Contents Abstract I Contents VI List of Table IX List of Figures IX Chapter 1 Introduction 1 1.1 Self-Assembly of BCPs 2 1.2 Association of Metallic Species with Polymers 4 1.2.1 Functional Polymers 5 1.2.1.1 PEO based BCPs 5 1.2.1.2 PAA based BCPs 6 1.2.1.3 PVP based BCPs 7 1.2.2 Association Strength of Various Metal Species with P4VP Block 10 1.2.3 Hybridized Methods 12 1.2.3.1 In-situ Hybridization 12 1.2.3.2 Ex-situ Hybridization 14 1.3 Phase Behavior of Homopolymer/BCP Blends 15 1.4 Phase Behavior of Inorganic/BCP Hybrids 19 1.4.1 Theoretical Predictions 19 1.4.1.1 Phase Transformation 19 1.4.1.2 Particle Size Effect 22 1.4.2 Practical Experiments 25 1.4.2.1 Phase Transformation 25 1.4.2.2 Associated Mechanism between Metal NPs and P4VP 30 1.5 Methods for Reduction 31 1.5.1 Electron Beam Reduction 32 1.5.2 Ultraviolet Radiation Reduction 33 1.5.3 Reduction by Chemical Agents 34 1.6 Flexible-conductive Materials from Inorganic/BCP Hybrids 38 1.6.1 Synthesis of Inorganic NPs 42 1.6.2 Advanced Inorganic Nanorods/BCP Hybrids 43 1.6.3 Synthesis of Inorganic Nanorods 46 Chapter 2 Objectives 51 Chapter 3 Materials and Experimental Methods 56 3.1 Synthesis of P4VP-PCL 56 3.1.1 Preparation of benzyl ester end-functionalized PCL-OHs 56 3.1.2 Preparation of PCL macroinitators, PCL-Cls 56 3.1.3 Synthesis of PCL-P4VP diblock copolymers 57 3.1.4 Inorganic Materials and Reduction Agent 60 3.2 Sample Preparation for P4VP-PCL BCPs 60 3.2.1 Sample Preparation for Hybridized P4VP-PCL BCPs 61 3.3 Interfacial Reduction for the Formation of Gold Nanoparticles 62 3.4 Instruments 63 3.4.1 Differential Scanning Calorimetry (DSC) 63 3.4.2 Electron Transmission Microscopy (TEM) 64 3.4.3 Small Angle X-ray Scattering (SAXS) 64 3.4.4 Ultraviolet Absorption Photometer (UV) 65 3.4.5 Fourier Transform Infrared Spectrometer (FTIR) 65 Chapter 4 Results and Discussion 66 4.1 Phase Behavior of Gold Ions/P4VP-PCL Hybrid .66 4.1.1 Thermal Behavior of P4VP-PCL BCPs .66 4.1.2 Microphase-Separated Morphologies of P4VP-PCL BCPs .68 4.1.3 Association of Au3+ ions with P4VP block .70 4.1.4 Phase Transformation .72 4.1.5 Molecular Weight and Composition Effects .75 4.1.6 Effective Excluded Volume for Hybridization .82 4.1.7 Mechanism of Phase Transformation .85 4.1.8 PCL Blocking versus Bridging .88 4.2 Phase Behavior of Various Metal Ions/P4VP-PCL Hybrids 95 4.2.1 Association Strength of Various Metal Ions with P4VP Block. .103 4.2.2 Domain Swelling in Metal Ions/P4VP-PCL Hybrids .105 4.3 Phase Behavior of Au NPs/P4VP-PCL Hybrids 111 4.3.1 Reduction for the Formation of Au NPs .111 4.3.2 Phase behavior of Au NPs/P4VP-PCL hybrids .115 4.3.3 Location of Au NPs within P4VP Microdomains .118 4.3.4 Interconnected Nanostructures in Au NPs/ P4VP-PCL Hybrids .119 4.4 Inorganic/Organic hybrids for Flexible Electrodes 120 4.4.1 Synthesis of Ag NPs 123 4.4.2 Phase Behavior of Ag NPs/PS-P4VP Hybrids 125 4.4.3 Synthesis of Ag Nanorods 129 4.4.4 Ag nanorods/PVA Hybrids 133 Chapter 5 Conclusions 135 Chapter 6 References 139 Publications 148 List of Tables Table 3.1 Characterization of P4VP-PCL BCPs 60 List of Figures Figure 1-1. (a) Schematic illustration of the self-assembly and self ordering behavior of BCPs at which the scale of microphase separation is about tens of nanometer. (b) Schematic phase diagram showing the various “classical” BCP morphologies adopted by non-crystalline linear diblock copolymer…4 Figure 1-2. (a) Schematic illustration of the formation of Au NPs in a PS-PEO micelle: 1. Micelle formation in a selective solvent; 2. Loading with the gold precursors; 3. Transformation to a single Au NP. (b) TEM images showing the formation of Au NPs after annealing at 90 °C for 1 hour. (c) (up) Schematic Illustration of the process for the formation of bicontinuous cubic inverse plumber’s nightmare structure; (down) TEM images of the bicontinuous cubic inverse plumber’s nightmare structures with different subunits………………………………………………….….6 Figure 1-3. AFM height images of micellar thin films: (a) as-cast film; (b) film treated in 0.04 M NaOH(aq). TEM images of films treated in (c) 0.0156 M Ca(OH)2(aq) and (d) 0.4 mM PbAc2(aq) 8 Figure 1-4. DSC scans for (a) zinc salt/P2VP and (b) zinc salt/P4VP blends having varying compositions 9 Figure 1-5. (a) Binding energies of various pyridine-metal complexes. (b) Normal Raman spectra of pure pyridine and pyridine aqueous solution with concentration of 0.1 M NaClO4 + 0.1 M pyridine and the surface-enhanced Raman spectra of pyridine adsorbed on Ag, Au, Cu and Pt surfaces in the solution of 0.1 M NaClO4 + 0.1 M pyridine, at which the band frequency at 1002 of pure pyridine solution is used as a indicator for the degree of pyridine stretching 11 Figure 1-6. (a) Common functional blocks for the incorporation of inorganic materials into polymer microdomains. (b) Various schenes that have been used to prepare inorganic colloids in BCPs. The various steps include polymerization (Pol), micellization (Mic), loading of the precursor (Ld), ordering (Ord), chemical transformation (CT), and nucleation and growth (N&G). 13 Figure 1-7. TEM image of a ternary blend of PS-PEP + AuR1 + SiO2R2, after microsectioning normal to the layer direction (no stain). Au NPs appear as dark spots along the intermaterial dividing surface (IMDS); silica NPs reside in the center of the PEP domain. Inset: Schematic of the particle distribution (size proportions are changed for clarity). 14 Figure 1-8. (a) Schematic illustration of the location of the HS within the HS/PS-PI blend. TEM images of the HS/PS-PI blends with different HS/SI ratio: (b) 0/100; (c) 20/80; (d) 50/50; (e) 65/35; (f) 80/20. The dark and white regions represent the PI and PS microdomains due to the OsO4 staining. (g) Corresponding SAXS profiles for the samples (b)-(f) 16 Figure 1-9. Schematic illustration of the dry brush systems formed in HS/PS-PI blends with (a) small amounts of HS and (b) large amounts of HS. TEM images of HS/PS-PI blends with different HS/SI ratio: (c) 0/100; (d) 60/40; (d) 70/30; (e) 80/20. The dark and white regions represent the PI and PS microdomains due to the OsO4 staining. 18 Figure 1-10. (a) Left box shows cylindrical morphology of the pure A-B BCP and right box shows lamellar morphology of the A-B BCP after adding appropriate amounts of small particles. (b) Simulated phase diagram of the small particles/A-B BCP hybrid, at which phase: D=disordered, S=spherical, C=cylindrical, L=lamellar. Theoretical phase diagrams of particles/A-B BCP hybrid with different particle sizes: (c) small particle; (d) intermediate particle; (e) large particle, at which phase: 2Φ=two-phase regions, SAL=self-assembled lamellar and SAC=self-assembled cylindrical. 21 Figure 1-11. Concentration profile of diblock-particle systems (ψA: density distribution of A blocks; ψP and ρP are distributions of particles and particle centers respectively). (a) Large particle and particle volume fraction; (b) Large particle and small particle volume fraction; (c) Small particle and large particle volume fraction; (d) A-block entropic free energy contribution -TSA (where SA is the conformational entropy of the A block) per polymer chain, for large particles (R = 0.3R0, down curve) and small particles (R = 0.15 R0, up curve), as a function of ψp. 24 Figure 1-12. (a) Schematic illustration of the approach for synthesizing organically modified silica mesostructures. Left: the morphology of the precursor block copolymer. Right: the resulting morphologies after addition of various amounts of the metal alkoxides. (b) SAXS profiles of PI-PEO with different amounts of the metal alkoxides. TEM images of (c) neat PI-PEO and its hybrid (d), at which (c) and (d) represents the sphere and cylinder phase, respectively.. 26 Figure 1-13. (a) Lamellar morphology of solution-cast sample, containing Co2(CO)8 10 wt % of P2VP block. (b) Lamellar morphology, containing Co2(CO)8 20 wt % of P2VP block. (c) Cylindrical morphology, with Co2(CO)8 30 wt % of P2VP block. Because the Co2(CO)8 is selectively sequestered into the P2VP domains, their volume fraction increases relative to the PS domains, resulting in a morphological transformation to PS cylinders embedded in a P2VP and organometallic additive matrix. Scale bar = 25 nm. 27 Figure 1-14. (a) Schematic illustration of the phase transformation from cylinder to lamellae phase in CdS/PS-P4VP hybrids. TEM images of (b) PS-P4VP BCP and its hybrid with (c) 7 and (d) 28 wt % CdS NPs. (e) Corresponding SAXS profiles for the PS-P4VP BCP and its hybrid with 7 and 28 wt % CdS NPs. 28 Figure 1-15. Cross-sectional TEM images of a film of gold particles/PS-b-P2VP (Mn = 59 kg mol–1). The overall volume fraction of PS-coated gold particles is 0.5. The distance from the top of the film (L) is a) 27, b) 36, c) 52, and d) 95 lm. The corresponding concentration of gold particles for different depth is calculated in below curve. All scale bars are 100 nm. 29 Figure 1-16. (a) Schematic illustrations of possible configurations of P2VP-PI adhered to a palladium NP, P2VP and PI chains are shown by solid and broke; (b) AFM image reveals a few of chains (up to about three) were observed to adhere to single particles and the absolute number itself is not important 31 Figure 1-17. TEM micrographs of Au NPs/ PS-P2VP hybrids with different P4VP chain length, at which the degrees of polymerization for the P4VP block in (a) and (b) are 300 and 75, respectively. The black dots represent the Au NPs formed by the electron beam. (c) Size of Au cluster as a function of electron beam energy. 32 Figure 1-18. Cross-sectional TEM images of thin PS-P4VP films containing Au NPs. 35 Figure 1-19. TEM images of (a) HAuCl4/PS-P4VP micelles and its reduced results with different reduction agents: (b) LiAlH4. (c) Et3SiH. The scale bars represent 100 nm. 37 Figure 1-20. (a) Schematic illustration of the process for preparation of the Pd-P2VP-PI hybrid system by in-situ reduction., (b) Experimental particle size vs time for the Pd reduction in 1-propanol/toluene/Pd(acac)2 at 85 °C extracted from particle analysis (full circles). Also shown are the power law predictions from the diffusion and coalescence model (without hydrodynamic interactions), full line, and the LSW theory, dashed line. (c) The number of particles in a 0.16 μm2 area of the TEM micrograph as a function of time, (d) Schematic of the various processes that will occur during the immersion of the gyroid network into the Pd reducing bath. 38 Figure 1-21. (a) Changes in surface morphology of a tensile specimen of annealed alloy. The amounts of deformation are (1) 0, (2) 4.3%, (3) 6.1%, and (4) 10.3%. (b) Schematic illustrations of ionic gels composed by the organic matrix (gray region) and ionic liquid, at which the ionic liquid is confined to the white channels. 39 Figure 1-22. Schematic illustrations of Pt NPs/BCP hybrid produced after each stage of the synthesis. (a) Chemical structure of the ligand used to produce moderately hydrophilic Pt NPs with high solubility. (b) A true-scale model of a NP with a 1.8-nmdiameter metal core and 1.4-nm ligand shell in which part of the metal surface is artificially exposed for illustrative purposes. (c) Chemical structure of PI-b-PDMAEMA (BCP). (d) Self-assembly of Pt NPs with BCP followed by annealing affords a hybrid with a regularly. (e) Pyrolysis of the hybrid under inert atmosphere produces a mesoporous Pt-Carbon composite. (f) An Ar-O plasma treatment or acid etch of the Pt-Carbon produces ordered mesoporous Pt. TEM image of (g) annealed inverse hexagonal hybrids and (f) examination of the hybrid from. 41 Figure 1-23. (a) Experimental and theoretical values of the melting-point temperature of gold nanoparticles with different scales. (b) Schematic of the procedure for the synthesis of Ag NPs. (c) TEM image of Ag NPs on a grid; (d) SEM image of Ag NPs formed film after annealing at 140 oC for 30 s. 42 Figure 1-24. Self-assembly of rods into a percolating network. (a) The 30:70 A/B mixture without rods. (b) N = 340 rods of length L = 13 and no fluid. (c) Rods and A/B mixture after 100,000 time steps. White regions are A domains, black regions are B domains, dark lines in the white areas depict rods. (d) N = 600 rods of length L = 13 (e) N = 1000 rods of length L = 11. 45 Figure 1-25. Schematic illustrations of six different strategies that have been demonstrated for achieving 1D growth: (a) direction by the anisotropic crystallographic structure of a solid; (b) confinement by a liquid droplet as in the vapor-liquid-solid process; (c) direction through the use of a template; (d) kinetic control provided by a capping reagent; (e) self-assembly of 0D nanoobjects and (f) size reduction of a 1D microstructure. 46 Figure 1-26. (a) Schematic illustration of the seed-mediated growth for Au and Ag nanorods. (b) TEM image of Au nanorods produced by the seed-mediated growth approach, at which the aspect ratio of Au nanorods is 18. (c) UV spectra of characteristic Plasmon band of silver nanorods with aspect ratio 1(a)-10(f). 48 Figure 1-27. (a) SEM image of uniform Ag nanorods that were synthesized via the self-aeeding, polyol process. (b) XRD pattern of these Ag nanorods, indicating the fcc structure of Ag. TEM and SEM images of Ag nanostructures with AgNO3/PVP ratios of (c) 1:15 and (d) 1:6, respectively. TEM (e) and SEM (f) images of Ag nanostructures that were obtained when PVP ligand was replaced with other coordination regands: (e) PEO; (f) PVA. 49 Figure 3-1. Synthesis route of P4VP-PCL diblock copolymers and PCL homopolymers 57 Figure 3-2. 400 MHz 1H NMR of PCL-Cl 58 Figure 3-3. GPC profile of PCL-Cl and P4VP-b-PCL 58 Figure 3-4 400 MHz 1H NMR of P4VP-b-PCL. 59 Figure 3-5. Schematic illustration of the procedures for the interfacial reduction: (a)-(c) liquid-gas interfacial reduction; (d)-(f) solid-liquid interfacial reduction 62 Figure 4-1. TGA thermograms of (a) V3C5 (fP4VPv=0.30) and (b) V2C7 (fP4VPv=0.24). DSC (c) heating and subsequent (d) cooling curves for the P4VP-PCL BCPs. The heating and cooling rates are 10 oC/min 67 Figure 4-2. TEM micrographs of P4VP-PCL BCPs with different compositions in which corresponding insets represent the top-view of cylindrical morphologies: (a) V2C7 (fP4VPv=0.24); (b) V3C5 (fP4VPv=0.37); (c) V4C7 (fP4VPv=0.38); (d) V5C5 (fP4VPv=0.5); (e) V15C5 (fP4VPv=0.75); (f) V22C5 (fP4VPv=0.81). The P4VP microdomains appear dark due to the staining of RuO4 while the microdomains of PCL appear bright 68 Figure 4-3. One-dimensional SAXS profile of P4VP-PCL samples with different compositions: (a) V2C7 (fP4VPv=0.24); (b) V3C5 (fP4VPv=0.37); (c) V4C7 (fP4VPv=0.38); (d) V5C5 (fP4VPv=0.5); (e) V15C5 (fP4VPv=0.75); (f) V22C5 (fP4VPv=0.81).The dashed curves of (a) and (c) represent the results examined at 70 oC (above the melting temperature of PCL) 70 Figure 4-4. FTIR spectrum of (a) V3C5 (fP4VPv=0.37) and (b) Au3+ ions/V3C5 (Au/N = 1/7) 71 Figure 4-5. TEM micrographs of the Au3+/V3C5 hybrids at the hybrid ratio of (a) 1/7, (b) 1/3 and (c) 1/1. The P4VP microdomains appear dark due to the RuO4 staining while the microdomains of PCL appear bright. (d) Schematic representation of the phase transformation from original cylinder to lamellar and finally disorder phase. The insets of (a) and (b) show the unstained results at equal magnification. Besides, the inset of (c) shows the aggregates of Au3+ ions at high magnification 73 Figure 4-6. One-dimensional SAXS profiles of (a) V3C5 and its hybrids at hybrid ratio of (b) 1/7, (c) 1/3 and (d) 1/1. It indicates that the phase transformation from original cylinder to lamellar and disorder-like phase can be achieved by increasing the adding amounts of Au3+ ions 74 Figure 4-7. TEM micrographs of (a) V4C7 (fP4VPv = 0.38) and its hybrids at hybrid ratio of (b) 1/7 and (c) 1/3 with RuO4 staining. The micrograph in the inset of (a) shows the top view of the cylinders 76 Figure 4-8. TEM micrographs of (a) V2C7 (fP4VPv = 0.24) and its hybrids at hybrid ratio of (b) 1/7 and (c) 1/3 with RuO4 staining. The micrograph in the inset of (a) shows the top view of the cylinders 77 Figure 4-9. One-dimensional SAXS profiles of (a) V4C7 (fP4VPv = 0.38) and its hybrids, (b) V2C7 (fP4VPv = 0.24) and its hybrids 78 Figure 4-10. TEM micrographs of (a) V15C5 (fP4VPv = 0.75) and (b) Au3+/V15C5 hybrid (Au/N: 1/14) with RuO4 staining. (c) Solutions of methanol and P4VP homopolymer (left), methanol and Au3+ ions (center), and methanol, P4VP homopolymer and Au3+ ions (right). The micrograph in the inset of (a) shows the top view of the cylinders 81 Figure 4-11. One-dimensional correlation function of (a) Au3+/V4C7 hybrids; (b) Au3+/V2C7 hybrids in which the thickness of lamellar long period was calculated by the position of first peak and the average thickness of the thinner layers was determined by the connection between tangent and baseline of the first wave trough 84 Figure 4-12. TEM micrographs of Au3+/V2C7 (Au/N: 1/30): (a) top view of the cylinder phase of pristine V2C7; (b) observation of the interconnection between neighboring cylinders caused by the loading of Au3+ ions; (c) observation of the interconnection induced the phase transformation from cylinder to lamellae. (d) Schematic representation of the change of the free energy with morphological transformation 86 Figure 4-13. The relation between the effective excluded volume of hybridized P4VP and the volume fraction of Au3+ ions in different hybrids 88 Figure 4-14. Schematic representation of calculated results for PCL and P4VP domain spacings. In the V2C7 (fP4VPv = 0.24) hybrids, the long period of lamellar phase decreases from 22.9 nm (1) to 21.6 nm (2) with increasing the loading of Au3+ ions from Au/N: 1/7 to 1/3. In the V4C7 (fP4VPv = 0.38) hybrids, the long period of lamellar phase increases from 20.8 nm (3) to 22.4 nm (4) with increasing the loading of Au3+ ions from Au/N: 1/7 to 1/3. In the V3C7 (fP4VPv = 0.3) hybrid, the long spacing is about 22.3 nm (5) 89 Figure 4-15. Schematic illustration of the bridging for hybridized P4VP chains and the PCL blocking effect in (a) PCL-rich P4VP-PCL hybrids: the phase transformation can be induced by interconnection of hybridized P4VP microdomains through the bridging of hybridized P4VP chains in which the ordered nanostructures from microphase separation can be consolidated because of long PCL brushes, namely strong PCL blocking. (b) P4VP-rich P4VP-PCL hybrids: the coverage of short PCL brushes on the hybridized P4VP microdomains is insufficient to against the strong interconnection of neighboring hybridized P4VP microdomains through the bridging of hybridized P4VP chains (it is referred to the weak PCL blocking) so as to result in disordered texture 91 Figure 4-16. TEM micrographs of (a) V5C5 (fP4VPv = 0.5) and (b) Au3+ ions/V5C5 (Au/N: 1/14) with RuO4 staining 93 Figure 4-17. One-dimensional SAXS profiles of (a) V2C7 (fP4VPv = 0.24) and its hybrids with (b) HAuCl4, (c) Cu(Ac)2, (d) CuAc, (e) AgNO3 at the hybrid ratio of 1/20 96 Figure 4-18. TEM micrographs of V2C7 hybrids with (a) HAuCl4, (b) Cu(Ac)2, (c) CuAc and (d) AgNO3 at the hybrid ratio of 1/20. The inset in the (a) shows the enlarge micrograph at which the silver aggregates are remarked by the white circles. All samples are stained by RuO4 at which the dark region represents the P4VP microdomain and the bright region is the PCL microdomain 97 Figure 4-19. One-dimensional SAXS profiles of V2C7 (fP4VPv = 0.24) hybrids with (a) HAuCl4, (b) Cu(Ac)2, (c) CuAc, (d) AgNO3 at the hybrid ratio of 1/10 99 Figure 4-20. TEM micrographs of V2C7 hybrids with (a) HAuCl4, (b) Cu(Ac)2, (c) CuAc and (d) AgNO3 at the hybrid ratio of 1/10. The inset in the (a) shows the enlarge micrograph at which the silver aggregates are remarked by the white circles. All samples are stained by RuO4 at which the dark region represents the P4VP microdomain and the bright region is the PCL microdomain 100 Figure 4-21. TEM micrographs of (a) V15C5 hybrids and (b) V22C5 with HAuCl4 at the hybrid ratio of 1/10. All samples are stained by RuO4 at which the dark region represents the P4VP microdomain and the bright region is the PCL microdomain 102 Figure 4-22. FTIR spectra of (a) V2C7 (fP4VPv = 0.24) and its hybrids with (b) HAuCl4, (c) Cu(Ac)2, (d) CuAc, (e) AgNO3 at the hybrid ratio of 1/20 103 Figure 4-23. Primay peak in one-dimensional SAXS profiles of V2C7 (fP4VPv = 0.24) and its hybrids at the hybrid ratio of (a) 1/20 and (b) 1/10 106 Figure 4-24. One-dimensional SAXS profiles of (a) V4C7 (fP4VPv = 0.38) and its hybrids with HAuCl4, Cu(Ac)2, CuAc and AgNO3 at the hybrid ratio of 1/20 and 1/10 in Figures (b)-(e) and (f)-(i), respectively 107 Figure 4-25. Primary peaks in 1D SAXS profiles of V4C7 (fP4VPv = 0.38) and its hybrids at the hybrid ratio of (a) 1/20 and (b) 1/10 108 Figure 4-26. (a) Illustrations of the P4VP chain stretching under weak association and strong association. (b) Molecular model of copper acetate monohydrate coordinated to one pyridine sidegroup in P4VP chain illustrating the concept of a “coordination pendant group”. It is proposed that only one pyridine in the P4VP chain can be associated with Cu2+ ion. 109 Figure 4-27. UV spectrum of (a) 1 wt % gold ions/V3C5 solution; (b) 1 wt % gold ions/V3C5 solution after liquid-solid interfacial reduction; (c) 1 wt % gold ions/V3C5 solution after liquid-gas interfacial reduction. The solvent used is dichloromethane (CH2Cl2). The schematic representation is used to explain the relation between reduction types and particle size as shown in (d) 112 Figure 4-28. TEM micrographs of (a) central packed gold NPs within P4VP microdomains by liquid-gas interfacial reduction (particle size is ca. 7~15 nm); (b) edged packed gold NPs within P4VP microdomains by solid-liquid interfacial reduction (particle size is ca. 4~7 nm). The insets represent the location of gold NPs within P4VP microdomains, in which the interfaces are marked by the dash line. All the microsections for TEM observation are stained by RuO4 113 Figure 4-29. (a) One-dimensional SAXS profiles of gold precursor/V2C7 hybrid system with different reduction periods: 1, 3, 5 min; (b) Corresponding TEM micrographs of gold ions/V2C7 with different reduction periods. All the microsections for TEM observation are stained by RuO4 115 Figure 4-30. TEM micrographs of (a) V4C7 (fP4VPv = 0.38) hybrids with HAuCl4 at the hybrid ratio of 1/7 and (b) its result after the reduction. All samples are stained by RuO4 at which the dark region represents the P4VP microdomain and the bright region is the PCL microdomain. (c) Schematic illustration of the molecular dispositions in the Au3+/V4C7 hybrid before (left) and after (right) the reduction 116 Figure 4-31. TEM micrograph of (a) Au NPs/V2C7 hybrid and (b) its result after 24 hours solid-liquid interfacial reduction. All the microsections for TEM observation are stained by RuO4 119 Figure 4-32. (a) Schematic illustration of the composites formed by the incorporation of bi-continuous phases (from BCP) and metallic NPs (b) TEM micrograph of Au NPs/V3C5 at the hybrid ratio of 1/3 with RuO4 staining. (c) Schematic illustration of the experimental procedures for the preparation of Ag NPs/BCP composites 122 Figure 4-33. TEM micrographs of Ag NPs with different sizes: (a) 10 nm; (b) 5~7nm; (c) 5 nm. (d) TEM micrograph of PS-P4VP BCPs with RuO4 staining. Schematic illustration represents the nucleation and growth mechanisms for the sample with the low and high concentration of reduction agent 124 Figure 4-34. TEM micrographs of Ag NPs/PS-P4VP hybrids with low (a) and (b) high concentration of Ag NPs. Figure (c) and (d) presents the sintering results of sample (a) and (b), respectively. The PS microdomains appear dark due to the staining of RuO4 while the P4VP microdomains appear gray due to the slight staining of RuO4 126 Figure 4-35. (a) Schematic illustration of the preparation of Ag nanorods/polymer hybrids. TEM micrographs of Ag nanomaterials synthesized by using different silver nitrate/PVP ratios: (b) 1/4, (c) 1/8 and (d) 1/16. (e) The corresponding SEM micrograph of Ag nanorods in Figure (c) 128 Figure 4-36. TEM micrographs of Ag nanomaterials synthesized by using different titration rate: (a) 2 ml/min (gravity titration); (b) 1 ml/min (gravity titration); (c) 0.3 ml/min (gravity titration); (d) 0.3 ml/min (automatic titration); (e) 0.16 ml/min (automatic titration). The (e) shows the high-magnification image of (e) 130 Figure 4-37. Optical (a) and TEM (b) images of dispersed Ag nanorods. 132 Figure 4-38. Optical images of Ag nanorods/PVA hybrids with the Ag nanorods/ PVA ratio of (a) 1/140 and (b) 1 133