Independent investigation on the influences of the processing conditions on the reclamation of crosslinked isoprene rubber after the impregnation of a reclaiming reagent

In this study, the reclamation of sulfur (S)‐cured isoprene rubber (IR) was investigated independently after the impregnation process of the reclaiming reagent diphenyl disulfide (DD) into the crosslinked IR matrix with supercritical carbon dioxide (scCO₂) as the transmission medium. According to the mass uptake of DD into IR and scanning electron microscopy–energy‐dispersive X‐ray spectrometry measurements, DD was highly impregnated and homogeneously dispersed in the network under 12 MPa at 80°C for 11 h in scCO₂. During the impregnation process, almost no reclaiming reaction occurred. Then, through three different reclaiming methods, a mechanochemical method, a chemical method with oxygen, and a chemical method without oxygen, the influences of the shear force, reclaiming atmosphere, reaction time, and amounts of reclaiming reagent on the reclamation with crosslinked IR with pre‐impregnated DD were independently investigated and compared with those of the reaction without pre‐impregnated DD. The sol fraction of the reclaimed rubber and molecular weight of the sol were measured. The results show that the reclaiming speed greatly depended on the amount of reclaiming reagent and that the reclaiming reaction was dramatically accelerated when the reclaiming reagents were pre‐impregnated into the crosslinked IR under the same processing conditions. This indicated that the impregnation time of the reclaiming reagent into the crosslinked network constituted a large proportion of the reclaiming time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40298.     

Structure-property relations of 55 nm particle-toughened epoxy

55-nm rubber particles significantly toughened two epoxy systems without loss of Young’s modulus, tensile strength and glass transition temperature. Transmission Electron Microscopy (TEM) showed that the nanoparticles are uniformly dispersed in matrix and have blurred interface with epoxy. 5 wt% rubber nanoparticles increased the critical strain energy release rate (G_1c) of Jeffamine D230 (J230)-cured epoxy from 175 J/m² to 1710 J/m², while the 10 wt% increased G_1c of diaminodiphenyl sulfone (DDS)-cured epoxy from 73 J/m² to 696 J/m². This is explained by comparing the surface-surface interparticle distance and total particle surface of nanocomposites with those of composites. The higher the matrix stiffness, the more nanoparticles needed for toughening. Although the 10 wt% J230-cured nanocomposite showed a 50% larger size of stress-whitened zone than the 5 wt% J230-cured nanocomposite, the 5 wt% nanocomposite showed a higher toughness. These nanoparticles were found to pose barriers to the vibration of crosslinked matrix molecules, leading to higher glass transition temperatures. While the matrix shear banding caused by nanoparticle expansion and growth is the major toughening mechanism for the J230-cured nanocomposites, the matrix plastic void growth and deformation are most probably the major mechanisms for the DDS-cured system. Under tensile loading, the nanoparticles in the DDS-cured epoxy created fibrils of 100-200 nm in diameter and 3-5 μm in length. TEM analysis in front of a subcritically propagated crack tip showed a number of voids of 30-500 nm in diameter in the vicinity of the crack, implying that rubber nanoparticles expanded, grew and deformed under loading. Unlike conventional epoxy/rubber composites in which all of the rubber particles in the crack front cavitated under loading, only a portion of the nanoparticles in this study expanded to create voids. Huang and Kinloch’s model developed from composites was found not fit well into these nanocomposites.     

In situ ATR-FT-IR study of the thermal decomposition of diethyl peroxydicarbonate in supercritical carbon dioxide

The thermal decomposition of the organic free-radical initiator, diethyl peroxydicarbonate (DEPDC), was monitored by in situ ATR-FT-IR in heptane, and in the green solvent supercritical carbon dioxide (scCO₂) both with and without supercritical ethylene. It was observed that the characteristic peaks of DEPDC at 1802-1803 and 1194-1203 cm⁻¹ decreased significantly upon heating corresponding to the decomposition of DEPDC, while two new intense peaks simultaneously appeared at 1747 and 1262 cm⁻¹ in heptane, and similarly at 1756 and 1250 cm⁻¹ in scCO₂. The changes in the absorbance intensity of the characteristic peaks of the initiator during the decomposition were used for the measurement of the decomposition rate constant (k_d) of DEPDC. It was found that the thermal decomposition of DEPDC at low concentration in either heptane under atmospheric N₂ or scCO₂ under high pressure was via the first-order kinetics of unimolecular decomposition. The activation energy of the thermal decomposition of DEPDC was found to be 115 kJ/mol in heptane from 40 to 74 °C and 118 kJ/mol in scCO₂ from 40 to 60 °C. These new peaks revealed the formation of carboxyl groups contained in the decomposed products, indicating incomplete decarboxylation. During removal of CO₂ after the reaction in scCO₂, the instable intermediate monoethyl carbonate was decarboxylated and converted into the major end product, ethanol.     

Direct electrochemistry and electrocatalysis of cytochrome c based on chitosan-room temperature ionic liquid-carbon nanotubes composite

A robust and effective composite film combined the benefits of room temperature ionic liquid (RTIL), chitosan (Chi) and multi-wall carbon nanotubes (MWNTs) was prepared. Cytochrome c (Cyt c) was successfully immobilized on glassy carbon electrode (GCE) surface by entrapping in the composite film. Direct electrochemistry and electrocatalysis of immobilized Cyt c were investigated in detail. A pair of well-defined and quasi-reversible redox peaks of Cyt c was obtained in 0.1 mol L⁻¹ pH 7.0 phosphate buffer solution (PBS), indicating the Chi-RTIL-MWNTs film showed an obvious promotion for the direct electron transfer between Cyt c and the underlying electrode. The immobilized Cyt c exhibited an excellent electrocatalytic activity towards the reduction of H₂O₂. The catalysis current was linear to H₂O₂ concentration in the range of 2.0 × 10⁻⁶ to 2.6 × 10⁻⁴ mol L⁻¹, with a detection limit of 8.0 × 10⁻⁷ mol L⁻¹ (S/N = 3). The apparent Michaelis-Menten constant (K_m) was calculated to be 0.45 ± 0.02 mmol L⁻¹. Moreover, the modified electrode displayed a rapid response (5 s) to H₂O₂, and possessed good stability and reproducibility. Based on the composite film, a third-generation reagentless biosensor could be constructed for the determination of H₂O₂.     

Direct synthesis of poly(l-lactic acid) in supercritical carbon dioxide with dicyclohexyldimethylcarbodiimide and 4-dimethylaminopyridine

The direct synthesis of poly(l-lactic acid) (PLLA) from an l-lactic acid oligomer has been performed in supercritical carbon dioxide (scCO₂) using an esterification promoting agent, dicyclohexyldimethylcarbodiimide (DCC), and 4-dimethylaminopyridine (DMAP) as a catalyst. PLLA within M_n of 13,500 g/mol was synthesised in 90% yield at 3500 psi and 80 °C after 24 h. The molecular weight distribution of the products was narrower than PLLA prepared with melt-solid phase polymerisation under conventional conditions. Both DCC and DMAP showed high solubility in scCO₂ (DCC: 7.6 wt% (1.63×10⁻² mol/mol CO₂) at 80 °C, 3385 psi, DMAP: 4.5 wt% (1.62×10⁻²mol/mol CO₂) at 80 °C, 3386 psi) and supercritical fluid extraction was found to be effective at removing excess DMAP and DCC after the polymerisation was complete. We show that DCC and DMAP are effective esterification promoting reagents with further applications for condensation polymerisations in scCO₂.     

New perfluorinated rhodium-BINAP catalysts and hydrogenation of styrene in supercritical CO2

New perfluorinated BINAP ligands and their cationic rhodium complexes have been synthesized and characterized. The catalysts have been tested in homogeneous hydrogenation of the styrene in both methanol and supercritical carbon dioxide (scCO₂). The selective hydrogenations of the styrene in scCO₂ were carried out under the same reaction conditions of 343.15 K temperature and 120 bar CO₂ pressure after 3 h (molar ratio of substrate to catalyst = 500). While all catalysts showed 100% conversion in methanol, same activity was not carried out in scCO₂. (R)-6,6′-diperflorooktil-2,2′-bis(diphenylphosphino)-1,1′-binaphtyl-[Rh(COD)]BArF was showed the highest conversion (96.4%) in scCO₂. Furthermore, methanol was used as co-solvent in the supercritical media in hydrogenation of styrene for the perfluorinated catalysts, which were inactive in scCO₂. Addition of methanol in scCO₂ has rather increased the conversion.     

Development of molecularly imprinted co-polymeric devices for controlled delivery of flufenamic acid using supercritical fluid technology

This work reports the development of a novel class of affinity co-polymeric materials using supercritical fluid technology. Polymeric materials with molecular recognition to flufenamic acid, were first synthesized in supercritical carbon dioxide (scCO₂) using the drug as template. Molecularly imprinted co-polymers of methacrylic acid (MAA) or N-isopropyl acrylamide (NIPAAm) crosslinked with ethylene glycol dimethacrylate (EGDMA) were synthesized using different crosslinking degrees and template:monomer ratios, at 65 °C and 21 MPa. High-pressure NMR experiments confirmed that the nature of the interactions between the drug and the functional monomers during the polymerization step are mainly hydrogen bonds. scCO₂-assisted impregnation revealed that the imprinted matrices were able to uptake higher amounts of flufenamic acid. This effect was particularly evidenced in the more crosslinked matrices, with P(MAA-EGDMA) imprinted copolymers binding up to 101.5 mg drug/g polymer against only 50.5 mg/g in the non-imprinted copolymer. In vitro drug delivery experiments showed that imprinted co-polymers release the drug in a more sustained way than the corresponding non-imprinted matrices. Overall it was shown that supercritical fluid technology is a viable approach for the development of self-assembly molecular recognition polymers with potential application in controlled drug delivery systems.     

Extraction of metal ions with non-fluorous bipyridine derivatives as chelating ligands in supercritical carbon dioxide

Three new non-fluorous bipyridine derivatives, bis(2-(2-butoxyethoxy)ethyl)-2,2′-bipyridine-4,4′-dicarboxylate (ligand 1), bis(2-(2-ethoxyethoxy)ethyl)-2,2′-bipyridine-4,4′-dicarboxylate (ligand 2), and bis(2-butoxyethyl)-2,2′-bipyridine-4,4′-dicarboxylate (ligand 3), were synthesized as chelating ligands to remove metal ions from solid matrix into supercritical CO₂ (scCO₂). These produced compounds 1-3 showed considerable solubilities in scCO₂ (8.0 g/l, 4.8 g/l, 7.8 g/l for ligands 1-3 at 313 K, respectively) and the tested solubility data were then calculated and correlated with semiempirical model at different pressures and temperatures, which showed satisfactory agreement with each other and the average absolute relative deviation were in the range of 0.1-28.3%. The effects of pressure, temperature, time, and ligand to metal ratio (5:1 to 75:1) on the extraction efficiency of metal ions were also systematically investigated. The extraction efficiency was 100% for Ni²⁺ and 95.9% for Cu²⁺ in scCO₂ with the system of ligand 1, ultrapure water, and perfluoro-1-octanesulfonic acid tetraethylammonium salt (PFOAT) under the optimized conditions (25 MPa, 313 K, 90 min, and ligand to metal ratio of 10). Although all ligands exhibited good efficiency for Ni²⁺ (>85%) and Cu²⁺ (>70%) extraction, the extraction of mixed metal ions indicated that the bipyridine derivatives had low selectivity. Finally, the detailed calculation results exhibited that the extraction constants (K_ex) of the metal ions increased with the increase of the extraction efficiency in the same extraction system for each same metal ion.     

Synthesis of cross-linked poly(4-vinylpyridine) and its copolymer microgels using supercritical carbon dioxide: Application in the adsorption of copper(II)

Compared with conventional precipitation polymerization method, cross-linked poly(4-vinylpyridine) (P4VP) and its microgels copolymerized with α-methacrylic acid (MAA) were synthesized through a new route of stabilizer-free polymerization in supercritical fluids. The yellow, dry, fine powders were directly obtained from precipitation polymerization of 4-vinylpyridine in supercritical carbon dioxide (scCO₂) at pressures ranging from 70.0 to 230 bar, using N,N′-methylenebisacrylamide as cross-linker. The effects of the reaction pressure, cross-linker ratio, initiator concentration, and reaction time were investigated. The capacity of this microgel for adsorption of copper(II) was also studied. At higher cross-linker concentrations, a high yield of the cross-linked P4VP microgel was generated in scCO₂, and its particle size was less than 300 nm. Polymerization of cross-linked P4VP in scCO₂ was extremely sensitive to the density of the continuous phase. The adsorption followed the Langmuir isotherm. The adsorption capacities of cross-linked P(4VP-co-MAA) and cross-linked P4VP were 47.2 and 26.9 mg g⁻¹, respectively.     

Effect of BNBTKNN on the electrical properties of bismuth ferrite thin films

BiFeO₃/[0.93(Bi_0.50Na_0.50TiO₃)-0.05BaTiO₃-0.02K_0.50Na_0.50NbO₃] (BFO/BNBTKNN) bilayered thin films were fabricated on Pt/TiO₂/SiO₂/Si substrates without any buffer layers by a combined sol-gel and radio frequency sputtering route. Effect of BNBTKNN on electrical properties of BFO/BNBTKNN thin films was investigated. A higher phase purity and a denser microstructure are induced for the BFO/BNBTKNN bilayered thin film by using the bottom BNBTKNN layer, resulting in its lower leakage current density. Moreover, the enhancement in dielectric behavior is also demonstrated for such a bilayer, where a high dielectric constant and a low dielectric loss are obtained. The BFO/BNBTKNN bilayered thin film has an improved multiferroic behavior: 2P_r ∼ 76.8 μC/cm², 2E_c ∼ 378.1 kV/cm, 2M_s ∼ 52.6 emu/cm³, and 2H_c ∼ 453.6 Oe, together with a low fatigue rate up to ∼1 × 10⁹ switching cycles.     

Purification of ionic liquids by supercritical CO2 monitored by infrared spectroscopy

Transmission infrared and Attenuated Total Reflection (ATR) in situ infrared spectroscopies were combined for the time-resolved monitoring of both liquid and supercritical phases during extraction of water and other impurities from ionic liquids with supercritical carbon dioxide (scCO₂). Cleaning and drying by scCO₂ at 100 bar and 40 °C proved to be efficient for all ionic liquids tested, including 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), and 1-butyl-3-methylimidazolium trifluoromethansulfonate ([bmim][TfO] or [bmim] triflate). Despite the moderate solubility of water in scCO₂ compared to other classical solvents, the amount of water decreased continuously during the drying. The extraction could be followed by simple transmission IR spectroscopy of the supercritical phase. During the extraction, organic impurities and water were removed rapidly from the ionic liquid phase as scCO₂ improved the transport properties in the ionic liquids.     

Effect of nano-sized PbO on the transport critical current density of (Bi1.6Pb0.4Sr2Ca2Cu3O10)/Ag tapes

The effect of nano-sized PbO (10–30 nm) addition on the transport critical current density, J_c of (Bi_1.6Pb_0.4)Sr₂Ca₂Cu₃O₁₀ (PbO)_x (x=0–0.15 wt%) was investigated. J_c of PbO added pellet samples showed the maximal value at x=0.05 wt%. Using this result, Ag-sheathed (Bi_1.6Pb_0.4)Sr₂Ca₂Cu₃O₁₀ (PbO)_x/Ag tapes (x=0 and 0.05 wt %) were fabricated by the powder-in-tube (PIT) method. The tapes were sintered for 50 h and 100 h at 845 °C. The temperature dependence of J_c for the non-added and PbO added tapes in applied field was investigated. J_c of the non-added tapes was 4510 A/cm² at 40 K and 949 A/cm² at 77 K. J_c of (Bi_1.6Pb_0.4)Sr₂Ca₂Cu₃O₁₀ (PbO)_0.05/Ag tape sintered for 100 h was 26,800 A/cm² at 40 K and 10,700 A/cm² at 40 K, which was higher than the tapes sintered for 50 h (8590 A/cm² at 40 K and 1880 A/cm² at 77 K). Nano-sized PbO added tapes sintered for 100 h showed a higher J_c (more than 10 times) under magnetic field (0–0.75 T) compared with the non-added tape. A combined effect of enhanced flux pinning and improved microstructure led to the significant increase in J_c of the nano-sized PbO added tapes.     

Polymeric nanoparticles from macroscopic crystalline monomers by facile solid-state polymerization in supercritical CO2

When macroscopic crystalline monomers were polymerized by a free-radical solid-state reaction in the presence of supercritical CO₂ (scCO₂), the resultant products were found to be composed of unexpected nanoparticle morphologies. In particular, the solid-state polymerization (SSP) of amino acid based monomers, acryloyl-β-alanine (ABA) and methacryloyl-β-alanine (MBA), initiated by azobisisobutyronitrile in scCO₂ (at 65 °C and 34.5 MPa), produced corresponding polymers having aggregated spherical architectures. The average diameters of the PABA and PMBA particles were measured to be 94 and 102 nm, respectively. In addition, high molecular weight polymers (PMBA, M_w = 3.8 × 10⁵ g/mol) with a high yield (∼96%) were obtained. The microscopic investigation revealed that a unique particle formation mechanism was involved in the SSP in which large sized crystalline monomers were chipped into small pieces during the initial stage of polymerization and subsequently converted into nanoscale objects after 24 h.     

Thermal conductivity in mullite/ZrO2 composite coatings

Mullite-based multilayered structures have been suggested as promising environmental barrier coatings for Si₃N₄ and SiC ceramics. Mullite has been used as bottom layer because its thermal expansion coefficient closely matches those of the Si-based substrates, whereas Y–ZrO₂ has been tried as top layer due to its stability in combustion environments. In addition, mullite/ZrO₂ compositions may work as middle layers to reduce the thermal expansion coefficient mismatch between the ZrO₂ and mullite layers. Present work studies the thermal behaviour of a flame sprayed mullite/ZrO₂ (75/25, v/v) composite coating. The changes in crystallinity, microstructure and thermal conductivity of free-standing coatings heat treated at two different temperatures (1000 and 1300 °C) are comparatively discussed. The as-sprayed and 1000 °C treated coatings showed an almost constant thermal conductivity (K) of 1.5 W m⁻¹ K⁻¹. The K of the 1300 °C treated specimen increased up to twice due to the extensive mullite crystallization without any cracking.     

Microstructural and electrical characterization of bulk YBa2Cu3O7−δ ceramics

The value of critical current density at 77 K in “zero” applied field (J_c) characterizing the superconducting state for YBa₂Cu₃O_7−δ ceramics is closely related to the microstructure.The interrelationships between the microstructural factors such as pore volume fraction, oxygen content, average grain size, are complex. However, these factors also influence the normal state resistivity measured at room temperature (ρ₃₀₀). We demonstrate how the current carrying cross section influences Jc and ρ₃₀₀ in a similar way. Data, reported for two classes of YBa₂Cu₃O_7−δ: small grain porous ceramics and larger-grain denser ceramics, reveal an approximate linear relation between ρ_300 K and J_c. Extrapolation of this relation to a fully dense small grain YBa₂Cu₃O_7−δ ceramic yields values of ρ₃₀₀ = 0.4 mΩ cm and J_c = 10³ A cm⁻².     

Kinetic resolution of 4-phenyl-2-azetidinone in supercritical carbon dioxide

The lipase-catalysed kinetic resolution of rac-4-phenyl-2-azetidinone was investigated in supercritical carbon dioxide (scCO₂). Water (0.5 mol equivalent) was used as nucleophilic donor. The effects of pressure and temperature were studied in a batch reactor (internal volume: 30 mL). The optimum pressure and temperature of the β-lactam ring-opening reaction proved to be 14 MPa and 70 °C. Under optimum conditions, full conversion was achieved in 120 h. The resulting (R)-β-phenylalanine (ee ≥ 98%) and (S)-4-phenyl-2-azetidinone (ee ≥ 99%) could be easily separated by scCO₂ extraction of the (S)-β-lactam and subsequent washing of the enzyme with hot water to recover the amino acid.     

Microstructure and piezoelectric properties of CuO added (K, Na, Li)NbO3 lead-free piezoelectric ceramics

Lead-free Na_0.5K_0.5NbO₃ (NKN) and Na_0.475K_0.475Li_0.05NbO₃ (NKLN) ceramics doped with CuO were prepared by the mixed oxide route. The powders were calcined at 850-930 °C and sintered at 850-1100 °C. Small additions of CuO reduced the sintering temperature and increased the density to 96% theoretical. Cu first appears to enter the A site then the B site. In NKLN the orthorhombic-tetragonal and tetragonal-cubic phase transitions are approximately 150 °C lower and 50 °C higher, respectively than in NKN. With increasing addition of Cu to NKN and NKLN the remanent polarization (P_r) increased and coercive field (E_c) decreased. NKLN prepared with 0.4 wt% CuO exhibited a saturation polarization (P_sat) of 30 μC/cm², remanent polarization (P_r) of 27 μC/cm² and coercive field (E_c) of 1.0 kV/mm. CuO caused the NKLN ceramics to harden considerably; the mechanical quality factor (Q_m) increased from 50 to 260, d₃₃ ∼ 285 and piezoelectric coupling factors were >0.4.     

Radiochemical ageing of an amine cured epoxy network. Part I: change of physical properties

An aromatic rich, amine cured epoxy network (initial glass transition temperature 250 °C), was irradiated in air (pressure 0.22 MPa), at 30 and 120 °C, by gamma rays with two dose rates 2 and 20 kGy/h, for doses upto 70 MGy. The following characteristics were recorded, thickness of oxidised layer (TOL) from IR microspectrophotometry, flexural strength σ_R, toughness K_IC and glass transition temperature T_g. σ_R decreases from 120 MPa to about 40 MPa in the most degraded samples. This decrease is sharply linked to TOL showing the key role of the oxidised layer in crack initiation. K_IC decreases from 0.7 to 0.55 MPa m^1/2. Data are too much scattered to allow a kinetic study but it appears that, in the early period of exposure, K_IC decreases more rapidly at 120 °C than at 30 °C. T_g decreases from 250 to 140 °C in the most degraded samples, and the decrease is faster at 30 °C than at 120 °C. The decrease of T_g is attributed to a predominant chain scission process. The decrease of K_IC can be attributed to a combination of chain scission and physical ageing or chain scission and crosslinking. A relationship between T_g and the number of chain scissions, derived from the Di Marzio's theory, is proposed.     

The performances of higher alcohol synthesis over nickel modified K2CO3/MoS2 catalyst

Ni modified K₂CO₃/MoS₂ catalyst was prepared and the performance of higher alcohol synthesis catalyst was investigated under the conditions: T = 280–340 °C, H₂/CO (molar radio) = 2.0, GHSV = 3000 h^− 1, and P = 10.0 MPa. Compared with conventional K₂CO₃/MoS₂ catalyst, Ni/K₂CO₃/MoS₂ catalyst showed higher activity and higher selectivity to C₂⁺OH. The optimum temperature range was 320–340 °C and the maximum space-time yield (STY) of alcohol 0.30 g/ml h was obtained at 320 °C. The selectivity to hydrocarbons over Ni/K₂CO₃/MoS₂ was higher, however, it was close to that of K₂CO₃/MoS₂ catalyst as the temperature increased. The results indicated that nickel was an efficient promoter to improve the activity and selectivity of K₂CO₃/MoS₂ catalyst.     

Electroless immobilization and electrochemical characteristics of nickel hexacyanoruthenate film at an aluminum substrate

The surface of an aluminum (Al) electrode was modified with a thin film of nickel hexacyanoruthenate (NiHCR) as a novel electrode material. The modification procedure of Al surface, includes two consecutive procedures: (i) the electroless deposition of metallic nickel on the Al electrode surface from NiCl₂ solution, and (ii) the chemical transformation of deposited nickel to nickel hexacyanoruthenate films in solution of 20 mM K₃[Ru(CN)₆] + 0.5 M KNO₃. Cyclic voltammogram of the modified Al electrode showed a well-defined redox reaction due to [Ni^IIRu^III/II(CN)₆]^1−/2− system. The effects of different supporting electrolytes and solution pH were studied on the electrochemical characteristics of the modified electrode. The diffusion coefficients of K⁺ and Na⁺ cations in the film (D), the transfer coefficient (α), and the charge transfer rate constant at the modifying film/electrode interface (k_s), were calculated in the presence of both K⁺ and Na⁺ cations. The stability of the modified electrode was investigated under various experimental conditions.