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Recent Advancements of Bio-Derived Flame Retardants for Polymeric Materials.
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-20 DOI: 10.3390/polym17020249
Min Chen, Qinhe Guo, Yao Yuan, Ao Li, Bo Lin, Yi Xiao, Lulu Xu, Wei Wang

The sustainable flame retardancy of polymeric materials is a key focus for the direction of the next generation in the field of fire safety. Bio-derived flame retardants are gaining attention as environmentally friendly additives due to their low ecological impact and decreasing costs. These compounds can enhance char formation in polymeric materials by swelling upon heating, attributed to their functional groups. This review explores various biomolecules used as flame retardants, including phytic acid, chitosan, lignin, tannic acid, and bio-derived phosphorus and nitrogen compounds, emphasizing their flame-retardant properties and compatibility with different polymer matrices. The primary focus is on the structural characteristics, modifications, and flame-retardant behaviors of these bio-derived additives, particularly regarding their mechanisms of action within polymeric materials. Finally, the review explores the opportunities, current challenges, and future directions for the practical application of bio-derived flame retardants in polymer materials.

{"title":"Recent Advancements of Bio-Derived Flame Retardants for Polymeric Materials.","authors":"Min Chen, Qinhe Guo, Yao Yuan, Ao Li, Bo Lin, Yi Xiao, Lulu Xu, Wei Wang","doi":"10.3390/polym17020249","DOIUrl":"10.3390/polym17020249","url":null,"abstract":"<p><p>The sustainable flame retardancy of polymeric materials is a key focus for the direction of the next generation in the field of fire safety. Bio-derived flame retardants are gaining attention as environmentally friendly additives due to their low ecological impact and decreasing costs. These compounds can enhance char formation in polymeric materials by swelling upon heating, attributed to their functional groups. This review explores various biomolecules used as flame retardants, including phytic acid, chitosan, lignin, tannic acid, and bio-derived phosphorus and nitrogen compounds, emphasizing their flame-retardant properties and compatibility with different polymer matrices. The primary focus is on the structural characteristics, modifications, and flame-retardant behaviors of these bio-derived additives, particularly regarding their mechanisms of action within polymeric materials. Finally, the review explores the opportunities, current challenges, and future directions for the practical application of bio-derived flame retardants in polymer materials.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768275/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Electrospinning Membrane with Polyacrylate Mixed Beta-Cyclodextrin: An Efficient Adsorbent for Cationic Dyes.
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-20 DOI: 10.3390/polym17020243
Chunling Zheng, Wei Zhao, Xiaoqian Tu, Shaoqiang Zhou

A simple and non-chemical binding nanofiber (β-CD/PA) adsorbent was obtained by electrospinning a mixture of β-cyclodextrin (β-CD) and polyacrylate (PA). The cationic dyes in wastewater were removed by the host-guest inclusion complex of the β-cyclodextrin and the electrostatic interaction between the polyacrylate and the dyes groups. The influence of the content of β-cyclodextrin on the surface morphology and adsorption capacity of the nanofiber membrane was discussed, and the optimized adsorption capacity of nanofiber adsorption material was determined. The adsorption capacity of nanofiber adsorbents for basic red 9, basic red 14, basic red 46, basic blue 9, basic yellow 19 and basic yellow 28 was 86.71 mg/g, 21.513 mg/g, 18.926 mg/g, 44.525 mg/g, 116.516 mg/g and 155.206 mg/g, respectively. The effects of different initial concentrations and pH values on the adsorption properties of adsorbent materials were studied. The kinetic analysis showed that the adsorption process of nanofibers for cationic dyes was more in line with the pseudo-second-order kinetic adsorption model. Moreover, nanofiber adsorbent could be easily separated from the dye solution and showed high recycling efficiency. These results indicated that the β-cyclodextrin/polyacrylate composite nanofibers are expected to be recyclable adsorbents in dye wastewater treatment.

{"title":"Electrospinning Membrane with Polyacrylate Mixed Beta-Cyclodextrin: An Efficient Adsorbent for Cationic Dyes.","authors":"Chunling Zheng, Wei Zhao, Xiaoqian Tu, Shaoqiang Zhou","doi":"10.3390/polym17020243","DOIUrl":"10.3390/polym17020243","url":null,"abstract":"<p><p>A simple and non-chemical binding nanofiber (<i>β</i>-CD/PA) adsorbent was obtained by electrospinning a mixture of <i>β</i>-cyclodextrin (<i>β</i>-CD) and polyacrylate (PA). The cationic dyes in wastewater were removed by the host-guest inclusion complex of the <i>β</i>-cyclodextrin and the electrostatic interaction between the polyacrylate and the dyes groups. The influence of the content of <i>β</i>-cyclodextrin on the surface morphology and adsorption capacity of the nanofiber membrane was discussed, and the optimized adsorption capacity of nanofiber adsorption material was determined. The adsorption capacity of nanofiber adsorbents for basic red 9, basic red 14, basic red 46, basic blue 9, basic yellow 19 and basic yellow 28 was 86.71 mg/g, 21.513 mg/g, 18.926 mg/g, 44.525 mg/g, 116.516 mg/g and 155.206 mg/g, respectively. The effects of different initial concentrations and pH values on the adsorption properties of adsorbent materials were studied. The kinetic analysis showed that the adsorption process of nanofibers for cationic dyes was more in line with the pseudo-second-order kinetic adsorption model. Moreover, nanofiber adsorbent could be easily separated from the dye solution and showed high recycling efficiency. These results indicated that the <i>β</i>-cyclodextrin/polyacrylate composite nanofibers are expected to be recyclable adsorbents in dye wastewater treatment.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768981/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Exploring the Effect of Annealing on PLA/Carbon Nanotube Nanocomposites: In Search of Efficient PLA/MWCNT Nanocomposites for Electromagnetic Shielding.
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-20 DOI: 10.3390/polym17020246
Flávio Urbano da Silva, Carlos Bruno Barreto Luna, Fabiano Santana da Silva, José Vinícius Melo Barreto, Debora Pereira Schmitz, Bluma Guenther Soares, Renate Maria Ramos Wellen, Edcleide Maria Araújo

In this research, poly(lactic acid) (PLA) nanocomposites with multi-walled carbon nanotubes (MWCNT) were produced by extrusion, injection, and compression molding, focusing on electromagnetic shielding. Various amounts of carbon nanotubes (MWCNTs) were tested in PLA matrix, specifically ranging from 1 to 4 parts per hundred resin (phr). The resulting nanocomposites were analyzed before and after undergoing annealing heat treatment. It was observed that as the MWCNT content increased, the melt flow index of PLA decreased. This reduction indicates that the nanotubes were effectively accommodated into the PLA chain. The PLA/MWCNT (2 phr) formulation presented the greatest balance of properties, with potential for electromagnetic shielding application. Scanning electron microscopy (SEM) demonstrated that incorporating 2 phr of carbon nanotubes in PLA promoted good distribution, favoring high electrical conductivity and electromagnetic shielding between 20-22 dB (8.2-18 GHz), corresponding to approximately 99% attenuation. Furthermore, its properties, such as elastic modulus (3156 MPa), tensile strength (65.1 MPa), hardness (77.8 Shore D), and heat deflection temperature (55.3 °C), increased compared to pure PLA. After annealing, the PLA/MWCNT (2 phr) nanocomposite underwent a molecular reordering, resulting in an increased crystalline fraction, as confirmed by X-ray diffraction (XRD). However, the electrical conductivity maintained the same order of magnitude, while the electromagnetic shielding varied from 19.7 to 20 dB. The results indicate that these nanocomposites are promising for electromagnetic shielding applications and can be manufactured in the molten state.

{"title":"Exploring the Effect of Annealing on PLA/Carbon Nanotube Nanocomposites: In Search of Efficient PLA/MWCNT Nanocomposites for Electromagnetic Shielding.","authors":"Flávio Urbano da Silva, Carlos Bruno Barreto Luna, Fabiano Santana da Silva, José Vinícius Melo Barreto, Debora Pereira Schmitz, Bluma Guenther Soares, Renate Maria Ramos Wellen, Edcleide Maria Araújo","doi":"10.3390/polym17020246","DOIUrl":"10.3390/polym17020246","url":null,"abstract":"<p><p>In this research, poly(lactic acid) (PLA) nanocomposites with multi-walled carbon nanotubes (MWCNT) were produced by extrusion, injection, and compression molding, focusing on electromagnetic shielding. Various amounts of carbon nanotubes (MWCNTs) were tested in PLA matrix, specifically ranging from 1 to 4 parts per hundred resin (phr). The resulting nanocomposites were analyzed before and after undergoing annealing heat treatment. It was observed that as the MWCNT content increased, the melt flow index of PLA decreased. This reduction indicates that the nanotubes were effectively accommodated into the PLA chain. The PLA/MWCNT (2 phr) formulation presented the greatest balance of properties, with potential for electromagnetic shielding application. Scanning electron microscopy (SEM) demonstrated that incorporating 2 phr of carbon nanotubes in PLA promoted good distribution, favoring high electrical conductivity and electromagnetic shielding between 20-22 dB (8.2-18 GHz), corresponding to approximately 99% attenuation. Furthermore, its properties, such as elastic modulus (3156 MPa), tensile strength (65.1 MPa), hardness (77.8 Shore D), and heat deflection temperature (55.3 °C), increased compared to pure PLA. After annealing, the PLA/MWCNT (2 phr) nanocomposite underwent a molecular reordering, resulting in an increased crystalline fraction, as confirmed by X-ray diffraction (XRD). However, the electrical conductivity maintained the same order of magnitude, while the electromagnetic shielding varied from 19.7 to 20 dB. The results indicate that these nanocomposites are promising for electromagnetic shielding applications and can be manufactured in the molten state.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768199/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Production and Characterization of H. perforatum Oil-Loaded, Semi-Resorbable, Tri-Layered Hernia Mesh.
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-19 DOI: 10.3390/polym17020240
Özlem Eğri, Feyza Güneş, Sinan Eğri

Hernia repair is the most common surgical operation applied worldwide. Mesh prostheses are used to support weakened or damaged tissue to decrease the risk of hernia recurrence. However, the patches currently used in clinic applications have significant short-term and long-term risks. This study aimed to design, produce, and characterize a three-layered semi-resorbable composite hernia mesh using the electrospinning technique, where the upper layer (parietal side) was made of non-resorbable polypropylene (PP-Cl) fibers, the partially resorbable middle layer was made of PP-Cl and polycaprolactone (PCL) fibers, and the fully resorbable lower layer (visceral side) was made of H. perforatum oil-loaded polyethylene glycol (PEG) fibers. The extracellular matrix-like fibrous structure of the patches provided low density and high porosity, minimizing the risk of long-term foreign body reactions, and the hydrophilic/hydrophobic character of the surfaces and the detected swelling rates supported biocompatibility. The patches exhibited mechanical properties comparable to commercially available products. Controlled release of therapeutic oil could be achieved from the oil-integrated patches due to the dissolution of PEG in the acute process. In vitro cell culture studies with the L929 mouse fibroblast cell line revealed that the meshes do not have a cytotoxic nor a biomaterial-induced necrotic effect that will induce apoptosis of the cells. The visceral side of the meshes exhibited non-adherence of cell-like structures to the surface due to the dissolution of PEG. The composite hernia patches were concluded to reduce the risk of adhering to internal organs in the hernia area, have the potential to be used in in vivo biomedical applications, and will support the search for an ideal hernia mesh that can be used in the treatment of abdominal hernias.

{"title":"Production and Characterization of <i>H. perforatum</i> Oil-Loaded, Semi-Resorbable, Tri-Layered Hernia Mesh.","authors":"Özlem Eğri, Feyza Güneş, Sinan Eğri","doi":"10.3390/polym17020240","DOIUrl":"10.3390/polym17020240","url":null,"abstract":"<p><p>Hernia repair is the most common surgical operation applied worldwide. Mesh prostheses are used to support weakened or damaged tissue to decrease the risk of hernia recurrence. However, the patches currently used in clinic applications have significant short-term and long-term risks. This study aimed to design, produce, and characterize a three-layered semi-resorbable composite hernia mesh using the electrospinning technique, where the upper layer (parietal side) was made of non-resorbable polypropylene (PP-Cl) fibers, the partially resorbable middle layer was made of PP-Cl and polycaprolactone (PCL) fibers, and the fully resorbable lower layer (visceral side) was made of <i>H. perforatum</i> oil-loaded polyethylene glycol (PEG) fibers. The extracellular matrix-like fibrous structure of the patches provided low density and high porosity, minimizing the risk of long-term foreign body reactions, and the hydrophilic/hydrophobic character of the surfaces and the detected swelling rates supported biocompatibility. The patches exhibited mechanical properties comparable to commercially available products. Controlled release of therapeutic oil could be achieved from the oil-integrated patches due to the dissolution of PEG in the acute process. In vitro cell culture studies with the L929 mouse fibroblast cell line revealed that the meshes do not have a cytotoxic nor a biomaterial-induced necrotic effect that will induce apoptosis of the cells. The visceral side of the meshes exhibited non-adherence of cell-like structures to the surface due to the dissolution of PEG. The composite hernia patches were concluded to reduce the risk of adhering to internal organs in the hernia area, have the potential to be used in in vivo biomedical applications, and will support the search for an ideal hernia mesh that can be used in the treatment of abdominal hernias.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768532/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041006","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Effects of Hydroxyapatite Additions on Alginate Gelation Kinetics During Cross-Linking.
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-19 DOI: 10.3390/polym17020242
Katarina Dimic-Misic, Monir Imani, Michael Gasik
<p><p>Alginate hydrogels have gathered significant attention in biomedical engineering due to their remarkable biocompatibility, biodegradability, and ability to encapsulate cells and bioactive molecules, but much less has been reported on the kinetics of gelation. Scarce experimental data are available on cross-linked alginates (AL) with bioactive components. The present study addressed a novel method for defining the crosslinking mechanism using rheological measurements for aqueous mixtures of AL and calcium chloride (CaCl<sub>2</sub>) with the presence of hydroxyapatite (HAp) as filler particles. The time-dependent crosslinking behaviour of these mixtures was exploited using a plate-plate rheometer, when crosslinking occurs due to calcium ions (Ca<sup>2+</sup>) binding to the guluronic acid blocks within the AL polymer, forming a stable "egg-box" structure. To reveal the influence of HAp particles as filler on crosslinked sample morphology, after rheological measurement and crosslinking, crosslinked samples were freeze-dried and their morphology was assessed using an optical microscope and SEM. It was found that the addition of HAp particles, which are known to enhance the mechanical properties and biocompatibility of crosslinked AL gels, significantly decreased (usually rapidly) the interaction between the Ca<sup>2+</sup> and AL chains. In this research, the physical "shielding" effect of HAp particles on the crosslinking of AL with Ca<sup>2+</sup> ions has been observed for the first time, and its crosslinking behaviour was defined using rheological methods. After crosslinking and rheometer measurements, the samples were further evaluated for morphological properties and the observations were correlated with their dewatering properties. While the presence of HAp particles led to a slower crosslinking process and a more uniform development of the rheological parameters, it also led to a more uniform porosity and improved dewatering properties. The observed effects allow for a better understanding of the crosslinking process kinetics, which directly affects the physical and chemical properties of the AL gels. The shielding behaviour (retardation) of filler particles occurs when they physically or chemically block certain components in a mixture, delaying their interaction with other reactants. In hydrogel formulations, filler particles like hydroxyapatite (HAp) can act as barriers, adsorbing onto reactive components or creating physical separation, which slows the reaction rate and allows for controlled gelation or delayed crosslinking. This delayed reactivity is beneficial for precise control over the reaction timing, enabling the better manipulation of material properties such as crosslinking distribution, pore structure, and mechanical stability. In this research, the physical shielding effect of HAp particles was observed through changes in rheological properties during crosslinking and was dependent on the HAp concentration. The addition
{"title":"Effects of Hydroxyapatite Additions on Alginate Gelation Kinetics During Cross-Linking.","authors":"Katarina Dimic-Misic, Monir Imani, Michael Gasik","doi":"10.3390/polym17020242","DOIUrl":"10.3390/polym17020242","url":null,"abstract":"&lt;p&gt;&lt;p&gt;Alginate hydrogels have gathered significant attention in biomedical engineering due to their remarkable biocompatibility, biodegradability, and ability to encapsulate cells and bioactive molecules, but much less has been reported on the kinetics of gelation. Scarce experimental data are available on cross-linked alginates (AL) with bioactive components. The present study addressed a novel method for defining the crosslinking mechanism using rheological measurements for aqueous mixtures of AL and calcium chloride (CaCl&lt;sub&gt;2&lt;/sub&gt;) with the presence of hydroxyapatite (HAp) as filler particles. The time-dependent crosslinking behaviour of these mixtures was exploited using a plate-plate rheometer, when crosslinking occurs due to calcium ions (Ca&lt;sup&gt;2+&lt;/sup&gt;) binding to the guluronic acid blocks within the AL polymer, forming a stable \"egg-box\" structure. To reveal the influence of HAp particles as filler on crosslinked sample morphology, after rheological measurement and crosslinking, crosslinked samples were freeze-dried and their morphology was assessed using an optical microscope and SEM. It was found that the addition of HAp particles, which are known to enhance the mechanical properties and biocompatibility of crosslinked AL gels, significantly decreased (usually rapidly) the interaction between the Ca&lt;sup&gt;2+&lt;/sup&gt; and AL chains. In this research, the physical \"shielding\" effect of HAp particles on the crosslinking of AL with Ca&lt;sup&gt;2+&lt;/sup&gt; ions has been observed for the first time, and its crosslinking behaviour was defined using rheological methods. After crosslinking and rheometer measurements, the samples were further evaluated for morphological properties and the observations were correlated with their dewatering properties. While the presence of HAp particles led to a slower crosslinking process and a more uniform development of the rheological parameters, it also led to a more uniform porosity and improved dewatering properties. The observed effects allow for a better understanding of the crosslinking process kinetics, which directly affects the physical and chemical properties of the AL gels. The shielding behaviour (retardation) of filler particles occurs when they physically or chemically block certain components in a mixture, delaying their interaction with other reactants. In hydrogel formulations, filler particles like hydroxyapatite (HAp) can act as barriers, adsorbing onto reactive components or creating physical separation, which slows the reaction rate and allows for controlled gelation or delayed crosslinking. This delayed reactivity is beneficial for precise control over the reaction timing, enabling the better manipulation of material properties such as crosslinking distribution, pore structure, and mechanical stability. In this research, the physical shielding effect of HAp particles was observed through changes in rheological properties during crosslinking and was dependent on the HAp concentration. The addition ","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768125/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Interactive Coupling Relaxation of Dipoles and Wagner Charges in the Amorphous State of Polymers Induced by Thermal and Electrical Stimulations: A Dual-Phase Open Dissipative System Perspective.
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-19 DOI: 10.3390/polym17020239
Jean Pierre Ibar

This paper addresses the author's current understanding of the physics of interactions in polymers under a voltage field excitation. The effect of a voltage field coupled with temperature to induce space charges and dipolar activity in dielectric materials can be measured by very sensitive electrometers. The resulting characterization methods, thermally stimulated depolarization (TSD) and thermal-windowing deconvolution (TWD), provide a powerful way to study local and cooperative relaxations in the amorphous state of matter that are, arguably, essential to understanding the glass transition, molecular motions in the rubbery and molten states and even the processes leading to crystallization. Specifically, this paper describes and tries to explain 'interactive coupling' between molecular motions in polymers by their dielectric relaxation characteristics when polymeric samples have been submitted to thermally induced polarization by a voltage field followed by depolarization at a constant heating rate. Interactive coupling results from the modulation of the local interactions by the collective aspect of those interactions, a recursive process pursuant to the dynamics of the interplay between the free volume and the conformation of dual-conformers, two fundamental basic units of the macromolecules introduced by this author in the "dual-phase" model of interactions. This model reconsiders the fundamentals of the TSD and TWD results in a different way: the origin of the dipoles formation, induced or permanent dipoles; the origin of the Wagner space charges and the Tg,ρ transition; the origin of the TLL manifestation; the origin of the Debye elementary relaxations' compensation or parallelism in a relaxation map; and finally, the dual-phase origin of their super-compensations. In other words, this paper is an attempt to link the fundamentals of TSD and TWD activation and deactivation of dipoles that produce a current signal with the statistical parameters of the "dual-phase" model of interactions underlying the Grain-Field Statistics.

{"title":"Interactive Coupling Relaxation of Dipoles and Wagner Charges in the Amorphous State of Polymers Induced by Thermal and Electrical Stimulations: A Dual-Phase Open Dissipative System Perspective.","authors":"Jean Pierre Ibar","doi":"10.3390/polym17020239","DOIUrl":"10.3390/polym17020239","url":null,"abstract":"<p><p>This paper addresses the author's current understanding of the physics of interactions in polymers under a voltage field excitation. The effect of a voltage field coupled with temperature to induce space charges and dipolar activity in dielectric materials can be measured by very sensitive electrometers. The resulting characterization methods, thermally stimulated depolarization (TSD) and thermal-windowing deconvolution (TWD), provide a powerful way to study local and cooperative relaxations in the amorphous state of matter that are, arguably, essential to understanding the glass transition, molecular motions in the rubbery and molten states and even the processes leading to crystallization. Specifically, this paper describes and tries to explain 'interactive coupling' between molecular motions in polymers by their dielectric relaxation characteristics when polymeric samples have been submitted to thermally induced polarization by a voltage field followed by depolarization at a constant heating rate. Interactive coupling results from the modulation of the local interactions by the collective aspect of those interactions, a recursive process pursuant to the dynamics of the interplay between the free volume and the conformation of dual-conformers, two fundamental basic units of the macromolecules introduced by this author in the \"dual-phase\" model of interactions. This model reconsiders the fundamentals of the TSD and TWD results in a different way: the origin of the dipoles formation, induced or permanent dipoles; the origin of the Wagner space charges and the T<sub>g,ρ</sub> transition; the origin of the T<sub>LL</sub> manifestation; the origin of the Debye elementary relaxations' compensation or parallelism in a relaxation map; and finally, the dual-phase origin of their super-compensations. In other words, this paper is an attempt to link the fundamentals of TSD and TWD activation and deactivation of dipoles that produce a current signal with the statistical parameters of the \"dual-phase\" model of interactions underlying the Grain-Field Statistics.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768542/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041469","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
An Extensive Study of an Eco-Friendly Fireproofing Process of Lignocellulosic Miscanthus × giganteus Particles and Their Application in Flame-Retardant Panels.
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-19 DOI: 10.3390/polym17020241
Yasmina Khalaf, Rodolphe Sonnier, Nicolas Brosse, Roland El Hage

Increasing the flame retardancy of lignocellulosic materials such as Miscanthus × giganteus can effectively enable their wide use. This study examines the fireproofing process of Miscanthus particles using an eco-friendly process by grafting phytic acid and urea in aqueous solution. Miscanthus particles underwent a steam explosion step before being grafted. Fireproof binderless particle panels were manufactured from miscanthus particles with or without adding olive pomace by hot-pressing. The effect of the steam explosion and/or the flame-retardant treatment on the morphology, chemical composition and thermal stability of the particles, as well as the thermal stability of the panels, was investigated. The results showed that water impregnation followed by a steam explosion at 210 °C for 8 min resulted in particles that were rich in lignin and more homogeneous in size (length and width). Fireproof particles were produced with relatively low P and N contents. The flame retardancy of the binderless particle panels was significantly improved when using miscanthus particles treated with phytic acid and urea, as shown by a reduced heat release (HRR) and an increased time-to-ignition. However, the presence of olive pomace significantly decreased the flame retardancy of the panels. Binderless particle panels prepared from grafted miscanthus particles showed the best fire properties and are considered fireproof.

{"title":"An Extensive Study of an Eco-Friendly Fireproofing Process of Lignocellulosic <i>Miscanthus</i> × <i>giganteus</i> Particles and Their Application in Flame-Retardant Panels.","authors":"Yasmina Khalaf, Rodolphe Sonnier, Nicolas Brosse, Roland El Hage","doi":"10.3390/polym17020241","DOIUrl":"10.3390/polym17020241","url":null,"abstract":"<p><p>Increasing the flame retardancy of lignocellulosic materials such as <i>Miscanthus</i> × <i>giganteus</i> can effectively enable their wide use. This study examines the fireproofing process of Miscanthus particles using an eco-friendly process by grafting phytic acid and urea in aqueous solution. Miscanthus particles underwent a steam explosion step before being grafted. Fireproof binderless particle panels were manufactured from miscanthus particles with or without adding olive pomace by hot-pressing. The effect of the steam explosion and/or the flame-retardant treatment on the morphology, chemical composition and thermal stability of the particles, as well as the thermal stability of the panels, was investigated. The results showed that water impregnation followed by a steam explosion at 210 °C for 8 min resulted in particles that were rich in lignin and more homogeneous in size (length and width). Fireproof particles were produced with relatively low P and N contents. The flame retardancy of the binderless particle panels was significantly improved when using miscanthus particles treated with phytic acid and urea, as shown by a reduced heat release (HRR) and an increased time-to-ignition. However, the presence of olive pomace significantly decreased the flame retardancy of the panels. Binderless particle panels prepared from grafted miscanthus particles showed the best fire properties and are considered fireproof.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768642/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041094","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Impact of Thermal Treatment and Aging on Lignin Properties in Spruce Wood: Pathways to Value-Added Applications.
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-18 DOI: 10.3390/polym17020238
František Kačík, Eva Výbohová, Tereza Jurczyková, Adriana Eštoková, Elena Kmeťová, Danica Kačíková

Thermal modification is an environmentally friendly process that does not utilize chemical agents to enhance the stability and durability of wood. The use of thermally modified wood results in a significantly extended lifespan compared with untreated wood, with minimal maintenance requirements, thereby reducing the carbon footprint. This study examines the impact of varying modification temperatures (160, 180, and 210 °C) on the lignin of spruce wood using the ThermoWood process and following the accelerated aging of thermally modified wood. Wet chemistry methods, including nitrobenzene oxidation (NBO), size exclusion chromatography (SEC), thermogravimetry (TG), differential thermogravimetry (DTG), and Fourier transform infrared spectroscopy (FTIR), were employed to investigate the alterations in lignin. At lower modification temperatures, the predominant reaction is the degradation of lignin, which results in a reduction in the molecular weight and an enhanced yield of NBO (vanillin and vanillic acid) products. At elevated temperatures, condensation and repolymerization reactions become the dominant processes, increasing these traits. The lignin content of aged wood is higher than that of thermally modified wood, which has a lower molecular weight and a lower decomposition temperature. The results demonstrate that lignin isolated from thermally modified wood at the end of its life cycle is a promising feedstock for carbon-based materials and the production of a variety of aromatic monomers, including phenols, aromatic aldehydes and acids, and benzene derivatives.

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引用次数: 0
Zero Waste Concept in Production of PLA Biocomposites Reinforced with Fibers Derived from Wild Plant (Spartium junceum L.) and Energy Crop (Sida hermaphrodita (L.) Rusby).
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-18 DOI: 10.3390/polym17020235
Zorana Kovačević, Ana Pilipović, Mario Meheš, Sandra Bischof

This research follows the principles of circular economy through the zero waste concept and cascade approach performed in two steps. Our paper focuses on the first step and explores the characteristics of developed biocomposite materials made from a biodegradable poly(lactic acid) polymer (PLA) reinforced with natural fibers isolated from the second generation of biomass (agricultural biomass and weeds). Two plants, Spartium junceum L. (SJL) and Sida hermaphrodita (SH), were applied. To enhance their mechanical, thermal, and antimicrobial properties, their modification was performed with environmentally friendly additives-linseed oil (LO), organo-modified montmorillonite nanoclay (MMT), milled cork (MC), and zinc oxide (ZnO). The results revealed that SH fibers exhibited 38.92% higher tensile strength than SJL fibers. Composites reinforced with SH fibers modified only with LO displayed a 27.33% increase in tensile strength compared to neat PLA. The addition of LO improved the thermal stability of both biocomposites by approximately 5-7 °C. Furthermore, the inclusion of MMT filler significantly reduced the flammability, lowering the heat release rate to 30.25%, and enabling the categorization of developed biocomposite in a group of flame retardants. In the second step, all waste streams generated during the fibers extraction process are repurposed into the production of solid biofuels (pellets, briquettes) or biogas (bio)methane.

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引用次数: 0
Damping Optimization and Energy Absorption of Mechanical Metamaterials for Enhanced Vibration Control Applications: A Critical Review.
IF 4.7 3区 工程技术 Q1 POLYMER SCIENCE Pub Date : 2025-01-18 DOI: 10.3390/polym17020237
Fayyaz, Salem Bashmal, Aamer Nazir, Sikandar Khan, Abdulrahman Alofi

Metamaterials are pushing the limits of traditional materials and are fascinating frontiers in scientific innovation. Mechanical metamaterials (MMs) are a category of metamaterials that display properties and performances that cannot be realized in conventional materials. Exploring the mechanical properties and various aspects of vibration and damping control is becoming a crucial research area. Their geometries have intricate features inspired by nature, which make them challenging to model and fabricate. The fabrication of MMs has become possible because of the emergence of additive manufacturing (AM) technology. Mechanical vibrations in engineering applications are common and depend on inertia, stiffness, damping, and external excitation. Vibration and damping control are important aspects of MM in vibrational environments and need to be enhanced and explored. This comprehensive review covers different vibration and damping control aspects of MMs fabricated using polymers and other engineering materials. Different morphological configurations of MMs are critically reviewed, covering crucial vibration aspects, including bandgap formation, energy absorption, and damping control to suppress, attenuate, isolate, and absorb vibrations. Bandgap formation using different MM configurations is presented and reviewed. Furthermore, studies on the energy dissipation and absorption of MMs are briefly discussed. In addition, the vibration damping of various lattice structures is reviewed along with their analytical modeling and experimental measurements. Finally, possible research gaps are highlighted, and a general systematic procedure to address these areas is suggested for future research. This review paper may lay a foundation for young researchers intending to start and pursue research on additive-manufactured MM lattice structures for vibration control applications.

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引用次数: 0
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Polymers
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