2023

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Open AccessArticle

Influence of Ageing on Optical, Mechanical, and Thermal Properties of Agricultural Films

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Polymers 2023, 15(17), 3638; https://doi.org/10.3390/polym15173638 - 04 Sep 2023

Viewed by 545

Abstract

Plastic films utilized as greenhouse coverings play a vital role in safeguarding plantations from diverse weather conditions like sunlight, rain, hail, and wind. It is essential for these films to preserve their properties even after extended exposure to sunlight and water, while also [...] Read more.

Plastic films utilized as greenhouse coverings play a vital role in safeguarding plantations from diverse weather conditions like sunlight, rain, hail, and wind. It is essential for these films to preserve their properties even after extended exposure to sunlight and water, while also maintaining transparency to support the unhindered growth of plants. The purpose of the study was to compare the properties of three types of plastic films: low density polyethylene diffuse film, low density polyethylene clear film, and ethylene tetrafluoroethylene film, before and after their ageing in weather test chamber with xenon-arc light in the presence of moisture. Two distinct types of PE films were chosen based on their suitability for specific regions in Croatia, whereas ETFE film was chosen as a potential new material that is gaining popularity across various industries, including agriculture. The properties investigated were tensile properties, transmittance by spectral analysis, and viscoelastic properties by dynamic mechanical analysis. Also, untreated films and the ones exposed to artificial ageing were compared by means of Fourier-transform infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis. The administered tests revealed a certain level of property degradation due to ageing in all three films. However, none of the films showed a substantial level of deterioration, indicating their suitability as greenhouse coverings. Full article

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Open AccessArticle

An Interval Prediction of Chloroprene Rubber Crack Propagation Characteristics Based on Thermal Accelerated Aging

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Polymers 2023, 15(11), 2445; https://doi.org/10.3390/polym15112445 - 25 May 2023

Cited by 1 | Viewed by 504

Abstract

Thermo-oxidative aging plays an important role in changing the properties of rubber materials; it significantly decreases the fatigue life of air spring bags and further causes safety hazards. However, due to the great uncertainty of rubber material properties, an effective interval prediction model [...] Read more.

Thermo-oxidative aging plays an important role in changing the properties of rubber materials; it significantly decreases the fatigue life of air spring bags and further causes safety hazards. However, due to the great uncertainty of rubber material properties, an effective interval prediction model has not been established considering the effect of aging on airbag rubber properties. To solve the problem, this study proposes an interval parameter correlation model that can more accurately describe rubber crack propagation characteristics by considering material uncertainty. Furthermore, an aging prediction model of the rubber crack propagation characteristic region is established based on the Arrhenius equation. The effectiveness and accuracy of the method are verified by comparing the test and prediction results under the temperature spectrum. The method can be used to determine the variations in the interval change of the fatigue crack propagation parameters during rubber aging and can guide fatigue reliability analyses of air spring bags. Full article

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Open AccessCommunication

Flame Retardancy Index (FRI) for Polymer Materials Ranking

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Polymers 2023, 15(11), 2422; https://doi.org/10.3390/polym15112422 - 23 May 2023

Cited by 2 | Viewed by 860

Abstract

In 2019, we introduced Flame Retardancy Index (FRI) as a universal dimensionless index for the classification of flame-retardant polymer materials (Polymers, 2019, 11(3), 407). FRI simply takes the peak of Heat Release Rate (pHRR), Total Heat Release (THR), and [...] Read more.

In 2019, we introduced Flame Retardancy Index (FRI) as a universal dimensionless index for the classification of flame-retardant polymer materials (Polymers, 2019, 11(3), 407). FRI simply takes the peak of Heat Release Rate (pHRR), Total Heat Release (THR), and Time-To-Ignition (t_i) from cone calorimetry data and quantifies the flame retardancy performance of polymer composites with respect to the blank polymer (the reference sample) on a logarithmic scale, as of Poor (FRI ˂ 10⁰), Good (10⁰ ≤ FRI ˂ 10¹), or Excellent (FRI ≥ 10¹). Although initially applied to categorize thermoplastic composites, the versatility of FRI was later verified upon analyzing several sets of data collected from investigations/reports on thermoset composites. Over four years from the time FRI was introduced, we have adequate proof of FRI reliability for polymer materials ranking in terms of flame retardancy performance. Since the mission of FRI was to roughly classify flame-retardant polymer materials, its simplicity of usage and fast performance quantification were highly valued. Herein, we answered the question “does inclusion of additional cone calorimetry parameters, e.g., the time to pHRR (t_p), affect the predictability of FRI?”. In this regard, we defined new variants to evaluate classification capability and variation interval of FRI. We also defined the Flammability Index (FI) based on Pyrolysis Combustion Flow Calorimetry (PCFC) data to invite specialists for analysis of the relationship between the FRI and FI, which may deepen our understanding of the flame retardancy mechanisms of the condensed and gas phases. Full article

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Open AccessEditorial

Sustainable Flame-Retardant Additives for Polymers: Future Perspectives

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Mohammad Reza Saeb

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Henri Vahabi

Polymers 2023, 15(6), 1469; https://doi.org/10.3390/polym15061469 - 16 Mar 2023

Viewed by 803

Abstract

The increased use of plastics, particularly in terms of the use of polymers in electronics and electrical devices commonly used in homes, offices, schools, restaurants, and vehicles, has caused increased fire risks [...] Full article

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Open AccessArticle

Packaging Materials Based on Styrene-Isoprene-Styrene Triblock Copolymer Modified with Graphene

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Traian Zaharescu

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Cristina Banciu

Polymers 2023, 15(2), 353; https://doi.org/10.3390/polym15020353 - 09 Jan 2023

Cited by 1 | Viewed by 988

Abstract

This study presents the improved stabilization effects of graphene on a polymer substrate, namely a styrene-isoprene-styrene triblock copolymer (SIS) which creates opportunities for long-term applications and radiation processing. The added graphene has a remarkable activity on the protection of polymer against their oxidation [...] Read more.

This study presents the improved stabilization effects of graphene on a polymer substrate, namely a styrene-isoprene-styrene triblock copolymer (SIS) which creates opportunities for long-term applications and radiation processing. The added graphene has a remarkable activity on the protection of polymer against their oxidation due to the penetration of free macroradical fragments into the free interlayer space. The chemiluminescence procedure used for the evaluation of the progress of oxidation reveals the delaying effect of oxidative degradation by the doubling extension of oxidation induction time, when the material formulation containing graphene is oxidized at 130 °C. The pristine polymer that is thermally aged requires an activation energy of 142 kJ mol⁻¹, while the modified material needs 148, 158 and 169 kJ mol⁻¹, for the oxidative degradation in the presence of 1, 2 and, respectively, 3 wt% of graphene. The contribution of graphene content (1 wt%) on the stability improvement of SIS is demonstrated by the increase of onset oxidation temperature from 190 °C for neat polymer to 196 °C in the presence of graphene and to 205 °C for the polymer stabilized with graphene and rosemary extract. The addition of graphene into the polymer formulations is a successful method for enlarging durability instead of the modification of receipt with synthesis antioxidants. The presumable applications of these studied materials cover the areas of medical wear, food packaging, commodities, sealing gaskets and others that may also be included through the products for nuclear power plants. Full article

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2022

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Open AccessArticle

Effect of the Current on the Fire Characteristics of Overloaded Polyvinyl Chloride Copper Wires

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Polymers 2022, 14(21), 4766; https://doi.org/10.3390/polym14214766 - 07 Nov 2022

Viewed by 1023

Abstract

In this study, the fire behavior variation of unenergized polyvinyl chloride (PVC) copper wires subjected to overload with different currents was investigated by a cone calorimeter. Overload currents were selected from 1 times safe-rated current (I_e) to 3.5 times I [...] Read more.

In this study, the fire behavior variation of unenergized polyvinyl chloride (PVC) copper wires subjected to overload with different currents was investigated by a cone calorimeter. Overload currents were selected from 1 times safe-rated current (I_e) to 3.5 times I_e to obtain tested sample wires. The mass fraction, time to ignition (TTI), heat release rate (HRR), gas emission, and residue were measured. If the current flowing through the wire increased up to 3.5 times I_e, the TTI of this unenergized wire increased drastically and the peak HRR (pHRR) decreased notably so that the flame growing index (FGI) reduced considerably. When the wire carried less than three times I_e, the FGI remained stable. For all overloaded PVC copper wires, the increase in the heat flux resulted in a higher pHRR and a lower burning duration. However, regardless of the external heat flux exposure, the FGI of copper wires overloaded at 3.5 times I_e was lower than that of copper wires carrying less than other times I_e. Moreover, the consumption of O₂ and generation of CO₂ as the heat flux varied were consistent with that of the HRR. Opposed to expectation, the flame propagation of unenergized PVC copper wires would decline in a fire, if the wire has been damaged by overload with some currents. Full article

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Open AccessArticle

Photochemical and Thermal Stability of Bionanocellulose/Poly(Vinyl Alcohol) Blends

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Aldona Długa

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Dagmara Bajer

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Halina Kaczmarek

Polymers 2022, 14(20), 4364; https://doi.org/10.3390/polym14204364 - 16 Oct 2022

Viewed by 929

Abstract

This research focuses on novel ecological materials for biomedical and cosmetic applications. The cellulose of bacterial origin is well suited for such purposes, but its functional properties must be modified. In this work, the blends of bionanocellulose and poly(vinyl alcohol), BNC/PVA, were prepared [...] Read more.

This research focuses on novel ecological materials for biomedical and cosmetic applications. The cellulose of bacterial origin is well suited for such purposes, but its functional properties must be modified. In this work, the blends of bionanocellulose and poly(vinyl alcohol), BNC/PVA, were prepared based on in situ and ex situ methodology combined with impregnation and sterilization, using different concentrations of PVA. The main purpose of this work was to check the influence of UV radiation and high temperature, which can be sterilizing factors, on the properties of these mixtures. It was found that the crystallinity degree increases in UV-irradiated samples due to the photodegradation of the amorphous phase. This changes the mechanical properties: the breaking stress and Young’s modulus decreased, while the strain at break increased in most UV-irradiated samples. The surface morphology, which we observed by using AFM, did not change significantly after exposure, but the roughness and surface free energy changed irregularly in samples obtained by different methods. However, the effects induced by UV-irradiation were not so crucial as to deteriorate the materials’ properties designed for medical applications. Thermogravimetric analysis exhibited good thermal stability for all samples up to at least 200 °C, which allows for the prediction of these systems also in industrial sectors. Full article

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Open AccessArticle

Hydrothermal Aging Mechanisms of All-Steel Radial Tire Composites

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Polymers 2022, 14(15), 3098; https://doi.org/10.3390/polym14153098 - 30 Jul 2022

Cited by 2 | Viewed by 896

Abstract

This work focused on the effects of the hydrothermal environment on the aging of all-steel radial tire (ASRT) composites. Composite specimens were conditioned by immersion in deionized water at 30, 60 and 90 °C. Its water absorption, thermal and mechanical properties (tensile strength, [...] Read more.

This work focused on the effects of the hydrothermal environment on the aging of all-steel radial tire (ASRT) composites. Composite specimens were conditioned by immersion in deionized water at 30, 60 and 90 °C. Its water absorption, thermal and mechanical properties (tensile strength, elasticity modulus, elongation at break and interfacial shear strength), morphological structure, as well as molecular cross-linking reaction were investigated before and after aging. Results indicated that there was no dynamic equilibrium of water absorption of ASRT composites after deviating from the Fickian model. The molecular cross-linking density of the rubber matrix showed an increase in the early stage of aging. Then, the mechanical properties suffered of a drop due to the degradation of the rubber matrix and the poor interface between the steel fiber and rubber matrix. Additionally, a systematic hygrothermal aging mechanism was proposed. Full article

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Open AccessArticle

A Molecular Dynamics Approach to the Impacts of Oxidative Aging on the Engineering Characteristics of Asphalt

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Wei Cao

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Elham Fini

Polymers 2022, 14(14), 2916; https://doi.org/10.3390/polym14142916 - 19 Jul 2022

Cited by 6 | Viewed by 1263

Abstract

Oxidative aging is an inevitable environmental factor that accelerates asphalt pavement deterioration. This study employed a molecular dynamics simulation to investigate the impact of aging on asphalt cement from the perspectives of thermodynamic properties, and diffusion and adhesion characteristics. Results indicate that aging [...] Read more.

Oxidative aging is an inevitable environmental factor that accelerates asphalt pavement deterioration. This study employed a molecular dynamics simulation to investigate the impact of aging on asphalt cement from the perspectives of thermodynamic properties, and diffusion and adhesion characteristics. Results indicate that aging increased bulk density from 1.008 to 1.081 g/cm³ and cohesive energy density by 15.6%, which was attributed to the promoted molecular polarity and intermolecular attractiveness. The enhanced molecular interactions also reduced molecular mobility, which led to an increase in the glass transition temperature by 30 K, suggesting that aging diminished the resistance of asphalt to thermal cracking. Simulations of the diffusion behaviors across different temperatures demonstrated that the Arrhenius relationship described well the temperature dependence of the diffusion coefficient, and that aging considerably slowed down the diffusion process as represented by Arrhenius prefactor D₀, which dropped by 38.2%. The asphalt–aggregate adhesion was assessed using layered models with and without a water interlayer of different thicknesses. The adhesion was enhanced upon aging due to the significantly improved electrostatic interactions at the interface. Evaluation of the residual adhesion with the presence of interfacial water suggested that aging would raise the moisture susceptibility of asphalt pavement. The increase in molecular polarity was considered to be highly responsible for these aging consequences, and was thus further investigated via the electrostatic potential surface and dipole moment. Full article

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Open AccessEditorial

Assessment of the Ageing and Durability of Polymers

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Mariaenrica Frigione

Polymers 2022, 14(10), 1934; https://doi.org/10.3390/polym14101934 - 10 May 2022

Cited by 2 | Viewed by 1011

Abstract

As any other natural or industrial material, polymers can experience some kind of degradation during their service life, resulting in minor to severe changes in their properties [...] Full article

Open AccessArticle

Thermal Degradation of Photoluminescence Poly(9,9-dioctylfluorene) Solvent-Tuned Aggregate Films

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Kang Wei Chew

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Nor Azura Abdul Rahim

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Pei Leng Teh

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Nurfatin Syafiqah Abdul Hisam

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Siti Salwa Alias

Polymers 2022, 14(8), 1615; https://doi.org/10.3390/polym14081615 - 15 Apr 2022

Cited by 2 | Viewed by 1426

Abstract

The progression of the green emission spectrum during the decomposition of polyfluorenes (PFs) has impeded the development and commercialization of the materials. Herein, we constructed a solvent-tuned aggregated PFO film with the aim of retarding the material’s thermal degradation behavior which causes a [...] Read more.

The progression of the green emission spectrum during the decomposition of polyfluorenes (PFs) has impeded the development and commercialization of the materials. Herein, we constructed a solvent-tuned aggregated PFO film with the aim of retarding the material’s thermal degradation behavior which causes a significant decline in optical properties as a result of phase transformation. The tuning of the aggregate amount and distribution was executed by applying a poor alcohol-based solvent in chloroform. It emerges that at a lower boiling point methanol evaporates quickly, limiting the aggregate propagation in the film which gives rise to a more transparent film. Furthermore, because of the modulated β-phase conformation, the absorption spectra of PFO films were red-shifted and broadened. The increase in methanol percentage also led to a rise in β-phase percentage. As for the thermal degradation reactions, both pristine and aggregated PFO films exhibited apparent changes in the UV-Vis spectra and PL spectra. In addition, a 97:3 (chloroform:methanol) aggregated PFO film showed a more defined emission spectrum, which demonstrates that the existence of β-phase is able to suppress the unwanted green emission. Full article

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Open AccessArticle

Effect of Antioxidants on Thermo-Oxidative Stability and Aging of Bio-Based PA56T and Fast Characterization of Anti-Oxidation Performance

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Polymers 2022, 14(7), 1280; https://doi.org/10.3390/polym14071280 - 22 Mar 2022

Cited by 4 | Viewed by 1700

Abstract

Bio-based polyamide 56T (PA56T) is a new type of bio-based polyamide regarded as a promising material for sustainable solutions. The stabilization of PA56T compounded with Irganox 1098, Doverphos S9228, or SH3368 was studied by using a rotational rheometer and a circulating air oven [...] Read more.

Bio-based polyamide 56T (PA56T) is a new type of bio-based polyamide regarded as a promising material for sustainable solutions. The stabilization of PA56T compounded with Irganox 1098, Doverphos S9228, or SH3368 was studied by using a rotational rheometer and a circulating air oven at 150 °C. The thermal-oxidative aging resulted in an increase of the yellow color index of the PA56T/GF composites, which due to the carbonyl group as a chromophore group, continuously formatted during the aging process. After 10 days of aging, the mechanical properties and dynamic mechanical properties increase due to the molecular cross-linking and annealing effects. When the aging time is beyond 20 days, the degradation of molecular chain segments dominates, and the mechanical properties of PA56T/GF deteriorate continuously. The addition of antioxidants only slowed this effect and did not change the process of thermal-oxidative aging, which destroys the molecular chain. The results from both methods are consistent after a series of characterizations by FTIR, XRD, and so on. In the case of samples without lubricant, the rotational rheometer has the benefit of being less time-consuming than the accelerated aging experiment. Full article

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Open AccessArticle

Effect of Aging on the Mechanical Properties of Highly Transparent Fluoropolymers for the Conservation of Archaeological Sites

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Maria Paola Bracciale

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Lorena Capasso

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Fabrizio Sarasini

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Jacopo Tirillò

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Maria Laura Santarelli

Polymers 2022, 14(5), 912; https://doi.org/10.3390/polym14050912 - 24 Feb 2022

Cited by 5 | Viewed by 1616

Abstract

In recent years, fluoropolymers have found numerous applications in the architectural field because of their combination of mechanical-chemical resistance and high transparency. In the present work, commercial fluorinated polymers, such as perfluoro alkoxy (PFA) and ethylene tetrafluoroethylene copolymer (ETFE), have been evaluated for [...] Read more.

In recent years, fluoropolymers have found numerous applications in the architectural field because of their combination of mechanical-chemical resistance and high transparency. In the present work, commercial fluorinated polymers, such as perfluoro alkoxy (PFA) and ethylene tetrafluoroethylene copolymer (ETFE), have been evaluated for use as protective and transparent layers on monumental and archaeological sites (to preserve mosaics or frescoes) during the phases of restoration or maintenance outdoors. Considering this specific application, the present study was developed by evaluating the evolution of the mechanical (tensile, tear propagation resistance, and low-velocity impact tests) and chemical (FTIR and DSC analysis) properties of the films after accelerated UV aging. The results that were obtained demonstrated the high resistance capacity of the ETFE, which exhibits considerably higher elastic modulus and critical tear energy values than PFA films (1075.38 MPa and 131.70 N/mm for ETFE; 625.48 MPa and 59.06 N/mm for PFA). After aging, the samples exhibited only a slight reduction of about 5% in the elastic modulus for both polymers and 10% in the critical tear energy values for PFA. Furthermore, the differences in impact resistance after aging were limited for both polymers; however, the ETFE film showed higher peak force than the PFA films (82.95 N and 42.22 N, respectively). The results obtained demonstrated the high resistance capacity of ETFE films, making them the most suitable candidate for the considered application. Full article

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Open AccessArticle

Microscopic Imaging Technology Assisted Dynamic Monitoring and Restoration of Micron-Level Cracks in the Painted Layer of Terracotta Warriors and Horses of the Western Han Dynasty

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Polymers 2022, 14(4), 760; https://doi.org/10.3390/polym14040760 - 15 Feb 2022

Cited by 1 | Viewed by 1631

Abstract

Cracks are one of the most common issues affecting colored pottery relics; these can be divided into macroscopic cracks, recognizable by the human eye, and micron cracks, which cannot be observed by the naked eye. The gradual development of micron cracks eventually leads [...] Read more.

Cracks are one of the most common issues affecting colored pottery relics; these can be divided into macroscopic cracks, recognizable by the human eye, and micron cracks, which cannot be observed by the naked eye. The gradual development of micron cracks eventually leads to large-scale cracks and the shedding of the coating layer. The repair of such micron cracks poses a key technical difficulty in restoring painted pottery remnants from the Western Han Dynasty. We attempt to solve this problem by reporting on a method that entails the use of a water-borne fluoropolymer material as the adhesive agent, as well as ultra-depth-of-field, digital microscopic imaging technology to build an operating platform for an optical imaging monitoring system. By making simulated ceramic samples, we systematically investigated the influences of water-borne fluoropolymer on chromaticity, adhesion, contact angle, surface morphology, and thermal stability of the paint layer. The results indicate that the color of the painted layer, when treated with the water-borne fluoropolymer, did not change, and the adhesion and contact angle of the painted layer were improved. Additionally, the outcomes of the SEM analysis show that the adhesion and hydrophobicity of the painted layer were improved because the water-borne fluoropolymer filled up the porous structure of the painted layer and covered the pigment particles. These findings demonstrate that aqueous, water-borne fluoropolymer can be used as an adhesive agent for micron cracks. Meanwhile, via the operating platform of the optical imaging monitoring system, the micron cracks of the painted terracotta warriors and horses from the Western Han Dynasty were successfully repaired using the water-borne fluoropolymer. The results imply that the microstructure, size, and geometric spaces of the cracks can be obtained directly utilizing microscopic imaging technology. The dynamic monitoring and imaging system described above can be employed to assist prosthetists in visualizing micro-repair operations in real time, assist with fine visual operations during the repair process, and realize dynamic video recording of the entire repair process. Our work provides a simple visualization method to repair micron-scale cracks in painted pottery relics by applying modern fluoropolymer and ultra-depth-of-field digital microscopic imaging technology. Full article

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2021

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Open AccessCorrection

Correction: Babo et al. Characterization and Long-Term Stability of Historical PMMA: Impact of Additives and Acrylic Sheet Industrial Production Processes. Polymers 2020, 12, 2198

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Maria Helena Casimiro

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Luís M. Ferreira

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Maria João Melo

Polymers 2021, 13(23), 4105; https://doi.org/10.3390/polym13234105 - 25 Nov 2021

Viewed by 850

Abstract

The authors wish to make a change to the published paper [...] Full article

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Open AccessArticle

High-Density Patterned Array Bonding through Void-Free Divinyl Siloxane Bis-Benzocyclobutene Bonding Process

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Polymers 2021, 13(21), 3633; https://doi.org/10.3390/polym13213633 - 21 Oct 2021

Cited by 3 | Viewed by 2020

Abstract

Divinylsiloxane-bis-benzocyclobutene (DVS-BCB) has attracted significant attention as an intermediate bonding material, owing to its excellent properties. However, its applications are limited, due to damage to peripheral devices at high curing temperatures and unoptimized compressive pressure. Therefore, it is necessary to explore the compressive [...] Read more.

Divinylsiloxane-bis-benzocyclobutene (DVS-BCB) has attracted significant attention as an intermediate bonding material, owing to its excellent properties. However, its applications are limited, due to damage to peripheral devices at high curing temperatures and unoptimized compressive pressure. Therefore, it is necessary to explore the compressive pressure condition for DVS-BCB bonding. This study demonstrates an optimization process for void-free DVS-BCB bonding. The process for obtaining void-free DVS-BCB bonding is a vacuum condition of 0.03 Torr, compressive pressure of 0.6 N/mm², and curing temperature of 250 °C for 1 h. Herein, we define two factors affecting the DVS-BCB bonding quality through the DVS-BCB bonding mechanism. For strong DVS-BCB bonding, void-free and high-density chemical bonds are required. Therefore, we observed the DVS-BCB bonding under various compressive pressure conditions at a relatively low temperature (250 °C). The presence of voids and high-density crosslinking density was examined through near-infrared confocal laser microscopy and Fourier-transform infrared microscopy. We also evaluated the adhesion of the DVS-BCB bonding, using a universal testing machine. The results suggest that the good adhesion with no voids and high crosslinking density was obtained at the compressive pressure condition of 0.6 N/mm². We believe that the proposed process will be of great significance for applications in semiconductor and device packaging technologies. Full article

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Open AccessArticle

An Effective Package of Antioxidants for Avoiding Premature Failure in Polypropylene Random Copolymer Plastic Pipes under Hydrostatic Pressure and High Temperature

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Enrique Blázquez-Blázquez

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Joaquín Lahoz

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Ernesto Pérez

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María L. Cerrada

Polymers 2021, 13(16), 2825; https://doi.org/10.3390/polym13162825 - 22 Aug 2021

Cited by 5 | Viewed by 2733

Abstract

Pipes of polypropylene random (PP-R) copolymers are the best choice for hot- and cold-water networks. Validation of a severe test, accomplishing the ISO 1167 standard, is mandatory to assess their service lifetime expectancy. This work evaluates the behavior shown by three commercial pipes, [...] Read more.

Pipes of polypropylene random (PP-R) copolymers are the best choice for hot- and cold-water networks. Validation of a severe test, accomplishing the ISO 1167 standard, is mandatory to assess their service lifetime expectancy. This work evaluates the behavior shown by three commercial pipes, either the original ones (new pipes) or after being subjected to a hydrostatic pressure test at elevated temperature (aged pipes). Several features with relevance for the final performance have been examined: crystalline characteristics, phase transitions in crystalline regions, effect of high temperature and pressure on these transitions, and oxidation induction time. Moreover, the presence of inorganic fillers, and the content of different antioxidants together with their depletion, have also been analyzed. Films from the new pipes were also prepared for replication of the different environments in order to achieve a better and complete understanding of the phase transitions in the crystalline regions and of the consumption of antioxidants. Distinct environments surrounded the inner and outer parts of the pipes exposed to the failure aging test at 110 °C: hot water and warm dry air, respectively. These features play a key role in the loss of additives and in the subsequent initiation of degradation. Even if the crystalline characteristics are appropriate in the polymeric matrix, the success of a pipe lies in the homogeneous dispersion of components for avoiding damage at interfacial properties, and in a correct package of antioxidants used in its formulation. Full article

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Open AccessArticle

Expandable Graphite for Flame Retardant PA6 Applications

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Polymers 2021, 13(16), 2733; https://doi.org/10.3390/polym13162733 - 15 Aug 2021

Cited by 8 | Viewed by 2332

Abstract

A new expandable graphite (EG) type was studied as a flame retardant additive in Polyamide 6 (PA6). The fire behavior was characterized by a cone calorimeter using external heat fluxes of 35, 50 and 65 kW/m², limiting the oxygen index (LOI) [...] Read more.

A new expandable graphite (EG) type was studied as a flame retardant additive in Polyamide 6 (PA6). The fire behavior was characterized by a cone calorimeter using external heat fluxes of 35, 50 and 65 kW/m², limiting the oxygen index (LOI) and UL-94 burning tests. Additionally, electric and thermal conductivity as well as rheological properties were characterized to provide a general property overview. Fire tests were conducted using dry and humid conditioned samples. Cone Calorimeter tests showed a minimum filling degree of 15 wt.% (8.6 vol.%) EG was required to achieve a significant fire inhibiting effect in PA6 independent of the sample condition. UL-94 fire tests show a V0 classification at filling degrees greater than 20 wt.% (humid) and 25 wt.% (dry), although the associated LOI values of 39% and 38% demonstrate good flammability inhibition. Correlation analyses were conducted to identify major influences given by the sample condition for most important key figures measured in cone calorimeter tests. Accordingly, humid-conditioned samples containing between 2.5 (PA6 + 25 wt.% EG) and 4.2 wt.% (PA6) water were found to reduce the total heat evolved (THE) on average by 16% and the total smoke production (TSP) on average by 22%. Full article

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Open AccessArticle

A Synergistic Flame Retardant System Based on Expandable Graphite, Aluminum (Diethyl-)Polyphospinate and Melamine Polyphosphate for Polyamide 6

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Polymers 2021, 13(16), 2712; https://doi.org/10.3390/polym13162712 - 13 Aug 2021

Cited by 10 | Viewed by 2147

Abstract

Expandable graphite (EG), aluminum (diethyl)polyphosphinate (AlPi) and melamine polyphophate (MPP) was used as flame retardant multi-material additive in a polyamide 6 (PA6) matrix. Flame inhabitation performances were conducted by cone calorimeter, LOI and UL-94 tests, synergisms identified analyzed by TGA-FTIR and TGA-GC/MS and [...] Read more.

Expandable graphite (EG), aluminum (diethyl)polyphosphinate (AlPi) and melamine polyphophate (MPP) was used as flame retardant multi-material additive in a polyamide 6 (PA6) matrix. Flame inhabitation performances were conducted by cone calorimeter, LOI and UL-94 tests, synergisms identified analyzed by TGA-FTIR and TGA-GC/MS and effects found were comprehensively discussed. SEM images were used for char residue characterization. For PA6 containing 20 wt.% EG and 5 wt.% AlPi/MPP (3:2), a well working synergism in limiting oxygen indices could be identified exhibiting the highest oxygen index (OI) measured: 46%. The study shows that the synergism due to the partial substitution of EG by AlPi/MPP can be attributed to two effects: (1) When PA6/AlPi/MPP mixtures decompose predominantly CO₂ evaporates in early decomposition stages. CO₂ evaporations was found to be sensitive to the heating rate applied, whereas specifically high heating rates increased the CO₂ yield measured. (2) Solid decomposition products of AlPi/MPP act as “glue” between expanded graphite and thus increase the mechanical residue stability. Full article

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Open AccessReview

Can Accelerated Aging Procedures Predict the Long Term Behavior of Polymers Exposed to Different Environments?

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Mariaenrica Frigione

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Alvaro Rodríguez-Prieto

Polymers 2021, 13(16), 2688; https://doi.org/10.3390/polym13162688 - 12 Aug 2021

Cited by 25 | Viewed by 4083

Abstract

During their useful life, polymers are subject to degradation processes due to exposure to specific environmental conditions over long times. These processes generally lead to changes, almost always irreversible, of properties and performances of polymers, changes which would be useful to be able [...] Read more.

During their useful life, polymers are subject to degradation processes due to exposure to specific environmental conditions over long times. These processes generally lead to changes, almost always irreversible, of properties and performances of polymers, changes which would be useful to be able to predict in advance. To meet this need, numerous investigations have been focused on the possibility to predict the long-term performance of polymers, if exposed to specific environments, by the so called “accelerated aging” tests. In such procedures, the long-term behavior of polymeric materials is typically predicted by subjecting them to cycles of radiations, temperatures, vapor condensation, and other external agents, at levels well above those found in true conditions in order to accelerate the degradation of polymers: this can produce effects that substantially deviate from those observable under natural exposure. Even following the standard codes, different environmental parameters are often used in the diverse studies, making it difficult to compare different investigations. The correlation of results from accelerated procedures with data collected after natural exposure is still a debated matter. Furthermore, since the environmental conditions are a function of the season and the geographical position, and are also characteristic of the type of exposure area, the environmental parameters to be used in accelerated aging tests should also consider these variables. These and other issues concerning accelerated aging tests applied to polymers are analyzed in the present work. However, bearing in mind the limitations of these practices, they can find useful applications for rating the durability of polymeric materials. Full article

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Open AccessArticle

New Aspects of Degradation in Silicone Rubber under UVA and UVB Irradiation: A Gas Chromatography–Mass Spectrometry Study

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Polymers 2021, 13(13), 2215; https://doi.org/10.3390/polym13132215 - 05 Jul 2021

Cited by 6 | Viewed by 2375

Abstract

In this paper, gas chromatography–mass spectrometry (GC–MS) and positron annihilation lifetime spectroscopy (PALS) were used to probe the changes of oligomers and the polydimethylsiloxane (PDMS) network in silicone rubber, after different durations of UVA/UVB irradiation. At the early stage (<300 h) of UVA/UVB [...] Read more.

In this paper, gas chromatography–mass spectrometry (GC–MS) and positron annihilation lifetime spectroscopy (PALS) were used to probe the changes of oligomers and the polydimethylsiloxane (PDMS) network in silicone rubber, after different durations of UVA/UVB irradiation. At the early stage (<300 h) of UVA/UVB irradiation, the concentration of D

_{4}

-D

_{9}

decreases. The o-Ps intensity of the extracted silicone rubber increases in the stage after UVB irradiation. These results indicate the crosslinking of oligomers into the PDMS network. After a long duration (>300 h) of UVB irradiation, D

_{4}

was generated and the lifetime of

τ_{3}

also increased, indicating the rupture of the Si-O bond in the PDMS network. These two aging processes were termed the post curing process and the chain session process. The new finding was that UVA could only induce the post curing process; UVB causes the rupture of the chemical bond in silicone rubber. Photons of UVB could break the C-H bond, and then trigger the backbiting decomposition of PDMS, breaking the Si-O bond, while the photons of UVA cannot. The fact that D

_{4}

was generated after UVB irradiation can be used to evaluate the UVB stability of silicone rubber in the future. Full article

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Open AccessArticle

Influence of Gamma Irradiation on Electric Cables Models: Study of Additive Effects by Mid-Infrared Spectroscopy

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Polymers 2021, 13(9), 1451; https://doi.org/10.3390/polym13091451 - 30 Apr 2021

Cited by 7 | Viewed by 2177

Abstract

Cables, especially their insulation and jacket materials made of polymers, are vulnerable to ageing degradation during normal operation. However, they must remain functional for the entire life of a nuclear power plant, or even in the event of an accident for cables with [...] Read more.

Cables, especially their insulation and jacket materials made of polymers, are vulnerable to ageing degradation during normal operation. However, they must remain functional for the entire life of a nuclear power plant, or even in the event of an accident for cables with a safety requirement. This study focuses on models of crosslinked polyethylene (XLPE)-based insulation of cables and deals with the structure modification and the behavior of XLPE for nuclear applications due to the effect of additives. Various additives are added to the polymer formulation to evaluate their impact on ageing. The samples are irradiated at room temperature by several gamma doses, up to 374 kGy, with two dose rates (40 Gy/h and 300 Gy/h) and compared with a non-irradiated sample used as reference. To understand the impact of gamma irradiation on the materials, the principal component analysis (PCA) method is applied on spectra recorded through attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy. The results highlight the effects of ageing depending on the dose rate and on the formulation of the materials, with the identification of different degradation products. A curve resolution study compares the effects of different additives on polymer oxidation and shows that the low dose rate leads to a higher degradation than the high dose rate. Full article

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Open AccessArticle

Reliability Prediction of Acrylonitrile O-Ring for Nuclear Power Applications Based on Shore Hardness Measurements

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Alvaro Rodríguez-Prieto

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Ernesto Primera

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Mariaenrica Frigione

and

Ana María Camacho

Polymers 2021, 13(6), 943; https://doi.org/10.3390/polym13060943 - 19 Mar 2021

Cited by 5 | Viewed by 2028

Abstract

The degradation of polymeric components is of considerable interest to the nuclear industry and its regulatory bodies. The objective of this work was the development of a methodology to determine the useful life—based on the storage temperature—of acrylonitrile O-rings used as mechanical sealing [...] Read more.

The degradation of polymeric components is of considerable interest to the nuclear industry and its regulatory bodies. The objective of this work was the development of a methodology to determine the useful life—based on the storage temperature—of acrylonitrile O-rings used as mechanical sealing elements to prevent leakages in nuclear equipment. To this aim, a reliability-based approach that allows prediction of the use-suitability of different storage scenarios (that involve different storage times and temperatures) considering the further required in-service performance, is presented. Thus, experimental measurements of Shore A hardness have been correlated with storage variables (temperature and storage time). The storage (and its associated hardening) was proved to have a direct effect on in-service durability, reducing this by up to 60.40%. Based on this model, the in-service performance was predicted; after the first three years of operation the increase in probability of failure (POF) was practically insignificant. Nevertheless, from this point on, and especially, from 5 years of operation, the POF increased from 10% to 20% at approximately 6 years (for new and stored). From the study, it was verified that for any of the analysis scenarios, the limit established criterion was above that of the storage time premise considered in usual nuclear industry practices. The novelty of this work is that from a non-destructive test, like a Shore A hardness measurement, the useful life and reliability of O-rings can be estimated and be, accordingly, a decision tool that allows for improvement in the management of maintenance of safety-related equipment. Finally, it was proved that the storage strategies of our nuclear power plants are successful, perfectly meeting the expectations of suitability and functionality of the components when they are installed after storage. Full article

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Open AccessArticle

Mathematical Modeling of Outdoor Natural Weathering of Polycarbonate: Regional Characteristics of Degradation Behaviors

by

Takato Ishida

and

Ryoma Kitagaki

Polymers 2021, 13(5), 820; https://doi.org/10.3390/polym13050820 - 07 Mar 2021

Cited by 4 | Viewed by 2160

Abstract

Many natural exposure sites have been developed to ensure the reliability of materials intended for outdoor use. However, the effects of local climate on aging have not been completely understood. This study aimed to elucidate the regional characteristics of natural aging. Non-stabilized and [...] Read more.

Many natural exposure sites have been developed to ensure the reliability of materials intended for outdoor use. However, the effects of local climate on aging have not been completely understood. This study aimed to elucidate the regional characteristics of natural aging. Non-stabilized and stabilized polycarbonates were monitored in terms of their appearance (yellowing and loss of gloss) during natural weathering at five exposure sites (Tokyo, Kagoshima, Okinawa, Florida, and Arizona) in conjunction with climate fluctuation for up to 24 months. Three approaches were employed to characterize the natural aging behaviors: (i) modeling the rate function of degradation, (ii) evaluating the contribution ratio of individual degradational factors, and (iii) estimating the “synchronicity” by cross-correlation analysis with the climate dataset. The aging rates were the highest in Arizona and lowest in Kagoshima among the five exposure sites. First, prediction curves were constructed from the degradation rate function (variables: UV irradiation, temperature, and humidity), and these curves were found to agree well with the measured aging behaviors. Second, the exposure data in Arizona demonstrated strong temperature dependence, while those in Okinawa and Florida had stronger dependence on UV irradiation compared to other sites. Lastly, the synchronicity between UV irradiation and temperature was the highest in Arizona and lowest in Kagoshima, which can explain the significantly faster deterioration in Arizona and the slow deterioration in Kagoshima. Full article

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Open AccessReview

Durability of Externally Bonded Fiber-Reinforced Polymer Composites in Concrete Structures: A Critical Review

by

Jovan Tatar

and

Sandra Milev

Polymers 2021, 13(5), 765; https://doi.org/10.3390/polym13050765 - 28 Feb 2021

Cited by 29 | Viewed by 3856

Abstract

Externally bonded fiber-reinforced polymer composites have been in use in civil infrastructure for decades, but their long-term performance is still difficult to predict due to many knowledge gaps in the understanding of degradation mechanisms. This paper summarizes critical durability issues associated with the [...] Read more.

Externally bonded fiber-reinforced polymer composites have been in use in civil infrastructure for decades, but their long-term performance is still difficult to predict due to many knowledge gaps in the understanding of degradation mechanisms. This paper summarizes critical durability issues associated with the application of fiber-reinforced polymer (FRP) composites for rehabilitation of concrete structures. A variety of factors that affect the longevity of FRP composites are discussed: installation, quality control, material selection, and environmental conditions. Critical review of design approaches currently used in various international design guidelines is presented to identify potential opportunities for refinement of design guidance with respect to durability. Interdisciplinary approaches that combine materials science and structural engineering are recognized as having potential to develop composites with improved durability. Full article

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Open AccessArticle

Synthesis of Carvedilol–Organotin Complexes and Their Effects on Reducing Photodegradation of Poly(Vinyl Chloride)

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Polymers 2021, 13(4), 500; https://doi.org/10.3390/polym13040500 - 06 Feb 2021

Cited by 15 | Viewed by 2142

Abstract

Poly(vinyl chloride) (PVC) undergoes photodegradation induced by ultraviolet (UV) irradiation; therefore, for outdoor applications, its photostability should be enhanced through the use of additives. Several carvedilol tin complexes were synthesized, characterized and mixed with PVC to produce thin films. These films were irradiated [...] Read more.

Poly(vinyl chloride) (PVC) undergoes photodegradation induced by ultraviolet (UV) irradiation; therefore, for outdoor applications, its photostability should be enhanced through the use of additives. Several carvedilol tin complexes were synthesized, characterized and mixed with PVC to produce thin films. These films were irradiated at 25 °C with a UV light (λ = 313 nm) for up to 300 h. The reduction in weight and changes in chemical structure and surface morphology of the PVC films were monitored. The films containing synthesized complexes showed less undesirable changes than the pure PVC film. Organotin with a high content of aromatics was particularly efficient in inhibiting photodegradation of PVC. The carvedilol tin complexes both absorbed UV light and scavenged radicals, hydrochloride, and peroxides and, therefore, photostabilized PVC. Full article

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Open AccessArticle

Effect of Nanoclay Particles on the Performance of High-Density Polyethylene-Modified Asphalt Concrete Mixture

by

Ghada S. Moussa

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Ashraf Abdel-Raheem

and

Talaat Abdel-Wahed

Polymers 2021, 13(3), 434; https://doi.org/10.3390/polym13030434 - 29 Jan 2021

Cited by 13 | Viewed by 2083

Abstract

Utilizing polymers for asphalt concrete (AC) mixture modification has many drawbacks that hinder its wide implementations for roadway construction. Recently, research on employing complementary materials, such as nanomaterials, to balance negative impacts of polymers while enhancing the AC mixture’s performance has received great [...] Read more.

Utilizing polymers for asphalt concrete (AC) mixture modification has many drawbacks that hinder its wide implementations for roadway construction. Recently, research on employing complementary materials, such as nanomaterials, to balance negative impacts of polymers while enhancing the AC mixture’s performance has received great attention. This study aimed to investigate the effect of incorporating nanoclay (NC) particles on the performance of a high-density polyethylene (HDPE)-modified AC mixture. A 60/70 asphalt binder was first modified with HDPE, and then NC particles were gradually added at a concentration of 1–4% by weight of the asphalt binder. The binders’ physical characteristics, storage stability, and chemical change were scrutinized. AC mixture performance, including pseudo-stiffness, moisture damage resistance, stripping susceptibility, and rutting tendency, was investigated. A statistical analysis on the experimental results was conducted using Kruskal–Wallis and Dunn tests. Test results showed that employing NC/HDPE significantly increased penetration index and thereby enhanced binder temperature sensitivity. Moreover, it prevented oxidation action and separation and, therefore, enhanced binder storage stability. Furthermore, incorporating NC amplified pseudo-stiffness and significantly improved resistance against moisture damage and stripping of HDPE-modified mixtures. Moreover, it improved both elastic (recoverable) and plastic (unrecoverable) deformations of mixtures. The most satisfactory results were attained when incorporating 3% of NC. Full article

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Open AccessArticle

Suppression of Smoldering of Calcium Alginate Flame-Retardant Paper by Flame-Retardant Polyamide-66

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Polymers 2021, 13(3), 430; https://doi.org/10.3390/polym13030430 - 29 Jan 2021

Cited by 10 | Viewed by 1870

Abstract

Calcium alginate (Ca-Alg) fibers are renewable fibers obtained from the ocean with essential flame retardancy, which have recently been applied as components of flame-retardant paper. However, the application of Ca-Alg fibers is limited because of their tendency to smolder. Therefore, composites papers were [...] Read more.

Calcium alginate (Ca-Alg) fibers are renewable fibers obtained from the ocean with essential flame retardancy, which have recently been applied as components of flame-retardant paper. However, the application of Ca-Alg fibers is limited because of their tendency to smolder. Therefore, composites papers were fabricated by blending using flame-retardant polyamide-66 (FR-PA), with a 5 wt% content of phosphorous flame retardant, which will form molten carbon during combustion. When the FR-PA content is 30% of the composite paper, FR-PA forms a compact carbon layer on the surface of the Ca-Alg fibers during combustion, which isolates the mass/heat transfer and effectively suppresses the smoldering of Ca-Alg. This consists of a condensed flame retardant mechanism. Furthermore, the combustion and thermal degradation behavior of paper were analyzed by cone calorimetry (CONE), TG and TG-IR. Ca-Alg in the composite paper decomposed and released CO₂ before ignition, which delayed the ignition time. Simultaneously, the FR-PA contained in the composite paper effectively inhibited the combustion of volatile combustibles in the gas phase. Overall, FR-PA and Ca-Alg improve the thermal stability of the composite paper in different temperature regions under air atmosphere. Ca-Alg reduces the formation of aromatic products and NH₃ in the composite paper under N₂ atmosphere. Ca-Alg-based paper with excellent flame retardancy was successfully prepared. Full article

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2020

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Open AccessCommunication

Effect of Panel Moisture Content on Internal Bond Strength and Thickness Swelling of Medium Density Fiberboard

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Polymers 2021, 13(1), 114; https://doi.org/10.3390/polym13010114 - 30 Dec 2020

Cited by 9 | Viewed by 1864

Abstract

Wood-based products usually have serious limitations concerning contact with water, both because wood is a hygroscopic material and because the commonly used binder has low moisture resistance. This paper studies the effect of panel moisture content (MC) on the physico-mechanical properties of medium [...] Read more.

Wood-based products usually have serious limitations concerning contact with water, both because wood is a hygroscopic material and because the commonly used binder has low moisture resistance. This paper studies the effect of panel moisture content (MC) on the physico-mechanical properties of medium density fiberboards (MDF). Several commercial MDF boards produced in Europe were stored at room temperature and relative humidity (RH) for 9 weeks (approx. range 15–20 °C and 50–85% RH). Every week, a strip of each MDF board was cut out, divided into 5 × 5 cm test pieces and its internal bond strength (IB) was measured. A strong influence of MDF moisture content on internal bond strength was observed and therefore IB test pieces were stored in a climatic chamber (either at 20 °C, 55% RH and at 20 °C, 70% RH). A decreasing linear relation was established between IB and MC. It was found that this effect is reversible: after drying, internal bond strength rises again (following a slight hysteresis). This work reinforces the importance of conditioned storage before board properties analysis, as described in European Standard EN 319. Full article

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Open AccessArticle

Physico-Mechanical and Biological Durability of Citric Acid-Bonded Rubberwood Particleboard

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Syeed SaifulAzry Osman Al-Edrus

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Nor Azowa Ibrahim

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Luqman Chuah Abdullah

and

Siti Fatahiyah Mohamad

Polymers 2021, 13(1), 98; https://doi.org/10.3390/polym13010098 - 29 Dec 2020

Cited by 10 | Viewed by 2092

Abstract

This study investigated the effects of different citric acid content on the physico-mechanical and biological durability of rubberwood particleboard. Particleboards with density of 700 kg/m³ were produced with three different citric acid contents, namely 10, 15 and 20 wt%. Particleboards made from [...] Read more.

This study investigated the effects of different citric acid content on the physico-mechanical and biological durability of rubberwood particleboard. Particleboards with density of 700 kg/m³ were produced with three different citric acid contents, namely 10, 15 and 20 wt%. Particleboards made from 10 wt% urea formaldehyde (UF) resin were served as control for comparison purposes. FTIR analysis was carried out and the formation of ester linkages between -OH on cellulose and carbonyl groups of citric acid was confirmed. The peak intensity increased along with increasing citric content, which indicated that a higher amount of ester linkages were formed at higher citric acid content. Citric acid-bonded particleboard had inferior physical properties (water absorption and thickness swelling) and mechanical properties (internal bonding strength, modulus of rupture and modulus of elasticity) compared to that of the UF-bonded particleboard. However, the performance of particleboard was enhanced with increasing citric acid content. Meanwhile, citric acid-bonded particleboard displayed significantly better fungal and termite resistance than UF-bonded particleboard owing to the acidic nature of citric acid. It can be concluded that citric acid is a suitable green binder for particleboard but some improvement is needed during the particleboard production process. Full article

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Open AccessArticle

Effect of Cyclotriphosphazene-Based Curing Agents on the Flame Resistance of Epoxy Resins

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Polymers 2021, 13(1), 8; https://doi.org/10.3390/polym13010008 - 22 Dec 2020

Cited by 8 | Viewed by 2233

Abstract

Epoxy resins are characterized by excellent properties such as chemical resistance, shape stability, hardness and heat resistance, but they present low flame resistance. In this work, the synthesized derivatives, namely hexacyclohexylamino-cyclotriphosphazene (HCACTP) and novel diaminotetracyclohexylamino-cyclotriphosphazene (DTCATP), were applied as curing agents for halogen-free [...] Read more.

Epoxy resins are characterized by excellent properties such as chemical resistance, shape stability, hardness and heat resistance, but they present low flame resistance. In this work, the synthesized derivatives, namely hexacyclohexylamino-cyclotriphosphazene (HCACTP) and novel diaminotetracyclohexylamino-cyclotriphosphazene (DTCATP), were applied as curing agents for halogen-free flame retarding epoxy materials. The thermal properties and combustion behavior of the cured epoxy resins were investigated. The obtained results revealed that the application of both derivatives significantly increased flame resistance. The epoxy resins cured with HCACTP and DTCATP exhibited lower total heat release together with lower total smoke production compared to the epoxy materials based on conventional curing agents (dipropylenetriamine and ethylenediamine). Comparing both derivatives, the HCACTP-cured epoxy resin was found to provide a higher flame resistance. The designed novel class of epoxy materials may be used for the preparation of materials with improved flame resistance properties in terms of flame spreading and smoke inhibition. Full article

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Open AccessArticle

The Impact of the Acidic Environment on the Mechanical Properties of Epoxy Compounds in Different Conditions

by

Anna Rudawska

Polymers 2020, 12(12), 2957; https://doi.org/10.3390/polym12122957 - 10 Dec 2020

Cited by 9 | Viewed by 1581

Abstract

The aim of this work was to determine the impact of the acidic environment on the mechanical properties of two epoxy compounds in different conditions. The samples were made from the epoxy compounds composed of the epoxy resin (based on Bisphenol A), triethylenetetramine [...] Read more.

The aim of this work was to determine the impact of the acidic environment on the mechanical properties of two epoxy compounds in different conditions. The samples were made from the epoxy compounds composed of the epoxy resin (based on Bisphenol A), triethylenetetramine curing agent (unmodified compound), and calcium carbonate (CaCO₃) (modified compound). The epoxy compound samples were seasoned for the following period of time (i.e., one week, one month, and three months). The environment was tap water and the acidic environment had three different concentrations of acetic acid (3%, 6%, and 9%). Strength tests of the epoxy compound samples were carried out in accordance with the ISO 604 standard. In the case of the modified composition, it is noted that the samples immersed in tap water were characterized by a higher strength than in acidic environments. A similar tendency was observed for unmodified compositions, although the differences were smaller than for the modified compositions. It was also noticed that the increase in the pH of the acidic solution in many analyzed cases contributed to the decrease in mechanical properties, although the immersion time in the acidic solution is important. Full article

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Open AccessArticle

Tin Complexes Containing an Atenolol Moiety as Photostabilizers for Poly(Vinyl Chloride)

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Mohammad Hayal Alotaibi

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Emad Yousif

Polymers 2020, 12(12), 2923; https://doi.org/10.3390/polym12122923 - 06 Dec 2020

Cited by 9 | Viewed by 1855

Abstract

The lifetime of poly(vinyl chloride) (PVC) can be increased through the addition of additives to provide protection against irradiation. Therefore, several new tin complexes containing atenolol moieties were synthesized and their photostabilizing effect on PVC was investigated. Reacting atenolol with a number of [...] Read more.

The lifetime of poly(vinyl chloride) (PVC) can be increased through the addition of additives to provide protection against irradiation. Therefore, several new tin complexes containing atenolol moieties were synthesized and their photostabilizing effect on PVC was investigated. Reacting atenolol with a number of tin reagents in boiling methanol provided high yields of tin complexes. PVC was then mixed with the tin complexes at a low concentration, producing polymeric thins films. The films were irradiated with ultraviolet light and the resulting damage was assessed using different analytical and surface morphology techniques. Infrared spectroscopy and weight loss determination indicated that the films incorporating tin complexes incurred less damage and less surface changes compared to the blank film. In particular, the triphenyltin complex was very effective in enhancing the photostability of PVC, and this is due to its high aromaticity (three phenyl rings) compared to other complexes. Such an additive acts as a hydrogen chloride scavenger, radical absorber, and hydroperoxide decomposer. Full article

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Open AccessArticle

Cellulose Structural Changes during Mild Torrefaction of Eucalyptus Wood

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Polymers 2020, 12(12), 2831; https://doi.org/10.3390/polym12122831 - 28 Nov 2020

Cited by 12 | Viewed by 1836

Abstract

The changes in the cellulose structure of eight Eucalyptus species (E. botryoides, E. globulus, E. grandis, E. maculata, E. propinqua, E. rudis, E. saligna and E. viminalis) in a mild torrefaction (from 160 °C to [...] Read more.

The changes in the cellulose structure of eight Eucalyptus species (E. botryoides, E. globulus, E. grandis, E. maculata, E. propinqua, E. rudis, E. saligna and E. viminalis) in a mild torrefaction (from 160 °C to 230 °C, 3 h) were studied in situ and after cellulose isolation from the wood by solid-state carbon nuclear magnetic resonance (¹³C NMR), wide angle X-ray scattering (WAXS), Fourier transform infrared spectroscopy (FTIR) and by analytic pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS). Changes in molecular weight were assessed by viscosimetry. A small decrease in cellulose crystallinity (ca. 2%–3%) was attributed to its amorphization on crystallite surfaces as a result of acid hydrolysis and free radical reactions resulting in the homolytic splitting of glycosidic bonds. The degree of the cellulose polymerization (DPv) decreased more than twice during the heat treatment of wood. It has been proposed that changes in the supramolecular structure of cellulose and in molecular weight during a heat treatment can be affected by the amount of lignin present in the wood. The limitations of FTIR and Py-GC/MS techniques to distinguish the minor changes in cellulose crystallinity were discussed. Full article

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Open AccessArticle

Dielectric Measurement Based Deducted Quantities to Track Repetitive, Short-Term Thermal Aging of Polyvinyl Chloride (PVC) Cable Insulation

by

Gergely Márk Csányi

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Semih Bal

and

Zoltán Ádám Tamus

Polymers 2020, 12(12), 2809; https://doi.org/10.3390/polym12122809 - 27 Nov 2020

Cited by 16 | Viewed by 2551

Abstract

The effect of short-term (3- and 6-h-long) periodic thermal aging was investigated at three different temperatures on PVC cables and PVC films. Three different temperatures (110, 125, and 140 °C) were used for aging PVC cables and one (110 °C) for PVC films. [...] Read more.

The effect of short-term (3- and 6-h-long) periodic thermal aging was investigated at three different temperatures on PVC cables and PVC films. Three different temperatures (110, 125, and 140 °C) were used for aging PVC cables and one (110 °C) for PVC films. PVC films were prepared for the investigation containing 0, 30, 40, and 50 weight percent of dioctyl phthalate plasticizer (DOP). The effect of short-term thermal aging was monitored by electrical (dielectric spectrum and voltage response measurement) and mechanical (Shore D hardness) methods. From the loss factor measurements, different deducted quantities were calculated and compared with Shore D hardness, which has been shown to be a parameter reflecting the effect of short-term thermal aging on PVC insulation. The measurements revealed that Shore D hardness is not the best property for monitoring aging. Instead, increasing dissipated power and the shifting behavior of tan δ–frequency curves proved to be the best phenomena for assessing the impact of thermal aging. Simple deducted quantities may provide a basis for following short-term thermal aging. Full article

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Open AccessArticle

Moving toward Smart Cities: Evaluation of the Self-Cleaning Properties of Si-Based Consolidants Containing Nanocrystalline TiO₂ Activated by Either UV-A or UV-B Radiation

by

José Santiago Pozo-Antonio

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Daniel Noya-Pintos

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Patricia Sanmartín

Polymers 2020, 12(11), 2577; https://doi.org/10.3390/polym12112577 - 02 Nov 2020

Cited by 3 | Viewed by 1570

Abstract

This study evaluated the self-cleaning ability and durability of Si-based consolidants (an ethyl silicate consolidant and a consolidant based on nanosized silica) spiked with nanocrystalline TiO₂ activated by either UV-A radiation (spectral region between 340 and 400 nm, and main peak at [...] Read more.

This study evaluated the self-cleaning ability and durability of Si-based consolidants (an ethyl silicate consolidant and a consolidant based on nanosized silica) spiked with nanocrystalline TiO₂ activated by either UV-A radiation (spectral region between 340 and 400 nm, and main peak at 365 nm) or UV-B radiation (spectral region between 270 and 420 nm, and main peak at 310 nm). Granite samples were coated with consolidant, to which nanocrystalline TiO₂ was added at different concentrations (0.5, 1, and 3%, by wt.). Diesel soot was then applied to the coated surfaces, and the samples were exposed to UV-A or UV-B radiation for 1650 h. The surface color changes, relative to the color of untreated granite, were determined every 330 h by color spectrophotometry. Slight color changes indicated a recovery of the reference color due to the degradation of the soot. The final surfaces of both the untreated and treated surfaces were compared by stereomicroscopy and scanning electron microscopy. The main findings were that: (1) In general, the consolidant containing nanosized silica induced the most intense photocatalytic activity. In the more compact xerogel coating formed by the nanosized silica, more TiO₂ nanoparticles were available to interact with the radiation. (2) For all consolidant mixtures, soot degradation remained constant or decreased over time, except with ethyl silicate with 0.5 wt % TiO₂ (no self-cleaning capacity). (3) Soot degradation increased with the concentration of TiO₂. (4) The UV-B radiation was the most effective in terms of soot degradation, except for the surface coated with the ethyl silicate and 3% wt. TiO₂. Full article

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Open AccessArticle

Effect of the B:Zn:H₂O Molar Ratio on the Properties of Poly(Vinyl Acetate) and Zinc Borate-Based Intumescent Coating Materials Exposed to a Quasi-Real Cellulosic Fire

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Polymers 2020, 12(11), 2542; https://doi.org/10.3390/polym12112542 - 30 Oct 2020

Cited by 3 | Viewed by 1599

Abstract

In order to investigate an influence of the B:Zn:H₂O molar ratio on the fire protection efficiency of poly(vinyl acetate)-based thermoplastic intumescent coating materials (ICs), systems containing ammonium polyphosphate, melamine, pentaerythritol and different types of zinc borates (ZBs) were tested in a [...] Read more.

In order to investigate an influence of the B:Zn:H₂O molar ratio on the fire protection efficiency of poly(vinyl acetate)-based thermoplastic intumescent coating materials (ICs), systems containing ammonium polyphosphate, melamine, pentaerythritol and different types of zinc borates (ZBs) were tested in a vertical position in quasi-real fire conditions. 3ZnO·2B₂O₃·6H₂O (ZB6), 2ZnO·3B₂O₃·3.5H₂O (ZB3.5) or 3ZnO·2B₂O₃ (ZB0) were added in amounts of 1–10 wt. parts/100 wt. parts of the other coating components mixture. Char formation processes and thermal insulation features were investigated using an open-flame furnace heated according to the cellulosic fire curve. Thermogravimetric features (DTG), chemical structures (FTIR) and mechanical strength of the ICs and the chars were analyzed as well. It was revealed that the type and dose of the ZBs significantly affect thermal insulation time (TIT) (up to 450 °C of a steel substrate) and sagging (SI) of the fire-heated coatings as well as the compressive strength of the created chars. The highest TIT value (+89%) was noted for the sample with 2.5 wt. parts of ZB3.5 while the lowest SI (−65%) was observed for the coatings containing 10 wt. parts of the hydrated borates (i.e., ZB3.5 or ZB6). The best mechanical strength was registered for the sample filled with the anhydrous modifier (3 wt. parts of ZB0). The presented results show that the ICs with the proper ZBs can be used for effective fire protection of vertically positioned steel elements. Full article

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Open AccessArticle

Aging Effects of Aqueous Environment on Mechanical Properties of Calcium Carbonate-Modified Epoxy Resin

by

Anna Rudawska

and

Mariaenrica Frigione

Polymers 2020, 12(11), 2541; https://doi.org/10.3390/polym12112541 - 30 Oct 2020

Cited by 13 | Viewed by 1622

Abstract

The purpose of this study was to assess the effects of different aqueous environments (i.e., demineralised, distilled and spring water) on the mechanical properties of a cold-cured bisphenolic epoxy resin modified with the addition of calcium carbonate filler, typically employed as structural adhesive. [...] Read more.

The purpose of this study was to assess the effects of different aqueous environments (i.e., demineralised, distilled and spring water) on the mechanical properties of a cold-cured bisphenolic epoxy resin modified with the addition of calcium carbonate filler, typically employed as structural adhesive. The parameters selected for the analysis have been; the kind of curing agent employed to cure the epoxy resin at ambient temperature (i.e., Mannich base and triethylenetetramine); the load of calcium carbonate added to liquid epoxy (i.e., from 1 to 3 g per 100 g of resin) and; the duration of the exposure to the different aging conditions (i.e., from 1 to 10 months). Cylindrical specimens of calcium carbonate-modified epoxy systems were tested in compression mode, before and after each of the aging regimes. The effect of the selected curing agents is very small, and they are both suitable for a cure at ambient temperature, on the unfilled epoxy on compressive maximum strength and strain at break; the choice of the hardener affects instead the compressive modulus. The CaCO3 amount was demonstrated to have a significant effect on the mechanical characteristics of un-aged epoxy systems, leading to growth in compressive modulus and maximum strength with reductions in strain at break. Generally speaking, the aging time noticeably affects the compressive properties of calcium carbonate-modified epoxies while almost negligible is the kind of water employed in each exposure regime. Notwithstanding the adverse effects of an aqueous environment on compressive mechanical properties of CaCO₃-filled epoxies, these systems keep compressive modulus and maximum strength greater than, and close to, respectively, the same characteristics measured on unaged unfilled control epoxies, demonstrating the positive effect of the addition of this kind of filler to epoxy-based structural adhesives, especially with the addition of 2 and 3 g of CaCO₃ per 100 g resin. The results obtained in this study demonstrated that it is possible to contrast the detrimental effects observed in cold-cured epoxy-based structural adhesives due to their aging in water upon the addition of limited amounts (particularly at 2 and 3 g per 100 g resin) of a cheap CaCO₃ filler. Full article

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Open AccessArticle

Flax/PP and Flax/PLA Thermoplastic Composites: Influence of Fire Retardants on the Individual Components

by

Baljinder K. Kandola

,

Wiwat Pornwannachai

and

John Russell Ebdon

Polymers 2020, 12(11), 2452; https://doi.org/10.3390/polym12112452 - 23 Oct 2020

Cited by 5 | Viewed by 2279

Abstract

This study is based on previously reported reaction to fire properties of flax fibre-reinforced polymeric (polypropylene, PP and polylactic acid, PLA) composites, prepared by pre-treating the fabrics with different fire retardants (FRs) prior to composite preparation. It was observed that while all of [...] Read more.

This study is based on previously reported reaction to fire properties of flax fibre-reinforced polymeric (polypropylene, PP and polylactic acid, PLA) composites, prepared by pre-treating the fabrics with different fire retardants (FRs) prior to composite preparation. It was observed that while all of these treatments were very effective in flax/PLA in terms of achieving a V-0 rating in a UL-94 test, only an organophosphonate FR was capable of achieving a V-0 rating for flax/PP. However, all fire-retardant treatments impaired the mechanical properties of the composites; the reduction was more in flax/PLA compared to flax/PP composites. To understand these effects further, here thermal analysis and pyrolysis combustion flow calorimetry of the composites and each component separately treated with FRs have been conducted and the results analysed in terms of the effect on each component so as to observe any interaction between the different components. The results indicated that in flax/PLA composites, the water released during FR catalysed dehydration-decomposition of flax may hydrolyse PLA, changing decomposition pathway of PLA to produce less flammable volatile, hence resulting in reduced flammability. Full article

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Open AccessArticle

Flame-Retardant Mechanism and Mechanical Properties of Wet-Spun Poly(acrylonitrile-co-vinylidene chloride) Fibers with Antimony Trioxide and Zinc Hydroxystannate

by

,

,

,

and

Polymers 2020, 12(11), 2442; https://doi.org/10.3390/polym12112442 - 22 Oct 2020

Cited by 7 | Viewed by 2170

Abstract

To produce flame retardant poly(acrylonitrile-co-vinylidene chloride) (PANVDC) fibers with limiting oxygen index (LOI) values above 28%, flame retardants are added to fibers. Because antimony trioxide (ATO) used widely for PANVDC is suspected as a carcinogen, non-toxic zinc hydroxystannate (ZHS) could be the alternative [...] Read more.

To produce flame retardant poly(acrylonitrile-co-vinylidene chloride) (PANVDC) fibers with limiting oxygen index (LOI) values above 28%, flame retardants are added to fibers. Because antimony trioxide (ATO) used widely for PANVDC is suspected as a carcinogen, non-toxic zinc hydroxystannate (ZHS) could be the alternative for reduction of ATO usage. Moreover, a flame retardant efficiency of the combination of ATO with ZHS could be expected because it was reported that ATO resists flame in the gas phase, whereas ZHS reacts in the condensed phase. Therefore, this study discussed the flame retardant mechanisms of ATO and ZHS in PANVDC, and evaluated the efficiency of the combination. PANVDC fibers with ATO and ZHS in 15 phr were produced by wet spinning. When ZHS was added, a more cyclized structure was detected (e.g., 1-methylnaphthalene) through pyrolysis−gas chromatography-mass spectrometry (Py-GC/MS). As a result of SEM-EDX analysis, Sb and Cl hardly remained in char layers of PANVDC-ATO; meanwhile, Zn, Sn, and Cl remained in that of PANVDC-ZHS. This implied that SbCl₃ from reaction of ATO and HCl reacts in the gas phase, whereas ZnCl₂ and SnCl₂ from ZHS and HCl promotes the cyclization reaction of PANVDC in the condensed phase. The LOI values of PANVDC, PANVDC-ATO, and PANVDC-ZHS were 26.4%, 29.0%, and 33.5%, respectively. This suggests that ZHS is a highly effective for PANVDC. Meanwhile, the LOI of PANVDC containing ATO-ZHS mixture is 31.0%. The combination of ATO and ZHS exhibited no efficiency. The addition of ATO and ZHS slightly reduced the tenacities of the fibers, respectively, 3.11 and 3.75 from 4.42 g/den. Full article

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Open AccessArticle

Reliability-Based Evaluation of the Suitability of Polymers for Additive Manufacturing Intended for Extreme Operating Conditions

by

Alvaro Rodríguez-Prieto

,

Ernesto Primera

,

Manuel Callejas

and

Ana M. Camacho

Polymers 2020, 12(10), 2327; https://doi.org/10.3390/polym12102327 - 12 Oct 2020

Cited by 2 | Viewed by 2033

Abstract

A reliability engineering program must be implemented from the conceptual phase of the physical asset to define the performance requirements of the components and equipment. Thus, in this work, the aim is to find the most optimal solution to manufacture polymer-based parts for [...] Read more.

A reliability engineering program must be implemented from the conceptual phase of the physical asset to define the performance requirements of the components and equipment. Thus, in this work, the aim is to find the most optimal solution to manufacture polymer-based parts for the nuclear power industry using additive manufacturing routes. This case study application has been selected because polymers processed by additive manufacturing (AM) can be well suited for nuclear applications. The methodology includes—firstly—an analysis of the suitability of materials based on high-temperature resistance, thermal aging and irradiation tolerance, considering operation conditions. Secondly, an analysis of materials’ processability considering their associated AM routes is performed based on thermal analysis and evaluation of physical properties of materials. A final assessment integrating the in-service suitability and AM processability is performed using a reliability approach, solving different emerging objective conflicts through defined constraints and selection criteria. According to the integrated in-service performance evaluation: Polypropylene-ethylene polyallomer (PPP), Epoxy (EP), Phenolics (Ph), Polyurethane (PU) and Acrylonitrile butadiene rubber (NBR) are the best options for mild operation conditions and EP, Ph and PU, considering high temperature along with radiation exposure. Considering AM techniques: EP and Ph can be manufactured using VAT photopolymerization-stereolithography (VP-SLA) with a good expected processability being these materials valid for high temperature environments. Consequently, this research work analyzes the viability, processability and in-service behavior of parts. Full article

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Open AccessArticle

The Toxicological Testing and Thermal Decomposition of Drive and Transport Belts Made of Thermoplastic Multilayer Polymer Materials

by

,

,

,

,

and

Dorota Czarnecka-Komorowska

Polymers 2020, 12(10), 2232; https://doi.org/10.3390/polym12102232 - 28 Sep 2020

Cited by 16 | Viewed by 2778

Abstract

The article presents the potential impact of flat drive and transport belts on people’s safety during a fire. The analysis distinguished belts made of classically used fabric–rubber composite materials reinforced with cord and currently used multilayer polymer composites. Moreover, the products’ multilayers during [...] Read more.

The article presents the potential impact of flat drive and transport belts on people’s safety during a fire. The analysis distinguished belts made of classically used fabric–rubber composite materials reinforced with cord and currently used multilayer polymer composites. Moreover, the products’ multilayers during the thermal decomposition and combustion can be a source of emissions for unpredictable and toxic substances with different concentrations and compositions. In the evaluation of the compared belts, a testing methodology was used to determine the toxicometric indicators (W_LC50SM) on the basis of which it was possible to determine the toxicity of thermal decomposition and combustion products in agreement with the standards in force in several countries of the EU and Russia. The analysis was carried out on the basis of the registration of emissions of chemical compounds during the thermal decomposition and combustion of polymer materials at three different temperatures. Moreover, the degradation kinetics of the polymeric belts by using the thermogravimetric (TGA) technique was evaluated. Test results have shown that products of thermal decomposition resulting from the neoprene (NE22), leder leder (LL2), thermoplastic connection (TC), and extra high top cower (XH) belts can be characterized as moderately toxic or toxic. Their toxicity significantly increases with the increasing temperature of thermal decomposition or combustion, especially above 450 °C. The results showed that the belts made of several layers of polyamide can be considered the least toxic in fire conditions. The TGA results showed that NBR/PA/PA/NBR belt made with two layers of polyamide and the acrylonitrile–butadiene rubber has the highest thermal stability in comparison to other belts. Full article

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Open AccessArticle

Characterization and Long-Term Stability of Historical PMMA: Impact of Additives and Acrylic Sheet Industrial Production Processes

by

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,

,

,

,

Maria Helena Casimiro

,

Luís M. Ferreira

and

Maria João Melo

Polymers 2020, 12(10), 2198; https://doi.org/10.3390/polym12102198 - 25 Sep 2020

Cited by 15 | Viewed by 4300 | Correction

Abstract

This work aims at understanding the influence of the production processes and materials in the properties and long term behavior of acrylic sheet, i.e., poly(methyl methacrylate) (PMMA), a material generally considered very stable in museum collections. A comparative study was conducted in samples [...] Read more.

This work aims at understanding the influence of the production processes and materials in the properties and long term behavior of acrylic sheet, i.e., poly(methyl methacrylate) (PMMA), a material generally considered very stable in museum collections. A comparative study was conducted in samples from cast acrylic sheets produced in the early 2000s, from which manufacturing details were known, and samples provided by the artist Lourdes Castro from acrylic sheets she had bought in the 1960s. Transparent and red opaque cast acrylic samples, containing cadmium red pigment, were used. All samples were artificially aged in a solarbox with irradiation λ > 300 nm for a total period of 8000 h, and alterations were followed by a multi-analytical approach which included Raman, infrared (FTIR-ATR) and UV-Vis spectroscopies; gravimetry; size exclusion chromatography (SEC); thermogravimetry (TGA); micro-indentation; colorimetry; and optical microscopy. Not all cast PMMA sheets presented similar stabilities. We have concluded that the production processes (which may include the polymerization conditions, the organic additives and the origin of the monomer) play a more important role in the properties and long-term behavior of these acrylic sheets than the presence of cadmium red and/or the age of the material. Full article

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Open AccessArticle

Degradation of Mechanical Properties of Pine Wood Under Symmetric Axial Cyclic Loading Parallel to Grain

by

Mariana D. Stanciu

,

Horațiu D. Teodorescu

and

Sorin Vlase

Polymers 2020, 12(10), 2176; https://doi.org/10.3390/polym12102176 - 23 Sep 2020

Cited by 1 | Viewed by 2446

Abstract

The mechanical properties of wood, respectively the elastic, plastic, and strength properties, depend on a large number of factors, due both to its structural and physical characteristics, as well as to the size, direction, nature, and speed of application of forces. Wood, generally [...] Read more.

The mechanical properties of wood, respectively the elastic, plastic, and strength properties, depend on a large number of factors, due both to its structural and physical characteristics, as well as to the size, direction, nature, and speed of application of forces. Wood, generally considered to be a viscous-elastic material, has creep deformations over time under the effect of a constant load. In this study the behavior of pine wood samples was investigated due to its large utilization in different finished products, such as roof construction, furniture, outdoor applications, garden furniture, and toys. The paper aims to analyze the viscoelastic behavior of pine wood subjected to cyclically loading to traction-compression with different loads (1 kN; 1.5 kN; 2 kN), applied at different speeds (1 mm/min; 10 mm/min). It was observed that, at low speeds (1 mm/min) and low intensities of the applied force, it was possible to distinguish the three creep regions specific to wood: the primary area (primary flow), the secondary area, and finally the tertiary creep. As the force increases, the law of variation of the wood flow changes. The degradation of longitudinal elasticity modulus occurs with the increase of the number of cycles, so after 20 alternating symmetrical cycles of traction-compression of the pine wood samples, there is a decrease of its values by 35%. Full article

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