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Structure Property Relationship of Polymeric Materials

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Physics".

Deadline for manuscript submissions: closed (20 April 2023) | Viewed by 23273

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Prof. Dr. Gisbert Riess

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Chair of Chemistry of Polymeric Materials, Montanuniversität Leoben, 8700 Leoben, Austria
Interests: polymer chemistry; barrier properties; flame-retardant polymers; polymeric foam
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Dr. Florian Arbeiter

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Materials Science and Testing of Polymers, Montanuniversitat Leoben, Leoben, Austria
Interests: fracture mechanics in polymers; application of fracture mechanics in additive manufacturing; impact fracture; fracture in multilayer systems
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Special Issue Information

Dear Colleagues,

Structure–property relationships of polymers are key aspects for the development of new materials. Regardless of the base material (thermoplastic, elastomeric, or resin-based), the resulting structure and morphology play a key role in tailoring the material for the intended application. Therefore, it is necessary to understand the structure–property relationships as well as processing-induced changes in the morphology of polymeric materials in detail.

The aforementioned relationships depend on the type and concentration of components, the interaction between matrix and additives, and the processing techniques. All of these parameters determine the morphology and structure of the final material, and are crucial for final applications.

The Special Issue “Structure–Property Relationships of Polymeric Materials” focuses on any aspect of the production, structure, and properties of polymeric materials, with particular attention given to mechanical, barrier, flame-retardant, and insulation properties.

We kindly invite you to submit your work for this Special Issue. Experimental studies as well as theoretical investigations are appreciated. Full research papers, communications, and reviews are all welcome.

Prof. Dr. Gisbert Riess
Dr. Florian Arbeiter
Guest Editors

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

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Keywords

mechanical properties
barrier properties
insulation properties
flame-retardant polymers
processing techniques

Published Papers (11 papers)

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Research

16 pages, 6249 KiB

Open AccessArticle

Testing the Performance of the Azo-Polyimide Supramolecular Systems as Substrate for Sensors Based on Platinum Electrodes

by Ion Sava, Mihai Asandulesa, Andreea Irina Barzic, Raluca Marinica Albu and Iuliana Stoica

Materials 2023, 16(14), 4980; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16144980 - 13 Jul 2023

Viewed by 933

Abstract

Azo-polyimide films with supramolecular structure were obtained by casting onto glass plates a mixture based on polyamidic acid and different quantities of azochromophore, followed by thermal treatment to realize the final azo-polyimide structure. The dielectric characteristics of the supramolecular structure of polymer films were investigated by broad-band dielectric spectroscopy measurements at different temperatures and frequencies. The free-standing films proved to be flexible and tough and maintained their integrity after repeated bending. The work of adhesion at the polymer/platinum interface was calculated after the evaluation of the surface energy parameters before and after plasma treatment. Atomic force microscopy was used to image the surface morphology, the evolution of the roughness parameters, and the adhesion force between the platinum-covered tip and the polymer surface, registered at the nanoscale with the quantity of the azo dye introduced in the system. The simulation of the columnar growth of a platinum layer was made to provide information about the deposition parameters that should be used for optimal results in the deposition of platinum electrodes for sensors. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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13 pages, 4110 KiB

Open AccessArticle

Complex Monte Carlo Light-Driven Dynamics of Monomers in Functionalized Bond Fluctuation Model Polymer Chains

by Grzegorz Pawlik and Antoni C. Mitus

Materials 2023, 16(12), 4373; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16124373 - 14 Jun 2023

Cited by 1 | Viewed by 687

Abstract

We study Monte Carlo dynamics of the monomers and center of mass of a model polymer chain functionalized with azobenzene molecules in the presence of an inhomogeneous linearly polarized laser light. The simulations use a generalized Bond Fluctuation Model. The mean squared displacements of the monomers and the center of mass are analyzed in a period of Monte Carlo time typical for a build-up of Surface Relief Grating. Approximate scaling laws for mean squared displacements are found and interpreted in terms of sub- and superdiffusive dynamics for the monomers and center of mass. A counterintuitive effect is observed, where the monomers perform subdiffusive motion but the resulting motion of the center of mass is superdiffusive. This result disparages theoretical approaches based on an assumption that the dynamics of single monomers in a chain can be characterized in terms of independent identically distributed random variables. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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11 pages, 1987 KiB

Open AccessFeature PaperArticle

Influence of Processing Parameters on the Mechanical Properties of Peek Plates by Hot Compression Molding

by Tong Li, Zhuoyu Song, Xiangfei Yang and Juan Du

Materials 2023, 16(1), 36; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16010036 - 21 Dec 2022

Cited by 5 | Viewed by 1897

Abstract

Thermoplastic components are gaining more and more attention due to their advantages which include high specific strength, high toughness, and low manufacturing costs. Despite the fast development of such materials in engineering applications, the major challenge for the wider use of thermoplastic components is the diverse mechanical properties that are caused by uncertain factors during the molding process. In this paper, the effects of processing parameters on the mechanical properties of PEEK plates by hot compression molding are systematically investigated, including the temperature, pressure, and compression time. It was found that both temperature and time can sensitively change the mechanical properties; however, a pressure larger than 1.5 MPa showed a limited impact on the mechanical behaviors of PEEK plates. The optimal process parameters include a hot compression temperature of 400 °C, a compression time of 30 min, and a pressure of 2.5 MPa. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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16 pages, 4062 KiB

Open AccessArticle

Thermal Properties and Flammability Characteristics of a Series of DGEBA-Based Thermosets Loaded with a Novel Bisphenol Containing DOPO and Phenylphosphonate Units

by Corneliu Hamciuc, Tăchiță Vlad-Bubulac, Diana Serbezeanu, Ana-Maria Macsim, Gabriela Lisa, Ion Anghel and Ioana-Emilia Şofran

Materials 2022, 15(21), 7829; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15217829 - 06 Nov 2022

Cited by 4 | Viewed by 1352

Abstract

Despite a recent sustained preoccupation for developing biobased epoxies with enhanced applicability, such products have not been widely accepted for industry because of their inferior characteristics compared to classic petroleum-based epoxy thermosets. Therefore, significant effort is being made to improve the flame retardance of the most commonly used epoxies, such as diglycidyl ether-based bisphenol A (DGEBA), bisphenol F (DGEBF), novalac epoxy, and others, while continuously avoiding the use of hazardous halogen-containing flame retardants. Herein, a phosphorus-containing bisphenol, bis(4-(((4-hydroxyphenyl)amino)(6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)methyl)phenyl) phenylphosphonate (BPH), was synthesized by reacting bis(4-formylphenyl)phenylphosphonate with 4-hydroxybenzaldehyde followed by the addition of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to the resulting azomethine groups. Environmentally friendly epoxy-based polymer thermosets were prepared by using epoxy resin as polymer matrix and a mixture of BPH and 4,4′-diaminodiphenylsulfone (DDS) as hardeners. A hyperbranched phthalocyanine polymer (HPc) and BaTiO₃ nanoparticles were incorporated into epoxy resin to improve the characteristics of the final products. The structure and morphology of epoxy thermosets were evaluated by infrared spectroscopy and scanning electron microscopy (SEM), while the flammability characteristics were evaluated by microscale combustion calorimetry. Thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry. The surface morphology of the char residues obtained by pyrolysis was studied by SEM analysis. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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11 pages, 1312 KiB

Open AccessArticle

Birch Tar Introduced into Polylactide and Its Influence on the Barrier, Thermal, Functional and Biological Properties of the Film Obtained by Industrial Extrusion

by Agnieszka Richert, Rafał Malinowski, Magda Ringwelska and Grażyna B. Dąbrowska

Materials 2022, 15(20), 7382; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15207382 - 21 Oct 2022

Cited by 4 | Viewed by 1075

Abstract

The aim of the study was to evaluate possibility of producing a polylactide film with birch tar by the industrial extrusion method and whether the addition of 10% birch tar can ensure adequate biocidal properties of PLA against pathogenic microorganisms (E. coli, S. aureus, P. aeruginosa, A. tumefaciens, X. campestris, P. brassicacearum, P. corrugate and P. syringae) and fungi (A. niger, A. flavus and A. versicolor) while ensuring beneficial functional properties, such as water vapor, nitrogen, oxygen and carbon dioxide permeability, which are of considerable importance in the packaging industry. The main test methods used were ISO 22196, ISO 846, ISO 2556, ASTM F 1927 and ASTM F 2476-20. The obtained results prove the possibility of extruding polymer films with a biocidal additive, i.e., birch tar, and obtaining favorable properties that qualify the produced film for applications in the packaging industry. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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15 pages, 2647 KiB

Open AccessArticle

Magnetically Actuated Shape Memory Polymers for On-Demand Drug Delivery

by Anand Utpal Vakil, Maryam Ramezani and Mary Beth B. Monroe

Materials 2022, 15(20), 7279; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15207279 - 18 Oct 2022

Cited by 6 | Viewed by 1403

Abstract

Repeated use of intravenous infusions to deliver drugs can cause nerve damage, pain, and infection. There is an unmet need for a drug delivery method that administers drugs on demand for prolonged use. Here, we developed magnetically responsive shape memory polymers (SMPs) to enhance control over drug release. Iron oxide magnetic nanoparticles (mnps) were synthesized and incorporated into previously developed SMPs to enable magnetically induced shape memory effects that can be activated remotely via the application of an alternating magnetic field. These materials were tested for their shape memory properties (dynamic mechanical analysis), cytocompatibility (3T3 fibroblast viability), and tunable drug delivery rates (UV–VIS to evaluate the release of incorporated doxorubicin, 6-mercaptopurine, and/or rhodamine). All polymer composites had >75% cytocompatibility over 72 h. Altering the polymer chemistry and mnp content provided methods to tune drug release. Namely, linear polymers with higher mnp content had faster drug release. Highly cross-linked polymer networks with lower mnp content slowed drug release. Shape memory properties and polymer/drug interactions provided additional variables to tune drug delivery rates. Polymers that were fixed in a strained secondary shape had a slower release rate compared with unstrained polymers, and hydrophobic drugs were released more slowly than hydrophilic drugs. Using these design principles, a single material with gradient chemistry and dual drug loading was synthesized, which provided a unique mechanism to deliver two drugs from a single scaffold with distinct delivery profiles. This system could be employed in future work to provide controlled release of selected drug combinations with enhanced control over release as compared with previous approaches. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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26 pages, 6675 KiB

Open AccessArticle

Influence of the Surface Chemistry of Graphene Oxide on the Structure–Property Relationship of Waterborne Poly(urethane urea) Adhesive

by Abir Tounici and José Miguel Martín-Martínez

Materials 2021, 14(16), 4377; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14164377 - 05 Aug 2021

Cited by 5 | Viewed by 2472

Abstract

Small amounts—0.04 wt.%—graphene oxide derivatives with different surface chemistry (graphene oxide—GO-, amine-functionalized GO—A-GO-, reduced GO—r-GO) were added during prepolymer formation in the synthesis of waterborne poly(urethane urea) dispersions (PUDs). Covalent interactions between the surface groups on the graphene oxide derivatives and the end NCO groups of the prepolymer were created, these interactions differently altered the degree of micro-phase separation of the PUDs and their structure–properties relationships. The amine functional groups on the A-GO surface reacted preferentially with the prepolymer, producing new urea hard domains and higher percentage of soft segments than in the PUD without GO derivative. All GO derivatives were well dispersed into the PU matrix. The PUD without GO derivative showed the most noticeable shear thinning and the addition of the GO derivative reduced the extent of shear thinning differently depending on its functional chemistry. The free urethane groups were dominant in all PUs and the addition of the GO derivative increased the percentage of the associated by hydrogen bond urethane groups. As a consequence, the addition of GO derivative caused a lower degree of micro-phase separation. All PUs containing GO derivatives exhibited an additional thermal decomposition at 190–206 °C which was ascribed to the GO derivative-poly(urethane urea) interactions, the lowest temperature corresponded to PU+A-GO. The PUs exhibited two structural relaxations, their temperatures decreased by adding the GO derivative, and the values of the maximum of tan delta in PU+r-GO and PU+A-GO were significantly higher than in the rest. The addition of the GO derivative increased the elongation-at-break, imparted some toughening, and increased the adhesion of the PUD. The highest T-peel strength values corresponded to the joints made with PUD+GO and PUD+r-GO, and a rupture of the substrate was obtained. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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10 pages, 1734 KiB

Open AccessEditor’s ChoiceArticle

Resins for Frontal Photopolymerization: Combining Depth-Cure and Tunable Mechanical Properties

by Catharina Ebner, Julia Mitterer, Joamin Gonzalez-Gutierrez, Gisbert Rieß and Wolfgang Kern

Materials 2021, 14(4), 743; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14040743 - 05 Feb 2021

Cited by 9 | Viewed by 2179

Abstract

Photopolymerization has undergone significant development in recent years. It enables fast and easy processing of materials with customized properties and allows precise printing of complex surface geometries. Nevertheless, photopolymerization is mainly applied to cure thin films since the low curing depth limits the fast production of large volumes. Frontal photopolymerization (FPP) is suitable to overcome these limitations so that curing of centimeter-thick (meth)acrylic layers can be accomplished within minutes by light induction only. Prerequisites, however, are the low optical density of the resin and bleaching ability of the photoinitiator. To date, tailored FPP-resins are not commercially available. This study discusses the potential of long-chain polyether dimethacrylates, offering high-temperature resistance and low optical density, as crosslinkers in photobleaching resins and investigates the mechanical properties of photofrontally-cured copolymers. Characteristics ranging from ductile to hard and brittle are observed in tensile tests, demonstrating that deep curing and versatile material properties are achieved with FPP. Analyzed components display uniform polymerization over a depth of four centimeters in Fourier transform infrared spectroscopy and swelling tests. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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19 pages, 7182 KiB

Open AccessArticle

Optimization of Mechanical Properties and Damage Tolerance in Polymer-Mineral Multilayer Composites

by Johannes Wiener, Hannes Kaineder, Otmar Kolednik and Florian Arbeiter

Materials 2021, 14(4), 725; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14040725 - 04 Feb 2021

Cited by 11 | Viewed by 2596

Abstract

Talcum reinforced polypropylene was enhanced with a soft type of polypropylene in order to increase the impact strength and damage tolerance of the material. The soft phase was incorporated in the form of continuous interlayers, where the numbers of layers ranged from 64 to 2048. A blend with the same material composition (based on wt% of the used materials) and the pure matrix material were investigated for comparison. A plateau in impact strength was reached by layered architectures, where the matrix layer thickness was as small or smaller than the largest talcum particles. The most promising layered architecture, namely, 512 layers, was subsequently investigated more thoroughly using instrumented Charpy experiments and tensile testing. In these tests, normalised parameters for stiffness and strength were obtained in addition to the impact strength. The multilayered material showed remarkable impact strength, fracture energy and damage tolerance. However, stiffness and strength were reduced due to the addition of the soft phase. It could be shown that specimens under bending loads are very compliant due to a stress-decoupling effect between layers that specifically reduces bending stiffness. This drawback could be avoided under tensile loading, while the increase in toughness remained high. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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22 pages, 19718 KiB

Open AccessArticle

Analysis of the Fire Behavior of Polymers (PP, PA 6 and PE-LD) and Their Improvement Using Various Flame Retardants

by Dieter Hohenwarter, Hannelore Mattausch, Christopher Fischer, Matthias Berger and Bernd Haar

Materials 2020, 13(24), 5756; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13245756 - 16 Dec 2020

Cited by 6 | Viewed by 3088

Abstract

The fire behavior of polymers is examined primarily with the time-dependent heat release rate (HRR) measured with a cone calorimeter. The HRR is used to examine the fire behavior of materials with and without flame retardants, especially Polypropylene (PP-Copo) and Polyethylene (PE-LD). Polypropylene is stored for up to 99 days under normal conditions and the heat release rate shows especially changes about 100 s after irradiation with cone calorimeter, which may be caused by aging effects. The effect of crosslinking to the burning behavior of PP was examined too. Polyamides (PA 6) are irradiated with a radiation intensity of 25 kW/m² to 95 kW/m² and fire-related principles between radiation intensity and time to ignition can be derived from the measurement results. In order to comprehensively investigate the fire behavior of PP (also with flame retardant additives), the samples were also exposed to a flame, according to UL 94 with small power (50 W) and is inflamed with the power of a few 100 W. The irradiation causes different trigger mechanisms for the flame retardant additives in a plastic than the flame exposure. It is shown that the compound, which is favorable for irradiation, is not necessarily good for flame exposure. It can be seen that expandable graphite alone or with the addition of other additives is a very effective flame retardant for PP. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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27 pages, 7958 KiB

Open AccessArticle

Addition of Graphene Oxide in Different Stages of the Synthesis of Waterborne Polyurethane-Urea Adhesives and Its Influence on Their Structure, Thermal, Viscoelastic and Adhesion Properties

by Abir Tounici and José Miguel Martín-Martínez

Materials 2020, 13(13), 2899; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13132899 - 28 Jun 2020

Cited by 12 | Viewed by 2413

Abstract

In this study, 0.04 wt % graphene oxide (GO) was added in different stages (before and after prepolymer formation, and during water addition) of the synthesis of waterborne polyurethane-urea dispersions (PUDs) prepared by using the acetone method. The structural, thermal, mechanical, viscoelastic, surface and adhesion properties of the polyurethane-ureas (PUUs) containing 0.04 wt % GO were studied. The addition of GO before and after prepolymer formation produced covalent bonds between the GO sheets and the NCO groups of the isocyanate, whereas the GO sheets were trapped between the polyurethane chains when added during water addition step. As a consequence, depending on the stage of the PUD synthesis in which GO was added, the degree of micro-phase separation between the hard and soft segments changed differently. The addition of GO before prepolymer formation changed more efficiently the polyurethane-urea structure, i.e., the covalently bonded GO sheets disturbed the interactions between the hard segments causing lower percentage of free urethane groups, higher crystallinity, lower storage modulus, higher yield stress and T-peel strength. The interactions between the GO sheets and the polymeric chains have been evidenced by plate-plate rheology, thermal gravimetric analysis and spectroscopy. On the other hand, physical interactions between GO and the polyurethane-urea chains were produced when GO was added in water during the synthesis, i.e., GO was acting as a nanofiller, which justified the improved mechanical properties and high lap-shear strength, but poor T-peel strength. Full article

(This article belongs to the Special Issue Structure Property Relationship of Polymeric Materials)

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