Synthesis and characterization of oxide materials

Nanostructured materials are central to the evolution of future electronics and biomedical applications amongst other applications. This thesis is focused on developing novel methods to prepare a number of nanostructured metal oxide particles and films by a number of different routes. Part of the aim was to see how techniques used in nanoparticle science could be applied to thin film methods to develop functional surfaces. Wet-chemical methods were employed to synthesize and modify the metal oxide nanostructures (CeO2 and SiO2) and their structural properties were characterized through advanced X-ray diffraction, electron microscopy, photoelectron spectroscopy and other techniques. Whilst particulates have uses in many applications, their attachment to surfaces is of importance and this is frequently challenging. We examined the use of block copolymer methods to form very well defined metal oxide particulate-like structures on the surface of a number of substrates. Chapter 2 describes a robust method to synthesize various sized silica nanoparticles. As-synthesized silica nanoparticles were further functionalized with IR-820 and FITC dyes. The ability to create size controlled nanoparticles with associated (optical) functionality may have significant importance in bio-medical imaging. Thesis further describes how non-organic modified fluorescent particles might be prepared using inorganic oxides. A study of the concentrations and distributions of europium dopants within the CeO2 nanoparticles was undertaken and investigated by different microscopic and spectroscopic techniques. The luminescent properties were enhanced by doping and detailed explanations are reported. Additionally, the morphological and structural evolution and optical properties were correlated as a function of concentrations of europium doping as well as with further annealing. Further work using positron annihilation spectroscopy allowed the study of vacancy type defects formed due to europium doping in CeO2 crystallites and this was supported by complimentary UV-Vis spectra and XRD work. During the last few years the interest in mesoporous silica materials has increased due to their typical characteristics such as potential ultra-low dielectric constant materials, large surface area and pore volume, well-ordered and uniform pores with adjustable pores between 2 and 50 nm. A simple, generic and cost-effective route was used to demonstrate the synthesis of 2D mesoporous silica thin films over wafer scale dimensions in chapter 5. Lithographic resist and in situ hard mask block copolymer followed by ICP dry etching were used to fabricate mesoporous silica nanostructures. The width of mesoporous silica channels can be varied by using a variety of commercially available lithographic resists whereas depth of the mesoporous silica channels can be varied by altering the etch time. The crystal structure, morphology, pore arrangement, pore diameters, thickness of films and channels were determined by XRD, SEM, ellipsometry and the results reported. This project also extended work towards the study of the antimicrobial study of nanopatterned silver nanodot arrays formed using the block copolymer approach defined above. Silver nanodot arrays were successfully tested for antimicrobial activity over S. aureus and P. aeruginosa biofilms and results shows silver nanodots has good antimicrobial activity for both S. aureus and P. aeruginosa biofilms. Thus, these silver nanodot arrays shows a potential to be used as a substitute for the resolution of infection complications in many areas.

Synthese und Untersuchung des Aggregationsverhaltens von Oligo(p-benzamid)-Rod-Coil-Blockcopolymeren

In dieser Arbeit wird das erste Beispiel einer automatisierten Oligo(p-benzamid)synthese beschrieben. Die auf diese Weise synthetisierten Oligo(p-benzamid)e wurden zu verschiedensten Block-co-polymeren umgesetzt und, nach Abspaltung der p-Methoxybenzylschutzgruppe, die Lösungsaggregation der resultierenden Rod-Coil Block-co-polymere mithilfe der Transmissionselektronen-Mikroskopie untersucht.

Rheological studies on the phase dissolution in a block copolymer

The microphase transition in a styrene-butadiene-styrene triblock copolymer was studied by rheometric mechanical spectroscopy. A high-temperature-melt rheological transition from the highly elastic, nonlinear viscous behavior typical of a multiphase structure to linear viscous behavior with insignificant elasticity typical of a single-phase structure was observed. The transition temperature is determined according to the discontinuity of the rheological properties across the transition region, which agrees well with the results obtained from the small angle X-ray scattering data and the expectation of the random phase approximation theory. Maybe for the first time, microphase dissolution was investigated theologically. The storage modulus (G') and the loss modulus (G '') increase with time during the process. An entanglement fluctuation model based on the segmental density fluctuations is presented to explain the rheological behavior in this dissolution process. (C) 1997 John Wiley & Sons.

Phase behavior in mixtures of a homopolymer and a block copolymer .4. SALS and SAXS studies

Phase behavior of blends of poly(vinyl methyl ether) (PVME) with four styrene-butadienestyrene (SBS) triblock copolymers, being of various molecular weights, architecture, and compositions, was investigated by small-angle light scattering. Small-angle X-ray scattering investigation was accomplished for one blend. Low critical solution temperature (LCST) and a unique phase behavior, resembling upper critical solution temperature (UCST), were observed. It was found that the architecture of the copolymer greatly influenced the phase behavior of the blends. Random phase approximation theory was used to calculate the spinodal phase transition curves of the ABA/C and BAB/C systems; LCST and resembling UCST phase behavior were observed as the parameters of the system changed. Qualitatively, the experimental and the theoretical results are consistent with each other. (C) 1996 John Wiley & Sons, Inc.

Fabrication using a rapid prototyping system and in vitro characterization of PEG-PCL-PLA scaffolds for tissue engineering

n the field of tissue engineering new polymers are needed to fabricate scaffolds with specific properties depending on the targeted tissue. This work aimed at designing and developing a 3D scaffold with variable mechanical strength, fully interconnected porous network, controllable hydrophilicity and degradability. For this, a desktop-robot-based melt-extrusion rapid prototyping technique was applied to a novel tri-block co-polymer, namely poly(ethylene glycol)-block-poly(epsi-caprolactone)-block-poly(DL-lactide), PEG-PCL-P(DL)LA. This co-polymer was melted by electrical heating and directly extruded out using computer-controlled rapid prototyping by means of compressed purified air to build porous scaffolds. Various lay-down patterns (0/30/60/90/120/150°, 0/45/90/135°, 0/60/120° and 0/90°) were produced by using appropriate positioning of the robotic control system. Scanning electron microscopy and micro-computed tomography were used to show that 3D scaffold architectures were honeycomb-like with completely interconnected and controlled channel characteristics. Compression tests were performed and the data obtained agreed well with the typical behavior of a porous material undergoing deformation. Preliminary cell response to the as-fabricated scaffolds has been studied with primary human fibroblasts. The results demonstrated the suitability of the process and the cell biocompatibility of the polymer, two important properties among the many required for effective clinical use and efficient tissue-engineering scaffolding.

Optical Characterization of the Hole Polaron in a Series of Diketopyrrolopyrrole Polymers Used for Organic Photovoltaics

Abstract: A strategy that is often used for designing low band gap polymers involves the incorporation of electron-rich (donor) and electron-deficient (acceptor) conjugated segments within the polymer backbone. In this paper we investigate such a series of Diketopyrrolopyrrole (DPP)-based co-polymers. The co-polymers consisted of a DPP unit attached to a phenylene, naphthalene, or anthracene unit. Additionally, polymers utilizing either the thiophene-flanked DPP or the furan-flanked DPP units paired with the naphthalene comonomer were compared. As these polymers have been used as donor materials and subsequent hole transporting materials in organic solar cells, we are specifically interested in characterizing the optical absorption of the hole polaron of these DPP based copolymers. We employ chemical doping, electrochemical doping, and photoinduced absorption (PIA) studies to probe the hole polaron absorption spectra. While some donor-acceptor polymers have shown an appreciable capacity to generate free charge carriers upon photoexcitation, no polaron signal was observed in the PIA spectrum of the polymers in this study. The relations between molecular structure and optical properties are discussed. Keywords: organic solar cell; organic photovoltaic; diketopyrrolopyrrole; chemical doping; spectroelectrochemistry; photoinduced absorption; hole polaron

Effect of copolymerized ethylene unit on the crystallization behavior of poly(propylene-co-ethylene)s

The crystallization behavior of two kinds of commercial poly(propylene-co-ethylene)s (PPE1, PPE2) with similar average molecular weight and molecular weight distribution, isotacticity and copolymerized ethylene unit content and their fractions was investigated by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and polarized optical microscopy (POM) techniques. The results indicate that the PPE1 isothermally crystallized films possess thicker and less cross-hatched lamellar structure than those of the PPE2. As for the fractionated samples, the thin films of low temperature (less than or equal to 90 degreesC) fractions (PPE1-80, PPE2-80) of both PPE1 and PPE2 exhibit similar crystallization behavior, while for the high temperature ( greater than or equal to 95 degreesC) fractions (PPE1-108, PPE2-108), the crystalline morphology has marked differences. Compared with PPE2-108, the PPE1-108 isothermally crystallized thin films possess thicker lamellae and less crosshatched lamellar structure, while for the fibrous crystal number, the former is less than that of the latter. The main reason to create the crystallization behavior differences between the two PPEs and their fractions is due to the effect of molecular chain structure, i.e. the different distribution of copolymerized ethylene unit in polypropylene chains.

Monte Carlo simulation of miscibility of polymer blends with repulsive interactions: effect of chain structure

The effects of the chain structure and the intramolecular interaction energy of an A/B copolymer on the miscibility of the binary blends of the copolymer and homopolymer C have been studied by means of a Monte Carlo simulation. In the system, the interactions between segments A, B and C are more repulsive than those between themselves. In order to study the effect of the chain structure of the A/B copolymer on the miscibility, the alternating, random and block copolymers were introduced in the simulations, respectively. The simulation results show that the miscibility of the binary blends strongly depends on the intramolecular interaction energy ((ε) over bar (AB)) between segments A and B within the A/B copolymers. The higher the repulsive interaction energy, the more miscible the A/B copolymer and homopolymer C are. For the diblock copolymer/homopolymer blends, they tend to form micro phase domains. However, the phase domains become so small that the blend can be considered as a homogeneous phase for the alternating copolymer/ homopolymer blends. Furthermore, the investigation of the average end-to-end distance ((h) over bar) in different systems indicates that the copolymer chains tend to coil with the decrease Of (ε) over bar (AB) whereas the (h) over bar of the homopolymer chains depends on the chain structure of the copolymers.

Morphology, structure, and properties of in situ compatibilized linear low-density polyethylene/polystyrene and linear low-density polyethylene/high-impact polystyrene blends

Blends of linear low-density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high-impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl3), was adopted to initiate the Friedel-Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl3 blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel-Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE-g-PS and LLDPE-g-HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m(2). Scanning electron microscopy micrographs showed that the size of the domains decreased from 4-5 to less than 1 mum, depending on the content of added AlCl3.

Monte Carlo simulation of phase separation of A/B/A-B ternary mixtures

Monte Carlo simulations were used to model A/B/A-B ternary mixtures with different AB diblock copolymer volume fractions for which both the dispersed and continuous phase volume fractions were kept constant. For concentrations of the diblock copolymer below a critical value, the domain size increment of the dispersed phase decreases linearly with the copolymer concentration. This is in agreement with the predictions of Noolandi and Hong. The dependence of the domain size as a function of the copolymer volume fraction can also be fitted by the equation of Tang and Huang. Our simulations indicate, for the first time, that the micelles form before saturation of the interface occurs. This means that the formation of the micelles is not a result of the saturation of the interface.

Crystallization of micelles and matrix in dilute diblock copolymer/homopolymer solutions

The crystallization, morphology, and crystalline structure of dilute solid solutions of tetrahydrofuran-methyl methacrylate diblock copolymer (PTHF-b-PMMA) in poly(ethylene oxide) (PEO) and PTHF have been studied with differential scanning calorimetry (DSC), X-ray, and optical microscopy. This study provides a new insight into the crystallization behavior of block copolymers. For the dilute PTHF-b-PMMA/PEO system containing only 2 to 7 wt % of PTHF content, crystallization of the PTHF micellar core was detected both on cooling and on heating. Compared the crystallization of the PTHF in the dilute solutions with that in the pure copolymer, it was found that the crystallizability of the PTHF micellar core in the solution is much greater than that of the dispersed PTHF microdomain in the pure copolymer. The stronger crystallizability in the solution was presumably due to a softened PMMA corona formed in the solution of the copolymer with PEG. However, the "soft" micelles formed in the solution (meaning that the glass transition temperatures (T-g) of the micelle is lower than the T-m of the matrix phase) showed almost no effects on the spherulitic morphology of the PEO component, compared with that of the pure PEO sample. In contrast, significant effects of the micelles with a "hard" PMMA core (meaning that the T-g of the core is higher than the T-m of the PTHF homopolymer) on the nucleation, crystalline structure, and spherulitic morphology were observed for the dilute PTHF-b-PMMA/PTHF system. (C) 1998 John Wiley & Sons, Inc.

COMPATIBILITY AND CRYSTALLIZATION OF TETRAHYDROFURAN-METHYL METHACRYLATE DIBLOCK COPOLYMER/POLYTETRAHYDROFURAN BLENDS

The compatibility and crystallization of tetrahydrofuran-methyl methacrylate diblock copolymer (PTHF-b-PMMA)/tetrahydrofuran homopolymer (PTHF) blends were studied. Our results showed that the crystallization and morphology of compatible PTHF-b-PMMA/PTHF

PREPARATION AND PROPERTIES OF THREAD-THROUGH COPOLYMERS OF POLYETHYLENE WITH POLYISOPRENE

Graft copolymers of polyethylene (PE) with polyisoprene (PI) were synthesized through polymerization of ethylene in toluene solution of PI (cis-1,4-: 95%; 3,4-: 5%) using a homogeneous V(acac)3/Et3Al2Cl3 catalyst. Copolymers are formed when the growing po

SPREADING AND TRANSFER BEHAVIOR OF POLY(2-ACRYLAMIDOHEXADECYLSULFONIC ACID-CO-STYRENE) MONOLAYERS

The spreading behavior of poly(2-acrylamidohexadecylsulfonic acid-co-styrene) (PAMC16SSt) random co-polymers with various compositions was investigated by measurements of the surface pressure-area (pi-A) isotherms. The random copolymers formed stable cond

Insertion of metal oxides into block copolymer nanopatterns as robust etch masks for nanolithography

Directed self-assembly (DSA) of block copolymers (BCPs) is a prime candidate to further extend dimensional scaling of silicon integrated circuit features for the nanoelectronic industry. Top-down optical techniques employed for photoresist patterning are predicted to reach an endpoint due to diffraction limits. Additionally, the prohibitive costs for “fabs” and high volume manufacturing tools are issues that have led the search for alternative complementary patterning processes. This thesis reports the fabrication of semiconductor features from nanoscale on-chip etch masks using “high χ” BCP materials. Fabrication of silicon and germanium nanofins via metal-oxide enhanced BCP on-chip etch masks that might be of importance for future Fin-field effect transistor (FinFETs) application are detailed.