Abrasion resistant inorganic/organic coating materials prepared by the sol-gel method

Novel abrasion resistant coating materials prepared by the sol-gel method have been developed and applied on the polymeric substrates bisphenol-A polycarbonate and diallyl diglycol carbonate resin (CR-39). These coatings are inorganic/organic hybrid network materials synthesized from 3-isocyanatopropyltriethoxysilane functionalized organics and metal alkoxide. The organic components are 3,3-iminobispropylamine (IMPA), resorcinol (RSOL), diethylenetriamine (DETA), poly(ethyleneimine) (PEI), glycerol and a series of diols. The metal alkoxides are tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS). These materials are spin coated onto bisphenol-A polycarbonate and CR-39 sheets and thermally cured to obtain a transparent coating of a few microns in thickness. Following the curing, the abrasion resistance is measured and compared with an uncoated control. It was found that the abrasion resistance of inorganic/organic hybrid coatings in the neat form or containing metal alkoxide can be very effective to improve the abrasion resistance of polymeric substrates. The adhesion tests show that the adhesion between coating and substrate can be greatly improved by treating the polymeric substrate surface with a primer solution of isopropanol containing 3-aminopropyltriethoxysilane (3-APS). The interaction between 3-APS and the polycarbonate surface was investigated by a molecular dynamics simulation. The results strongly suggest that the hydrogen bonding between the amino group of the 3-APS and ester group in the polycarbonate backbone are sufficiently strong to influence the orientation of the primer molecules. The abrasion resistance of these new coating systems is discussed in light of the structure of the organic components. All of these results show that these coating materials have excellent abrasion resistance and have potential applications as coating materials for lenses and other polymeric products.     

化学键组装稀土/无机/有机聚合物杂化光功能材料的最新研究进展

本文针对近五年来光功能稀土/无机/有机聚合物杂化材料的最新进展进行了评述,其重点着眼于高分子化合物作为构筑基元的发光稀土杂化材料体系的化学键组装.内容主要涉及稀土有机高分子杂化材料、配位键构筑的稀土/无机/有机高分子杂化材料、共价键构筑的稀土/无机/有机高分子杂化材料、自由基聚合构筑的稀土/无机/有机高分子杂化材料几个重要方面.主要结合我们自己的近期研究工作,通过系统总结来展现该领域的研究现状并提出未来展望.     

Morphology stability of lamellar composite magnetic materials

The aim of this study was to investigate the role of the copolymers and nanoparticles during elaboration of new stable composite materials. We have shown that the interactions between the mesophases that form the copolymers and nanoscopic particles can lead to highly organized hybrid materials. The morphology of such composites depends on the characteristics of both copolymers and nanoparticles. On one hand, diblock copolymers must form a strong segregation limit and have a higher mass. On the other hand, nanoparticles must show strong affinity for one of the two polymeric species of the copolymer and be as small as possible. In this case, a composite organic-inorganic material can be obtained with a periodic distribution of the particles in the polymeric matrix. This study can be applied to other copolymer-nanoparticle mixtures and used to design advanced composite architectures.     

All‐Nanoporous Hybrid Membranes: Redefining Upper Limits on Molecular Separation Properties

New membrane‐based molecular separation processes are an essential part of the strategy for sustainable chemical production. A large literature on “hybrid” or “mixed‐matrix” membranes exists, in which nanoparticles of a higher‐performance porous material are dispersed in a polymeric matrix to boost performance. We demonstrate that the hybrid membrane concept can be redefined to achieve much higher performance if the membrane matrix and the dispersed phase are both nanoporous crystalline materials, with no polymeric phase. As the first example of such a system, we find that surface‐treated nanoparticles of the zeolite MFI can be incorporated in situ during growth of a polycrystalline membrane of the MOF ZIF‐8. The resulting all‐nanoporous hybrid membrane shows propylene/propane separation characteristics that exceed known upper‐bound performance limits defined for polymers, nanoporous materials, and polymer‐based hybrid membranes. This serves as a starting point for a new generation of chemical separation membranes containing interconnected nanoporous crystalline phases.     

Spatial arrangement of metal nanoparticles supported by porous polymer substrates studied by transmission electron microtomography

Fine metal particles (nanoparticles) stabilized on porous (polymeric) substrates can be considered as a model system of a high-performance catalyst. In the present study, the substrate was made using the periodic microphase-separated structure of a block copolymer as the template, and the Pd nanoparticles were formed inside the porous material by reduction of the Pd2+ ions with 1-propanol as the reductant. The three-dimensional morphology of such a polymer-Pd hybrid material was studied by transmission electron microtomography. The characteristic structural parameters of the hybrid, e.g., the penetration of the Pd nanoparticles into the polymer substrate, number density of the Pd nanoparticles, and size distribution of the Pd nanoparticles, were measured for the first time.     

Glass Strengthening Using Ormosil Polymeric Coatings

Ormosil polymeric coatings comprised of an epoxy resin, an amine hardener and a silane have been applied to glass samples containing large, controlled defects introduced by Vicker's indentation. The coatings can completely overcome these controlled defects. The strengthening effect is due to penetration of the defects by the coatings. Therefore, the reactions between the components of these hybrid materials and the glass substrate are of crucial importance in determining both the degree of strengthening that is achieved and the hydrolytic durability of the coatings. The maximum strengthening effect of these ormosil polymeric coatings is obtained when 25% of the active hydrogen is supplied by the silane (7.2 wt% silane). More than 7.2 wt% silane reduces coating cohesion and thus gives a reduced strengthening effect. Studies on silane primed systems show that both good coating adhesion and cohesion are required for significant strengthening. Coatings with good adhesion also have greater hydrolytic durability.     

Adhesion of Sol-Gel-Derived Organic-Inorganic Hybrid Coatings on Polyester

Inorganic coatings, including metal-oxide coatings, provide polymer surfaces with excellent abrasion and wear resistance, and protection against environmental degradation. However, one drawback associated with the incorporation of such ceramic coatings to polymeric materials is the adhesion characteristic at the ceramic-polymer interface. In this paper, two strategies for adhesion enhancement of ceramic coatings on polymer substrates were proposed: (1) formation of chemical bonds through surface condensation reactions, and (2) development of interlocked ceramic and polymeric networks through diffusion of alkoxide precursors. The current research has focused on the adhesion of sol-gel-derived organic-inorganic hybrid coatings on polyester by forming chemical bonds between the polymer substrate and the hybrid coatings, as well as developing interlocked polymeric and inorganic networks at the interface. Contact angle, wettability tests, and chemicalanalysis were done to verify the effectiveness of the adhesion of organic-inorganic hybrid coatings on polyester substrates. In addition, dry and wet thermal cycling tests were done to analyze the adhesion behavior of the hybrid coatings on polyester, followed by microscopy examination. It was found that although both approaches resulted in excellent adhesion of hybrid coatings on polyester, adhesion with interlocked ceramic and polymeric networks was far better than that with chemical bonds in the presence of water at elevated temperatures.     

New reactive polymeric systems for use as waveguide materials in integrated optics

Cross-linked polymeric materials are used in a wide range of applications. Special compositions are used in micro-system technologies and its utilization is extending to integrated optics. We have been working for several years in the field of polymers for optical applications. Highly fluorinated polycyanurate systems have been proven as promising waveguide materials in integrated optics. The refractive index can be adjusted reproducibly in a wide range almost continuously. The layer quality was optimized. Low optical losses of less than 0.3 dB/cm@1550nm were obtained and working optical prototypes were developed. The birefringence had been a major problem, but this was solved by adjusting the coefficient of thermal expansion of substrate and film. We will report in this paper on the polycyanurate ester resins and the new triazine containing polymeric systems.     

Hybrid organic–inorganic sol–gel materials for micro and nanofabrication

In this review hybrid organic–inorganic (HOI) resists as emerging materials alternative to organic polymers for micro and nanolithography are presented and discussed. In particular, results on sol–gel materials belonging to 3-glycidoxypropyltrimethoxysilane based HOI are presented and reviewed, highlighting as various lithographic techniques can be used to pattern their surface and showing examples of micro- and nano-patterned structures achieved with radiation assisted lithography (UV, X-rays and electron beam) or imprint techniques. It will be demonstrated the particular versatility shown by some of these materials, that in some case can be processed with all the lithographic methods herein considered, without any significant modification of their main composition and synthesis procedure. Moreover, results about the investigation of interaction between radiation and HOI materials and thermal treatment will be discussed, as well as possible synthesis strategies and composition modification developed in order to improve efficiency of curing, tailor HOI properties to specific needs (optical properties, resist composition, mechanical stability, etc.) and explore innovative and non conventional patterning techniques. The reported results highlight as these novel materials, thanks to their solution processability and higher performances respect to commercial polymeric resists, allow to use the above mentioned lithographic techniques in a direct patterning process, strongly simplifying conventional technique and reducing their processing time and costs.     

Nonlinear chemical dynamics in synthetic polymeric systems: motivations and strategies for success

Two motivations for studying nonlinear chemical dynamics with polymeric systems are considered: observing new nonlinear phenomena and developing new materials because of nonlinearities in polymerization processing. Examples from frontal polymerization are given. Three strategies are considered: coupling polymerizations to nonlinear systems such as oscillating reactions, using inherent nonlinearities in polymerization reactions and investigating the effects of polydispersity on known instabilities.     

Ethylene Glycol-Citric Acid-Silica Hybrid Organic-Inorganic Materials Obtained by the Sol-Gel Method

The combination of inorganic polymeric networks with organic molecules leads to hybrid materials. Tetraethoxysilane (TEOS) was used as the precursor for the inorganic component, covalently bonded to ethylene glycol (EG) and citric acid (CA) molecules, whose esterification provides the in situ water for hydrolysis of TEOS. Ethanol was added in various amounts to the TEOS-EG-CA mixtures in order to induce different molecular separations among the reacting molecules, thus modifying the molecular weight distributions of the resulting materials. Characterization of these hybrid materials was performed by several techniques, with consistent results among them. The materials obtained are thermoplastic systems which can be used as coatings, or as bulk materials. In particular, their rheological and thermal properties suggest their possible use as components of drilling fluids in the tertiary recovery of petroleum.     

(Bio)polymeric Hydrogels as Therapeutic Agents

Hydrogels derived from both natural and synthetic polymers have gained significant scientific attention in recent years for their potential use as biomedical materials to treat human diseases. While a great deal of research efforts have been directed towards investigating polymeric hydrogels as matrices for drug delivery systems, examples of such hydrogels exhibiting intrinsic therapeutic properties are relatively less common. Characteristics of synthetic and natural polymers such as high molecular weight, diverse molecular architecture, chemical compositions, and modulated molecular weight distribution are unique to polymers. These characteristics of polymers can be utilized to discover a new generation of drugs and medical devices. For example, polymeric hydrogels can be restricted to the gastrointestinal tract, where they can selectively recognize, bind, and remove the targeted disease-causing substances from the body without causing any systemic toxicity that are associated with traditional small molecule drugs. Similarly hydrogels can be implanted at specific locations (such as knee and abdomen) to impart localized therapeutic benefits. The present article provides an overview of certain recent developments in the design and synthesis of functional hydrogels that have led to several polymer derived drugs and biomedical devices. Some of these examples include FDA-approved marketed products.     

The Potential of Microencapsulated Self-healing Materials for Microcracks Recovery in Self-healing Composite Systems: A Review

The autonomic self-healing materials based on microcapsules have made major advancements for the repairing of microcracks in polymers and polymer composite systems. Self-healing encapsulated materials have the inborn ability to heal polymeric composites after being damaged by chemical and mechanical progressions. These intelligent micro-encapsulated self-healing materials possess great capabilities for recovering the mechanical as well aesthetic properties and barrier properties of the polymeric structures. Based on real world observations and experimental data, it is believed that microcracks and microcracking in polymeric materials can result because of many chemical and physical routes and is one of the foremost critical issues for polymeric materials. Especially in polymeric coatings, these microcracks can lead towards disastrous failure, and conventional healing systems like patching and welding cannot be used to repair microcracks at such a micro-level. Self-healing materials, especially, capsule based self-healing materials is a new field sought as an alternative to the conventional repairing techniques, requiring no manual intrusion and uncovering. This review covers the basic and major aspects of the microencapsulated self-healing approach like the effect of synthesis parameters on the size of microcapsules, healing efficiency determination, and the potential of the existing developed microencapsulated agents.     

Cubic Polyhedral Oligomeric Silsesquioxane Based Functional Materials: Synthesis,Assembly, and Applications

Organically modified cubic polyhedral oligomeric silsesquioxanes (POSS) have attracted increasing attention in the design of novel functional hybrid materials for applications such as porous materials, liquid crystals, semiconductors, high‐temperature lubricants, fuel cells, and lithium batteries. The nanosized POSS moiety can be conveniently modified on the periphery with a variety of functional groups to lead to hybrid materials with desired functions. In addition, suitable mono‐functionalized POSS derivatives can be incorporated into polymers as side chains via various synthetic strategies to offer a wide class of functional polymeric materials with tunable physical properties for targeted applications. In this Focus Review, we aim to summarize the recent developments on the chemistry and applications of POSS‐based molecules and polymers. Moreover, the properties as well as assembly behavior of the POSS‐based functional hybrid materials will be reviewed, and the relationship of the performance of the hybrid materials with the intrinsic nature of the POSS unit will be addressed.     

Smart polymeric materials: emerging biochemical applications

Smart polymeric materials respond with a considerable change in their properties to small changes in their environment. Environmental stimuli include temperature, pH, chemicals, and light. "Smart" stimuli-sensitive materials can be either synthetic or natural. This review discusses the application of smart materials as tools to solve biological problems such as bioseparation, drug delivery, biosensor design, tissue engineering, protein folding, and microfluidics. The goal for these endeavors is to mimic the "smartness" of biological systems and ultimately moderate complex systems such as immune responses at desired levels. The versatility and untapped potential of smart polymeric materials makes them one of the most exciting interfaces of chemistry and biology.     

Performance and mechanisms of fire retardants in polymers—A review

The fundamental mechanisms by which fire retardant additives can interrupt the self-sustained combustion cycle of organic polymers are reviewed. Evaluation of fire retardant performance and methods used for mechanism assessment are discussed. Examples are given of recent mechanistic studies of halogen-based and intumescent systems indicating that some previous generalisations should be revised. It is shown that a deeper understanding of fire retardance mechanisms acquired through detailed thermal degradation studies is the only way to answer the ever increasing demand for polymeric materials characterised by minimised overall fire hazard.     

Polymeric composite systems modified with allotropic forms of carbon (review)

Most widely occurring classes of carbon nanoparticles used to create polymeric composite systems are considered. The possibility is demonstrated of using “polymer-carbon nanoparticles” composites for raising the level of mechanical properties of polymeric materials, creating friction units with improved tribological characteristics, developing new electrochemical, microelectronic, and optical devices, and modifying barrier properties of polymeric membranes. Methods for treatment of nanoparticles to provide their compatibility with polymeric matrices and preclude their aggregation are discussed.     

Composite Particles: Design of Hybrid Materials on the Nano-Scale

Summary: In the last decade there has been a steady increased interest in the techniques providing design of nano-structured materials. It has been demonstrated that colloidal polymeric particles can be successfully used for the deposition of different functional nano-materials. Due to their numerous attractive properties polymeric particles have been used as templates for the synthesis, storage and transportation of nanostructured materials. This contribution demonstrates the synthetic ways for the preparation of hybrid particles by effective control over the size, morphology and distribution of the non-miscible phases. Developed methods allow design of the composite particles on the nanometer scale and opens new possibilities for the preparation of the materials with advanced properties. The synthesis, characterization and applications of hybrid particles are discussed in detail.     

Monte carlo simulation of self-assembled ordered hybrid materials

Lattice Monte Carlo simulations were performed to study the structure of hybrid organic-inorganic materials. Several cases were modeled where the composition corresponds to high surfactant concentration phases similar to that obtained from the synthesis of hybrid materials resulting from a phase separation. When using hybrid inorganic precursors, comparable to organosilicas, we observe that the organic segment is well mixed with the inorganic precursor and surfactant heads and no preferential location of the organic groups is observed. We show that the behavior of surfactant/hybrid precursor systems is analogous to those where co-surfactants or co-solvents are used, and that the lack of ordering in some cases can be explained by the change in solvent quality when using hybrid precursors. A comparison of structural characterization of the different phases using several tools, such as aggregate size distribution, density profiles, and pair radial distribution function is presented.     

Dynamic interfacial effect of electroosmotic slip flow with a moving capillary front in hydrophobic circular microchannels

Miniaturization of chemical analysis using microfabrication is an emerging technology. The use of polymeric materials as opposed to conventional glass substrate is also a promising alternative. As most polymeric materials are hydrophobic relative to glass, we describe here the implication for the loading process of electroosmotic flow (EOF) when a three-phase (solid-liquid-vapor) contact line exists. The presence of these interfaces can result in a large Laplace pressure that resists EOF and hence hinders its flow performance. This effect depends on the phenomenological contact angle at the solid-liquid interface. In our model for EOF, we considered simultaneously the presence of an electric double layer, liquid slips via a weaker solid-liquid interaction and Laplace pressure across a liquid-vapor interface.