An epoxy resin composites with excellent thermal stability and acid corrosion resistance modified by glass flake and polyurethane

A novel phosphorus-nitrogen-containing flame retardant (DOPT) has been successfully synthesized via the substitution reaction of cyanuric chloride, pentaerythritol phosphate and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. The chemical structure of DOPT was confirmed by 1H, 31P and 13C nuclear magnetic resonance, Fourier transform infrared spectroscopy and elemental analysis. Then, flame retardants were added to epoxy resin to prepare epoxy resin composites by pouring method. Thermal properties, flame retardancy, and combustion behavior of epoxy resin composites were evaluated by thermogravimetric analysis, vertical burning, limiting oxygen index and cone calorimeter test. Thermogravimetric analysis test showed that the carbon residue rate of DOPT at 800°C reached 52.53%, which indicated that the introduction of high-efficiency char-forming agent triazine and pentaerythritol phosphate groups could significantly improve its char-forming performance and thermal stability. The epoxy resin composite achieved vertical burning V-0 grade and the limiting oxygen index value reached 35.5% when 7 wt% DOPT was incorporated. Furthermore, the cone calorimeter test results manifested that the addition of DOPT stimulated degradation of the epoxy resin matrix during the combustion process and accelerated the formation of an expanded and dense carbon layer. Additionally, the incombustible gas produced during the decomposition of DOPT had played a flame-retardant effect in the gas phase. Hence, compared with neat epoxy resin, the total heat release and total smoke production of the EP-7 wt% DOPT composite decreased by 14.0% and 25.3%, respectively. Moreover, owing to the excellent compatibility and the strong interface effect between DOPT and epoxy resin, the addition of DOPT also enhanced the mechanical and fire resistance properties of the epoxy resin composite. Therefore, it is proposed that DOPT could be exploited as an economical and high-efficiency flame retardant, and it has considerable prospects in flame retardant epoxy resin composites.

Purpose – The purpose of this research is to synthesize modified thermoplastic sago starch (TPS) through in-situ mechanism by reacting sago starch with diphenylmethanediisocyanate (MDI) and castor oil simultaneously, resulting in a more homogenous and finer-sized polyurethane prepolymer (PUP). Design/Methodology/Approach – The methods used were Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) for thermal characterization and stability of PUP, modified TPS non-extracted and extracted with toluene and water. Findings – TGA test results presented shows that PUP begins to decompose thermally at a temperature of 300–500 °C. Weight loss occurs rapidly between these temperatures and is completely discharged at a temperature of 500°C, which is called weight loss transition. Research Limitations/Implications – When extracted with toluene and a water solvent, the melting point and latent heat of fusion slightly decreased; however, it is still higher than the original value of sago. In terms of thermal stability, modified TPS decomposes and loses weight at 150–200 °C in small quantities, continues with weight loss rapidly, and is completely discharged at 500°C. The thermal stability is considered high; thus, modified TPS application can be varied. Practical Implications – DSC analysis and TGA shows that modified TPS has good thermal characteristics and thermal stability. Modified TPS has a melting point of 104.69°C, and the latent heat of fusion (ΔH) is 234.27 J/g. This value is close to the PUP melting point and latent heat of fusion, which reveals the formation of cross-link between the starch and PUP.

Development and characterization of silicone/phosphorus modified epoxy materials and their application as anticorrosion and antifouling coatings

A novel phosphazene-based compound called hexaphenoxycyclotriphosphazene (HPCTP) was synthesized and characterized by Fourier transform infrared spectroscopy as well as proton and phosphorus nuclear magnetic resonance spectroscopies. Epoxy (EP) resin composites containing HPCTP and octapropylglycidylether polyhedral oligomeric silsesquioxane (OGPOSS) were prepared using 4,4′-diamino diphenylmethane as curing agent. Differential scanning calorimetry, thermogravimetric analysis, UL 94 vertical burning test, and cone calorimetry test were used to assess thermal stability and flame retardancy of the composites. Evaluation of thermal properties demonstrated that the resulting composites achieved less thermal stability compared with control EP resin but possessed high char yields at high temperatures. It indicated that both HPCTP and OGPOSS could induce the formation of intumescent char layer that retarded the degradation and combustion process of EP resin. The peak heat release rate of EP resin composite containing 15 wt% HPCTP was 61% less than that of control EP resin. Meanwhile, other flame-retardant parameters were also improved. Results of scanning electron microscopy and energy-dispersive x-ray spectroscopy of residual chars confirmed that both HPCTP and OGPOSS can enhance thermal stability and flame retardancy of EP resin.

Different kinds of composites based on polymer matrix are present on the market. In particular, composites based on epoxy resin are used as high-performance polymers due to their excellent mechanical properties, chemical resistance, thermal stability and low cost production. Recently, in composites production the attention has been focused on the study of materials derived from biomass and organic waste to be used as filler. Hydrochar is a carbonaceous material obtained from hydrothermal carbonization (HTC) of biomasses and organic waste. During HTC biomass is carbonized in an aqueous environment at temperatures of 180-250 °C under saturated pressure (autogenous or provided by a gas) for several hours. For its characteristics, hydrochar can be potentially used as filler in composite materials in view of the growing concern about environmental sustainability. In this work, hydrochar obtained from hydrothermal carbonization of green waste was used as filler for the preparation of diglycidyl ether of bisphenol A-type epoxy composite materials. Two different epoxy matrices were used; the content of hydrochar was varied between 5 and 15 wt%. The resulting samples were characterized by morphologic and mechanical analyses, and electrical properties were evaluated. The addition of hydrochar to epoxy resins resulted in a slight increase of the elastic modulus, although there was a decrease in tensile strength and toughness. Moreover, electrical properties of epoxy resins were not significantly modified by the addition of hydrochar. Therefore, the study provided encouraging results for the production of innovative hydrochar-based epoxy composites, allowing the recycling and re-use of industrial waste.

ABSTRACTThree kinds of inherent flame‐retardant epoxy resin (EP) composites with 20 wt % benzoxazine (BOZ) were prepared with different curing processes with 2‐methyl‐1H‐imidazole (MI) as a catalyst or/and changes in the curing temperature. The effects of the curing process on the flame retardancy, thermal stability, mechanical properties, and curing behaviors were investigated. The composite with added MI cured at low temperature (EBM–LT) had the best properties. It possessed a 35.3% limiting oxygen index and achieved a UL 94 V‐0 rating. Thermogravimetric analysis indicated that EBM–LT had the best thermal stability among the three kinds of EP composites with BOZ. The EP composites with BOZ mainly displayed a condensed‐phase flame‐retardant mechanism. The mechanical properties improvement was attributed to the formation of a heterogeneous network. Differential scanning calorimetry indicated that MI reacted with EP and catalyzed the homopolymerization of BOZ, and EP reacted with BOZ. Fourier transform infrared spectroscopy analysis indicated that curing at lower temperature caused the formation of more homopolymers of BOZ. The relationship of the curing process, network structure, and properties of EP composites with BOZ was established; this could help with the design of high‐performance EP composites with BOZ. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47847.

New FeNiCrMo(P, C, B) high-entropy bulk metallic glasses with unusual thermal stability and corrosion resistance

Epoxy resins are increasingly finding applications in the field of structural engineering. A wide variety of epoxy resins are available, and some of them are characterized by a relatively low toughness. One approach to improve epoxy resin toughness includes the addition of either a rigid phase or a rubbery phase. A more recent approach to toughen brittle polymers is through interpenetrating network (IPN) grafting. It has been found that the mechanical properties of polymer materials with an IPN structure are fairly superior to those of ordinary polymers. Therefore, the present work deals with epoxy resin toughening using a polyurethane (PU) prepolymer as modifier via IPN grafting. For this purpose, a PU prepolymer based on hydroxyl-terminated polyester has been synthesized and used as a modifier at different concentrations. First, the PU-based hydroxyl-terminated polyester has been characterized. Next, an IPN (Epoxy–PU) has been prepared and characterized using Fourier transform infrared (FTIR) spectroscopy, thin-layer chromatography (TLC), and scanning electron microscopy (SEM) prior to mechanical testing in terms of impact strength and toughness. In this study, a Desmophen 1200-based PU prepolymer was used as a modifier at different concentrations within the epoxy resin. The results also showed that, further to the IPN formation, the epoxy and the PU prepolymer reacted chemically (via grafting). Compared to virgin resin, the effect on the mechanical properties was minor. The impact strength varies from 3–9 J/m and Kc from 0.9–1.2 MPa m1/2. Furthermore, the incorporation of a chain extender with the PU prepolymer as a modifier into the mixture caused a drastic improvement in toughness. The impact strength increases continuously and reaches a maximum value (seven-fold that of virgin resin) at a modifier critical concentration (40 phr). Kc reaches 2.5 MPa m1/2 compared to 0.9 MPa m1/2 of the virgin resin. Finally, the SEM analysis results suggested that internal cavitation of the modifier particles followed by localized plastics shear yielding is probably the prevailing toughening mechanism for the epoxy resin considered in the present study. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2603–2618, 1998

Role of surface functionalization on corrosion resistance and thermal stability of epoxy/glass flake composite coating on cold rolled steel

Epoxy resin compositions are used in modern railways, replacing other materials. However, epoxy composites in public transport are subject to many requirements, including that they should be flame retardant and resistant to weather conditions. The aim of the research was to analyse the resistance to solar ageing of epoxy resin composites containing flame retardants and the addition of the natural stabilising substance-quercetin. The homogeneity of the samples (optical microscopy and FTIR spectroscopy) and their thermal stability (TGA thermogravimetry) were analysed. The T5 temperature, which is the initial temperature of thermal decomposition of the samples, was 7 °C higher for the epoxy resin containing quercetin, so the material with polyphenol was characterised by better thermal resistance. Changes in material properties (hardness, surface energy, carbonyl index, colour) after 800 h solar ageing were investigated. The tensile tests on materials were executed for three different directions before and after ageing effect. The samples showed good resistance to degradation factors, i.e., they retained the functional properties (hardness and mechanical properties). However, analysis of carbonyl indices and surface energies showed that changes appeared in the composites after solar ageing, suggesting the beginning of material degradation. An approximately 3-fold increase in the polar component in epoxy resin compositions (from approximately 3 mN/m to approximately 11 mN/m) is associated with an increase in their hydrophilicity and the progress of ageing of the materials' surface. The obtained results are an introduction to further research on the long-term degradation processes of epoxy resins with plant stabilisers.

Anti-corrosion of amphoteric metal enhanced by MAO/corrosion inhibitor composite in acid, alkaline and salt solutions

Phosphorus‐containing flame retardant (HBAEA‐DOPO) for epoxy resin was synthesized by addition reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) with bis[2‐(4‐hydroxybenzylideneamino)ethyl]amine (HBAEA) that was synthesized via 4‐hydroxybenzaldehyde with diethylenetriamine. HBAEA‐DOPO was mixed with 4,4′‐diaminodiphenyl sulfone to co‐cure the epoxy resin of diglycidyl ether bisphenol A. The silane modified nano‐silica (nano‐SiO2) was used to reinforce the epoxy resin. Thermal stability and dynamic mechanical properties of the cured epoxy materials were studied with the use of thermogravimetric analysis and dynamic mechanical thermal analysis. Flame retardance and burning behavior were evaluated by the limiting oxygen index (LOI), vertical burning test, and the cone calorimetry. The cured epoxy materials have excellent thermal stability, and the temperatures at the maximum weight loss rate are over 384.0°C. The characteristic temperature corresponding to 5.00 wt% of thermal decomposition reaches 341.5°C as 1.00 wt% of phosphorus content is loaded. Flame retardant grade meets the V‐0 level. The fire residue mass gradually increases with HBAEA‐DOPO and nano‐SiO2. The characteristics of high flame retardance and smoke suppression of HBAEA‐DOPO and nano‐SiO2 on the cured epoxy composites have been demonstrated to be related to char formation and intumescent flame retardance in the condensed phase.

The epoxy polymers are characterized by low thermal stability and high flammability. Nanoparticles are considered to be effective fillers of polymer composites for improving their thermal and functional properties. In this work, the epoxy composites were prepared using epoxy resin ED-20, polyethylene polyamine as a hardener, aluminum nanopowder and boric acid fine powder as flame-retardant filler. The thermal characteristics of the obtained samples were studied using thermogravimetric analysis and differential scanning calorimetry. The mechanical characteristics of epoxy composites were also studied. It was found that an addition of all fillers enhances the thermal stability and mechanical characteristics of the epoxy composites. The best thermal stability showed the epoxy composite filled with boric acid. The highest flexural properties showed the epoxy composite based on the combination of boric acid and aluminum nanopowder.

This study investigates the utilization of sugarcane bagasse and glass fiber to reinforce epoxy composites, enhancing both mechanical and fire resistance properties. Initially, bagasse is collected, sun‐dried, and finely ground before being treated with lime water at concentrations of 3%, 5%, and 7% by weight. The treated bagasse is then mixed with epoxy resin and a hardening agent, followed by a curing process. For samples incorporating glass fibers, the fibers are manually integrated and cured similarly. The methodology involved detailed preparation of the bagasse, its treatment, and subsequent integration with epoxy resin. The mixture was processed under controlled conditions to ensure uniformity and quality. Mechanical properties such as tensile strength, flexural strength, compressive strength, and impact resistance were measured. Thermogravimetric analysis (TGA) was employed to assess thermal stability, while fire resistance was evaluated using the limiting oxygen index (LOI) and the 94‐V test method. Results demonstrated significant improvements in both mechanical and thermal properties with the addition of bagasse and glass fibers. The optimal treatment was identified at a 5% lime water concentration, yielding a tensile strength of 295.08 MPa, flexural strength of 371.24 MPa, compressive strength of 255.39 MPa, and Izod impact strength of 157.04 kJ/m2. TGA results showed the highest thermal stability at 5% concentration, with decomposition temperatures peaking at 402.52 °C. Fire resistance was markedly enhanced, achieving an LOI of 29.8% and meeting V2 level standards according to the 94‐V test method. In conclusion, treating sugarcane bagasse with a 5% lime water solution significantly enhances the mechanical and fire‐resistant properties of epoxy composites. The combination of sugarcane bagasse and glass fiber creates a robust material with high thermal stability and fire resistance, making it a viable option for applications requiring these enhanced properties.

Besides polyurethanes and polyesters, phenolic and epoxy resins are the most prominent applications for technical lignins in thermosetting materials. To evaluate the potential application of lignin raw materials in phenol formaldehyde and epoxy resins, three types of alkaline lignins were characterized in terms of their structures and thermal properties. The lignin samples analyzed were kraft lignin (LIG-1), soda–rice straw lignin (LIG-2), and soda-wheat straw lignin (LIG-3). FTIR and 1H-NMR methods were used to determine their structure. Gel permeation chromatography (GPC) was used to determine the molecular weight distribution (MWD). Differential scanning calorimetry (DSC) was used to measure the glass transition temperature (Tg), and thermogravimetric analysis (TGA) to determine the thermal stability of lignin samples. Results showed that kraft lignin (LIG-1) has moderate hydroxyl-group content, is rich in G-type units, and has good thermal stability. These properties make it more suitable for direct use in phenol formaldehyde resins, and it is therefore a good raw material for this purpose. The alkaline soda-rice straw lignin (LIG-2) with a high hydroxyl-group content and excellent thermal stability is most suited to preparing lignin-based epoxy resins.