• Polymer(Korea)
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• v.38 no.2
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• pp.257-264
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• 2014

In this study, we modified silica nanoparticles with bis[3-(trimethoxysilyl)propyl]ethylenediamine (BTPED) silane coupling agent, which has two secondary amino groups in a molecule, to introduce amino groups on the silica surface. After modification of silica, we used acrylate group containing 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) to introduce polymerizable methacrylate groups by Michael addition reaction. We used Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and liquid and solid state cross polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy (NMR) to understand the reactions between N-H groups of BTPED modified silica surface and acrylate groups of AHM monomer. We confirmed Michael addition reaction between BTPED modified silica and AHM completed in 2 hr reaction time. We also found increased methacrylate group introduction with increase of mol ratio of the acrylate group of AHM to N-H group of BTPED modified silica by increase of C=O peak area of measured FTIR spectra. These results were also supported by EA and solid state $^{13}C$ and $^{29}Si$ NMR results.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3805-3810
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• 2013

The surface modification of silica particles (SPs) was systemically conducted by the treatment of 0.1-10 wt % phenylsilanetriol (PST) on the basis of SPs used through two step processes: 1) the PST coating of SPs via evaporation under reduced pressure and 2) their thermal condensation leading to Si-O-Si bond formation via heating at $130^{\circ}C$. The evaluation of the modified SPs was conducted by the simple floating test on water and the measurement of the contact angle (CA) of water droplet on the 2-dimensional layer of modified SPs on slide glass. When PST was used about 2 wt % or above on the basis of SPs (about average size: 50 nm) used, the modified SPs were fully floated on the water and all dispersed into upper organic solvent layer after a shaking with the mixture of the water and benzene, indicating that the modified SPs have hydrophobic properties. The modified SPs were characterized by $^{29}Si$ MAS NMR and physicochemical properties including SEM, TEM, BET, adsorption/desorption isotherms, etc. were measured and compared each other in details. This research demonstrates that the organosilanetriol is a good modifier applicable for the surface modification of inorganic oxide particles using a low amount of modifier on the basis of oxide particles used.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1275-1279
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• 2010

We have carried out the surface modification of photocatalytic $TiO_2$ with triethoxysilane through dehydrogenation reaction and characterized the modified photocatalyst by spectroscopic methods, such as FT-IR, solid-state $^{29}Si$ MAS NMR, XPS, and XRF, etc. We also examined photocatalytic activity of the immobilized photocatalytic titanium dioxide with triethoxysilane by decolorization reaction of dyes such as cong red and methylene blue under visible light. Dispersion test showed that the photocatalytic titanium dioxide immobilized with triethoxysilane group has kept higher dispersibility than titanium dioxide itself. No appreciable precipitation takes place even after standing for 24 h in the 4:6 mixture ratio of ethanol and water.

• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.965-968
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• 2004

H-montmorillonite was modified by interlayer surface silylation using 3-aminopropyltriethoxysilane and dodecylamine in ethanol without a pre-swelling step. Dodecylamine acts as a gallery expander and silylation catalyst. The evaporation of ethanol from the dispersion yields well-ordered silylated montmorillonites with large basal spacing between 1.50 and 4.20 nm. Solid-state $^29Si$ CP MAS NMR of the silylated samples showed $Q^2\;and\;Q^3$ signals as well as $T^2\;and\;T^3$ signals. The increase in the relative intensity of $Q^3\;for\;Q^2$ and the appearance of $T^2\;and\;T^3$ signals was attributed to the grafting of 3-aminopropyltriethoxysilane to the interlayer surface silanol groups.

• Polymer(Korea)
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• v.37 no.3
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• pp.308-315
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• 2013

In this study, we performed surface modification of silica nanoparticles with bis[3-(triethoxysilylpropyl)]tetrasulfide (TESPT) silane coupling agent to study the effects of treatment temperature, treatment time, and amount of TESPT used on the silanization degree with Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), elemental analysis (EA) and solid state $^{13}C$ and $^{29}Si$ cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy (NMR). We found peak area of isolated silanol groups at $3747cm^{-1}$ decreased, but peak area of $-CH_2$ asymmetric stretching of TESPT at $2938cm^{-1}$ increased with the amount of TESPT from FTIR measurements. We also used universal testing machine (UTM) to study mechanical properties of styrene butadiene rubber (SBR) nanocomposites with 20 phr (parts per hundred of rubber) of pristine and TESPT modified silicas, respectively. The tensile strength and 100% modulus of modified silica/SBR nanocomposite were enhanced from 5.65 to 9.38MPa, from 1.62 to 2.73 MPa, respectively, compared to those of pristine silica/SBR nanocomposite.

• Korean Chemical Engineering Research
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• v.46 no.2
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• pp.291-300
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• 2008

Catalytic cracking of n-octane was carried out over H-ZSM-5 zeolite catalysts after calcination with air and steaming with 100% steam in the temperature range of $550-750^{\circ}C$ for 24 h and compared with the results of thermal cracking. The increase of calcination and steaming temperature resulted in the decrease of surface area, pore volume, and strong acid sites, which was mainly caused by the dealumination of H-ZSM-5 framework. It was found by $^{27}Al$ and $^{29}Si$ MAS NMR that the dealumination was proceeded through the transformation process of tetrahedral framework Al${\rightarrow}$penta-cordinated Al ${\rightarrow}$ octahedral framework Al and the phenomena was much more severe in steaming conditions than that of calcination. In the catalytic cracking of n-octane, as the temperatures of calcination and steaming were increased, the conversion of n-octane, the selectivity of light olefins and ethylene to propylene ratio were decreased due to the dealumination of framework aluminum resulting the loss of acidic strengths. The conversion, selectivity of light olefins and ethylene to propylene ratio reached almost to the level of thermal cracking after steaming at $750^{\circ}C$ for 24 h.

• Journal of the Korean Ceramic Society
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• v.45 no.5
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• pp.303-308
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• 2008

Mullite precursors were synthesized with aluminosilicate gels from mixture of aluminum nitrate and sodium orthosilicate by the geopolymer technique at ambient temperature. Then, the gel was heat-treated in air up to $1200^{\circ}C$ at intervals of $100^{\circ}C$. Raw and heat-treated gels were characterized by TG-DTA, XRD, FTIR, $^{29}Si$ MAS-NMR, TEM. The result to examine the crystallization of behavior though DTA, the synthesized precursors were crystallized in the temperature range from $950^{\circ}C$ to $1050^{\circ}C$. The XRD results showed that the gel compositions were begun to crystallize at various temperature. Also, it was found that the precursors of M-4 begun to crystallize at about $950^{\circ}C$. The M-4 XRD peaks were characterized better than $M-1{\sim}M-3$ at $1000^{\circ}C$. The formation temperature of mullite in this study is much lower than that of previous sol-gel methods, which crystallized at up of $1200^{\circ}C$. TEM investigations revealed that the sample with 10 nm particle size was obtained via heat-treated at $1000^{\circ}C$ for M-4.

• International Journal of Railway
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• v.7 no.3
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• pp.85-89
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• 2014

The use of pozzolanic materials in concrete mixtures can enhance the mechanical properties and durability of concrete. By reactions with pozzolanic materials and calcium hydroxide in cement matrix, calcium-silicate-hydrate (C-S-H) increases and calcium hydroxide decreases in cement matrix of concrete. Consequently, the volume of solid materials increases. The pozzolanic particles also fill spaces between clinker grains, thereby resulting in a denser cement matrix and interfacial transition zone between cement matrix and aggregates; this lowers the permeability and increases the compressive strength of concrete. Moreover, the total contents of alkali in concrete are reduced by replacing cements with pozzolanic materials; this prevents cracks due to alkali-aggregate reaction (AAR). In this study, nanosilica is incorporated in cement pastes. The differences of microstructural compositions between the hydrated cements with and without nanosilica are examined using nanoindentation, XRDA and $^{29}Si$ MAS NMR. The results can be used for a basic research to enhance durability of concrete slab tracks and concrete railway sleepers.

• Bulletin of the Korean Chemical Society
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• v.34 no.9
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• pp.2747-2752
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• 2013

Surface modification of colloidal silica nanoparticles without disrupting the electric double layer of nanoparticles is a major challenge. In the work, silane was employed to modify colloidal silica nanoparticles without inducing bridge flocculation obviously. The effect of pH value of the silica sol, the amount of silane in feed, and reaction temperature on the graft amount and the final size of modified particles was investigated. The increased weight loss by TG and the appearance of $T_2$ and $T_3$ except for $Q_2$ and $Q_3$ signals by CP/MAS $^{29}Si$ NMR of the modified samples verified the successful grafting of silane. The graft amount reached 0.57 mmol/g, which was slightly lower than theory value, and the particle size remained nearly the same as unmodified particles for acidic silica sol at the optimum condition. For alkaline silica sol after modification, aggregates composed of several nanoparticles connected together with silane moleculars as the bridge appeared.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.371-378
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• 2012

Hydrophilic silica nanoparticles (SNPs) were treated by using 3-glycidoxypropyltrimethoxy silane (GPTMS) and then they were blended with polyurethane-urea (PUU) emulsions to obtain SNPs/PUU nanocomposite films. Thermo-mechanical properties of the nanocomposite films were investigated by varying the grafted amount of GPTMS onto SNPs and the contents of SNPs in the PUU matrix. The thermo-mechanical properties of the nanocomposite films were also compared in terms of the dispersibility of SNPs in the PUU matrix and thermal curing of the GPTMS-grafted SNPs. The maximum amount of grafted GPTMS was $1.99{\times}10^{-6}\;mol/m^2$, and which covered ca. 53% of the total SNP surface area. $^{29}Si$ CP/MAS NMR analyses with the deconvolution of peaks revealed the details of polycondensation degree and patterns of GPTMS in the surface modification of SNPs. The surface modification did not significantly affect colloidal stability of the SNPs in aqueous medium; however, the hydrophobic modification of SNPs offered a favorable effect on the dispersibility of SNPs in the PUU matrix as well as better thermal stability. XRD patterns revealed that GPTMS-grafted SNPs broadened the reduced the characteristic peak of polyol in PUU matrix. The composite films became rigid and less flexible as the SNP content increased from 5 wt.% to 20 wt.%. Particularly, Young's modulus and tensile modulus significantly increased after the thermal curing reaction of the epoxy groups in the SNPs.