阻燃及可瓷化硅橡胶成炭结构的研究进展

简单介绍了硅橡胶的阻燃和瓷化机理。依据阻燃剂、填料及炭层结构的不同,将硅橡胶分为阻燃和可瓷化两大类.综述了阻燃硅橡胶和可瓷化硅橡胶的阻燃性能和成炭结构的研究进展。分析表明:添加物理或化学膨胀型阻燃剂的硅橡胶,燃烧过程中形成的炭层疏松多孔,阻燃隔热性能优异,但炭层强度差;添加非膨胀型阻燃剂的硅橡胶,炭层结构相对密实,但表面不平整,存在孔洞和裂缝,阻燃效果不好;添加可瓷化填料的硅橡胶燃烧形成的陶瓷炭层坚硬而致密,具有优异的耐火持久性,但在隔绝热量方面不如膨胀炭层。炭层的疏松隔热与坚固耐久兼顾是阻燃硅橡胶未来可能的发展方向。     

Moisture–absorption,dielectric relaxation,and thermal conductivity studies of polymer composites

In the search for new packaging materials for the electrical/electronics industry, three types of polymer composites have been studied. Silicone/boron nitride powders, polyurethane/alumina powders, and polyurethane/carbon fibers have all been synthesized to study the moisture–absorption kinetics, thermal conductivities, and the dielectric loss spectra under various levels of humidity. The water uptake data indicate that water molecules are absorbed not only by the polymer matrix, but also by the interfaces introduced by the fillers. For all materials, the dielectric relaxation spectroscopy shows the presence of a peak in the 175–200 K range, which is largely due to absorbed water. The silicone/boron nitride samples absorbed the least amount of moisture. Incorporating this result with the thermal conductivity data of the three types of polymer composites, it is concluded that silicone polymers embedded with boron nitride can best serve as the coating for the electronic devices that require heat dissipation and moisture resistance, in addition to electrical insulation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2259–2265, 1998     

无氧/低氧环境中zigzag型焦炭N的迁移转化特性

采用量子化学方法探究了还原区高浓度NO存在下zigzag结构焦炭氮中N的迁移转化规律，并通过构建含羟基焦炭N模型，从分子层面对氧存在下焦炭N的转化特性进行了系统的理论计算。结果表明，还原区NO的存在会与焦炭中的N结合为N₂释放；并且氧的存在增强了焦炭表面化学活性，进一步促进了焦炭中N的析出。还原区氧和NO的共存使得焦炭中N的释放与C的燃烧同时发生，表现为NO与焦炭中N结合为N₂的同时，伴随有氧将焦炭中C氧化成CO₂或CO。动力学计算C燃烧产物的限速步速率常数发现，低温低氧条件下C更容易氧化生成CO；随着温度的升高，CO₂生成速率明显增大，高温更利于CO₂的生成。     

热解温度对生物质焦理化特性的影响

利用SEM、BET及TGA对在873、1 073和1 273 K下制得的麦秆焦的理化特性进行分析,进行了用制得的麦秆焦还原NO的实验,同时考虑了焦样及NO初始浓度对该反应的影响,得出了热解温度对麦秆焦的各种物理化学特性及其与NO反应活性的影响。结果表明,1 073 K焦样的孔隙特征最为发达,燃烧活性最高,并对应最高的NO还原效率。焦作用下NO的还原率随着焦样浓度的增大线性升高,而随着初始NO浓度的增大呈幂函数的规律下降。不同热解温度下麦秆焦样与NO的反应均在1 173 K附近存在动力学控制和扩散控制的转折温度;在动力学控制的反应温度范围内,热解温度对麦秆焦与NO反应活化能的影响不大(89.78~95.41 kJ/mol),其中,NO浓度项和焦浓度项的反应级数分别为0.89和1.00。     

Effects of retorting factors on combustion properties of shale char

For obtaining high shale oil yield as well as treating shale char efficiently and in an environmentally friendly way in a new comprehensive utilization system of oil shale, a series of fundamental experiments have been conducted for exploring the effects of retorting factors on shale oil yield and shale char characteristics. Based on these previous studies, in this article, combustion experiments of shale chars obtained under various retorting conditions were performed with a Q5000IR thermogravimetric analyzer and a Leitz II-A heatable stage microscope and the effects of retorting factors were discussed on the combustion characteristics of shale char. Among four studied retorting parameters, retorting temperature and residence time exert very significant influence on the combustion characteristics of shale char. Either elevating the retorting temperature from 430 to 520 °C or lengthening the residence time at a low retorting temperature will largely decrease residual organic matters within shale char, resulting in decreasing mass loss in the low-temperature stage of combustion process of shale char, an elevation of ignition temperature and a shift of ignition mechanism from homogeneous to heterogeneous. One set of retorting condition was also recommended as a reference for designing the comprehensive utilization system of oil shale studied in this work: retort temperature of 460–490 °C, residence time of 20–40 min, particle size of <3 mm, and low heating rate of <10 °C/min.     

Thermal degradation and intumescent flame retardation of cellulose whisker/epoxy resin composite

The morphology, thermal degradation, and flame retardancy of epoxy (EP) composites containing microcrystalline cellulose whisker (MCW) and microencapsulated ammonium polyphosphate (MFAPP) were investigated using optical microscopy, limiting oxygen index (LOI), UL-94, thermogravimetry (TG), microscale combustion calorimeter, and TG-FTIR. EP/MFAPP/MCW composites can pass V-0 in UL-94 test at 6 wt% loading, and its peak heat release rate decreases when compared with EP and EP/MFAPP. The reason is that the presence of MCW strengthens the charring capacity of EP composites in a fire. The results of TG and TG-FTIR show that at low temperature, MFAPP stimulates the dehydration of MCW and EP, and produces gas which is helpful for the formation of an intumescent char. Moreover, the residue at high temperature does not release any flammable gas and is a good insulation layer on the surface of the sample, which protects the underlying material in a fire.     

Effect of Combustion Improver on Combustion Behavior of Cigarette Paper by Simultaneous TG/DSC Detection

Combustion behavior of cigarette paper containing different content of combustion improver was investigated in order to provide direct experiment data to elucidate lower components in cigarette smoke caused by combustion improver in cigarette paper. The content of the combustion improver was denoted as "organic" potassium index and determined by atomic absorption spectroscopy and ionic spectroscopy. The combustion process obtained by simultaneous thermal analysis was divided into four stages: weight loss due to loss of absorbent water, decomposition of the cellulose, the oxidation of the cellulose char and decomposition of calcium carbonate. Combustion improver reduced the temperature of cellulose decomposition 3–12 K and contributed to oxidation of the cellulose char. Ignition point was gained and reduced 3–8 K by combustion improver. Above results were further verified by samples from two other cigarette paper factories. Mechanism of lower components in cigarette smoke by the combustion improver in cigarette paper was discussed.     

炭化程度对核桃壳焦孔隙结构和燃烧特性的影响

利用傅里叶变换红外光谱仪(FT-IR)、扫描电子显微镜(SEM)和X射线衍射仪(XRD)研究了炭化程度对核桃壳焦孔隙及微晶结构的影响,并使用热重-差示扫描量热仪(TG-DSC)对核桃壳焦及其原料的燃烧特性进行了分析。结果表明,合适的炭化程度(焦炭挥发分含量为6%-15%)使焦炭内乱层石墨变得无序,碳质微晶结构中缺陷增多,导致焦炭内孔隙结构相对发达;热解温度为500℃时,核桃壳焦的比表面积最大,为374.60 m~2/g;热解温度为600℃时,核桃壳焦的燃烧特性最优,其燃烧特性指数为7.16×10~6;合适的炭化程度可使焦炭内的挥发分含量减少,从而使得核桃壳焦的高位热值升高,且由于相对发达的孔隙使焦炭在燃烧时与空气的接触面积增大,导致焦炭的燃烧速率加快。     

Molecular motion of ends of isolated poly(isobutylene) chains tethered on the poly(tetrafluoroethylene) surface in vacuo

Poly(isobutylene) (PIB) chains with a radical at the chain end were graft-copolymerized on the poly(tetrafluoroethylene) (PTFE) surface in vacuo at 77 K. The PIB chains tethered on the PTFE surface in vacuo were regarded as isolated chains from neighboring tethered PIB chains. The molecular motion of the ends of the isolated PIB chains was observed by an electron spin resonance (ESR) spectrometer in the temperature range from 3 to 125 K, which was lower than T_g of PIB, 200 K,¹ and two motion modes were found: One is a quantum tunneling of the methyl group located at the chain end at 3 K, and the other is an interconformation transition with freely rotating methyl group at the end at 77 K, where the transition rate was estimated to be 15 MHz at that temperature. The transition rate increased with an increase in temperature. The activation energy of the transition was estimated to be 370 J/mol. The high mobility and low activation energy was attributed to the isolation of PIB chains in vacuo. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2095–2102, 1998     

Flame-retardant Wrapped Ramie Fibers towards Suppressing “Candlewick Effect” of Polypropylene/Ramie Fiber Composites

In this work, a flame-retardant polypropylene(PP)/ramie fiber(RF) composite was prepared. The ramie fibers were wrapped chemically by a phosphorus- and nitrogen-containing flame retardant(FR) produced via in situ condensation reaction so as to suppress their candlewick effect. Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM) demonstrated that the ramie fibers wrapped chemically by FR(FR-RF) were obtained successfully. Thermogravimatric test showed that the PP/FR-RF composite had more residue and better thermal stability at high temperatures than the PP/RF composite. Cone calorimeter(CC) results indicated that the peak of heat release rate(PHRR) and total heat release(THR) correspondingly decreased by 23.4% and 12.5% compared with the values of neat PP/RF. The PP/FR-RF composite created a continuous and compact char layer after the combustion. Combining FTIR analysis of char residue after CC test with heat conduction coefficient results, it could be concluded that the charring of FR on RF greatly weakened the candlewick effect of RF, and more char residue in the RF domain facilitated the formation of more continuous and compact char layer in the whole combustion zone, consequently protected PP composites during combustion, resulting in the better flame retardancy of PP/FR-RF composite than that of PP/RF composite.     

可瓷化硅橡胶材料的研究

研究了一种可瓷化硅橡胶,其特点是在火灾发生时可在金属线外形成瓷化绝缘保护层,600℃的成瓷温度大幅度低于目前文献报道的成瓷温度。实验得到的优化瓷化填料配方为:相对于100份混炼胶,氧化铝10份、硅灰石15份、结构控制剂9份、碳酸锂3份。在此配方条件下,未瓷化硅橡胶的断裂伸长率316%、拉伸强度10.79MPa、体积电阻率134×10~(12)Ω·cm,其在600℃、800℃瓷化后的抗压强度分别为3.47MPa、10.13MPa、体积电阻率≥28×10~(12)Ω·cm,满足电缆用硅橡胶的力学和绝缘要求。经热重分析及SEM分析可知加入瓷化填料后,试样烧蚀重量减少了39.4%,烧蚀残留率大大提高,且成瓷试样结构致密。     

Residual stress and optical properties of fully rod-like poly(p-phenylene pyromellitimide) in thin films: Effects of soft-bake and thermal imidization history

A soluble poly(amic acid) precursor solution of fully rod-like poly(p-phenylene pyromellitimide) (PMDA-PDA) was spin cast on silicon substrates, followed by soft bake at 80–185°C and subsequent thermal imidization at various conditions over 185–400°C in nitrogen atmosphere to be converted to the polyimide in films. Residual stress generated at the interface was measured in situ during imidization. In addition, the imidized films were characterized in the aspect of polymer chain orientation and ordering by prism coupling and X-ray diffraction. The soft-baked precursor film revealed a residual stress of 16–28 MPa at room temperature, depending on the soft bake condition: higher temperature and longer time in the soft bake gave higher residual stress. The stress variation in the soft-baked precursor film was not significantly reflected in the final stress in the resultant polyimide film. However, the residual stress in the polyimide film varied sensitively with variations in imidization process parameters, such as imidization temperature, imidization steps, heating rate, and film thickness. The polyimide film exhibited a wide range of residual stress, −7 MPa to 8 MPa at room temperature, depending on the imidization condition. Both rapid imidization and low-temperature imidization generated high stress in the tension mode in the polyimide film, whereas slow imidization as well as high temperature imidization gave high stress in the compression mode. Thus, a moderate imidization condition, a single- or two-step imidization at 300°C for 2 h with a heating rate of < 10 K/min was proposed to give a relatively low stress in the polyimide film of < 10 μm thickness. However, once a precursor film was thermally imidized at a chosen process condition, the residual stress–temperature profile was insensitive to variations in the cooling process. All the films imidized were optically anisotropic, regardless of the imidization history, indicating that rod-like PMDA-PDA polyimide chains were preferentially aligned in the film plane. However, its degree of in-plane chain orientation varied on the imidization history. It is directly correlated to the residual stress in the film, which is an in-plane characteristic. For films with residual stress in the tension mode, higher stress films exhibited lower out-of-plane birefringence, that is, lower in-plane chain orienta-tion. In contrast, in the compression mode, higher stress films showed higher in-plane chain orientation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1261–1273, 1998     

用真比重分离法研究一种飞灰残炭的生成途径和再燃特性

根据煤在足够高温度下，停留时间越长，分子结构的晶格化程度越高，因而反应活性越低，同时真比重也越大的原理，采用重液将一种链条锅炉飞灰中的残炭颗粒富集并按不同真比重分开。各比重组颗粒表面积测定结果符合不同燃尽度焦炭比表面积变化规律；小流化床燃烧实验证明随真比重增大，残炭颗粒本征反应活性降低。说明真比重分离法对于判断飞灰残炭颗粒的形成途径和再燃特性很有效。实验结果表明，链条炉飞灰残炭并不主要由原煤中的细小颗粒形成，由中等和大颗粒原煤形成的飞灰残炭占相当比例；在真比重最大的残炭组中，细小颗粒所拥有的总碳量最大。估计它们是由大颗粒或大块原煤经过炉内高温区、停留时间长，燃烧后期碎裂形成的。     

煤-焦炉气共热解半焦燃烧动力学特性研究──燃烧模型的建立及其表观活化能动态描述

采用热重分析方法（ＴＧＡ）对煤－焦炉气共热解半焦燃烧动力学特性进行研究,建立了半焦燃烧动力学模型,采用新的数学处理方法,实现了表观活化能在半焦燃烧过程中的动态描述及平均表观活化能的求取。分析结果表明,表观活化能在半焦燃烧过程中呈“两头高、中间低”的“钟”型动态分布,其变化范围为：４７～９５ｋＪ／ｍｏｌ,其中主要燃烧失重阶段（转化率为２０％～８０％）的表观活化能较低且变化幅度较小,约为４７～６０ｋＪ／ｍｏｌ,在燃烧转化率为４０％左右出现最低活化能约４７ｋＪ／ｍｏｌ。同一半焦燃烧过程中,表观活化能与燃烧速率动态分布具有良好的对应关系,即较大燃烧速率对应着较低表观活化能,这说明表观活化能的大小直接体现了半焦燃烧反应活性的高低     

不同彬县焦的水蒸气气化反应动力学研究

在常压,900℃～1050℃考察了彬县煤的三种焦样（常规方法制焦、快速热解焦和脱灰快速热解焦）在热天平上的水蒸气气化反应。考察了温度和焦种对水蒸气气化反应的影响。对比了三种焦的动力学参数和比表面积。结果表明,气化温度是影响煤焦气化反应速率的主要因素,提高50℃,反应速率增加一倍。快速热解焦的反应速率在相同反应条件下明显大于慢速焦。三种焦的表观活化能以快速焦最大,因而反应速率受温度的影响也最大,快速脱灰焦次之,慢速焦最小。     

Analysis of the dynamics of coal char combustion with ignition and extinction phenomena: Shrinking core model

Single‐particle combustion of coal char is analyzed using a generalized shrinking core model. Finite volume method, which was earlier employed by the authors in solving moving boundary problems involving fluid–solid noncatalytic reactions in general, is used to solve fully transient mass and energy equations. The model takes into account convection and diffusion inside the particle as well as in the boundary layer. The computed results are compared with the experimental data of the authors for combustion of coal char in a fluidized bed combustor. The effects of parameters such as bulk temperature and initial particle radius on the combustion dynamics are examined. The phenomena of ignition and extinction are also investigated. Finally, the importance of Stefan flow, originating due to nonequimolar counterdiffusion, on combustion of coal char is analyzed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 569–582, 2008     

Flame retarding mechanism of polycarbonate containing methylphenyl-silicone

The thermal degradation of polycarbonate (PC) containing methylphenyl-silicone with a branched structure (SFR-PC) was investigated by the thermogravimetric analysis (TGA). The decomposition activation energies were determined using the Ozawa method. It was found that the decomposition activation energy and the degradation residue of the SFR-PC at 800 °C in air atmosphere were much higher than those of the PC. The addition of methylphenyl-silicone enhanced the thermal stability of PC and promoted the formation of char. The silicone was found effective in retarding the combustion of the PC. The limited oxygen index of the PC containing 5 wt.% of methylphenyl-silicone was 34%. Surfaces of the SFR-PC before and after combustion were analyzed by energy dispersive X-ray analysis (EDX) and infrared (IR) spectroscopy. Based on these results obtained, the flame retarding mechanism of the SFR-PC was discussed.     

Synergism of polysiloxane and zinc borate flame retardant polycarbonate

Liquid polysiloxane (PSI) and zinc borate (ZB) were combined for the flame retardance of polycarbonate (PC). During polymer combustion, for the PC flame-retarded with PSI only, PSI can form char residue containing silica on the material surface. But the liquid silicone tends to drip with melting polymer and volatilize in high temperature, thus decreasing the charring performance. In the case of only ZB flame retardant involved, this inorganic flame retardant and possible some of its decomposition products (B₂O₃) more difficultly move to the surface and it appears that they do not effectively contribute to the char formation. Present study suggests that the existing synergism between PSI and ZB is the result of chemical reaction via forming cross-linking B–O–Si structure. As results, the loss of Si/silicone is reduced by eliminating the melt dripping. Meanwhile, boron species can be “dragged” by PSI (in the form of borosiloxane) to the surface of the char residue. Consequently, Si and B elements together contribute to the integrity of char residue layer with better quality, achieving obviously improved flame retardance compared with only PSI and only ZB flame retardant systems.     

Fluorescence spectroscopy and thermal relaxation processes of anthracenyl‐labeled polysiloxanes

A fluorescent silicone network was prepared by a hydrosilylation reaction using poly(dimethylsiloxane‐co‐methylhydrogensiloxane) terminated by dimethylhydrogensilyloxy groups, poly(dimethylsiloxane‐co‐methylvinylsiloxane) terminated by dimethylvinylsilyloxy groups and 9‐vinylanthracene, as the fluorescent group. These silicone‐based materials were strongly fluorescent. Steady state emission was a convenient technique to prove that reaction occurred, based on the blue‐shift of the emission from anthracenyl moieties compared with the 9‐vinylanthracene. Thermal transitions were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and by fluorescence spectroscopy, indicating that networks with and without lumophores had similar thermal properties. Networks with and without lumophores had the same swelling capability in toluene. Fluorescence spectroscopy was a more sensitive technique to the onset of the glass transition temperature (T = 145 K) than DSC or DMA. Nevertheless, the crystallization temperature at 192 K was determined more precisely by DSC, and the melting point at 237 K was indentified more clearly by both DSC and DMA. These three techniques provided complementary information about transitions in silicone networks. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 74–81, 2010     

煤焦部分气化、燃烧集成热重分析研究

在热天平上进行了煤焦部分气化、燃烧的实验研究。所得到的三种不同煤焦 (神木、彬县、西山 )在不同温度 ,不同气化碳转化率下的部分气化 ,燃烧失重曲线表明 :煤种、气化碳转化率对燃烧失重均有影响。气化碳转化率越高 ,所得到的焦燃烧速率越小。同时从实验中得到 :正确选择气化碳转化率在进行部分气化、燃烧集成优化中是非常重要的。