Parallel microwave chemistry in silicon carbide microtiter platforms: a review

In this review, applications of silicon carbide-based microtiter platforms designed for use in combination with dedicated multimode microwave reactors are described. These platforms are employed not only for the efficient parallel synthesis of compound libraries, but also in the context of high-throughput reaction screening/optimization and a number of other (bio)analytical and biomedical applications. Since the semiconducting plate material (silicon carbide) is strongly microwave absorbing and possesses high thermal conductivity, no temperature gradients across the microtiter plate exist. Therefore, many of the disadvantages experienced in attempting to perform microtiter plate chemistry under conventional microwave conditions can be eliminated. In general, the silicon carbide-based microtiter platforms allow sealed vessel processing (either directly in the well or in glass vials placed into the wells) of volumes ranging from 0.02–3.0 mL at a maximum temperature/pressure limit of 200°C/20 bar. Depending on the specific plate and rotor configuration, a maximum of 80–192 transformations can be carried out in parallel in a single microwave irradiation experiment under strict temperature control. A platform type utilizing HPLC/GC vials as reaction vessels allows analysis directly from the reaction vessel eliminating the need for a transfer step from the reaction to the analysis vial. The latter system is particularly useful for analytical applications as well as reaction optimization/screening.     

Diffusion Processes in Semiconductor Structures During Microwave Annealing

We present the results of experimental studies of the influence of microwave radiation on the diffusion processes in two different semiconductor materials, namely, InGaAs heterostructures with quantum wells and boron-ion implanted silicon. The experiments were performed in a 30 GHz gyrotron device for microwave processing of materials. We compare the results of heterostructure annealing under microwave and thermal heating. It is found that under microwave heating, the coefficient of In–Ga interdiffusion in InGaAs heterostructures is about an order of magnitude smaller than that under thermal heating at the same temperatures, while the activation energy of diffusion is approximately the same for both heating regimes. In boron-ion implanted silicon, the sheet resistance after annealing at a higher microwave power turns out to be lower than that after annealing at the same temperature and a lower power. This indicates that the microwave field exerts a nonthermal effect on electric activation of dopant atoms. The results show the possibility of optimization of the microwave-annealing regimes to obtain the maximum electric activation at a limited diffusion spreading of the density profile of implanted atoms.     

高温空气电阻炉内强化传热性能实验研究

本文对基于碳化硅泡沫陶瓷的高温空气电阻炉内的传热性能进行了实验研究。通过在高温空气电阻炉内插入不同数量的泡沫陶瓷片,研究陶瓷片数量对空气出口温度的影响。同时研究了泡沫陶瓷片的位置对空气出口温度的影响。实验结果表明:当炉膛内不插入泡沫陶瓷片时,在空气流量为200 m~3/h时,空气出口温度为650℃,当炉膛内插入五块泡沫陶瓷片时,空气出口温度达到980℃。本文从实验方面验证了将碳化硅泡沫陶瓷应用到太阳能热发电的吸收器中,强化空气与吸热材料之间的换热的可行性。     

Direct-energy processes and phase transitions in silicon

Summary The phase transition of amorphous to single-crystal silicon has been investigated not only by conventional heating in a furnace but under direct-energy processes like pulsed-laser and ion beam irradiation. The first method allows the experimental determination of the free-energy-temperature diagram for amorphous, liquid and crystalline silicon. Due to the very fast heating and cooling the amorphous-to-liquid transition can be investigated in both directions. Ion beam irradiation induces either a layer-by-layer amorphization or crystallization by the movement of the initial α-Si/c-Si interface according to the substrate temperature. The two processes are governed by different types of defects created by the beam in the amorphous and in the crystalline side of the interface. The existence of a native-oxide layer at the interface between single crystal and deposited layer retards the ion beam crystallization until oxygen atoms are dispersed by beam mixing in the matrix. A recent alternative way of crystallizing deposited layers is by short high-temperature anneals obtained by incoherent-light irradiations. In this case the rupture of the native-oxide layer is achieved by the agglomeration of oxide into beads, thus allowing the realignment. This technique appears to be particularly promising for several technological applications. In honour of Prof. Fausto Fumi on the occasion of his retirement from teaching.     

Bulk and Surface Quenching of Structural Steel: Morphological Analysis of the Structure

Structures formed in medium-carbon low-alloy steels during bulk quenching from furnace heating and surface quenching initiated by a low-power high-current electron beam are investigated by the methods of diffraction electron microscopy. The influence of the carbon concentration, initial austenite grain size, and cooling rate on the morphology of martensitic crystals and self-tempered carbide particles, long-range stress fields inside a packet and plates, and their dislocation substructure is analyzed. The temperature intervals for the formation of high-temperature plate martensitic crystals and packet (lath) martensite are estimated. It is demonstrated that the structure formed at ultrahigh heating and cooling rates is determined mostly by the morphology of martensite in the initial steel samples.     

微波辐照对胶原蛋白三股螺旋结构的影响

胶原蛋白的三股螺旋结构是其不同于其他蛋白质的特殊结构，也是其具有特殊功能的基础，然而，胶原的三股螺旋结构易在外界条件的影响下被破坏。目前微波已被越来越多的应用于胶原蛋白的提取和改性过程，但是关于微波辐照对胶原蛋白结构影响的研究还相对较少。首先从牛跟腱中提取胶原蛋白，然后采用0.5 mg·mL-1的胶原蛋白溶液在30 ℃下以微波辐照保温为实验样，水浴加热和未经加热处理为对比样，最后采用紫外-可见光谱、傅里叶变换红外光谱、圆二色谱以及荧光发射光谱等方法，对不同加热方法中胶原蛋白的三股螺旋结构和超分子结构进行表征，研究了微波辐照对胶原蛋白结构的影响。实验结果表明，在低于胶原变性温度的条件下，无论是微波辐照还是水浴加热都不会破坏胶原蛋白的三股螺旋结构，也不会使胶原蛋白变性。但是，与水浴加热相比，微波辐照会对胶原蛋白的聚集行为产生抑制作用。微波辐照对胶原蛋白的作用既有与常规加热相同的热效应，又有常规加热过程中不存在的非热效应，非热效应表现为抑制胶原蛋白的聚集行为。研究结果可为微波场中胶原蛋白结构和性质的变化提供科学依据。     

Research on pyrolysis of toluene under microwave heating by using ReaxFF molecular dynamics simulations

ReaxFF molecular dynamics (MD) simulations are performed to study high-temperature pyrolysis of toluene under microwave heating. It is observed that the temperature of the reaction system under microwave heating has a rapidly rising stage, which is similar to the phenomenon of thermal runaway often appeared in reactions under microwave heating. Simulations indicate that the consumption rate of toluene and generating rates of H₂ and CH₄ obtained under microwave heating are always lower than those obtained under conventional heating at the early stage. Analyses of the pyrolysis of toluene show that ReaxFF MD simulations can provide an efficient way to study chemical reactions under microwave heating.     

强激光辐照对3C-SiC晶体结构稳定性的影响

使用基于密度泛函微扰理论的线性响应方法, 模拟研究了强激光辐照对闪锌矿结构的碳化硅晶体结构稳定性的影响. 通过计算在不同电子温度下3C-SiC晶体的声子色散曲线, 发现3C-SiC的横声学声子频率随电子温度的升高会出现虚频, 其临界电子温度是3.395 eV. 结果表明, 在强激光辐照下3C-SiC 晶体变得不稳定, 这与以前对金刚石结构的碳、硅和闪锌矿结构的砷化镓、锑化铟的研究结果非常类似. 电子温度在0–4.50 eV 范围内时, 3C-SiC晶体在Γ 点的LO-TO分裂度随电子温度的升高而增大, 超过4.50 eV后随电子温度的升高而减小. 这表明只有在足够强的激光辐照下, 电子激发才会削弱晶体的离子性强度.     

Experimental evidence of selective heating of molecules adsorbed in nanopores under microwave radiation

We have performed in situ quasielastic neutron scattering (QENS) measurements on zeolite-guest systems under microwave irradiation, for comparison with corresponding simulations. Both experiment and simulation reveal selective heating of methanol in silicalite, but little to no heating of benzene in silicalite. Effective translational and rotational temperatures extracted from QENS data under microwave heating were found to depend on microwave power. In agreement with simulation, QENS rotational temperatures significantly exceed translational ones at high microwave power, thus providing the first microscopic proof for athermal effects in microwave-driven nanopores.     

燃煤底灰-微波法降解亚甲基蓝的研究

燃煤底灰中含有丰富的金属,这些金属在微波作用下可以对有机物进行有效降解,燃煤底灰-微波法降解亚甲基蓝溶液主要是通过羟基自由基来降解有机物的。底灰中的金属及稀有金属可以作为深度氧化有机物的催化剂,可降低处理成本、减少环境污染。考查了燃煤底灰用量、H₂O₂用量、以及微波时间对亚甲基蓝降解效率的影响,并测定了亚甲基蓝溶液处理前后的紫外可见光谱。结果表明,亚甲基蓝在燃煤底灰与H₂O₂微波条件下降解率接近100%。燃煤底灰的用量增加可以加快反应进程,增加亚甲基蓝的降解;H₂O₂的增加可以提供更多的·OH,加快反应进程,但当增加到一定量后,对反应进程的影响减弱;微波时间的加长可以提高反应温度,促使亚甲基蓝完全降解。对于0.125 g·L-1的亚甲基蓝,加入1.0 g燃煤底灰、5 mL H₂O₂在中温微波下反应4 min即可全部降解。     

Milestone's microwave labstation

In the actual research world, the laboratory has different needs, correlated to the field and level of research. Some researchers work with small volumes, others with large ones; in homogeneous or heterogeneous conditions, with solvent or dry media; at normal pressure or under pressure. And if we look at the field of drug discovery, during the last decade combinatorial chemistry, along with combinatorial and parallel synthesis, has held a fundamental role. This technique is becoming more and more popular because it concerns the quick synthesis of a high number of compounds with pharmaceutical activity. In this context, the efficency of microwave heating to speed up chemical reactions matches perfectly the need of short and clean chemical reactions. Milestone's MicroSYNTH labstation combined with the microwave technology, satisfies the need of the various chemical research laboratories. In fact, the different accessories that can be fitted inside the multimode microwave cavity cover a large ramp of volume, from 2 ml to 500 ml, different values of pressure, from 1 to 50 bar, and give the possibility to reach temperature up to 250 degrees C. And this is not all, you can also choose to perform one reaction at a time or to perform parallel synthesis with Milestone's rotors for up to 24 reactions at the same time.     

Formation of titanium oxide films on the surface of porous silicon carbide

The influence of rapid thermal annealing (RTA) on the properties of a titanium film on the surface of porous silicon carbide is considered. It is shown that an increase in the RTA temperature to 900°C stabilizes the phase composition of the forming titanium oxide over the film, which is identified as rutile. Due to the formation of titanium oxide nanoclusters under the action of RTA, an additional photoluminescence band arises near 2.5 eV. Based on Auger spectrometry data, a multilayer model to calculate the optical parameters of titanium oxide films covering porous silicon carbide is suggested.     

Application of continuous flow and alternative energy devices for 5-hydroxymethylfurfural production

Dehydration of fructose and glucose in dipolar, aprotic solvents leads to formation of 5-hydroxymethylfurfural. Conditions for continuous flow reactions using a cartridge-based reactor system and a stop-flow microwave reactor were established showing very good product yields and selectivity without the limitation of a batch process such as upscaling and precise temperature monitoring and control. A maximum product HPLC yield of 90.3% under cartridge-based heating and 85.6% under microwave heating could be achieved using mild and quick reaction conditions. Formation of levulinic acid as a by-product could not be detected under the optimized reaction conditions.     

Real-time Thermal Imaging of Microwave Accelerated Metal-Enhanced Fluorescence (MAMEF) Based Assays on Sapphire Plates

In this paper, we describe an optical geometry that facilitates our further characterization of the temperature changes above silver island films (SiFs) on sapphire plates, when exposed to microwave radiation. Since sapphire transmits IR, we designed an optical scheme to capture real-time temperature images of a thin water film on sapphire plates with and without SiFs during the application of a short microwave pulse. Using this optical scheme, we can accurately determine the temperature profile of solvents in proximity to metal structures when exposed to microwave irradiation. We believe that this optical scheme will provide us with a basis for further studies in designing metal structures to further improve plasmonic-fluorescence clinical sensing applications, such as those used in microwave accelerated metal-enhanced fluorescence (MAMEF).     

基于激光旋转加热的非导电材料高温光谱发射率测试方法与装置

光谱发射率是表征材料热物理性能的重要参数。对于非导电材料的高温光谱发射率测试,一般采用高温加热炉加热或辐射加热的方式来进行发射率测试,存在的问题是采用高温石墨炉加热时,样品可能会与高温石墨发生化学反应,从而破坏材料原有物性;采用辐射加热,一般是单向静止加热,会存在样品温场梯度非均匀分布的问题。基于激光旋转加热和样品/黑体整体一体化设计,提出了一种“样品动中测”的非导电材料高温光谱发射率测试新方法,建立了相应的测量模型,突破了传统的 “样品静中测”的局限,样品与参考黑体共形一体化设计,采用微区域光谱辐射成像方法,同时测量参考黑体和样品的光谱辐射能量与温度。建立了激光旋转加热状态下的热传导方程,对典型样品材料的温度分布进行了仿真计算,结果表明旋转样品温场分布较为均匀,分析了温场分布与红外光谱发射率测量误差间的关系,给出了适用于本测试方法的材料的热导率下限值。基于该方法,搭建了相应的测量装置,对典型材料碳化硅在1 000 K时的光谱发射率进行了测试,在4 μm处对各个典型高温温度点的光谱发射率进行了测试,得到了碳化硅材料在红外波段的光谱发射率波长变化和温度变化规律特性。与国外的测量结果进行了比对,结果较为一致,验证了激光旋转加热光谱发射率测试方法的可行性。采用此方法,不破坏样品本身的理化特性,样品加热升温速度快,测量温度范围上限高,有效减小了激光静止单向加热带来的温度不均匀性,可同时测量出样品和参考黑体的光谱辐射亮度及温度,无需另外再设计标准高温黑体,解决了现有非导电材料高温光谱发射率测试中非均匀加热和辐射能量同步比对测量的问题,可应用于多种非导电材料高温光谱发射率的测试。     

Investigation of the 4H-SiC surface

The silicon carbide (SiC) surface is more complex than that of silicon and can be carbon-terminated or silicon-terminated, and can exist as several reconstructions. Investigations of the surface structure as a function of temperature, under ultrahigh vacuum (UHV) conditions using scanning tunneling microscopy (STM) and low energy electron diffraction (LEED), are presented. The 4H-SiC surface can be passivated using a silicon deposition/evaporation technique to reconstruct the surface. This has a significant effect on the electrical behaviour of metal contacts to the silicon carbide surface, critical in any electronic device. Atomic resolution STM studies of the 4H-SiC surface have revealed step features and micropipe defects in unprecedented detail. STM has also been used to image clusters of metal deposited on the 4H-SiC surface. The effect of annealing on the behaviour of these nickel clusters is also presented. The surface of the silicon carbide is extremely important in the fabrication of silicon carbide electronic devices and this paper presents a discussion of the SiC surface with particular reference to its impact on SiC device applications in power electronics.     

微波辐射法制备水溶性CdTe量子点及其光谱学研究

用半胱胺作为稳定剂,采用微波辐射加热的方法快速合成了水溶性的CdTe量子点。吸收光谱和荧光光谱表明所合成的量子点具有优异的发光性能。透射电子显微镜(TEM)和X射线粉末衍射(XRD)表征了量子点的结构和粒径分布。通过荧光发射光谱研究了反应温度、加热时间和配体浓度对量子点晶体生长速度的影响。反应温度提高或稳定剂半胱胺的浓度减小,纳米晶体的生长速度加快。在一定温度下,随着反应时间的延长,量子点发射波长发生红移。与传统的水相回流方法相比微波加热制备水溶性的CdTe量子点具有反应速度快、得到的量子点尺寸分布均匀、半峰宽较窄和量子产率较高等特点。     

Model of silicon carbide formation on porous substrates

The formation of thin silicon carbide layers as a result of solid-phase processes is related to the evolution of nanoscale porosity and chemical reactions on pore surfaces. Numerical experiments, which simulate blistering under the action of Xe+ ions in the metal-insulator (Mo/Si) bilayer make it possible to establish the relationship between the porosity parameters and layer stresses and the irradiation conditions. Similar patterns in the formation of defects (pores and cracks) in crystalline silicon characterize its interaction with carbon dioxide when silicon carbide is formed. The calculated characteristics of the nucleation in the Mo/Si bilayers are analyzed to optimize the solid-phase epitaxy of silicon carbide.     

Electrically Detected Magnetic Resonance Signal Intensity at Resonant Frequencies from 300 to 900 MHz in a Constant Microwave Field

A method for electrically detected magnetic resonance (EDMR) measurement at different ESR frequencies under a constant alternating magnetic field has been established wherein the accurate relationship between EDMR signal intensity (from a photoexcited silicon crystal and a silicon diode) and a resonant frequency of 300 to 900 MHz (UHF band) was systematically clarified. EDMR signal intensity from a photoexcited silicon crystal against a resonant frequency fitted the curve of y = a(1 - e(-bx)) well, which approached a constant value at higher frequencies. The increase in the EDMR signal intensity from the silicon diode at higher resonant frequencies was smaller than that from the photoexcited silicon crystal. The difference can be explained by the influence of the skin effect; i.e., the microwaves do not penetrate deep into a highly conductive sample at higher frequencies. EDMR signal intensities of samples vs microwave power were measured at 890 MHz. The EDMR signal intensity from the silicon diode continued to increase as the microwave power was increased, while the signal intensity from the photoexcited silicon crystal saturated within the range. The difference can be similarly explained: due to the skin effect, the microwaves gradually penetrate into the silicon diode as the power increases, so that even when saturation has been reached outside, the microwave field inside the diode does not reach the saturation level.     

A preliminary study on numerical simulation of microwave heating process for chemical reaction and discussion of hotspot and thermal runaway phenomenon

The nonlinear process of microwave heating chemical reaction is studied by means of numerical simulation. Especially, the variation of temperature in terms of space and time, as well as the hotspot and thermal runaway phenomena are discussed. Suppose the heated object is a cylinder and the incident electromagnetic (EM) wave is plane wave, the problem turns out to be a coupling calculation of 2D multi-physical fields. The integral equation of EM field is solved using the method of moment (MoM) and the thermal conduction equation is solved using a semi-analysis method. Moreover, a method to determine the equivalent complex permittivity of reactant under the heating is presented in order to perform the calculation. The numerical results for water and a dummy chemical reaction (A) show that the hotspot is a ubiquitous phenomenon in microwave heating process. When the radius of the heated object is small, the highest temperature occurs somewhere inside the object due to the concentration of the EM wave. While the radius increases to a certain degree, the highest temperature occurs somewhere close to the surface due to the skin effect, and the whole high temperature area shows crescent-shaped. That is in accordance with basic physical principles. If the radius is kept the same in the heating process, the hotspot position of water does not change, while that of reaction A with several radius values varies. For either water or A, the thermal runaway phenomenon in which small difference of radius results in large difference of highest temperature, occurs easily when the radius is small. On the contrary, it is not evident when the radius is large. Moreover, it is notable that the highest temperature in water shows oscillating decreasing trend with the increase of radius, but in reaction A almost decreases monotonously. Further study should be performed to determine if this difference is only an occasional occurrence. Supported by the National Natural Science Foundation of China (Grant Nos. 60801035 and 60531010)