Synthesis of iron-dispersed carbons by pressure pyrolysis of divinylbenzene-vinylferrocene copolymer

Versatile carbons with finely dispersed iron were synthesized by pressure pyrolysis of a copolymer prepared from divinylbenzene and vinylferrocene at temperatures below 680? C and pressures of 125 MPa. The pyrolysis conditions of the copolymer were found to influence the final morphology of carbons to give fibrils, spheres and polyhedra. The resulting carbons contained uniformly fine particles of cementite (Fe₃C) which were less than 30 nm in size, whereas the magnetite was dispersed in the carbon matrix by pressure pyrolysis in the presence of water. Highly dispersed cementite in carbon was found to decompose into metallic iron by further heat treatment above 850? C. Porous spherulitic carbons were also synthesized by heat treatment of magnetite containing carbon spherulites.     

Synthesis and properties of platinum-dispersed carbon by pressure pyrolysis of organoplatinum copolymer

Platinum-dispersed carbon was synthesized by pressure pyrolysis of divinylbenzenebis (2-allylphenyl)platinum (APPt) and phenylacetylene-APPt at 550 °C and 125 MPa. The crystallinity of platinum dispersed in the carbon matrix synthesized from phenylacetylene(PA)-APPt was higher than that from divinylbenzene(DVB)-APPt. Platinum particles less than 60 nm were dispersed in the carbon matrix synthesized from DVB-APPt at 550 °C and 125 MPa. The carbon matrix formed from PA-APPt contained platinum particles of about 120 nm. The specific area of platinum-dispersed carbon synthesized at 550 °C and 125 MPa increased on subsequent heat treatments in argon, and reached 90 m² g^–1 after heat treatment at 800 °C for 1 h. The activity of platinum-dispersed carbon for the hydrogenation of cyclohexene increased with increasing specific area. Platinum-dispersed carbon formed from DVBAPPt was more active for hydrogenation reaction than that from PA-APPt. The highly active platinum-dispersed carbon could be synthesized from DVB-APPt at 520 °C. The surface area reached 154 m² g^–1 after heat treatment at 800 °C.     

Synthesis of boron-dispersed carbon by pressure pyrolysis of organoborane copolymer

Boron-dispersed carbon was synthesized by pressure pyrolysis of divinylbenzene-tris(allyl)-borane and styrene-tris(allyl)borane at 125 MPa below 650° C. Amorphous boron dispersed in a carbon matrix was oxidized easily to yield boric acid by heat treatment under air at 300° C. The BK image of the product showed that boron was dispersed uniformly in a carbon matrix. Boron-dispersed carbon had the morphology of coalescing spherulite and polyhedra depending upon the concentration of boron in the parent copolymer. The grain size of carbon polyhedra decreased from 2.0m to 0.2m with an increase in the boron concentration from 1.3 to 5.7 wt%. The presence of 0.5 wt% boron in a carbon matrix enhanced the graphitization at 4.0 GPa and 1200° C, decreasing the lattice spacing with an increase in the crystallite size. The crystallite sizes were comparable to each other after heat treatment at 1100° C and 4.0 GPa when the specimen contained boron from 0.5 to 2.5 wt%. The lattice constant (c ₀) and crystallite size (L _c) of boron-dispersed carbon containing 2.5 wt% boron were 677.0 pm and 30 nm, respectively, after heat treatment at 1200° C and 4.0 GPa.     

Synthesis and properties of carbons dispersed with α-iron particles from divinylbenzene-vinylferrocene

α-Iron-dispersed carbon was synthesized, through pressure pyrolysis of divinylbenzene-vinylferrocene above 750°C, and by reduction of magnetite-dispersed carbon. Divinylbenzenevinylferrocene copolymer was pyrolysed at 125 MPa above 750°C to yield carbons dispersed with α-iron accompanied by cementite. Magnetite in the carbon matrix was reduced to α-iron after heat treatments at 500°C in a flow of hydrogen. Carbons synthesized by the pressure pyrolysis of divinylbenzene-vinylferrocene at 800°C and 125 MPa contained iron-compound particles up to 200 nm, whereas the median diameter of α-iron particles in the carbon matrix after reduction treatments was 20 nm. α-Iron-dispersed carbon had a Curie temperature of 770°C. The saturation magnetization of iron-dispersed carbon increased with increasing the pyrolysis temperature of divinylbenzene-vinylferrocene copolymer, and reached a constant value of 183 e.m.u.g⁻¹ at 800°C. The saturation magnetization of α-iron-dispersed carbon after the reduction treatment revealed practically the theoretical value of α-iron. Carbons finely dispersed with only α-iron particles were synthesized successfully by reduction of magnetitedispersed carbons.     

Synthesis and properties of nickel-dispersed carbons by pressure pyrolysis of nickelocene-divinylbenzene

Nickel-dispersed carbon was synthesized by pressure pyrolysis of nickelocene-divinylbenzene at temperatures below 700° C at 125 MPa. The carbon so produced contained uniformly dispersed metallic nickel particles less than 40 nm in size with low crystallinity. The magnetization of nickelocene-divinylbenzene polymer increased abruptly at 280° C. The morphology of carbon changed from coalescing polyhedra to filaments via coalescing spherulites as the temperature increased from 550 to 700° C. Carbon tubes of 30 nm diameter were formed by pyrolysis of nickelocene-divinylbenzene at 650° C and 125 MPa. The Curie point of nickel-dispersed carbon was 360° C. The uniform dispersion of nickel with comparable crystallinity in the carbon matrix gave a linear relation between the saturation magnetization and the nickel concentration. The saturation magnetization of nickel-dispersed carbons synthesized at temperatures below 650° C and at 700° C were 60 and 85% of the theoretical value, respectively. The saturation magnetization of the nickel-dispersed carbon could be increased to reach 90% of the theoretical value with an increase in the crystallinity of dispersed nickel particles by subsequent heat treatment at 700° C for 7 h.     

Synthesis and properties of cobalt-dispersed carbons by pressure pyrolysis of organocobalt polymers

Cobalt-dispersed carbons were synthesized by pressure pyrolysis of cobaltocene-divinylbenzene and phenylallylcobaltocene-divi nylbenzene at 125 MPa below 700° C. The carbons resulting from cobaltocene-divinylbenzene contained uniformly dispersed fine particles, < 20 nm diameter, of metallic cobalt of lower crystallinity, which were composed of ferromagnetic and superparamagnetic particles. Metallic cobalt particles of cubic and hexagonal structures with higher crystallinity were formed during pyrolysis of phenylallylcobaltocene-divinyibenzene. Cobaltucence-divinylbenzene and phanylallylcobaltocene-divinylbenzene changed their magnetic properties from diamagnetism to paramagnetism at 250 and 200° C, respectively. The infrared absorption band of the cyclopentadienyl ring at 995 cm^–1 disappeared at 350° C in cobaltocene divinylbenzene and at 300° C in phenylallylcobaltocene-divinylbenzene. Superparamagnetic particles from cobaltocene-divinylbenzene aggregated and crystallized to produce larger particles of diameter 30 to 100 nm, which increased the magnetization during thermomagnetic measurement. The saturation magnetization of cobalt-dispersed carbons from phenylallylcobaltocene-divinylbenzene was higher by about 10% than that from cobaltocene-divinylbenzene. The coercive forces of cobalt-dispersed carbon from phenylallylcobaltocene-divinylbenzen and cqbaltocene-divinylbenzene were 350 and 250 Oe (2.79 × 10⁴ and 1.99 × 10⁴ Am^–1), respectively.     

Synthesis of nickel ferrite-dispersed carbon composites by pressure pyrolysis of organometallic polymer

Nickel ferrite-dispersed carbon could be synthesized by pressure pyrolysis of divinylbenzene (DVB)-vinylferrocene (VF)-nickelocene (Cp₂Ni) polymer in the presence of water under 125 MPa and at temperatures below 700°C. By heat treatment at 550°C with water, nickel ferrite particles could be dispersed finely in the carbon matrix, although a small amount of nickel-iron carbide also began to form above 600°C. The morphologies of the carbon particles formed were observed to be polyhedral, coalescing spherulitic and spherulitic. When 30 wt% H₂O, spherulitic carbons a few micrometres in diameter were prepared, in which nickel ferrite particles from 10–30 nm were dispersed in the carbon matrix. The saturation magnetization of carbon composites formed from DVB-3.0 mol% Cp₂Ni-6.0 mol% VF and 20 wt% H₂O at 550°C was about 30 e.m.u.g^–1 and increased with pyrolysis temperature. The coercive force of the carbon composite was 120 Oe and was affected by the amount of added water using pressure pyrolysis. Thermomagnetic measurement shows that the Curie temperature of nickel ferrite-dispersed carbon was about 580 °C.     

Synthesis and properties of carbons dispersed with Fe-Co alloy by pressure pyrolysis of organoiron-organocobalt copolymer

Carbons dispersed with Fe-Co alloy were synthesized by the pressure pyrolysis of vinylferro cene-phenylethynylcobaltocene-divinylbenzene copolymer at temperatures below 700° C and at 125 M Pa. As-prepared carbon synthesized at 550° C contained finely dispersed metallic particles of less than 10nm diameter with low crystallinity, which crystallized to form Fe-Co alloy particles with a higher crystallinity by subsequent heat treatment at 800° C. Larger particles of the alloy of more than 50nm diameter were dispersed in the carbon matrix synthesized at 700° C. Thermomagnetization measurement of the as-prepared carbon synthesized from divinylbenzene-2.1 mol% vinylferrocene-4.8mol% phenylethynylcobaltocene copolymer at 550° C and 125 M Pa confirmed that iron formed an alloy with cobalt in the carbon matrix. Fine, superparamagnetic metallic particles in the as-prepared carbon aggregated and crystallized by the heat treatment during the thermomagnetic measurement to increase the magnetization of the alloy-dispersed carbon. The saturation magnetization and the coercive force of alloy-dispersed carbon increased from 128 to 187e.m.u.g^–1 and from a few to 50 Oe, respectively, on increasing the pyrolysis temperature of the starting copolymer from 550 to 700° C. The saturation magnetization of alloy-dispersed carbon from divinylbenzene containing iron and cobalt with a ratio of 52 was higher than that from divinylbenzene including those with a ratio of 25. The carbon with finely dispersed Fe-Co alloy showed a high saturation magnetization of 213 e.m.u.g^–1 and a coercive force of 230 Oe, and the magnetization persisted above 800° C.     

Synthesis of cementite-dispersed carbons by pressure pyrolysis of organoiron copolymers

Cementite-dispersed carbons were synthesized by pressure pyrolysis of divinylbenzene-vinylferrocene and styrene-vinylferrocene copolymer at temperatures below 600° C and the pressure of 125 MPa. The pyrolysis process of both copolymers was analysed by infrared spectra and magnetization of the pyrolysed substances. The absorption band of iron-carbon bond of divinylbenzene-vinylferrocene copolymer decreased on increasing its pyrolysis temperature from 300 to 450° C and finally disappeared at 500° C. The carbonization of divinylbenzene-vinylferrocene proceeded more rapidly than styrene-vinylferrocene at temperatures between 450 and 500° C. Styrene-vinylferrocene was heat-treated at 250° C for 2 h under 100 MPa affording a paramagnetic product, whereas the paramagnetic character of divinylbenzene-vinylferrocene was revealed after heat-treatment at 380° C. The saturation magnetization of cementite-dispersed carbon synthesized from both kinds of copolymers was comparable when the pressure pyrolysis was carried out at temperatures between 520 to 600° C at 125 MPa. The saturation magnetization of cementite-dispersed carbon formed at 550° C under 125 MPa was correlated linearly with the iron content in carbon. Threedimensional cross-linked divinylbenzene-vinylferrocene copolymer gave the highly dispersed cementite particles less than 50 nm with the coercive force of 950 Oe. On the other hand, the larger particle size of cementite up to 120 nm and the lower coercive force about 400 Oe were obtained in carbon matrix prepared by the pressure pyrolysis of styrene-vinylferrocene copolymer.     

Formation of non-graphitizable isotropic spherulitic carbon from poly-divinylbenzene by pressure pyrolysis

Isotropic spherulites of carbon stable at 2000° C were synthesized by the pressure pyrolysis of divinylbenzene polymer sealed in a capsule. The morphology of the synthesized carbon was pressure and temperature dependent being influenced by the state of polymerization of the starting polymer. Using a polymer prepared at atmospheric pressure and 150° C without catalyst, isolated spherulitic carbon was formed at 700° C and pressures of 1000 to 1250 kg cm^–2. These spherulitic carbons were optically isotropic, hard and non-graphitizable after heat treatment at 2000° C. Such carbons originate in the co-existence of higher and lower molecular weight products of pressure pyrolysis and the survival cross-linkages in the original polymer.     

Synthesis of submicron carbon spheres by the ultrasonic spray pyrolysis method

Submicron carbon spherical particles were obtained by polycondensation of resorcinol and formaldehyde in a solution and subsequent ultrasonic spray pyrolysis of the prepared sol. Microscopic characterization indicates the regular spherical shape of the obtained particles and sphere diameters in 200-700 nm range. The carbon spheres are amorphous as confirmed by electron diffraction, EELS, XRD and HREM characterization. Activation procedure was performed with H₂O in a nitrogen flow for 15 and 30 min at 800 °C. The activation procedure preserved the initial spherical shapes of the particles while the particle porosity and specific surface area were increased. The amount of surface oxygen functionalities was also increased by activation procedure as indicated by FTIR analysis.     

Synthesis, characterization and properties of carbon nanotubes microspheres from pyrolysis of polypropylene and maleated polypropylene

Microspheres assembled from carbon nanotubes (MCNTs), with the diameters ranging from 5.5 to 7.5 μm, were synthesized by means of pyrolysis of polypropylene and maleated polypropylene in an autoclave. The characterization of structure and morphology was carried out by X-ray diffractometer (XRD), field-emission scanning electron microscopy (FESEM), (high resolution) transmission electron microscope [(HR)TEM)], selected-area electron diffraction (SAED) and Raman spectrum. As a typical morphology, the possible growth process of MCNTs was also investigated and discussed. The results of nitrogen adsorption-desorption indicate that the Brunauer-Emett-Teller (BET) surface area (140.6 m²/g) of the MCNTs obtained at 600 °C is about twice as that (74.5 m²/g) of carbon nanotubes obtained at 700 °C. The results of catalytic experiment show that MCNTs based catalyst has higher catalytic activity than the carbon nanotubes based catalyst for the preparation of methanol and dimethoxy-ethane by oxidation of dimethyl ether.     

用气相流动催化热解法合成单壁碳纳米管

以正硅酸乙酯(TEOS)为前驱体，二茂铁为催化剂前驱体，利用气相流动催化热解法在850～1160℃连续合成了单壁碳纳米管(SWNTs)．在此过程中，以由TEOS分解得到的二氧化硅颗粒和二茂铁分解得到的铁颗粒在气流中直接形成的复合粒于作为催化剂，二氧化硅作为铁颗粒的载体．电于显微镜和激光拉曼光谱的观测和分析表明，在所得到的产物中SWNTs的含量约为10％，其直径为1～2nm。     

The internal pressure,mechanical properties,and water absorption of carbon fibre composites with spiro-epoxy copolymer matrices

High-performance fibre composites embodying a new principle have been manufactured and tested. In these composites the polymer matrix exerts a controlled pressure on the fibres. Although some pressure between fibres and matrix is necessary to permit the transfer of loads, the pressure normally present (about 40–50 M Pa) is much in excess of what is needed for carbon fibre composites (roughly 10 M Pa). This leads to undesirably high internal stresses, and is a primary cause of the low Izod impact strength of these composites, as compared with glass fibre composites. A four-year investigation of carbon fibre reinforced epoxies has shown that spiro orthocarbonate monomers, copolymerized with the epoxy, can reduce shrinkage pressures by nearly 70%, and increase the impact strength by about the same amount. At the same time fatigue life is improved. No important change in other mechanical properties is observed, and the water resistance of the composite is increased slightly.     

常压干燥法制备的炭气凝胶的电化学性能研究

采用常压干燥法制备了炭气凝胶,对所制得的炭气凝胶进行了电化学性能的测试,并与日本进口的超级电容器用超级活性炭进行比较.实验结果表明,炭气凝胶具有优良的电容性能,电双层比电容量和高扫描速度下(100mV/s)的质量比电容量分别达到21μF/cm2和89F/g,高于日本进口超级电容器用超级活性炭.     

Structural state and mechanical properties of nanocrystalline carbon films obtained by methane pyrolysis in electric field

We describe a method of carbon film synthesis on single-crystalline silicon substrate, which is based on methane pyrolysis in electric field. The calculated values of pressures and temperatures developed during the bombardment of substrates by C^4? carbon ions in the course of pyrolysis amount to P ～ 1.3 GPa and T ～ 2300 K, respectively. These conditions lead to the formation of nucleation centers that are necessary for the growth of carbon film. Measurements show that the microhardness of obtained carbon films reaches 60–80% of the hardness of natural diamond. The structural state of the film material was studied by X-ray diffraction, electron microscopy, and atomic force microscopy. It is established that the synthesized films represent a composite material with a carbon matrix containing nanodimensional inclusions of another phase.     

Synthesis and properties of plasma-deposited carbon condensates

Structural data, thermal characteristics, and theoretically calculated binding energies are reported for a graphite condensate obtained by carbon deposition from plasma. It is demonstrated that this condensate can be effectively used in self-propagating high-temperature synthesis processes.     

不同压力下碳纳米管的电弧法合成及其表征

采用电弧放电法在氦气/乙炔混合气氛中,在不同压力下合成了碳纳米管.运用场发射扫描电镜、场发射透射电镜、X-射线衍射仪和拉曼光谱对碳纳米管的形貌进行了表征.采用可见发射光谱对碳纳米管的形成过程进行了原位诊断研究.场发射扫描电镜结果表明,在氦气/乙炔气氛中合成的碳纳米管的长度大于50微米,许多碳颗粒沉积在碳纳米管壁上.场发射透射电镜结果表明,在0.100MPa下合成的碳纳米管的壁厚明显大于0.035MPa下合成的碳纳米管的壁厚.可见发射光谱诊断结果表明,CH和C2物种可能作为碳纳米管形成的前驱体,其中,以H原子作为无定形炭的刻蚀物种.阳极消耗速率和产物在阴极的沉积速率随着反应器中压力的增加而增加.因此,可以通过加强阳极和乙炔的蒸发速率及CH和C2物种的沉积速率而增加碳纳米管的形成速率.     

Synthesis and characterization of carbon nanotubes via ultrasonic spray pyrolysis method on zeolite

Ultrasonic spray pyrolysis method for the synthesis of carbon nanotubes (CNTs) has been investigated with zeolite supporting material. Single wall carbon nanotubes (SWCNTs) were obtained at 850 °C in nitrogen environment. Such deposition system makes it possible to grow CNTs without reducing agent at atmospheric pressure in a simple setup. Iron and cobalt acetate were used as catalyst and ethanol as carbon source for the synthesis of CNTs. Results show that nature of zeolite and cobalt concentration play important roles for SWCNTs production. Interestingly, we notice that in catalyst particles of sharp shape, nucleation of a nanotubes cap occurs dominantly in the forward direction.