Nanoclay and carbon nanotubes as potential synergists of an organophosphorus flame-retardant in poly(methyl methacrylate)

This study explores whether nanoparticles incorporated in polymers always act as synergists of conventional flame-retardant additives. For this purpose, two different filler nanoparticles, namely organically modified layered-silicate clay minerals or nanoclays and multi-walled carbon nanotubes, were incorporated in poly(methyl methacrylate) filled with an organophosphorus flame-retardant that acts through intumescence. Effective dispersion techniques specific to each nanoparticle were utilized and prepared samples were thoroughly characterized for their nanocomposite morphologies. Nanoclays were shown to outperform carbon nanotubes in respect of improving the fire properties of intumescent formulations assessed by cone calorimeter analysis. An intriguing explanation for the observed behaviour was the restriction of intumescence by strong carbon nanotube networks formed on the flaming surfaces during combustion contrary to enhanced intumescent chars by nanoclays. Carbon nanotubes surpassed nanoclays considering the thermal stability of intumescent formulations in thermogravimetry whereas mechanical properties were significantly superior with nanoclays to those with carbon nanotubes.     

Structural studies of the new carbon-coated silicon anode materials using synchrotron-based in situ XRD

The structural changes of graphite-mixed and carbon-coated silicon, used as lithium intercalation materials, have been studied during discharge–charge using synchrotron-based in situ X-ray diffraction. The lithium intercalation (de-intercalation) takes place in the graphite first during discharge (charge), and then in the silicon. This graphite–lithium buffer combined with the uniformly distributed carbon coating greatly improve the quality and morphology of the Li–Si alloys formed at the surface of silicon powders. Therefore, the superior specific capacity and cycling performance are obtained for the graphite-mixed and carbon-coated silicon materials.     

Co-microencapsulate of ammonium polyphosphate and pentaerythritol in intumescent flame-retardant coatings

Co-microencapsulated ammonium polyphosphate (APP) and pentaerythritol (PER) [M (A&P)] is prepared using melamine–formaldehyde resin by in situ polymerization method and characterized using energy dispersive spectrometer and Fourier transform infrared spectra. Thermal stability and fire resistance behavior have been analyzed and compared. The co-microencapsulation of APP and PER leads to a great improvement of its thermal stability investigated by thermogravimetric analysis. The temperature of maximum mass loss rate of M (A&P) is 30 °C higher than that of APP/PER mixture. The flame-retardant effect of M (A&P) in coating composite is evaluated by carbonization volume, flame spread rate, and cone calorimeter. Results show that the flame-retardant properties of M (A&P) in coating composite is much better than that of APP/PER mixture coating composite.     

Influence of T31 content on combustion and thermal degradation behaviors on flame-retardant epoxy composites

To study the influence of the T31 content on the combustion properties and thermal degradation behaviors of flame-retardant epoxy composites, a series of flame-retardant epoxy composites were prepared using E-44 epoxy resin as matrix, T31 curing agent as curing agent, and intumescent flame retardant (IFR, based on phosphorus acid, melamine, and pentaerythritol) as flame retardant. The influence of T31 content on combustion behaviors and thermal degradation properties of the flame-retardant epoxy composites were studied using cone calorimeter test (CCT) and thermal-gravimetric analysis (TG), respectively. The cone calorimeter test results indicate that the decrease of T31 can significantly decrease the HRR, THR, SPR, and enhance the char residue of the epoxy composites. EP-4 with 7.0 wt% T31 shows the lowest HRR, SPR and the highest char residue. Furthermore, the TG results indicate that the EP-4 has the highest char residue among all the epoxy composites.     

Intumescent flame retardation of polypropylene/bamboo fiber semi-biocomposites

Polypropylene/bamboo fiber (BFP) semi-biocomposites were prepared by melted blend method. Microencapsulated ammonium polyphosphate was added to the BFP semi-biocomposites to improve the flame-retardant properties of the BFP semi-biocomposites. The flame-retardant properties of the BFP semi-biocomposites have been investigated by limited oxygen index, UL-94 test and cone calorimeter test. The results of cone calorimeter show that the peak of heat release rate (pHRR) and total heat release (THR) of the flame-retardant BFP semi-biocomposites decrease substantially compared with that without MCAPP. The pHRR value of flame-retardant BFP semi-biocomposite decreases from 540.0 to 227.5 kW m^?2, and the THR value decreases from 75.3 to 49.2 MJ m^?2. The thermal degradation and gas products of the flame-retardant BFP semi-biocomposites were monitored by thermogravimetric analysis and thermogravimetric analysis-infrared spectrometry.     

Preparation and characterization of phenolic foams with eco-friendly halogen-free flame retardant

The high solid resol phenolic resin was prepared via step polymerization of formaldehyde, paraformaldehyde, and phenol using sodium hydroxide and calcium oxide as catalysts, and employed to prepare the phenolic foams (PFs) by the introduction of retardant additives including eco-friendly halogen-free flame retardants (ammonium polyphosphate), char-forming agents (pentaerythritol), and synergists (zinc oxide, molybdenum trioxide, cuprous chloride, and stannous chloride). The effects of these additives on flame retardancy, heat resistance, and fire properties of flame-retardant composite phenolic foams (FRCPFs) were evaluated by limiting oxygen index (LOI) tests, thermogravimetric analyzer, and cone calorimeter tests. It was found that the flame retardan significantly increased the LOIs of FRCPFs. Compared with PF, heat release rate, total heat release, effective heat of combustion, production or yield of carbon monoxide (COP or COY), and Oxygen consumption (O₂C) of FRCPFs all remarkably decreased. However specific extinction area and total smoke release significantly increased, which agreed with the gas-phase mechanism of the flame-retardant system. The results indicate that FRCPFs have excellent fire-retardant performance and less smoke release. APP/PER/ZnO is shown to be better flame-retardant system for PFs.     

Preparation of Polylactide Composite with Excellent Flame Retardance and Improved Mechanical Properties

Despite the good biodegradable and mechanical properties, poly(lactic acid) still suffers from a highly inherent flammability, which restricts its applications in the electric and automobile fields. In order to improve the flame retardancy of PLA, in this work, melamine polyphosphate (MPP) and zinc bisdiethylphosphinate (ZnPi) were firstly incorporated into PLA, and the synergistic effect of them on flame retardance of PLA was investigated using limiting oxygen index (LOI), UL-94 vertical measurement, scanning electron microscopy (SEM) and cone calorimeter tests etc. The results showed that PLA composite with 15 wt% of MPP/ZnPi (3:2) had the best flame-retardant efficiency with LOI value of 30.1 and V0 rating in UL-94 tests, which was far better than using MPP or ZnPi alone. What is more, although a wide range of flame retardants have been developed to reduce the flammability, so far, they normally compromise the mechanical properties of PLA. On the premise of maintaining good flame-retardant performance, we improved the toughness of flame-retardant PLA composite, and the impact strength of flame-retardant PLA composite was more than tripled (8.08 kJ/m²) by adding thermoplastic urethanes (TPU). This work offers an innovative method for the design of the unique integration of extraordinary flame retardancy and toughening reinforcement for PLA materials.     

Study of the fire resistant behavior of unfilled and carbon nanofibers reinforced polybenzimidazole coating for structural applications

With increasing interest in epoxy‐based carbon fiber composites for structural applications, it is important to improve the fire resistant properties of these materials. The fire resistant performance of these materials can be improved either by using high performance epoxy resin for manufacturing carbon fiber composite or by protecting the previously used epoxy‐based composite with some fire resistant coating. In this context, work is carried out to evaluate the fire resistance performance of recently emerged high performance polybenzimidazole (PBI) when used as a coating material. Furthermore, the effect of carbon nanofibers (CNFs) on fire resistant properties of inherently flame retardant PBI coating was studied. Thermogravimetric analysis of carbon/epoxy composite, unfilled PBI and nano‐filled PBI shows that the carbon/epoxy composite maintained its thermal stability up to a temperature of 400°C and afterwards showed a large decrease in mass, while both unfilled PBI and nano‐filled PBI have shown thermal stability up to a temperature of 575°C corresponding to only 11% weight loss. Cone calorimeter test results show that unfilled PBI coating did not improve the fire retardant performance of carbon/epoxy composite. Conversely, nano‐filled PBI coating has shown a significant improvement in fire retardant performance of the carbon/epoxy composite in terms of increased ignition time, reduced average and peak heat release rate and reduced smoke and carbon monoxide emission. These results indicate that addition of carbon nanofibers to inherently flame retardant coating can significantly be helpful for improving the fire resistance performance of composite materials even with low coating thickness. Copyright © 2013 John Wiley & Sons, Ltd.     

Synergistic effect of carbon nanotubes and decabromodiphenyl oxide/Sb2O3 in improving the flame retardancy of polystyrene

Brominated flame retardant polystyrene composites were prepared by melt blending polystyrene, decabromodiphenyl oxide, antimony oxide, multi-wall carbon nanotubes and montmorillonite clay. Synergy between carbon nanotubes and clay and the brominated fire retardant was studied by thermogravimetric analysis, microscale combustion calorimetry and cone calorimetry. Nanotubes are more efficient than clay in improving the flame retardancy of the materials and promoting carbonization in the polystyrene matrix. Comparison of the results from the microscale combustion calorimeter and the cone calorimeter indicate that the rate of change of the peak heat release rate reduction in the microscale combustion calorimeter was slower than that in the cone. Both heat release capacity and reduction in the peak heat release rate in the microscale combustion calorimeter are important for screening the flame retardant materials; they show good correlations with the cone parameters, peak heat release rate and total heat released.     

Synergistic effect between expandable graphite and ammonium polyphosphate on flame retarded polylactide

Synergistic effect was observed between expandable graphite (EG) and ammonium polyphosphate (APP) on flame retarded polylactide (PLA) in this paper using limiting oxygen index (LOI), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM) and X-ray spectroscopy (XPS) and cone calorimeter tests etc. In the experiments, PLA composites with 15 wt% of APP/EG(1:3) combinations showed a LOI value of 36.5 and V-0 rating in UL-94 tests, greatly improved flame retardant properties from composites with APP or EG alone. Results from TGA and cone calorimeter demonstrated that APP/EG combination could retard the degradation of polymeric materials above the temperature of 520 °C by promoting the formation of a compact char layer. This char layer protects the matrix effectively from heat penetrating inside and prevents its further degradation, resulting in lower weight loss rate and better flame retarded performance.     

Polyamide 6 with a flame retardant encapsulated by polyamide 66: Flame retardation, thermo-decomposition and the potential mechanism

A novel encapsulated flame retardant containing phosphorus-nitrogen(MSMM-Al-P) was prepared by encapsulating with polyamide 66(PA66-MSMM-Al-P) for the flame retardation of polyamide 6(PA6).The structure and thermal properties of PA66-MSMM-Al-P were characterized by Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy and thermogravimetric analysis.The flammability of PA6 containing flame retardants(MSMM-Al -P and PA66-MSMM-Al-P) was investigated by the limiting oxygen index test,vertical burning test and cone calorimeter. The flame retardancy and cone calorimetric analyses suggested a synergistic effect between PA66 and MSMM-Al-P in the flame-retardant PA6.Thermal stability of the flame-retardant PA6 was also investigated.     

Advanced environmentally friendly anticorrosive materials prepared from water-based polyacrylate/Na-MMT clay nanocomposite latexes

A series of novel advanced environmentally friendly anticorrosive materials have been successfully prepared by effectively dispersing nanolayers of Na⁺-montmorillonite (Na⁺-MMT) clay into water-based polyacrylate latex (i.e., vinyl acrylic terpolymers). First of all, a polyacrylate latex was synthesized through co-polymerizing organic monomers of MMA, BMA and styrene (St) using conventional emulsion polymerization technique with SDS, 1-pentanol and KPS as surfactant, co-surfactant and initiator, respectively. Subsequently, the commercial purified hydrophilic Na⁺-MMT was effectively dispersing into the polyacrylate latex through the direct solution dispersion technique.The as-prepared neat polyacrylate and the series of water-based polyacrylate/Na⁺-MMT clay nanocomposite (Na⁺-PCN) materials were subsequently characterized by FTIR spectroscopy, XRD, TEM and GPC. The water-based Na⁺-PCN materials loaded with low content of Na⁺-MMT when in the form of coating on the cold rolled steel (CRS) coupons was found to be remarkably superior in anticorrosion efficiency over those of neat polyacrylate based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current, and impedance spectroscopy in saline. Effect of material composition on the molecular barrier, optical clarity and thermal stability were also studied by molecular permeability analysis, ultraviolet-visible transmission spectra, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. Organo-PCN materials were also prepared as a control experiment for comparative studies.     

Development and characterisation of flame-retardant fibres from isotactic polypropylene melt-compounded with melamine-formaldehyde microcapsules

Intumescent flame-retardant textiles have been developed from flame-retardant microcapsules. The work is based on the synthesis of different melamine-formaldehyde microcapsules containing di-ammonium hydrogen phosphate and/or poly(1,6-hexamethylene adipate) by in-situ polymerisation. Two types of shell have been produced, composed of melamine formaldehyde or melamine formaldehyde-poly(hexamethylene adipate glycol). The microcapsules obtained were melt-compounded at 5%-wt with an isotactic polypropylene matrix using a twin-screw extruder, and multi-filaments have afterwards been spun from the various extrudates. The manufactured fibres were mechanically characterized by measuring their tensile properties, and their thermal properties were investigated by DSC and TGA. Finally, knitted fabrics were processed from the multi-filaments: their flame-retardant properties were evaluated by performing a fire test with a cone calorimeter, and their thermal conductivity measured with a Hot Disk. The different thermal behaviours are discussed in terms of the influence of system formulation on the overall thermal degradation, due to interactions between the different components of the flame-retardant microcapsules. The results showed that for one of the structures, an intrinsic intumescent flame-retardant system has been achieved.     

Synergistic flame retarded poly(methyl methacrylate) by nano-ZrO2 and triphenylphosphate

The synergistic flame-retarded systems consisting of nano-ZrO₂ and triphenylphosphate(TPP) for poly(methyl methacrylate)(PMMA) are reported. The synergistic effects were studied by cone calorimeter test, thermal gravimetric analysis (TG), Raman spectra, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The synergistic effect of nano-ZrO₂ with TPP could be clearly observed by cone calorimeter test. The Raman spectra, SEM, and XPS results provide evidence that nano-ZrO₂ can efficiently promote the formation of charred layers composed of varying amounts of graphite and amorphous carbon. The possible mechanisms for synergy are discussed.     

The effect of thermal stability of carbon nanotubes on the flame retardancy of epoxy and bismaleimide/carbon fiber/buckypaper composites

Single-walled carbon nanotube (SWCNT) and multi-walled carbon nanotube (MWCNT) membranes (buckypaper) were incorporated onto the surface of epoxy and bismaleimide (BMI) carbon fiber composites. Their flammability behaviors were investigated by a cone calorimeter. The composites with buckypaper reduced the heat release rate (HRR) by more than 60% peak and smoke generation by 50% during combustion. The effects of different buckypaper on the flame retardancy of epoxy and BMI were compared and discussed. Our research team found that buckypapers acted as an effective flame-retardant shield to dramatically reduce the fire hazards of composites if they survived during fire combustion. Thermogravimetric analyses was used to compare the thermo-oxidation stability of the resins and buckypapers to explain the different effects of SWCNT and MWCNT buckypaper on flammability of epoxy and BMI carbon fiber composites.     

Morphology,thermal stability,and flammability of polymer matrix composites coated with hybrid nanopapers

In this study, a hybrid nanopaper consisting of carbon nanofiber (CNF) and polyhedral oligomeric silsequioxane (POSS) or cloisite Na⁺ clay, has been fabricated through the papermaking process. The hybrid nanopaper was then coated on the surface of glass fiber (GF) reinforced polymer matrix composites through resin transfer molding (RTM) process. The morphologies of the hybrid nanopaper and resulting nanocomposites were characterized with scanning electron microscopy (SEM). It can be seen that the nanopaper had a porous structure with highly entangled carbon nanofibers and the polyester resin completely penetrated the nanopaper throughout the thickness. The thermal decomposition behavior of the hybrid nanopapers and nanocomposites was studied with the real‐time thermogravimetric analysis/ flourier transform infrared spectrometry (TGA/FTIR). The test results indicate that the addition of pristine nanoclay increased the thermal stability of the nanopaper, whereas the POSS particles decreased the thermal stability of the nanopaper. The fire retardant performance of composite laminates coated with the hybrid nanopaper was evaluated with cone calorimeter tests using a radiated heat flux of 50 kW/m². The cone calorimeter test results indicate that the peak heat release rate (PHRR) decreased dramatically in composite laminates coated with the CNF‐clay nanopaper. However, the PHRRs of the CNF‐POSS nanopaper coated composite laminates increased. The formation of compact char materials was observed on the surface of the residues of the CNF‐clay nanopaper after cone calorimeter test. The flame retardant mechanisms of the hybrid nanopaper in the composite laminates are discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Revisiting Surface Modification of Graphite: Dual‐Layer Coating for High‐Performance Lithium Battery Anode Materials

Surface modification of electrode active materials has garnered considerable attention as a facile way to meet stringent requirements of advanced lithium‐ion batteries. Here, we demonstrated a new coating strategy based on dual layers comprising antimony‐doped tin oxide (ATO) nanoparticles and carbon. The ATO nanoparticles are synthesized via a hydrothermal method and act as electronically conductive/electrochemically active materials. The as‐synthesized ATO nanoparticles are introduced on natural graphite along with citric acid used as a carbon precursor. After carbonization, the carbon/ATO‐decorated natural graphite (c/ATO‐NG) is produced. In the (carbon/ATO) dual‐layer coating, the ATO nanoparticles coupled with the carbon layer exhibit unprecedented synergistic effects. The resultant c/ATO‐NG anode materials display significant improvements in capacity (530 mA h g^?1), cycling retention (capacity retention of 98.1 % after 50 cycles at a rate of C/5), and low electrode swelling (volume expansion of 38 % after 100 cycles) which outperform that of typical graphite materials. Furthermore, a full‐cell consisting of a c/ATO‐NG anode and an LiNi_0.5Mn_1.5O₄ cathode presents excellent cycle retention (capacity retention of >80 % after 100 cycles). We envision that the dual‐layer coating concept proposed herein opens a new route toward high‐performance anode materials for lithium‐ion batteries.     

Rapeseed oil as main component in synthesis of bio-polyurethane-polyisocyanurate porous materials modified with carbon fibers

Porous polyurethane-polyisocyanurate (PUR-PIR) composites have been synthesized using two types of rapeseed oil-based bio-polyols. The bio-polyols from rapeseed oil were synthesized using two methods: (i) transesterification and (ii) epoxidation followed by oxirane ring opening. The PUR-PIR porous materials were prepared with two isocyanate indices, 150 and 250, and were modified with carbon fibres (CF) in an amount of 3 and 6 wt% of the total foam mass. The structure of the composites was examined using scanning electron microscopy. Thermal and mechanical properties of the composites were determined through a thermogravimetric analysis and measurements of the thermal conductivity, compressive strength, and Young modulus. The influence of CF on the composite flammability was analyzed using oxygen index and cone calorimeter tests. The investigations of the mechanical properties have shown that the compressive strength is the most beneficial in the case of the PUR-PIR foams modified with 6 wt % of CF. The studies have shown that the oxygen index of the composites increases with an increasing CF content and isocyanate index. An addition of CF reduces the heat rate release, especially for the materials with an isocyanate index of 250. An introduction of CF into the PUR-PIR foam structure is a way to improve the thermal stability and to decrease the flammability of final porous composites.     

Synergistic effects between hollow glass microsphere and ammonium polyphosphate on flame-retardant thermoplastic polyurethane

It is mainly studied that the smoke-suppression properties and synergistic flame-retardant effect of hollow glass microsphere (HM) in flame retardant thermoplastic polyurethane (TPU) composites based on ammonium polyphosphate (APP) as a flame-retardant. Also, the smoke suppression properties and flame-retardant effect were investigated by smoke density test (SDT), cone calorimeter test (CCT), limiting oxygen index, and thermogravimetric analysis, separately. The char residues left after CCT were examined by scanning electron microscopy. The data of SDT shows that HM could effectively decrease smoke production of TPU composites. The results of CCT reveal that the system of APP/HM could reduce heat release rate, smoke production rate, and total smoke release. It is shown that APP/HM is a good system with smoke-suppression and synergistic flame-retardant properties in flame-retardant TPU composites.     

PtPd-nanoparticles supported by new carbon materials

Nanocomposites based on PtPd nanoparticles with chemical ordering like disordered solid solution on surface of multilayer graphene have been prepared through thermal shock of mechanically obtained mixture of double complex salt [Pd(NH₃)₄][PtCl₆] and different carbon materials–exfoliated graphite, graphite oxide and graphite fluoride. An effect of original carbon precursors on formation of PtPd bimetallic nanoparticles was studied using X-ray absorption spectroscopy (XAFS), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). It was shown that the distribution of bimetallic nanoparticles over the multilayer graphene surface as well as the particles size distribution is controlled by the graphene precursors. For all nanocomposites, the surface of the nanoparticles was found to be Pd-enriched. In case when the thermal exfoliated graphite and graphite oxide were used as the graphene precursors a thin graphitized layer covered the nanoparticles surface. Such a graphitized layer was not observed in the nanocomposite, which used the fluorinated graphite as the precursor.