Rigid Rod Polymer Fillers in Acrylic Denture and Dental Adhesive Resin Systems

Polymeric materials have been used in dental applications for decades. Adhesion of polymeric materials to each other and to the tooth substrate is essential to their successful use. The aim of this series of studies was two-folded. First, to improve adhesion of poly(paraphenylene) based rigid rod polymer (RRP) to other dental polymers, and secondly, to evaluate the usability of a new dentin primer system based on RRP fillers. Poly(paraphenylene) based RRP would be a tempting material for dental applications because of its good mechanical properties. To be used in dental applications, reliable adhesion between RRP and other dental polymers is required. In this series of studies, the adhesion of RRP to denture base polymer and the mechanical properties of RRP-denture base polymer-material combination were evaluated. Also adhesion of BisGMA-TEGDMA-resin to RRP was determined. Different surface treatments were tested to improve the adhesion of BisGMA-TEGDMA-resin to RRP. Results were based on three-point bending testing, Vickers surface hardness test and scanning electron microscope analysis (SEM), which showed that no reliable adhesion between RRP and denture base polymer was formed. Addition of RRP filler to denture base polymer increased surface hardness and flexural modulus but flexural strength decreased. Results from the shear bond strength test and SEM revealed that adhesion between resin and RRP was possible to improve by surface treatment with dichloromethane (DCM) based primer and a new kind of adhesive surface can be designed. The current dentin bonding agents have good immediate bond strength, but in long term the bond strength may decrease due to the detrimental effect of water and perhaps by matrix metalloproteinases. This leads to problems in longevity of restorations. Current bonding agents use organic monomers. In this series of studies, RRP filled dentin primer was tested in order to decrease the water sorption of the monomer system of the primers. The properties of new dentin primer system were evaluated in vitro by comparing it to commercial etch and rinse adhesive system. The results from the contact angle measurements and SEM showed that experimental primer with RRP reinforcement provided similar resin infiltration to dentin collagen and formed the resin-dentin interface as the control primer. Microtensile bond strength test and SEM revealed that in short term water storing, RRP increased bond strength and primer with BMEP-monomer (bis[2-(methacryloyloxy)-ethyl]phosphate) and high solvent concentration provided comparable bonding properties to the commercial control primers. In long term water storing, the high solvent-monomer concentration of the experimental primers decreased bond strength. However, in low solvent-monomer concentration groups, the long-term water storing did not decrease the bond strength despite the existence of hydrophilic monomers which were used in the system. These studies demonstrated that new dentin primer system reached the mechanical properties of current traditional etch and rinse adhesive system in short time water storing. Improved properties can be achieved by further modifications of the monomer system. Studies of the adhesion of RRP to other polymers suggest that adhesion between RRP and other dental polymers is possible to obtain by certain surface treatments.

Analysis and Control of Excitation, Field Weakening and Stability in Direct Torque Controlled Electrically Excited Synchronous Motor Drives

Direct torque control (DTC) is a new control method for rotating field electrical machines. DTC controls directly the motor stator flux linkage with the stator voltage, and no stator current controllers are used. With the DTC method very good torque dynamics can be achieved. Until now, DTC has been applied to asynchronous motor drives. The purpose of this work is to analyse the applicability of DTC to electrically excited synchronous motor drives. Compared with asynchronous motor drives, electrically excited synchronous motor drives require an additional control for the rotor field current. The field current control is called excitation control in this study. The dependence of the static and dynamic performance of DTC synchronous motor drives on the excitation control has been analysed and a straightforward excitation control method has been developed and tested. In the field weakening range the stator flux linkage modulus must be reduced in order to keep the electro motive force of the synchronous motor smaller than the stator voltage and in order to maintain a sufficient voltage reserve. The dynamic performance of the DTC synchronous motor drive depends on the stator flux linkage modulus. Another important factor for the dynamic performance in the field weakening range is the excitation control. The field weakening analysis considers both dependencies. A modified excitation control method, which maximises the dynamic performance in the field weakening range, has been developed. In synchronous motor drives the load angle must be kept in a stabile working area in order to avoid loss of synchronism. The traditional vector control methods allow to adjust the load angle of the synchronous motor directly by the stator current control. In the DTC synchronous motor drive the load angle is not a directly controllable variable, but it is formed freely according to the motor’s electromagnetic state and load. The load angle can be limited indirectly by limiting the torque reference. This method is however parameter sensitive and requires a safety margin between the theoretical torque maximum and the actual torque limit. The DTC modulation principle allows however a direct load angle adjustment without any current control. In this work a direct load angle control method has been developed. The method keeps the drive stabile and allows the maximal utilisation of the drive without a safety margin in the torque limitation.

Dynamical and structural properties of dendrimer macromolecules

This work is devoted to the study of the dynamical and structural properties of dendrimers. Different approaches were used: analytical theory, computer simulation results and experimental NMR studies. The theory of the relaxation spectrum of dendrimer macromolecules was developed. Relaxation processes which are manifest in the local orientational mobility of dendrimer macromolecules were established and studied in detail. Theoretical results and conclusions were used for experimental studies of carbosilane dendimers.

Quasiconformal mappings and inequalities involving special functions

This PhD thesis in Mathematics belongs to the field of Geometric Function Theory. The thesis consists of four original papers. The topic studied deals with quasiconformal mappings and their distortion theory in Euclidean n-dimensional spaces. This theory has its roots in the pioneering papers of F. W. Gehring and J. Väisälä published in the early 1960’s and it has been studied by many mathematicians thereafter. In the first paper we refine the known bounds for the so-called Mori constant and also estimate the distortion in the hyperbolic metric. The second paper deals with radial functions which are simple examples of quasiconformal mappings. These radial functions lead us to the study of the so-called p-angular distance which has been studied recently e.g. by L. Maligranda and S. Dragomir. In the third paper we study a class of functions of a real variable studied by P. Lindqvist in an influential paper. This leads one to study parametrized analogues of classical trigonometric and hyperbolic functions which for the parameter value p = 2 coincide with the classical functions. Gaussian hypergeometric functions have an important role in the study of these special functions. Several new inequalities and identities involving p-analogues of these functions are also given. In the fourth paper we study the generalized complete elliptic integrals, modular functions and some related functions. We find the upper and lower bounds of these functions, and those bounds are given in a simple form. This theory has a long history which goes back two centuries and includes names such as A. M. Legendre, C. Jacobi, C. F. Gauss. Modular functions also occur in the study of quasiconformal mappings. Conformal invariants, such as the modulus of a curve family, are often applied in quasiconformal mapping theory. The invariants can be sometimes expressed in terms of special conformal mappings. This fact explains why special functions often occur in this theory.

Metabolic syndrome in young adults – prevalence, childhood predictors and association with subclinical atherosclerosis

Background: Metabolic syndrome (MetS) is a cluster of cardiovascular risk factors including central obesity, insulin resistance, impaired glucose tolerance, hypertension and dyslipidemia. The prevalence of MetS is increasing worldwide in all age groups. MetS is associated with increased risk of cardiovascular disease and type 2 diabetes mellitus. Aims: The aim of the present study was to investigate the prevalence, secular trends and childhood predictors of MetS in young adults. Furthermore, the relations between MetS and subclinical atherosclerosis were studied and whether apolipoproteins (apo) B and A-I, C-reactive protein (CRP) and type II secretory phospholipase A2 (sPLA2) were associated with MetS, and to what extent the atherogenicity of MetS was explained by these factors. Participants and Methods: The present thesis is part of the large scale population-based, prospective study, the Cardiovascular Risk in Young Finns Study. The first cross-sectional study was conducted in 1980 and included 3,596 participants aged 3-18 years. Carotid and brachial ultrasound studies were performed for 2,283 of these participants in 2001 and 2,200 of these participants in 2007. Results: The overall prevalence of MetS in young adults aged 24-39 years in 2001 was 10-15 % and 6 years later in 30-45 year-old adults it was 15-23 % depending on the MetS definition used. Between the years 1986 and 2001, MetS prevalence increased from 1.0 % to 7.5 % (p<0.0001) in 24-year-old participants that was mostly driven by the increased central obesity. Participants with MetS had increased carotid intima-media thickness (cIMT) and decreased carotid elasticity compared to those without the syndrome. Impaired brachial flow-mediated dilatation (FMD) was not related to MetS but it modified the relationship between MetS and cIMT (P for interaction 0.023). High levels of apoB, CRP, sPLA2 and low levels of apoA-I associated with MetS in young adults. In prospective analysis both MetS and high apoB predicted (P<0.0001) incident high cIMT, defined as cIMT>90th percentile and/or plaque. The association between MetS and incident high cIMT was attenuated by ~40 % after adjustment with apoB. Conclusions: MetS is common in young adults and increases with age. Screening for risk factors, especially obesity, at an early life stage could help identify children and adolescents at increased risk of developing MetS and cardiovascular disease later in life. MetS identifies a population of young adults with evidence of increased subclinical atherosclerosis. Impaired brachial endothelial response is not a hallmark of MetS in young adults, but the status of endothelial function modifies the association between metabolic risk factors and atherosclerosis. In addition, the atherogenicity of MetS in this population assessed by incident high cIMT appears to be substantially mediated by elevated apoB.

Generation and Characterization of Knockout Mice and Analysis of Patient Material Demonstrates a Role for Tissue Inhibitor of Metalloproteinases 4 (Timp4) in the Cardiovascular System and Tumor Metastasis

This thesis focuses on tissue inhibitor of metalloproteinases 4 (TIMP4) which is the newest member of a small gene and protein family of four closely related endogenous inhibitors of extracellular matrix (ECM) degrading enzymes. Existing data on TIMP4 suggested that it exhibits a more restricted expression pattern than the other TIMPs with high expression levels in heart, brain, ovary and skeletal muscle. These observations and the fact that the ECM is of special importance to provide the cardiovascular system with structural strength combined with elasticity and distensibility, prompted the present molecular biologic investigation on TIMP4. In the first part of the study the murine Timp4 gene was cloned and characterized in detail. The structure of murine Timp4 genomic locus resembles that in other species and of the other Timps. The highest Timp4 expression was detected in heart, ovary and brain. As the expression pattern of Timp4 gives only limited information about its role in physiology and pathology, Timp4 knockout mice were generated next. The analysis of Timp4 knockout mice revealed that Timp4 deficiency has no obvious effect on the development, growth or fertility of mice. Therefore, Timp4 deficient mice were challenged using available cardiovascular models, i.e. experimental cardiac pressure overload and myocardial infarction. In the former model, Timp4 deficiency was found to be compensated by Timp2 overexpression, whereas in the myocardial infarct model, Timp4 deficiency resulted in increased mortality due to increased susceptibility for cardiac rupture. In the wound healing model, Timp4 deficiency was shown to result in transient retardation of re-epithelialization of cutaneous wounds. Melanoma tumor growth was similar in Timp4 deficient and control mice. Despite of this, lung metastasis of melanoma cells was significantly increased in Timp4 null mice. In an attempt to translate the current findings to patient material, TIMP4 expression was studied in human specimens representing different inflammatory cardiovascular pathologies, i.e. giant cell arteritis, atherosclerotic coronary arteries and heart allografts exhibiting signs of chronic rejection. The results showed that cardiovascular expression of TIMP4 is elevated particularly in areas exhibiting inflammation. The results of the present studies suggest that TIMP4 has a special role in the regulation of tissue repair processes in the heart, and also in healing wounds and metastases. Furthermore, evidence is provided suggesting the usefulness of TIMP4 as a novel systemic marker for vascular inflammation.

Ultralujien terästen pienahitsien staattinen lujuus

Kandidaatintyön tarkoituksena oli selvittää hitsausliitosten mitoitusohjeita ultralujille teräksille. Työhön kuului laboratoriotestauksia, joiden avulla tarkasteltiin laskujen soveltuvuutta ultralujille teräksille. Laskuissa verrattiin erityisesti kimmoteorian ja plastisuusteorian toimivuutta. Työn tuloksena tuotettiin mitoitusohjeet otsapienahitseille, eli mitoitusvoimaan nähden poikittaisille hitseille. Myös kylkipienahitseille, eli mitoitusvoimaan nähden yhdensuuntaisille hitseille saatiin alustavia tuloksia.

Paperitehtaan sähkötasehallinta ja sähkön kysyntäjousto energiakustannusten hallinnassa

Paperiteollisuus on energiaintensiivistä teollisuutta, jossa on tehty pitkään työtä tuotantoprosessien energiatehokkuuden parantamiseksi. Paperitehtaan energiakustannuksiin voidaan kuitenkin vaikuttaa myös sähkötaseen hallinnalla ja sähkön kysyntäjouston avulla. Tehtaan seuraavan vuorokauden sähkön kulutus pyritään ennustamaan mahdollisimman tarkasti, mutta esimerkiksi paperitehtaan häiriötilanteissa sähkötase poikkeaa ennustetusta. Tällöin sähkötasetta voidaan korjata ensisijaisesti sähkön jälkimarkkinoiden eli Elbas- kaupankäynnin avulla. Ellei tasetta saada korjattua sähkön jälkimarkkinoilla tase-ero korjataan tasesähköllä, jonka hinta muodostuu säätösähkömarkkinoilla. Tasesähkön hinta saattaa poiketa Elspot- markkinahinnasta voimakkaasti, jolloin tase-erosta joko hyödytään tai hävitään kustannusmielessä. Tämän työn tarkoituksena on selvittää sähkötasehallinnan parantamisen ja sähkön kysyntäjouston vaikutukset paperitehtaan energiakustannuksiin. Työssä tutkittiin tehtaan sähkö-tasehallinnan nykytilannetta ja selvitettiin tase-erojen kustannusvaikuttavuutta. Lisäksi työssä luotiin ajomalleja sähkön kysyntäjouston toteuttamiselle massatehtaan eri tuotantoprosesseille, sekä määritettiin rajahintoja seuraavan vuorokauden energiaennusteeseen. Onnistunut energiaennuste perustuu paperitehtaan käynnin tarkkoihin ja ajankohtaisiin lähtötietoihin. Sähkötaseen poikkeamiin voidaan puolestaan varautua paremmin, kun informaatio tehtaan prosessien alasajosta tulee voimalaitoksen tietoon mahdollisimman aikaisin. Sähkötaseen poikkeamien hallinta voidaan tehdä, joko Elbas- kaupan tai tasesähkön avulla. Ajankohdasta ja tasepoikkeaman volyymista riippuen täytyy tehdä valinta, kumpi vaihtoehdoista on kustannusmielessä kannattavampi. Paperitehtaan eri prosesseille luoduilla ajomalleilla saatiin esiin huomattava säästöpotentiaali. Ajomallien noudattaminen vaatii suunnitelmallista tuotannon hallintaa ja sähkön Elspot- hinnan käyttäytymisen säännöllistä seurantaa. Seuraavan vuorokauden rajahintatietojen määrittämisen pohjalta voidaan arvioida, millä Elspot- hinnalla sähkön myynti muuttuu paperin tuotantoa kannattavammaksi.

Hyperbolic type metrics and distortion of quasiconformal map pings

This Ph.D. thesis consists of four original papers. The papers cover several topics from geometric function theory, more specifically, hyperbolic type metrics, conformal invariants, and the distortion properties of quasiconformal mappings. The first paper deals mostly with the quasihyperbolic metric. The main result gives the optimal bilipschitz constant with respect to the quasihyperbolic metric for the M¨obius self-mappings of the unit ball. A quasiinvariance property, sharp in a local sense, of the quasihyperbolic metric under quasiconformal mappings is also proved. The second paper studies some distortion estimates for the class of quasiconformal self-mappings fixing the boundary values of the unit ball or convex domains. The distortion is measured by the hyperbolic metric or hyperbolic type metrics. The results provide explicit, asymptotically sharp inequalities when the maximal dilatation of quasiconformal mappings tends to 1. These explicit estimates involve special functions which have a crucial role in this study. In the third paper, we investigate the notion of the quasihyperbolic volume and find the growth estimates for the quasihyperbolic volume of balls in a domain in terms of the radius. It turns out that in the case of domains with Ahlfors regular boundaries, the rate of growth depends not merely on the radius but also on the metric structure of the boundary. The topic of the fourth paper is complete elliptic integrals and inequalities. We derive some functional inequalities and elementary estimates for these special functions. As applications, some functional inequalities and the growth of the exterior modulus of a rectangle are studied.

Etäluentamittareiden tuomat tuotteistamismahdollisuudet sähkönmyyjille

Diplomityön tavoitteena oli selvittää etäluentamittareiden mahdollistamia tuotteita ja palveluita sekä niiden toteutettavuutta Mäntsälän Sähkö Oy:ssä. Työssä perehdytään yksityisasiakkaille suunnattuihin palveluihin, joita mittaritekniikka mahdollistaa. Mittarit tulee olla asennettuna 80%:lle verkkoyhtiön sähkönkäyttöpaikoista vuoteen 2014 mennessä. Mäntsälän Sähköllä mittareiden vaihtoprojektin alkamisen vuoksi haluttiin selvittää mahdollisten uusien tuotteiden toteutettavuutta. Työssä esitellään Mäntsälän Sähkö Oy:lle tulevan mittarijärjestelmän. Mittarijärjestelmä käyttää eri tietoliikennetapoja, jotka ovat GPRS, RS485 ja radio. Työ sisältää internet-paneelina suoritetun asiakaskyselyn, jossa selvitettiin asiakkaiden tarpeita ja mielipiteitä mahdollisten uusien tuotteiden osalta. Työssä käsiteltäviä tuotteita ovat kuormanohjaus, kysynnän hintajousto, spot-hinnoittelu, laskutus sekä raportointipalvelu. Kulutuksen hintajousto, kuormanohjaus ja spot-hinnoittelu toimivat toisiaan tukevina tuotteina. Tasasuuruista laskutusta voisi tarjota toteutuneen kulutuksen mukaisen laskutuksen ohessa lisäpalveluna. Raportointipalvelu internetissä on hyvä tapa toimittaa asiakkaalle lain velvoittamat tiedot.

Heart rate variability in young adults - Reference values and associations with cardiometabolic risk factors and vascular properties. The Cardiovascular Risk in Young Finns Study.

Background: The function of the autonomic nervous system (ANS) can be evaluated with heart rate variability (HRV). Decreased HRV is associated with aging, the male sex, increased heart rate, and overall increased cardiometabolic risk. It has been hypothesized that early atherosclerotic vascular changes and ANS function are related. Aims: The aims were to assess reference values on HRV in young adults, and examine associations with HRV and cardiometabolic risk factors and metabolic syndrome (MetS) and to study relations between HRV and ultrasonographically measured vascular properties. Participants and methods: The present thesis is part of the Cardiovascular Risk in Young Finns Study. The thesis is based on the follow-up study in 2001, when the study individuals were 24-39 years of age. HRV data were available on 1 956 individuals. Results: HRV was inversely associated with age and heart rate (for all p<0.001). Highfrequency HRV (HF) was higher, and low-frequency HRV (LF) lower in women than men (p<0.0001 for both). MetS was associated with 11% decreased HF and 12% increased LF/HF-ratio in women, and 8% decreased HF and 4% increased LF/HF-ratio in men. Carotid artery distensibility was independently associated with HF and total HRV (for both p<0.05). Conclusions: The reference values in young adults were generated. Decreased HRV was associated with age, the male sex and increased heart rate. Women had higher HF and lower LF variability than men. MetS was related to decrease in HRV. The observed associations between carotid elasticity and HRV, supports the hypothesis that reduction in carotid elasticity may lead to decrease in autonomic cardiac control.

Kylmälaitekoneikon runkorakenteen kehittäminen

Kylmälaitekoneikot ovat kylmäkomponentteja sisältäviä rakenteita, joiden avulla toteutetaan suurten tilojen, kuten elintarvikemyymälöiden sisäilman jäähdytys. Lisäksi koneikkojen avulla jäähdytetään matalampiin lämpötiloihin pienempiä kylmähuoneita. Osa koneikoista ottaa talteen kylmäprosessissa syntyvän lämmön, jota hyödynnetään tilojen lämmityksessä. Tämän diplomityön tavoitteena oli suunnitella ja mitoittaa kahdeksalle eri kylmälaitekoneikolle entistä kustannustehokkaammat runkorakenteet, jotka ovat niin kestäviä, että koneikkoja on mahdollista pinota tilan säästämiseksi kolme päällekkäin. Lisäksi runkorakenteilta vaadittiin helppoa kuljetettavuutta, hyviä kiinnitysominaisuuksia ja korroosionkestävyyttä. Aluksi työssä selvitettiin runkorakenteisiin kohdistuvat vaatimukset, jonka jälkeen materiaalin valinta tehtiin materiaaliin kohdistuvien vaatimusten perusteella. Rakenteiden palkit mitoitettiin tarvittavan taivutusvastuksen ja kiepahduksen mukaan. Pilarit puolestaan mitoitettiin nurjahduksen ja kaksiaksiaalisen taivutustilan perusteella. Tämän jälkeen mitoitettiin eri sauvojen väliset hitsi- ja ruuviliitokset siten, että rakenne hajoaa ylikuormitustilanteessa mahdollisimman turvallisesti. Työssä tehdyt laskelmat varmennettiin elementtimenetelmän avulla ja lopullisille rakenteille tehtiin elementtimenetelmällä vielä ominaistaajuusanalyysejä. Lopuksi työssä suunniteltiin runkorakenteille sopiva korroosionsuojaus.

Sähkönmyyntiyhtiöiden riskienhallinnan haasteet ja kehittäminen

Diplomityön tavoitteena on esitellä sähkökaupan ja erityisesti sähköyhtiöiden kokemia sähkönmyynnin riskejä sekä kuvata sähkönmyyntiin liittyvää riskienhallinnan problematiikkaa. Tarkastelun näkökulmana on tietojärjestelmien ja saatavissa olevan tiedon hyödyntäminen energiayhtiöiden riskienhallinnassa. Toinen päätavoitteista on tutkia, kuinka saatavilla olevaa tiedon hyödyntämistä voidaan kehittää sähkönmyynnin hinnoittelussa sekä suojausten suunnittelussa. Työ toteutettiin työskentelemällä asiantuntijana energia-alaan keskittyneessä ohjelmistoyrityksessä sekä haastattelemalla yhdeksän suomalaisen sähkönmyyntiyhtiön henkilöitä riskienhallinnan haasteiden sekä tietojärjestelmien näkökulmasta. Saatavilla olevien tietojen nykyistä parempi hyödyntäminen ja automatisointi voivat auttaa pienentämään yhtiöiden riskitasoa ja parantaa menestymisen edellytyksiä sähkönmyynnin vähittäismarkkinoilla. Lisäksi kulloiseenkin markkinatilanteeseen sopivat sähkön hankintahinnan suojausstrategiat sekä monipuoliset dynaamiset hinnoittelumallit auttavat pienentämään yhtiön kokemia riskejä tai niiden vaikutuksia. Näiden hyödyntäminen vaatii laajaa ymmärrystä sähkö- ja johdannaismarkkinoiden toiminnasta sekä usein myös nykyisten tietojärjestelmien kehittämistä. Tulevaisuudessa yhä yleistyvä hajautettu tuotanto sekä kysynnän jousto asettavat tietojärjestelmille uusia vaatimuksia, jotka toteutuessaan mahdollistavat uudenlaisten palveluiden käyttöönoton sekä voivat tuoda tilaa myös alan uusille toimijoille. Työssä käsitellään energiayhtiöiden kokemia riskejä sähkönmyynnin näkökulmasta, esitellään alan yleisimmät riskit sekä keinot ja työkalut niiltä suojautumiseen. Työn lopuksi tarkastellaan sähkönmyynnin ja –hankinnan oleellisimpia prosesseja riskienhallinnan kehittämisen näkökulmasta.

Public-private partnership investments in dry ports – Russian logistics markets and risks

The investments have always been considered as an essential backbone and so-called ‘locomotive’ for the competitive economies. However, in various countries, the state has been put under tight budget constraints for the investments in capital intensive projects. In response to this situation, the cooperation between public and private sector has grown based on public-private mechanism. The promotion of favorable arrangement for collaboration between public and private sectors for the provision of policies, services, and infrastructure in Russia can help to address the problems of dry ports development that neither municipalities nor the private sector can solve alone. Especially, the stimulation of public-private collaboration is significant under the exposure to externalities that affect the magnitude of the risks during all phases of project realization. In these circumstances, the risk in the projects also is becoming increasingly a part of joint research and risk management practice, which is viewed as a key approach, aiming to take active actions on existing global and specific factors of uncertainties. Meanwhile, a relatively little progress has been made on the inclusion of the resilience aspects into the planning process of a dry ports construction that would instruct the capacity planner, on how to mitigate the occurrence of disruptions that may lead to million dollars of losses due to the deviation of the future cash flows from the expected financial flows on the project. The current experience shows that the existing methodological base is developed fragmentary within separate steps of supply chain risk management (SCRM) processes: risk identification, risk evaluation, risk mitigation, risk monitoring and control phases. The lack of the systematic approach hinders the solution of the problem of risk management processes of dry port implementation. Therefore, management of various risks during the investments phases of dry port projects still presents a considerable challenge from the practical and theoretical points of view. In this regard, the given research became a logical continuation of fundamental research, existing in the financial models and theories (e.g., capital asset pricing model and real option theory), as well as provided a complementation for the portfolio theory. The goal of the current study is in the design of methods and models for the facilitation of dry port implementation through the mechanism of public-private partnership on the national market that implies the necessity to mitigate, first and foremost, the shortage of the investments and consequences of risks. The problem of the research was formulated on the ground of the identified contradictions. They rose as a continuation of the trade-off between the opportunities that the investors can gain from the development of terminal business in Russia (i.e. dry port implementation) and risks. As a rule, the higher the investment risk, the greater should be their expected return. However, investors have a different tolerance for the risks. That is why it would be advisable to find an optimum investment. In the given study, the optimum relates to the search for the efficient portfolio, which can provide satisfaction to the investor, depending on its degree of risk aversion. There are many theories and methods in finance, concerning investment choices. Nevertheless, the appropriateness and effectiveness of particular methods should be considered with the allowance of the specifics of the investment projects. For example, the investments in dry ports imply not only the lump sum of financial inflows, but also the long-term payback periods. As a result, capital intensity and longevity of their construction determine the necessity from investors to ensure the return on investment (profitability), along with the rapid return on investment (liquidity), without precluding the fact that the stochastic nature of the project environment is hardly described by the formula-based approach. The current theoretical base for the economic appraisals of the dry port projects more often perceives net present value (NPV) as a technique superior to other decision-making criteria. For example, the portfolio theory, which considers different risk preference of an investor and structures of utility, defines net present value as a better criterion of project appraisal than discounted payback period (DPP). Meanwhile, in business practice, the DPP is more popular. Knowing that the NPV is based on the assumptions of certainty of project life, it cannot be an accurate appraisal approach alone to determine whether or not the project should be accepted for the approval in the environment that is not without of uncertainties. In order to reflect the period or the project’s useful life that is exposed to risks due to changes in political, operational, and financial factors, the second capital budgeting criterion – discounted payback period is profoundly important, particularly for the Russian environment. Those statements represent contradictions that exist in the theory and practice of the applied science. Therefore, it would be desirable to relax the assumptions of portfolio theory and regard DPP as not fewer relevant appraisal approach for the assessment of the investment and risk measure. At the same time, the rationality of the use of both project performance criteria depends on the methods and models, with the help of which these appraisal approaches are calculated in feasibility studies. The deterministic methods cannot ensure the required precision of the results, while the stochastic models guarantee the sufficient level of the accuracy and reliability of the obtained results, providing that the risks are properly identified, evaluated, and mitigated. Otherwise, the project performance indicators may not be confirmed during the phase of project realization. For instance, the economic and political instability can result in the undoing of hard-earned gains, leading to the need for the attraction of the additional finances for the project. The sources of the alternative investments, as well as supportive mitigation strategies, can be studied during the initial phases of project development. During this period, the effectiveness of the investments undertakings can also be improved by the inclusion of the various investors, e.g. Russian Railways’ enterprises and other private companies in the dry port projects. However, the evaluation of the effectiveness of the participation of different investors in the project lack the methods and models that would permit doing the particular feasibility study, foreseeing the quantitative characteristics of risks and their mitigation strategies, which can meet the tolerance of the investors to the risks. For this reason, the research proposes a combination of Monte Carlo method, discounted cash flow technique, the theory of real options, and portfolio theory via a system dynamics simulation approach. The use of this methodology allows for comprehensive risk management process of dry port development to cover all aspects of risk identification, risk evaluation, risk mitigation, risk monitoring, and control phases. A designed system dynamics model can be recommended for the decision-makers on the dry port projects that are financed via a public-private partnership. It permits investors to make a decision appraisal based on random variables of net present value and discounted payback period, depending on different risks factors, e.g. revenue risks, land acquisition risks, traffic volume risks, construction hazards, and political risks. In this case, the statistical mean is used for the explication of the expected value of the DPP and NPV; the standard deviation is proposed as a characteristic of risks, while the elasticity coefficient is applied for rating of risks. Additionally, the risk of failure of project investments and guaranteed recoupment of capital investment can be considered with the help of the model. On the whole, the application of these modern methods of simulation creates preconditions for the controlling of the process of dry port development, i.e. making managerial changes and identifying the most stable parameters that contribute to the optimal alternative scenarios of the project realization in the uncertain environment. System dynamics model allows analyzing the interactions in the most complex mechanism of risk management process of the dry ports development and making proposals for the improvement of the effectiveness of the investments via an estimation of different risk management strategies. For the comparison and ranking of these alternatives in their order of preference to the investor, the proposed indicators of the efficiency of the investments, concerning the NPV, DPP, and coefficient of variation, can be used. Thus, rational investors, who averse to taking increased risks unless they are compensated by the commensurate increase in the expected utility of a risky prospect of dry port development, can be guided by the deduced marginal utility of investments. It is computed on the ground of the results from the system dynamics model. In conclusion, the outlined theoretical and practical implications for the management of risks, which are the key characteristics of public-private partnerships, can help analysts and planning managers in budget decision-making, substantially alleviating the effect from various risks and avoiding unnecessary cost overruns in dry port projects.

A reaction engineering approach to homogeneously catalyzed glycerol hydrochlorination

The production of biodiesel through transesterification has created a surplus of glycerol on the international market. In few years, glycerol has become an inexpensive and abundant raw material, subject to numerous plausible valorisation strategies. Glycerol hydrochlorination stands out as an economically attractive alternative to the production of biobased epichlorohydrin, an important raw material for the manufacturing of epoxy resins and plasticizers. Glycerol hydrochlorination using gaseous hydrogen chloride (HCl) was studied from a reaction engineering viewpoint. Firstly, a more general and rigorous kinetic model was derived based on a consistent reaction mechanism proposed in the literature. The model was validated with experimental data reported in the literature as well as with new data of our own. Semi-batch experiments were conducted in which the influence of the stirring speed, HCl partial pressure, catalyst concentration and temperature were thoroughly analysed and discussed. Acetic acid was used as a homogeneous catalyst for the experiments. For the first time, it was demonstrated that the liquid-phase volume undergoes a significant increase due to the accumulation of HCl in the liquid phase. Novel and relevant features concerning hydrochlorination kinetics, HCl solubility and mass transfer were investigated. An extended reaction mechanism was proposed and a new kinetic model was derived. The model was tested with the experimental data by means of regression analysis, in which kinetic and mass transfer parameters were successfully estimated. A dimensionless number, called Catalyst Modulus, was proposed as a tool for corroborating the kinetic model. Reactive flash distillation experiments were conducted to check the commonly accepted hypothesis that removal of water should enhance the glycerol hydrochlorination kinetics. The performance of the reactive flash distillation experiments were compared to the semi-batch data previously obtained. An unforeseen effect was observed once the water was let to be stripped out from the liquid phase, exposing a strong correlation between the HCl liquid uptake and the presence of water in the system. Water has revealed to play an important role also in the HCl dissociation: as water was removed, the dissociation of HCl was diminished, which had a retarding effect on the reaction kinetics. In order to obtain a further insight on the influence of water on the hydrochlorination reaction, extra semi-batch experiments were conducted in which initial amounts of water and the desired product were added. This study revealed the possibility to use the desired product as an ideal “solvent” for the glycerol hydrochlorination process. A co-current bubble column was used to investigate the glycerol hydrochlorination process under continuous operation. The influence of liquid flow rate, gas flow rate, temperature and catalyst concentration on the glycerol conversion and product distribution was studied. The fluid dynamics of the system showed a remarkable behaviour, which was carefully investigated and described. Highspeed camera images and residence time distribution experiments were conducted to collect relevant information about the flow conditions inside the tube. A model based on the axial dispersion concept was proposed and confronted with the experimental data. The kinetic and solubility parameters estimated from the semi-batch experiments were successfully used in the description of mass transfer and fluid dynamics of the bubble column reactor. In light of the results brought by the present work, the glycerol hydrochlorination reaction mechanism has been finally clarified. It has been demonstrated that the reactive distillation technology may cause drawbacks to the glycerol hydrochlorination reaction rate under certain conditions. Furthermore, continuous reactor technology showed a high selectivity towards monochlorohydrins, whilst semibatch technology was demonstrated to be more efficient towards the production of dichlorohydrins. Based on the novel and revealing discoveries brought by the present work, many insightful suggestions are made towards the improvement of the production of αγ-dichlorohydrin on an industrial scale.