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1.
Bis(diisopropyl)thiophosphoryl disfulfide (DIPDIS) can be successfully used to form a blend comprising polar carboxylated nitrile rubber (XNBR) and nonpolar NR through a chemical link between the two. It is revealed from the study that the physical properties of the vulcanizates obtained from the NR-XNBR blend could be significantly improved by the judicious selection of the NR:XNBR ratio. These properties can further be improved by two-stage vulcanization as described in the procedure. The SEM study reveals that it is possible to form a coherent blend of NR and XNBR in the presence of DIPDIS. © 1994 John Wiley & Sons, Inc. 相似文献
2.
UV‐cured silicone composites obtained via hydrosilation and in‐situ generation of inorganic particles
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Sophie Marchi Marco Sangermano Patrick Meier Xavier Kornmann 《Polymer Engineering and Science》2016,56(1):3-8
The in situ generation of particles is an efficient way to prepare organic‐inorganic hybrid materials. This approach has been widely used to enhance the dispersion within the matrix and therefore to improve the composites’ properties. This method was used in the present paper to produce silicone composites. The crosslinking of the polymer matrix was achieved by hydrosilation reaction that is typically the addition of a Si‐H bond across a double bond, in the presence of a platinum catalyst. The generation of silica particles was carried out prior the hydrosilation reaction. We previously demonstrated that this usually thermally activated reaction can also be induced under UV‐light and that a front propagation allows the formation of thick unfilled samples. However, the presence of inorganic particles directly dispersed in the matrix lead to a reduction of thickness curability. That is the reason why the addition of particles by sol‐gel process is studied in the present article. The lower dimension and better dispersion of the particles within the material promote the formation of thicker cured composites. The effect of the silica precursor's amount on the system's reactivity was evaluated and samples thick up to 2 cm were obtained with the most suitable conditions of reaction. POLYM. ENG. SCI., 56:3–8, 2016. © 2015 Society of Plastics Engineers 相似文献
3.
The present study aims to enhance EPDM rubber–silica interaction by employing a special technique called Two‐Stage Vulcanization, with the help of a multifunctional rubber additive, bis diisopropyl thiophosphoryl disulfide (DIPDIS). In this process EPDM rubber was heated along with rubber additives up to the time just before the commencement of cure and then filler was incorporated to the preheated rubber to get the final mix. The efficiency of this novel technique is evaluated by the enhancement of physical properties of the silica‐filled vulcanizates. This novel technique is also employed to investigate the effect of a silane‐coupling agent, viz., bis (3‐triethoxy silyl propyl) tetrasulphide (TESPT), in addition to DIPDIS, on the rubber–filler interaction. The positive role of this technique in enhancing the rubber–filler interaction is evidenced by the dynamic mechanical analysis and scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1132–1139, 2006 相似文献
4.
Synergistic combinations of diisopropyl thiophosphoryl‐N‐oxydiethylene sulfenamide (DIPTOS) with some disulfide accelerators or sulfur donors improve the physical properties of NR–EPDM blend vulcanizates. Various combinations of DIPTOS with dibenzothiazyl disulfide (MBTS), tetramethyl thiuram disulfide (TMTD), bis(N‐oxydiethylene) disulfide (ODDS) and bis(diisopropyl) thiophosphoryl disulfide (DIPDIS) were used in this study. DIPTOS when used alone produces NR vulcanizates with a moderate range of physical properties, whereas in conjunction with MBTS and DIPDIS it exhibits significant mutual activities. Morphological studies of the tensile‐fractured surfaces of the blend vulcanizates by scanning electron microscopy corroborate the physical data. Copyright © 2003 Society of Chemical Industry 相似文献
5.
Accurate information on the interactions between water and silica is critical to the understanding of its properties including mechanical strength under stress and long‐term chemical durability of silica and silicate glasses. In this study, interactions between water and nanoporous amorphous silica models were investigated using density functional theory (DFT) based ab initio molecular dynamics (AIMD) simulations which accurately describe bond breakage and formation as well as chemical reactions. AIMD simulations up to 30 ps were performed for systems containing water and nanoporous silica with a wide range of porosities (31%–67%). Partial removal of defects, such as two‐membered rings, was observed during the AIMD runs whereas more reactive coordination defects were removed during the initial geometry optimization. The limited two‐membered ring removal can be attributed to restricted water‐defect movement or the increased stability of rings located on concave surfaces. Two‐membered ring removal mechanisms included the formation of an overcoordinated silicon (Si5) intermediate defect from the dynamic simulations. Si5 defects continued to develop throughout the simulations, indicating a thermodynamic drive for two‐membered ring removal which is kinetically limited. Changes in the electronic structures, such as atomic charges, and bond length‐bond angle correlation functions were monitored during the hydroxylation process. 相似文献
6.
High‐temperature (180°C) molding of epoxidized natural rubber (ENR) filled with precipitated silica leads to chemical bond formation between epoxy groups of ENR and silanol groups of silica. The extent of chemical bond formation is further enhanced in the presence of the silane coupling agent N‐3‐N‐(vinyl benzyl amino)ethyl‐γ‐amino‐propyl trimethoxy silane mono hydrogen chloride (trade name Z‐6032). The results of hysteresis loss measurements show that hysteresis loss increases with increase in coupling agent loading as a result of the higher modulus of the compounds compared to that of the ENR–silica mix. The dynamic mechanical property measurements show that the addition of coupling agent increases the glass‐transition temperature. Whereas strain‐dependent dynamic mechanical properties show that filler structure breakdown increases with increasing loading of coupling agent. Sulfur‐cured systems show higher filler structure breakdown compared to that of nonsulfur systems. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2171–2177, 2002 相似文献
7.
《Journal of Sulfur Chemistry》2013,34(2):103-108
The reaction between phenacyl bromide and 2-mercaptobenzimidazole has been studied in 12 different protic and aprotic solvents. The kinetic study shows that the reaction is second-order with first-order dependence each on (phenacyl bromide) and (2-mercaptobenzimidazole). Analysis of rate data shows that there is no direct correlation between the rate constant and dielectric constant of the solvent. Correlation of rate data with different solvent parameters like hydrogen bond acceptor basicity, polarizability and solvent electrophilicity, using linear multiple regression analysis shows that the reaction is influenced by these properties of the solvent. From the regression coefficients, information on the mode of solvation of the reactants and the transition state is obtained. The reaction has also been studied at different temperatures and the thermodynamic parameters Δ H #, Δ S # and Δ G # are evaluated. 相似文献
8.
Angela Dibenedetto Michele Aresta Carlo Fragale Monica Distaso Carlo Pastore Anna M. Venezia Chang-jun Liu Mingbo Zhang 《Catalysis Today》2008,137(1):44
The oxidation of propene-to-propene oxide (PO) has been achieved via oxygen-transfer from transition-metal oxides to the olefin. Under the operative conditions, the cleavage of the olefinic double bond is not observed. The only co-products are acetone (AC) and propinoaldehyde (PA), that can be considered as isomerisation products of propene oxide. The “parameter space” of the reaction has been investigated using a High Throughput Experiment (HTE) approach. However, it has been shown that the reaction yield and selectivity are sensitive to: temperature, time of the reaction, nature of the metal and its oxidation state and redox potential, lattice energy of the oxide, shape of the oxide (massive or supported), nature of the support, presence of the solvent, and the presence of CO2. Several metal oxides have been investigated. In this paper, we report the general trend for the tested oxides and discuss in detail the behaviour of PdOx and V2O5, either in the massive form or as supported oxides (on alumina or silica). The oxides have been monitored using UV–vis and XPS and the organic products have been identified and determined by GC–MS. 相似文献
9.
From the chloroform/methanol extract of the fruiting bodies of the ascomycete Chinese truffle Tuber indicum Cooke et Massee, a new trihydroxylated monounsaturated fatty acid (1) has been isolated. The structure of this new linoleic acid-derived metabolite was established as 9,10,11-trihydroxy-(12Z)-12-octadecenoic
acid by means of spectroscopic and chemical methods. The fatty acid composition of the chloroform-soluble fraction of this
fungus was analyzed by gas chromatography-mass spectrometry. The content of the predominant unsaturated fatty acids (oleic
and linoleic acids) is as high as 68%. The use of dimethyl disulfide adduct was effective in the determination of the position
of the double bond, and the glycol oxidation fission reaction with sodium metaperiodate supported on silica gel was helpful
in establishing the location of the trihydroxylic groups in the new fatty acid. 相似文献
10.
Xiaoqiang Hou Leslie J. Struble R.James Kirkpatrick 《Cement and Concrete Research》2004,34(9):1683-1696
Experimental investigations of the reactions between silica, alkali hydroxide solution, and calcium hydroxide show that alkali-silicate-hydrate gel (A-S-H) comparable to that formed by the alkali-silica reaction (ASR) in concrete does not form when portlandite or the Ca-rich, Si-poor C-S-H of ordinary portland cement (OPC) paste is available to react with the silica. Under these conditions, we observe either the formation of additional C-S-H by reaction of Ca(OH)2 with the dissolving silica or the progressive polymerization of C-S-H. The A-S-H dominated by Q3 polymerization forms only after portlandite has been consumed and the C-S-H polymerized. These conclusions are consistent with previously published results and indicate that the ASR gel of concrete forms only in chemical environments in which the pore solution is much lower in Ca and higher in Si than bulk pore solution of OPC paste. These results highlight the similarity between ASR and the pozzolanic reaction and are supported by data for mortar bar specimens. 相似文献
11.
Saleem J. Denholme Jamie B. Gallagher Phillip S. Dobson John M. R. Weaver Duncan H. Gregory 《Israel journal of chemistry》2010,50(4):515-523
Highly symmetrical, isotropic nickel disulfide (NiS2) nanocubes have been synthesised via a Physical Vapour Transport (PVT) method in which sulfur vapour generated in situ is reacted with nickel-coated silica substrates. Systematic studies demonstrate the effect of the reactant ratio, substrate, metal layer thickness, and reaction temperature on the synthesis and growth process. The evolution of structure and composition has been followed by diffraction and electron microscopy techniques, and the size of the NiS2 cubes can be varied from below 200 nm to 1–2 μm across. Magnetic properties of the disulfide nanomaterials have been determined using SQUID magnetometry. Initial experiments also demonstrate that related Chemical Vapour Transport (CVT) techniques can be exploited to produce alternative compositions in the Ni–S system with varying morphologies that can be controlled via chemical and physical reaction parameters. 相似文献
12.
Maria Cazacu Angelica Vlad Anton Airinei Mihaela Alexandru 《Polymer International》2008,57(9):1067-1074
BACKGROUND: Because of its properties, silica gel is an excellent host for different compounds. Many types of chemical species (organics, organometallics, proteins, enzymes, etc.) can be encapsulated in xerogels, and the sol–gel technique has been shown to be very useful for this aim. RESULTS: Some host–guest systems based on silica and complexed lanthanum were prepared in order to develop fluorescence properties. Three pathways were used to prepare such systems: (1) obtaining the lanthanum complex with a dimethylsiloxane‐based ligand and its incorporation into a silica network; (2) preparation of a silica network having hydroxyazomethine groups and in situ lanthanum complexation; and (3) preparation of polydimethylsiloxane (PDMS)/silica composites that possess hydroxyazomethine groups on the silica and in situ lanthanum complexation. The sol–gel technique was used in all cases. CONCLUSION: The photophysical properties of the prepared compounds were evaluated using fluorescence spectroscopy. The investigations revealed that the systems belonging to the second series are the most fluorescent. In the third series, the presence of PDMS provokes a decrease of the fluorescence intensity, until its complete quenching when the PDMS content exceeds a certain threshold value. However, there is a range of silica/PDMS ratio for which fluorescent free‐standing films can be obtained. The presence of complexed lanthanum induces changes in the morphology of the silica/PDMS matrix, as evidenced by scanning electron microscopy studies. Copyright © 2008 Society of Chemical Industry 相似文献
13.
Correlation between IR peak position and bond parameter of silica glass: Molecular dynamics study on fictive temperature (cooling rate) effect
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Jiawei Luo Yuxing Zhou Carlo G. Pantano Seong H. Kim 《Journal of the American Ceramic Society》2018,101(12):5419-5427
The fictive temperature of glass is a consequence of its thermal history (cooling rate, primarily) and has a direct effect on physical and chemical properties of the glass. But, it is not easy to measure. The ability to nondestructively and spectroscopically measure it at room temperature would be of great benefit. Although empirical correlations have been established between fictive temperature and selected absorption peaks in the infrared spectra of silica glass, the fundamental understanding for this correlation has not been reported. Here, we use molecular dynamics simulations to show that the blue shift in the Si–O–Si asymmetric stretching peak of pure silica glass, which is known to correlate with a decrease in fictive temperature, can be attributed to a decrease in the average length of the Si–O bond in the silica network, not changes in the density or the Si–O–Si bond angle. The decrease in density at higher fictive temperatures of silica is associated with a decreased population of 5‐ and 6‐membered rings and broadening of the ring‐size distribution, and an increase in the average Si–O–Si bond angle. 相似文献
14.
Reduction of dielectric constant by nanovoids formed through chemical treatment on silica crosslinked polyimide and its effect on properties
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Taewon Yoo Ravindra V. Ghorpade Kwangin Kim Juheon Lee Sangyoup Lee Seungsu Baek Jungkun Song Haksoo Han 《应用聚合物科学杂志》2018,135(11)
In this study, 2,7‐diamino‐9‐fluorenol (DAF) has been introduced to bond silica to the main chain of the polyimide (PI) copolymer. DAF contains a hydroxyl group that could covalently bond with silica particles. 4,4′‐(Hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 4,4′‐oxydianiline (4,4′‐ODA) have been used as monomers to form a copolymer with DAF. The variation of silica content was controlled as 5%, 7.5, 10, 12.5 wt %. Variation in silica content contributes to the formation of various size (100–410 nm) of macroporous voids after hydrofluoric acid (HF) treatment. HF etching process was introduced to dissolve the silica and form voids in the structure of PI copolymer films. Compared with conventional PI films, air voids that were formed in the PI copolymer film reduced the dielectric from 4.40 to 1.86. The reduction in the dielectric constants can be explained in terms of creating silica particles that increase the presence of air voids after HF treatment. The thermal stability was stable up to 500 °C and the modulus change was confirmed with a dynamic mechanical analysis (DMA) to evaluate the effect of silica on thermal and mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45982. 相似文献
15.
The synergistic activity of bis(diisopropyl) thiophosphoryl disulfide (DIPDIS) in the presence of dithio bis(N-β-OH ethyl piperazine) (DTEP), a safe amine-based accelerator, has been studied both in gum and filled stock vulcanization of NR. This study, concerning the effect of variation of sulfur concentration on the gum vulcanization of NR, reveals that, although modulus values of the vulcanizates increase with the level of sulfur, the tensile strength values attain a maximum at 1.5 phr sulfur for an equimolar (4.5:4.5) concentration of DIPDIS and DTEP. The concentration of accelertors was varied from 6 mmol to 18 mmol phr, keeping the molar ratio at 1:1. It was noticed that, although the torque and modulus values increased, the tensile strength values decreased after attaining a maximum at 12 mmolar concentration of DIPDIS and DTEP accelerators, when the sulfur concentration was fixed at 1.5 phr. The synergistic activity of DIPDIS-DTEP accelerated mixes is considered to arise from the generation of some intermediate accelerators that are governed by the proportion of accelerators, sulfur, filler, etc., present in the mix. Some investigations were also carried out to optimize the amount of carbon black at these fixed levels of accelerators and sulfur. A regarding tensile strength, it increased up to a loading of 50 phr carbon black, but beyond this level a gradual fall in the value was noticed. However, modulus, torque, and hardness increased with the concentration of carbon black. The optimum dispersion of carbon black for this system was obtained following Lee's method. © 1995 John Wiley & Sons, Inc. 相似文献
16.
A thermodynamic analysis of the doping of silica glass with nitrogen by the chemical vapor deposition methods has been carried
out. The fundamental differences are revealed between the plasma chemical vapor deposition and modified chemical vapor deposition
methods. The basic parameters of nitrogen introduction into silica glass are determined by thermodynamic calculations. It
is found that the main factor that ensures doping of silica glass with nitrogen by the modified chemical vapor deposition
is an extremely low partial oxygen pressure in the reaction zone. The results of theoretical analysis are used in practice
for nitrogenizing silica glass by modified chemical vapor deposition. The increment in the refractive index is equal to 0.0015. 相似文献
17.
A thermodynamic analysis of the doping of silica glass with nitrogen by the chemical vapor deposition methods has been carried
out. The fundamental differences are revealed between the plasma chemical vapor deposition and modified chemical vapor deposition
methods. The basic parameters of nitrogen introduction into silica glass are determined by thermodynamic calculations. It
is found that the main factor that ensures doping of silica glass with nitrogen by the modified chemical vapor deposition
is an extremely low partial oxygen pressure in the reaction zone. The results of theoretical analysis are used in practice
for nitrogenizing silica glass by modified chemical vapor deposition. The increment in the refractive index is equal to 0.0015. 相似文献
18.
Wei Wu Xiangheng Xiao Shaofeng Zhang Lixia Fan Tangchao Peng Feng Ren Changzhong Jiang 《Nanoscale research letters》2010,5(1):116-123
The development of synthetic process for hollow silica materials is an issue of considerable topical interest. While a number
of chemical routes are available and are extensively used, the diameter of hollow silica often large than 50 nm. Here, we
report on a facial route to synthesis ultrafine hollow silica nanoparticles (the diameter of ca. 24 nm) with high surface area by using cetyltrimethylammmonium bromide (CTAB) and sodium bis(2-ethylhexyl) sulfosuccinate
(AOT) as co-templates and subsequent annealing treatment. When the hollow magnetite nanoparticles were introduced into the
reaction, the ultrafine magnetic hollow silica nanoparticles with the diameter of ca. 32 nm were obtained correspondingly. Transmission electron microscopy studies confirm that the nanoparticles are composed
of amorphous silica and that the majority of them are hollow. 相似文献
19.
Photosensitive polyimide/silica hybrid materials were synthesized by reaction between 4,4′‐hexafluoroisopropylidene diphthalic anhydride (6FDA) and 4,4′‐oxydianiline. The intrachain chemical bonding and the interchain hydrogen bonding between the polyimide and silica moieties were increased by the incorporation of 2‐(dimethylamino) ethyl acrylate and 3‐aminopropyl trimetho xysilane, respectively. The photoinitiator was bis(2,4,6‐trimethyl benzoyl) phenylphosphine oxide (Irgacure‐819). The various coupling agents were utilized included tetrakis (allyloxy) silane (TAL). Most silica hybrid films showed better volume shrinkage and temperature resistance. The cooperation of octavinyl POSS, as the coupling agent, can lower dielectric constant (k) down to 2.48 but with the poorer volume shrinkage and temperature resistance than the other silica hybrid films. The addition of tetramethyl orthosilicate and 3‐methacryloxy propyltrimethoxysilane with silica content of 5.6 wt % can reduce k down to 2.26 but with worse volume shrinkage than the incorporation with TAL. The TAL hybrid film with degree of polymerization of 25 showed the best properties that optimized photolithography, dielectric constant (k = 3.81), volume shrinkage, and temperature resistance (Td5% = 378°C) with only 0.22 wt % silica content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
20.
Silica coating on Gd2O3:Eu particles was obtained by a simple method, e.g. solid-state reaction at room temperature. The urea homogeneous precipitation method was used to synthesize the Gd2O3:Eu cores. Transmission electron microscopy (TEM) shows that the core particles are spherical with submicrometer size which is the soft agglomerates with nanometer crystallites. The TEM morphology of coated particles shows that a thin film is coated on the surface of Gd2O3:Eu cores. Scanning electron microscopy (SEM) and energy-dispersive spectrometer (EDS) analysis indicate that the coating of silica can be used to avoid agglomeration of Gd2O3:Eu particles to obtain smaller particles. X-ray photoelectron spectra (XPS) show that silica is coated on the surface of core particles by forming the chemical bond. Photoluminescence (PL) spectra conform that Gd2O3:Eu phosphors remain well-luminescent properties by the silica coating. 相似文献