Micro-flowers of poly(p-phenylene pyromelliteimide) crystals

Morphology control of poly(p-phenylene pyromelliteimide) (PPPI) crystals was examined using reaction-induced crystallization of oligomers during solution polymerization of self-polymerizable N-(4′-aminophenyl)-3-carboxyl-4-alkoxycarbonylphthalimide. Micro-flowers of the PPPI needle-like crystals were formed in which the needle-like crystals grew radially from the center part as petals. The molecules aligned regularly along the long axis of the needle-like crystal. The structure of alkoxy group in the monomer and the monomer concentration influenced the size of the needle-like crystals, and their average length and width were changeable from 640 nm to 1.69 μm and from 110 nm to 210 nm, respectively. The average thickness was 20 nm. The obtained micro-flowers possessed high crystallinity and exhibited excellent thermal stability.     

Morphological architecture of poly(p-oxybenzoyl) by modification of oligomer end-group

Influence of oligomer end-group on morphology of poly(4-oxybenzoyl) (POB) was examined by polymerizations of 4-acyloxybenzoic acids having different acyl groups. Polymerizations of 4-propionyloxybenzoic acid, 4-hexanoyloxybenzoic acid, 4-octanoyloxybenzoic acid and 4-decanoyloxybenzoic acid in liquid paraffin at 320 °C yielded needle-like or pillar-like POB crystals via crystallization of oligomers. On the other hand, the polymerization of 4-perfluorooctanoyloxybenzoic acid (FOBA) afforded microspheres having needle-like crystals on the surfaces. At an initial stage in the polymerization, microspheres having smooth surface were formed via liquid-liquid phase separation of oligomers prepared from FOBA owing to the low miscibility of perfluorooctanoyl end-group. Thereby the phase-separation behaviour of oligomers changed from liquid-liquid phase separation to crystallization at a middle stage in the polymerization and then needle-like crystals were formed on the surface of the microspheres. Chemical structure of the oligomer end-group affected significantly the phase-separation behaviour of oligomers and ultimately the morphology of POB.     

Preparation of needle-like poly(azomethine) crystals by means of reaction-induced crystallization of oligomers

Needle-like poly(azomethine) crystals were successfully prepared by the polycondensation of 1,4-phenylenediamine and 1,4-terephthalaldehyde in liquid paraffin at 180 °C. The favorable polymerization concentration for the preparation of the well-defined needle-like crystals was 2.0×10⁻² mol l⁻¹. The average length and width of the needle-like crystals were 7.7 and 0.6 μm, respectively. These crystals possessed high crystallinity and good thermal stability. The extended polymer chains were aligned along the long axis of the needle-like crystal. The morphological observations indicated that the needle-like crystals were formed through the spiral growth of the oligomer lamellae caused by the screw dislocation.     

Morphology control of poly(2,2′-phenylene-5,5′-bibenzimidazole) by reaction-induced crystallization during polymerization

Morphology control of polybenzimidazoles was examined by reaction-induced phase separation during polymerization. Polymerizations of 3,3′-diaminobenzidine with terephthalic acid or diphenyl terephthalate were carried out in poor solvents. The morphology of the precipitated poly[2,2′-(1,4-phenylene)-5,5′-bibenzimidazole] (PpBBI) was significantly influenced by the polymerization conditions, and the aggregates of nano-scale PpBBI fibers were obtained by the polymerization at a concentration of 3-5% and 320-350 °C in dibenzyltoluene. The average diameter of the fibers was ca. 50 nm and inherent viscosities of the precipitates were 0.35-0.58 dL g⁻¹. They possessed high crystallinity and thermal stability. The oligomers were precipitated first by the reaction-induced crystallization to form the highly crystalline lath-like crystals at an initial stage of polymerization. Then the lath-like crystals were split into disentangled aggregates of fine fibers with maintaining the high crystallinity. The polymerization mainly proceeded when the oligomers were registered into the crystals. The obtained aggregates of nano-scale fibers could be recognized as nonwoven fabrics. Morphology control of poly[2,2′-(1,3-phenylene)-5,5′-bibenzimidazole] was also examined and particles were mainly formed.     

Continuous reaction crystallization of struvite from diluted aqueous solution of phosphate(V) ions in the presence of magnesium ions excess

Continuous reaction crystallization of struvite MgNH₄PO₄·6H₂O from diluted aqueous solution containing phosphate(V) ions of concentration 0.20 wt% PO₄³⁻ was investigated experimentally. The tests were carried out in a continuous DT MSMPR type crystallizer in temperature 298 K assuming 20% excess of magnesium ions at the inlet point in respect to struvite synthesis reaction stoichiometry. Influence of pH (8.5–10) and mean residence time of suspension in a crystallizer (900–3600 s) on the product crystals size distribution, their size-homogeneity and process kinetics were identified. Crystals of mean size from ca. 19 to ca. 73 μm, of diverse size-homogeneity (CV 60–87%) were produced. Struvite particles of the largest sizes and acceptable homogeneity were produced at pH 8.5 for prolonged mean residence time 3600 s. Under these conditions struvite nucleation rate did not exceed 5.3 × 10⁷ l/(s m³) according to SIG MSMPR model predictions. Crystal linear growth rate within the investigated process parameter values varied from 3.62 × 10⁻⁹ to 1.68 × 10⁻⁸ m/s. Magnesium ions excess in a process environment influenced yield of continuous reaction crystallization of struvite advantageously – contrary to product crystals quality. Concentration of phosphate(V) ions in mother solution decreased from inlet 0.20 wt% to 0.9 × 10⁻³ – 9.2 × 10⁻³ wt% (9–92 mg/kg) depending on pH and mean residence time of suspension in a crystallizer, what can be regarded as a very good result of their recovering from solution.     

Innovative fabrication of PZT pillar arrays by a colloidal approach

An innovative approach for fabricating pillar arrays for ultrasonic transducer applications is disclosed. It involves the preparation of concentrated piezoelectric lead zirconate titanate (PZT) suspensions in aqueous solutions of epoxy resin and its polymerization upon adding a polyamine based hardener. Zeta potential and rheological measurements revealed that 1 wt.% dispersant, 20 wt.% of epoxy resin and a hardener/epoxy resin ratio of 0.275 mL g⁻¹, were the optimized contents to obtain strong PZT samples with high green strength (35.21 ± 0.39 MPa). Excellent ellipsoidal and semi-circle shaped pillar arrays presenting lateral dimensions lower than 10 μm and 100 μm height were successfully achieved. The organics burning off was conducted at 500 °C for 2 h at a heating rate of 1 °C min⁻¹. Sintering was then carried out in the same heating cycle at 1200 °C for 1 h. The microstructures of the green and sintered ceramics were homogeneous and no large defects could be detected.     

Development of functional mesoporous microparticles for controlled drug delivery

Mesoporous microbeads can be easily obtained by radical polymerization of biocompatible glycerol dimethacrylate (GDMA) in supercritical carbon dioxide. Small mass density microparticles (ρ = 0.19-0.37 g cm⁻³) with controlled size (1-3 μm) and homogeneous morphology are obtained by the addition of different stabilizers to the polymerization media. The microbeads were obtained in quantitative yield as white, dry powders directly from the reaction vessel possessing a pollen-like morphology. The (S)-ibuprofen loading (up to 120 mg g⁻¹) and release profile from the PGDMA microbeads is highly promising which makes them potential drug delivery vehicles.     

Development of a new graded-porosity FeAl alloy by elemental reactive synthesis

A new graded-porosity FeAl alloy can be fabricated through Fe and Al elemental reactive synthesis. FeAl alloy with large connecting open pores and permeability were used as porous supports. The coating was obtained by spraying slurries consisting of mixtures of Fe powder and Al powder with 3-5 μm diameter onto porous FeAl support and then sintered at 1100 °C. The performances of the coating were compared in terms of thickness, pore diameter and permeability. With an increase in the coating thickness up to 200 μm, the changes of maximum pore size decreased from 23.6 μm to 5.9 μm and the permeability decreased from 184.2 m³ m^− 2 kPa^− 1 h^− 1 to 76.2 m³ m^− 2 kPa^− 1 h^− 1, respectively, for a sintering temperature equal to 1100 °C. The composite membranes have potential application for excellent filters in severe environments.     

Polyvinylpyrrolidone-assisted synthesis of microscale C-LiFePO4 with high tap density as positive electrode materials for lithium batteries

Carbon-coated LiFePO₄ (C-LiFePO₄) with micron particle size (6 μm) and high tap density (1.6 g cm⁻³) was prepared from spherical FePO₄·2H₂O powder via the co-precipitation method. The C-LiFePO₄ powder was calcined at temperatures between 650 and 800 °C. The 6 μm C-LiFePO₄ prepared at 800 °C exhibited an excellent rate capability, delivering 150 mAh g⁻¹ on discharge at the 0.1 C-rate and 108 mAh g⁻¹ at the 5 C-rate. The volumetric capacity of the 6 μm C-LiFePO₄ corresponded to 225 mAh cm⁻³, since the large secondary particles (6 μm) C-LiFePO₄ sufficiently allowed tight packing of the particles. The 6 μm C-LiFePO₄ powder with high tap density makes an attractive positive electrode candidate for lithium-ion batteries designed for high energy density.     

Filling of mesoporous silicon with copper by electrodeposition from an aqueous solution

Copper filling into mesopores formed in highly doped p-type silicon was investigated. When the copper electrodeposition was carried out at a very small constant current density (−6.4 μA cm⁻²), the mesopores with 4 μm depth were filled with copper continuously from the bottom to the opening. When the electrodeposition current was set at an absolute value twice as large as in the above condition, the isolated particles were electrodeposited in the mesopores. The depth also affected the filling behavior. The pores with 8 μm in depth were not continuously filled with copper even in the condition at which the pores of 4 μm in length were completely filled. Electrodeposition behavior in mesopores was also simulated using a simple model. The numerical simulation suggested that the diffusion-limited electrodeposition could be achieved in mesopores at a very small current, at which the diffusion-limited condition had never been realized on a planar electrode.     

Platinum-modified titanium anodes for the electrolytic destruction of nitric acid

Three sets of electrodes, namely Pt electroplated Ti (PET) and diffusion annealed PET (DAPET) of plating thickness 3, 5, 7 and 10 μm and thermochemically glazed mixed oxide coated titanium anode (MOCTA-G) were evaluated for their performance, with a view to optimizing the current density conditions for maximum efficiency during the electrolytic destruction of nitric acid. In the acid killing by electro-reduction process, concentration of nitric acid in the high level waste (HLW) from the spent nuclear fuel reprocessing plant was brought down from about 4 to 0.5 M in order to reduce the amount of HLW by subsequent evaporation and to minimise the corrosion in waste tanks during storage of the concentrated waste solution. The electrochemical reduction of 4 and 8 M nitric acid to near neutral conditions was carried out with the above-said anodes and Ti cathode at various cathodic current densities ranging from 10 to 80 mA cm⁻². At current densities below 15 mA cm⁻² MOCTA-G electrode worked satisfactorily, whereas PET and DAPET electrodes could withstand and function well at much higher cathodic current densities (up to 80 mA cm⁻²). The life assessment of a 3 μm thick PET electrode at a cathodic current density of 60 mA cm⁻² in 8 M HNO₃ for a period of 110 h showed no failure. Phase identification of the plated electrodes was done by XRD measurements and their surface morphology was investigated by SEM.     

Supercritical fluid extraction of piceid, resveratrol and emodin from Japanese knotweed

In the present study, the use of supercritical fluid extraction was investigated for selected compounds from the plant Japanese knotweed (Polygonum cuspidatum Siebold & Zucc.). The effects of parameters such as type of modifier, pressure, temperature and time on the extraction efficiency of piceid, resveratrol and emodin were studied. The optimal conditions were found as follows: modifier acetonitrile, 40 MPa, 100 °C and 45 min. SFE results were compared with those obtained by conventional Soxhlet extraction carried out for 4 h. The extracts obtained using these two techniques were analysed by liquid chromatography coupled with UV detection. LiChrospher^® 100, RP-18 column (125 mm × 4 mm, 5 μm) coupled with gradient elution acetonitrile in acidified water was used for the separation of compounds at flow rate 0.5 mL min⁻¹. Detection was carried out at 306 nm. Limits of detection were 21, 8 and 52 μg L⁻¹ for piceid, resveratrol and emodin, respectively. The linear range was 0.5-10 mg L⁻¹ for piceid and resveratrol, and 1-50 mg L⁻¹ for emodin with correlation coefficients above 0.9981. Based on the comparison of both methods extracted amount of piceid by Soxhlet extraction is approximately 10 times higher than by SFE method, while the extraction yield of emodin by Soxhlet extraction in approx. 2.5 times lower than by SFE. The advantage of SFE over Soxhlet extraction method is more than 5 times shorter extraction time period.     

Electrochemical and surface properties of nanocrystalline β-MnO2 in aqueous electrolyte

Surface and electrochemical properties of micrometric and nanometric tetragonal β-MnO₂ of, respectively, 4 and 61 m² g⁻¹ surface area were studied. The monodispersed nanocrystalline phase prepared by spray pyrolysis and characterized by transmission electron microscopy (TEM), is made of facetted crystals with 70 nm × 40 nm edges. Three types of energy domains were identified by surface acid-base titration. Slow step linear voltammetry reduction (10 mV/2 h scan rate) showed one current peak at −0.6 V (versus Hg-HgO 1 M KOH) for the micrometric phase, but three current peaks at −0.18, −0.36 and −0.55 V for the nanometric phase. They were assigned to the reduction of: (1) surface Mn atoms related to 〈1 1 1〉 and 〈3 1 1〉 faces; (2) more stable surface Mn atoms related to 〈1 0 0〉 and 〈1 1 0〉 faces; (3) bulk Mn atoms, respectively. The presence of new reduction peaks at higher potential is ascribed to the increase in Gibbs free energy caused by the surface energy of the nanometric particle.     

Plastic deformation of polyethylene crystals as a function of crystal thickness and compression rate

Plastic deformation of polyethylene (PE) samples with crystals of various thickness was studied during uniaxial compression with initial compressive strain rates of 5.5×10⁻⁵, 1.1×10⁻³ and 5.5×10⁻³ s⁻¹. Samples with a broad range of crystals thickness, from usual 20 up to 170 nm, were obtained by crystallization under high pressure. The samples underwent recoverable compression below the compression ratio of 1.05-1.07. Following yield, plastic flow sets in above a compression ratio of 1.12. At a compression rate of 5.5×10⁻⁵ s⁻¹ the yield stress increases with the increase of crystal thickness up to 40 nm. For crystals thicker than 40 nm the yield stress levels off and remains constant. This experimental dependence was compared with the model developed on the basis of classical crystal plasticity and the monolithic nucleation of screw dislocations from polymer crystals. In that model contrary to the experimental evidence, the yield stress does not saturate with increase of crystal thickness. The activation volumes determined from strain rate jump experiments and from stress relaxation for crystals thicker than 40 nm are nearly constant at a level of 8.1 nm³. This activation length agrees very well with 40 nm for crystal thickness above which the yield stress levels off. It is proposed, as shown in a companion communication, that for PE crystals thicker than 40 nm two other modes of dislocation emission in the form of half loops of edge and screw dislocations begin to govern the strain rate, which no longer depend on lamella thickness.     

Preparation and characterization of multilayer-type electrolyte membranes with hydrocarbon polymers

Multilayer-type polymer electrolyte membranes composed of a sulfonated poly(4-phenoxybenzoyl-1,4-phenylene) (S-PPBP) layer and a mono[poly(propylene oxide)methacrylate]phosphate ester (PPHP) layer were fabricated by solution-casting procedure (Method 1) and hot-pressing procedure (Method 2) in order to suppress methanol permeability of electrolyte membranes. No delamination was observed by SEM measurements of S-PPBP/PPHP interfaces, indicating that PPHP had good adhesive properties to S-PPBP surfaces. The methanol permeability of S-PPBP/PPHP membranes was lower than that of S-PPBP membranes and decreased with increasing the thickness of PPHP layers. The bilayer membrane with 12 μm PPHP and 40 μm S-PPBP layers showed a methanol permeability of 2.97 × 10⁻⁷ cm² s⁻¹ in 1 mol dm⁻³ methanol aqueous solution at 25 °C, which was 13% less than that of the S-PPBP membranes. The conductivity of this membrane reached its optimum with values as high as 1.57 × 10⁻¹ S cm⁻¹ at 80 °C and 90%RH.     

Modification of glassy carbon electrode with multi-walled carbon nanotubes and iron(III)-porphyrin film: Application to chlorate, bromate and iodate detection

In this study, multi-wall carbon nanotubes (MWCTs) is evaluated as a transducer, stabilizer and immobilization matrix for the construction of amperometric sensor based on iron-porphyrin. 5,10,15,20-Tetraphenyl-21H,23H-porphine iron(III) chloride (Fe(III)P) adsorbed on MWCNTs immobilized on the surface of glassy carbon electrode. Cyclic voltammograms of the Fe(III)P-incorporated-MWCNTs indicate a pair of well-defined and nearly reversible redox couple with surface confined characteristics at wide pH range (2-12). The surface coverage (Γ) and charge transfer rate constant (k_s) of Fe(III)P immobilized on MWCNTs were 7.68 × 10⁻⁹ mol cm⁻² and 1.8 s⁻¹, respectively, indicating high loading ability of MWCNTs for Fe(III)P and great facilitation of the electron transfer between Fe(III)P and carbon nanotubes immobilized on the electrode surface. Modified electrodes exhibit excellent electrocatalytic activity toward reduction of ClO₃⁻, IO₃⁻ and BrO₃⁻ in acidic solutions. The catalytic rate constants for catalytic reduction of bromate, chlorate and iodate were 6.8 × 10³, 7.4 × 10³ and 4.8 × 10² M⁻¹ s⁻¹, respectively. The hydrodynamic amperometry of rotating-modified electrode at constant potential versus reference electrode was used for detection of bromate, chlorate and iodate. The detection limit, linear calibration range and sensitivity for chlorate, bromate and iodate detections were 0.5 μM, 2 μM to 1 mM, 8.4 nA/μM, 0.6 μM, 2 μM to 0.15 mM, 11 nA/μM, and 2.5 μM, 10 μM to 4 mM and 1.5 nA/μM, respectively. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantages of this sensor. The obtained results show promising practical application of the Fe(III)P-MWCNTs-modified electrode as an amperometric sensor for chlorate, iodate and bromate detections.     

Effect of pore size distribution of coal-based activated carbons on double layer capacitance

A series of coal-based activated carbons representing a wide range of mesopore content, from 16.7 to 86.9%, were investigated as an electrode in electric double layer capacitors (EDLCs) in 1 mol l⁻¹ H₂SO₄ and 6 mol l⁻¹ KOH electrolytic solutions. The activated carbons (ACs) used in this study were produced from chemically modified lignite, subbituminous and bituminous coals by carbonization and subsequent activation with steam. The BET surface area of ACs studied ranged from 340 to 1270 m² g⁻¹. The performance of ACs as EDLC electrodes was characterized using voltammetry, galvanostatic charge/discharge and impedance spectroscopy measurements. For the carbons with surface area up to 1000 m² g⁻¹, the higher BET surface area the higher specific capacitance (F g⁻¹) for both electrolytes. The surface capacitance (μF cm⁻²) increases also with the mesopore content. The optimum range of mesopore content in terms of the use of ACs studied for EDLCs was found to be between 20 and 50%. A maximum capacitance exceeding 160 F g⁻¹ and a relatively high surface capacitance about 16 μF cm⁻² measured in H₂SO₄ solution were achieved for the AC prepared from a sulfonated subbituminous coal. This study shows that the ACs produced from coals exhibit a better performance as an electrode material of EDLC in H₂SO₄ than in KOH electrolytic solutions. For KOH, the capacitance per unit mesopore surface is slightly lower than that referred to unit micropore surface (9.1 versus 10.1 μF cm⁻²). However, in the case of H₂SO₄ the former capacitance is double and even higher compared with the latter (23.1 versus 9.8 μF cm⁻²). On the other hand, the capacitance per micropore surface area is the same in both electrolytes used, about 10.0 μF cm⁻².     

Application of bismuth-film electrode for cathodic electroanalytical determination of sulfadiazine

A bismuth-film electrode for use in cathodic electrochemical detection was employed in order to quantify sulfadiazine in pharmaceutical formulations. The bismuth film was deposited ex situ onto a glassy carbon substrate. Analysis of two sulfa drugs was carried out by differential-pulse voltammetry in 0.05 mol L⁻¹ Britton-Robinson pH 4.5 solution. Sulfadiazine reduction was observed at −0.74 V vs. Ag/AgCl in one well-resolved irreversible reduction peak. The analytical curve with two slopes was obtained in the concentration range of 3.2-97.0 μmol L⁻¹. The detection limit was 2.1 μmol L⁻¹ for concentrations of 3.2-20.0 μmol L⁻¹ (r = 0.9949) and 12.2 μmol L⁻¹ for concentrations between 20.0 and 97.0 μmol L⁻¹ (r = 0.9951). Recovery studies carried out with both sulfadiazine samples gave values from 93.6 to 109.3%. The accuracy of the results supplied by the bismuth-film electrode was compared to those obtained by the standard amperometric titration method. The relative error between them was lower than 2.0%.     

Simple synthesis of surface-modified hierarchical copper oxide spheres with needle-like morphology as anode for lithium ion batteries

Hierarchical, nanostructured copper oxide spheres were synthesized in a stirred solution of cupric acetate and ammonium hydroxide. Cetyltrimethylammonium bromide (CTAB) was used as a surfactant to modify the surface morphology of CuO spheres. Ordered nano-needle arrays can be formed on the surface of the CuO spheres (instead of disordered nano-leaves) in the presence of CTAB. Each CuO sphere is about 2 μm in diameter and possesses a large number of nano-needles that are about 20-40 nm in width and more than 300 nm in length. The needle-like hierarchical structure can greatly increase the contact area between CuO and electrolyte, which provides more sites for Li⁺ accommodation, shortens the diffusion length of Li⁺ and enhances the reactivity of electrode reaction, especially at high rates. After 50 cycles, the reversible capacity of the prepared needle-like CuO can sustain 62.4% and 56.4% of the 2nd cycle at a rate of 0.1C and 1C, respectively.     

Poly(methyl methacrylate)/carbonated hydroxyapatite composite applied as coating on ultra high molecular weight polyethylene

Poly(methyl methacrylate)/carbonated hydroxyapatite (PMMA/CHA) composite in the form of solution for its application as coating on ultra high molecular weight polyethylene (UHMWPE) substrate was studied. The coating has been prepared by mixing the carbonated hydroxyapatite in situ with the poly(methyl methacrylate) polymerization. The carbonated hydroxyapatite (CHA) was prepared by a conventional method. Fourier transformed infrared spectroscopy (FTIR) technique was used to study the hydroxyapatite synthesis and composite coating. The characterization of coating thickness was performed by light microscopy whereas the surface morphology was characterized by scanning electron microscopy (SEM) finding out a rough coating with a thickness of 29 μm. We have performed a pin-on-disk test to investigate the wear and friction behavior of the PMMA/CHA coating in dry conditions with loads ranging from 2 to 10 N; the same methodology was applied to test the UHMWPE substrates for comparatives studies. We also estimate the wear rate values of PMMA/CHA coating at each load, which are found to be ranging from k = 3.75 × 10⁻⁵ to 8.13 × 10⁻⁵ mm³/Nm. Additionally, the adhesion strength value between PMMA/CHA coating and UHMWPE substrate was 0.89 MPa.