Future sources of organic raw materials

Industrial organizations, academic institutions, and national governments should agree on the cooperative roles each will play in planning the decadesahead raw materials needs of the chemical industry, which is vital to a modern, international economic system. The raw material future of the industry depends as much on political and social concerns as it does on technical and economic considerations. The generation in charge now cannot in good conscience go on consuming the world's supply of hydrocarbons and not acknowledge a duty to generations that will follow.     

Design and application of electron-transporting organic materials

Operating lifetime is the main problem that complicates the use of polymeric light-emitting diodes (LEDs). A class of electron transport (ET) polymers [poly(aryl acrylate) and poly(aryl ether)s] is reported in which moieties with high electron affinities are covalently attached to stable polymer backbones. Devices based on poly(p-phenylenevinylene) (PPV) prepared with these materials exhibited a 30-fold improvement in stability and, in one case, dramatically lower (10 volts versus about 30 volts) operating voltage relative to those having conventional ET layers. The current-carrying capacity of indium tin oxide-PPV-polymeric ET layer-aluminum LEDs was also increased by a factor of 30. These improvements lead to an enhancement in power efficiency of nearly an order of magnitude. Choosing polymers with high glass transition temperatures increases device lifetime.     

Pyrolysis mass spectrometry of complex organic materials

Pyrolysis mass spectrometry in combination with computerized multivariate statistical analysis enables qualitative and quantitative analysis of nonvolatile organic materials containing molecular assemblies of a complexity and size far beyond the capabilities of direct mass spectrometry. The state of the art in pyrolysis mass spectrometry techniques is illustrated through specific applications, including structural determination and quality control of synthetic polymers, quantitative analysis of polymer mixtures, classification and structural characterization of fossil organic matter, and nonsupervised numerical extraction of component patterns from complex biological samples.     

Silica-like malleable materials from permanent organic networks

Permanently cross-linked materials have outstanding mechanical properties and solvent resistance, but they cannot be processed and reshaped once synthesized. Non-cross-linked polymers and those with reversible cross-links are processable, but they are soluble. We designed epoxy networks that can rearrange their topology by exchange reactions without depolymerization and showed that they are insoluble and processable. Unlike organic compounds and polymers whose viscosity varies abruptly near the glass transition, these networks show Arrhenius-like gradual viscosity variations like those of vitreous silica. Like silica, the materials can be wrought and welded to make complex objects by local heating without the use of molds. The concept of a glass made by reversible topology freezing in epoxy networks can be readily scaled up for applications and generalized to other chemistries.     

有机光电材料与有机光电器件

近年来,有机光电子学在基础研究和应用方面取得了突飞猛进的发展,已经成为一个较为成熟的跨学科新兴领域。主要介绍有机光电材料的分子结构、导电与发光机理、有机光电器件的分类与工作原理以及有机光电材料在光电器件方面的应用,包括有机发光二极管和发光电化学池、有机太阳能电池、有机场效应晶体管、有机生物化学传感器、有机光泵浦激光器以及有机非线性光学材料等。     

不同还田方式下有机物料有机碳分解规律研究

利用网袋法和砂滤管法模拟田间还田方式,研究不同处理下各有机物料有机碳的腐解特征。结果表明,网袋法玉米、大豆秸秆经过150 d后,其秸秆生物量有38.9%～46.6%被分解。秸秆还田分解趋势为:土埋处理露天处理;土埋玉米秸秆土埋大豆秸秆;露天大豆秸秆和玉米秸秆分解规律一致。从组织结构上看,玉米秸秆随着还田时间的增加,组织结构模糊、松散,基本组织和维管束遭到破坏,大豆秸秆组织结构变化不明显。不同还田方式下秸秆有机碳的分解规律为:玉米秸秆大豆秸秆。在砂滤管模拟条件下玉米、大豆秸秆和根茬有机碳分解趋势基本相似,均表现为埋管初期分解较快,后期分解较慢,其有机碳分解率趋势为:玉米秸秆大豆秸秆;降低C/N后,各有机物料有机碳分解率均高于不调节C/N。     

Packaged organic materials as monitoring tools for radionuclides

Pint-size perforated polyethylene bags were used as containers to test preserved tea, spinach, ion-exchange resin, live filamentous green algae, and dead filamentous green algae for the sorption and concentration of radionuclides from natural aquatic habitats and from a variety of laboratory controlled nutrient media. These packaged materials have been used to detect trace levels of radionuclides not found by the usual methods of analysis of the raw water itself for dissolved radionuclides.     

有机物料中砷快速检测方法的研究

有机物料中砷含量的检测技术,采用快速微波酸消解前处理技术,原子荧光光谱仪定量。与国家标准检验方法GB/T 5009.11-2003《食品中总砷及无机砷的测定》比较,比国标前处理方法节省时间50%,试剂用量节省约50%。两种方法准确度未见显著性差异,精密度优于国家标准方法,适合对有机物料中砷进行快速测定。     

有机物料不同配比堆肥过程的差异分析

为了促进当地农业有机废弃物资源的循环利用,以牛粪、猪粪和鸡粪等为堆肥的主要原料,在协调所有处理的碳氮比相同和添加EM菌液的条件下进行堆肥试验,分析有机物料的不同配比在堆肥过程中的温度、p H、EC、全氮、铵态氮、硝态氮和发芽指数的变化趋势,比较不同处理堆肥前后养分含量的差异。结果表明,牛粪—鸡粪—谷壳处理的升温最快,高温阶段温度基本上维持在70℃上下,堆肥前后氮素损失率最大为22.8%,而猪粪—食用菌渣—鸡粪处理的高温阶段温度低于65℃,氮素损失率最小为3.47%,发芽指数在堆肥进行20 d就达到了52%,堆肥腐熟快于其他处理,但是在堆肥32 d后,所有处理的p H在7.7-8.5之间,满足堆肥腐熟后呈弱碱性的要求,发芽指数在80%左右,基本上达到了有机肥完全腐熟的标准。研究表明堆肥32 d后可以完全腐熟;但合理的配比,同时调节其通风性,控制堆体温度在45-65℃之间,可减少氮素损失,提高有机物料堆肥的效果。     

有机高分子材料添加对沼渣颗粒肥理化特性的影响

采用造粒方法,将羟乙基纤维素、羟丙甲基纤维素、聚乙烯醇及羧甲基纤维素钠4种有机高分子材料应用到沼渣颗粒造粒中,测定沼渣颗粒肥的粒径、成球率、颗粒强度、吸水率以及保水率等指标,研究有机粘结剂的种类及其含量对沼渣颗粒肥的影响规律。结果表明:沼渣颗粒成球率方面,聚乙烯醇作为粘结材料其质量分数为9.09%时,制备的牛粪沼渣颗粒肥造粒成球率达到82.31%。在沼渣颗粒强度方面,羟乙基纤维素质量分数为6.25%时制备的肥料颗粒最低强度为6.3N;聚乙烯醇质量分数为9.09%时,沼渣肥料颗粒强度可以达到90.3N。在沼渣颗粒肥吸水方面,牛粪沼渣颗粒肥的吸水能力与有机粘结材料的质量分数呈正相关关系。沼渣颗粒肥崩解时间试验显示,羟乙基纤维素适用于制备速效沼渣颗粒肥料,聚乙烯醇适用于制备缓释沼渣颗粒肥料。     

不同有机物料对土壤肥力及团聚体稳定性的影响

【目的】研究不同有机物料对土壤肥力及土壤团聚体稳定性的影响。【方法】采用室内培养法,将采集到的土样分别与木屑、棉花、小麦秸秆按9∶1的质量比混合均匀,以土样中不添加有机物料为对照(CK),各处理中均加入EM菌剂,在25～30℃下堆放180d,且每7d翻堆1次。试验结束后,测定不同处理的土壤速效养分、中微量元素及有机质含量和阳离子交换量(CEC),采用因子分析法计算各处理的土壤肥力综合得分并进行排名,采用干筛法与湿筛法测定不同处理土壤水稳性团聚体的平均重量直径,并计算土壤团聚体的稳定性指数。【结果】与CK相比,3种有机物料均能提高土壤速效养分、中微量元素、有机质含量和CEC。采用因子分析法计算后可知,木屑处理的土壤肥力综合得分最高,达65.57,小麦秸秆、棉花处理土壤次之,但均高于CK。与CK相比,各有机物料处理土壤团聚体稳定性均有明显提高,其中以木屑处理土壤团聚体的稳定性指数最高,为4.111。【结论】采用木屑、小麦秸秆及棉花3种有机物料对土壤培肥后,均能不同程度地提高土壤肥力和土壤团聚体的稳定性,其中木屑的培肥效果最好。     

有机物料添加后滨海盐渍土壤溶解性有机碳变化 及其紫外-可见光谱特征

利用紫外-可见光谱技术研究不同盐分水平(低盐、高盐)土壤中添加不同有机物料后土壤DOC的紫外-可见光(UV-Vis)光谱特征变化,探究盐渍土壤碳库的稳定性.结果显示,添加有机物料能显著增加DOC含量,与生物炭和有机肥相比,秸秆处理后的土壤DOC含量更高.在200～800 nm波长范围内,两种盐分土壤DOC溶液的吸光值随着波长增加均呈降低趋势,在230～280 nm内出现吸收平台.低盐土壤,DOC含量和紫外-可见光谱特征区域面积积分比值均对应地高于高盐土壤的值,而A250/A365及A240/A420比值则低于高盐.相关性分析表明,土壤DOC含量与254 nm处吸光值呈显著线性相关(R2＞0.9,P＜0.05),用于表征DOC特征的紫外光谱特征参数之间的相关性在高盐、低盐土壤上并不完全一致.由此说明,有机物料处理后,低盐土壤的DOC腐殖化程度、芳香性、相对分子量和团聚化程度都对应的比高盐土壤的更高.在高盐土壤上,添加不同物料的土壤DOC各项紫外特征参数之间无显著差异;在低盐土壤上,秸秆处理后土壤DOC的芳香性及疏水性与其他处理有显著差异.DOC结构复杂且受环境影响较大,需要结合多种参数判断其结构特征.     

纯有机物料腐解形成腐殖物质性质的动态变化

采用培养试验 ,对玉米秸、绿豆秸、猪粪、羊粪 4种有机物料腐解过程腐殖物质的组成 (H/ F)、胡敏酸性质、结构的动态变化进行了研究。结果表明 ,玉米秸从腐解 15～ 6 0 d,H/ F明显增大 ,胡敏酸结构趋于复杂 ;6 0～ 2 10 d,H/ F逐渐减小 ,胡敏酸由复杂趋于简单 ;2 10～ 36 0 d,H/ F呈增大趋势 ,胡敏酸趋于复杂。而绿豆秸、羊粪从腐解 15～ 90 d,H/ F呈减小趋势 ,胡敏酸芳构化度降低 ;随后 H/ F逐渐上升 ,胡敏酸趋于复杂。猪粪在整个腐解过程中 H/ F一直呈上升趋势 ,胡敏酸由简单趋于复杂。腐殖物质的形成是一个氧化过程 ,酚羟基氧化转化为羧基     

密闭小室测定建材有机挥发物散发特性的研究

为研究室内装修材料有机挥发物(VOCs)的散发情况,提出一种改进的测定建材VOCs散发特性(初始VOCs平均浓度、分离系数)和对流传质系数的模型及计算方法,并应用该方法得到几种常见建材(复合地板、大芯板、地板砖和地毯)的VOCs散发特性和对流传质系数.结果表明:当实验时间有限、密闭小室与测试建材体积比较大时,模型计算能...     

施用高量有机物料对新垦耕地红壤有机碳积累及性态的影响

为了解新垦红壤培肥过程中有机物料用量对土壤有机碳积累、培肥效率及土壤性态的影响,选择一新垦耕地红壤,设置秸秆、秸秆加氮和猪粪等3种添加物各7个施用水平共19个处理,每种有机物料用量设0(对照)、25、50、100、150、200和250 g·kg-1等7个级别,进行了为期24个月的模拟培养试验,观察了有机物料分解率、土壤C/N、活性有机碳和养分的动态变化.结果表明,随有机物料用量的增加,土壤中活性有机碳、总有机碳含量均增加,C/N比下降,土壤有效磷、速效钾和水溶性盐分含量增加,有机物料在土壤中的分解率也随之增加.猪粪碳的矿化速率低于水稻秸秆,加氮可增加秸秆的腐殖化系数.研究发现,有机物料添加越多,培肥效率(腐殖化系数)越低.同时,高量施用猪粪容易引起土壤盐害.猪粪用量为50g·kg-1(相当于7.5t·亩-1)时土壤盐分含量超过了 2g·kg-1;高量施用水稻秸秆可引起土壤有效氮的下降,秸秆用量超过100 g·kg-1(相当于15 t·亩-1)时土壤碱解氮明显下降;秸秆加氮处理会引起土壤酸化.结果显示,为减免有机物质的过度分解,有机物料的施用量控制在50g·kg-1以下为宜.     

长期施用有机物料对稻田生态系统服务功能的影响

基于长期定位试验,测定稻田温室气体排放通量、土壤和糙米重金属、淋溶水中氮磷含量,收集整理水稻产量和土壤肥力长期数据,以研究长期施用有机物料对稻田生态系统服务功能的影响。选择净经济效益(NEB)作为生态系统服务功能的评价指标。研究结果表明:与单施化肥(F)相比,长期施用猪粪(FM)显著提高土壤有机碳、全氮、全磷和有效磷含量,秸秆还田(FS)显著提高土壤有机碳和速效钾,提高了全氮、全磷、速效氮和全钾,但差异不显著,说明长期施用有机物料可提高土壤肥力;FM和FS提高水稻平均产量分别达4.1%和4.3%;FS和FM显著增加CH_4累积排放量,减少N_2O排放,但差异不显著;FM和FS提高土壤有机碳固存率。与F和FS相比,FM降低了淋溶水中氮淋溶量,但显著增加了田面水磷含量和20 cm深淋溶水磷淋溶量,而对60 cm和80 cm深淋溶水磷淋溶量没有影响;FM显著提高土壤Zn、Cu和Cd含量,所有处理重金属含量均没有超过土壤环境质量二级标准,FM没有引起水稻糙米中重金属含量的累积。与F相比,FM增加NEB 5.2%,达到1 056.8元·hm~(-2)。上述结果表明,20年尺度下,施用猪粪对稻田生态系统服务功能的正面影响远大于其所带来的负面影响,但随着猪粪施用时间的延长其负面效应可能进一步扩大,应引起重视。     

施入有机物料对葡萄连作土壤速效养分及微生物的影响

采用盆栽试验,研究施入不同比例的稻草和玉米秸秆对葡萄连作土壤速效养分及微生物数量的影响.结果表明,施入稻草和玉米秸秆后并没有增加连作土壤中速效N的含量,但不同程度的增加了速效P和速效K的含量.对微生物的影响表现为,增加了连作土中细菌、放线菌和真菌的数量,稻草处理使细菌、真菌比值增加,放线菌比值降低;秸秆处理后,真菌比值下降,且随着玉米秸秆含量增加,下降幅度越大,除99.5%连作土+0.5%玉米秸秆处理之外,细菌比值增加,放线菌比值降低.     

不同因素对包膜尿素材料有机物分解的影响

在不同温度、水分等条件下,将有机物料进行发酵培养,培养7 d后检测其水溶性有机质/氮含量。结果表明:微生物G对物料中有机氮的分解比微生物H的分解能力强,微生物H对物料中有机质的分解比微生物G的分解能力强。当激活剂添加量为0.33%、水分含量为80%、温度为30℃时,微生物G的活性最高,物料J在微生物G的作用下,其水溶性有机质和水溶性有机氮含量均达到最大值,发酵效果最好。     

Adsorption of Cu(II) on humic acids derived from different organic materials

The adsorption of Cu(II) from aqueous solution onto humic acid(HA) which was isolated from cattle manure(CHA), peat(PHA), and leaf litter(LHA) as a function of contact time, p H, ion strength, and initial concentration was studied using the batch method. X-ray absorption spectroscopy(XAS) was used to examine the coordination environment of the Cu(II) adsorbed by HA at a molecular level. Moreover, the chemical compositions of the isolated HA were characterized by elemental analysis and solid-state 13 C nuclear magnetic resonance spectroscopy(NMR). The kinetic data showed that the adsorption equilibrium can be achieved within 8 h. The adsorption kinetics followed the pseudo-second-order equation. The adsorption isotherms could be well fitted by the Langmuir model, and the maximum adsorption capacities of Cu(II) on CHA, PHA, and LHA were 229.4, 210.4, and 197.7 mg g–1, respectively. The adsorption of Cu(II) on HA increased with the increase in p H from 2 to 7, and maintained a high level at p H>7. The adsorption of Cu(II) was also strongly influenced by the low ionic strength of 0.01 to 0.2 mol L–1 Na NO3, but was weakly influenced by high ionic strength of 0.4 to 1 mol L–1 Na NO3. The Cu(II) adsorption on HA may be mainly attributed to ion exchange and surface complexation. XAS results revealed that the binding site and oxidation state of Cu adsorbed on HA surface did not change at the initial Cu(II) concentrations of 15 to 40 mg L–1. For all the Cu(II) adsorption samples, each Cu atom was surrounded by 4 O/N atoms at a bond distance of 1.95 ? in the first coordination shell. The presence of the higher Cu coordination shells proved that Cu(II) was adsorbed via an inner-sphere covalent bond onto the HA surface. Among the three HA samples, the adsorption capacity and affinity of CHA for Cu(II) was the greatest, followed by that of PHA and LHA. All the three HA samples exhibited similar types of elemental and functional groups, but different contents of elemental and functional groups. CHA contained larger proportions of methoxyl C, phenolic C and carbonyl C, and smaller proportions of alkyl C and carbohydrate C than PHA and LHA. The structural differences of the three HA samples are responsible for their distinct adsorption capacity and affinity toward Cu(II). These results are important to achieve better understanding of the behavior of Cu(II) in soil and water bodies in the presence of organic materials.     

有机发泡剂制备聚乙烯醇--碱木质素发泡材料及性能研究

为改进造纸黑液中木质素再利用情况和PVA泡沫的力学性能,以甲醛为交联剂,采用BSH发泡剂发泡制备聚乙烯醇-碱木质素发泡材料(PLFM)并测定其相关性能。结果表明:相对于PVA用量,发泡剂用量0.5%、甲醛用量0.8mL/g、麦草碱木质素用量30%时,制备的PLFM力学性能最好,拉伸强度最大,为28.94MPa;吸水率最低,为2.455倍;表观密度0.28g/cm3。PLFM的耐溶剂性能随碱木质素用量的增大而降低;碱木质素、PVA和甲醛交联较好,发生芳环的5位取代;泡沫均匀、孔隙规则;具有较好的生物相容性;热稳定性不因碱木质素的加入而降低,且热降解性好。