Direct-Ink-Writing of Electroactive Polymers for Sensing and Energy Storage Applications

Considering the high levels of materials used in the fields of electronics and energy storage systems, it is increasingly necessary to take into consideration environmental impact. Thus, it is important to develop devices based on environmentally friendlier materials and/or processes, such as additive manufacturing techniques. In this work, poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) are prepared by direct-ink-writing (DIW) by varying solvent evaporation temperature and fill density percentage. Different morphologies for both polymers are obtained, including dense films and porous membranes, as well as different electroactive β-phase content, thermal and mechanical properties. The dielectric constant and piezoelectric d₃₃ coefficient for dense films reaches up to 16 at 1 kHz and 4 pC N⁻¹, respectively for PVDF-HFP with a fill density of 80 and a solvent evaporation temperature of 50 °C. Porous structures are developed for battery separator membranes in lithium-ion batteries, with a highest ionic conductivity value of 3.8 mS cm⁻¹ for the PVDF-HFP sample prepared with a fill density of 100 and a solvent evaporation temperature of 25 °C, the sample showing an excellent cycling performance. It is demonstrated that electroactive films and membranes can be prepared by direct-ink writing suitable for sensors/actuators and energy storage systems.     

氟硅酸钾滴定法测定粗制氟化钠中二氧化硅

采用硝酸-氢氟酸混合酸为消解溶剂,通过微波消解技术对粗制氟化钠进行快速消解,并用氟硅酸钾滴定法测定其二氧化硅含量。选择饱和氯化钾溶液替代固体氯化钾作为沉淀剂,考察了消解酸体系、饱和氯化钾溶液用量、沉淀温度、沉淀放置时间、共存元素干扰及指示剂选择等条件对测定结果的影响并进行优化。确定了最优测试条件：以8 mL硝酸+2 mL氢氟酸为消解溶剂,以8 mL饱和氯化钾溶液为沉淀剂,控制沉淀温度为20~25 ℃、沉淀放置时间为15 min,选择50 g/L氯化钾-50%乙醇溶液洗涤沉淀,采用溴麝香草酚蓝-酚红指示剂。该方法应用于回收粗制氟化钠中二氧化硅含量的测定可大幅度缩短分解试样的时间,有效降低检测成本,回收率为99.15%~100.63%,相对标准偏差（RSD,n=8）小于1%,与传统高温碱熔法测定结果相符,方法的准确度和精密度较好。     

改性羧甲基壳聚糖的制备及其去除冶炼废水中的氟

采用自制铁基生物絮凝剂（BPFS）对羧甲基壳聚糖(CMC)进行改性,并研究其对废水中氟的去除。考察了羧甲基壳聚糖CMC/Fe质量比、BPFS-CMC投加量、pH、反应时间对氟离子去除效果的影响。结果表明,水中残余氟离子浓度随CMC/Fe质量比升高而升高;随改性羧甲基壳聚糖投加量的增加而降低,而且与羧甲基壳聚糖单独处理含氟废水相比,氟离子去除效果有明显提高,当BPFS-CMC投加量为3%（体积分数）时,氟离子去除率由33.05%提高到62.70%;酸性条件有利于氟离子的去除;随反应时间的增加,氟离子浓度缓慢下降。当羧甲基壳聚糖CMC/Fe质量比为0.05,投加量3%,pH=5,反应时间10 min时,水中残余氟离子浓度为7.78 mg/L,低于国家《铅、锌工业污染物排放标准》(GB 25466—2010)规定的限值。     

过磷酸钙生产中排氟风机防腐结构改进

40万t/a化成法生产过磷酸钙,采用4 72 10 N o12.5离心式钢衬胶排风机,该风机使用中出现泄漏、腐蚀等问题,经对上下机壳密封方法、清理门结构等的改进,使风机检修工作量大大减少,风机寿命延长。     

聚偏氟乙烯膜生物反应器处理城市污水的膜污染分析

膜污染是制约膜生物反应器应用的关键因素,通过实验分析了聚偏氟乙烯膜生物反应器运行操作压力的变化.膜通量为10/L(h·m2)时,操作压力在3.73×104Pa以下,比较了降低膜污染的不同方法:水力清洗能恢复操作压力77%;倾斜50°放置,压力增长缓慢;膜组件离容器底部最佳位置为20 cm.计算了膜总阻力的组成.     

氟化铝生产废水处理工艺的研究

对氟化铝生产废水的处理方法进行了研究。结果表明，一级中和沉淀法和二级中和二级沉淀法均不宜用于氟化铝生产废水的结果，理想的处理方法是碱过量中和酸回调法，辅加氯化钙的石灰乳中和法也可考虑采用。     

Multiple melting in blends of poly(vinylidene fluoride) with isotactic poly(ethyl methacrylate)

Multiple melting phenomena have been studied in blends of poly(vinylidene fluoride) (PVF₂) with low molar mass isotactic poly(ethyl methacrylate) (it-PEMA). In all blends, as well as in pure PVF₂, a transition (T₁) was observed prior to the main melting point (T₂). T₁ is probably connected with the melting of secondarily-crystallized material. In addition to this, a high temperature melting endotherm (T₃) was observed, which could be ascribed completely to recrystallization of PVF₂. The highest transition (T₄) was caused by melting of the σ form of PVF₂. From Hoffman-Weeks plots—T₂ vs. crystallization temperature, T_c — it could be concluded that no thermody amic depression of the melting point of PVF₂ occurred in the blends. The stabilities of PVF₂ crystallites in the various blends were derived from the slopes of Hoffman-Weeks plots and were in good agreement with lamellar thicknesses found from SAXS measurements.     

Gas phase synthesis of MTBE on fluoride-modified zeolites

The gas phase synthesis of MTBE was studied using three series of zeolites modified by ion-exchange with ammonium fluoride, the parent materials being HY, H-mordenite, and HZSM-5. Modification of zeolites by fluoride-exchange was found to enhance the MTBE synthesis activity for all three types of zeolites without impairing their excellent selectivity to MTBE. The mechanism of activity enhancement by fluoride-modification appears to be related to the formation of extra-lattice Al rather than the presence of fluoride-ions.     

Low frequency ac conduction and dielectric relaxation behavior of solution grown and uniaxially stretched poly(vinylidene fluoride) films

The measurements of ac conductivity [σ_m(ω)], dielectric constant [?′(ω)] and loss [?″(ω)] have been performed on solution grown (thickness ∼85 μm) and uniaxially stretched (thickness ∼25, 45 and 80 μm) films of poly(vinylidene fluoride) (PVDF) in the frequency range 0.1 kHz-10 MHz and in the temperature range 77-400 K. The σ_m(ω) can be described by the relation σ(ω) = Aω^s, where s is close to unity and decreases with increase in temperature. Three relaxations, observed in the present investigation, have been designated as the α_c-, the α_a- and the β-relaxations appearing from high temperature side to the low temperature side. The α_c-relaxation could not be observed in the case of uniaxially stretched poly(vinylidene fluoride) films. The α_c- and α_a-relaxations are associated with the molecular motions in the crystalline regions and micro-Brownian motion in the amorphous regions of the main polymer chain, respectively, whereas the β-relaxation is attributed to the rotation of side group dipoles or to the local oscillations of the frozen main polymer chain.     

哈格曼乙酯与硝基乙烷在不同碱催化下的迈克尔加成反应

研究了在不同有机碱催化下,哈格曼乙酯和硝基乙烷经迈克尔加成合成3 甲基 3 (1′ 硝基乙基) 4 乙氧甲酰环己酮的反应。结果表明,氟化四丁基铵的催化效果最好,且当n(氟化四丁基铵)∶n(哈格曼乙酯)=1∶2时,合成产物3 甲基 3 (1′ 硝基乙基) 4 乙氧甲酰环己酮的收率达到最高值56%。