Ultrafast and reversible multiblock formation by the SET-Nitroxide radical coupling reaction

The single electron transfer-nitroxide radical coupling (SET-NRC) reaction has been used to produce multiblock polymers with high molecular weights in under 3 min at 50◦C by coupling a difunctional telechelic polystyrene (Br-PSTY-Br)with a dinitroxide. The well known combination of dimethyl sulfoxide as solvent and Me6TREN as ligand facilitated the in situ disproportionation of CuIBr to the highly active nascent Cu0 species. This SET reaction allowed polymeric radicals to be rapidly formed from their corresponding halide end-groups. Trapping of these carbon-centred radicals at close to diffusion controlled rates by dinitroxides resulted in high-molecular-weight multiblock polymers. Our results showed that the disproportionation of CuI was critical in obtaining these ultrafast reactions, and confirmed that activation was primarily through Cu0. We took advantage of the reversibility of the NRC reaction at elevated temperatures to decouple the multiblock back to the original PSTY building block through capping the chain-ends with mono-functional nitroxides. These alkoxyamine end-groups were further exchanged with an alkyne mono-functional nitroxide (TEMPO–≡) and ‘clicked’ by a CuI-catalyzed azide/alkyne cycloaddition (CuAAC) reaction with N3–PSTY–N3 to reform the multiblocks. This final ‘click’ reaction, even after the consecutive decoupling and nitroxide-exchange reactions, still produced high molecular-weight multiblocks efficiently. These SET-NRC reactions would have ideal applications in re-usable plastics and possibly as self-healing materials.

Irradiation-mediated tailoring of carbon nanotubes

The ever-increasing demand for faster computers in various areas, ranging from entertaining electronics to computational science, is pushing the semiconductor industry towards its limits on decreasing the sizes of electronic devices based on conventional materials. According to the famous law by Gordon E. Moore, a co-founder of the world s largest semiconductor company Intel, the transistor sizes should decrease to the atomic level during the next few decades to maintain the present rate of increase in the computational power. As leakage currents become a problem for traditional silicon-based devices already at sizes in the nanometer scale, an approach other than further miniaturization is needed to accomplish the needs of the future electronics. A relatively recently proposed possibility for further progress in electronics is to replace silicon with carbon, another element from the same group in the periodic table. Carbon is an especially interesting material for nanometer-sized devices because it forms naturally different nanostructures. Furthermore, some of these structures have unique properties. The most widely suggested allotrope of carbon to be used for electronics is a tubular molecule having an atomic structure resembling that of graphite. These carbon nanotubes are popular both among scientists and in industry because of a wide list of exciting properties. For example, carbon nanotubes are electronically unique and have uncommonly high strength versus mass ratio, which have resulted in a multitude of proposed applications in several fields. In fact, due to some remaining difficulties regarding large-scale production of nanotube-based electronic devices, fields other than electronics have been faster to develop profitable nanotube applications. In this thesis, the possibility of using low-energy ion irradiation to ease the route towards nanotube applications is studied through atomistic simulations on different levels of theory. Specifically, molecular dynamic simulations with analytical interaction models are used to follow the irradiation process of nanotubes to introduce different impurity atoms into these structures, in order to gain control on their electronic character. Ion irradiation is shown to be a very efficient method to replace carbon atoms with boron or nitrogen impurities in single-walled nanotubes. Furthermore, potassium irradiation of multi-walled and fullerene-filled nanotubes is demonstrated to result in small potassium clusters in the hollow parts of these structures. Molecular dynamic simulations are further used to give an example on using irradiation to improve contacts between a nanotube and a silicon substrate. Methods based on the density-functional theory are used to gain insight on the defect structures inevitably created during the irradiation. Finally, a new simulation code utilizing the kinetic Monte Carlo method is introduced to follow the time evolution of irradiation-induced defects on carbon nanotubes on macroscopic time scales. Overall, the molecular dynamic simulations presented in this thesis show that ion irradiation is a promisingmethod for tailoring the nanotube properties in a controlled manner. The calculations made with density-functional-theory based methods indicate that it is energetically favorable for even relatively large defects to transform to keep the atomic configuration as close to the pristine nanotube as possible. The kinetic Monte Carlo studies reveal that elevated temperatures during the processing enhance the self-healing of nanotubes significantly, ensuring low defect concentrations after the treatment with energetic ions. Thereby, nanotubes can retain their desired properties also after the irradiation. Throughout the thesis, atomistic simulations combining different levels of theory are demonstrated to be an important tool for determining the optimal conditions for irradiation experiments, because the atomic-scale processes at short time scales are extremely difficult to study by any other means.

Tailored interface and enhanced elastic modulus in epoxy-based composites in presence of branched poly(ethyleneimine) grafted multiwall carbon nanotubes

In this study, branched poly(ethyleneimine), BPEI, was synthesized from carboxylic acid terminated multi-walled carbon nanotubes (c-MWNTs) and characterized using FTIR, TEM and TGA. The BPEI was then chemically grafted onto MWNTs to enhance the interfacial adhesion with the epoxy matrix. The epoxy composites with c-MWNTs and the BPEI-g-MWNTs were prepared using a sonication and mechanical stirring method, followed by curing at 100 degrees C and post-curing at 120 degrees C. The dynamic mechanical thermal analysis showed an impressive 49% increment in the storage elastic modulus in the composites. In addition, the nanoindentation on the composites exhibited significant improvement in the hardness and decrease in the plasticity index in the presence of the BPEI-g-MWNTs. Thus, epoxy composites with BPEI-g-MWNTs can be further explored as self-healing materials.

Sensing and Actuation from Biology to Electronics

We introduce an in vitro diagnostic magnetic biosensing platform for immunoassay and nucleic acid detection. The platform has key characteristics for a point-of-use (POU) diagnostic: portability, low-power consumption, low cost, and multiplexing capability. As a demonstration of capabilities, we use this platform for the room temperature, amplification-free detection of a 31 bp DNA oligomer and interferon-gamma (a protein relevant for tuberculosis diagnosis). Reliable assay measurements down to 100 pM for the DNA and 1 pM for the protein are demonstrated. We introduce a novel "magnetic freezing" technique for baseline measurement elimination and to enable spatial multiplexing. We have created a general protocol for adapting integrated circuit (IC) sensors to any of hundreds of commercially available immunoassay kits and custom designed DNA sequences.

We also introduce a method for immunotherapy treatment of malignant gliomas. We utilize leukocytes internalized with immunostimulatory nanoparticle-oligonucleotide conjugates to localize and retain immune cells near the tumor site. As a proof-of-principle, we develop a novel cell imaging and incubation chamber for in vitro magnetic motility experiments. We use the apparatus to demonstrate the controlled movement of magnetically loaded THP-1 leukocytes.

Finally, we introduce an IC transmitter and power ampli er (PA) that utilizes electronic digital infrastructure, sensors, and actuators to self-heal and adapt to process, dynamic, and environmental variation. Traditional IC design has achieved incredible degrees of reliability by ensuring that billions of transistors on a single IC die are all simultaneously functional. Reliability becomes increasingly difficult as the size of a transistor shrinks. Self-healing can mitigate these variations.

群组通信环境中的密钥管理协议

随着群组通信业务的普及，群组通信的相关安全研究也随之兴起。群组密码学的概念首先由 Desmedt 提出。与传统通信中的密码学方案相比，群组密码学具有很多优点，并已经成功地运用到视频点播和分布式系统等一些应用场景中。群签名，环签名，广播加密等密码学体制作为群组密码学的重要分支都得到了学术界的密切关注。本文的研究工作集中在群组密码学的一个重要组成部分：群组密钥管理，即多个（群组）用户在不安全的开放网络环境中通过一定的协议产生一个共享的会话密钥，为后面的通信提供各种安全性保护。 本文的研究工作主要包含两个方面，群组密钥分发协议和可证明安全的认证群组密钥协商协议。在对已有的群组密钥管理方案进行了大量的调查与分析后，我们在此基础上提出了一些有价值的研究成果。本文的主要成果包括： 1. 在第二章中，提出了一种高效的长期 self-healing 群组密钥分发方案。和已有方案相比，新方案的优势包括：（1）我们避免了使用指数运算, 而只是域上多项式的相关运算；（2）群组管理者广播消息次数比 Staddon 等人和Blundo 等人的方案少一次；（3）用户端存储私钥数目比 Staddon 等人的方案少将近一半；（4）新协议的安全性为无条件安全。 2. 在第三章中，构造了一个从一般群组密钥协商协议向基于口令认证的群组密钥协商协议转换的编译器。编译器的构造利用了对称加密体制，NM-CCA2 和 IK-CCA2 安全的公钥加密体制，以及 UF-CMA 安全的数字签名体制，从而使得编译器可以避免在线/离线字典攻击。 3. 在第四章中，提出了一个基于口令认证的群组密钥协商协议，使得网关在认证服务器的协助下和多个用户之间建立一个会话密钥，同时认证服务器不知道此会话密钥的任何信息（网关和认证服务器之间的信道是专用信道）。由于意识到口令的泄露往往是由于用户的不当使用造成的，所以，不同于已有的基于口令认证的门限密钥协商机制，我们的门限方案是在用户端实施。我们的门限方案要求把用户群组和认证服务器预先共享的口令（称之为群组口令）以秘密共享方式分散共享在群组用户之间，并且每个用户所存储口令的子秘密（share）值依然是一个易记忆的口令（称之为用户口令）。只有不少于 k 个用户一起才能恢复出群组口令。 4. 在第五章中，利用了Unified 模型（把用户长期私钥嵌入到密钥协商过程）构造了一个在 Strong Corruption 模型下可证明安全的强健的认证群组密钥协商协议。和已有类似方案相比，新方案所需要的签名数量明显减少，从而，计算复杂度和通信复杂度也随之降低。另外，新协议是在 Strong Corruption 模型下可证明安全，在此模型下的类似协议比较少。 5. 在第六章中，对 Desmedt 等人提出的 BD-II（树型）群组密钥协商协议做出改进。利用在树中各个节点上应用遮罩函数，我们把由于群组关系变化而对密钥更新所产生的影响限制在一个比较小的群组范围中，从而提高了协议在动态情况下运行的效率。新协议通过四个子算法：初始化，成员加入，成员撤销，子群组合并来分别应对群组密钥协商过程中所遇到的各种（动态）情况。

Constructing Thin Polythiophene Film Composed of Aligned Lamellae via Controlled Solvent Vapor Treatment

Thin poly(3-butylthiophene) (P3BT) film composed of aligned lamellae attached to the edge of the original film has been achieved via a controlled solvent vapor treatment (C-SVT) method. The polarized optical microscopy operated at both single-polarization and cross-polarization modes has been used to investigate the alignment of the fiber-like lamellae. A numerical simulation method is used to quantitatively calculate angle distributions of the lamellae deviated from the film growth direction. Prepatterned P3BT film edge acts as nuclei which densely initialize subsequent crystal growth by exhausting the materials transported from the partially dissolved film. The growth of new film upon crystallization is actually a self-healing process where the two-dimensional geometric confinement is mainly responsible for this parallel alignment of P3BT crystals. The solvent vapor pressure should be carefully chosen so as to induce crystal growth but avoid liquid instability which will destroy the continuity of the film.

Vascular structures for volumetric cooling and mechanical strength

When solid material is removed in order to create flow channels in a load carrying structure, the strength of the structure decreases. On the other hand, a structure with channels is lighter and easier to transport as part of a vehicle. Here, we show that this trade off can be used for benefit, to design a vascular mechanical structure. When the total amount of solid is fixed and the sizes, shapes, and positions of the channels can vary, it is possible to morph the flow architecture such that it endows the mechanical structure with maximum strength. The result is a multifunctional structure that offers not only mechanical strength but also new capabilities necessary for volumetric functionalities such as self-healing and self-cooling. We illustrate the generation of such designs for strength and fluid flow for several classes of vasculatures: parallel channels, trees with one, two, and three bifurcation levels. The flow regime in every channel is laminar and fully developed. In each case, we found that it is possible to select not only the channel dimensions but also their positions such that the entire structure offers more strength and less flow resistance when the total volume (or weight) and the total channel volume are fixed. We show that the minimized peak stress is smaller when the channel volume (φ) is smaller and the vasculature is more complex, i.e., with more levels of bifurcation. Diminishing returns are reached in both directions, decreasing φ and increasing complexity. For example, when φ=0.02 the minimized peak stress of a design with one bifurcation level is only 0.2% greater than the peak stress in the optimized vascular design with two levels of bifurcation. © 2010 American Institute of Physics.

Engineering emergence for cluster configuration

Distributed applications are being deployed on ever-increasing scale and with ever-increasing functionality. Due to the accompanying increase in behavioural complexity, self-management abilities, such as self-healing, have become core requirements. A key challenge is the smooth embedding of such functionality into our systems. Natural distributed systems such as ant colonies have evolved highly efficient behaviour. These emergent systems achieve high scalability through the use of low complexity communication strategies and are highly robust through large-scale replication of simple, anonymous entities. Ways to engineer this fundamentally non-deterministic behaviour for use in distributed applications are being explored. An emergent, dynamic, cluster management scheme, which forms part of a hierarchical resource management architecture, is presented. Natural biological systems, which embed self-healing behaviour at several levels, have influenced the architecture. The resulting system is a simple, lightweight and highly robust platform on which cluster-based autonomic applications can be deployed.

Force-induced activation of covalent bonds in mechanoresponsive polymeric materials

Mechanochemical transduction enables an extraordinary range of physiological processes such as the sense of touch, hearing, balance, muscle contraction, and the growth and remodelling of tissue and
bone1–6. Although biology is replete with materials systems that actively and functionally respond to mechanical stimuli, the default mechanochemical reaction of bulk polymers to large external stress is the unselective scission of covalent bonds, resulting in damage or failure7. An alternative to this degradation process is the rational molecular design of synthetic materials such that mechanical stress
favourably altersmaterial properties. A few mechanosensitive polymers with this property have been developed8–14; but their active response is mediated through non-covalent processes, which may
limit the extent to which properties can be modified and the longterm stability in structural materials. Previously, we have shown with dissolved polymer strands incorporating mechanically sensitive chemical groups—so-called mechanophores—that the directional nature of mechanical forces can selectively break and re-form covalent bonds15,16. We now demonstrate that such forceinduced covalent-bond activation can also be realized with mechanophore-linked elastomeric and glassy polymers, by using a mechanophore that changes colour as it undergoes a reversible electrocyclic ring-opening reaction under tensile stress and thus allows us to directly and locally visualize the mechanochemical reaction. We find that pronounced changes in colour and fluorescence emerge with the accumulation of plastic deformation, indicating that in these polymeric materials the transduction of mechanical force into the ring-opening reaction is an activated process. We anticipate that force activation of covalent bonds can serve as a general strategy for the development of new mechanophore building blocks that impart polymeric materials with desirable functionalities ranging from damage sensing to fully regenerative self-healing.

Active corrosion protection of AA2024 by sol-gel coatings with corrosion inhibitors

A indústria aeronáutica utiliza ligas de alumínio de alta resistência para o fabrico dos elementos estruturais dos aviões. As ligas usadas possuem excelentes propriedades mecânicas mas apresentam simultaneamente uma grande tendência para a corrosão. Por esta razão essas ligas necessitam de protecção anticorrosiva eficaz para poderem ser utilizadas com segurança. Até à data, os sistemas anticorrosivos mais eficazes para ligas de alumínio contêm crómio hexavalente na sua composição, sejam pré-tratamentos, camadas de conversão ou pigmentos anticorrosivos. O reconhecimento dos efeitos carcinogénicos do crómio hexavalente levou ao aparecimento de legislação banindo o uso desta forma de crómio pela indústria. Esta decisão trouxe a necessidade de encontrar alternativas ambientalmente inócuas mas igualmente eficazes. O principal objectivo do presente trabalho é o desenvolvimento de prétratamentos anticorrosivos activos para a liga de alumínio 2024, baseados em revestimentos híbridos produzidos pelo método sol-gel. Estes revestimentos deverão possuir boa aderência ao substrato metálico, boas propriedades barreira e capacidade anticorrosiva activa. A protecção activa pode ser alcançada através da incorporação de inibidores anticorrosivos no prétratamento. O objectivo foi atingido através de uma sucessão de etapas. Primeiro investigou-se em detalhe a corrosão localizada (por picada) da liga de alumínio 2024. Os resultados obtidos permitiram uma melhor compreensão da susceptibilidade desta liga a processos de corrosão localizada. Estudaram-se também vários possíveis inibidores de corrosão usando técnicas electroquímicas e microestruturais. Numa segunda etapa desenvolveram-se revestimentos anticorrosivos híbridos orgânico-inorgânico baseados no método sol-gel. Compostos derivados de titania e zirconia foram combinados com siloxanos organofuncionais a fim de obter-se boa aderência entre o revestimento e o substrato metálico assim como boas propriedades barreira. Testes industriais mostraram que estes novos revestimentos são compatíveis com os esquemas de pintura convencionais actualmente em uso. A estabilidade e o prazo de validade das formulações foram optimizados modificando a temperatura de armazenamento e a quantidade de água usada durante a síntese. As formulações sol-gel foram dopadas com os inibidores seleccionados durante a primeira etapa e as propriedades anticorrosivas passivas e activas dos revestimentos obtidos foram estudadas numa terceira etapa do trabalho. Os resultados comprovam a influência dos inibidores nas propriedades anticorrosivas dos revestimentos sol-gel. Em alguns casos a acção activa dos inibidores combinou-se com a protecção passiva dada pelo revestimento mas noutros casos terá ocorrido interacção química entre o inibidor e a matriz de sol-gel, de onde resultou a perda de propriedades protectoras do sistema combinado. Atendendo aos problemas provocados pela adição directa dos inibidores na formulação sol-gel procurou-se, numa quarta etapa, formas alternativas de incorporação. Na primeira, produziu-se uma camada de titania nanoporosa na superfície da liga metálica que serviu de reservatório para os inibidores. O revestimento sol-gel foi aplicado por cima da camada nanoporosa. Os inibidores armazenados nos poros actuam quando o substrato fica exposto ao ambiente agressivo. Numa segunda, os inibidores foram armazenados em nano-reservatórios de sílica ou em nanoargilas (halloysite), os quais foram revestidos por polielectrólitos montados camada a camada. A terceira alternativa consistiu no uso de nano-fios de molibdato de cério amorfo como inibidores anticorrosivos nanoparticulados. Os nano-reservatórios foram incorporados durante a síntese do sol-gel. Qualquer das abordagens permitiu eliminar o efeito negativo do inibidor sobre a estabilidade da matriz do sol-gel. Os revestimentos sol-gel desenvolvidos neste trabalho apresentaram protecção anticorrosiva activa e capacidade de auto-reparação. Os resultados obtidos mostraram o elevado potencial destes revestimentos para a protecção anticorrosiva da liga de alumínio 2024.

A governance approach to integrated rural tourism: factors influencing organisational performance and tourism support of local development organisations

Ao longo das últimas três décadas, o envolvimento das comunidades na formulação de políticas locais tem vindo a ganhar cada vez mais atenção como uma abordagem sustentável para o desenvolvimento rural na União Europeia (UE) e no mundo. Emergendo da globalização, novas estruturas de governação têm desafiado a base territorial restricta da autoridade do Estado soberano através do envolvimento de uma rede complexa e de autoorganização de atores governamentais e não-governamentais na tomada de decisões coletivas. A reestruturação territorial e institucional das zonas rurais, associada à expansão da governança rural, ganhou atenção considerável na literatura. No entanto, o potencial de empregar princípios de governança como fatores que determinam as direções de desenvolvimento rural através de desempenho organizacional e apoio no turismo não tem sido amplamente explorado na literatura. Deste modo, o principal objetivo desta tese consiste no emprego de ‘integração’, ‘participação’ e ‘empowerment’ como fatores críticos que influenciam os rumos do desenvolvimento rural (1) através do desempenho organizacional das organizações de governança rural e (2) apoio no turismo de organizações de desenvolvimento rural tendo em vista a validação da abordagem de governança para o turismo integrado. Ao longo deste duplo objectivo geral, a tese é dividida numa componente qualitativa de ‘desempenho’ e numa componente quantitativa de ‘apoio’. Seguindo uma abordagem sistemática baseada num sistema conceptual, foram realizadas 38 entrevistas em profundidade com pessoas chave envolvendo gestores do programa LEADER da UE na Hungria (34% do número total de Grupos de Ação Local [GAL]), seguido por um levantamento de campo transversal realizado através de um sistema de recolha de dados na Internet, tendo resultado em 662 questionários válidos para uma taxa de resposta de 63.6%. Os resultados da componente “desempenho” revelaram padrões na implementação dos princípios de governança, que por sua vez permitiram a identificação de fatores que permitem e restringem o desempenho organizacional. Os resultados da componente “apoio” permitiram destacar que o ponto de vista de redes de desenvolvimento local nos princípios de governança não é homogéneo. Diferenças significativas foram encontradas entre organizações responsáveis pelo planeamento e os grupos de aconselhamento. Contudo, os resultados sugeriram que a dimensão sustentável de turismo rural integrado é um prognosticador da contribuição do turismo para o desenvolvimento global da comunicade e para o apoio do turismo ao longo das redes de desenvolvimento local. Este estudo responde a uma necessidade crescente de investigação, que resulta da proliferação à escala mundial de formações de governança em sistemas de administração pública, tanto no lado dos investigadores como no lado dos praticantes.

Alkaline-earth aluminosilicate-based glass and glass-ceramic sealants for functional applications

The planar design of solid oxide fuel cell (SOFC) is the most promising one due to its easier fabrication, improved performance and relatively high power density. In planar SOFCs and other solid-electrolyte devices, gas-tight seals must be formed along the edges of each cell and between the stack and gas manifolds. Glass and glass-ceramic (GC), in particular alkaline-earth alumino silicate based glasses and GCs, are becoming the most promising materials for gas-tight sealing applications in SOFCs. Besides the development of new glass-based materials, new additional concepts are required to overcome the challenges being faced by the currently existing sealant technology. The present work deals with the development of glasses- and GCs-based materials to be used as a sealants for SOFCs and other electrochemical functional applications. In this pursuit, various glasses and GCs in the field of diopside crystalline materials have been synthesized and characterized by a wide array of techniques. All the glasses were prepared by melt-quenching technique while GCs were produced by sintering of glass powder compacts at the temperature ranges from 800−900 ºC for 1−1000 h. Furthermore, the influence of various ionic substitutions, especially SrO for CaO, and Ln2O3 (Ln=La, Nd, Gd, and Yb), for MgO + SiO2 in Al-containing diopside on the structure, sintering and crystallization behaviour of glasses and properties of resultant GCs has been investigated, in relevance with final application as sealants in SOFC. From the results obtained in the study of diopside-based glasses, a bilayered concept of GC sealant is proposed to overcome the challenges being faced by (SOFCs). The systems designated as Gd−0.3 (in mol%: 20.62MgO−18.05CaO−7.74SrO−46.40SiO2−1.29Al2O3 − 2.04 B2O3−3.87Gd2O3) and Sr−0.3 (in mol%: 24.54 MgO−14.73 CaO−7.36 SrO−0.55 BaO−47.73 SiO2−1.23 Al2O3−1.23 La2O3−1.79 B2O3−0.84 NiO) have been utilized to realize the bi-layer concept. Both GCs exhibit similar thermal properties, while differing in their amorphous fractions, revealed excellent thermal stability along a period of 1,000 h. They also bonded well to the metallic interconnect (Crofer22APU) and 8 mol% yttrium stabilized zirconium (8YSZ) ceramic electrolyte without forming undesirable interfacial layers at the joints of SOFC components and GC. Two separated layers composed of glasses (Gd−0.3 and Sr−0.3) were prepared and deposited onto interconnect materials using a tape casting approach. The bi-layered GC showed good wetting and bonding ability to Crofer22APU plate, suitable thermal expansion coefficient (9.7–11.1 × 10–6 K−1), mechanical reliability, high electrical resistivity, and strong adhesion to the SOFC componets. All these features confirm the good suitability of the investigated bi-layered sealant system for SOFC applications.