Cross-Sectional Chemical Nanoimaging of Composite Polymer Nanoparticles by Infrared Nanospectroscopy

Goikoetxea, Monika; Amenabar, Ibán; Chimenti, Stefano; Paulis, Marı́a; Leiza, José R.; Hillenbrand, Rainer

doi:10.1021/acs.macromol.0c02287

Cited by 18 publications

(10 citation statements)

References 54 publications

(77 reference statements)

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“…The two Tg in PMB1 and PMB3 correspond to the two incompatible phases present in the particles, namely, one rich in POA (lower Tg) and one rich in the MMA/BA comonomers (higher Tg). The nanoFTIR analysis done for the PMB1 sample [16] indicated the presence of three phases two of them rich in MMA/BA (core and outer shell) comonomers and one rich in POA monomer (inner shell). The morphology of PMB3 presents two phases that correspond to pure POA homopolymer and a copolymer of MMA/BA synthesized under starved conditions.…”

Section: Film Propertiesmentioning

confidence: 99%

“…The morphology of experiment PMB1 is a core-shellshell with a core composed by terpolymer chains rich in MMA/BA (67%), an inner shell composed by terpolymer chains rich in POA (70%), and the external shell composed by terpolymer chains rich in MMA/BA (73%). The exact compositions of each of the phases were determined by nanoFTIR as described in a recent work, and the reader is referred to there for details [16]. For the purposes of this work, it suffices to say that the morphology achieved was clearly a non-equilibrium morphology because the inner shell is substantially more hydrophobic than the core, and hence, it was expected to be in the core.…”

Section: Particle Morphologymentioning

confidence: 99%

“…Fig.3 HAADF-STEM (a, b, and d) and TEM (c) micrographs of the polymer particles produced which each polymerization strategy. In HAADF-STEM images, bright regions correspond to electronically dense regions (i.e., F atom containing regions) as opposed to TEM (Figure4ais reprinted with permission from reference[16])…”

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confidence: 99%

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Strategies to incorporate a fluorinated acrylate monomer into polymer particles: from particle morphology to film morphology and anticorrosion properties

et al. 2022

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Four strategies to incorporate a fluorinated monomer (perfluoro octyl acrylate, POA) into a waterborne polymeric dispersion are investigated. Due to the very low water solubility of the POA monomer, three of the strategies use miniemulsion droplets containing the whole POA monomer in the initial charge. The rest of the comonomers of the formulation (methyl methacrylate, MMA, and n-butyl acrylate, BA) are partially incorporated in the initial miniemulsion or fed to the reactor as a preemulsion. In the fourth strategy, a conventional seeded semibatch emulsion polymerization is carried out using cyclodextrin in the seed and feeding the POA/MMA/BA preemulsion to the reactor. Each process strategy led to a distinct particle morphology and hence a particular film morphology. We found that the strategy that produced core–shell particles with the core composed by pure polyPOA yielded the films that showed the best corrosion protection as measured in salt-spray test (1200 h standing without damage).

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Section: Film Propertiesmentioning

confidence: 99%

Section: Particle Morphologymentioning

confidence: 99%

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Strategies to incorporate a fluorinated acrylate monomer into polymer particles: from particle morphology to film morphology and anticorrosion properties

et al. 2022

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“…[61][62][63][64] IR s-SNOM at infrared frequencies provides both the spectral and spatial information at nanoscale. [65,66] Near-field amplitude (reflectivity or absorption) image at a specific wavelength enables the direct examination of the staining-free chemical distribution of nanoscale polymers in blends. The infrared spectroscopy curves of PM6, N3, and SEBS neat films obtained by Fourier transform infrared (FTIR) spectrometer were shown in Figure S6 (Supporting Information).…”

Section: Film Morphology Of Ternary Blend Filmsmentioning

confidence: 99%

Thermoplastic Elastomer Tunes Phase Structure and Promotes Stretchability of High‐Efficiency Organic Solar Cells

et al. 2021

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the power conversion efficiencies (PCEs) of OSCs show rapid increase and the values have increased to over 18%. [16][17][18][19][20][21][22][23][24] However, owing to the brittle nature of small molecules, [25] the mechanical properties of polymer:NF-SMA blends are generally insufficient and can hardly meet the requirement of stretchable electronics. [26,27] The mechanical imperceptibility of OSCs requires low stiffness and high extensibility for wearable and portable applications. The human skin exhibits a ductility of about 30%, which is the benchmark for skin-wearable devices. [28] Studies have been carried out to determine the mechanical properties of nonfullerene OSCs [29][30][31] and drive the development of stretchable OSCs. [32][33][34][35] For instance, the fracture strain of the well-known PTB7-Th:(3,9-bis(2-methylene-(3-(1,1dicyanomethylene)-indanone))-5,5,11,11tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene) (ITIC) blend films decreased dramatically with the increase of ITIC, and the blend films became significantly stiffer as a result of increased elastic modulus. [26,36] Therefore, methods should be adopted to improve the stretchability and reduce the stiffness of OSCs based on polymer:NF-SMA blends.As the mechanical performance of polymer:NF-SMA blends are often poor, a representative high-efficiency Top-performance organic solar cells (OSCs) consisting of conjugated polymer donors and nonfullerene small molecule acceptors (NF-SMAs) deliver rapid increases in efficiencies. Nevertheless, many of the polymer donors exhibit high stiffness and small molecule acceptors are very brittle, which limit their applications in wearable devices. Here, a simple and effective strategy is reported to improve the stretchability and reduce the stiffness of highefficiency polymer:NF-SMA blends and simultaneously maintain the high efficiency by incorporating a low-cost commercial thermoplastic elastomer, polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS). The microstructure, mechanical properties, and photovoltaic performance of PM6:N3 with varied SEBS contents and the molecular weight dependence of SEBS on microstructure and mechanical properties are thoroughly characterized. This strategy for mechanical performance improvement exhibits excellent applicability in some other OSC blend systems, e.g., PBQx-TF:eC9-2Cl and PBDB-T:ITIC. More crucially, the elastic modulus of such complex ternary blends can be nicely predicted by a mechanical model. Therefore, incorporating thermoplastic elastomers is a widely applicable and cost-effective strategy to improve mechanical properties of nonfullerene OSCs and beyond.

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“…The IR contrast in the on-resonance images are compared to that of the off-resonance images obtained at laser frequency of 1570 cm –1 that does not have significant overlap with any of the vibrational frequencies of the P4VP or P3HT components as illustrated in Figure S1. Ideally, the distribution of the P3HT domains should be obtained by recording the s-SNOM image at the corresponding vibrational frequencies (e.g., at 1456 cm –1 , Figure S1) similar to the recent study by Goikoetxea et al Unfortunately, all the vibrational frequencies of the P3HT component are outside the tunability range of our QCL. Nevertheless, a negative correlation between the topographic height and IR phase must indicate the P3HT domain as there are only two components in the blend that is considered in this study.…”

Section: Experimental Methodsmentioning

confidence: 94%

Hierarchical Self-Assembly and Chemical Imaging of Nanoscale Domains in Polymer Blend Thin Films

et al. 2022

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Self-assembly of polymers driven by intermolecular and intramolecular interactions leads to rich structural variations in thin films of polymer blends. In this work, ordering of poly(3-hexylthiophene-2,5-diyl) (P3HT) to form nanoparticles (NPs) and the self-assembly pattern of the NPs in poly(4-vinylpyridine) (P4VP) matrix are revealed by using scattering-type scanning near-field optical microscopy (s-SNOM). The P3HT NPs are formed spontaneously when the P3HT/P4VP/chloroform solution is spin-cast on unpatterned silicon wafer at room temperature. We find that the P3HT NPs organize within the P4VP matrix forming continuous stripes along the parallel striations, depending on the solution composition and spin-coating angular speed. The spacing between the parallel P3HT stripes that runs along the center of the ridges varies from sample to sample within 4–12 μm, whereas the width of the P3HT stripes confined within the ridges ranges from 0.2 to 1.1 μm as determined from the s-SNOM infrared phase contrast. The sizes of the P3HT NPs range from 5 to over 100 nm depending on the composition of the blend as determined by using an atomic force microscope after selectively dissolving the P4VP matrix. The smallest size observed in our experiment is significantly smaller than the smallest diameter (larger than 20 nm) reported in the literature. The results presented here show that interaction between immiscible polymers during solvent evaporation can be manipulated to control hierarchical self-assembly from molecular ordering to mesoscale dimensions, and high-resolution chemical imaging is necessary to resolve nanoscale domains so that solution processes can be optimized.

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Cross-Sectional Chemical Nanoimaging of Composite Polymer Nanoparticles by Infrared Nanospectroscopy

Cited by 18 publications

References 54 publications

Strategies to incorporate a fluorinated acrylate monomer into polymer particles: from particle morphology to film morphology and anticorrosion properties

Strategies to incorporate a fluorinated acrylate monomer into polymer particles: from particle morphology to film morphology and anticorrosion properties

Thermoplastic Elastomer Tunes Phase Structure and Promotes Stretchability of High‐Efficiency Organic Solar Cells

Hierarchical Self-Assembly and Chemical Imaging of Nanoscale Domains in Polymer Blend Thin Films

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