First principles modeling of metallic alloys and alloy surfaces

By alloying metals with other materials, one can modify the metal’s characteristics or compose an alloy which has certain desired characteristics that no pure metal has. The field is vast and complex, and phenomena that govern the behaviour of alloys are numerous. Theories cannot penetrate such complexity, and the scope of experiments is also limited. This is why the relatively new field of ab initio computational methods has much to give to this field. With these methods, one can extend the understanding given by theories, predict how some systems might behave, and be able to obtain information that is not there to see in physical experiments. This thesis pursues to contribute to the collective knowledge of this field in the light of two cases. The first part examines the oxidation of Ag/Cu, namely, the adsorption dynamics and oxygen induced segregation of the surface. Our results demonstrate that the presence of Ag on the Cu(100) surface layer strongly inhibits dissociative adsorption. Our results also confirmed that surface reconstruction does happen, as experiments predicted. Our studies indicate that 0.25 ML of oxygen is enough for Ag to diffuse towards the bulk, under the copper oxide layer. The other part elucidates the complex interplay of various energy and entropy contributions to the phase stability of paramagnetic duplex steel alloys. We were able to produce a phase stability map from first principles, and it agrees with experiments rather well. Our results also show that entropy contributions play a very important role on defining the phase stability. This is, to the author’s knowledge, the first ab initio study upon this subject.

Some defects in two-dimensional spin-1/2 Heisenberg antiferromagnets: a numerical study of magnetic effects

En del av de intressantaste fenomenen inom dagens materialfysik uppstår ur ett intrikat samspel mellan myriader av elektroner. Högtemperatursupraledare är det mest berömda exemplet. Varken klassiska teorier eller modeller där elektronerna är oberoende av varandra kan förklara de häpnadsväckande effekterna i de starkt korrelerade elektronsystemen. I vissa kopparoxider, till exempel La2CuO4, är det känt att valenselektronerna till följd av en stark ömsesidig växelverkan lokaliseras en och en till kopparatomerna i föreningens CuO2 plan. Laddningarnas inneboende magnetiska moment—spinnet—får då en avgörande roll för materialets elektriska och magnetiska egenskaper, vilka i exemplets fall kan beskrivas med Heisenbergmodellen som är den grundläggande teoretiska modellen för mikroskopisk magnetism. Men exakt varför föreningarna kan bli supraledande då de dopas med överskottsladdningar är än så länge en obesvarad fråga. Min avhandling undersöker orenheters inverkan på Heisenbergmodellens magnetiska egenskaper—ett problem av både experimentell och teoretisk relevans. En etablerad numerisk metod har använts—en kvantmekanisk Monte Carlo teknik—för att utföra omfattande datorsimuleringar av den matematiska modellen på två dedikerade Linux datorkluster. Arbetet hör till området beräkningsfysik. De teoretiska modellerna för starkt korrelerade elektronsystem, däribland Heisenbergmodellen, är ytterst invecklade matematiskt sett och de kan inte lösas exakt. Analytiska utredningar bygger för det mesta på antaganden och förenklingar vars inverkningar på slutresultatet är ofta oklara. I det avseende kan numeriska studier vara exakta, det vill säga de kan behandla modellerna som de är. Oftast behövs bägge tillvägagångssätten. Den röda tråden i arbetet har varit att numeriskt testa vissa högaktuella analytiska förutsägelser rörande effekterna av orenheter i Heisenbergmodellen. En del av dem har vi på basen av mycket noggranna data kunnat bekräfta. Men våra resultat har också påvisat felaktigheter i de analytiska prognoserna som sedermera delvis reviderats. En del av avhandlingens numeriska upptäckter har i sin tur stimulerat till helt nya teoretiska studier.

Erikoispuristimen kehitys liikkuvalle raaka-ainerainalle

Tutkimuksen tavoitteena oli kehittää Lappeenrannan teknilliselle yliopistolle nopeasti ja ketterästi liikkuva, lävistyksiä ja muovauksia tekevä puristin. Laitteisto on tarkoitus liittää osaksi tuotantolinjaa, jossa suulakepuristin eli ekstruuderi tuottaa pehmeä, ei-metallista materiaalia katkeamattomasti. Teoriaosuudessa esitellään vaihtoehdot puristimen, ohjauksen, työkalun ja liikutuslaitteiston osalta. Empiriaosuudessa suoritetaan laitteiston eri komponenttien valinta hinnan, nopeuden, kestävyyden, käytettävyyden ja koon perusteella. Tutkimuksen lopussa arvioidaan laitteistokokonaisuuden nopeutta suulakepuristimen tuotaman materiaalin maksiminopeuteen. Laitteiston nopeuden rajoittavana tekijänä toimii puristimen iskunopeus, jonka perusteella suulakepuristimen tuottaman materiaalin etenemisnopeus joudutaan pudottamaan hieman alle puoleen tavoitteena olleesta nopeudesta. Laitteiston kestävyyden heikon kohta on työstöä tekevien komponenttien liikuttamiseen tarkoitettu laitteisto. Puristuslaitteistoa on tarkoitus käyttää kahdeksan tuntia päivässä, viitenä päivänä viikossa, 52 viikkoa vuodessa. Näiden käyttötietojen perusteella koko laitteiston käyttöikä on useita vuosia.

Modern Metallic Materials for Arctic Environment

This thesis is part of the Arctic Materials Technologies Development –project, which aims to research and develop manufacturing techniques, especially welding, for Arctic areas. The main target of this paper is to clarify what kind of European metallic materials are used, or can be used, in Arctic. These materials include mainly carbon steels but also stainless steels and aluminium and its alloys. Standardized materials, their properties and also some recent developments are being introduced. Based on this thesis it can be said that carbon steels (shipbuilding and pipeline steels) have been developed based on needs of industry and steels exist, which can be used in Arctic areas. Still, these steels cannot be fully benefited, because rules and standards are under development. Also understanding of fracture behavior of new ultra high strength steels is not yet good enough, which means that research methods (destructive and non-destructive methods) need to be developed too. The most of new nickel-free austenitic and austenitic-ferritic stainless steels can be used in cold environment. Ferritic and martensitic stainless steels are being developed for better weldability and these steels are mainly developed in nuclear industry. Aluminium alloys are well suitable for subzero environment and these days high strength aluminium alloys are available also as thick sheets. Nanotechnology makes it possible to manufacture steels, stainless steels and aluminium alloys with even higher strength. Joining techniques needs to be developed and examined properly to achieve economical and safe way to join these modern alloys.

Experimental Studies on Non-Metallic Composite Bone Implants With a Special Reference to Staphylococcal Biofilm Infection

Non-metallic implants made of bioresorbable or biostable synthetic polymers are attractive options in many surgical procedures, ranging from bioresorbable suture anchors of arthroscopic surgery to reconstructive skull implants made of biostable fiber-reinforced composites. Among other benefits, non-metallic implants produce less interference in imaging. Bioresorbable polymer implants may be true multifunctional, serving as osteoconductive scaffolds and as matrices for simultaneous delivery of bone enhancement agents. As a major advantage for loading conditions, mechanical properties of biostable fiber-reinforced composites can be matched with those of the bone. Unsolved problems of these biomaterials are related to the risk of staphylococcal biofilm infections and to the low osteoconductivity of contemporary bioresorbable composite implants. This thesis was focused on the research and development of a multifunctional implant model with enhanced osteoconductivity and low susceptibility to infection. In addition, the experimental models for assessment, diagnostics and prophylaxis of biomaterial-related infections were established. The first experiment (Study I) established an in vitro method for simultaneous evaluation of calcium phosphate and biofilm formation on bisphenol-Aglycidyldimethacrylate and triethylenglycoldimethacrylate (BisGMA-TEGDMA) thermosets with different content of bioactive glass 45S5. The second experiment (Study II) showed no significant difference in osteointegration of nanostructured and microsized polylactide-co-glycolide/β-tricalcium phosphate (PLGA /β-TCP) composites in a minipig model. The third experiment (Study III) demonstrated that positron emission tomography (PET) imaging with the novel 68Ga labelled 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) CD33 related sialic-acid immunoglobulin like lectins (Siglec-9) tracer was able to detect inflammatory response to S. epidermidis and S. aureus peri-implant infections in an intraosseous polytetrafluoroethylene catheter model. In the fourth experiment (Study IV), BisGMATEGDMA thermosets coated with lactose-modified chitosan (Chitlac) and silver nanoparticles exhibited antibacterial activity against S. aureus and P. aeruginosa strains in an in vitro biofilm model and showed in vivo biocompatibility in a minipig model. In the last experiment (Study V), a selective androgen modulator (SARM) released from a poly(lactide)-co-ε-caprolactone (PLCL) polymer matrix failed to produce a dose-dependent enhancement of peri-implant osteogenesis in a bone marrow ablation model.

An IP capable data link layer protocol for narrow band half-duplex packet data radio networks

The wide adaptation of Internet Protocol (IP) as de facto protocol for most communication networks has established a need for developing IP capable data link layer protocol solutions for Machine to machine (M2M) and Internet of Things (IoT) networks. However, the wireless networks used for M2M and IoT applications usually lack the resources commonly associated with modern wireless communication networks. The existing IP capable data link layer solutions for wireless IoT networks provide the necessary overhead minimising and frame optimising features, but are often built to be compatible only with IPv6 and specific radio platforms. The objective of this thesis is to design IPv4 compatible data link layer for Netcontrol Oy's narrow band half-duplex packet data radio system. Based on extensive literature research, system modelling and solution concept testing, this thesis proposes the usage of tunslip protocol as the basis for the system data link layer protocol development. In addition to the functionality of tunslip, this thesis discusses the additional network, routing, compression, security and collision avoidance changes required to be made to the radio platform in order for it to be IP compatible while still being able to maintain the point-to-multipoint and multi-hop network characteristics. The data link layer design consists of the radio application, dynamic Maximum Transmission Unit (MTU) optimisation daemon and the tunslip interface. The proposed design uses tunslip for creating an IP capable data link protocol interface. The radio application receives data from tunslip and compresses the packets and uses the IP addressing information for radio network addressing and routing before forwarding the message to radio network. The dynamic MTU size optimisation daemon controls the tunslip interface maximum MTU size according to the link quality assessment calculated from the radio network diagnostic data received from the radio application. For determining the usability of tunslip as the basis for data link layer protocol, testing of the tunslip interface is conducted with both IEEE 802.15.4 radios and packet data radios. The test cases measure the radio network usability for User Datagram Protocol (UDP) based applications without applying any header or content compression. The test results for the packet data radios reveal that the typical success rate for packet reception through a single-hop link is above 99% with a round-trip-delay of 0.315s for 63B packets.