Grafting Cellulose Nanocrystals With Phosphazene-containing Compound for Simultaneously Enhancing the Flame Retardancy and Mechanical Properties of Polylactic Acid

Cellulose nanocrystals (CNCs) have been used as bio-based carbon source in intumescent system. However, CNCs have the disadvantages of low onset decomposition temperature and decompose and carbonize during processing. We, herein, demonstrated the design of phosphazene-containing CNCs (P/N-CNCs) with great thermal stability and outstanding charring ability. The TGA results showed that the initial decomposition temperature of P/N-CNCs was increased from 202.4 ℃ to 272.2 ℃ (increased by 34.5%), and the residual char at 700 ℃ was increased from 24.9 wt% to 55.8 wt% compared with CNCs. Then, flame retardant PLA composites were prepared by blending PLA, P/N-CNCs with ammonium polyphosphate (APP), melamine (MPP), aluminum hypophosphite (AHP) and piperazine pyrophosphate (PPAP), respectively. The thermal stability, flame retardant properties and mechanical properties of PLA composites were investigated. The results showed that the flame retardant system constructed by 7 wt% APP and 3 wt% P/N-CNCs had the best effect in PLA. PLA/7APP/3P/N-CNCs had the highest limit oxygen index value (28.1%), the lowest peak heat release rate (266 kW/m2) and reached UL 94 V-0 rating. Moreover, the tensile strength, impact strength and elongation at break of PLA/7APP/3P/N-CNCs were increased by 7.3%, 18.6% and 29.4%, respectively, compared with these properties of PLA/7APP/ 3CNCs. This work provides a new idea for the design of CNCs with great thermal stability and outstanding charring ability, and offers a new method for the preparation of high-performance flame-retardant PLA composites.

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

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.

Kalsiyum Hipofosfit ve Magnezyum Hipofosfit Emdirilmiş Jüt Elyaf Katkılı Poli (Laktik Asit) Biyokompozitlerinin Isıl Ve Güç Tutuşurluk Özelliklerinin İncelenmesi

The aim of this study is to investigate the thermal and flammability properties of poly(lactic acid) (PLA) biocomposites reinforced with calcium hypophosphite (CHP) and magnesium hypophosphite (MHP) impregnated jute fiber (JE). For this purpose,biocomposites were produced by adding the jute fibers (JEs), which are treated separately with 5% and 10% CHP and MHP solutions and dried, to the PLA at a constant rate (20% wt) by melt blending method. Thermal properties of the PLA biocomposites produced were evaluated by thermogravimetic analysis (TGA), also their flammability properties were investigated by using limit oxygen index (LOI), vertical (UL-94V) and horizontal burning (UL-94HB) tests. As a result of the TGA tests, it was determined that the addition of JEs impregnated with CHP and MHP, the thermal stability and char residue amount of PLA biocomposites increased, and consequently the flame retardancy of the composites were also improved. From the LOI test results, it was observed that the LOI values of PLA biocomposites increased as the percentage of hypophosphites in the JE treatment solution increased. UL-94V and UL-94HB tests indicate that PLA biocomposite reinforced with JEs treated with 10% wt CHP has the highest flame retardancy performance.

Synergistic Action of Montmorillonite with an Intumescent Formulation: The Impact of the Nature and the Strength of Acidic Sites on the Flame-Retardant Properties of Polypropylene Composites

A raw montmorillonite (Mt) was submitted to different acidic activation times in order to investigate the influence of the strength and the nature (Brønsted and Lewis) of acidic sites on the synergistic action with an intumescent formulation (IF) composed of ammonium polyphosphate (APP) and pentaerythritol (PER) when incorporated into a polypropylene (PP) matrix. The acidity of the Mt samples was quantified by ammonia temperature-programmed desorption (TPD-NH3) and Fourier transform infrared spectroscopy (FTIR) with pyridine adsorption. The mineral clays were also characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), nitrogen adsorption analysis and particle size distribution. Thermogravimetric analysis (TGA), limit oxygen index (LOI) and UL-94 were performed to evaluate the flame-retardant properties and the thermal stability. The TGA results show that the final residue increased 2 to 3 fold in comparison to the values predicted theoretically. The flammability properties achieved a maximum for the system containing an excess of moderate-strength Brønsted sites relative to the Lewis ones, reaching 38% in the LOI test. This result suggests that the presence of these Brønsted acidic sites is important, as they take part in the esterification reaction between APP and PER which gives rise to the char formation. The FTIR-Pyr adsorption and flammability results indicate that both the nature and strength of the acidic sites influence the flame-retardant properties.

Improving Flame Retardancy of Epoxy Resin Nanocomposites by Carbon Nanotubes Grafted CuAl-Layered Double Hydroxide Hybrid

To solve the issues of the poor dispersion performance of the inorganic flame retardant filler in epoxy resin (EP) matrix, the three-dimensional (3D) hybrid carbon nanotubes-copper aluminum (sodium dodecyl sulfate)-layered double hydroxide (CNTs-OLDH) is designed and synthesized by co-precipitation. The results indicate that the CNTs-OLDH hybrid with 3D-structure is successfully fabricated and well dispersed in EP matrix. The thermostability of EP/CNTs-OLDH nanocomposites is raised and the residue is obviously increased. When the amount of CNTs-OLDH is only 4 wt%, limit oxygen index value of EP/CNTs-OLDH nanocomposites reaches 28.5. Compared with pure EP, the heat release, smoke and gas of EP/FePP nanocomposites are inhibited by CNTs-OLDH hybrid, and the PHRR, THR and SPR values of EP/4CNTs-OLDH nanocomposites decrease by 41.7%, 27.8% and 31.7%. The improved fire retardant performances and thermal stability are attributed to the excellent homogeneous dispersion, the network structure formed by the 3D hybrid in the matrix and the outstanding flame retardant effect of CNTs and OLDH.

Study on flame retardancy and smoke suppression of PET by the synergy between Fe2O3 and new phosphorus-containing silicone flame retardant

To reduce the environmental hazard from the flame retardant, a halogen-free phosphorus-containing silicone flame-retardant poly N, N dimethylene phosphate aminopropyl siloxane (PDPSI) was prepared following the Mannich reaction. Then, PDPSI and ferric oxide (Fe2O3) were used for the preparation of synergistic flame-retardant polyethylene terephthalate (PET). The flame-retardant test results revealed that at 2% PDPSI/Fe2O3 content and 1:2 mass ratio of PDPSI to Fe2O3, the limit oxygen index value of the PDPSI/Fe2O3/PET composite material was 27.9%, reaching the flame-retardant level and passing the V-0 rating in the UL-94 test. In addition, the PDPSI/Fe2O3/PET composites had a char residue content of 17.5% at 700°C, an increase of 30.6% compared to that of the pristine PET. In the cone calorimeter test, the addition of PDPSI/Fe2O3 significantly reduced the peak heat release rate (PHRR), total heat release (THR) rate, and total smoke production (TSP) value of the resulting PET composites. PHRR and THR decreased by 66.05% and 14.3%, respectively. The TSP value decreased from 14.4 m2 to 8.1 m2, a decrease of 43.8%. The scanning electron microscopy images and Fourier-transform infrared spectra of the char residue showed a significant synergy between Fe2O3 and PDPSI, changing the structure of the carbon layer in continuous and dense form, thus the flame retardancy and smoke suppression of the PET composites improved. In addition, the tensile strength of the PET composite was 42.11 MPa, which was only 1.84% less than that of the pristine PET.

Sound absorption, thermal, and flame retardant properties of nonwoven wall cloth with waste fibers

In order to solve the recycling problem of waste fibers, the nonwoven wall cloth was prepared with waste wool fibers and low-melting-point polyamide fibers as raw materials by combing into a net and hot-pressing method. The effect of fiber length, hot pressing temperature, mass fraction of the waste wool fibers, volume density, thickness of materials, and thickness of the rear air layer on the sound absorption properties were studied by single factor experiments. Under the optimized technological conditions, the sound absorption coefficient was above 0.91 and the noise reduction coefficient was 0.56. Then, the sound absorption mechanism was analyzed. In order to meet the fire resistance requirements of materials in the construction industry, by the orthogonal experiments, range analysis, and variance analysis, the optimal process conditions were as follows: potassium fluotitanate concentration of 8%, treatment time of 40 min, and treatment temperature of 80°C. The limit oxygen index of the nonwoven wall cloth was 32.5%. The nonwoven wall cloth had good sound absorption and flame retardant properties.

Structure and Flame-Retardant Actions of Rigid Polyurethane Foams with Expandable Graphite

In this paper, rigid polyurethane foams that were filled with expandable graphite (RPUF/EG) composites were prepared by the liquid blending method, and then the structure and flame retardancy performance of materials were investigated through optical microscope, scanning electron microscope, limit oxygen index, cone calorimeter, thermogravimetric analysis coupled to fourier transform infrared spectrum, and X-ray photoelectron spectroscopy. The results showed that a large number of EG could be good to the exhibition of flame retardancy of RPUF, where the optimal material was found at loading 15 phr EG that showed an increased limit oxygen index value and a decreased calorific or fuming value. TGA coupled FTIR and XPS revealed that EG could disassembled before RPUF under heating treatment, and it could form a pyknotic and enahnced residual carbon layer on RPUF surface after the fire, which restricted the transfer of gas, like oxygen or heat into PU matrix, finally resulting in the promotion of flame retardancy of RPUF.

Effect of Zinc Borate on Flammability of PET Woven Fabrics

Zinc borate (ZnB) has been used as a flame retardant, a smoke suppressant, and an antitracking agent in several applications. It may show synergistic effects with antimony oxide and metal hydroxides in fire retardant systems. In this work, the effect of ZnB on the flame retardancy of PET (poly(ethylene terephthalate)) woven fabrics was investigated. In order to provide the homogenous application of ZnB to the fabrics, the particle size of ZnB powders was reduced from 9 μm to submicron scale by wet-milling with zirconia balls followed by high shear fluid processing. ZnB dispersion was mixed with low-formaldehyde melamine resin based cross-linking agent and it was applied to PET fabrics by pad dry cure method. ZnB dispersion was then added in different ratios to alkyl phosphonate and organophosphorus compound based commercial flame retardant finishing agents and applied to the fabrics. The effect of zinc borate with phosphorus based flame retardant (FR) finishing agents was examined by cone calorimetry under a heat flux of 35 kW/m2, vertical flame test, and limit oxygen index. Thermogravimetric analysis was performed up to 800°C under N2 flow. Test results show that zinc borate can be combined with the organophosphorus based commercial FR finishing agents. Zinc borate could not improve the flammability properties of PET fabrics significantly but decreased mean CO, total smoke release, and total smoke production values.

Study on the flame retardancy of nano-Sb2O3/BPS-PBT composites

To improve the flame retardancy of polybutylene terephthalate (PBT), PBT-based flame retardant composites containing antimony trioxide nanoparticles (nano-Sb2O3) and brominated polystyrene (BPS) were investigated. Nano-Sb2O3, BPS, and PBT were dispersed by ball milling method to obtain composite powders, and the nano-Sb2O3/BPS-PBT samples were prepared by melt blending and injection molding methods. The flame retardancy of nano-Sb2O3/BPS-PBT composites was investigated. The results showed that nano-Sbs2O3 can obviously improve the flame retardancy of PBT-based composites. When the nano-Sb2O3/BPS-PBT composite contains nano-Sb2O3 with 5 wt% of mass fraction and BPS with 10 wt% of mass fraction, the nano-Sb2O3/BPS-PBT composite has excellent flame retardancy, in which the UL94 degree of flame retardancy achieves V-0 grade and the limit oxygen index is 28.3%.