炭化烧蚀材料热解膨胀和线膨胀对内部温度场影响研究

本文根据炭化烧蚀材料的防热机理,认为防热材料表面化学烧蚀后退、热解膨胀和内部温度升高引起线膨胀是造成防热层厚度变化的因素,国内外学者主要研究了表面化学烧蚀后退对飞行器外形变化和温度场的影响,而对于后两者的具体影响却少有研究。本文数值模拟了高硅氧-酚醛炭化材料的烧蚀热响应过程,分析和解释了计算结果,说明了防热材料的线膨胀和热解膨胀对外形和温度场有较大的影响。     

Synergistic effects between a triazine-based charring agent and aluminum phosphinate on the intumescent flame retardance of thermoplastic polyether ester

The triazine-based charring agent (CFA) with perfect charring ability was synthesized and characterized. The synergistic effects between CFA and aluminum phosphinate (AlPi) on flame retardancy, thermal degradation, and flammability properties of thermoplastic polyester-ether elastomer (TPEE) were investigated by limiting oxygen index (LOI), vertical burning test (UL-94), cone calorimeter test (CCT), thermogravimetric analysis (TGA), laser Raman spectroscopy (LSR) and scanning electron microscopy (SEM). The results from UL-94 test showed that, by compounding 14 wt% AlPi and 4 wt% CFA with TPEE, the LOI value reached 28.5% and the UL-94 rating reached V-0 (1.6 mm). TGA results indicated that there is good synergistic charring ability between CFA and AlPi, especially the increased residues at high temperature (T > 700 °C). The CCT test results showed that CFA could change the combustion behavior of TPEE and effectively accelerate the formation of expanded carbon layers. The residues after combustion were measured by LRS and SEM, demonstrating that CFA can promote the formation of dense and stable carbon layers during the combustion, which could inhibit the melt dropping and improve the fire retardancy of TPEE composites. Thus, CFA was a promising synergistic agent in halogen-free flame retardant TPEE.     

Synergistic effect between a novel hyperbranched charring agent and ammonium polyphosphate on the flame retardant and anti-dripping properties of polylactide

A novel hyperbranched polyamine charring agent (HPCA), a derivative of triazines, was synthesized and well characterized by ¹H NMR and FTIR. HPCA and ammonium polyphosphate (APP) were added into polylactide (PLA) resin as an intumescent flame retardant (IFR) system to impart flame retardancy and dripping resistance to PLA. The flammability and thermal stability of IFR-PLA composites were investigated by limiting oxygen index (LOI), UL-94 vertical burning, cone calorimetry and thermogravometric analysis (TGA) tests. The results showed that the IFR system had both excellent flame retardant and anti-dripping abilities for PLA. The TGA curves suggested that HPCA has good ability of char formation and when combined with APP, would induce synergistic effect which could be clearly observed. This effect greatly promoted the char formation of IFR-PLA composites, hence improved the flame retardant property. Additionally, the structure and morphology of char residues were studied by XPS, FTIR and SEM.     

Synthesis of a triazine-based macromolecular hybrid charring agent containing zinc borate and its flame retardancy and thermal properties in polypropylene

Abstract

A triazine-based macromolecular hybrid charring agent containing zinc borate (MCA-K-ZB) was synthesized and combined with ammonium polyphosphate (APP) to improve the flame retardancy of polypropylene (PP). The flame retardancy and thermal properties of PP composites were investigated using limited oxygen index, vertical burning test, and thermogravimetric analysis. The results showed APP/MCA-K-ZB can improve the flame retardancy of PP compared with APP/MCA-K/ZB. The morphology of the char residues was investigated by scanning electron microscopy (SEM). The SEM result shows that MCA-K-ZB can improve the compactness and continuity of char residue compared with MCA-K/ZB, therefore improving the flame retardancy of PP composites.     

新型三嗪类氮-硅成炭剂的合成及其热稳定性

以三聚氯氰(1)和γ-氨丙基三乙氧基硅烷(2)为原料,经亲核取代反应合成了一种新型三嗪类氮-硅成炭剂——2-氯-4,6-二(3-三乙氧基硅烷基-1-氨丙基)-1,3,5-三嗪(3),其结构和热性能经1H NMR,IR和TGA表征。考察了溶剂、缚酸剂、原料比和反应温度对3产率的影响。合成3的最佳反应条件为:以丙酮为溶剂,Na2CO3为缚酸剂,1 10 mmol,n(2)∶n(1)=2.4,于50℃反应6 h,产率98.1%。3的初始分解温度为292℃,700℃时成炭率34.5%。     

防热材料起泡现象的物理建模和计算方法研究

一些烧蚀试验发现特定配方的有机涂层防热材料在受到加热时,在有机物热解时除产生通常的炭化层外,在热解区附近还会出现较严重的起泡物理现象,在防热层内部区域形成很明显的较大泡沫,使防热层厚度增加,改变了防热材料的传热性能和物理模型,减缓了热量向内部结构的传递,降低内部结构的温升,对防热结构设计非常有利.本文细致分析了外部加热时有机涂层的热解烧蚀过程,初步建立防热材料起泡现象的物理模型和控制方程,数值模拟了起泡现象对内部温度场结果的具体影响,并与试验结果进行了比较.     

煤焦制备条件对其气化反应性的影响

改变制焦条件（温度、升温速率、保温时间）制备了八个煤焦样品。－７８℃下ＣＯ２物理吸附和２００℃下Ｏ２化学吸附分别测定了它们的总比表面积和活性表面积。用ＸＲＤ测定了它们的碳微晶尺寸。ＴＧ法测定了煤焦与空气在４５０、５００、５５０℃下的等温气化反应活性，并用Ａｒｒｈｅｎｉｕｓ方程和半衰期法分别求得了每个样品的反应活化能Ｅ和指前因子Ａ。结果表明：制焦温度越高，升温速率越慢，保温时间越长，煤焦的反应活性越     

Effect of charring agents on solvent‐free fireproof coatings

The choice of charring agent is one of the major issues for solvent‐free fireproof coatings. The effects of processing method and charring agent on the thermal insulation and fire resistance of the coatings were investigated in simulated fire scenarios. Dipentaerythritol (DPER), triazine agent (CFA), and pentaerythritol phosphate (PEPA) were compared as charring agent, and the thermal, combustion, fire resistance, and charring behaviors in different fire scenario were characterized for the fireproof coatings. Compared with high‐speed dispersing equipment, kneading processing equipment is favorable for improving the thermal stability and fire resistance of the coatings, because the stronger shearing force has promoted mixing and dispersion of the ingredients in solvent‐free fireproof coatings. As for charring agents, it is found that the fireproof coatings containing CFA or PEPA show better thermal and flame‐retardant performances. More residue was observed under nitrogen atmosphere in thermogravimetric analysis, less heat and smoke were released in cone calorimetry test. However, during the high temperature fire resistance test, their char layers were prone to delaminate while DPER‐containing coatings produced intact and stronger char layer with better heat insulation. For practical applications, the coating formulations need to be optimized to achieve both fire resistance and flame retardancy.     

Simultaneous Determination of Aluminum,Cadmium and Lead in Whole Blood by Simultaneous Atomic Absorption Spectrometry with Oxygen Charring

A method for the simultaneous determination of aluminum (Al), cadmium (Cd) and lead (Pb) in whole blood has been developed by using simultaneous atomic absorption spectrometry (SIMAAS) with oxygen charring. The optimized conditions for the simultaneous determination of Al, Cd and Pb were obtained in the presence of palladium (Pd) as the chemical modifier, using 600 °C and 2400 °C as the pyrolysis and the atomization temperature, respectively. The whole blood samples were diluted 1+5 (v/v) directly with 0.1% (v/v) Triton X‐100. Oxygen was employed to eliminate the interference of carbonaceous residues in the charring step before pyrolysis. The calibration curves were carried out with aqueous standard solutions and the linear ranges were 0–40 ng mL⁻¹, 0–4 ng mL⁻¹ and 0–40 ng mL⁻¹ for Al, Cd and Pb, respectively. The detection limits were 0.96 ng mL⁻¹ (19.2 pg) for Al, 0.03 ng mL⁻¹ (0.6 pg) for Cd and 0.60 ng mL⁻¹ (12.0 pg) for Pb. The spiked recoveries of Al, Cd and Pb in whole blood were 98.0%, 100.0% and 101.7%, respectively. The accuracy of the proposed method was evaluated with the analysis of a whole blood certified reference material (Seronorm, level 2). The found concentrations were in agreement with the recommended values. The proposed method has been successfully applied to the simultaneous determination of Al, Cd and Pb in whole blood of healthy volunteers before and after eating barbecued foods.     

Synthesis and Application of a Novel Charring Agent Poly(p-ethylene terephthalamide)

A novel charring agent poly(p-ethylene terephthalamide) (PETA) was synthesized by using terephthaloyl chloride and ethylenediamine through solution polycondensation at low temperature. Poly(p-ethylene terephthalamide) was used together with ammonium polyphosphate (APP) to prepare a novel intumescent flame retardant (IFR) for acrylonitrile–butadiene–styrene (ABS). The thermal degradation behavior and flame retardancy were investigated by thermogravimetric analysis and limiting oxygen index (LOI) tests, and the morphology and structures of residues generated in different conditions were investigated by scanning electron microscopy and Fourier transform infrared spectra. The results showed that PETA could be effective as a charring agent, the flame retardancy of ABS and the weight of residues improved greatly with the addition of IFR. When the content of APP was 25 wt% and PETA was 12.5 wt%, the LOI value of IFR–ABS system was found to be 33, and class V-0 of UL-94 test was passed. The microstructures observed by scanning electron microscope indicated that the charring agent (PETA) can promote formation of uniform and compact intumescent charred layers in IFR–ABS system after burning.