Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal-rich silicon phosphides RuSi₄P₄ and IrSi₃P₃ are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X-ray diffraction and ²⁹Si and ³¹P magic angle spinning NMR. In agreement with previous report RuSi₄P₄ crystallizes in NCS space group P1, while IrSi₃P₃ is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi₄P₄ and IrSi₃P₃ to be wide bandgap (E_g) semiconductors, E_g = 1.9 and 1.8 eV, respectively. RuSi₄P₄ and IrSi₃P₃ outperform the current state-of-the-art infrared SHG material, AgGaS₂, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi₄P₄ and IrSi₃P₃ are promising candidates for longer wavelength NLO materials.     

Influence of α′‐/α‐crystal polymorphism on properties of poly(l‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry     

Enhanced strains of Nb-doped BNKT-4ST piezoelectric ceramics via phase boundary and domain design

A strategy that constructs the morphotropic phase boundary and manipulates the domain structure has been used to design the component of 0.96[Bi_0.5(Na_0.84K_0.16)_0.5Ti_(1-x)Nb_xO₃]-0.04SrTiO₃ (BNKT-4ST-100xNb) to enhance the strain properties for actuator application. Non-equivalent Nb⁵⁺ donor doping modulates the phase transition from the mixture of rhombohedral and tetragonal phases to the pseudocubic phase and results in the coexistence of multiple phases. Moreover, the high-resolution TEM confirms the existence of polar nano regions that contribute to the macroscopic relaxor behaviour. The size of the domains is reduced with increasing Nb⁵⁺, resulting in an enhanced relaxor behaviour. The ferroelectric-relaxor transition temperature decreases from 85 to below 30 °C, implying a non-ergodic to ergodic relaxor transition. An improved strain of 0.56% and a giant normalized strain of 1120 pm/V were achieved for BNKT-4ST-1.5Nb, which were attributed to the unique domain structure in which nanodomains are embedded in an undistorted cubic matrix. Ferroelectric, antiferroelectric, and relaxor phases coexist. As the electric field is large enough, a reversible phase transition occurs. Furthermore, good temperature stability was obtained due to the stability of the nanodomains, and no degradation in strains was observed even after 10⁴ cycles, which may originate from the reversible phase transition and dynamic domain wall. The results show that this design strategy offers a reference way to improve the strain behaviour and that BNKT-4ST-100xNb ceramics could be a potential material for high-displacement actuator applications.     

低分子量聚丙烯酸钾的合成及其应用

采用水溶液聚合法制备了低分子量聚丙烯酸钾（PAAK），并作为新型消焰剂加入单基发射药中。通过火焰原子吸收光谱法测试了PAAK中钾的含量；用乌氏黏度计测定了特性黏度；采用DSC法研究不同pH值的PAAK与硝化棉（NC）的相容性；利用充氮氧弹法对添加PAAK、硝酸钾KNO₃、硫酸钾K₂SO₄的单基发射药的燃烧残渣进行了对比研究。结果表明，合成的PAAK中，钾的质量分数为15.21%，相对分子量在3 000左右，有利于和NC均匀混合，且在中性或微碱性（pH＝7.0~7.5）的情况与NC相容性良好。与传统的KNO₃、K₂SO₄消焰剂相比，PAAK能够和NC均匀混合，制备均质透明的单基发射药；PAAK发射药的燃烧残渣最少，占发射药质量的0.18%。     

离子液体体系卤水提锂的洗涤工艺研究

溶剂萃取法是盐湖提锂的重要工艺方法。采用磷酸三丁酯（TBP）/1-丁基-3-甲基咪唑双三氟甲基磺酰亚胺盐（[C₄mim][NTf₂]）离子液体体系对高镁锂比盐湖卤水中的锂进行萃取分离提取实验,对负载有机相的洗涤和反萃过程进行了研究。萃取实验：在TBP与[C₄mim][NTf₂]体积比为9∶1、相比（有机相与水相的体积比）为2∶1条件下,锂离子与其他离子的分离系数分别为β（锂/钠）=94.70、β（锂/钾）=148.85、β（锂/镁）=131.81。洗涤实验：系统考察了洗涤剂种类及浓度、相比、洗涤次数等因素对杂质离子洗脱率的影响,结果发现氯化锂和盐酸的混合溶液是从负载有机相中洗涤除去杂质离子的有效洗涤剂。洗涤过程适宜条件：洗涤剂中氯化锂浓度为4 mol/L、盐酸浓度为0.5 mol/L,相比为5∶1,洗涤次数为2次。反萃实验：用稀盐酸（1.0 mol/L）对负载有机相进行反萃取,在相比为1∶1条件下,单级反萃率达到97.81%。研究表明,离子液体体系作为一种新型萃取体系,在高镁锂比盐湖卤水中提取锂具有较好的应用前景。     

三种硫化氢吸收剂吸收效率对比及碘酸钾体系吸收条件优化研究

硫化氢具有腐蚀性与毒性，采用吸收剂吸收硫化氢气体是重要的脱硫处理方式。不同的吸收剂在吸收效率上存在较大差别。首先对比了三氯化铁体系、碘酸钾体系和碱性铁氰化钾体系三种不同硫化氢吸收剂的吸收效率。在此基础上重点优化了碘酸钾体系吸收条件参数，讨论了包含浓度、温度、pH、气体流量及时间等因素对硫化氢吸收效率的影响。并建立了四因素三水平正交试验研究较优吸收条件，得到正交试验优化吸收条件为：温度55℃，pH 6.01，硫化氢流量0.3 L·min^-1，吸收时间1 min，该条件下8%（质量）碘酸钾体系的三级吸收效率为51.56%。研究结果对硫化氢吸收处理提供了理论参考，也为间接电解法循环处理研究提供了支持。     

Multi-discharge EDM coring of single crystal SiC ingot by electrostatic induction feeding method

A new technique of EDM coring of single crystal silicon carbide (SiC) ingot was proposed in this paper. Currently single crystal SiC devices are still of high cost due to the high cost of bulk crystal SiC material and the difficulty in the fabrication process of SiC. In the manufacturing process of SiC ingot/wafer, localized cracks or defects occasionally occur due to thermal or mechanical causes resulted from fabrication processes which may waste the whole piece of material. To save the part of ingot without defects and maximize the material utilization, the authors proposed EDM coring method to cut out a no defect ingot from a larger diameter ingot which has localized defects. A special experimental setup was developed for EDM coring of SiC ingot in this study and its feasibility and machining performance were investigated. Meanwhile, in order to improve the machining rate, a novel multi-discharge EDM coring method by electrostatic induction feeding was established, which can realize multiple discharges in single pulse duration. Experimental results make it clear that EDM coring of SiC ingot can be carried out stably using the developed experimental setup. Taking advantage of the newly developed multi-discharge EDM method, both the machining speed and surface integrity can be improved.     

硫磷混合酸溶样重铬酸钾容量法测定全铁

介绍了硫磷混合酸溶样重铬酸钾容量法测定矿石中铁含量的方法和步骤。重点讨论了一线生产中的质量控制。     

生物质纤维和改性木质素对聚乳酸结晶性能的影响

采用改性木质素(MZS)作为成核剂,生物质纤维(BF)作为增强剂,通过双螺杆挤出机制备了生物降解的聚乳酸(PLA)/BF/MZS材料。采用差式扫量热仪(DSC)、电子万能试验机和扫描电子显微镜(SEM)分析了BF和MZS对PLA材料性能的影响。结果表明,BF和MZS有效提高了PLA的结晶能力和力学性能。当BF和MZS的含量分别为15%和1%时,PLA材料结晶度提高至67.1%,在50℃/min降温速率下仍具有较高的结晶能力。105℃等温结晶时,15%BF和1%MZS的PLA材料半结晶时间降低至9.0 s,比纯PLA缩短了72.2%。当PLA含有3%BF和1%MZS时,拉伸强度和冲击强度分别为70.1 MPa和7.4 kJ/m^2,比纯PLA分别提高了7.8%和10.4%,根据SEM显示,当BF含量为3%时,在PLA材料中分布较均匀。     

Crystal violet dye sorption and transport in/through biobased PVA cryogel membranes

Cryogels based on poly(vinyl alcohol) [PVA] and three types of bioinsertions such as scleroglucan, cellulose microfibers, and zein, respectively, have been prepared using capacity of PVA to crosslink by repeated freezing–thawing cycles. The effect of the incorporation of biopolymers on the properties of PVA cryogel has been studied by using several techniques such as: scanning electron microscopy, differential scanning calorimetry, and Fourier transform infrared studies. The obtained biobased cryogel membranes were subjected to sorption and to diffusion experiments using Crystal Violet (CV), a dye commonly used in the textile industry and in medicine. Image analysis with CIELAB system was used both to monitor the cryogels loading with CV and to gain insight in the dye state into the gel, in correlation with the bioinsertion type and gels morphology. Dye diffusion but also sorption capacity of the cryogels was found to be closely related to the type of biopolymer. In this article the equilibrium (sorption isotherms) and transport properties (diffusion and permeability coefficients) of CV, in/through physical cross‐linked PVA hydrogel membranes with bioinsertions has been reported. The highest efficiency for the CV removal from aqueous solutions was obtained for the PVA/Scl cryogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41838.