Grafting of Dispersants on MoS2 Nanoparticles in Base Oil Lubrication of Steel

Solid lubricant nanoparticles in suspension in oil are good lubricating options for practical machinery. In this article, we select a range of dispersants, based on their polar moieties, to suspend 50-nm molybdenum disulfide particles in an industrial base oil. The suspension is used to lubricate a steel on steel sliding contact. A nitrogen-based polymeric dispersant (aminopropyl trimethoxy silane) with a free amine group and an oxygen-based polymeric dispersant (sorbital monooleate) when grafted on the particle charge the particle negatively and yield an agglomerate size which is almost the same as that of the original particle. Lubrication of the contact by these suspensions gives a coefficient of friction in the similar to 0.03 range. The grafting of these surfactants on the particle is shown here to be of a chemical nature and strong as the grafts survive mechanical shear stress in tribology. Such grafts are superior to those of other silane-based test surfactants which have weak functional groups. In the latter case, the particles bereft of strong grafts agglomerate easily in the lubricant and give a coefficient of friction in the 0.08-0.12 range. This article investigates the mechanism of frictional energy dissipation as influenced by the chemistry of the surfactant molecule.

Room temperature gas sensing properties of ultrathin carbon nanotubes by surfactant-free dip coating

Large-scale production of reliable carbon nanotubes (CNTs) based gas sensors involves the development of scalable and reliable processes for the fabrication of films with controlled morphology. Here, we report for the first time on highly scalable, ultrathin CNT films, to be employed as conductometric sensors for NO2 and NH3 detection at room temperature. The sensing films are produced by dip coating using dissolved CNTs in chlorosulfonic acid as a working solution. This surfactant-free approach does not require any post-treatment for the removal of dispersants or any CNTs functionalization, thus promising high quality CNTs for better sensitivity and low production costs. The effect of CNT film thickness and defect density on the gas sensing properties has been investigated. Detection limits of 1 ppm for NO2 and 7 ppm for NH3 have been achieved at room temperature. The experimental results reveal that defect density and film thickness can be controlled to optimize the sensing response. Gas desorption has been accelerated by continuous in-situ UV irradiation.

Organized Nanostructures of Thermoresponsive Poly(N-isopropylacrylamide) Block Copolymers Obtained Through Controlled RAFT Polymerization

Kontrolloidut radikaalipolymerointimenetelmät, kuten RAFT-polymerointi, ovat moderni tapa valmistaa polymeerejä säädellysti. RAFT-polymeroinnilla polymeerien ketjunpituutta, moolimassajakaumaa, mikrorakennetta (taktisuus, järjestys), koostumusta ja funktionaalisuutta kyetään hallitsemaan. Siten menetelmällä voidaan valmistaa uudenlaisia polymeeriarkkitektuureja, kuten blokki- ja tähtipolymeerejä, sekä hybridimateriaaleja ja biokonjugaatteja. Polymeeristen rakennuspalikoiden itsejärjestyminen, missä huolellisesti syntetisoidut polymeerit järjestyvät halutulla tavalla nanoskaalassa, on suosittu tutkimuskohde materiaalitieteessä. On huomattava, että blokkipolymeerien itsejärjestyminen on vielä suhteellisen nuori tutkimusaihe. Tämän hetkiset polymeeriset nanomateriaalit ovat suhteellisen yksinkertaisia luonnon luomuksiin verrattuina, tarjoten jatkuvasti uusia mahdollisuuksia seuraavan sukupolven polymeereille. Tässä työssä RAFT-polymeroinnilla syntetisoitiin amfifiilisiä di- ja triblokkikopolymeerejä sekä tutkittiin niiden järjestymistä nanorakenteiksi. Kaikissa blokkikopolymeereissä käytettiin lämpöherkkää poly(N-isopropyyliakryyliamidia). Siten polymeerit ja tutkitut materiaalit reagoivat lämpötilanmuutokseen ympäristössä eli ovat ns. ympäristöherkkiä. Työssä tutkittiin taktisuuden kontrollointia N-isopropyyliakryyliamidin RAFT-polymeroinnissa. Polymeerin taktisuutta sekä ketjunpituutta ja blokkijärjestystä säätämällä voitiin hallita polymeerin itsejärjestymistä vesiliuoksessa. Amfifiiliset polymeerit järjestyivät laimeissa vesiliuoksissa erilaisiksi misellirakenteiksi, muodostaen ns. mikrosäiliöitä. Tällaisilla polymeereillä odotetaan olevan sovelluksia esim. lääkeainevapautuksessa. Amfifiilejä käytetään myös esimerkiksi apuaineina pinnoitteissa ja kosmetiikassa. Kiinteässä tilassa tutkitut triblokkikopolymeerit muodostivat teoreettisesti ennustettuja morfologioita. Lämpöherkän materiaalin hydrogeelit toimivat suodatinmembraanina nanokokoluokassa. RAFT-polymeroinnilla syntetisoituja polymeereja voidaan sellaisenaan käyttää kultananopartikkeleiden päällystämiseen. Kultananopartikkelit ovat erittäin kiinostavia mm. niiden stabiilisuuden ja ainutlaatuisten pintaominaisuuksien vuoksi. Kun amfifiilisiä polymeerejä kiinnitettiin kultapartikkelin pinnalle, sen liuos- ja optisia ominaisuuksia voitiin säädellä pH:n ja lämpötilan avulla. Tällaisilla kultananopartikkeleilla on sovelluksia mm. diagnostiikassa, sensoreina ja solukuvauksessa.

Mechanics of Deformation under Traction and Friction of a Micrometric Monolithic MoS2 Particle in Comparison with those of an Agglomerate of Nanometric MoS2 Particles

Tribology of small inorganic nanoparticles in suspension in a liquid lubricant is often impaired because these particles agglomerate even when organic dispersants are used. In this paper we use lateral force microscopy to study the deformation mechanism and dissipation under traction of two extreme configurations (1) a large MoS2 particle (similar to 20 mu m width) of about 1 mu m height and (2) an agglomerate (similar to 20 mu m width), constituting 50 nm MoS2 crystallites, of about 1 mu m height. The agglomerate records a friction coefficient which is about 5-7 times that of monolithic particle. The paper examines the mechanisms of material removal for both the particles using continuum modeling and microscopy and infers that while the agglomerate response to traction can be accounted for by the bulk mechanical properties of the material, intralayer and interlayer basal planar slips determine the friction and wear of monolithic particles. The results provide a rationale for selection of layered particles, for suspension in liquid lubricants.

Hydrolysis and dispersion properties of aqueous Y2Si 2O7 suspensions

The dispersion of aqueous γ-Y2Si2O7 suspensions, which contain only one component but have a complex ion environment, was studied by the introduction of two different polymer dispersants, polyethylenimine (PEI) and polyacrylic acid (PAA). The suspension without any dispersant remains stable in the pH range of 9-11.5 because of electrostatic repulsion, while it is flocculated upon stirring due to the readsorption of hydrolyzed ions on the colloid surface. However, suspensions with 1 dwb% PEI exhibit greater stability in the pH range of 4-11.5. The addition of PEI shifts the isoelectric point (IEP) of the suspensions from pH 5.8 to 10.8. Near the IEP (pHIEP=10.8), the stability of the suspensions with PEI is dominated by the steric effect. When the pH is decreased to acid direction, the stabilization mechanism is changed from steric hindrance to an electrosteric effect little by little. PAA also has the effect of reducing the hydrolysis speed via a "buffer effect" in the basic pH range, but the lack of adsorption between the highly ionized anionic polymer molecules and the negative colloid particle surfaces shows no positive effect on hydrolysis of colloids and on the stabilization of Y2Si 2O7 suspensions.

Dispersibility of Barium Titanate Suspension in the Presence of Polyelectrolytes: A Review

Dispersibility of colloidal barium titanate suspensions is reviewed with an emphasis on the use of various polyelectrolytes as dispersants. The fundamentals of colloidal stability are discussed followed by the colloidal properties of barium titanate powder. Dispersion behavior of BaTiO3 in both nonaqueous and aqueous media has been reviewed. Several studies on the stabilization of micron and nano-sized barium titanate using various polymeric dispersants and a rhamnolipid biosurfactant are presented and discussed. The article attempts to provide a comprehensive review of the current state-of-the-art in the area of colloidal processing of barium titanate.

Characterisation of cellulose- and lignin-based materials using x-ray scattering methods

Wood is an important material for the construction and pulping industries. Using x-ray diffraction the microfibril angle of Sitka spruce wood was studied in the first part of this thesis. Sitka spruce (Picea sitchensis [Bong.] Carr.) is native to the west coast of North America, but due to its fast growth rate, it has also been imported to Europe. So far, its nanometre scale properties have not been systematically characterised. In this thesis the microfibril angle of Sitka spruce was shown to depend significantly on the origin of the tree in the first annual rings near the pith. Wood can be further processed to separate lignin from cellulose and hemicelluloses. Solid cellulose can act as a reducer for metal ions and it is also a porous support for nanoparticles. By chemically reducing nickel or copper in the solid cellulose support it is possible to get small nanoparticles on the surfaces of the cellulose fibres. Cellulose supported metal nanoparticles can potentially be used as environmentally friendly catalysts in organic chemistry reactions. In this thesis the size of the nickel and copper containing nanoparticles were studied using anomalous small-angle x-ray scattering and wide-angle x-ray scattering. The anomalous small-angle x-ray scattering experiments showed that the crystallite size of the copper oxide nanoparticles was the same as the size of the nanoparticles, so the nanoparticles were single crystals. The nickel containing nanoparticles were amorphous, but crystallised upon heating. The size of the nanoparticles was observed to be smaller when the reduction of nickel was done in aqueous ammonium hydrate medium compared to reduction made in aqueous solution. Lignin is typically seen as the side-product of wood industries. Lignin is the second most abundant natural polymer on Earth, and it possesses potential to be a useful material for many purposes in addition to being an energy source for the pulp mills. In this thesis, the morphology of several lignins, which were produced by different separation methods from wood, was studied using small-angle and ultra small-angle x-ray scattering. It was shown that the fractal model previously proposed for the lignin structure does not apply to most of the extracted lignin types. The only lignin to which the fractal model could be applied was kraft lignin. In aqueous solutions the average shape of the low molar mass kraft lignin particles was observed to be elongated and flat. The average shape does not necessarily correspond to the shape of the individual particles because of the polydispersity of the fraction and due to selfassociation of the particles. Lignins, and especially lignosulfonate, have many uses as dispersants, binders and emulsion stabilisers. In this thesis work the selfassociation of low molar mass lignosulfonate macromolecules was observed using small-angle x-ray scattering. By taking into account the polydispersity of the studied lignosulfonate fraction, the shape of the lignosulfonate particles was determined to be flat by fitting an oblate ellipsoidal model to the scattering intensity.

Deformation and friction of MoS2 particles in liquid suspensions used to lubricate sliding contact

Tribology of a well known solid lubricant molybdenum disulphide is studied here in water and oil medium, over a large range of contact dimensions. Lateral force microscopy is used to identify the deformation modes, intra-crystalline slip, plastic grooving, fragmentation and fracture, of single particles The medium and agglomeration were found to dictate the deformation mode Steel on steel tribology lubricated by suspensions of these particles in liquid media was conducted over a range of contact pressure and sliding velocity. A scrutiny of the frictional data with the aid of Raman spectroscopy to identify the transfer film, suggested that the particle size, as it is at contact, is an important tribological parameter Ultrasonication of the suspension and dispersion of the particle by surfactants were used to control the apriori particle size fed into the suspension.Correspondence of friction data of the gently sonicated suspension with that of the ultrasonicated suspension with dispersants indicated the importance of liquid ingestion by these particles as it controls their mode of deformation and consequent tribology. (C) 2010 Elsevier B V All rights reserved.

Sol-gel derived, magnesium based ionically conducting composites

Composite ionic conductors based on magnesium salts and sol-gel derived silicate-tetraethylene glycol hybrids have been synthesized. The structure of these materials has been studied by FT-IR, FT-Raman, Si-29 and C-13 NMR and XRD techniques. The composite systems can be best described as diphasic with silicate as filters in the organic phase that provides solubility of the ionic dispersants. The ionic interactions in the matrix are clearly observed in the FT-Raman spectra. The ionic conductivity is determined to be of the order of 10(-7) to 10(-5) S cm(-1) at room temperature for MgCl2 and Mg(ClO4)(2) salts respectively. The conductivity reaches 10(-4) and 10(-3) S cm(-1) at 80degreesC respectively.

Microbially induced separation of quartz from hematite using yeast cells and metabolites

The utility of yeast, Saccharomyces cerevisiae, in the separation of quartz from hematite is demonstrated. Yeast cells; as well as their metabolites, functioned as flotation collectors, depressants or flocculants and dispersants for hematite and quartz. Interaction between yeast and the above minerals resulted in significant surface chemical changes, rendering quartz surfaces hydrophobic and hematite hydrophilic. Mineral-specific extracellular proteins and exopolysaccharides were secreted by yeast cells when grown in the presence of quartz and hematite, respectively. Quartz could be efficiently separated from hematite through microbially induced flotation and selective flocculation.

A settlement inhibition assay with cyprid larvae of the barnacle Balanus amphitrite

A settlement inhibition assay using barnacle cyprid larvae, Balanus amphitrite, was developed with Cd2+ and phenol as standard reference toxicants. Mean percentage settlement of cyprid larvae showed a progressive reduction with increasing concentrations of Cd2+ and phenol. A significant reduction in settlement was found when cyprids were exposed to 0.1 mgL(-1) Cd2+ or 10 mgL(-1) phenol. The assay was used to assess the sublethal toxicity of three oil dispersants (Vecom B-1425 GL, Norchem OSD-570 and Corexit 9905) commonly used in Hong Kong waters. Results of this investigation show that the barnacle settlement inhibition assay can be incorporated into the battery of tests currently available for ecotoxicological assessment of marine contaminants. (C) 1997 Elsevier Science Ltd.

两种超微细矿物粉体材料的制备及应用研究

Superfine mineral materials are mainly resulted from the pulverization of natural mineral resources, and are a type of new materials that can replace traditional materials and enjoy the most extensive application and the highest degree of consumption in the present day market. As a result, superfine mineral materials have a very broad and promising prospect in terms of market potential. Superfine pulverization technology is the only way for the in-depth processing of most of the traditional materials, and is also one of the major means for which mineral materials can realize their application. China is rich in natural resources such as heavy calcite, kaolin, wollastonite, etc., which enjoy a very wide market of application in paper making, rubber, plastics, painting, coating, medicine, environment-friendly recycle paper and fine chemical industries, for example. However, because the processing of these resources is generally at the low level, economic benefit and scale for the processing of these resources have not been realized to their full potential even up to now. Big difference in product indices and superfine processing equipment and technologies between China and advanced western countries still exists. Based on resource assessment and market potential analysis, an in-depth study was carried out in this paper about the superfine pulverization technology and superfine pulverized mineral materials from the point of mineralogical features, determination of processing technologies, analytical methods and applications, by utilizing a variety of modern analytical methods in mineralogy, superfine pulverization technology, macromolecular chemistry, material science and physical chemistry together with computer technology and so on. The focus was placed on the innovative study about the in-depth processing technology and the processing apparatus for kaolin and heavy calcite as well as the application of superfine products. The main contents and the major achievements of this study are listed as follows: 1. Superfine pulverization processing of mineral materials shall be integrated with the study of their crystal structures and chemical composition. And special attention shall be put on the post-processing technologies, rather than on the indices for particle size, of these materials, based on their fields of application. Both technical feasibility and economic feasibility shall be taken into account for the study about superfine pulverization technologies, since these two kinds of feasibilities serve as the premise for the industrialized application of superfine pulverized mineral materials. Based on this principle, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in this study, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in this study. Heavy calcite and kaolin are two kinds of superfine mineral materials that enjoy the highest consumption in the industry. Heavy calcite is mainly applied in paper making, coating and plastics industries, the hard kaolin in northern China is mainly used in macromolecular materials and chemical industries, while the soft kaolin in southern China is mainly used for paper making. On the other hand, superfine pulverized heavy calcite and kaolin can both be used as the functional additives to cement, a kind of material that enjoys the biggest consumption in the world. A variety of analytical methods and instruments such as transmission and scanning electron microscopy, X-ray diffraction analysis, infrared analysis, laser particle size analysis and so on were applied for the elucidation of the properties and the mechanisms for the functions of superfine mineral materials as used in plastics and high-performance cement. Detection of superfine mineral materials is closely related to the post-processing and application of these materials. Traditional detection and analytical methods for superfine mineral materials include optical microscopy, infrared spectral analysis and a series of microbeam techniques such as transmission and scanning electron microscopy, X-ray diffraction analysis, and so on. In addition to these traditional methods, super-weak luminescent photon detection technology of high precision, high sensitivity and high signal to noise ratio was also utilized by the author for the first time in the study of superfine mineral materials, in an attempt to explore a completely new method and means for the study of the characterization of superfine materials. The experimental results are really exciting! The innovation of this study is represented in the following aspects: 1. In this study, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in an innovative way, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in the industrialized production process*. Moreover, a new modification technology and related directions for producing the chemicals were invented, and the modification technology was even awarded a patent. 2. The detection technology of super-weak luminescent photon of high precision, high sensitivity and high signal to noise ratio was utilized for the first time in this study to explore the superfine mineral materials, and the experimental results can be compared with those acquired with scanning electron microscopy and has demonstrated its unique advantages. It can be expected that further study may possibly help to result in a completely new method and means for the characterization of superfine materials. 3. During the heating of kaolinite and its decomposition into pianlinite, the diffraction peaks disappear gradually. First comes the disappearance of the reflection of the basal plane (001), and then comes the slow disappearance of the (hkl) diffraction peaks. And this was first discovered during the experiments by the author, and it has never before reported by other scholars. 4. The first discovery of the functions that superfine mineral materials can be used as dispersants in plastics, and the first discovery of the comprehensive functions that superfine mineral materials can also be used as activators, water-reducing agents and aggregates in high-performance cement were made in this study, together with a detailed discussion. This study was jointly supported by two key grants from Guangdong Province for Scientific and Technological Research in the 10th Five-year Plan Period (1,200,000 yuan for Preparation technology, apparatus and post-processing research by using sub-micron superfine pulverization machinery method, and 300,000 yuan for Method and instruments for biological photon technology in the characterization of nanometer materials), and two grants from Guangdong Province for 100 projects for scientific and technological innovation (700,000 yuan for Pilot experimentation of superfine and modified heavy calcite used in paper-making, rubber and plastics industry, and 400,000 yuan for Study of superfine, modified wollastonite of large length-to-diameter ratio).