Nanocomposites Prepared by Solution Blending: Microstructure and Mechanical Properties

Composites of poly(vinyl chloride) (PVC) filled with micron‐ and nanosized calcium carbonate (CaCO₃) particles were prepared by solution blending. The influences of particle size and CaCO₃ content on the microstructure and mechanical properties of the PVC composites were investigated by means of polarized optical microscopy and mechanical testing. The polarized optical microscope images revealed that nanosized CaCO₃ particles were more agglomerated than micron‐sized CaCO₃ particles and the amount of agglomerates increased with increasing particle content. PVC/CaCO₃‐0.22 composites (PVC nanocomposite filled with 220‐nm‐particle‐sized CaCO₃) 5 phr CaCO₃ content had the maximum tensile strength. The Young's modulus of all composites increased with increasing particle content. The energy at break of all composites showed a decreasing trend as a function of CaCO₃ content and varied with particle size.     

Effect of Surface Structure of Nano-CaCO3 Particles on Mechanical and Rheological Properties of PVC Composites

To study the effect of different surface structures on resultant mechanical and rheological properties, nano-CaCO₃ particles were treated with isopropyl tri-stearyl titanate (H928), isopropyl tri-(dodecylbenz-enesulfonyl) titanate (JN198), and isopropyl tri-(dioctylpyrophosphato) titanate (JN114). Scanning electron microscopy (SEM) and dynamic mechanic analysis (DMA), carried out to characterize the effective interfacial interaction between the nano-CaCO₃ particles and a poly(vinyl chloride) (PVC) matrix, indicated that JN114 treated nano-CaCO₃ particles had the strongest interfacial interaction with a PVC matrix, while H928 treated nano-CaCO₃ had the weakest. The rheological and mechanical properties of PVC/nano-CaCO₃ composites were investigated as a function of surface structure and filler volume fraction. The tensile yield stress and elongation at break decreased with the increasing of calcium carbonate content while tensile modulus increased. PVC filled with JN114 treated nano-CaCO₃ had the highest tensile modulus and tensile yield stress, while those filled with H928 treated nano-CaCO₃ had the highest elongation at break at the same filler content. The impact strength of PVC/nano-CaCO₃ composites increased with the increasing of CaCO₃ content, and PVC composites filled with JN198 treated nano-CaCO₃ particle had a higher impact strength than those with JN114 or H928 treated, with the value reaching 23.9 ± 0.7 kJ/m² at 11 vol% CaCO₃, four times as high as that of pure PVC. Rheological properties indicated that a suitable interfacial interaction and a good dispersion of inorganic filler in a PVC matrix could reduce the viscosity of PVC/nano-CaCO₃ composites. The interfacial interaction was quantitatively characterized by semiempirical parameters calculated from the tensile strength of PVC/nano-CaCO₃ composites to confirm the results from the SEM and DMA experiments.     

Thermal Stabilities of Poly(Vinyl Chloride)/Calcium Carbonate (PVC/CaCO3) Composites

Poly(vinyl chloride)/calcium carbonate (PVC/CaCO₃) composites with micrometer or nanometer CaCO₃ as fillers were prepared by the solution blending method. The thermogravimetric analysis (TGA) of the composite films conducted in N₂ atmosphere showed that the addition of the CaCO₃ fillers could improve their thermal stabilities. It was also found that the nanometer CaCO₃ filler provided better thermal stabilities than the micrometer fillers even with a smaller amount. The mechanism of the improvements was investigated by a facile chemical analysis developed to examine the thermal stabilizing effect of calcium carbonate particles with different sizes in PVC/CaCO₃ composites after the pyrolysis of the samples in an air atmosphere in an oven.     

A Study on the Morphology and Mechanical Properties of PVC/nano‐SiO2 Composites

Three methods were used to modify nano‐SiO₂ particles with various interfaces and interfacial interactions between the particles and Poly(vinyl chloride) (PVC) matrix. The experimental results show that direct surface treatment of nano‐SiO₂ particles with a silane coupling agent (KH‐550) is not effective for improving the mechanical properties of PVC/SiO₂ composites. Both ultrasonic oscillations and high energy vibromilling improve the interfacial interactions between SiO₂ particles and PVC matrix. With these methods, the aggregation of SiO₂ particles was inhibited and a good dispersion of SiO₂ particles in PVC matrix was obtained, which improved the mechanical properties of the PVC/SiO₂ composite. The mechanical properties of the PVC/SiO₂ composite with high energy vibromilling modified SiO₂ particles were remarkably improved. Scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), dynamic mechanical analysis (DMA), and theoretical calculations demonstrate these improvements.     

Preparation and characterization of novel Pd/SiO2 and Ca-Pd/SiO2 egg-shell catalysts with porous hollow silica

Novel egg-shell structured monometallic Pd/SiO₂ and bimetallic Ca-Pd/SiO₂ catalysts were prepared by an impregnation method using porous hollow silica (PHS) as the support and PdCl₂ and Ca(NO₃)₂·4H₂O as the precursors. It was found from transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) that Pd was loaded on PHS with a particle size of 5-12 nm in Pd/SiO₂ samples and the Pd particle size in Ca-Pd/SiO₂ was smaller than that in Pd/SiO₂ since Ca could prevent Pd particles from aggregating. X-ray photoelectron spectroscopy (XPS) analyses exhibited that Pd 3d_5/2 binding energies of Pd/SiO₂ and Ca-Pd/SiO₂ were 0.2 and 0.9 eV lower than that of bulk Pd, respectively, as a result of the shift of the electron cloud from Pd to oxygen in Pd/SiO₂ and to both oxygen and Ca in Ca-Pd/SiO₂. The activity of Ca-Pd/SiO₂ egg-shell catalyst for CO hydrogenation and the selectivity to methanol, with a value of 36.50 mmol_CO mol⁻¹_Pd s⁻¹ and 100%, respectively, were much higher than those of the catalysts prepared with traditional silica gel as the support, owing to the porous core-shell structure of the PHS support.     

Synthesis of CaCO3 Nanoparticles by Mechanochemical Processing

The synthesis of calcite (CaCO₃) nanoparticles by mechanochemical reaction and subsequent heat treatment was investigated. A solid-state displacement reaction CaCl₂ + Na₂CO₃ CaCO₃+2NaCl was induced during mechanical milling of a CaCl₂+ Na₂CO₃ powder mixture. Heat treatment of the as-milled powder at 350°C completed the reaction, forming crystalline CaCO₃ nanoparticles separated from each other in a dry-salt matrix. A simple washing process to remove the matrix yielded calcite single phase ultrafine powder. The mean particle size was controlled by changing the volume fraction of CaCO₃ in the matrix. 20% volume fraction yielded nanoparticles of ~ 140 nm in size, whereas 10% volume fraction led to ~ 80 nm size nanoparticles.     

Effect of particle size on the photochromic response of PWA/SiO2 nanocomposite

A series of photochromic phosphotungstic acid (PWA)/SiO₂ composites were synthesized using the sol-gel method. Depending on the feeding schedule of PWA during synthesis, the size of the formed PWA/SiO₂ particles varied considerably from as small as 1.2 nm to ca. 10 nm. With decreasing silica particle size, the total contact area/interaction between SiO₂ and PWA increases, as revealed by FT-IR and solid-state ²⁹Si-NMR analyses. Particularly, when the size of PWA/SiO₂ is ~1 nm, crystallization of PWA is inhibited, and PWA presents as amorphous molecular entities distributing uniformly in the SiO₂ host, which is in evidence in the XRD spectroscopy and HR-TEM imaging. In contrast, substantial crystallization of PWA takes place when PWA/SiO₂ particles are as large as 10 nm, in which case less amount of surface free Si-OH is available for PWA to make bonds with. Photochromism occurs activated by ultraviolet light irradiation. The rate of coloration/bleaching is found to depend strongly on the particle size of PWA/SiO₂; specifically, the rate increases twice when the particle size is reduced from 10 nm to 1.2 nm.     

Mechanochemically conjugated PMHS/nano-SiO2 hybrid and subsequent optimum grafting density study

In this paper, we reported the preparation of poly(methylhydrosiloxane) (PMHS)/SiO₂ hybrid particles by mechanochemical method based on high energy ball milling (HEBM). The obtained hybrid particles were characterized by Fourier transform infrared (FT-IR) spectroscopy, ²⁹Si CP (cross-polarization) MAS NMR, viscosity measurement, particle size distribution, thermal analysis (TGA, DSC and DTG), static contact angle (CA), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). FT-IR and ²⁹Si CP MAS NMR spectra indicate that PMHS is chemically anchored onto the surface of nano-SiO₂. Viscosity measurement, particle size distribution, FE-SEM and TEM demonstrate that an appropriate grafting density optimizes the dispersion of nanoparticles in poly(dimethylsiloxane) (PDMS) matrix, so lower viscosity can be achieved. Too high or too low grafting density may only achieve suboptimal and poor dispersions. The optimum grafting density of PMHS on nano-SiO₂ was determined by thermal analysis, with approximately 0.0531 PMHS/nm². Static contact angle measurement indicates that the water contact angle of hybrid particles is modulated by changing the grafting density of PMHS on nano-SiO₂. The CA value of PMHS/SiO₂ hybrid with optimum grafting density is 139.4°, and the highest CA value of PMHS/SiO₂ hybrid is approximately 158.2°.     

Preparation of ZnO–Al2O3 Particles in a Premixed Flame

Zinc oxide (ZnO) and alumina (Al₂O₃) particles are synthesized by the combustion of their volatilized acetylacetonate precursors in a premixed air–methane flame reactor. The particles are characterized by XRD, transmission electron microscopy, scanning mobility particle sizing and by measurement of the BET specific surface area. Pure (-)alumina particles appear as dendritic aggregates with average mobile diameter 43–93 nm consisting of partly sintered, crystalline primary particles with diameter 7.1–8.8 nm and specific surface area 184–229 m²/g. Pure zinc oxide yields compact, crystalline particles with diameter 25–40 nm and specific surface area 27–43 m²/g. The crystallite size for both oxides, estimated from the XRD line broadening, is comparable to or slightly smaller than the primary particle diameter. The specific surface area increases and the primary particle size decreases with a decreasing flame temperature and a decreasing precursor vapour pressure. The combustion of precursor mixtures leads to composite particles consisting of zinc aluminate ZnAl₂O₄ intermixed with either ZnO or Al₂O₃ phases. The zinc aluminate particles are dendritic aggregates, resembling the alumina particles, and are evidently synthesized to the full extent allowed by the overall precursor composition. The addition of even small amounts of alumina to ZnO increases the specific surface area of the composites significantly, for example, zinc aluminate particles increases to approximately 150 m²/g. The gas-to-particle conversion is initiated by the fast nucleation of Al₂O₃ or ZnAl₂O₃, succeeded by a more gradual condensation of the excess ZnO with a rate probably controlled by the cooling rate for the flame.     

ZnSe/SiO2复合薄膜光学常数与荧光光谱的研究

采用溶胶-凝胶工艺与原位生长技术，制备了ZnSe/SiO₂复合薄膜.X射线衍射分 析表明薄膜中ZnSe晶体呈立方闪锌矿结构.X射线荧光分析结果显示薄膜中Zn与Se摩尔比为1 ∶1.01—1∶1.19.利用场发射扫描电子显微镜观察了复合薄膜的表面形貌，结果表明复合薄 膜表面既存在尺寸约为400nm的ZnSe晶粒，也存在尺寸小于100nm的ZnSe晶粒.利用椭偏仪测 量了薄膜椭偏角Ψ，Δ与波长λ的关系，采用Maxwell-Garnett有效介质理论对薄膜的光学 常数、厚度、气孔率、ZnS 关键词： 2复合薄膜')" href="#">ZnSe/SiO₂复合薄膜 光学性质 椭偏光度法 荧光光谱     

Effect of Particle Size on the Thermal Stability and Flammability of Mg(OH)2/EVA Nanocomposites

The effect of the Mg(OH)₂ particle size on the thermal degradation and flammability of a model nanocomposite is presented. In order to investigate the effect of particle size on the flammability and thermal stability of materials intended for cable coatings, the ethylene–vinyl acetate copolymer (EVA) was filled with two types of magnesium hydroxide (Mg(OH)₂) with the average particle size 20 nm and 2000 nm. The thermogravimetric experiments performed under nitrogen and air atmosphere did not reveal any substantial effect of particle size on the mechanisms and kinetics of Mg(OH)₂ decomposition. Both types of Mg(OH)₂, at temperatures above 350°C, decomposed endothermally to MgO and H₂O. At the same filler volume fraction, composites with the larger Mg(OH)₂ particles exhibited greater value of the limiting oxygen index (LOI) compared to Mg(OH)₂ nanocomposites. It is proposed that the reduction of Mg(OH)₂ particle size below 200 nm results in the catalytic effect of Mg²⁺ to become more prominent compared to coarser particles. In the case of nano-sized Mg(OH)₂, a large portion of polymer matrix is in direct contact with filler surface due to the high specific surface area of the filler used. Large filler–matrix contact area most probably resulted in the surface-induced catalytic effects of the Mg²⁺ ion on degradation of polyolefins, already described in the literature, accelerating thermal degradation of EVA matrix. This process acts against the flame retarding effect of the Mg(OH)₂ thermal decomposition. Furthermore, larger filler surface of nano-filler led to the indispensable change of the deformation response of EVA compared to the micro-filled composite.     

Study of silica templates in the rice husk and the carbon–silica nanocomposites produced from rice husk

Carbon–silica nanocomposites obtained by rice husk carbonization in a fluidized-bed reactor using a deep oxidation copper–chromium catalyst were studied. Dispersion characteristics of the silica phase in these systems were determined by small-angle X-ray scattering (SAXS) using the full contrast technique. SiO₂ was found in the initial rice husk as compact nanoparticles having a wide size distribution. This distribution consists of a narrow fraction with particle sizes from 1 to 7 nm and a wider fraction with particle sizes from 8 to 22 nm. Oxidative heat treatment of rice husk in a fluidized bed in the presence of the catalyst decreased the fraction of small SiO₂ particles and increased the fraction of large ones. It was demonstrated that the particle size of silica in the carbon matrix can be determined selectively for deliberate design of porous carbon materials with desired properties.     

Synthesis and characterization of monodisperse spherical core-shell structured SiO2@Y3Al5O12:Ce3+/Tb3+ phosphors for field emission displays

Nanocrystalline Y₃Al₅O₁₂: Ce³⁺/Tb³⁺ (average crystalline size 30 nm) phosphor layers were coated on non-aggregated, monodisperse and spherical SiO₂ particles by the sol-gel method, resulting in the formation of core-shell structured SiO₂@Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ particles. X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the core-shell structured SiO₂@Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ phosphor particles. The obtained core-shell structured phosphors consist of well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ shells on the SiO₂ cores (average size about 500 nm, crystalline size about 30 nm) could be easily tailored by varying the number of deposition cycles (100 nm for four deposition cycles). Under the excitation of ultraviolet and low-voltage electron beams (1–3 kV), the core-shell SiO₂@Y₃Al₅O₁₂:Ce³⁺/Tb³⁺ particles show strong yellow-green and green emission corresponding to the 5d–4f emission of Ce³⁺ and ⁵D₄–⁷F _J (J = 6, 5, 4, 3) emission of Tb³⁺, respectively. These phosphors may have potential application in field emission displays.     

Synthesis of nanoparticles and its effect on properties of elastomeric nanocomposites

Calcium carbonate (CaCO₃) nanoparticles (9, 15, and 21 nm) were synthesized by solution spray of CaCl₂ and NH₄HCO₃ with sodium lauryl sulfate (SLS) as a stabilizing agent, and their effect was studied on polybutadiene rubber (PBR) with variations in wt% loading (4, 8, and 12%). The results of PBR nanocomposites were compared with commercial CaCO₃ (40 μm) and fly ash (75 μm) filled PBR microcomposites. Properties such as tensile strength, young modulus, elongation at break, glass transition temperature, decomposition temperature, and abrasion resistances were determined. Profound effect in properties was observed, because nanometric size of CaCO₃ particles synthesized using solution spray technique. Maximum improvement in mechanical and flame retarding properties was observed at 8 wt% of filler loading. This increment in properties was more pronounced in 9-nm size CaCO₃. The results were not appreciable above 8 wt% of nanofillers because of agglomeration of nanoparticles. In addition, an attempt was made to consider modeling Young’s modulus of PBR–nano CaCO₃ which was predicted by modified Halpin–Tsai equation. It was observed that the predication by the Guth equation and modified Halpin–Tsai equation agreed very well with experimental, whereas the Halpin–Tsai equation can only applied to predict the modulus of rubber nanocomposites in the range of low addition of nanofiller, which agrees the Nielsen equation.     

A facile synthesis of monodisperse CoFe2O4/SiO2 nanoparticles

Aminated-CoFe₂O₄/SiO₂ magnetic nanoparticles (NPs) were prepared from primary silica particles using modified StÖber method. By optimizing the preparation conditions, monodisperse CoFe₂O₄/SiO₂ NPs with high amino groups’ density were obtained, which is necessary for enzyme immobilization. TEM confirm that the sample is a core/shell structure. These aminated-CoFe₂O₄/SiO₂ NPs have narrow size distributions with a mean size of about 60 nm. Moreover, the aminated-CoFe₂O₄/SiO₂ NPs can be easily dispersed in aqueous medium. The experimental results also show that the NPs have superparamagnetism, indicating that the aminated-CoFe₂O₄/SiO₂ NPs can be used as an effective carrier for the enzyme immobilization.     

Fabrication and characterization of Au/SiO2 nanocomposite films grown by radio-frequency cosputtering

Au/SiO₂ nanocomposite films were prepared on Si wafers by cosputtering of SiO₂ and gold wires. Au/Si atomic ratios in Au/SiO₂ nanocomposite films were varied from 0.53 to 0.92 by controlling the length of gold wire to study the evolution of the crystallization of gold, the size of Au/SiO₂ nanocomposite particles, and the optical properties of as-deposited Au/SiO₂ nanocomposite films. An X-ray photoelectron spectroscopy reveals that Au exists as a metallic phase in the bulk of SiO₂ matrix. Dome-shaped Au/SiO₂ nanocomposite particles and both Au (1 1 1) and (2 0 0) planes were observed in a field-emission scanning electron microscopy and X-ray diffraction studies respectively. With an ultraviolet-visible, absorption peaks of Au/SiO₂ nanocomposite films were observed at 525 nm.     

Synthesis and Optical Properties of SiO2-Coated CeO2 Nanoparticles

Silica (SiO₂)-coated ceria (CeO₂) nanoparticles were prepared using water-in-oil microemulsion. Polyoxyethylene (15) cetylether and cyclohexane were used as a surfactant and organic solvent. SiO₂-coated CeO₂ nanoparticles were obtained by hydrolysis of metal alkoxide (tetraethylorthosilicate, TEOS) in the solution containing CeO₂ precursor nanoparticles. The effects of CeO₂ sources (Ce metal salt) and CeO₂ particle-forming agents on the morphology of SiO₂–CeO₂ particles were investigated. Observation via transmission electron microscopy revealed that the type of particle-forming agent affected the nanoparticles' morphology and that CeO₂ nanoparticles were spherically coated with SiO₂ when using oxalic acid ((COOH)₂) as a particle-forming agent of CeO₂. Furthermore, the transmittance of the particles was high in the visible region (above 400 nm) and decreased in the ultraviolet region.     

Immobilization of metalloporphyrins on P(4VP-co-St)/SiO2 by the quaternarization reaction

Poly(4vinylpyridine-co-styrene) (P(4VP-co-St)) was grafted on silica gel particles in the manner of “grafting from”, and the grafting particle P(4VP-co-St)/SiO₂ was gained. The chloromethylation reaction for the tetraphenylporphyrin (TPP) was performed using a chloromethylation reagent, 1,4-bis(chloromethyoxy)butane which was uncarcinogenic, and the tetra-chloromethylphenyl-porphyrin (TMCPP) was prepared. Then, the quaternization reaction between the benzyl chloride groups on TMCPP and pyridine groups of the grafted P(4VP-co-St) macromolecules occurred and the bonding of TMCPP on the particles P(4VP-co-St)/SiO₂ was realized, resulting in the functional composite-type particles TMCPP-P(4VP-co-St)/SiO₂. Subsequently, the metallation of the bonded particles TMCPP-P(4VP-co-St)/SiO₂ was carried out via the coordination reaction between TMCPP-P(4VP-co-St)/SiO₂ and metal salt, resulting in the supported metalloporphyrin (MP) catalysts MP-P(4VP-co-St)/SiO₂. The supported catalysts were characterized by UV-Vis spectra. The effects of various factors on the bonding process of TMCPP on P(4VP-co-St)/SiO₂ were studied in detail. In addition, the catalytic activity of the supported catalysts MP-P(4VP-co-St)/SiO₂ have been studied in oxidation process of ethyl benzene with molecular oxygen to acetophenone without the use of sacrificial co-reductant. The experimental results showed that the tetra-chloromethylphenyl-porphyrin (TMCPP) could be successfully bonded onto the P(4VP-co-St)/SiO₂ surfaces by means of the quaternization reaction between TMCPP and the pyridine groups on grafted P(4VP-co-St) macromolecules. The supported catalysts MP-P(4VP-co-St)/SiO₂ exhibited the fine catalytic activity. Moreover, the supported cobalt porphyrin was more active than the supported iron and manganese porphyrins.     

Synthesis and characterization of Mn-doped Zn2SiO4/SiO2 phosphor particles in core-shell structure

Manganese-doped zinc silicate (Zn₂SiO₄:Mn) is a kind of phosphor material that has a photo-luminescent (PL) and cathode-luminescent (CL) properties with intensive green light emission at 520 nm. The particles consisting of SiO₂@Zn₂SiO₄:Mn (SiO₂ core-Zn₂SiO₄:Mn shell) were synthesized via colloidal process and forced precipitation. After drying, the Zn/Mn precipitates were coated on the surface of SiO₂ particles. The Zn/Mn precipitates reacted with SiO₂ and transformed to Zn₂SiO₄:Mn by suitable calcination. The microstructure, crystalline phase, and luminescent characteristics of the products were studied. Besides, a CL device consisting of the core-shell powder was characterized.     

Roles of oleic acid during micropore dispersing preparation of nano-calcium carbonate particles

In the present work, nano-calcium carbonate powder was prepared by micropore dispersion method with assistance of oleic acid as surfactant. CO₂ gas was dispersed into the Ca(OH)₂/H₂O slurry via a glass micropore-plate with the diameter of micropore about 20 μm. To investigate the effect of oleic acid on the size of CaCO₃ particles, different amount of oleic acid was added in Ca(OH)₂/H₂O slurry at 5 °C and 25 °C, respectively. XRD patterns show that cubic calcite is the only crystalline phase in all cases. ZPA data and TEM photo indicate that the average particle size synthesized at 5 °C without oleic acid is of about 40 nm, slightly smaller than that of prepared at 25 °C, and that the dispersity of sample prepared at 5 °C is better than that of 25 °C. When oleic acid is added in both temperatures, the average particle size decreases a little. FT-IR spectra demonstrate that oleic acid interacts with Ca²⁺ and carbon-carbon double bond existed on the surface of particle. Consequently, two opposite roles of oleic acid during the process of preparation of nano-CaCO₃ were proposed, namely preventing nanoparticles from growing during reaction and making nanoparticles reunite to a certain extent after reaction.