Enhancing exterior performance of clear coatings through photostabilization of wood. Part 2: coating and weathering performance

Clear-coated boards have not been recommended for use in exterior conditions since irradiation with visible and UV radiation darkens them and photodegrades the lignin in the wooden surface beneath the coating, leading to delamination and subsequent catastrophic coating failure due to the continued action of sun, rain, and biological factors. Many approaches to rectify this problem have been explored. Chemical modification of the surface with hexavalent chromium, reaction with various anhydrides, grafting of UV absorbers, and esterification are among the methods attempted. A second approach has been via the clear coating itself where UV absorbers, antioxidants, and ultrafine titanium and iron oxides have been added. However, these have had limited or no success in stopping photodegradation processes. Since the main cause of photodegradation is photooxidation of lignin in the wooden surface as a consequence of free radical reactions initiated by UV irradiation, the approach taken in the present study, in an attempt to enhance the weathering performance of clear-coated boards outdoors, was to delignify the surfaces of wooden boards and then apply clear coatings to try and retard possible photodegradation. Two different pretreatments were used. Firstly, chemical surface delignification with a peracetic acid treatment created a partial delignification to a depth of 2–3 mm while still retaining the structural integrity of the surface. Secondly, a preweathering treatment, which resulted in a 100-μm-deep delignification zone, was compared. The coatings applied to the exposure surface of the pretreated boards were either polyurethane or an acrylic varnish. The clear-coated boards were exposed to exterior and accelerated weathering regimes for 3 years or 3000 h, respectively. Pretreated coated boards did not darken and yellow on exposure but untreated coated boards did. However, despite apparently arresting photodegradative processes on board surfaces, there were no significant gains in the performance ratings of coated pretreated boards over those of coated untreated control boards. Explanations for this involve the effectiveness of design factors incorporated into boards for exposure trials. These factors were the fungicidal dipping of boards before coating, precoating the exposure surface with a reactive primer, and applying a full polyurethane system to the back side and edges of boards. Both pretreatments resulted in clear-coated board surfaces that performed very similarly on exposure outperforming systems reported previously. It was surprising to observe that the preweathering treatment, which resulted in a 100-μm-deep delignification zone, performed as effectively as the chemically pretreated boards with 2- to 3-mm treatment zone. However, preweathered surfaces had lost all lignin in the middle lamella and there was cell separation, whereas in peracetic acid-treated boards, there was more or less complete lignin removal from the cell corner middle lamella only and partial lignin removal from other cell wall regions. Furthermore, it is anticipated that refinements in treatment methods and coating formulations will bring desired benefits and future work should focus in this area.     

The effects of regeneration-phase CO and/or H2 amount on the performance of a NOX storage/reduction catalyst

The effects of regeneration-phase CO and/or H₂, and their amounts as a function of temperature on the trapping and reduction of NO_X over a model and a commercial NO_X storage/reduction catalyst have been evaluated. Overall, for both catalysts, their NO_X removal performance improved with each incremental increase in H₂ concentration. For the commercial sample, using CO at 200 °C, beyond a small amount added, was found to decrease performance. The addition of H₂ to the CO-containing mixtures resulted in improved performance at 200 °C, but the presence of the CO still resulted in decreased performance in comparison to activity when just H₂ was used. With the model sample, the presence of CO resulted in very poor performance at 200 °C, even with H₂. The data suggest that CO poisons Pt sites, including Pt-catalyzed nitrate decomposition. At 300 °C, H₂, CO, and mixtures of the two were comparable for trapping and reduction of NO_X, although with the model sample H₂ did prove consistently better. With the commercial sample, H₂ and CO were again comparable at 500 °C, but mixtures of the two led to slightly improved performance, while yet again H₂ and H₂-containing mixtures proved better than CO when testing the model sample. NH₃ formation was observed under most test conditions used. At 200 °C, NH₃ formation increased with each increase in H₂, while at 500 °C, the amount of NH₃ formed when using the mixtures was higher than that when using either H₂ or CO. This coincides with the improved performance observed with the mixtures when testing the commercial.     

Electrochemical atomic layer deposition of a CuInSe2 thin film on flexible multi-walled carbon nanotubes/polyimide nanocomposite membrane: Structural and photoelectrical characterizations

This study describes a method for the fabrication of an electrochemical atomic layer deposition (EC-ALD) used to fabricate the ternary, semiconducting compound, CuInSe₂ (CISe), onto a flexible, carboxyl-functionalized multi-walled carbon nanotube/polyimide (COOH-MWCNT/PI) nanocomposite membrane. The elements were deposited using amperometric methods (I–t) in the following sequence: Se/Cu/Se/In/Se/Cu/Se/In and so on, in which the optimum deposition potential for each element was obtained via a cyclic voltammetry (CV) technique. Field emission scanning electron microscopy (FE-SEM) showed that the deposits consisted of many spherical nanoparticles, and energy dispersive spectroscopy (EDS) analysis indicated that the atomic ratio of the deposits (CuInSe) was 1.14 1.00 2.18, similar to the stoichiometric value of the compound. Near Fourier transform infrared spectroscopy (FT-IR) transmission measurements provided a band gap of 1.05 eV, which was confirmed by the absorption spectrum. Open-circuit potential (OCP) and current-voltage (I–V) measurements showed the resulting composite had a good p-type property. CISe spherical NPs electrodeposited on the CNTs/PI membrane may have promising applications in optoelectronic nanodevices and nanotechnologies; in addition, the CNTs/PI membrane could be used as raw material for manufacturing solar cells.     

Metallo-Supramolecular Polymerization: A Route to Easy-To-Process Organic/Inorganic Hybrid Materials

The self-assembly polymerization of ditopic macromolecules via metal–ligand binding is a facile route for the preparation of metallo-supramolecular polymers (MSPs). We herein review our recent work focused on the synthesis and investigation of metallo-supramolecular polymers based on 2,6-bis(1′-methylbenzimidazolyl)pyridine endcapped poly(p-phenylene ethynylene) and poly(p-xylene) macromonomers. These materials are readily solution-processable and display appreciable mechanical properties as well as other attractive properties such as specific opto/electrical functions or high thermal stability. Our work illustrates that metallosupramolecular polymerization offers an attractive approach to assemble high-molecular-weight macromolecules from well-defined, easy to process precursors. Variation of the ditopic ligands and metal ions allows one to easily tailor the desired properties. This paper is dedicated to Professor Ian Manners and his scientific accomplishments.     

Enhancing exterior performance of clear coatings through photostabilization of wooden surfaces. Part 1: Treatment and characterization

The aim of this work was to produce a less photodegradation-prone substrate for clear coating by partially delignifying the surface cells of Pinus radiata boards to a depth of 2–3 mm while maintaining the integrity of the wood surface tissues in the delignified zone. To achieve this, several surface oxidative delignification treatments were trialled in the method development process and peracetic acid was chosen as the method for refinement and deployment. The treatment method was optimized to yield a significant degree of delignification compatible with the aim of producing a photostabilized yet intact wooden surface. A preweathering technique was also used as a second delignification method for producing photostabilized boards. Microscopic and chemical techniques were used to characterize the effects of chemical and preweathering treatments, which produced delignified surface envelopes 2–3 mm and 100 μm deep, respectively. Acetyl bromide lignin analyses, infrared spectroscopic analyses, and density changes of 30-μm-thick sections of peracetic-acid-treated samples, as a function of depth from the wood surface, suggested that a partial delignification had occurred that diminished with depth. Light and transmission electron microscopy provided evidence of delignification at the cellular level. In the surface layers of peracetic-acid-treated boards, all cell wall regions were delignified, with the middle lamella being the most severely affected. Lignin appeared to be completely removed from the cell corner middle lamella regions, but tracheids were still joined in other parts of the middle lamella. The S₁, S₂, and S₃ walls were also delignified. In subsurface layers, cell walls were only partially delignified and the tissues held their integrity. In contrast, in the preweathered boards, cell walls in the outermost layers were completely separated at the middle lamella from photodegradation. Preferential lignin removal over that of hemicelluloses was achieved via oxidative treatment of solid wood. The outcome of this was the successful fulfillment of our aim to produce partially delignified wooden surfaces that retained sufficient strength and aesthetic appearance and were suitable for application in wooden structures, provided that the necessary protection measures were carried out. Due to the narrow surface zone produced, machining of such surfaces would not be recommended as the most delignified zone would be removed first. In Part 2 of this series, the photostability of treated boards, which had been clear coated and weathered, will be considered.     

Thermo pervap: The next step in energy efficient pervaporation

Thermo pervaporation (PV) is a pervaporation process that makes use of low quality heat to recover or purify solvents from water. Based on this technology it is possible to integrate the condensation energy for the direct heating of the feed during pervaporation in one single module.This concept was experimentally investigated for the separation of ethanol from a mixture of ethanol-water. It was possible to obtain a heat recovery of 33% (meaning that 33% of the heat transferred to the feed stream is condensation heat) and fluxes up to 0.5 kg/m² h at high ethanol concentration.     

The depth profiling of TiO2 pigmented coil coatings using step scan phase modulation photoacoustic FTIR

The depth distribution of a TiO₂ pigment within the polyurethane (PU) coil coatings is investigated using step scan phase modulation photoacoustic (SS-PM-PA) FTIR. Coil coatings with different pigment contents were prepared and the modulation frequency (MF) of the SS-PM-PA FTIR varied to record the depth distribution of the pigment within the coating. The TiO₂ pigment was shown to contribute significantly to the SS-PM-PA FTIR signal. A TiO₂ aggregated region within the topcoat is found close to the topcoat-primer interface and further away from the topcoat surface. A deeper TiO₂ aggregated region can be identified when pigment content is relatively low. The SS-PM-PA FTIR signal shows a considerable contribution from the primer originated signal, provided the TiO₂ pigment content is sufficiently high and the modulation frequency applied is relatively low. SEM cross-section imaging results show a strong correlation of the TiO₂ depth distribution with SS-PM-PA FTIR results, which confirms the applicability of the SS-PM-PA FTIR technique to the depth profiling study of TiO₂ pigmented coil coatings.     

Electrochemical performance of CoSb3/MWNTs nanocomposite prepared by in situ solvothermal synthesis

In situ solvothermally synthesized composite (SSC) and mechanically blended composite (MBC) of nanosized CoSb₃ and multiwalled carbon nanotubes (MWNTs) were prepared and investigated as potential anode materials for Li-ion batteries. It was found that SSC exhibits an entanglement structure of nanosized CoSb₃ and MWNTs and shows significantly better cycling stability than MBC. The reversible capacity of SSC electrode reaches 312 mA h g⁻¹ at the first cycle and remains above 265 mA h g⁻¹ after 30 cycles.     

FA selectivity of lipases in acyl-transfer reactions with acetate esters of polyols in organic media

FA reaction selectivity of Burkholderia cepacia, Rhizomucor miehei, and Candida antarctica fraction B lipases was compared between acyl-transfer and esterification reactions. Multicompetitive reaction mixtures containing a series of n-chain FA (a C₄–C₁₈ series; and a C_18∶x series, where X=0-3 double bonds) and a single acetate ester co-substrate [triacetin, 1,2-propanediol (1,2-PD)diacetate, and 1,3-PD diacetate] were studied in tert-butyl methyl ether at an a _w of 0.69. For B. cepacia lipase, FA optima for C₈, C₁₆, and C_18∶2 were observed in all reactions with 1.0- to 5.9-fold differences in FA selectivity. For R. miehei lipase, an optimum for C₈ FA was observed in all reactions with 1.2- to 6.7-fold differences in FA selectivity. For C. antarctica lipase, FA optima for C₈/C₁₀ were observed in all reactions with 1.0- to 2.8-fold differences in FA selectivity. FA selectivities were broadly modulated upon changing from free polyol to acetate ester co-substrates for B. cepacia and R miehei lipases, whereas FA selectivity modulations were more specific upon this change in reaction configuration for C. antarctica B lipase. For all lipases, reactivity toward unsaturated C_18∶x FA was enhanced in acyl-transfer relative to esterification reactions with these polyol co-substrates.     

Synthesis, characterization and enhanced photocatalytic activity of TiO2/SiO2 nanocomposite in an aqueous solution and acrylic-based coatings

In this study, TiO₂/SiO₂ nanocomposites were synthesized via a sol-gel route by adding tetraethylorthosilicate (TEOS) to a solution containing different molar ratios of Degussa P25 TiO₂ nanoparticles. FTIR, TGA, EDAX and XRD techniques were used to characterize the modified nanoparticles. Photocatalytic activity of the nanoparticles in an aqueous solution and into the acrylic based coating was evaluated using colour coordinate data measurements, SEM analysis, gloss measurements and FTIR spectroscopy, in the presence of Rhodamine B (Rh.B) dyestuff, as a pollutant model, before and after exposure to the UVA (340 nm) irradiation and compared to their unmodified counterparts.The results showed that silica grafting effectively reduced the photocatalytic activity of the TiO₂ nanoparticles as evidenced by absorption spectra and colour changes of Rh.B aqueous solutions during the UVA irradiation. The results revealed the effectiveness of sol-gel route for preparation of TiO₂/SiO₂ nanocomposites. The optimum result was obtained with 1% molar ratio of TiO₂:TEOS. Addition of TiO₂/SiO₂ nanocomposites into the acrylic based coating revealed reduction of photo-degradation of Rh.B compared to untreated nanoparticles. Finally, inclusion of TEOS treated TiO₂ nanoparticles into the aqueous organic coatings, provides photocatalytic property and as a result, it can possibly be considered for self-cleaning coatings.     

Cyclopropenoic fatty acids in gymnosperms: The seed oil of Welwitschia

The seed oil of the gymnosperm Welwitschia mirabilis was found to contain malvalic acid, a cyclopropenoic fatty acid. This is in sharp contrast to most other gymnosperms, which contain Δ5cis-fatty acids as well as the normal set of fatty acids. The importance of this finding in relation to questions of the evolution of the Gymnospermae and Angiospermae, the two main branches of higher plants, is briefly discussed.     

Synthesis and characterization of per-substituted spermine-bridged cyclophosphazene derivatives: the first example of syn/anti conformational polymorphism in a bridged cyclophosphazene

The synthesis and characterization of a series of per-substituted spermine-bridged cyclophosphazene derivatives are reported based on the known compound [N₃P₃X₄(NHCH₂CH₂CH₂N)CH₂CH₂]₂, (1a) (where X = Cl), to give a number of new compounds (1b–1h) in which X = OPh, [spiro-O(CH₂)₃O]_0.5, OCH₂CF₃, NHPh, NC₄H₈, Ph and NHBu^t, respectively. Two synthetic routes were utilized: (i) using the chloro-precursor 1a in nucleophilic substitution reactions with a variety of anionic and neutral nucleophiles to give compounds 1b–1f and (ii) reaction of spermine with the appropriate di-gem tetrasubstituted cyclophosphazene to give compounds 1g and 1h. Bridged compounds such as 1a–1h may exist as syn or anti conformers in the solid state and the first example of syn and anti conformational polymorphism is reported for a bridged cyclophosphazene, viz. for compound 1a.     

Rapid degradation of new disinfection by-products in drinking water by UV irradiation: N-Nitrosopyrrolidine and N-nitrosopiperidine

Disinfection by-products (DBPs) have caused a great threat to drinking water security. Nitrosoamines that are potent carcinogenic, mutagenic, and teratogenic have been discovered in disinfection process as a new kind of DBPs. Accordingly, nitrosoamines elimination from water should be of particular concern. In this paper, UV irradiation was used to degrade the model DBPs: N-nitrosopyrrolidine (NPyr) and N-nitrosopiperidine (NPip). The results showed that UV irradiation was an effective method for the removal of both NPyr and NPip from water. NPip was easier to be degraded compared with NPyr. Water pH had little effect on NPyr photodegradation, but had great influence on NPip photodegradation. The characteristic of the natural water influenced the removal efficiency of NPyr and NPip slightly, suggesting that UV irradiation was effectual to eliminate NPyr and NPip in practice. Due to N–N bond fission, pyrrolidine and piperidine were generated as the primary products of NPyr and NPip photodegradation, respectively. Then aliphatic amines with low molecular weight were formed as further degradation products of NPyr, including methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine and n-methylethylamine. Methylamine, dimethylamine, n-propylamine, n-methylethylamine, diethylamine, n-butylamine and n-amylamine were formed as the further degradation products of NPip.     

Improving electrochemical performance of graphitic carbon in PC-based electrolyte by nano-TiO2 coating

Graphitic carbon was coated with nano-TiO₂ by a simple mechanical process. X-ray diffraction and scanning electron microscopy were used to measure the crystal structure and surface morphology of the coated composite. Tests of galvanostatic discharge and charge and cyclic voltammograms suggest that the decomposition of propylene carbonate and the exfoliation of graphite are greatly suppressed. Lithium ions can reversibly intercalate into and deintercalate from the TiO₂-coated graphite, and quite stable cycling behavior in propylene carbonate-based electrolyte is achieved.     

Advanced De-SOx catalyst: Mixed solid solution spinels with cerium oxide

Mixed solid solution spinels impregnated with cerium, Ce/MgO·MgAl_2-xM_xO₄ (M=Fe, V, Cr, x≤0.4), were studied for controlling the SO_x emission from the fluid catalytic cracking (FCC) regenerator. An insufficient sulfur release problem inherent to the earlier De---SO_x catalyst, Ce/MgO·MgAl₂O₄, was effectively overcome by incorporating a transition metal into the spinel structure. Studies of the SO_x pick-up, temperature profile for the sulfate reduction, the thermal analysis, and the De---SO_x cycle test in the batch as well as the automated continuous reactor are discussed to define the role of a transition metal in the mixed spinels for the De---SO_x performance. These advanced De---SO_x catalysts have led to a commercial success for the simultaneous control of SO_x and NO_x emissions from the FCC regenerator.     

NOx storage behavior and sulfur-resisting performance of the third-generation NSR catalysts Pt/K/TiO2–ZrO2

The NO_x storage and reduction (NSR) catalysts Pt/K/TiO₂–ZrO₂ were prepared by an impregnation method. The techniques of XRD, NH₃-TPD, CO₂-TPD, H₂-TPR and in situDRIFTS were employed to investigate their NO_x storage behavior and sulfur-resisting performance. It is revealed that the storage capacity and sulfur-resisting ability of these catalysts depend strongly on the calcination temperature of the support. The catalyst with theist support calcined at 500 °C, exhibits the largest specific surface area but the lowest storage capacity. With increasing calcination temperature, the NO_x storage capacity of the catalyst improves greatly, but the sulfur-resisting ability of the catalyst decreases. In situ DRIFTS results show that free nitrate species and bulk sulfates are the main storage and sulfation species, respectively, for all the catalysts studied. The CO₂-TPD results indicate that the decomposition performance of K₂CO₃ is largely determined by the surface property of the TiO₂–ZrO₂ support. The interaction between the surface hydroxyl of the support and K₂CO₃ promotes the decomposition of K₂CO₃ to form –OK groups bound to the support, leading to low NO_x storage capacity but high sulfur-resisting ability, while the interaction between the highly dispersed K₂CO₃ species and Lewis acid sites gives rise to high NO_x storage capacity but decreased sulfur-resisting ability. The optimal calcination temperature of TiO₂–ZrO₂ support is 650 °C.     

The interconnected CaCO3 coated SnO2 nanocrystalline dye-sensitized solar cell with superior performance

Design, Development, fabrication and investigation of the I–V characteristics of the DSSC based on interconnected 15 nm SnO₂ nanoparticles covered with a nano-scale thin layer of CaCO₃ are described. The presence of CaCO₃ has been confirmed by its characteristic XRD pattern and EDX plots. The thickness of the protective layer can be conveniently controlled by the molar ratio of SnO₂:CaCO₃ used in the preparation of the thin film and the optimum conditions for best performance of the DSSC are presented together with possible explanations for the variations observed when the molar ratio is changed. An optimum light-to-electricity conversion efficiency of 5.4% in the presence of a layer of CaCO₃ has been obtained which is 3.2 times enhancement over the cell prepared without CaCO₃. The characterization of the surface using different techniques is explained.     

Synthesis of CaCO3–P(MMA–BA) nanocomposite and its application in water based alkyd emulsion coating

As part of broader effort to synthesize a new class of water-based composite, hybrid emulsion polymerization was carried out with acrylic monomers [methyl methacrylate (MMA), n-butyl acrylate (BA)]. Nanocomposite of P(MMA–BA)/nano CaCO₃ was synthesized by in situ emulsion polymerization. Water-based alkyd coating with various proportions nano CaCO₃, P(MMA–BA) and its nanocomposite was formulated. Extent of polymerization with and without nano CaCO₃ was measured using gravimetric method. Thermal properties of neat polymer, nanocomposite and coating films were evaluated by TGA and DSC, DTA analysis. Uniform dispersion of nano CaCO₃ in polymer matrix was ensured from SEM/TEM images. Incorporation of nanoparticles to hybrid polymer and nanocomposite to alkyd emulsion showed significant enhancement in mechanical and thermal properties. Dual role of nanocomposite in coating; as a partial binder and a filler to improve property profile of neat coating has been reported.     

Highly active TiO2−x−yNxFy visible photocatalyst prepared under supercritical conditions in NH4F/EtOH fluid

A novel N and F co-doped TiO₂ (TiO_2−x−yN_xF_y) photocatalyst is prepared by treating the TiO₂ precursor in NH₄F/ethanol fluid under supercritical conditions. During photocatalytic degradation of methylene blue under visible light irradiation, the as-prepared TiO_2−x−yN_xF_y exhibits higher activity than the undoped TiO₂, N-doped TiO₂ (TiO_2−xN_x), and F-doped TiO₂ (TiO_2−yF_y). Based on the characterizations including XRD, Raman, FTIR, TEM, PLS, UV–vis DRS, N₂ adsorption–desorption isotherms, XPS and NH₃-TPD, the synergetic promotions of N- and F-dopants incorporated into the TiO₂ lattice are discussed based on the enhanced spectral response in visible region, oxygen vacancies, and surface acidic sites. Meanwhile, the supercritical treatment also promotes the activity owing to the increase in both the surface area and the crystallization degree of anatase, and the enhanced incorporation of N- and F-dopants into the TiO₂ lattice.