Organic—inorganic hybrid materials

Composite materials formed by the combination of inorganic materials and organic polymers are attractive for the purpose of creating high-performance or high-functional polymeric materials. Of particular interest is the molecular level combination of two different components that may lead to new composite materials, termed ‘organic—inorganic hybrid materials’. Recently, new methods for preparing these hybrid materials have been reported. Some improvements of the properties or modifications of these materials have also been explored from the viewpoint of industrial applications.     

Beyond solvents and electrolytes: Ionic liquids-based advanced functional materials

Instead of being seen as alternative solvents and electrolytes for organic reactions, catalysis, separation, electrochemistry, and so on, ionic liquids (ILs) consisting of discrete cations and anions have recently emerged as versatile building blocks for advanced functional materials. A number of functional ILs and IL-containing composite materials have been realized by either chemical modification (covalent functionalization or ion-exchange metathesis) or physical integration of ILs and traditional materials. The unique structure and behavior of ILs as a platform not only provides additional opportunities to adjust the physicochemical properties of these ionic materials for task-specific applications, but also offers other attractive features such as intrinsic ionic conductivity and high thermal, chemical, and electrochemical stability. These soft materials combine the favorable features of ILs and the original chemistries of the functional groups or materials; some even possess unexpected functions resulting from synergetic interaction between these two components. Materialization of ILs is truly a novel, promising research direction for both IL chemistry and materials science. In this article, we review recent advances in IL-based functional materials, focusing on smart and sensitive materials, optical materials, energetic materials, and IL/carbon hybrid materials.     

SMA混杂复合材料单层的被动阻尼

由形状记忆合金纤维、普通纤维、基体构成的混杂复合材料是一类用途广泛的智能材料结构系统。阻尼性能研究是结构被动振动控制的一项重要研究内容。本文采用混杂复合材料阻尼预测的细观力学理论计算SMA纤维混杂复合材料单层的阻尼特性。首先计算包含普通纤维和基体材料的复合材料介质的阻尼性能,其次计算由横观各向同性介质和SMA纤维构成的混杂材料的阻尼性能。通过计算实例分析SMA纤维混杂复合材料单层的正轴阻尼特性及其偏轴阻尼的特性随SMA纤维体积含量、纤维铺设角等参数改变的规律。     

Fluorescence in nanobiotechnology: sophisticated fluorophores for novel applications

Nanobiotechnology is one of the fastest growing and broadest-ranged interdisciplinary subfields of the nanosciences. Countless hybrid bio-inorganic composites are currently being pursued for various uses, including sensors for medical and diagnostic applications, light- and energy-harvesting devices, along with multifunctional architectures for electronics and advanced drug-delivery. Although many disparate biological and nanoscale materials will ultimately be utilized as the functional building blocks to create these devices, a common element found among a large proportion is that they exert or interact with light. Clearly continuing development will rely heavily on incorporating many different types of fluorophores into these composite materials. This review covers the growing utility of different classes of fluorophores in nanobiotechnology, from both a photophysical and a chemical perspective. For each major structural or functional class of fluorescent probe, several representative applications are provided, and the necessary technological background for acquiring the desired nano-bioanalytical information are presented.     

Photocurrent generation in a CdS nanocrystals/poly[2-methoxy-5-(2′-ethyl-exyloxy)phenylene vinylene] electrochemical cell

In this paper the photoelectrochemical processes occurring in composites formed of organic-capped CdS nanocrystals and low molecular weight poly[2-methoxy-5-(2′-ethyl-exyloxy)phenylene vinylene] conjugated polymer were investigated. High quality colloidal CdS nanoparticles were synthesized by means of thermal decomposition of suitable precursors in non coordinating solvents, using oleic acid as surface capping agent.

The absorption and emission properties of the prepared heterojunctions were studied both in solutions and in composite films.

The dispersed hybrids were also investigated as photoactive materials, focusing on the photoinduced charge transfer and recombination processes at the interface between the two components. The composites have shown a fundamental role in photoelectrochemical applications due to the presence of a great number of interfaces able to enhance the charge transfer between mixture components.

Blend solutions prepared with octylamine capped CdS nanocrystals showed an improvement of the photoconductivity with respect to hybrids containing longer oleate surfactants.     

具有离子识别能力的新型有机光致变色材料

有机光致变色材料是在特定波长的光照射下,生成同分异构体,同时在另一波长光照射或加热的条件下,该异构体可发生逆反应并伴随着明显的光物理化学性能变化的有机材料。将超分子化学的分子识别和光致变色相结合,可以实现客体操控材料的光致变色性能。基于其特殊的光切换性质,人们已开发出多种多响应、多功能材料并将其广泛应用于分子开关、分子逻辑门、分子机器、化学传感、生物成像等诸多领域。其中,具有离子识别能力的光致变色化合物因其易操作和廉价而成为最理想的该类材料之一。该类化合物不仅光致变色性质可以被离子所调节,同时也可以作为特异检测离子的新型光控探针。着重介绍近几年具有离子识别能力的光致变色材料的研究进展。最后结合现阶段的研究情况,对其前景和应用进行了展望。     

Versatile and Switchable Responsive Properties of a Lanthanide‐Viologen Metal–Organic Framework

Metal–organic frameworks (MOFs) provide intriguing platforms for the design of responsive materials. It is challenging to mobilize as many components as possible of a MOF to collaboratively accomplish multiple responsive properties. Here, reversible photochromism, piezochromism, hydrochromism, ionochromism, and luminescence modulation of an ionic Eu(III) MOF is reported furnished by cationic electron‐deficient viologen units and exchangeable guest anions. Mechanistically, the extraordinarily versatile responsive properties are owed to electron transfer (ET), charge transfer (CT), and energy transfer, involving viologen as electron acceptor, anion as electron donor, luminescing Eu(III) as energy donor, and anion‐viologen CT complex or ET‐generated radical as energy acceptor (luminescence quencher). Moreover, guest anions and waters provide flexible handles to control the ET‐based responsive properties. Water release/reuptake or exchange with organic solvents can switch on/off the response to light, while reversible anion exchange can disenable or awaken the responses to pressure, light, and water release/reuptake. The impacts of water and anions on ET are justified by the high polarity and hydrogen‐bonding capability of water, the different electron donor strength of anions, and the strong I^?‐viologen CT interactions. The rich responsive behaviors have great implications for applications such as pressure sensors, iodide detection, and chemical logic gates.     

有机硅改性丙烯酸酯聚合物研究进展

从共混和共聚两个方面综述了有机硅改性丙烯酸酯聚合物的制备方法 ,指出乳液聚合法是目前制备该类材料最重要的手段。介绍了国际上几个大公司在该领域研究开发方面的最新进展 ,简要说明了该类材料在塑料、橡胶、涂料和粘合剂等方面的应用。     

3D‐Printable Photochromic Molecular Materials for Reversible Information Storage

The formulation of advanced molecular materials with bespoke polymeric ionic‐liquid matrices that stabilize and solubilize hybrid organic–inorganic polyoxometalates and allow their processing by additive manufacturing, is effectively demonstrated. The unique photo and redox properties of nanostructured polyoxometalates are translated across the scales (from molecular design to functional materials) to yield macroscopic functional devices with reversible photochromism. These properties open a range of potential applications including reversible information storage based on controlled topological and temporal reduction/oxidation of pre‐formed printed devices. This approach pushes the boundaries of 3D printing to the molecular limits, allowing the freedom of design enabled by 3D printing to be coupled with the molecular tuneability of polymerizable ionic liquids and the photoactivity and orbital engineering possible with hybrid polyoxometalates.     

Impact properties of glass/plant fibre hybrid laminates

The use of plants fibre reinforced composites has continuously increased during recent years. Their low density, higher environmental friendliness, and reduced cost proved particularly attractive for low-tech applications e.g., in building, automotive and leisure time industry. However, a major limitation to the use of these materials in structural components is unsatisfactory impact performance. An intermediate approach, the production of glass/plant fibre hybrid laminates, has also been explored, trying to obtain materials with sufficient impact properties, whilst retaining a reduced cost and a substantial environmental gain. A survey is given on some aspects, crucial for the use of glass/plant fibre hybrid laminates in structural components: performance of hybrids when subjected to impact testing; the effect of laminate configuration, manufacturing procedure and fibre treatment on impact properties of the composite. Finally, indications are provided for a suitable selection of plant fibres with minimal extraction damage and sufficient toughness, for introduction in an impact-resistant glass/plant fibre hybrid laminate.     

Shaping Colloidal Rutile into Thermally Stable and Porous Mesoscopic Titania Balls

High crystallinity and controlled porosity are advantageous for many applications such as energy conversion and power generation. Despite many efforts in the last decades, the direct synthesis of organic–inorganic composite materials with crystalline transition metal oxides is still a major challenge. In general, molecules serve as inorganic precursors and heat treatment is required to convert as‐synthesized amorphous composites to stable crystalline materials. Herein, an alternative approach to the direct synthesis of crystalline polymer–metal oxide composites by using a spherical polyelectrolyte brush as the template system is presented. Pre‐synthesized electrostatically stabilized rutile nanocrystals that carry a positive surface charge are used as inorganic precursors. In this approach, the strong Coulomb interactions between anionic polyelectrolyte brush chains and cationic crystalline rutile colloids, whose surfaces are not capped and therefore reactive, are the key factors for the organic–inorganic crystalline composite formation. Stepwise calcination first under argon and followed with a second calcination in air lead to the complete removal of the polymer template without collapse and porous rutile balls are obtained. The results suggest that any colloids that carry a surface charge might serve as inorganic precursors when charged templates are used. It is expected that this hierarchical route for structuring oxides at the mesoscale is generally applicable.     

Microstructural investigation on antifriction characteristics of self-lubricating copper hybrid composite

Abstract

Owing to good antifriction properties and high wear resistance, copper hybrid composites reinforced with hard ceramic particles and solid lubricant components are regarded as promising materials for applications in sliding electrical contacts. The present work investigates the antifriction mechanism of a (SiC+Gr)/Cu composite from a microstructural viewpoint, so as to assist the development and application of this material. A graphite rich tribolayer formed on the worn surface was responsible for good tribological properties of the composites. Testing results showed that nanoparticles of graphite were involved in a mechanically mixing process by adhering to both the other wear debris and the two contacting surfaces, thereby developing a solid lubricant tribolayer. The nanographite to nanographite contacting mode, formed between the composite and the counterface, significantly improved wear resistance and friction stability. The forming and failure process of the graphite rich tribolayer was studied. A mechanism has been developed based on the experimental results.     

Ceramic composite components with gradient porosity by powder injection moulding

Various components used in the industries may benefit from having layered structures with gradient porosity in each layer. In this paper, bi-layer composite components with gradient porosity made by Powder Injection Moulding (PIM) have been investigated. The ceramic spinel materials of AR7845 having coarse particle size and AR7820 having fine particle size were used. It shows that AR7820 and AR7845 powders have different sintering behaviour with the fine powder having faster shrinkage as compared to coarse powder. Curling or bending is found in the bi-layer rectangular composite component fabricated from these two powders. This is due to induced stress caused mainly by strain rate mismatch of the two materials during sintering. The degree of curling is also related to thickness ratio of two materials in each layer. Composite components can be designed into cylindrical shape so as to avoid curling as observed in rectangular composite components. No interfacial debonding and part cracking are observed in both rectangular and cylindrical composite components. The microstructure shows that continuously straight joining lines along the interfaces are formed in these composite components.     

Making the most of your electrons: Challenges and opportunities in characterizing hybrid interfaces with STEM

Inspired by the unique architectures composed of hard and soft materials in natural and biological systems, synthetic hybrid structures and associated hard-soft interfaces have recently evoked significant interest. Soft matter is typically dominated by structural fluctuations even at room temperature, while hard matter is governed by rigid mechanical behavior. This dichotomy offers considerable opportunities to leverage the disparate properties offered by these components across a wide spectrum spanning from basic science to engineering insights with significant technological overtones. Such hybrid structures, which include polymer nanocomposites, DNA functionalized nanoparticle superlattices, and metal organic frameworks to name a few, have delivered promising insights into the technologically relevant applications such as catalysis, environmental remediation, optoelectronics, and medicine.The interfacial structure between the hard and soft phases demonstrates features across a variety of length scales and often strongly influence the functionality of hybrid systems. While scanning/transmission electron microscopy (S/TEM) has proven to be a valuable tool for acquiring intricate molecular and nanoscale details of these interfaces, the unusual nature of hybrid composites presents a suite of challenges that make assessing or establishing structure–property relationships especially difficult. There are additional considerations at all stages of sample analysis from preparing electron-transparent samples to obtaining sufficient contrast to resolve the interface between dissimilar materials given the dose sensitivity of soft materials.We discuss each of these challenges and supplement a review of recent developments in the field with additional experimental investigations and simulations to present solutions for attaining a nano or molecular-level understanding of these interfaces. These solutions present a host of opportunities for investigating the role interfaces play in this unique class of functional materials.     

稀土配合物杂化材料的制备与性能研究

综述了近年来稀土配合物杂化材料的制备和性能．按基质的不同，稀土配合物杂化材料可分为稀土配合物，无机杂化材料，稀土配合物，有机杂化材料以及稀土配合物，混合基质杂化材料。本文对以上3种杂化材料的优缺点进行了较为详细的分析，并提出一步法制备稀土配合物杂化材料，以简化合戍步骤，提高稀土配合物在基质分布的均匀性，因而该方法有望戍为制备稀土配合物杂化材料的一个重要发展方向。     

The Effect of Materials Architecture in TiO2/MOF Composites on CO2 Photoreduction and Charge Transfer

CO₂ photoreduction to C₁/C₁₊ energized molecules is a key reaction of solar fuel technologies. Building heterojunctions can enhance photocatalysts performance, by facilitating charge transfer between two heterojunction phases. The material parameters that control this charge transfer remain unclear. Here, it is hypothesized that governing factors for CO₂ photoreduction in gas phase are: i) a large porosity to accumulate CO₂ molecules close to catalytic sites and ii) a high number of “points of contact” between the heterojunction components to enhance charge transfer. The former requirement can be met by using porous materials; the latter requirement by controlling the morphology of the heterojunction components. Hence, composites of titanium oxide or titanate and metal–organic framework (MOF), a highly porous material, are built. TiO₂ or titanate nanofibers are synthesized and MOF particles are grown on the fibers. All composites produce CO under UV–vis light, using H₂ as reducing agent. They are more active than their component materials, e.g., ≈9 times more active than titanate. The controlled composites morphology is confirmed and transient absorption spectroscopy highlights charge transfer between the composite components. It is demonstrated that electrons transfer from TiO₂ into the MOF, and holes from the MOF into TiO₂, as the MOF induces band bending in TiO₂.     

Polymers in concrete: a vision for the 21st century

Polymers in concrete have received considerable attention over the past 25 years. Polymer-impregnated concrete (PIC) was the first concrete polymer composite to receive widespread publicity. PIC has excellent strength and durability properties, but it has few commercial applications. Polymer concrete (PC) became well known in the 1970s and is used for repair, thin overlays for floors and bridges, and for precast components. Polymer-modified concrete (PMC) has been used primarily for repair and overlays. Several limitations have slowed the use of concrete polymer materials. However, there are many current and future uses for these materials that will effectively use their unique properties. Improved, automated repair methods, improvements in materials, replacements for metals, structural applications, and architectural components will prove to be popular uses of concrete-polymer materials.     

Microwave detection and depth determination of disbonds in low-permittivity and low-loss thick sandwich composites

Nondestructive evaluation (NDE) of disbonded low-permittivity and low-loss dielectric multilayered composite media is of considerable interest in many applications. The ability of microwaves to penetrate inside dielectric materials makes microwave NDE techniques very suitable for interrogating structures made of multilayered dielectric composites. Additionally, the sensitivity of microwaves to the presence of dissimilar layers in such materials allows for accurate detection of a disbonded layer. In a multilayered composite, a disbond may occur between any two (or more) layers. The potential of utilizing microwave NDE techniques for the detection and depth estimation of disbonds in a thick sandwich composite is investigated. This study utilizes a theoretical model developed for investigating the interaction of microwave radiation from an open-ended rectangular waveguide sensor with ann-layer dielectric composite medium. The influence of the standoff distance between the sensor and the medium and the operating frequency on the sensitivity of disbond detection and depth estimation is studied to obtain an optimum set of parameters for enhanced detection sensitivity. Results of the theoretical study are presented with a discussion on the optimization process for a thick sandwich composite composed of 13 dielectric layers.     

New Design Concept for a Lifting Platform Made of Composite Material

Elevating work platforms are hoists equipment that are increasingly used in many applications, like in the construction industry and in the maintenance field. The maintenance of the hub of the wind turbines, for example, can be done through the use of a working platform; these structures have to reach great heights and obviously they have to satisfy the constraints induced by the highway standards, like the maximum axle load and the maximum overall dimensions. To satisfy these requests the material of the structures changed from the classic structural steel (S235 JR, S275 JR or S355JR) to high strength steel (S700 to S1100 or more), characterized by a significantly higher specific resistance. The idea of this paper is to use a composite material for the construction of the arms of an elevating platform in order to reduce the global weight of the machine. The analyses on the new kind of platform show the technical possibility to change the material of the arms with composite materials and this produces a significant reduction of the weight of the machine components, about 50 %. Being a feasibility study, still remain open some problems such as the mechanical behavior of the used composite materials (fatigue, environment effects, etc.).     

Recent Advances of Using Hybrid Nanocarriers in Remotely Controlled Therapeutic Delivery

The development of hybrid biomaterials has been attracting great attention in the design of materials for biomedicine. The nanosized level of inorganic and organic or even bioactive components can be combined into a single material by this approach, which has created entirely new advanced compositions with truly unique properties for drug delivery. The recent advances in using hybrid nanovehicles as remotely controlled therapeutic delivery carriers are summarized with respect to different nanostructures, including hybrid host–guest nanoconjugates, micelles, nanogels, core–shell nanoparticles, liposomes, mesoporous silica, and hollow nanoconstructions. In addition, the controlled release of guest molecules from these hybrid nanovehicles in response to various remote stimuli such as alternating magnetic field, near infrared, or ultrasound triggers is further summarized to introduce the different mechanisms of remotely triggered release behavior. Through proper chemical functionalization, the hybrid nanovehicle system can be further endowed with many new properties toward specific biomedical applications.