CN106892684A - A kind of preparation method of C/C composite material surfaces ZrC coatings - Google Patents
A kind of preparation method of C/C composite material surfaces ZrC coatings Download PDFInfo
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- CN106892684A CN106892684A CN201710100435.7A CN201710100435A CN106892684A CN 106892684 A CN106892684 A CN 106892684A CN 201710100435 A CN201710100435 A CN 201710100435A CN 106892684 A CN106892684 A CN 106892684A
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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
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Abstract
The present invention relates to a kind of preparation method of C/C composite material surfaces ZrC coatings.Comprise the following steps：(1) C/C composites are pre-processed；(2) alloyage raw material, melting obtains liquid reactive sintering Si Zr alloys；(3) liquid reactive sintering alloy and C/C composites are put into graphite crucible, are placed in high vacuum carbon pipe sintering furnace；Vacuumize, be heated to liquid reactive sintering temperature；Insulation is cooled down after terminating and come out of the stove, that is, obtain C/C composite material surface ZrC coatings.The inventive method is simple to operate, cycle is short, low cost, and obtained ZrC coatings and substrate combinating strength are high, and heat resistanceheat resistant circulation and impact property are good.
Description
Technical field
The present invention relates to a kind of preparation method of C/C composite material surfaces coating, a kind of C/C composite material surfaces are referred specifically to
The high-efficiency and low-cost preparation method of high bond strength anti-yaw damper ZrC coatings.
Background technology
The high temperature resistant component of reusable launch vehicle, solid rocket motor nozzle and hypersonic vehicle etc. is on active service
Temperature is up to more than 1800 DEG C, and the erosion of high pressure draught and high-velocity particles is born under ablation environment, and development has excellent anti-
The high temperature structural materials of ablation property have turned into the key for promoting field development.
C/C composites are a kind of composites by fibre reinforced phase and carbon base body phase composition, with low-density, height
Intensity, high-heat resistance shock resistant, low thermal coefficient of expansion, zero hygral expansion, elevated temperature strength and modulus are raised and increased with temperature, and excellent rubs
Polishing machine is wiped, is one of preferable high-temperature heat-resistance structural material.But, C/C composites are in the case where high-temperature high-speed airflow washes away
Significantly oxidation and ablation, can not meet requirement of the high-performance aerospace device of new generation to high-temperature heat-resistance structural material.
Research shows that it is to improve C/C composites anti-yaw damper and erosion resistibility, drop that surface prepares refractory carbides coating
The effective way of low ablating rate, can make C/C composites bear fuel gas temperature or the longer working time higher.At present, C/C
Composite material surface is used to improve the refractory carbides coating of its anti-yaw damper and erosion resistibility mainly including HfC, TaC and ZrC
Coating etc..There is lower density, hardness and modulus high, and cheap preparation cost compared to TaC and HfC, ZrC, be C/C
The ideal anti-yaw damper coating of composite material surface.2009,《carbon》C/C composites are reported disclosed in volume 47
The chemical vapour deposition technique technology of preparing (3365-3380 of CARBON 47 (2009)) of surface ZrC coatings, in ZrCl4+C3H6+H2+
ZrC coatings are successfully prepared in Ar systems, coating is fine and close, uniform, anti-yaw damper excellent performance.But, chemical vapour deposition technique is applied
Preparation cost is high for layer, produce HCl in coating preparation process, strong to equipment corrosion.Additionally, prepared by chemical vapour deposition technique
ZrC coatings and C/C matrices of composite material directly contacts, interface cohesion residual stress are big, and coating bears easily to be sent out during big thermal shock
It is raw to ftracture and come off.Therefore, the low cost preparation of bond strength high, heat resistanceheat resistant circulation and the excellent ZrC coatings of impact property is developed
Application of the method for expanding C/C composites is significant.
The content of the invention
It is an object of the invention to provide a kind of preparation method of C/C composite material surfaces ZrC coatings so that coating prepares work
Skill is simple, cycle is short, and the ZrC coatings and C/C matrices of composite material bond strengths of preparation are high, and heat resistanceheat resistant circulation and impact property are good.
A kind of preparation method of C/C composite material surfaces ZrC coatings that the present invention is provided, comprises the following steps：
(1) C/C composites are pre-processed；
(2) alloyage raw material, melting obtains liquid reactive sintering Si-Zr alloys；
(3) the C/C composites after step (1) treatment are placed in the liquid reactive sintering of step (2) with Si-Zr alloys
In high vacuum sintering furnace, heating, insulation；Insulation is cooled down after terminating and come out of the stove, that is, obtain C/C composite material surface ZrC coatings.
The method of pretreatment C/C composites is in step (1)：By the 300-2500 sand paperings of C/C composites,
It is cleaned by ultrasonic 5-10 minutes in water and acetone successively；C/C composites after cleaning are dried in 60-200 DEG C of air atmosphere
10-100 minutes, then heated 10-150 minutes in 300-600 DEG C of air atmosphere, cooled down standby.
Step (2) is from the pure silicon that purity is more than 99% and pure zirconium alloyage raw material.
It is former that step (2) prepares Si-Zr alloys according to alloying element atomic percent Si 75%-95%, Zr 5%-25%
Material.
Step (2) obtains liquid reactive sintering Si-Zr alloys with vacuum arc melting furnace or induction melting furnace melting.For
Ensure the uniformity of alloying component, Si-Zr alloys can melt back 2-4 times.
In the high vacuum sintering furnace of step (3), vacuum is 8 × 10-2-10Pa。
Step (3) described heating, its method is the heating rate using 5-25 DEG C/min by high vacuum sintering furnace temperature rise
To liquid reactive sintering temperature, the liquid reactive sintering temperature is higher than 50-500 DEG C of Si-Zr alloy melting points.
Step (3) insulation refers in liquid reactive sintering temperature 0.5-10h.
Step (3) cools to less than 100 DEG C with the furnace and goes out after being cooled to 300-500 DEG C with the cooldown rate of 2-25 DEG C/min
Stove, that is, obtain C/C composite material surface ZrC coatings.
In an embodiment of the present invention, it is by the liquid reactive sintering Si-Zr alloys of step (2) preparation and step (1) place
The C/C composites managed are put into graphite crucible, are placed in high vacuum carbon pipe sintering furnace, are evacuated to 8 × 10-2-10Pa。
The invention provides application of the above-mentioned preparation method in the aerospace material of resistance to ablation is prepared.
The advantage of the invention is that prepare ZrC in C/C composite material surfaces using Si-Zr alloy liquid phases reaction sintering applying
Layer, ZrC coatings are formed by reaction, and itself simultaneous reactions and C/C matrices of composite materials between forms one layer of SiC transition zone.One side
Face, the ZrC coatings and matrix for reacting formation are metallurgical binding, and anchoring strength of coating is high；On the other hand, the formation of SiC transition zones
The thermal mismatching between ZrC coatings and C/C matrices of composite materials can effectively be alleviated, reduce thermal residual strain, reduced coating and followed in heat
Ring and impact under cracking and come off.Additionally, the present invention can be prepared with SiC transition in the step of C/C composite material surfaces one
The ZrC coatings of layer, without preparing transition zone in C/C composite material surfaces using other techniques are special, process is simple, cycle is short,
It is practical.
Brief description of the drawings
Fig. 1 is the XRD of C/C composite material surfaces ZrC coating surfaces obtained in embodiment 1.
Fig. 2 is ZrC coating surfaces ESEM shape appearance figure obtained in embodiment 1.
Fig. 3 A are coating cross sections ESEM pattern and power spectrum line scanning collection of illustrative plates.Fig. 3 B are coating cross sections described in Fig. 3 A
Si element energy spectral line scanning spectras.Fig. 3 C are the C element energy spectral line scanning spectra of coating cross sections described in Fig. 3 A.Fig. 3 D are Fig. 3 A
The Zr element energy spectral line scanning spectras of the coating cross sections.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
If not specified, the raw material described in the embodiment of the present application is commercially available.
Embodiment 1
It is 1.83g/cm by density3C/C composites cut into the fritter of 20mm × 20mm × 5mm, respectively with 400,
1200 and No. 2400 sand paperings；It is cleaned by ultrasonic 10 minutes in water and acetone successively；200 DEG C of 30 points of dryings in drying box
Clock, then in Muffle furnace 400 DEG C heat 60 minutes, cool down it is standby.112 grams of silica flours (purity 99.5%) and 91 grams are weighed respectively
Zirconium powder (purity 99.5%), Si-Zr alloy blocks are smelted into being put into arc-melting furnace after grinding uniformly in mortar, will be melted
Alloy block crush it is standby.Treated C/C composites and the Si-Zr alloys crushed are put into graphite crucible, then by stone
Black crucible is put into high vacuum sintering furnace, is evacuated to 9 × 10-2Pa；Start heating schedule, using the rate of heat addition of 10 DEG C/min
1600 DEG C are heated to, 3h is incubated；Insulation is cooled to 400 DEG C after terminating with the cooldown rate of 5 DEG C/min, closes power supply furnace cooling
It is to obtain surface to prepare the C/C composites for having ZrC coatings that graphite crucible is opened to room temperature, after blow-on.
The XRD spectrum of obtained C/C composites ZrC coating surfaces is shown in Fig. 1.Fig. 1 shows the diffraction maximum for comprising only ZrC,
Illustrate that prepared coating is ZrC coatings.From the scanning electron microscope (SEM) photograph (Fig. 2) of coating surface it can be seen that coating surface it is fine and close,
Completely, there is no the defects such as hole.The scanning electron microscope (SEM) photograph (Fig. 3 A) of coating cross sections and its power spectrum line scanning collection of illustrative plates (figure at interface
3B, 3C, 3D) show that coating and matrix are combined closely, form a layer thickness between ZrC coatings and C/C matrices of composite materials
About 7 μm of SiC transition zones.The formation of SiC transition zones can effectively alleviate the heat mistake between ZrC coatings and C/C matrices of composite materials
Match somebody with somebody, reduce thermal residual strain, reduce coating thermal cycle and impact under cracking and come off.
Embodiment 2
It is 1.68g/cm by density3C/C composites cut into the fritter of 40 × 20 × 5mm, respectively with 400,800 and
No. 1200 sand paperings；It is cleaned by ultrasonic 10 minutes in water and acetone successively；100 DEG C of dryings 50 minutes in drying box, then
500 DEG C are heated 40 minutes in Muffle furnace, are cooled down standby.126 grams of silica flours (purity 99.5%) and 45.6 grams of zirconium powders are weighed respectively
(purity 99.5%), is smelted into Si-Zr alloy blocks, by melted conjunction in being put into arc-melting furnace after grinding uniformly in mortar
Gold bullion is crushed standby.C/C composites and the Si-Zr alloys crushed are put into graphite crucible, graphite crucible is then put into height
In vacuum sintering furnace, 5Pa is evacuated to；Start heating schedule, using the heating rate of 15 DEG C/min to 1800 DEG C, insulation
1h；Insulation is cooled to 400 DEG C after terminating with the cooldown rate of 5 DEG C/min, closes power supply and cools to room temperature with the furnace, is opened after blow-on
Graphite crucible is to obtain surface to prepare the C/C composites for having ZrC coatings.
The XRD spectrum of obtained C/C composites ZrC coatings is similar to Example 1, comprises only the diffraction maximum of ZrC.Coating
Structure is same as Example 1, forms one layer of SiC transition zone between ZrC coatings and C/C matrices of composite materials, coating is fine and close,
Completely, there is no the defects such as hole.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of preparation method of C/C composite material surfaces ZrC coatings, comprises the following steps：
(1) C/C composites are pre-processed；
(2) alloyage raw material, melting obtains liquid reactive sintering Si-Zr alloys；
(3) the C/C composites after step (1) treatment and the liquid reactive sintering of step (2) are placed in Gao Zhen with Si-Zr alloys
In empty sintering furnace, heating, insulation；Insulation is cooled down after terminating and come out of the stove, that is, obtain C/C composite material surface ZrC coatings.
2. preparation method according to claim 1, it is characterised in that the method for pretreatment C/C composites in step (1)
For：By the 300-2500 sand paperings of C/C composites, it is cleaned by ultrasonic 5-10 minutes in water and acetone successively；After cleaning
C/C composites dry 10-100 minutes in 60-200 DEG C of air atmosphere, then heated in 300-600 DEG C of air atmosphere
10-150 minutes, cool down standby.
3. preparation method according to claim 1, it is characterised in that step (2) be from purity be more than 99% it is pure
Silicon and pure zirconium alloyage raw material.
4. preparation method according to claim 3, it is characterised in that step (2) is according to alloying element atomic percent Si
75%-95%, Zr 5%-25% prepare Si-Zr alloys.
5. preparation method according to claim 1, it is characterised in that step (2) is molten with vacuum arc melting furnace or sensing
Furnace melting obtains liquid reactive sintering Si-Zr alloys, and in order to ensure the uniformity of alloying component, Si-Zr alloys can be repeatedly
Melting 2-4 times.
6. preparation method according to claim 1, it is characterised in that in the high vacuum sintering furnace of step (3), vacuum is
8×10-2-10Pa。
7. according to any described preparation methods of claim 1-6, it is characterised in that step (3) described heating, its method is to adopt
With the heating rate of 5-25 DEG C/min by high vacuum sintering furnace temperature rise to liquid reactive sintering temperature, the liquid reactive sintering
Temperature is higher than 50-500 DEG C of Si-Zr alloy melting points.
8. according to any described preparation methods of claim 1-6, it is characterised in that step (3) insulation refers in liquid phase
Reaction-sintered temperature 0.5-10h.
9. according to any described preparation methods of claim 1-6, it is characterised in that step (3) is with the cooling of 2-25 DEG C/min
Speed is cooled to 300-500 DEG C, then cools to less than 100 DEG C with the furnace and comes out of the stove, that is, obtain C/C composite material surface ZrC coatings.
10. application of any described preparation methods of claim 1-9 in the aerospace material of resistance to ablation is prepared.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710100435.7A CN106892684B (en) | 2017-02-23 | 2017-02-23 | Preparation method of ZrC coating on surface of C/C composite material |
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| CN201710100435.7A CN106892684B (en) | 2017-02-23 | 2017-02-23 | Preparation method of ZrC coating on surface of C/C composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113213472A (en) * | 2021-05-20 | 2021-08-06 | 哈尔滨工业大学 | Method for preparing complex-structure carbon material anti-oxidation coating with assistance of metal liquid phase |
| CN114920589A (en) * | 2022-07-20 | 2022-08-19 | 湖南泰坦未来科技有限公司 | Carbon-based composite material and preparation method and application thereof |
-
2017
- 2017-02-23 CN CN201710100435.7A patent/CN106892684B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 仝永刚: "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", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113213472A (en) * | 2021-05-20 | 2021-08-06 | 哈尔滨工业大学 | Method for preparing complex-structure carbon material anti-oxidation coating with assistance of metal liquid phase |
| CN114920589A (en) * | 2022-07-20 | 2022-08-19 | 湖南泰坦未来科技有限公司 | Carbon-based composite material and preparation method and application thereof |
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