Plasma modification of polypropylene surfaces and grafting copolymerization of styrene onto polypropylene

The surface of polypropylene(iPP) is modified with glow discharge plasma of Ar,so that the modified surfaces of iPP films are obtained.The studies of scanning electron microscopy(SEM) show the surface etching pattern of iPP films. The chemical structures of iPP films are confirmed by X-ray photoelectron spectroscopy(XPS) and Fourier transform infrared(FTIR) spectroscopy.The wetting properties of modified surfaces of iPP films are characterized by contact angle, and the free energy of surfaces is calculated.The free radical of modification surfaces of iPP is measured by chemical method.The surfaces of iPP are achieved with Ar plasma treatment followed by grafting copolymerization with styrene(St) in St.The grafting polymer of St onto iPP is characterized by FTIR.The grafting rate is dependent on plasma exposure time and discharge voltage.The studies show that homopolymerization of St is undergone at the same time during the grafting-copolymerization of St onto iPP.     

Low-temperature diffusion of oxygen through ordered carbon vacancies in Zr2C(x): the formation of ordered Zr2C(x)O(y)

Investigations are performed on low-temperature oxygen diffusion in the carbon vacancy ordered ZrC(0.6)and thus induced formation of the oxygen atom ordered ZrC(0.6)O(0.4). Theoretically, a superstructure of Zr(2)CO can be constructed via the complete substitution of carbon vacancies with O atoms in the Zr(2)C model. In the ordered ZrC(0.6), the consecutive arrangement of vacancies forms the vacancy channels along some zone axes in the C sublattice. Through these vacancy channels, the thermally activated oxygen diffusion is significantly facilitated. The oxygen atoms diffuse directly into and occupy the vacancies, producing the ordered ZrC(0.6)O(0.4). Relative to the ordered ZrC(0.6), the Zr positions are finely tuned in the ordered ZrC(0.6)O(0.4) because of the ionic Zr-O bonds. Because of this fine adjustment of Zr positions and the presence of oxygen atoms, the superstructural reflections are always observable in a selected area electron diffraction (SAED) pattern, despite the invisibility of superstructural reflections in ZrC(0.6) along some special zone axes. Similar to the vacancies in ordered ZrC(0.6), the ordering arrangement of O atoms in the ordered ZrC(0.6)O(0.4) is in nanoscale length, thus forming the nano superstructural domains with irregular shapes.     

Three novel isomeric zinc metal-organic frameworks from a tetracarboxylate linker

Three porous supramolecular isomers (IZE-1, IZE-2, and IZE-3) with the same framework component [Zn(2)(EBTC)(H(2)O)(2)] (EBTC = 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate) were successfully constructed by finely tuning the reaction condition. Although both IZE-1 and IZE-2 are constructed from the linear EBTC subunits and one kind of regular [Zn(2)(CO(2))(4)] paddlewheels, their frameworks exhibit two different (3,4)-c net of fof (sqc1575) and sqc1572, respectively, resulting in cavities with different size and shape. However, as for isomer IZE-3, the EBTC ligands are bent and one-half of the [Zn(2)(CO(2))(4)] paddlewheels are distorted, leading to a novel (3,4,4)-c hyx net with point symbol (6.7(2))(4)(6(2).8(2).10(2))(7(2).8(2).11(2)) and vertex symbol (6.7.7)(4)(7(2).7(2).8.8.12.12)(6.6.8.8.10(2).10(2)). Quantum chemical calculations by DFT indicate that the three isomers have very close thermodynamic stabilities, which may explain that subtle condition change leads to variation of the frameworks. Further theoretical semiempirical investigation on the interactions between solvent molecules and compounds shows different hydrogen binding patterns in good agreement with the experimental observations. Furthermore, they exhibit good solid-state luminescence properties with long lifetime.     

Probing the structures and chemical bonding of boron-boronyl clusters using photoelectron spectroscopy and computational chemistry: B(4)(BO)(n) (-) (n = 1-3)

The electronic and structural properties of a series of boron oxide clusters, B(5)O(-), B(6)O(2) (-), and B(7)O(3) (-), are studied using photoelectron spectroscopy and density functional calculations. Vibrationally resolved photoelectron spectra are obtained, yielding electron affinities of 3.45, 3.54, and 4.94 eV for the corresponding neutrals, B(5)O, B(6)O(2), and B(7)O(3), respectively. Structural optimizations show that these oxide clusters can be formulated as B(4)(BO)(n) (-) (n = 1-3), which involve boronyls coordinated to a planar rhombic B(4) cluster. Chemical bonding analyses indicate that the B(4)(BO)(n) (-) clusters are all aromatic species with two π electrons.     

2D sheet-like architectures constructed from main-group metal ions, 4,4'-bpno and 1,2-alternate p-sulfonatothiacalix[4]arene

Two novel 2D sheet-like complexes 1 and 2 have been prepared by reaction of p-sulfonatothiacalix[4]arene (TC4AS) with main-group metal ions (lead(II) or barium(II)) and 4,4'-bipyridine-N,N'-dioxide (4,4'-bpno). In both complexes 1 and 2, TC4AS molecules prefer 1,2-alternate conformation, forming 2D sheet-like layers in the presence of divalent ions and 4,4'-bpno ligand. The layers extend to 3D architectures via strong hydrogen bonding interactions. In addition, complexes 1 and 2 are thermally stable up to ca. 335 and 305 °C, respectively. It seems that the strong hydrogen bonds between the sheet-like layers impart the extraordinarily high degrees of stability to the structures. Further analysis indicates that complexes 1 and 2 are significantly different: (a) the divalent ions have different coordination environments due to the nature of the different ions; (b) TC4AS within complexes 1 and 2 connects to four Pb(II) or six Ba(II) ions, respectively; (c) 4,4'-bpno shows different connection modes; (d) in the solid state, complex 1 exhibits intense orange luminescence with triexponential decays, while complex 2 does not exhibit any obvious luminescence at cryogenic temperatures.     

Three novel organic-inorganic complexes based on decavanadate [V10O28]6- units: special water layers, open 3D frameworks and yellow/blue luminescences

Three unusual polyoxovanadate-based inorganic-organic hybrid complexes, [Zn(Im)(2)(DMF)(2)](2)[H(2)V(10)O(28)]·Im·DMF (1), [Zn(3)(Htrz)(6)(H(2)O)(6)][V(10)O(28)]·10H(2)O·Htrz (2) and {[Zn(3)(trz)(3)(H(2)O)(4)(DMF)](2)[V(10)O(28)]·4H(2)O}(n) (3) (Im = imidazole, Htrz = 1,2,4-triazole, DMF = N,N'-dimethylammonium) have been synthesized at room temperature via evaporative crystallization, and characterized by single-crystal X-ray diffraction. Complex 1 shows the structure of a discrete [V(10)O(28)](6-) cluster grafted by two [Zn(Im)(2)(DMF)(2)](2+) fragments through two bridged oxygen atoms, representing a rarely observed coordination mode. Complex 2 consists of a linear trinuclear Zn(II) unit bridging six Htrz ligands and a [V(10)O(28)](6-) cluster as the counter anion, where the extensive hydrogen-bonding interactions lead to {Zn(3)-V(10)}(SMF) and a special water layer involving (H(2)O)(36) rings, and consequently forms a unique 3D metal-organic-water supramolecular network. Complex 3 can be described as a 3,4-connected fsc-type network, and is the first example of open coordination 3D framework based on [V(10)O(28)](6-) and the other two different secondary building units, involving mononuclear and binuclear Zn(II)-Htrz motifs. The optical properties of complexes 1-3 in the solid state are investigated at room temperature. The results show that complexes 1 and 3 emit intense blue luminescences attributed to the ligands, while complex 2 exhibits an infrequent fluorescent property, emitting both blue and yellow luminescences at 472 and 603 nm simultaneously. Furthermore, powder X-ray diffraction and thermogravimetric analyses of 1-3 are also investigated, which demonstrate their high purities and thermal stabilities.     

Electrochemical performance of B and M phases VO2 nanoflowers

VO₂ exists in four phases, among which, the M/R phase VO₂ is well known for its reversible metal‐semiconductor phase transition at about 68 °C, and VO₂ (B) is a promising candidate cathode material to be applied in aqueous lithium‐ion battery owing to its proper electrode potential and layered structure. In this study, VO₂ (B) nanoflowers was synthesized via one‐step hydrothermal process and then successfully transformed into the VO₂ (M) by heat treatment. Electrochemical behaviors of the two samples were evaluated by cycling discharge and cyclic voltammetry (CV). The results showed that flower‐like VO₂ (B) had the first discharge capacity of 180.33 mAhg‐1, an outstanding value of 52.8% for the capacity retention after 50 cycles. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and Crystal Structure of a Pure Inorganic Network Based Tetra-Sodium Capped Sandwich-Type Polyanion

Abstract  

The synthesis and single-crystal structure of a Na-salt compound Na₁₀[Co₄(OH₂)₂(AsW₉O₃₄)₂]·32H₂O (1) was reported. Compound 1 crystallizes in triclinic system, space group P−1, with the lattice parameters: a = 11.6040(10) ?, b = 12.9361(13) ?, c = 17.396(2) ?, α = 97.4120(10)°, β = 106.8590(10)°, γ = 111.867(2)° and Z = 1. Compound 1 consists of a pure inorganic network based on tetra-sodium capped sandwich-type anionic clusters [Co₄(OH₂)₂(AsW₉O₃₄)₂]¹⁰⁻ bridged through Na–OH₂ subunits. The thermogravimetric and electrochemistry measurements had also been studied.     

Effects of oxide buffer layers on the microstructure and electrical properties of PLZST 2/87/10/3 antiferroelectric thin films

In the present work, the effects of oxide buffer layers, such as ZrO₂, CeO₂ and TiO₂, on the microstructure and electrical properties of (Pb_0.97La_0.02)(Zr_0.87Sn_0.10Ti_0.03)O₃ (PLZST 2/87/10/3) antiferroelectric (AFE) thin films were investigated systematically. X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) pictures illustrated that the crystalline orientation and surface microstructure of PLZST 2/87/10/3 AFE thin films had a close relation with these oxide buffer layers. As a result, the final electrical properties of AFE films were tuned by these buffer layers. Electrical measurements result showed that the dielectric properties, polarization characteristic and current–field curves of AFE thin films could be tailored by selecting a proper oxide buffer layer.     

Investigation of the structure evolution process in sol-gel derived CaO-B2O3-SiO2 glass ceramics

A sol-gel method was used to prepare CaO-B₂O₃-SiO₂ (CBS) glass powder for making low-temperature cofired ceramics. This paper was focused on the mechanism of hydrolysis and polymerization and also on the structural evolution of xerogel at various temperatures. The xerogel was transformed into glass ceramics containing CaSiO₃ and CaB₂O₄ crystalline phases through nucleation and crystallization processes. The results indicated that the xerogel exhibits [BO₄] or [SiO₄] based three-dimensional network structure whose interstices Ca ions fill in, which becomes more orderly and stable after heat treatments. The CBS glass ceramics through controlled crystallization have a potential as electronic packaging materials.