One-Step Reduction of Graphene Oxide with Phosphorus/Silicon-Containing Compound and Its Flame Retardancy in Epoxy Resin

A novel graphene-based phosphorus/silicon-containing flame retardant (GO-DOPO-V) was obtained via one-step reduction of graphene oxide (GO) with phosphorus/silicon-containing compound (DOPO-V). The Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectrometer (XPS), Atomic force microscope (AFM) and Thermogravimetric analysis (TGA) measurements were used to confirm the structure and morphology. After incorporation of 2 wt% GO-DOPO-V, the maximum decreases of 28.8% in peak heat release rate and 15.6% in total heat release are achieved compared to that of pure epoxy resin (EP). Furthermore, TGA and Scanning electron microscopy (SEM) measurement showed that GO-DOPO-V significantly enhanced the thermal stability and residual char strength of EP. Thus, attributed to the barrier effect of GO and phosphorus/silicon layer formation by DOPO-V, GO-DOPO-V was a high-efficient flame retardant to improve the combustion behavior of EP nanocomposite.

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Functionalization of Graphene Oxide with Polysilicone: Synthesis, Characterization, and Its Flame Retardancy in Epoxy Resin

Polymers ◽

10.3390/polym13213857 ◽

2021 ◽

Vol 13 (21) ◽

pp. 3857

Author(s):

Jiangbo Wang

Keyword(s):

Graphene Oxide ◽

Heat Release ◽

Epoxy Resin ◽

Flame Retardancy ◽

Mechanical Analysis ◽

Silica Layer ◽

Atomic Force ◽

Peak Heat Release Rate ◽

Ep Matrix ◽

The Fourier Transform

A novel polysilicone flame retardant (PMDA) has been synthesized and covalently grafted onto the surfaces of graphene oxide (GO) to obtain GO-PMDA. The chemical structure and morphology of GO-PMDA was characterized and confirmed by the Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectrometer (XPS), atomic force microscope (AFM), and thermogravimetric analysis (TGA). The results of dynamic mechanical analysis (DMA) indicated that the grafting of PMDA improved the dispersion and solubility of GO sheets in the epoxy resin (EP) matrix. The TGA and cone calorimeter measurements showed that compared with the GO, GO-PMDA could significantly improve the thermal stability and flame retardancy of EP. In comparison to pure EP, the peak heat release rate (pHRR) and total heat release (THR) of EP/GO-PMDA were reduced by 30.5% and 10.0% respectively. This greatly enhanced the flame retardancy of EP which was mainly attributed to the synergistic effect of GO-PMDA. Polysilicone can create a stable silica layer on the char surface of EP, which reinforces the barrier effect of graphene.

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Preparation and Characterization of DOPO-Functionalized MWCNT and Its High Flame-Retardant Performance in Epoxy Nanocomposites

Polymers ◽

10.3390/polym12030613 ◽

2020 ◽

Vol 12 (3) ◽

pp. 613 ◽

Cited By ~ 2

Author(s):

Liqiang Gu ◽

Chen Qiu ◽

Jianhui Qiu ◽

Youwei Yao ◽

Eiichi Sakai ◽

...

Keyword(s):

Heat Release ◽

Flame Retardant ◽

Epoxy Resin ◽

Epoxy Resins ◽

Phosphorus Content ◽

Co2 Production ◽

Peak Heat Release Rate ◽

Multi Walled Carbon Nanotubes ◽

Walled Carbon Nanotubes

In this work, functionalized multi-walled carbon nanotubes (MWCNT) were synthesized by the reaction between acylated MWCNT and 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (ODOPB). The obtained MWCNT-ODOPB was well dispersed into epoxy resins together with aluminum diethylphosphinate (AlPi) to form flame-retardant nanocomposites. The epoxy resin nanocomposite with phosphorus content of 1.00 wt % met UL 94 V-0 rating, exhibited LOI value of 39.5, and had a higher Tg compared to neat epoxy resin, which indicates its excellent flame retardant performance. These experimental results indicated that MWCNT-ODOPB was a compatible and efficient flame retardant for epoxy resins. Moreover, cone calorimeter analysis showed that the peak heat release rate (pHRR), total heat release (THR) values, and CO2 production profiles of the composites decreased with an increase in the additional amount of phosphorus.

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Synthesis of a Reactive Template-Induced Core–Shell PZS@ZIF-67 Composite Microspheres and Its Application in Epoxy Composites

Polymers ◽

10.3390/polym13162646 ◽

2021 ◽

Vol 13 (16) ◽

pp. 2646

Author(s):

Kunpeng Song ◽

Yinjie Wang ◽

Fang Ruan ◽

Weiwei Yang ◽

Zhuqing Fang ◽

...

Keyword(s):

Heat Release ◽

Flame Retardant ◽

Epoxy Resin ◽

Mechanical Performance ◽

Hydroxyl Group ◽

Limit Oxygen Index ◽

Composite Microspheres ◽

Peak Heat Release Rate ◽

Interfacial Compatibility ◽

Index Value

Developing superior properties of epoxy resin composites with high fire resistance, light smoke, and low toxicity has been the focus of the research in the flame-retardant field. In particular, it is essential to decrease the emissions of toxic gases and smoke particles generated during the thermal decomposition of epoxy resin (EP) to satisfy the industrial requirements for environmental protection and safety. Consequently, the PZS@ZIF-67 composite was designed and synthesized by employing the hydroxyl group-containing polyphosphazene (poly(cyclotriphosphazene-co-4,4′-dihydroxydiphenylsulfone), PZS) as both the interfacial compatibility and an in situ template and the ZIF-67 nanocrystal as a nanoscale coating and flame-retardant cooperative. ZIF-67 nanocrystal with multidimensional nanostructures was uniformly wrapped on the surface of PZS microspheres. Subsequently, the acquired PZS@ZIF-67 composite was incorporated into the epoxy resin to prepare composite samples for the study of their fire safety, toxicity suppression, and mechanical performance. Herein, the EP/5% PZS@ZIF-67 passed the V-0 rating in a UL-94 test with a 31.9% limit oxygen index value. More precisely, it is endowed with a decline of 51.08%, 28.26%, and 37.87% of the peak heat release rate, the total heat release, and the total smoke production, respectively. In addition, the unique structure of PZS@ZIF-67 microsphere presented a slight impact on the mechanical properties of EP composites at low loading. The PZS@ZIF-67 possible flame-retardant mechanism was speculated based on the analysis of the condensed phase and the gas phase of EP composites.

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Synthesis and characterization of flame-retardant-wrapped carbon nanotubes and its flame retardancy in epoxy nanocomposites

Polymers and Polymer Composites ◽

10.1177/09673911211024582 ◽

2021 ◽

pp. 096739112110245

Author(s):

Jiangbo Wang

Keyword(s):

Carbon Nanotubes ◽

Heat Release ◽

Flame Retardant ◽

Flame Retardancy ◽

Total Heat Release ◽

Pristine Cnts ◽

Peak Heat Release Rate ◽

Ep Matrix ◽

Better Than

A novel phosphorus-silicon containing flame-retardant DOPO-V-PA was used to wrap carbon nanotubes (CNTs). The results of FTIR, XPS, TEM and TGA measurements exhibited that DOPO-V-PA has been successfully grafted onto the surfaces of CNTs, and the CNTs-DOPO-V-PA was obtained. The CNTs-DOPO-V-PA was subsequently incorporated into epoxy resin (EP) for improving the flame retardancy and dispersion. Compared with pure EP, the addition of 2 wt% CNTs-DOPO-V-PA into the EP matrix could achieve better flame retardancy of EP nanocomposites, such as a 30.5% reduction in peak heat release rate (PHRR) and 8.1% reduction in total heat release (THR). Furthermore, DMTA results clearly indicated that the dispersion for CNTs-DOPO-V-PA in EP matrix was better than pristine CNTs.

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Dual UV-Thermal Curing of Biobased Resorcinol Epoxy Resin-Diatomite Composites with Improved Acoustic Performance and Attractive Flame Retardancy Behavior

Sustainable Chemistry ◽

10.3390/suschem2010003 ◽

2021 ◽

Vol 2 (1) ◽

pp. 24-48

Author(s):

Quoc-Bao Nguyen ◽

Henri Vahabi ◽

Agustín Rios de Anda ◽

Davy-Louis Versace ◽

Valérie Langlois ◽

...

Keyword(s):

Heat Release ◽

Flame Retardant ◽

Epoxy Resin ◽

Flame Retardancy ◽

Sound Absorption ◽

Flexural Modulus ◽

Construction Materials ◽

Acoustic Properties ◽

Low Frequencies ◽

Compacting Pressure

This study has developed novel fully bio-based resorcinol epoxy resin–diatomite composites by a green two-stage process based on the living character of the cationic polymerization. This process comprises the photoinitiation and subsequently the thermal dark curing, enabling the obtaining of thick and non-transparent epoxy-diatomite composites without any solvent and amine-based hardeners. The effects of the diatomite content and the compacting pressure on microstructural, thermal, mechanical, acoustic properties, as well as the flame behavior of such composites have been thoroughly investigated. Towards the development of sound absorbing and flame-retardant construction materials, a compromise among mechanical, acoustic and flame-retardant properties was considered. Consequently, the composite obtained with 50 wt.% diatomite and 3.9 MPa compacting pressure is considered the optimal composite in the present work. Such composite exhibits the enhanced flexural modulus of 2.9 MPa, a satisfying sound absorption performance at low frequencies with Modified Sound Absorption Average (MSAA) of 0.08 (for a sample thickness of only 5 mm), and an outstanding flame retardancy behavior with the peak of heat release rate (pHRR) of 109 W/g and the total heat release of 5 kJ/g in the pyrolysis combustion flow calorimeter (PCFC) analysis.

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One-step surface modification of graphene oxide and influence of its particle size on the properties of graphene oxide/epoxy resin nanocomposites

European Polymer Journal ◽

10.1016/j.eurpolymj.2018.02.036 ◽

2018 ◽

Vol 101 ◽

pp. 211-217 ◽

Cited By ~ 24

Author(s):

Miroslav Huskić ◽

Silvester Bolka ◽

Alenka Vesel ◽

Miran Mozetič ◽

Alojz Anžlovar ◽

...

Keyword(s):

Particle Size ◽

Surface Modification ◽

Graphene Oxide ◽

Epoxy Resin ◽

One Step ◽

Epoxy Resin Nanocomposites

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Synthesis of a phosphorus–nitrogen-containing flame retardant and its application in epoxy resin

High Performance Polymers ◽

10.1177/0954008318756496 ◽

2018 ◽

Vol 31 (2) ◽

pp. 186-196 ◽

Cited By ~ 12

Author(s):

Shuang Yang ◽

Yefa Hu ◽

Qiaoxin Zhang

Keyword(s):

Heat Release ◽

Flame Retardant ◽

Epoxy Resin ◽

Heat Release Rate ◽

Flame Retardancy ◽

Release Rate ◽

Epoxy Resins ◽

Proton Nuclear Magnetic Resonance ◽

Scanning Calorimetry ◽

Cone Calorimeter Test

In this article, a phosphorus–nitrogen-containing flame retardant (DOPO-T) was successfully synthesized by nucleophilic substitution reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and cyanuric chloride. The chemical structure of DOPO-T was characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance (NMR) and phosphorous-31 NMR, and elemental analysis. DOPO-T was then blended with diglycidyl ether of bisphenol-A to prepare flame-retardant epoxy resins. Thermal properties, flame retardancy, and combustion behavior of the cured epoxy resins were evaluated by differential scanning calorimetry, thermogravimetric analysis, limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The results indicated that the glass transition temperature ( Tg) and temperature at 5% weight loss of epoxy resin (EP)/DOPO-T thermosets were gradually decreased with the increasing content of DOPO-T. DOPO-T catalyzed the decomposition of EP matrix in advance. The flame-retardant performance of EP thermosets was significantly enhanced with the addition of DOPO-T. EP/DOPO-T-0.9 sample had an LOI value of 36.2% and achieved UL94 V-1 rating. In addition, the average of heat release rate, peak of heat release rate, average of effective heat of combustion, and total heat release (THR) of EP/DOPO-T-0.9 sample were decreased by 32%, 48%, 23%, and 31%, respectively, compared with the neat EP sample. Impressively, EP/DOPO-T thermosets acquired excellent flame retardancy under low loading of flame retardant.

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A facile one-step synthesis of highly efficient melamine salt reactive flame retardant for epoxy resin

Journal of Materials Science ◽

10.1007/s10853-020-04935-6 ◽

2020 ◽

Vol 55 (27) ◽

pp. 12836-12847 ◽

Cited By ~ 3

Author(s):

Zongmin Zhu ◽

Panlong Lin ◽

Hao Wang ◽

Luoxin Wang ◽

Bin Yu ◽

...

Keyword(s):

Flame Retardant ◽

Epoxy Resin ◽

Highly Efficient ◽

Melamine Salt ◽

One Step ◽

Reactive Flame Retardant

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A novel curing agent based on diphenylphosphine oxide for flame-retardant epoxy resin

High Performance Polymers ◽

10.1177/0954008317745957 ◽

2017 ◽

Vol 30 (10) ◽

pp. 1229-1239 ◽

Cited By ~ 9

Author(s):

Shan Huang ◽

Xiao Hou ◽

Jiaojiao Li ◽

Xiujuan Tian ◽

Qing Yu ◽

...

Keyword(s):

Heat Release ◽

Flame Retardant ◽

Epoxy Resin ◽

Energy Dispersive Spectrometer ◽

Diglycidyl Ether ◽

Curing Agent ◽

Diphenylphosphine Oxide ◽

Excellent Thermal Stability ◽

Cone Calorimeter Test ◽

Ul 94

A phosphorous/nitrogen-containing diphenylphosphine oxide (DPO) derivative (DPO-SS) was designed and synthesized via a two-step reaction of 4,4′-diaminodiphenylsulfone, 2-hydroxy-benzaldehyde, and DPO. The structure of DPO-SS was confirmed by Fourier transform infrared spectroscopy (FTIR), 1H and 31P nuclear magnetic resonance (NMR) spectroscopy, and mass spectrometry (MS). DPO-SS was used as a flame retardant and curing agent for copolymerizing with diglycidyl ether of bisphenol-A. Thermal and flame-retardant properties of the obtained flame-retardant epoxy resin (F-EP) were investigated by thermogravimetric analysis, dynamic thermomechanical analysis, limited oxygen index (LOI) measurement, vertical burning test (UL-94), and cone calorimeter test. Results indicated that all F-EP samples exhibited excellent thermal stability and flame-retardant property. Especially for F-EP with P content of 0.7 wt% (denoted as EP/P-0.7), it achieved high LOI values (32.4%) and UL-94 V-0 rating. Compared with pure EP, all F-EP samples showed lower heat release rate, total heat release, total smoke produce, and little Tg fluctuation. In order to study the flame-retardant mechanism, the char residues were investigated by FTIR, scanning electron microscopy, and energy-dispersive spectrometer analysis. The results manifested that DPO-SS acted as flame retardant in both gas phase and condensed phase. Water absorption properties of pure EP and F-EP were also compared through immersion experiments. Results showed that EP/P-0.7 sample had apparently lower water absorptivity than pure EP.

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Combustion properties and pyrolysis kinetics of flame-retardant polyurethane elastomers

Journal of Thermoplastic Composite Materials ◽

10.1177/0892705715598361 ◽

2016 ◽

Vol 30 (2) ◽

pp. 255-272 ◽

Cited By ~ 4

Author(s):

Xilei Chen ◽

Lili Huo ◽

Jianbo Liu ◽

Chuanmei Jiao ◽

Shaoxiang Li ◽

...

Keyword(s):

Heat Release ◽

Flame Retardant ◽

Pyrolysis Kinetics ◽

Cone Calorimetry ◽

Polyurethane Elastomers ◽

Conversion Rates ◽

Combustion Properties ◽

Peak Heat Release Rate ◽

Fwo Method ◽

Kinetics Of

Flame-retardant polyurethane elastomers (PUEs) have been prepared using trichloroethyl phosphate (TCEP) as flame retardant. The combustion performances and thermal decomposition properties of PUEs were studied using cone calorimetry test and thermogravimetric analysis, respectively. Kissinger method and Flynn–Wall–Ozawa (FWO) method were adopted to discuss the pyrolysis kinetics of PUEs. The experimental results showed that TCEP has good flame-retardant effect for PUE. With the increase of TCEP, the peak heat release rate and total heat release values decrease. A good diagram of linear regression can be obtained from both Kissinger and FWO methods. The activation energy values of flam- retardant PUE can be calculated from FWO method at different conversion rates.

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