Aerosol‐Assisted Synthesis of Porous TiNxOy@C Nanocomposites

Porous TiN_xO_y‐based particles were synthesized by an aerosol spray process. At first, the starting sol solution containing the metal precursor and the nitrogen source is sprayed to form an aerosol that is subsequently pyrolysed at different temperatures. The obtained dried particles are an amorphous coordination “polymer” rich in carbon and nitrogen. These “glassy” particles are finally thermally treated at 800 °C, promoting the crystallization of the particles and the release of a major part of the carbon. As the particles keep their original shape, carbon loss and density increase during the crystallization step and lead to the development of an accessible pore structure. The process was analyzed and extended to the synthesis of other metal nitrides, such as VN and W₂N, thereby showing its general validity for the production of functional nanocrystalline nitride ceramics with high porosity still occupying a relatively small volume, and otherwise not easily accessible.     

Preparation and lithium doping of gallium oxynitride by ammonia nitridation via a citrate precursor route

Gallium oxynitride, isostructural to hexagonal gallium nitride (h-GaN), was obtained by ammonia nitridation of a precursor prepared from the addition of citric acid to an aqueous solution of gallium nitrate. Gallium oxynitride produced at 750 °C had a small amount of gallium vacancies, and was formulated as (Ga_0.89□_0.11) (N_0.66O_0.34) where the symbol □ stands for gallium vacancy. Both the gallium vacancies and oxygen substituted for nitrogen were randomly distributed within the structure. The amount of vacancies decreased with nitridation temperatures in the range of 750-850 °C. Approximately, 10 at% Li⁺ was doped into the gallium oxynitride, using a similar preparation with the additional presence of lithium nitrate, resulted in the random substitution of Ga³⁺ in an atomic ratio of Li/Ga<1 at 750 °C. Oxygen was codoped with lithium and substituted nitrogen in the wurtzite-type crystal lattice. These substitutions reduced the electrical conductivity in the gallium oxynitride semiconductor. A new oxynitride, Li₂Ga₃NO₄, was also obtained with Li₂CN₂ impurity using similar preparations from a mixture of Li/Ga?1. The crystal structure was isostructural with h-GaN, and was refined as P6₃mc with a=0.31674(1) nm, and c=0.50854(2) nm. The Ga and Li occupancies at the 2b site were refined to be 0.6085 and 0.3915, respectively, assuming that the other 2b site was randomly occupied with 1/5O and 4/5N. When the new compound was washed for over 1 min for the removal of Li₂CN₂ impurities, it was decomposed to a mixture of α-GaOOH and α-LiGaO₂. The as-prepared product with Li/Ga=1 showed the highest intensity in yellow luminescence among the products under excitation at 254 nm.     

Synthesis of poly(isopropenylphenoxy propylene carbonate) and its facile side‐chain functionalization into hydroxy‐polyurethanes

4‐Isopropenyl phenol ( 4‐IPP ) is a versatile dual functional intermediate that can be prepared readily from bisphenol‐A ( BPA ). Through etherification with epichlorohydrin to the phenolic group of 4‐IPP , it can be converted into 4‐isopropenyl phenyl glycidyl ether ( IPGE ). On further reaction with carbon dioxide in the presence of tetra‐n‐butyl ammonium bromide ( TBAB ) as the catalyst, IPGE was transformed into 4‐isopropenylphenoxy propylene carbonate ( IPPC ) in 90% yield. Cationic polymerization of IPPC with strong acid such as trifluoromethanesulfonic acid or boron trifluoride diethyl etherate as the catalyst at ?40 °C gave a linear poly(isopropenylphenoxy propylene carbonate), poly( IPPC ), with multicyclic carbonate groups substituted uniformly at the side‐chains of the polymer. The cyclic carbonate groups of poly( IPPC ) were further reacted with different aliphatic amines and diamines resulting in formation of polymers with hydroxy‐polyurethane on side‐chains. Syntheses, characterizations of poly( IPPC ) and its conversion into hydroxy‐polyurethane crosslinked polymers were presented. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 802–808     

Synthesis of Mg–Al–Fe–NO3 layered double hydroxides via a mechano-hydrothermal route

Mg–Al–Fe–NO₃ layered double hydroxides (LDHs) with a constant Mg²⁺/(Al³⁺ + Fe³⁺) molar ratio but varying Al³⁺/Fe³⁺ molar ratios were successfully synthesized by a mechano-hydrothermal (MHT) method from Mg(OH)₂, Al(OH)₃ and Fe(NO₃)₃·9H₂O or Mg(NO₃)₂·6H₂O as starting materials. The resulting LDHs (MHT-LDHs) were characterized by XRD, TEM, SEM, FT-IR, and zeta potential, size distribution and specific surface area analyses. It was found that pre-milling played a key role in the LDH formation during subsequent hydrothermal treatment. The MHT route is advantageous in terms of low reaction temperature compared with the conventional hydrothermal method, and the target products are of high crystallinity and good dispersion compared with the conventional mechanochemical (MC) method. The MHT-LDHs had higher specific surface area and zeta potential, and lower hydrodynamic diameter than LDHs obtained by MC method (MC-LDHs). Furthermore, the removal of Cr(VI) from aqueous solutions using the LDHs was examined, showing that the MHT-LDHs are of higher removal efficiency than MC-LDHs for the heavy metal pollutant.     

Diisocyanate route as a convenient method for the preparation of novel optically active poly(amide-imide)s based on N-trimellitylimido-S-valine

A new class of optically active poly(amide-imide)s based on an α-amino acid was synthesized via direct polycondensation reaction of different diisocyanates with a chiral diacid monomer. The step-growth polymerization reactions of N-trimellitylimido-S-valine (TISV) (1) with 4,4′-methylene-bis(4-phenylisocyanate) (MDI) (2) was performed under microwave irradiation, as well as solution polymerization under graduate heating and reflux conditions. The optimized polymerization conditions for each method were performed with tolylene-2,4-diisocyanate (TDI) (3), hexamethylene diisocyanate (HDI) (4), and isophorone diisocyanate (IPDI) (5) to produce optically active poly(amide-imide)s via diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.02-1.10 dL/g. Decomposition temperatures for 5% weight loss (T₅) occurred above 300 °C (by TGA) in nitrogen atmospheres. These polymers are optically active, thermally stable and soluble in amide-type solvents. Some structural characterization and physical properties of this new optically active poly(amide-imide)s are reported.     

水相湿法改性纳米碳酸钙表面性质的研究

用特定的表面改性剂在水相中对纳米碳酸钙的悬浮液进行了湿法改性。红外光谱和热失重分析证明,改性剂与碳酸钙之间以化学键结合;沉降体积和接触角的测定结果说明改性粒子在液体石蜡中的润湿性和疏水性得到了提高;透射电子显微镜照片显示改性粒子在液体石蜡中有更好的分散性;体系粘度实验表明改性粒子与液体石蜡之间有较好的相容性。     

New synthetic way to prepare 2-aryl-8-(piperidin-4-yl)-5,7-dimethoxy-4H-chromen-4-one as key intermediate for CDK inhibitor

As an important intermediate to study cyclin-dependent kinase(CDK)inhibitors,2-aryl-8-(piperidin-4-yl)-5,7-dimethoxy-4H- chromen-4-one derivatives were prepared usingβ-diketone route with low yield.In our study,chalcone route has been investigated and the result suggested that the benzaldehydes substituted with electron-donating group give much better yield thanβ-diketone route.This new method will be an efficient way to start further research on new anticancer flavonoids.     

Facile solvothermal synthesis of graphene-MnOOH nanocomposites

In this paper, we report a facile solvothermal route capable of aligning MnOOH nanocrystals on graphene. X-ray diffraction (XRD) and transmission electron microscopy (TEM) observations indicate that the exfoliated graphene sheets are decorated randomly by MnOOH nanocrystals, forming well-dispersed graphene-MnOOH nanocomposites. Dissolution-crystallization and oriented attachment are speculated to be the vital mechanisms in the synthetic process. The attachment of additives, such as MnOOH nanoparticles, are found to be beneficial for the exfoliation of GO as well as preventing the restack of graphene sheets. Moreover, cyclic voltammetry (CV) analyses suggest that the electrochemical reversibility is improved by anchoring MnOOH on graphene. Notably, the as-fabricated nanocomposites reveal unusual catalytic performance for the thermal decomposition of ammonium perchlorate (AP) due to the concerted effects of graphene and MnOOH. This template-free method is easy to reproduce, and the process proceeds at a low temperature and can be readily extended to prepare other graphene-based nanocomposites.     

Mechanoluminescence and thermoluminescence of Mn doped ZnS nanocrystals

This paper reports the synthesis of ZnS:Mn nanocrystals by the chemical route in which mercaptoethanol was used as the capping agent. The particle size of such nanocrystals was measured using XRD and TEM patterns and was found to be in between 3and 5 nm. It was found that the peak position of TL glow curve and the TL intensity of ZnS:Mn nanoparticles increases as the particle size is decreased. The isothermal decay technique is used to determine the trap-depth. The stability of the charge carriers in the traps increase with the decrease in size of the nanoparticles. The higher stability may be attributed to the higher surface/volume ratio and also to the increase in the trap-depth with decreasing particle size. When a ZnS:Mn nanocrystal is deformed the peak intensity I_m increases linearly with the increasing height of the load. After I_m, initially the ML intensity decreases at a fast rate, and later on it decreases at a slow rate. The ML in ZnS:Mn nanocrystals can be understood on the basis of the piezoelectrically induced electron detrapping model.     

激光冲击与渗碳复合工艺改善12CrNi3A钢磨损性能

为了提高12CrNi3A钢渗碳层质量及其抗磨损性能,提出了激光冲击与渗碳不同顺序复合的工艺方法。球磨实验结果表明,相比渗碳处理,激光冲击后渗碳试样的比磨损率降低了51%,而渗碳后激光冲击强化试样的比磨损率降低了13%,说明激光冲击后渗碳的复合工艺能更好地改善抗磨损性能。在摩擦系数差别不大的情况下,抗磨损性能的提升与显微硬度提高、微观组织变化有关,从这两方面讨论抗磨损性能提升的机理。研究表明:激光冲击强化可促进渗碳的过程,强化后渗碳形成的渗碳层结构致密,大量细小碳化物形成,固溶强化、第二相强化作用增强,显微硬度增大,从而提高抗磨损性能;而渗碳后激光冲击强化只使渗层表面发生了形变强化,与渗碳工艺相比,显微硬度略有提高,抗磨损性能提高有限。