Use of fiber-reinforced composite framework and thermochromic pigment in maxillofacial prostheses

The purpose of this investigation was to evaluate the possibility to enhance certain qualities of facial prostheses. Polymethyl methacrylate is still being used as base mate¬rial or clip carrier material, but it is hard and heavy, and debonding of the silicone from the acrylic base material is a frequent problem. This thesis aims to evaluate the use of fiber-reinforced composite (FRC) as framework material for maxillofacial silicone prostheses. FRC has been used as reinforcement in removable and fixed partial dentures since the 1990s. This material is lightweight and can be fabricated to compress the margins of the prosthesis slightly, to keep it tightly against the skin during jaw movements and facial expressions. Additionally, the use of a thermochromic pigment, colorless in room temperature and red in a cold environment, was studied in order to evaluate the possibility of using this color changing pigment in facial prostheses to mimic the color change of facial skin in cold weather. The tensile bond strength between pre-impregnated, unidirectional FRC and maxillofacial silicone elastomer was studied. Three different bonding agents or primers were compared. Bond strength was improved by one of the primers and by roughening the surface. The effect of a skin compressing glass fiber-reinforced composite framework on facial skin blood flow was studied by using a face mask, constructed with a compression pad corresponding to the outer margin of a glass fiber-reinforced framework beam of a facial prosthesis. The skin blood flow of ten healthy volunteers, aged 23-25 years, was measured during touch, light, and moderate compression of the skin, by using laser Doppler imaging technique. None of the compressions showed any marked effects on local skin blood flow. There were no significant differences between blood flow during compression and at baseline. Maxillofacial silicone elastomer was colored intrinsically with conventional color pigments: a control group containing only conventional pigments was compared to two test groups with 0.2 wt% and 0.6 wt% thermochromic pigment added. The color of the material was measured with a spectrophotometer in room temperature and after storage in a freezer. The color stability of the maxillofacial silicone elastomer colored with thermo¬chromic pigment was evaluated by artificial aging. The color dif¬ference of the L* (lightness) and a* values (redness), comparing color after the samples were stored at room temperature and in a freezer (-19°C), was statistically significant for both 0.2 wt% and 0.6 wt% thermo¬chromic pigment groups. The differences in the b* values (yellowness) were statistically significant for the 0.6 wt% group. Exposure to ultraviolet (UV) radiation led to visually noticeable and statistically signifi¬cant color changes (ΔE) in all color values in both test groups. The specimens containing thermochromic pigment were very sensitive to UV radiation. In conclusion, a framework of fiber-reinforced composite can successfully be bonded to maxillofacial silicone elastomer, and a framework beam, compressing the facial skin, did not remarkably alter the skin blood flow on healthy, young adults. The thermochromic pigment showed color change in maxillofacial silicone elastomer. However, artificial aging showed that it was too sensitive to UV radiation to be used, as such, in maxillofacial prostheses.

Older consumers adopting information and communication technology: Evaluating opportunities for health care applications

The purpose of this dissertation is to analyse older consumers' adoption of information and communication technology innovations, assess the effect of aging related characteristic, and evaluate older consumers' willingness to apply these technologies in health care services. This topic is considered important, because the population in Finland (as in other welfare states) is aging and thus offers a possibility for marketers, but on the other hand threatens society with increasing costs for healthcare. Innovation adoption has been under research from several aspects in both organizational and consumer research. In the consumer behaviour, several theories have been developed to predict consumer responses to innovation. The present dissertation carefully reviews previous research and takes a closer look at the theory of planned behaviour, technology acceptance model and diffusion of innovations perspective. It is here suggested that there is a possibility that these theories can be combined and complemented to predict the adoption of ICT innovations among aging consumers, taking the aging related personal characteristics into account. In fact, there are very few studies that have concentrated on aging consumers in the innovation research, and thus there was a clear indent for the present research. ICT in the health care context has been studied mainly from the organizational point of view. If the technology is thus applied for the communication between the individual end-user and service provider, the end-user cannot be shrugged off. The present dissertation uses empirical evidence from a survey targeted to 55-79 year old people from one city in Southern-Carelia. The empirical analysis of the research model was mainly based on structural equation modelling that has been found very useful on estimating causal relationships. The tested models were targeted to predict the adoption stage of personal computers and mobile phones, and the adoption intention of future health services that apply these devices for communication. The present dissertation succeeded in modelling the adoption behaviour of mobile phones and PCs as well as adoption intentions of future services. Perceived health status and three components behind it (depression, functional ability, and cognitive ability) were found to influence perception of technology anxiety. Better health leads to less anxiety. The effect of age was assessed as a control variable, in order to evaluate its effect compared to health characteristics. Age influenced technology perceptions, but to lesser extent compared to health. The analyses suggest that the major determinant for current technology adoption is perceived behavioural control, and additionally technology anxiety that indirectly inhibit adoption through perceived control. When focusing on future service intentions, the key issue is perceived usefulness that needs to be highlighted when new services are launched. Besides usefulness, the perception of online service reliability is important and affects the intentions indirectly. To conclude older consumers' adoption behaviour is influenced by health status and age, but also by the perceptions of anxiety and behavioural control. On the other hand, launching new types of health services for aging consumers is possible after the service is perceived reliable and useful.

Mild Cognitive Impairment and Early Detection of Alzheimer`s Disease. A Positron Emission Tomography Study

Alzheimer`s disease (AD) is characterised neuropathologically by the presence of extracellular amyloid plaques, intraneuronal neurofibrillary tangles, and cerebral neuronal loss. The pathological changes in AD are believed to start even decades before clinical symptoms are detectable. AD gradually affects episodic memory, cognition, behaviour and the ability to perform everyday activities. Mild cognitive impairment (MCI) represents a transitional state between normal aging and dementia disorders, especially AD. The predictive accuracy of the current and commonly used MCI criteria devide this disorder into amnestic (aMCI) and non-amnestic (naMCI) MCI. It seems that many individuals with aMCI tend to convert to AD. However many MCI individuals will remain stable and some may even recover. At present, the principal drugs for the treatment of AD provide only symptomatic and palliative benefits. Safe and effective mechanism-based therapies are needed for this devastating neurodegenerative disease of later life. In conjunction with the development of new therapeutic drugs, tools for early detection of AD would be important. In future one of the challenges will be to detect at an early stage these MCI individuals who will convert to AD. Methods which can predict which MCI subjects will convert to AD will be much more important if the new drug candidates prove to have disease-arresting or even disease–slowing effects. These types of drugs are likely to have the best efficacy if administered in the early or even in the presymptomatic phase of the disease when the synaptic and neuronal loss has not become too widespread. There is no clinical method to determine with certainly which MCI individuals will progress to AD. However there are several methods which have been suggested as predictors of conversion to AD, e.g. increased [11C] PIB uptake, hippocampal atrophy in MRI, low CSF A beta 42 level, high CSF tau-protein level, apolipoprotein E (APOE) ε4 allele and impairment in episodic memory and executive functions. In the present study subjects with MCI appear to have significantly higher [¹¹C] PIB uptake vs healthy elderly in several brain areas including frontal cortex, the posterior cingulate, the parietal and lateral temporal cortices, putamen and caudate. Also results from this PET study indicate that over time, MCI subjects who display increased [¹¹C] PIB uptake appear to be significantly more likely to convert to AD than MCI subjects with negative [¹¹C] PIB retention. Also hippocampal atrophy seems to increase in MCI individuals clearly during the conversion to AD. In this study [¹¹C] PIB uptake increases early and changes relatively little during the AD process whereas there is progressive hippocampal atrophy during the disease. In addition to increased [¹¹C] PIB retention and hippocampal atrophy, the status of APOE ε4 allele might contribute to the conversion from MCI to AD.

Choosing the target loci : heat shock factors HSF1 and HSF2 as regulators of cell stress and development

Heat shock factors (HSFs) are an evolutionarily well conserved family of transcription factors that coordinate stress-induced gene expression and direct versatile physiological processes in eukaryote organisms. The essentiality of HSFs for cellular homeostasis has been well demonstrated, mainly through HSF1-induced transcription of heat shock protein (HSP) genes. HSFs are important regulators of many fundamental processes such as gametogenesis, metabolic control and aging, and are involved in pathological conditions including cancer progression and neurodegenerative diseases. In each of the HSF-mediated processes, however, the detailed mechanisms of HSF family members and their complete set of target genes have remained unknown. Recently, rapid advances in chromatin studies have enabled genome-wide characterization of protein binding sites in a high resolution and in an unbiased manner. In this PhD thesis, these novel methods that base on chromatin immunoprecipitation (ChIP) are utilized and the genome-wide target loci for HSF1 and HSF2 are identified in cellular stress responses and in developmental processes. The thesis and its original publications characterize the individual and shared target genes of HSF1 and HSF2, describe HSF1 as a potent transactivator, and discover HSF2 as an epigenetic regulator that coordinates gene expression throughout the cell cycle progression. In male gametogenesis, novel physiological functions for HSF1 and HSF2 are revealed and HSFs are demonstrated to control the expression of X- and Y-chromosomal multicopy genes in a silenced chromatin environment. In stressed human cells, HSF1 and HSF2 are shown to coordinate the expression of a wide variety of genes including genes for chaperone machinery, ubiquitin, regulators of cell cycle progression and signaling. These results highlight the importance of cell type and cell cycle phase in transcriptional responses, reveal the myriad of processes that are adjusted in a stressed cell and describe novel mechanisms that maintain transcriptional memory in mitotic cell division.

Methyl and ethyl chloride synthesis in microreactors

Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.

Weldability of high strength aluminium alloys

The need for reduced intrinsic weight of structures and vehicles in the transportation industry has made aluminium research of interest. Aluminium has properties that are favourable for structural engineering, including good strength-to-weight ratio, corrosion resistance and machinability. It can be easily recycled saving energy used in smelting as compared to steel. Its alloys can have ultimate tensile strength of up to 750 MPa, which is comparable to steel. Aluminium alloys are generally weldable, however welding of high strength alloys like the 7xxx series pose considerable challenges. This paper presents research on the weldability of high strength aluminium alloys, principally the 7xxx series. The weldability with various weld processes including MIG, TIG, and FSW, is discussed in addition to consideration of joint types, weld defects and recommendations for minimizing or preventing weld defects. Experimental research was carried out on 7025-T6 and AW-7020 alloys. Samples were welded, and weld cross sections utilized in weld metallurgy studies. Mechanical tests were carried out including hardness tests and tensile tests. In addition, testing was done for the presence of Al2O3 on exposed aluminium alloy. It was observed that at constant weld heat input using a pulsed MIG system, the welding speed had little or no effect on the weld hardness. However, the grain size increased as the filler wire feed rate, welding current and welding speed increased. High heat input resulted in lower hardness of the weld profile. Weld preheating was detrimental to AW- 7020 welds; however, artificial aging was beneficial. Acceptable welds were attained with pulsed MIG without the removal of the Al2O3 layer prior to welding. The Al2O3 oxide layer was found to have different compositions in different aluminium alloys. These findings contribute useful additional information to the knowledge base of aluminium welding. The application of the findings of this study in welding will help reduce weld cost and improve high strength aluminium structure productivity by removing the need for pre-weld cleaning. Better understanding of aluminium weld metallurgy equips weld engineers with information for better aluminium weld design.

Visualisointiympariston suunnittelu

Diplomityossa kartoitetaan Visualisointiympäristön rakentamiseen ja toteuttamiseen soveltuvia tekniikoita. Kartoituksen perusteella laadittiin lista tarvittavista komponenteista Visualisointiympäristön toteuttamiseksi Lappeenrannan teknillisen yliopiston konetekniikan osastolle mekatroniikan ja virtuaalisuunnittelun laboratoriolle. Työssä tarkastellaan keinotodellisuuden ulottuvuuksia ja esitellään sen hyödyntämismahdollisuuksia eri aloilla nyt ja tulevaisuudessa. Keinotodellisuuteen liittyvät tekniikat eri toteuttamistapoineen esitellaan käyttäen esimerkkeinä tällä hetkellä markkinoilla olevia tuotteita. Lopuksi arvioitiin virtuaalitekniikan kehitystä ja sen merkitystä tulevaisuudessa. Tutkimus osoittaa, etta keinotodellisuudelle löytyy runsaasti sovelluksia eri aloilla, ja edullisen PC-tekniikan kehittyessä kustannukset laskevat jatkuvasti, jolloin vähitellen keinotodellisuus yleistyy.

Nestepakkauskartongin runkokerroksen rakenteen optimointi

Diplomityön tavoitteena oli optimoida KA4:n nestepakkauskartongin runkokerroksen massakoostumus ja rakenne kartonkikoneen uusinnan jälkeen. Työssä tutkittiin Natura 285 –laatua, jota käytetään yhden litran vetoisissa maitopurkeissa. Pääasiallisena tavoitteena oli lisätä CTMP:n osuutta ja vähentää mäntysellun osuutta rungossa siten, että kartongin laatu ei heikkene. Työn kirjallisuusosassa perehdyttiin nestepakkauskartongin kriittisiin ominaisuuksiin ja CTMP:n vaikutuksiin runkokerroksessa. Rainanmuodostusta ja kuituverkoston lujuuden syntymistä käsiteltiin omina kokonaisuuksinaan. CTMP:n freeness-tason huomattava vähentäminen kasvattaa kartongin z-lujuutta ja palstautumislujuutta merkittävästi. Samalla höyrynkulutus kuitenkin kasvaa ja kartongin jäykkyys laskee jonkin verran paksuuden vähenemisen seurauksena. CTMP:n freeness-tason alentaminen arvosta 420 ml CSF arvoon 380 ml CSF ei alenna bulkkia merkittävästi. CTMP:n määrän kasvattaminen yli 60 %:in keskikerroksessa alentaa palstautumislujuutta ja z-lujuutta merkittävästi. Runkokerroksen mäntysellun korvaaminen koivusellulla parantaa kartongin sileyttä merkittävästi vakiopaksuudessa. Runkokerroksen massakomponenttien jauhatuksen lisäämisestä huolimatta z-lujuus ja palstautumislujuus laskevat vastaavasti huomattavan paljon. Koivusellun käytöllä valmiin pakkauksen ominaisuudet eivät heikkene, mutta painatusominaisuudet paranevat. CTMP-laitoksen pääjauhinten uudella LE-terämallilla saavutetaan huomattava energian säästö vanhaan terämalliin verrattuna. Kuidun keskipituus laskee jonkin verran LE-terien ikääntyessä ja samalla kuitujen sitoutumiskyky heikkenee.

Multispectral Analysis of Paper Production Phases

Paperitehtaissa paperin väriä arvioidaan L*a*b –arvojen perusteella. Tämä lähestymistapa ei ole tarkka ja johtaa siihen, että saman luokkaan kuuluvat paperit saatetaan havaita eri värisinä. Tässä diplomityössä tarkastellaan värien arviointia multispektraalisen kuvantamisen avulla. Menetelmän ajatuksena on verrata standardoidun heijastuman spektriä kohteena olevan paperirullan heijastuman spektriin mittaustapojen avulla. 12:n kirjallisuuteen perustuvan ja yhden tutkimusryhmämme kehittämän mittaustavan joukosta pyrittiin valitsemaan parhaat mittaustavat tutkimuksien perusteella. Mittaustavan tehokkuus tarkoittaa kykä tunnistaa eroavaisuuksia värisävyn, värikylläisyyden ja valoisuuden perusteella. Mittaustapoja tutkittiin sekä keinotekoisilla kuvilla että aidoilla paperinäytteillä. Tuloksena maksimi-minimi-, aritmeettisen keskiarvon minimi- ja geometrisen keskiarvon minimimenetelmä olivat parhaita mittaustapoja.

Luotettavuuspohjaisen verkostoanalysointijärjestelmän kehittäminen

Sähköverkon luotettavuuden tarkastelu sähköverkkoyhtiöissä on hyvin ajankohtaista tällä hetkellä. Siihen löytyvät hyvät kannusteet sähköverkkoliiketoimintaa säätelevästä regulaatiomallista sekä nykyisestä ikääntyvästä sähköverkosta. Se on monin paikoin lähellä käyttöikänsä loppua, ja sitä rakennettaessa ei välttämättä ole kiinnitetty kovin suurta huomiota luotettavuustarkasteluun. Kandidaatintyönä on kehitetty analysointijärjestelmä, jonka avulla pystytään tarkastelemaan sähköverkon pitkän aikavälin suunnittelua ottamalla huomioon myös sähköverkon keskeytyksistä aiheutuvat kustannukset. Analysoinnissa käytettävä järjestelmä toimii Microsoftin Excel taulukkolaskennassa. Analysointijärjestelmän avulla saadaan mallinnettua keskeytyskustannusten vaikutuksia erilaisiin investointiohjelmiin ja voidaan helposti vertailla useiden verkostorakeiden tuomia hyötyjä ja niistä aiheutuvia kustannuksia.

Gerontologia & geriatria

Gerontologian ja geriatrian pääkokoelma sijaitsee Terveystieteiden osastokirjastossa, jossa painettu yleiskokoelma koostuu 251 nimekkeestä monografioita. Kokoelmassa on runsaasti (38 %) sosiaaligerontologian kirjallisuutta, jolloin vanhenemisesta tarkastellaan yhteiskunnallisesta näkökulmasta. Kokoelmasta noin viidennes (22 %) on vanhenemiseen liittyviä yleisteoksia. Vanhenemista prosessina (13 %) ja geriatrista psykiatriaa (12 %) käsittelevät kirjat ovat myös selvästi edustettuina. Painettuja edelleen tulevia lehtiä on 3 kpl (Gerontechnology, Gerontologia, International Journal of Aging and Human Development). Sähkökirjoja on noin 150 nimekettä Ebrary-tietokannassa ja noin 40 nimekettä SpringerLink-tietokannassa. Lisäksi Books@Ovid, MDConcult ja Oxford Medical Handook Online -kokoelmissa yksi kirja. Tietosanakirjoja on 1 kpl (Encyclopedia of Gerontology). Sanastoja on 5 kpl( Hoidokki, Medical Subject Headings (MeSH), Sosiaali- ja terveydenhuollon sanasto, Swedish MeSH, Termix). Verkkolehtiä on kokoelmassa noin 80 nimekettä. ISI Web of Knowledge Journal Citation Reports -tietokannan listaamista 52 gerontologian & geriatrian lehdistä kokoelmissa on 38 nimekettä eli 73 prosenttia. Gerontologiaan ja geriatriaan liittyviä artikkeleita löytyy usean tieteenalan, kuten lääketieteen, hoitotieteen, kansanterveystieteen ja sosiaalitietieteiden, viitetietokannoista. Tietokantoja on noin 15-20, joista keskeisimpiä ovat esimerkiksi Medline, Web of Science ja Cinahl. Tämän lisäksi käytössä on useita lehtitietokantoja, esimerkiksi ScienceDirect ja EbscoHost.

Defects in Persistent Luminescence Materials

Persistent luminescence materials can store energy from solar radiation or artificial lighting and release it over a period of several hours without a continuous excitation source. These materials are widely used to improve human safety in emergency and traffic signalization. They can also be utilized in novel applications including solar cells, medical diagnostics, radiation detectors and structural damage sensors. The development of these materials is currently based on methods based on trial and error. The tailoring of new materials is also hindered by the lack of knowledge on the role of their intrinsic and extrinsic lattice defects in the appropriate mechanisms. The goal of this work was to clarify the persistent luminescence mechanisms by combining ab initio density functional theory (DFT) calculations with selected experimental methods. The DFT approach enables a full control of both the nature of the defects and their locations in the host lattice. The materials studied in the present work, the distrontium magnesium disilicate (Sr₂MgSi₂O₇) and strontium aluminate (SrAl₂O₄) are among the most efficient persistent luminescence hosts when doped with divalent europium Eu²⁺ and co-doped with trivalent rare earth ions R³⁺ (R: Y, La-Nd, Sm, Gd-Lu). The polycrystalline materials were prepared with the solid state method and their structural and phase purity was confirmed by X-ray powder diffraction. Their local crystal structure was studied by high-resolution transmission electron microscopy. The crystal and electronic structure of the nondoped as well as Eu²⁺, R^2+/3+ and other defect containing materials were studied using DFT calculations. The experimental trap depths were obtained using thermoluminescence (TL) spectroscopy. The emission and excitation of Sr₂MgSi₂O₇:Eu²+,Dy³⁺ were also studied. Significant modifications in the local crystal structure due to the Eu²⁺ ion and lattice defects were found by the experimental and DFT methods. The charge compensation effects induced by the R³⁺ co-doping further increased the number of defects and distortions in the host lattice. As for the electronic structure of Sr₂MgSi₂O₇ and SrAl₂O₄, the experimental band gap energy of the host materials was well reproduced by the calculations. The DFT calculated Eu²⁺ and R^2+/3+ 4fn as well as 4f^n-15d¹ ground states in the Sr₂MgSi₂O₇ band structure provide an independent verification for an empirical model which is constructed using rather sparse experimental data for the R³⁺ and especially the R²⁺ ions. The intrinsic and defect induced electron traps were found to act together as energy storage sites contributing to the materials’ efficient persistent luminescence. The calculated trap energy range agreed with the trap structure of Sr₂MgSi₂O₇ obtained using TL measurements. More experimental studies should be carried out for SrAl₂O₄ to compare with the DFT calculations. The calculated and experimental results show that the electron traps created by both the rare earth ions and vacancies are modified due to the defect aggregation and charge compensation effects. The relationships between this modification and the energy storage properties of the solid state materials are discussed.

Seksismi ja ikäsorto : vanhenevien naisten elämän kurjistajat

Kirjallisuusarvostelu