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°.     

Surface tailoring of SiO2 nanoparticles by mechanochemical method based on simple milling

An appropriate modifying agent is obviously important with regard to the surface treatment of nanoparticles. Moreover, a right physical mixer that can provide enough energy to break up the secondary structure (aggregate and agglomerate) of nanoparticles is absolutely critical to the modification as well. However, it is not easy to give consideration to both of them during the process of modification. As is often the case, we tend to take care of the modifying agent but lose sight of the physical mixer. In this paper, hybrid particles of SiO₂/2,4-Diisocyanatotoluene (SiO₂/TDI) and SiO₂/2,4-Diisocyanatotoluene/hydroxyl silicone oil (SiO₂/TDI/(PDMS-OH)) were fabricated by mechanochemical method based on simple milling. The prepared hybrid particles (SiO₂/TDI and SiO₂/TDI/(PDMS-OH)) were characterized by infrared spectroscopy (FT-IR), static contact angle (CA), water sorption measurement, thermal analysis (TGA and DSC) and transmission electron microscopy (TEM). FT-IR spectra and thermal analysis (DSC) results demonstrate that TDI together with PDMS-OH is chemically anchored to the surface of nano-SiO₂. TGA results show that the grafting density of TDI is as high as 2.62 TDI/nm², while the grafting density of PDMS-OH is 0.0156 PDMS-OH/nm². Deduced from static contact angle (CA) and water sorption measurement, both hybrid particles exhibit strong hydrophobic (140^o for SiO₂/TDI and 144^o for SiO₂/TDI/(PDMS-OH)) after modification. TEM images reveal that hybrid particles (SiO₂/TDI and SiO₂/TDI/(PDMS-OH)) prepared by ball milling method exhibit much better miscibility and dispersibility in PDMS matrix when compared with those particles prepared by a common mixing device.     

Preparation and characterization of PES/TiO2 composite membranes

Polyethersulfone (PES)/TiO₂ composite membranes were prepared by phase inversion method with nano-TiO₂ as additive. The influence of TiO₂ on the morphologies and the performances of PES/TiO₂ membranes were investigated through the methods of SEM, XRD, TGA, contact angle goniometer, mechanical strength tests and filtration experiments. The results showed that the structure of membrane was not obviously affected by addition of TiO₂, and the performances such as hydrophilicity, thermal stability, mechanical strength and anti-fouling ability of membrane were enhanced through adding TiO₂ nanoparticles. At 0.5 wt.% TiO₂ content, the composite membrane has an excellent performance, however higher TiO₂ content (than 0.5 wt.%) resulted in defective pore structure of the membranes and decline of the performances, such as permeability and mechanical strength. TGA and mechanical strength analyses indicated good compatibility between polymers and TiO₂ nanoparticles.     

Chemical synthesis of nanocrystalline SnO2 thin films for supercapacitor application

Nanocrystalline SnO₂ thin films were deposited by simple and inexpensive chemical route. The films were characterized for their structural, morphological, wettability and electrochemical properties using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy techniques (SEM), transmission electron microscopy (TEM), contact angle measurement, and cyclic voltammetry techniques. The XRD study revealed the deposited films were nanocrystalline with tetragonal rutile structure of SnO₂. The FT-IR studies confirmed the formation of SnO₂ with the characteristic vibrational mode of Sn-O. The SEM studies showed formation of loosely connected agglomerates with average size of 5-10 nm as observed from TEM studies. The surface wettability showed the hydrophilic nature of SnO₂ thin film (water contact angle 9°). The SnO₂ showed a maximum specific capacitance of 66 F g⁻¹ in 0.5 Na₂SO₄ electrolyte at 10 mV s⁻¹ scan rate.     

Synthesis and characterization of superhydrophobic functionalized Cu(OH)2 nanotube arrays on copper foil

Superhydrophobic functionalized cupric hydroxide (Cu(OH)₂) nanotube arrays were prepared on copper foils via a facile alkali assistant surface oxidation technique. Thus nanotube arrays of Cu(OH)₂ were directly fabricated on the surface of copper foil by immersing in an aqueous solution of NaOH and (NH₄)₂S₂O₈. The wettability of the surface was changed from surperhydrophilicity to superhydrophobicity by chemical modification with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS). The morphologies, microstructures, crystal structure, chemical compositions and states, and hydrophobicity of the films on the copper foil substrates were analyzed by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. It was found that the rough structure of the surface helped to magnify the wettability. The static contact angle (CA) for water is larger than 160° and the contact angle hysteresis (CAH) is lower than 5° on the modified surface. The high roughness of the nanotube arrays along with the generated C-F chains by chemical modification contributed to the improved superhydrophobicity. The present research is expected to be significant in providing a new strategy for the preparation of novel multifunctional materials with potential industrial applications on copper substrates.     

Facile fabrication of Zn/Zn5(OH)8Cl2·H2O flower-like nanostructure on the surface of Zn coated with poly (N-methyl pyrrole)

Zn/Zn₅(OH)₈Cl₂·H₂O flower-like nanostructures was electrodeposited on the coated Zn with poly (N-methyl pyrrole) in 0.1 M Zn (NO₃)₂ and 0.1 M KCl solution. The morphology and the structure of the Zn/Zn₅(OH)₈Cl₂·H₂O were characterized by Field Emission Scanning Electron Microscopy (FESEM), Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction analysis (XRD). The FT-IR results showed special peaks at 908 and 728 cm⁻¹ related to Zn₅(OH)₈Cl₂·H₂O. The FESEM results indicated that Zn/Zn₅(OH)₈Cl₂·H₂O consists of a flower-like nanostructure and these flower-shaped structures contain many shaped nanopetals with the thickness of 27.8 nm. The XRD result confirmed that the major phase of electrodeposited product in 0.1 M KCl as supporting electrolyte was Zn₅(OH)₈Cl₂·H₂O. The ability of PMPy to create a thin film and the existence of several pores in its matrix act as a mold for the growth of Zn/Zn₅(OH)₈Cl₂·H₂O flower-like nanostructure. The trapping of Cl⁻ and OH⁻ within pores can be considered as the reason for the formation of flowerlike Zn/Zn₅(OH)₈Cl₂·H₂O nanostructures in 0.1 M KCl.     

Application of TiO2 nano-particles on the electrode of dye-sensitized solar cells

In this study, nano-TiO₂ thin film electrode and solar cell have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible absorption spectra, contact angle, X-ray photoelectron spectroscopy (XPS), and current-voltage characteristics analyses. X-ray diffraction patterns show that the best sintering temperature of a nano-TiO₂ film is 600 °C, at which TiO₂ anatase phase forms best and the particle size of 8-10 nm can be obtained. The SEM images of a nano-TiO₂ thin film show that the surface of the film is smooth and porous, and the thickness of the nano-TiO₂ film is 4 μm. The measurements of contact angle between nano-TiO₂ film and deionized water (DI water) reveal that the nano-TiO₂ film is super-hydrophilic when solarized under ultraviolet. The electrode of dye-sensitized solar cell is used as a free-base porphyrin with carboxyl group, 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP) as the sensitizer to adsorb onto the TiO₂ thin film. From the results of ultraviolet-visible absorption spectra and XPS analyses of the electrode, the effects of nano-TiO₂ particles’ addition to the electrode of dye-sensitized solar cell can improve the absorption of visible light (400-700 nm) and increase electrons transferred from TCPP to the conduction band of TiO₂, resulting in the enhancement of efficiency for dye-sensitized solar cells.     

Study on successively preparation of nano-TiO2 ethanol colloids by pulsed laser ablation and fluorescence property

Nano-TiO₂ colloids have been successively prepared by focused, pulsed laser ablation (PLA) at the interface of solid titanium dioxide and flowing liquid. Three factors influenced the luminescence of the nano-TiO₂ colloids. The first factor was the flowing rates of the flowing liquid. The second factor was the pulsed laser output power. The third factor was the age of the colloids. The nano-TiO₂ colloids products were characterized by transmission electron microscopy (TEM), ultraviolet visible spectroscopy (UV-vis) and fluorescence spectroscopy. The results revealed that anhydrous ethanol was the best flowing liquid, and cyclohexane or water was found to be not suitable for this system; under the conditions of the lowest flowing rates of the flowing liquids in the range of 0.017-0.15 mL/s, the highest pulsed laser output power in the range of 100-250 mJ/pulse and with the proper aging time of the colloids, nano-TiO₂ ethanol colloids with strong fluorescence emission intensity at about 414 nm can be obtained.     

Fabrication of chain-like Mn2O3 nanostructures via thermal decomposition of manganese phthalate coordination polymers

A novel manganese coordination polymer [Mn(Pht)(H₂O)]_n as a precursor was obtained by chemical precipitation involving an aqueous solution of anhydrous manganese acetate and phthalate anion as a potential O-banded ligand. Fourier transform infrared (FT-IR) results proved that phthalate anions coordinate to metal cations as a chelating bidentate ligand, making polymeric structure. The Mn₂O₃ nanostructures have been prepared via thermal decomposition of as-prepared manganese phthalate polymers as precursor in the presence of oleic acid (OA) and triphenylphosphine (TPP) as a stabilizer and capping. Different approaches such as FT-IR, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were applied to characterize the products. TEM images and XRD analysis indicated that the as-synthesized chain-like Mn₂O₃ has a crystal phase of cubic syngony with a mean size of ∼40 nm.     

Facile synthesis and capacitive performance of the Co(OH)2 nanostructure via a ball-milling method

Co(OH)₂ nanoparticles were synthesized using only CoSO₄·7H₂O and NaOH as reactants without other auxiliary reagents via a simple, low-cost and practical ball-milling technique and investigated as the active electrode materials for supercapacitors. The structure and morphology of the resulting Co(OH)₂ samples were examined by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM). The observations revealed the formation of brucite-like phase of β-Co(OH)₂, which had an irregular sphere-like shape with an average size of 50-100 nm. When investigated as electrode materials for supercapacitors, the β-Co(OH)₂ exhibited good energy-storage performances in terms of high specific capacitance of 599 F g⁻¹ and excellent capacity retention, suggesting its potential application in the electrode material for supercapacitors.     

Preparation and characterization of polyaniline (PANI)-Mn3O4 nanocomposite

Polyaniline (PANI)-Mn₃O₄ nanocomposite was synthesized by a combination of sonochemical synthesis of Mn₃O₄ NP's and in-situ polymerization of aniline. Structural characteristics were evaluated by XRD, FT-IR, TGA, VSM, TEM and SEM analysis, and conduction characteristics were evaluated by total conductivity measurements in the temperature range of 20-100 °C and frequency range of 0.1 Hz-1 MHz. Our findings show that PANI is successfully coated on nanoparticles surface and overall conductivity of nanocomposite is approximately 50-1000 times higher than that of uncapped Mn₃O₄ or PANI base with increase in temperature. Morphology of the synthesized powder was observed to be thin nanosheets with a thickness of 2-3 nm based on SEM analysis. Room temperature magnetization curves for nanocomposite show no hysteresis, indicating the super-paramagnetic character of the sample in the region of measured field strength. σ_AC increased after polyaniline coating.     

CF4 radio frequency plasma surface modification of silicone rubber for use as outdoor insulations

For further prolonging the serve life of silicone rubber (SIR) for outdoor insulation and increasing its resistance of pollution flashover, surface modifications of SIR were carried out via CF₄ capacitively coupled plasma at radio frequency (RF) power of 60, 100 and 200 W for a treatment time up to 20 min under CF₄ flow rate of 20 sccm. Static contact angle measurement was employed to estimate the change of hydrophobicity of the modified SIR. The variation of the surface functional groups of the modified SIR was observed by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectrum and X-ray photoelectron spectroscopy (XPS). The surface topography was observed by atom force microscopy (AFM). The results indicate that the static contact angle of SIR surface is improved from 100.7° to 150.2° via the CF₄ plasma modification, and the super-hydrophobic surface of modified SIR, which corresponds to a static contact angle of 150.2°, appears at RF power of 200 W for a 5-min treatment time. According to the results, it is suggested that the formation of super-hydrophobic surface is ascribed to the co-action of the increase of roughness created by the ablation reaction of CF₄ plasma and the formation of [SiF_x(CH₃)_2−xO]_n (x = 1, 2) structure produced by the direct attachment of F atoms to Si.     

Super-hydrophobicity and oleophobicity of silicone rubber modified by CF4 radio frequency plasma

Owing to excellent electric properties, silicone rubber (SIR) has been widely employed in outdoor insulator. For further improving its hydrophobicity and service life, the SIR samples are treated by CF₄ radio frequency (RF) capacitively coupled plasma. The hydrophobic and oleophobic properties are characterized by static contact angle method. The surface morphology of modified SIR is observed by atom force microscope (AFM). X-ray photoelectron spectroscopy (XPS) is used to test the variation of the functional groups on the SIR surface due to the treatment by CF₄ plasma. The results indicate that the static contact angle of SIR surface is improved from 100.7° to 150.2° via the CF₄ plasma modification, and the super-hydrophobic surface of modified SIR, which the corresponding static contact angle is 150.2°, appears at RF power of 200 W for a 5 min treatment time. It is found that the super-hydrophobic surface ascribes to the coaction of the increase of roughness created by the ablation action and the formation of [-SiF_x(CH₃)_2−x-O-]_n (x = 1, 2) structure produced by F atoms replacement methyl groups reaction, more importantly, the formation of [-SiF₂-O-]_n structure is the major factor for super-hydrophobic surface, and it is different from the previous studies, which proposed the fluorocarbon species such as C-F, C-F₂, C-F₃, CF-CF_n, and C-CF_n, were largely introduced to the polymer surface and responsible for the formation of low surface energy.     

Biosynthesis and magnetic properties of mesoporous Fe3O4 composites

Magnetic Fe₃O₄ materials with mesoporous structure are synthesized by co-precipitation method using yeast cells as a template. The X-ray diffraction (XRD) pattern indicates that the as-synthesized mesoporous hybrid Fe₃O₄ is well crystallized. The Barrett-Joyner-Halenda (BJH) models reveal the existence of mesostructure in the dried sample which has a specific surface area of 96.31 m²/g and a pore size distribution of 8-14 nm. Transmission electron microscopy (TEM) measurements confirm the wormhole-like structure of the resulting samples. The composition and chemical bonds of the Fe₃O₄/cells composites are studied by Fourier transform infrared (FT-IR) spectroscopy. Preliminary magnetic properties of the mesoporous hybrid Fe₃O₄ are characterized by a vibrating sample magnetometer (VSM). The magnetic Fe₃O₄/cells composites with mesoporous structure have potential applications in biomedical areas, such as drug delivery.     

Multiple nano-TiO2 layers to prevent dye/nano-TiO2 from photodegradation under a UV-exposure environment

A device of multiple nano-TiO₂ layers was proposed and fabricated to prevent a dye/nano-TiO₂ region from serious photo-degradation. In this device, the top of the dye/TiO₂ region was designed to be coated using sol-gel nano-TiO₂ thin films to shield UV irradiation from the photo-degradation effect. The sol-gel TiO₂ was prepared in a low temperature (75 °C) and verified as nano-sized particles and an anatase crystalline structure. Different devices of the multi-layer samples fabricated using different compositions of nano-TiO₂ were produced and exposed for UV irradiation tests. Results show that the presence of the sol-gel TiO₂ films coated on top of the dye/TiO₂ region can significantly alleviate the dye photo-degradation under UV irradiation. This multi-layer device can effectively improve the photo-stability of the dye/TiO₂ region in a UV-exposure environment.     

Efficient fluorescence of dissolved CaF2:Tb and CaF2:Ce, Tb nanoparticles through surface coating sensitization

Oleic acid (OA)-modified CaF₂:Tb³⁺ nanoparticles with various Tb³⁺ concentrations and CaF₂:Ce³⁺, Tb³⁺ nanoparticles were synthesized. The as-prepared nanoparticles were shown to be well dissolved in some common organic solvents, such as chloroform and toluene. The nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-Ray diffraction (XRD) and transmission electron microscopy (TEM). The investigation of fluorescence properties of CaF₂:Tb³⁺ nanoparticles showed that the Tb³⁺ ions could be sensitized efficiently by the surface coating of OA and CaF₂:Tb³⁺ nanoparticles with 10 mol% Tb³⁺ concentrations possess the highest emission intensity. The comparison of emission for CaF₂:Ce³⁺, Tb³⁺ and CaF₂:Tb³⁺ (10 mol%) nanoparticles revealed that the emission intensity of the former is about 4.5 times as strong as that of the latter.     

A simple and low temperature process for super-hydrophilic rutile TiO2 thin films growth

We investigate an environmentally friendly aqueous solution system for rutile TiO₂ violet color nanocrystalline thin films growth on ITO substrate at room temperature. Film shows considerable absorption in visible region with excitonic maxima at 434 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), UV-vis, water surface contact angle and energy dispersive X-ray analysis (EDX) techniques in addition to actual photo-image that shows purely rutile phase of TiO₂ with violet color, super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 3.15 ± 0.4 nm, characterize the films. Band gap energy of 4.61 eV for direct transition was obtained for the rutile TiO₂ films. Film surface shows super-hydrophilic behavior, as exhibited water contact angle was 7°. Strong visible absorption (not due to chlorine) leaves future challenge to use these films in extremely thin absorber (ETA) solar cells.     

Synthesis of original spherical α-Ni(OH)2 architectures by microwave-assisted hydrothermal method and their in situ thermal convention to NiO

The original spherical α-Ni(OH)₂ architectures with many cubic particles growing from the surface were successfully synthesized by a microwave-assisted hydrothermal method using urea as hydrolysis-controlling agent and polyethylene glycol (PEG) as surfactant. The NiO architectures with similar morphology were obtained by simple thermal decomposition of the precursor α-Ni(OH)₂. The as-obtained products were well characterized by XRD, FTIR, TGA, SEM, TEM, UV–Vis and CVs. The experimental results showed that the diameter of spherical α-Ni(OH)₂ architectures was in the range of 2–4 μm. The side length of the cubic particles was uniform about 200 nm. The cyclic voltammetric results showed that the reversible behavior of NiO electrode change better with the increasing of the cycle index. The original NiO we have prepared are expected to have good electrochemical behavior.     

Chemical synthesis of spinel nickel ferrite (NiFe2O4) nano-sheets

The present investigation is related to the deposition of single-phase nano-sheets spinel nickel ferrite (NiFe₂O₄) thin films onto glass substrates using a chemical method. Nano-sheets nickel ferrite films were deposited from an alkaline bath containing Ni²⁺ and Fe²⁺ ions. The films were characterized for their structural, surface morphological and electrical properties by means of X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and two-point probe electrical resistivity techniques. The X-ray diffraction pattern showed that NiFe₂O₄ nano-sheets are oriented along (3 1 1) plane. The FT-IR spectra of NiFe₂O₄ films showed strong absorption peaks around 600 and 400 cm⁻¹ which are typical for cubic spinel crystal structure. Microstructural study of NiFe₂O₄ film revealed nano-sheet like morphology with average sheet thickness of 30 nm. The room temperature electrical resistivity of the NiFe₂O₄ nano-sheets was 10⁷ Ω cm.     

Synthesis and separation property of flower-like Cd(OH)2 microstructures via a simple solution route

Well-defined flower-like Cd(OH)₂ microstructures have been successfully synthesized via a simple aqueous solution route, using CdCl₂ and NaOH as the reactants, and triethanolamine (TEA) as the modifying agent. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-vis spectrometer were used to characterize the products. SEM and TEM images illustrated that the flower-like Cd(OH)₂ bundles consisted of hexagonal nanoplates with thickness of about 50 nm. The adsorption of TEA on (0 0 1) plane of the growing Cd(OH)₂ crystal leads to the flower petals in appearance. Further experiments evidenced that the positively charged Cd(OH)₂ could effectively adsorb or separate the negatively charged dye molecules.