Engineered silica nanoparticles as additives in lubricant oils

Silica nanoparticles (SiO₂ NPs) synthesized by the sol–gel approach were engineered for size and surface properties by grafting hydrophobic chains to prevent their aggregation and facilitate their contact with the phase boundary, thus improving their dispersibility in lubricant base oils. The surface modification was performed by covalent binding of long chain alkyl functionalities using lauric acid and decanoyl chloride to the SiO₂ NP surface. The hybrid SiO₂ NPs were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, simultaneous differential thermal analysis, nuclear magnetic resonance and dynamic light scattering, while their dispersion in two base oils was studied by static multiple light scattering at low (0.01% w/v) and high (0.50%w/v) concentrations. The nature of the functional layer and the functionalization degree seemed to be directly involved in the stability of the suspensions. The potential use of the functional SiO₂ NPs as lubricant additives in base oils, specially designed for being used in hydraulic circuits, has been outlined by analyzing the tribological properties of the dispersions. The dendritic structure of the external layer played a key role in the tribological characteristics of the material by reducing the friction coefficient and wear. These nanoparticles reduce drastically the waste of energy in friction processes and are more environmentally friendly than other additives.     

Palladium infiltration in high surface area microporous silica nanoparticles

Metallic Pd clusters were embedded into a host matrix of microporous SiO₂ nanoparticles via a solution reduction of Pd(NO₃)₂ by hydrazine hydrate. The infiltration of 33 wt.% Pd leads to a 13% porosity loss of SiO₂ nanoparticles, which demonstrated an initial surface area of 748 m²/g. The presence of Pd in the pores was demonstrated by EDS spectroscopy and by X-ray diffraction. The metallic guest species presumably reside in the accessible micropores with an estimated size about 1.3 nm. Hydrogen uptake was measured for Pd-infiltrated SiO₂ nanoparticles. A possible mechanism for the formation of composite nanoparticles is proposed based on electrostatic interaction between Pd²⁺ and SiO₂ nanoparticles.     

SiO2/MoS2复合纳米基润滑油在镁合金冷轧中的摩擦学性能及润滑机理

镁合金在轧制过程中通常采用铝合金轧制液,甚至进行无润滑轧制。轧制过程中无润滑油会导致轧后板材表面质量差、能耗高,而铝合金轧制液通常采用含氯、硫、磷等元素的有机化合物作为添加剂,此类添加剂不容易分解,废液的排放会对环境造成一定污染。基于此,本工作采用不同比例的SiO_2和MoS_2纳米颗粒复合加入EOT5#机械油中,在双辊轧机上研究两种纳米颗粒复合比例对AZ31镁合金冷轧过程中轧制力和轧后板材表面质量的影响。采用场发射扫描电镜(FESEM)和X射线光电子能谱仪(XPS)对SiO_2/MoS_2复合纳米基润滑油润滑条件下轧后板材表面形貌和成分进行了分析,探讨了SiO_2/MoS_2复合纳米基润滑油的协同润滑机理。结果表明,SiO_2和MoS_2纳米颗粒在基础油中添加质量分数之比为0.25∶0.75时具有最佳的润滑性能。SiO_2/MoS_2复合纳米基润滑油优良的润滑性能降低了镁合金轧制过程中的轧制力,改善了轧后板材的表面质量。分析认为,不同形貌和润滑机理的SiO_2和MoS_2纳米颗粒共同作用是实现协同润滑的关键因素。     

Dissolution properties of BaTiO3 nanoparticles in aqueous suspensions

Dissolution of barium ion from aqueous suspensions of commercial nano-sized barium titanate powders (BaTiO₃) has been studied at various pH values, solids loading, different time intervals and different electrolyte concentrations. Zeta potential measurements at various pH values and Fourier transform infrared spectroscopy study were also carried out to know the surface behaviour. Dissolution of Ba²⁺ depends on the suspension pH and stirring time period. The iso-electric points were found at 3.4 and 12.2 for as-received BaTiO₃ powder and 2.3 for the leached BaTiO₃. The Ba²⁺-leached BaTiO₃ suspension retards further leaching of Ba²⁺ ions at different pH values, which favours the achievement of stable suspension.     

Gas-liquid detonation synthesis of graphite coated copper nanoparticles and tribological performance as lubricant additives

Graphite coated copper (Cu@G) nanoparticles were successfully prepared by a gas-liquid detonation method, using copper acetate, ethanol, hydrogen and oxygen as the detonation precursors. The composition, morphology and microstructure of detonation products were analyzed by X-ray diffraction (XRD) and transmission electron microscopy-energy dispersive X-ray spectrometry (TEM-EDX). And a four-ball wear test was carried out to clarify the tribological properties of the mixed lubricating oils, which mainly consisted of the SN150 base oils containing five different concentrations of Cu@G nanoparticles. The results indicated that Cu@G nanoparticles are made up of face-centered cubic (FCC) copper nanocrystal and graphitic shells. The size distribution of core-shell structural products is mainly in range of 10–40 nm and the graphitic shells is about 4–8 nm. From the four-ball tests, the friction coefficient and wear scar diameter (WSD) decrease firstly and then increase with the increase of the contents of Cu@G nanoparticles. When the content of Cu@G nanoparticles is 0.6%, there is a minimum friction coefficient and WSD.     

Thermal evolution and optical properties of Cu nanoparticles in SiO2 by ion implantation

SiO₂ samples were implanted by 45 keV Cu ions at a dose of 1 × 10¹⁷ /cm², and subjected to furnace annealing at temperatures ranging from 200 to 600 °C in nitrogen atmosphere. The results indicate that the Cu nanoparticles have been synthesized by Cu ion implantation, and subsequent annealing induces the diffusion and nucleation of nanoparticles partially. The results from XPS measurements show that the Cu⁰ is the dominate charge state in the implanted and subsequent annealed samples. With increasing annealing temperature, the size and distribution of Cu nanoparticles have been modified gradually. The surface plasmon resonance (SPR) of Cu nanoparticles at 570 nm has been observed by optical transmission spectroscopy. The strongest SPR signal at 400-600 °C indicates that lots of Cu nanoparticles have grown and show good optical properties. Moreover, the luminescence has been investigated in Cu implanted and subsequent annealed samples. Possible luminescence mechanisms, such as radiation induced defects, Cu (ions or atoms) related luminescence centers, etc., have been discussed.     

酸碱条件对水玻璃为源制备SiO2气凝胶的影响

以廉价的工业水玻璃为凝胶前躯体,柠檬酸为凝胶促进剂,使用溶胶-凝胶与CO2超临界干燥工艺制备了块状的SiO2气凝胶,并探讨了酸性和碱性条件对所制备SiO2气凝胶结构与性能的影响.实验结果表明:水玻璃在酸性条件(pH≈4)和碱性条件(pH≈10)下均可以制备出完整、无开裂的二氧化硅气凝胶块体样品,酸性和碱性环境对水凝胶和最终SiO2气凝胶结构和性能的影响较大.酸性条件下获得的水凝胶呈透明块体,而碱性条件下所得水凝胶为白色不透明体.与碱性条件下制备的SiO2气凝胶相比,酸性条件下所得气凝胶具有更高的比表面积、较大的密度以及尺寸较小的胶体粒子.     

Synthesis and optical properties of luminescent core-shell structured silicate and phosphate nanoparticles

Monodisperse, luminescent core-shell structured inorganic nanoparticles were synthesized by sol-gel technology. They exhibit an amorphous SiO₂ core and a crystalline luminescent shell. Zn₂SiO₄:Mn²⁺ and Ca₁₀(PO₄)₆OH:Eu³⁺ shell materials are investigated. The influence of the doping concentration on optical and structural properties was studied. The resulting nanoparticles were characterized by X-ray diffraction analysis, transmission electron microscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy.     

Assembly of Fe3O4 nanoparticles on SiO2 monodisperse spheres

The assembly of superparamagnetic Fe₃O₄ nanoparticles on submicroscopic SiO₂ spheres have been prepared by an in situ reaction using different molar ratios of Fe³⁺/Fe²⁺ (50–200%). It has been observed that morphology of the assembly and properties of these hybrid materials composed of SiO₂ as core and Fe₃O₄ nanoparticles as shell depend on the molar ratio of Fe³⁺/Fe²⁺.     

聚四氟乙烯/二氧化硅杂化材料的性能研究

为解决纳米粒子在聚四氟乙烯(PTFE)树脂中难分散均匀的问题,使用PTFE乳液通过原位溶胶-凝胶法(Sol-Gel)制备了聚四氟乙烯/二氧化硅(SiO2)杂化材料,并对其性能进行了表征与研究.研究表明:杂化材料的拉伸强度在SiO2含量为1.05%(记为FS-2)时达到最大值20.96 MPa,为纯PTFE的两倍;断裂伸长率随着SiO2含量的增加而降低,硬度逐渐升高,接触角由121°降至79°.由SEM结果发现,试样FS-2中SiO2的粒径仅为100 nm左右,但随着SiO2含量的增加,粒径变大.杂化材料的耐热性较PTFE有一定提高,当杂化材料中SiO2含量达到5.00%时,热分解温度由纯PTFE的503℃上升至528℃.     

Study of the mechanisms involved in reactive silica

The microstructure of a heterogeneous SiO₂ submitted to a depolymerisation process is studied using Transmission Electron Microscope (TEM), Environmental SEM (ESEM), and X-ray diffraction (XRD). With ESEM the formation of micro domain induced by the dissolution phenomena is shown. XRD shows the formation of a halo that is associated with the formation of amorphous phase. The parameters “position and FWHM” of the halo, enabled us to show the evolution of the disorderly phase when the reaction progresses. The hypothesis of formation of nanoparticles with different structural states was confirmed by the TEM.     

Optical and magnetic properties of elliptical hematite (α-Fe2O3) nanoparticles coated with uniform continuous layers of silica of different thickness

Elliptical-type α-Fe₂O₃ nanoparticles with/without silica shell have been prepared. The core particles were coated with uniform continuous layers of silica of two different thicknesses by hydrolysis of TEOS. The obtained HCP structure elliptical α-Fe₂O₃ nanoparticles with ∼ 240 nm length and 100 nm width is polycrystalline in nature. The thicknesses of SiO₂ shell coated on α-Fe₂O₃ are about 55 and 30 nm, respectively. The optical and magnetic properties of these nanoparticles have been investigated.     

Fabrication and characterization of transparent superhydrophilic/superhydrophobic silica nanoparticulate thin films

The realization of transparent and superhydrophilic/superhydrophobic surfaces by silica nanoparticulate thin films was exploited in this work. An aqueous electrostatic layer-by-layer assembly process was utilized to fabricate nanoparticulate thin films with adhesion/body/top layer structure on glass substrates by using SiO₂ nanoparticles and polyelectrolytes. The effects of volume ratio of differently sized silica nanoparticle solutions for the body layer deposition on transmittance in visible light region and surface wettability of the nanoparticulate thin films were systematically studied. The experimental results revealed that both optical transparency and superhydrophobicity/superhydrophilicity can be achieved on the same SiO₂ nanoparticulate thin film by using appropriate volume ratios of differently sized silica nanoparticle solutions for body layer deposition, and with and without silane treatment in the fabrication process. The high contrast of wettability that can be achieved by this way suggests the possibility of the creation of superhydrophilic/superhydrophobic patterning and superhydrophilic-superhydrophobic gradient on the same surfaces.     

A novel application of iron oxide nanoparticles for detection of hydrogen peroxide in acid rain

Determining the concentration of hydrogen peroxide (H₂O₂) is of great importance in food, pharmaceutical, environmental and clinical analyses. Horseradish peroxidase (HRP), an enzyme specifically catalyzing the oxidative reaction of H₂O₂ to develop color reaction, has been widely used for measuring H₂O₂ concentration. However, owing to the instability and high cost of this enzyme, discovering efficient mimics of peroxidase has been important to conquer these disadvantages of protein catalyst. Recently we have found that Fe₃O₄ magnetic nanoparticles (Fe₃O₄ MNPs) possess intrinsic peroxidase-like activity, which can catalyze oxidation of various peroxidase substrates in the presence of H₂O₂. Based on this finding, we developed a spectrometric method using Fe₃O₄ MNPs as a catalyst to determine H₂O₂ in rainwater. Our data show that the Fe₃O₄ MNPs are efficient catalysts to determine H₂O₂ in rainwater. Compared to HRP, the Fe₃O₄ MNPs are reusable and economical and these characteristics make the particles a board range of applications in determining H₂O₂ in the rainwater.     

Formation of SiC nanowhiskers by carbothermic reduction of silica with activated carbon

The silicon carbide (SiC) nanowhiskers were obtained by a carbothermic reduction of silica (SiO₂) with activated carbon at 1450 °C. The products were characterized by X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HR-TEM). The SiC nanowhiskers were grown as crystalline β-SiC with the diameter ranging from 20 to 150 nm grew along (111) direction with the length up to several tens of micrometers. Yield of β-SiC is very high with the moderate amount of un-reacted SiO₂. This is the first report on the synthesis of high yield of β-SiC by simple direct heating method.     

The preparation and the friction and wear behaviours of TiO2/CNT/PI composite film

Recently, the tribological properties of polyimide composites filled with TiO₂ nanoparticles and short pitch-based carbon nanotubes (CNTs) were investigated. Sliding tests were performed on a co-rotating twin-screw extruder under different temperatures and regular pressure and speed. It was found that the composite with 4 wt% TiO₂ and 6 wt% CNT could reduce the frictional coefficient and wear rate in the most effective way. Compared to the conventional hybrid composites up to now, the above composite was characterised by relatively lower filler content, which would reduce the manufacturing cost. Therefore, it could be largely processed in practice. Increased surface hardness, lubricating effect of the sheet-like wear debris reinforced by TiO₂ and rapidly formed transfer film were believed to be the key issues accounting for the obvious wear-resisting and friction-reducing behaviours.     

Cr-induced modifications in the structural,photoluminescence and acetone-sensing behaviour of hydrothermally synthesised SnO2 nanoparticles

Cr-doped SnO₂ nanoparticles have been synthesised by the hydrothermal route, using SnCl₄·5H₂O as the host precursor and C₁₅H₂₁CrO₆ as the source of dopant. The structural and morphological studies have been carried out by X-ray diffraction, transmission electron microscopy and scanning electron spectroscopy, which reveal a tetragonal rutile structure of SnO₂ nanoparticles and improvement in the crystallinity upon Cr doping. Compositional analyses by energy-dispersive X-ray confirm the incorporation of Cr ions into the SnO₂ lattice. The existence of defect levels in the visible region has been studied by photoluminescence. The room-temperature electrical conductivity decreases with Cr doping due to the replacement of Sn⁴⁺ ions by Cr³⁺ ions. The response to acetone has been found to improve with the increase of Cr-doping concentration relative to the undoped SnO₂, except in the case of 0.5 at% Cr-doped sample where it decreases at low concentrations (up to 30 ppm) and operating temperatures (up to 200 °C). The response time decreases with the increasing Cr-doping concentration and is found to be minimum for the 1.5 at% Cr-doped SnO₂. A possible reaction mechanism of acetone sensing has been explained.     

Structure and characterization of TeO2 nanoparticles prepared in acid medium

The preparation of tellurium dioxide (TeO₂) nanoparticles in a mild condition had been studied. The acid medium, such as gallic acid or acetum was used to prepare the TeO₂ nanoparticles at room temperature. The functions of acids were investigated by Nano-ZS, TEM, SEM, FTIR, Raman spectra and XRD. The results showed that the modification and modulation of gallic acid on the TeO₂ nanoparticles were stronger than that of acetum. The TeO₂ nanoparticles prepared in gallic acid were the orthorhombic phase β-TeO₂ spheres in the range of 30-200 nm. The TeO₂ nanoparticles prepared in acetum were the tetragonal phase α-TeO₂ irregular flakes in the range of 40-400 nm.     

油溶性离子液体作为润滑油添加剂的摩擦学性能研究

为解决离子液体在基础油中溶解性差、不宜用作润滑添加剂的问题,通过分子设计制备了极性较小的十六烷基三辛基季膦磷酸二异辛酯盐和十六烷基三辛基季胺多库酯钠盐2种油溶性离子液体,其在碳氢润滑油聚ɑ烯烃(PAO10)中均具有较好的溶解性。采用铜片腐蚀试验考察了2种离子液体的腐蚀性;通过Optimol SRV-IV往复振动摩擦磨损试验机测试了2种离子液体作为PAO10基础油添加剂的摩擦学性能,通过多功能X射线光电子能谱仪(XPS)和原位接触电阻(ECR)表征推导了离子液体添加剂在PAO基础油中的润滑机理。结果表明:2种离子液体作为PAO10的添加剂无腐蚀,完全符合对润滑添加剂的要求。2种离子液体添加剂比空白基础油和传统工业添加剂ZDDP均具有更好的减摩抗磨性能。2种离子液体添加剂会在摩擦副表面形成有效的吸附膜和发生复杂的摩擦化学反应,因而使离子液体具有优异的减摩抗磨性能。     

Speciation of Cr(III) and Cr(VI) in environmental samples determined by selective separation and preconcentration on silica gel chemically modified with niobium(V) oxide

In this study a new method for chromium speciation in water using solid phase extraction coupled to a flow injection system and flame atomic absorption spectrometry was developed. The adsorption behavior of Cr(III) and Cr(VI) on Nb2O5-SiO2 allowed the selective separation of Cr(III) from Cr(VI) in the pH range of 6-9. Thus, a method for Cr(III) preconcentration and extraction using Nb2O5-SiO2 was developed. Total chromium was determined after the reduction of Cr(VI) to Cr(III) using sodium sulfite in acidic medium. The operational variables of the preconcentration and reduction procedures were optimized through full factorial and Doehlert designs. The limit of detection for Cr(III) was 0.34microgL(-1) and the precision was below 4.6%. Results for recovery tests using different environmental samples were between 90 and 105%. Certified reference materials (NIST 1640 and NIST 1643e) were analyzed in order to check the accuracy of the proposed method, and the results were in agreement with the certified values.