天然鳞片石墨制备可膨胀石墨的工艺研究

以攀枝花天然鳞片石墨为原料,高锰酸钾和双氧水为氧化剂,硝酸、硫酸和高氯酸作为插层剂,制备膨胀石墨。实验发现较佳的膨化温度为950 ℃,并以此温度制备膨胀石墨。结果显示,以双氧水和硫酸制备的膨胀石墨其膨胀容积为130.97~221.80 mL/g;以高锰酸钾和硝酸制备的可膨胀石墨其膨胀容积为150.65~247.19 mL/g;以高锰酸钾和高氯酸制备的膨胀石墨,在干燥温度和时间分别为50 ℃和4~5 h时膨胀容积可达300 mL/g以上。实验还采用XRD和SEM对制备的膨胀石墨结构和形貌进行分析,测试结果发现膨胀石墨的结构完整,可用于进一步制备复合相变材料。     

Flame retardation and thermal stability of novel phosphoramide/expandable graphite in rigid polyurethane foam

A novel flame retardant named diethylene N,N',N''‐tri (diethoxy)phosphoramide (DTP) was synthesized using diethyl phosphate and diethylenetriamine via Atherton–Todd reaction. Then, series of flame‐retardant water‐blown rigid polyurethane foams (RPUFs) with expandable graphite (EG) and DTP were prepared through box‐foaming. The results of thermogravimetric analysis showed that DTP/EG changed thermal degradation process of RPUF and promoted enhancing char residues. The complex flame‐retardant system (EG/DTP) endowed RPUF higher limiting oxygen index (LOI) values (29.1%–30.2%) and lower heat release rate peak (PHRR) values according to LOI and microscale combustion calorimeter tests. More importantly, the synergistic flame‐retardant effect between EG and DTP in RPUF was proved by the analysis of synergistic effectivity values. Based on the analysis of cone calorimetric tests, EG/DTP revealed remarkable effects to inhibit the fire intensity and smoke release of RPUF with decreased PHRR and total smoke production due to good char‐forming action. To further investigate the char‐residues of the foams after combustion, scanning electron microscope and energy dispersive X‐ray spectroscopy analyses were conducted. The results suggested that EG/DTP flame‐retardant system promoted RPUF forming a compact, continuous and phosphorus‐rich char layer as a good fire barrier in combustion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46434.     

Effect of expandable graphite on the properties of intumescent flame‐retardant polyurethane foam

Water‐blown rigid polyurethane foam (PUF) with two different particle sizes (180 and 300 μm) of expandable graphite (EG) as a flame‐retardant additive were prepared, and the effects on the mechanical, morphological, water absorption, thermal conductivity, thermal, and flame‐retardant properties were studied. In this investigation, EG content was varied from 5 to 50 php by weight. The mechanical properties of PUF decreased with increasing EG loading in both cases. The water absorption of the PUF increased with an increase in the EG loading mainly because of the collapse of foam cells, as evidenced from the scanning electron microscopy pictures. The thermal conductivity of the EG‐filled PUF showed that the insulation properties decreased with EG loading. The flame‐retardant properties (limiting oxygen index and char yield measurement) of the PUF improved with increasing EG loading. PUF filled with the higher particle size EG showed better mechanical properties and fire‐retardant properties than the PUF filled with the lower particle size EG. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

反应型磷氮阻燃剂/可膨胀石墨复配阻燃聚氨酯泡沫

将反应型阻燃剂六(4-磷酸二乙酯羟甲基苯氧基)环三磷腈(HPHPCP)和可膨胀石墨(EG)复配,制备了阻燃聚氨酯泡沫,详细研究了复配阻燃剂对聚氨酯泡沫的物理力学性能、热稳定性以及阻燃性能的影响。结果表明,阻燃聚氨酯泡沫的密度和热导率随着复配阻燃剂中EG含量的增加而升高;压缩强度随着EG含量的增加呈现先增加后降低的趋势。热失重表明复配阻燃剂大大提高了聚氨酯泡沫的热稳定性。聚氨酯泡沫的初始分解温度(T_10%)从212.9℃,分别提高到222.0、231.2和243.2℃;700℃残炭量从7.6%分别提高到26.3%、31.6%和37.9%。聚氨酯泡沫的阻燃性能随着复配阻燃剂中EG含量的增加而提高。阻燃聚氨酯泡沫的极限氧指数从19%提高到29%,均能通过UL-94水平燃烧HF-1等级和垂直燃烧V-0等级。     

Development of mesophase pitch derived high thermal conductivity graphite foam using a template method

A simple and inexpensive method is described for preparing high thermal conductivity graphite foam by impregnating a coal tar pitch based mesophase pitch into a substrate polyurethane foam template. Mesophase pitch impregnated polyurethane foam was converted into graphite foam by several heat treatments in air as well as in an inert atmosphere. Scanning electron microscope images show the retention of an excellent open pore structure despite volume shrinkage of over 50%. The graphite foam prepared by this sacrificial template method is found to possess a thermal conductivity of 60 W/m K with a compressive strength in the range of 3.0–5.0 MPa. The X-ray diffraction pattern shows an interlayer spacing (d₀₀₂) of 0.3388 nm at a heat treatment temperature of 2400 °C. Different concentrations of slurries of mesophase pitch in water were used in combination with substrate foams of different densities to prepare graphite foams of density in the range 0.23–0.58 g cm⁻³. The specific thermal conductivity of the carbon foam with a low density of 0.58 g cm⁻³ is found to be higher than that of copper metal traditionally used in thermal management applications.     

Dependence of flame‐retardant properties on density of expandable graphite filled rigid polyurethane foam

Different density rigid polyurethane foams (RPUF) filled with various expandable graphite loadings were fabricated by cast molding. The flame retardant properties of these composites were assessed by limiting oxygen index and horizontal and vertical burning tests. The results showed that the flame retardant efficiency got better with increase in the foam density at the fixed EG weight percent or with increase in the EG weight percent at the fixed foam density. After burning, the low density (0.065 g/cm³) pure burned RPUF produced the highly collapsed and carbonized material, while the high density (0.510 g/cm³) pure RPUF had little change in size and had reduced destruction of the material. Moreover, the scanning electronic microscope (SEM) observation showed that the higher density EG/RPUF composites had a more compact outer layer (burned layer) after burned, in which more wormlike materials composed of expanded graphite particles appeared. In addition, higher foam density led to less plastic deformation in the interface layer between the burned and the inside layers. These results indicated that a weight percent of a flame retardant additive that achieves satisfactory flame retardancy for a certain density foam cannot effectively be applied for another density foam. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synergistic effect of expandable graphite and aluminum hypophosphite on flame‐retardant properties of rigid polyurethane foam

A series of flame retarding rigid polyurethane foam (RPUF) composites based on expandable graphite (EG) and aluminum hypophosphite (AHP) were prepared by the one‐pot method. The properties were characterized by limiting oxygen index (LOI) test, cone calorimeter test, thermogravimetric analysis (TGA), real‐time Fourier transform‐infrared spectra (RT‐FT‐IR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), etc. The results indicate that both EG and AHP could enhance the flame retardency of RPUF composites. Besides, the flame retardant effect of EG was better than that of AHP. The results also show that partial substitution of EG with AHP could improve the flame retardency of RPUF, and EG and AHP presented an excellent synergistic effect on flame retardancy. What is more, compared with RPUF/20EG and RPUF/20AHP, the heat release rate (HRR) and total heat release (THR) of RPUF/15EG/5AHP were lower.TGA results indicate that partial substitution of EG with AHP could improve the char residue which provided better flame retardancy for RPUF composites. The thermal degradation process of RPUF composites and the chemical component of the char residue were investigated by RT‐FT‐IR and XPS. And the results prove that RPUF/15EG/5AHP had higher heat resistance in the later stage. Compared with the RPUF composites filled with EG, a better cell structure and mechanical properties were observed with the substitution of AHP for part of EG. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42842.     

超细鳞片石墨制备可膨胀石墨工艺及影响因素

以325目超细鳞片石墨为原材料,K2Cr2O7为氧化剂,浓H2SO4为插层剂,用化学氧化法制备可膨胀石墨(EG),通过正交试验法筛选出最优配方及工艺条件,即m(石墨)誜V(98%H2SO4)誜m(K2Cr2O7)=1誜3誜0.3,反应温度30℃,反应时间15 min,膨胀容积45 mL/g。制取最大膨胀容积EG的最优工艺条件和石墨粒径有关,用小粒径石墨制备EG比用大粒径石墨制备EG需要的氧化剂的量多,完成插层反应所需的时间短。     

Isotropic carbon and graphite fibers from chemically modified coal-tar pitch

A precursor for a general purpose carbon fiber was prepared from coal tar pitch (CP) modified with 10 % p-benzoquinone (BQ) at 380 ?C for 3 hours. Such a modification raised the softening of the pitch from 85 ?C to 271 ?C at a yield of 43 %. The modified pitch was spun smoothly at a rate of 480 m/min into a fiber of 20 Μm diameter. The fiber was stepwise stabilized at 236 ?C (5 ?C/min) and 312 ?C (1 ?C/min) for 3 hours at each temperature. Successively,carbonization and graphitization were performed at 1,000 ?C and 2,400 ?C, respectively, for one hour. Both the carbonized and graphitized fibers exhibited tensile strength of 570 MPa. The structural parameters of carbon and graphite fibers were their orientation values of 56.2 and 58.1 %, relatively low Lc(002) of 11.24 and 25 å, and large interlayer spacing (d₀₀₂) of 3.86 and 3.49 å, respectively.     

采用改质沥青与中温沥青生产石墨电极对比

随着我国电炉炼钢的发展,对石墨电极的质量提出了更高的要求。煤沥青作为生产石墨电极的黏结剂,很大程度上影响着石墨电极的质量。目前国内石墨电极生产厂家一部分采用中温沥青,一部分采用改质沥青,逐步摆脱了传统的黏结剂与浸渍剂     

A graphite foam reinforced by graphite particles

Graphite foam was obtained after carbonization and graphitization of a pitch foam formed by the pyrolysis of coal tar based mesophase pitch mixed with graphite particles in a high pressure and temperature chamber. The graphite foam possessed high mechanical strength and exceptional thermal conductivity after adding the graphite particles. Experimental results showed that the thermal conductivity of modified graphite foam reached 110 W/m K, and its compressive strength increased from 3.7 MPa to 12.5 MPa with the addition of 5 wt% graphite particles. Through the microscopic observation, it was also found that fewer micro-cracks were formed in the cell wall of the modified foam as compared with pure graphite foam. The graphitization degree of modified foam reached 84.9% and the ligament of graphite foam exhibited high alignment after carbonization at 1200 °C for 3 h and graphitization at 3000 °C for 10 min.     

Effects of pitch fluoride on the thermal conductivity of carbon foam derived from mesophase pitch

Carbon foams with high thermal conductivity were obtained from mixtures of mesophase pitch and pitch fluoride. The addition of pitch fluoride in mesophase pitch could significantly increase the specific thermal conductivity of as-prepared carbon foams. After graphitization at 2873 K, the specific thermal conductivity of carbon foams increased from 82 up to 155.4 (W/mK)/(g/cm³) when the content of pitch fluoride was 3% in the raw material.     

Microwave processing of syntactic foam from an expandable thermoset/thermoplastic mixture

In this work, a microwave expansion process to produce thermoset‐matrix syntactic foam containing thermoplastic foam beads was designed and developed. Expandable polystyrene (EPS) microspheres and epoxy resin were chosen as a model material system. This process is featured with a capability to effectively expand EPS microspheres in syntactic foam with high EPS loading. The resin viscosity and specific microwave energy are found to be the two primary control parameters determining the process window. Mechanical characterization showed that the specific flexural strength and modulus of the syntactic foam are similar to those of the neat epoxy. By comparison, the flexural moduli over density squared or cubed of the foam are much higher, especially at high EPS loadings, than those of the neat resin. The foamed EPS microspheres can also effectively toughen the syntactic foam, preventing propagation of cracks. Furthermore, the microwave expansion process was found to be capable of molding syntactic foam parts of relatively sophisticated geometry with smooth surfaces. POLYM. ENG. SCI., 55:1818–1828, 2015. © 2014 Society of Plastics Engineers     

Irradiation effects on graphite foam

The solid state reactor is an advanced reactor concept that takes advantage of newly developed materials with enhanced heat transfer characteristics to provide an inherently safe, self-regulated heat source. High conductivity graphite foam, developed and produced at Oak Ridge National Laboratory, is being evaluated as a candidate material for the core of basic heat source modules.Irradiation studies at the Oak Ridge National Laboratory High Flux Isotope Reactor were conducted to obtain preliminary data on the effects of neutron damage on the thermal properties and volume change behavior of the graphite foam as a function of neutron dose up to 2.6 displacements per atom at an irradiation temperature of ∼740 °C. Samples were characterized for dimensional and structural changes, and thermal transport as a function of dose. Following the initial effects of the irradiation, the samples were annealed at 1000 and 1200 °C and the thermal diffusivity measured as a function of temperature. A simple microstructural model was developed for graphite foam and, by coupling this model to the known single crystal and polycrystalline irradiation behavior of graphite; a mechanism by which the irradiation-induced volume and dimensional changes in graphite foam may be explained is postulated.     

不同氧化剂制备可膨胀石墨的研究

通过混酸法制备了两种不同氧化剂体系的可膨胀石墨(EG),并采用膨胀容积和X射线(XRD)对EG进行了表征。实验结果表明:K2Cr2O7为氧化剂制备的可膨胀石墨,氧化充分,插层效果好,膨胀容积(EC)大,K2Cr2O7同石墨的最佳比例是0.8∶10。     

Graphite produced by extrusion of pitch mesophase

It is shown that an ideal pitch mesophase can be extruded to form a rod in which the flow anisotropy induced by shear and stretch is preserved. This rod can be coked and graphitized to form a new graphite with prescribed dimensions and structure imposed during extrusion. Optical microscopy, X-ray diffraction and dilatometric analysis served to determine the structural anisotropy of the new coke and the changes taking place during heat treatment. The graphitized product exhibits a highly anisotropic structure and low volume coefficient of thermal expansion similar to premium grade needle coke produced by the delayed coking process.