Polymer encapsulation of surface-modified carbon blacks using surfactant-free emulsion polymerisation

Polymer encapsulations of two different grades of water-dispersible, surface-sulfonated carbon black, Sterling-4620 with an aggregate size of 260 nm and Black Pearls-800 (BP-800) with an aggregate size of 45.7 nm, were carried out using surfactant-free emulsion polymerisation of butyl acrylate, methyl methacrylate and allyl methacrylate. High levels of initiator were required because carbon black acts as an efficient radical trap. Although polymerisation in the presence of Sterling-4620 proceeded satisfactorily using ammonium persulfate (APS), the much larger specific surface area of BP-800 inhibited polymerisation with APS and the sodium salt of 4,4′-azobis(4-cyanopentanoic acid), a non-oxidising initiator, was necessary for effective polymerisation in the presence of BP-800. Several polymer-encapsulated Sterling-4620 and BP-800 products were prepared successfully using different amounts and compositions of polymer, and have been characterised using solvent extraction, pyrolysis, thermogravimetry, infrared spectroscopy, transmission electron microscopy, differential scanning calorimetry and dynamic mechanical thermal analysis.     

Synthesis and photophysics of new highly luminescent poly(alkylthiophene) derivatives with pyridine in the backbone

Starting from 2,6-bis-(3-octylthiophene-2yl)-pyridine, two new poly(alkylthiophene) derivatives, POTPyOT and POTPy, containing pyridine in the backbone were prepared from nickel(0)-mediated Stille coupling or by palladium-catalyzed Yamamoto coupling. These polymers exhibited good solubility in common organic solvents, thermal stability up to 400 °C, and facile film formation. They were amorphous and give strong luminescence both in CHCl₃ solution and solid state film. The polymers emitted blue light in solution with photoluminescence (PL) emission maximum at 420-484 nm and green light with PL emission maximum at 500-514 nm in thin films. These polymers showed a reversible redox reaction at potential from 0 to 1.3 V (vs. SCE). Nevertheless, the reduced form of the polymer was very unstable; it decomposed in the presence of oxygen or water. The emission and UV-vis absorption of the polymer were influenced by the solvent polarity, protonation, and acid-base treatment. These may be the results of the stabilization of the polar excited state by solvation and the change of the conformation in polymer backbone. Electroluminescence (EL) was achieved from a single-layer PLED with the configuration of ITO/POTPyOT/Al. The turn-on voltage of the device is 10 V and the λ_max (550 nm) of the EL is voltage independent.     

Morphology of heat-treated tunsgten doped monolithic carbon aerogels

The morphology of a tungsten-doped monolithic organic aerogel, prepared by the sol-gel method from the polymerisation of a resorcinol, formaldehyde and ammonium tungstate mixture, and of its carbonized derivatives at 500 and 1000 °C was studied by scanning and high-resolution electron microscopy. Tungsten influenced the surface morphology of the carbon aerogels. The tungsten-containing phase was homogeneously distributed in the organic aerogel and its heat treatment produced changes in the metal phase distribution throughout the pellets. Tungsten oxide particles of needle-like structure similar to hollow tubules were detected after heat treatments at different temperatures. In addition, particles of dendritic appearance, formed by tungsten carbide and an intermediate Magnelli phase, appeared when the heat treatment was carried out at 1000 °C.     

Self-ordering of anodic porous alumina formed in organic acid electrolytes

New self-ordering porous alumina films were fabricated in organic acid electrolytes. Highly ordered cell arrangements of porous alumina films were realized in malonic acid at 120 V and tartaric acid at 195 V having 300 nm and 500 nm pore intervals, respectively. Self-organization was achieved at the maximum voltage required to induce high-current-density anodization while preventing burning, i.e., an extremely high-current flow concentrated at local points. The cells of the film grown at a high field must be pressed against each other, so that the self-ordering proceeds with the porous layer growth. When the self-ordering of cell arrangement proceeds, the cells became smaller. To improve the regularity of the cell configuration, a low electrolyte temperature and a relatively high electrolyte concentration were effective for maintaining a high-current-density to prevent burning. Surface flatness was an essential factor for self-ordering, however, the surface oxide film produced by electropolishing an aluminum substrate prevented quick pore growth in the organic acids having a low dissociation constant. It is confirmed that electropolishing followed by alkaline treatment was most appropriate as the pre-treatment in preparing flat surfaces.     

High glass transition and thermal stability of new pyridine-containing polyimides: Effect of protonation on fluorescence

A new diamine monomer containing heterocyclic pyridine and triphenylamine groups, 4-(4,4′-diaminotriphenylamine)-2,6-bis(4-methylphenyl)pyridine (4), was synthesized by Chichibabin and nucleophilic fluoro-displacement reactions. The diamine was used to prepare a series of novel polyimides via polycondensation with various aromatic tetracarboxylic dianhydrides in N-methyl-2-pyrrolidinone. The polyimide 4a derived from the diamine 4 with 4,4′-hexafluoroisopropylidenediphthalic anhydride and having high T_g (313 °C), mechanical, and thermal properties was soluble in various organic solvents, such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, pyridine, chloroform, tetrahydrofuran, at room temperature. The polyimide (4a) could be cast into a self-standing film from DMAc solution and was thermally converted into tough and flexible film. The film had high tensile modulus of 2.2 GPa and exhibited excellent thermal stability in both nitrogen and air (T_d¹⁰ > 550 °C). The pristine polymer exhibited the UV-vis absorption bands in the region 240-400 nm and protonated polymer exhibited absorption in the region 390-500 nm. The protonated polymer possessed strong orange fluorescence (around 600 nm) in THF solution after protonation with acids as excited at 438 nm. The fluorescent intensity was influenced by the acid concentrations and the chemical structure of conjugated bases. The fluorescent intensity at 600 nm increased as acid concentration from a lower to a moderate concentration and decreased at higher concentrations.     

Optical and thermo-optical properties of space durable polymer/carbon nanotube films: experimental results and empirical equations

The incorporation of purified high-pressure carbon monoxide prepared single-walled carbon nanotubes (HiPco SWNTs) into the bulk of space environmentally durable polymers at loading levels ≥0.05 wt% has afforded thin films with surface and volume resistivities sufficient for electrostatic charge mitigation. However, the optical transparency at 500 nm decreased and the solar absorptivity increased with increased SWNT loading. Besides showing a loading dependency, these properties were also dependent upon film thickness. The absorbance of the films at 500 nm as a function of SWNT loading and film thickness was determined to follow the classic Beer-Lambert law. Based on these results, a simple empirical relationship was derived to provide a predictive approximation of these properties. The molar absorptivity determined for the purified HiPco SWNTs dispersed in the polymer by this simple treatment was of the same order of magnitude to reported solution determined values for HiPco SWNTs.     

Single-monomer acrylate-based resin for three-dimensional photonic crystal fabrication

A single-monomer acrylate resin (SR348, Sartomer) with an aromatic ketone photoinitiator (Irgacure 369, Ciba) has been developed to produce photonic crystal structures by two-photon photopolymerisation. Compared with more complex acrylate-based resins, this one-component resin is easily prepared. The material is homogeneous before and after photocuring and has a high photosensitivity. SR348 (ethoxylated (2) bisphenol A dimethacrylate) is a difunctional monomer, which generates an insoluble crosslinked network by free radical polymerisation. The polymerised material is thermally stable up to 300 °C. Its refractive index jumps from 1.54 to 1.59 upon polymerisation. Scanning electron microscopy images of photonic crystal structures reveal a minimum structural element size of approximately 300 nm. The photonic crystals were fabricated in a 40 layer woodpile structure at a layer-spacing of 500 nm and an in-plane rod spacing of 1.5 μm. Fundamental stop gaps were observed in the stacking direction at wavelengths of 1.9-2.3 μm dependent on the rod size. Suppression of infrared light transmission of as much as 40% in the stop gap region and gap/midgap ratios of up to 0.15 demonstrate the high degree of correlation of structural elements in three dimensions.     

Preparation and characterization of thin organosilicon films deposited on SPR chip

The paper reports on the preparation and characterization of organosilicon thin polymer films deposited on glass slides coated with 5 nm adhesion layer of titanium and 50 nm of gold. The polymer was obtained by the decomposition of 1,1,3,3-tetramethyldisiloxane precursor (TMDSO) premixed with oxygen induced in a N₂ plasma afterglow using remote plasma-enhanced chemical vapor deposition (PECVD) technique. The film thickness was controlled by laser interferometry and was 9 nm. The chemical stability of the gold substrate coated with the organosilicon polymer film (p-TMDSO) was studied in different acidic and basic solutions (pH 1-14). While the gold/polymer interface showed a high stability in acidic media, the film was almost completely removed in basic solutions. The resulting surfaces were characterized using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), water contact angle measurements, cyclic voltammetry, and surface plasmon resonance (SPR).     

Electric double layer capacitors with gelled polymer electrolytes based on poly(ethylene oxide) cured with poly(propylene oxide) diamines

Using a gel electrolyte for electric double layer capacitors usually encountered a drawback of poor contact between the electrolyte and the electrode surface. A gel electrolyte consisting of poly(ethylene oxide) crosslinked with poly(propylene oxide) as a host, propylene carbonate (PC) as a plasticizer, and LiClO₄ as a electrolytic salt was synthesized for double layer capacitors. Diglycidyl ether of bisphenol-A was blended with the polymer precursors to enhance the mechanical properties and increase the internal free volume. This gel electrolyte showed an ionic conductivity as high as 2 × 10⁻³ S cm⁻¹ at 25 °C and was electrochemically stable over a wide potential range (ca. 5 V). By sandwiching this gel-electrolyte film with two activated carbon cloth electrodes (1100 m² g⁻¹ in surface area), we obtained a capacitor with a specific capacitance of 86 F g⁻¹ discharged at 0.5 mA cm⁻², while the capacitance was 82 F g⁻¹ for a capacitor equipped with a liquid electrolyte of 1 M LiClO₄/PC. The capacitance decrease with the current density was less significant for the gel-electrolyte capacitor. We found that the less restricted ion diffusion near the electrolyte/electrode interface led to the smaller overall resistance of the gel-electrolyte capacitor. The high performance of the gel-electrolyte capacitor has demonstrated that the developed polymer network not only facilitated ion motion in the electrolyte bulk phase but also gave an intimate contact with the carbon surface. The side chains of the polymer in the amorphous phase could stretch across the boundary layer at the electrolyte/electrode interface to come into contact with the carbon surface, thus improving transport of Li⁺ ions by the segmental mobility in polymer.     

Hexadecyl-functionalized lamellar mesostructured silicates and aluminosilicates designed for polymer-clay nanocomposites. Part I. Clay synthesis and structure

Motivated by a need for synthetic clays that can be dispersed and exfoliated in polymer melts without added compatibilizers, lamellar mesostructured silicates and aluminosilicates with covalently attached hexadecyl functional groups (C₁₆-LMS and C₁₆-LMAS, respectively) were prepared by sol-gel syntheses and their structures were characterized. Based on XRD and TEM data, lamellar products with layer spacings of 4.8-4.9 nm were obtained between room temperature and 60 °C (C₁₆-LMS) or 70 °C (C₁₆-LMAS). The degree of condensation of the aluminosilicate layers increased at the higher synthesis temperatures. Attachment of organic groups to the inorganic sheets was confirmed by ²⁹Si solid state MAS NMR and IR spectroscopy. The sheets of C₁₆-LMS consisted of single or double layers of tetrahedral silicate groups, each attached to a hexadecyl chain. C₁₆-LMAS was composed of pyrophyllite-like layers (Si:Al=2) with an octahedral aluminum layer sandwiched between two tetrahedral silicate layers and hexadecyl surface groups. Tetrahedral aluminum sites were also present. The clay layer spacing could be increased to 5.2 nm by addition of tetraethoxysilanes during the synthesis (C₁₆-SiO₂-LMAS). C₁₆-SiO₂-LMAS was structurally similar to C₁₆-LMAS; however, the presence of additional silicate groups in this structure increased the inorganic layer thickness and introduced further structural disorder.     

The effect of heat treatment on formation of graphene thin films from graphene oxide nanosheets

Graphene thin films with very low concentration of oxygen-containing functional groups were produced by reduction of graphene oxide nanosheets (prepared by using a chemical exfoliation) in a reducing environment and using two different heat treatment procedures (called one and two-step heat treatment procedures). The effects of heat treatment procedure and temperature on thickness variation of graphene platelets and also on reduction of the oxygen-containing functional groups of the graphene oxide nanosheets were studied by atomic force microscopy and X-ray photoelectron spectroscopy. While formation of the thin films composed of single-layer graphene nanosheets with minimum thickness of 0.37 nm and nearly without any functional group bonds was observed at the high temperature of 1000 °C in the one-step reducing procedure, similar high quality graphene thin films were obtained at the lower temperature of 500 °C in our two-step reducing temperature. The results also indicated possibility of efficient reduction of the graphene oxide thin films at even lower heat treatment temperatures (?500 °C).     

Synthesis and characterization of polyesters containing fluorescein dye units

Low molecular weight polyesters containing fluorescein units in their backbones were successfully synthesized. These fluorescent polymers showed a high solubility in most of the common organic solvents. The onset degradation temperatures of the polymers were greater than that of fluorescein. The glass transition temperatures were in the range 126-194 °C. The bathochromic fluorescence emissions in organic solutions at high concentrations, which resulted from the aggregation of fluorescein moieties, were prohibited by protecting the OH end groups with benzoyl groups. The polymer powders exhibited a maximum photoluminescence intensity at about 580 nm.     

Raman spectroscopy and nitrogen vapour adsorption for the study of structural changes during purification of single-wall carbon nanotubes

Raman spectroscopy and nitrogen adsorption measurements were combined to study the surface features of semi-conducting and metallic single-wall nanotubes (SWNTs). The nanotubes were treated chemically and with heat under moderate conditions that more than doubled the mesopore volume of the tested samples, which consistently led to a significant rise in the total surface area of up to 1550 m²/g. The large increase in the number of micropores of less than 1 nm in diameter was associated with the loosening of nanotube bundles as well as the creation of structural flaws on the surface of individual SWNTs due to chemical treatment. Micropores in the 1.0-1.8 nm range were associated with the holes created on the surface of individual tubes. Heating at 1000 °C was shown to restore nanotube diameter to their initial pre-chemical treatment levels with the change in the chirality of SWNTs and diminish the porosity by closing small holes. It was assumed that the intermediate frequency range (500-1100 cm⁻¹) was associated with the degree of imperfection of HiPco SWNTs crystalline structures, and therefore provided information about the degree of tube surface damage due to the presence of functional groups. A hypothesis explaining the transformation of SWNT porous structure during heat treatment is proposed.     

Unobstructed electron transfer on porous polyelectrolyte nanostructures and its characterization by electrochemical surface plasmon resonance

Thin organic films with desirable redox properties have long been sought in biosensor research. We report here the development of a polymer thin film interface with well-defined hierarchical nanostructure and electrochemical behavior, and its characterization by electrochemical surface plasmon resonance (ESPR) spectroscopy. The nano-architecture build-up is monitored in real time with SPR, while the redox response is characterized by cyclic voltammetry in the same flow cell. The multilayer assembly is built on a self-assembled monolayer (SAM) of 1:1 (molar ratio) 11-ferrocenyl-1-undecanethiolate (FUT) and mercaptoundecanoic acid (MUA), and constructed using a layer-by-layer deposition of cationic poly(allylamine hydrochloride) (PAH) and anionic poly(sodium 4-styrenesulfonate) (PSS). Electron transfer (ET) on the mixed surface and the effect of the layer structures on ET are systematically studied. Under careful control, multiple layers can be deposited onto the 1:1 FUT/MUA SAM that presents unobstructed redox chemistry, indicating a highly ordered, extensively porous structure obtained under this condition. The use of SPR to trace the minute change during the electrochemical process offers neat characterization of local environment at the interface, in particular double layer region, allowing for better control over the redox functionality of the multilayers. The 1:1 SAM has a surface coverage of 4.1 ± 0.3 × 10⁻¹⁰ mol cm⁻² for ferrocene molecules and demonstrates unperturbed electrochemistry activity even in the presence of a 13 nm polymer film adhered to the electrode surface. This thin layer possesses some desirable properties similar to those on a SAM while presenting ∼15 nm exceedingly porous structure for high loading capacity. The high porosity allows perchlorate to freely partition into the film, leading to high current density that is useful for sensitive electrochemical measurements.     

Characterization of Chinese, American and Estonian oil shale semicokes and their sorptive potential

The primary byproduct of current oil shale oil extraction processes is semicoke. Its landfill deposition presents a potential threat to the environment and represents a waste of a potentially useable byproduct. Here we examine the sorptive characteristics of oil shale semicoke. Oil shale samples from Estonia, China and the United States were pyrolyzed at 500 and 1000 °C and their products analyzed for organic char content, surface area and porosity. Pyrolysis of the oil shales at temperatures of 500-1000 °C yields semicokes with organic char contents from 1.7% to 17.5% and BET surface areas of 4.4-57 m² g⁻¹, corresponding to 100-550 m² g⁻¹ of organic char. For comparison, the BET surface areas of class F coal fly ashes (combustion byproducts of bituminous coals) typically range from 2 to 5 m² g⁻¹, corresponding to 30-60 m² g⁻¹ of carbon while class C fly ash (from low rank coals) have carbon BET surface areas comparable to oil shale semicoke organic char surface areas.     

Electrochemically synthesized nano size copolymer, poly (aniline-co-ethyl 4-aminobenzoate) and its spectroelectrochemical studies

Electroactive conducting copolymers of aniline (ANI) and ethyl 4-aminobenzoate (EAB) were prepared electrochemically. Cyclic voltammetric studies were carried out with different feed concentration of EAB on glassy carbon electrode surface. The voltammograms exhibited different behavior for different concentrations of EAB. The copolymers exhibited high solubility in many polar solvents. The scan rate exerted good influence on the polymer effect on this GCE copolymer film, revealing electroactive film’s excellent adherent properties. The effect of pH on the copolymer film showed that the polymer was electrochemically active up to pH 7.0. Spectroelectrochemical analysis of the copolymer film, carried out on an indium tin oxide (ITO) plate, showed multicolor electrochromic behavior when the applied potential was changed. The color of the copolymer was changed from neutral yellow (422 nm) to green (760 nm) and to blue (600 nm) at the concentration of 0.1 M aniline and 0.1 M EAB in 0.1 M H₂SO₄ medium. The copolymer was characterized by FT-IR spectral data. The surface morphology were studied using SEM and TEM analysis. The grain size of the copolymer was measured using XRD studies and was found to be 80 nm. The electrical conductivity of the copolymer was 3.21 × 10⁻² S cm⁻¹, as determined using a four-probe conductivity meter.     

Copolymerisation of 1,9-decadiene and propylene with binary and isolated metallocene systems

1,9-Decadiene/propylene copolymers were obtained with isolated metallocenes and with a binary metallocene catalyst system activated by methylaluminoxane. The metallocenes under investigation were syndiospecific diphenylmethyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (1) and isospecific rac-dimethylsilylbis(4-tert-butyl-2-methyl-cyclopentadienyl)zirconium dichloride (2). A copolymer structure, in which 1,9-decadiene linked isotactic and syndiotactic polymer chains, was obtained when copolymerisation was started with catalyst 2 at 80 °C followed by injection of catalyst 1 and instantaneous lowering of polymerisation temperature to 40 °C after 15 min of polymerisation. The copolymer was also shown to work as a compatibiliser in a blend of syndiotactic and isotactic polypropylene. We propose that catalyst 2 incorporates 1,9-decadiene into the isotactic main chain without any significant crosslinking within the first 15 min of polymerisation at 80 °C and the produced isotactic macromonomers are further incorporated at 40 °C into the syndiotactic main chain in polymerisation with catalyst 1.     

Preparation and surface characteristics of low-temperature curing fluorinated cathodic electrodeposition coating

Fluorinated cationic cathodic electrodepositing (CED) resins were synthesized by copolymerization of several acrylic monomers including Zonyl. Water dispersible cationic blocked-diisocyanate (denoted as TId) was also synthesized from isophorone diisocyanate (IPDI), cationic triethanolamine (TEOA), and dimethylpyrazole as the cross-linker for the low temperature curing at 90–120 °C. The emulsion stability of the cationic fluorinated CED resin was improved by ionization of the cross-linker TId, showing a mean particle diameter of 140–150 nm and a narrow distribution. 0.5 wt% of curing catalyst dibutyltin dilaurate (DBTL) was enough to accelerate the curing reaction and the gel content of the TId cured fluorinated CED film was higher than 90 wt% after being cured at 130 °C for 40 min. The contact angle and XPS spectrum of the CED film demonstrated that the surface enrichment of C–F₂ and C–F₃ groups effectively reduced the surface tension of the fluorinated CED coating and its surface tension γ_sv is even lower than 15 mN m⁻¹ for PTFE. The preheating of the CED film above T_g but below curing temperature promoted this surface enrichment of the fluorinated groups. Thermal fragmentation of the fluorinated side chains in the CED resins was successfully avoided due to using TId for low temperature curing.     

The electrochemical redox processes in PMMA gel electrolytes—behaviour of transition metal complexes

Electrochemical properties of polymer gel electrolytes based on polymethylmethacrylate (PMMA) were studied by cyclic voltammetry and impedance spectroscopy using new solid-state PMMA-Cd-Cd²⁺ reference electrode. The suitable potential window of the PC-PMMA system was estimated from -0.2 to + 1.5 V versus Cd-Cd²⁺. New polymer gels containing ferrocene-ferricinium (Fc-Fc⁺) couple and other transition metal complexes were prepared by the direct polymerisation of methylmethacrylate (MMA) monomer and the solution of metal complex and supporting electrolyte in anhydrous aprotic solvent—propylene carbonate (PC). The half-wave potentials and apparent diffusion coefficients of used complexes and their dependence on the composition of the system (liquid or gel) were estimated. Time dependent electrochemical measurements showed almost three order decrease of the diffusion coefficients of ferrocene (Fc) and ferricinium (Fc⁺) cation from 6 × 10⁻⁵ to 2 × 10⁻⁹ cm² s⁻¹ during the polymerisation from the liquid to the polymer state. The results show that the PC-PMMA gel electrolyte can be described as a system of embedded solvent in the polymer network of PMMA without present monomer.     

Effect of carbon fiber surface functional groups on the mechanical properties of carbon-carbon composites with HTT

The present investigation describes the quantitative measurement of surface functional groups present on commercially available different PAN based carbon fibers, their effect on the development of interface with resol-type phenol formaldehyde resin matrix and its effect on the physico-mechanical properties of carbon-carbon composites at various stages of heat treatment. An ESCA study of the carbon fibers has revealed that high strength (ST-3) carbon fibers possess almost 10% reactive functional groups as compared to 5.5 and 4.5% in case of intermediate modulus (IM-500) and high modulus (HM-45) carbon fibers, respectively. As a result, ST-3 carbon fibers are in a position to make strong interactions with phenolic resin matrix and HM-45 carbon fibers make weak interactions, while IM-500 carbon fibers make intermediate interactions. This observation is also confirmed from the pyrolysis data (volume shrinkage) of the composites. Bulk density and kerosene density more or less increase in all the composites with heat treatment up to 2600 °C. It is further observed that bulk density is minimum and kerosene density is maximum upon heat treatment at 2600 °C in case of ST-3 based composites compared to HM-45 and IM-500 composites. It has been found for the first time that the deflection temperature (temperature at which the properties of the material start to decrease or increase) of flexural strength as well as interlaminar shear strength is different for the three composites (A, B and C) and is determined by the severity of interactions established at the polymer stage. Above this temperature, flexural strength and interlaminar shear strength increase in all the composites up to 2600 °C. The maximum value of flexural strength at 2600 °C is obtained for HM-45 composites and that of ILSS for ST-3 composites.