CN106892684B - Preparation method of ZrC coating on surface of C/C composite material - Google Patents
Preparation method of ZrC coating on surface of C/C composite material Download PDFInfo
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- CN106892684B CN106892684B CN201710100435.7A CN201710100435A CN106892684B CN 106892684 B CN106892684 B CN 106892684B CN 201710100435 A CN201710100435 A CN 201710100435A CN 106892684 B CN106892684 B CN 106892684B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
Abstract
The invention relates to a preparation method of a ZrC coating on the surface of a C/C composite material. The method comprises the following steps: (1) pretreating the C/C composite material; (2) preparing alloy raw materials, and smelting to obtain a Si-Zr alloy for liquid-phase reaction sintering; (3) putting the alloy for liquid phase reaction sintering and the C/C composite material into a graphite crucible, and putting the graphite crucible into a high-vacuum carbon tube sintering furnace; vacuumizing, heating to a liquid phase reaction sintering temperature, and preserving heat; and cooling and discharging the product after heat preservation is finished to obtain the ZrC coating on the surface of the C/C composite material. The method has the advantages of simple operation, short period and low cost, and the prepared ZrC coating has high bonding strength with the matrix and good thermal cycle resistance and impact resistance.
Description
Technical Field
The invention relates to a preparation method of a C/C composite material surface coating, in particular to a high-efficiency low-cost preparation method of an anti-ablation ZrC coating with high bonding strength on the surface of a C/C composite material.
Background
The service temperature of high-temperature resistant components of a reusable spacecraft, a solid rocket engine nozzle, a hypersonic aircraft and the like is as high as 1800 ℃ or higher, the high-temperature resistant components bear the erosion of high-pressure airflow and high-speed particles in an ablation environment, and the development of high-temperature resistant structural materials with excellent ablation resistance becomes a key for promoting the development of the field.
The C/C composite material is a composite material consisting of a carbon fiber reinforced phase and a carbon matrix phase, has low density, high strength, high thermal shock resistance, low thermal expansion coefficient, zero wet expansion, high-temperature strength and modulus which are increased along with the increase of temperature, and excellent frictional wear performance, and is one of ideal high-temperature heat-resistant structural materials. However, the C/C composite material is significantly oxidized and ablated under the high-temperature and high-speed airflow scouring, and the requirements of a new generation of high-performance aerospace vehicle on high-temperature and heat-resistant structural materials cannot be met.
Researches show that the surface preparation of the refractory carbide coating is an effective way to improve the ablation resistance and the scouring resistance of the C/C composite material and reduce the ablation rate, and the C/C composite material can bear higher gas temperature or longer working time. At present, refractory carbide coatings for improving ablation resistance and scouring resistance of the surfaces of C/C composite materials mainly comprise HfC, TaC, ZrC and the like. Compared with TaC and HfC, ZrC has lower density, high hardness and modulus and low preparation cost, and is an ideal anti-ablation coating on the surface of a C/C composite material. In 2009, volume 47 of CARBON, the chemical vapor deposition preparation technology (CARBON 47(2009) of a ZrC coating on the surface of a C/C composite material (CARBON 47 (2009)) 3365-3380) is published and reported, wherein ZrCl is adopted as the raw material4+C3H6+H2The ZrC coating is successfully prepared in the + Ar system, and is compact and uniform, and the ablation resistance is excellent. However, the chemical vapor deposition method has high coating preparation cost, generates HCl in the coating preparation process, and has strong corrosion to equipment. In addition, the ZrC coating prepared by the chemical vapor deposition method is directly contacted with the C/C composite material substrate, the interface bonding residual stress is large, and the coating is easy to crack and fall off when bearing large thermal shock. Therefore, the development of the low-cost preparation method of the ZrC coating with high bonding strength, excellent thermal cycle resistance and excellent impact resistance has important significance for expanding the application of the C/C composite material.
Disclosure of Invention
The invention aims to provide a preparation method of a ZrC coating on the surface of a C/C composite material, which has the advantages of simple preparation process and short period of the coating, and the prepared ZrC coating and the C/C composite material have high bonding strength and good thermal cycle resistance and impact resistance.
The invention provides a preparation method of a ZrC coating on the surface of a C/C composite material, which comprises the following steps:
(1) pretreating the C/C composite material;
(2) preparing alloy raw materials, and smelting to obtain a Si-Zr alloy for liquid-phase reaction sintering;
(3) placing the C/C composite material treated in the step (1) and the Si-Zr alloy for liquid phase reaction sintering in the step (2) into a high vacuum sintering furnace, heating and preserving heat; and cooling and discharging the product after heat preservation is finished to obtain the ZrC coating on the surface of the C/C composite material.
The method for pretreating the C/C composite material in the step (1) comprises the following steps: polishing the C/C composite material by using 300-; drying the cleaned C/C composite material in an air atmosphere at 60-200 ℃ for 10-100 minutes, then heating in an air atmosphere at 300-600 ℃ for 10-150 minutes, and cooling for later use.
And (2) preparing alloy raw materials by selecting pure silicon and pure zirconium with the purity of more than 99 percent.
And (2) preparing a Si-Zr alloy raw material according to the atomic percentages of Si 75-95% and Zr 5-25% of alloy elements.
And (2) smelting by using a vacuum arc smelting furnace or an induction smelting furnace to obtain the Si-Zr alloy for liquid phase reaction sintering. In order to ensure the uniformity of the alloy components, the Si-Zr alloy can be repeatedly smelted for 2-4 times.
In the high vacuum sintering furnace of the step (3), the vacuum degree is 8 multiplied by 10-2-10Pa。
And (3) heating, wherein the temperature of the high vacuum sintering furnace is increased to a liquid phase reaction sintering temperature by adopting a temperature increase rate of 5-25 ℃/min, and the liquid phase reaction sintering temperature is 50-500 ℃ higher than the melting point of the Si-Zr alloy.
The heat preservation in the step (3) refers to heat preservation for 0.5-10h at the liquid phase reaction sintering temperature.
And (3) cooling to 500 ℃ at a cooling rate of 2-25 ℃/min, then cooling to below 100 ℃ along with the furnace, and discharging to obtain the ZrC coating on the surface of the C/C composite material.
In the embodiment of the invention, the liquid phase reaction sintering Si-Zr alloy prepared in the step (2) and the C/C composite material treated in the step (1) are put into a graphite crucible, put into a high vacuum carbon tube sintering furnace and vacuumized to 8 x 10-2-10Pa。
The invention provides application of the preparation method in preparation of ablation-resistant aerospace materials.
The method has the advantages that the ZrC coating is prepared on the surface of the C/C composite material by adopting a Si-Zr alloy liquid phase reaction sintering method, the ZrC coating is formed by reaction, and the ZrC coating and a C/C composite material matrix react simultaneously to form a SiC transition layer. On one hand, the ZrC coating formed by reaction is metallurgically bonded with the substrate, and the bonding strength of the coating is high; on the other hand, the formation of the SiC transition layer can effectively relieve the thermal mismatch between the ZrC coating and the C/C composite material matrix, reduce the thermal residual stress and reduce the cracking and falling of the coating under the thermal cycle and impact. In addition, the ZrC coating with the SiC transition layer can be prepared on the surface of the C/C composite material in one step, the transition layer is specially prepared on the surface of the C/C composite material without adopting other processes, the process is simple, the period is short, and the practicability is high.
Drawings
FIG. 1 is an XRD pattern of the ZrC coating surface of the C/C composite material surface prepared in example 1.
FIG. 2 is a scanning electron microscope topography of the surface of the ZrC coating prepared in example 1.
FIG. 3A is a scanning electron microscope profile and energy spectrum line scanning analysis map of the coating cross section. FIG. 3B is a Si element spectral line scan of a cross-section of the coating depicted in FIG. 3A. FIG. 3C is a C element spectral line scan of a cross-section of the coating depicted in FIG. 3A. FIG. 3D is a Zr element spectral line scan of a cross-section of the coating depicted in FIG. 3A.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Unless otherwise specified, the starting materials described in the examples of the present application are all commercially available.
Example 1
The density is 1.83g/cm3Cutting the C/C composite material into small blocks of 20mm multiplied by 5mm, and respectively grinding with No. 400, No. 1200 and No. 2400 abrasive paper; ultrasonic cleaning in water and acetone for 10 min; drying in a drying oven at 200 deg.C for 30 min, heating in a muffle furnace at 400 deg.C for 60 min, and cooling. 112 g of silicon powder (with the purity of 99.5%) and 91 g of zirconium powder (with the purity of 99.5%) are respectively weighed, evenly ground in a mortar and then placed in an electric arc melting furnace to be melted into Si-ZAnd r, crushing the smelted alloy blocks for later use. Putting the treated C/C composite material and the crushed Si-Zr alloy into a graphite crucible, then putting the graphite crucible into a high-vacuum sintering furnace, and vacuumizing to 9 multiplied by 10-2Pa; starting a heating program, heating to 1600 ℃ at a heating rate of 10 ℃/min, and preserving heat for 3 h; and after the heat preservation is finished, cooling to 400 ℃ at a cooling rate of 5 ℃/min, turning off a power supply, cooling to room temperature along with the furnace, opening the furnace, and opening the graphite crucible to obtain the C/C composite material with the ZrC coating on the surface.
The XRD pattern of the surface of the ZrC coating of the prepared C/C composite material is shown in figure 1. FIG. 1 shows a diffraction peak containing only ZrC, illustrating that the coating produced is a ZrC coating. From the scanning electron microscope image (figure 2) of the coating surface, it can be seen that the coating surface is dense and complete, and has no defects such as holes. The scanning electron micrograph of the coating cross-section (FIG. 3A) and the spectral line scanning analysis of its interface (FIGS. 3B, 3C, 3D) show that the coating and the substrate are tightly bonded, forming a SiC transition layer of about 7 μm thickness between the ZrC coating and the C/C composite substrate. The formation of the SiC transition layer can effectively relieve the thermal mismatch between the ZrC coating and the C/C composite material matrix, reduce the thermal residual stress and reduce the cracking and falling of the coating under the thermal cycle and impact.
Example 2
The density is 1.68g/cm3Cutting the C/C composite material into small blocks of 40 multiplied by 20 multiplied by 5mm, and respectively grinding with No. 400, No. 800 and No. 1200 sand paper; ultrasonic cleaning in water and acetone for 10 min; drying in a drying oven at 100 deg.C for 50 min, heating in a muffle furnace at 500 deg.C for 40 min, and cooling. 126 g of silicon powder (with the purity of 99.5%) and 45.6 g of zirconium powder (with the purity of 99.5%) are respectively weighed, ground uniformly in a mortar, then put into an electric arc melting furnace to be melted into Si-Zr alloy blocks, and the melted alloy blocks are crushed for standby. Putting the C/C composite material and the crushed Si-Zr alloy into a graphite crucible, then putting the graphite crucible into a high vacuum sintering furnace, and vacuumizing to 5 Pa; starting a heating program, heating to 1800 ℃ at a heating rate of 15 ℃/min, and keeping the temperature for 1 h; cooling to 400 ℃ at a cooling rate of 5 ℃/min after heat preservation, turning off a power supply, cooling to room temperature along with the furnace, opening the furnace, and opening the graphite crucible to obtain the ZrC coating prepared on the surfaceThe C/C composite material of (1).
The XRD pattern of the prepared C/C composite material ZrC coating is similar to that of example 1, and only contains a diffraction peak of ZrC. The structure of the coating is the same as that of the embodiment 1, a SiC transition layer is formed between the ZrC coating and the C/C composite material matrix, and the coating is compact and complete and has no defects such as holes.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (5)
1. A preparation method of a ZrC coating on the surface of a C/C composite material comprises the following steps:
(1) pretreating the C/C composite material;
wherein, the steps of pretreating the C/C composite material are as follows in sequence:
firstly, grinding the C/C composite material by 400, 1200 and 2400 # sandpaper respectively;
ultrasonic cleaning in water and acetone for 5-10 min;
thirdly, drying the cleaned C/C composite material for 10-100 minutes in an air atmosphere at the temperature of 60-200 ℃;
fourthly, heating the mixture for 10 to 150 minutes in the air atmosphere at the temperature of 300-600 ℃;
cooling for standby;
(2) preparing Si-Zr alloy raw materials according to the atomic percentages of Si 75-95% and Zr 5-25%, and smelting to obtain Si-Zr alloy for liquid-phase reaction sintering;
(3) placing the C/C composite material treated in the step (1) and the Si-Zr alloy for liquid phase reaction sintering in the step (2) into a high vacuum sintering furnace, heating and preserving heat;
the heating is to raise the temperature of the high vacuum sintering furnace to a liquid phase reaction sintering temperature by adopting a temperature rise rate of 5-25 ℃/min, wherein the liquid phase reaction sintering temperature is 50-500 ℃ higher than the melting point of the Si-Zr alloy;
the heat preservation refers to preserving the heat for 0.5 to 10 hours at the liquid phase reaction sintering temperature;
and cooling and discharging the material after the heat preservation is finished, wherein the temperature of the material discharged from the cooling furnace is reduced to 500 ℃ at a cooling rate of 2-25 ℃/min, and then the material discharged from the cooling furnace is cooled to below 100 ℃ along with the furnace, so that a ZrC coating on the surface of the C/C composite material is obtained, and a SiC transition layer is formed between the ZrC coating and the C/C composite material matrix.
2. The method according to claim 1, wherein the step (2) is carried out by selecting pure silicon and pure zirconium alloy raw materials with purity of more than 99%.
3. The preparation method according to claim 1, wherein the Si-Zr alloy for liquid phase reaction sintering is obtained by melting in the step (2) in a vacuum arc melting furnace or an induction melting furnace, and the Si-Zr alloy is repeatedly melted for 2 to 4 times in order to ensure the uniformity of the alloy composition.
4. The production method according to claim 1, wherein the degree of vacuum in the high vacuum sintering furnace of step (3) is 8X 10-2-10Pa。
5. Use of the process according to any one of claims 1 to 4 for the preparation of ablation-resistant aerospace materials.
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| Si-Zr 二元系合金反应熔渗改性C/C 复合材料及其性能研究;仝永刚;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20170215(第02期);第17-18页，表2.2，图2.1，第101-107页，第122页 * |
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