Improving the Flame Retardancy of Polybenzoxazines with a Reactive Phosphorus-Containing Compound

A novel flame retardant resin was prepared by modifying benzoxazines with a reactive phosphorus-containing compound, 2-(6-Oxido-6H-dibenzo[c,e][1,2]oxa-phosphorin-6-yl) 1,4-benzenediol (ODOPB). The curing reactions of the benzoxazines containing ODOPB (ODOPB-BOZ) and a type of bifunctional benzoxazine (B-BOZ) were investigated via differential scanning calorimetry. The ODOPB-BOZ precursors exhibited lower curing temperature in comparison with the B-BOZ. Through dynamic mechanical analysis tests, it was found that the glass transition temperature and storage modulus of the cured ODOPB-BOZ were lower than those of the cured B-BOZ. Moreover, the tensile and flexural properties of the cured ODOPB-BOZ were also lower than those of the cured B-BOZ. The TGA tests proved that, owing to the presence of ODOPB, the char yield of the polybenzoxazines were remarkably raised while the decomposition rates at higher temperature were reduced. It was found that the flame retardancy of cured ODOPB-BOZ attained V-0 grade upon the UL-94 tests while that of cured B-BOZ was V-1 grade. SEM images showed that more compact char layers were formed in the cured ODOPB-BOZ after combustion, resulting in the improvement of flame retardance.     

Flamelet structure in turbulent premixed swirling oxy-combustion of methane

Two key flame macrostructures in swirling flows have been observed in experiments of oxy-combustion (as well as air-combustion); as the equivalence ratio is raised, the flame moves from being stabilized on just the inner shear layer (Flame III) to getting stabilized on both the inner and outer shear layers (Flame IV). We report results of an LES investigation of two different inlet oxy-fuel mixtures, in a turbulent swirling flow at $\text{Re}=20,000,$ that capture these two macrostructures. Previous work on the effects of heat loss have mostly focused on its impact on macro-scale observations. In this paper, we examine how heat loss impacts the flame microstructures as well for these two macrostructures. For both flames, the flamelet structure, as represented by a scatter plot of the normalized fuel concentration against the normalized temperature, depends on whether the combustor walls are adiabatic or non-adiabatic. For the adiabatic case, the flamelets of both macrostructures behave like strained flames. When wall heat transfer is included, Flame III microstructure is more bimodal. Since this flame extends farther downstream and part of it propagates along the walls, heat transfer has a greater impact on it’s microstructure. These results show that heat loss impacts not just the macro properties of the flame such as its shape or interactions with the wall, but also fundamentally changes its internal structure. Scatter plots of the turbulent flames are constructed and compared to different 1D laminar flame profiles (e.g., strained or with heat loss), and comparisons suggest the important role of the wall thermal boundary conditions in the accurate simulations of combustion dynamics and interpretations of experimental data, including data reduction and scaling.     

“蜡烛火焰划分”实验的局限成因分析及改进研究

人教版初中化学首个探究性实验"蜡烛及其燃烧"明确指出火焰的划分方法，但在实际教学中肉眼观察法和火柴梗燃烧法对蜡烛火焰的划分存在一定的局限性。采用文献研究法和实验验证法分析其局限性的成因——燃料的析炭能力强弱、材料结构的不同等，并提出相应的改进建议。     

受限空间油气爆燃火焰形态

通过受限空间油气爆燃可视化实验发现，在不同初始油气体积分数下，爆燃火焰呈现出不同的表观特征，据此提出了受限空间油气爆燃的3种火焰形态，即光滑球形火焰、褶皱球形火焰和卷曲絮状火焰。分析了3种火焰形态的形成机理，并通过实验观测与理论分析，给出了区分3种火焰形态的临界条件。结合实验中采集到的关键参数，总结了不同的火焰形态下受限空间油气爆燃的反应产物、最大压力、升压速率、反应时间、火焰强度等关键参数的特征与变化规律。     

Construction of Charring-Functional Polyheptanazine towards Improvements in Flame Retardants of Polyurethane

Nitrogen-containing flame retardants have been extensively applied due to their low toxicity and smoke-suppression properties; however, their poor charring ability restricts their applications. Herein, a representative nitrogen-containing flame retardant, polyheptanazine, was investigated. Two novel, cost-effective phosphorus-doped polyheptazine (PCN) and cobalt-anchored PCN (Co@PCN) flame retardants were synthesized via a thermal condensation method. The X-ray photoelectron spectroscopy (XPS) results indicated effective doping of P into triazine. Then, flame-retardant particles were introduced into thermoplastic polyurethane (TPU) using a melt-blending approach. The introduction of 3 wt% PCN and Co@PCN could remarkably suppress peak heat release rate (pHRR) (48.5% and 40.0%), peak smoke production rate (pSPR) (25.5% and 21.8%), and increasing residues (10.18 wt%→17.04 wt% and 14.08 wt%). Improvements in charring stability and flame retardancy were ascribed to the formation of P–N bonds and P=N bonds in triazine rings, which promoted the retention of P in the condensed phase, which produced additional high-quality residues.     

CH4/空气简化动力学机理数值验证

选择绕圆柱预混燃烧算例，验证CH₄/空气三种简化动力学机理（16s41r、15s19r和53s325r）.考虑均匀来流，忽略湍流和湍流与燃烧相互作用以及燃料扩散效应，假设层流有限反应速率，采用保自由流5阶WENO格式求解多组分Euler方程组，得到CH₄/空气预混燃烧流场温度等值线、沿驻点线压力和温度及其CH₄、CO和CO₂质量百分数分布.结果表明：三种简化动力学机理给出的流场均出现弓形激波和火焰面，弓形激波和火焰驻点距离及其形状、诱导区宽度和简化动力学机理相关.当圆柱直径增大，弓形激波和火焰向圆柱上游移动，对应的驻点距离均增大，诱导区宽度变短，点火延时变小，但火焰和弓形激波位置次序未变化.53s325r模型要比16s41r模型和15s19r模型精度要高，点火延时覆盖的压力和温度范围也较宽，所有简化机理均未完全反应，在较大圆柱直径下游达到化学平衡.     

Novel cardo polyamides with high solubility,thermally stability,and flame retardancy

Abstract

A new monomeric building block was prepared via three consecutive reactions. 4-(4-Nitrobenzyl)pyridine was catalytically reduced to 4-(4-aminobenzyl)pyridine by converting the nitro to amino group. In second step, the later compound was reacted with 3,5-dinitrobenzoyl chloride to obtain a dinitro compound which finally was converted to a new diamine by reduction of nitro groups. Polycondensation reactions of the diamine with diacidchlorides led to preparation of novel cardo polyamides with high thermal stability and flame retardancy, as well as improved solubility. The structure-property relations were studied by varying the diacidchlorides to investigate the effect of symmetry and aromaticity on the polymers.     

Investigation of melamine and DOPO-derived flame retardants for the bioplastic cellulose acetate

In order to identify suitable flame retardant additives for the eco-friendly polymer cellulose acetate (CA), high-melting derivatives of the known flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were combined with the thermoplastic CA and the combustion properties were tested. CA mixtures with bis-phosphonamidates (EDA-DOPO and PIP-DOPO) showed distinct flame retardation effects and a reduction of peak heat release rates (PHRR) by up to 18%. CA mixtures with MDOP, a melamine salt of DOPA (an oxidation product of DOPO), also showed considerable effects and a reduction of PHRR by up to 27%. While producing more smoke than pure CA and CA plus melamine, owing to its aromatic component, MDOP was superior to the CA mixtures with DOPO, EDA-DOPO and PIP-DOPO in this regard. The mixture of CA with melamine gave rise to a distinctly reduced formation of toxic CO and smoke when compared with pure CA. Thus, these additives can be considered for future applications of CA-based polymers with enhanced flame protection.