Polymers

2024

Jump to: 2020, 2019, 2018

24 pages, 5355 KiB

Open AccessArticle

Hygrothermal Degradation of Epoxy Electrical Insulating Material—Testing and Mathematical Modeling

by Jan Leffler, Jan Kaska, Petr Kadlec, Pavel Prosr, Vaclav Smidl and Pavel Trnka

Polymers 2024, 16(14), 2026; https://doi.org/10.3390/polym16142026 - 16 Jul 2024

Cited by 1 | Viewed by 756

Abstract

The degradation of electrical insulating materials has been a subject of interest for decades as they are commonly applied in many fields of electrical engineering. Suitably modeling such a process is important since the known and well-described degradation process reveals the effect of [...] Read more.

The degradation of electrical insulating materials has been a subject of interest for decades as they are commonly applied in many fields of electrical engineering. Suitably modeling such a process is important since the known and well-described degradation process reveals the effect of ambient conditions, and this allows us to possibly estimate a material’s remaining useful life. However, not many studies are dealing with the effect of the hygrothermal degradation of impregnating mono-component epoxy resins in the context of electrical engineering. Therefore, this study deals with this issue and discusses both the dielectric response (based on the measurement of relative permittivity, dissipation factor, and dielectric strength) and the mechanical response (based on measurements of tensile strength and Shore D hardness) to a hygrothermal degradation experiment. In addition, the results of thermal analyses are presented for the evaluation of the pristine specimen manufacturing process and possible post-curing processes. Furthermore, this study presents several methodologies for modeling the degradation process, including a novel methodology in this area based on Bayesian experimental design. As an outcome, mechanical parameters are proven to be specific in terms of the actual condition of the material and the Bayesian enhanced degradation model seems to be superior to the conventional evaluation methods in this particular study. Full article

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15 pages, 10528 KiB

Open AccessArticle

Biodegradation of Nitrile Gloves as Sole Carbon Source of Pseudomonas aeruginosa in Liquid Culture

by Javier Alejandro Delgado-Nungaray, David Grajeda-Arias, Eire Reynaga-Delgado and Orfil Gonzalez-Reynoso

Polymers 2024, 16(8), 1162; https://doi.org/10.3390/polym16081162 - 20 Apr 2024

Cited by 1 | Viewed by 1790

Abstract

Nitrile gloves have become a significant environmental pollutant after the COVID-19 pandemic due to their single-use design. This study examines the capability of P. aeruginosa to use nitrile gloves as its sole carbon energy source. Biodegradation was determined by P. aeruginosa adapting to [...] Read more.

Nitrile gloves have become a significant environmental pollutant after the COVID-19 pandemic due to their single-use design. This study examines the capability of P. aeruginosa to use nitrile gloves as its sole carbon energy source. Biodegradation was determined by P. aeruginosa adapting to increasing nitrile glove concentrations at 1%, 3%, and 5% (w/v). The growth kinetics of P. aeruginosa were evaluated, as well as the polymer weight loss. Topographic changes on the glove surfaces were examined using SEM, and FT-IR was used to evaluate the biodegradation products of the nitrile gloves. Following the establishment of a biofilm on the glove surface, the nitrile toxicity was minimized via biodegradation. The result of the average weight loss of nitrile gloves was 2.25%. FT-IR analysis revealed the presence of aldehydes and aliphatic amines associated with biodegradation. SEM showed P. aeruginosa immersed in the EPS matrix, causing the formation of cracks, scales, protrusions, and the presence of semi-spherical particles. We conclude that P. aeruginosa has the capability to use nitrile gloves as its sole carbon source, even up to 5%, through biofilm formation, demonstrating the potential of P. aeruginosa for the degradation of nitrile gloves. Full article

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2020

Jump to: 2024, 2019, 2018

21 pages, 7601 KiB

Open AccessArticle

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

by Lucie Zarybnicka, Jana Machotova, Radka Kopecka, Radek Sevcik, Martina Hudakova, Jaroslav Pokorny and Jiri Sal

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

Cited by 13 | Viewed by 3342

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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19 pages, 3977 KiB

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 9 | Viewed by 3090

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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12 pages, 5068 KiB

Open AccessArticle

Role of Organo-Modifier and Metal Impurities of Commercial Nanoclays in the Photo- and Thermo-Oxidation of Polyamide 11 Nanocomposites

by Martina Ussia, Giusy Curcuruto, Daniela Zampino, Nadka Tzankova Dintcheva, Giovanni Filippone, Raniero Mendichi and Sabrina Carola Carroccio

Polymers 2020, 12(5), 1034; https://doi.org/10.3390/polym12051034 - 2 May 2020

Cited by 4 | Viewed by 2923

Abstract

The photo-oxidative degradation processes of bio-based PA11 nanocomposites containing montmorillonite (MMT) and the organo-modified Cloisite^®30B were investigated to discriminate the influence of organo-modified components on the polymer durability. Indeed, despite the extensive studies reported, there are still ambiguous points to be [...] Read more.

The photo-oxidative degradation processes of bio-based PA11 nanocomposites containing montmorillonite (MMT) and the organo-modified Cloisite^®30B were investigated to discriminate the influence of organo-modified components on the polymer durability. Indeed, despite the extensive studies reported, there are still ambiguous points to be clarified from the chemical point of view. To this aim, UV-aged materials were analyzed by Size Exclusion Chromatography (SEC), Inductively Coupled Plasma–Mass Spectrometry (ICP-MS) and Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS). This enabled determining changes in both chemical structure and Molar Masses (MMs) induced by light, heat and oxygen exposure. The addition of organo-modified nanoclays strongly affected the PA11 light durability, triggering the macromolecular chains scission due to the typical αH, Norrish I and II mechanisms. However, the main contribution in boosting the photo-oxidative degradation is induced by iron impurities contained into the clays. Conversely, thermo-oxidation process performed at 215 °C was unambiguously affected by the presence of the organo-modifiers, whose presence determined an enhancement of crosslinking reactions. Full article

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2019

Jump to: 2024, 2020, 2018

18 pages, 4654 KiB

Open AccessArticle

Combustion Performance and Thermal Stability of Basalt Fiber-Reinforced Polypropylene Composites

by Chunhong Tang, FengXiang Xu and Guangyao Li

Polymers 2019, 11(11), 1826; https://doi.org/10.3390/polym11111826 - 6 Nov 2019

Cited by 18 | Viewed by 3569

Abstract

In this study, the thermal stability and combustion performance of basalt fiber reinforced polypropylene (BFRPP) composite and pure polypropylene (PP) were compared. The results show that the basalt fiber has no positive effect on increasing the initial decomposition temperature of PP, but it [...] Read more.

In this study, the thermal stability and combustion performance of basalt fiber reinforced polypropylene (BFRPP) composite and pure polypropylene (PP) were compared. The results show that the basalt fiber has no positive effect on increasing the initial decomposition temperature of PP, but it could reduce the maximum thermal decomposition rate and increase the temperature of the maximum thermal decomposition rate. Adding basalt fiber to PP could slightly reduce the limiting oxygen index. At the same oxygen concentration, the BFRPP burned significantly more slowly than the PP. In addition, during the combustion, it was observed that the BFRPP showed a better anti-melt dripping effect than the PP. The results from the cone calorimeter test show that, under the same external heat flux, the time-to-ignition (TTI) of BFRPP was less than that of PP. This indicated that BFRPP was easier to ignite than PP. It was also found that the reciprocal of the square root of the TTI of both has a linear relationship with external heat flux. BFRPP has a lower peak heat release rate and total heat release than PP. Moreover, BFRPP produced less smoke than PP when burned. Full article

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14 pages, 4709 KiB

Open AccessArticle

Effect of Nitrogen-Doped Graphene Oxide on the Aging Behavior of Nitrile–Butadiene Rubber

by Songbo Chen, Tianxiang Li, Songhan Wan, Xing Huang, Shuwei Cai, Xianru He and Rui Zhang

Polymers 2019, 11(10), 1637; https://doi.org/10.3390/polym11101637 - 10 Oct 2019

Cited by 13 | Viewed by 3562

Abstract

Nitrogen-doped graphene oxide (GO), namely, NG, was prepared by o-phenylenediamine (OPD) grafting onto GO. The structure and morphology of NG were characterized by FITR, XRD, SEM, EDS, Raman spectroscopy, and TGA. OPD was linked to the GO surface by covalent bonds, and the [...] Read more.

Nitrogen-doped graphene oxide (GO), namely, NG, was prepared by o-phenylenediamine (OPD) grafting onto GO. The structure and morphology of NG were characterized by FITR, XRD, SEM, EDS, Raman spectroscopy, and TGA. OPD was linked to the GO surface by covalent bonds, and the absorption peak of the C=N bond in the phenazine structure was identified in the FITR spectra. The aging resistance properties of nitrile-butadiene rubber (NBR)-NG composites was investigated by mechanical testing, before and after aging. The resistance of the NBR/NG composites with the addition of 3 phr NG fillers was the highest. The aging mechanism was investigated by TGA-DSC, DMA, equilibrium swelling testing, and ATR-FTIR. The results showed that NG could effectively inhibit chain cross-linking in NBR. Full article

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18 pages, 4849 KiB

Open AccessArticle

A Quantitative Spectroscopic Study of the Bleaching Phenomena in Plasticized Formulations Containing PVC Exposed to Outdoor Conditions

by Elizabeth González-Falcón, Martin Arellano, M. Judith Sanchez-Peña and L. Javier González-Ortiz

Polymers 2019, 11(9), 1481; https://doi.org/10.3390/polym11091481 - 11 Sep 2019

Cited by 5 | Viewed by 2725

Abstract

In this work, a quantitative spectroscopic study of the bleaching phenomena occurring in plasticized formulations containing poly(vinyl chloride) was performed, proposing a general methodology to comparatively analyze the effect of degrading conditions on the polyene accumulation behaviors (PABs) exhibited by a set of [...] Read more.

In this work, a quantitative spectroscopic study of the bleaching phenomena occurring in plasticized formulations containing poly(vinyl chloride) was performed, proposing a general methodology to comparatively analyze the effect of degrading conditions on the polyene accumulation behaviors (PABs) exhibited by a set of tested formulations. In the study, a set of environmental indexes (temperature (T*), UV energy (UV*), and days with rain) were proposed, which allowed for the suitable globalization of the changing environmental conditions occurring throughout the different degrading periods. A procedure to numerically describe the PAB, followed by each formulation undergoing each degrading condition was also proposed, which required only two primary fitting parameters and four secondary fitting parameters. Then, the combined effects of certain environmental conditions on the PABs were studied, quantifying the stabilizing effects of the rain and the combined decrement on the T* and UV* indexes. Finally, on the basis of the proposed fitting equation and the values of its fitting parameters, the relative importance of the dehydrochlorination reactions as compared with the photo-oxidative reactions simultaneously occurring in the studied systems was estimated. Full article

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23 pages, 10984 KiB

Open AccessEditor’s ChoiceArticle

Effect of Fibers Configuration and Thickness on Tensile Behavior of GFRP Laminates Exposed to Harsh Environment

by Milad Bazli, Hamed Ashrafi, Armin Jafari, Xiao-Ling Zhao, R.K. Singh Raman and Yu Bai

Polymers 2019, 11(9), 1401; https://doi.org/10.3390/polym11091401 - 26 Aug 2019

Cited by 48 | Viewed by 5224

Abstract

The present study indicates the importance of using glass fiber reinforced polymer (GFRP) laminates with appropriate thickness and fibers orientation when exposed to harsh environmental conditions. The effect of different environmental conditions on tensile properties of different GFRP laminates is investigated. Laminates were [...] Read more.

The present study indicates the importance of using glass fiber reinforced polymer (GFRP) laminates with appropriate thickness and fibers orientation when exposed to harsh environmental conditions. The effect of different environmental conditions on tensile properties of different GFRP laminates is investigated. Laminates were exposed to three environmental conditions: (1) Freeze/thaw cycles without the presence of moisture, (2) freeze/thaw cycles with the presence of moisture and (3) UV radiation and water vapor condensation cycles. The effect of fiber configuration and laminate thickness were investigated by considering three types of fiber arrangement: (1) Continuous unidirectional, (2) continuous woven and (3) chopped strand mat and two thicknesses (2 and 5 mm). Microstructure and tensile properties of the laminates after exposure to different periods of conditioning (0, 750, 1250 and 2000 h) were studied using SEM and tensile tests. Statistical analyses were used to quantify the obtained results and propose prediction models. The results showed that the condition comprising UV radiation and moisture condition was the most aggressive, while dry freeze/thaw environment was the least. Furthermore, the laminates with chopped strand mat and continuous unidirectional fibers respectively experienced the highest and the lowest reductions properties in all environmental conditions. The maximum reductions in tensile strength for chopped strand mat laminates were about 7%, 32%, and 42% in the dry freeze/thaw, wet freeze/thaw and UV with moisture environments, respectively. The corresponding decreases in the tensile strength for unidirectional laminates were negligible, 17% and 23%, whereas those for the woven laminates were and 7%, 24%, and 34%. Full article

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16 pages, 7058 KiB

Open AccessArticle

High Moisture Accelerated Mechanical Behavior Degradation of Phosphor/Silicone Composites Used in White Light-Emitting Diodes

by Jiajie Fan, Zhen Wang, Xunwei Zhang, Zhentao Deng, Xuejun Fan and Guoqi Zhang

Polymers 2019, 11(8), 1277; https://doi.org/10.3390/polym11081277 - 31 Jul 2019

Cited by 20 | Viewed by 3981

Abstract

In a high-power white light emitting diode (LED) package, the phosphor/silicone composite is typically used for photometric and colorimetric conversions, ultimately producing the white light. However, the phosphor/silicone composite is always exposed under harsh environments with high temperature, high blue light irradiation and [...] Read more.

In a high-power white light emitting diode (LED) package, the phosphor/silicone composite is typically used for photometric and colorimetric conversions, ultimately producing the white light. However, the phosphor/silicone composite is always exposed under harsh environments with high temperature, high blue light irradiation and high moisture when the LED operates. Therefore, its reliability issue has become one of the critical bottlenecks to improve the lifetime of a high-power white LED package. As the curing process and mechanical behavior of phosphor/silicone composite essentially determine its reliability, this paper firstly uses an in situ viscosity monitoring approach combined with Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR) analysis to explain the curing mechanism of a phosphor/silicone composite by taking the effects of temperature and phosphor mass fraction into consideration. Then, the mechanical properties of phosphor/silicone composites aged under a long-term high moisture condition are evaluated by using the tensile test. Meanwhile, the finite element (FE) simulations, the Mori–Tanaka theoretical estimations and the microstructure analysis are applied to investigate the high moisture induced degradation mechanisms. The results show that: (1) the in situ measured isothermal viscosity curves of both pristine silicone and phosphor/silicone composites follow the Arrhenius empirical model, and high temperature and high phosphor mass fraction can increase the curing rate; (2) the hydrosilylation reaction between silicones determines the curing mechanism of phosphor/silicone composite; (3) the tensile test, FE simulation and Mori–Tanaka theoretical prediction results confirm that the Young’s modulus of phosphor/silicone composite increases by gradually adding phosphors; and (4) the Young’s modulus of phosphor/silicone composite increases after the high moisture ageing test, which can be attributed to the oxidation and cross-linking reaction of silicone and the hydrolysis of phosphor powders. Full article

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18 pages, 4230 KiB

Open AccessArticle

Design and Synthesis of a New Mannitol Stearate Ester-Based Aluminum Alkoxide as a Novel Tri-Functional Additive for Poly(Vinyl Chloride) and Its Synergistic Effect with Zinc Stearate

by Wenyuan Han, Manqi Zhang, Degang Li, Tianbao Dong, Bing Ai, Jianping Dou and Hongqi Sun

Polymers 2019, 11(6), 1031; https://doi.org/10.3390/polym11061031 - 11 Jun 2019

Cited by 20 | Viewed by 6182

Abstract

Thermal stabilizers, lubricant, and plasticizers are three crucial additives for processing poly(vinyl chloride) (PVC). In this study, a new mannitol stearate ester-based aluminum alkoxide (MSE-Al) was designed and synthesized as a novel additive for PVC. The thermal stability and processing performance of PVC [...] Read more.

Thermal stabilizers, lubricant, and plasticizers are three crucial additives for processing poly(vinyl chloride) (PVC). In this study, a new mannitol stearate ester-based aluminum alkoxide (MSE-Al) was designed and synthesized as a novel additive for PVC. The thermal stability and processing performance of PVC stabilized by MSE-Al were evaluated by the Congo red test, conductivity measurement, thermal aging test, ultravioletevisible (UV–Vis) spectroscopy test, and torque rheometer test. Results showed that the addition of MSE-Al could not only markedly improve the long-term thermal stability of PVC, but also greatly accelerate the plasticizing and decrease the balance torque, which demonstrated that MSE-Al possessed a lubricating property. Thus, MSE-Al was demonstrated to be able to provide tri-functional additive roles, e.g., thermal stabilizer, plasticizer, and lubricant. The test results for the thermal stability of PVC indicated that the initial whiteness of PVC stabilized by MSE-Al was not good enough, thus the synergistic effect of MSE-Al with zinc stearates (ZnSt₂) on the thermal stability of PVC was also investigated. The results showed that there is an appreciable synergistic effect between MSE-Al and ZnSt₂. The thermal stabilization mechanism and synergism effect of MSE-Al with ZnSt₂ are then discussed. Full article

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12 pages, 4606 KiB

Open AccessArticle

Inhibition Effect of Graphene Nanoplatelets on Electrical Degradation in Silicone Rubber

by Tao Han, Boxue Du, Jingang Su, Yu Gao, Yunqi Xing, Shengchen Fang, Chuanyang Li and Zhipeng Lei

Polymers 2019, 11(6), 968; https://doi.org/10.3390/polym11060968 - 3 Jun 2019

Cited by 9 | Viewed by 3010

Abstract

Silicone rubber (SIR) is widely used as an insulation material in high voltage cable accessories. Electrical tree is a typical electrical degradation and is easily initiated because of the distorted electric field. In this study, graphene nanoplatelets at contents of 0.001–0.010 wt % [...] Read more.

Silicone rubber (SIR) is widely used as an insulation material in high voltage cable accessories. Electrical tree is a typical electrical degradation and is easily initiated because of the distorted electric field. In this study, graphene nanoplatelets at contents of 0.001–0.010 wt % (0.00044–0.00436 vol %) were added into SIR to improve the electrical tree inhibiting ability. Scanning electron microscopy, conductivity and surface potential decay tests were conducted to analyze the characteristics of graphene/SIR nanocomposites. The typical electrical treeing experiment was employed to observe the electrical tree inhibition of graphene in SIR. The results show that graphene nanoplatelets were well dispersed in SIR. The conductivity was higher after the addition of graphene nanoplatelets, and the trap distribution was affected by graphene nanoplatelets. The tree was changed from a bush-branch structure to a bush structure after the addition of graphene. Tree inception voltage improved and reached the highest mean value at 0.003 wt %. The tree length was inhibited at 0.001 to 0.007 wt % and the lowest tree length occurred at 0.005 wt %. Full article

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13 pages, 3866 KiB

Open AccessArticle

Degradation of Metal-Organic Framework Materials as Controlled-Release Fertilizers in Crop Fields

by Ke Wu, Changwen Du, Fei Ma, Yazhen Shen, Dong Liang and Jianmin Zhou

Polymers 2019, 11(6), 947; https://doi.org/10.3390/polym11060947 - 1 Jun 2019

Cited by 28 | Viewed by 5254

Abstract

The behavior of a metal-organic framework (MOF) compound synthesized in hydrothermal reaction conditions and rich in N, P, and Fe nutrients was explored in the field. The attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy and laser induced breakdown spectroscopy (LIBS) characterization results showed [...] Read more.

The behavior of a metal-organic framework (MOF) compound synthesized in hydrothermal reaction conditions and rich in N, P, and Fe nutrients was explored in the field. The attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy and laser induced breakdown spectroscopy (LIBS) characterization results showed that the chemical structures changed during the degradation process in crop field soil. The scanning electron microscope images showed that the micro-rod of the MOF peeled off and degraded in layers. During the growth period of wheat, the MOF degraded by 50.9%, with the degradation rate being closely related to soil temperature. It was also found that the degradation rate increased with soil temperature. Moreover, the nutrient concentration of the soil indicated that the MOF had stable nutrients release efficiencies and could provide a continuous supply of nutrients throughout the wheat growth period, which showed a great alternative for MOF as a fertilizer both benefiting agricultural production and environmental protection. Full article

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20 pages, 4577 KiB

Open AccessEditor’s ChoiceArticle

Influence of Oxidation Level of Graphene Oxide on the Mechanical Performance and Photo-Oxidation Resistance of a Polyamide 6

by Roberto Scaffaro and Andrea Maio

Polymers 2019, 11(5), 857; https://doi.org/10.3390/polym11050857 - 10 May 2019

Cited by 39 | Viewed by 4445

Abstract

The aim of this work is to study the relationship between the chemical-physical properties of graphene oxide (GO) and the performance of a polyamide 6 (PA6) in terms of mechanical reinforcement and resistance to UV-exposure. For this purpose, two samples of GO possessing [...] Read more.

The aim of this work is to study the relationship between the chemical-physical properties of graphene oxide (GO) and the performance of a polyamide 6 (PA6) in terms of mechanical reinforcement and resistance to UV-exposure. For this purpose, two samples of GO possessing different oxidation degrees were added (0.75 wt.%) to PA6 by way of a two-step technique and the materials achieved were carefully analysed from a morphological, chemical-physical, mechanical point of view. Photo-oxidation tests were carried out to assess the performance of this class of nanohybrids after 240 h of UV-exposure. The results reveal that both nanocomposites exhibit enhanced mechanical performance and durability of PA6. However, the most oxidized GO led to a higher increase of mechanical properties and a stronger resistance to UV-exposure. All the analyses confirm that both GO samples are well dispersed and covalently attached to PA6. However, the higher the oxidation level of GO the stronger and the more extended the chemical interphase of the nanocomposite. As regards photochemical stability, both GO samples display UV-shielding capacity but the most oxidized GO also shows radical scavenging activity by virtue of its nanocavities and defects, imparted by prolonged oxidation, which endows PA6 with an outstanding durability even after 240 h of UV-exposure. Full article

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16 pages, 7337 KiB

Open AccessArticle

Facile Synthesis of Di-Mannitol Adipate Ester-Based Zinc Metal Alkoxide as a Bi-Functional Additive for Poly(Vinyl Chloride)

by Yuepeng Li, Degang Li, Wenyuan Han, Manqi Zhang, Bing Ai, Lipeng Zhang, Hongqi Sun and Zhen Cui

Polymers 2019, 11(5), 813; https://doi.org/10.3390/polym11050813 - 6 May 2019

Cited by 15 | Viewed by 4303

Abstract

A new di-mannitol adipate ester-based zinc metal alkoxide (DMAE-Zn) was synthesized as a bi-functional poly(vinyl chloride) (PVC) thermal stabilizer for the first time. The materials were characterized with Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). Characterization results confirmed the formation of [...] Read more.

A new di-mannitol adipate ester-based zinc metal alkoxide (DMAE-Zn) was synthesized as a bi-functional poly(vinyl chloride) (PVC) thermal stabilizer for the first time. The materials were characterized with Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). Characterization results confirmed the formation of Zn–O bonds in DMAE-Zn, and confirmed that DMAE-Zn had a high decomposition temperature and a low melting point. The thermal stability of DMAE-Zn on PVC also was tested by a conductivity test, a thermal aging test, and a UV-visible spectroscopy (UV-VIS) test. PVC stabilized by DMAE-Zn had a good initial color and excellent long-term stability. UV-VIS also showed that the conjugated structure in PVC stabilized by DMAE-Zn was almost all of the triene, suggesting that the addition of DMAE-Zn would suppress the formation of conjugated structures above tetraene. The dynamic processing performance of PVC samples tested by torque rheometer indicated that, having a good compatibility with PVC chains in the amorphous regions, DMAE-Zn contributed a good plasticizing effect to PVC. DMAE-Zn thus effectively demonstrates bi-functional roles, e.g., thermal stabilizers and plasticizers to PVC. Furthermore, FT-IR, a HCl absorption capacity test, and a complex ZnCl₂ test were also used to verify the thermal stability mechanism of DMAE-Zn for PVC. Full article

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13 pages, 4715 KiB

Open AccessArticle

Probing Chemical Changes in Holocellulose and Lignin of Timbers in Ancient Buildings

by Chencheng Zhao, Xiaochun Zhang, Lina Liu, Youming Yu, Wei Zheng and Pingan Song

Polymers 2019, 11(5), 809; https://doi.org/10.3390/polym11050809 - 6 May 2019

Cited by 20 | Viewed by 3949

Abstract

Wooden structures in China’s ancient buildings hold highly historical and cultural values. There is an urgent need to repair and replace the damaged wooden structures after hundreds and thousands of years of exposure to weather. Unfortunately, to date there is still a lack [...] Read more.

Wooden structures in China’s ancient buildings hold highly historical and cultural values. There is an urgent need to repair and replace the damaged wooden structures after hundreds and thousands of years of exposure to weather. Unfortunately, to date there is still a lack of insightful understanding on how the chemical structure, composition, and micro-morphology evolve over the long-term natural aging before artificial ancient timbers can be developed. This work aims to systematically examine the outer surface, middle layer, and inner surface of the same piece of Chinese fir (Cunninghamia lanceolate) collected from an ancient Chinese building. Based on qualitative and quantitative analysis, both cellulose and hemicellulose in aged woods are found to experience significant degrees of degradation. The crystalline regions of cellulose are also determined to undergo moderate degradation as compared to the control fresh wood. In comparison, the lignin basically remains unchanged and its content in the inner layer slightly increases, as evidenced by more free phenol groups determined. Relative to the outer and inner layer, the middle layer of the ancient wood shows the lowest degree of degradation close to that of the fresh wood. This work offers guidelines for fabricating artificial ancient woods to repair the destroyed ones in China’s ancient architectures. Full article

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16 pages, 5100 KiB

Open AccessArticle

Improving Thermal Stability of Polyurethane through the Addition of Hyperbranched Polysiloxane

by Shang-Hao Liu, Ming-Yuan Shen, Chen-Feng Kuan, Hsu-Chiang Kuan, Cing-Yu Ke and Chin-Lung Chiang

Polymers 2019, 11(4), 697; https://doi.org/10.3390/polym11040697 - 16 Apr 2019

Cited by 50 | Viewed by 6921

Abstract

Polydimethylsiloxane with hydroxy groups was functionalized to form functionalized polydimethylsiloxane, which subsequently underwent an addition reaction with isophorone diisocyanate to form the prepolymer. Next, 3-aminopropyltriethoxysilane (APTS) reacted with 3-glycidoxypropyltrimethoxysilane (GPTS) to produce bridged polysilsesquioxanes, and sol-gel technology was employed to form hyperbranched polysiloxane [...] Read more.

Polydimethylsiloxane with hydroxy groups was functionalized to form functionalized polydimethylsiloxane, which subsequently underwent an addition reaction with isophorone diisocyanate to form the prepolymer. Next, 3-aminopropyltriethoxysilane (APTS) reacted with 3-glycidoxypropyltrimethoxysilane (GPTS) to produce bridged polysilsesquioxanes, and sol-gel technology was employed to form hyperbranched polysiloxane nanoparticles with hydroxy groups, APTS-GPTS, which was used as the additive. The hyperbranched polysiloxane and the prepolymer containing NCO functional groups then underwent an addition reaction to produce the hybrid materials. Fourier-transform infrared spectroscopy and ²⁹Si nuclear magnetic resonance were used to characterize the structure of the polyurethane hybrid. Regarding thermal stability, after the hyperbranched polysiloxane nanoparticles was introduced, the integral procedural decomposition temperature increased from 348 °C for polyurethane matrix to 859 °C for the hybrid material. The results reveal that the thermal stability of the hybrid material substantially increased by approximately 247%. Full article

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20 pages, 2297 KiB

Open AccessArticle

The Effect of Accelerated Aging on Polylactide Containing Plant Extracts

by Krzysztof Moraczewski, Magdalena Stepczyńska, Rafał Malinowski, Tomasz Karasiewicz, Bartłomiej Jagodziński and Piotr Rytlewski

Polymers 2019, 11(4), 575; https://doi.org/10.3390/polym11040575 - 28 Mar 2019

Cited by 36 | Viewed by 5228

Abstract

In this study, natural extracts of plant origin were used as anti-aging compounds of biodegradable polymers. Coffee (0.5–10 wt%), cocoa, or cinnamon extracts were added to the polylactide matrix. The obtained materials were subjected to an accelerated aging process (720, 1440, or 2160 [...] Read more.

In this study, natural extracts of plant origin were used as anti-aging compounds of biodegradable polymers. Coffee (0.5–10 wt%), cocoa, or cinnamon extracts were added to the polylactide matrix. The obtained materials were subjected to an accelerated aging process (720, 1440, or 2160 h) at 45 °C and 70% relative humidity under continuous UV radiation. The effectiveness of the tested extracts was compared to a commercially available anti-aging compound, 2 wt% of butylated hydroxytoluene. Visual evaluation, scanning electron microscopy, melt flow rate, thermogravimetry, differential scanning calorimetry, tensile strength, and impact tensile tests were performed. We show that the use of smaller amounts of tested extracts is particularly advantageous, which do not adversely affect the properties of polylactide-based materials at low contents. At the same time, their effectiveness in stabilizing tested properties during the accelerated aging process is mostly comparable to or greater than the reference compound. Full article

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18 pages, 11651 KiB

Open AccessArticle

Development and Investigation of Lanthanum Sulfadiazine with Calcium Stearate and Epoxidised Soyabean Oil as Complex Thermal Stabilizers for Stabilizing Poly(vinyl chloride)

by Qiufeng Ye, Xiaotao Ma, Bobin Li, Zhe Jin, Yingying Xu, Cheng Fang, Xiaoya Zhou, Yeqian Ge and Feng Ye

Polymers 2019, 11(3), 531; https://doi.org/10.3390/polym11030531 - 21 Mar 2019

Cited by 20 | Viewed by 5811

Abstract

Lanthanum sulfadiazine (LaSD) was synthesized from sulfadiazine and lanthanum nitrate using water as solvent under alkaline conditions, and was used as a novel rare earth thermal stabilizer to stabilize poly(vinyl chloride) (PVC). The structure of LaSD was characterized by elemental analysis (EA), Fourier [...] Read more.

Lanthanum sulfadiazine (LaSD) was synthesized from sulfadiazine and lanthanum nitrate using water as solvent under alkaline conditions, and was used as a novel rare earth thermal stabilizer to stabilize poly(vinyl chloride) (PVC). The structure of LaSD was characterized by elemental analysis (EA), Fourier transform infrared spectroscopy (FTIR) and thermo- gravimetric analysis (TGA). The influence of lanthanum sulfadiazine with calcium stearate (CaSt₂) and epoxidized soybean oil (ESBO) on stabilizing PVC was studied by using the Congo red test, oven discoloration test, UV-vis spectroscopy and thermal decomposition kinetics. The results showed that the addition of LaSD as a thermal stabilizer can significantly improve the initial whiteness and long-term stability of PVC. In addition, the synergies between LaSD, ESBO, and CaSt₂ can provide outstanding improvement in the long-term thermal stability of PVC. When the ratio of LaSD/ESBO/CaSt₂ is 1.8/0.6/0.6, its thermal stability time is 2193 s which is the best state for stabilizing PVC. Furthermore, comparing the reaction energy (E_a) and the variations in the conjugate double bond concentration in PVC samples, the order of thermal stability of PVC was PVC/LaSD/ESBO/CaSt₂ > PVC/LaSD/ESBO > PVC/LaSD. The thermal stability mechanism of LaSD on PVC was studied by the AgCl precipitation method and FTIR spectrum. The results showed that the action of LaSD on PVC was achieved through replacing unstable chlorine atoms and absorbing hydrogen chloride. Full article

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16 pages, 5846 KiB

Open AccessArticle

Synthesis and Study of Zinc Orotate and Its Synergistic Effect with Commercial Stabilizers for Stabilizing Poly(Vinyl Chloride)

by Feng Ye, Qiufeng Ye, Haihua Zhan, Yeqian Ge, Xiaotao Ma, Yingying Xu and Xu Wang

Polymers 2019, 11(2), 194; https://doi.org/10.3390/polym11020194 - 23 Jan 2019

Cited by 23 | Viewed by 5996

Abstract

Zinc orotate (ZnOr₂), which is a new kind of poly(vinyl chloride) (PVC) stabilizer, is prepared in this work through the precipitation method, and its impact on the thermal stability of PVC is measured by thermogravimetric analysis (TG), Congo red test, and [...] Read more.

Zinc orotate (ZnOr₂), which is a new kind of poly(vinyl chloride) (PVC) stabilizer, is prepared in this work through the precipitation method, and its impact on the thermal stability of PVC is measured by thermogravimetric analysis (TG), Congo red test, and discoloration test. The results exhibit that the thermal stability of PVC is positively enhanced after the addition of ZnOr₂. In contrast with a commercial thermal stabilizer, zinc stearate (ZnSt₂), a noteworthy improvement was observed that ZnOr₂ could postpone the “zinc burning” of PVC. This is principally ascribed to the Or anion in the structure of ZnOr₂ being able to absorb the HCl released by PVC, and to supersede unstable chlorine atoms in the structure of PVC. In addition, blending ZnOr₂ with calcium stearate (CaSt₂) in diverse mass ratios can significantly accelerate the thermal stability of PVC. Optimum performance was achieved with a CaSt₂:ZnOr₂ ratio of 1.8:1.2. Moreover, an outstanding synergistic effect can be observed when CaSt₂/ZnOr₂ is coupled with other commercial auxiliary stabilizers. The initial color and long-term stability of PVC including CaSt₂/ZnOr₂ is significantly increased when pentaerythritol (PER) is added, while dibenzoylmethane (DBM) can only improve its long-term thermal stability. Full article

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15 pages, 6410 KiB

Open AccessArticle

A Study on the Modified Arrhenius Equation Using the Oxygen Permeation Block Model of Crosslink Structure

by Byungwoo Moon, Namgyu Jun, Soo Park, Chang-Sung Seok and Ui Seok Hong

Polymers 2019, 11(1), 136; https://doi.org/10.3390/polym11010136 - 14 Jan 2019

Cited by 31 | Viewed by 9412

Abstract

Polymers are widely used in various industries because of their characteristics such as elasticity, abrasion resistance, fatigue resistance and low temperature. In particular, the tensile characteristic of rubber composites is important for the stability of industrial equipment because it determines the energy absorption [...] Read more.

Polymers are widely used in various industries because of their characteristics such as elasticity, abrasion resistance, fatigue resistance and low temperature. In particular, the tensile characteristic of rubber composites is important for the stability of industrial equipment because it determines the energy absorption rates and vibration damping. However, when a product is used for a long period of time, polymers become hardened owing to the changes in characteristics because of aging, thereby reducing the performance and increasing the possibility of accidents. Therefore, accurately predicting the mechanical properties of polymers is important for preventing industrial accidents while operating a machine. In general reactions, the linear Arrhenius equation is used to predict the aging characteristics; however, for rubber composites, it is more accurate to predict the aging characteristics using nonlinear equations rather than linear equations. However, the reason that the characteristic equation of the polymer appears nonlinear is not well known, and studies on the change in the characteristics of the natural and butadiene rubber owing to degradation are still lacking. In this study, a tensile test is performed with different aging temperatures and aging time to evaluate the aging characteristics of rubber composites using strain energy density. We propose a block effect of crosslink structure to express the nonlinear aging characteristics, assuming that a limited reaction can occur owing to the blocking of reactants in the rubber composites. Consequently, we found that a relationship exists between the crosslink structure and aging characteristics when the reduction in crosslink space owing to aging is represented stochastically. In addition, a modified Arrhenius equation, which is expressed as a function of time, is proposed to predict the degradation rate for all aging temperatures and aging times, and the formula is validated by comparing the degradation rate obtained experimentally with the degradation rate predicted by the modified Arrhenius equation. Full article

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2018

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15 pages, 1759 KiB

Open AccessArticle

A Statistical Analysis on the Effect of Antioxidants on the Thermal-Oxidative Stability of Commercial Mass- and Emulsion-Polymerized ABS

by Rudinei Fiorio, Dagmar R. D’hooge, Kim Ragaert and Ludwig Cardon

Polymers 2019, 11(1), 25; https://doi.org/10.3390/polym11010025 - 25 Dec 2018

Cited by 23 | Viewed by 5825

Abstract

In the present work, statistical analysis (16 processing conditions and 2 virgin unmodified samples) is performed to study the influence of antioxidants (AOs) during acrylonitrile-butadiene-styrene terpolymer (ABS) melt-blending (220 °C) on the degradation of the polybutadiene (PB) rich phase, the oxidation onset temperature [...] Read more.

In the present work, statistical analysis (16 processing conditions and 2 virgin unmodified samples) is performed to study the influence of antioxidants (AOs) during acrylonitrile-butadiene-styrene terpolymer (ABS) melt-blending (220 °C) on the degradation of the polybutadiene (PB) rich phase, the oxidation onset temperature (OOT), the oxidation peak temperature (OP), and the yellowing index (YI). Predictive equations are constructed, with a focus on three commercial AOs (two primary: Irganox 1076 and 245; and one secondary: Irgafos 168) and two commercial ABS types (mass- and emulsion-polymerized). Fourier transform infrared spectroscopy (FTIR) results indicate that the nitrile absorption peak at 2237 cm⁻¹ is recommended as reference peak to identify chemical changes in the PB content. The melt processing of unmodified ABSs promotes a reduction in OOT and OP, and promotes an increase in the YI. ABS obtained by mass polymerization shows a higher thermal-oxidative stability. The addition of a primary AO increases the thermal-oxidative stability, whereas the secondary AO only increases OP. The addition of the two primary AOs has a synergetic effect resulting in higher OOT and OP values. Statistical analysis shows that OP data are influenced by all three AO types, but 0.2 m% of Irganox 1076 displays high potential in an industrial context. Full article

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16 pages, 3219 KiB

Open AccessArticle

Effect of Aging on Chemical and Rheological Properties of Bitumen

by Zhen Yang, Xiaoning Zhang, Zeyu Zhang, Bingjie Zou, Zihan Zhu, Guoyang Lu, Wei Xu, Jiangmiao Yu and Huayang Yu

Polymers 2018, 10(12), 1345; https://doi.org/10.3390/polym10121345 - 5 Dec 2018

Cited by 74 | Viewed by 5821

Abstract

Engineering performance of asphalt pavement highly depends on the properties of bitumen, the bonding material to glue aggregates and fillers together. During the service period, bitumen is exposed to sunlight, oxygen and vehicle loading which in turn leads to aging and degradation. A [...] Read more.

Engineering performance of asphalt pavement highly depends on the properties of bitumen, the bonding material to glue aggregates and fillers together. During the service period, bitumen is exposed to sunlight, oxygen and vehicle loading which in turn leads to aging and degradation. A comprehensive understanding of the aging mechanism of bitumen is of critical importance to enhance the durability of asphalt pavement. This study aims to determine the relations between micro-mechanics, chemical composition, and macro-mechanical behavior of aged bitumen. To this end, the effect of aging on micro-mechanics, chemical functional groups, and rheological properties of bitumen were evaluated by atomic force microscope, Fourier transform infrared spectroscopy and dynamic shear rheometer tests, respectively. Results indicated that aging obviously increased the micro-surface roughness of bitumen. A more discrete distribution of micromechanics on bitumen micro-surface was noticed and its elastic behavior became more significant. Aging also resulted in raised content of carbonyl, sulfoxide, and aromatic ring functional groups. In terms of rheological behavior, the storage modulus of bitumen apparently increased after aging due to the transformation of viscous fractions to elastic fractions, making it stiffer and less viscous. By correlation analysis, it is noted that the bitumen rheological behavior was closely related to its micro-mechanics. Full article

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9 pages, 3390 KiB

Open AccessArticle

Degradation of Polyacrylate in the Outdoor Agricultural Soil Measured by FTIR-PAS and LIBS

by Dong Liang, Changwen Du, Fei Ma, Yazhen Shen, Ke Wu and Jianmin Zhou

Polymers 2018, 10(12), 1296; https://doi.org/10.3390/polym10121296 - 22 Nov 2018

Cited by 30 | Viewed by 8381

Abstract

Recently, polyacrylates (PA) have been applied in coated controlled-release fertilizer (CRF), but the impacts of the soil on the degradation of PA have not been evaluated. In this study, an outdoor agriculture soil buried test was carried out for 12 months to investigate [...] Read more.

Recently, polyacrylates (PA) have been applied in coated controlled-release fertilizer (CRF), but the impacts of the soil on the degradation of PA have not been evaluated. In this study, an outdoor agriculture soil buried test was carried out for 12 months to investigate the degradation of PA films. The residual degraded films were taken regularly from the soil and analyzed by SEM, Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) and laser-induced breakdown spectroscopy (LIBS). The concentration of C–H and C=O molecular groups of PA were decreased, and the element concentrations of C, O, K, Si of PA were increased under the degradation process. The surface of PA became rough and the degradation of PA occurred on the surface layer. Principal component analysis (PCA) showed that soil invaded PA. The results indicated that PA were environmentally friendly when applied to CRF. FTIR-PAS and LIBS were advanced in the in-situ surface analysis of the degradation process of the polymer. Full article

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11 pages, 3095 KiB

Open AccessArticle

Influence of Amine Compounds on the Thermal Stability of Paper-Oil Insulation

by Ningchuan Liang, Ruijin Liao, Min Xiang, Yang Mo and Yuan Yuan

Polymers 2018, 10(8), 891; https://doi.org/10.3390/polym10080891 - 9 Aug 2018

Cited by 10 | Viewed by 4021

Abstract

Amine compounds can greatly enhance the thermal stability of the insulating paper used in paper-oil insulation. Many research documents focus on paper‘s excellent thermal stability, but less attention has been paid to the effect of oil on paper’s degradation. In this research paper, [...] Read more.

Amine compounds can greatly enhance the thermal stability of the insulating paper used in paper-oil insulation. Many research documents focus on paper‘s excellent thermal stability, but less attention has been paid to the effect of oil on paper’s degradation. In this research paper, we study the influence of different amine compounds on the thermal stability of both paper and oil, and a mechanism for the influence on paper-oil insulation as well as an optimal formula are proposed. First, six groups of paper were modified with different proportions of dicyandiamide (DICY), melamine, and polyacrylamide (PAM). Then, an accelerated thermal aging test at 130 °C was conducted for 30 days and the thermal aging characteristics of the oil-modified paper insulation were measured. The results showed that the thermal stability of the insulation paper modified with the amine compounds was remarkably improved, and P2 (2.25 wt % melamine, 0.75 wt % DICY, and 0.2 wt % PAM) presented the best anti-aging properties. However, certain properties of oil were influenced, such as acid value, and it was found that the ammonia produced by the amine stabilizers increased the copper compound content, which led to the deterioration of the insulating oil. Moreover, using a front-line orbital energy analysis by molecule modeling, it was determined that melamine was the core thermal stabilizer for the paper among the three amine compounds used in P2. Full article

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10 pages, 1934 KiB

Open AccessArticle

Study on the Aging Behavior of Natural Rubber/Butadiene Rubber (NR/BR) Blends Using a Parallel Spring Model

by Byungwoo Moon, Jongmin Lee, Soo Park and Chang-Sung Seok

Polymers 2018, 10(6), 658; https://doi.org/10.3390/polym10060658 - 12 Jun 2018

Cited by 49 | Viewed by 7160

Abstract

Natural rubber/butadiene rubber (NR/BR) blends are widely used in industrial areas for absorbing vibrations and shocks because of their excellent elastic stability. However, when an industrial-equipment surface is exposed to sunlight and oxygen over a long period of time, the rubber hardens. As [...] Read more.

Natural rubber/butadiene rubber (NR/BR) blends are widely used in industrial areas for absorbing vibrations and shocks because of their excellent elastic stability. However, when an industrial-equipment surface is exposed to sunlight and oxygen over a long period of time, the rubber hardens. As a result, the tensile properties of the rubber material and the behavior of the strain-energy density function are changed, greatly reducing the performance of the rubber product. However, only a few experimental studies on the aging characteristics of NR/BR blends are available, and it is difficult to find a study that analyzes the organic relationship of the changes in the mechanical (stress–strain curves, strain-energy density, etc.) and chemical (cross-linked structure, crosslink density, etc.) properties. In this study, a swelling test was performed on an aged rubber compound, and the result was substituted into the Flory–Rehner equation to obtain the quantitative crosslink density. The results revealed a linear relationship between the strain-energy density (SED) and the crosslink density (CLD) when the cross-linked structure increase was represented by a parallel spring model. Finally, the relationship between the strain-energy density and the crosslink density was summarized as a formula, and a method for predicting the aging behavior of NR/BR blends using the crosslink density was proposed. Full article

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