Glasses

The darkening of silica sol-gel glasses doped with 0.05 mol% silver was studied. Six sols were prepared from TEOS and silver nitrate. Different additives were used, to influence the chemical and physical states of silver: oxidizing or reducing agents (H₂O₂, As₂O₅), colloid stabilizer (sodium citrate) and network modifiers (Li₂O, CaO). Sols were gelified at 60°C and densified at 600°C. The samples without additives and those prepared with H₂O₂ at room temperature even if they were protected from light. With increased temperature, the darkening became samples were heated above, 400°C, reversible bleaching took place. This darkening-bleaching is of thermal nature (“thermochromic effect”) and seems to be determined by a reversible aggregation-disaggregation of tiny silver particles. The presence of sodium citrate, as an additive delayed the darkening effect and the presence of CaO delayed it even further. Lithium oxide inhibited it totally.     

Two-Step Structure Phase Transition,Dielectric Anomalies,and Thermochromic Luminescence Behavior in a Direct Band Gap 2D Corrugated Layer Lead Chloride Hybrid of [(CH3)4N]4Pb3Cl10

A direct band gap 2D corrugated layer lead chloride hybrid, [(CH₃)₄N]₄Pb₃Cl₁₀ ( 1 ), shows analogous topology to the {Mg₃F₁₀⁴⁻}_∞ layer in Cs₄Mg₃F₁₀, and with the (CH₃)₄N⁺ cations locating in the inorganic layer voids and between the interlayers. Two reversible structural phase transitions occur in 1 at 225/210 K and 328/325 K upon heating/cooling, respectively. On going from the low- to intermediate-temperature phase, the space group changes from P2₁/c to Cmca, and the crystallographic axis perpendicular to the layers is doubled with the order–disorder transformation of (CH₃)₄N ⁺ cations between the interlayers. The intermediate- and high-temperature phases are isomorphic with similar cell parameters and packing structure; their main difference concerns the disorder degree of the (CH₃)₄N ⁺ cations between the interlayers. The two-step structural phase transitions lead to dielectric anomalies around the corresponding T_c. Interestingly, 1 shows multiband emission, originating from the recombination of exciton and emission of defects. Moreover, 1 exhibits divergent thermochromic luminescent features around the T_c on the intermediate to low temperature transition.     

A Water‐Soluble Mechanochromic Luminescent Pyrene Derivative Exhibiting Recovery of the Initial Photoluminescence Color in a High‐Humidity Environment

Switching of the luminescence properties of molecular materials in response to mechanical stimulation is of fundamental interest and also has a range of potential applications. Herein, a water‐soluble mechanochromic luminescent pyrene derivative having two hydrophilic dendrons is reported. This pyrene derivative is the first example of a mechanochromic luminescent organic compound that responds to relative humidity. Mechanical stimulation (grinding) of this pyrene derivative in the solid state results in a change of the photoluminescence from yellow to green. Subsequent exposure to water vapor induces recovery of the initial yellow photoluminescence. The color change is reversible through at least ten cycles. It is also demonstrated that this compound can be applied as a mechano‐sensing material in frictional wear testing for grease, owing to its immiscibility in non‐polar solvents and its non‐crystalline behavior. Transmission electron microscope and atomic force microscope observations of samples prepared from dilute aqueous solutions of the pyrene derivative on suitable substrates, together with dynamic light scattering measurements for the compound in aqueous solution, indicate that this amphiphilic dumbbell‐shaped molecule forms micelles in water.     

热分解法和碳热还原法制备掺钨VO2 /云母复合粉体的热致变色性能

用溶胶凝胶法和喷雾干燥技术在云母微粉表面包覆了不同nW/nV的掺钨V2O5溶胶,分别采用热分解和碳热还原得到了掺钨VO2/云母复合粉体。通过XRD、SEM对复合粉体进行了物相组成、微观形貌的表征。将复合粉体添加到紫外光固化树脂中形成复合薄膜,通过FTIR测试了复合薄膜相变过程中的红外透过率图谱,并通过DSC测试了复合粉体的相变温度(Tt)。结果表明两种热处理方法均得到了VO2(M),VO2晶体以蠕虫状附着在云母表面,同时钨的掺入使云母表面的VO2颗粒更加细小。不同掺杂量的复合粉体均表现出较优异的热致变色性能,相变前后在2 200 cm-1波数处的红外透过率变化量(ΔTr)均超过20%。随着nW/nV增加,复合粉体的ΔTr逐渐减小,Tt逐步降低,同时相变陡然性减缓。     

A Molecular Thermochromic Ferroelectric

Molecular ferroelectrics have attracted considerable interests because of their easy and environmentally friendly processing, low acoustical impedance and mechanical flexibility. Herein, a molecular thermochromic ferroelectric, N,N′‐dimethyl‐1,4‐diazoniabicyclo[2.2.2]octonium tetrachlorocuprate(II) ([DMe‐DABCO]CuCl₄) is reported, which shows both excellent ferroelectricity and intriguing thermochromism. [DMe‐DABCO]CuCl₄ undergoes a ferroelectric phase transition from Pca2₁ to Pbcm at a significantly high Curie temperature of 413 K, accompanied by a color change from yellow to red that is due to the remarkable deformation of [CuCl₄]^2? tetrahedron, where the ferroelectric and paraelectric phases correspond to yellow and red, respectively. Combined with multiple bistable physical properties, [DMe‐DABCO]CuCl₄ would be a promising candidate for next‐generation smart devices, and should inspire further exploration of multifunctional molecular ferroelectrics.     

光(热)致变色剂:单和双吲哚啉螺苯并吡喃

用乙醇作溶剂,在哌啶存在下,通过2,3,3-三甲基-N-(β-羟乙基)吲哚啉碘化物(1)与3-或5-硝基水杨醛反应,分别制得螺环异构体(2a)与(2b)。它们再进一步与异氰酸苯酯进行加成反应,合成一对单螺环异构体(3a)与(3b),将2a 与2b 分别和2,4-二异氰酸甲苯酯(TDI)反应,合成一对双螺环异构体(4a)与(4b)。2a,3a,4a,4b 是光致变色化合物;2b 与3b 是热致变色化合物。     

Strain‐Visualization with Ultrasensitive Nanoscale Crack‐Based Sensor Assembled with Hierarchical Thermochromic Membrane

As eidetic signal recognition has become important, displaying mechanical signals visually has imposed huge demands for simple readability and without complex signal processing. Such visualization of mechanical signals is used in delicate urgent medical or safety‐related industries. Accordingly, chromic materials are considered to facilitate visualization with multiple colors and simple process. However, the response and recovery time is very long, such that rapid regular signals are unable to be detected, i.e., physiological signals, such as respiration. Here, the simple visualization of low strain ≈2%, with ultrasensitive crack‐based strain sensors with a hierarchical thermochromic layer is suggested. The sensor shows a gradient color change from red to white color in each strain, which is attributed to the hierarchical property, and the thermal response (recovery) time is dramatically minimized within 0.6 s from 45 to 37 °C, as the hierarchical membrane is inspired by termite mounds for efficient thermal management. The fast recovery property can be taken advantage of in medical fields, such as monitoring regular respiration, and the color changes can be delicately monitored with high accuracy by software on a mobile phone.     

Semiconductor-to-metallic phase transition of VO<Subscript>2</Subscript> by laser excitation

VO₂ thin films deposited on MgO and fused silica glass substrates were prepared by the pulsed laser deposition (PLD) technique, which shows phase transition (PT) from the monoclinic semiconductor phase to a metallic tetragonal rutile structure at temperatures over 68°C. The observed PT is reversible, showing a typical hysteresis. The PT can also be induced through optical pumping by laser excitation. In this case, it was found that the optically induced PT is ultrafast and passive, but not thermally initiated. In order to understand the PT mechanism, a study of transient holography using degenerate-four-wavemixing (DFWM) measurement was conducted. A Nd:YAG pulsed laser with pulse duration of 30 psec operating at 532 nm was employed as the coherent light source. This showed that the observed transient holography in VO₂ thin film is associated with the excited state dynamical process, which essentially causes the structural change, or so-called optically induced PT. The observed extremely large polarizability is believed to relate to the large offset in the potential well minimum between the ground state and excited state. Through an unidentified intermediate state, the transient lattice distortion triggered the structural change.     

Highly Stretchable and Wearable Thermotherapy Pad with Micropatterned Thermochromic Display Based on Ag Nanowire–Single‐Walled Carbon Nanotube Composite

Due to the increasing interest in wearable devices, flexible and stretchable film heaters have been widely studied, as alternatives to heaters with conventional rigid shapes. Herein, a highly stretchable film heater (SFH) based on the silver nanowire (Ag NW)–single‐walled carbon nanotube composite with a thermochromic display on a polydimethylsiloxane (PDMS) substrate is successfully fabricated. The SFH shows excellent electrical conductivity, high mechanical stretchability, and outstanding reliability, with no significant degradation after 10 000 stretching cycles under tensile strain. The SFH can be heated to the target temperature (≈60 °C) within 30 s at a low applied voltage. In addition, a thermochromic display is fabricated to help prevent the risk of low‐temperature burns. Red (R), green (G), and blue (B) thermochromic microparticles (TMPs) are synthesized using drop‐based microfluidic technology. The TMPs show RGB colors at room temperature but change to a white color above a certain temperature. The TMPs are arrayed into a PDMS stencil on the basis of their particle sizes using the rubbing technique. The micropatterned thermochromic display, which functions as a visual alarm, combined with the SFH can pave the way for the development of thermotherapy pads for next‐generation wearable devices in the medical field.     

3D Printing of a Thermo‐ and Solvatochromic Composite Material Based on a Cu(II)–Thymine Coordination Polymer with Moisture Sensing Capabilities

This work presents the fabrication of 3D‐printed composite objects based on copper(II) 1D coordination polymer ( CP1 ) decorated with thymine along its chains with potential utility as an environmental humidity sensor and as a water sensor in organic solvents. This new composite object has a remarkable sensitivity, ranging from 0.3% to 4% of water in organic solvents. The sensing capacity is related to the structural transformation due to the loss of water molecules that CP1 undergoes with temperature or by solvent molecules' competition, which induces significant change in color simultaneously. The CP1 and 3D printed materials are stable in air over 1 year and also at biological pHs (5–7), therefore suggesting potential applications as robust colorimetric sensors. These results open the door to generate a family of new 3D printed materials based on the integration of multifunctional coordination polymers with organic polymers.