A MAS NMR investigation of aluminosilicate, silicophosphate, and aluminosilicophosphate gels and the evolution of crystalline structures on heating the gels

Gels of various composition containing SiO2, Al2O3, and P2O5 have been investigated by employing high resolution magic-angle-spinning (MAS) 27Al, 29Si, and 31P NMR spectroscopy. Changes occurring in the NMR spectra as the gels are progressively heated have been examined to understand the nature of structural changes occurring during the crystallization of the gels. 27Al resonance is sensitive to changes in the coordination number even when the Al concentration is as low as 1 mol%. As the percentage of Al increases, the hydroxyl groups tend to be located on the Al sites while Si remains as SiO4/2 (Q4). Mullite is the major phase formed at higher temperature in the aluminosilicate gels. In the case of the silicophosphate gels, Si is present in the form of Q4 and Q3 species. There is a change in the coordination of Si from four to six as the gel is heated. The formation of six-coordinated Si is facilitated even at lower temperatures (~673 K) when the P2O5 content is high. The phosphorus atoms present as orthophosphoric acid units in the xerogels change over to metaphosphate-like units as the gel is heated to higher temperatures. In aluminosilicophosphates, Si is present as Q4 and Q3 species while P is present as metaphosphate units; Al in these gels seems to be inducted into the tetrahedral network positions.

In-situ crystallization studies of gels in the ZrO2---SiO2 system

The in-situ investigation of amorphous gels is important in understanding the evolution of structures and the influence of environmental factors on crystallization. In this paper, the ZrO2---SiO2 system has been studied in-situ under electron beam heating. The study reveals that both the size of the ZrO2 particles and the presence of hydroxyl ions influence the nature of the crystalline phase of the ZrO2 particles formed.

Structural Relationships in 2,3-Bis-n-decyloxyanthracene and 12-Hydroxystearic Acid Molecular Gels and Aerogels Processed in Supercritical CO2

Supercritical carbon dioxide is used to prepare aerogels of two reference molecular organogelators, 2,3-bis-n-decyloxyanthracene (DDOA) (luminescent molecule) and 12-hydroxystearic acid (HSA). Electron microscopy reveals the fibrillar morphology of the aggregates generated by the protocol. SAXS and SANS measurements show that DDOA aerogels are crystalline materials exhibiting three morphs: (1) arrangements of the crystalline solid (2D p6m), (2) a second hexagonal morph slightly more compact, and (3) a packing specific of the fibers in the gel. Aggregates specific of the aerogel (volume fraction being typically phi approximate to 0.60) are developed over larger distances (similar to 1000 angstrom) and bear fewer defaults and residual strains than aggregates in the crystalline and gel phases. Porod, Scherrer and Debye-Bueche analyses of the scattering data have been performed. The first five diffraction peaks show small variations in position and intensity assigned to the variation of the number of fibers and their degree of vicinity within hexagonal bundles of the related SAFIN according to the Oster model. Conclusions are supported by the guidelines offered by the analysis of the situation in HSA aerogels for which the diffraction pattern can be described by two coexisting lamellar-like arrangements. The porosity of the aerogel, as measured by its specific surface extracted from the scattering invariant analysis, is only 1.8 times less than that of the swollen gel and is characteristic of a very porous material.

Long-term Accelerated Weathering of Outdoor Silicone Rubber Insulators

Multistress aging/weathering of outdoor composite polymeric insulators has been a topic of interest for power transmission research community in the last few decades. This paper deals with the long-term accelerated weathering of full-scale distribution class silicone rubber composite insulators. To evaluate the long-term synergistic effect of electric stress, temperature and UV radiation on insulators, they were subjected to accelerated weathering in a specially designed multistress-aging chamber for 30,000 h. All the insulators were subjected to the same level of electrical and thermal stresses but different UV radiation levels. Chemical, physical and electrical changes due to degradation have been assessed using various techniques. It was found that there was a monotonous reduction of the content of low molecular weight (LMW) molecules with the duration of the weathering. Further, due to oxidation and weathering there is an appreciable increase in surface roughness and atomic percentage of oxygen. There is no change in the leakage current of new and aged insulators under both wet and dry conditions at the end of the aging. The results also indicate that there is no influence of UV radiation on the silicone rubber for the durations and conditions under which the studies were made.

Investigations of the reduction behavior of Iron-impregnated alumina gels (Fe/AlOOH) and the formation of Fe0-Al2O3 metal-ceramic composites

Fe/AlOOH gels calcined and reduced at different temperatures have been investigated by a combined use of Mossbauer spectroscopy, x-ray diffraction, and electron microscopy in order to obtain information on the nature of the iron species formed as well as the various reduction processes. Calcination at or below 1070 K mainly gives reducible Fe3+ while calcination at higher temperatures gives substitutional Fe3+ in the form of Al2-xFexO3. The Fe3+ species in the calcined samples are, by and large, present in the form of small superparamagnetic particles. Crystallization of Al2O3 from the gels is catalyzed by Fe2O3 as well as FeAl2O4. Fe (20 wt. %)/AlOOH gels calcined at or below 870 K give FeAl2O4 when reduced in hydrogen at 1070 K or lower and a ferromagnetic Fe0-Al2O3 composite (with the metallic Fe particles >100 angstrom) when reduced at 1270 K. Samples calcined at 1220 K or higher give the Fe0-Al2O3 composite when reduced in the 870-12,70 K range, but a substantial proportion of Fe3+ remains unreduced in the form of Al2-xFexO3, showing thereby the extraordinary stability of substitutional Fe3+ to reduction even at high temperatures. Besides the ferromagnetic Fe0-Al2O3 composite, high-temperature reduction of Al2-xFexO3 yields a small proportion of superparamagnetic Fe0-Al2O3 wherein small metallic particles (<100 angstrom) are embedded in the ceramic matrix. In order to preferentially obtain the Fe0-Al2O3 composite on reduction, Fe/AlOOH gels should be calcined at low temperatures (less-than-or-equal-to 1100 K); high-temperature calcination results in Al2-xFexO3. Several modes of formation of FeAl2O4 are found possible during reduction of the gels, but a novel one is that involving the reaction, 2Fe3+ + Fe0 --> 3Fe2+.

Tracking and erosion resistance of silicone rubber nanocomposites under positive and negative dc voltages

ASTM D2303 standard provides a method for evaluating the tracking and erosion resistance of polymeric insulators under ac voltages. In this paper, the above method has been extended for evaluating the performance of the insulators under dc stresses. Tests were conducted on polymeric silicone rubber (SR) insulators under positive and negative dc stresses. Micron sized Alumina trihydrate (uATH) and nano sized Alumina (nALU) were used as fillers in SR matrix to improve the resistance to tracking and erosion. Results suggest that SR composites perform better under negative dc than under positive dc voltages. Eroded mass and leakage current data support the above result. Samples with low concentration of nano alumina fillers performed on par with the samples with large loadings of uATH.

Self-organization of multiple components in a steroidal hydrogel matrix: design, construction and studies on novel tunable luminescent gels and xerogels

The present work combines two rapidly growing research areas-functional supramolecular gels and lanthanide based hybrid materials. Facile hydrogel formation from several lanthanide(III) cholates has been demonstrated. The morphological and mechanical properties of these cholate gels were investigated by TEM and rheology. The hydrogel matrix was subsequently utilized for the sensitization of Tb(III) by doping a non-coordinating chromophore, 2,3-dihydroxynaphthalene (DHN), at micromolar concentrations. In the mixed gels of Tb(III)-Eu(III), an energy transfer pathway was found to operate from Tb(III) to Eu(III) and by utilizing this energy transfer, tunable multiple-color luminescent hydrogels were obtained. The emissive properties of the hydrogels were also retained in the xerogels and their suspensions in n-hexane were used for making luminescent coating on glass surface.

Synthesis and characterization of silicone polymer/functionalized mesostructured silica composites

A thermally stable and flexible composite has been synthesized by following a consecutive `two-step', solvent free route. Silicone polymer containing internal hydrides was used as a polymer matrix and mesoporous silica functionalized with allytrimethoxysiloxane was used as a filler material. In the second step, the composite preparation was carried out using the hydrosilylation reaction mediated by `Karastedt' platinum catalyst. The results of the studies suggest that the composites are thermally stable, hydrophobic and flexible and can be potentially used for encapsulating flexible electronic devices.

Tracking and Erosion of Silicone Rubber Nanocomposites under DC Voltages of both Polarities

In order to improve the tracking and erosion performance of outdoor polymeric silicone rubber (SR) insulators used in HV power transmission lines, micron sized inorganic fillers are usually added to the base SR matrix. In addition, insulators used in high voltage dc transmission lines are designed to have increased creepage distance to mitigate the tracking and erosion problems. ASTM D2303 standard gives a procedure for finding the tracking and erosion resistance of outdoor polymeric insulator weathershed material samples under laboratory conditions for ac voltages. In this paper, inclined plane (IP) tracking and erosion tests similar to ASTM D2303 were conducted under both positive and negative dc voltages for silicone rubber samples filled with micron and nano sized particles to understand the phenomena occurring during such tests. Micron sized Alumina Trihydrate (ATH) and nano sized alumina fillers were added to silicone rubber matrix to improve the resistance to tracking and erosion. The leakage current during the tests and the eroded mass at the end of the tests were monitored. Scanning Electron Microscopy (SEM) and Energy dispersive Xray (EDX) studies were conducted to understand the filler dispersion and the changes in surface morphology in both nanocomposite and microcomposite samples. The results suggest that nanocomposites performed better than microcomposites even for a small filler loading (4%) for both positive and negative dc stresses. It was also seen that the tracking and erosion performance of silicone rubber is better under negative dc as compared to positive dc voltage. EDX studies showed migration of different ions onto the surface of the sample during the IP test under positive dc which has led to an inferior performance as compared to the performance under negative dc.

Yielding and large deviations in micellar gels: a model

We present a simple model that can be used to account for the rheological behaviour observed in recent experiments on micellar gels. The model combines attachment detachment kinetics with stretching due to shear, and shows well-defined jammed and flowing states. The large-deviation function (LDF) for the coarse-grained velocity becomes increasingly non-quadratic as the applied force F is increased, in a range near the yield threshold. The power fluctuations are found to obey a steady-state fluctuation relation (FR) at small F. However, the FR is violated when F is near the transition from the flowing to the jammed state although the LDF still exists; the antisymmetric part of the LDF is found to be nonlinear in its argument. Our approach suggests that large fluctuations and motion in a direction opposite to an imposed force are likely to occur in a wider class of systems near yielding.

Surface Degradation of Silicone Rubber Nanocomposites Due to DC Corona Discharge

Corona discharge is recognized as one of the mechanisms that can influence the surface hydrophobicity of Silicone Rubber (SR) because of the chemical changes that occur on its surface. In this study SR samples were exposed to positive and negative DC corona for 25 and 50 hours using a needle-plane electrode system. Hydrophobicity changes were monitored using a sessile drop contact angle measurement facility. The physical changes on the surface were studied using Scanning Electron Microscopy (SEM) and surface roughness measurements. The effect of positive dc corona was found to be different from that of negative dc corona. Significant surface degradation and loss of hydrophobicity was found in the case of negative dc corona exposed samples. Significant improvement in the above mentioned properties were obtained by adding small quantities of nSIL into the SR matrix.

Role of Crosslinking and Entanglements in the Mechanics of Silicone Networks

The goal of this study is to investigate the applicability of different constitutive models for silicone networks using comprehensive multiaxial experimental tests, including non-equibiaxial mechanical tests which introduce differential constraints on the networks in the two orthogonal directions, on samples prepared using various crosslinking densities. Uniaxial stress-strain experiments show that a decrease in crosslinker amounts used in the preparation of silicone networks lead to more compliant material response as compared to that obtained using higher amounts of crosslinker. Biaxial data were used to obtain fits to the neo- Hookean, Mooney-Rivlin, Arruda-Boyce and the Edward-Vilgis slip-link constitutive models. Our results show that the slip-link model, based on separation of the individual contributions of chemical crosslinks and physical entanglements, is better at describing the stress-strain response of highly crosslinked networks at low stretches as compared to other constitutive models. Modulus obtained using the slip-link model for highly crosslinked networks agrees with experimentally determined values obtained using uniaxial tension experiments. In contrast, moduli obtained using coefficients to the other constitutive models underpredict experimentally determined moduli by over 40 %. However, the slip-link model did not predict the experimentally observed stiffening response at higher stretches which was better captured using the Arruda-Boyce model.

Effect of Coldfog on the Corona Induced Degradation of Silicone Rubber Samples

Corona is an unavoidable phenomena in high voltage power transmission system, in spite of suitably designed insulator accessories and transmission line hardware. It is a proven fact that the continuous occurrence of corona can subject the polymeric insulator to a severe degradation. Further, moisture in the air has a positive influence on the corona activity. This paper presents the methodology to evaluate the corona performance of the silicone rubber housing material with simultaneous application of cold fog. Analysis conducted after corona treatment by the Fourier Transform Infrared Spectroscopy (FTIR) present an interesting results showing a higher hydroxylation of sample surface under the moisture application than in the normal condition for both AC and DC excitation. FTIR spectrum also indicates the presence of nitric acid on the treated surface with coldfog application. Results obtained from SEM analysis are also presented.

Multifarious facets of sugar-derived molecular gels: molecular features, mechanisms of self-assembly and emerging applications

The remarkable capability of nature to design and create excellent self-assembled nano-structures, especially in the biological world, has motivated chemists to mimic such systems with synthetic molecular and supramolecular systems. The hierarchically organized self-assembly of low molecular weight gelators (LMWGs) based on non-covalent interactions has been proven to be a useful tool in the development of well-defined nanostructures. Among these, the self-assembly of sugar-derived LMWGs has received immense attention because of their propensity to furnish biocompatible, hierarchical, supramolecular architectures that are macroscopically expressed in gel formation. This review sheds light on various aspects of sugar-derived LMWGs, uncovering their mechanisms of gelation, structural analysis, and tailorable properties, and their diverse applications such as stimuli-responsiveness, sensing, self-healing, environmental problems, and nano and biomaterials synthesis.