scholarly journals Phosphorus-Containing Silsesquioxane Derivatives as Additive or Reactive Components of Epoxy Resins

Materials ◽  
2020 ◽  
Vol 13 (23) ◽  
pp. 5373
Author(s):  
Mariusz Szołyga ◽  
Michał Dutkiewicz ◽  
Marek Nowicki ◽  
Kamila Sałasińska ◽  
Maciej Celiński ◽  
...  
Keyword(s):  
Epoxy Resin ◽  
Hybrid Materials ◽  
Flame Retardants ◽  
Epoxide Ring ◽  
Cone Calorimetry ◽  
Scanning Calorimetry ◽  
Water Contact ◽  
Phosphorus Containing ◽  
The Impact ◽  
Phosphate Groups

Two phosphorus-containing cage-like silsesquioxane derivatives were synthesized as reactive or additive flame retardants for epoxy resin. The silsesquioxanes were obtained via an epoxide ring-opening reaction using a 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPA). In one derivative containing in its structure 4 glycidoxypropyl and 4 phosphate groups, denoted as 4P4GS, only half of the epoxy rings was reacted with phosphate to obtain a reactive additive, while in the second derivative containing 8 phosphate groups, denoted as 8PS, all epoxy groups were converted, thus an additive modifier was obtained. The silsesquioxanes containing phosphorus atoms and the reactive phosphorus-free silsesquioxane derivative (octakis[(3-glycidoxypropyl)dimethylsiloxy]octasilsesquioxane (8GS)) were used to prepare hybrid materials based on epoxy resin. To compare the impact of the structure of silsesquioxane derivatives on the properties of hybrid materials, a number of samples containing 1, 5, and 10% of the modifiers making a series of epoxy materials containing additive or reactive modifiers, were obtained. The modified epoxies were studied using scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), nanoindentation, water contact angle, and cone calorimetry tests to assess the effects of the modifier structure on the physicochemical properties of the investigated materials.

scholarly journals Synthesis of Novel Polymeric Acrylate-Based Flame Retardants Containing Two Phosphorus Groups in Different Chemical Environments and Their Influence on the Flammability of Poly (Lactic Acid)

Polymers ◽  
2020 ◽  
Vol 12 (4) ◽  
pp. 778 ◽  
Author(s):  
Jacob Sag ◽  
Philipp Kukla ◽  
Daniela Goedderz ◽  
Hendrik Roch ◽  
Stephan Kabasci ◽  
...  
Keyword(s):  
Flame Retardant ◽  
Mode Of Action ◽  
Flame Retardants ◽  
Fire Behavior ◽  
Heat Fluxes ◽  
Poly Lactic Acid ◽  
Cone Calorimetry ◽  
Scanning Calorimetry ◽  
Fire Scenarios ◽  
Physical Phenomena

Novel polymeric acrylate-based flame retardants (FR 1–4) containing two phosphorus groups in different chemical environments were synthesized in three steps and characterized via nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mass spectrometry (MS). Polylactic acid (PLA) formulations with the synthesized compounds were investigated to evaluate the efficiency of these flame retardants and their mode of action by using TGA, UL94, and cone calorimetry. In order to compare the results a flame retardant polyester containing only one phosphorus group (ItaP) was also investigated in PLA regarding its flame inhibiting effect. Since the fire behavior depends not only on the mode of action of the flame retardants but also strongly on physical phenomena like melt dripping, the flame retardants were also incorporated into PLA with higher viscosity. In the UL94 vertical burning test setup, 10% of the novel flame retardants (FR 1–4) is sufficient to reach a V-0 rating in both PLA types, while a loading of 15% of ItaP is not enough to reach the same classification. Despite their different structure, TGA and cone calorimetry results confirmed a gas phase mechanism mainly responsible for the highly efficient flame retardancy for all compounds. Finally, cone calorimetry tests of the flame retardant PLA with two heat fluxes showed different flame inhibiting efficiencies for different fire scenarios.

scholarly journals Curing Kinetics, Mechanical Properties and Thermomechanical Analysis of Carbon Fiber/epoxy Resin Laminates with Different Ply Orientations

2021 ◽  
Author(s):  
Chenglin Zhang ◽  
Guohua Gu ◽  
Shuhua Dong ◽  
Zhitao Lin ◽  
Chuncheng Wei ◽  
...  
Keyword(s):  
Carbon Fiber ◽  
Impact Strength ◽  
Epoxy Resin ◽  
Composite Laminates ◽  
Bending Strength ◽  
Fiber Composite ◽  
Curing Process ◽  
Scanning Calorimetry ◽  
The Impact ◽  
Carbon Fiber Epoxy

Abstract In this study, the nonisothermal differential scanning calorimetry (DSC) was carried out to evaluate the curing reaction of fiber/epoxy laminates. The optimal curing process of the prepreg was obtained by T-β extrapolation method and nth-order reaction curing kinetic equation. The bending strength, impact strength and thermodynamic properties of the composite laminates with different ply orientations were investigated, respectively. The results show that the apparent activation energy and the reaction order of the prepregs are 82.89 kJ/mol and 0.92, respectively. The curing process of carbon fiber/epoxy resin prepreg is 130 ℃ /60min + 160 ℃/30 min. The bending strength of [0]10 laminate is 1948.3 MPa, which is 11.8 times higher than that of [+ 45/-45]5s laminate, and 96.4% higher than that of [0/90]5s laminate. The impact strength of [0]10 laminate is higher than that of [+ 45/-45]5s and [0/90]5s laminates. The glass transition temperature (Tg) of the laminates is 142 ~ 146 ℃, and the loss factor of [0]10 laminate is significantly higher than that of [+ 45/-45]5s and [0/90]5s laminates. This research provides a theoretical basis for the further application of prepregs to fiber composite materials.

scholarly journals New Biosourced Flame Retardant Agents Based on Gallic and Ellagic Acids for Epoxy Resins

Molecules ◽  
2019 ◽  
Vol 24 (23) ◽  
pp. 4305 ◽  
Author(s):  
Valeriia Karaseva ◽  
Anne Bergeret ◽  
Clément Lacoste ◽  
Hélène Fulcrand ◽  
Laurent Ferry
Keyword(s):  
Phenolic Compounds ◽  
Epoxy Resin ◽  
Epoxy Resins ◽  
Flame Retardants ◽  
Fire Behavior ◽  
Diglycidyl Ether ◽  
Scanning Calorimetry ◽  
Burning Behavior ◽  
Borate Ester ◽  
Thermal Stability Of

The aim of this work was an investigation of the ability of gallic (GA) and ellagic (EA) acids, which are phenolic compounds encountered in various plants, to act as flame retardants (FRs) for epoxy resins. In order to improve their fireproofing properties, GA and EA were treated with boric acid (to obtain gallic acid derivatives (GAD) and ellagic acid derivatives (EAD)) to introduce borate ester moieties. Thermogravimetric analysis (TGA) highlighted the good charring ability of GA and EA, which was enhanced by boration. The grafting of borate groups was also shown to increase the thermal stability of GA and EA that goes up respectively from 269 to 528 °C and from 496 to 628 °C. The phenolic-based components were then incorporated into an epoxy resin formulated from diglycidyl ether of bisphenol A (DGEBA) and isophorone diamine (IPDA) (72, 18, and 10 wt.% of DGEBA, IPDA, and GA or EA, respectively). According to differential scanning calorimetry (DSC), the glass transition temperature (Tg) of the thermosets was decreased. Its values ranged from 137 up to 108 °C after adding the phenolic-based components. A cone calorimeter was used to evaluate the burning behavior of the formulated thermosets. A significant reduction of the peak of heat release rate (pHRR) for combustion was detected. Indeed, with 10 wt.% of GA and EA, pHRR was reduced by 12 and 44%, respectively, compared to that for neat epoxy resin. GAD and EAD also induced the decrease of pHRR values by 65 and 33%, respectively. In addition, a barrier effect was observed for the resin containing GAD. These results show the important influence of the biobased phenolic compounds and their boron derivatives on the fire behavior of a partially biobased epoxy resin.

Studies of the Physical Properties of Cycloaliphatic Epoxy Resin Reacted with Anhydride Curing Agents

2017 ◽  
Vol 737 ◽  
pp. 248-255 ◽  
Author(s):  
Tae Hee Kim ◽  
Dae Yeon Kim ◽  
Choong Sun Lim ◽  
Bong Kuk Seo
Keyword(s):  
Physical Properties ◽  
Reaction Kinetics ◽  
Epoxy Resin ◽  
High Performance ◽  
Industrial Applications ◽  
Scanning Calorimetry ◽  
Low Viscosity ◽  
High Performance Polymer ◽  
Curing Agents ◽  
The Impact

The preparation of high performance epoxy composites for industrial applications has been extensively researched. In this report, we study the change in physical properties and reaction kinetics between epoxy resin and curing agents of similar geometry. For the experiments, celloxide 2021P, an epoxy resin having low viscosity, was blended with three different curing agents: methylhexahydropthalic acid, methyltetrahydropthalic acid, and 5-norbornene-2, 3-dicarboxylic anhydride. The amount of 1, 2-dimethylimidazole catalyst was controlled, and the highest heat flow temperature (Tpeak) was observed at around 145 °C. The impact on reaction kinetics relative to the change in heating rate was studied with differential scanning calorimetry (DSC) for each of the curing agents. The glass transition temperature (Tg) of each composition was measured with a second DSC cycle. The prepared epoxy compositions were thermally cured in a metallic mold to provide pure epoxy resins without fillers. Finally, the flexural strengths of these resins were compared to each other. The authors believe that insights into choosing an appropriate epoxy binder are useful when it comes to the overall preparation of high performance polymer composites.

Cage-ladder-structure, phosphorus-containing polyhedral oligomeric silsesquinoxanes as promising reactive-type flame retardants for epoxy resin

2019 ◽  
Vol 136 (23) ◽  
pp. 47607 ◽  
Author(s):  
Shengnan Li ◽  
Xiaojuan Zhao ◽  
Xinghua Liu ◽  
Xin Yang ◽  
Ran Yu ◽  
...  
Keyword(s):  
Epoxy Resin ◽  
Flame Retardants ◽  
Ladder Structure ◽  
Phosphorus Containing

scholarly journals Properties of epoxy-thiokol materials based on the products of the preliminary reaction of thioetherification

2021 ◽  
pp. 128-136
Author(s):  
K.M. Sukhyy ◽  
◽  
E.A. Belyanovskaya ◽  
A.N. Nosova ◽  
M.K. Sukhyy ◽  
...  
Keyword(s):  
Mechanical Properties ◽  
Epoxy Resin ◽  
Adhesive Strength ◽  
Impact Resistance ◽  
Maximum Level ◽  
Scanning Calorimetry ◽  
Mechanical Mixtures ◽  
The Impact ◽  
Fracture Work ◽  
Specific Impact

In order to improve the adhesive and physical-mechanical properties of epoxy-thiocol compositions cured without heat treatment, we propose to carry out the reaction of interaction between thiokol mercaptan groups and oxirane cycles of epoxy resin at an elevated temperature before introducing a curing agent, and then use the product of this thioetherification reaction for curing at room temperature. The temperature range of the thioetherification reaction (90–1800С) was determined by the method of differential scanning calorimetry. The optimal temperature (1600С) and duration of the preliminary thioetherification reaction (2 hours) were determined, which ensure the maximum level of adhesive strength and physical-mechanical properties. It was shown that composite materials based on the products of the thioetherification reaction significantly outperform analogs based on mechanical mixtures of epoxy resin and thiokol in terms of cohesive and adhesive strength, deformation capacity, fracture work and specific impact strength. The impact resistance and shear strength of adhesive joints are especially significantly increased during the curing of the compositions without external heat supply.

scholarly journals Impact of the Surface Properties of Cellulose Nanocrystals on the Crystallization Kinetics of Poly(Butylene Succinate)

Crystals ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 196 ◽  
Author(s):  
Hatem Abushammala ◽  
Jia Mao
Keyword(s):  
Contact Angle ◽  
Surface Properties ◽  
Cellulose Nanocrystals ◽  
Toluene Diisocyanate ◽  
Scanning Calorimetry ◽  
Water Contact ◽  
Butylene Succinate ◽  
Avrami Model ◽  
Nucleation Activity ◽  
The Impact

The hydrophilicity of cellulose nanocrystals (CNCs) is a major challenge for their processing with hydrophobic polymers and matrices. As a result, many surface modifications have been proposed to hydrophobize CNCs. The authors showed in an earlier study that grafting alcohols of different chain lengths onto the surface of CNCs using toluene diisocyanate (TDI) as a linker can systematically hydrophobize CNCs to a water contact angle of up to 120° depending on the alcohol chain length. Then, the hydrophobized CNCs were used to mechanically reinforce poly(butylene succinate) (PBS), which is a hydrophobic polymer. As a result of hydrophobization, PBS/CNCs interfacial adhesion and the composite mechanical properties significantly improved with the increasing CNC contact angle. Continuing on these results, this paper investigates the impact of CNC surface properties on the crystallization behavior of PBS using differential scanning calorimetry (DSC). The results showed that the crystallization temperature of PBS increased from 74.7 °C to up to 86.6 °C as a result of CNC nucleation activity, and its value was proportionally dependent on the contact angle of the CNCs. In agreement, the nucleation activity factor (φ) estimated using Dobreva and Gutzow’s method decreased with the increasing CNC contact angle. Despite the nucleation action of CNCs, the rate constant of PBS crystallization as estimated using the Avrami model decreased in general as a result of a prevailing impeding effect. This decrease was minimized with increasing the contact angle of the CNCs. The impeding effect also increased the average activation energy of crystallization, which was estimated using the Kissinger method. Moreover, the Avrami exponent (n) decreased because of CNC addition, implying a heterogeneous crystallization, which was also apparent in the crystallization thermograms. Overall, the CNC addition facilitated PBS nucleation but retarded its crystallization, and both processes were significantly affected by the surface properties of the CNCs.

scholarly journals Phosphorus-Containing Flame Retardants from Biobased Chemicals and Their Application in Polyesters and Epoxy Resins

Molecules ◽  
2019 ◽  
Vol 24 (20) ◽  
pp. 3746 ◽  
Author(s):  
Jacob Sag ◽  
Daniela Goedderz ◽  
Philipp Kukla ◽  
Lara Greiner ◽  
Frank Schönberger ◽  
...  
Keyword(s):  
Flame Retardant ◽  
Renewable Resources ◽  
Epoxy Resins ◽  
Flame Retardants ◽  
Oxygen Index ◽  
Polymer Structure ◽  
Cone Calorimetry ◽  
Limiting Oxygen Index ◽  
Phosphorus Containing ◽  
Biobased Chemicals

Phosphorus-containing flame retardants synthesized from renewable resources have had a lot of impact in recent years. This article outlines the synthesis, characterization and evaluation of these compounds in polyesters and epoxy resins. The different approaches used in producing biobased flame retardant polyesters and epoxy resins are reported. While for the polyesters biomass derived compounds usually are phosphorylated and melt blended with the polymer, biobased flame retardants for epoxy resins are directly incorporated into the polymer structure by a using a phosphorylated biobased monomer or curing agent. Evaluating the efficiency of the flame retardant composites is done by discussing results obtained from UL94 vertical burning, limiting oxygen index (LOI) and cone calorimetry tests. The review ends with an outlook on future development trends of biobased flame retardant systems for polyesters and epoxy resins.

scholarly journals Potential Synergism between Novel Metal Complexes and Polymeric Brominated Flame Retardants in Polyamide 6.6

Polymers ◽  
2020 ◽  
Vol 12 (7) ◽  
pp. 1543 ◽  
Author(s):  
Alistair F. Holdsworth ◽  
A. Richard Horrocks ◽  
Baljinder K. Kandola
Keyword(s):  
Flame Retardants ◽  
Vapour Phase ◽  
Environmental Concerns ◽  
Antimony Trioxide ◽  
Release Rates ◽  
Cone Calorimetry ◽  
Phosphorus Containing ◽  
Brominated Polystyrene ◽  
Polyamide 6.6 ◽  
Phase Activity

While environmental concerns have caused polymeric brominated primary flame retardants (PolyBrFRs) to be effective replacement monomeric species, few alternatives for antimony trioxide (ATO) have been developed beyond the zinc stannates (ZnSs). Previous research, which explored the interactions of aluminium (AlW), tin (II) (SnW) and zinc (ZnW) tungstates with several phosphorus-containing flame retardants in polyamide 6.6 (PA66), is extended to two PolyBrFRs: brominated polystyrene (BrPS), and poly(pentabromobenzyl acrylate) (BrPBz). On assessing the effect of each tungstate on the thermal degradation and flammability in combination with each PolyBrFR using TGA, UL94, LOI, cone calorimetry and TGA-FTIR, only ZnW and SnW showed significant increases in LOI (>26 vol.%). Both ZnW-BrPS- and ZnW-BrPBz-containing formulations yielded average UL94 ratings ≥ V-2 and TGA char residues (corrected for metals content at 500 °C) in air > 15 wt.%. BrPS-containing samples, especially those containing ZnW and SnW, generated peak heat release rates approximately 50% lower than the equivalent BrPBz samples. These reductions did not correlate with respective increases in LOI, suggesting that tungstate-PolyBrFR combinations influence pre-ignition differently to post-ignition behaviour. Calculated synergistic effectivities indicate that ZnW functions as a synergist in both pre- and post-ignition stages, especially with BrPS. TGA-FTIR and char analyses showed that, in addition to the vapour-phase activity normally associated with PolyBrFRs, condensed-phase processes occurred, especially for the ZnW-PolyBrFR combinations. Additionally, ZnW demonstrated significant smoke-suppressing properties comparable with zinc stannate (ZnS).

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