Studies on a nanocomposite solid polymer electrolyte with hydrotalcite as a filler

We have prepared a new nanocomposite polymer electrolyte using nanoparticles of hydrotalcite, an anionic clay, as the filler. Hydrotalcite has the chemical composition [M-1-x(2+) M-x(3+) (OH)(2)](x+) [A(x/n)(n-)center dot mH(2)O] where M2+ is a divalent cation (e.g. Mg2+, Ni2+, Co2+,etc.) and M3+ is a trivalent cation (e.g. Al3+, Fe3+, Cr3+, etc.). A(n-) is an anion intercalated between the positively charged double hydroxide layers. The nanoparticles of [Mg0.67Al0.33 (OH)(2)] [(CO3)(0.17)center dot mH(2)O] were prepared by the co-precipitation method (average particle size as observed by TEM similar to 50 nm) and were doped into poly(ethylene glycol) PEG (m.w.2000) complexed with LiCIO4. Samples with different wt.% of hydrotalcite were prepared and characterized using XRD, DSC, TGA, impedance spectroscopy and NMR. Ionic conductivity for the pristine sample, similar to 7.3 x 10(-7) S cm(-1), was enhanced to a maximum of = 1.1 x 10(-5) S cm(-1) for 3.6 wt.% nanoparticle doped sample. We propose that the enhancement of ionic conductivity is caused by percolation effects of the high conductivity paths provided by interfaces between the nanoparticles and the polymer electrolyte. (C) 2010 Elsevier B.V. All rights reserved.

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.

On formation, growth and concentrations of air ions

Aerosol particles have effect on climate, visibility, air quality and human health. However, the strength of which aerosol particles affect our everyday life is not well described or entirely understood. Therefore, investigations of different processes and phenomena including e.g. primary particle sources, initial steps of secondary particle formation and growth, significance of charged particles in particle formation, as well as redistribution mechanisms in the atmosphere are required. In this work sources, sinks and concentrations of air ions (charged molecules, cluster and particles) were investigated directly by measuring air molecule ionising components (i.e. radon activity concentrations and external radiation dose rates) and charged particle size distributions, as well as based on literature review. The obtained results gave comprehensive and valuable picture of the spatial and temporal variation of the air ion sources, sinks and concentrations to use as input parameters in local and global scale climate models. Newly developed air ion spectrometers (Airel Ltd.) offered a possibility to investigate atmospheric (charged) particle formation and growth at sub-3 nm sizes. Therefore, new visual classification schemes for charged particle formation events were developed, and a newly developed particle growth rate method was tested with over one year dataset. These data analysis methods have been widely utilised by other researchers since introducing them. This thesis resulted interesting characteristics of atmospheric particle formation and growth: e.g. particle growth may sometimes be suppressed before detection limit (~ 3 nm) of traditional aerosol instruments, particle formation may take place during daytime as well as in the evening, growth rates of sub-3 nm particles were quite constant throughout the year while growth rates of larger particles (3-20 nm in diameter) were higher during summer compared to winter. These observations were thought to be a consequence of availability of condensing vapours. The observations of this thesis offered new understanding of the particle formation in the atmosphere. However, the role of ions in particle formation, which is not well understood with current knowledge, requires further research in future.

Synthesis and characterization of Pd(0), PdS, and Pd@PdO core-shell nanoparticles by solventless thermolysis of a Pd-thiolate cluster

Colloids of palladium nanoparticles have been prepared by the solvated metal atom dispersion (SMAD) method. The as-prepared Pd colloid consists of particles with an average diameter of 2.8 +/- 0.1 nm. Digestive ripening of the as-prepared Pd colloid, a process involving refluxing the as-prepared colloid at or near the boiling point of the solvent in the presence of a passivating agent, dodecanethiol resulted in a previously reported Pd-thiolate cluster, Pd(SC12H25)(2)](6) but did not render the expected narrowing down of the particle size distribution. Solventless thermolysis of the Pd-thiolate complex resulted in various Pd systems such as Pd(0), PdS, and Pd@PdO core-shell nanoparticles thus demonstrating its versatility. These I'd nanostructures have been characterized using high-resolution electron microscopy and powder X-ray diffraction methods. (C) 2010 Elsevier Inc. All rights reserved.

Jauheiden erottuminen

Partikkelisysteemien segregaatio eli erottuminen on ilmiö, jossa tasalaatuisen jauheseoksen komponenteilla on taipumus erota toisistaan. Jauheen erottumistaipumus riippuu partikkelien ominaisuuksista, ympäröivistä olosuhteista ja partikkelien välisistä vuorovaikutuksista. Segregaatiomekanismeja on esitetty kirjallisuudessa valtava määrä ja pienetkin erot partikkelien välisissä ominaisuuksissa ja vuorovaikutuksissa voivat johtaa täysin eri segregaatiomekanismeihin. Segregaatioilmiö on lääketeollisuuden näkökulmasta hyvin keskeinen, eikä sitä tunneta vielä riittävän hyvin, jotta siltä osattaisiin systemaattisesti välttyä. Nykyinen segregaatiotutkimus perustuu suurelta osin yrityksen ja erehdyksen kautta tapahtuvaan oppimiseen. Todellisen segregaatioilmiön ymmärtämiseen tarvittaisiin innovatiivisia tutkimusmenetelmiä. Kokeellisen osan tarkoituksena oli kehittää ja perustestata menetelmä, jolla voidaan tutkia erilaisten partikkelisysteemien erottumiskäyttäytymistä, ja käyttää tätä menetelmää farmaseuttisten rae- ja pellettiseosten segregaation tutkimiseen. Tavoitteena oli todistaa kehitetyn Babel-laitteen toimintaperiaatteen soveltuvuus partikkelisysteemien erottumiskäyttäytymisen tutkimiseen, mutta suoritetut kokeet olivat lähinnä menetelmän ja laitteen testausta. Ongelmiksi muodostuivat Babel-laitteen asettamat rajoitukset, partikkelien sähköistyminen ja partikkelien väliset vuorovaikutukset. Käytetyt suoraviivaiset lähestymistavat eivät riittäneet segregaation aiheuttamiseen Babel-laitteella. Vertikaalisen ravistelun seurauksena syntynyt konvektiopyörre esti segregaation syntymisen. Johtopäätöksenä voidaan sanoa, että Babel-laite mittaa hyvin ja toistettavasti sekä se kykenee erottamaan erikokoiset partikkelit ja erilaiset kokojakaumat toisistaan. Laitteen kehittämistavoitteena olisi saada segregaatio paremmin näkyviin jauheseoksissa ravistelun seurauksena. Tällöin voitaisiin tehdä päätelmiä jauheseoksen erottumistaipumuksesta ja systeemissä vallitsevista erottumismekanismeista. Laitteen ja menetelmän jatkokehittäminen voisi tuottaa hyödyllistä lisätietoa, mikä edesauttaisi segregaation ymmärtämistä ilmiönä entistä paremmin

Effect of water vapour stabilization of raw materials on the quality of the inhalation product

Generation of raw materials for dry powder inhalers by different size reduction methods can be expected to influence physical and chemical properties of the powders. This can cause differences in particle size, size distribution, shape, crystalline properties, surface texture and energy. These physical properties of powders influence the behaviour of particles before and after inhalation. Materials with an amorphous surface have different surface energy compared to materials with crystalline surface. This can affect the adhesion and cohesion of particles. Changes in the surface nature of the drug particles results in a change in product performance. By stabilization of the raw materials the amorphous surfaces are converted into crystalline surfaces. The primary aim of the study was to investigate the influence of the surface properties of the inhalation particles on the quality of the product. The quality of the inhalation product is evaluated by measuring the fine particle dose (FPD). FDP is the total dose of particles with aerodynamic diameters smaller than 5,0 μm. The secondary aim of this study was to achieve the target level of the FPD and the stability of the FPD. This study was also used to evaluate the importance of the stabilization of the inhalation powders. The study included manufacturing and analysing drug substance 200 μg/dose inhalation powder batches using non-stabilized or stabilized raw materials. The inhaler formulation consisted of micronized drug substance, lactose <100μm and micronized lactose <10μm. The inhaler device was Easyhaler®. Stabilization of the raw materials was done in different relative humidity, temperature and time. Surface properties of the raw materials were studied by dynamic vapour sorption, scanning electron microscopy and three-point nitrogen adsorption technique. Particle size was studied by laser diffraction particle size analyzer. Aerodynamic particle size distribution from inhalers was measured by new generation impactor. Stabilization of all three raw materials was successful. A clear difference between nonstabilized and stabilized raw materials was achieved for drug substance and lactose <10μm. However for lactose <100μm the difference wasn’t as clear as wanted. The surface of the non-stabilized drug substance was more irregular and the particles had more roughness on the surface compared to the stabilized drug substances particles surface. The surface of the stabilized drug particles was more regular and smoother than non-stabilized. Even though a good difference between stabilized and non-stabilized raw materials was achieved, a clear evidence of the effect of the surface properties of the inhalation particles on the quality of the product was not observed. Stabilization of the raw materials didn’t lead to a higher FPD. Possible explanations for the unexpected result might be too rough conditions in the stabilization of the drug substance or smaller than wanted difference in the degree of stabilization of the main component of the product <100μm. Despite positive effects on the quality of the product were not seen there appears to be some evidence that stabilized drug substance results in smaller particle size of dry powder inhalers.

Photocatalytic treatment of municipal wastewater using modified neodymium doped TiO2 hybrid nanoparticles

Photocatalytic degradation of municipal wastewater was investigated using reagent grade TiO2 and modified neodymium doped TiO2 hybrid nanoparticles. For the first time, surface modification of Nd3+ doped TiO2 hybrid nanoparticles were carried out with n-butylamine as surface modifier under mild hydrothermal conditions. The modified nanoparticles obtained were characterized by Powder XRD, FTIR, DLS, TEM, BET surface area, zeta potential and UV-Vis Spectroscopy. The characterization results indicated better morphology, particle size distribution and low agglomeration of the nanoparticles synthesized. It was found that photodegradation of wastewater using surface modified neodymium doped TiO2 nanoparticles was more compared to pure TiO2, which can be attributed to the doping and modification with n-butylamine.

Interfacial Phenomena in Pharmaceutical Low Moisture Content Powder Processing

Powders are essential materials in the pharmaceutical industry, being involved in majority of all drug manufacturing. Powder flow and particle size are central particle properties addressed by means of particle engineering. The aim of the thesis was to gain knowledge on powder processing with restricted liquid addition, with a primary focus on particle coating and early granule growth. Furthermore, characterisation of this kind of processes was performed. A thin coating layer of hydroxypropyl methylcellulose was applied on individual particles of ibuprofen in a fluidised bed top-spray process. The polymeric coating improved the flow properties of the powder. The improvement was strongly related to relative humidity, which can be seen as an indicator of a change in surface hydrophilicity caused by the coating. The ibuprofen used in the present study had a d50 of 40 μm and thus belongs to the Geldart group C powders, which can be considered as challenging materials in top-spray coating processes. Ibuprofen was similarly coated using a novel ultrasound-assisted coating method. The results were in line with those obtained from powders coated in the fluidised bed process mentioned above. It was found that the ultrasound-assisted method was capable of coating single particles with a simple and robust setup. Granule growth in a fluidised bed process was inhibited by feeding the liquid in pulses. The results showed that the length of the pulsing cycles is of importance, and can be used to adjust granule growth. Moreover, pulsed liquid feed was found to be of greater significance to granule growth in high inlet air relative humidity. Liquid feed pulsing can thus be used as a tool in particle size targeting in fluidised bed processes and in compensating for changes in relative humidity of the inlet air. The nozzle function of a two-fluid external mixing pneumatic nozzle, typical for small scale pharmaceutical fluidised bed processes, was studied in situ in an ongoing fluidised bed process with particle tracking velocimetry. It was found that the liquid droplets undergo coalescence as they proceed away from the nozzle head. The coalescence was expected to increase droplet speed, which was confirmed in the study. The spray turbulence was studied, and the results showed turbulence caused by the event of atomisation and by the oppositely directed fluidising air. It was concluded that particle tracking velocimetry is a suitable tool for in situ spray characterisation. The light transmission through dense particulate systems was found to carry information on particle size and packing density as expected based on the theory of light scattering by solids. It was possible to differentiate binary blends consisting of components with differences in optical properties. Light transmission showed potential as a rapid, simple and inexpensive tool in characterisation of particulate systems giving information on changes in particle systems, which could be utilised in basic process diagnostics.

Breakup of drops around the edges of Rushton turbine

A detailed experimental and simulation study has been carried out in the present work to understand drop breakup in regions around the edge of the Rushton turbine in agitated vessels. The effect of impeller speed, impeller size, interfacial tension, and the viscosities of the two phases is studied on drop breakup through their effect on dmax, the size of the largest drop in the system, and the whole size distribution. The measurements were carried out using Galai particle size analyser and optical microscope. Experimental analysis shows that the dmax, maximum stable drop diameter varies with impeller tip velocity to the power -1. The variation of dmax with interfacial tension is studied using different surfactants. The effect of viscosity ratio, achieved by changing the dispersed phase viscosity, on dmax is captured. For the same dmax values obtained from two different dispersed phases show that the wider drop size distribution is observed for higher dispersed phase viscosity.

Tuning the interfacial properties of supported metal nanoclusters

Nanoclusters are objects made up of several to thousands of atoms and form a transitional state of matter between single atoms and bulk materials. Due to their large surface-to-volume ratio, nanoclusters exhibit exciting and yet poorly studied size dependent properties. When deposited directly on bare metal surfaces, the interaction of the cluster with the substrate leads to alteration of the cluster properties, making it less or even non-functional. Surfaces modified with self-assembled monolayers (SAMs) were shown to form an interesting alternative platform, because of the possibility to control wettability by decreasing the surface reactivity and to add functionalities to pre-formed nanoclusters. In this thesis, the underlying size effects and the influence of the nanocluster environment are investigated. The emphasis is on the structural and magnetic properties of nanoclusters and their interaction with thiol SAMs. We report, for the first time, a ferromagnetic-like spin-glass behaviour of uncapped nanosized Au islands tens of nanometres in size. The flattening kinetics of the nanocluster deposition on thiol SAMs are shown to be mediated mainly by the thiol terminal group, as well as the deposition energy and the particle size distribution. On the other hand, a new mechanism for the penetration of the deposited nanoclusters through the monolayers is presented, which is fundamentally different from those reported for atom deposition on alkanethiols. The impinging cluster is shown to compress the thiol layer against the Au surface and subsequently intercalate at the thiol-Au interface. The compressed thiols try then to straighten and push the cluster away from the surface. Depending on the cluster size, this restoring force may or may not enable a covalent cluster-surface bond formation, giving rise to various cluster-surface binding patterns. Compression and straightening of the thiol molecules pinpoint the elastic nature of the SAMs, which has been investigated in this thesis using nanoindentation. The nanoindenation method has been applied to SAMs of varied tail groups, giving insight into the mechanical properties of thiol modified metal surfaces.

Characterization and evaluation of melibiose as novel excipient in tablet compaction

Lactose is probably the most used tablet excipient in the field of pharmacy. Although lactose is thoroughly characterized and available in many different forms there is a need to find a replacer for lactose as a filler/binder in tablet formulations because it has some downsides. Melibiose is a relatively unknown disaccharide that has not been thoroughly characterized and not previously used as an excipient in tablets. Structurally melibiose is close to lactose as it is also formed from the same two monosaccharides, glucose and galactose. Aim of this research is to characterize and to study physicochemical properties of melibiose. Also the potential of melibiose to be used as pharmaceutical tablet excipient, even as a substitute for lactose is evaluated. Current knowledge about fundamentals of tableting and methods for determinating of deformation behavior and tabletability are reviewed. In this research Raman spectroscopy, X-ray powder diffraction (XRPD), near-infrared spectroscopy (NIR) and Fourier-transform infrared spectroscopy (FT-IR) were used to study differences between two melibiose batches purchased from two suppliers. In NIR and FT-IR measurements no difference between materials could be observed. XPRD and Raman however found differences between the two melibiose batches. Also the effects of moisture content and heating to material properties were studied and moisture content of materials seems to cause some differences. Thermal analytical methods, differential scanning calorimetry (DSC) and thermogravimetry (TG) were used to study thermal behaviour of melibiose and difference between materials was found. Other melibiose batch contains residual water which evaporates at higher temperatures causing the differences in thermal behaviour. Scanning electron microscopy images were used to evaluate particle size, particle shape and morphology. Bulk, tapped and true densities and flow properties of melibiose was measured. Particle size of the melibiose batches are quite different resulting causing differences in the flowability. Instrumented tableting machine and compression simulator were used to evaluate tableting properties of melbiose compared to α-lactose monohydrate. Heckel analysis and strain-rate sensitivity index were used to determine deformation mechanism of melibiose monohydrate in relation to α–lactose monohydrate during compaction. Melibiose seems to have similar deformation behaviour than α-lactose monohydrate. Melibiose is most likely fragmenting material. Melibiose has better compactibility than α – lactose monohydrate as it produces tablets with higher tensile strength with similar compression pressures. More compression studies are however needed to confirm these results because limitations of this study.

Effect of microstructure and hardness on the grinding abrasive wear resistance of a ball bearing steel

Grinding media wear appears to be non-linear with the time of grinding in a laboratory-scale ball mill. The kinetics of wear can be expressed as a power law of the type w=atb, where the numerical constant a represents wear of a particular microstructure at time t = 1 min and b is the wear exponent which is independent of the particle size prevailing inside a ball mill at any instant of time of grinding. The wear exponent appears to be an indicator of the cutting wear mechanism in dry grinding: a plot of the inverse of the normalised wear exponent (Image ) versusHs (where Hs is the worn surface hardness of the media) yields a curve similar to that of a wear resistance plot obtained in the case of two-body sliding abrasive wear. This method of evaluating the cutting wear resistance of media is demonstrated by employing 15 different microstructures of AISI-SAE 52100 steel balls in dry grinding of quartz in a laboratory-scale ball mill.

Metal-Insulator Transitions in Anion-Excess LaMnO3+? Controlled by the Mn4+ Content

LaMnO3+? samples with Mn4+ content up to 50% have been prepared by different methods. The structure of LaMnO3+? changes from orthorhombic to cubic (via rhombohedral) with increase in the Mn4+ content. LaMnO3+? samples containing greater than 20% Mn4+ are ferromagnetic and show resistivity maxima at a temperature Tt which is close to the ferromagnetic Curie temperature. The resistivity maximum is due to the occurrence of a metal-insulator transition. In samples heated to the same temperature, the value of Tt increases with % Mn4+. For a given sample, Tt increases with the temperature of heat treatment due to the increase in particle size. The onset of ferromagnetism in LaMnO3+? accompanied by an insulator-metal transition is similar to that found in La1-xCaxMnO3 and La1-xSrxCoO3.

Superconductivity in rapidly quenched metallic systems with nanoscale structure

Nanocomposites of Al?In, Al?Pb, and Zn?Pb have been prepared and characterized using rapid quenching techniques and the nature of superconducting transitions in them has been studied by resistivity measurements. The precipitated second phases (In and Pb) have particle sizes (d) of a few tens of nanometers such that ?0?d?dmin, where ?0 is the superconducting zero temperature coherence length and dmin is the minimum particle size that supports superconductivity. The onset of superconductivity generally starts in samples with d??0 and progressively other grains with d??0 become superconducting. We suggest that the proximity effect of the matrix plays a significant role. In an Al?In system, even with 40?wt.% In, the zero resistivity state is obtained at T?1.33 times the Tc of Al. But in Al?Pb and Zn?Pb, the zero resistivity state is obtained at T?4 and 5 times the Tc of Al and Zn with only 10�15 wt?% Pb, respectively.

CoMn2O4 spinel from a MOF: synthesis, structure and magnetic studies

A hydrothermal reaction of Mn(OAc)(2)center dot 4H(2)O, Co(OAc)(2)center dot 4H(2)O and 1,2,4 benzenetricarboxylic acid at 220 degrees C for 24 h gives rise to a mixed metal MOF compound, CoMn2(C6H3(COO)(3))(2)], I. The structure is formed by the connectivity between octahedral CoO6 and trigonal prism MnO6 units connected through their vertices forming a Kagome layer, which are pillared by the trimellitate. Magnetic susceptibility studies on the MOF compound indicate a canted anti-ferromagnetic behavior, due to the large antisymmetric DM interaction between the M2+ ions (M = Mn, Co). Thermal decomposition studies indicate that the MOF compound forms a tetragonal mixed-metal spinel phase, CoMn2O4, with particle sizes in the nano regime at 400 degrees C. The particle size of the CoMn2O4 can be controlled by varying the decomposition temperature of the parent MOF compound. Magnetic studies of the CoMn2O4 compound suggests that the coercivity and the ferrimagnetic ordering temperatures are dependent on the particle size.