Some aspects of tailoring flame retardancy in HET-acid-based flame retardants

HET acid was condensed with either ethylene glycol or 1,4-butanediol to yield the respective oligoesters. These oligoesters were characterized by molecular weight, measured by vapor-pressure osmometry. The degradation mechanism of oligoesters of HET acid with either ethylene glycol or 1,4-butanediol was elucidated. The thermal properties of these polyesters were studied using differential thermal analysis and thermal volatilization analysis. The mechanism of degradation was proposed on the basis of pyrolysis–gas chromatography studies, the degradation products being subsequently identified by mass spectrometry. It turned out that in the course of decomposition, hexachlorocyclopentadiene was formed, which is believed to be the active substance for flame retardance in these systems. The aspect of tailoring flame retardancy by changing the chemical environment, i.e., by using different diols, is discussed.     

Preparation and flame retardancy of reactive flame retardant for cotton fabric

Journal of Thermal Analysis and Calorimetry - Monochlorotriazine aminopropyl silanol phosphate (MCASP) was synthesized as a novel flame retardant agent for cotton fabric. It was characterized by...     

Chain-thermal flame propagation

Summary An equation was derived relating the flame propagation rate to the diffusion coefficient of the leading active center and the thermal conductivity; it was used to calculate the ratio of the flame propagation rates in three methane-oxygen mixtures containing nitrogen (air mixture), argon instead of nitrogen, and helium instead of nitrogen. The theoretical ratios of the propagation rates were in agreement with experimental ratios.     

Infrared flame spectra

Summary This paper presents a summary of recent work on the emission spectra of hydrocarbon flames in the region from 1 to 5.5 microns. The temperature of flames as determined by intensities of the infrared rotational and vibrational bands is found to be about 2600° K. Further temperature measurements on the incandescent particles in an oxyacetylene flame have been made and it was found that the values determined agree with those obtained from the spectral measurements.

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Zusammenfassung Eine Übersicht neuerer Arbeiten über Emissionsspektren von Kohlenwasserstoff-Flammen im Gebiet von 1 bis 5,5 Mikron wird gegeben. Die Messung der Intensität der infraroten Rotations- und Vibrationsbanden ergab eine Flammentemperatur von etwa 2600° K. Weitere Temperaturmessungen wurden an unverbrannten Teilchen in einer Acetylen-Sauerstoff-Flamme vorgenommen. Die dabei erhaltenen Werte stimmen mit den spektrometrischen Messungen überein.

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Résumé On présente dans cette communication un résumé des travaux récents sur le spectre d'émission des flammes dans la région spectrale de 1 à 5,5 microns. La température des flammes est déterminée à partir des intensités des bandes infra-rouges de vibration et de rotation; elle est environ 2600° K. On a fait d'autres mesures de température de particules incandescentes dans une flamme oxy-acétylénique; les valeurs trouvées sont en bon accord avec celles qu'on déduit de mesures spectrales.

     

Thermal degradation and flame retardancy of epoxy resins containing intumescent flame retardant

Pentaerythritol diphosphonate melamine-urea-formaldehyde resin salt, a novel cheap macromolecular intumescent flame retardants (IFR), was synthesized, and its structure was a caged bicyclic macromolecule containing phosphorus characterized by IR. Epoxy resins (EP) were modified with IFR to get the flame retardant EP, whose flammability and burning behavior were characterized by UL 94 and limiting oxygen index (LOI). 25 mass% of IFR were doped into EP to get 27.2 of LOI and UL 94 V-0. The thermal properties of epoxy resins containing IFR were investigated with thermogravimetry (TG) and differential thermogravimetry (DTG). Activation energy for the decomposition of samples was obtained using Kissinger equation. The resultant data show that for EP containing IFR, compared with EP, IFR decreased mass loss, thermal stability and R _max, increased the char yield. The activation energy for the decomposition of EP is 230.4 kJ mol⁻¹ while it becomes 193.8 kJ mol⁻¹ for EP containing IFR, decreased by 36.6 kJ mol⁻¹, which shows that IFR can catalyze decomposition and carbonization of EP.     

Thermal and flame retardant properties of novel intumescent flame retardant polypropylene composites

Novel intumescent flame retardant polypropylene (PP) composites were prepared based on a char forming agent (CFA) and silica-gel microencapsulated ammonium polyphosphate (Si-MCAPP). The thermal and flame retardancy of flame retardant PP composites were investigated by limiting oxygen index, UL-94 test, cone calorimetry, thermogravimetric analysis, scanning electron micrograph, and water resistance test. The results of cone calorimetry show that the flame retardant properties of PP with 30 wt% novel intumescent flame retardants (CFA/Si-MCAPP = 1:3) improve greatly. The peak heat release rate and total heat release decrease, respectively, from 1,140.0 to 156.8 kW m^?2 and from 96.0 to 29.5 MJ m^?2. The PP composite with CFA/Si-MCAPP = 1:3 has the excellent water resistance, and it can still obtain a UL-94 V-0 rating after 168 h soaking in water.     

Thermal stabilities and flame retardancies of nitrogen-phosphorus flame retardants based on bisphosphoramidates

Various nitrogen-phosphorus (P-N) compounds based on phosphoramidate were synthesized as model compounds to investigate the relationships among the chemical structure of linker connecting diphenylphoryl groups between the phosphoramidates, the N content, thermal stability, and flame-retarding ability. The flame-retarding efficiencies were evaluated by the limiting oxygen index (LOI) and UL-94 vertical test methods. It was found that bisphosphoramidates are more thermally stable and produce more charred residues when compared to the corresponding bisphosphate compounds. Aromatic phosphoramidates show fairly good flame retardancy for PC and UL-94 V-0 ratings are achieved with addition of as small amount as 3-5 wt%. However, no rating is found for ABS at 30 wt% loading of bisphosphoramidate FRs which leave the remarkably high residues at 600 °C. The thermogravimetric analysis (TGA) results indicate that these compounds work in condensed phase rather than in gas phase. The effect of chemical structure of linker on the flame retardancy is also discussed.     

Study on intumescent flame retarded polystyrene composites with improved flame retardancy

The flame retardancy and thermal stability of ammonium polyphosphate/tripentaerythritol (APP/TPE) intumescent flame retarded polystyrene composites (PS/IFR) combined with organically-modified layered inorganic materials (montmorillonite clay and zirconium phosphate), nanofiber (multiwall carbon nanotubs), nanoparticle (Fe₂O₃) and nickel catalyst were evaluated by cone calorimetry, microscale combustion calorimetry (MCC) and thermogravimetric analysis (TGA). Cone calorimetry revealed that a small substitution of IFR by most of these fillers (≤2%) imparted substantial improvement in flammability performance. The montmorillonite clay exhibited the highest efficiency in reducing the peak heat release rate of PS/IFR composite, while zirconium phosphate modified with C₂₁H₂₆NClO₃S exhibited a negative effect. The yield and thermal stability of the char obtained from TGA correlated well with the reduction in the peak heat release rate in the cone calorimeter. Since intumesence is a condensed-phase flame process, the MCC results showed features different from those obtained from the cone calorimeter.     

Solubilities,thermostabilities and flame retardance behaviour of phosphorus-containing flame retardants and copolymers

Thirteen phosphorus-containing flame retardants were synthesized in this work. The solubilities of flame retardant [(6-oxide-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)-methyl]-butanedioic acid (DDP) in selected solvents are measured. TGA measurements of the 13 phosphorus-containing flame retardants were carried out and thermal stabilities of three flame-resistant PET (FRPET) resins were investigated. A FRPET incorporated by DDP with terephthalic acid and ethylene glycol reported in literature was also discussed and compared. The thermal stability of the FRPET is improved by the incorporation of phosphorus-containing flame retardants. The LOI values of all phosphorus-containing polyesters are higher than 27%. The improvement of the flame-resistant ability is due to the formation of the char that is not only caused by the existence of phosphorus elements in the resin but also by the relative large number of carbon atoms of the phenyl group in the flame retardants.     

Condensed phases in flame spectrometry: an equilibrium model of the acetylene flame

An equilibrium model for a wet acetylene flame has been used for the calculation of the distribution of carbon, aluminium and silicon between gaseous and condensed phases. Calculated values of free atom vapour fractions are in agreement with published experimental data. It is thermodynamically probable that the formation of condensed phases limits atom vapour formation. There is a relationship between the position of an element in the Periodic Table and the nature of the condensed phase.     

Effects of analyte reduction by flame gases through heterogenous reactions in flame spectrometry

A simplified model describing vaporisation with simultaneous reduction to an involatile species and assuming that the rate of reduction is limited by the diffusion of reducing species from the flame gases to the particle surface is presented. Under these conditions the fraction vaporised may be independent of the particle size and linear calibration curves may be found even with incompletely vaporised aerosol particles.     

Use of a continuous source of excitation,an argon-hydrogen-air flame. and an extended flame cell for atomic absorption flame spectrophotometry

A continuous source of excitation in conjunction with an argon-hydrogen-entrained air flame, an extended flame cell, a medium-dispersion monochromator and a typical detection system is shown to give good sensitivities for the atomic absorption flame spectrophotometric measurement of 21 elements. Useful working curves over a 100-fold concentration range are obtained for each of the 21 elements using the simple experimental system. The advantages gained with this system are discussed.     

A novel intumescent flame retardant imparts high flame retardancy to epoxy resin

Intumescent flame retardant (IFR) has received the considerable attention ascribed to the inherent advantages including non‐halogen, low toxicity, low smoke release and environmentally friendly. In this work, a novel charring agent poly (piperazine phenylaminophosphamide) named as PPTA was successfully synthesized and characterized by Fourier transform infrared spectra (FTIR) and X‐ray photoelectron spectroscopy (XPS). Then, a series of flame‐retardant EP samples were prepared by blending with ammonium polyphosphate (APP) and PPTA. Combustion tests include oxygen Index (LOI), vertical Burning Test (UL‐94) and cone calorimeter testing,these test results showed that PPTA greatly enhances the flame retardancy of EP/APP. According to detailed results, EP containing 10 wt% APP had a LOI value of 30.2%,but had no enhancement on UL‐94 rating. However, after both 7.5 wt% APP and 2.5 wt% PPTA were added, EP‐7 passed UL‐94 V‐0 rating with a LOI value of 33.0%. Moreover, the peak heat release rate (PHRR) and peak of smoke product rate (PSPR) of EP‐7 were greatly decreased. Meanwhile, the flame‐retardant mechanism of EP‐7 was investigated by scanning electron microscopy (SEM), thermogravimetric analysis/infrared spectrometry (TG‐IR) and X‐ray photoelectron spectroscopy (XPS). The corresponding results presented PPTA significantly increased the density of char layer, resulting in the good flame retardancy.     

Multichannel integrating flame photometer

A new high-speed optical chopping and demodulation system is described for use in flame photometry. Methods are described which allow integration of signal and noise over many optical pulses of flame energy. The method has been used to develop a direct-reading instrument for sodium, potassium and calcium. With this method, 4 signal channels are integrated simultaneously. With the integration technique, ordinary flame noise is significantly reduced. By using an internal standard, all signal channels are referenced to known energy levels regardless of flame variations.