We compare polarized neutron reflectometry, non-polarized neutron reflectometry, and x-ray reflectometry for pure, magnetically polarized, air-passivated iron. Magnetism in the underlying metal enhances contrast with the surface oxide leading to precise magnetic and composition profiles of the oxide layer. The native passive film is a uniform, fully dense, non-ferromagnetic oxide with an average thickness of 31.9 +/- 0.7 & Aring;. Non-polarized neutron reflectometry gives substantial errors in the inferred interfacial profiles.

This review covers the basics of sol–gel technology and the chemistry of alkoxysilanes, which are the most valuable sol–gel precursors in preparation of sol–gel materials and coatings. Results from early and recent studies are presented showing that sol–gel coatings provide strong corrosion protection for metals. Protection is mainly attributed to the formation of highly cross-linked siloxane structure on a metal surface for improved water resistance and the formation of a high density of metallosiloxane bonds at the interface for strong coating/metal adhesion. The evolution of water-based sol–gel coatings is presented with a focus on their use in military coating applications: (1) water-based sol–gel pretreatment coatings as a replacement for chromate and phosphate pretreatments and (2) waterborne coatings enhanced by organofunctional trialkoxysilanes (“super primer”) as a replacement for military chromated epoxy primers.

This work exploits gas adsorption and small-angle X-ray scattering (SAXS) to determine the morphology of complex nanoporous materials. We resolve multiple classes of porosity including previously undetected large-scale texture that significantly compromises the canonical interpretation of gas adsorption. Specifically, a UVM-7 class mesoporous silica was synthesized that has morphological features on three length scales: macropores due to packing of 150 nm globules, 1.9 nm radius spherical mesopores inside the globules, and >7 nm pockets on and between the globules. The total and external surface areas, as well as the mesopore volume, were determined using gas adsorption (αs-plot) and SAXS. A new approach was applied to the SAXS data using multilevel fitting to determine the surface areas on multiple length scales. The SAXS analysis code is applicable to any two-phase system and is freely available to the public. The total surface area determined by SAXS was 12% greater than that obtained by gas adsorption. The macropore interfacial area, however, is only 30% of the external surface area determined by the αs-plot. The overestimation of the external surface area by the αs-plot method is attributed to capillary condensation in nanoscale surface irregularities. The discrepancy is resolved assuming that the macropore-globule interfaces harbor fractally distributed nooks and crannies, which lead to gas adsorption at pressures above the mesopore filling pressure.

Pseudomonas aeruginosa is a metabolically voracious bacterium that is easily manipulated genetically. We have previously shown that the organism is also highly electrogenic in microbial fuel cells (MFCs). Polarization studies were performed in MFCs with wild-type strain PAO1 and three mutant strains (pilT, bdlA and pilT bdlA). The pilT mutant was hyperpiliated, while the bdlA mutant was suppressed in biofilm dispersion chemotaxis. The double pilT bdlA mutant was expected to have properties of both mutations. Polarization data indicate that the pilT mutant showed 5.0- and 3.2-fold increases in peak power compared to the wild type and the pilT bdlA mutant, respectively. The performance of the bdlA mutant was surprisingly the lowest, while the pilT bdlA electrogenic performance fell between the pilT mutant and wild-type bacteria. Measurements of biofilm thickness and bacterial viability showed equal viability among the different strains. The thickness of the bdlA mutant, however, was twice that of wild-type strain PAO1. This observation implicates the presence of dead or dormant bacteria in the bdlA mutant MFCs, which increases biofilm internal resistance as confirmed by electrochemical measurements.

2,366,516 l/1945 Gefficken et al. ................... 17/124 2,466, 19 4/1949 Moulton et al. .......................... 88/1 3,094,436 6/1963 Schroder ........... 7/25 4,059,658 11/1977 Shoup et al. ... ... 264/43 4, 65,224 8/1979 Irven et al. ............ ... 65/3.2 4,323,381 4/1982 Matsuyama et al. .. ... 65/90 4,605,428 8/986 Johnson et al. .... ... 65/18. 4,680,046 7/1987 Matsuo et al. ..... ... 6.5/90 4,680,048 7/1987 Motoki et al. ..... ... 65/90 4,840,653 6/1989 Rabinovich ........ ... 65/90 4,872,895 10/1989 Fleming et al. ...................... 65/18.1 4,92.73 5/1990 Clark et al. ........ ... 427/376.4 4.941,905 7/1990 Narasimham ......................... 65/90 4,944,895 7/1990 Buckley et al. ... ... 65/18. 4,952,225 8/1990 Le Sergent et al.................. 65/3.2

Nanocasting is an emerging method to prepare organic polymers with regular, nanometer pores using inorganic templates. This report assesses the impact of imperfect template replication on the sorption properties of such polymer castings. Existing X-ray diffraction data show that substantial diffuse scattering exists in the small-angle region even though TEM images show near perfect lattices of uniform pores. To assess the origin of the diffuse scattering, the morphology of the phenol-formaldehyde foams (PFF) was investigated by small-angle X-ray scattering (SAXS). The observed diffuse scattering is attributed to interfacial roughness due to fractal structures. Such roughness has a profound impact on the sorption properties. Conventional pore-filling models, for example, overestimate protein sorption capacity. A mathematical framework is presented to calculate sorption properties based on observed morphological parameters. The formalism uses the surface fractal dimension determined by SAXS in conjunction with nitrogen adsorption isotherms to predict lysozyme sorption. The results are consistent with measured lysozyme loading.

This report documents the first observation of a urine-powered microbial fuel cell operating with a genetically engineered bacterial strain. Under identical conditions, a pilT mutant of the Gram-negative bacterium Pseudomonas aeruginosa showed a 2.7-fold increase in peak power density compared to the wild-type strain, PAO1. The reduced twitching motility and hyperpiliation of the pilT mutant enhances the formation of electrogenic biofilms. For both strains, the observed high internal resistance near open-circuit voltage is attributed to sluggish redox reactions on the anode surface and not to slow bacterial metabolism. This work lays the groundwork for optimization of multiple bacterial traits leading to increased electroactive properties and opens new opportunities for urine-based mini-devices.

Because of the great importance of the surface properties of the polysiloxanes, this topic is treated separately in this chapter. Hydrophobic polysiloxanes having simple aliphatic or aromatic side groups have surfaces that show essentially no attraction to water. In fact, polysiloxanes can serve as water repellants. This property is very useful for applications such as protective coatings on historical monuments and for controlling the surfaces of other polymers, sensors, and quantum dots. Hydrophobic surfaces can be readily regenerated if the surface becomes damaged. Regeneration occurs by rearrangements of the polysiloxane chains so that the hydrophobic methyl groups are once again covering the surface. The flexibility of the siloxane chain backbone facilitates this process. It is also possible to prepare hydrophobic films using methyl-modified siloxane melting gels. Glass surfaces or wool fibers can be coated with polydimethylsiloxane (PDMS) to make them more hydrophobic. In some cases, it is necessary to modify a polysiloxane surface to make it hydrophilic or hydrophobic. Hydrophobization is one aspect of the general topic of modifying and managing the properties of polymer surfaces. An important example involves soft contact lenses that contain PDMS, which is often used because of its very high permeability to oxygen, which is required for metabolic processes within the eye. Such lenses do not feel comfortable however because they do not float properly on the aqueous tears that coat the eye. There are a number of ways to modify the surfaces. There is even a way to make “unreactive” silicones react with inorganic surfaces. In some applications it is useful to have hydrophilicity in the bulk of the polymer instead of just at the surface. One way of doing this is by simultaneously end linking hydrophilic poly(ethylene glycol) (PEG) chains and hydrophobic PDMS chains. Another way is to make a PDMS network with a trifunctional organosilane R’Si(OR) end linker that contains a hydrophilic R’ side chain, such as a polyoxide. Treating only the surfaces is another possibility, for example, by adding hydrophilic brushes by vapor deposition/hydrolysis cycles. Such hydrophilic polysiloxanes can also serve as surfactants.

Random copolymers are prepared by the copolymerization of a mixture of cyclic oligomers. Although the resulting polymer can be quite blocky (figure 8.1), taking the reaction to equilibrium can give a polymer that is essentially random in its chemical sequencing. One reason for preparing copolymers is to introduce functional species, such as hydrogen or vinyl side groups, along the chain backbone to facilitate cross linking. Another reason is the introduction of sufficient chain irregularity to make the polymer inherently noncrystallizable. Specific examples of comonomers include imides, perylenediimide, urethane-ureas, epoxies, other siloxanes, amides, styrene, divinylbenzene, acrylics, silsesquioxanes, polythiophenes, and poly(lactic acid). One novel combination is the preparation of polysiloxanebased episulfide resins. An unusual application is the use of monomethylitaconate- grafted polymethylsiloxane to induce crystal growth of CaCO3. Polysiloxanes containing thermally curable brenzoxazine moieties in the main chain are also in the category. These and other copolymers have been extensively characterized by nuclear magnetic resonance (NMR) spectroscopy. The sequential coupling of functionally terminated chains of different chemical structure can be used to make block copolymers, including those in which one or more of the blocks is a polysiloxane. If the blocks are relatively long, separation into a two-phase system invariably occurs. Frequently, one block will be in a continuous phase and the other will be dispersed in domains having an average size the order of a few hundred angstroms. Such materials can have unique mechanical properties not available from homopolymer species. Sometimes similar properties can be obtained by the simple blending of two or more polymers. Examples of blocks used with polydimethylsiloxane (PDMS) include imides, epoxies, butadienes, ε-caprolactones, amides having trichlorogermyl pendant groups, urethanes, ureas, poly(ethylene glycols), polystyrene, vinyl acetates, acrylates or methacrylates, 2-vinylpyridine, and even other polysiloxanes. Some results have also been reported for polyesters, polyethers, hydroxyethers of bisphenol A, bisphenol A arylene ether sulfones, vinylpyridinebenzoxazines, methyloxazolines, terpyridines, polysulfones, γ-benzyl-Lglutamate, and carboranes. Two other examples are foamed polypropylene and melamine resins. Even ABA, ABC triblock copolymers, and ABCBA pentablock copolymers involving PDMS have been reported.

Gelation is the cross-linking process that leads to the network structures required for rubberlike elasticity. In some cases, gelation can be reversible. There have been numerous studies involving theory and simulations exploring gelation and the mechanical properties of the resulting networks. Cross linking with free radicals is still quite common. Radiation has often been used to carry out the cross linking, as have new techniques known as “click” chemistry. Hydrosilylation is also popular. Networks have even been designed with movable cross links. Finally, reactive groups can be placed at the chain ends or within the chains themselves. Related studies have involved polydimethylsiloxane (PDMS)-based organogelators, web-to-pillar transitions of gels, and silica aerogels. There has also been interest in polysiloxanes in interpenetrating hydrogels with high oxygen permeabilities and viscoelastic magnetic gels. Organic-inorganic hybrids with relatively low melting temperatures also exist, some of which can be made to be self-healing. Gels are also formed in swelling experiments, which are useful for equilibrium experiments to characterize network structures. One of the recent topics in this area involves stimuli-responsive gels, under the descriptive title of “self-walking gels” “wormlike motion of gels,” and “peristaltic motion of gels.” The earliest studies of networks formed in solution were undertaken to investigate some subtle aspects of the elastic free energy expression— whether or not an additional term in the logarithm of the volume was required. Other studies focused on the properties of networks in general. As can be gathered from chapter 4, it is difficult to obtain information on the topology of a network. Some studies have therefore taken an indirect approach. Networks were prepared in a way as to simplify their topologies, and their properties were measured and interpreted in terms of reduced degrees of network-chain entanglement. The two techniques employed involved separating the chains prior to cross linking by either dissolution or stretching. After cross linking, the solvent is removed or the stretching force is relaxed, and the network is studied (unswollen) with regard to its stress-strain properties, typically in elongation.

The polysiloxane of greatest commercial importance and scientific interest is poly(dimethylsiloxane) (PDMS), [Si(CH3)2 –O –]x, a member of the symmetrical dialkyl polysiloxanes, with repeat unit [SiR2 –O –]x. This polymer is discussed extensively in the following chapters, particularly in chapter 5. Other members of this series are poly(diethylsiloxane) [Si(C2H5) –O–]x, and poly(di-n-propylsiloxane) [SiC3H7)2–O–]x. An example of an aryl member of the symmetrically substituted series is poly(diphenylsiloxane), with repeat unit [Si(C6H5)2–O–]x. This polymer is unusual because of its very high melting point and the mesophase it exhibits. The closely related polymer, poly(phenyl/tolylsiloxane), has also been prepared and studied. The unsymmetrically substituted polysiloxanes have the repeat unit [SiRR’O–]x, and are exemplified by poly(methylphenylsiloxane) [Si(CH3) (C6H5) –O–]xand poly(methylhydrosiloxane) [Si(CH3)(H) –O–]x. In some cases, one of the side chains has been unusually long, for example C6H13, C16H33, and C18H37, including a branched side chain—CH(CH3– (CH2)m–CH3. Another example has methoxy-substituted aromatic fragments as one of the two side chains in the repeat unit. Such chains have stereochemical variability in analogy with the vinyl polymers such as polypropylene [CH(CH3) –CH2–]xand vinylidene polymers such as poly(methyl methacrylate) [C(CH3)(C = OOCH3) –CH2–]xOne can also introduce optically active groups as side chains, the simplest example being the secondary butyl group—CH(CH3)(C2H5). Another example involves redox-active dendritic wedges containing ferrocenyl and carbonylchromium moieties. Other substituents have included phenylethenyl groups, cyclic siloxane groups, and Cr-bound carbazole chromophores. In a reversal of roles, some polymers were prepared to have PDMS side chains on a poly(phenylacetylene) main chain. Siloxane-terminated solubilizing side chains are used to improve the properties of thin-film transistors. Silalkylene polymers have methylene groups replacing the oxygen atoms in the backbone. Poly(dimethylsilmethylene) is an example, [Si(CH3)2–CH2]x. A variation on this theme is to include aryl groups, for example, in poly(dimethyldiphenylsilylenemethylene) [Si(CH3)2CH2Si(C6H5)2]x. Other aryl substituents, specifically tolyl groups, have also been included as side chains. It is also possible to insert a silphenylene group [Si(CH3)2–C6H4–] into the backbone of the polysiloxane repeat unit to give [Si(CH3)2–C6H4– Si(CH3)2O–], in which the phenylene can be para or ortho or meta. A specific example is poly(tetramethyl-p-silphenylene-siloxane).

Many of the properties of the polysiloxanes have been tabulated in handbooks of polymer science and engineering. Recent work has included the stretching of polydimethylsiloxane (PDMS) chains, in some cases to their rupture points. The nature of the bonding in siloxane molecules has been of long-standing interest. Force fields for calculations of PDMS properties have been revised over the years and are now at an advanced state of development. Some of the simplest approaches employ the methods of molecular mechanics. Most of the experimental results have been obtained on solutions of polysiloxanes in thermodynamically good solvents. The first member of this series, poly(dimethylsiloxane) (PDMS), [–Si(CH3)2O–]x, has been studied extensively with regard to its configuration-dependent properties. PDMS (figure 2.1) is very similar in structure to the polyphosphate chain in that the successive bond angles are not equal. The Si–O bond length in polysiloxanes is 1.64 Å, and bond angles at the Si and O atoms are 110 and 143°, respectively. This inequality of bond angles causes the all-trans form of the molecule (with rotational angles ϕ = 0°) to form a closed structure after approximately eleven repeat units. The torsional barrier for rotations about the skeletal bonds is very low, which accounts for the high dynamic flexibility and low glasstransition temperature of the PDMS chain. Not surprisingly, low temperature properties are superb. Trans states are of lower energy than gauche states (ϕ = ±120°) in the PDMS chain. This conformational preference may arise from favorable van der Waals interactions between pairs of CH3 groups separated by four bonds in trans states. This factor is apparently more important than favorable coulombic interactions between oppositely charged Si and O atoms separated by three bonds, which are larger in gauche states because of the reduced distance. Comparisons between experimental and theoretical values of various configuration-dependent properties, however, yield a value for this energy difference that is significantly larger than that obtained from the semi-empirical calculations of interactions between nonbonded atoms.

Elemental silicon on which the entire technology is based is typically obtained by reduction of the mineral silica with carbon at high temperatures: . . . SiO2 + 2C → Si 2CO (2.1) . . . The silicon is then converted directly to tetrachlorosilane by the reaction . . . Si + 2Cl2 → SiCl4 (2.2) . . Tetrachlorosilane can be used to form an organosilane by the Grignard Reaction . . . SiCl4 + 2 RMgX → R2SiCl2 + 2 MgClX (2.3). . . This relatively complicatreaction has been replaced by the so-called Direct Process or Rochow Process, which starts from elemental silicon as is illustrated by the reaction . . . Si + 2 RCl → R2SiCl2 (2.4) . . . This process also yields RSiCl3 and R3SiCl, which­­ can be removed by distillation. Compounds of formula R2SiCl2 are extremely important as intermediates to a variety of substances having both organic and inorganic character. Hydrolysis gives dihydroxy structures, which can condense to give the basic [–SiR2O–] repeat unit. The nature of the product obtained depends greatly on the reaction conditions. Basic catalysts and higher temperatures favor higher molecular weight linear polymers. Acidic catalysts tend to produce cyclic small molecules or low molecular weight polymers. The hydrolysis approach to polysiloxane synthesis has been largely replaced by ring-opening polymerization of organosilicon cyclic trimers and tetramers, with ionic initiation. These cyclic monomers are produced by the hydrolysis of dimethyldichlorosilane. Under the right conditions, at least 50 wt % of the products are cyclic oligomers. The desired cyclic species are separated from the mixture for use in ring-opening polymerizations such as those described in the following section. In addition, “click” chemistry has been developed for new synthesis techniques in general, and polymerizations in particular. These approaches have been used to prepare polysiloxane elastomers and polydimethylsiloxane (PDMS) copolymers that can function as thermoplastic elastomers. New synthetic strategies for structured silicones, based on B(C6F5)3 have also been developed. Another new approach involves enzymes, such as the lipase enzymatically catalyzed synthesis of silicone aromatic polyesters and silicone aromatic polyamides.

Polysiloxanes are the most studied inorganic and semi-inorganic polymers because of their many medical and commercial uses. The Si-O backbone endows polysiloxanes with intriguing properties: the strength of the Si-O bond imparts considerable thermal stability, and the nature of the bonding imparts low surface free energy. Prostheses, artificial organs, objects for facial reconstruction, vitreous substitutes in the eyes, and tubing take advantage of the stability and pliability of polysiloxanes. Artificial skin, contact lenses, and drug delivery systems utilize their high permeability. Such biomedical applications have led to biocompatibility studies on the interactions of polysiloxanes with proteins, and there has been interest in modifying these materials to improve their suitability for general biomedical application. Polysiloxanes examines novel aspects of polysiloxane science and engineering, including properties, work in progress, and important unsolved problems. The volume, with ten comprehensive chapters, examines the history, preparation and analysis, synthesis, characterization, and applications of these polymeric materials.

Ultra-small angle X-ray scattering (USAXS), small-angle neutron scattering (SANS), X-ray reflectomety (XRR) and neutron reflectometry (NR) were used to probe structure evolution induced by sealing of anodized aluminum. While cold nickel acetate sealing and hot-water sealing decrease pore size, these methods do not alter the cylindrical porous framework of the anodic aluminum oxide layer. Hot nickel acetate both fills the pores and deposits on the air surface (air-oxide interface), leading to low porosity and small mean pore radius (39 A). Electrochemical impedance spectroscopy and direct current polarization show that samples sealed by hot nickel acetate outperform samples sealed by other sealing methods. (C) 2015 Elsevier Ltd. All rights reserved.

A relatively new area that involves silicon-containing materials is the synthesis of “ultrastructure” materials (i.e., materials in which structure can be controlled at the level of 100 Å). An example is the “sol-gel” hydrolysis of alkoxysilanes (organosilicates) to give silica, SiO2. The reaction is complicated, involving polymerization and branching, but the overall reaction may be written . . . Si(OR4 + 2H2O → SiO2 + 4ROH (9.1) . . . where the Si(OR)4 organometallic species is typically tetraethoxysilane such as tetraethylorthosilicate (TEOS, with R being C2H5). In this application, the precursor compound is hydrolyzed and then condensed to yield branched polymers. Eventually a continuous swollen gel is formed. The gel is dried at moderately low temperatures to remove volatile species, and then it is fired into a porous ceramic object that can then be densified and machined into a final ceramic part. The production of ceramics by this novel route triggered interest in the ceramics community because of advantages over the conventional powder-processing approach to ceramics. Advantages include (i) the higher purity of the starting materials, (ii) the relatively low temperatures required, (iii) the possibility of controlling the ultrastructure to reduce the microscopic flaws that lead to failure, (iv) the ease with which ceramic coatings can be formed, and (v) the ease with which ceramic alloys can be prepared (e.g., by hydrolyzing solutions of both silicates and titanates). The sol-gel approach has been used to form ceramic-like phases in a variety of polymers. Poly(dimethylsiloxane) (PDMS) is the most popular. PDMS is relatively weak and stands to benefit most from reinforcement. PDMS is easily absorbs the precursor materials generally used in the solgel process. Nearly monodisperse silica microparticles can be obtained using siloxane elastomer mixtures. In some cases, the PDMS has been part of a copolymer, with ureas, imides, amideimides, and dianilines. In other approaches, the particle surface is modified, for example, with a polysiloxane. Siloxane/silica nanocomposites have also been used as “culture-stone-protective materials.” Sol-gel hydrolysis and condensation can be carried out within a polymeric matrix to generate particles of the ceramic material, typically with an average diameter of a few hundred angstroms.

The general approach used in choosing a polymer suitable for a particular application is: . . . Polymerization ↔ Structure ↔ Properties ↔ Application . . . For example, if one wants a polymer for fire-resistant fabrics, then a polymer with good high-temperature properties is required, which implies aromatic structures, which suggest condensation polymerizations. More relevant here, however, would be that a polymer remains elastomeric at low temperatures. This requirement evokes a polymer with high flexibility (low glass transition temperature), which indicates use of the polymerization techniques used with the polysiloxanes. An example of a relevant optical property is the birefringence of a deformed polymer network. This strain-induced birefringence can be used to characterize segmental orientation, and both Gaussian and non-Gaussian elasticity. Infrared dichroism has also been helpful in this regard. In the case of the crystallizable polysiloxane elastomers, orientation is of critical importance with regard to strain-induced crystallization and the tremendous reinforcement it provides. Segmental orientation has also been characterized by fluorescence polarization, deuterium nuclear magnetic resonance (NMR), and polarized infrared spectroscopy. Infrared spectroscopy has been used to characterize the structures of silica-filled polydimethylsiloxane (PDMS). Other optical and spectroscopic techniques are also important, including positron annihilation lifetime spectroscopy, spectroscopic ellipsometry, confocal Raman spectroscopy, and photoluminescence spectroscopy. Surface-enhanced Raman spectroscopy has been made tunable using gold nanorods and strain control on elastomeric PDMS substrates. A great deal of information is now being obtained on filler dispersion and other aspects of elastomer structure and morphology through the use of scanning probe microscopy, which consists of several approaches. One approach is that of scanning tunneling microscopy (STM), in which an extremely sharp metal tip on a cantilever is passed along the surface while measuring the electric current flowing through quantum mechanical tunneling. Monitoring the current then permits maintaining the probe at a fixed height above the surface. Display of probe height as a function of surface coordinates then gives the desired topographic map. One limitation of this approach is the requirement that the sample be electrically conductive. Atomic force microscopy (AFM), on the other hand, does not require a conducting Surface.

•Series of siliceous MCFs were synthesized using micro-emulsion templating.•MCFs display bimodal pore structures constituting polyhedral nano-foam phases.•USAXS reveals that the wall thickness is nearly independent of synthesis conditions.•A definitive correlation was observed between pore volume and lysozyme loading.