Mesostructured Polymer–Inorganic Hybrid Materials from Blocked Macromolecular Architectures and Nanoparticles

Kamperman, Marleen; Wiesner, Ulrich

doi:10.1002/9783527610570.ch14

Cited by 4 publications

(4 citation statements)

References 97 publications

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“…[6] Different mesophases are observed by systematically increasing the inorganic to block copolymer weight fraction. [4,7] A major advantage of this control is the enabling of the synthesis of ordered organic/inorganic hybrid materials. While there is a tremendous body of literature on the mechanical properties of non-ordered polymerinorganic hybrid materials, [8][9][10][11][12] studies on mechanical properties of ordered organic-inorganic hybrids are very limited.…”

Section: Communicationmentioning

confidence: 99%

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Tuning Mechanical Properties of Block Copolymer/Aluminosilicate Hybrid Materials

Verploegen¹,

Dworken²,

Faught³

et al. 2007

Macromol. Rapid Commun.

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In this work the primary mechanical property profiles of a specific class of nano‐structured polymer/inorganic hybrid materials are characterized. By utilizing sol‐gel aluminosilicate synthesis with amphiphilic polyisoprene‐block‐poly(ethylene oxide) block copolymers as structure‐directing agents, block copolymer/aluminosilicate hybrid materials are prepared with nanometer scale hexagonally packed cylinders and lamellae of the inorganic hybrid components, as evidenced by small‐angle X‐ray scattering. Systematic thermal and dynamic mechanical analyses are performed on these hybrids as well as on the constituting components. Results reveal two transitions from the low temperature, glassy state of the hybrids into high temperature elastic plateau regions, with moduli that vary over orders of magnitude as a function of composition and morphology. The first transition can be assigned to the glass transition of the PI domains while the second is ascribed to a temperature induced softening of the organic components within the PEO/hybrid domains. The results suggest that in the present nanostructured block copolymer/aluminosilicate hybrid materials composition and morphology provide a powerful tool to tailor mechanical property profiles.magnified image

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Section: Communicationmentioning

confidence: 99%

“…(II) Summary of the data collected from thirteen different synthesizes of the hexagonal cylinder morphology. Samples were synthesized using both P1 (synthesis batch 1-5) and P2 (synthesis batch[6][7][8][9][10][11][12][13]. No noticeable difference in the mechanical properties was observed as a function of molecular weight.…”

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confidence: 99%

Tuning Mechanical Properties of Block Copolymer/Aluminosilicate Hybrid Materials

Verploegen¹,

Dworken²,

Faught³

et al. 2007

Macromol. Rapid Commun.

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“…[1][2][3] BCPs have been used as structure directing agents to incorporate different loadings of functional inorganic species into select blocks of BCPs, resulting in ordered nanostructured organic-inorganic hybrid materials. [4][5][6] BCPs in hybrids with high inorganic loading can be removed by chemical, photochemical, and/or thermal treatments without collapse of the structures, resulting in nanoporous functional materials. This methodology has been successfully applied to various inorganic systems, such as aluminosilicates, 7 orthosilicates, [8][9][10] transition metal oxides 11,12 and nonoxide ceramics.…”

Section: Introductionmentioning

confidence: 99%

“…Block copolymer (BCP) self-assembly is considered a powerful route to achieve nanoscale (2−50 nm) materials because of its ability to form various periodic structures with tunable length scale. − BCPs have been used as structure directing agents to incorporate different loadings of functional inorganic species into select blocks of BCPs, resulting in ordered nanostructured organic−inorganic hybrid materials. − BCPs in hybrids with high inorganic loading can be removed by chemical, photochemical, and/or thermal treatments without collapse of the structures, resulting in nanoporous functional materials. This methodology has been successfully applied to various inorganic systems, such as aluminosilicates, orthosilicates, − transition metal oxides , and nonoxide ceramics. , Despite the achievements in the field, synthesizing ordered nanostructured metal hybrids and metals thereof using BCPs remains challenging due to the high surface energies of metals.…”

Section: Introductionmentioning

confidence: 99%

Metal Nanoparticle−Block Copolymer Composite Assembly and Disassembly

Li¹,

Sai²,

Warren³

et al. 2009

Chem. Mater.

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Ligand-stabilized platinum nanoparticles (Pt NPs) were self-assembled with poly(isoprene-blockdimethylaminoethyl methacrylate) (PI-b-PDMAEMA) block copolymers to generate organicinorganic hybrid materials. High loadings of NPs in hybrids were achieved through usage of N,Ndi-(2-(allyloxy)ethyl)-N-3-mercaptopropyl-N-3-methylammonium chloride as the ligand, which provided high solubility of NPs in various solvents as well as high affinity to PDMAEMA. From NP synthesis, existence of sub-1 nm Pt NPs was confirmed by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. Estimations of the Pt NP ligand head group density based on HAADF-STEM images and thermogravimetric analysis (TGA) data yielded results comparable to what has been found for alkanethiol self-assembled monolayers (SAMs) on flat Pt {111} surfaces. Changing the volume fraction of Pt NPs in block copolymer-NP composites yielded hybrids with spherical micellar, wormlike micellar, lamellar and inverse hexagonal morphologies. Disassembly of hybrids with spherical, wormlike micellar, and lamellar morphologies generated isolated metal-NP based nano-spheres, cylinders and sheets, respectively. Results suggest the existence of powerful design criteria for the formation of metal-based nanostructures from designer blocked macromolecules.

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Block‐Copolymer‐Architected Materials in Electrochemical Energy Storage

Werner,

Li,

Wiesner

2023

Small Science

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The multiscale architecture of electrochemical energy storage (EES) materials critically impacts device performance, including energy, power, and durability. The pore space of nano‐ to macrostructured electrodes determines mass transport within the electrolyte and defines the effective energy density. The dimensions of the active charge‐storing materials can increase stability during cycling by accommodating strains from electrochemical–mechanical coupling while also defining surface area that increases capacitive charge storage, decreases charge‐transfer resistance, but also leads to low efficiency and degradation from interfacial reactions. Thus, elucidating and developing a fundamental understanding of these correlations requires materials with precisely tunable nanoscale architectures. Herein, approaches that take advantage of the nanoscale control offered by block copolymer (BCP) self‐assembly are reviewed and insights gained from associated nanoscale phenomena observed in EES are highlighted. Systematic studies that use custom‐tailored BCPs to reveal fundamental nanostructure–property–performance relationships are emphasized. Importantly, most reports of nanostructured materials utilize low loadings and thin electrodes and results represent mass transfer limitations at the particle scale. However, as cell‐level performance involves mass transport over 10–100s of micrometers, recently emerging BCP‐based processes are further highlighted, leading to hierarchical meso/macroporous materials needed for creating multiscale structure–performance relationships and next‐generation energy storage material architectures.

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Mesostructured Polymer–Inorganic Hybrid Materials from Blocked Macromolecular Architectures and Nanoparticles

Cited by 4 publications

References 97 publications

Tuning Mechanical Properties of Block Copolymer/Aluminosilicate Hybrid Materials

Tuning Mechanical Properties of Block Copolymer/Aluminosilicate Hybrid Materials

Metal Nanoparticle−Block Copolymer Composite Assembly and Disassembly

Block‐Copolymer‐Architected Materials in Electrochemical Energy Storage

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