Kind Of Functional Material Research Articles

Investigation of Bauxites of Various Deposits as Raw Materials for Special Alumina Cements

AbstractThe study deals with the bauxites of deposits of Turkey, Guinea and Guyana, which are used in alumina production, as raw materials for special alumina cements. The chemical and mineralogical compositions of bauxites of various deposits have been determined and bauxites quality relative to alumina cements obtaining has been analyzed. It is ascertained that: Turkish bauxite contains more than 9 wt. % SiO2; Guinean bauxite (deposit Kindia) has a reduced content of Al2O3 (below 45 wt. %); and Guyanese bauxite (deposit Aroaima) complies with requirements for alumina cement completely. Cements of different purity, based on the bauxites being studied, have been obtained and the possibility of using the low‐grade bauxites as raw materials for special alumina cements has been proved. Medium‐purity cements with high content of Al2O3 can be used for heat‐resistant concretes, and low‐purity cements with high content of Fe2O3 can be applied for a new kind of functional materials – sacrificial binders in passive safety systems (core‐catchers) of nuclear power plants.

Application of Covalent Organic Frameworks in Sulfur‐Based Battery Separators

Owing to the high storage capacity and multiple‐electron‐transfer chemistry of sulfur (S), sulfur‐based (S‐based) batteries with merits of high theoretical capacity/energy density, eco‐friendliness, and abundant supply hold much potential for energy‐storage/conversion devices. The capacity of S‐based batteries is much higher than that of traditional‐metal‐oxide cathode‐based lithium‐ion batteries, which is regarded as the highest capacity of solid‐state cathode materials at the current stage. As a vital component of S‐based batteries, separators play a profound role in resolving urgent issues (e.g., shuttling effect, volume expansion, poor conductivity, and metal dendrites, etc.). So far, some pioneering works have been reported in the exploration of separators for S‐based battery. On this basis, covalent organic frameworks (COFs), as a kind of functional materials, offer much possibility for S‐based battery separators due to their advantages such as high porosity, crystalline and well‐defined structures, designable struts, and tunable functions, etc. Herein, the reported works about COFs in S‐based battery separators including their structural characteristics, preparation methods, application forms, and battery properties are summarized. Moreover, also, a brief perspective is proposed on the challenges of COFs applied in S‐based battery separators, and new insights are provided for scientists in this field.

Cellulose nanocrystals enhanced viscoelasticity and temperature-resistance of rosin-based wormlike micelles: Inducing the formation of hydrogels

Wormlike micelles are attractive soft materials, their further combinations with nanoparticles providing a novel kind of functional materials in various applications. Using rosin as the starting materials, a biobased surfactant (CMPA2Na) was synthesized. Its structure was characterized using 1H NMR, FT-IR and MS. Viscoelastic wormlike micelles were prepared using CMPA2Na with cetyltrimethylammonium bromide (CTAB). Wormlike micellar system enchanced by cellulose nanocrystals (CNCs) was further constructed. The viscoelasticity, microstructure and interaction mechanism of the CMPA2Na/CTAB/CNCs system were comprhesively investigated using FT-IR, rheology and Cryo-TEM. The viscoelasticity monotonously increased with increasing addition amount of CNCs. And the viscoelastic solutions transformed into hydrogels as the addition amount of CNCs was larger than 0.5 %. Unexpectedly, a dramatical increase of 67 times in viscosity and 10 times in elasticity were obtained, surpassing the reported wormlike micelles combined with nanoparticles. In addition, the wormlike micelles enhanced with CNCs could maintain the excellent viscoelasticity under high temperature. The network of the wormlike micelles was prominently strengthened by the strong hydrogen bonds and electrostatic interactions between the wormlike micelles and CNCs. The study provided a biobased wormlike micelle modified by nanoparticles with high viscoelasticity and excellent temperature-resistance, facilitating the applications of biomass resources in the petroleum industry.

Preparation and aggregate structure of polyacrylonitrile and microcrystalline cellulose hygroscopic thermal composite fibers

AbstractHygroscopic thermal fibers are a kind of functional material that makes use of moisture to generate heat for fabrics. In this work, composite fibers of polyacrylonitrile (PAN) and microcrystalline cellulose (MCC) with various compositions were prepared using a solution spinning method. Besides the promotion of mechanical properties of PAN by addition of cellulose reported in previous research, this study focused on the hygroscopic thermal property of blends and spun fibers of PAN and cellulose. The content of MCC in the composite fibers has a significant effect on the hygroscopic thermal property. At a temperature of 17 °C and humidity of 90%, the maximum temperature increase of composite fibers could reach 4.9 °C. The composite fibers exhibited an obvious temperature response of on–off humidity circulation during testing. The breaking strength of the composite fibers was higher than 100 MPa. The influence of addition of cellulose on morphology, especially on the crystallinity and lateral size of PAN microfibrils, and the relationship between the morphology and hygroscopic thermal property were investigated by means of wide‐angle X‐ray diffraction and small‐angle X‐ray scattering in terms of experiment and theory. A smaller lateral size of microfibril led to a better hydroscopic thermal property. The composite fibers were expected to be used in temperature regulation clothing. © 2022 Society of Industrial Chemistry.

Ferroelectric and antiferroelectric distortions coupling of nitride perovskite LaWN3 under epitaxial strain using first-principles calculations

LaWN3, a novel nitride perovskite, have been synthesized and its piezoelectric properties have been investigated (Talley K. R. et al., Science, 374 (2021) 1488). However, the understanding of its ferroelectric properties under the external strain is still lacking. Here, the misfit-strain–dependent coupling between antiferrodistortions (AFD) and ferroelectric (FE) distortions has been studied by using a first-principle approach. It can be observed that AFD and FE distortions can work cooperatively with each other as the compressive strain increases, and the coupling energy between them is found to work in different ways under various strains. Our results show that the coupling tends to stabilize the ground structure when the compressive strain is smaller than −1.9%, it works oppositely when the compressive strain becomes larger than 1.9%. Our results can provide us with more hints about the influence of the epitaxial strains on the intrinsic coupling behavior in the perovskite ferroelectric compounds, which is very important for us to design and fabricate new kinds of functional materials.

Clusteroluminescence: A gauge of molecular interaction

Clusteroluminescence (CL) materials, as an emerging class of luminescent materials with unique photophysical properties, have received increasing attention owing to their great theoretical significance and potential for biological applications. Although much progress has been made in the design, synthesis and application of CL materials, there is still a big challenge in the emission mechanism. So far, through-space interaction has been proposed as the preliminary mechanism of the corresponding clusterization-triggered emission (CTE) effect, but a systematic theory is still needed. This review summarizes the current mechanistic understanding of CL materials including organic/inorganic small molecules, and polymers with/without isolated aromatic structures. In addition, some strategies to achieve high quantum yield, adjustable emission color, and persistent room temperature phosphorescence in CL materials are also summarized. At last, a perspective of the mechanism and application of CL materials are demonstrated, which inspire the researchers working on the development of new kinds of functional materials.

Synthesis and Characterization of a Liquid Crystal-Modified Polydimethylsiloxane Rubber with Mechanical Adaptability Based on Chain Extension in the Process of Crosslinking.

The mechanical adaptive material is a kind of functional material that can effectively dissipate energy and suppress the increase of its stress under continuous strain in a large deformation area, which are vital in artificial muscles, connection devices, soft artificial intelligence robots, and other areas. Scientists have been working to broaden the platform of the material’s mechanical adaptive platform and improve its mechanical strength by specific structure design. Based on it, we expect to introduce a mechanism of energy dissipation from the molecular chain scale to further improve mechanical adaptability. We developed a liquid crystal-modified polydimethylsiloxane rubber with mechanical adaptability based on chain extension in the process of crosslinking. Results showed that liquid crystal (0.7 mol %)-modified silicone rubber can obviously dissipate energy to achieve mechanical adaptive function, and the energy dissipation ratio of polydimethylsiloxane rubber (MQ), 4-propyl-4′-vinyl-1,1′-bi(cyclohexane)-modified polydimethylsiloxane rubber (3CCV-MQ), and 4-methoxyphenyl-4-(3-butenyloxy) benzoate-modified polydimethylsiloxane rubber (MBB-MQ) gradually decreases from 30 to 24%. Excessive thiol groups of liquid crystal-modified polydimethylsiloxane react with its vinyl group to achieve the chain extension, which significantly improves the mechanical strength from 2.74 to 5.83 MPa and elongation at break from 733 to 1096%. This research offers some new insights into improving the mechanical strength of silicone rubber and is of great significance for the application of the mechanical adaptive material.

Layered double hydroxides (LDHs) modified cement-based materials: A systematic review

AbstractIon erosion and carbonization in concrete are the key factors leading to the deterioration of durability. Layered double hydroxides (LDHs) are a kind of functional material with layered structures and ion exchange properties, which can capture a variety of harmful anions in concrete pore solutions. Therefore, LDHs exhibit great potential in improving the durability of concrete as new modified material. This article reviews the recent progress of LDHs. Based on the structural characteristics of LDHs, this work discusses the binding effect of LDHs on Cl−,SO42−{\text{SO}}_{4}^{2-}, andCO32−{\text{CO}}_{3}^{2-}in cement-based materials. We also analyze the influence of LDHs on the physical, mechanical, and hydration properties of cement-based materials and describe the modification mechanisms. Further, the improved durability of concrete and the corrosion inhibition of reinforcement by LDHs were summarized. Finally, we briefly point out some problems in the current research and development trends in the future on LDHs modified cement-based materials.

Hydrothermal synthesis of Cs0.3WO3 with uniform morphology and size via a dynamic balance of pH

Nanoscale tungsten bronze, MxWO3 (M: alkali elements or NH4+, 0 < x < 1), is a kind of functional material with a property of near-infrared absorption that is closely related to its morphology and size. A change of pH corresponds to a shift in composition and structure of tungstate polyanion, along with the resultant mutations in the morphology and size related with the properties of nano-MxWO3. Consequently, a reversible imine reaction was conducted to create a dynamic balance of pH system, in where uniform CsxWO3 was expected to synthesize in this study. The results show that an initial nucleation stage, morphology directing of CH3CH2COO−, and Oswald ripening work synergistically to evolve both morphology and size of Cs0.3WO3. Under a moderate pH level, chemical reaction inhibits growth of Cs0.3WO3 nuclei and gains uniform particles. Under a higher pH, Oswald ripening following the nucleating period ultimately dominates uniform Cs0.3WO3.

Facile Synthesis of Nitrogen Self-Doped Porous Carbon Derived from Cicada Shell via KOH Activation for Simultaneous Detection and Removal of Cu2+

Sensitive detection and efficient removal of heavy metal ions with high toxicity and mobility are of great importance for environmental monitoring and control. Although several kinds of functional materials have been reported for this purpose, their preparation processes are complicated. Herein, nitrogen self-doped activated porous biochar (NAC) was synthesized in a facile process via an activation–carbonization strategy from cicada shell rich in chitin, and subsequently employed as an effective functional material for the simultaneous determination and removal of Cu2+ from aqueous media. With its unique porous structure and abundant oxygen-containing functional groups, along with the presence of heteroatoms, NAC exhibits high sensitivity for the electrochemical sensing of Cu2+ in concentrations ranging from 0.001 to 1000 μg·L−1, with a low detection limit of 0.3 ng·L−1. Additionally, NAC presents an excellent removal efficiency of over 78%. The maximum adsorption capacity is estimated at 110.4 mg/g. These excellent performances demonstrate that NAC could serve as an efficient platform for the detection and removal of Cu2+ in real environmental areas.

Bioinspired 3D Printing of Functional Materials by Harnessing Enzyme‐Induced Biomineralization

AbstractNature builds structurally ordered and environmentally adaptive composite materials by harnessing biologically catalyzed mineralization under mild conditions. Despite recent advancements in engineering conventional materials with microorganisms through biomimetic mineralization, it remains difficult to produce mineralized composites that integrate the hierarchical structure and living attributes of their natural counterparts. Here, a kind of functional material is developed by integrating 3D printed hydrogel architectures with enzyme‐induced biomineralization. It is shown that the enzyme‐induced mineralization intensely transforms flexible and soft hydrogels (modulus of 125 kPa) to rigid (150 MPa) and highly mineralized hydrogel composites. Coupling with embedded 3D printing, sophisticated and mineralized free‐form architectures are fabricated in the absence of sacrificial inks, which were previously unattainable through conventional manufacturing strategies. Moreover, by exploiting multi‐material 3D printing to tailor the construct composition, exquisite control over the mineral distribution within the hydrogel constructs can be achieved, thus composite materials with tessellated architectures and unconventional mechanics could be obtained. The study provides a viable means to fabricate composite materials with high‐fidelity architectures and tailored mechanical properties, unlocking paths to the next generation of functional materials and structures by integrating 3D printing with biomineralization.

Spiro[cyclopentadithiophene-dioxolane]-Based D-A-D Type Organic Molecule for Both Crystallization Improvement and Band Adjustment of Perovskites.

To improve the crystallization and meanwhile adjust the band levels of perovskites, we design and synthesize a novel organic molecule, 4,4'-(spiro[cyclopenta[1,2-b:5,4-b']dithiophene-4,2'-[1,3]dioxolane]-2,6-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) (TM1), to dissolve in an antisolvent for the antisolvent engineering of perovskite solar cells (PSCs). The coordination interactions between TM1 and Pb2+ ions in perovskites and the hydrogen bonds between the O atoms in the methoxy of TM1 and the MA+ in perovskites are characterized with X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Owing to these interactions, TM1 can improve the perovskite crystallization, which reduces the trap density, enhances the interfacial hole extraction, and retards charge recombination as well, boosting short-circuit photocurrent notably. TM1 also shifts the valence band of perovskites upward by 0.17 eV, which aligns better with the highest occupied molecular orbital of hole transport materials and thus increases the open-circuit photovoltage significantly. As a result, the power conversion efficiency is enhanced from 17.22 to 20.21% by TM1. Moreover, TM1 can also improve device stability significantly. These findings demonstrate that TM1 is a kind of functional material as an additive in an antisolvent for both crystallization improvement and energy level adjustment of perovskites toward highly efficient and stable PSCs.

Performance Optimization for PbTe-Based Thermoelectric Materials

Thermoelectric material is a kind of functional material that uses the movement of carriers inside a solid to realize the direct mutual conversion of heat and electric energy. It provides a safe, reliable, pollution-free, noise-free, all-solid-state power generation and cooling method and has a wide range of application prospects. Among them, the characteristics of low valence band degeneracy, low effective quality of conduction band, strong phonon non-harmonicity, simple crystal structure and adjustable microstructure have made PbTe-based materials the focus of research in the thermoelectric field. In this review, two latest strategies to improve the thermoelectric properties of PbTe-based materials are discussed, and the challenges for the further development of PbTe-based thermoelectric materials and the prospects for the future are also outlined.

Investigation of Physical Properties of Fe(III) Containing Metal-Organic Polymers

In this work, we studied the properties of a specially synthesized organometallic coordination polymer - a porous coordination polymer with biocompatible structural elements based on oxoclusters of iron muconate (III). The samples were investigated by scanning electron microscopy, thermogravimetric analysis combined with differential scanning calorimetry, and the study of low-temperature nitrogen adsorption of a sample obtained by a modified solvothermal technique. It is shown that most of the pores of the sample have an average radius of 18,8 Å ~ 1,88 nm. Also, as a result of the study, it is necessary to conclude that the synthesized material has a developed surface area - it is 512,1 m2/g and the pore volume is ~ 0,48 cm3/g. It should be concluded that such materials are promising as components for a new generation of various kinds of functional materials with improved or unique characteristics. It is obvious that further research in this area is important from both fundamental and applied points of view.

Printable Smart Materials and Devices: Strategies and Applications.

Smart materials are a kind of functional materials which can sense and response to environmental conditions or stimuli from optical, electrical, magnetic mechanical, thermal, and chemical signals, etc. Patterning of smart materials is the key to achieving large-scale arrays of functional devices. Over the last decades, printing methods including inkjet printing, template-assisted printing, and 3D printing are extensively investigated and utilized in fabricating intelligent micro/nano devices, as printing strategies allow for constructing multidimensional and multimaterial architectures. Great strides in printable smart materials are opening new possibilities for functional devices to better serve human beings, such as wearable sensors, integrated optoelectronics, artificial neurons, and so on. However, there are still many challenges and drawbacks that need to be overcome in order to achieve the controllable modulation between smart materials and device performance. In this review, we give an overview on printable smart materials, printing strategies, and applications of printed functional devices. In addition, the advantages in actual practices of printing smart materials-based devices are discussed, and the current limitations and future opportunities are proposed. This review aims to summarize the recent progress and provide reference for novel smart materials and printing strategies as well as applications of intelligent devices.

Development of Flowerlike Ce1-XZrxO2-δ-Dispersed Paper-Structured Catalyst for Direct-Biogas SOFC

Performance of direct internal reforming (DIR)-solid oxide fuel cell (SOFC) can be improved by the application of the paper-structured catalyst (PSC) on the anode material. In the ceramic fiber network of the PSC, any kinds of functional materials can be easily dispersed during paper-making process.The solid solution based on the equimolar mixture of ceria and zirconia (Ce0.5Zr0.5O2-δ), hereafter called CZ, is a promising oxide support of the Ni metal catalyst due to its high specific surface area and high oxygen storage capacity (OSC). By employing the two-step hydrothermal process developed in this study, we could successfully prepare the CZ with flowerlike geometry, which can prevent Ni from sintering under reducing atmosphere.Ni-loaded PSCs with and without the dispersion of CZ, Ni/CZ-PSC and Ni-PSC, respectively, were prepared. Structures of the PSCs were characterized by X-ray diffractometry (XRD), BET specific surface area measurement, field emission scanning electron microscopy (FESEM), inductively coupled plasma spectrometry (ICP) and thermogravimetric analysis (TG). Catalytic performances of these PSCs for the dry reforming of methane (DRM) in the feed of the equimolar mixture of CH4 and CO2 were evaluated by an automatic gas chromatograph (GC) with the posttest analysis by FESEM observation, temperature-programmed oxidation (TPO) and TG to estimate carbon deposition.In the durability (160 h) tests of the prepared-PSCs for DRM at 750oC under gas hourly space velocity (GHSV) of 2300 h-1 revealed that, for both cases with and without CZ dispersion, methane conversions were stable with the degradation rates (estimated after 10 h) of 13.7 and 21.8% 1000 h-1, respectively. TG measurements after the 160 h tests under oxidizing atmosphere in the range from 300 to 750oC revealed that the weights of the deposited carbon were 0.2 and 3.4 folds of those of PSCs for Ni/CZ-PSC and Ni-PSC, respectively. In the case without CZ dispersion (Ni-PSC), after the TG measurement to burn out the deposited carbon, Ni agglomeration and its detachment from the ceramic fiber could be clearly observed. On the other hand, for the Ni/CZ-PSC, these phenomena were considerably suppressed thanks to the flowerlike morphology for better dispersion of Ni metal particles and higher OSC of CZ solid solution to consume deposited carbon by the lattice oxygen.The developed PSCs will be applied on the anode of electrolyte-supported cell to demonstrate the stable operation of DIR-SOFC fueled by biogas (direct-biogas SOFC).

Ice-resistant surface with three dimensional spherical halloysite aerogel: Construction and anti-icing mechanism

A novel 3D microsphere fabricated with halloysite nanotubes was reported in our previous work. The hollow tubular structure in nano-scale of halloysite and the hollow structure in micro-scale of microsphere have attracted our attention. In this paper, phase change materials (methylmyristate and n-dodecane) were loaded in the spaces for the construction of anti-icing surface, and the related behavior and mechanism were investigation. The anti-icing performance of slippery liquid-infused porous surfaces (SLIPSs) were characterized by ice adhesion strength, freezing temperature and ice nucleation rate. The results showed that the phase change materials loaded in anti-icing coating eliminated the possibility of water vapor condensation in porous structure, greatly reduced the probability of nucleation on a concave surface, thus showed better anti-icing effect. Phase change materials play an important role in supercooling, effectively increasing the substrate temperature by 5.4 °C. Phase change anti-icing coating is a kind of functional material with great development potential.

Five functional Cd/Zn-based MOFs constructed from V-shaped tricarboxylate ligand for rapidly selective adsorption and efficiently photocatalytic degradation of hazardous aromatic dyes

In this work, five novel Cd/Zn-based MOFs with different topological framework, namely {[Cd(bimb)(Hbipa)]·H2O}n(1), {[Cd3(dimb)3(bipa)2(H2O)2]·2H2O}n(2), [Cd(bimd)(Hbipa)(H2O)]n(3), {[Zn(bipd)(Hbipa)]·H2O}n(4) and [Zn(bimb)(Hbipa)]n(5) had been synthesized and characterized. Worth noting, Complex 1 and 2 had effective separation behaviors towards MO and MBE dyes respectively, which could reach the adsorption equilibrium within a quite short time even if there existed another kind of dye in the system. Meanwhile, Complex 3–5 showed great performance in CR adsorption. Additionally, Complex 3–5 also showed excellent photocatalytic degradation capabilities toward MB and MV dyes under UV irradiation. According to the study, these five metal-organic frameworks can be used as a kind of functional materials in the adsorption and photocatalytic degradation of organic dyes in wastewater.

Thermal and field-rate dependence of multi-step magnetization switching of synthetic antiferromagnetic multilayers

Synthetic antiferromagnetic (SAF) multilayers are a kind of functional materials with great potential for spintronic devices. Many excellent properties of SAF multilayers have been widely reported in previous works. Here, we experimentally found that the magnetization switching steps n of [Pt/Co]2/Ru/[Co/Pt]4 SAF multilayers with perpendicular magnetic anisotropy are highly dependent on the temperature and magnetic field sweeping rate by magneto-optic Kerr effect and anomalous Hall resistance measurement. It is found that the contribution of the upper and lower layers of the SAF multilayers to the anomalous Hall coefficients is different. The switching steps n change from 2 to 3 by reducing the thickness of the non-magnetic spacer, decreasing the sweeping rate of the magnetic field, and increasing the temperature of the measuring environment. Our findings could provide a method to achieve multi-step magnetization switching for functional spintronic devices.

Hybrid Perovskites, Metal-Organic Frameworks, and Beyond: Unconventional Degrees of Freedom in Molecular Frameworks.

ConspectusThe structural degrees of freedom of a solid material are the various distortions most straightforwardly activated by external stimuli such as temperature, pressure, or adsorption. One of the most successful design strategies in materials chemistry involves controlling these individual distortions to produce useful collective functional responses. In a ferroelectric such as lead titanate, for example, the key degree of freedom involves asymmetric displacements of Pb2+ and Ti4+ cations; it is by coupling these together that the system as a whole interacts with external electric fields. Collective rotations of the polyhedral units in oxide ceramics are another commonly exploited distortion, driving anomalous behavior such as negative thermal expansion—the counterintuitive phenomenon of volume contraction on heating. An exciting development in the field has been to take advantage of the interplay between different distortion types: generating polarization by combining two different polyhedral rotations, for example. In this way, degrees of freedom act as geometric “elements” that can themselves be combined to engineer materials with new and interesting properties. Just as the discovery of new chemical elements quite obviously diversified chemical space, we might expect that identifying new and different types of structural degrees of freedom to be an important strategy for developing new kinds of functional materials. In this context, the broad family of molecular frameworks is emerging as an extraordinarily fertile source of new and unanticipated distortion types, the vast majority of which have no parallel in the established families of conventional solid-state chemistry.Framework materials are solids whose structures are assembled from two fundamental components: nodes and linkers. Quite simply, linkers join the nodes together to form scaffolding-like networks that extend from the atomic to the macroscopic scale. These structures usually contain cavities, which can also accommodate additional ions for charge balance. In the well-established systems—such as lead titanate—node, linker, and extra-framework ions are all individual atoms (Ti, O, and Pb, respectively). But in molecular frameworks, at least one of these components is a molecule.In this Account, we survey the unconventional degrees of freedom introduced through the simple act of replacing atoms by molecules. Our motivation is to understand the role these new distortions play (or might be expected to play) in different materials properties. The various degrees of freedom themselves—unconventional rotational, translational, orientational, and conformational states—are summarized and described in the context of relevant experimental examples. The much-improved prospect for generating emergent functionalities by combining these new distortion types is then discussed. We highlight a number of directions for future research—including the design and application of hierarchically structured phases of matter intermediate to solids and liquid crystals—which serve to highlight the extraordinary possibilities for this nascent field.