碳化硅材料热导率计算研究进展

从声子散射机制出发,介绍了Si C热导率的温度特性和微观导热机理。综述了Si C单晶热导率的2种主要计算方法。Boltzmann-弛豫时间近似(RTA)适用于各个温度段的热导率计算,而分子动力学方法更适用于高温热导率计算。分子动力学方法相比于Boltzmann-RTA方法的优点在于它可以考虑所有高次项的非谐作用。介绍了3种Si C陶瓷热导率近似计算模型,包括界面热阻模型、Debye-Callaway模型及多相系统热导率模型。下一步研究的主要方向仍然是优化计算模型及减少拟合参数。     

Thermal Diffusivity/Conductivity of Alumina—Silicon Carbide Composites

Thermal diffusivity and conductivity values for several Al₂O₃-SiC whisker composites were determined. The thermal diffusivity values spanned the range from 373 to 1473 K, and thermal conductivity data wre obtained between 305 and 365 K. The thermal diffusivity decreased with increasing temperature and increased with SiC-whisker content. An estimate of the thermal conductivity of the whiskers was obtained from the direct thermal conductivity measurements, but attempts to derive whisker conductivity values from the thermal diffusivity data were not successful because the laser flash method lacks the required accuracy and precision. Specimens were subjected to two different thermal quench experiments to investigate the effect of thermal history on diffusivity. In the most severe case, multiple 1073- to 373-K quenches, radial cracks were observed in the test specimens; however, there was no change in diffusivity. The lack of sensitivity to thermal cycling appears to be related to the sample size.     

氧化铝和碳化硅填充硅橡胶的导热性能研究

研究氧化铝和碳化硅填充硅橡胶的导热性能。结果表明:采用不同粒径碳化硅填充硅橡胶时,随着碳化硅用量的增大,硅橡胶的热导率逐渐增大;在相同填料用量下,粒径小的碳化硅填充硅橡胶热导率高于粒径大的碳化硅填充胶;氧化铝/碳化硅并用填充硅橡胶的导热性能优于单用氧化铝填充胶;当氧化铝/碳化硅质量比为8:2、填充量为600份时,硅橡胶的导热性能最佳。     

Multiscale Genome Modeling for Predicting the Thermal Conductivity of Silicon Carbide Ceramics

Silicon carbide (SiC) ceramics have been widely used in industry due to its high thermal conductivity. Understanding the relations between the microstructure and the thermal conductivity of SiC ceramics is critical for improving the efficiency of heat removal in heat sink applications. In this paper, a multiscale model is proposed to predict the thermal conductivity of SiC ceramics by bridging atomistic simulations and continuum model via a materials genome model. Interatomic potentials are developed using ab initio calculations to achieve more accurate molecular dynamics (MD) simulations. Interfacial thermal conductivities with various additive compositions are predicted by nonequilibrium MD simulations. A homogenized materials genome model with the calculated interfacial thermal properties is used in a continuum model to predict the effective thermal conductivity of SiC ceramics. The effects of grain size, additive compositions, and temperature are also studied. The good agreement found between prediction results and experimental measurements validates the capabilities of the proposed multiscale genome model in understanding and improving the thermal transport characteristics of SiC ceramics.     

Effect of Vapor—Liquid—Solid and Vapor—solid Silicon Carbide Whiskers on the Effective Thermal Diffusivity/Conductivity of Silicon Nitride Matrix Composites

A study was conducted of the relative effect of vapor—liquid—solid (VLS) and vapor—solid (VS) SiC whiskers on the effective thermal diffusivity and conductivity of pressed-densified silicon nitride. It was found that VLS whiskers cause an increase in the thermal diffusivity/conductivity, whereas the opposite effect was found for the VS-SiC whiskers. Comparison with composite theory suggests that the VS-SiC whiskers have a thermal conductivity as low as 25 to 30 W/(m·K). In contrast the VLS-SiC whiskers appear to have a value for the thermal conductivity of at least about 100 W/(m·K) to as high as 250 W/(m·K). These large differences in thermal conductivity for these two types of SiC whiskers are attributed to the much larger density of structural defects in the VS-SiC whiskers, which act as phonon scatterers, thereby lowering the thermal conductivity.     

Secondary Phases in Hot-Pressed Aluminum-Boron-Carbon–Silicon Carbide

Silicon carbide hot-pressed with aluminum, boron, and carbon as sintering aids (ABC–SiC), was studied by transmission electron microscopy. Both grain-boundary films and inclusions were prevalent in this material. The present study characterized the inclusions located in triple-junctions, grain boundaries, and the interior of the SiC grains, with emphases on phases not scrutinized before. These inclusions were crystalline, in contrast to the amorphous grain-boundary films. Two dominant types of boron-free triple-junction phases containing Al(Si)-O-C-(S) and Al(Si)-O were identified, where sulfur was an unexpected contaminant, and silicon came from SiO₂ or from dissolution of SiC. Boron-containing inclusions with a composition Al-O-B-C were frequently observed inside SiC grains. Although the boron-free aluminum-rich phases wet the grain boundaries completely and are, therefore, effective sintering additives, the boron-containing Al(Si)-O-B-C did not wet the grain boundaries. The structure and chemical composition of these boron-containing intragranular inclusions were determined, and their mechanism of formation is discussed.     

Pressure Effects on the Thermal Stability of Silicon Carbide Fibers

Commerically available polymer-derived SiC fibers were treated at temperatures from 1000° to 2200°C under vacuum and at argon gas pressures of 0.1 and 138 MPa. Effects of increasing inert gas pressure on the thermal stability of the fibers were determined through studies of the fiber microstructure, weight loss, grain growth, and tensile strength. The 138-MPa argon gas treatment was found to shift the onset of fiber weight loss from 1200° to above 1500°C. Grain growth and tensile strength degradation were correlated with weight loss and were thus also inhibited by high-pressure treatments. Retreatment in 0.1 MPa of argon of the fibers initially treated in 138 MPa of argon caused further weight loss and tensile strength degradation, thus indicating that high-pressure inert gas conditions were effective only in delaying fiber strength degradation and that no permanent microstructural changes were induced.     

Effect of Sintering Atmosphere on Grain Shape and Grain Growth in Liquid-Phase-Sintered Silicon Carbide

We investigated the effects of the sintering atmosphere on the interface structure and grain-growth behavior in 10-vol%-YAG-added SiC. When α-SiC was liquid-phase-sintered in an Ar atmosphere, the grain/matrix interface was faceted, and abnormal grain growth occurred, regardless of the presence of α-seed grains. In contrast, when the same sample was sintered in N₂, the grain interface was defaceted (rough), and no abnormal grain growth occurred, even with an addition of α-seed grains. X-ray diffraction analysis of this sample showed the formation of a 3C (β-SiC) phase, together with a 6H (α-SiC) phase. These results suggest that the nitrogen dissolved in the liquid matrix made the grain interface rough and induced normal grain growth by an α→β reverse phase transformation. Apparently, the growth behavior of SiC grains in a liquid matrix depends on the structure of the grain interface: abnormal growth for a faceted interface and normal growth for a rough interface.     

Role of the Interfacial Thermal Barrier in the Effective Thermal Diffusivity/Conductivity of SiC-Fiber-Reinforced Reaction-Bonded Silicon Nitride

Experimental thermal diffusivity data transverse to the fiber direction for composites composed of a reaction bonded silicon nitride matrix reinforced with uniaxially aligned carbon-coated silicon carbide fibers indicate the existence of a significant thermal barrier at the matrix-fiber interface. Calculations of the interfacial thermal conductances indicate that at 300°C and 1-atm N₂, more than 90% of the heat conduction across the interface occurs by gaseous conduction. The magnitude of the interfacial conductance is decreased significantly under vacuum or by removal of the carbon surface layer from the fibers by selective oxidation. Good agreement is obtained between thermal conductance values for the oxidized composite at 1 atm calculated from the thermal conductivity of the N₂ gas and those inferred from the data for the effective composite thermal conductivity.     

Grain Boundaries in Silicon from Zero Temperature through Melting

The results of atomistic simulations of twist grain boundaries in covalent silicon are presented and compared with similar studies in metals. Three aspects are discussed in detail: (i) the zero-temperature structure-energy correlation, (ii) the elastic anomalies near a twist boundary at zero temperature, and (iii) the high-temperature stability of a boundary and its role in thermodynamic melting. In each case striking similarities with studies on metals are found, which are attributed to the important role played by atoms in close proximity. By contrast the covalent nature of bonding in silicon appears to play only a minor role.     

Oxidation of Silicon and Silicon Carbide in Ozone-Containing Atmospheres at 973 K

The oxidation behavior of a silicon wafer, chemically vapor-deposited SiC, and single-crystal SiC was investigated in an oxygen—2%–7% ozone gas mixture at 973 K. The thickness of the oxide film that formed during oxidation was measured by ellipsometry. The oxidation rates in the ozone-containing atmosphere were much higher than those in a pure oxygen atmosphere. The parabolic oxidation kinetics were observed for both silicon and SiC. The parabolic rate constants varied linearly with the ozone-gas partial pressure. Inward diffusion of atomic oxygen formed by the dissociation of ozone gas through the SiO₂ film apparently was the rate-controlling process.     

Effects of Grain-Boundary Structure on the Strength, Toughness, and Cyclic-Fatigue Properties of a Monolithic Silicon Carbide

An in situ -toughened silicon carbide (ABC-SiC) has been examined in the as-processed condition, where the grain-boundary films are predominantly amorphous, and following thermal exposure at a temperature of 1300°C, where the films become fully crystalline. Previous work has shown that, at elevated temperatures (up to 1300°C), after the grain-boundary films crystallize in situ , only a marginal reduction in strength, fracture toughness, and cyclic-fatigue crack-growth properties is observed, in comparison with those of the as-processed microstructure at 25°C. In the present study, the effect of such crystallization on the subsequent strength, toughness, and fatigue properties at 25°C is examined. Little or no degradation is observed in the room-temperature properties with the crystallized grain-boundary films/phase; in fact, although the strength shows a small reduction (∼3%), the fracture toughness and fatigue-crack-growth threshold both increase by ∼20%, compared with that of the as-processed structure with amorphous grain-boundary films.     

Effect of Interfacial Reaction on the Thermal Conductivity of Al–SiC Composites with SiC Dispersions

The effect of interfacial reactions between Al and SiC on the thermal conductivity of SiC-particle-dispersed Al-matrix composites was investigated by X-ray diffraction and transmission electron microscopy (TEM), and the thermal barrier conductance ( h _c) of the interface in the Al–SiC composites was quantified using a rule of mixture regarding thermal conductivity. Al–SiC composites with a composition of Al (pure Al or Al–11 vol% Si alloy)–66.3 vol% SiC and a variety of SiC particle sizes were used as specimens. The addition of Si to an Al matrix increased the thermal barrier conductance although it decreased overall thermal conductivity. X-ray diffraction showed the formation of Al₄C₃ and Si as byproducts in addition to Al and SiC in some specimens. TEM observation indicated that whiskerlike products, possibly Al₄C₃, were formed at the interface between the SiC particles and the Al matrix. The thermal barrier conductance and the thermal conductivity of the Al–SiC composites decreased with increasing Al₄C₃ content. The role of Si addition to an Al matrix was concluded to be restraining an excessive progress of the interfacial reaction between Al and SiC.     

Local Viscosity of Si-O-C-N Nanoscale Amorphous Phases at Ceramic Grain Boundaries

Internal friction characterization has been used to quantitatively assess the viscosity characteristics of Si-O-C-N glasses segregated to nanometer-sized grain boundaries of polycrystalline Si₃N₄ and SiC ceramics. A relaxation peak of internal friction, which arises with rising temperature from the viscous sliding of glassy grain boundaries, was systematically collected and analyzed with respect to its shift upon changing the oscillation frequency. As a result of such an analysis, both activation energy for viscous grain-boundary flow and inherent viscosity of the intergranular glass film could be quantitatively evaluated. Two main features are shown: (i) the presence of N and/or C greatly affects the viscosity characteristics of SiO₂ phases at Si₃N₄ and SiC grain boundaries; and (ii) the internal friction method has potential as a unique experimental tool for understanding the local properties of nanoscale amorphous phases in new ceramic materials.     

Role of Interfacial Carbon layer in the Thermal Diffusivity/Conductivity of Silicon Carbide Fiber-Reinforced Reaction-Bonded Silicon Nitride Matrix Composites

The role of an interfacial carbon coating in the heat conduction behavior of a uniaxial silicon carbide nitride was investigated. For such a composite without an interfacial carbon coating the values for the thermal conductivity transverse to the fiber direction agreed very well with the values calculated from composite theory using experimental data parallel to the fiber direction, regardless of the ambient atmosphere. However, for a composite made with carbon-coated fibers the experimental values for the thermal conductivity transverse to the fiber direction under vacuum at room temperature were about a factor of 2 lower than those calculated from composite theory assuming perfect interfacial thermal contact. This discrepancy was attributed to the formation of an interfacial gap, resulting from the thermal expansion mismatch between the fibers and the matrix in combination with the low adhesive strength of the carbon coating. In nitrogen or helium the thermal conductivity was found to be higher because of the contribution of gaseous conduction across the interfacial gap. On switching from vacuum to nitrogen a transient effect in the thermal diffusivity was observed, attributed to the diffusion-limited entry of the gas phase into the interfacial gap. These effects decreased with increasing temperature, due to gap closure, to be virtually absent at 1000°C.     

Flexural Creep of an in Situ-Toughened Silicon Carbide

Flexural creep behavior is reported for an in situ -toughened SiC between 1100° and 1500°C in four-point bending. The flexural creep rate of this SiC, sintered with aluminum, boron, and carbon (ABC-SiC), exhibits linear stress dependence, low apparent activation energy, and low incidence of cavitation and dislocation production. Most grain boundaries in this ceramic contain 1–5 nm intergranular films. The creep rate is consistent with a grain-boundary transport mechanism involving diffusion along the grain-boundary film-SiC interfaces. The microstructure and grain boundaries have been examined using transmission electron microscopy to assess possible changes during creep, particularly in relation to the applied stress direction.     

SiC纳米粉体悬浮液导热系数研究

本文作采用非稳态热丝法,测量了水中加平均粒为25nm的碳化硅粉（简称n-SiC),乙二醇中加n-SiC,水中加平均粒径为0.6μm的碳化硅粉（简称μ-SiC）和乙醇中加μ-SiC等4个系列不同固体积含量悬浮液的有效热系数,实验结果表明：对于所研究的悬浮液,其有效导热系数相对增加量随固相加入量的增加而线性增加;固相颗粒形貌对有效导热系数相对增加量有显著影响;基体液体虽对有效导热系数相对增加量无明显影响,但有效导热系数的绝对量由基体液体的导热系数决定。     

Thermal Shock Behavior of Porous Silicon Carbide Ceramics

Using the water-quenching technique, the thermal shock behavior of porous silicon carbide (SiC) ceramics was evaluated as a function of quenching temperature, quenching cycles, and specimen thickness. It is shown that the residual strength of the quenched specimens decreases gradually with increases in the quenching temperature and specimen thickness. Moreover, it was found that the fracture strength of the quenched specimens was not affected by the increase of quenching cycles. This suggests a potential advantage of porous SiC ceramics for cyclic thermal-shock applications.     

Thermal Expansion of Laminated, Woven, Continuous Ceramic Fiber/Chemical-Vapor-Infiltrated Silicon Carbide Matrix Composites

Thermal expansions of three two-dimensional laminate, continuous fiber/chemical-vapor-infiltrated silicon carbide matrix composites reinforced with either FP-Alumina (alumina), Nextel (mullite), or Nicalon (Si-C-O-N) fibers are reported. Experimental thermal expansion coefficients parallel to a primary fiber orientation were comparable to values calculated by the conventional rule-of-mixtures formula, except for the alumina fiber composite. Hysteriesis effects were also observed during repeated thermal cycling of that composite. Those features were attributed to reoccurring fiber/matrix separation related to the micromechanical stresses generated during temperature changes and caused by the large thermal expansion mismatch between the alumina fibers and the silicon carbide matrix.     

Conversion of Oak to Cellular Silicon Carbide Ceramic by Gas-Phase Reaction with Silicon Monoxide

Oak has been converted to a porous biocarbon template by annealing in an inert atmosphere above 800°C. Subsequent infiltration with gaseous SiO at 1550–1600°C under flowing argon of atmospheric pressure finally resulted in the formation of a porous, cellular β-SiC ceramic. The conversion retains the biomorphic cellular morphology of oak tissue. While pores in the cell walls with a diameter less than ∼1 μm vanished, two distinct pore channel maxima representing tracheidal cells and large vessels remained in the SiC ceramic. Depending on the cellular morphology of different kinds of wood, e.g., strut thickness and pore size distribution, gas-phase conversion to single-phase β-SiC can be used to manufacture cellular ceramics with a wide range of pore channel diameters.