Enhanced photoluminescence of Nd2O3 nanoparticles modified with silane-coupling agent: Fluorescent resonance energy transfer analysis

A liquid laser medium with a lifetime of 492 mu s and a fluorescent quantum efficiency of 52.5% has been presented by stably dispersing dimethyl dichorosilane-modified Nd2O3 nanoparticles in dimethylsulfoxide. Its optical properties and mechanism were investigated and explained by fluorescence resonance energy transfer theory. The calculation result shows that the quenching of Nd-III F-4(3/2)-> I-4(11/2) transition via O-H vibrational excitation can be eventually neglected. The main reason is that the silane-coupling agent molecules remove the -OH groups on Nd2O3 nanoparticles and form a protective out layer. (c) 2007 American Institute of Physics.

Covalent functionalization of chemically converted graphene sheets via silane and its reinforcement

Polydisperse, functionalized, chemically converted graphene (f-CCG) nanosheets, which can be homogeneously distributed into water, ethanol, DMF, DMSO and 3-aminopropyltriethoxysilane (APTS), were obtained via facile covalent functionalization with APTS. The resulting f-CCG nanosheets were characterized by FTIR, XPS, TGA, EDX, AFM, SEM, and TEM. Furthermore, the f-CCG nanosheets as reinforcing components were extended into silica monoliths. Compressive tests revealed that the compressive failure strength and the toughness of f-CCG-reinforced APTS monoliths at 0.1 wt% functionalized, chemically converted graphene sheets compared with the neat APTS monolith were greatly improved by 19.9% and 92%, respectively.

Polymer immobilized silane bridged metallocene catalysts for ethylene polymerization

Ansa-zirconocene complex with an allyl substituted silane bridge [(CH2=CHCH2)CH3Si(C5H4)(2)]ZrCl2 (1a) has been synthesized and characterized. The molecular structure of la has been determined by X-ray crystallographic analysis. The polymer immobilized metallocene catalyst 1b is prepared by the co-polymerization of la with styrene in the presence of radical initiator. The result of ethylene polymerization showed that the polymer immobilized metallocene catalyst kept high activity for ethylene polymerization and was a potential supported catalyst for olefin polymerization.

Silane bridged polymerized metallocene catalyst for ethylene polymerization

The polymerized metallocene catalyst 4 was prepared by the co-polymerization of ansa-zirconocene complex [CH3Si(2)]ZrCl2 (3) containing vinyl substituted silane bridge with styrene in the presence of radical initiator. Catalyst 4 was found to display high ethylene polymerization activity of 2.28 x 10(6) g PE/(mol . h) with a viscosity average molecular weight (M-eta) value of 61.6 x 10(3) using methylalumoxane (MAO) as a co-catalyst. The ethylene polymerization has been investigated under different conditions.

X-ray crystal structure and molecular mechanics calculations of (2,6-iso-dipropyl-phenylamide) dimethyl (tetra-methylcyclopenta-dienyl) silane titanium dichloride

Crystal and molecular structure of (2.6-dipropylphenylamide) dimethyl (tetra-methyl cyclopentadienyl) silane titanium dichloride (I) was fully characterized by X-ray diffraction. The crystal is obtained from a mixture of ether/hexane as orthorhombic. with a = 12.658 (3) Angstrom. b = 16.62 (3) Angstrom. c = 11.760 (2) Angstrom. V = 2474.2 (9) Angstrom(3). Z = 4, space group Pnma. R = 0.0399; Componud I compose of the pi-bounded ring with its dimethylsilyl-dipropyl phenyl amido group and the two terminal chloride atoms coordinated to central metal to form a so-called constrained geometry catalyst (CGC) structure. The result of molecular mechanics (MM) calculations on compound I shows that bond lengths and bond angles from the MM calculation are comparable to the data obtained from the X-ray diffraction study. The relation of the structure of CGCs and their catalytic activity by MM calculations is also discussed.

Half-sandwich silane complexes of ruthenium and iron : synthesis, structure and application to catalysis

The present thesis describes syntheses, structural studies, and catalytic reactivity of new non-classical silane complexes of ruthenium and iron. The ruthenium complexes CpRu(PPri3)CI(T]2-HSiR3) (1) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were prepared by reactions of the new unsaturated complex CpRu(PPri3)CI with silanes. According to NMR studies and X-ray analyses, the complexes la-c exhibit unusual simultaneous Si··· H and Si··· CI-Ru interactions. The complex CpRu(PPri3)CI was also used for the preparation of the first examples of late transition metal agostic silylamido complexes CpRu(PPri3)(N(T]2-HSiMe2)R) (2) (R= Ar or But), which were characterized by NMR spectroscopy. The iron complexes CpFe(PMePri2)H2(SiR3) (3) (SiR3 = SiCh (a), SiClzMe (b), SiCIMe2 (c), SiH2Ph (d), SiMe2Ph (e» were synthesized by the reaction of the new borohydride iron complex CpFe(PMePri2)(B~) with silanes in the presence NEt3. The complexes 3 exhibit unprecedented two simultaneous and equivalent Si··· H interactions, which was confirmed by X-ray analyses and DFT calculations. A series of cationic ruthenium complexes [CpRu(PR3)(CH3CN)(112-HSiR'3)]BAF (PR3 = PPri 3 (4), PPh3 (5); SiR'3 = SiCh (a), SiClzMe (b), SiClMe2 (c), SiH2Ph (d), SiMe2Ph (e» was obtained by substitution of one of the labile acetonitrile ligands in [CpRu(PR3)(CH3CNh]BAF with sHanes. Analogous complexes [TpRu(PR3)(CH3CN)(T]2 -HSiR' 3)]BAF (5) were obtained by the reaction of TpRu(PR3)(CH3CN)CI with LiBAF in the presence of silanes. The complexes 4-5 were characterized by NMR spectroscopy, and the observed coupling constants J(Si-H) allowed us to estimate the extent of Si-H bond activation in these compounds. The catalytic activity in hydrosilylation reactions of all of the above complexes was examined. The most promising results were achieved with the cationic ruthenium precatalyst [CpRu(PPri3)(CH3CN)2t (6). Complex 6 shows good to excellent catalytic activity in the hydrosilylation of carbonyls, dehydrogenative coupling of silanes with alcohols, amines, acids, and reduction of acid chlorides. We also discovered very selective reduction of nitriles and pyridines into the corresponding N-silyl imines and l,4-dihydropyridines, respectively, at room temperature with the possibility of catalyst recycling. These chemoselective catalytic methods have no analogues in the literature. The reactions were proposed to proceed via an ionic mechanism with intermediate formation of the silane a-complexes 4.

Effect of Silane Coupling Agent on Cure Characteristics and Mechanical Properties of Nitrile Rubber/Reclaimed Rubber Blend

Blends of nitrile rubber and reclaimed rubber containing different levels of a coupling agent, Si 69 (bis(3- triethoxysilyl propyl)(tetrasulphide) were prepared and the cure characteristic's and mechanical properties were studied. Optimum loading of Si-69 was found to be a function of blend ratio. 3 phi- of Si 69 in a 70:30. Blend was found to be the optimum combination with respect to the mechanical properties. The rate and state of cure were also affected bv the conp/ing agent. Tensile strength, tear strength and abrasion resistance were improved in the presence of coupling agent. While the state of cure improved, the cure rate and scorch time decreased with increasing silane content. Ageing studies showed that the blends containing the coupling agent were inferior to the unmodified blends.

Effect of Silane Coupling Agent on Cure Characteristics and Mechanical Properties of Chloroprene Rubber/Reclaimed Rubber Blend

Chloroprene rubber was blended with whole tire reclaimed rubber (WTR) in presence of different levels of a coupling agent Si69 [bis- (3-(triethoxysilyl)propy1)tetrasuIfide] and the cure characteristics and mechanical properties were studied. The rate and state of cure were also affected by the coupling agent. While the cure time was increased, the cure rate and scorch time were decreased with increasing silane content. Tensile strength, tear strength, and abrasion resistance were improved in the presence of coupling agent. Compression set and resilience were adversely affected in presence of silane-coupling agent.Aging studies showed that the blends containing the coupling agent were inferior to the unmodified blends.

Silane Grafting of Polyethylenes

Reactive extrusion is an attractive means of polymer processing since the shaping and reaction take place in a single operation. In this paper we report the silane grafting of polyethylenes in a single screw extruder. The optimum conditions for silane grafting, viz. temperature, shear rate, silane and DCP concentrations, were determined on a torque rheometer and then actual extrusion was performed using these conditions. The study shows that an optimum low level of grafting/ crosslinking can be introduced into polyethylene during its extrusion for better mechanical behavior and=or thermal stability without affecting the processability.

The Effect of Periodic Silane Burst on the Properties of GaN on Si (111) Substrates

The periodic silane burst technique was employed during metalorganic chemical vapor deposition of epitaxial GaN on AlN buffer layers grown on Si (111). Periodic silicon delta doping during growth of both the AlN and GaN layers led to growth of GaN films with decreased tensile stresses and decreased threading dislocation densities, as well as films with improved quality as indicated by x-ray diffraction, micro-Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. The possible mechanism of the reduction of tensile stress and the dislocation density is discussed in the paper.

Can Heat Treatment Procedures of Pre-hydrolyzed Silane Replace Hydrofluoric Acid in the Adhesion of Resin Cement to Feldspathic Ceramic?

Purpose: To evaluate the influence of heat treatment (HT) procedures of a pre-hydrolyzed silane on bond strength of resin cement to a feldspathic ceramic.Materials and Methods: Ceramic and composite blocks (N = 30) were divided into six groups (n = 5) and subjected to the following conditioning procedures: G1: 9.6% hydrofluoric acid (HF) for 20 s + silane (RelyX Ceramic Primer, 3M ESPE) + resin cement (Panavia F2.0, Kuraray) (control); G2: HF (20 s) + silane + heat treatment in furnace (HTF) (100 degrees C, 2 min) + resin cement; G3: silane + HTF + resin cement; G4-HF (20 s) + silane + heat treatment with hot air (HTA) (50 +/- 5 degrees C for 1 min) + resin cement; G5: silane + HTA + resin cement; G6: silane + resin cement. The microtensile bond strength (MTBS) test was performed using a universal testing machine (1 mm/min). After debonding, the substrate and adherent surfaces were analyzed using a stereomicroscope and SEM to categorize the failure types. The data were statistically evaluated using one-way ANOVA and Tukey's test (5%).Results: The control group (G1) showed no pre-test failures and presented significantly higher mean MTBS (16.01 +/- 1.12 MPa) than did other groups (2.63 +/- 1.05 to 12.55 +/- 1.52 MPa) (p = 0.0001). In the groups where HF was not used, HTF (G3: 12.55 +/- 1.52 MPa) showed significantly higher MTBS than did HTA (G5: 2.63 +/- 1.05 MPa) (p < 0.05). All failure types were mixed, ie, adhesive between the resin cement and ceramic accompanied by cohesive failure in the cement.Conclusion: Heat treatment procedures for the pre-hydrolyzed silane either in a furnace or with the application of hot air cannot replace the use of HF gel for the adhesion of resin cement to feldspathic ceramic. Yet when mean bond strengths and incidence of pre-test failures are considered, furnace heat treatment delivered the second best results after the control group, being considerably better than hot air application.

Heat treatment of pre-hydrolyzed silane increases adhesion of phosphate monomer-based resin cement to glass ceramic

This study evaluated the influence of different forms of heat treatment on a pre-hydrolyzed silane to improve the adhesion of phosphate monomer-based (MDP) resin cement to glass ceramic. Resin and feldspathic ceramic blocks (n=48, n=6 for bond test, n=2 for microscopy) were randomly divided into 6 groups and subject to surface treatments: G1: Hydrofluoric acid (HF) 9.6% for 20 s + Silane + MDP resin cement (Panavia F); G2: HF 9.6% for 20 s + Silane + Heat Treatment (oven) + Panavia F; G3: Silane + Heat Treatment (oven) + Panavia F; G4: HF 9.6% for 20 s + Silane + Heat Treatment (hot air) + Panavia F; G5: Silane + Heat Treatment (hot air) + Panavia F; G6: Silane + Panavia F. Microtensile bond strength (MTBS) test was performed using a universal testing machine (1 mm/min). After debonding, the substrate and adherent surfaces were analyzed using stereomicroscope and scanning electron microscope (SEM) to categorize the failure types. Data were analyzed statistically using two-way test ANOVA and Tukey's test (=0.05). Heat treatment of the silane containing MDP, with prior etching with HF (G2: 13.15 ± 0.89a; G4: 12.58 ± 1.03a) presented significantly higher bond strength values than the control group (G1: 9.16 ± 0.64b). The groups without prior etching (G3: 10.47 ± 0.70b; G5: 9.47 ± 0.32b) showed statistically similar bond strength values between them and the control group (G1). The silane application without prior etching and heat treatment resulted in the lowest mean bond strength (G6: 8.05 ± 0.37c). SEM analysis showed predominantly adhesive failures and EDS analysis showed common elements of spectra (Si, Na, Al, K, O, C) characterizing the microstructure of the glass-ceramic studied. Heat treatment of the pre-hydrolyzed silane containing MDP in an oven at 100 °C for 2 min or with hot air application at 50 ± 5 ºC for 1 min, was effective in increasing the bond strength values between the ceramic and resin cement containing MDP.