Materials

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18 pages, 2394 KiB

Open AccessEditor’s ChoiceArticle

The Morphology, Mechanical and Dynamic Properties, Fire Hazard and Toxicity of Chloroprene and Butadiene Rubber Composites Cross-Linked with Zinc

by Aleksandra Smejda-Krzewicka, Przemysław Rybiński, Dariusz Bradło and Witold Żukowski

Materials 2023, 16(3), 1240; https://doi.org/10.3390/ma16031240 - 31 Jan 2023

Cited by 4 | Viewed by 1383

Abstract

This paper presents the influence of zinc on the cross-linking process, mechanical and dynamic properties, morphologies and balance of thermal degradation of blends containing chloroprene rubber (CR) and butadiene rubber (BR). The novel aspect of this research is a comprehensive approach presenting a [...] Read more.

This paper presents the influence of zinc on the cross-linking process, mechanical and dynamic properties, morphologies and balance of thermal degradation of blends containing chloroprene rubber (CR) and butadiene rubber (BR). The novel aspect of this research is a comprehensive approach presenting a new curing agent for the CR/BR blends to increase their cross-linking density and final properties, including non-flammability and low fire hazard. This is due to the need to find an alternative to zinc oxide, which is the standard curing agent for chloroprene rubber. The regulations of the European Union enforce a significant limitation on the use of this compound in elastomer technology, due to its harmful effect on aquatic organisms. In this paper, the CR/BR composites were cured with zinc and filled with natural silica fillers (sillitin or chalcedonite) or synthetic silica filler (aerosil). The investigation focused on the morphology characterization of the obtained compounds, their cross-linking degree, swelling, mechanical and dynamic properties, fire hazard and toxicity. The structure of cured CR/BR blends was characterized via scanning electron microscopy (SEM). The fire resistance studies were performed using cone calorimetry or oxygen index methods, whereas toxicity tests were performed with the use of the FB-FTIR (fluidized bed reactor coupled with FTIR analyzer) method. The results showed that obtained CR/BR products were characterized by satisfactory final properties. The properties determined by the oxygen index and cone calorimetry methods, including the behaviors of the tested CR/BR vulcanizates in fire conditions, showed that the produced compounds were characterized by a low fire hazard and can be classified as non-combustible rubber products. However, the toxicity of the decomposition products, determined at 450, 550 and 750 °C, was very high. Full article

(This article belongs to the Special Issue Morphology, Flammability, Thermal and Mechanical Properties of Polymer Composites)

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26 pages, 11077 KiB

Open AccessArticle

Modeling of the Kinetics of Polyoxymethylene Decomposition under Oxidative and Non-Oxidative Conditions

by Tomasz M. Majka, Gabriela Berkowicz-Płatek and Witold Żukowski

Materials 2021, 14(9), 2281; https://doi.org/10.3390/ma14092281 - 28 Apr 2021

Cited by 4 | Viewed by 1622

Abstract

Research on the thermal and thermo-oxidative degradation of polyacetals allows for the development of effective methods of utilization of the waste of these polymers towards the recovery of monomers. For this purpose, in addition to qualitative analysis, it is necessary to understand the [...] Read more.

Research on the thermal and thermo-oxidative degradation of polyacetals allows for the development of effective methods of utilization of the waste of these polymers towards the recovery of monomers. For this purpose, in addition to qualitative analysis, it is necessary to understand the mechanisms of chemical reactions accompanying the decomposition process under the influence of temperature. Therefore, in this article, with the experimental results from the thermal analysis of the POM homopolymer of three various stages of life—POM-P—unprocessed sample; POM-R—recycled sample, and POM-O—sample waste—we took steps to determine the basic kinetic parameters using two well-known and commonly used kinetic models: Friedman and Ozawa-Flynn-Wall (OFW). Knowing the values of the course of changes in apparent activation energy as a function of partial mass loss, theoretical curves were fitted to the experimental data. The applied calculation models turned out to be consistent in terms of the nature of the curve changes and similar in terms of E_a in the entire range of mass loss. Both kinetic models showed a very similar course of the E_a curves. The samples that decompose under oxidative conditions obtained the best fit for the reaction of nth order with autocatalysis by product B model and the samples that decompose under inert conditions for the n-dimensional nucleation according to the Avrami–Erofeev model. Full article

(This article belongs to the Special Issue Morphology, Flammability, Thermal and Mechanical Properties of Polymer Composites)

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30 pages, 9541 KiB

Open AccessArticle

Common Nettle (Urtica dioica L.) as an Active Filler of Natural Rubber Biocomposites

by Marcin Masłowski, Andrii Aleksieiev, Justyna Miedzianowska and Krzysztof Strzelec

Materials 2021, 14(7), 1616; https://doi.org/10.3390/ma14071616 - 26 Mar 2021

Cited by 15 | Viewed by 3797

Abstract

Common nettle (Urtíca Dióica L.), as a natural fibrous filler, may be part of the global trend of producing biocomposites with the addition of substances of plant origin. The aim of the work was to investigate and explain the effectiveness of common [...] Read more.

Common nettle (Urtíca Dióica L.), as a natural fibrous filler, may be part of the global trend of producing biocomposites with the addition of substances of plant origin. The aim of the work was to investigate and explain the effectiveness of common nettle as a source of active functional compounds for the modification of elastomer composites based on natural rubber. The conducted studies constitute a scientific novelty in the field of polymer technology, as there is no research on the physico-chemical characteristics of nettle bio-components and vulcanizates filled with them. Separation and mechanical modification of seeds, leaves, branches and roots of dried nettle were carried out. Characterization of the ground plant particles was performed using goniometric measurements (contact angle), Fourier transmission infrared spectroscopy (FTIR), themogravimetric analysis (TGA) and scanning electron microscopy (SEM). The obtained natural rubber composites with different bio-filler content were also tested in terms of rheological, static and dynamic mechanical properties, cross-linking density, color change and resistance to simulated aging processes. Composites with the addition of a filler obtained from nettle roots and stems showed the highest mechanical strength. For the sample containing leaves and branches, an increase in resistance to simulated ultraviolet and thermo-oxidative aging processes was observed. This phenomenon can be attributed to the activity of ingredients with high antioxidant potential contained in the plant. Full article

(This article belongs to the Special Issue Morphology, Flammability, Thermal and Mechanical Properties of Polymer Composites)

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34 pages, 20836 KiB

Open AccessArticle

Straw/Nano-Additive Hybrids as Functional Fillers for Natural Rubber Biocomposites

by Justyna Miedzianowska, Marcin Masłowski, Przemysław Rybiński and Krzysztof Strzelec

Materials 2021, 14(2), 321; https://doi.org/10.3390/ma14020321 - 09 Jan 2021

Cited by 14 | Viewed by 2494

Abstract

Currently, up to 215 million metric tons of harvestable straw are available in Europe, 50% of the crops come from wheat, 25% from barley and 25% from maize. More than half of the production remains undeveloped. The overproduction of straw in the world [...] Read more.

Currently, up to 215 million metric tons of harvestable straw are available in Europe, 50% of the crops come from wheat, 25% from barley and 25% from maize. More than half of the production remains undeveloped. The overproduction of straw in the world means that the current methods of its management are insufficient. The article describes the production method and characterization of natural rubber biocomposites containing cereal straw powder modified with functional nano-additives in the form of carbon black, silica and halloysite nanotubes. The use of cereal straw in the elastomer matrix should contribute to obtaining a product with good mechanical properties while ensuring a low cost of the composite. In turn, the application of the mechanical modification process will allow the combination of specific properties of raw materials to obtain new, advanced elastomeric materials. As part of the work, hybrid fillers based on mechanically modified cereal straw were produced. The impact of hybrid fillers on mechanical, rheometric and damping properties was assessed. The flammability and susceptibility of the obtained biocomposites to aging processes were determined. The use of hybrid fillers based on mechanically modified straw allowed us to obtain a higher cross-linking density of vulcanizates (even up to 40% compared to the reference sample), and thus higher values of the rheometric moment during the vulcanization process of rubber mixtures (from approx. 10% (10 phr of filler) up to 50% (30 phr of filler) in relation to the unfilled system) and higher hardness of vulcanizates (by about 30–70%). The curing time of the blends was slightly longer, but the obtained composites were characterized by significantly higher tensile strength. The use of fillers in the elastomer matrix increased the modulus at 100, 200 and 300% and the elongation at break. Moreover, greater resistance of vulcanizates to the combustion process was confirmed. Full article

(This article belongs to the Special Issue Morphology, Flammability, Thermal and Mechanical Properties of Polymer Composites)

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19 pages, 2051 KiB

Open AccessArticle

Anti-Oxidative Activity of Alcohol-Water Extracts from Field Horsetail (Equisteum arvense) in Elastomer Vulcanizates Subjected to Accelerated Aging Processes

by Marcin Masłowski, Justyna Miedzianowska, Agnieszka Czylkowska, Magdalena Efenberger-Szmechtyk, Agnieszka Nowak and Krzysztof Strzelec

Materials 2020, 13(21), 4903; https://doi.org/10.3390/ma13214903 - 31 Oct 2020

Cited by 11 | Viewed by 1902

Abstract

The article aimed to highlight the antioxidant potential of natural extracts obtained from Equisteum arvense in elastomer vulcanizatec made of natural rubber. Horsetail extracts were prepared using four solvent systems at different volume ratios: methanol–water (50/50 and 70/30) and ethanol–water (50/50 and 70/30), [...] Read more.

The article aimed to highlight the antioxidant potential of natural extracts obtained from Equisteum arvense in elastomer vulcanizatec made of natural rubber. Horsetail extracts were prepared using four solvent systems at different volume ratios: methanol–water (50/50 and 70/30) and ethanol–water (50/50 and 70/30), which were then lyophilized and added to the polymer matrix. A deep characterization of the obtained bio-additives was performed. The obtained vulcanizates were subjected to various aging processes: thermo-oxidative, ultraviolet and solar. Then, the resistance and susceptibility of vulcanizates to selected processes of accelerated, simulated degradation were determined based on the changes in the spatial structure (network nodes), material strength and physical properties (color). The research showed the presence of polyphenols in the extracts of horsetail, which resulted in their high anti-oxidative activity. Moreover, the extracts were able to absorb UV radiation. As a consequence, they were active additives that protected rubber vulcanizates against the damaging effects of the aging processes, securing their functional properties. Samples containing natural extracts were characterized by better stability of: mechanical strength parameters, the increase in cross-linking density and color changes after simulating aging processes in comparison with the control sample. Full article

(This article belongs to the Special Issue Morphology, Flammability, Thermal and Mechanical Properties of Polymer Composites)

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23 pages, 4659 KiB

Open AccessArticle

Properties of Chemically Modified (Selected Silanes) Lignocellulosic Filler and Its Application in Natural Rubber Biocomposites

by Justyna Miedzianowska, Marcin Masłowski, Przemysław Rybiński and Krzysztof Strzelec

Materials 2020, 13(18), 4163; https://doi.org/10.3390/ma13184163 - 18 Sep 2020

Cited by 27 | Viewed by 2328

Abstract

This article concerns the functional properties of elastomeric composites reinforced with modified lignocellulosic material obtained from cereal straw. The aim of the research was to acquire new knowledge on the effectiveness of cereal straw modification methods in multifunctional properties, while reducing the flammability [...] Read more.

This article concerns the functional properties of elastomeric composites reinforced with modified lignocellulosic material obtained from cereal straw. The aim of the research was to acquire new knowledge on the effectiveness of cereal straw modification methods in multifunctional properties, while reducing the flammability of newly designed elastomeric materials made of natural rubber. The article deals with investigating and explaining dependencies that affect the performance and processing properties of polymer biocomposites containing modified cereal straw. Three different silanes were used to modify the lignocellulosic filler: n-Propyltriethoxysilane, Vinyltriethoxysilane, and 3,3′-Tetrathiobis(propyl-triethoxysilane). The influence of the conducted modifications on the morphology and structure of straw particles was investigated using a scanning electron microscope, contact angle measurements, and thermogravimetric analysis technique. The increase in hydrophobicity and thermal stability of natural fibers was confirmed. In turn, the impact of silanization on the properties of filled composites was determined on the basis of rheometric characteristics and cross-linking density, static mechanical properties, tear resistance, thermal stability, and flammability tests. Noteworthy was the improvement of the mechanical strength of biocomposites and their resistance to burning. Correlations affecting the structure, morphology, dispersion, and properties of produced composites can facilitate the indication of a further research path in the field of development of new elastomeric biomaterials. Full article

(This article belongs to the Special Issue Morphology, Flammability, Thermal and Mechanical Properties of Polymer Composites)

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21 pages, 8634 KiB

Open AccessArticle

Silane Treatment as an Effective Way of Improving the Reinforcing Activity of Carbon Nanofibers in Nitrile Rubber Composites

by Bolesław Szadkowski, Anna Marzec and Przemysław Rybiński

Materials 2020, 13(16), 3481; https://doi.org/10.3390/ma13163481 - 07 Aug 2020

Cited by 16 | Viewed by 3412

Abstract

Two different silane treatment methods were used to improve the reinforcing activity of carbon nanofibers (CNF) in acrylonitrile-butadiene rubber (NBR) composites. The first method was chemical silanization with [3-(2-aminoethylamino)propyl]trimethoxysilane (APTS) in ethanol solution, preceded by oxidation of the CNF with H₂SO [...] Read more.

Two different silane treatment methods were used to improve the reinforcing activity of carbon nanofibers (CNF) in acrylonitrile-butadiene rubber (NBR) composites. The first method was chemical silanization with [3-(2-aminoethylamino)propyl]trimethoxysilane (APTS) in ethanol solution, preceded by oxidation of the CNF with H₂SO₄/HNO₃. The second method was direct incorporation of silanes during preparation of the composites (in-situ silanization). Three different silane coupling agents were used: [3-(2-aminoethylamino)propyl]trimethoxysilane, (3-mercaptopropyl)trimethoxysilane (MPTS), and 3-ureidopropyltrimethoxysilane (UPTS). The NBR composites were prepared in an internal laboratory mixer, with increasing concentrations of pure or modified CNF. The crosslink density and flammability of the NBR-filled composites were analyzed, as well as their rheological and mechanical properties. The electrical conductivity of the composites was measured to assess the formation of CNF networks in the elastomer matrix. The morphology of the CNF was assessed by scanning electron microscopy (SEM). Both the dispersion of the CNF in the NBR matrix and the polymer-filler interactions were improved following silane modification, as shown in SEM images and by the Payne Effect. The composites were also found to have enhanced moduli, tensile strength, hardness, damping, and electrical conductivity. Chemical treatment proved to be more effective at improving the reinforcing effect of CNF in the elastomer matrix than in-situ silanization. The results of this study demonstrate the great potential of both in-situ and chemical silanization for the preparation of reinforced polymer composites filled with CNF. Full article

(This article belongs to the Special Issue Morphology, Flammability, Thermal and Mechanical Properties of Polymer Composites)

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8 pages, 2823 KiB

Open AccessCommunication

Compressible, Flame-Resistant and Thermally Insulating Fiber-Reinforced Polybenzoxazine Aerogel Composites

by Yunyun Xiao, Liangjun Li, Fengqi Liu, Sizhao Zhang, Junzong Feng, Yonggang Jiang and Jian Feng

Materials 2020, 13(12), 2809; https://doi.org/10.3390/ma13122809 - 22 Jun 2020

Cited by 19 | Viewed by 3099

Abstract

The preparation of novel polymer aerogel materials with enhanced flame-retardancy, superior thermal insulation and mechanical strength is of great practical significance in energy-savings and fire-prevention for buildings. Herein, we reported the fiber-reinforced polybenzoxazine (PBO) aerogel composites with flame retardance and thermal insulation, which [...] Read more.

The preparation of novel polymer aerogel materials with enhanced flame-retardancy, superior thermal insulation and mechanical strength is of great practical significance in energy-savings and fire-prevention for buildings. Herein, we reported the fiber-reinforced polybenzoxazine (PBO) aerogel composites with flame retardance and thermal insulation, which were prepared under room temperature and atmospheric pressure, and using 4,4′-diaminodiphenlymethane (MDA) benzoxazine monomer as the raw material and oxalic acid (OA) as the catalyst. Several outstanding attributes were achieved in the aerogel composites, such as relatively low thermal conductivity (0.069 W/m·K at 10⁵ Pa, 0.031 W/m·K at 5 Pa), high limiting oxygen index (LOI) up to 32.5, and enhanced mechanical properties. It can be compressed to more than 80% of the deformation without obvious cracks, and shows high compressive modulus and specific modulus (20.69 MPa and 5.05 × 10⁴ N·m/Kg, respectively). All the excellent comprehensive properties mean that fiber-reinforced PBO aerogel composites have broad application prospects in the fields of flame retardancy and thermal insulation. Full article

(This article belongs to the Special Issue Morphology, Flammability, Thermal and Mechanical Properties of Polymer Composites)

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