Solution-based Chemical Strategies to Purposely Control the Microstructure of Functional Materials

Micro/nanostructured crystals with controlled architectures are desirable for many applications in optics, electronics, biology, medicine, and energy conversions. Low-temperature, aqueous chemical routes have been widely investigated for the synthesis of particles, and arrays of oriented nanorods and nanotubes. In this paper, based on the ideal crystal shapes predicted by the chemical bonding theory, we have developed some potential chemical strategies to tune the microstructure of functional materials, ZnS and Nb205 nanotube arrays, MgO wiskers and nestlike spheres, and cubic phase Cu2O microcrystals were synthesized here to elucidate these strategies. We describe their controlled crystallization processes and illustrate the detailed key factors controlling their growth by examining various reaction parameters. Current results demonstrate that our designed chemical strategies for tuning microstructure of functional materials are applicable to several technologically important materials, and therefore may be used as a versatile and effective route to the controllable synthesis of other inorganic functional materials.

SrGa_(12)O_(19):The first low-ε_(r) Ga-based microwave dielectric ceramic with anomalous positiveτ_(f)

Dielectric ceramics with low permittivity(ε_(r)),high quality factor(Q×f),and near-zero resonant frequency(τ_(f))in the microwave bands are key materials used in fifth/sixth-generation(5G/6G)telecommunication,whileτ_(f) of most low-εr microwave dielectric ceramics is relatively negative.In this work,the first low-εr Ga-based ceramic SrGa_(12_O_(19) with an anomalous positiveτ_(f) was reported,and the causes of the positiveτ_(f),intrinsic polarization,and loss mechanism were systematically studied.X-ray diffraction(XRD)and transmission electron microscopy(TEM)revealed that the SrGa_(12_O_(19) ceramic formed a pure hexagonal magnetoplumbite structure with spinel blocks and rock-salt blocks stacked along the crystallographic c-axis.When sintered at 1430℃,it possessed the optimal microwave dielectric properties of a lowεr of 14.46,high Q×f of 64,705 GHz,and exceptional positiveτ_(f) of+55.7 ppm/℃,along with a low linear thermal expansion coefficient(αL)of 11.617 ppm/℃.The large positive deviation betweenεr andεr(C–M)of 45.31%resulted from the rattling effect of atoms in the rock-salt block.The unique positiveτ_(f)(+55.7 ppm/℃)was governed by the rattling effect,resulting in a positiveταm(the temperature coefficient of ion polarizability)of 8.489 ppm/℃ and a large negative temperature coefficient of permittivity(τε)of−132.864 ppm/℃.Phillips–Vechten–Levine(P–V–L)chemical bond theory revealed greater contributions of the spinel block to bond ionicity(fi,52.95%),permittivity(ε,55.15%),bond energy(E,56.87%),and lattice energy(U,74.88%)than those of the rock-salt block.The intrinsic dielectric properties were analyzed using infrared(IR)reflectivity spectra.The favorable performance of the SrGa_(12_O_(19) ceramic indicated that it is a novelτ_(f) compensator.This selection of compounds with different structural layer combinations provides a new idea for exploring excellent microwave dielectric ceramics.

Theoretical Investigation on Mechanical and Thermal Properties of a Promising Thermal Barrier Material:Yb_3Al_5O_(12)

An investigation on the mechanical and thermal properties of Yb3Al5O12 is conducted by a combination of first- principles calculations and chemical bond theory calculation. Density functional theory （DFT） computations were performed for the structural, mechanical, and thermal properties, and the results are confirmed by chemical bond theory. Based on the calculated equilibrium crystal structure, heterogeneous bonding nature is revealed. The full set of elastic constants and mechanical properties of Yb3Al5O12 are presented for the first time. The thermal expansion coefficient of Yb3Al5O12 is calculated to be 7.5 × 10^-6 K-1 by chemical bond theory. In addition, the minimum thermal conductivity of Yb3Al5O12 is estimated to be 1.22 W m-t K-1, and the origin of such low thermal conductivity is discussed. Our theoretical results highlight the potential of Yb3Al5O12 as a prospective thermal barrier coating material.

Pulling growth technique towards rare earth single crystals

Pulling growth technique serves as a popular method to grow congruent melting single crystals with multiscale sizes ranging from micrometers to centimeters.In order to obtain high quality single crystals,the crystal constituents would be arranged at the lattice sites by precisely controlling the crystal growth process.Growing interface is the position where the phase transition of crystal constituents occurs during pulling growth process.The precise control of energy at the growing interface becomes a key technique in pulling growth.In this work,we review some recent advances of pulling technique towards rare earth single crystal growth.In Czochralski pulling growth,the optimized growth parameters were designed for rare earth ions doped Y_3Al_5O_(12)and Ce:(Lu_(1-x)Y_x)_2Si O_5on the basis of anisotropic chemical bonding and isotropic mass transfer calculations at the growing interface.The fast growth of high quality rare earth single crystals is realized by controlling crystallization thermodynamics and kinetics in different size zones.On the other hand,the micro pulling down technique can be used for high throughput screening novel rare earth optical crystals.The growth interface control is realized by improving the crucible bottom and temperature field,which favors the growth of rare earth crystal fibers.The rare earth laser crystal fiber can serve as another kind of laser gain medium between conventional bulk single crystal and glass fiber.The future work on pulling technique might focus on the mass production of rare earth single crystals with extreme size and with the size near that of devices.

Fast growth of cerium-doped lutetium yttrium orthosilicate single crystals and their scintillation properties

The growth of high-quality and large-size cerium-doped lutetium yttrium orthosilicate(Ce:(LuY)2 SiO5,Ce:LYSO)crystals with lower cost has great influence on their applications in various physical devices.According to the chemical bonding theory of single crystal growth,the fast thermodynamic growth direction of Ce:LYSO is[010]direction.In this work,the maximum pulling rate of 3.5 mm/h is obtained along[010]direction of Ce:LYSO via the Czochralski(Cz)method.Finally,Ce:LYSO bulk single crystals with diameter of 64 mm and length of 220 mm and mass of 4.2 kg are grown.The luminescence performance of low-doped Ce:LYSO for nuclear irradiation(^(22)Na)detector device was studied.Light yield of26193 ph/MeV and decay time of 38 ns are obtained.The present work provides a promising fast growth approach to achieving large size functional bulk crystal via both thermodynamic and kinetic controls.

Theoretical investigations on the thiol–thioester exchange steps of different thioesters

As the rate-determining step in native chemical ligation reactions, the thiol–thioester exchange step is important in determining the efficiency of the ligations of peptides. In the present study, systematic theoretical calculations were carried out on the relationships between the structure of different thioesters and the free energy barriers of the thiol–thioester exchange step. According to the calculation results, the thiol–thioester exchange step is disfavored by the steric hindrance around the carbonyl center, while the electronic effect（i.e. conjugation and hyper-conjugation effects） becomes important when the steric hindrance is insignificant.