温度设置对热光法测定气溶胶中黑碳的影响

热光法中的无氧阶段最高温度(MT)和各温度阶梯的保持时间(HT)是测定大气气溶胶中黑碳的两个关键参数.该文采集了34个气溶胶样品(含20个大气样品和14个源排放样品),并设计了6个温度程序用以系统研究MT和HT对黑碳(BC)测定的影响.实验表明,提高MT的设置,会使BC测定值降低,最高温度为850℃时的BC值为550 ℃时的62%;而有机碳(OC)发生热解(碳化)与最高温度的关系没有固定的模式,这是由样品的化学成分不同造成的.增加保持时间,使BC的测定值下降约5%,使热解率下降10%.     

黑碳对大气环境的影响与控制

黑碳气溶胶是大气气溶胶的重要组成部分,主要是由富含碳的物质不完全燃烧产生的,比如化石原料和生物质原料燃烧等。黑碳气溶胶具有较为特殊的物理化学性质。黑碳气溶胶具有多孔性,粒径约在0．01-1μm。在化学成分上非常接近于石墨,在温度高于400％时才可以发生氧化。黑碳气溶胶对可见光和部分红外光谱有很强的吸收能力,它在大气中的各种化学和光化学反应、非均相反应以及气粒转化过程中起着重要作用。     

塔克拉玛干沙漠资源与环境

本文以综合科学考察为基础,论述了塔克拉玛干沙漠自然环境的基本特征和沙漠水、土、生物、气候、油气资源的真实状况,证明这个曾被人们认为是“死亡之海”的沙漠,是一个具有潜在开发能力的希望之地。     

基于单颗粒黑碳光度计(SP2)方法的青藏高原冰芯黑碳记录研究

青藏高原冰川蕴含了丰富的历史环境变化信息。通过青藏高原冰芯钻取及环境指标分析,可在季节至万年时间尺度上重建高分辨率环境变化历史。黑碳气溶胶来源于生物和化石燃料燃烧排放,对光具有强烈的吸收作用,是气候环境变化的敏感因子之一。准确测量冰芯中的黑碳粒子浓度,是恢复其排放历史、评估其气候环境效应的必要手段。单颗粒黑碳光度计(Single Particle Soot Photometer, SP2)是近些年发展起来的用于雪冰样品中黑碳测量的主要方法之一,能够获得准确的黑碳浓度信息。近10年来,实验室开展了大量的冰芯黑碳样品测量,从野外冰芯钻取、样品前处理、仪器原理及测试、黑碳数据处理等全过程对SP2在青藏高原冰芯黑碳研究中的应用与问题进行了全面系统的阐述。同时,将SP2与热光学(Thermal-optical method)等测试方法进行对比,强调了SP2对冰芯黑碳样品研究的可靠性,并对未来黑碳研究的进一步发展作出了展望。     

NO2在黑碳表面的非均相反应

HONO是大气中OH自由基的重要来源,NO2在黑碳表面可反应生成HONO,因此NO2在黑碳表面的非均相反应引起了人们的关注。目前不同研究小组测量的摄取系数可相差7个数量级,选择不同的摄取系数去评估非均相反应的重要性将得到完全不同的结果。本文在深入分析NO2在黑碳表面反应机理的基础上,从反应体系、黑碳表面性质、反应条件等角度对不同小组测量的摄取系数存在差异的原因进行了分析,为模式中摄取系数的选取提供了依据。     

环境及生物样品中黑碳的质谱分析技术研究进展

黑碳是由生物质及化石燃料燃烧产生的含碳颗粒,是除CO₂外对全球气候变暖贡献最大的辐射强迫因子。因此,黑碳对全球气候和环境系统具有重大影响。其次,黑碳超小(<100 nm)的粒径使其能够通过呼吸系统进入到人体内,其本身以及表面负载的有毒物质也会对人体健康产生严重危害。为了厘清黑碳对环境和人类健康的影响,研究人员已发展了多种针对黑碳颗粒的分析技术,其中质谱技术凭借出色的抗干扰能力和强大的定性定量分析性能成为研究黑碳环境效应和健康风险最有潜力的技术之一。该文综述了复杂介质中黑碳颗粒质谱分析技术的原理、技术特征和应用实例,并对未来黑碳的分析技术发展进行了展望。     

硫酸钙及硫酸铵气溶胶对二次有机气溶胶生成的影响

二次有机气溶胶(SOA)是大气光化学反应的产物, 也是城市和郊区大气中细粒子的主要成分. 本研究致力于考察高浓度无机气溶胶颗粒对SOA生成的影响. 实验系统采用2 m³的温控烟雾箱, 以干燥的CaSO₄和(NH₄)₂SO₄为无机种子气溶胶, 研究了间二甲苯/NO_x/空气体系光氧化生成SOA的过程. 实验结果显示间二甲苯和NO_x在紫外光照下会产生大量SOA, SOA产率可用单产物模型表征. CaSO₄气溶胶的存在对SOA产率曲线没有明显的影响, 而(NH₄)₂SO₄气溶胶的存在使气相半挥发性氧化产物的生成量增加36%, 显著地增加了SOA的产率. (NH₄)₂SO₄粒子在含水有机物作用下显现的弱酸性可能是导致这一影响的主要原因. 该实验结果有助于更详尽地阐明中国颗粒物污染严重城市SOA的生成机理, 从而为进一步修正空气质量模型提供依据.     

基于气溶胶质谱的二次有机气溶胶识别

二次有机气溶胶(SOA)是大气气溶胶十分重要的组成部分,也是目前人们认识最为薄弱的气溶胶组分.由于有机气溶胶化学组成的复杂性,对SOA进行有效的识别和估算一直是国际气溶胶研究领域的热点和难点问题.本研究尝试使用一种新方法来定量识别深圳冬季大气中的SOA:利用气溶胶质谱仪在线观测的高时间分辨率优势和质谱中的特征碎片离子,应用正定矩阵因子解析(PMF)模型对细粒子组分的主要来源进行解析,识别出其中的二次有机物.结果表明:深圳冬季大气细粒子中SOA浓度平均为9.41±6.33μg/m3,占总有机物质量的39.9±21.8%;相比于一次有机气溶胶(POA),SOA浓度水平变化较为平缓,体现了区域性二次污染物的特征.SOA/BC比值具有鲜明的日变化规律,且与Ox(O3+NO2)的日变化规律相似,说明SOA的生成过程显著地受控于大气光化学活性.深圳冬季大气SOA生成最活跃的时段约为9～15时,期间SOA/BC比值增长了122%.本文为研究我国大气二次有机气溶胶提供了一种新的技术方法和思路.     

气溶胶单粒子化学成分在线聚类分析

为了在线快速、自动处理气溶胶激光飞行时间质谱仪在运行过程中产生的海量数据并提取有价值的信息,将基于神经网络的自适应共振算法运用于气溶胶单粒子化学成分在线聚类分析.利用该算法对NaCl粒子、NaCl和CaCl2的气溶胶混合物、三聚氰胺气溶胶单粒子以及大气气溶胶单粒子进行在线分类,被成功分类的粒子数占命中粒子总数的100%,当警戒阈值为0.1,学习速率为0.05时,获得的每类聚类中心都能很好地代表该类物质的特征;深入研究了警戒阈值对NaCl粒子在线聚类数的影响.结果表明: 当警戒阈值增大到0.8时,在线聚类数增多,分类更加精细.本算法的质谱分析软件基本满足大气气溶胶单粒子在线聚类分析的要求.     

Characteristics and source of black carbon aerosol over Taklimakan Desert

Black carbon(BC) and PM10 in the center of the Taklimakan Desert were online monitored in the whole year of 2007.In addi-tion,TSP samples were also synchronously daily collected by medium-volume samplers with Whatman41 filters in the spring of 2007.BC in the dust aerosol was up to 1.14%of the total mass of PM10.A remarkable seasonal variation of BC in the aerosol was observed in the order of winter>spring>autumn>summer.The peak value of BC appeared at midnight while the lowest one in the evening each day,w...     

甲烷在石墨化热解碳黑和活性炭上的吸附

为研究影响碳基吸附剂吸附超临界温度气体的主要因素,选择石墨化热解碳黑BP280和Ajax活性炭,分析超临界温度高压甲烷在其上的吸附平衡。应用容积法,在压力0~20.5 MPa、温度253 K~313 K测定甲烷的吸附平衡数据,并由等量吸附线标绘和亨利定律常数确定等量吸附热。引入通用吸附等温方程,再由方程的Langmuir标绘确定最大吸附容量,进而通过方程的线性化计算吸附平衡态中甲烷分子的作用能。结果表明,甲烷在两种吸附剂上的最大吸附容量均随温度而变化,并都小于液态甲烷的密度;甲烷在碳黑和活性炭上的等量吸附热分别为11.9 kJ/mol~12.5 kJ/mol和17.5 kJ/mol~22.5 kJ/mol,体现了两种吸附剂不同的表面能量分布;甲烷分子间作用能随吸附量的变化特点反映了超临界温度甲烷以类似于压缩气体状态聚集的特点和吸附剂结构上的差异。碳基吸附剂的比表面积和微孔容积是影响其储存甲烷容量的重要因素。     

Fe/炭黑、Ni/炭黑催化剂对渣油加氢反应的影响

使用模型化合物在微型反应釜中研究了载体炭黑对渣油内部氢转移反应的影响。结果表明,炭黑可以明显地促进四氢萘到蒽的氢转移反应。使用等体积浸渍法制备了Fe/炭黑、Ni/炭黑催化剂并对Fe/炭黑催化剂进行了XRD、SEM表征,结果表明,金属硫化物附着在炭黑颗粒的表面,直径为1μm左右。在高压反应釜中研究了载体炭黑和以炭黑为载体的催化剂对克拉玛依常压渣油430℃加氢反应的影响,并于传统的水溶性分散型催化剂的抑焦性能进行了对比。 结果表明,Fe/炭黑、Ni/炭黑催化剂可以明显地抑制渣油加氢反应的生焦,水洗后的催化剂效果比未经水洗的催化剂抑制生焦的效果好;Ni/炭黑催化剂抑焦效果比Fe/炭黑催化剂好;Fe/炭黑催化剂比同等浓度的水溶性Fe催化剂抑焦效果好。对反应产物馏分的分析表明,Fe/炭黑催化剂可以有效地抑制渣油缩合生焦,同时在一定程度上抑制裂化反应。     

Complementary effects of multiwalled carbon nanotubes and conductive carbon black on polyamide 6

This article introduces a newly innovative idea for preparation of superconductive ternary polymeric composites of polyamide 6 (PA6), conductive carbon black (CCB), and multiwalled carbon nanotubes (MWCNTs) with different weight ratios by a melt‐mixing technique. The complementary effects of CCB and MWCNTs at different compositions on rheological, physical, morphological, thermal, and dynamic mechanical and electrical properties of the ternary composites have been examined systematically. We have used a novel formulation to produce high‐weight fraction ternary polymer composites that show extremely higher conductivity when compared with their corresponding binary polymer composites at the same carbon loading. For example, with an addition of 10 wt % MWCNTs into the CCB/PA6 composite preloaded with 10 wt % CCB, the electrical conductivity of these ternary composites was about 5 S/m, which was 10 times that of the CCB/PA6 binary composite (0.5 S/m) and 125 times that of the MWCNT/PA6 binary composite (0.04 S/m) at 20 wt % carbon loading. The incorporation of the MWCNTs effectively enhanced the thermal stability and crystallization of the PA6 matrix in the CCB/PA6 composites through heterogeneous nucleation. The MWCNTs appeared to significantly affect the mechanical and rheological properties of the PA6 in the CCB/PA6 composites, a way notably dependent on the MWCNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1203–1212, 2010     

炭黑/聚苯胺纳米复合粒子的制备与表征

用现场原位聚合法制备了炭黑/聚苯胺纳米复合粒子,讨论了聚合反应条件对产物电导率的影响,并表征了复合粒子的形态和耐热性能.结果表明,所得的炭黑/聚苯胺纳米复合粒子粒度约为50 nm并具有核-壳结构,其电导率达30 S.cm-1,热分解温度约为600℃.     

Effect of nanosized carbon black on thermal stability and flame retardancy of polypropylene/carbon nanotubes nanocomposites

Nanosized carbon black (CB) was introduced into polypropylene/carbon nanotubes (PP/CNTs) nanocomposites to investigate the effect of multi‐component nanofillers on the thermal stability and flammability properties of PP. The obtained ternary nanocomposites displayed dramatically improved thermal stability compared with neat PP and PP/CNTs nanocomposites. Moreover, the flame retardancy of resultant nanocomposites was greatly improved with a significant reduction in peak heat release rate and increase of limited oxygen index value, and it was strongly dependent on the content of CB. This enhanced effect was attributed mainly to the formation of good carbon protective layers by CB and CNTs during combustion. Rheological properties further confirmed that CB played an important role on promoting the formation of crosslink network on the base of PP/CNTs system, which were also responsible for the improved thermal stability and flame retardancy of PP. Copyright © 2013 John Wiley & Sons, Ltd.     

Retention of diphenyls,terphenyls, phenylalkanes and fluorene on graphitized thermal carbon black

Summary This paper defines values of retention volumes for zero surface coverage (Henry's constant) at different temperatures, retention indices and variations of the internal energy (differential heats of adsorption) of diphenyl and its alkyl derivatives, terphenyls, diphenylmethane, triphenylmethane, diphenylethanes and fluorene on graphitized thermal carbon black (GTCB). Adsorption on GTCB takes place in accordance with the geometry of these molecules, the strongest adsorption being observed for para-terphenyl with least inhibited internal rotation of the molecule, while the weakest adsorption occurs for 2,6,2,6-tetramethyldiphenyl with the most inhibited internal rotation of the molecules. The flat molecules of fluorene are adsorbed on GTCB more readily than the nonflat molecules of diphenylmethane.     

Surface modification and characterization of carbon black by sodium lignosulphonate

Carbon black (CB) was encapsulated by the sodium lignosulphonate via the strong π–π* interaction force of aromatic ring in the planetary ball milling instrument. The use of new surfactant and ball milling instrument met the requirements about the low‐cost standard and provided an important sense to industrialization in comparison with the old surfactant, the poly(sodium 4‐styrenesulfonate). The successful encapsulation was confirmed by Raman spectroscopy, X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermal gravimetric analysis. Encapsulation ratio of the modified CB increased to 15.9% when CB was prepared at longer milling time and with agate balls in different size. The morphology and dispersibility of samples studied by transmission electron microscope, sedimentation experiment and ultraviolet–visible spectroscopy showed that the modified CB dispersed stably in the deionized water. The average diameter and absolute value of zeta potential of the modified CB decreased and increased compared with those of CB, respectively, which confirmed further that sodium lignosulphonate encapsulated on the surface of CB make CB disperse better. In addition, the average diameter and zeta potential of the samples were affected by ball milling conditions. The modified CB prepared at longer milling time and with different sizes of agate balls had better dispersibility than the ones prepared at shorter milling time and with same size of agate balls. Copyright © 2016 John Wiley & Sons, Ltd.     

Grafting of maleic anhydride onto carbon black surface via ultrasonic irradiation

The grafting of maleic anhydride onto carbon black surface based on the Diels–Alder addition via ultrasonic irradiation was investigated. Fourier transform infrared spectroscopy (FT‐IR) and thermogravimetric analysis (TGA) were used to determine the chemical structure of the resulting products. The anhydride ring in the modified products can be opened into two carboxylic groups. Accordingly, the carboxylated carbon black was analyzed quantitatively through acid‐based titration to determine the concentration of anhydride ring on the modified carbon black's surface. The grafted molecules amount calculated from the concentration of the anhydride ring was consistent with the results of TGA data. Comparison of zeta potential measurement demonstrated that there were more negative charges attached to the surface of carbon black after ultrasonic modification. TEM observations showed that the conglomeration degree of modified carbon black decreased more than that of initial carbon black. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface modification and characterization of carbon black through oxidation

This study focuses on modifying the surface of carbon black (CB) with hydrogen peroxide to raise light absorbance of dispersed CB in water without capping agent. Four kinds of commercial CB, trademarked as M900, M1000, M1100, and Mogul L, respectively, were used as study materials. The ultrasonic bath was utilized to disperse the treated CB in de-ionic (DI) water in the absence of capping agent. The surface properties of treated CB were characterized by thermal gravimetric analysis, X-ray photoelectron spectroscope, and Fourier transform infrared spectroscopy, as well as the light absorbance, stability, and morphology of treated CB particles dispersed in DI water were analyzed by ultraviolet-visible light absorption spectroscopy, dynamic light scattering, and transmission electron microscopy. As shown in the results, in particular, it was found that the oxygen on the surface of CB could be increased by the treatment of peroxide hydrogen, resulting in stable dispersion without capping agent to sharply increase light absorption value of Mogul L CB in DI water from 38 to 545 g⁻¹ dm².