CN112851358A - ZrB2-SiC-Mo(Six,Al1-x)2Zero ablation coating and hot pressing preparation method thereof - Google Patents

ZrB2-SiC-Mo(Six,Al1-x)2Zero ablation coating and hot pressing preparation method thereof Download PDF

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CN112851358A
CN112851358A CN202110005868.0A CN202110005868A CN112851358A CN 112851358 A CN112851358 A CN 112851358A CN 202110005868 A CN202110005868 A CN 202110005868A CN 112851358 A CN112851358 A CN 112851358A
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房师阁
王文明
杨诗瑞
刘志福
赵云飞
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Beijing Power Machinery Institute
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Abstract

The invention discloses a ZrB2‑SiC‑Mo(Six,Al1‑x)2The preparation method of the zero ablation coating comprises the following steps: weighing the powder raw materials according to a predetermined mass percentage; ball-milling the powder raw materials by using a ball mill to uniformly mix the powder raw materials to form a powder material; adding a binder and deionized water into the powder material, and uniformly stirring to form a mixture; coating the mixture on the surface of the component; placing the component in a mold and filling the component with a liquidFilling with filling powder; hot pressing by a hot press under a protective atmosphere; freely cooling the die and the sintered body and adding a pressure maintaining process for pressure maintaining; and (4) decompressing to form the carbon/carbon composite material zero ablation coating. The method has the advantages of easy control of process conditions and low cost, and can solve the problem of poor surface oxidation resistance of the existing carbon/carbon composite material in an aerobic environment.

Description

ZrB2-SiC-Mo(Six,Al1-x)2Zero ablation coating and hot pressing preparation method thereof
Technical Field
The invention relates to the technical field of carbon/carbon composite materials, in particular to ZrB2-SiC-Mo(Six,Al1-x)2A zero ablation coating and a hot pressing preparation method thereof.
Background
The carbon/carbon composite material is widely applied due to a plurality of excellent characteristics, the high-temperature longitudinal tensile strength, the shear strength and the transverse tensile strength of the carbon/carbon composite material are increased along with the increase of the temperature, and the carbon/carbon composite material has the special thermal properties of corrosion resistance, thermal shock resistance, high thermal conductivity, low expansion coefficient and the like of the carbon material; the material has low density, ablation resistance, good heat conduction, thermal shock resistance and is used as the best material for the missile nose cone and the solid rocket engine nozzle; and the friction material is also an ideal friction material due to the characteristics of light weight, high temperature resistance, friction resistance and large energy absorption of braking.
However, the surface of the carbon/carbon composite material has relatively poor oxidation resistance in an aerobic environment, and researches show that the carbon/carbon composite material starts to perform an oxidation reaction under an oxygen-containing atmosphere of more than 370 ℃, and the reaction speed is also rapidly increased at 500 ℃, which causes destructive damage to the material. The oxidation process of the carbon/carbon composite material comprises the steps of transmitting reaction gas to the surface of the carbon material, adsorbing the reaction gas on the surface of the carbon material, carrying out oxidation reaction on the surface of the material, desorbing a gas reaction product and reversely transmitting the gas product into the environment. The oxidation influencing factors are as follows: the oxygen migration rate to the material surface, the composition and flow rate of the oxidizing atmosphere, the oxygen partial pressure, the effective surface area of the material in contact with oxygen, the microstructure and phase composition of the material, the content of easily-oxidizable impurities in the material and the catalytic oxidation of the impurities, the heat treatment temperature, the sample shape, the oxidation temperature and time, the desorption and migration rate of gas oxidation products, the effective diffusion coefficient of oxygen in the material interior and in the gas boundary layer, the thermal emissivity of the material, and the like. This greatly limits the use of carbon/carbon composites as high temperature refractory materials, and severely limits their use in the field of thermal structural materials and other fields.
Disclosure of Invention
In view of the above, the present invention provides a ZrB2-SiC-Mo(Six,Al1-x)2The zero ablation coating and the hot-pressing preparation method thereof can prepare ZrB by a hot-pressing sintering method with easily controlled process conditions and low cost2-SiC-Mo(Six,Al1-x)2A zero ablation coating, which aims to solve the problem that the surface oxidation resistance of the existing carbon/carbon composite material is poor in an aerobic environment and broadens the application of the carbon/carbon composite material in the fields of thermal structural materials and other fields.
The technical scheme adopted by the invention is as follows:
ZrB2-SiC-Mo(Six,Al1-x)2The hot pressing preparation method of the zero ablation coating comprises the following steps:
weighing powder raw materials according to a predetermined mass percentage, wherein the powder raw materials comprise ZrB2Powder, SiC powder, MoSi2Powder, Al2O3Powder and Si powder;
ball-milling the powder raw materials by using a ball mill to uniformly mix the powder raw materials to form a powder material;
adding a binder and deionized water into the powder material, and uniformly stirring to form a mixture;
coating the mixture on the surface of the component;
placing the component into a mold, and filling the filler powder around the component;
hot pressing by a hot press under the protective atmosphere, wherein the hot pressing temperature is 600-2100 ℃, the pressure is 30-50 MPa, and the pressure is maintained for 0.5-3 h;
keeping the pressure for 20-60 min by adding a pressure maintaining process while freely cooling the die and the sintered body;
and (4) decompressing to form the carbon/carbon composite material zero ablation coating.
Preferably, in the step of weighing the powder raw material according to the predetermined mass percentage, the powder raw material comprises 40 to 70 mass percent of ZrB2Powder, SiC powder with the mass percent of 4-20 percent and MoSi with the mass percent of 10-40 percent2Powder, Al with the mass percent content of 4-20%2O3Powder and Si powder with the mass percent content of 4-15%;
ZrB2powder, SiC powder, MoSi2Powder, Al2O3The granularity of the powder and the Si powder is 200-600 meshes.
Preferably, in the step of ball-milling the powder raw material by using a ball mill, ethanol is added into the powder raw material, the mass ratio of the powder raw material to the ethanol is 1: 2-6, and the ball-milling time is 20-35 h.
Preferably, in the step of adding the binder and the deionized water to the powder material, the binder is polyvinyl alcohol or 108 glue.
Preferably, in the step of adding the binder and the deionized water into the powder material, the mass ratio of the binder to the deionized water is 1: 1-4.
Preferably, when the mixture is coated on the surface of the member, the coating is applied in a thickness of 5 to 10 μm.
Preferably, in the step of placing the member in a mold and filling the member with the filler powder, the filler powder is spherical graphite powder or boron nitride powder.
Preferably, in the step of hot pressing by using a hot press under a protective atmosphere, the protective gas is an inert gas.
Preferably, the protective gas is argon.
ZrB2-SiC-Mo(Six,Al1-x)2The zero ablation coating is prepared by any preparation method provided by the technical scheme, wherein the zero ablation coating comprises 40% of the components in percentage by mass-70% ZrB2SiC with the mass percent content of 4-20 percent and MoSi with the mass percent content of 10-40 percent2Al with the mass percent content of 4-20%2O3And 4 to 15 mass percent of Si.
Has the advantages that:
using the above-mentioned ZrB2-SiC-Mo(Six,Al1-x)2The hot pressing preparation method of the zero ablation coating uses ZrB2、SiC、 MoSi2、Al203Preparing ZrB of carbon/carbon composite material by using Si as raw material through hot pressing method2-SiC-Mo(Six,Al1-x)2The zero ablation coating has the characteristics of simple process, easily controlled process conditions and low cost; the high-temperature oxidation resistant composite ceramic coating prepared by the method has the advantages of high temperature resistance and high-temperature oxidation resistance, so that the zero-ablation coating can be used as a protective layer of a high-temperature ablation-resistant oxidation-resistant component and can be widely applied to the field of aerospace.
Drawings
FIG. 1 shows ZrB of the present invention2-SiC-Mo(Six,Al1-x)2A process flow chart of a hot pressing preparation method of the zero ablation coating.
Detailed Description
The invention is described in detail below by way of example with reference to the accompanying drawings.
In the prior art, as for the antioxidant approach, antioxidant means can be classified into three major categories, namely modification technology, coating technology and self-healing method. The invention uses an ultrahigh temperature ceramic material coating to improve the oxidation resistance of the carbon/carbon composite material, reduce the ablation rate and bear higher gas temperature or longer working time.
Example one
Referring to fig. 1, an embodiment of the invention provides a ZrB2-SiC-Mo(Six,Al1-x)2The hot pressing preparation method of the zero ablation coating comprises the following steps:
step S10, weighing according to the preset mass percentageTaking powder raw material, wherein the powder raw material comprises ZrB2Powder, SiC powder, MoSi2Powder, Al2O3Powder and Si powder; the powder raw material can comprise 40 to 70 mass percent of ZrB2Powder, SiC powder with the mass percent of 4-20 percent and MoSi with the mass percent of 10-40 percent2Powder, Al with the mass percent content of 4-20%2O3Powder and Si powder with the mass percent content of 4-15%; ZrB2The mass percentage of the powder can be 40%, 42%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 65%, 66%, 68%, 70%; the mass percentage of the SiC powder can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%; MoSi2The mass percentage of the powder may be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 13%, 34%, 35%, 36%, 37%, 38%, 39%, 40%; al (Al)2O3The mass percentage of the powder can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%; the mass percentage of the Si powder can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% and 15%; ZrB2Powder, SiC powder, MoSi2Powder, Al2O3The granularity of the powder and the Si powder can be 200-600 meshes, such as: 200 meshes, 300 meshes, 400 meshes, 500 meshes and 600 meshes;
step S20, ball-milling the powder raw materials by a ball mill to uniformly mix the powder raw materials to form a powder material; in the step S20 of ball-milling the powder raw material by using a ball mill, ethanol is added to the powder raw material, the mass ratio of the powder raw material to the ethanol is 1: 2-6, and the ball-milling time is 20-35 h, such as: the mass ratio of the powder raw material to the ethanol can be 1:2, 1:3, 1:4, 1:5 and 1:6, and the ball milling time can be 20h, 24h, 25h, 26h, 27h, 28h, 30h, 32h and 35 h.
Step S30, adding a binder and deionized water into the powder material, and uniformly stirring to form a mixture; in the step S30 of adding the binder and the deionized water to the powder material, the binder may be polyvinyl alcohol or 108 glue, and the mass ratio of the binder to the deionized water may be 1: 1-4, such as: 1:1, 1:2, 1:3, 1: 4; 108 glue, also known as "polyvinyl formal glue", is a macromolecular binding solution prepared by the condensation reaction of polyvinyl alcohol and formaldehyde in an acidic medium, and belongs to a translucent or transparent aqueous solution. No odor, no taste, no toxicity, good bonding property, and bonding strength up to 0.9 Mpa;
step S40, coating the mixture on the surface of the component; during the coating process, the coating thickness can be 5 μm to 10 μm, such as: 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm;
step S50, placing the component into a mould, and filling the periphery of the component with filling powder; the filling powder can be spherical graphite powder or boron nitride powder; when the mould is selected, the mould with the corresponding size can be selected according to the size of the component;
step S60, hot pressing by a hot press under protective atmosphere, starting the hot press during hot pressing, wherein the hot pressing temperature is 600-2100 ℃, the pressure is 30-50 MPa, and the pressure is maintained for 0.5-3 h; the hot pressing temperature can be 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C, 1000 deg.C, 1100 deg.C, 1200 deg.C, 1300 deg.C, 1400 deg.C, 1500 deg.C, 1600 deg.C, 1700 deg.C, 1800 deg.C, 1900 deg.C, 2000 deg.C, 2100 deg.C; the pressure intensity can be 30MPa, 35MPa, 40MPa, 45MPa and 50 MPa: the dwell time can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3 h: the protective gas forming the protective atmosphere may be an inert gas such as: argon, helium;
step S70, freely cooling the die and the sintered body, and adding a pressure maintaining process to maintain the pressure for 20-60 min; the additional dwell time may be: 20min, 30min, 40min, 50min, 60 min; after the heating is stopped, the die and the sintered body are in a free cooling state, and a pressure maintaining process is added for maintaining pressure;
and step S80, relieving pressure after the additional pressure maintaining process is stopped, and forming the carbon/carbon composite material zero ablation coating.
In the above-mentioned ZrB2-SiC-Mo(Six,Al1-x)2In the hot pressing preparation method of the zero ablation coating, ZrB can be improved by adding SiC2The outer layer of the oxide is rich in SiO2Glass, the inner layer being rich in-ZrO2Oxide layer, ZrO-rich layer produced by the glass phase of the outer layer having good surface wettability and healing properties2The oxide layer forms a thermal barrier layer which can effectively prevent external heat from diffusing to the interior of the material, thereby improving the high-temperature oxidation resistance and being capable of being used at the temperature of over 2200 ℃; simultaneously, SiC/MoSi2The composite coating also shows good long-term high-temperature oxidation resistance; MoSi2Has a melting point of 2030 ℃ and excellent high-temperature oxidation resistance (in air)>1800 ℃) and has stronger high-speed airflow and ion erosion resistance; mo (Six, Al1-x)2Is a cermet material similar to intermetallic compound and has a specific MoSi ratio2More excellent low/high temperature oxidation resistance; with the change of the content of the Al element, Mo (Six, Al1-x)2Shows properties such as melting point, mechanical strength, thermal conductivity and expansion coefficient which can be regulated and controlled; the invention adopts a hot pressing method and uses Si and Al2O3、SiC、MoSi2、ZrB2ZrB for preparing C/C composite material by using same as raw material2-SiC-Mo(Six,Al1-x)2Zero ablation high temperature oxidation resistant composite ceramic coating.
Using the above-mentioned ZrB2-SiC-Mo(Six,Al1-x)2The hot pressing preparation method of the zero ablation coating uses ZrB2、SiC、 MoSi2、Al203Preparing ZrB of carbon/carbon composite material by using Si as raw material through hot pressing method2-SiC-Mo(Six,Al1-x)2The zero ablation coating has the characteristics of simple process, easily controlled process conditions and low cost; the high-temperature oxidation resistant composite ceramic coating prepared by the method has the advantages of high temperature resistance and strong high-temperature oxidation resistance.
Example two
The embodiment of the invention also provides ZrB2-SiC-Mo(Six,Al1-x)2The zero ablation coating is prepared by adopting any one of the preparation methods provided in the embodiments, wherein the zero ablation coating comprises ZrB with the mass percent of 40-70%2SiC with the mass percent content of 4-20 percent and MoSi with the mass percent content of 10-40 percent2Al with the mass percent content of 4-20%2O3Si with the mass percent content of 4-15%; the mass percent content of each component in the zero ablation coating can refer to the specific mass percent content value.
In the actual production process, ZrB2-SiC-Mo(Six,Al1-x)2The following specific embodiments can be adopted for various raw material proportions of the zero-ablation coating:
in a first mode, the zero-ablation coating comprises 55 mass percent of ZrB2SiC with the mass percent of 10 percent and MoSi with the mass percent of 20 percent27% by mass of Al2O3And 8% by mass of Si.
In a second mode, the zero-ablation coating comprises 50 mass percent of ZrB212 percent of SiC and 25 percent of MoSi by mass percentage26% by mass of Al2O3And 7% by mass of Si.
In a third mode, the zero-ablation coating comprises 60 mass percent of ZrB2SiC with the mass percent of 5 percent and MoSi with the mass percent of 18 percent211% by mass of Al2O3And 6% by mass of Si.
Although ZrB is exemplified2-SiC-Mo(Six,Al1-x)2The three specific raw material ratios of the zero ablation coating are not limited to the three embodiments, and other raw material ratios can be adopted in the actual production process.
ZrB mentioned above2-SiC-Mo(Six,Al1-x)2The zero ablation coating has excellent high-temperature ablation resistance and oxidation resistance.
In the case of the above ZrB2-SiC-Mo(Six,Al1-x)2After the zero ablation coating is subjected to a wind tunnel ablation test under the conditions of 2500K, water addition and 600s, the coating structure is complete, and the matrix is not damaged.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. ZrB2-SiC-Mo(Six,Al1-x)2The hot-pressing preparation method of the zero ablation coating is characterized by comprising the following steps of:
weighing powder raw materials according to a predetermined mass percentage, wherein the powder raw materials comprise ZrB2Powder, SiC powder, MoSi2Powder, Al2O3Powder and Si powder;
ball-milling the powder raw materials by using a ball mill to uniformly mix the powder raw materials to form a powder material;
adding a binder and deionized water into the powder material, and uniformly stirring to form a mixture;
coating the mixture on the surface of the component;
placing the component into a mold, and filling the filler powder around the component;
hot pressing by a hot press under the protective atmosphere, wherein the hot pressing temperature is 600-2100 ℃, the pressure is 30-50 MPa, and the pressure is maintained for 0.5-3 h;
keeping the pressure for 20-60 min by adding a pressure maintaining process while freely cooling the die and the sintered body;
and (4) decompressing to form the carbon/carbon composite material zero ablation coating.
2. The method of claim 1, wherein the step of preparing the composition is carried out in a reactorIn the step of weighing the powder raw material according to the predetermined mass percentage, the powder raw material comprises 40 to 70 mass percent of ZrB2Powder, SiC powder with the mass percent of 4-20 percent and MoSi with the mass percent of 10-40 percent2Powder, Al with the mass percent content of 4-20%2O3Powder and Si powder with the mass percent content of 4-15%;
ZrB2powder, SiC powder, MoSi2Powder, Al2O3The granularity of the powder and the Si powder is 200-600 meshes.
3. The preparation method of claim 1, wherein in the step of ball milling the powder raw material by using a ball mill, ethanol is added to the powder raw material, the mass ratio of the powder raw material to the ethanol is 1: 2-6, and the ball milling time is 20-35 h.
4. The method of claim 1, wherein in the step of adding a binder and deionized water to the powder material, the binder is polyvinyl alcohol or 108 glue.
5. The preparation method according to claim 5, wherein in the step of adding the binder and the deionized water to the powder material, the mass ratio of the binder to the deionized water is 1: 1-4.
6. The method of claim 1, wherein the mixture is coated on the surface of the member to a thickness of 5 to 10 μm.
7. The method of claim 1, wherein in the step of placing the member in a mold and filling the member with the filler powder, the filler powder is spherical graphite powder or boron nitride powder.
8. The method according to any one of claims 1 to 7, wherein in the step of hot pressing with a hot press under a protective atmosphere, the protective gas is an inert gas.
9. The method of claim 8, wherein the shielding gas is argon.
10. ZrB2-SiC-Mo(Six,Al1-x)2Zero-ablation coating, characterized in that it is produced by a method according to any one of claims 1 to 9, wherein it comprises ZrB in a mass percentage of 40 to 70%2SiC with the mass percent content of 4-20 percent and MoSi with the mass percent content of 10-40 percent2Al with the mass percent content of 4-20%2O3And 4 to 15 mass percent of Si.
CN202110005868.0A 2021-01-05 2021-01-05 ZrB2-SiC-Mo(Six,Al1-x)2Zero ablation coating and hot pressing preparation method thereof Pending CN112851358A (en)

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Application publication date: 20210528