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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Networks".

Deadline for manuscript submissions: closed (31 May 2023) | Viewed by 19638

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Prof. Dr. Longquan Chen

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School of Physics, University of Electronic Science and Technology of China, Chengdu 610054, China
Interests: surface modification; surface characterization; fluid mechanics; mechanical engineering; material characterization; nanomaterials materials; polymers; surface science; polymeric materials

Prof. Dr. Duyang Zang

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Functional Soft Matter & Materials Group, MOE Key Laboratory of Material Physics and Chemistry under Extraordinary Conditions, School of Science, Northwestern Polytechnical University, Xi’an 710129, China
Interests: soft matter physics and complex fluids

Prof. Dr. Carlo Antonini

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Department of Materials Science, University of Milano-Bicocca, 20125 Milan, Italy
Interests: wetting; hydrophobicity; icephobicity; omniphobicity; nanocellulose; nanomaterials; coatings
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Anna Maria Coclite

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Institute of Solid State Physics, Graz University of Technology, NAWI Graz, Graz, Austria
Interests: chemical vapor deposition; gels, coating

Special Issue Information

Dear Colleagues,

Polymers make up many of the natural and artificial materials, ranging from proteins, nucleic acids and living organisms to plastics and rubbers. As a consequence, characterizing and understanding the chemical, physical, mechanical, or biological properties and processes of polymers has been a long research subject. Given the fact that the interaction between two matters initiates and proceeds from the interface that separates them, exploring the interfacial phenomena occurring at the polymer surfaces and interfaces, and finding out their principles and controlling strategies are significantly crucial in polymer science and technology. This Special issue is devoted to collect experimental, theoretical and numerical studies of novel interfacial effects of different polymeric materials, which include, but are not limited to, polymer films, polymer particles, and biopolymers.

Prof. Dr. Longquan Chen
Prof. Dr. Duyang Zang
Prof. Dr. Carlo Antonini
Prof. Dr. Anna Maria Coclite
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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Keywords

chemical/physical modification of polymer surfaces
self-assembly of polymer chains, nano-particles or micro-particles
nano-mechanical measurements of polymer films
functional polymer surfaces with special wettability
capillary phenomena on polymeric surfaces
mechanical instability (buckling, wrinkling, etc.) of soft polymer surfaces and interfaces
interfacial rheology
polymer tribology
numerical simulations on polymer surfaces
bioinspired polymer materials
biomolecular surfaces and interfaces
characterization methods for interfacial phenomena in polymers
polymer thin films deposited from the vapor phase

Published Papers (9 papers)

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Research

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18 pages, 10186 KiB

Open AccessArticle

Surface-Enhanced Raman Scattering (SERS) Substrates Based on Ag-Nanoparticles and Ag-Nanoparticles/Poly (methyl methacrylate) Composites

by Mayra Matamoros-Ambrocio, Enrique Sánchez-Mora and Estela Gómez-Barojas

Polymers 2023, 15(12), 2624; https://doi.org/10.3390/polym15122624 - 09 Jun 2023

Cited by 1 | Viewed by 1958

Abstract

SERS substrates formed by spherical silver nanoparticles (Ag-NPs) with a 15 nm average diameter adsorbed on Si substrate at three different concentrations and Ag/PMMA composites formed by an opal of PMMA microspheres of 298 nm average diameter were synthesized. The Ag-NPs were varied at three different concentrations. We have observed from SEM micrographs, in the Ag/PMMA composites, the periodicity of the PMMA opals is slightly altered as the Ag-NP concentration is increased; as a consequence of this effect, the PBGs maxima shift toward longer wavelengths, decrease in intensity, and broaden as the Ag-NP concentration is increased in the composites. The performance of single Ag-NP and Ag/PMMA composites as SERS substrates was determined using methylene blue (MB) as a probe molecule with concentrations in the range of 0.5 µM to 2.5 µM. We found that in both single Ag-NP and Ag/PMMA composites as SERS substrates, the enhancement factor (EF) increases as the Ag-NP concentration is increased. We highlight that the SERS substrate with the highest concentration of Ag-NPs has the highest EF due to the formation of metallic clusters on the surface, which generates more “hot spots”. The comparison of the EFs of the single Ag-NP with those of Ag/PMMA composite SERS substrates shows that the EFs of the former are nearly 10-fold higher than those of Ag/PMMA composites. This result is obtained probably due to the porosity of the PMMA microspheres that decreases the local electric field strength. Furthermore, PMMA exerts a shielding effect that affects the optical efficiency of Ag-NPs. Moreover, the metal–dielectric surface interaction contributes to the decrease in the EF. Other aspect to consider in our results is in relation to the difference in the EF of the Ag/PMMA composite and Ag-NP SERS substrates and is due to the existing mismatch between the frequency range of the PMMA opal stop band and the LSPR frequency range of the Ag metal nanoparticles adsorbed on the PMMA opal host matrix. Full article

(This article belongs to the Special Issue Polymer Surfaces and Interfaces)

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14 pages, 4191 KiB

Open AccessArticle

Preparation and Properties of Poly(butylene adipate-co-terephthalate)/thermoplastic Hydroxypropyl Starch Composite Films Reinforced with Nano-Silica

by Zehao Li, Hui Li, Muxi Wang, Zhongyan Zhang, Liting Yang, Lijun Ma and Hong Liu

Polymers 2023, 15(9), 2026; https://doi.org/10.3390/polym15092026 - 24 Apr 2023

Cited by 4 | Viewed by 1602

Abstract

The use of biodegradable plastics is gradually increasing, but its expensive cost limits promotion. In this study, poly(butylene adipate-co-terephthalate)/thermoplastic hydroxypropyl starch reinforced with nano-silica (PBAT/TPHS_g-SiO2) composite films with high hydroxypropyl starch content were prepared in a two-step process. The effect of reinforced thermoplastic hydroxypropyl starch on the mechanical, thermal, processing properties, and micromorphology of the composite films was investigated. The results showed that the tensile strength of the composite films was significantly improved by the addition of nano-silica, with 35% increase in horizontal tensile strength and 21% increase in vertical tensile strength after the addition of 4 phr of nano-silica. When the content of thermoplastic hydroxypropyl starch reinforced with nano-silica (TPHS_g-4SiO2) is 40%, the horizontal and vertical tensile strengths of the films are 9.82 and 12.09 MPa, respectively, and the elongation at break of the films is over 500%. Electron micrographs show that TPHS_g-4SiO2 is better homogeneously dispersed in the PBAT and exhibits a bi-continuous phase structure at a TPHS_g-4SiO2 content of 40%. In this study, the blowing PBAT/TPHS_g-4SiO2 composite films effectively reduce the cost and still show better mechanical properties, which are suitable for packaging applications. Full article

(This article belongs to the Special Issue Polymer Surfaces and Interfaces)

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13 pages, 2157 KiB

Open AccessArticle

The Energy Characteristics of the Surface of Statistical Copolymers

by Anatoly E. Chalykh, Valentina Y. Stepanenko, Tatiana F. Petrova and Anna A. Shcherbina

Polymers 2023, 15(8), 1939; https://doi.org/10.3390/polym15081939 - 19 Apr 2023

Viewed by 771

Abstract

The results of systematic studies on the surface energy γ and its polar γ^P and dispersion γ^D components of statistical copolymers of styrene and butadiene, acrylonitrile and butadiene, and butyl acrylate and vinyl acetate, with regard to their thermal prehistory, are generalized. Along with copolymers, the surfaces of their composing homopolymers were examined. We obtained the energy characteristics of the adhesive surfaces of copolymers that contacted with air, high-energy aluminium Al (γ = 160 mJ/m²), and the low-energy substrate surface of polytetrafluoroethylene F4 (PTFE) (γ = 18 mJ/m²). The surfaces of copolymers in contact with air, aluminium, and PTFE were investigated for the first time. It was found that the surface energy of these copolymers tended to occupy an intermediate value between the surface energy of the homopolymers. The additive nature of the change in the surface energy of the copolymers with their composition, as previously established in the works of Wu, extends to the dispersive component of the free surface energy γ^D and the critical surface energy γ_cr, according to Zisman. It was shown that a significant influence on the adhesive activity of copolymers was exerted by the substrate surface upon which the adhesive was formed. Thus, for the butadiene–nitrile copolymer (BNC) samples formed in contact with a high-energy substrate, their surface energy growth was associated with a significant increase in the polar component of the surface energy γ^P from 2 mJ/m² for the samples formed in contact with air, to an increase from 10 to 11 mJ/m² for the samples formed in contact with Al. The reason why the interface influenced the change in the energy characteristics of the adhesives was the selective interaction of each macromolecule fragment with the active centres of the substrate surface. As a result, the composition of the boundary layer changed and it became enriched with one of the components. The structure of such layers is nonequilibrium. The thermal annealing of copolymers in the mode of a stepwise temperature increase led to a convergence in the values of γ, asymptotically tending to the value characteristic of the surface of the copolymers formed in air. The activation energies for the processes of the conformational rearrangements of the macromolecules in the surface layers of the copolymers were calculated. It was found that the conformational rearrangements of the macromolecules in the surface layers occurred as a result of the internal rotation of the functional groups that determined the polar component of the surface energy. Full article

(This article belongs to the Special Issue Polymer Surfaces and Interfaces)

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15 pages, 5460 KiB

Open AccessArticle

Solid-State Surface Patterning on Polymer Using the Microcellular Foaming Process

by Jaehoo Kim, Shin Won Kim, Byung Chul Kweon, Kwan Hoon Kim and Sung Woon Cha

Polymers 2023, 15(5), 1153; https://doi.org/10.3390/polym15051153 - 24 Feb 2023

Viewed by 1489

Abstract

This study proposes a novel process that integrates the molding and patterning of solid-state polymers with the force generated from the volume expansion of the microcellular-foaming process (MCP) and the softening of solid-state polymers due to gas adsorption. The batch-foaming process, which is one of the MCPs, is a useful process that can cause thermal, acoustic, and electrical characteristic changes in polymer materials. However, its development is limited due to low productivity. A pattern was imprinted on the surface using a polymer gas mixture with a 3D-printed polymer mold. The process was controlled with changing weight gain by controlling saturation time. A scanning electron microscope (SEM) and confocal laser scanning microscopy were used to obtain the results. The maximum depth could be formed in the same manner as the mold geometry (sample depth: 208.7 μm; mold depth: 200 μm). Furthermore, the same pattern could be imprinted as a layer thickness of 3D printing (sample pattern gap and mold layer gap: 0.4 mm), and surface roughness was increased according to increase in the foaming ratio. This process can be used as a novel method to expand the limited applications of the batch-foaming process considering that MCPs can impart various high-value-added characteristics to polymers. Full article

(This article belongs to the Special Issue Polymer Surfaces and Interfaces)

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12 pages, 1267 KiB

Open AccessArticle

Thermal Analysis of Parylene Thin Films for Barrier Layer Applications

by Sébastien Buchwalder, Aurelio Borzì, Juan J. Diaz Leon, Florian Bourgeois, Cléo Nicolier, Sylvain Nicolay, Antonia Neels, Olaf Zywitzki, Andreas Hogg and Jürgen Burger

Polymers 2022, 14(17), 3677; https://doi.org/10.3390/polym14173677 - 04 Sep 2022

Cited by 8 | Viewed by 2840

Abstract

Biocompatible polymer films demonstrating excellent thermal stability are highly desirable for high-temperature (>250 °C) applications, especially in the bioelectronic encapsulation domain. Parylene, as an organic thin film, is a well-established polymer material exhibiting excellent barrier properties and is often the material of choice for biomedical applications. This work investigated the thermal impact on the bulk properties of four types of parylene films: parylene N, C, VT4, and AF4. The films, deposited using the standard Gorham process, were analyzed at varying annealing temperatures from room temperature up to 450 °C. Thermal properties were identified by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) methods, while X-ray diffraction (XRD) analysis showed the effect of high-temperature exposure on the structural properties. In addition to thermal and structural analysis, the barrier properties were measured through the helium transmission rate (HTR) and the water vapor transmission rate (WVTR). Fluorinated parylene films were confirmed to be exceptional materials for high-temperature applications. Parylene AF4 film, 25um thick, demonstrated excellent barrier performance after 300 °C exposure, with an HTR and a WVTR of 12.18 × 10³ cm³ (STP) m⁻² day⁻¹ atm⁻¹ and 6.6 g m⁻² day⁻¹, respectively. Full article

(This article belongs to the Special Issue Polymer Surfaces and Interfaces)

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10 pages, 3164 KiB

Open AccessArticle

Dynamics of Rising Bubbles and Their Impact with Viscoelastic Fluid Interfaces

by Yongjian Zhang, Chenlong Liu, Xiuxing Tang, Xin Dong, Tan He, Heyi Wang and Duyang Zang

Polymers 2022, 14(14), 2948; https://doi.org/10.3390/polym14142948 - 21 Jul 2022

Cited by 1 | Viewed by 1539

Abstract

Bubble dynamics plays a significant role in a wide range of industrial fields, such as food, pharmacy and chemical engineering. The physicochemical properties of complex fluids can greatly affect the speed with which bubbles rise, and the lifetime of bubbles, which in turn can affect the efficiency of food and drug manufacturing and also sewage purification. Therefore, it is of great scientific and practical significance to study the influence mechanism of nanoparticles and surfactants on bubble rising and impact in a complex fluid interface. This paper selects a mixed dispersion liquid of nanoparticles (SiO₂) and a surfactant (SDS) as the objects of the study, observes in real-time the entire processes of bubbles rising, impact at the gas-liquid interface, and rupture, and analyzes the dynamic mechanism of bubble impact in a complex fluid interface. By analyzing the morphological changes of the rising bubbles, the rising velocity and the lifetime of the bubbles, it is found that the surfactant molecules are distributed in the ultrapure water liquid pool and the liquid film surrounding the bubbles. Such distribution can reduce the viscoelasticity between bubbles and the liquid surface, and lower the surface tension of the liquid, which can reduce the rising velocity of bubbles, delay the drainage process of bubbles on a liquid surface, and enhance the lifetime of bubbles. If the liquid surface is covered with nanoparticles, a reticulate structure will be formed on the bubble liquid film, which can inhibit bubble discharge and prolong bubble lifetime. In addition, the influence of such a reticulate structure on liquid surface tension is limited and its function is far smaller than a surfactant. Full article

(This article belongs to the Special Issue Polymer Surfaces and Interfaces)

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15 pages, 4477 KiB

Open AccessArticle

Modification of the Maxwell–Wagner Heterogeneous Dielectric Model for Heterogeneous Polymers and Emulsions

by Jiangbo Qian, Shimi Yan, Zhenyu Li, Ling Yu, Xinlei Wang, Zhijie Zhang, Junze Sun and Xu Han

Polymers 2022, 14(13), 2743; https://doi.org/10.3390/polym14132743 - 05 Jul 2022

Cited by 3 | Viewed by 1557

Abstract

In heterogeneous polymers and emulsions, the volume fraction of the discrete phase and the frequency of electromagnetic waves affect the accuracy of the dielectric model. The integral method was used to modify the Maxwell–Wagner (M–W) heterogeneous dielectric theory, and a new model for the complex dielectric constant of polymers and emulsions was established. The experimental data were compared with the results of the M–W heterogeneous dielectric integral modification model and other theoretical models for different frequencies and volume fractions of the discrete phase. We discovered that with a decreasing volume fraction of the discrete phase, the dominant frequency range of the integral modification model expanded. When the volume fraction of the discrete phase is 10%, the dominant frequency range reaches 3 GHz. When the volume fraction of the discrete phase is 1%, the dominant frequency range reaches 4 GHz. When the volume fraction of the discrete phase is 0.06%, the dominant frequency range of the real part reaches 9.6 GHz, and the dominant frequency range of the imaginary part reaches 7.2 GHz. These results verify the advantages of the M–W modification model, which provides a theoretical basis to study the dielectric properties of polymers and emulsions, as well as for microwave measurement. Full article

(This article belongs to the Special Issue Polymer Surfaces and Interfaces)

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22 pages, 3061 KiB

Open AccessArticle

Equilibrium and Dynamic Surface Tension Behavior in Colloidal Unimolecular Polymers (CUP)

by Ashish Zore, Peng Geng and Michael R. Van De Mark

Polymers 2022, 14(11), 2302; https://doi.org/10.3390/polym14112302 - 06 Jun 2022

Cited by 2 | Viewed by 2609

Abstract

Studies of the interfacial behavior of pure aqueous nanoparticles have been limited due tothe difficulty of making contaminant-free nanoparticles while also providing narrow size distribution. Colloidal unimolecular polymers (CUPs) are a new type of single-chain nanoparticle with a particle size ranging from 3 to 9 nm, which can be produced free of surfactants and volatile organic contents (VOCs). CUP particles of different sizes and surface charges were made. The surface tension behavior of these CUP particles in water was studied using a maximum bubble pressure tensiometer. The equilibrium surface tension decreased with increasing concentration and the number of charges present on the surface of the CUP particles influences the magnitude of the interfacial behavior. The effect of electrostatic repulsion between the particles on the surface tension was related. At higher concentrations, surface charge condensation started to dominate the surface tension behavior. The dynamic surface tension of CUP particles shows the influence of the diffusion of the particles to the interface on the relaxation time. The relaxation time of the CUP polymer was 0.401 s, which is closer to the diffusion-based relaxation time of 0.133s for SDS (sodium dodecyl sulfate). Full article

(This article belongs to the Special Issue Polymer Surfaces and Interfaces)

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Review

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32 pages, 17266 KiB

Open AccessReview

Advances in Bioinspired Superhydrophobic Surfaces Made from Silicones: Fabrication and Application

by Zhe Li, Xinsheng Wang, Haoyu Bai and Moyuan Cao

Polymers 2023, 15(3), 543; https://doi.org/10.3390/polym15030543 - 20 Jan 2023

Cited by 14 | Viewed by 3895

Abstract

As research on superhydrophobic materials inspired by the self-cleaning and water-repellent properties of plants and animals in nature continues, the superhydrophobic preparation methods and the applications of superhydrophobic surfaces are widely reported. Silicones are preferred for the preparation of superhydrophobic materials because of their inherent hydrophobicity and strong processing ability. In the preparation of superhydrophobic materials, silicones can both form micro-/nano-structures with dehydration condensation and reduce the surface energy of the material surface because of their intrinsic hydrophobicity. The superhydrophobic layers of silicone substrates are characterized by simple and fast reactions, high-temperature resistance, UV resistance, and anti-aging. Although silicone superhydrophobic materials have the disadvantages of relatively low mechanical stability, this can be improved by the rational design of the material structure. Herein, we summarize the superhydrophobic surfaces made from silicone substrates, including the cross-linking processes of silicones through dehydration condensation and hydrosilation, and the surface hydrophobic modification by grafting hydrophobic silicones. The applications of silicone-based superhydrophobic surfaces have been introduced such as self-cleaning, corrosion resistance, oil–water separation, etc. This review article should provide an overview to the bioinspired superhydrophobic surfaces of silicone-based materials, and serve as inspiration for the development of polymer interfaces and colloid science. Full article

(This article belongs to the Special Issue Polymer Surfaces and Interfaces)

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