Synthesis of a novel DOPO‐based polyphosphoramide with high char yield and its application in flame‐retardant epoxy resins

A novel and highly effective flame retardant (FR), DOPO‐TPMP oligomer, was synthesized by a simple condensation of 4‐(hydroxymethyl)‐2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane‐1‐oxide and phosphorus oxychloride followed by a polycondensation reaction with 6‐(2,5‐dihydroxyphenyl)‐6H‐dibenzo[c,e][1,2]oxaphosphinine‐6‐oxide. The chemical structure of DOPO‐TPMP was well characterized using Fourier transform infrared and NMR spectra. DOPO‐TPMP was used as an additive‐type FR for epoxy resin (EP). The FR properties of the resultant EP composites were investigated by limiting oxygen index (LOI) test, UL‐94 vertical burning test and cone calorimeter measurements. Specifically, the EP composite containing 10.0% DOPO‐TPMP achieved a LOI value of 36.1%, V‐0 rating in the UL‐94 test and a 58% reduction in peak heat release rate. Further mechanism analysis attributed the enhanced flame retardancy to the increased char yield on the addition of DOPO‐TPMP. © 2019 Society of Chemical Industry     

Study on downward flame spread over extruded polystyrene foam in a vertical channel: Influence of opening area

Experimental methods and theoretical analysis are employed to investigate effects of channel opening area on downward flame spread characteristics of extruded polystyrene (XPS) thermal insulation materials on building facade. The average flame height first drops and then rises as dimensionless opening area (the ratio of sidewall opening area to sidewall area, ie, S^*) increases. As S^* rises, both the average and maximum temperature of the curtain wall decrease, and the decreasing of the average temperature is linear. XPS surface temperature history can be divided into four stages, ie, inapparent rising stage (preheating), significant rising stage (melting), dropping stage (pyrolysis), and rerising stage (ignition). The preheating length first rises and then drops as S^* increases. The XPS flame spreads steadily at the early period while acceleration occurs at the later period. For different opening areas, the difference in spread distance history is not apparent in the early stage while this difference is significant in the later stage. The flame spread rate (V_f) first increases and then decreases as S^* rises. A downward flame spread model for XPS in vertical channel with openings is built. The varied trend of V_f predicted using this model corresponds to the experimental result.     

热处理对等离子喷涂铁基非晶合金涂层微观结构和耐腐蚀性能的影响

采用等离子喷涂技术在Q235钢基体上制备Fe48Cr15Mo14C15B6Y2非晶合金涂层,之后对涂层进行200,300,500,600,700℃热处理,研究了热处理对涂层微观结构、耐电化学腐蚀性能和耐均匀腐蚀性能的影响。结果表明:随着热处理温度的升高,涂层的非晶含量降低,孔隙率先减小后增大,经300℃热处理后涂层的孔隙率最低,且低于未热处理涂层的;热处理后涂层中的晶体相主要包括α-Fe,Fe-Cr,Fe63Mo37,Fe3C等;随着热处理温度的升高,涂层的自腐蚀电流密度先减小后增大,经300℃热处理后,自腐蚀电流密度最小,涂层的耐电化学腐蚀性能最好;经过热处理后,涂层在NaCl溶液中浸泡31d后的单位面积质量损失减小,且热处理温度越高,单位面积质量损失越小,涂层的耐均匀腐蚀性能提高。     

A model of splats deposition state and wear resistance of WC-10Co4Cr coating

In this research both low temperature high velocity oxygen-fuel flame (LT-HVOF) and high velocity oxygen-fuel flame (HVOF) techniques were employed to prepare WC-10Co4Cr splats and coatings. In situ cutting of WC-10Co-4Cr splats was carried out with focused ion beam (FIB), and a model was proposed to describe how the wear resistance of WC-10Co4Cr coatings was correlated with its residual stress state and the splats deposition state. It was observed that in LT-HVOF spraying process, WC-10Co4Cr splats were slightly melted showing "hill" shape, while in HVOF spraying process, the splats were half melted having the appearance of "concavity". The residual stress of WC-10Co4Cr coatings is determined by the size, melting state, flight speed and temperature gradient of splats. In this paper, the quantitative function formula involving heating temperature and the flight speed of the powder is put forward for the first time to predict the wear resistance of the WC-10Co4Cr coatings. This will provide a theoretical basis for engineering practice and an effective way to save costs.     

Thermal cycling and hot corrosion behavior of a novel LaPO4/YSZ double-ceramic-layer thermal barrier coating

LaPO₄ powders were produced by a chemical co-precipitation and calcination method. The ceramic exhibited a monazite structure, kept phase stability at 1400?°C for 100?h, and had low thermal conductivity (~ 1.41?W/m?K, 1000?°C). LaPO₄/Y₂O₃ partially stabilized ZrO₂ (LaPO₄/YSZ) double-ceramic-layer (DCL) thermal barrier coatings (TBCs) were fabricated by air plasma spray. The LaPO₄ coating contained many nanozones. Thermal cycling tests indicated that the spallation of LaPO₄/YSZ DCL TBCs initially occurred in the LaPO₄ coating. The failure mode was similar to those of many newly developed TBCs, probably due to the low toughness of the ceramics. LaPO₄/YSZ DCL TBCs were highly resistant to V₂O₅ corrosion. Exposed to V₂O₅ at 700–900?°C for 4?h, La(P,V)O₄ formed as the corrosion product, which had little detrimental effect on the coating microstructure. At 1000?°C for 4?h, a minor amount of LaVO₄ was generated.     

二甲醚球形扩散火焰的熄火机理研究

采用改进的PREMIX模型及"化学爆炸模式分析(CEMA)"方法,对二甲醚(DME)球形扩散火焰的熄火机理进行数值诊断,分析环境氧气摩尔分数(X_(O_2))及详细基元反应对熄火极限的影响,利用"爆炸因子"和"分岔因子"的概念,确定控制DME球形扩散火焰熄火的关键反应动力学因素。结果表明:DME冷焰具有比热焰更宽的可燃范围;冷焰对X_(O_2)的敏感性弱很多,热焰中具有正特征值的CEM首次出现在最高温度处;在熄火极限附近,CEM的特征值变为虚数,说明熄火伴随着振荡;热焰的熄火主要由小分子所参与的高温反应所控制,而冷焰熄火主要由大分子所参与的低温反应所控制。     

Wet abrasive wear behavior of WC-based cermet coatings prepared by HVOF spraying

In this study, three kinds of WC-based cermet coatings including WC–CoCr coating, WC–Ni coating and WC–Cr₃C₂–Ni coating were prepared by the high-velocity oxygen-fuel (HVOF) spraying process. Scanning electron microscopy (SEM), energy disperse spectroscopy (EDS) and Vickers hardness tester were used to analyze the microstructure and mechanical properties of these coatings. The WC–CoCr coating presented the highest average microhardness of 1205 HV_0.3, and then followed by the WC–Cr₃C₂–Ni coating (1188 HV_0.3) and the WC–Ni coating (1105 HV_0.3). The abrasive wear behavior of the WC-based coatings under the conditions of different applied loads and sediment concentrations were studied by a wet sand-rubber wheel tester. The results indicated that the abrasive wear loss rates of all the coatings increased with the increment of applied load or sediment concentration. In addition, the coatings with higher microhardness appeared to have higher abrasive wear resistance. The abrasive wear resistance of the WC-based coatings was 4–90 times higher than that of AISI 304 stainless steel under the same testing condition. The abrasive wear mechanism of the WC-based coatings was deduced to be the extrusion and removal of binder phases, as well as the fragmentation and peel-off of hard phases.     

Chemical exposures from upholstered furniture with various flame retardant technologies

Upholstered furniture is often manufactured with polyurethane foam (PUF) containing flame retardants (FRs) to prevent the risk of a fire and/or to meet flammability regulations, however, exposure to certain FRs and other chemicals have been linked to adverse health effects. This study developed a new methodology for evaluating volatile organic compound (VOC) and FR exposures to users of upholstered furniture by simulating use of a chair in a controlled exposure chamber and assessing the health significance of measured chemical exposure. Chairs with different fire-resistant technologies were evaluated for VOC and FR exposures via inhalation, ingestion, and dermal contact exposure routes. Data show that VOC exposure levels are lower than threshold levels defined by the US and global indoor air criteria. Brominated FRs were not detected from the studied chairs. The organophosphate FRs added to PUF were released into the surrounding air (0.4 ng/m³) and as dust (16 ng/m²). Exposure modeling showed that adults are exposed to FRs released from upholstered furniture mostly by dermal contact and children are exposed via dermal and ingestion exposure. Children are most susceptible to FR exposure/dose (2 times higher average daily dose than adults) due to their frequent hand to mouth contact.     

Different chemical effect of hydrogen addition on soot formation in laminar coflow methane and ethylene diffusion flames

Previous studies showed that adding hydrogen (H₂) can have an opposite chemical effect on soot formation: its chemical effect enhances and suppresses soot formation in methane (CH₄) and ethylene (C₂H₄) diffusion flames, respectively. Such opposite chemical effect of H₂ (CE-H₂) remains unresolved. The different CE-H₂ is studied numerically in the two laminar coflow diffusion flames. A detailed chemical mechanism with the addition of a chemically inert virtual species FH₂ is used to model the gas-phase combustion chemistry in this study. Particularly, a reaction pathway analysis was performed based on the numerical results to gain insights into how H₂ addition to fuel affects the pathways leading to the formation of benzene (A₁) in CH₄ and C₂H₄ flames. The numerical results show that the CE-H₂ in CH₄ diffusion flame to prompt soot formation is ascribed that the higher mole fraction of H atom promotes the formation of A₁ and Acetylene (C₂H₂) and leads to higher nucleation rate and eventually higher soot surface growth rate. In contrast, adding H₂ to C₂H₄ diffusion flames decreases soot nucleation and surface growth rate. The lower soot nucleation rate is due to the lower mole fractions of pyrene (A₄), while the lower soot surface growth rate is due to the lower mole fractions of H atom and C₂H₂, higher mole fraction of H₂ and lower soot nucleation rate. Furthermore, the CE-H₂ in C₂H₄ diffusion flames promotes the formation of A₁, but suppresses the formation of A₄.     

Structure of turbulent rich hydrogen‐air premixed flames

In the present article, series of experiments were conducted to study the structure characteristics of premixed flames in turbulent rich hydrogen‐air mixtures within a constant‐volume turbulent combustion system, 7 equivalence ratios (1.2, 1.4, 1.6, 1.8, 2.0, 2.2, and 2.5), and 5 turbulent intensity (0, 0.494, 0.742, 1.080, and 1.309 m/s) were studied. With the increase of turbulent intensity, the cellularity degree was obviously enhanced for turbulence promoted the formation and the development of initial cracks by wrinkling flame‐front; furthermore, the enhanced hydrodynamic instability was also one important reason. Turbulence would change the linear growth of critical radius to equivalence ratio into nonlinear, but the variation extents had limitation. The wrinkling index of flame‐front would rise as flame expanded, and the wrinkling index on flames with similar size would be increased with the increase of turbulence once the turbulent intensity was sufficiently high. From the variations of the root mean square of related oscillation on flame‐front, it could be found that the partial amount of oscillation induced by sole turbulence was declined as flame expanded for the breakup of large eddies.