A Review of the Fate and Effects of Silicones in the Environment

Silicones are well-known useful materials varying in structure, reactivity, and chemical and physical properties, but they all contain a covalent bond between the silicon atom and an organic group. Most common of these polymers are those based on polydimethylsiloxane (PDMS) having a siloxane (Si–O–Si) repeat unit and two methyl groups on each silicon atom. All these polymers are manmade, and the organosilicon linkage is not found in nature. It was therefore erroneously assumed that these polymers do not degrade naturally in the environment. It is the purpose of this review to refute this myth and to describe the degradation processes of PDMS in the environment and any potential ecological impact on the terrestrial, aquatic, and atmospheric compartments. Although it was found that minor degradation takes place by hydrolysis of PDMS to dimethylsilandiol followed by oxidation of the methyl group to aldehyde and ultimately to CO₂ by Arthobacter and Fusarium oxysporium schlechtendahl, the major degradation processes are abiotic. High molecular weight PDMS are initially depolymerized by soil hydrolysis of the siloxane bonds to yield organosilanol terminated oligomers. These organosilanols and low molecular weight linear PDMS and cyclics are evaporated into the atmosphere and are oxidized there by hydroxyl radicals to benign silica, water, and CO₂.     

Synthesis and characteristic analysis of coal dust explosion suppressant based on surface modification of ammonium dihydrogen phosphate with methyl hydrogen-containing silicone oil

Coal dust explosion is easy to happen in the process of coal pulverization. In order to reduce the risk of coal dust explosion and promote the safety of coal chemical industry, surface modification of the ammonium dihydrogen phosphate (ADP) explosion suppressant was performed with methyl hydrogen-containing silicone oil to obtain modified ammonium dihydrogen phosphate (MADP) powder. The explosion suppression and hydrophobic properties of MADP were tested. The experimental results show that after surface modification, MADP overcomes the defect that the traditional ammonium dihydrogen phosphate explosion suppressant is easily affected by moisture, which results in agglomeration; further, MADP has little or no solubility in water and has excellent hydrophobic properties. After surface modification, MADP has better thermal stability and can withstand higher ambient temperatures. MADP can significantly increase the minimum ignition energy, thus reducing the possibility of combustion and explosion. With the increase in the mass concentration of the explosion suppressant, the maximum explosion pressure gradually decreases and delays. Compared with ADP, MADP has better explosion suppression characteristics and can quickly and efficiently suppress explosion.     

有机硅提高除草剂在紫茎泽兰叶片上润湿性能的研究

市售的氨氯吡啶酸与甲嘧磺隆制剂用四川省西昌市当地自来水稀释1250、2500、5000、10000和625、1250、2500、5000倍后,得到的药液的表面张力大于紫茎泽兰的临界表面张力,药液滴与紫茎泽兰叶片的接触角在接触4min后仍为50°～70°。虽然氨氯吡啶酸和甲嘧磺隆对紫茎泽兰（Eupatorium adenophorum Spreng）防除效果较好,可喷药后药剂不容易被植物持留,造成巨大浪费和当地的环境污染。从农药应用角度来看,这两种农药制剂中表面活性剂存在不合理性。笔者通过添加有机硅表面活性剂,探索合理的有机硅添加浓度,减小氨氯吡啶酸、甲嘧磺隆与紫茎泽兰叶片的接触角,改善该药剂对紫茎泽兰叶片润湿性,提高其利用率,减少损失,避免环境污染。文章测定了有机硅临界胶束浓度、紫茎泽兰临界表面张力及添加不同浓度有机硅药液的表面张力,得到有机硅质量分数大于等于0．05％（有机硅临界胶束浓度）,药液即可以在叶面铺展的结论。通过有机硅添加量与药液铺展速率的关系的测定,得到结论：有机硅添加质量浓度达到0．05％时,添加浓度越大,铺展速率越大。     

以液体硅胶与聚苯乙烯塑料泡沫小球为主体的掩蔽剂对污水暂存空间中恶臭气体的控制

为控制污水暂存空间产生的恶臭气体对周围环境造成的不利影响,在污水表面覆盖以液体硅胶(LSR)与聚苯乙烯塑料泡沫小球(EPS)为主体的掩蔽剂,通过增加污水中H₂S向气相扩散的传质阻力来控制恶臭气体从污水中的释放。分别探究了掩蔽剂的成分组成、配比和平铺厚度对掩蔽效果的影响,以及掩蔽剂对下部水体水质的影响。结果表明：以LSR+EPS为载体的掩蔽剂可以阻断H₂S的释放,其中以半透明LSR+EPS为载体的掩蔽剂效果最好;当半透明LSR与EPS载体的质量比为15~40,平铺厚度为0.1~0.5 cm时,其使用效果最好;掩蔽剂下部水体硫化物的浓度随污水停留时间的增加而增大;若利用SRB产物(高浓度H₂S)抑制微生物,尚需较长时间达到毒性阈值。该掩蔽剂增加了H₂S的传质阻力,有助于控制恶臭气体释放对所处环境的危害。     

Sources of polychlorinated biphenyl blank contamination and their impact on fingerprinting

Abstract

The development of high-resolution mass spectrometry methods for the measurement of polychlorinated biphenyls (PCBs) in environmental samples has dramatically reduced detection limits, leading to problems obtaining clean blanks. When PCBs are detected in samples at concentrations similar to the blanks, blank contamination must be addressed before fingerprinting and source apportionment through positive matrix factorization (PMF) can be successful. We tested a variety of blank correction methods using data from a study of water column concentrations of PCBs in the Spokane River, where concentrations of Σ₂₀₉PCBs in whole water samples averaged 171?pg/L without blank correction and Σ₂₀₉PCBs in the blanks averaged 88?pg/L. The results suggest that subtracting blank masses from sample masses can lead to erroneous results. Instead, censoring at one times the batch-specific blank level is a better approach. The sources of PCBs in field and method blanks were investigated by examining their congener profiles via PMF. The results suggest that commercial PCB formulations (in the US, Aroclors) continue to be the primary source of PCBs in blanks forty years after PCB production and use were banned in the United States. Other sources of PCBs to blanks include PCB 11 from pigments; PCBs 44?+?47?+?65, 45?+?51, and 68 arising from polymers cured using bis(2,4-dichlorobenzoyl) peroxide; and PCBs 1, 2, 3, 4, 8, 15 and others arising from silicone products derived from phenylsiloxanes, such as silicone-based adhesives.     

GP/APP膨胀阻燃体系对硅橡胶复合材料阻燃及抑烟性能的影响

为了探究石墨粉 (GP) 与聚磷酸铵 (APP) 膨胀阻燃体系对硅橡胶复合材料的阻燃及抑烟特性的影响,采用锥形量热仪 (CCT)、热重分析仪 (TG) 及极限氧指数测试仪 (LOI) 对阻燃硅橡胶复合材料进行表征。研究结果表明:与单独添加膨胀阻燃剂APP的阻燃硅橡胶相比,添加GP/APP膨胀阻燃体系可有效提升燃烧过程中形成的膨胀碳层的致密度,降低阻燃硅橡胶复合材料的热释放速率及总烟释放量,提高阻燃硅橡胶复合材料高温阶段的热稳定性,提升阻燃硅橡胶复合材料的燃烧成炭率和质量保持率; 使阻燃硅橡胶复合材料的氧指数值增大。     

硅油改性尿素基膨胀型阻燃剂的制备与表征

为提高膨胀型阻燃剂的阻燃性能与耐久性能,在水性聚氨酯树脂、聚磷酸铵、聚丙烯酰胺和磷酸铝的基础配方上,通过加入不同掺量的尿素以及不同掺量的硅油,对此阻燃体系配方进行耐久性优化设计,制备出尿素-硅油改性且具有一定耐水性的膨胀型阻燃涂层。通过锥形量热仪测试分析表征其阻燃性能来确定尿素-硅油的最佳掺量;并测量阻燃涂层的水接触角。结果表明:当掺加2 wt%的尿素时样品的阻燃效果最佳,掺量过多时会降低水接触角,影响样品耐水性;当掺加0.5 wt%的硅油时,样品的阻燃效果最佳,且随着掺量增多水接触角逐渐增大。     

膜萃取处理高盐水杨酸废水传质特性研究

采用膜萃取分离法处理高盐水杨酸废水。讨论了料液流量F、反应温度T、萃取液pH值、料液进水浓度Cf,in等因素对膜传质性能和水杨酸去除效果的影响。结果表明:总传质系数Kov受料液流量和反应温度两因素影响较大;在Cf,in=854.2±19.7 mg/L、F=3 L/d、T=323 K、萃取液侧pH=11.5±0.2、膜管长L=50 m的条件下,水杨酸去除率可达97%。     

硅橡胶低温环境性能研究

目的 研究低温环境对硅橡胶性能的影响。方法 探究硅橡胶6141和6144在-55℃长期低温环境下的压缩永久变形性能变化规律,以及不同低温环境对2种硅橡胶邵氏硬度和拉伸性能的影响,并通过DSC和TMA对材料热效应和弹性恢复行为进行分析。结果 在-55℃的低温环境下,随着时间的延长,硅橡胶的低温压缩永久变形会发生突变。当低温持续时间达到27 d后,硅橡胶6141和6144的低温压缩永久变形分别达到81%和92%,出现失效。对比-25℃和-55℃低温环境下的硬度和拉伸性能发现,随着温度的降低,材料拉断伸长率先增加、后降低,拉伸强度和硬度逐渐增大。当温度降低到-55℃时,由于材料产生结晶,硅橡胶6141和6144的拉伸强度分别增大58%和72%,稳定后的硬度值分别增加25和36。通过DSC和TMA研究发现,硅橡胶会在低温下产生结晶,回弹性降低。在-55℃低温环境下,通过TMA测试得到的6141和6144压缩永久变形分别为60%和62%。结论 在长时间的极端低温环境下,硅橡胶会缓慢发生结晶,使硅橡胶材料在高于其玻璃化转变温度和结晶温度范围内出现性能突变,发生失效。     

O_3/Mn-Fe(3∶1)/载体硅胶催化降解硝基苯的动态试验研究

非均相催化臭氧化技术能够快速、有效地去除污水中较高浓度难降解有机污染物,比较适用于处理突发环境污染事故。通过对O3/Mn-Fe(3∶1)/载体硅胶在不同试验条件下处理高浓度硝基苯废水进行了动态试验研究,并考察了连续处理实际有机废水效果。试验结果表明:硝基苯废水为2 L、进水流速为0.2 m/s、催化剂投加量为20 mg/l、引发剂H2O2投加量为20 ml时,连续运行1小时后,硝基苯的去除率达到75.4%;反应器连续运行30天,出水中的硝基苯去除率稳定在65%左右。