In powder metallurgy research field, Direct Metal Laser Sintering (DMLS) and Metal Powder Starch Consolidation (MPSC) are relatively new rapid forming techniques to fabricate complex and near net-shaped components. The working principles of DMLS are to melt and fuse metal powder layer by layer in computer controlled systems to pile up components like three dimensional printing. It has been for instance extensively used for mould inserts, die parts, and functional metal prototypes. Another, less explored method, starch consolidation is a pressureless direct casting method which consists principally of mixing powder slurry, casting into moulds, consolidation, drying, and sintering. With a strong focus on both methods, the study here combines several strong material technology sectors; powder, rapid forming, mechanical property testing and surface technology. It covers the processing chain from green body preparation, optimization of sintering, nitriding, post sinter heat treatment, to modeling and assessment of material behaviour for end-user applications. An iron based powder and a high vanadium high speed steel powder with low and high carbon contents were used in the DMLS and MPSC processes, respectively. The overall aim of the study is to synthesize near net-shaped powder-based components, to characterize pores and microstructure, and to establish a fundamental understanding of failure mechanisms of powder based materials in bending fatigue, thermal fatigue and wear. The study showed the DMLS and MPSC technologies could produce shaped components with a multi-phased structure, controllable nitriding depth and high relative densities in a range of 97 - 99.7 %. Materials' heterogeneity and porosity have detrimental influence on mechanical properties, especially on crack initiation and subsequent propagation.

An ionic liquid (IL) is a salt, which usually is in the liquid state at normal temperature and pressure. The properties of ILs can be adjusted for various processes and applications by choosing different combinations of ions. Similar to other salts, ILs contain only ions with positive (cations) and negative (anions) charges in equal proportions. However, to prevent solidification, ions in ionic liquids usually contain bulky organic chemical groups, which, apart from electrostatic interactions, promote other types of interactions between ions, such as: (i) van-der-Waals interactions; (ii) hydrogen bonding; (iii) - stacking, etc., depending on the particular chemical structure of the ions. All these interactions, in combination, may lead to formation of specific microstructures in ILs, which may vary with temperature caused by changing thermal rotational and translational energies of the ions. Ions in these microstructures may have preferential orientations relative to each other, maintain anisotropic properties similar to those in liquid crystals or, in some specific cases, may even separate into microscopically organised liquid phases. Therefore, the dynamics of ILs may also be dependent on their microstructure. In many practical applications ionic liquids are placed on surfaces or in confinements. Solid surfaces introduce extra forces, which may be specific to the charge of the ions or/and to functional groups in the ILs. The geometry and interactions of ions in confinements or/and pores of materials may also disrupt specific bulk microstructures of ILs. Both confinement effects and interactions of ions with surfaces are manifested in the translational dynamics of the ions. One of the most direct and informative methods to study translational dynamics of ILs is pulse-field-gradient nuclear magnetic resonance (PFG-NMR).In this thesis the results of PFG-NMR studies on a few classes of ILs are reported: (i) the historically “standard” (since Walden’s discovery in 1914) ionic liquid, the ethylammonium nitrate (EAN) and (ii) halogen-free orthoborate-based phosphonium, imidazolium and pyrrolidinium ILs with varied structure and lengths of alkyl chains in cations, and varied structures of orthoborate anions. These ILs were studied in bulk at different temperatures, and also in confinements, such as between parallel glass and Teflon plates and in mesoporous Vycor glass. It was found that diffusion coefficients of cations and anions in EAN, phosphonium and pyrrolidinium orthoborate ILs in bulk are different, but according to the standard Stocks-Einstein model, they correspond to diffusion of ions in homogeneous liquids. A change in the chemical structure of one of the ions results in a change in both the diffusion coefficient of the oppositely charged ion and the activation energy of diffusion for both ions in an IL. Similar effects were observed from the chemical shifts and diffusion coefficients measured by NMR for imidazolium orthoborate ILs dissolved in polyethylene glycol solutions, in which imidazolium cations strongly interact with PEG molecules, further affecting the diffusion of orthoborate anions via electrostatic interactions. A liquid-liquid phase separation was suggested for a few phosphonium and pyrrolidinium bis(mandelato)borate ILs, in which a divergence of diffusion coefficients and activation energies of diffusion for cations and anions was detected at temperatures below ca 50 °C. In addition, a free-volume theory was invoked to explain the dependences of density of ILs on the alkyl chain length in cations.It was also found that for a phosphonium bis(salicylato)borate IL confined in 4 nm mesoporous Vycor glass the diffusion coefficients of ions increase by a factor of 35! This phenomenon was explained by the dynamic heterogeneity of this IL in micropores and empty voids of the Vycor glass. For EAN IL in confinements between glass and Teflon plates, the diffusion of ethylammonium cations and nitrate anions is significantly anisotropic, i.e. slower in the direction of the normal to the plates and faster along the plates compared to diffusion of the ions in bulk. A plausible explanation of this PFG NMR data is that EAN forms layers near polar and non-polar solid surfaces. A similar phenomenon, to a lesser extent, was also observed for phosphonium cations of bis(mandelato)borate, bis(salicylato)borate and bis(oxalato)borate confined between glass plates. The results of these studies may have implications in modeling tribological performance, i.e., friction and wear reduction for contact pairs of different materials lubricated by various classes of ionic liquids. / För godkännande; 2016; 20160420 (andfil)

<p>Combination of the Calphad method and theoretical calculations provides new possibilities for the study of materials science. This work is a part of the efforts within the CCT project (Centre of Computational Thermodynamics) to combine these methods to facilitate modeling and to extend the thermodynamic databases with critically assessed volume data. In this work, the theoretical calculations refer to first-principles and Debye-Grüneisen calculations. The first-principles (i.e. ab initio) electronic structure calculations, based on the Density- Functional Theory (DFT), are capable of predicting various physical properties at 0 K, such as formation energy, volume and bulk modulus. The ab initio simulation software, VASP, was used to calculate the binding curves (i.e. equation of state at 0 K) of metallic elements, cubic carbides and nitrides. From the binding curves, the equilibrium volumes at 0 K were calculated for several metastable structures as well as stable structures. The vibrational contribution to the free energy was calculated using the Debye-Grüneisen model combined with first-principles calculations. Two different approximations for the Grüneisen parameter, γ, were used in the Debye-Grüneisen model, i.e. Slater’s and Dugdale-MacDonald’s expressions. The thermal electronic contribution was evaluated from the calculated electronic density of states. The calculated thermal expansivities for metallic elements, cubic carbides and nitrides were compared with Calphad assessments. It was found that the experimental data are within the limits of the calculations using the two approximations for γ. By fitting experimental heat capacity and thermal expansivity around Debye temperatures, we obtained optimal Poisson’s ratio values and used them to evaluate Young’s and Shear moduli. In order to reach a reasonable agreement with the experiments, it is necessary to use the logarithmic averaged mass of the constitutional atoms. The agreements between the calculations and experiments are generally better for bulk modulus and Young’s modulus than that for shear modulus. A new model describing thermodynamic properties at high pressures was implemented in Thermo-Calc. The model is based on an empirical relation between volume and isothermal bulk modulus. Pure Fe and solid MgO were assessed using this model. Solution phases will be considered in a future work to check the model for compositional dependence.</p>

<p>Mechanical property and thermal stability of Zr-Si-N films of varying silicon contents deposited on Al₂O₃ (0001) substrates are characterized. All films provided for characterization were deposited by reactive DC magnetron sputter deposition technique from elemental Zr and Si targets in a N₂/Ar plasma at 800 ^oC. The hardness and microstructures of the as deposited films and post-annealed films up to 1100 ^oC are evaluated by means of nanoindentation, X-ray diffractometry and transmission electron microscopy. The Zr-Si-N films with 9.4 at.% Si exhibit hardness as high as 34 GPa and a strong (002) texture within which vertically elongated ZrN crystallites are embedded in a Si₃N₄ matrix. The hardness of these two dimensional nanocomposite films remains stable up to 1000 ^oC annealing temperatures which is in contrast to ZrN films where hardness degradation occurs already above 800 ^oC. The enhanced thermal stability is attributed to the presence of Si₃N₄ grain boundaries which act as efficient barriers to hinder the oxygen diffusion. X-ray amorphous or nanocrystalline structures are observed in Zr-Si-N films with silicon contents > 13.4 at.%. After the annealing treatments, crystalline phases such as ZrSi₂, ZrO₂ and Zr₂O are formed above 1000 ^oC in the Si-containing films while only zirconia crystallites are observed at 800 ^oC in pure ZrN films because oxygen acts as artifacts in the vacuum furnace. The structural, compositional and hardness comparison of as-deposited and annealed films reveal that the addition of silicon enhances the thermal stability compared to pure ZrN films and the hardness degradation stems from the formation of oxides at elevated temperatures.</p>

Combination of the Calphad method and theoretical calculations provides new possibilities for the study of materials science. This work is a part of the efforts within the CCT project (Centre of Computational Thermodynamics) to combine these methods to facilitate modeling and to extend the thermodynamic databases with critically assessed volume data. In this work, the theoretical calculations refer to first-principles and Debye-Grüneisen calculations. The first-principles (i.e. ab initio) electronic structure calculations, based on the Density- Functional Theory (DFT), are capable of predicting various physical properties at 0 K, such as formation energy, volume and bulk modulus. The ab initio simulation software, VASP, was used to calculate the binding curves (i.e. equation of state at 0 K) of metallic elements, cubic carbides and nitrides. From the binding curves, the equilibrium volumes at 0 K were calculated for several metastable structures as well as stable structures. The vibrational contribution to the free energy was calculated using the Debye-Grüneisen model combined with first-principles calculations. Two different approximations for the Grüneisen parameter, γ, were used in the Debye-Grüneisen model, i.e. Slater’s and Dugdale-MacDonald’s expressions. The thermal electronic contribution was evaluated from the calculated electronic density of states. The calculated thermal expansivities for metallic elements, cubic carbides and nitrides were compared with Calphad assessments. It was found that the experimental data are within the limits of the calculations using the two approximations for γ. By fitting experimental heat capacity and thermal expansivity around Debye temperatures, we obtained optimal Poisson’s ratio values and used them to evaluate Young’s and Shear moduli. In order to reach a reasonable agreement with the experiments, it is necessary to use the logarithmic averaged mass of the constitutional atoms. The agreements between the calculations and experiments are generally better for bulk modulus and Young’s modulus than that for shear modulus. A new model describing thermodynamic properties at high pressures was implemented in Thermo-Calc. The model is based on an empirical relation between volume and isothermal bulk modulus. Pure Fe and solid MgO were assessed using this model. Solution phases will be considered in a future work to check the model for compositional dependence.

Alumino-silicate systems are of great interest for materials scientists and geochemists. Thermodynamic knowledge of these systems is useful in steel and ceramic industries, and for understanding geochemical processes. A popular and efficient approach used to obtain a self-consistent thermodynamic dataset is called CALPHAD. It couples phase diagram information and thermochemical data with the assistance of computer models. The CALPHAD approach is applied in this thesis to the thermodynamic modelling and assessments of the CaO-Al2O3-SiO2, MgO-Al2O3-SiO2 and Y2O3-Al2O3-SiO2 systems and their subsystems. The compound energy formalism is used for all the solution phases including mullite, YAM, spinel and halite. In particular, the ionic two sub-lattice model is applied to the liquid solution phase. Based both on recent experimental investigations and theoretical studies, a new species, AlO2-1, is introduced to model liquid Al2O3. Thus, the liquid model corresponding for a ternary Al2O3-SiO2-M2Om system has the formula (Al+3,M+m)P (AlO2-1,O-2, SiO4-4,SiO20)Q, where M+m stands for Ca+2, Mg+2 or Y+3. This model overcomes the long-existing difficulty of suppressing the liquid miscibility gap in the ternary systems originating from the Al2O3-free side during the assessments. All the available and updated experimental information in these systems are critically evaluated and finally a self-consistent thermodynamic dataset is achieved. The database can be used along with software for Gibbs energy minimization to calculate any type of phase diagram and all thermodynamic properties. Various phase diagrams, isothermal and isoplethal sections, and thermochemical properties are presented and compared with the experimental data. Model calculated site fractions of species are also discussed. All optimization processes and calculations are performed using the Thermo-Calc software package. / QC 20100607

In this thesis, the focus has been on micro-mechanical mechanisms in polymer-based materials and structures. The first part of the thesis treats length-scale effects on polymer materials. Experiments have showed that the smaller the specimen, the stronger is the material. The length-scale effect was examined experimentally in two different polymers materials, polystyrene and epoxy. First micro-indentations to various depths were made on polystyrene. The experiments showed that length-scale effects in inelastic deformations exist in polystyrene. It was also possible to show a connection between the experimental findings and the molecular length. The second experimental study was performed on glass-sphere filled epoxy, where the damage development for tensile loading was investigated. It could be showed that the debond stresses increased with decreasing sphere diameter. The debonding grew along the interface and eventually these cracks kinked out into the matrix. It was found that the length to diameter ratio of the matrix cracks increased with increasing diameter. The experimental findings may be explained by a length-scale effect in the yield process which depends on the strain gradients. The second part of the thesis treats mechano-sorptive creep in paper, i.e. the acceleration of creep by moisture content changes. Paper can be seen as a polymer based composite that consists of a network of wood fibres, which in its turn are natural polymer composites. A simplified network model for mechano-sorptive creep has been developed. It is assumed that the anisotropic hygroexpansion of the fibres leads to large stresses at the fibre-fibre bonds when the moisture content changes. The resulting stress state will accelerate creep if the fibre material obeys a constitutive law that is non-linear in stress. Fibre kinks are included in order to capture experimental observations of larger mechano-sorptive creep effects in compression than in tension. Furthermore, moisture dependent material parameters and anisotropy are taken into account. Theoretical predictions based on the developed model are compared to experimental results for anisotropic paper both under tensile and compressive loading at varying moisture content. The important features in the experiments are captured by the model. Different kinds of drying conditions have also been examined. / QC 20100910

The work presented in this thesis deals with optical studies of semiconductor quantum dots (QDs) in the InGaAs material system. It is shown that for self-assembled InAs QDs, the interaction with the surrounding GaAs barrier and the InAs wetting layer (WL) in particular, has a very large impact on their optical properties. The ability to control the charge state of individual QDs is demonstrated and attributed to a modulation in the carrier transport dynamics in the WL. After photo-excitation of carriers (electrons and holes) in the barrier, they will migrate in the sample and with a certain probability become captured into a QD. During this migration, the carriers can be affected by exerting them to an external magnetic field or by altering the temperature. An external magnetic field applied perpendicular to the carrier transport direction will lead to a decrease in the carrier drift velocity since their trajectories are bent, and at sufficiently high field strength become circular. In turn, this decreases the probability for the carriers to reach the QD since the probability for the carriers to get trapped in WL localizing potentials increases. An elevated temperature leads to an increased escape rate out of these potentials and again increases the flow of carriers towards the QD. These effects have significantly different strengths for electrons and holes due to the large difference in their respective masses and therefore it constitutes a way to control the supply of charges to the QD. Another effect of the different capture probabilities for electrons and holes into a QD that is explored is the ability to achieve spin polarization of the neutral exciton (X0). It has been concluded frequently in the literature that X0 cannot maintain its spin without application of an external magnetic field, due to the anisotropic electron – hole exchange interaction (AEI). In our studies, we show that at certain excitation conditions, the AEI can be by-passed since an electron is captured faster than a hole into a QD. The result is that the electron will populate the QD solely for a certain time window, before the hole is captured. During this time window and at polarized excitation, which creates spin polarized carriers, the electron can polarize the QD nuclei. In this way, a nuclear magnetic field is built up with a magnitude as high as ~ 1.5 T. This field will stabilize the X0 spin in a similar manner as an external magnetic field would. The build-up time for this nuclear field was determined to be ~ 10 ms and the polarization degree achieved for X0 is ~ 60 %. In contrast to the case of X0, the AEI is naturally cancelled for the negatively charged exciton (X-) and the positively charged exciton (X+) complexes. This is due to the fact that the electron (hole) spin is paired off in case of X- (X+).  Accordingly, an even higher polarization degree (~ 73 %) is measured for the positively charged exciton. In a different study, pyramidal QD structures were employed. In contrast to fabrication of self-assembled QDs, the position of QDs can be controlled in these samples as they are grown in inverted pyramids that are etched into a substrate. After sample processing, the result is free-standing AlGaAs pyramids with InGaAs QDs inside. Due to the pyramidal shape of these structures, the light extraction is considerably enhanced which opens up possibilities to study processes un-resolvable in self-assembled QDs. This has allowed studies of Auger-like shake-up processes of holes in single QDs. Normally, after radiative recombination of X+, the QD is populated with a ground state hole. However, at recombination, a fraction of the energy can be transferred to the hole so that it afterwards occupies an excited state instead. This process is detected experimentally as a red-shifted luminescence satellite peak with an intensity on the order of ~ 1/1000 of the main X+ peak intensity. The identification of the satellite peak is based on its intensity correlation with the X+ peak, photoluminescence excitation measurements and on magnetic field measurements. / Arbetet som presenteras i denna avhandling rör studier av kvantprickars optiska egenskaper. En kvantprick är en halvledarkristall som endast är några tiotals nanometer stor. Den ligger oftast inbäddad inuti en större kristall av ett annat halvledarmaterial och pga. den begränsade storleken får en kvantprick mycket speciella egenskaper. Bland annat så kommer elektronerna i en kvantprick endast att kunna anta vissa diskreta energinivåer liknande situationen för elektronerna i en atom. Följaktligen kallas kvantprickar ofta för artificiella atomer. För halvledarmaterial gäller det generellt att det inte endast är fria elektroner i ledningsbandet, som kan leda ström utan även tomma elektrontillstånd i valens­bandet, vilka uppträder som positivt laddade partiklar, kan leda ström. Dessa kallas kort och gott för hål. I en kvantprick har hålen såsom elektronerna helt diskreta energinivåer. Precis som är fallet i en atom, så kommer elektroniska övergångar mellan olika energi­nivåer i en kvantprick att resultera i att ljus emitteras. Energin (dvs. våglängden alt. färgen) för detta ljus bestäms av hur energinivåerna i kvant­pricken ligger, för elektronerna och hålen, och genom att analysera ljuset kan man således studera kvantprickens egenskaper. Studierna i den här avhandlingen visar att växelverkan mellan en kvantprick och den omgivande kristallen, som den ligger inbäddad i, har stor inverkan på kvantprickens optiska egenskaper. T.ex. visas att man kan kontrollera antalet elektroner, som kommer att finnas i kvantpricken genom att modifiera hur elektronerna kan röra sig i omgivningen. Dessa rörelser modifieras här genom att variera temperaturen och genom att lägga på ett magnetiskt fält. Ett magnetiskt fält, vinkelrätt mot en elektrons rörelse, kommer att böja av dess bana och dess chans att nå fram till kvantpricken kan således minskas. Elektronen kan då istället fastna i andra potentialgropar i kvantprickens närhet. Genom att öka temperaturen, vilket ger elektronerna större energi, kan deras chans att nå fram till kvantpricken å andra sidan öka. En annan effekt, som studerats, är möjligheten att kontrollera spinnet hos elektronerna i en kvantprick. Även i dessa studier visar det sig att växelverkan med omgivningen spelar stor roll och kan användas till att kontrollera elektronens spin. Mekanismen som föreslås är att om elektronerna hinner före hålen till kvantpricken, så hinner de överföra sitt spin till atomkärnorna i kvantpricken. På detta sätt kan man få atomkärnornas spin polariserat, vilket resulterar i ett inbyggt magnetfält, i storleksordningen 1.5 Tesla, som i sin tur hjälper till att upprätthålla en hög grad av spinpolarisering även hos elektronerna. För att få elektronerna att hinna först, måste deras rörelser i omgivningen kontrolleras. I en ytterligare studie undersöktes den process där en elektronisk övergång i kvantpricken inte enbart resulterar i emission av ljus, utan även i att en annan partikel tar över en del av energin och blir exciterad. Dessa processer avspeglas i att en del av det ljus som emitteras har lägre energi. Detta ljus är också mycket svagt, ca 1000 ggr lägre intensitet, och möjligheten att kunna mäta detta är helt beroende på hur ljusstarka kvantprickarna är. De prover som använts i denna studie består av pyramidstrukturer, ca 7.5 mikrometer stora, med kvantprickar inuti. Denna geometri ger ca 1000 ggr bättre ljusutbyte jämfört med traditionella strukturer, vilket möjliggjort studien.

Mechanical property and thermal stability of Zr-Si-N films of varying silicon contents deposited on Al2O3 (0001) substrates are characterized. All films provided for characterization were deposited by reactive DC magnetron sputter deposition technique from elemental Zr and Si targets in a N2/Ar plasma at 800 oC. The hardness and microstructures of the as deposited films and post-annealed films up to 1100 oC are evaluated by means of nanoindentation, X-ray diffractometry and transmission electron microscopy. The Zr-Si-N films with 9.4 at.% Si exhibit hardness as high as 34 GPa and a strong (002) texture within which vertically elongated ZrN crystallites are embedded in a Si3N4 matrix. The hardness of these two dimensional nanocomposite films remains stable up to 1000 oC annealing temperatures which is in contrast to ZrN films where hardness degradation occurs already above 800 oC. The enhanced thermal stability is attributed to the presence of Si3N4 grain boundaries which act as efficient barriers to hinder the oxygen diffusion. X-ray amorphous or nanocrystalline structures are observed in Zr-Si-N films with silicon contents &gt; 13.4 at.%. After the annealing treatments, crystalline phases such as ZrSi2, ZrO2 and Zr2O are formed above 1000 oC in the Si-containing films while only zirconia crystallites are observed at 800 oC in pure ZrN films because oxygen acts as artifacts in the vacuum furnace. The structural, compositional and hardness comparison of as-deposited and annealed films reveal that the addition of silicon enhances the thermal stability compared to pure ZrN films and the hardness degradation stems from the formation of oxides at elevated temperatures.

Ceramics are distinguished from metals and polymers by their inorganic nature and lack of metallic properties. They can be highly crystalline to amorphous, and their physical and chemical properties can vary widely. Ceramics can, for instance, be made to resemble the mineral phase in bone and are therefore an excellent substitute for damaged hard tissue. They can also be made porous, surface active, chemically inert, mechanically strong, optically transparent or biologically resorbable, and all these properties are of interest in the development of new materials intended for a wide variety of applications. In this thesis, the focus was on the development of different ceramics for use in the controlled release of drugs and ions. These concepts were developed to obtain improved therapeutic effects from orally administered opioid drugs, and to reduce the number of implant-related infections as well as to improve the stabilization of prosthetic implants in bone. Geopolymers were used to produce mechanically strong and chemically inert formulations intended for oral administration of opioids. The carriers were developed to allow controlled release of the drugs over several hours, in order to improve the therapeutic effect of the substances in patients with severe chronic pain. The requirement for a stable carrier is a key feature for these drugs, as the rapid release of the entire dose, due to mechanical or chemical damage to the carrier, could have lethal effects on the patient because of the narrow therapeutic window of opioids. It was found that it was possible to profoundly retard drug release and to achieve almost linear release profiles from mesoporous geopolymers when the aluminum/silicon ratio of the precursor particles and the curing temperature were tuned. Ceramic implant coatings were produced via a biomimetic mineralization process and used as carriers for various drugs or as an ion reservoir for local release at the site of the implant. The formation and characteristics of these coatings were examined before they were evaluated as potential drug carriers. It was demonstrated that these coatings were able to carry antibiotics, bisphosphonates and bone morphogenetic proteins to obtain a sustained local effect, as they were slowly released from the coatings. / <p>Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 710</p>