通过与热塑性树脂共热处理来改造性炭的孔结构研究

三种具有不同比表面积的活性炭-椰壳基AC-C、粒状AC-P和竹基AC-B分别与四种热塑性前驱体(改性剂)-聚乙烯醇(PVA),羟基丙基纤维素(HPC),柠檬酸(CiA),含氟聚酰亚氨(FPI)混合后,在900℃热处理1h.通过氮气吸附法和扫描电镜对改性后活性炭的孔结构进行了表征.实验发现,热塑性树脂对活性炭AC-B的孔结构改性最显著;而另外三种改性剂PVA,HPC和CiA的改性结果使得AC-B的表面积降低,这是由于对其微孔结构改性效果不同所引起的:PVA可消除所有微孔,HPC可以有效消除极微孔,而CiA仅减少极微孔体积,但增加了超微孔体积.一方面,30%CiA的添加量,导致AC-B的外表面积增加了170%;另一方面,改性剂FPI通过增加极微孔,使其表面积增加达2倍之多.通过选择改性剂,能够改变活性炭基体中的微孔孔径分布,实际上是通过增加或减少其中的极微孔来实现.     

通过与热塑性树脂共热处理来改造活性炭的孔结构研究

三种具有不同比表面积的活性炭—椰壳基AC—C、粒状AC—P和竹基AC—B分别与四种热塑性前驱体（改性剂）—聚乙烯醇（PVA），羟基丙基纤维素（HPC），柠檬酸（CiA），含氟聚酰亚氨（FPI）混合后，在900℃热处理1h。通过氮气吸附法和扫描电镜对改性后活性炭的孔结构进行了表征。实验发现，热塑性树脂对活性炭AC—B的孔结构改性最显著；而另外三种改性剂PVA，HPC和CiA的改性结果使得AC—B的表面积降低，这是由于对其微孔结构改性效果不同所引起的：PVA可消除所有微孔，HPC可以有效消除极微孔，而CiA仅减少极微孔体积，但增加了超微孔体积。一方面，30％CiA的添加量，导致AC-B的外表面积增加了170％；另一方面，改性剂FPI通过增加极微孔，使其表面积增加达2倍之多。通过选择改性剂，能够改变活性炭基体中的微孔孔径分布，实际上是通过增加或减少其中的极微孔来实现。     

结构有序、双重孔隙中孔炭材料的合成与表征

采用纳米涂层技术,以介孔分子筛SBA 15为模板,在其纳米孔道内引入糠醇/草酸溶液,经原位聚合,炭化后制得炭/SBA 15复合物。采用化学法脱除模板后制得具有规则结构的中孔炭。高分辨TEM表征结果显示该中孔炭是由纳米炭管相互联接、堆积而成,且具有六方对称结构。氮吸附结果显示其比表面积高达2000m2/g,孔径呈双峰分布。孔径相对较大的孔隙来源于SBA 15孔道经纳米涂层后所保留的孔隙;孔径相对较小的孔隙来源于SiO2移除后遗留的纳米孔空间。该方法可应用于以其他多孔氧化硅为模板制备新型纳米复合物的研究过程。     

Correlation between the capacitor performance and pore structure of ordered mesoporous carbons

Mesoporous carbons were synthesized by organic–organic self-assembly of triblock copolymer F127 and phenolic resin oligomers composed of resorcinol–formaldehyde or resorcinol–furfural. The mesostructure control was performed by using different polymerization catalysts, ammonia and acetic acid. The effects of the aldehyde and polymerization catalyst on pore architecture of mesoporous carbons were investigated. Disordered mesostructure with poorly disconnected mesopores was formed using furfural. In contrast, when formaldehyde was used, ordered structure with mesochannels was formed. In addition, changes in mesochannel length and the degree of long-range order are found to depend on polymerization catalyst. The porous carbons with different structure were used as a model material to investigate the ion storage/transfer behavior in electrical double-layer capacitor. Electrochemical cyclic voltammetry measurements were conducted in 1 M sulfuric acid electrolyte solution. The ordered mesoporous carbons show superior capacitances and rate performance over the disordered carbons. Electrochemical impedance spectroscopy was used to assess the transport properties. The impedance data clearly demonstrated that the degree of long-range order and channel length can influence the ion transport, resulting in superior capacitive performances.     

印刻法制备中间相沥青基中孔炭

用中间相沥青作碳源,硅胶水溶液作造孔剂,采用胶体印刻法制得一系列中孔碳。实验发现当适量纳米级硅源添加到中间相沥青中,会在彼此颗粒间形成一定的纳米孔道,从而导致中间相沥青在炭化过程中没有沥青由固相向液相转化的过程。结果表明：碳硅比、印刻温度以及中间相沥青的基本物化性质都将对中孔碳的孔结构发生重要影响。且制得比表面积和孔容分别为482m2/g和1.62cm3/g的中孔碳。     

以纳米SO_2粒子为模板由不同炭前躯体制备中孔炭(英文)

以纳米SO2粒子为模板,酚醛树脂、中间相沥青和聚丙烯腈为炭前躯体制备中孔炭。利用氮气吸附、元素分析和X-射线光电子能谱等分析了不同种类炭前躯体对中孔炭的影响。结果表明:在炭化温度和纳米粒子添加量相同的情况下,不同炭前躯体所制中孔炭的孔结构和表面化学性质不同。中间相沥青基中孔炭中微孔和中孔含量最少,酚醛基中孔炭中含有丰富的微孔和中孔,聚丙烯腈基中孔炭中含有大量的含氮官能团。     

不同结构中孔炭材料的制备和热稳定性研究

利用溶剂挥发自组装的方法制备了2种不同孔结构中孔炭材料。低温N2吸脱附、SAXS、HRSEM和TEM测试表明,所制备的材料分别具有柱状结构和墨水瓶状的中孔结构。考察了不同炭化温度对2种结构中孔炭的影响,结果表明柱状结构的中孔炭材料具有较好的热稳定性。     

以不同聚合物和有机前驱体模板法制备纳米孔炭及其热性能(英文)

以糠醇(FA)、4,4-双马来酰亚胺二苯基甲醇(BM)、BM与二乙烯基苯共聚物(BM-DVB)和蔗糖(S)为炭前驱体,硅胶为硬模板制备了六种纳米孔炭。在氦气气氛中800℃～1 000℃炭化30 min,炭化后利用质量分数40%HF脱除模板。利用元素分析、氮气吸附、热分析和漫反射红外表征产物的孔结构和化学结构及它们对多孔炭热性能的影响。结果表明,前驱体对多孔炭的性能有一定的影响。前驱体的化学结构和热处理条件对炭的孔隙结构,亲水性和热稳定性都有影响。最稳定的产物中含有氮和磷元素。     

Effect of particle size and adsorption equilibrium time on pore structure characterization in low pressure N2 adsorption of coal: An experimental study

This study examined the influence of particle sizes and adsorption equilibrium time (AET) on pore structure characterization using low pressure N₂ adsorption (LPGA-N₂) method. The results demonstrate that pore structures change with progressive crushing. The increase in pore volume in the minipore and mesopore with decreasing coal particle sizes was caused by creating additional large pores during the crushing. The tendency of decreasing at first and then increasing was observed for both the specific surface area (SSA) and micropore volume, demonstrating that the micropore structure was primarily damaged and then followed by additional micropores being created when the sample was broken down smaller than 80 mesh. It is difficult to choose a suitable coal particle size for LPGA-N₂ measurement to yield pore structure parameters closest to the “real” values due to the difficulty in evaluating the compound effect of crushing on pore structures. To make testing results closer to the coal structure under in situ conditions, we propose 1∼3 mm as the preferred coal particle size. Additionally, many replicate experiments were performed by adjusting the AET to ensure LPGA-N₂ isotherms in equilibrium states. The results indicate that a decrease in particle size did not reduce the time for reaching N₂ adsorption equilibrium. Comparison of pore size distributions under different AETs shows that the AETs' increase has a little influence on the measurement of minipore and mesopore but has a positive correlation with micropore, revealing that N₂ adsorption equilibrium is mainly influenced by the micropore whose volume is underestimated at small AETs. The optimal AET for LPGA-N₂ measurement was 8 min and its yielded data can more accurately characterize the pore structure parameters.     

孔结构对煤基活性炭电极材料电化学性能的影响(英文)

以太西无烟煤为前驱体,NaOH为活化剂制备电化学电容器电极材料。采用N2吸附法及电化学测试对活性炭的孔结构和电化学性能进行了表征。在1mol/L(C2H5)4NBF4/碳酸丙烯酯有机电解液体系中,研究了孔结构对活性炭电极材料的电化学性能的影响。结果表明:以NaOH为活化剂可制备出比表面积943mol/L～2479mol/L、比电容57F/g～167F/g的活性炭电极材料。活性炭电极材料的比电容不仅取决比表面积,而且与活性炭的孔径分布有关。孔径为2nm～3nm的中孔的存在可以有效降低电解液的扩散阻力,提高电极材料比表面积的利用率,从而使电容器的电化学性能得到增强。     

Influence of superplasticizer and curing on porosity and pore structure of cement paste

Most concrete produced today contains admixtures. Superplasticizers (SP) are used for the purpose of improving workability and reducing the water to cement ratio; therefore producing more durable concrete. SP cause better dispersion even at high water to cement ratio. Although SP improves the dispersion of particles, it is not quite clear how the addition of SP affect the porosity and pore size distribution of cement paste. The purpose of this study was to examine the influence of one type of SP on porosity and pore size distribution under different curing regimes. Paste specimens with and without SP were prepared at constant water to cement ratio of 0.45. Specimens were cured for 28 days and some for six months. Specimens were exposed to high temperature (45°C) and normal temperature curing (20°C) and also subjected to different relative humidities (100%, 55% and 25%). Curing at high temperature was carried out to simulate temperature in hot climates. Tests on porosity and pore size distribution were conducted using mercury intrusion porosimetry. The results show that the inclusion of SP decreases the total intruded pore volume of paste. The dominant pore diameter, however, does not seem to be affected and the percentage of pores smaller than 100 nm increases in the presence of SP.     

浸渍处理对管式炭膜孔结构的影响(英文)

为有效调整和控制管式炭膜(TCM)内表面的孔结构,采用浸渍法对管式炭膜进行处理,并通过调整浸渍液浓度和改变浸渍处理的次数分析浸渍对膜内孔径分布的影响。扫描电子显微镜(SEM)观察得知:浸渍处理能够有效修复管式炭膜表面上的孔缺陷。同时,浸渍前后样品的孔径分布数据揭示出管式炭膜的微孔尺寸随着浸渍液浓度和浸渍次数的增加而变小,且孔分布也随之变窄。说明通过调整浸渍条件可以实现管式炭膜孔径和孔结构的有效控制。     

粉末粒度对FeAl金属间化合物多孔材料孔结构的影响

研究了粉末粒度对FeAl金属间化合物多孔材料孔结构的影响.研究表明,当粉末粒径在60μm以上时,随着粉末粒径的增加,FeAl金属间化合物多孔材料的总孔隙度和开孔隙度变化不大,即粉末粒度不是决定FeAl多孔材料孔隙度的主要因素;粉末粒度是决定FeAl金属间化合物多孔材料最大孔径的主要因素,在18～125μm的粒度范围内,多孔体最大孔径与粉末粒径之间严格遵循dm=0.4·d.的直线变化规律.     

Fabrication of Ni nanoparticles on ordered mesoporous carbon using an immersion-electrodeposition method

Ni nanoparticles have been fabricated on the surface of CMK-3 mesoporous carbon through an immersion-electrodeposition (IE) technique. Transmission electron microscopy analysis indicated that it was a facile approach to electrochemically prepare nano-sized Ni clusters. The electrocatalytic properties of Ni/CMK-3 nanocomposites electrode for hydrogen evolution reaction have been investigated by liner scanning voltammetry in alkaline solution, and high electrocatalytic activity was observed. Therefore, for the first time, we report this IE method as a new route to prepare metal/CMK-3 nanocomposites which have potential applications in the catalytic field.     

The effect of carbon precursor on the pore size distribution of mesoporous carbon during templating synthesis process

The starch and cyclodextrin were selected as the precursors and the mixture of surfactant and tetraethyl orthosilicate (TEOS) as template to prepare mesoporous carbon. The result showed that a bimodal pore size distribution in mesoporous carbon derived from starch appeared; one was around 3.4 nm and the other ranged from 3.8 to 16.2 nm. However, there existed a concentrated pore size distribution from 3.2 to 4.2 nm in mesoporous carbon derived from cyclodextrin. The different molecular structure of starch and cyclodextrin and their polymerization process in the presence of sulfur acid were responsible for the resulted mesoporous carbon structure; the starch could polymerize by head to head or side by side, but the cycleodextrin was only polymerized by head to head.     

前驱体对炭泡沫孔结构的影响

分别以煤沥青、石油中间相沥青和AR沥青为前驱体制备炭泡沫材料。采用GPC测定前驱体分子量,SEM观察所制炭泡沫的孔结构,光学显微镜测量所制炭泡沫的孔径及其分布。结果发现,由于煤焦油沥青不含中间相,且QI含量较高,导致在实验条件下不能直接制备出合格的炭泡沫。以石油中间相沥青和AR沥青为原料均能制备出具有分布均匀开孔结构,且微观各向异性的炭泡沫。由AR沥青制备的炭泡沫呈现平均孔径较小(212μm)、孔壁较薄、孔径分布较窄(180μm~300μm)、开孔率较高、以及韧带排列较规整等特点,表明低QI含量、低分子量且分布较窄的前驱体有利于发泡。     

Improving strength, drying shrinkage, and pore structure of concrete using metakaolin

This paper presents the results of an investigation on the use of metakaolin (MK) as a supplementary cementing material to improve the performance of concrete. Two MK replacement levels were employed in the study: 10% and 20% by weight of the Portland cement used. Plain and PC-MK concretes were designed at two water–cementitious materials (w/cm) ratios of 0.35 and 0.55. The performance characteristics of the concretes were evaluated by measuring compressive and splitting tensile strengths, water absorption, drying shrinkage, and weight loss due to the corresponding drying. The porosity and pore size distribution of the concretes were also examined by using mercury intrusion porosimetry (MIP). Tests were conducted at different ages up to 120 days. The results revealed that the inclusion of MK remarkably reduced the drying shrinkage strain, but increased the strengths of the concretes in varying magnitudes, depending mainly on the replacement level of MK, w/cm ratio, and age of testing. It was also found that the ultrafine MK enhanced substantially the pore structure of the concretes and reduced the content of the harmful large pores, hence made concrete more impervious, especially at a replacement level of 20%.     

Surface area, pore size distribution and microstructure of vacuum getter

An effective getter is necessary in vacuum technology. In order to obtain the adsorption mechanism of the getter, its microstructure information must be studied. Surface area, pore size distribution and microstructure of vacuum getter were studied with XRD, SEM and N₂ adsorption technique.Vacuum getter is composed of the different proportions of PdO and Ag₂O. The crystalline size of 3^# vacuum getter that includes W₂AgO = 22% and W_PdO = 78% is the maximum among all the vacuum getters. SEM images showed that vacuum getters expose a large number of nanometer-size pores. The adsorption isotherms of the vacuum getters are typical of type Ⅳ, characteristic of mesoporous material, and a type H₂ hysteresis loop is observed. Langmuir model describes N₂ adsorption at low pressure region. At the medium pressure, N₂ adsorption can be modeled by BET model. The pore size distributions of the vacuum getters are calculated by applying BJH method to the adsorption branch of N₂ isotherms at 77 K. With percentage of Ag₂O elevation, Langmuir surface area, BET specific surface area, the adsorption capacity and the pore volume become larger. But the average pore diameter becomes smaller. However, above Ag₂O content of 22%, an inverse behavior is observed. 3^# vacuum getter has the highest surface area and pore volume among all the vacuum getters. The experimental results and related analysis can be adopted in the later design of the vacuum tank.     

加热条件对炭泡沫材料孔结构和性能的影响

以AR沥青为原料,利用高压釜在不同恒温条件下制备了炭泡沫,并测定了其孔结构、体积密度、显气孔率、压缩强度、常温热导率以及微晶参数.结果表明:相对于短恒温时间,长恒温时间制得的炭泡沫孔径大(412nm)、显气孔率高(83.82%)、体积密度小(0.34g/cm~3)、压缩强度高(4.92MPa),多孔连通结构更丰富.经过石墨化处理后,石墨泡沫呈现出较高的常温热导率(71.34W/(m·K))和较小的层片间距d_(002)(0.33556nm).石墨泡沫的常温比导热率能达到210(W·(m·K)~(-1)) /(g·cm~(-3)),是铜的5倍,铝的4倍.