Browsing by master's degree program "Master's Programme in Materials Research"

Dendrite prevention can be achieved by manipulating the local chemical concentration gradient by ultrasound. An ultrasonic field, which generates acoustic streaming, can manipulate the ionic flux at the electrode surface by altering the local ion concentration gradient at said surface according to the streaming pattern. The pattern is determined by the ultrasonic field and the geometry of the sonication volume. The preventive action can be directed to an arbitrary point on the surface, or be swept across it to achieve a smoother electroplating. Dendritic growth is concentrated to areas of higher concentration gradient. This is because at the electrode surface both the electric and convective fluxes tend to zero. If the reduction of ions into their metallic form is fast enough, the metal layer growth rate is determined by the diffusive flux, which is determined by the ion concentration gradient and the diffusion constant of the ion in the electrolyte. In this study, tin was used as the transported ion instead of lithium for safety reasons. A custom-made battery mockup cell was constructed for the experiments. The anode was imaged with a usb microscope camera to determine the growth of the dendrites during the process. The electroplating current and piezo driving power were varied between 100 mA to 275 mA and 0 to 6.6 W, respectively. With piezo driving electrical power less than 10 W, it was possible to lower the maximum lengths of dendrites. Finite element method simulations were conducted to validate the hypothesis and experimental results. This ultrasonic method could be used to allow rechargeable, lightweight, high capacity lithium metal batteries. The piezos could be integrated into battery chargers.

Scanning probe microscopy (SPM), which includes atomic force microscopy (AFM), is an affordable and powerful tool for investigating surfaces. However, to ensure accuracy, a metrologically informed approach is required. In this thesis, a commercial Jupiter XR AFM was used for calibration experiments testing its reliability and accuracy. AFMs can further be improved by the use of active probes with added capabilities that allow for faster scanning speeds and other improvements. Efforts have been made to enable their broader use. At VTT MIKES, the commercial Jupiter XR AFM is being modified to use active probes capable of self-sensing and self-actuation. A simple AFM was first built as a test setup to better understand the probes and to split their integration into the Jupiter AFM into a step-by-step process where the mechanical, electronic, and software changes necessary could be separated into distinct parts. In this thesis, I describe experiments done to test the reliability of the commercial AFM, and the process of constructing and using the test setup AFM, after which I present some results obtained using them, and discuss the experiments and the integration process. Included is also an overview of metrology and some of the physics and other theory relevant to AFM, and a summary of the principles of AFM and its role in microscopy. This work is part of the MetExSPM project, which seeks to develop traceable high speed scanning probe microscopy, for example by achieving higher scanning speeds and larger scanning areas, while maintaining good resolution and metrologically traceable high accuracy. This will greatly increase the utility of SPMs, especially for industrial applications.

Omnidirectional microscopy (OM) is an emerging technology capable of enhancing the threedimensional (3D) microscopy widely applied in life sciences. In OM, precise position and orientation control are required for the sample. However, the current OM technology relies on destructive, mechanical methods to hold the samples, such as embedding samples in gel or attaching them to a needle to permit orientation control. A non-contacting alternative is the levitation of the sample. But, until now, the levitation methods have lacked orientation control. I enable omnidirectional access to the sample by introducing a method for acoustic levitation that provides precise orientation control. Such control around three axes of rotation permits imaging of the sample from any direction with a fixed camera and subsequent 3D shape reconstruction. The control of non-spherical particles is achieved using an asymmetric acoustic field created with a phase-controlled transducer array. The technology allows 3D imaging of delicate samples and their study in a time-lapse manner. I foresee that the described method is not only limited to microscopy and optical imaging, but is also compatible with automated sample handling, light-sheet microscopy, wall-less chemistry, and noncontacting tomography. I demonstrate the method by performing a surface reconstruction of three test samples and a biological sample. In addition, a simulation study and the levitation of test samples were used to characterize the levitation technique's performance. Both the shape reconstruction and orientation recovery were done by a computer vision based approach where the different images are stitched together. The results show the rotation stability and the wide angle range of the method.

Electroencephalography (EEG) is a non-invasive neurophysiological method for evaluating brain activity by measuring electrical potential at the scalp. The electrical potentials originate mainly from postsynaptic cortical currents created by neuronal activity. It is a valuable tool for both research and clinical practice. EEG can be used e.g. to diagnose epilepsy, focal brain disorders, brain death, and coma. Intermittent photic stimulation (IPS) is an important tool in clinical EEG. Healthcare professionals use it to induce epileptic activity in patients to help diagnose their conditions. In these tests, various IPS frequencies are used with eyes-closed, eyes-open, and eye-closure conditions. IPS test is listed in clinical practice guidelines in EEG globally, and it is mainly used to diagnose photosensitive epilepsy, i.e., to detect epilepsy-related abnormal sensitivity to flickering light. Magnetoencephalography (MEG) is a non-invasive neurophysiological method in which minute magnetic fields — produced by the same postsynaptic currents as in EEG — are measured with special superconductive sensors around the head. MEG is a valuable tool for research and clinical practice with increasing world-wide utilization. The main advantages of MEG over EEG are easier source modelling and higher resolution at cortical areas. IPS has not been introduced to MEG since the IPS stimulators used in EEG are not compatible with MEG. IPS in MEG could improve the analysis of IPS and provide better tools for diagnoses. Currently, data analysis of IPS is typically limited to healthcare professionals examining the visualization of the raw data while looking for induced epileptiform activites and lateralizing them. In this thesis, an MEG-compatible IPS stimulator is introduced and alternative ways of analyzing IPS data for both MEG and EEG are showcased. Although analysis methods were applied with decent signal-to-noise ratios, further research is needed—especially to compare responses between patients with epilepsy and healthy subjects.

The sub-λ/2 focusing, also known as super resolution, is widely studied in optics, but only few practical realizations are done in acoustics. In this contribution, I show a novel way to produce sub- λ/2 focusing in the acoustic realm. I used an oil-filled cylinder immersed in liquid to focus an incident plane wave into a line focus. Three different immersion liquids were tested: water, olive oil, and pure ethanol. In addition to the practical experiment, we conducted a series of finite element simulations, by courtesy of Joni Mäkinen, to compare to the experimental results.

Chiral assemblies of metal nanoparticles absorb and/or scatter left and right handed circularly polarized light with different intensities usually from the visible light spectral region. This difference in the absorption called circular dichroism (CD) and closely related anisotropy factor (g-factor), which is the CD spectrum normalized with the overall absorption, describe the optical activity of the chiral assemblies. The aim of this thesis was to study and optimize the different structural parameters affecting the g-factor of a chiral gold nanorod (AuNR) dimer to reach the highest possible value. The structure consisted of two AuNRs bound together with a DNA origami in a crossed fingers conformation. The properties studied were silver as a coating material of the AuNRs, the dimensions of the AuNRs, angle between the long axes of the AuNRs and the interparticle distance. The dimensions comparison was studied with different sized AuNRs, the angle was controlled by changing the DNA strands working as a bridge between the two bundles in the DNA origami and the distance between the AuNRs was controlled by the length of the thiol treated DNA strands used for the AuNR binding to the origami. The experiments showed that the best g-factor was achieved with 33×74 nm sized AuNRs with an angle of approximately 55° and an interparticle distance of 24nm. Optimized assembly made a notable increase in the g-factor from 0.05 to 0.12. This is a highest g-factor recorded in a AuNR dimer structure up to date and thus the assembly could be of great use in the chiral sensing field in the future.

Polysiloxanes are silicon-based polymers consisting of R2SiO repeating units. They are commonly used in many commercial applications, for example, as adhesives, additives, or waterproof coatings. This thesis concentrates on polysiloxanes used as optically clear adhesives, which are needed in display applications to, for instance, bond cover lenses to touch panel sensors. This kind of a material needs to have a high refractive index to match glass or plastic, and it has to be transparent and thermally stable. In addition, it must resist degradation and yellowing from UV exposure and humidity. Anionic ring-opening polymerization was used to synthesize optically transparent polysiloxanes with varying side-groups. These polymers exhibited high refractive index values, which were adjusted by changing the amount of phenyl group -containing monomers or with chain terminating agents. End-functionalization reactions were performed for the synthesized polymers to introduce methacrylate groups to the chain ends, which could later be used in crosslinking trials involving a photoinitiator. The results present an effective synthetic route for the ring-opening polymerization for transparent, high refractive index poly(dimethylsiloxane-co-diphenylsiloxane) and poly(methylphenylsiloxane) that could be used as adhesives after selective chain end functionalization and crosslinking reactions. The properties of the synthesized polysiloxanes were characterized with several different methods, such as size exclusion chromatography, rheology, and NMR spectroscopy. End functionalization reactions were performed for some of the synthesized polymers. These were then further characterized to verify the suitability of the reaction.

In this master’s thesis, linear zwitterionic poly(ethylene imine) methyl-carboxylates (l-PEI-MCs) were synthesized through a four-step synthesis. The synthesis started with the polymerization of 2-ethyl-2-oxazoline (EtOx) monomers into poly(2-ethyl-2-oxazoline) (PEtOx) homopolymers with polymerization degree of 50 and 100. Living cationic ring-opening polymerization (LCROP) enabled a good control over the molecular weights. Subsequently, the side chains of PEtOxs were cleaved off by acidic hydrolysis. This resulted in linear poly(ethylene imine)s (l-PEIs) bearing a secondary amine group in repeating units of the polymer chain. These amine units were then functionalized with methyl-carboxylate moieties by first introducing tert-butyl ester functionalities to l-PEI chains, and subsequently cleaving off the tert-butyl groups. The final polymer is a polyzwitterion, featuring both an anionic carboxylate and a cationic tertiary amine group within a single repeating unit. Polymers produced in each step were characterized via 1H-NMR and FT-IR spectroscopy and their thermal properties were analyzed by differential scanning calorimetry (DSC). The molecular weights and dispersities (Ð) of PEtOx polymers were additionally estimated by gel permeation chromatography (GPC). Via 1H-NMR, the degree of polymerization for PEtOxs and the hydrolysis degree for l-PEIs were determined. FT-IR gave a further insight into the structures of polymers, successfully confirming the ester functionality of modified l-PEI. The disappearance of the tert-butyl proton signal in 1H-NMR spectrum after deprotection verified the successful removal of tert-butyl groups, resulting in the final product with methyl-carboxylate functionalities. By DSC, different thermal transitions, i.e., glass transition (Tg), melting (Tm) and crystallization (Tc), were observed, and the effects of molar mass and polymer modifications on these transitions were being investigated. The state of the art explores the literature regarding synthesis and properties of poly(2-oxazoline)s (POx), poly(ethylene imine)s (PEIs), and polyzwitterions. The theory behind living cationic ring-opening polymerization of 2-oxazolines and acidic hydrolysis of POxs is described. Different post-polymerization modification strategies to functionalize PEIs are being discussed. In addition, possible applications for each of these polymer classes are shortly outlined.

In this thesis, thermoresponsive poly(N-acryloyl glycinamide-co-methacrylic acid) (P(NAGA-co-MAA)) microgels were synthesized via surfactant stabilized free radical precipitation polymerization. Also, PNAGA microgel was synthesized as reference. The upper critical solution temperature (UCST) behavior of the microgels was tuned by changing the molar ratio of the monomers in the copolymer. The phase transition behavior of the formed microgel particles were characterized with NMR spectroscopy, microcalorimetry, turbidimetry and light scattering. It was observed that both PNAGA and P(NAGA-co-MAA) microgels display UCST type temperature response. However, in neutral pH, the phase transition of the copolymer gels was prevented due to the deprotonated acid groups of MAA. Hence, all the measurements were made in pH 3, below the pKa of MAA. The phase transition became sharper when the amount of MAA repeating units was increased in the copolymer. Also, the phase transition temperature of the copolymer gels increased when the amount of MAA was increased. In addition to phase transition behavior studies, the reactivity ratios of the monomers were studied during polymerization to analyze the structure of the forming copolymer gels. It was concluded that, as the both monomers had similar reactivity rates, statistical random copolymer gels are formed.

Two different bio transfer standards (BTS), composed of fatty acid bilayers, NanoRuler and NanoStar were developed. NanoRuler consists of a nanometer scale staircase with eight steps that are 5 nm tall each and NanoStar is designed to have topological structure with sharp edge and three height planes 5 nm elevated with respect to each other. With NanoRuler nanometer vertical calibration from 5 nm to 40 nm is possible and NanoStar allows the evaluation of the instrument transfer function (ITF). Due to the soft nature of the standards, the topographical stability was researched. Thus, an investigation of the topographical stability of three NanoRulers and one NanoStar across 24 months was done by measuring the surface topography with a custom-built Scanning White Light Interferometer (SWLI). The BTS were measured over 100 times during the experiments and were stored in laboratory conditions. The step heights of the structures were calculated with a histogram method and the surface roughness of the samples was evaluated using the Sq parameter. The step height analysis method was compared to the standard method (ISO 5436-1) where applicable and no notable differences were found. In both roughness and step height data no linear or non-linear trends were found, and the step heights compared well with the literature values. For NanoRuler the step heights were 4.9 nm, 10.1 nm, 15.1 nm, 20.1 nm, 25 nm, 30.1 nm, 35.1 nm and 40.2 nm and the respective stabilities were 0.3 nm, 0.3 nm, 0.6 nm, 0.9 nm, 1.3 nm, 1.6 nm, 2.1 nm, and 2.5 nm. For NanoStar the step heights were -5.1 nm and 5.2 nm with stabilities 0.3 nm and 0.4 nm respectively. The NanoRuler had a surface roughness stability of 0.02 nm whereas NanoStar had a roughness stability of 0.01 nm. After 24 months both BTS types preserved their topographical structure and no issues with surface topographical stability were observed.