Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2018. / Cataloged from PDF version of thesis. / Includes bibliographical references (pages 127-136). / The functional versatility and endurable self-healing capacity of soft materials in nature is found to originate from the dynamic supramolecular scaffolds assembled via reversible interactions. To mimic this strategy, extensive efforts have been made to design polymer networks with transient crosslinks, which lays the foundation for synthetic self-healing hydrogels. Towards the development of stronger and faster self-healing hydrogels, understanding and controlling the gel network dynamics is of critical importance, since it provides design principles for key properties such as dynamic mechanics and self-healing performance. For this purpose, a universal strategy independent of exact crosslinking chemistry would be regulating the polymer material's dynamic behavior by optimal network design, yet current understanding of the relationship between network structure and macroscopic dynamic mechanics is still limited, and implementation of complex network structure has always been challenging. In this thesis, we show how the dynamic mechanical properties in a hydrogel can be controlled by rational design of polymer network structures. Using mussel-inspired reversible catechol coordination chemistry, we developed a nanocomposite hydrogel network (NP gel) with hierarchical assembly of polymer chains on iron oxide (Fe3O4) nanoparticles as network crosslinks. With NP gel as a model system, we first investigated its unique dynamic mechanics in comparison with traditional permanent and dynamic gels, and discovered a general approach to manipulate the network dynamics by controlling the crosslink structural functionality. Then we further explored the underlying relationship between polymer network structure and two key parameters in relaxation mechanics, which elucidated universal approaches for designing relaxation patterns in supramolecular transient gel network. Finally, by utilizing these design principles, we designed a hybrid gel network using two crosslinking structures with distinct relaxation timescales. By simply adjusting the ratio of two crosslinks, we can precisely tune the material's dynamic mechanics from a viscoelastic fluid to a rigid solid. Such controllability in dynamic mechanics enabled performance optimization towards mechanically rigid and fast self-healing hydrogel materials. / by Qiaochu Li. / Ph. D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1993. / Includes bibliographical references (leaves 183-190). / by Omar Salman Abdul-Hamid. / Ph.D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1997. / Includes bibliographical references (leaves 187-196). / by Libby K. Louie. / Ph.D.

<p> Three dimensional fiber reinforced foam cores (3DFRFC) can have improved mechanical properties under specific strain rates and fiber volumes. This study explored different manufacturing techniques for the 3DFRFC and tested the specimens at dynamic loading rates of 69&ndash;10³ s^&ndash;1. Flexural bend test showed that glass fibers made the samples stronger yet more brittle while quasi-static compression tests showed a decrease in performance with 3DFRFC. High strain impact tests validated previously published studies by showing an 18&ndash;20% reduction in the maximum force experienced by the fiber reinforced core and its ability to dissipate the impact force in the foam core sandwich panel. The results show potential for the cost-effective manufacturing method used in this study to produce an improved composite foam core sandwich panel for armored applications where high strain rates are present and reduce the overall weight of vehicles while maintaining the desired strength performance.</p><p>

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2007. / Includes bibliographical references (leaves 63-65). / Thin film component properties are critical design elements in almost all industries. These films are particularly important in the performance of micro- and nano-electromechanical systems (MEMS and NEMS). Residual stress in thin film components is often treated as an unavoidable side effect of processing steps and the degree of residual stress can drastically affect the performance and properties of the final product. While high levels of residual stress are often detrimental to performance, control of the stress and stress gradients can also be used to enhance performance and even generate new capabilities. The work presented in this thesis examines the role of island coalescence in the development of structure and stress in thin films. The primary methods of investigation are molecular dynamics (MD) and finite element analysis (FEA). The semi-empirical MD calculations show that coalescence is a very rapid process for unconstrained spheres and for hemispheres allowed to slide on a frictionless substrate. Particle rotations are commonly observed during the coalescence calculations. The extent of neck formation between 2 particles is consistent with continuum models even down to length scales which would normally be outside the range in which the models might be expected to be applicable. The MD calculations also show that internal island defects may be induced by the island coalescence process, but only for a particular range of island sizes. We present an energetic model for the existence of such a size range and have located experimental evidence in the literature for such defects. Our FEA work extends an earlier study on the effects of contact angle on island coalescence. Our FEA study of islands with greater than 90 degree contact angle coalescence shows that neck formation occurs very similarly to the free sphere coalescence case. We conclude that MD and FEA calculations are useful tools in analyzing the island coalescence process and can provide mechanistic insight beyond what is available from the more general continuum models. / by Andrew Rikio Takahashi. / S.M.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2011. / This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections. / Cataloged from PDF version of thesis. / Includes bibliographical references (p. 167-184). / T cells are required by their immunological roles to recirculate in the body and migrate to tissue sites, a journey that exposes them to distorting forces and physical obstacles that hinder their movement. Therefore, they must possess appropriate deformability to accommodate and adapt to these mechanical stimuli to migrate unimpeded. Since T cells alter their physical properties and migration routes upon activation, they may possess dissimilar mechanical properties as a result of this process. This hypothesis was tested using the techniques micropipette aspiration and atomic force microscopy, which allow the investigation of the elastic and viscous responses of single T cells. It was discovered that the activation process reduced T cell stiffness by more than three folds, a finding that agrees with the motility gain observed in activated T cells. The same testing procedure was applied to Wiskott-Aldrich syndrome protein (WASp)-deficient T cells that exhibit abnormal morphology and impaired chemotaxis. The stiffness of the diseased cells in the naive state was 1.5 times less than that of the non-diseased cells, a result that may be due to the disrupted polymerization and cross-linking of the actin cytoskeleton in the absence of WASp, a regulator of actin growth and organization. Furthermore, the viscous response of the diseased cells in the activated state was found to be impaired. Chemokines were found to dramatically reduce the stiffness of naive T cells that were induced to migrate. These findings suggest that WASp plays an important role in maintaining cell mechanical property and facilitating T cell extravasation by tailoring the cells' deformability. At the molecular level, activation of T cells is triggered by the binding of their surface receptors to antigens, a mechanism that is also key in T cell development. In both cases, the bond strength, conventionally measured by the affinity (KD) or the dissociation rate (koff) of the interacting pair, dictates the biological outcome. Since a few weak interactions may nudge a sub-threshold signal over the threshold strength, and observing that the current methods for measuring KD and koff lack the resolution to detect very weak bonds, this work explored the possibility of utilizing dynamic force spectroscopy (DFS) to study very weak binding strengths. Preliminary results confirm this capability. / by Irene Yin-Ting Chang. / Ph.D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1996. / Includes bibliographical references (p. 191-204). / by Gerardo Damián Garbulsky. / Ph.D.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1986. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Bibliography: leaves 47-48. / by James Forrest Kirk. / M.S.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2005. / Includes bibliographical references (p. 147-158). / Monolithic integration has been implemented successfully in complementary metal oxide semiconductor (CMOS) technology and led to improved device performance, increased reliability, and overall cost reduction. The next element to be incorporated on the silicon chip is the power unit; possibly as part of the back end process of the very large scale integrated (VLSI) circuits' production. This thesis describes the work done in developing and studying thin film integrated lithium ion batteries compatible with microelectronics with respect to the material system employed, the cells' fabrication methods, and performance. The project consisted of three stages; first, a material system new to the battery application field was explored and power cells were fabricated and characterized. In the second stage, the fabrication process of the first material system cells was optimized thereby improving their performance. The third stage dealt with a more conventional battery material system, utilizing thin film technology to fabricate and explore power cells. / (cont.) All the cells fabricated in this work were created using microelectronic technology and were characterized by thin film analysis techniques and by measurement equipment commonly used for microelectronic device testing. The cells were fabricated in four sizes of active areas: 5x5 mm², 2x2 mm², lxl mm², and 0.5x0.5 mm². The first material system consisted of a novel lithium-free electrolyte in the form of an ultra-thin SiO₂ layer, thermally grown from sacrificial polysilicon layer on a doped polysilicon anode. The concept of SiO₂ as an electrolyte is innovative since common solid state lithium and lithium ion batteries consist of 1-2 ptm thick lithium-containing electrolytes. The controlled transport of lithium through SiO₂, 9-40 nm thick, was studied for electrolyte application. The fabricated LiCoO₂/SiO₂/polysilicon cells were successfully charged and discharged. This stage of the project demonstrated the concept of an ultra-thin lithium free electrolyte layer and introduces SiO₂ as an interesting candidate material. The second stage of the project focused on improving the LiCoO₂/SiO₂/polysilicon cell's performance and optimizing its fabrication process. / (cont.) Chemical mechanical polishing (CMP), a typical planarization method in microelectronics, new to the battery application field, was introduced in order to enhance the cell's properties and performance. LiCoO₂/SiO₂/polysilicon cells consisting of Si0₂ layers 7-40 nm thick were studied. Cells with the planarized polysilicon anode were characterized and the planarization effect was evaluated. This stage demonstrates the importance of interfacial quality in thin film batteries and the advantages incorporation of CMP as a planarization step in the fabrication process. Finally, the third stage of the project focused on applying the thin film technology knowledge and expertise to a more commonly used material system V₂0₅/LiPON/LiCoO₂. With the aim of reducing interfacial roughness, a surface morphology study of V₂0₅ was performed, tailoring different deposition conditions and surface morphology. Implementing the optimized conditions obtained from this analysis, a V₂0₅/LiPON/LiCoO₂ rocking-chair battery was studied next. The cells consisted of approximately 100 or 350 nm thick lithium phosphorus oxynitride (LiPON) electrolyte. / (cont.) This stage demonstrated the advantage of thin film technology in reducing film thickness and the performance enhancement achieved. The work described in this thesis approached the thin film battery subject from the microelectronic perspective, in order to "bring the battery into the clean room". / by Nava Ariel. / Ph.D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2007. / This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections. / Includes bibliographical references (p. 207-225). / Polyelectrolyte multilayers (PEMs) are a versatile type of thin film that is created via layer-by-layer assembly of positively and negatively charged polymers from aqueous solutions. Precise control of the PEM thickness, chemical functionality, and molecular architecture is made possible by changing the polyelectrolytes and assembly conditions during film growth, allowing films to be designed with properties suitable for a given application. This thesis elucidates the intra-film structure and interactions of PEMs through the use of optical, mechanical, and chemical techniques. PEM rugate filters, wherein the refractive index varies through the depth of the film in a continuous, periodic fashion, were constructed by confining silver nanoparticle growth to layers of nanometer-scale thickness. The ability to construct such structures is shown to be dependent on the ability to precisely control the concentration of metal-binding carboxylic acid groups throughout the depth of the film. Software to enable the computation design and optical simulation of these and similar structures was developed. / (cont.) A buckling instability technique was used to probe the Young's modulus of PEM assemblies as a function of polyelectrolyte type, assembly pH, and the relative humidity of the ambient environment. In particular, a two-plate methodology was developed to allow testing on a broad array of multilayer films, and an experimental apparatus was constructed to allow in situ modulus measurements of PEM films under controlled humidity conditions. These techniques are used to elucidate the strong effects that polyelectrolyte type, assembly pH, and the ambient humidity can have on the stiffness of PEM films. The controlled removal of material from assembled PEMs was accomplished via etching of films in solutions of increasing ionic strength. The properties of etched films and process dynamics point to evidence of a polydispersity-enabled phenomenon driven by dissolution of polyelectrolyte complexes containing chains of disproportionate molecular weight. Kinetic and equilibrium data are presented that support this hypothesis. Beyond elucidation of the underlying mechanisms governing molecular interactions within PEMs, possible practical applications for the particular PEM assemblies described in this thesis are discussed, including conformable interference filters and buckling-enabled patterning. / by Adam John Nolte. / Ph.D.