Theoretical analysis of optical properties of dielectric coatings dependence on substrate subsurface defects

A model for refractive index of stratified dielectric substrate was put forward according to theories of inhomogeneous coatings. The substrate was divided into surface layer, subsurface layer and bulk layer along the normal direction of its surface. Both the surface layer (separated into N-1 sublayers of uniform thickness) and subsurface layer (separated into N-2 sublayers of uniform thickness), whose refractive indices have different statistical distributions, are equivalent to inhomogeneous coatings, respectively. And theoretical deduction was carried Out by employing characteristic matrix method of optical coatings. An example of mathematical calculation for optical properties of dielectric coatings had been presented. The computing results indicate that substrate subsurface defects can bring about additional bulk scattering and change propagation characteristic in thin film and Substrate. Therefore, reflectance, reflective phase shift and phase difference of an assembly of coatings and substrate deviate from ideal conditions. The model will provide some beneficial theory directions for improving optical properties of dielectric coatings via substrate surface modification. (c) 2005 Elsevier B.V. All rights reserved.

Theoretical analysis of influence of substrate microdefects on polarized light properties of dielectric coatings

A model for refractive index of stratified dielectric substrate was presented according to inhomogeneous coatings theories. The substrate was divided into surface layer, subsurface layer and bulk layer along the normal direction of its surface. The former two layers were equivalent to inhomogeneous coatings. Theoretical deduction was executed by employing the characteristic matrix method of optical coatings, and one mathematical calculation example was presented. The results indicate that reflectance, reflective phase shift and phase difference of polarized light deviate from ideal conditions. It shows that substrate microdefects can induce volume scattering and change propagation characteristic of light both in coatings and substrate. (c) 2005 Elsevier GmbH. All rights reserved.

双源共蒸法制备非均匀膜的模型分析

探讨了双源共蒸法制备非均匀薄膜的堆积模型，并给出了非均匀膜的沉积速率与两种膜料沉积速率的关系．当两种膜料的沉积单分子大小近似相等或者小分子沉积速率远大于大分子时，可以近似认为混合介质膜的沉积速率等于两种膜料的沉积速率之和；当两种膜料的沉积单分子大小不满足近似相等且两种膜料的沉积速率可比较时，非均匀膜的沉积速率不能简单地用两种膜料的沉积速率之和来近似，它将随两种膜料沉积单分子的大小不同和沉积速率比不同按照不同的规律变化，并在文中给出了不同情况下的非均匀膜的沉积速率变化规律。

共蒸法制备非均匀膜的速率控制分析

渐变折射率薄膜，又称为非均匀膜。利用德鲁德理论分析了混合介质膜的介电常量与各个膜料的介电常量之间的关系，介绍了共蒸法制备非均匀膜的制备机理。对混合膜的沉积速率为两种膜料的沉积速率之和的情况，分别从两种膜料的单分子体积是否相等和总的沉积速率是否为常数两个方面，探讨了双源共蒸法制备的非均匀膜的折射率分布规律与膜料的沉积速率之间的关系，并给出了几种常见的折射率分布如线性变化、正弦变化、指数变化和双曲变化规律的膜料沉积速率表达式。最后以混合介质膜的总沉积速率为常数、折射率按照线性变化为例进行了说明。

德鲁德分布非均匀膜的光学特性模拟分析

从德鲁德理论出发，对多元共蒸法镀制的非均匀膜的折射率分布与沉积速率的关系进行了探讨；然后利用计算机辅助模拟，对德鲁德分布非均匀光学薄膜，从单周期和多周期、正变和负变、完整周期和存在半周期几个方面对其光学特性进行了系统分析．研究发现：其透射率的极小值和周期数的关系遵从周期数的三次多项式衰减规律，不同规律的德鲁德分布非均匀膜可用来设计不同功能的滤光片．

线性共蒸法制备非均匀膜的误差特性模拟分析

对双源线性共蒸法制备的非均匀薄膜折射率分布与光学特性的关系作了探讨，并与均匀介质膜的光学特性作了对比；从折射率正变和负变两个方面．讨论了混合介质膜折射率不同变化规律对光学性能带来的影响；讨论了厚度误差和折射率极值误差对非均匀膜光学性能的影响。结果发现：折射率变化规律误差主要对非均匀膜的应用波段范围产生影响，而膜层厚度误差和折射率极值误差超过一定值时，将对薄膜光学特性产生重要影响。

Porous polyurethane coatings bonded onto surface-modified titanium substrates for the growth of an endothelial cell layer

Cardiovascular diseases refer to the class of diseases that involve the heart or blood vessels (arteries and veins). Examples of medical devices for treating the cardiovascular diseases include ventricular assist devices (VADs), artificial heart valves and stents. Metallic biomaterials such as titanium and its alloy are commonly used for ventricular assist devices. However, titanium and its alloy show unacceptable thrombosis, which represents a major obstacle to be overcome. Polyurethane (PU) polymer has better blood compatibility and has been used widely in cardiovascular devices. Thus one aim of the project was to coat a PU polymer onto a titanium substrate by increasing the surface roughness, and surface functionality. Since the endothelium of a blood vessel has the most ideal non-thrombogenic properties, it was the target of this research project to grow an endothelial cell layer as a biological coating based on the tissue engineering strategy. However, seeding endothelial cells on the smooth PU coating surfaces is problematic due to the quick loss of seeded cells which do not adhere to the PU surface. Thus it was another aim of the project to create a porous PU top layer on the dense PU pre-layer-coated titanium substrate. The method of preparing the porous PU layer was based on the solvent casting/particulate leaching (SCPL) modified with centrifugation. Without the step of centrifugation, the distribution of the salt particles was not uniform within the polymer solution, and the degree of interconnection between the salt particles was not well controlled. Using the centrifugal treatment, the pore distribution became uniform and the pore interconnectivity was improved even at a high polymer solution concentration (20%) as the maximal salt weight was added in the polymer solution. The titanium surfaces were modified by alkli and heat treatment, followed by functionlisation using hydrogen peroxide. A silane coupling agent was coated before the application of the dense PU pre-layer and the porous PU top layer. The ability of the porous top layer to grow and retain the endothelial cells was also assessed through cell culture techniques. The bonding strengths of the PU coatings to the modified titanium substrates were measured and related to the surface morphologies. The outcome of the project is that it has laid a foundation to achieve the strategy of endothelialisation for the blood compatibility of medical devices. This thesis is divided into seven chapters. Chapter 2 describes the current state of the art in the field of surface modification in cardiovascular devices such as ventricular assist devices (VADs). It also analyses the pros and cons of the existing coatings, particularly in the context of this research. The surface coatings for VADs have evolved from early organic/ inorganic (passive) coatings, to bioactive coatings (e.g. biomolecules), and to cell-based coatings. Based on the commercial applications and the potential of the coatings, the relevant review is focused on the following six types of coatings: (1) titanium nitride (TiN) coatings, (2) diamond-like carbon (DLC) coatings, (3) 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer coatings, (4) heparin coatings, (5) textured surfaces, and (6) endothelial cell lining. Chapter 3 reviews the polymer scaffolds and one relevant fabrication method. In tissue engineering, the function of a polymeric material is to provide a 3-dimensional architecture (scaffold) which is typically used to accommodate transplanted cells and to guide their growth and the regeneration of tissue. The success of these systems is dependent on the design of the tissue engineering scaffolds. Chapter 4 describes chemical surface treatments for titanium and titanium alloys to increase the bond strength to polymer by altering the substrate surface, for example, by increasing surface roughness or changing surface chemistry. The nature of the surface treatment prior to bonding is found to be a major factor controlling the bonding strength. By increasing surface roughness, an increase in surface area occurs, which allows the adhesive to flow in and around the irregularities on the surface to form a mechanical bond. Changing surface chemistry also results in the formation of a chemical bond. Chapter 5 shows that bond strengths between titanium and polyurethane could be significantly improved by surface treating the titanium prior to bonding. Alkaline heat treatment and H2O2 treatment were applied to change the surface roughness and the surface chemistry of titanium. Surface treatment increases the bond strength by altering the substrate surface in a number of ways, including increasing the surface roughness and changing the surface chemistry. Chapter 6 deals with the characterization of the polyurethane scaffolds, which were fabricated using an enhanced solvent casting/particulate (salt) leaching (SCPL) method developed for preparing three-dimensional porous scaffolds for cardiac tissue engineering. The enhanced method involves the combination of a conventional SCPL method and a step of centrifugation, with the centrifugation being employed to improve the pore uniformity and interconnectivity of the scaffolds. It is shown that the enhanced SCPL method and a collagen coating resulted in a spatially uniform distribution of cells throughout the collagen-coated PU scaffolds.In Chapter 7, the enhanced SCPL method is used to form porous features on the polyurethane-coated titanium substrate. The cavities anchored the endothelial cells to remain on the blood contacting surfaces. It is shown that the surface porosities created by the enhanced SCPL may be useful in forming a stable endothelial layer upon the blood contacting surface. Chapter 8 finally summarises the entire work performed on the fabrication and analysis of the polymer-Ti bonding, the enhanced SCPL method and the PU microporous surface on the metallic substrate. It then outlines the possibilities for future work and research in this area.

Photoclickable surfaces for profluorescent covalent polymer coatings

The nitrile imine-mediated tetrazole-ene cycloaddition reaction (NITEC) is introduced as a powerful and versatile conjugation tool to covalently ligate macromolecules onto variable (bio)surfaces. The NITEC approach is initiated by UV irradiation and proceeds rapidly at ambient temperature yielding a highly fluorescent linkage. Initially, the formation of block copolymers by the NITEC methodology is studied to evidence its efficacy as a macromolecular conjugation tool. The grafting of polymers onto inorganic (silicon) and bioorganic (cellulose) surfaces is subsequently carried out employing the optimized reaction conditions obtained from the macromolecular ligation experiments and evidenced by surface characterization techniques, including X-ray photoelectron spectroscopy and FT-IR microscopy. In addition, the patterned immobilization of variable polymer chains onto profluorescent cellulose is achieved through a simple masking process during the irradiation. Photoinduced nitrile imine-alkene 1,3-dipolar cycloaddition (NITEC) is employed to covalently bind well-defined polymers onto silicon oxide or cellulose. A diaryl tetrazole-functionalized molecule is grafted via silanization or amidification, respectively. Under UV light, a reactive nitrile imine rapidly forms and reacts with maleimide-functionalized polymers yielding a fluorescent linkage. Via a masking method, polymeric fluorescent patterns are achieved.

Contribution to single-point closure Reynolds-stress modelling of inhomogeneous flow

This paper is concerned with recent advances in the development of near wall-normal-free Reynolds-stress models, whose single point closure formulation, based on the inhomogeneity direction concept, is completely independent of the distance from the wall, and of the normal to the wall direction. In the present approach the direction of the inhomogeneity unit vector is decoupled from the coefficient functions of the inhomogeneous terms. A study of the relative influence of the particular closures used for the rapid redistribution terms and for the turbulent diffusion is undertaken, through comparison with measurements, and with a baseline Reynolds-stress model (RSM) using geometric wall normals. It is shown that wall-normal-free rsms can be reformulated as a projection on a tensorial basis that includes the inhomogeneity direction unit vector, suggesting that the theory of the redistribution tensor closure should be revised by taking into account inhomogeneity effects in the tensorial integrity basis used for its representation.

Multidirectional effects of Sr, Mg and Si-containing bioceramic coatings with high bonding strength on inflammation, osteoclastogenesis and osteogenesis

Ideal coating materials for implants should be able to induce excellent osseointegration, which requires several important parameters, such as good bonding strength, limited inflammatory reaction, balanced osteoclastogenesis and osteogenesis, to gain well-functioning coated implants with long-term life span after implantation. Bioactive elements, like Sr, Mg and Si, have been found to play important roles in regulating the biological responses. It is of great interest to combine bioactive elements for developing bioactive coatings on Ti-6Al-4V orthopedic implants to elicit multidirectional effects on the osseointegration. In this study, Sr, Mg and Si-containing bioactive Sr2MgSi2O7 (SMS) ceramic coatings on Ti-6Al-4V were successfully prepared by plasma-spray coating method. The prepared SMS coatings have significantly higher bonding strength (~37MPa) than conventional pure hydroxyapatite (HA) coatings (mostly in the range of 15-25 MPa). It was also found that the prepared SMS coatings switch the macrophage phenotype into M2 extreme, inhibiting the inflammatory reaction via the inhibition of Wnt5A/Ca2+ and Toll-like receptor (TLR) pathways of macrophages. In addition, the osteoclastic activities were also inhibited by SMS coatings. The expression of osteoclastogenesis related genes (RANKL and MCSF) in bone marrow derived mesenchymal cells (BMSCs) with the involvement of macrophages was decreased, while OPG expression was enhanced on SMS coatings compared to HA coatings, indicating that SMS coatings also downregulated the osteoclastogenesis. However, the osteogenic differentiation of BMSCs with the involvement of macrophages was comparable between SMS and HA coatings. Therefore, the prepared SMS coatings showed multidirectional effects, such as improving bonding strength, reducing inflammatory reaction and downregulating osteoclastic activities, but maintaining a comparable osteogenesis, as compared with HA coatings. The combination of bioactive elements of Sr, Mg and Si into bioceramic coatings can be a promising method to develop bioactive implants with multifunctional properties for orthopaedic application.