Thermomechanical modelling the fire properties of fibre–polymer composites

Simple-to-use models are presented in this paper for determining the residual tension, compression and flexural properties of burnt fibre reinforced polymer composite materials following a fire. The post-fire mechanical properties are calculated using analytical equations that combine the properties of the fire-damaged (i.e. char) and undamaged regions of a composite. Fire tests were performed on composites containing carbon, glass or Kevlar fibres with an epoxy, polyester, vinyl ester or phenolic resin matrix to assess the accuracy of the models. The composites were tested to a wide range of fire conditions with temperatures from 525 to 850 °C for times up to 30 min. It is found that the post-fire properties drop rapidly with increasing heat flux and duration of a fire due to the thermal degradation of the polymer matrix. It is shown that the reduction to the post-fire properties of the burnt composites can be accurately determined using the models. In almost all test cases, the agreement between the calculated and measured residual mechanical properties is within 10%.     

Post-fire flexural performance of epoxy-nanocomposite matrix glass fibre composites containing conventional flame retardants

This paper investigates the effect of varied nanoparticles (silicate nanoclays and double-walled carbon nanotubes) and micro-sized flame retardants (FRs) on the post heat/fire flexural performance of glass fibre-reinforced (GFR) epoxy composites. The fire reaction properties of GFR epoxy composites containing different combinations of nano- and micro-sized FRs were studied at varied incident heat fluxes (35–75 kW/m²). The flexural stiffness and modulus values of radiant heat-damaged GFR composites decreased rapidly with increasing incident heat flux. On another hand, the post-fire flexural properties of these specimens exposed for 30–90 s post-ignition at 50 kW/m² retained only 20% of their room temperature flexural properties. Despite significant improvements in the fire reaction properties, their post-fire flexural performance was least affected. This suggests that, while these flame retardants are effective in promoting char formation, the formed char networks are not consolidated enough to effectively constrain the fibre reinforcements.     

ZrB2-SiC复相陶瓷涂层制备及其保护C/C-SiC复合材料性能

为提高C/C-SiC复合材料的超高温抗烧蚀性能,通过浆料涂刷和高温烧结相结合的方法在C/C-SiC复合材料表面制备了ZrB₂-SiC复相陶瓷涂层,利用EDS、SEM对涂层的成分及微观形貌进行了分析。对涂层材料的力学性能和抗烧蚀性能进行了表征,结果表明：制备的ZrB₂-SiC复相陶瓷涂层保护C/C-SiC复合材料的拉伸强度、弯曲强度及剪切强度分别为147 MPa、355 MPa和21.9 MPa,与无涂层保护的针刺C/C-SiC复合材料的力学性能相比略有下降。涂层材料具有良好的抗氧化烧蚀性能,经过热流密度为3 200 kW/m²的氧乙炔火焰烧蚀600 s试验,其线烧蚀率和质量烧蚀率分别为0.001 mm/s和0.0006 g/s。     

Compression properties of fire-damaged polymer sandwich composites

The effect of fire-induced damage on the edgewise compression properties of polymer sandwich composites is investigated. Fire tests were performed using a cone calorimeter on sandwich composites with high or low flammability. The highly flammable composite had a poly(vinyl chloride) foam core, while the flame resistant composite had a phenolic foam core. The residual edgewise compression properties of the burnt composites were determined after fire testing at room temperature. The compression stiffness and strength of the two sandwich composites decreased rapidly with increasing heat flux and heating time of the fire due to thermal decomposition of the face skin and foam core. A large reduction to the edgewise compression properties of the phenolic-based sandwich composite occurred despite having good flame resistance, and the reasons for this are described. Preliminary analytical models are presented for estimating the edgewise compression failure load of fire-damaged sandwich composites that fail by core shear or buckling.     

膨胀蛭石/酚醛阻燃保温复合材料的制备及性能

以膨胀蛭石为阻燃剂,采用中温发泡方法与酚醛树脂复合制备膨胀蛭石/酚醛阻燃保温复合材料。阻燃保温复合材料通过极限氧指数、锥形量热、导热系数和表观密度分析了发泡温度、固化剂含量、发泡剂含量、表面活性剂含量、固化时间以及蛭石含量对膨胀蛭石/酚醛阻燃保温复合材料阻燃及保温性能的影响。结果表明:以膨胀蛭石为阻燃剂制备的膨胀蛭石/酚醛阻燃保温复合材料的阻燃保温性能优越、表观密度低。单因素实验结果表明,膨胀蛭石/酚醛阻燃保温复合材料的最优条件为发泡温度80℃、固化剂含量10wt%、发泡剂含量10wt%、表面活性剂含量5wt%、固化时间2 h以及蛭石含量60wt%。最优条件下的膨胀蛭石/酚醛阻燃保温复合材料表观密度为190.08 kg/m3、压缩强度为0.32 MPa、导热系数为0.054 9 W/（m·K）、极限氧指数为71.1%、平均热释放速率为15 kW/m2。      

POSS/粘土/多壁碳纳米管杂化碳纳米纸基复合材料防火性研究

多壁碳纳米管(MWCNTs)、粘土和多面齐聚半硅氧烷(POSS)组成的杂化碳纳米纸是通过碳纳米管巴基纸制备工艺制备而成, 碳纳米纸可做为表面防火层与聚合物基复合材料共固化成型。利用场发射扫描电镜(FESEM)和BJH法分别对碳纳米纸和杂化碳纳米纸微观结构和平均孔径分布进行表征。利用锥形量热仪在热辐射功率50 kW/m²条件下分析外贴碳纳米纸复合材料及复合材料对比样的防火特性。燃烧实验结果表明: 碳纳米纸和杂化碳纳米纸作为防火层的复合材料的峰值热释放速率(PHRR)与复合材料对比样相比分别下降20.2%和35%, 同时CO释放量和烟释放量也明显降低。通过FESEM研究表明燃烧实验后外贴杂化碳纳米纸复合材料的燃烧残余物表面形成了一层致密的积炭物结构, 防火阻燃性能明显提高。     

Ablation behavior of ZrB2–SiC ultra high temperature ceramics under simulated atmospheric re-entry conditions

ZrB₂–20vol%SiC ultra high temperature ceramic (UHTC) was prepared by hot-pressing. Ablation tests of the flat-face models were conducted under ground simulated atmospheric re-entry conditions using arc-jet testing with heat fluxes of 1.7 MW/m² and 5.4 MW/m² under subsonic conditions, respectively. There was little weight or configuration change after ablation at a heat flux of 1.7 MW/m². However, ZrB₂–SiC composite underwent severe ablation and whose surface temperatures exceeded 2300 °C at a heat flux of 5.4 MW/m². Sharp-shape leading edge models were ablated under supersonic conditions with the stagnation pressure and Mach number of 1.2 atm and 2.7 M, respectively, and sharp-shaped leading edge C/SiC models were also ablated under the same condition for comparison. ZrB₂–SiC composite exhibited an excellent thermal-oxidative and configurational stability in the simulated re-entry environment compared with C/SiC material. Results indicate that ZrB₂–SiC ultra high temperature ceramics are the potential candidates for leading edges. The temperature limit for UHTC is controlled by the softening and degradation of the formed oxide scale.     

Influence of Fabric Parameters on Microstructure,Mechanical Properties and Failure Mechanisms in Carbon-Fibre Reinforced Composites

The effects of fibre/matrix bonding, fabric density, fibre volume fraction and bundle size on microstructure, mechanical properties and failure mechanisms in carbon fibre reinforced composites （plastic and carbon matrix） have been investigated. The microstructure of unloaded and cracked samples was studied by optical microscopy and scanning electron microscopy （SEM）, respectively whereas the mechanical behaviour was examined by 3- point bending experiments. Exclusively one type of experimental resole type phenolic resin was applied. A strong fibre/matrix bonding, which is needed for high strength of carbon fibre reinforced plastic （CFRP） materials leads to severe composite damages during the pyrolysis resulting in low strength, brittle failure and a very low utilisation of the fibres strain to failure in C/C composites. Inherent fabric parameters such as an increasing fabric density or bundle size or a reduced fibre volume fraction introduce inhomogenities to the CFRP＇s microstructure. Results are lower strength and stiffness whereas the strain to failure increases or remains unchanged. Toughness is almost not affected. In C/C composites inhomogenities due to a reduced bundle size reduce strain to failure, strength, stiffness and toughness. Vice versa a declining fibre volume fraction leads to exactly the opposite behaviour. Increasing the fabric density （weight per unit area） causes similar effects as in CFRPs.     

碳化硼颗粒级配对硅反应结合碳化硼复合材料结构与性能的影响

本研究探讨了碳化硼原料颗粒尺寸对反应结合碳化硼复合材料相组成、结构与性能的影响。研究结果表明:颗粒级配可以使粉体堆积更加密实, 有效提高压制坯体的体积密度, 最终降低复合材料中游离Si的含量; 加入粗颗粒可减缓B₄C与Si的反应, 减少SiC相的生成; 当原料中粒径为3.5、14、28、45 μm的B₄C粉体按质量比为1.5 : 4 : 1.5 : 3配比时, 所制备的复合材料维氏硬度、抗弯强度、断裂韧性和体积密度分别为(29±5) GPa、(320±32) MPa、(3.9±0.2) MPa·m^1/2和2.51 g/cm³。在制备复合材料过程中减缓B₄C与Si反应速度、减少游离Si的含量和缩小Si区域尺寸是其性能升高的主要原因。     

Post-fire flexural properties of fibre-reinforced polyester, epoxy and phenolic composites

The effect of fire damage on the flexural properties of fibre-reinforced polymer (FRP) composites is investigated. The FRP composites studied contained glass, carbon or Kevlar fibres with a polyester, epoxy or phenolic resin matrix. Artificial fire tests were performed on the composites using a cone calorimeter. The residual flexural modulus and strength of the burnt composites were determined at room temperature after the fire tests. The post-fire flexural properties of all the composites decreased rapidly with increasing heating time. Even the properties of the fibre-reinforced phenolic materials were severely degraded despite their low flammability and excellent fire resistance. The flexural properties of the phenolic-based composites were reduced due to thermal degradation and cracking of the resin matrix. In comparison, the properties of the polyester- and epoxy-based composites were reduced by combustion of the resin and formation of delamination cracks. A model is presented for determining the post-fire flexural properties of FRP composites with good accuracy.     

Post fire behavior of carbon fibers Polyphenylene Sulfide- and epoxy-based laminates for aeronautical applications: A comparative study

Through the comparison of two carbon fiber-reinforced polymers (Epoxy and Polyphenylene Sulfide – PPS), this work was aimed at investigating the influence of different fire conditions on the high temperature tensile mechanical behavior. In order to better understand the influence of matrix nature on post-fire properties, the fiber – or matrix-dominated mechanical responses of laminates have been investigated by means of quasi-isotropic or angle-ply stacking sequences. Compared to carbon/PPS laminates, the mechanical properties of carbon/Epoxy laminates are higher in the virgin state (no prior fire exposure). The analysis of the post fire tensile properties shows that prior severe fire exposures are more detrimental to carbon/Epoxy than to carbon/PPS laminates. Although the PPS matrix behavior is highly ductile at a test temperature higher than glass transition temperature, it clearly appears that the decrease in the tensile properties laminates of PPS-based composites is much slower than the one observed in carbon/Epoxy laminates subjected to severe prior fire conditions. Provided the heat flux is high enough to lead to the outset of pyrolysis, PPS-based composites yield higher amounts of char, whose formation retains the structural integrity of fire-damaged composites.     

Modelling the tension and compression strengths of polymer laminates in fire

Thermo-mechanical models are presented for predicting the time-to-failure of polymer laminates loaded in tension or compression and exposed to one-sided radiant heating by fire. Time-to-failure is defined as the time duration that a polymer laminate can support an externally applied load in a fire without failing. The models predict the temperature rise and through-thickness temperature profile in a hot decomposing laminate exposed to fire. Using this thermal data, mechanics-based models based on residual strength analysis are used to calculate the time-to-failure. A preliminary evaluation of the accuracy of the models is presented using failure times measured in fire-under-load tests on a woven glass/vinyl ester laminate. The model was evaluated at temperatures between ∼250 and 800 °C by testing the laminate at heat flux levels between 10 and 75 kW/m². It was found that the time-to-failure of the laminate decreased with increasing heat flux and increasing applied stress for both the compression and tension load conditions. The tests also revealed that the failure times were much shorter (by about one order of magnitude) when the laminate was loaded in compression. The models can predict the time-to-failure with good accuracy for both compression and tension loading for certain heat flux levels. However, because the models have only been evaluated for one type of laminate (woven glass/vinyl ester), further evaluation is necessary for other laminate systems. The paper also presents new experimental insights into the strengthening mechanisms of laminates at high temperature.     

SiC含量对机械合金化-热压制备B4C-SiC复合陶瓷的影响

以B₄C、SiC粗粉为原料, 采用机械合金化辅助热压烧结工艺, 在不添加任何助烧剂的情况下于1950℃制备出致密的B₄C-SiC复合陶瓷。通过对烧结样品进行相对密度、维氏硬度、抗弯强度和断裂韧性测试, 研究SiC含量对复合陶瓷力学性能的影响; 结合XRD、SEM和TEM对样品进行组分和微观结构分析, 研究其微观结构与力学性能之间的关系。结果表明: 复合陶瓷的相对密度和断裂韧性随SiC含量的增加而增大, 当SiC含量为50wt%时获得最大值为96.1%和4.6 MPa•m^1/2; 复合陶瓷的硬度和抗弯强度随SiC含量的增加呈先增大后减小的趋势, 在SiC含量为20wt%时获得最大值25.5 GPa和480 MPa。SiC相均匀分布在B₄C基体中使得复合陶瓷具有较高的强度; B₄C与SiC之间好的界面相容性以及SiC的高断裂韧性是该B₄C基复合陶瓷韧性得到显著提高的原因。     

Effect of bulk lubricant concentration on the excess surface density during R123 pool boiling

This paper investigates the effect that bulk lubricant concentration has on the non-adiabatic lubricant excess surface density on a roughened, horizontal flat (plain) pool-boiling surface. Both pool boiling heat transfer data and lubricant excess surface density data are given for pure R123 and three different mixtures of R123 and a naphthenic mineral oil. A spectrofluorometer was used to measure the lubricant excess density that was established by the boiling of a R123/lubricant mixture on a test surface. The fluorescent technique was used to measure the effect of bulk lubricant concentration on the lubricant excess layer during refrigerant/lubricant mixture boiling. The refrigerant preferentially boils, thus, concentrating and accumulating the lubricant on the surface in excess of the bulk concentration. The excess lubricant resides in a very thin layer on the surface and influences the boiling performance. Accordingly, the ability to measure the effect of bulk lubricant composition on the lubricant excess density and in turn the effect on the heat transfer would lead to a fundamental understanding of the mechanism by which lubricants can degrade or improve boiling performance. In support of this effort, heat transfer data are provided for pure R123 and three R123/lubricant mixtures at 277.6 K. For heat fluxes between approximately 25 to 45 kW/m², an average enhancement of the heat flux of 9 and 5% was achieved for the 0.5 and 1% lubricant mass fractions, respectively, and an average degradation of 5% in the heat flux was obtained for the 1.8% lubricant mass fraction mixture.

Résumé

This paper investigates the effect that bulk lubricant concentration has on the non-adiabatic lubricant excess surface density on a roughened, horizontal flat (plain) pool-boiling surface. Both pool boiling heat transfer data and lubricant excess surface density data are given for pure R123 and three different mixtures of R123 and a naphthenic mineral oil. A spectrofluorometer was used to measure the lubricant excess density that was established by the boiling of a R123/lubricant mixture on a test surface. The fluorescent technique was used to measure the effect of bulk lubricant concentration on the lubricant excess layer during refrigerant/lubricant mixture boiling. The refrigerant preferentially boils, thus, concentrating and accumulating the lubricant on the surface in excess of the bulk concentration. The excess lubricant resides in a very thin layer on the surface and influences the boiling performance. Accordingly, the ability to measure the effect of bulk lubricant composition on the lubricant excess density and in turn the effect on the heat transfer would lead to a fundamental understanding of the mechanism by which lubricants can degrade or improve boiling performance. In support of this effort, heat transfer data are provided for pure R123 and three R123/lubricant mixtures at 277.6 K. For heat fluxes between approximately 25 kW/m² to 45 kW/m², an average enhancement of the heat flux of 9% and 5% was achieved for the 0.5% and 1% lubricant mass fractions, respectively, and an average degradation of 5% in the heat flux was obtained for the 1.8% lubricant mass fraction mixture.     

PBT/氧化石墨烯纳米复合材料的制备及热处理

先用Hummer法合成氧化石墨烯(GO),然后用熔融共混法制备了不同GO含量的聚对苯二甲酸丁二醇酯(PBT)纳米复合材料(PBT/GO)。随着GO含量的提高PBT/GO纳米复合材料的拉伸强度和冲击强度都先提高后降低,GO的含量为0.5%的材料性能最佳。将GO含量为0.5%的PBT/GO纳米复合材料在不同温度(150、180和200℃)热处理不同时间(30、60和90 min),研究了热处理对其结构和性能的影响。结果表明,随着热处理温度的提高PBT/GO纳米复合材料的拉伸强度和冲击强度最高达63.2 MPa和11.6 kJ/m²,比热处理前分别提高了36.1%和59.3%。而随着热处理时间的延长其拉伸强度和冲击强度最高分别为62.3 MPa和11.0 kJ/m²,分别提高了34.2%和51.9%。DSC分析结果表明,提高热处理温度和延长热处理时间都能提高复合材料的结晶度,结晶度比热处理前最多分别提高了11.4%和8.6%,温度对结晶度的影响更甚。XRD测试结果表明,热处理并不改变复合材料的晶型结构,只影响其结晶度。导热性能测试结果表明,复合料的结晶度越高则导热性能越好。提高热处理温度,复合材料在50℃和100℃的热导率最高分别为0.49 W/(m·K)和0.42 W/(m·K),比热处理前分别提高了24.1%和18.6%;延长热处理时间,复合材料在50℃和100℃的热导率最高分别为0.46 W/(m·K)和0.37 W/(m·K),比热处理前分别提高了14.6%和5.9%,热处理温度对导热性能的影响更显著。     

Fe-Si磁性颗粒/环氧树脂复合材料的冲击和磁学性能

采用双酚A型WSR-615和缩水甘油胺型AG-80环氧树脂为基体,以Fe-Si磁性颗粒为填料,通过热压成型方法制备了高含量磁性Fe-Si颗粒/环氧树脂复合材料。研究了环氧树脂基体的玻璃化温度和冲击强度及Fe-Si磁性颗粒含量对Fe-Si/环氧树脂复合材料的冲击强度和磁化强度的影响及温度敏感性。研究结果表明：随着磁性颗粒含量的增加,Fe-Si/环氧树脂复合材料的冲击强度和磁性能增加。当磁性颗粒体积分数由54 vol%增加到66 vol% 时,Fe-Si/环氧树脂的冲击强度和饱和磁化强度分别由4.03 kJ/m²和162.07 emu/g增加到7.16 kJ/m²和175.04 emu/g。Fe-Si/环氧复合材料在-60 ℃~140 ℃ 范围内的温度敏感性低,符合实际应用对复合材料稳定性的要求。     

新型磷氮型阻燃剂的制备及其阻燃聚氨酯泡沫塑料

以三（2-羟乙基）异氰尿酸酯（THEIC）和苯氧基磷酰二氯（PDCP）为主要原料,合成了一种新型磷氮型阻燃剂（PNFR）,借助FTIR、核磁共振光谱（1H-NMR、31P-NMR）对其结构与组成进行了表征。将PNFR与聚磷酸铵（APP）复配用于制备聚磷酸铵-新型磷氮型阻燃剂阻燃聚氨酯泡沫（APP-PNFR/PUF）复合材料,通过极限氧指数（LOI）、垂直燃烧测试、锥形量热和热失重分析对APP-PNFR/PUF复合材料的阻燃性能和热性能进行了研究。结果表明:成功获得了PNFR;此外,PNFR的TGA表明PNFR在N₂气氛下的初始分解温度为249℃,800℃时的残炭量可达33.7%,其具有较高的热稳定性能。APP-PNFR的加入能有效改善PUF的阻燃性能,且当PNFR的添加量与组合聚醚的质量比为7.5%时,可获得综合性能较好的阻燃PUF材料,其中LOI从19%提高至24%,UL-94垂直燃烧等级达到V-0级,热释放速率峰值从110.6 kW/m2降低到94.5 kW/m2;同时,APP-PNFR/PUF3在N₂气氛下的初始分解温度提高了6℃,最大分解速率降低了16.3%,800℃时的残炭量可达33.5%。PNFR的加入不会削弱PUF的物理力学性能。      

尼龙66纤维/6061铝合金复合板静电植绒工艺及隔声性能

为研究不同植绒工艺条件下尼龙66纤维/6061铝合金复合板的植绒性能与隔声性能,首先,采用静电植绒工艺将6061铝合金板与尼龙66纤维复合,制成隔音复合板;然后,研究了植绒时间、植绒电压、极板间距以及胶黏剂涂覆量等工艺参数对植绒面密度和植绒纤维耐磨性能的影响;最后,利用混响室-消声室法研究了尼龙66纤维/6061铝合金复合板在不同入射声频下和不同纤维结构参数时的隔声性能。结果表明:在0~40s植绒时间范围内,随着植绒时间的延长,植绒面密度持续增大,而后保持不变;同时,在0~90kV电压范围内,随着电压的增加,植绒面密度连续增大,而后因极板间距不同植绒面密度增大或减小;植绒纤维的耐磨性能随胶黏剂涂覆量的增加而提高,但当涂覆量超过155g/m2后会产生气泡;当植绒时间为40s、植绒电压为90kV、极板间距为11.5cm且胶黏剂涂覆量为155g/m2时,尼龙66纤维/6061铝合金复合板的性能最好。该复合板具有较高的中高频隔声性能,隔声量在500~1 600Hz频率范围内满足6dB/倍频程规律;在2 000Hz后出现吻合效应。提高植绒面密度以及减小尼龙66纤维直径均可增大该尼龙66纤维/6061铝合金复合板的隔声量。研究结论可为建筑用新型隔音复合材料的开发与应用奠定基础。     

碗状C@FeS2@NC复合材料的制备及其电化学性能

在二氧化硅微球表面包覆一层酚醛树脂并在高温下将其转化为碳壳,然后进行溶剂热反应、多巴胺包覆、高温硫化以及氢氧化钠刻蚀,制备出碗状C@FeS₂@NC(氮掺杂碳层)复合材料。这种复合材料具有开放性三维碗状结构,能释放体积变化产生的应力,其较大的比表面积(70.67 m²·g^-1)有很多的活性点位。内外双层碳壳提高了这种复合材料的导电性并提供了稳定的机械结构,外层NC具有很好的保护作用。将这种复合材料用作锂离子电池负极,在0.2 A·g^-1电流密度下首圈放电比容量和充电比容量分别为954.3 mAh·g^-1和847.2 mAh·g^-1,对应的首圈库伦效率为88.78%。循环100圈后,其放电比容量稳定在793.8 mAh·g^-1。     

Measurement of spray boiling refrigerant coefficients in an integral-fin tube bundle segment simulating a full bundle

Outside (refrigerant) boiling coefficients for a combination of spray and drip boiling for a low pressure refrigerant have been obtained from overall heat transfer coefficients in a 1024 fins per meter tube bundle segment. The tubes were heated by water on the inside; liquid refrigerant was sprayed and/or dripped on the outside. Also, refrigerant vapor was supplied at the bottom of the bundle segment. This configuration simulates an actual flooded evaporator under spray boiling conditions. The dripping corresponds to liquid film falling from upper rows while the inlet vapor is equivalent to the vaporized refrigerant rising from lower tubes; the refrigerant vapor can influence heat transfer performance by the combined effects of gas convection and liquid shear on the tubes. For a nominal heat flux of 23,975 W/m², a bundle average outside heat transfer coefficient of 8522 W/m² °C, based on nominal tube outer diameter, was found at an average bundle vapor mass flux equal to 12.4 kg/s m². The distributor plate below the bundle enhanced the heat transfer, especially at lower vapor mass fluxes, by providing a level of liquid hold-up just below the bottom tube row.