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Amphiphilic block copolymers based on poly(ethylene glycol) (PEG) and poly(vinylidene fluoride) (PVDF) were synthesized by RAFT polymerization. The commercial poly(ethylene glycol) methyl ether (Me-PEG-OH, 20 Kg/mol) and difunctional polyethylene glycol (OH-PEG-OH, 20 Kg/mol) were used to synthesize diblock copolymers (Me-PEG-b-PVDF), and triblock copolymers (PVDF-b-PEG-b-PVDF) respectively. For the synthesis, the esterification reaction followed by the SN2 reaction was employed to make macro CTA (Me-PEG-XA, XA-PEG-XA, XA refers to the xanthate group). The macro CTAs were used further for VDF polymerization in dimethyl carbonate (DMC) inside the autoclave. Different molecular weights of the PVDF block (whether in the diblocks or the tribolcks) were obtained based on changes in the reaction time. The resulting block copolymers were molecularly characterized by FT-IR, 1H,19F-NMR, and SEC. The thermal properties were studied by DSC and TGA. Furthermore, the crystalline phase characterization was investigated by XRD and FT-IR. Being the obtained block copolymers are amphiphilic, their self-assembly was achieved by nanoprecipitation in DMF/water, and they were analyzed by DLS and TEM.

Present-day commonly used systems like Cassandra, Spanner, and CockroachDB require high availability and strict consistency guarantees. High availability is attained through redundancy. In the field of computing, redundancy is attained through state machine repli- cation. Protocols like Raft, Multi-Paxos, ZAB, or other variants of Paxos are commonly used to achieve state machine replication. These protocols choose one of the processes from multiple processes running on various machines in a distributed setting as the leader. The leader is responsible for client interactions, replicating client operations on all the followers, and maintaining a consistent view across the system. In these protocols, the leader is more loaded than other nodes or followers in the system, making the leader a significant scalabil- ity bottleneck for multi-datacenter and edge deployments. The overall commit throughput and latency are further exacerbated in majority agreement with the hardware and network heterogeneity. This work aims to reduce the load on the leader by using reduced dynamic latency-aware flexible quorums while maintaining strict correctness guarantees like linearizability. In this thesis, we implement dynamic reduced-size commit quorums to reduce the leader’s load and improve throughput and latency, called FDRaft. The commit quorums are computed based on an exponentially moving weighted average of the followers’ time to respond to the leader, accounting for the heterogeneity in hardware and network. The reduced commit quorum requires a bigger election quorum, but elections rarely happen, and a single leader can serve for significant durations. We evaluate this protocol using a key-value store built on FDRaft and Raft and compare multi-datacenter and edge deployments. The evaluation shows 2x improved throughput and around 55% improved latency over Raft during normal operations and 45% improvement over Raft with vanilla flexible-quorums under failure conditions. / M.S. / In our day-to-day life, we rely heavily on different internet applications, be it Instagram for sharing pictures, Amazon for our shopping, Doordaash for our food orders, Spotify for listening to music, or Uber for traveling. These applications share many commonalities, like the scale at which they operate, maintaining strict latency guarantees, high availability to serve the users, and using databases to maintain shared states. The data is replicated across multiple servers to provide fault tolerance against failures. The replication across multiple servers is achieved through state-machine replication. In state-machine replication, multiple servers start with the same initial state and perform operations in the same order to reach the same final state. This process of replication in computing is achieved through a consensus algorithm. Con- sensus means agreement, and consensus algorithms are used to reach an agreement for a particular value. Raft, Multi-Paxos, or any other variant of Paxos are the commonly used consensus algorithms to achieve agreement on a particular value in a distributed setting. In these algorithms, one of the servers is chosen as the leader responsible for client interactions, replicating and maintaining the same state across all the servers, even when faced with server and network failures. Every time the leader receives a client operation, it starts the consensus process by forwarding the client request to all the servers and committing the client request after receiving an agreement from the majority. As the leader does most of the work, it is more loaded than other servers and becomes a significant scalability bottleneck. The leader bottleneck becomes more evident in multi-datacenters and edge deployments. The hardware and network heterogeneity also severely affects the overall commit throughput and latency in majority agreement. In this thesis, we reduce the load on the leader by building a smaller-sized dynamic commit quorum with latency-aware server selection based on an exponentially weighted moving av- erage of the followers’ response time to the leader’s requests without compromising safety and liveness properties. Our design also provides a higher efficiency for throughput and commit latency. We evaluate this protocol against multiple workloads and failure conditions and find that it outperforms Raft by 2x in terms of throughput and around 55% in latency over Raft during normal operations. It also shows improvement in throughput and latency by 45% over Raft with vanilla flexible-quorums under failure conditions.

Plastic waste is a severe environmental problem in today's society which has been noticed and discussed during the last couple of years. A constant increase of production over the last decades hasled to a large amount of plastic waste ending up in oceans as microplastics. With harder restrictions of plastic use from the European Parliament, alternative plastics that are bio-based and therefore degradable have increased in demand. The aim of this project was therefore to synthesize alignocellulose-based material which contains the minimum amount of latex, the plastic component, while still satisfying the same requirements as a thermoplastic. The original idea was to create the latex with PISA-RAFT technique however, this was not possible since the needed materials could not be delivered due to COVID-19, therefore radical emulsion polymerization was carried out. Two latexes were synthesized to create composites with wheat-straw, latex A and latex B. Both latexes consisted of 75% of monomer vinyl acetate (VAc) which was the main component but with different weight percentages of monomers methacrylic acid (MAA) and methyl methacrylate (MMA). Latex A consisted of 20 % MAA and 5% MMA and latex B consisted of 20% MMA and 5% MAA. Latex A and latex B were then mixed with wheat straw to create composites. Due to problems withthe wheat-straw composites one additional composite was created to be able to do all of the analyses. This composite was created by using filter paper as biofiber to mix with the two different latexes. Various characterization analyses including FE-SEM, DLS, DSC, FTIR, NMR, TGA and tensile tests were performed on the composites. The NMR and DSC analyses indicated that the actual composition of monomers differs from the theoretical composition and demonstrates that the presence of MAA is hard to detect. This is due to the DSC value for latex A experimental Tg being lower than latex B experimental Tg when latex A consists of more MAA which has a higher detected Tg. During the NMR analysis MAA was also not detected in either latex A nor latex B. The analyses of FTIR contradicts the NMR and DSC analyses hence peaks believed to be from MAA are detected. When comparing the analysis for latex A and B, DLS analysis resulted in latex A having a low PDI and a bigger emulsion sphere size which is preferred when producing composites. The tensile test resulted in latex B achieving the higher values for Young’s modulus and max stress while latex A had a higher value for strain at break. The TGA and DSC analysis however resulted in latex B having a higher Tg and higher thermal stability. The overall analyses indicated that latex B was the most optimal choice for composite production with aslight difference. The analysis of the composites indicated by FE-SEM that the interaction between latex and filter paper were higher than for latex and wheat straw. A total of four wheat-straw composites were created with the weight-ratio of wheat-straw:latex, 50:50 and 75:50 for both latex A and B. Due to not being able to grind the wheat straw to the minimum size needed to create composites only FE-SEM and FTIR analyses of the wheat-straw composites could be made. Because of this no conclusion could be made whether the 75:50 or 50:50 weight ratio was the most optimal. / Plastavfall är ett allvarligt miljöproblem i dagens samhälle som uppmärksammats mycket under de senaste åren. En ständig ökning i produktionen under de senaste decennier har lett till att stora mängder plast hamnat i haven där de sönderdelas till mikroplaster. Med strängare krav av plastanvändning från Europaparlamentet har nya alternativa plaster som är biobaserade och därmed nedbrytbara ökat i efterfråga. Målet med detta projekt var därför att syntetisera ett lignocellulosabaserat material som innehåller så lite icke-nedbrytbar latex, plastkomponenten, som möjligt utan att behöva mista de egenskaper som efterfrågas av termoplaster idag. Den ursprungliga idén var att syntetisera latexen genom PISA-RAFT tekniken, dessvärre pga rådande omständigheter gällande COVID-19 var detta inte möjligt då materialen som behövdes inte kunde levereras. Därför syntetiserades latexen genom emulsionspolymerisation istället. På grund av problem med halmen skapades två olika typer av kompositer, halm kompositer och filterpapper kompositer. De två kompositerna gjordes i två varianter, en innehållande latex A och en med latex B. Latex A och B syntetiserades av olika mängd monomerer vilka var metakrylsyra (MAA) och metylmetakrylat (MMA). Både latex A och B innehöll 75 % av monomeren vinylacetat (VAc). Olika karakteriseringsmetoder, FE-SEM, DLS, DSC, FTIR, NMR, TGA och tensile test utfördes på kompositerna. NMR och DSC analyserna indikerade att den analyserade kompositionen av monomererna skiljer sig åt från den teoretiska kompositionen då närvaron av MAA var svår att detektera. FTIR analysen motsäger dock de analyserade värdena av NMR och DSC då MAA tros ha detekteras då. För jämförelsen av latex A och B resulterade DLS i lägre PDI och större emulsions sfärer för latex A vilket föredras vid produktion av kompositer. Genom analys av tensile test uppnådde latex B högre värden för Young`s modul och max stress medans latex A uppnådde högre värden för belastning vid brottet. TGA och DSC analysen resulterade dock i högre Tg och högre termisk stabilitet för latex B. Den övergripande analysen indikerade att latex B var det mer optimala valet för kompositproduktion meden liten skillnad i jämförelse. Analysen av kompositerna genom FE-SEM indikerade att interaktionen mellan latex och filterpapper var högre än latex och halmen. Total skapades fyra halm kompositer med halm:latex viktförhållandet 50:50 och 75:50 för både latex A och B. Till följd av att halmen inte kunde malas ned till den minimala storleken som behövdes för att bilda kompositer, kunde endast FE-SEM och FTIR analyser utföras. På grund av detta kunde ingen slutsats dras om vilket viktförhållande, 50:50 eller 75:50, som bildade den mest optimala kompositen.

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