The removal and detection of highly toxic mercury(II) ions (Hg2+) in water used daily is essential for human health and monitoring environmental pollution. Efficient porous organic polymers (POPs) can provide a strong adsorption capacity toward heavy metal ions, although the complex synthetic process and inconvenient phase separation steps limit their application. Hence, a combination of POPs and magnetic nanomaterials was proposed and a new magnetic porous organic polymer adsorbent was fabricated by a green and mild redox reaction in the aqueous phase with trithiocyanuric acid (TA) and its sodium salts acting as reductive monomers and iodine acting as an oxidant. In the preparation steps, no additional harmful organic solvent is required and the byproducts of sodium iodine are generally considered to be non-toxic. The resulting magnetic poly(trithiocyanuric acid) polymers (MPTAPs) are highly porous, have large surface areas, are rich in sulfhydryl groups and show easy magnetic separation ability. The experimental results show that MPTAPs exhibit good adsorption affinity toward Hg2+ with high selectivity, rapid adsorption kinetics (10 min), a large adsorption capacity (211 mg g-1) and wide adsorption applicability under various pH environments (pH 2~8). Additionally, MPTAPs can be reused for up to 10 cycles, and the magnetic separation step of MPTAPs is fast and convenient, reducing energy consumption compared to centrifugation and filtration steps required for non-magnetic adsorbents. These results demonstrate the promising capability of MPTAPs as superior adsorbents for effective adsorption and separation of Hg2+. Based on this, the prepared MPTAPs were adopted as magnetic solid-phase extraction (MSPE) materials for isolation of trace Hg2+ from aqueous samples. Under optimized conditions, the extraction and quantification of trace Hg2+ in water samples were accomplished using inductively coupled plasma mass spectrometry (ICP-MS) detection after MSPE procedures. The proposed MPTAPs-based MSPE-ICP-MS method is efficient, rapid, sensitive and selective for the determination of trace Hg2+, and was successfully employed for the accurate analysis of trace Hg2+ in tap water, wastewater, lake water and river water samples.
{"title":"Green and Mild Fabrication of Magnetic Poly(trithiocyanuric acid) Polymers for Rapid and Selective Separation of Mercury(II) Ions in Aqueous Samples.","authors":"Qianqian Li, Boxian Ruan, Yue Yu, Linshu Ye, Aoxiong Dai, Sasha You, Bingshan Zhao, Limin Ren","doi":"10.3390/polym16213067","DOIUrl":"10.3390/polym16213067","url":null,"abstract":"<p><p>The removal and detection of highly toxic mercury(II) ions (Hg<sup>2+</sup>) in water used daily is essential for human health and monitoring environmental pollution. Efficient porous organic polymers (POPs) can provide a strong adsorption capacity toward heavy metal ions, although the complex synthetic process and inconvenient phase separation steps limit their application. Hence, a combination of POPs and magnetic nanomaterials was proposed and a new magnetic porous organic polymer adsorbent was fabricated by a green and mild redox reaction in the aqueous phase with trithiocyanuric acid (TA) and its sodium salts acting as reductive monomers and iodine acting as an oxidant. In the preparation steps, no additional harmful organic solvent is required and the byproducts of sodium iodine are generally considered to be non-toxic. The resulting magnetic poly(trithiocyanuric acid) polymers (MPTAPs) are highly porous, have large surface areas, are rich in sulfhydryl groups and show easy magnetic separation ability. The experimental results show that MPTAPs exhibit good adsorption affinity toward Hg<sup>2+</sup> with high selectivity, rapid adsorption kinetics (10 min), a large adsorption capacity (211 mg g<sup>-1</sup>) and wide adsorption applicability under various pH environments (pH 2~8). Additionally, MPTAPs can be reused for up to 10 cycles, and the magnetic separation step of MPTAPs is fast and convenient, reducing energy consumption compared to centrifugation and filtration steps required for non-magnetic adsorbents. These results demonstrate the promising capability of MPTAPs as superior adsorbents for effective adsorption and separation of Hg<sup>2+</sup>. Based on this, the prepared MPTAPs were adopted as magnetic solid-phase extraction (MSPE) materials for isolation of trace Hg<sup>2+</sup> from aqueous samples. Under optimized conditions, the extraction and quantification of trace Hg<sup>2+</sup> in water samples were accomplished using inductively coupled plasma mass spectrometry (ICP-MS) detection after MSPE procedures. The proposed MPTAPs-based MSPE-ICP-MS method is efficient, rapid, sensitive and selective for the determination of trace Hg<sup>2+</sup>, and was successfully employed for the accurate analysis of trace Hg<sup>2+</sup> in tap water, wastewater, lake water and river water samples.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548154/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142625879","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}
Emma Valdés, Enric Stern-Taulats, Nicolas Candau, Lluís Mañosa, Eduard Vives
We study the enhancement of the elastocaloric effect in natural rubber by using forced air convection to favour heat extraction during the elongation stage of a stretching-unstretching cycle. Elastocaloric performance is quantified by means of the adiabatic undercooling that occurs after fast removal of the stress, measured by infrared thermography. To ensure accuracy, spatial averaging on thermal maps of the sample surface is performed since undercooled samples display heterogeneities caused by various factors. The influence of the stretching velocity and the air velocity is analysed. The findings indicate that there is an optimal air velocity that maximises adiabatic undercooling, with stretching velocities needing to be high enough to enhance cooling power. Our experiments allowed the characterisation of the dependence of the Newton heat transfer coefficient on the air convection velocity, which revealed an enhancement up to 600% for air velocities around 4 m/s.
{"title":"Enhancement of the Elastocaloric Performance of Natural Rubber by Forced Air Convection.","authors":"Emma Valdés, Enric Stern-Taulats, Nicolas Candau, Lluís Mañosa, Eduard Vives","doi":"10.3390/polym16213078","DOIUrl":"10.3390/polym16213078","url":null,"abstract":"<p><p>We study the enhancement of the elastocaloric effect in natural rubber by using forced air convection to favour heat extraction during the elongation stage of a stretching-unstretching cycle. Elastocaloric performance is quantified by means of the adiabatic undercooling that occurs after fast removal of the stress, measured by infrared thermography. To ensure accuracy, spatial averaging on thermal maps of the sample surface is performed since undercooled samples display heterogeneities caused by various factors. The influence of the stretching velocity and the air velocity is analysed. The findings indicate that there is an optimal air velocity that maximises adiabatic undercooling, with stretching velocities needing to be high enough to enhance cooling power. Our experiments allowed the characterisation of the dependence of the Newton heat transfer coefficient on the air convection velocity, which revealed an enhancement up to 600% for air velocities around 4 m/s.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548639/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142627061","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}
Heitor Luiz Ornaghi Júnior, Benoit Duchemin, Sanae Azzaye, Márcio Ronaldo Farias Soares, Bárbara Schneider, Carlos Henrique Romoaldo
Radiopaque polyurethanes are extensively used in biomedical fields owing to their favorable balance of properties. This research aims to investigate the influence of particle concentration on various properties, including rheological, radiopacity, structural, thermal, and mechanical attributes, with a thorough analysis. The findings are benchmarked against a commercial product (PL 8500 A) that contains 10% weight barium sulfate. Two more thermoplastic polyurethanes (TPU) were formulated with two different concentrations of barium sulfate (10 wt.% and 20 wt.%) and compared to the commercially available product. FTIR demonstrated similar absorption bands among all samples, indicating that the fabrication method did not impact the TPU matrix. DSC indicated a predominantly amorphous structure for PL 8500 A compared to the other samples, while the kinetic degradation was more influenced by the higher barium sulfate content. The rheological analysis showed a decrease in the complex viscosity and storage modulus with the radiopacifier and an increase in the radiopacity, as demonstrated by the X-radiography. X-ray microtomography showed a more spherical particle format with a heterogeneous particle structure for PL 8500 A compared to the other polyurethanes. These findings enhance the comprehension of the structure-property relationships inherent in these materials and facilitate the development of customized materials for targeted applications.
不透射线聚氨酯因其良好的性能平衡而被广泛应用于生物医学领域。本研究旨在通过全面分析,研究颗粒浓度对各种性能(包括流变性、不透射线性、结构性、热性能和机械性能)的影响。研究结果以含有 10% 重量硫酸钡的商用产品(PL 8500 A)为基准。此外,还使用两种不同浓度的硫酸钡(10 wt.% 和 20 wt.%)配制了两种热塑性聚氨酯 (TPU),并与市售产品进行了比较。傅立叶变换红外光谱(FTIR)显示所有样品的吸收带相似,表明制造方法对热塑性聚氨酯基质没有影响。DSC 显示,与其他样品相比,PL 8500 A 主要为无定形结构,而动力学降解受硫酸钡含量较高的影响更大。流变学分析表明,添加了增塑剂后,复合粘度和储存模量降低,而 X 射线照相术则表明,不透明度增加。X 射线显微层析技术显示,与其他聚氨酯相比,PL 8500 A 的颗粒结构更不均匀,呈球形。这些发现加深了人们对这些材料固有的结构-性能关系的理解,有助于为目标应用开发定制材料。
{"title":"Radiopaque Polyurethanes Containing Barium Sulfate: A Survey on Thermal, Rheological, Physical, and Structural Properties.","authors":"Heitor Luiz Ornaghi Júnior, Benoit Duchemin, Sanae Azzaye, Márcio Ronaldo Farias Soares, Bárbara Schneider, Carlos Henrique Romoaldo","doi":"10.3390/polym16213086","DOIUrl":"10.3390/polym16213086","url":null,"abstract":"<p><p>Radiopaque polyurethanes are extensively used in biomedical fields owing to their favorable balance of properties. This research aims to investigate the influence of particle concentration on various properties, including rheological, radiopacity, structural, thermal, and mechanical attributes, with a thorough analysis. The findings are benchmarked against a commercial product (PL 8500 A) that contains 10% weight barium sulfate. Two more thermoplastic polyurethanes (TPU) were formulated with two different concentrations of barium sulfate (10 wt.% and 20 wt.%) and compared to the commercially available product. FTIR demonstrated similar absorption bands among all samples, indicating that the fabrication method did not impact the TPU matrix. DSC indicated a predominantly amorphous structure for PL 8500 A compared to the other samples, while the kinetic degradation was more influenced by the higher barium sulfate content. The rheological analysis showed a decrease in the complex viscosity and storage modulus with the radiopacifier and an increase in the radiopacity, as demonstrated by the X-radiography. X-ray microtomography showed a more spherical particle format with a heterogeneous particle structure for PL 8500 A compared to the other polyurethanes. These findings enhance the comprehension of the structure-property relationships inherent in these materials and facilitate the development of customized materials for targeted applications.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548690/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626719","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}
Yunseok Jang, Seung-Hyun Lee, Youn-Ki Lee, Inyoung Kim, Taik-Min Lee, Sin Kwon, Boseok Kang
In order to enhance the sensitivity of elastomers, pores were integrated into their structure. These pores facilitate the adjustment of thickness in response to external pressure variations, thereby improving the sensitivity of pressure sensors. Pores were introduced by emulsifying immiscible polydimethylsiloxane (PDMS) and water with a surfactant. By controlling the water content in the PDMS and water emulsion, we controlled the size, density, uniformity, and spatial distribution (2D or 3D) of the pores within the PDMS matrix. The presence of these pores significantly improved the sensitivity of PDMS under low external pressure conditions compared to high pressures. Specifically, porous PDMS exhibited approximately 10-times greater sensitivity under low-pressure conditions than non-porous PDMS. The effectiveness of porous PDMS was demonstrated through dynamic loading and unloading detection of a small Lego toy and monitoring of human heartbeats. These results highlight the efficacy of our pressure sensor based on porous PDMS, which is fabricated through a simple and cost-effective process using a PDMS and water emulsion. This approach is highly suitable for developing the ability to detect applied pressures or contact forces.
{"title":"Fabrication of Highly Sensitive Porous Polydimethylsiloxane Pressure Sensor Through Control of Rheological Properties.","authors":"Yunseok Jang, Seung-Hyun Lee, Youn-Ki Lee, Inyoung Kim, Taik-Min Lee, Sin Kwon, Boseok Kang","doi":"10.3390/polym16213075","DOIUrl":"10.3390/polym16213075","url":null,"abstract":"<p><p>In order to enhance the sensitivity of elastomers, pores were integrated into their structure. These pores facilitate the adjustment of thickness in response to external pressure variations, thereby improving the sensitivity of pressure sensors. Pores were introduced by emulsifying immiscible polydimethylsiloxane (PDMS) and water with a surfactant. By controlling the water content in the PDMS and water emulsion, we controlled the size, density, uniformity, and spatial distribution (2D or 3D) of the pores within the PDMS matrix. The presence of these pores significantly improved the sensitivity of PDMS under low external pressure conditions compared to high pressures. Specifically, porous PDMS exhibited approximately 10-times greater sensitivity under low-pressure conditions than non-porous PDMS. The effectiveness of porous PDMS was demonstrated through dynamic loading and unloading detection of a small Lego toy and monitoring of human heartbeats. These results highlight the efficacy of our pressure sensor based on porous PDMS, which is fabricated through a simple and cost-effective process using a PDMS and water emulsion. This approach is highly suitable for developing the ability to detect applied pressures or contact forces.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548559/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142625411","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}
Jahir J Ramos, Steven Nieto, Gonzalo R Quezada, Williams Leiva, Pedro Robles, Fernando Betancourt, Ricardo I Jeldres
This study analyzes the behavior of sodium polyacrylate (NaPA) as a rheological modifier for clay-based tailings. Special emphasis is placed on the impact of calcium and magnesium ions in industrial water, which are analyzed through rheograms, zeta potential measurements, and molecular dynamics simulations. The results are interpreted as electrostatic interactions, steric phenomena, and cation solvation. This interpretation integrates experimental studies with microscopic analyses, employing molecular dynamics simulations to elucidate the underlying mechanisms. In all cases, a decrease in the yield stress of synthetic slurries is observed as the dosing of NaPA increases due to greater repulsion between tailings particles through an increase in electrostatic repulsion and larger steric forces that hinder agglomeration. However, efficiency is reduced in the presence of divalent cations as zeta potential measurements suggest a reduction in the electrical charges of the particles and the polymer, making its application more challenging. The differences obtained in the presence of calcium compared to magnesium are explained in terms of the solvation of these ions and their impact on the polymer conformation in solution and adsorption on the mineral surfaces. This explanation is reinforced by molecular dynamics studies, which indicate that polymer adsorption on minerals depends on the type of mineral and type of ion. Particularly for quartz, the highest adsorption of NaPA occurs in the presence of calcium, whereas for a kaolinite surface, the highest polymer adsorption is obtained in the presence of magnesium. The competitive effect of these phenomena leads to the rheological behavior of the tailings being dominated by the effects originating in the clay.
{"title":"Rheological Behavior of Clay Tailings in the Presence of Divalent Cations and Sodium Polyacrylate: Insights from Molecular Dynamics Simulations.","authors":"Jahir J Ramos, Steven Nieto, Gonzalo R Quezada, Williams Leiva, Pedro Robles, Fernando Betancourt, Ricardo I Jeldres","doi":"10.3390/polym16213091","DOIUrl":"10.3390/polym16213091","url":null,"abstract":"<p><p>This study analyzes the behavior of sodium polyacrylate (NaPA) as a rheological modifier for clay-based tailings. Special emphasis is placed on the impact of calcium and magnesium ions in industrial water, which are analyzed through rheograms, zeta potential measurements, and molecular dynamics simulations. The results are interpreted as electrostatic interactions, steric phenomena, and cation solvation. This interpretation integrates experimental studies with microscopic analyses, employing molecular dynamics simulations to elucidate the underlying mechanisms. In all cases, a decrease in the yield stress of synthetic slurries is observed as the dosing of NaPA increases due to greater repulsion between tailings particles through an increase in electrostatic repulsion and larger steric forces that hinder agglomeration. However, efficiency is reduced in the presence of divalent cations as zeta potential measurements suggest a reduction in the electrical charges of the particles and the polymer, making its application more challenging. The differences obtained in the presence of calcium compared to magnesium are explained in terms of the solvation of these ions and their impact on the polymer conformation in solution and adsorption on the mineral surfaces. This explanation is reinforced by molecular dynamics studies, which indicate that polymer adsorption on minerals depends on the type of mineral and type of ion. Particularly for quartz, the highest adsorption of NaPA occurs in the presence of calcium, whereas for a kaolinite surface, the highest polymer adsorption is obtained in the presence of magnesium. The competitive effect of these phenomena leads to the rheological behavior of the tailings being dominated by the effects originating in the clay.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548682/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626744","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}
Zhenzhen Deng, Tao Tang, Junjie Huo, Hui He, Kang Dai
To enhance the fire safety performance in polystyrene (PS), a novel organic-inorganic hybrid material (FGO-AHP) was successfully prepared by the combination of functionalized graphene oxide (FGO) and aluminum hypophosphite (AHP) via a chemical deposition method. The resulting FGO-AHP nanohybrids were incorporated into PS via a masterbatch-melt blending to produce PS/FGO-AHP nanocomposites. Scanning electron microscope images confirm the homogeneous dispersion and exfoliation state of FGO-AHP in the PS matrix. Incorporating FGO-AHP significantly improves the thermal behavior and fire safety performance of PS. By incorporating 5 wt% FGO-AHP, the maximum mass loss rate (MMLR) in air, total heat release (THR), and maximum smoke density value (Dsmax) of PS nanocomposite achieve a reduction of 53.1%, 23.4%, and 50.9%, respectively, as compared to the pure PS. In addition, thermogravimetry-Fourier transform infrared (TG-FTIR) results indicate that introducing FGO-AHP notably inhibits the evolution of volatile products from PS decomposition. Further, scanning electron microscopy (SEM), FTIR, and Raman spectroscopy were employed to investigate the char residue of PS nanocomposite samples, elaborating the flame-retardant mechanism in PS/FGO-AHP nanocomposites.
{"title":"Fabrication of Functionalized Graphene Oxide-Aluminum Hypophosphite Nanohybrids for Enhanced Fire Safety Performance in Polystyrene.","authors":"Zhenzhen Deng, Tao Tang, Junjie Huo, Hui He, Kang Dai","doi":"10.3390/polym16213083","DOIUrl":"10.3390/polym16213083","url":null,"abstract":"<p><p>To enhance the fire safety performance in polystyrene (PS), a novel organic-inorganic hybrid material (FGO-AHP) was successfully prepared by the combination of functionalized graphene oxide (FGO) and aluminum hypophosphite (AHP) via a chemical deposition method. The resulting FGO-AHP nanohybrids were incorporated into PS via a masterbatch-melt blending to produce PS/FGO-AHP nanocomposites. Scanning electron microscope images confirm the homogeneous dispersion and exfoliation state of FGO-AHP in the PS matrix. Incorporating FGO-AHP significantly improves the thermal behavior and fire safety performance of PS. By incorporating 5 wt% FGO-AHP, the maximum mass loss rate (MMLR) in air, total heat release (THR), and maximum smoke density value (D<sub>smax</sub>) of PS nanocomposite achieve a reduction of 53.1%, 23.4%, and 50.9%, respectively, as compared to the pure PS. In addition, thermogravimetry-Fourier transform infrared (TG-FTIR) results indicate that introducing FGO-AHP notably inhibits the evolution of volatile products from PS decomposition. Further, scanning electron microscopy (SEM), FTIR, and Raman spectroscopy were employed to investigate the char residue of PS nanocomposite samples, elaborating the flame-retardant mechanism in PS/FGO-AHP nanocomposites.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548397/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142625030","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}
Katerina Papadopoulou, Nina Maria Ainali, Ondřej Mašek, Dimitrios N Bikiaris
In the present study, biocomposite materials were created by incorporating biochar (BC) at rates of 1, 2.5, and 5 wt.% into a poly(butylene succinate) (PBSu) matrix using a two-stage melt polycondensation procedure in order to provide understanding of the aging process. The biocomposites in film form were exposed to UV irradiation for 7, 14, and 21 days. Photostability was examined by several methods, such as Fourier transform infrared spectroscopy (FTIR), which proved that new carbonyl and hydroxyl groups were formed during UV exposure. Moreover, Differential Scanning Calorimetry (DSC) measurements were employed to record the apparent UV effect in their crystalline morphology and thermal transitions. According to the molecular weight measurements of composites, it was apparent that by increasing the biochar content, the molecular weight decreased at a slower rate. Tensile strength tests were performed to evaluate the deterioration of their mechanical properties during UV exposure, while Scanning Electron Microscopy (SEM) images illustrated the notable surface alternations. Cracks were formed at higher UV exposure times, to a lesser extent in PBSu/BC composites than in neat PBSu. Furthermore, the mechanism of the thermal degradation of neat PBSu and its biocomposites prior to and upon UV exposure was studied by Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS). From all the obtained results it was proved that biochar can be considered as an efficient UV-protective additive to PBSu, capable of mitigating photodegradation.
{"title":"Biochar as a UV Stabilizer: Its Impact on the Photostability of Poly(butylene succinate) Biocomposites.","authors":"Katerina Papadopoulou, Nina Maria Ainali, Ondřej Mašek, Dimitrios N Bikiaris","doi":"10.3390/polym16213080","DOIUrl":"10.3390/polym16213080","url":null,"abstract":"<p><p>In the present study, biocomposite materials were created by incorporating biochar (BC) at rates of 1, 2.5, and 5 wt.% into a poly(butylene succinate) (PBSu) matrix using a two-stage melt polycondensation procedure in order to provide understanding of the aging process. The biocomposites in film form were exposed to UV irradiation for 7, 14, and 21 days. Photostability was examined by several methods, such as Fourier transform infrared spectroscopy (FTIR), which proved that new carbonyl and hydroxyl groups were formed during UV exposure. Moreover, Differential Scanning Calorimetry (DSC) measurements were employed to record the apparent UV effect in their crystalline morphology and thermal transitions. According to the molecular weight measurements of composites, it was apparent that by increasing the biochar content, the molecular weight decreased at a slower rate. Tensile strength tests were performed to evaluate the deterioration of their mechanical properties during UV exposure, while Scanning Electron Microscopy (SEM) images illustrated the notable surface alternations. Cracks were formed at higher UV exposure times, to a lesser extent in PBSu/BC composites than in neat PBSu. Furthermore, the mechanism of the thermal degradation of neat PBSu and its biocomposites prior to and upon UV exposure was studied by Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS). From all the obtained results it was proved that biochar can be considered as an efficient UV-protective additive to PBSu, capable of mitigating photodegradation.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548502/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626773","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}
In this study, a novel unit cell design is proposed, which eliminates the buckling tendency of the auxetic honeycomb. The novel unit cell design is a more balanced, diagonally reinforced doubly re-entrant auxetic honeycomb structure (x-reinforced auxetic honeycomb for short). We investigated and compared this novel unit cell design against a wide parameter range. Compression tests were carried out on specimens 3D-printed with a special, unique, flexible but tough resin mixture. The results showed that the additional, centrally pronounced reinforcements resulted in increased deformation stability; parameter-independent, non-buckling deformation behaviour is achieved; however, the novel structure is no longer auxetic. Mechanical properties, such as compression resistance and energy absorption capability, also increased significantly-An almost four times increase can be observed. In contrast to the deformation behaviour (which became predictable and constant), the mechanical properties can be precisely adjusted for the desired application. This novel structure was also investigated in a highly accurate, validated finite element environment, which showed that critical stress values are formed in well-supported regions, meaning that critical failure is unlikely. Our novel lattice unit cell design elevated the auxetic honeycomb to the realm of modern, high performance and widely applicable lattice structures.
本研究提出了一种新型单元格设计,它能消除辅助蜂窝的屈曲趋势。这种新型单元单元设计是一种更加平衡、对角线增强的双重入射辅助蜂窝结构(简称 x 增强辅助蜂窝)。我们对这种新型单元结构进行了研究,并在广泛的参数范围内对其进行了比较。我们在用一种特殊、独特、柔韧而坚固的树脂混合物 3D 打印的试样上进行了压缩试验。结果表明,额外的、中心明显的加强筋提高了变形稳定性;实现了与参数无关的非屈曲变形行为;但是,这种新型结构不再具有辅助性。抗压性和能量吸收能力等机械性能也显著提高--几乎提高了四倍。与变形行为(变得可预测且恒定)不同的是,机械性能可根据所需应用进行精确调整。我们还在高精度、经过验证的有限元环境中对这种新型结构进行了研究,结果表明,临界应力值是在支撑良好的区域形成的,这意味着不太可能出现临界失效。我们的新型晶格单元设计将辅助蜂窝提升到了现代、高性能和广泛应用的晶格结构领域。
{"title":"Parameter-Independent Deformation Behaviour of Diagonally Reinforced Doubly Re-Entrant Honeycomb.","authors":"Levente Széles, Richárd Horváth, Mihály Réger","doi":"10.3390/polym16213082","DOIUrl":"10.3390/polym16213082","url":null,"abstract":"<p><p>In this study, a novel unit cell design is proposed, which eliminates the buckling tendency of the auxetic honeycomb. The novel unit cell design is a more balanced, diagonally reinforced doubly re-entrant auxetic honeycomb structure (x-reinforced auxetic honeycomb for short). We investigated and compared this novel unit cell design against a wide parameter range. Compression tests were carried out on specimens 3D-printed with a special, unique, flexible but tough resin mixture. The results showed that the additional, centrally pronounced reinforcements resulted in increased deformation stability; parameter-independent, non-buckling deformation behaviour is achieved; however, the novel structure is no longer auxetic. Mechanical properties, such as compression resistance and energy absorption capability, also increased significantly-An almost four times increase can be observed. In contrast to the deformation behaviour (which became predictable and constant), the mechanical properties can be precisely adjusted for the desired application. This novel structure was also investigated in a highly accurate, validated finite element environment, which showed that critical stress values are formed in well-supported regions, meaning that critical failure is unlikely. Our novel lattice unit cell design elevated the auxetic honeycomb to the realm of modern, high performance and widely applicable lattice structures.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548329/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142635799","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}
Yue Xu, Wenjia Zhang, Ru Yin, Jun Sun, Bin Li, Lubin Liu
Epoxy resins (EPs) are highly flammable, and traditional flame retardant modifications often lead to a significant reduction in their mechanical performance, limiting their applications in aerospace and electrical and electronic fields. In this study, a novel flame retardant, bis(4-(((diphenylphosphoryl)oxy)methyl)phenyl)phenyl phosphate (DMP), was successfully prepared and introduced into the EP matrix. When the addition of DMP was 9 wt%, the EP/9 wt% DMP thermosets passed the UL-94 V-0 rating, and their LOI was increased from 24.5% of EP to 35.0%. With the introduction of DMP, the phosphoric acid compounds from the decomposition of DMP promoted the dehydration and charring of the EP matrix, and the compact, dense char layer effectively exerted the shielding effect in the condensed phase. Meanwhile, the produced phosphorus-containing radicals played a quenching effect in the gas phase. As a result, the peak heat release rate (PHRR) and total heat release (THR) of EP/9 wt% DMP were reduced by 68.9% and 18.1% compared to pure EP. In addition, the polyaromatic structure of DMP had good compatibility with the EP matrix, and the tensile strength, flexural strength and impact strength of EP/9 wt% DMP were enhanced by 116.38%, 17.84% and 59.11% in comparison with that of pure EP. This study is valuable for expanding the application of flame-retardant EP/DMP thermosets in emerging fields.
环氧树脂(EPs)极易燃烧,传统的阻燃剂改性往往会导致其机械性能显著下降,从而限制了其在航空航天、电气和电子领域的应用。本研究成功制备了一种新型阻燃剂--双(4-(((二苯基磷酰)氧基)甲基)苯基)苯基磷酸酯(DMP),并将其引入 EP 基体中。当 DMP 的添加量为 9 wt% 时,EP/9 wt% DMP 热固性塑料通过了 UL-94 V-0 评级,其 LOI 从 EP 的 24.5% 提高到 35.0%。引入 DMP 后,DMP 分解产生的磷酸化合物促进了 EP 基体的脱水和炭化,紧密致密的炭层有效地发挥了冷凝相的屏蔽作用。同时,产生的含磷自由基在气相中起到了淬火作用。因此,与纯 EP 相比,EP/9 wt% DMP 的峰值放热率(PHRR)和总放热率(THR)分别降低了 68.9% 和 18.1%。此外,DMP 的多芳香族结构与 EP 基体具有良好的相容性,与纯 EP 相比,EP/9 wt% DMP 的拉伸强度、弯曲强度和冲击强度分别提高了 116.38%、17.84% 和 59.11%。这项研究对于扩大阻燃 EP/DMP 热固性塑料在新兴领域的应用具有重要价值。
{"title":"Novel Aryl Phosphate for Improving Fire Safety and Mechanical Properties of Epoxy Resins.","authors":"Yue Xu, Wenjia Zhang, Ru Yin, Jun Sun, Bin Li, Lubin Liu","doi":"10.3390/polym16213049","DOIUrl":"10.3390/polym16213049","url":null,"abstract":"<p><p>Epoxy resins (EPs) are highly flammable, and traditional flame retardant modifications often lead to a significant reduction in their mechanical performance, limiting their applications in aerospace and electrical and electronic fields. In this study, a novel flame retardant, bis(4-(((diphenylphosphoryl)oxy)methyl)phenyl)phenyl phosphate (DMP), was successfully prepared and introduced into the EP matrix. When the addition of DMP was 9 wt%, the EP/9 wt% DMP thermosets passed the UL-94 V-0 rating, and their LOI was increased from 24.5% of EP to 35.0%. With the introduction of DMP, the phosphoric acid compounds from the decomposition of DMP promoted the dehydration and charring of the EP matrix, and the compact, dense char layer effectively exerted the shielding effect in the condensed phase. Meanwhile, the produced phosphorus-containing radicals played a quenching effect in the gas phase. As a result, the peak heat release rate (PHRR) and total heat release (THR) of EP/9 wt% DMP were reduced by 68.9% and 18.1% compared to pure EP. In addition, the polyaromatic structure of DMP had good compatibility with the EP matrix, and the tensile strength, flexural strength and impact strength of EP/9 wt% DMP were enhanced by 116.38%, 17.84% and 59.11% in comparison with that of pure EP. This study is valuable for expanding the application of flame-retardant EP/DMP thermosets in emerging fields.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548273/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626566","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}
Ivana Solis Vizcaino, Efraín Rubio Rosas, Eva Águila Almanza, Marco Marín Castro, Heriberto Hernández Cocoletzi
In Mexico, the Ataulfo mango crop faces significant challenges due to anthracnose, a disease caused by the fungus Colletotrichum gloeosporioides. The need to use eco-friendly fungicides is crucial to avoid the use of harmful synthetic chemicals. This study aimed to prepare chitosan nanoparticles through a simple and effective ultrasound-assisted top-down method, with high antifungal efficiency. The nanoparticles were prepared from chitosan (DD = 85%, MW = 553 kDa) and Tween 20 under constant sonication. The formation of the nanoparticles was initially confirmed by Fourier-transform infrared (FTIR) spectroscopy; and their physicochemical properties were subsequently characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The antifungal potential of the chitosan nanoparticles against the phytopathogen Colletotrichum gloeosporioides was evaluated with isolated fungi obtained directly from mango tissues showing anthracnose symptoms in the state of Guerrero, Mexico. The fungus was identified through SEM imaging, showing a regular and smooth conidial layer, with cylindrical shape (r = 2 µm, h = 10 µm). In vitro tests were conducted with three different concentrations of chitosan nanoparticles to assess their inhibitory effects. After seven days of incubation, a maximum inhibition rate of 97% was observed with the 0.5% nanoparticle solution, corresponding to a fungal growth rate of 0.008 cm/h. At this time, the control mycelial growth was 7 cm, while the treated sample reached a radius of 0.55 mm. These results demonstrated the antifungal effect of the nanoparticles on the membrane and cell wall of the fungus, suggesting that their composition could induce a resistance response. The inhibitory effect was also influenced by the particle size (30 nm), as the small size facilitated penetration into fungal cells. Consequently, the parent compound could be formulated and applied as a natural antifungal agent in nanoparticle form to enhance its activity. The method described in this study offers a viable alternative for the preparation of chitosan nanoparticles, by avoiding the use of toxic reagents.
{"title":"Ultrasonic Production of Chitosan Nanoparticles and Their Application Against <i>Colletotrichum gloeosporioides</i> Present in the Ataulfo Mango.","authors":"Ivana Solis Vizcaino, Efraín Rubio Rosas, Eva Águila Almanza, Marco Marín Castro, Heriberto Hernández Cocoletzi","doi":"10.3390/polym16213058","DOIUrl":"10.3390/polym16213058","url":null,"abstract":"<p><p>In Mexico, the Ataulfo mango crop faces significant challenges due to anthracnose, a disease caused by the fungus <i>Colletotrichum gloeosporioides</i>. The need to use eco-friendly fungicides is crucial to avoid the use of harmful synthetic chemicals. This study aimed to prepare chitosan nanoparticles through a simple and effective ultrasound-assisted top-down method, with high antifungal efficiency. The nanoparticles were prepared from chitosan (DD = 85%, MW = 553 kDa) and Tween 20 under constant sonication. The formation of the nanoparticles was initially confirmed by Fourier-transform infrared (FTIR) spectroscopy; and their physicochemical properties were subsequently characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The antifungal potential of the chitosan nanoparticles against the phytopathogen <i>Colletotrichum gloeosporioides</i> was evaluated with isolated fungi obtained directly from mango tissues showing anthracnose symptoms in the state of Guerrero, Mexico. The fungus was identified through SEM imaging, showing a regular and smooth conidial layer, with cylindrical shape (r = 2 µm, h = 10 µm). In vitro tests were conducted with three different concentrations of chitosan nanoparticles to assess their inhibitory effects. After seven days of incubation, a maximum inhibition rate of 97% was observed with the 0.5% nanoparticle solution, corresponding to a fungal growth rate of 0.008 cm/h. At this time, the control mycelial growth was 7 cm, while the treated sample reached a radius of 0.55 mm. These results demonstrated the antifungal effect of the nanoparticles on the membrane and cell wall of the fungus, suggesting that their composition could induce a resistance response. The inhibitory effect was also influenced by the particle size (30 nm), as the small size facilitated penetration into fungal cells. Consequently, the parent compound could be formulated and applied as a natural antifungal agent in nanoparticle form to enhance its activity. The method described in this study offers a viable alternative for the preparation of chitosan nanoparticles, by avoiding the use of toxic reagents.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548500/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626895","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}