Blends of novel L‐tyrosine‐based polyurethanes and polyphosphate for potential biomedical applications

Elastomeric biodegradable polyurethanes and polyphosphate have been developed using an L ‐ tyrosine‐based diphenolic monomer desaminotyrosine‐tyrosine hexyl ester (DTH). Soft segments, which are polycaproloctone diol (PCL) and polyethylene glycol (PEG) have been used for the synthesis of two biodegradable L ‐tyrosine polyurethanes (LTUs), which are PEG‐C‐DTH and PCL‐C‐DTH. An investigation of the physico‐chemical properties shows that these polymers have dramatically different properties. By blending LTUs with L ‐tyrosine polyphosphate (LTP), we hope to produce a family of materials with a wide range of thermal, morphological, surface, and degradative properties. Examination of the blends shows a smooth surface morphology with a partially phase‐separated structure. These findings are consistent with the results obtained from thermal analysis of the blends. Hydrophilic nature of PEG imparts the PEG‐based blends (PEG‐C‐DTH/LTP) with a significantly higher surface and bulk hydrophilicity compared with the PCL‐based blends (PCL‐C‐DTH/LTP). Finally, the blends demonstrate a rapid initial hydrolytic degradation in phosphate buffered saline (PBS) followed by a significantly slower, prolonged degradation. The observed trend may occur due to the rapid hydrolytic degradation rate of the polyphosphate polymer followed by the degradation of the polyurethane component. Thus, tuning the physical properties by blending LTUs with LTP may be useful for drug delivery device and soft tissue engineering scaffold applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Adsorption of basic dyes from model aqueous solutions onto novel spherical silica support

Removal of CI Basic Blue 9 or CI Basic Red 5 from model aqueous solutions has been studied with spherical silica precipitated in an emulsion system used as an adsorbent. The process of removal of the dye impurities has been studied for the dyes in a wide range of concentrations (50–2000 mg dm⁻³) in model systems. The degree of dye adsorption, chemical stability of the pigments obtained and their detailed physicochemical and morphological characterisation have been ascertained. In particular, the dye removal method proposed has been found to be highly effective in removing CI Basic Blue 9 (99.9%). The degree of dye extraction from the silica (SiO₂) surface at the dye concentration in the model solutions in the range 1000–2000 mg dm⁻³ did not exceed 1.0%. The pigment composites produced are characterised by high uniformity of the particles (polydispersity index = 0.005) with the diameters ranging from 360 to 510 nm. The pigment particles are spherical in shape and of intense blue or red colour.     

Chemical Vapor Infiltration of TiB2-Matrix Composites

The efficiency of the Hall–Heroult electrolytic reduction of aluminum can be substantially improved by the use of a TiB₂ cathode. The use of TiB₂ components, however, has been hampered by the brittle nature of the material and the grain boundary attack of sintering-aid phases by molten aluminum. In the current work, TiB₂ is toughened through the use of reinforcing fibers, with chemical vapor infiltration used to produce the TiB₂ matrix. In early efforts it was observed that the formation of TiB₂ from chloride precursors at fabrication temperatures below 900–1000°C may have allowed the retention of destructive levels of chlorine. At higher fabrication temperatures (>1000°C), using appropriate infiltration conditions as determined from the use of a process model, TiB₂/THORNEL P-25 fiber composites have been fabricated in 20 h. The improved composite material has been demonstrated to be stable in molten aluminum in short-duration (24 h) tests.     

Nitridation Effect on Properties of Stannous-Lead Phosphate Glasses

Stannous-lead phosphorus oxynitride (Sn-Pb-P-O-N) glasses were prepared by remelting under an anhydrous ammonia atmosphere. Glasses that contained up to ∼4.2 wt% (9 at.%) of nitrogen were obtained. The rate of nitrogen dissolution was studied as a function of remelting time (3–66 h) and temperature (400°–600°C). The onset nitridation temperature was extrapolated to be 315°C; higher nitridation temperatures accelerated nitrogen dissolution. Nitridation of the stannous-lead oxyphosphate (Sn-Pb-P-O) glasses decreased the dissolution rate in water and the thermal expansion coefficient; however, it increased the dilatometric softening temperature, the glass-transition temperature, the microhardness, and the density. The chemical durability of the nitrided glasses increased more than four orders of magnitude with 3.0 wt% of nitrogen content. An increase in the lead oxide content in the stannous phosphate glasses also improved the chemical durability. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that nitrogen replaces the terminating hydroxyl ion and the bridging and nonbridging oxygen atoms in the PO4 tetrahedra to form the functional groups –NH<, –N<, and –N=, which leads to enhanced crosslinking of the glass network. Quantitative results regarding these bondings have been given.     

Influence of Phase Modifiers on the Degradation of Tri-n-octylamine/dodecane Extracting Mixture by an Acidic Solution of Vanadium (V)

The kinetics of degradation of a mixture of tri-n-octylamine (extractant) and various alcoholic phase modifiers in n-dodecane in contact with acidic aqueous sulfate solutions containing vanadium (V) has been investigated. The nature of the modifier influences the kinetics of degradation and an improvement of the resistance against the chemical degradation is obtained when secondary alcohol (2-nonanol) or tertiary alcohols such as 9-octyl-9-heptadecanol are used as phase modifiers instead of 1-tridecanol. For instance, the kinetic constant of degradation is divided by one half when 9-octyl-9-heptadecanol is used as phase modifier instead of 1-tridecanol. On the contrary, the alcohols containing aromatic substituents or fluorine atoms are responsible for an increase of the chemical degradation of the extraction solvent.     

High-Temperature Mechanical Properties and Chemical Stability of Ba1+xZr4P6–2xSi2XO24 Low-Thermal-Expansion Ceramics

The NaZr₂P₃O₁₂ (NZP) family of materials is attracting increasing attention due to its low-thermal-expansion behavior. The system Ba_1+xZr₄P_6–2xSi_2xO₂₄ (0 ≤ x ≤ 1), belonging to the NZP family, shows ultralow thermal expansion over a wide temperature range. It also shows anisotropy in its lattice thermal expansion. This causes microcracking as the sintered specimens are cooled, which results in degradation of the mechanical properties. In this work, the chemical stability, strength, and Young's modulus of Ba_1+xZr₄P_6–2xO₂₄ ( X = 0.25 and 0.5) ceramics at high temperatures have been determined. An attempt has been made to correlate the mechanical properties to the thermal expansion anisotropy.     

Production of Hydroxyapatite/Bioactive Glass Biomedical Composites by the Hot-Pressing Technique

Biomedical composites of hydroxyapatite (HA) and bioactive glass (BG) have been difficult to obtain as a dense body without the undesirable occurrence of thermal reactions and phase degradation. Herein, HA–BG dense composites were produced by the hot-pressing technique. A range of HA–BG powder mixtures (30–50 wt% BG) was fully densified by hot pressing at temperatures as low as ∼700°–800°C. On the other hand, the HA–BG composites could not be densified by pressureless sintering because their composition was degraded due to a severe thermal reaction. The hot-pressed composites had significantly improved flexural strengths (∼60 MPa) as compared with those subjected to pressureless sintering (∼30 MPa) or the pure HA control (∼40 MPa). The hot-pressed HA–BG composites showed significantly enhanced bioactivity in a simulated body fluid, as well as osteoblast cell activity with respect to the pure HA, confirming their excellent in vitro biocompatibility.     

Degradation mechanisms of nickel oxide electrodes in zinc/nickel oxide cells with low-zinc-solubility electrolytes

Nickel oxide electrodes that suffered capacity degradation during extended cycling in zinc/nickel oxide cells were examined by a variety of chemical and physical techniques. Nickel hydroxyzincates, which have been speculated to cause such capacity degradation, were also examined. Powder X-ray diffraction experiments indicated that the intersheet distance between layers of turbostratic nickel hydroxide increased when zinc was incorporated. Photoelectron spectra (XPS) showed that this material is probably a mixture of NiOH)₂ and ZnO or Zn(OH)₂. Raman spectroscopy data also supported this conclusion. XPS indicated that the form of zinc in degraded nickel oxide electrodes is probably ZnO or Zn(OH)₂. Significant increases in resistivity were found in cycled nickel oxide electrodes, and optical microscopy provided visible evidence of mechanical damage during cycling. These results suggest that the observed capacity degradation was largely mechanical in nature, and not due to the formation of nickel-zinc double hydroxides, as had been reported by others. Cell-cycling experiments indicated that the mechanical degradation is largely irreversible.     

Sintering Behavior of Nanocrystalline Zirconia Doped with Alumina Prepared by Chemical Vapor Synthesis

Powders of nanocrystalline zirconia doped with 3–30 mol% alumina have been synthesized using chemical vapor synthesis (CVS). Dense or mesoporous ceramics of small and narrowly distributed grain and pore sizes in the nanometer range are obtained via pressureless vacuum sintering. The microstructural development of the doped samples is strongly dependent on the alumina content. Sintering of zirconia samples with 3 and 5 mol% alumina at temperatures of 1000°C for 1 h results in fully dense, transparent ceramics with grain sizes of 40–45 nm and homogeneous microstructures.     

Substrate utilisation by plant-cell cultures

Plant cell cultures have been grown on a wide range of carbon sources in addition to the traditional ones of sucrose and glucose. Biomass yields and growth rates vary greatly between the different carbon sources and there is a variation in response between different cell cultures to individual carbon sources. Some attempts have been made to grow cell cultures on ‘waste’ and related carbon sources, such as lactose, maltose, starch, molasses and milk whey. Only maltose was found to support growth to anything near the levels observed with glucose and sucrose. In the case of molasses carbon source cell growth was either non-existent or only just measurable. All the data point to glucose as being the most suitable carbon source, principally on the grounds of biomass yield and growth rate. It should be noted, however, that other carbon sources do appear to have a major (positive) influence on natural product synthesis. Uptake into the cell is an important aspect of carbohydrate utilisation. There is strong evidence that from disaccharides upwards, major degradation to smaller units occurs before uptake. In some cases the necessary enzymes appear to be excreted into the culture broth, in others they may be located within the cell wall; invertase that hydrolyses sucrose is a good example. Once the products of carbohydrate degradation and mobilisation enter the cell they may suffer one of two fates, oxidation or utilisation for biosynthesis. The precise split between these two varies depending on such factors as cell growth rate, cell size, nutrient broth composition and carbohydrate status of the cells. In general rapidly growing cells have a high rate of oxidation, whereas cells growing more slowly tend to be more directed towards biosynthesis. Carbohydrate utilisation is a key area of study, underpinning as it does both biomass yield and natural product synthesis.     

Controlled release of biocide from silica microparticles in wood paint

Porous microparticles represent an attractive encapsulation platform as they provide a feasible route to a wide range of encapsulated chemical compounds. This assures an increased lifetime of the encapsulated compound by protecting it from the surrounding environment as well as providing a way to control the release rate. Porous microparticles encapsulating the commonly used biocide for wood protection, 3-iodoprop-2-ynyl N-butylcarbamate (IPBC), have been synthesized. The microparticles are spherical with an average size distribution of roughly 1 μm as determined by scanning electron microscopy (SEM). Determination of the release rate of the biocide from microcapsules incorporated into the paint film has been performed under diluted conditions. These experiments show that a slower release of the biocide can be obtained by encapsulation. Additionally, the microparticles have been shown to prolong the biocidal effect of the fungicide under accelerated weathering tests by protecting the biocide from UV-induced chemical degradation.     

Some corrosion mechanisms in attack of resin and resin-glass laminates

In contrast to metallic corrosion where electrochemical corrosion mechanisms are dominant, a variety of mechanisms play a role in degradation of fiber reinforced plastic (FRP) structures. Attack may occur by physical or chemical means or by a combination of both. Although some actions of particular attacking species may be quite specific, there are a number of general corrosion mechanisms and broad guidelines that can be established in order to choose a resin suitable for a particular service. Corrosion mechanisms are illustrated by interactions of environments with vinyl ester resins. Attack in non-aqueous media is often related to chemical similarity between attacking specie and the resin. Among chemically similar resins, the extent of this type of attack is often influenced by the crosslink density of the resin. It is shown that the solubility parameter of the attacking specie is useful in predicting suitability of a resin for service, if the resin has been evaluated by a test sequence in organic media of varying solubility parameters. In aqueous media it is found that physical attack can occur by means of an osmotic permeation of the resin by water. Degradation by pure water is often more severe than that caused by ionic solutions. Such physical attack can cause delamination and blistering of laminates and must be regarded as a potentially serious corrosive mechanism, although not primarily chemical in nature. In addition to physical attack, chemical attack can occur. Saponification by sodium hydroxide and oxidation by sodium hypochlorite are discussed in some detail as examples. It is shown that in both these cases the chemical corrosive process may be inhibited by controlling the physical corrosion process due to water.     

Enhanced sunlight driven photocatalytic activity and electrochemical sensing properties of Ce-doped MnFe2O4 nano magnetic ferrites

This research deals with the facile combustion synthesis of manganese ferrite (MFO) nanoparticle with different cerium concentration and their potential application as an efficient photocatalyst and chemical sensor. The concentration of introduced cerium affects the size, structure, compositional, morphological, optical, photoluminescence and magnetic properties of the ferrite nanoparticle. The X-ray diffraction pattern affirmed the arrangement of cubic spinel structure with the formation of secondary phase CeO₂ as the cerium concentration exceed 3 mol%. SEM micrographs revealed irregular morphology with more number of pores and voids. HRTEM along with SAED pattern revealed the crystalline cubic nature. The optical band gap deduced from UV–Vis-DRS spectra was observed to be in the range 2.3–2.8 eV. PL studies indicated a significant minimization in combination of electrons & holes in MnFe₂O₄ on addition of Ce dopant. VSM investigation demonstrated the soft magnetic nature of the prepared sample with moderate magnetization value. An excellent photocatalytic performance of Cerium doped MFO (3 mol%) towards MB and AR dye degradation was found to be 1.5 and 1.67 times more compared to host matrix under Sunlight irradiation that correlated to reduced band gap, Ce dopant and efficient separation of charge carriers. Cerium doped MFO (3 mol%) have high specific capacitance value of 471.7 and 1546.8 Fg^-1 for NaNO₃ and HCl electrolytes respectively, indicating the pseudo capacitance nature due to which it can be used as a supercapacitor. The synthesized nanoparticles can sense d-Glucose and Paracetamol even at a lower concentration varying from 1 to 10 mM. The synthesized Ce-doped MnFe₂O₄ nanomaterials have great potential to be used in the future production of promising active photocatalysts and sensitive chemical sensors for the identification and degradation of toxic industrial dyes for improved safety in the fields of environment and health care.     

Environmental and time dependence of moisture transportation in an epoxy coating and its significance for accelerated weathering

It is increasingly appreciated that water is one of the most important factors in the durability behavior of coatings. The rate of water transportation and the degree of saturation of polymeric coatings depends on exposure history, exposure environment, and the nature of a coating. The focus here is on the time taken for transport of water and the variation it causes in thermal and mechanical properties, which have also been shown previously to have time-dependence that leads to discrepancies between different weathering regimes. This paper studied the effect of moisture on coatings’ mechanical properties and the effect of moisture and temperature on recovery of surface indentation. The reduction of mechanical properties and the increasing rate of surface defect relaxation can be explained in terms of plasticization by water. Recovery of surface defects is related to the appearance and diffusion activity of coatings during exposure. Thermogravimetric analysis showed that the content of moisture in the sample is determined by the ambient humidity, temperature, and the rate of change in these environmental parameters. Diffusion coefficients were determined from the weight change data and an activation energy was obtained via Arrhenius equation. Changes in yellowness, as an example, and signature of chemical degradation, indicated that the cycling period in accelerated weathering may affect the degradation via the amount and distribution of moisture in coatings. Diffusion of moisture is typically slow and limits the possibility of complete drying or saturation in an exposure cycle. Results from the cumulative effect of many cycles will be different depending on the conditions.     

The fate of organic nitrogen in photocatalysis: an overview

Photocatalytic processes taking place on TiO₂ have been widely employed and investigated. However, nitrogen-containing substances have not received the same attention as other substrates. Mineralization of such compounds is expected to lead to the formation of N₂ gas, ammonium and/or nitrate ions through photooxidative and/or photoreductive pathways. Herein, we will focus the attention on how the chemical structure may influence both the ratio and the extent of formation of the inorganic nitrogen. This review will consider heteroaromatic compounds, containing two or three-nitrogen in the ring, and small molecules, that could be formed as intermediate during the degradation of more complex substrates (i.e. pesticides), such as amino-alcohols, and molecules containing amide groups and nitriles. The fate final of the nitrogen in all these structures has been rationalized on the basis of the nature of N–N and C–N bonds in which the organic nitrogen is involved.     

Mechanisms of degradation of polymer composites by galvanic reactions between metals and carbon fiber

Toughened and untoughened epoxy and BMI carbon fiber reinforced composites were evaluated in terms of their matrix chemical stability in galvanic reactions between metals and composites. It has been known that the presence of moisture and salts and contact between unprotected metals and BMI carbon fiber composition constitute prerequisite conditions for composite degradation. This study has further demonstarated that these conditions were necessary, but not sufficient. It was found that the OH species generated by galvanic reactions had to be concentrated in localized spots to induce composite degradation at a significant rate. A mechanism was proposed to elucidate how degradation took place under those necessary conditions with the aid of localized aggregation of the OH⁻ species. Additionally, thoughening of BMI composite matrix resins resulted in poorer resistance to degradation by galvanic reactions. On the other hand, none of the eposy composites (toughened or untoughened) exhibited any degradation due to galvanic reactions at room temperature, nor did they degrade in a concentrated caustic NaOH solution (pH = 14,82°C) that simulated a highly accelerated galvanie reaction.     

Synthesis of Aragonite by the Carbonation Process

The conditions necessary for synthesizing aragonite by the carbonation process were investigated. Aragonite formation was found to have no relation to the pH value, the mole ratio of MgCl₂/Ca(OH)₂, or the magnesium/calcium ion concentration in a solution. The synthesis of aragonite requires a concentration of magnesium ions in the appropriate range (∼0.1–0.26 mol/L) and a concentration of calcium ions below a certain range (less than ∼0.16–0.25 mol/L). An excess of calcium ions or magnesium ions favors calcite formation. Needlelike aragonite with a large aspect ratio was successfully synthesized in the present study.     

Effects of nitrogen and carbon dioxide gases on the degradation of low‐density polyethylene during extrusion and origin of the color

The effect of inert gases, nitrogen and carbon dioxide, on the oxidative degradation of low‐density polyethylene appearing as colored spots has been studied during an extrusion process in competition with an antioxidant. Extrusion under inert gases significantly decreases the degradation level in the critical region of the process in comparison with classical extrusion under air. The effect of antioxidants on degradation during extrusion at a high temperature is weak. The main processes acting on this reduction of polymer oxidation and the origin of the color of degraded domains have been investigated. Energy‐dispersive spectra of particles have confirmed that degradation is caused by thermooxidation. The nature of chromophore groups in degraded areas has been identified by IR microscopy. We found that β‐conjugated ketoenols are present inside colored spots and seem to be responsible for the color of degraded parts. Quantum calculations have confirmed that such chemical structures absorb visible light and create reddish and brown colors. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Carbon K-edge XANES spectromicroscopy of natural graphite

Carbon K-edge soft X-ray spectromicroscopy was used to obtain information on the orientation, purity and chemical composition of graphite within natural samples. Highly crystalline natural graphite had spectra indistinguishable from highly ordered pyrolytic graphite, but contained a wide variety of internal structures in the 100-500 nm size range. These structures were both physical (domains with differing sheet orientations) and chemical in nature. Graphite sheet orientations could vary from normal to the X-ray beam to nearly perpendicular within a few hundred nanometers. Chemical compositions ranged from pure crystalline material to nearly amorphous carbon. Little evidence for significant addition of O- or N-bearing groups was observed in these samples, although this may have been a result of the extraction techniques used. The range of carbon types found in the environment may provide clues to the types of thermal alteration and source mechanisms behind graphitic kerogen fractions.     

Vermiculites intercalated with Al2O3 pillars and modified with transition metals as catalysts of DeNOx process

Vermiculites intercalated with alumina pillars and modified with transition metals (Cu, Fe) were studied as catalysts of selective reduction of NO with ammonia. Prior to the pillaring process, a raw vermiculite was treated with a solution of nitric acid and then citric or oxalic acid in order to reduce the overall charge of layers. This modification was necessary for a successful pillaring of the clay. Transition metals (Fe, Cu) were deposited on the surface of the modified vermiculites by an ion-exchange method. The obtained samples were characterized with respect to composition (EPMA), structure (XRD), texture (BET) and chemical nature of deposited transition metal species (UV–vis–DRS). The vermiculite based materials have been found to be active and selective catalysts of the DeNOx process. The Cu-containing samples were catalytically active at lower temperatures than the pillared clays modified with iron. A side reaction of ammonia oxidation by oxygen decreased the effectiveness of the DeNOx process in the high temperature range.