CN106816395B - A kind of silicon nitride passive oxidation thickness degree determines method - Google Patents

A kind of silicon nitride passive oxidation thickness degree determines method Download PDF

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CN106816395B
CN106816395B CN201611162293.9A CN201611162293A CN106816395B CN 106816395 B CN106816395 B CN 106816395B CN 201611162293 A CN201611162293 A CN 201611162293A CN 106816395 B CN106816395 B CN 106816395B
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oxidation
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silicon nitride
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张赢
罗晓光
俞继军
邓代英
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China Academy of Aerospace Aerodynamics CAAA
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Abstract

A kind of silicon nitride passive oxidation thickness degree determines that method, the present invention are directed to silicon nitride (Si3N4) material oxidation process, establish containing gas boundary layer, full compact surfaces SiO2Oxide layer, porous SiO2The Si of oxide layer and original material layer3N4Material oxidation model.Using thermogravimetric analyzer isothermal oxidation experimental technique, oxidation weight gain and oxidated layer thickness growth curve of the silicon nitride material at a temperature of 1273-1873K are obtained.It is good that result of study shows that theoretical prediction oxidated layer thickness growth curve and experimental result coincide, and better than the calculated result of Marschall model of oxidation, the oxidation layer model established can preferably capture oxidated layer thickness growth behavior.

Description

A kind of silicon nitride passive oxidation thickness degree determines method
Technical field
The present invention relates to the passive oxidation models and its calculation method of a kind of thermally protective materials, for solving the passive of material Oxidation susceptibility prediction.
Background technique
Silicon nitride (Si3N4) ceramic material has intensity high, thermostabilization and a good chemical stability, and with quartz, BN Etc. good dielectric properties can be obtained after compound, it is suitable as high temperature wave-transparent material.To guarantee Si3N4In high temperature aerobic environment Under usage safety, must be to Si3N4Oxidation behaviors under high temperature are studied.
It is similar with other heat proof materials containing element silicon, Si3N4Material is divided into the different oxidation mechanisms of partial pressure of oxygen and temperature Actively oxidation and passive oxidation mechanism.When actively aoxidizing, Si3N4Oxidation generates gaseous volatile substance SiO, and material surface occurs Ablation；When passive oxidation, material surface forms protectiveness SiO2Film makes it have good antioxygenic property.Deal and Grove, which most generates discovery silicon face in technique early in monocrystalline silicon, SiO2The presence of thin layer simultaneously obtains SiO2Oxidated layer thickness and when Between parabolic equation relational expression.The relational expression exists in partial pressure of oxygen 0.1-1.0atm, temperature 973-1573K, oxidated layer thickness Experimental verification is obtained in the range of 0.3-20 μm.Galanov analyzes oxygen, nitrogen in Si3N4The stable state of oxide layer structure is spread, and is mentioned Go out three layers of oxide layer evolutionary model of diffusion control and dynamics Controlling, and gives corresponding the calculated results. Marschall-Chen has studied SiC material surface model of oxidation and combination typical examples progress under of short duration Aerodynamic Heating environment Theory deduction.Parthasarathy proposes the ZrB based on the diffusion of oxygen stable state2Three layers of model of oxidation, and done corresponding reason By analysis, and obtain experimental verification.
Summary of the invention
Technology of the invention solves the problems, such as:
The technical scheme is that a kind of silicon nitride passive oxidation thickness degree determines method, steps are as follows:
(1) assume that silicon nitride material only reacts with oxygen and chemically reacts in thermodynamic equilibrium state, passing through It learns reactional equation and sets up Si3N4The thermodynamical model and then building silicon nitride passive oxidation prediction model of oxidation；Described is passive Aoxidize prediction model successively includes gas boundary layer, compact oxidation layer, porous oxide coatings and original material layer from outside to inside；
(2) ring is equal to according to gas stagnation pressure after the chemical equilibrium constant association reaction of chemical reaction each in thermodynamical model The principle of border pressure calculates SiO after reaction2Vapour pressure；
(3) according to SiO after reaction2Vapour pressure, calculate compact oxidation layer and gas boundary layer interface SiO2Concentration, And then obtain the O in the boundary layer2Concentration
(4) in oxidation process, it is assumed that the interface between original material layer and porous oxide coatings is reacted in thermodynamics Equilibrium state obtains the partial pressure of oxygen of the interface using the thermodynamic data of Barin, and then obtains the O of the interface2Concentration
(5) according to the diffusion flux conservation of gas and the thermochemical equilibrium conserva-tion principle of reaction, according to step (3), (4) Determining O2Concentration calculates the thickness of oxide layer.
The thermodynamical model is as follows:
Si3N4(s)+3O2(g)=3SiO2(l)+2N2(g)
Si3N4(s)+3O2(g)=3SiO2(g)+2N2(g)
SiO2(l)=SiO2(g)
Si3N4(s)+3/2O2(g)=3SiO (g)+2N2(g)
2SiO2(l)=2SiO (g)+O2(g)
SiO after reaction2Vapour pressure calculation formula it is as follows:
In formula, T chemical reaction temperature.
Partial pressure of oxygen calculation formula in step (4) is as follows:
In formula, T chemical reaction temperature.
The oxidated layer thickness L calculation formula is as follows:
L=q1L2；
In formula, L indicates the overall thickness of porous oxide coatings, compact oxidation layer, L2Indicate porous oxide coatings, compact oxidation layer and The overall thickness of gas boundary layer；q1Indicate the proportionate relationship between oxidated layer thickness；Indicate O2In compact oxidation layer Diffusion coefficient,Indicate O2Aerial diffusion coefficient；Indicate the oxygen concentration of the outer surface of gas boundary layer.
The overall thickness calculation formula of the porous oxide coatings, compact oxidation layer and gas boundary layer is as follows:
In formula,The SiO of expression2Molecular weight,Indicate SiO2Density；The hole of f expression porous oxide coatings Rate.
F value range 0.01-0.05.
F is optimal to take 0.03.
The present invention compared with prior art the utility model has the advantages that
1、Si3N4The thermodynamical model of oxidation considers multiple chemical reaction equations, meets actual physical and chemical process, Oxygen is lower closer to compact oxidation layer surface concentration, and oxygen concentration is related to oxidizing temperature, and can accurately calculate side The concentration of oxygen in interlayer, improves the precision of prediction of silicon nitride passive oxidation model.
2, in oxidation process, at the interface between original material layer and porous oxide coatings reaction speed quickly, therefore It is believed that interfacial reaction is in thermodynamic equilibrium state.Using the thermodynamic data of Barin, original material layer surface can be obtained Partial pressure of oxygen improves the precision of prediction of silicon nitride passive oxidation model.
3, influence of the microcellular structure for gas diffusion is considered, the prediction essence of silicon nitride passive oxidation model is improved Degree.
Detailed description of the invention
Fig. 1 is nitridation silicon oxide layer model structure schematic diagram；
Fig. 2 is that the experiment of 1273-1873K oxidated layer thickness growth curve is compared with theoretical.
Specific embodiment
It elaborates with reference to the accompanying drawing to the present invention.A kind of silicon nitride passive oxidation thickness degree of the invention determination side Method, steps are as follows:
(1) assume that silicon nitride material only reacts with oxygen and chemically reacts in thermodynamic equilibrium state, passing through It learns reactional equation and sets up Si3N4The thermodynamical model and then building silicon nitride passive oxidation prediction model of oxidation；Heating power of the present invention It learns chemical reaction involved in model and considers following five reaction equations:
Si3N4(s)+3O2(g)=3SiO2(l)+2N2(g) (1)
Si3N4(s)+3O2(g)=3SiO2(g)+2N2(g) (2)
SiO2(l)=SiO2(g) (3)
Si3N4(s)+3/2O2(g)=3SiO (g)+2N2(g) (4)
2SiO2(l)=2SiO (g)+O2(g) (5)
Assuming that environmental pressure is 1atm, constituent of air N2(78%) and O2(22%), then there is PN2=0.78atm, PO2= 0.22atm.When temperature is lower than 1800K, the saturation vapour pressure of SiO gas is less than 10-3Pa, it is believed that Si3N4Material is raw Seldom, the Si at the amount of SiO3N4Oxidation product to generate SiO2Passive oxidation based on, the foundation of model of oxidation considers that chemistry is anti- Answer (1)-(3).
Si3N4When passive oxidation occurs for material surface, the SiO of generation is chemically reacted2Solid can agglomerate to be formed on the surface of the material The thickness of oxide layer, oxide layer can increase with the reaction time.Based on Si3N4Oxide layer microstructure observing contains as a result, establishing Gas boundary layer, full compact surfaces SiO2Oxide layer, porous SiO2The Si of oxide layer and original material layer3N4Material oxidation structure Model.As shown in Figure 1, Si3N4It reacts between oxide layer and raw material interface with oxygen and generates nitrogen, due to existing not The supersaturated nitrogen of dissolution causes to generate porous SiO between fine and close oxide layer and ceramics2Layer；Outermost layer is gas border Layer, SiO2Gas concentration is higher closer to compact oxidation layer surface concentration, O2It is lower closer to compact oxidation layer surface concentration.I.e. The passive oxidation prediction model successively includes gas boundary layer, compact oxidation layer, porous oxide coatings and original from outside to inside Material layer.
(2) ring is equal to according to gas stagnation pressure after the chemical equilibrium constant association reaction of chemical reaction each in thermodynamical model The principle of border pressure calculates SiO after reaction2Vapour pressure；
(3) according to SiO after reaction2Vapour pressure, calculate compact oxidation layer and gas boundary layer interface SiO2Concentration, And then obtain the O in the boundary layer2Concentration
According to chemical equation (1), under quasi-steady state diffusion conditions, O2Diffusion flux and N2Diffusion flux and SiO2Production quantity there are following corresponding relationships:
O2Flow in surface gas boundary layer is as follows:
N2Flow in surface gas boundary layer is as follows:
D indicates that diffusion coefficient, C indicate concentration, and δ indicates the thickness of gas boundary layer,Indicate SiO2The generation of gas Rate, f indicates the porosity of oxide layer, related to the diffusion of gas.The friendship of subscript " i " expression compact oxidation layer and gas boundary layer Junction.The outer surface of subscript " a " expression gas boundary layer.Similarly, extraneous SiO is flowed to2Gas flow is as follows:
(quasi-steady state), simultaneous solution equation (6)-(9) can obtain:
Value do not determined by local partial pressure of oxygen, pass through SiO2Vapour pressure calculate obtain:
(4) in oxidation process, it is assumed that the interface between original material layer and porous oxide coatings is reacted in thermodynamics Equilibrium state obtains the partial pressure of oxygen of the interface using the thermodynamic data of Barin, and then obtains the O of the interface2Concentration
In oxidation process, reaction speed quickly, therefore can at the interface between original material layer and porous oxide coatings Think that interfacial reaction is in thermodynamic equilibrium state.Consider reaction (1), chemical equilibrium constant indicates are as follows:
Using the thermodynamic data of Barin, the partial pressure of oxygen of original material layer surface can be obtained by formula (13):
In turn,
(5) according to the diffusion flux conservation of gas and the thermochemical equilibrium conserva-tion principle of reaction, according to step (3), (4) Determining O2Concentration calculates the thickness of oxide layer.
O2In SiO2Diffusion coefficient in oxide layer is obtained from document:
By the relational expression of oxygen diffusing capacity, the relational expression of oxidated layer thickness can be obtained:
Indicate that diffusion coefficient of the oxygen in porous oxide coatings, subscript " j " indicate porous oxide coatings and original material The interface of the bed of material.L indicates the thickness of oxide layer, L1Indicate the thickness of porous oxide coatings, L2It indicates to include the total of gas boundary layer Thickness.Q indicates the proportionate relationship between oxidated layer thickness.
The interface oxygen concentration of compact oxidation layer and porous oxide coatingsMeet the condition of continuity:
To obtainCalculating formula:
The variation of oxidated layer thickness and the variation relation of quality of oxide layer are as follows:
Simultaneous equations (7), obtain:
Equation (20) are solved to obtain:
The back amount of original material layer is as follows:
Pass through Si3N4Isothermal oxidation experiment, obtains Si3N4Sample unit area oxidation weight gain changes with time, and then To the experimental data curve of oxidated layer thickness L at any time.Oxidated layer thickness (L) is bent at a temperature of Fig. 2 gives 1273K and 1873K Line experiment is compared with theoretical, and experimental situation pressure is 1atm, and group is divided into N2(78%) and O2(22%), oxidization time 5h, oxide layer Porosity f=0.03.As shown in Fig. 2, the theoretical expectation values of model of oxidation and experimental data are coincide well, and it is better than Marschall [4] establishes the calculated result of oxidation layer model.Reason mainly has the following: (a) this model considers chemistry Reaction equation (1)-(5), the model of oxidation of Marschall only considered chemical equation (1)；(b) this model considers surface gas The influence in body boundary layer, oxygen is lower closer to compact oxidation layer surface concentration, and oxygen concentration is related to oxidizing temperature, and The model of oxidation of Marschall thinks that the oxygen concentration of oxide layer outer surface is only related with external environment.(c) this oxidation layer model Structure considers influence of the micropore for gas diffusion, and does not account in Marschall model.
The present invention is not disclosed technology and belongs to common sense well known to those skilled in the art.

Claims (8)

1. a kind of silicon nitride passive oxidation thickness degree determines method, it is characterised in that steps are as follows:
(1) assume that silicon nitride material only reacts with oxygen and chemically reacts in thermodynamic equilibrium state, by chemical anti- Establishing equation is answered to play Si3N4The thermodynamical model and then building silicon nitride passive oxidation prediction model of oxidation；The passive oxidation Prediction model successively includes gas boundary layer, compact oxidation layer, porous oxide coatings and original material layer from outside to inside；
(2) environment pressure is equal to according to gas stagnation pressure after the chemical equilibrium constant association reaction of chemical reaction each in thermodynamical model Strong principle calculates SiO after reaction2Vapour pressure；
(3) according to SiO after reaction2Vapour pressure, calculate compact oxidation layer and gas boundary layer interface SiO2Concentration, in turn Obtain the O in the boundary layer2Concentration
(4) in oxidation process, it is assumed that the interface between original material layer and porous oxide coatings is reacted in thermodynamical equilibrium State obtains the partial pressure of oxygen of the interface using the thermodynamic data of Barin, and then obtains the O of the interface2Concentration
(5) it according to the diffusion flux conservation of gas and the thermochemical equilibrium conserva-tion principle of reaction, is determined according to step (3), (4) O2Concentration calculates the thickness of oxide layer.
2. according to the method described in claim 1, it is characterized by: the thermodynamical model is as follows:
Si3N4(s)+3O2(g)=3SiO2(l)+2N2(g)
Si3N4(s)+3O2(g)=3SiO2(g)+2N2(g)
SiO2(l)=SiO2(g)
Si3N4(s)+3/2O2(g)=3SiO (g)+2N2(g)
2SiO2(l)=2SiO (g)+O2(g)。
3. according to the method described in claim 2, it is characterized by: reaction after SiO2Vapour pressure calculation formula it is as follows:
In formula, T indicates chemical reaction temperature.
4. according to the method described in claim 2, it is characterized by: the partial pressure of oxygen calculation formula in step (4) is as follows:
In formula, T indicates chemical reaction temperature.
5. according to the method described in claim 2, it is characterized by: the oxidated layer thickness L calculation formula is as follows:
L=q1L2；
In formula, L indicates the overall thickness of porous oxide coatings, compact oxidation layer, L2Indicate porous oxide coatings, compact oxidation layer and gas The overall thickness in boundary layer；q1Indicate the proportionate relationship between oxidated layer thickness；Indicate O2Expansion in compact oxidation layer Coefficient is dissipated,Indicate O2Aerial diffusion coefficient；Indicate the oxygen concentration of the outer surface of gas boundary layer.
6. according to the method described in claim 5, it is characterized by: the porous oxide coatings, compact oxidation layer and gas side The overall thickness calculation formula of interlayer is as follows:
In formula,Indicate SiO2Molecular weight,Indicate SiO2Density；F indicates the porosity of porous oxide coatings, t table Show the time.
7. according to the method described in claim 6, it is characterized by: f value range is 0.01-0.05.
8. according to the method described in claim 7, it is characterized by: f value is 0.03.
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