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21 pages, 5274 KiB

Open AccessArticle

“To Be or Not to Be” of a Polymer Nanogel—Unravelling the Relationship of Product Properties vs. Synthesis Conditions Governing the Radiation Crosslinking of Poly(acrylic acid) Using GPC/SEC—MALLS

by Sławomir Kadłubowski, Beata Paulina Rurarz, Joanna Raczkowska, Carlo Dessy and Piotr Ulański

Materials 2023, 16(23), 7467; https://doi.org/10.3390/ma16237467 - 30 Nov 2023

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Abstract

In this paper, a state-of-the-art multi-detection gel permeation chromatography/size exclusion chromatography (GPC/SEC) system including multi-angle laser light scattering (MALLS) is applied to monitor radiation-induced synthesis of internally crosslinked nanostructures from poly(acrylic acid) (PAA). The aim is to demonstrate that this modern tool yields [...] Read more.

In this paper, a state-of-the-art multi-detection gel permeation chromatography/size exclusion chromatography (GPC/SEC) system including multi-angle laser light scattering (MALLS) is applied to monitor radiation-induced synthesis of internally crosslinked nanostructures from poly(acrylic acid) (PAA). The aim is to demonstrate that this modern tool yields a more detailed picture of reaction mechanism and product structure than the techniques used to date. The prevailing intramolecular crosslinking narrows the molecular weight distribution from M_w/M_n = 3.0 to 1.6 for internally crosslinked structures. A clear trend from over 0.7 to 0.5 in the Mark–Houwink exponent and a decrease in R_g/R_h from 1.7 to 1.0 point to the formation of nanogels, more rigid and less permeable than the starting coils. Changes in the coil contraction factor (g′ = [η]_irradiated/[η]_linear) as a function of the radical density revealed the existence of two modes in intramolecular crosslinking, the initial one (up to 0.075 radicals per monomer unit) where the compactness of products changes strongly with progressing crosslinking and a second one where further compacting is suppressed by the lower flexibility of the partially crosslinked chain segments. This indicates a transition from soft, still internally crosslinkable nanogels to more rigid structures, less prone to further intramolecular loop formation. Our findings provide means for the tailored design of new PAA nanomaterials. Full article

(This article belongs to the Special Issue Synthesis and Structure of Advanced Materials)

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21 pages, 9759 KiB

Open AccessArticle

Morphology and Phase Compositions of FePt and CoPt Nanoparticles Enriched with Noble Metal

by Yuri A. Zakharov, Anna N. Popova, Valery M. Pugachev, Nikita S. Zakharov, Irina N. Tikhonova, Dmitry M. Russakov, Vadim G. Dodonov, Denis G. Yakubik, Natalia V. Ivanova and Lilia R. Sadykova

Materials 2023, 16(23), 7312; https://doi.org/10.3390/ma16237312 - 24 Nov 2023

Cited by 1 | Viewed by 1580

Abstract

The article reveals for the first time the features of nanoparticle morphology, phase compositions, and their changes when heating FePt and CoPt nanoalloys. Nanoparticles were obtained by co-reduction of precursor solution mixtures with hydrazine hydrate. The features were found by a complex of [...] Read more.

The article reveals for the first time the features of nanoparticle morphology, phase compositions, and their changes when heating FePt and CoPt nanoalloys. Nanoparticles were obtained by co-reduction of precursor solution mixtures with hydrazine hydrate. The features were found by a complex of methods of X-ray diffraction (in situ XRD and X-ray scattering), TEM HR, and cyclic voltammetry. In addition, adsorbometry results were obtained, and the stability of different nanocluster structures was calculated by the molecular dynamics method. There were only FCC solid solutions in the X-ray patterns of the FePt and CoPt nanoalloys. According to XRD, in the case of nanoparticle synthesis with Fe and Co content less than 10 at. %, the composition of solid solutions was close to or practically equal to the composition of the as-synthesized nanoparticles quantified by inductively coupled plasma optical emission spectrometry. For systems synthesis with Fe and Co content greater than the above, the solubility limits (SLs) of Fe and Co in Pt were set 11.4 ± 0.7 at. % and 17.5 ± 0.6 at. %, respectively. Therefore, there were non-registered XRD extra-phases (XRNDPh-1) in the systems when C_Fe,Co ≥ SL. This statement was supported by the results of TEM HR and X-ray scattering: the smallest nanocrystals (1–2 nm) and amorphous particles were found, which qualitatively agreed with the sorbometry and SAXS results. Molecular dynamics calculations of stability for FePt and CoPt alloys claimed the structures of the most stable phase corresponded to phase diagrams (A1 and L12). Specific peculiarities of the morphology and compositions of the solid solutions of nanoalloys were established: structural blockiness (domain) and composition heterogeneity, namely, platinum enrichment of internal (deep) layers and homogenization of the nanoalloy compositions at relatively low temperatures (130–200 °C). The suggested model of the formation of nanoalloys during the synthesis, qualitatively, was compliant with the results of electrochemical deposition of FePt films on the surface of various electrodes. When nanocrystals of solid solutions (C(Fe, Co) < SL) were heated above specific temperatures, there were phase transformations with the formation of two-phase regions, with solid solutions enriched with platinum or iron (non-registered XRD phase XRNDPh-2). The newly formed phase was most likely intermetallic compounds, FePt₃, CoPt₃. As a result of the study, the model was developed, taking into account the nanoscale of the particles: XRDPh (A1, Fe_aPt_1−a) → XRDPh (A1, Fe_m_×a−xPt_m_−m×a+x) + XRNDPh-2 (Fe_n_×a+yPt_n_−n×a−y) (here, m + n = 1, m ≤ 1, n ≤ 1). Full article

(This article belongs to the Special Issue Synthesis and Structure of Advanced Materials)

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13 pages, 2594 KiB

Open AccessArticle

Theoretical and Experimental Investigation of 3D-Printed Polylactide Laminate Composites’ Mechanical Properties

by Arthur E. Krupnin, Arthur R. Zakirov, Nikita G. Sedush, Mark M. Alexanyan, Alexander G. Aganesov and Sergei N. Chvalun

Materials 2023, 16(22), 7229; https://doi.org/10.3390/ma16227229 - 19 Nov 2023

Cited by 4 | Viewed by 1742

Abstract

The purpose of this work is to theoretically and experimentally investigate the applicability of the Tsai–Hill failure criterion and classical laminate theory for predicting the strength and stiffness of 3D-printed polylactide laminate composites with various raster angles in mechanical tests for uniaxial tension [...] Read more.

The purpose of this work is to theoretically and experimentally investigate the applicability of the Tsai–Hill failure criterion and classical laminate theory for predicting the strength and stiffness of 3D-printed polylactide laminate composites with various raster angles in mechanical tests for uniaxial tension and compression. According to the results of tensile and compression tests, the stiffness matrix components of the orthotropic individual lamina and strength were determined. The Poisson’s ratio was determined using the digital image correlation method. It was found that the Tsai–Hill criterion is applicable for predicting the tensile strength and yield strength of laminate polymer composite materials manufactured via fused deposition modeling 3D printing. The calculated values of the elastic moduli for specimens with various raster angles correlate well with the values obtained experimentally. In tensile tests, the error for the laminate with a constant raster angle was 3.3%, for a composite laminate it was 4.4, in compression tests it was 11.9% and 9%, respectively. Full article

(This article belongs to the Special Issue Synthesis and Structure of Advanced Materials)

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16 pages, 3945 KiB

Open AccessArticle

Characterization of Silicate Glass/Mullite Composites Based on Coal Fly Ash Cenospheres as Effective Gas Separation Membranes

by Elena V. Fomenko, Elena S. Rogovenko, Natalia N. Anshits, Leonid A. Solovyov and Alexander G. Anshits

Materials 2023, 16(21), 6913; https://doi.org/10.3390/ma16216913 - 27 Oct 2023

Cited by 1 | Viewed by 1209

Abstract

Membrane technology is a promising method for gas separation. Due to its low energy consumption, environmental safety, and ease of operation, membrane separation has a distinct advantage over the cryogenic distillation conventionally used to capture light inert gases. For efficient gas recovery and [...] Read more.

Membrane technology is a promising method for gas separation. Due to its low energy consumption, environmental safety, and ease of operation, membrane separation has a distinct advantage over the cryogenic distillation conventionally used to capture light inert gases. For efficient gas recovery and purification, membrane materials should be highly selective, highly permeable, thermally stable, and low-cost. Currently, many studies are focused on the development of high-tech materials with specific properties using industrial waste. One of the promising waste products that can be recycled into membrane materials with improved microstructure is cenospheres—hollow aluminosilicate spherical particles that are formed in fly ash from coal combustion during power generation. For this purpose, based on narrow fractions of fly ash cenospheres containing single-ring and network structure globules, silicate glass/mullite composites were prepared, characterized, and tested for helium–neon mixture separation. The results indicate that the fragmented structure of the cenosphere shells with areas enriched in SiO₂ without modifier oxides, formed due to the crystallization of defective phases of mullite, quartz, cristobalite, and anorthite, significantly facilitates the gas transport process. The permeability coefficients He and Ne exceed similar values for silicate glasses; the selectivity corresponds to a high level even at a high temperature: αHe/Ne—22 and 174 at 280 °C. Full article

(This article belongs to the Special Issue Synthesis and Structure of Advanced Materials)

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11 pages, 7639 KiB

Open AccessArticle

Sintering Temperature Effect of Near-Zero Thermal Expansion Mn₃Zn_0.8Sn_0.2N/Ti Composites

by Yongxiao Zhou, Lianyu Zhang, Jinrui Qian, Zhiying Qian, Baoxin Hao, Qiang Cong and Chang Zhou

Materials 2023, 16(17), 5919; https://doi.org/10.3390/ma16175919 - 29 Aug 2023

Cited by 2 | Viewed by 1267

Abstract

Metal matrix composites with near-zero thermal expansion (NZTE) have gained significant popularity in high-precision industries due to their excellent thermal stability and mechanical properties. The incorporation of Mn₃Zn_0.8Sn_0.2N, which possesses outstanding negative thermal expansion properties, effectively suppressed [...] Read more.

Metal matrix composites with near-zero thermal expansion (NZTE) have gained significant popularity in high-precision industries due to their excellent thermal stability and mechanical properties. The incorporation of Mn₃Zn_0.8Sn_0.2N, which possesses outstanding negative thermal expansion properties, effectively suppressed the thermal expansion of titanium. Highly dense Mn₃Zn_0.8Sn_0.2N/Ti composites were obtained by adjusting the fabrication temperature. Both composites fabricated at 650 °C and 700 °C exhibited NZTE. Furthermore, finite element analysis was employed to investigate the effects of thermal stress within the composites on their thermal expansion performance. Full article

(This article belongs to the Special Issue Synthesis and Structure of Advanced Materials)

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11 pages, 3795 KiB

Open AccessArticle

Impact of Sintering Temperature Variation on Porous Structure of Mo₂TiAlC₂ Ceramics

by Junsheng Yang, Yiquan Fan, Hua Tan, Wenkang Liu, Yijian Kuang, Xuejin Yang, Meili Cao and Jie Li

Materials 2023, 16(16), 5682; https://doi.org/10.3390/ma16165682 - 18 Aug 2023

Cited by 2 | Viewed by 1700

Abstract

Mo, TiH₂, Al and graphite elemental powders were used as starting materials for the activation reaction sintering process, which was employed to fabricate porous Mo₂TiAlC₂. The alteration of phase constitution, volume expansion, porosity, pore size and surface [...] Read more.

Mo, TiH₂, Al and graphite elemental powders were used as starting materials for the activation reaction sintering process, which was employed to fabricate porous Mo₂TiAlC₂. The alteration of phase constitution, volume expansion, porosity, pore size and surface morphology of porous Mo₂TiAlC₂ with sintering temperatures ranging from 700 °C to 1500 °C were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and pore size tester. Both the pore formation mechanism and activation reaction process at each temperature stage were investigated. The experimental results illustrate that the sintered discs of porous Mo₂TiAlC₂ exhibit obvious volume expansion and pore structure change during the sintering process. Before 1300 °C, the volume expansion rate and porosity increase with the increment of temperature. However, with the sintering temperature above 1300 °C, the volume expansion rate and porosity decrease. At the final sintering temperature of 1500 °C, porous Mo₂TiAlC₂ with a volume expansion rate of 35.74%, overall porosity of 47.1%, and uniform pore structure was synthesized. The pore-forming mechanism of porous Mo₂TiAlC₂ is discussed, and the evolution of pressed pores, the removal of molding agents, the decomposition of TiH₂, and the Kirkendall effect caused by different diffusion rates of elements in the diffusion reaction are all accountable for the formation of pores. Full article

(This article belongs to the Special Issue Synthesis and Structure of Advanced Materials)

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18 pages, 4212 KiB

Open AccessArticle

High-Temperature Behavior of Laser Electrodispersion-Prepared Pd/ZSM-5 Hydrocarbon Traps under CO Oxidation Conditions

by Tatiana N. Rostovshchikova, Marina I. Shilina, Konstantin I. Maslakov, Sergey A. Gurevich, Denis A. Yavsin, Grigory B. Veselov, Vladimir O. Stoyanovskii and Aleksey A. Vedyagin

Materials 2023, 16(12), 4423; https://doi.org/10.3390/ma16124423 - 15 Jun 2023

Cited by 2 | Viewed by 1507

Abstract

Zeolites and metal-doped zeolites are now widely considered as low-temperature hydrocarbon traps to be a part of emission control systems in automobiles. However, due to the high temperature of exhaust gases, the thermal stability of such sorbent materials is of great concern. To [...] Read more.

Zeolites and metal-doped zeolites are now widely considered as low-temperature hydrocarbon traps to be a part of emission control systems in automobiles. However, due to the high temperature of exhaust gases, the thermal stability of such sorbent materials is of great concern. To avoid the thermal instability problem, in the present work, laser electrodispersion was used to deposit Pd particles on the surface of ZSM-5 zeolite grains (SiO₂/Al₂O₃ = 55 and SiO₂/Al₂O₃ = 30) to obtain Pd/ZSM-5 materials with a Pd loading as low as 0.03 wt.%. The thermal stability was evaluated in a prompt thermal aging regime involving thermal treatment at temperatures up to 1000 °C in a real reaction mixture (CO, hydrocarbons, NO, an excess of O₂, and balance N₂) and a model mixture of the same composition with the exception of hydrocarbons. Low-temperature nitrogen adsorption and X-ray diffraction analysis were used to examine the stability of the zeolite framework. Special attention was paid to the state of Pd after thermal aging at varied temperatures. By means of transmission electron microscopy, X-ray photoelectron spectroscopy, and diffuse reflectance UV–Vis spectroscopy, it was shown that palladium, having been initially located on the surface of zeolite, undergoes oxidation and migrates into the zeolite’s channels. This enhances the trapping of hydrocarbons and their subsequent oxidation at lower temperatures. Full article

(This article belongs to the Special Issue Synthesis and Structure of Advanced Materials)

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Review

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45 pages, 6788 KiB

Open AccessReview

Biomimetic Sol–Gel Chemistry to Tailor Structure, Properties, and Functionality of Bionanocomposites by Biopolymers and Cells

by Yury Shchipunov

Materials 2024, 17(1), 224; https://doi.org/10.3390/ma17010224 - 30 Dec 2023

Cited by 7 | Viewed by 2411

Abstract

Biosilica, synthesized annually only by diatoms, is almost 1000 times more abundant than industrial silica. Biosilicification occurs at a high rate, although the concentration of silicic acid in natural waters is ~100 μM. It occurs in neutral aqueous solutions, at ambient temperature, and [...] Read more.

Biosilica, synthesized annually only by diatoms, is almost 1000 times more abundant than industrial silica. Biosilicification occurs at a high rate, although the concentration of silicic acid in natural waters is ~100 μM. It occurs in neutral aqueous solutions, at ambient temperature, and under the control of proteins that determine the formation of hierarchically organized structures. Using diatoms as an example, the fundamental differences between biosilicification and traditional sol–gel technology, which is performed with the addition of acid/alkali, organic solvents and heating, have been identified. The conditions are harsh for the biomaterial, as they cause protein denaturation and cell death. Numerous attempts are being made to bring sol–gel technology closer to biomineralization processes. Biomimetic synthesis must be conducted at physiological pH, room temperature, and without the addition of organic solvents. To date, significant progress has been made in approaching these requirements. The review presents a critical analysis of the approaches proposed to date for the silicification of biomacromolecules and cells, the formation of bionanocomposites with controlled structure, porosity, and functionality determined by the biomaterial. They demonstrated the broad capabilities and prospects of biomimetic methods for creating optical and photonic materials, adsorbents, catalysts and biocatalysts, sensors and biosensors, and biomaterials for biomedicine. Full article

(This article belongs to the Special Issue Synthesis and Structure of Advanced Materials)

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