Effect of fast neutrons and γ radiation on cobalt‐gelatin film

The real and imaginary parts of the dielectric constant (ε′ and ε″) were measured as a function of temperature at 10 kHz for a cobalt‐gelatin film before and after exposure to different values of fast neutron fluences and γ doses. The values of the ac conductivity were found to be affected to some extent by the type of irradiation in comparison with that of the unirradiated ones. However, the behavior of ε′, ε″, and ac conductivity seemed to be the same at higher and lower doses of both types of radiation. This behavior was also observed by comparing the calculated values of the activation energies for co‐gelatin films before and after irradiation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1749–1755, 2001     

Synthesis,Thermal Stability and Impact Stability of Novel Tetranitro‐Dipyridotetraazapentalene Derivatives

The synthetic details for the construction of three new dipyridotetraazapentalene derivatives, 5H‐pyrido[3″,4″:4′,5′] [1,2,3]triazolo‐ [1′,2′:1,2][1,2,3]triazolo[5,4‐b]pyridin‐6‐ium inner salt ( 8 ), 5H‐pyrido[3″,2″:4′,5′] [1,2,3]triazolo[1′,2′:1,2] [1,2,3]triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 15 ) and 5H‐pyrido[2″,3″:4′,5′] [1,2,3]‐triazolo[1′,2′:1,2][1,2,3]triazolo[4,5‐b]pyridin‐6‐ium inner salt ( 16 ) are presented. Nitration of ( 8 ) and ( 15 ) afforded the novel tetranitrodipyridotetraazapentalene derivatives, 2,4,8,10‐tetranitro‐5H‐pyrido[3″,4″:4′,5′][1,2,3]triazolo[1′,2′:1,2][1,2,3]‐triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 3 ) and 2,4,8,10‐tetranitro‐5H‐pyrido[3″,2″:4′,5′][1,2,3]triazolo[1′,2′:1,2][1,2,3]‐triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 4 ) in good yields. Both isomers, ( 3 ) and ( 4 ), exhibited high thermal stability (differential scanning calorimetric analysis and thermal gravimetric analysis) and were insensitive to impact (hammer/anvil test).     

Crystallography and Structure–Property Relationships in 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐Dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐ Quaterphenyl (DODECA)

X‐ray crystallographic study of 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐quaterphenyl (DODECA) has been carried out. Nonbonding interatomic distances of oxygen atoms inside of all the nitro groups are shorter than those corresponding to the intermolecular contact radii for oxygen. By means of the DFT B3LYP/6‐31(d, p) method a difference of 136 kJ mol⁻¹ between the X‐ray and DFT structures of DODECA was found. The bearer of the highest initiation reactivity in its molecule in solid phase should be the nitro group at 4′′′‐position, in contrast to those at 2′‐ or 2″‐positions in its isolated molecule. The most reactive nitro group in the DODECA molecule can be well specified by the relationship between net charges on nitro groups and charges on their nitrogen atoms, both of them for the X‐ray structure. The ¹⁵N chemical shift, corresponding to this nitro group for the initiation by impact and shock, correlates very well with these shifts of the reaction centers of the other six “genuine” polynitro arenes.     

Electrochemical investigation of thin films of cobalt phthalocyanine and cobalt-4,4′,4″,4′″-tetracarboxyphthalocyanine and the reduction of carbon monoxide,formic acid and formaldehyde mediated by the Co(I) complexes

Cyclic voltammetric investigations of thin films of cobalt(II) phthalocyanine(1) and cobalt(II)-4,4′,4″,4′″-tetracarboxyphthalocyanine(2) in N₂-saturated 1 M sulfuric acid solution revealed that both compounds gave irreversibly semi-stable reduction products, R-1 and R-2, at around −0.70 V vs sce. Reductions of CO, formaldehyde and formic acid by R-1 or R-2 were conducted with vibrating carbon fiber electrode (cfe) modified with 1 or 2. Products of the reduction of CO were mainly formaldehyde and a small amount of methanol. In the reduction of CO, R-2/cfe was ca 17 times more efficient than R-1/cfe, which was however more efficient than the former in the reduction of formaldehyde. Reduction of formic acid by R-2 and R-1 seemed to be difficult under the conditions. Reduction of CO on the 2/cfe polarized with rectangular potential pulse (−0.659 V for 5s and 0.20 V vs Ag/AgCl for 85s) produced nearly quantitative yield of formaldehyde and small amount of methanol.     

Relationship Between the Low Temperature Thermolysis and Detonation Temperature of Carbocyclic Nitroaromatic Compounds

In this paper, a new relationship between the activation energies (E_a) of the low temperature thermolysis and detonation temperature for different carbocyclic nitroaromatic compounds is introduced. Two structural parameters are needed to obtain a relatively good correlation for E_a. The resulting R² value of the new correlation is 0.942. The new equation assumes that the calculated detonation temperature can be applied to predict E_a of carbocyclic nitroaromatic compounds with the general formula C_aH_bN_cO_d and any complicated molecular structure. The proposed new method was also used to predict E_a of some technologically attractive high thermostable polynitro arenes with complex molecular structure, e.g., 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐dodecanitro‐[1,3′,1′,1″] quaterphenyl (DODECA).     

Frequency dependence of the complex dielectric constant of sodium carboxymethyl cellulose

The dielectric constant, ε′, and dielectric loss, ε″, were determined for three solid carboxymethyl cellulose samples having different levels of substitution and different degrees of polymerization over a frequency range of 0.1 – 10 000 kHz at temperatures from 10–60°C. In contrast to the two relaxation processes, γ and β, previously observed in native cotton cellulose, only one relaxation process within a frequency range of 0.1 – 1 kHz was identified. It was found that the dielectric properties do not only depend on the degree of substitution, but also on the weight-average degree of polymerization and uniformity of distribution.     

Crystallography and Structure–Property Relationships of 2,2″,4,4′,4″,6,6′,6″‐Octanitro‐1,1′ : 3′,1″‐Terphenyl (ONT)

An X‐ray crystallographic study of 2,2″,4,4′,4″,6,6′,6″‐octanitro‐1,1′ : 3′,1″‐terphenyl (ONT) has been carried out. The dihedral angles between benzene rings vary from 84.9° to 89.4°. Nonbinding interatomic distances of oxygen atoms inside all the nitro groups are shorter than the intermolecular contact radii for oxygen. On the basis of the DFT B3LYP/6‐31(d, p) method it was found that the difference between the X‐ray structure in the solid phase and DFT result for the gas phase is 98 kJ mol⁻¹, and the bearer of the highest initiation reactivity of the ONT molecule in the solid phase should be the nitro group at 4″‐position, in contrast to those at 4′‐ or 6′‐position that play this role in the isolated molecule. It has been stated that the nitro groups at the reaction centers of the ONT molecule are relatively well specified by their ¹⁵N NMR chemical shifts.     

Synthesis and Characterization of New Cobalt(II)–Pyrazine Coordination Polymer as Precursor for Preparation of Co(II) Oxide Nanoparticles: Surprising Coordination,DFT Calculation and Spectroscopic Studies

The new 2-D cobalt(II) coordination polymer with pyrazine was synthesized surprisingly from reaction of CoCl₂ and tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2?,3?-j]phenazine (tpphz) in methanol as medium and characterized by means of Fourier transform infrared spectroscopy (FT-IR), UV–Vis spectroscopy and X-ray single crystal analysis. The results showed that coordination polymer consist of cobalt(II) chain with pyrazine-bridged which crystallizes in orthorhombic unit cell (a?=?10.1307, b?=?10.1310, c?=?10.6838 Å) and space group Pban. Density functional theory (DFT) calculations were also done to figure out the electronic structure of the compound from theoretical aspect. The electronic spectrum of coordination polymer was investigated and the DFT/TDDFT procedures were employed to assign the absorption bands. The thermal decomposition of the title compound resulted in formation of cobalt(II) oxide nanoparticles with average size of 50 nm.     

Synthesis and characterization of novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives

Two novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylenevinylene} (EDP‐PPV) and poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDMP‐PPV), and their copolymer, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylene‐vinylene‐co‐2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDP‐co‐EDMP‐PPV; 4:1, 1:1, and 1:4), were successfully synthesized according to the Gilch route. The structures and properties of the monomers and the resulting conjugated polymers were characterized with ¹H‐NMR, ¹³C‐NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, ultraviolet–visible absorption spectroscopy, and photoluminescence and electroluminescence (EL) spectroscopy. The EL polymers possessed excellent solubility in common solvents and good thermal stability with a 5% weight loss temperature of more than 380°C. The weight‐average molecular weights and polydispersity indices of EDP‐PPV, EDMP‐PPV, and EDP‐co‐EDMP‐PPV were 1.40–2.58 × 10⁵, and 1.19–1.52, respectively. Double‐layer light‐emitting diodes with the configuration of indium tin oxide/polymer/tris(8‐hydroxyquinoline)aluminum/Al devices were fabricated, and EDP‐co‐EDMP‐PPV (1:1) showed the highest EL performance and exhibited a maximum luminance of 1050 cd/m² at 19.5 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1259–1266, 2005     

Resistive switching characteristics of polyimides derived from 2,2′‐aryl substituents tetracarboxylic dianhydrides

2,2′‐Position aryl‐substituted tetracarboxylic dianhydrides including 2,2′‐bis(biphenyl)‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride and 2,2′‐bis[4‐(naphthalen‐1‐yl)phenyl)]‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride were synthesized. A new series of aromatic polyimides (PIs) were synthesized via a two‐step procedure from 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride and the newly synthesized tetracarboxylic dianhydrides monomers reacting with 2,2′‐bis[4′‐(3″,4″,5″‐trifluorophenyl)phenyl]‐4,4′‐biphenyl diamine. The resulting polymers exhibited excellent organosolubility and thermal properties associated with T_g at 264 °C and high initial thermal decomposition temperatures (T_5%) exceeding 500 °C in argon. Moreover, the fabricated sandwich structured memory devices of Al/PI‐a/ITO was determined to present a flash‐type memory behaviour, while Al/PI‐b/ITO and Al/PI‐c/ITO exhibited write‐once read‐many‐times memory capability with different threshold voltages. In addition, Al/polymer/ITO devices showed high stability under a constant stress or continuous read pulse voltage of ? 1.0 V. Copyright © 2011 Society of Chemical Industry     

Fabrication of deodorizing fabric by grafting of metal phthalocyanine derivative onto nonwoven polypropylene fabric

Fabrication of deodorizing fabric was tried by grafting metal phthalocyanine derivative, a catalytic deodorant, onto polypropylene (PP) nonwoven fabric. Fe(III)-4,4′,4″,4‴-tetra carboxamide phthalocyanine (Fe-TCMP) was synthesized. The Fe-TCMP showed high-deodorizing performance when tested for the elimination of 2-mercaptoethanol, an index material for bad-smelling compounds. The Fe-TCMP was converted to Fe(III)-4,4′,4″,4‴-tetracarboxylic acid phthalocyanine (Fe-TCAP) by hydrolysis to have carboxyl groups. It was chemically grafted on the surface of PP nonwoven fabric, which was surface modified to have amine groups with diaminocyclohexane (DACH) plasma. Such fabricated deodorizing fabric showed high-deodorizing performance for 2-mercaptoethanol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 839–846, 2001     

One-Pot Formation of a Metallosupramolecularly Assembled and Redox-Active Adlayer at the Solid–Liquid Interface

A redox-active adlayer consisting of cobalt ions and terpyridine ligands, 4′,4′′′′-(1,4-phenylene)bis(2,2′:6′,2′′-terpyridine), was prepared on a Au(111) surface by a stepwise coordination method. The obtained adlayer produced a well-defined, stable redox wave associated with cobalt ions coordinated to 4′,4′′′′-(1,4-phenylene)bis(2,2′:6′,2′′-terpyridine), as compared to a tetra-2-pyridinyl-pyrazine adlayer, for which no redox wave was observed. In situ scanning tunneling microscopy revealed a structural change in the redox-active adlayer consisting of 4′,4′′′′-(1,4-phenylene)bis(2,2′:6′,2′′-terpyridine) and cobalt ions. It was found that the ability of cobalt ions to coordinate on Au(111) was clearly dependent on the chemical structure of the ligand, suggesting that ligand coordination with metal ions on the Au surface is determined by the molecular orientation and configuration of the ligand when the ligand is adsorbed on a Au substrate.     

The effects of catalyst and deactivator species in atom transfer radical polymerization of n-butyl methacrylate

Iranian Polymer Journal - Atom transfer radical polymerization (ATRP) of n-butyl methacrylate (n-BMA) was performed using CuIBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA)...     

H01双基推进剂老化的动态力学性能表征

用动态热机械分析仪测定了65℃下双基固体推进剂H01的老化性能。在低温段（-10～40℃）,随老化时间的增加tanδ值有明显下降,β松弛峰也越来越明显。H01的α松弛的损耗角正切tanδ的峰温、动态柔量J＇和J＂的值以及动态模量E＇和E＂、动态柔量J＇和J＂主曲线的叠合垂直位移因子与老化时间存在一定规律。TG-DTG试验表明,随着老化时间的增加,试样在183℃时的质量损失逐渐减小,说明增塑剂含量随老化时间增加而减小。因此,除了因结构松弛造成的“物理老化”外,这是造成上述各力学损耗量随老化时间下降的又一主要原因。     

Dielectric properties of polyethylene terephthalate/polyphenylene sulfide/barium titanate nanocomposite for application in electronic industry

Polymer/ceramic nanocomposites designed for application as electronic packaging were prepared using corotating twin‐screw extruder. The dielectric properties of the composites made from polyethylene terephthalate (PET), polyphenylene sulfide, and barium titanate were studied as a function of BaTiO₃ fraction in the range between 0.75 and 1.5 wt%. Processing parameters were optimized in order to obtain the nanocomposites with appropriate dielectric properties like dielectric permittivity ε′, dielectric losses ε″, and their temperature stability in a wide frequency range. The measurements showed the increase of the dielectric permittivity value ε′ in the composites in comparison to both pure polymers. The dielectric loss factor tgδ of the composites was found to be much smaller than that of the pure PET. The weak influence of the ceramics on the temperature stability of the dielectric properties of the composites was stated. POLYM. ENG. SCI., 50:1613–1619, 2010. © 2010 Society of Plastics Engineers     

A novel polymerization process using rotating disk atomizer

Macroporous highly crosslinked styrene(St)-divinylbenzene(DVB) copolymers were prepared by solution and suspension polymerization techniques. The obtained materials allowed the grafting of poly(N-vinyl-tert-butylcarbamate) (PVCa) either by addition of VCa macroradicals to the solid bound double bonds or by termination involving the reaction of VCa macroradicals with radicals present on the carrier. Poly(vinylamine) (PVAm) grafted on St-DVB carriers was obtained after the hydrolysis of grafted PVCa with HCl and the subsequent removal of the aminebonded HCl by means of NaOH. Heterogeneous bifunctional catalysts were obtained by attachment of cobalt(II) 4,4′,4″,4?-tetracarboxyphthalocyanine (CoPc(COOH)₄) to the grafted PVAm. The prepared catalysts were applied to the autoxidation of thiols to disulfides, both in predominantly apolar media and in aqueous media. It was demonstrated, that important prerequisites for the applicability of macroporous St-DVB copolymers as carriers for the PVAm-CoPc(COOH)₄ catalyst include a high surface area, a sufficiently large average pore diameter and accessibility of the pendent double bonds.     

A new (4,8)-connected topological MOF as potential drug delivery

A new compound of (NH₂(CH₃)₂[Zn₃(L)₂·3.5DMF]) (1) (H₄L = 1,1′,4′,1″,4″,1‴-quaterphenyl-3,5,3‴,5‴-tetracarboxylic acid 1,3,5-benzenetrisbenzoate) was synthesized and characterized. The coordination polymer shows an unusual 4,8-connected 3D net with (4⁶)₂(4¹²·6¹²·8⁴) topology. The incorporation of the drug 5-fluorouracil (5-FU) into the desolvated 1 was around 22.5 wt.% per gram of dehydrated 1. 5-Fu is released in a highly controlled and progressive fashion with 92% of the drug released after 120 h. The result from this work provides a new avenue for MOF to be used as potential drug delivery.     

Standard Enthalpy of Formation of the Bimolecular Crystal of CL-20 with Tris-Oxadiazolo-Azepine and Its Thermal Stability

The standard enthalpies of combustion and formation of 7H-tris([1,2,5]oxadiazolo) [3,4-b:3′,4′-d:3″,4″-f]azepine, its bimolecular crystal with the γ-polymorph of CL-20, and the γ-polymorph of CL-20 have been experimentally determined. The standard enthalpies of formation of the bimolecular crystal and an equimolecular mechanical mixture of γ-CL-20 with azepine differ by less than 12.8 kJ/mol. This small difference is validated by quantum chemical calculations. It has been experimentally found that the presence of azepine in the bimolecular crystal inhibits the thermal decomposition of γ-CL-20 and increases the thermal stability of γ-CL-20 in the bimolecular crystal as compared to original γ-CL-20.     

Reaction of Cyclohexylamine with Formaldehyde: The structure of N′,N″,N″′-tricyclohexylhexahydro-symtriazine

A reported preparation of 1,3-dicyclohexyl-1,3-diazacyclobutane ( 2 ) is rebutted: the correct structure is that of N′,N″,N″′-tricyclohexylhexahydro-sym-triazine ( 5 ), having a diequatorial-axial conformation in the solid state, as shown by mass spectrometry and X-ray diffraction. Theoretical calculations were carried out in order to predict the stabilities of 1,2- and 1,3-diazacyclobutane ( 14 and 1 ) and their geometries.     

Low temperature relaxation of DGEBA epoxy resins: A thermally stimulated discharge current (TSDC) study

The effect of curing conditions on the low temperature relaxation behavior of catalyst-cured epoxy systems based on digliycidyl ether of bisphenol A (DGEBA) has been characterized by the thermally stimulated discharge current (TSDC) technique. In these chemically relatively simple epoxy systems, five relaxation processes, designated as γ, β, β′, β_OH, and β″, have been observed: Their molecular origins are discussed in detail. The results are in agreement with prior suggestions of an inhomogeneous cross-link density morphology.