ПОРІВНЯННЯ АМІНІВ ЯК ГАЗОУТВОРЮВАЧІВ ВОГНЕЗАХИСНИХ КОМПОЗИЦІЙ ІНТУМЕСЦЕНТНОГО ТИПУ

Purpose. Study of influence of blowing agents amines structure on the construction processes of thermal insulating char layer of intumescent system ammonium polyphosphate/pentaerythritol/amine and fire protection efficiency of this system at high temperatures. Methodology. A fire retardant mixture of ammonium polyphosphate/pentaerythritol/amine was chosen as a model intumescent system. Dispersion of vinyl acetate copolymer with vinyl ether of versatic acid was used as a polymeric component. A step-by-step study of the characteristics of the char layer of the intumescent composition was applied in the study, consisting in the analysis of the characteristics of the char formed after keeping the intumescent composition samples at a certain temperature between 100 and 800 °C, char residue mass (m, %), structure and density of the formed char layer. The method of infrared spectroscopy was used for identification of products of thermolysis of intumescent systems. Determination of fire protection efficiency of intumescent coatings was carried out in a mini-oven under standard fire conditions. Findings. The influence of the structure of amines blowing agents on the formation of char layer of intumescent system ammonium polyphosphate/pentaerythritol/amine was studied. Physico-chemical parameters of char layer formed during high temperature swelling of intumescent system components with varying amine: urea, melamine, dicyandiamide, guanidine, thiocarbamide, formylthiosemicarbazide, thiosemicarbazide, phenylethylcarbamide have been determined. In the temperature range 200–400 oC for systems with linear amines (urea, thiocarbamide, thiosemicarbazide), there is a rapid formation of insulating layer with intense outgassing (high intumescent coefficients K) and the same rapid its destruction with significant losses of char residue mass (Δm). The presence of melamine, dicyandiamide and guanidine in intumescent system provides constancy of intumescent coefficient at minimal mass loss. Chemical transformations of intumescent systems were studied by the method of infrared spectroscopy when the investigated amines were varied. It was found that linear diamines do not form stable spatially branched phosphamide compounds with phosphates as the basis of a thermostable heat-insulating frame. At the same time in IR spectra of char residue systems with melamine, dicyandiamide and guanidine the absorption bands of P-N-C bonds (1070–1050 cm-1) and P-N (980–950 cm-1) up to 600–700 oC are observed. Fire tests proved that melamine, dicyandiamide and guanidine are blowing agents providing maximum protection of metal against fire and can be used for composition of fire retardants for steel constructions.Originality. It has been proved that amines in intumescent polyphosphate system perform at least two functions: blowing agents by means of thermal destruction to incombustible gases and nucleophilic compound that takes part in char layer formation by aminolysis of electrophilic substrates.Practical value. The optimum amine blowing agents for developing formulations of intumescent coatings with enhanced flame retardant properties have been established.

Influence of the Process of Synthesis of Zeolites from Volcanic Ash in Its Synergistic Action as a Flame-Retardant for Polypropylene Composites

In this research, the influence of natural zeolites obtained from the volcanic ash of the Ubinas volcano has been studied as synergistic agents in a flame-retardant system (composed of ammonium polyphosphate, pentaerythritol, and polypropylene). Four zeolites were synthesized from volcanic ash, including those that had been calcined and those that had not. These were then placed in an alkaline solution at three synthesis temperatures. Zeolites were characterized through X-ray diffraction, specific surface area by nitrogen adsorption analysis (Brunauer–Emmett–Teller) and scanning electron microscopy. Polypropylene matrix composites were prepared with ammonium polyphosphate, pentaerythritol and zeolites at 1, 5 and 9%. Its thermal stability and fire resistance were evaluated by thermogravimetric analysis, limiting oxygen index, vertical burning test and cone calorimeter and its morphological structure by scanning electron microscopy. It was determined that the synthesis temperature and the use of calcined and without calcined volcanic ash have an influence on the characteristics of the zeolites and on its synergistic action.

Preparation of Mn2+ Doped Piperazine Phosphate as a Char-Forming Agent for Improving the Fire Safety of Polypropylene/Ammonium Polyphosphate Composites

A piperazine phosphate doped with Mn2+ (HP-Mn), as a new char-forming agent for intumescent flame retardant systems (IFR), was designed and synthesized using 1-hydroxy ethylidene-1,1-diphosphonic acid, piperazine, and manganese acetate tetrahydrate as raw materials. The effect of HP-Mn and ammonium polyphosphate (APP) on the fire safety and thermal stability of polypropylene (PP) was investigated. The results showed that the combined incorporation of 25 wt.% APP/HP-Mn at a ratio of 1:1 endowed the flame retardant PP (PP6) composite with the limiting oxygen index (LOI) of 30.7% and UL-94 V-0 rating. In comparison with the pure PP, the peak heat release rate (PHRR), the total heat release (THR), and the smoke production rate (PSPR) of the PP6 were reduced by 74%, 30%, and 70%, respectively. SEM and Raman analysis of the char residues demonstrated that the Mn2+ displayed a catalytic cross-linking charring ability to form a continuous and compact carbon layer with a high degree of graphitization, which can effectively improve the flame retardancy of PP/APP composites. A possible flame-retardant mechanism was proposed to reveal the synergistic effect between APP and HP-Mn.

Enhancements on Flame Resistance by Inorganic Silicate-Based Intumescent Coating Materials

Flame-retardant coatings have drawn much attention in recent years. In this study, an inorganic sodium silicate-based intumescent flame-resistance coating with an excellent flameproof properties is developed by mainly utilizing sodium silicate as the ceramizable binder, via hydrolysis and self-condensation reaction. Fly ash, metakaoline, and wollastonite behave as supplement cementing materials. Major formulation encompasses the combination of the ammonium polyphosphate and pentaerythritol as the flame-retardant additives, and aluminum hydroxide or expandable graphite as the intumescence-improving filler agents. Expandable graphite was found to play an important role in the eventual performance of flame-resistance testing. The results showed that solid interaction forces can be formed between metakaoline and sodium silicate, resulting in a similar material to geopolymer with excellent physical properties. After high-temperature flame testing, a densely complex protective layer of carbon-char created on top of the robust silicon dioxide networks offers notable flame resistance. An optimal ratio in this inorganic intumescent coating contains sodium silicate—metakaoline (weight ratio = 9:1)—ammonium polyphosphate and pentaerythritol, aluminum hydroxide (3, 3, 10 wt.%)—expandable graphite (1 wt.%), which can create 4.7 times higher expansion ratio compared with neat sodium silicate matrix. The results of flame testing demonstrate only 387.1 °C and 506.3 °C on the back surface of steel substrate after one and three hours flaming (>1000 °C) on the other surface, respectively, which could meet the requirements according to the level of fire rating.