From Micro- to Nano-porous Cellular Materials with Layered 2D Microstructure

A large body of work has been committed to studying the unique properties of 2D materials such as graphene, with advancements in both the material quality and scale of mechanical exfoliation and chemical vapour deposition (CVD) methods. These emergent 2D materials have recently been engineered as the cell walls in three-dimensional structures, but their superb material properties are yet to be fully realized in this new form. This thesis investigates the CVD processing of a range of catalytic templates to open new routes towards the controlled fabrication of graphitic foams and lattices. As part of a full feedback loop, mechanical characterization of these unique cellular materials was undertaken in order to examine their deformation and failure mechanisms, including capturing their behaviour in a new hierarchical model framework. These novel structures have the potential to combine the properties of structured porous materials, i.e. low density, high geometric surface area, permeability and mechanical stability, with the intrinsic properties of 2D materials such as enhanced electrical and thermal conductivity, high mechanical strength and stiffness as well as resistance to damage from extreme temperatures and chemical attack. Such high quality 2D-material based cellular structures have manifold potential applications in electrochemistry, catalysis and filtration. Herein, freestanding graphitic foams are fabricated across a range of relative densities, and their uniaxial compressive responses are measured to investigate the operative deformation and failure mechanisms that govern the mechanical response of such foams. For this purpose, a hierarchical micromechanical model is developed, which traces the deformation of the hollow cell struts to the axial stretching of the cell walls. The waviness of the multilayered graphitic wall increases the axial compliance of each cell wall, and it is established that axial straining within the cell wall occurs by interlayer shearing. Crucially, this mechanism demonstrates that the continuum properties of such foams are dictated by the weak out-of-plane shear properties of the layered cell wall material, leading to a large knockdown in the macroscopic mechanical properties of the foam. Ordered graphene gyroid lattices possessing nanoscale unit cell sizes are then fabricated and characterized through a combination of nanoindentation and a multi-scale finite element analysis (FEA) study. These structured nanolattices were found to be highly conductive and possessed a high degree of elastic recovery and strength owing to the structural efficiency afforded by the stretching-dominated cellular architecture. However, the nanoscale interlayer shearing deformation mechanism was again found to be active in the cell walls of these structures, attenuating the continuum response of the lattice. The hierarchical micromechanical model developed herein rationalizes why CVD-grown multilayer graphitic foams and lattices possess diminished continuum elastic moduli and yield strengths in comparison to the exemplary in-plane mechanical properties of 2D materials, presenting a first step towards the understanding of porous materials whose cell walls are comprised of emergent 2D materials. In addition, the direct shrinkage of commercial polymer foams and 3D printed templates is used herein to offer a very simple and low-cost method for reaching identically-shaped structures with sub-200 μm unit cell sizes. The conformal addition of different thicknesses of alumina is shown to control the level of isotropic shrinkage, reducing the shrinkage ratio from 125x to 4x after addition of 25 nm of alumina, while inducing a surface stress mismatch that drastically increases the surface roughness of the material. Furthermore, efficient graphitization was demonstrated through the use of an electrolessly deposited Nickel film, resulting in the formation of a conductive multilayer graphenic coating at temperatures below 1100°C. These processes present the flexible production of multifunctional cellular materials with sub-mm unit cells, tuneable size, roughness and conductivity. A final study investigates the preparation of a nascent 2D material, WS$_2$, through the use of a deconstructed metal organic chemical vapour deposition (MOCVD) process which allowed insight into the role of each process step. The catalytic effect of an Au substrate is unambiguously demonstrated, which allowed for a reduction in the precursor partial pressures required to nucleate and grow WS$_2$ by over an order of magnitude in comparison to competing methods. This enabled the efficient low-pressure growth of WS$_2$ films with low levels of carbon contamination. Furthermore, the reaction process developed herein exhibited a self-limiting monolayer growth behaviour with exposure cycles lasting just 10 minutes, a significant improvement over prior MOCVD processes requiring growth times in excess of 1 hour. These insights foster our understanding of the key underlying mechanisms of WS$_2$ growth for future integrated manufacturing of transition metal dichalcogenides (TMDCs) and other 2D materials.Funded by the EPSRC (EP/G037221/1) - Cambridge NanoScience through Engineering to Application Doctoral Training Centre: Assembly of Functional NanoMaterials and NanoDevices, EPSRC (EP/K016636/1) - CVD enabled Graphene Technology and Devices (GRAPHTED), ERC (279342) - In-situ metrology for the controlled growth and interfacing of nanomaterials and ERC (206409) - Multi-phase lattice materials

複合加工機の熱変形評価法の開発とその応用に関する研究

13301甲第4938号博士（工学）金沢大学博士論文要旨Abstrac

SU(3)L⋊(Z3×Z3)SU(3)_{\rm L} \rtimes (\mathbb{Z}_3 \times \mathbb{Z}_3) gauge symmetry and Tri-bimaximal mixing

We study an effective gauge theory whose gauge group is a semidirect product $G = G_c \rtimes \mathit{\Gamma}$ with $G_c$ and $\mathit{\Gamma}$ being a connected Lie group and a finite group, respectively. The semidirect product is defined through a projective homomorphism $\gamma$ (i.e., homomorphism up to the center of $G_c$) from $\mathit{\Gamma}$ into $G_c$. The (linear) representation of $G$ is made from $\gamma$ and a projective representation of $\mathit{\Gamma}$ over $\mathbb{C}$. To be specific, we take $SU(3)_L$ as $G_c$ and $\mathbb{Z}_3 \times \mathbb{Z}_3$ as $\mathit{\Gamma}$. It is noticed that the irreducible projective representations of $\mathit{\Gamma}$ are three-dimensional in spite of its Abelian nature. We give a toy model on the lepton mixing which illustrates the peculiar feature of such gauge symmetry. It is shown that under a particular vacuum alignment the tri-bimaximal mixing matrix is reproduced.Comment: 10 page

Prevention of Hepatocellular Carcinoma Development Associated with Chronic Hepatitis by Anti-Fas Ligand Antibody Therapy

A persistent immune response to hepatitis viruses is a well-recognized risk factor for hepatocellular carcinoma. However, the molecular and cellular basis for the procarcinogenic potential of the immune response is not well defined. Here, using a unique animal model of chronic hepatitis that induces hepatocellular carcinogenesis, we demonstrate that neutralization of the activity of Fas ligand prevented hepatocyte apoptosis, proliferation, liver inflammation, and the eventual development of hepatocellular carcinoma. The results indicate that Fas ligand is involved not only in direct hepatocyte killing but also in the process of inflammation and hepatocellular carcinogenesis in chronic hepatitis. This is the first demonstration that amelioration of chronic inflammation by some treatment actually caused reduction of cancer development

Compressive behavior and failure mechanisms of freestanding and composite 3D graphitic foams

Open-cell graphitic foams were fabricated by chemical vapor deposition using nickel templates and their compressive responses were measured over a range of relative densities. The mechanical response required an interpretation in terms of a hierarchical micromechanical model, spanning 3 distinct length scales. The power law scaling of elastic modulus and yield strength versus relative density suggests that the cell walls of the graphitic foam deform by bending. The length scale of the unit cell of the foam is set by the length of the struts comprising the cell wall, and is termed level I. The cell walls comprise hollow triangular tubes, and bending of these strut-like tubes involves axial stretching of the tube walls. This length scale is termed level II. In turn, the tube walls form a wavy stack of graphitic layers, and this waviness induces interlayer shear of the graphitic layers when the tube walls are subjected to axial stretch. The thickness of the tube wall defines the third length scale, termed level III. We show that the addition of a thin, flexible ceramic Al2O3 scaffold stiffens and strengthens the foam, yet preserves the power law scaling. The hierarchical model gives fresh insight into the mechanical properties of foams with cell walls made from emergent 2D layered solids

動物モデルにおける骨髄間質細胞シートの乱軸型皮弁の延長効果

BACKGROUND: Bone marrow stromal cells can be applied therapeutically to enhance angiogenesis; however, the use of bone marrow stromal cell suspensions reduces efficiency because of low-level attachment. The authors hypothesized that bone marrow stromal cell sheets would facilitate cell fixation, thus enhancing angiogenesis. The authors investigated flap survival area and enhancement of angiogenic factors in a rat random-pattern skin flap model after application of bone marrow stromal cell sheets. METHODS: Bone marrow stromal cell sheets (prepared from 7-week-old rat femurs) were cultured under four different hypoxic conditions. Sheets with the highest angiogenic potential, determined by an in vitro pilot study, were injected into subcutaneous layers of the rat dorsum (bone marrow stromal cell sheet group). A control group (phosphate-buffered saline only) was included. On day 2 after injection, caudally based random-pattern skin flaps (12 × 3 cm) were elevated. On day 7 after elevation, surviving skin flap areas were measured. Skin samples were harvested from each flap and gene expression levels of vascular endothelial growth factor and basic fibroblast growth factor were measured by quantitative real-time polymerase chain reaction. RESULTS: Skin flap survival area (71.6 ± 2.3 percent versus 51.5 ± 3.3 percent) and levels of vascular endothelial growth factor and basic fibroblast growth factor were significantly higher in the bone marrow stromal cell sheet group than in the control group (p < 0.05). CONCLUSIONS: Implantation of bone marrow stromal cell sheets increased the survival area of random-pattern skin flaps. Expression of angiogenic factors may have contributed to the increased flap survival.博士（医学）・甲第658号・平成28年11月24日Copyright © 2015 American Society of Plastic SurgeonsThe definitive version is available at " http://dx.doi.org/10.1097/PRS.0000000000001679