Equilibrium Melting Temperature of Poly(ferrocenyl dimethylsilane) in Homopolymers and Lamellar Diblock Copolymers with Polystyrene

Xu, Jianjun; Bellas, Vasilios; Jungnickel, B.‐J.; Stühn, Bernd; Rehahn, Matthias

doi:10.1002/macp.200900718

Cited by 17 publications

(32 citation statements)

References 54 publications

(81 reference statements)

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“…For a comprehensive illustration, Table 1 contains thermal transition and molecular weight data for PFS homopolymers determined by differential scanning calorimetry (DSC) and gel permeation chromatography (GPC), respectively. 90 This value corresponds to a 100% perfect crystallite of infinite size, which cannot be obtained experimentally. 30,78 One notable property of these materials is their high thermal stabilities to weight loss; for example, PFS with two hydrogen substituents retained 90% of its initial mass when heated to 600 1C.…”

Section: Morphology In the Solid State: Crystalline And Amorphous Matmentioning

confidence: 95%

“…16 Generally, for PFSs with hydrogen substituents on the Cp rings, T g values can range from À51 1C with long, flexible substituents at silicon, such as R = R 0 = OC 6 H 13 , to 99 1C for materials with ferrocenyl and methyl substituents, demonstrating the substantial influence of the side group structure. 90 Moreover, using the Gibbs-Thomson approach resulted in the prediction of an equilibrium melting temperature of ca. 6,7,51,60,68,71,75,78 A significant increase in T g also occurs when the hydrogens on the cyclopentadienyl ligands are replaced with more sterically demanding alkyl groups.…”

Section: Morphology In the Solid State: Crystalline And Amorphous Matmentioning

confidence: 99%

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Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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This in-depth review covers progress in the area of polyferrocenylsilanes (PFS), a well-established, readily accessible class of main chain organosilicon metallopolymer consisting of alternating ferrocene and organosilane units. Soluble, high molar mass samples of these materials were first prepared in the early 1990s by ring-opening polymerisation (ROP) of silicon-bridged [1]ferrocenophanes (sila[1]ferrocenophanes). Thermal, transition metal-catalysed, and also two different living anionic ROP methodologies have been developed: the latter permit access to controlled polymer architectures, such as monodisperse PFS homopolymers and block copolymers. Depending on the substituents, PFS homopolymers can be amorphous or crystalline, and soluble in organic solvents or aqueous media. PFS materials have attracted widespread attention as high refractive index materials, electroactuated redox-active gels, fibres, films, and nanoporous membranes, as precursors to nanostructured magnetic ceramics, and as etch resists to plasmas and other radiation. PFS block copolymers form phase-separated iron-rich, redox-active and preceramic nanodomains in the solid state with applications in nanolithography, nanotemplating, and nanocatalysis. In selective solvents functional micelles with core-shell structures are formed. Block copolymers with a crystallisable PFS core-forming block were the first to be found to undergo "living crystallisation-driven self-assembly" in solution, a controlled method of assembling block copolymers into 1D or 2D structures that resembles a living covalent polymerisation, but on a longer length scale of 10 nm-10 μm.

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Section: Morphology In the Solid State: Crystalline And Amorphous Matmentioning

confidence: 95%

Section: Morphology In the Solid State: Crystalline And Amorphous Matmentioning

confidence: 99%

Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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“…The PS‐ b ‐PFDMS diblock copolymer under investigation here (Figure 1) was prepared by sequential living anionic polymerization as described recently 57. Its overall molar mass ($\overline {M} _{{\rm n}} $ ) was 24.3 kg · mol −1 (polydispersity index (PDI) = 1.05).…”

Section: Experimental Partmentioning

confidence: 99%

“…As PFDMS crystallizes very slowly, the self‐seeding technique1, 57, 64–73 was applied to ensure PFDMS crystallization in experimentally acceptable periods of time. The required pre‐crystallized samples were obtained by first heating the powdery ‘as‐synthesized’ PS‐ b ‐PFDMS to 180 °C for 60 min in order to destroy any kind of preformed crystalline order.…”

Section: Experimental Partmentioning

confidence: 99%

“…Even determination of the equilibrium melting temperature, T m,0 , has, therefore, been a challenge: using the linear Hoffmann–Weeks (HW) approach,1, 24, 55, 56 a T m,0 of 144 °C was obtained,30, 31, 57 but following the Gibbs–Thomson (GT) procedure,1, 24, 58 a T m,0 of 215 °C was the result 57. Moreover, a T m,0 of 179 °C was determined when the melting of PFDMS as part of a phase‐separated PS‐ b ‐PFDMS diblock copolymer (PS: polystyrene) of lamellar micro‐morphology was addressed 57. Since understanding the quite special PFDMS crystallization characteristics could significantly contribute to a well‐grounded knowledge of crystallization in phase‐separated block copolymers in general, we started a profound analysis of PS‐ b ‐PFDMS systems.…”

Section: Introductionmentioning

confidence: 99%

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A Novel Crystallization Scheme in Poly[styrene‐block‐(ferrocenyl dimethylsilane)] Diblock Copolymers

Bellas

Jungnickel

et al. 2010

Macro Chemistry & Physics

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Isothermal crystallization of the poly(ferrocenyl dimethylsilane) (PFDMS) segments in a poly[styrene‐block‐(ferrocenyl dimethylsilane)] (PS‐b‐PFDMS) diblock copolymer of lamellar micro‐morphology has been investigated. The PFDMS is shown to crystallize in a confined and grain‐by‐grain fashion. Here a ‘grain’ is defined as an ensemble of stacked lamellae wherein the PFDMS crystallization spreads quickly but stops at its surroundings. Such crystallization propagates not only along the PFDMS lamellae but across the amorphous PS layers as well. We suggest that conformational changes in the PS as induced by the PFDMS crystallization (‘squeezing transfer’) are responsible for the latter pathway of the crystallization's spread.

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Capillary Stamping of Functional Materials: Parallel Additive Substrate Patterning without Ink Depletion

Runge

Hübner

Grimm

et al. 2020

Adv Materials Inter

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functional inks; in this way, substrates may be patterned with functional materials and tailored nanoparticle arrays may be generated. An ideal additive lithographic substrate patterning technique would allow the execution of an unlimited number of parallel large-area ink deposition steps characterized by short cycle times without process-intrinsic interruptions caused, for example, by ink depletion. However, stateof-the-art substrate patterning techniques do not meet this requirement. Contactless ballistic pattering methods including inkjet printing, aerosol jet printing [2] and laser-induced forward transfer [3] can, in principle, be carried out continuously because ink can continuously be supplied to the substrate. However, these methods involve serial pixel-by-pixel writing associated with limitations regarding patternable areas and/or throughput. Additive substrate patterning by microcontact printing [4] and variations thereof such as polymer pen lithography (PPL), [5] capillary force lithography, [6] wet lithography, [7] and particle transfer printing [8] are parallel and allow simultaneous patterning of large substrate areas. However, these methods involve transfer of ink coated on the outer surfaces of solid elastomeric stamps to substrates. Consequently, ink depletion in the course of successive stamp-substrate contacts results in deteriorating quality of the stamped patterns. Automated stamping devices for parallel additive surface manufacturing would be commercially available, [9] but stamping needs to be interrupted after a limited number of stamping steps to recoat Patterned substrates for optics, electronics, sensing, lab-on-chip technologies, bioanalytics, clinical diagnostics as well as translational and personalized medicine are typically prepared by additive substrate manufacturing including ballistic printing and microcontact printing. However, ballistic printing (e.g., ink jet and aerosol jet printing, laser-induced forward transfer) involves serial pixelby-pixel ink deposition. Parallel additive patterning by microcontact printing is performed with solid elastomeric stamps suffering from ink depletion after a few stamp-substrate contacts. The throughput limitations of additive stateof-the art patterning thus arising may be overcome by capillary stampingparallel additive substrate patterning without ink depletion by mesoporous silica stamps, which enable ink supply through the mesopores anytime during stamping. Thus, either arrays of substrate-bound nanoparticles or colloidal nanodispersions of detached nanoparticles are accessible. Three types of model inks are processed: 1) drug solutions, 2) solutions containing metallopolymers and block copolymers as well as 3) nanodiamond suspensions representing colloidal nanoparticle inks. Thus, aqueous colloidal nanodispersions of stamped drug nanoparticles, regularly arranged ceramic nanoparticles by post-stamping pyrolysis of stamped metallopolymeric precursor nanoparticles and regularly arranged nanodiamond nanoaggregates are obtained. Capillary sta...

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Equilibrium Melting Temperature of Poly(ferrocenyl dimethylsilane) in Homopolymers and Lamellar Diblock Copolymers with Polystyrene

Cited by 17 publications

References 54 publications

Polyferrocenylsilanes: synthesis, properties, and applications

Polyferrocenylsilanes: synthesis, properties, and applications

A Novel Crystallization Scheme in Poly[styrene‐block‐(ferrocenyl dimethylsilane)] Diblock Copolymers

Capillary Stamping of Functional Materials: Parallel Additive Substrate Patterning without Ink Depletion

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