Thermal Degradation and Flame Retardance of Biobased Polylactide Composites Based on Aluminum Hypophosphite

Tang, Gang; Wang, Xin; Xing, Weiyi; Zhang, Ping; Wang, Bibo; Nie, Hong; Yang, Wei; Hu, Yuan; Song, Lei

doi:10.1021/ie3008133

Cited by 167 publications

(137 citation statements)

References 31 publications

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“…The good compactness and continuity of char layer are known to be efficient and beneficial with respect to thermal and mass loss insulation. 35 After a cone calorimeter test, hoary crystals with gloss were observed on the surface of exterior char for MoS 2 /GNS/EP composites. The exterior and interior chars of MoS 2 /GNS/EP composites were more surveyed by XRD analysis.…”

Section: Industrial and Engineering Chemistry Researchmentioning

confidence: 99%

Surface Modification of Graphene with Layered Molybdenum Disulfide and Their Synergistic Reinforcement on Reducing Fire Hazards of Epoxy Resins

Wang

Zhou

Yang

et al. 2013

Ind. Eng. Chem. Res.

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119

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In this work, molybdenum disulfide (MoS 2 )−modified graphene (MoS 2 /GNS) hybrids were prepared by the hydrothermal method and characterized by X-ray diffraction (XRD), Laser Raman spectroscopy (LRS) and transmission electron microscope (TEM). The characterization results show layered molybdenum disulfide was deposited on the surface of graphene nanosheets (GNSs) and grahene oxide was reduced simultaneously. Thermogravimetric analysis results of MoS 2 , GNS and MoS 2 /GNS hybrids showed that incorporation of MoS 2 increased the thermal oxidation resistance of the graphene evidently. Compared to pure epoxy resins (EP), the addition of MoS 2 /GNS hybrids into EP enhanced the onset thermal degradation temperature (T onset ) with an 53°C increment under air atmosphere and an 18°C increment under nitrogen atmosphere. The addition of MoS 2 /GNS hybrids endows excellent flame retardant properties to EP, confirmed by the dramatically reduced peak heat release rate value and total heat release value. Moreover, the addition of MoS 2 /GNS hybrids dramatically decreased the smoke products.

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Section: Industrial and Engineering Chemistry Researchmentioning

confidence: 99%

Surface Modification of Graphene with Layered Molybdenum Disulfide and Their Synergistic Reinforcement on Reducing Fire Hazards of Epoxy Resins

Wang

Zhou

Yang

et al. 2013

Ind. Eng. Chem. Res.

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119

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“…It has no obvious cold crystallization temperature, which is consistent with the relevant research. 19 The incorporation of LaHP and CeHP does not significantly change the T g value of the composites, but the T m value is slightly increased. The T c is also found to be consistent with the above literature.…”

Section: ■ Results and Discussionmentioning

confidence: 93%

Section: ■ Introductionmentioning

confidence: 99%

“…Braun and Schartel found that aluminum hypophosphite exhibited good flame retardance for glass fiber reinforced PA-6,6. 18 Furthermore, Tang et al 19 introduced aluminum hypophosphite into polylactide and found that 20 wt % AHP loading resulted in a V0 rating in UL-94 testing.Rare earth metal salts, such as lanthanum and cerium, have been widely used as an effective flame retardant synergist and smoke suppressant. 20−24 Inspired by the reported flame retardance of aluminum hypophosphite and rare earth oxide, two kinds of trivalent rare earth hypophosphite, lanthanum hypophosphite and cerium hypophosphite, were synthesized and used to improve the flame retardance of PLA composites to provide a new strategy to prepare flame retardant PLA composites.…”

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confidence: 99%

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Effect of Rare Earth Hypophosphite Salts on the Fire Performance of Biobased Polylactide Composites

Tang

Wang

Zhang

et al. 2013

Ind. Eng. Chem. Res.

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In this work, two kinds of rare earth hypophosphites (REHP), lanthanum hypophosphite (LaHP) and cerium hypophosphite (CeHP), were synthesized and characterized. Subsequently, LaHP and CeHP were added into polylactide to improve its flame retardant properties. Thermal gravimetric analysis was employed to investigate the thermal decomposition behavior of REHP and flame retardant polylactide composites (FR-PLA). The fire performance evaluated by microscale combustion calorimetry and cone calorimeter clearly demonstrated that the addition of LaHP and CeHP resulted in significant reduction of the heat release rate, low total heat release, and compact intumescent char layer. Thermogravimetric analysis− infrared spectrometry testing indicated that the addition of REHP significantly decreased the yields of pyrolysis products. Furthermore, the crystallization behaviors of FR-PLA composites were investigated by differential scanning calorimetry. The char residue of FR-PLA composites after cone calorimeter testing were also be investigated by scanning electron microscope, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. ■ INTRODUCTIONIn recent years, the increasing awareness of petroleum source and the environmental problems caused by persistent plastic wastes has impelled people to develop new ecofriendly and renewable materials to replace petroleum-based plastics. 1−3 Among these materials, polylactide (PLA) has received considerable attention because of its biodegradable, abundant renewable source, transparency and excellent mechanical properties. PLA holds tremendous promise in many fields, such as biomedical, household, engineering, packing industries, and so on. 4−8 However, like many other plastics, PLA presents poor flammability (typical limiting oxygen index (LOI) of 19.5 vol %, easily dripping in burning) in fire testing, which restricts its further development in some important fields. Therefore, it is meaningful to investigate flame-retarded PLA.It is well-known that intumescent flame retardant (IFR) shows good performance in some polymers as a halogen-free additive due to the advantage of little smoke production and low toxicity. 9 Reti et al. 10 studied the efficiency of different intumescent formulations to flame retard PLA, and the quantity of the additives has been optimized. Feng and Zhan et al. have researched different intumescent flame retardant systems for preparation of FR-PLA composites that showed good performance in the testing. 10−12 Other flame retardant additives, such as expanded graphite, 13 aluminum hydroxide, 14 and silica gel 15 have also been reported.Recently, aluminum hypophosphite (AHP) has been used as a flame retardant that has achieved effective flame retardance in polymer materials. Yang et al. found aluminum hypophosphite showed perfect flame retardancy in PET and PBT composites; 16,17 20 wt % of AHP could make glass-fiber/PBT composite reach an UL-94 V0 rating with a LOI value of 29 vol %, and 10 wt % of AHP could make glass-fiber/PET comp...

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“…Especially, AHP as a novel class of phosphorous-based flame retardants, which is expected as a promising candidate for replacing halogenbased flame retardants, also it has been applied in the treatment of organic materials such as glass-filled polyamide 6 [3], polybutylene terephthalate (PBT) [4,5], poly(ethylene terephthalate) [6], and polylactide [7]. These publications have described the flame retardancy and speculated the thermal degradation mechanism of the metal hypophosphites.…”

Section: Introductionmentioning

confidence: 99%

Using TG–FTIR and TG–MS to study thermal degradation of metal hypophosphites

Liu

et al. 2014

J Therm Anal Calorim

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Three typical metal hypophosphite flame retardants La(H 2 PO 2 ) 3 ÁH 2 O (LHP), Ce(H 2 PO 2 ) 3 ÁH 2 O (CHP), and Al(H 2 PO 2 ) 3 (AHP) were synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis (TG), derivative thermogravimetric analysis, and differential thermal analysis. The thermal degradation products from the synthesized metal hypophosphites were also investigated using thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR) and thermogravimetry coupled with mass spectrometry (TG-MS). The synthesized metal hypophosphites were also used as flame retardants for poly (1,4-butylene terephthalate) (PBT), and the combustion properties of flame-retarded PBT were evaluated using the limiting oxygen index and UL-94 tests. The results showed that the metal hypophosphites LHP, CHP, and AHP can be used as effective flame retardants for PBT, and these compounds can be obtained through a simple precipitation method. TG-FTIR and TG-MS results showed that the degradation process of AHP involves two steps, corresponding to the removal PH 3 reaction and the further dehydration reaction of the hydrogen phosphate aluminum. While LHP and CHP have three degradation steps, the additional step is due to that LHP and CHP which will loss the crystal water at lower temperature.

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Thermal Degradation and Flame Retardance of Biobased Polylactide Composites Based on Aluminum Hypophosphite

Cited by 167 publications

References 31 publications

Surface Modification of Graphene with Layered Molybdenum Disulfide and Their Synergistic Reinforcement on Reducing Fire Hazards of Epoxy Resins

Surface Modification of Graphene with Layered Molybdenum Disulfide and Their Synergistic Reinforcement on Reducing Fire Hazards of Epoxy Resins

Effect of Rare Earth Hypophosphite Salts on the Fire Performance of Biobased Polylactide Composites

Using TG–FTIR and TG–MS to study thermal degradation of metal hypophosphites

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