Microscopic mechanism of perfluorocarbon gas formation in aluminum electrolysis process

In view of the unclear cause of perfluorocarbons (PFCs) emission in the anode effect stage of aluminum electrolysis, the microscopic formation mechanism of PFCs was studied by density functional theory calculation and X-ray photoelectron spectroscopy (XPS). It is found that the discharge of fluorine containing anions ([F]^?) on carbon anode first causes the substitution of C—H by C—F and further results in the saturation of aromatic C—C bonds, leading to the appearance of —CF₃ or —C₂F₅ group through six-carbon-ring opening. Elimination of —CF₃ and —C₂F₅ with F atom could be a likely mechanism of CF₄ and C₂F₆ formation. XPS results confirm that different types of —CF_x group can be formed on anode surface during electrolysis, and the possibility that [F]^? discharges continuously at the C edge and finally forms different C—F bonds in quantum mechanical calculation was verified.     

Etching characteristics of thin SiON films using a liquefied perfluorocarbon precursor of C6F12O with a low global warming potential

Perfluorocarbon gas is widely used in the semiconductor industry. However, perfluorocarbon has a negative effect on the global environment owing to its high global warming potential (GWP) value. An alternative solution is essential. Therefore, we evaluated the possibility of replacing conventional perfluorocarbon etching gases such as CHF₃ with C₆F₁₂O, which has a low GWP and is in a liquid state at room temperature. In this study, silicon oxynitride (SiON) films were plasma-etched using inductively coupled CF₄ +C₆F₁₂O+O₂ mixed plasmas. Subsequently, the etching characteristics of the film, such as etching rate, etching profile, selectivity over Si, and photoresist, were investigated. A double Langmuir probe was used and optical emission spectroscopy was performed for plasma diagnostics. In addition, a contact angle goniometer and x-ray photoelectron spectroscope were used to confirm the change in the surface properties of the etched SiON film surface. Consequently, the etching characteristics of the C₆F₁₂O mixed plasma exhibited a lower etching rate, higher SiON/Si selectivity, lower plasma damage, and more vertical etched profiles than the conventional CHF₃ mixed plasma. In addition, the C₆F₁₂O gas can be recovered in the liquid state, thereby decreasing global warming. These results confirmed that the C₆F₁₂O precursor can sufficiently replace the conventional etching gas.     

Enhanced Particle Removal in Fluorinated Liquids—An Application in Nuclear Decontamination

An experimental cleaning system has been developed to demonstrate the decontamination of model electronic circuit boards by this cleaning process. The media used in this process are a wash solution of a high molecular weight fluorocarbon surfactant in a perfluorinated carrier liquid which results in enhanced particle removal, followed by a perfluorinated carrier liquid rinse. The perfluorinated liquids of interest, which are recycled in the process, are inert, nonflammable, generally safe to use, and do not present a hazard to the atmospheric ozone layer. The cleaning experiments were performed at the MIT Nuclear Reactor Laboratory. The radioactive particles removed from the circuit boards were captured by 0.22 μm filters with a filtration efficiency of 99.5% per stage. Compatibility tests were performed on these model electronic circuit boards. The results obtained show that neither the process fluids used nor the maximum level of the ultrasonic agitation applied harmed the circuit boards or the circuit components. All the circuit boards used in these tests were still functional after the cleaning experiments. A three log reduction in contamination was obtained in 1 hour. These data indicate that this process, once implemented on a large scale, will offer users in the nuclear industry a practical and cost effective means of decontaminating and recovering a wide variety of tools and instruments.     

氟碳化合物与环糊精包合物的制备及其对牛血清白蛋白的影响

以氟碳化合物FC-77作为模型药物,制备FC-77与β-环糊精（卢一cD）包合物。考察包合物与牛血清白蛋白（BSA）的相互作用。通过紫外-可见光谱、红外光谱、热重分析等方法研究包合物的物理化学性能。通过荧光光谱法研究包合物对BSA的荧光猝灭作用。结果为Fc-77与β-cD之间存在强烈的相互作用,从而增加了FC-77的稳定性和水中的溶解性。荧光猝灭结果显示FC-77分子能进入BSA的疏水区域。结论是以β-CD为介质,能显著改善FC-77的理化性能,使FC-77粉末化,便于制成多种剂型,扩大给药方式。     

全氟烃分解反应催化剂的研究进展

对有效消除全氟烃的催化分解法进行了评述,重点对近年来报道的用于全氟烃催化分解的过渡金属改性γ-Al2O3、磷酸盐、磷酸盐改性γ-Al2O3催化剂进行了总结和比较。磷酸盐催化剂的初活性较高,但比表面积较小,反应稳定性欠佳;过渡金属改性γ-Al2O3催化剂表面的铝酸盐保护层在一定程度上抑制了γ-Al2O3转化为惰性物相,稳定性比纯γ-Al2O3催化剂有所提高,但经长时间反应,催化剂表面酸量不断减少,催化活性逐渐下降。相比较而言,磷酸盐改性γ-Al2O3有望成为高活性和高稳定性的全氟烃分解催化剂。     

有机氟聚合物的应用研究进展

有机氟聚合物是一类重要的有机高分子化合物，本文主要介绍了该类聚合物的物化性质、应用以及未来的发展前景。     

PFC emission‐reduction strategy for the LCD industry

Abstract— The perfluorocarbons (PFCs) used as etching‐process and chamber‐cleaning gases in the manufacture of LCD devices have a high global‐warming potential and a long atmospheric lifetime. Thus, to voluntarily reduce these environmentally harmful PFCs, in 2001 the Japanese LCD association established the World LCD Industry Cooperation Committee (WLICC), together with its counterpart associations in the Republic of Korea and Taiwan. Since that time involving many discussions, the WLICC reached a consensus on reducing the aggregate absolute PFC emissions to the equivalent of less than 0.82 million metric tons of carbon by 2010. Each association has been taking whatever emission reduction steps it considers best to achieve this goal. Thanks to these measures, the PFC emissions from the Japanese LCD industry have remained at the same level, or less, than those of the year 2000, in spite of the fact that PFC purchases have continually increased. In the interim, the Japanese LCD association has been obtaining experimental data for the 2006 IPCC Inventory Guidelines, which will give the emission factors needed to estimate the PFC emissions. As a result, some data are quite different from emission factors given in the current 2000 Inventory Guidelines. All the data obtained have been submitted to the IPCC to be adopted in the new 2006 Guidelines.     

Insulation characteristics of perfluorocarbon liquid/solid insulation for nonflammable large power transformer

A new type nonflammable large power transformer system is proposed in which the excellent cooling characteristics and insulation properties of nonflammable perfluorocarbon (PFC) liquid is utilized. In the system, transformer windings are put in an insulating cylinder filled with PFC liquid. The core includes cooling panel through the liquid. The space between the insulating cylinder and tank is filled with compressed SF⁶ gas. This paper describes the insulation characteristics of main insulation and inter-winding insulation models which simulate the transformer. It is found that (1) higher withstand voltage is expected by means of insulation barriers in the main insulation model; (2) partial discharge in inter-winding insulation model is beginning to behave in a constant electric field strength on the point of 0.1 mm liquid gap length.     

The perfluoropolymer upper bound

Perfluoropolymers have fundamentally distinct thermodynamic partitioning properties compared to those of their hydrocarbon counterparts. However, current upper bound theory assumes hydrocarbon solubility behavior for all polymers. Herein, the fundamental presupposition of invariance in solubility behavior to upper bound performance is critically assessed for perfluoropolymers and hydrocarbon polymers. By modifying solubility relationships, theoretical perfluoropolymer upper bounds are established, showing a positive shift of the upper bound front as a result of beneficial solubility selectivities for certain gas pairs, including N₂/CH₄, He/H₂, He/N₂, He/CH₄, and He/CO₂. Within the framework of the solution–diffusion model, an analysis is presented to compare two independent approaches often pursued in efforts to surpass the polymer upper bound: (a) achieving solubility selectivity via perfluoropolymers and (b) improving diffusion selectivity via rigid hydrocarbon polymers. This analysis demonstrates the significant benefit that can be achieved by considering both the chemical composition and morphology of solid-state macromolecules when designing membrane materials.     

A Versatile Theranostic Nanoemulsion for Architecture‐Dependent Multimodal Imaging and Dually Augmented Photodynamic Therapy

To design a clinically translatable nanomedicine for photodynamic theranostics, the ingredients should be carefully considered. A high content of nanocarriers may cause extra toxicity in metabolism, and multiple theranostic agents would complicate the preparation process. These issues would be of less concern if the nanocarrier itself has most of the theranostic functions. In this work, a poly(ethylene glycol)‐boron dipyrromethene amphiphile (PEG‐F₅₄‐BODIPY) with 54 fluorine‐19 (¹⁹F) is synthesized and employed to emulsify perfluorohexane (PFH) into a theranostic nanoemulsion (PFH@PEG‐F₅₄‐BODIPY). The as‐prepared PFH@PEG‐F₅₄‐BODIPY can perform architecture‐dependent fluorescence/photoacoustic/¹⁹F magnetic resonance multimodal imaging, providing more information about the in vivo structure evolution of nanomedicine. Importantly, this nanoemulsion significantly enhances the therapeutic effect of BODIPY through both the high oxygen dissolving capability and less self‐quenching of BODIPY molecules. More interestingly, PFH@PEG‐F₅₄‐BODIPY shows high level of tumor accumulation and long tumor retention time, allowing a repeated light irradiation after a single‐dose intravenous injection. The “all‐in‐one” photodynamic theranostic nanoemulsion has simple composition, remarkable theranostic efficacy, and novel treatment pattern, and thus presents an intriguing avenue to developing clinically translatable theranostic agents.