Facile route for preparation of silver nanoparticle-coated precipitated silica

In this research, a facile route was used to prepare silver nanoparticle-coated precipitated silica using sodium silicate, a cheap precursor. Precipitated silica (PS) was synthesized by dropping 8% H₂SO₄ into a mixed solution of sodium silicate 24% (Na₂O·3.4SiO₂) and NaCl 4%; under constant stirring. The precipitated silica was then modified by simultaneous addition of 3-aminopropyltriethoxysilane (3-APTES) and 8% H₂SO₄. The resulting material was aged at 80 °C for 1 h to produce amino-functionalized precipitated silica (AFPS). Silver nanoparticle-coated precipitated silica (Ag-NPS) was synthesized by adding silver nitrate (AgNO₃). The synthesis procedure also involved mixing for 2 h and dropping 0.05 M sodium borohydride (NaBH₄). The final products, namely, PS, AFPS, and Ag-NPS were characterized using BET analyzer, FE-SEM, TEM and XRD. Silver nanoparticles with an average size ranging from 18 to 25 nm were found mostly coated on the exterior layer of the precipitated silica. The synthesis method reported in this work is facile and might be used for large-scale industrial production of inexpensive Ag-NPS.     

Facile Fabrication of Dendritic Mesoporous SiO2@CdTe@SiO2 Fluorescent Nanoparticles for Bioimaging

A seeded watermelon‐like mesoporous nanostructure (mSiO₂@CdTe@SiO₂, mSQS) composed of a novel dendritic mesoporous silica core, fluorescent CdTe quantum dots (QDs), and a protective solid silica shell is successfully fabricated by loading QDs into dendritic mesoporous silica nanoparticles through electrostatic interaction, and then coating with a solid silica shell by the modified Stöber method. The shell thickness of mSQS can be tuned from 0 to 32 nm as desired by controlling the reaction parameters, including the amount of silica precursor, tetraethyl orthosilicate, that is introduced, the solvent ratio (H₂O:ethanol), and the amount of catalyst (NH₃?H₂O). These fluorescent mSiO₂@QDs@SiO₂ nanoparticles possess excellent stability and thickness‐dependent cytotoxicity, and are successfully applied to bioimaging.     

Properties of Natural Rubber Vulcanizates/Nanosilica Composites Prepared Based on the Method of In-situ Generation and Coagulation

Using the characteristics of silica sol dispersing well in water and easy formation of silica gel when the silica sol is heated, by mixing a system of concentrated natural rubber latex and silica sol, the silica sol can in-situ generate SiO₂ particles when heated. After coagulation of the mixed system, natural rubber/nanosilica composites C(NR/nSiO₂) were obtained. The composites C(NR/nSiO₂) and their vulcanizates were studied using a rubber processing analyzer (RPA), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The influence of silica contents on the C(NR/nSiO₂) vulcanizates mechanical properties, cross-linking degree, Payne effect, dissipation factor (tanδ), and the particle size and dispersion of SiO₂ in NR were investigated. The results obtained were compared with the NR/SiO₂ composites based on traditional dry mixing of bale natural rubber and precipitated silica (white carbon black). The results showed that when using a sulfur curing system with a silica coupling agent (Si69) in C(NR/nSiO₂), the vulcanizate had better mechanical properties, higher wet resistance, and lower rolling resistance than those without Si69. In the composites C(NR/nSiO₂) and their vulcanizates, the SiO₂ particles’ average grain diameter was 60 nm, and the good-dispersion of the in-situ generated SiO₂ in the rubber matrix were a significant contribution to the satisfactory properties of C(NR/nSiO₂) composites and their vulcanizates.     

A novel approach to fabrication of superparamagnetite hollow silica/magnetic composite spheres

We described a method for synthesizing hollow silica/magnetic composite spheres using sulfonic acid functionalized hollow silica spheres (SAFHSS) as templates. The Fe₃O₄ nanoparticles were deposited on or imbedded in the hollow silica shell by a precipitation reaction. The morphologies, composition and properties of the hollow composite spheres were characterized by transmission electron microscopy, Fourier transform infrared analysis, X-ray diffraction measurement and vibrating-sample magnetometry measurement. The results indicated crystal sizes and amount of the Fe₃O₄ nanoparticles on the SAFHSS. The magnetic properties of the hollow composite spheres were controlled by adjusting the proportion between Fe²⁺ and Fe³⁺ and iron ion total concentration. When appropriate loading species were added into the system, superparamagnetite hollow composite spheres were obtained. The method also could be applicable to prepare other superparamagnetite hollow silica/ferrite composite spheres.     

NMR T1–T2 correlation analysis of molecular absorption inside a hardened cement paste containing silanised silica fume

ABSTRACT

The influence of silanised silica fume addition on the pore size distribution and wettability of white cement paste was investigated using T₁–T₂ correlation nuclear magnetic resonance (NMR) relaxometry. Surface silanisation of silica fume particles was achieved by the hydrolysis reaction of APTES (3-Aminopropyltriethoxysilane) and condensation of the silanol functional groups on the surface. The methods used for characterisation of the silanised silica fume particles were scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). By adding silanised silica fume to the cement paste, the accessibility of water molecules to the porous system becomes restricted, leading to a lower permeability in comparison with the unmodified cement paste. Differential scanning calorimetry (DSC) measurements on the cement pastes saturated with Octamethylcyclotetrasiloxane confirm also that the size of inter-C–S–H and capillary pores is not influenced by the addition of silica fume in a detectable manner.     

The effect of ionisation of silica nanoparticles on their binding to nonionic surfactants in oil–water system: an atomistic molecular dynamic study

ABSTRACT

In this study, the adsorption of nonionic surfactant, triethylene glycol monododecyl ether (C₁₂E₃), on a surface of silica nanoparticle (NP) has been studied with variation in the degree of ionisation (DI) of silica NP using all-atom molecular dynamic simulations in hexadecane–water system. Hydrogen bonding is found to be responsible for the adsorption of C₁₂E₃ on NP, particularly at low DI. We observe that with increasing DI of NP, the amount of adsorption of C₁₂E₃ on NP reduces, which is negligible beyond DI ～ 0.5. The decrease in the adsorption with increasing DI is due to the decrease in the number of hydrogen bonds formed by the silica NP with surfactant molecules. Potential of mean force (PMF) profiles indicate attractive interactions between NP and C₁₂E₃ for DI < 0.5, and for larger DI depletion effect is observed. This work explains the unusual effect of nonionic surfactant on interfacial tension in the presence of silica particles as observed in recent experiments.     

Effect of Nanoparticles on the Phase Behavior of Polystyrene/Poly(vinyl methyl ether) Blends with Different Polydispersities

Effects of two kinds of silica nanoparticles on the phase behavior of blends of poly (vinyl methyl ether) (PVME) and two kinds of polystyrene (PS), with the same number average molecular weight but different polydispersities, were studied by using optical microscopy. The addition of both the hydrophilic A200-SiO₂ and hydrophobic R974-SiO₂ nanoparticles made the miscibility become worse. The decrease in the phase separation temperatures of PS/PVME with polydisperse PS (pPS) was larger than that of PS/PVME with monodisperse PS (mPS) in the presence of A200-SiO₂; the shifts of the phase separation temperatures of mPS/PVME and pPS/PVME were comparable for the incorporation of R974-SiO₂. The addition of both kinds of silica accelerated the phase separation during the nonisothermal phase separation. The domain size changes of the phase morphology of mPS/PVME (50/50) and pPS/PVME (50/50) were almost the same during the nonisothermal phase separation in the presence of nanoparticles. During the isothermal phase separation, the introduction of silica slowed down the phase separation dynamics by hindering the phase structure transition. The morphology changes of pPS/PVME (50/50) were more evident than those of mPS/PVME (50/50) with the incorporation of SiO₂.     

Engineering the Internal Structure of Magnetic Silica Nanoparticles by Thermal Control

Calcination of hydrated iron salts in the pores of both spherical and rod‐shaped mesoporous silica nanoparticles (NPs) changes the internal structure from an ordered 2D hexagonal structure into a smaller number of large voids in the particles with sizes ranging from large hollow cores down to ten nanometer voids. The voids only form when the heating rate is rapid at a rate of 30 °C min^?1. The sizes of the voids are controlled reproducibly by the final calcination temperature; as the temperature is decreased the number of voids decreases as their size increases. The phase of the iron oxide NPs is α‐Fe₂O₃ when annealed at 500 °C, and Fe₃O₄ when annealed at lower temperatures. The water molecules in the hydrated iron (III) chloride precursor salts appear to play important roles by hydrolyzing Si? O? Si bonding, and the resulting silanol is mobile enough to affect the reconstruction into the framed hollow structures at high temperature. Along with hexahydrates, trivalent Fe³⁺ ions are assumed to contribute to the structure disruption of mesoporous silica by replacing tetrahedral Si⁴⁺ ions and making Fe? O? Si bonding. Volume fraction tomography images generated from transmission electron microscopy (TEM) images enable precise visualization of the structures. These results provide a controllable method of engineering the internal shapes in silica matrices containing superparamagnetic NPs.     

Preparation and Characterization of Poly(Vinyl Alcohol) (PVA)/SiO2, PVA/Sulfosuccinic Acid (SSA) and PVA/SiO2/SSA Membranes: A Comparative Study

Abstract

New organic–inorganic nanocomposites based on PVA, SiO₂ and SSA were prepared in a single step using a solution casting method, with the aim to improve the thermomechanical properties and ionic conductivity of PVA membranes. The structure, morphology, and properties of these membranes were characterized by Raman spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), water uptake (Wu) measurements and ionic conductivity measurements. The SAXS/WAXS analysis showed that the silica deposited in the form of small nanoparticles (～ 10?nm) in the PVA composites and it also revealed an appreciable crystallinity of pristine PVA membrane and PVA/SiO₂ membranes (decreasing with increasing silica loading), and an amorphous structure of PVA/SSA and PVA/SSA/SiO₂ membranes with high SSA loadings. The thermal and mechanical stability of the nanocomposite membranes increased with the increasing silica loading, and silica also decreased the water uptake of membranes. As expected, the ionic conductivity increased with increasing content of the SSA crosslinker, which is a donor of the hydrophilic sulfonic groups. Some of the PVA/SSA/SiO₂ membranes had a good balance between stability in aqueous environment (water uptake), thermomechanical stability and ionic conductivity and could be potential candidates for proton exchange membranes (PEM) in fuel cells.     

Mesoporous Silica Promoted Deposition of Bioinspired Polydopamine onto Contrast Agent: A Universal Strategy to Achieve Both Biocompatibility and Multiple Scale Molecular Imaging

Polydopamine (PDA) preserves universal coating and metal‐binding ability, and is suitable for application in synthesizing multifunctional agents. Herein, utilizing mesoporous silica assisted deposition to enhance both heterogeneous nucleation and loading amounts of PDA, the magnetic resonance (MR) T₁ component (PDA‐Fe³⁺) and MR T₂/computed tomography (CT)/multiphoton luminescence (MPL) component (FePt) have been successfully integrated in aqueous solution. This four‐in‐one (T₁, T₂, CT, MPL) imaging nanocomposite, FePt@mSiO₂ @PDA‐polyethylene glycol (PEG), demonstrated its multi‐imaging power both in vitro/in vivo. According to our in vitro/in vivo results, FePt@mSiO₂@PDA‐PEG reveals water‐content‐dependent property in T₁ MR imaging, which suggests the necessity of having dual‐modal MR ability in a single particle for the precision diagnosis. Most importantly, this dual (T₁,T₂)‐MRI/CT contrast agent is demonstrated complementary to each other in the in vivo testing. PDA coated mesoporous silica also offers an advantage of delayed degradation that prevents adverse effects caused by silica fragments before excretion. The potential of this nanocomposites in both drug carrier and photothermal agent was further evaluated by using doxorubicin and monitoring solution temperature after irradiating 808 nm continuous‐wave, respectively The merits of controlled polymerization, enhanced PDA loading, and biofavorable degradation make this methodology promising to other nanoparticle@mSiO₂ for a wide range of bioapplications.     

水蒸气对二氧化硅膜的影响：吸附性能与渗流效应

研究了在50和90 oC时水蒸气对孔径约为4 ?的二氧化硅膜的吸附性能和渗流效应影响,采用椭圆偏振光谱分析水蒸气的吸附性能,以及测定氦气-H₂O二元混合气体的透过性能. 研究表明水蒸气在二氧化硅膜上的吸附行为符合一阶Langmuir等温线,同时,在H₂O分子存在的条件下,氦气的透过率会急剧下降. 通常,在极小孔内气体分子的传输被认为是不连续的,而是在势能下从一个占有位置跳跃到另外一个空位上. 当在二氧化硅表面的H₂O分子覆盖率上升时,氦气的透过率急剧下降可能与渗流效应有关,其中吸附在二氧化硅表面的H₂O分子阻碍了氦气分子的跳跃.     

Novel titration method for surface-functionalised silica

This paper describes three inexpensive and fast analytical methods to characterise grafted particle surfaces. The reaction of silica with (3-aminopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane and N-(phosphonomethyl)iminodiacetic acid hydrate, respectively, leads to NH₂-, SO₃H- or COOH-functionalised silica, which were characterised by X-ray photoelectron spectrometry and titration in nonaqueous media as well as with two titration methods in a water-based environment. In the work presented, factors influencing the titrations are pointed out and solutions are presented to overcome these limiting factors are shown.     

Development of porous silica production by hydrothermal method

Abstract

A new process for porous silica production has been developed using a hydrothermal method. Hydrothermally synthesized calcium silicate was used as the starting material in this study, which was produced from a mixture of Ca(OH)₂ and amorphous silica (white carbon) under hydrothermal conditions of 140°C and 0.4 MPa, for 8 hours. The calcium silicate was subsequently treated with an acid solution, facilitating the leaching of Ca ions. After washing with pure water, the multant Ca²⁺ -free silica powder was allowed to dry. The Ca²⁺ -free silica powder was found to have an amorphous structure, with 0.9 ml/g pore volume, up to 610m²/g BET specific surface area, and an average 5 ～ 8 nm pore size. Our hydrothermal process is simple and low cost, and is anticipated to have numerous applications to the petrochemical industry.     

Ultrasonic-assisted ultra-rapid synthesis of monodisperse meso-SiO2@Fe3O4 microspheres with enhanced mesoporous structure

A core–shell-type of meso-SiO₂@Fe₃O₄ microsphere was synthesized via an ultrasonic-assisted surfactant-templating process using solvothermal synthesized Fe₃O₄ as core, tetraethoxysilane (TEOS) as silica source, and cetyltrimethyl ammonium bromide (CTAB) as templates. The samples were characterized by FT-IR, XRD, TEM, N₂ adsorption–desorption technology, and vibrating sample magnetometer (VSM). The results show that as-prepared meso-SiO₂@Fe₃O₄(E) and meso-SiO₂@Fe₃O₄(C) microspheres, treated by acetone extraction and high temperature calcination, respectively, still maintain uniform core–shell structure with desirable mesoporous silica shell. Therein, the meso-SiO₂@Fe₃O₄(E) microspheres possess a distinct pore size distribution in 1.8–3.0 nm with large specific surface area (468.6 m²/g) and pore volume (0.35 cm³/g). Noteworthily, the coating period of this ultrasonic-assisted method (40 min) is much shorter than that of the conventional method (12–24 h). The morphology of microspheres and the mesoporous structure of silica shell are significantly influenced by initial concentration of CTAB (C_CTAB), ultrasonic irradiation power (P) and ultrasonic irradiation time (t). The acceleration roles of ultrasonic irradiation take effect during the whole coating process of mesoporous silica shell, including hydrolysis-condensation process of TEOS, co-assembly of hydrolyzed precursors and CTAB, and deposition of silica oligomers. In addition, the use of ultrasonic irradiation is favorable for improving the homogeneity of silica shell and the monodispersity of meso-SiO₂@Fe₃O₄ microspheres.     

Modification of nano-fibriform silica by dimethyldichlorosilane

The modification of nano-fibriform silica by dimethyldichlorosilane was studied by transmission electron microscopy, X-ray powder diffraction, infrared spectroscopy, Raman spectroscopy, physical N₂ adsorption techniques, differential thermal and thermogravimetric analysis, scanning electron microscopy, and elemental analyzer.The results show that dimethyl silane derivatives have been successfully covalently grafted on nano-fibriform silica. The polarity of the modified product decreases with the substitution of -OH groups by siloxyl groups. Therefore, the modified product can be easily dispersed in organic solvent and its compatibility with organic molecules is improved. After modification the pore volume decreases and the ductility greatly increases, indicating that the modified product is of a higher strength than before. The study demonstrates that the modified product can be used as an ideal additive to reinforce the strength of organic materials.     

Surface properties and water treatment capacity of surface engineered silica coated with 3-(2-aminoethyl) aminopropyltrimethoxysilane

This study's focus was on the water-based, one-pot preparation and characterisation of silica particles coated with 3-(2-aminoethyl)aminopropyltrimethoxysilane (Diamo) and the efficiency of the material in removing the pathogens Escherichia coli, Pseudomonas aeruginosa, Mycobacterium immunogenum, Vibrio cholerae, poliovirus, and Cryptosporidium parvum. The water-based processing resulted in Diamo coated silica particles with significantly increased positive surface charge as determined by zeta potential measurements. In addition, X-ray photoelectron spectrometry of pure and Diamo coated silica confirmed the presence of Diamo on the surface of the particles. Thermogravimetric measurements and chemical analysis of the silica indicated a surface concentration of amine groups of about 1 mmol/g_silica. Water treatment tests with the pathogens showed that a dose of about 10 g appeared to be sufficient to remove pathogens from pure water samples which were spiked with pathogen concentrations between about 10² and 10⁴ cfu/mL.     

A First Approach of Silica Effect on the Sintering of Nd:YAG

The effect of silica addition on the sintering of yttrium aluminium garnet doped by neodymium (Nd:YAG) was investigated on the basis of microstructural and thermal characterizations as well as of chemical analysis. The samples were sintered under secondary vacuum at temperatures ranging from 1473 to 1973 K. The role of silica, added as a sintering aid, appears significant between 1673 and 1873K when high silica contents have been introduced in reactive mixtures. The positive effect of the silica phase on densification is linked to the appearance of secondary phases issued from reactions with the YAG matrix phase. In particular, two main secondary phases have been detected. One is a silica-rich phase which prevails at lower temperatures while the second possesses a more complex composition. When the sintering temperature increases, the composition of the latter phase evolves in the ternary SiO₂−Y₂O₃−Al₂O₃ system near the eutectic compositions, the melting point of which could lie in the vicinity of 1673 K. It is then suggested that sintering occurs via a liquid phase.     

Surface diffusion and entrapment of simple molecules on porous silica

Interactions of simple molecules with the surface of porous silica have been investigated using time-of-flight secondary ion mass spectrometry and temperature programmed desorption. A monolayer of water diffuses into pores at temperatures higher than 110 K. Multilayers of water are also incorporated in pores via sequential surface diffusion. In contrast, a methanol monolayer tends to stay on the surface up to 150 K, and carbon dioxide diffuses into pores rather gradually. Results can be explained as the contribution of hydrogen bonds between the adsorbate–substrate and adsorbate–adsorbate interactions. The predominance of the former (latter) might be responsible for single-molecule migration of methanol and carbon-dioxide (collective diffusion of water molecules) on the surface. These molecules are entrapped at higher coordination sites in pores, as revealed from thermal desorption peaks appearing at higher temperatures than those from non-porous silica. However, no significant difference is observed in desorption kinetics of CF₂Cl₂, Kr, CH₄, and N₂ molecules between the porous and non-porous silica substrates.     

Growth and characterization of Fe3O4 nanoparticles in silica matrix

Nano-magnetic Fe₃O₄ particles coated with silica are synthesized. The study of structural and magnetic properties was carried out using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometer (VSM) techniques. The VSM results show that these kinds of composite particles exhibit superparamagnetic behavior with zero coercivity and remanence. The magnetic spheroid alumina carriers containing these magnetic composite particles were prepared by an internal gelation process. The SiO₂ coatings prevent the reaction between Fe₃O₄ and Al₂O₃ during the sintering process and maintain the superparamagnetic behavior of the catalyst carriers.     

Polydimethylsiloxane at the interfaces of fumed silica and zirconia/fumed silica

Polydimethylsiloxane (PDMS)/fumed silica A-300 and PDMS/ZrO₂/A-300 were studied using adsorption, thermogravimetry, temperature-programmed desorption (TPD) mass-spectrometry, infrared spectroscopy, XRD, and broadband dielectric relaxation spectroscopy. ZrO₂ was synthesized on fumed silica with zirconium acetylacetonate in CCl₄ at 350 K for 1 h and calcinated at 773 K for 1 h (1-4 reaction cycles). PDMS (5-40 wt.%) was adsorbed onto silica and zirconia/silica from hexane solution and then dried. Grafted zirconia changes the chemistry of the surface (because of its catalytic capability) and the topology of secondary particles (because of occupation of voids in aggregates of primary silica particles by zirconia nanoparticles) responsible for the textural porosity of the powders. Therefore, many properties (such as structural characteristics of the composites, reactions on heating in air and vacuum, interfacial relaxation phenomena, hydrophobicity as a function of treatment temperature, etc.) of PDMS/zirconia/silica strongly differ from those of PDMS/A-300. Broadening of the α-relaxation of PDMS at the interfaces of disperse oxides suggests both weakening of the PDMS-PDMS interaction and strengthening of the PDMS-oxide interaction.