Enhanced interlaminar fracture toughness of unidirectional carbon fiber/epoxy composites modified with sprayed multi-walled carbon nanotubes

A recently reported solvent spraying technique was used herein for incorporation of multi-walled carbon nanotubes (MWCNTs) on unidirectional carbon fiber/epoxy prepregs. The role of the agglomerates reduction of oxidized MWCNTs on Mode-I interlaminar fracture toughness (G_IC) of laminated composites was investigated using double cantilever beam tests. Multiscale laminate composites were fabricated using MWCNTs without and with an acid oxidation, agglomerates reduction (AR) and a sequential treatment based on oxidation and AR. For comparison, specimens without MWCNTs were also prepared and tested. Fourier transform infrared analysis shows evidence of an important amount of oxygenated functional groups on the surface of as-received and oxidized MWCNTs. The results also show Mode-I fracture toughness improvements for all the laminated composites compared to reference samples. A substantial 52% increase in the average G_IC initiation was achieved for laminated composites reinforced with oxidized AR-MWCNTs prepared with only 0.05 wt.% MWCNTs.     

Nucleophilicity of metal carbonyl anions in vinylic substitution reactions

Second order rate constants are reported for the reactions of metal carbonyl anions ([M(CO)_nL]^?) with several vinyl halides: PhCCl?C(CN)₂, Z‐ and E‐Ph(CN)C?CHHal (Hal = Cl, Br) which follow the addition–elimination (Ad_NE) substitution mechanism. The obtained data show that the nucleophilic reactivity of [M(CO)_nL]^? anions towards vinyl halides increases in the same order as in aliphatic S_N2 reactions, but much more steeply, by 14 orders of magnitude in the row log{ }: [CpFe(CO)₂]^? (～14), [Re(CO)₅]^? (7.8), [Mn(CO)₅]^? 2.1, [CpW(CO)₃]^? (0.7) > [CpMo(CO)₃]^? (0). A good correlation exists between nucleophilicities of [M(CO)_nL]^? anions towards vinyl (sp²‐carbon) and alkyl halides (sp³‐carbon) with slope 2.7. The reactivity of [M(CO)_nL]^? in a halogen–metal exchange process (with Z‐PhC(CN)?CHI) follows a similar ‘large’ scale as in the Ad_NE process. The nucleophilicity of [M(CO)_nL]^? anions correlates better with their one‐electron oxidation potentials (E_ox) than with their basicity (pK_a of [M(CO)_nL]H). Copyright © 2008 John Wiley & Sons, Ltd.     

Carbon materials with quasi-graphene layers: the dielectric, percolation properties and the electronic transport mechanism

We investigate the dielectric properties of multi-walled carbon nanotubes (MWCNTs) and graphite filling in SiO₂ with the filling concentration of 2-20 wt.% in the frequency range of 10²-10⁷ Hz. MWCNTs and graphite have general electrical properties and percolation phenomena owing to their quasi-structure made up of graphene layers. Both permittivity ε and conductivity σ exhibit jumps around the percolation threshold. Variations of dielectric properties of the composites are in agreement with the percolation theory. All the percolation phenomena are determined by hopping and migrating electrons, which are attributed to the special electronic transport mechanism of the fillers in the composites. However, the twin-percolation phenomenon exists when the concentration of MWCNTs is between 5-10 wt.% and 15-20 wt.% in the MWCNTs/SiO₂ composites, while in the graphite/SiO₂ composites, there is only one percolation phenomenon in the graphite concentration of 10-15 wt.%. The unique twin-percolation phenomenon of MWCNTs/SiO₂ is described and attributed to the electronic transfer mechanism, especially the network effect of MWCNTs in the composites. The formation of network plays an essential role in determining the second percolation threshold of MWCNTs/SiO₂.     

Passivation of aluminium–n+ silicon contacts for solar cells by ultrathin Al2O3 and SiO2 dielectric layers

Ultra‐thin thermally grown SiO₂ and atomic‐layer‐deposited (ALD) Al₂O₃ films are trialled as passivating dielectrics for metal–insulator–semiconductor (MIS) type contacts on top of phosphorus diffused regions applicable to high efficiency silicon solar cells. An investigation of the optimum insulator thickness in terms of contact recombination factor J_{0_cont} and contact resistivity ρ_c is undertaken on 85 Ω/□ and 103 Ω/□ diffusions. An optimum ALD Al₂O₃ thickness of ～22 Å produces a J_{0_cont} of ～300 fAcm^–2 whilst maintaining a ρ_c lower than 1 mΩ cm² for the 103 Ω/□ diffusion. This has the potential to improve the open‐circuit voltage by a maximum 15 mV. The thermally grown SiO₂ fails to achieve equivalently low J_{0_cont} values but exhibits greater thermal stability, resulting in slight improvements in ρ_c when annealed for 10 minutes at 300 °C without significant changes in J_{0_cont}. The after‐anneal J_{0_cont} reaches ～600 fAcm^–2 with a ρ_c of ～2.5 mΩ cm² for the 85 Ω/□ diffusion amounting to a maximum gain in open‐circuit voltage of 6 mV. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Functionalization of multiwall carbon nanotubes with nitrogen containing polyelectrolyte by a simple method

Commercially available multiwall carbon nanotubes (MWCNTs) have been functionalized with poly(diallyl dimethylammonium) chloride (PDDA), a nitrogen containing polyelectrolyte by a simple on-off ultrasonication method. The results obtained from Raman and X-ray photoelectron spectroscopy (XPS) studies confirm the functionalization of MWCNTs with PDDA. An up- shift in the positions of C1s XPS peak and a down-shift in the positions of the N1s XPS peak, has been observed along with an up-shift in the G-peak position in the Raman spectra, which suggest the occurrence of inter-molecular charge transfer from carbon atoms in MWCNTs to N⁺ centres in PDDA. The preliminary linear sweep voltammetry (LSV) results show good electrocatalytic activity of MWCNTs functionalized with nitrogen containing polyelectrolyte, which is comparable to the results with platinum based electrodes. Thus, MWCNTs non-covalently functionalized with a nitrogen containing polyelectrolyte (PDDA) by a simple on-off ultrasonication method could be advantageous for developing efficient metal-free electrocatalysts for the oxygen reduction reaction (ORR).     

Evolution of structures,stabilities, and electronic properties of anionic [AunRb]− (n = 1–10) clusters: comparison with pure gold clusters

The geometric structures, stabilities, and electronic properties of small size anionic [Au_nRb]^? and Au_n+1^? (n = 1–10) clusters have been systematically investigated by using density functional theory. The optimised geometries show that the structures of [Au_nRb]^? clusters favour the three-dimensional structure at n ≥ 8. The Rb atoms tend to occupy the most highly coordinated position and form the largest probable number of bonds with gold atoms. One Au atom capped on [Au_n-1Rb]^? structures is the dominant growth pattern for n = 2–8 and Rb atom capped on Au_n^? structures for n = 9–10. The averaged atomic bonding energies, fragmentation energies, second-order difference of energies, and highest occupied molecular orbital–lowest unoccupied molecular orbital gaps exhibit a pronounced even–odd alternations phenomenon. The charges in [Au_nRb]^? clusters transfer from the Rb atoms to Au_n host. In addition, it is found that the most favourable dissociation channel of the [Au_nRb]^? clusters is to eject a Rb atom and the highest energy dissociation path is Rb^? anion ejection.     

Probing the structural and electronic properties of cationic rubidium–gold clusters: [AunRb]+ (n = 1–10)

Density functional theory has been applied to study the geometric structures, relative stabilities, and electronic properties of cationic [Au_nRb]⁺ and Au_{n + 1}⁺ (n = 1–10) clusters. For the lowest energy structures of [Au_nRb]⁺ clusters, the planar to three-dimensional transformation is found to occur at cluster size n = 4 and the Rb atoms prefer being located at the most highly coordinated position. The trends of the averaged atomic binding energies, fragmentation energies, second-order difference of energies, and energy gaps show pronounced even–odd alternations. It indicated that the clusters containing odd number of atoms maintain greater stability than the clusters in the vicinity. In particular, the [Au₆Rb]⁺ clusters are the most stable isomer for [Au_nRb]⁺ clusters in the region of n = 1–10. The charges in [Au_nRb]⁺ clusters transfer from the Rb atoms to Au_n host. Density of states revealed that the Au-5d, Au-5p, and Rb-4p orbitals hardly participated in bonding. In addition, it is found that the most favourable channel of the [Au_nRb]⁺ clusters is Rb⁺ cation ejection. The electronic localisation function (ELF) analysis of the [Au_nRb]⁺ clusters shown that strong interactions are not revealed in this study.     

High vertical breakdown strength in with low specific on‐resistance AlGaN/AlN/GaN HEMTs on silicon

Off‐state and vertical breakdown characteristics of AlGaN/AlN/GaN high‐electron‐mobility transistors (HEMTs) on high‐resistivity (HR)‐Si substrate were investigated and analysed. Three‐terminal off‐state breakdown (BV_gd) was measured as a function of gate–drain spacing (L_gd). The saturation of BV_gd with L_gd is because of increased gate leakage current. HEMTs with L_gd = 6 µm exhibited a specific on‐resistance R_DS[ON] of 0.45 mΩ cm². The figure of merit (FOM = BV_gd²/R_DS[ON]) is as high as 2.0 × 10⁸ V² Ω^–1 cm^–2, the highest among the reported values for GaN HEMTs on Si substrate. A vertical breakdown of ～1000 V was observed on 1.2 µm thick buffer GaN/AlN grown on Si substrate. The occurrence of high breakdown voltage is due to the high quality of GaN/AlN buffer layers on Si substrate with reduced threading dislocations which has been confirmed by transmission electron microscopy (TEM). This indicates that the AlGaN/AlN/GaN HEMT with 1.2 µm thick GaN/AlN buffer on Si substrate is promising candidate for high‐power and high‐speed switching device applications. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Quantum chemical investigation on the structure and first hyperpolarizability for N‐substituted [n]cyclacene

Six N‐substituted [n]cyclacene (n = 5, 6, 7,…,10) molecules were designed to study the relationship between the structure and first hyperpolarizability. Their static first hyperpolarizabilities (β₀) were obtained by MP2/6‐31 + g(d) level. Two interesting relationships between the β₀ value and the structure have been found: (1) The β₀ value increases with the increase of the number n when n is odd: 3155 ([5]cyclacene) < 48,905 ([7]cyclacene) < < 393,444 ([9]cyclacene), and when n is even: 357,620 ([6]cyclacene) < 618,608 ([8]cyclacene) < 3,513,644 a.u. ([10]cyclacene). (2) The β₀ values (in the range of 357,620 ~ 3,513,644 a.u.) of the N‐substituted [n]cyclacene (when n is odd) are much larger (in the range of 3155~393,444 a.u.) than that of the N‐substituted [n]cyclacene (when n is even). Furthermore, their frequency‐dependent β (?2ω; ω, ω) and β (?ω; ω, 0) (ω = 0.005, 0.01, and 0.0239 a.u.) were also estimated by Møller–Plesset perturbation/6‐31 + g(d) level. Among the frequency‐dependent β (ω), [10]cyclacene has the largest β (?ω; ω, 0) and β (?2ω; ω, ω) to be 1.2 × 10⁸ (ω = 0.01) and 2.9 × 10⁷ a.u. (ω = 0.005 a.u.), which are much larger than the static β₀ = 3.5 × 10⁶ a.u. by 34 and 8 times. Our present work may offer a new idea in the design of high‐performance tubiform nonlinear optical materials. Copyright © 2011 John Wiley & Sons, Ltd.     

Comment: On charged analogue of shear-free fluids

Recently, Gupta et al. [2] claim that solutions with NDG have no uncharged analogue. This claim seems to be partially correct as it is seen in present article that neutral shear-free fluid (f =α₁ x ^−5/2α₁ being a constant) given by Stephani [3] can be charged.     

Oxovanadium (IV) complexes of bidentate [N,O] donor Schiff-base ligands: synthesis and mesomorphism

A series of new oxovanadium(IV) Schiff-base complexes of the type [VO(L)₂], [L?=?N-(4-n-alkoxysalicylaldimine)-4′-dodecyloxyaniline, n?=?6, 8, 16, and 18] have been synthesized. The compounds were characterized by FT-IR, ¹H-NMR, ¹³C-NMR, UV-Vis, FAB-mass, and magnetic susceptibility measurements. The mesomorphic behavior of the compounds was studied by polarized optical microscopy and differential scanning calorimetry. The compounds are all highly thermally stable exhibiting smectic mesomorphism. Non-electrolytic nature of the complexes was ascertained by solution electrical conductance measurements. Cyclic voltammetry revealed a quasireversible single-electron response for VO(V)/VO(IV) couple. A ν_V=O stretching mode at ～970?cm^?1 indicates absence of any intermolecular V=O?···?V=O interactions. Density functional theory study was carried out using DMol3 at BLYP/DNP level to determine energy optimized structure revealed a distorted square pyramidal geometry for the vanadyl complexes.     

Self-assembly of metal–organic frameworks and graphene oxide as precursors for lithium-ion battery applications

We fabricated composites of Fe₂O₃/reduced graphene oxide as lithium-ion batteries anode material with controlled structures by employing self-assembly of metal–organic frameworks (MOFs) and polymer-functionalized graphene oxide as precursors. By electrostatic interaction, the negatively charged MOFs, Prussian Blue (PB), are assembled on poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene oxide (positive charge). Then the PB cubes become FeOOH nanosheets when treated with sodium hydroxide. Upon further annealing, the FeOOH nanosheets transform to Fe₂O₃ nanoparticles while the graphene oxide become reduced graphene oxide simultaneously. It was found that the composites have good performance as anode of lithium-ion battery. This work shows a new way for self-assembling MOFs and 2D materials.     

Structures and reactions of biomolecular ions produced with electrospray ionization

Photo-induced reaction of [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with dimethylsulfoxide (DMSO) is investigated by using a tandem mass spectrometer with electrospray ionization. We measure the photodissociation yields of mass-selected hemin⁺(DMSO)_n clusters for n = 0-3. The mass spectra of the fragment ions show the -cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules. Yield of the -cleavage reaction is found to depend strongly on the excitation energy and the number of solvent molecules. We also examine photo-induced reactions of multiply-charged cytochrome c ions, (M + nH)^{n +} ( n = 9-17). Photoionization is found to be the dominant process for the lower charged states ( n = 9-12) and its yield decreases rapidly with increasing the charge. The photoionization is ascribed to the emission of electron by multiphoton excitation of heme under the influence of Coulomb attractive potential arising from the charges in the polypeptide chain. Model calculations of the Coulomb potential suggest that the structure of the polypeptide chain is completely elongated.     

Structure and stability of small zinc oxide clusters

The structure and stability of small neutral and positively charged zinc oxide (ZnO) _n clusters (n = 2−9) have been studied within the density functional theory. For n ≤ 7, the most stable clusters are shown to be flat rings; for n = 8, 9, the clusters are mainly three-dimensional cage structures. The energies and main channels of fragmentation of the clusters have been determined. It has been found that the fragmentation of the charged clusters with n > 6 occurs predominantly with formation of a (ZnO)₄⁺ ion, which explains the available mass spectrometric data on ionization of the zinc oxide clusters by electron impact.     

Ξ− and Ξ− inclusive production in Ξ− Be interactions at 116 GeV/c

The cross sections for Ξ^? and Ω^? inclusive production in Ξ^? Be collisions at 116 GeV/c have been measured in the kinematic domain [0.1<x _F <0.9, 0<p _T <1.7 GeV/c]. The integrated cross sections per nucleon are found to be about twice as large as in Ξ^? p collisions. The invariant cross sections increase by a factor of 70 for the Ξ^? s and of 100 for the Ω^? s between the central region (x _F ～0.2) and the projectile fragmentation region (x _F ～0.8). In the central region, they have about the same magnitude as the ones for Ξ^? and Ω^? inclusive production inp nucleon collisions. The Ξ^? and Ω^? polarisations have been measured over the same kinematic domain and are found to be compatible with zero.     

On the energy dependence of the yield of doubly charged negative ions during the capture of free electrons by C60(CF3)12 trifluoromethylfullerene molecules

Peaks of C₆₀(CF₃) _n ^2? doubly charged negative ions (n = 6–12) have been observed in the mass spectra of the resonance electron capture by trifluoromethylfullerene C₆₀(CF₃)₁₂ molecules. It has been established that these ions are formed owing to the attachment of two free isoenergetic electrons. The autodetachment of an extra electron has been detected for the doubly charged molecular ions (n = 12). It has been established from the observation of the delayed fragmentation of the most abundant ions with n = 8 and 10 that the doubly charged negative ions, like their singly charged analogs, are metastable with respect to the separation of the CF₃ fragment(s). The yield of doubly charged negative ions has been obtained as a function of the electron energy. By comparing them with the analogous dependences for the singly charged ions, the specific features have been revealed which were associated with the presence of the repulsive Coulomb barrier and the regular effect of the doubled energy of two additional electrons on the energy dependence of the dissociative decay of the doubly charged negative ions. The absolute cross section for the formation of the C₆₀(CF₃) ₁₀ ^2? ions has been measured. At the energy of their yield maximum near the 5 eV, it is ～1 × 10^?19 cm².     

Quasi-free Compton scattering and the polarizabilities of the neutron

Differential cross-sections for quasi-free Compton scattering from the proton and neutron bound in the deuteron have been measured using the Glasgow/Mainz photon tagging spectrometer at the Mainz MAMI accelerator together with the Mainz [48]cm ;SPMOslash; × [64]cm NaI(Tl) photon detector and the G?ttingen SENECA recoil detector. The data cover photon energies ranging from [200]MeV to [400]MeV at θ^LAB _γ = 136.2^°. Liquid deuterium and hydrogen targets allowed direct comparison of free and quasi-free scattering from the proton. The neutron detection efficiency of the SENECA detector was measured via the reaction p(γ,π⁺ n). The “free” proton Compton scattering cross-sections extracted from the bound proton data are in reasonable agreement with those for the free proton which gives confidence in the method to extract the differential cross-section for free scattering from quasi-free data. Differential cross-sections on the free neutron have been extracted and the difference of the electromagnetic polarizabilities of the neutron has been determined to be α_n - β_n = 9.8±3.6(stat)^+2.1 _-1.1(syst)±2.2(model) in units of [10^-4]fm ³. In combination with the polarizability sum α_n + β_n = 15.2±0.5 deduced from photoabsorption data, the neutron electric and magnetic polarizabilities, α_n = 12.5±1.8(stat)^+1.1 _-0.6(syst)±1.1(model) and β_n = 2.7±1.8(stat)^+0.6 _-1.1(syst)±1.1(model) are obtained. The backward spin polarizability of the neutron was determined to be γ⁽ⁿ⁾ _π = (58.6±4.0)×10^-4 fm ⁴. Received: 21 August 2002 / Accepted: 16 October 2002 / Published online: 11 February 2003 RID="a" ID="a"Part of the Doctoral Thesis. RID="b" ID="b"Present address: Physikalisch-Technische Bundesanstalt, Bundesallee 100, D-38116 Braunschweig. RID="a" ID="a"Part of the Doctoral Thesis. RID="b" ID="b"Present address: Physikalisch-Technische Bundesanstalt, Bundesallee 100, D-38116 Braunschweig. RID="c" ID="c"Part of the Habilitation Thesis. RID="d" ID="d"e-mail: schumacher@physik2.uni-goettingen.de Communicated by Th. Walcher     

Surface plasmon resonance biosensor modified with multilayer silver nanoparticles films

We alternately deposited negatively charged Ag-(3-mercaptopropionic acid) (Ag-MPA) sol and positively charged poly-(diallyldimethylammonium) (PDDA) on gold substrate modified with 4-aminothiophenol (4-ATP), through electrostatic layer-by-layer (LBL) self-assembly. We characterized the prepared three-dimensional Ag/PDDA multilayer films by surface plasmon resonance (SPR) and atomic force microscope (AFM). The thickness of each film in the multilayer films, the deposition effect of Ag nanoparticles, and the processing of DNA adsorption are characterized by SPR. AFM characterization shows that DNA/3(PDDA/Ag)/4-ATP composite is uniformly and firmly distributed on the surface of gold films. Compared with other sensors, gentamicin could be highly sensitively measured by DNA/3(PDDA/Ag)/4-ATP/Au sensor. There is a good linear relationship in the concentration range of 5 × 10⁻⁸ to 1 × 10⁻⁴ mol/L. The linear equation is found to be Δθ_SPR = 1.3521 × 10⁻⁵c + 0.08641 (the correlation coefficient is 0.9983) with detection limit of 1 × 10⁻⁹ mol/L. Since such LBL assembly film is simple to prepare, the work described here provides an effective method for studying small molecule drugs on SPR.     

Room-temperature power factor of CuAlO2 composite tablets enhanced by MWCNTs

CuAlO₂ with high theoretical thermoelectric performance has potential applications in thermal energy conversion. Herein, multi-wall carbon nanotubes (MWCNTs)/CuAlO₂ composite tablets are prepared by using different amounts of MWCNTs and solid paraffin binder, where MWCNTs served as a conductive agent and rendered three orders of magnitude increase in electrical conductivity. Seebeck coefficient of the composites was reduced with increasing MWCNTs content. Consequently, an optimal room-temperature thermoelectric power factor (PF) of 1.31 μW m⁻¹K⁻² has been rendered by MWCNTs/CuAlO₂ composite tablet with 1 wt % MWCNTs. Moreover, PF value increased with increasing temperature after a slight decrease at 333 K, which can be ascribed to the modulation of electrical conductivity. Current work provides an effective strategy to improve thermoelectric performance of CuAlO₂ materials.     

Preparation and characterization of PbTiO3–epoxy resin compositionally graded thick films

The preparation and properties of compositionally graded PbTiO₃ (PT)–epoxy resin (EPR) composite thick films are reported in this study. Various graded specimens were prepared using gravity casting method by embedding PT powders into the EPR matrix. The existence of a graded structure with two distinct phases, a good intermixing, some air pores, and different morphologies, was confirmed by scanning electron microscopy micrographs. The dielectric constants of these composites have values in the range 5–12 at the frequency of ～10⁴?Hz and about 3–13 at ～5?×?10^8?Hz. The composites with permittivity gradient act as a natural impedance match system in the frequency range 2–4?GHz, resulting in very low reflections. Therefore, the compositionally graded PT–EPR composite thick films are suitable as adapting impedance materials for microwave applications.