Study on the thermodynamics and the growth kinetics of synthesis of the β-SiC whiskers

The thermodynamics and the growth kinetics of synthesis of the SiC whiskers (SiC w ) from rice hulls are studied in this paper. The results show that the intimate contact of SiO 2 with C in the rice hulls resulted in the formation of SiC particle (SiC p ) at lower temperature, and the external ash of the hulls (w (SiO 2 )>98%) is the main silicon source for SiCw growth. The metallic composite catalyst increases the selectivity for SiCw growth and the reaction rate. The growth mechanism of the SiCw can be characterized as the VLS (vapour liquid solid) with the presence of the whisker forming catalyst: from SiC nucleation through enlargement and growing with the <1 1 1> crystallographic orientation in a certain diameter, then the SiC w is a complete single crystal of β SiC. The generation reaction of SiO is the rate determing step for synthesis of SiC w .

Mg_2(OH)_2CO_3·3H_2O Whiskers Growth Mechanism

From the perspective of growth units, the growth mechanism of Mg2（OH）2CO3.3H2O whisker is investigated in this paper. Results show that the growth morphology of Mg2（OH）2CO33H2O whisker is consistent with the model of anion coordination polyhedron growth units. The growth solution Raman shift of Mg2（OH）2CO;3H2O was monitored using Raman spectroscopy. The growth units are [Mg-（OH）4]2- and H2COv The growth process of Mg2（OH）2COf3H2O whisker is as follows： growth unit [Mg-（OH）4]2- first incorporates into the larger dimension [Mg-（OH）4]2-, then the [Mg-（OH）4]2-n combines with H2CO3 into a linear skeleton Mg2（OH）2CO3 in the same line. Mg2（OH）2CO3 combines with H2O by hydrogen bonds and ultimately transforms into Mg2（OH）2COf3H2O whisker. Magnesium carbonate whiskers have a layered structure, each of which is made of magnesium, carbon, oxygen, with H2O in between each layer. When skeletons are superimposed within the same plane as a parallelepiped one, they grow into solid cuboid-shaped whiskers. When the parallelepiped skeletons planes combine with each other through the cascading links, they grow into hollow cylindrical whiskers.

Synthesis and growth mechanism of SiC/SiO2 nanochains by catalyst-free thermal evaporation method in Ar/CO atmosphere

SiC/SiO2 nanochains were synthesized on a carbon fiber substrate by a catalyst-free thermal evaporation method in the Ar/CO atmosphere.X-ray diffraction(XRD),Fourier-transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM)and transmission electron microscopy(TEM)revealed that the as-synthesized SiC/SiO2 nanochains are composed of single-crystalline SiC nanowires and amorphous SiO2 beads.The introduction of CO can promote the formation of SiO2,so that the SiC/SiO2 nanochains are subsequently formed during cooling.In addition,the photoluminescence spectrum of SiC/SiO2 nanochains showed a broad emission peak at around 350 nm,which is ascribed to the oxygen discrepancy in the SiO2 beads as well as the SiC/SiO2 interfacial effect.These findings can provide guidance for further study of the vapor growth of 1D SiC-based materials.

ANALYSIS OF THE GROWTH MECHANISM OF TiAl_3 WHISKERS PREPARED BY IN SITU REACTION IN MOLTEN ALUMINUM

Some TiAl3 whiskers are found to be produced simultaneously during the formation process of TiB2 Particulates fabricated by in situ reaction in molten aluminum. The thec t of temperature of molten aluminum on the morphologies of the TiAl3 whiskers and the growth mechanism of the whiskers are studied in this paper. The results show that the aspect rutio of the TiAl3 whiskers decreases with the increase of the temperoture. The growth of the whiskers is proved to be controlled by a Vapor-LiquidSoltd (VLS) mechanism. The titanium and aluminum atoms in the catalytic droplet,however, have been coofrmed to react with each othen which is dtherent from other whlskcrs growing by a VLS mcchanism where the compostion in the catalytic droplet is a constant.

The influence of ablation products on the ablation resistance of C/C-SiC composites and the growth mechanism of SiO_2 nanowires

Ablation under oxyacetylene torch with heat flux of 4186.8（10%kW/m2 for 20 s was performed to evaluate the ablation resistance of C/C-SiC composites fabricated by chemical vapor infiltration（CVI） combined with liquid silicon infiltration（LSI） process.The results indicated that C/C-SiC composites present a better ablation resistance than C/C composites without doped SiC.The doped SiC and the ablation products SiO2 derived from it play key roles in ablation process.Bulk quantities of SiO2 nanowires with diameter of 80 nm-150 nm and length of tens microns were observed on the surface of specimens after ablation.The growth mechanism of the SiO_2 nanowires was interpreted with a developed vapor-liquid-solid（VLS） driven by the temperature gradient.

Synthesis of SiC Whiskers from Silicon Nitride in Argon Atmosphere

SiC whiskers were synthesized by carbothermal reduction of silicon nitride, α-Si3N4 and β-Si3N4 powders were used as silicon sources, and graphite, active carbon and black carbon as carbon sources, as well as boron oxide as catalyst. The synthesized SiC whiskers were characterized by XRD and SEM. The results showed that the synthesizing temperature should be above 1716 K; the decomposition of Si3N4 was the limited step in the synthesis of SiC whiskers; and catalyst not only offered the liquid condition, but also restricted the growth of SiC whiskers along one dimension. LS mechanism seems to explain well the growth of SiC whiskers.

The growth mechanism of the basic magnesium chloride whisker

Based on the theoretical model of anion coordination polyhedron growth units, the growth mechanism of the basic magnesium chloride whisker was discussed in this paper.It was found that the basic magnesium chloride whisker habits were related to the different environments in which anion coordination polyhedra grew. The growth units of basic magnesium chloride whiskers are [Mg - (OH) 4]2 -and [Mg - Cl 4]2 -. The growth process is the incorporation process of growth units. Growth units will have different incorporations and orientations caused by different system characters or heating. Furthermore, the formation mechanism of basic magnesium chloride whiskers was also interpreted using anion coordination polyhedron growth units.

GROWTH MECHANISM OF TiC WHISKERS PREMRED BY A MODIFIED CHEMICAL VAPOR DEPOSITION METHOD

High quality TiC whiskers have been prepared by a modified chemical vapor deposition (CVD) method using TiCl4 and CH4 as reactant gases and Ni as substrate. The deposition temperature and gas flow mies have ampreciable effect on the whisker growth.The whisker orientations and morphology are determined by X-my diffraction (XRD),scanning electron micmpmph (SEM) and transmission electron microgmph (TEM).In addition to the spherical tips, spiral growth microsteps and obvious terraces are observed at the tips and side faces of whiskers in the present eoperiment. The whiskers grow mostly along (100) direction. The whisker growth mechanism is discussed in detail.

Mg_(2)Sn-induced whisker growth on the surfaces of Mg/Sn/Mg ultrasonic-assisted soldering joints

In this paper,the phenomena of Mg_(2)Sn-induced Sn whisker growth were explored on the surfaces of Mg/Sn/Mg ultrasonic-assisted soldering joints after aging treatment.The in-situ observation and thermal analysis confirmed that the formation and the corrosion of Mg_(2)Sn nanoparticles were the dominant reason of Sn whisker growth.The Mg_(2)Sn accumulation at the grain boundaries would pin the dislocation slip and affect the continuity of whisker growth,and the boundary angle would thus play a decisive role in the growth shape of Sn whiskers due to the pining effect of Mg_(2)Sn.This study might be conducive to elucidating the growth behavior of Sn whiskers and provide the exploration strategy to further improve the bonding strength of Mg/Sn/Mg ultrasonic-assisted soldering joints.

Heteroepitaxial Growth and Characterization of 3C-SiC Films on Si Substrates Using LPVCVD

3C-SiC films have been deposited on Si （111） substrates by the low-pressure vertical chemical vapor deposition （LPVCVD） with gas mixtures of SiH4, Calls and H2. The growth mechanism of SiC films can be obtained through the observations using field emission scanning electron microscope （FESEM）. It is found that the growth process varies from surface control to diffusion control when the deposition temperature increases from 1270 to 1350℃. The X-ray diffraction （XRD） patterns show that the SiC films have good crystallinity and strong preferred orientation.The results of the high resolution transmission electron microscopy （HRTEM） image and the transmission electron diffraction （TED） pattern indicate a peculiar superlattice structure of the film. The values of the binding energy in the high resolution X-ray photoelectron spectra （XPS） further confirm the formation of SiC.

High-aspect-ratio ZrC whiskers:Synthesis,growth mechanism and electromagnetic wave absorption properties

Stealth materials with high dependability at elevated temperatures and outstanding mechanical properties are urgently needed for practical applications.As one-dimensional ultrahigh temperature ceramic(UHTC)materials,zirconium carbide whiskers(ZrCw)have attracted a great deal of attention due to their desirable mechanical and ablation resistance performance in high-temperature environments.We have successfully synthesized ZrCw using a carbothermal reduction technique without the introduction of metal catalytic in this paper.ZrCw shows a typically prismatic structure with the diameter of 1e2 mm and the aspect ratio of up to 250.The growth of ZrCw is controlled by a solid-liquid-solid(SLS)and vaporsolid(VS)compound mechanism in conjunction with the auxiliary action of mesophase Na3ZrF7.The ZrCw/paraffin hybrids achieve the minimum reflection loss(RL(min))of
25.77 dB at 13.28 GHz under the thickness of 1.25 mm,and reach an effective absorption bandwidth(EAB)of 3.04 GHz(14.96 e18.00 GHz)with a thickness of only 1.0 mm.This work presents a promising approach for large-scale producing high-purity whiskers,and verifies that ZrCw has extensive application prospects in the field of stealth materials.

碳热还原法制备SiC晶须试验研究

分别以SiO2微粉、石英砂和高岭土为硅源,用不同粒度的石墨为碳源,Fe2O3、H3BO3和NaCl作为催化剂,采用碳热还原法制备了碳化硅晶须.通过扫描电镜和电子探针分析晶须的形貌和组成,研究了3种硅源、不同种类的催化剂和不同粒度的石墨对SiC晶须生成及形貌的影响,探讨了晶须的生长机理.结果表明:选用SiO2微粉作为硅源,H3BO3作为催化剂所合成的SiC晶须生成量和形貌都较好;不同粒度的原料会在反应空间和反应速度上对晶须的生成产生不同的影响,当石墨粒度为100目时效果较好;在晶须的顶端发现催化剂熔球,推测合成机理为VLS机理.

Characterization of SiC nanowires prepared on C/C composite without catalyst by CVD

SiC nanowires were prepared on C/C composite surface without catalyst by chemical vapor deposition（CVD） using CH3 SiCl3 as precursor.SEM images of the CVD-product reveal that some long nanowires have grown to tens of micrometers with some gathered as a ball.Some short nanowires agglomerate like chestnut shell with many thorns accompanied by some deposited nano-particles.XRD,Raman-spectrum and FTIR patterns indicate that the product is a typical β-SiC.TEM images show that the nanowires have a wide diameter range from 10 to 100 nm,and some thin nanowires are bonded to the thick one by amorphous CVD-SiC.A SiC branch generates from an amorphous section of a thick one with an angle of 70° between them,which is consistent with the [111] axis stacking angle of the crystal.SAED and fast Fourier transform（FFT） patterns reveal that the nanowires can grow along with different axes,and the bamboo-nodes section is full of stacking faults and twin crystal.The twisted SiC lattice planes reveal that the screw dislocation growth is the main mechanism for the CVD-SiC nanowires.

SiC晶须VLS生长机理及生长动力学研究

对ＶＬＳ机理下稻壳合成ＳｉＣ晶须（ＳｉＣＷ）及生长动力学进行了研究。结果表明，ＳｉＯ２与Ｃ在高温下生成ＳｉＯ的反应是ＳｉＣ晶须生长的速率控制步骤；在形成晶须的催化剂作用下，ＳｉＣ晶须的生长速率与ＳｉＯ在催化剂熔球周围的浓度成正比；ＳｉＣ晶须生长的催化选择性随温度的增加而提高；复合催化剂可提高合成ＳｉＣ晶须的反应速率及催化选择性。

碳热还原法合成TiC-SiC复合粉末及其生长机理

以硅溶胶、炭黑和TiO2为原料,采用碳热还原法合成TiC-SiC复合粉末。研究反应温度和TiO2添加量对合成TiC-SiC复合粉末的物相组成和显微形貌的影响;对反应过程进行热力学分析和计算,探讨TiC-SiC复合粉末的生长机理。结果表明:TiC-SiC复合粉末适宜的合成条件为在1 600℃保温1 h;在反应过程中,TiC先于SiC形成,TiC的形成抑制了SiC颗粒的生长;当复合粉末中TiC的含量(质量分数)为10%左右时,SiC的合成过程由气-固(V-S)机理反应转变为气-固机理和气-气机理共同反应;复合粉末主要由球状颗粒、短棒状颗粒以及少量晶须组成;随着复合粉末中TiC含量的增加,SiC晶须的生长受到抑制,其形貌逐步由长纤维状向短棒状和颗粒状过渡。

稻壳SiC晶须合成的热力学基础及VLS催化生长机理

本文对稻壳合成ＳｉＣ晶须（简称ＳｉＣｗ）及ＳｉＣ颗粒（简称ＳｉＣｐ）进行了热力学分析，确定了基元反应，设计了ＳｉＣｗＶＬＳ生长的新型复合催化剂。研究表明：在稻壳合成ＳｉＣｗ的反应中，ＳｉＣｐ的生成是不可避免的；在新型复合催化剂作用下，ＳｉＣｗ的生成率可达３０％以上；ＳｉＣｗ的生长为粗糙界面生长机制，ＳｉＣｗ表面光滑。

SiC_w在Al_2O_3-C复合耐火材料中的原位生长

通过引入金属Ｓｉ和活性Ｃ对ＳｉＣ晶须在Ａｌ２Ｏ３－Ｃ复合耐火材料中的原位生长进行了实验研究，利用ＳＥＭ结合电子探针（ＥＰＭＡ）研究了ＳｉＣｗ在Ａｌ２Ｏ３－Ｃ复合耐火材料中的原位生长机理，提出了液－固生长机理，并讨论了其热力学和动力学条件．

不同原料合成SiC晶须的形貌结构特征和生长机理研究

分别以SiO2微粉和Si3N4为硅源,炭黑为碳源,氧化硼为催化剂,采用碳热还原法在1500℃氩气气氛下合成了SiC晶须。通过透射电镜和扫描电镜对所合成SiC晶须的形貌和晶体结构特征进行了分析。结果表明,采用两种硅源所合成的晶须均为β-SiC单晶,晶须的生长面为(111)面,生长方向为[111]方向。两种硅源所合成的晶须形貌特点存在较大差别,表明其合成SiC晶须的生长机理不同,VLS生长和螺旋位错的延伸生长可以分别用来解释以SiO2微粉为硅源和以Si3N4为硅源合成的晶须在形貌结构特征上的差别。

碳热还原法合成TiB_2-SiC复合粉末及其机理分析

以硅溶胶、炭黑、TiO2和B4C为原料,采用碳热还原法合成TiB2-SiC复合粉末.研究了反应温度、TiO2添加量对合成TiB2-SiC复合粉末的物相组成和显微形貌的影响;对反应过程进行了热力学分析和计算,并探讨了TiB2-SiC复合粉末的生长机理.结果表明:TiB2-SiC复合粉末适宜的合成条件为在1 600℃保温1h.在反应过程中,TiB2先于SiC生成,TiB2的生成改变了SiC的生长方式.当复合粉末中TiB2的质量分数为10%左右时,SiC的合成过程由气-固(V-S)反应转变为气-固(V-S)和气-气(V-V)共同反应,复合粉末主要由少量球状颗粒、短棒状颗粒以及大量的晶须组成.当体系中生成的TiB2质量分数(≥20%左右)较大时,生成的晶须数量减少,同时球状、片状和短棒状等结构颗粒明显增多,出现多样化结构并存的现象,SiC的生长仍然由V-S反应和V-V反应共同控制.

β-SiC晶须的生长及微观结构研究

以高岭土、超细碳粉为原料,采用高温碳热还原方法合成出性能良好的β-SiC晶须。运用XRD,SEM,TEM,EDAX等分析检测技术研究了该晶须的结晶特征及生长机理。结果表明:晶须沿<111>方向具有平行的堆垛层错,横断面呈正三角形,晶须顶端存在螺旋位错。该方法生产的β-SiC晶须,其生长过程为“VS”机理。