CN104130019B - The crystal whisker toughened C-AlPO of carbon/carbon composite mullite 4-MoSi 2the preparation method of compound coating - Google Patents

The crystal whisker toughened C-AlPO of carbon/carbon composite mullite 4-MoSi 2the preparation method of compound coating Download PDF

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CN104130019B
CN104130019B CN201410328526.2A CN201410328526A CN104130019B CN 104130019 B CN104130019 B CN 104130019B CN 201410328526 A CN201410328526 A CN 201410328526A CN 104130019 B CN104130019 B CN 104130019B
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alpo
carbon
crystal whisker
powder
mosi
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CN104130019A (en
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黄剑锋
张博
曹丽云
李翠艳
费杰
吴建鹏
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Yancheng hi tech Pioneer Park Co.,Ltd.
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Shaanxi University of Science and Technology
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Abstract

The invention provides the crystal whisker toughened C-AlPO of a kind of carbon/carbon composite mullite 4-MoSi 2the preparation method of compound coating: by C-AlPO 4powder and molybdenum disilicide powder and mullite crystal whisker are scattered in propylene glycol, ultrasonic vibration, stir to obtain suspending liquid A; In suspending liquid A, add elemental iodine, heat while stirring after ultrasonic vibration to obtain suspension B; Suspension B is poured in water heating kettle, then the negative electrode of the carbon/carbon compound material sample holder with SiC coating in water heating kettle is pressed from both sides, under magnetic field and ultrasonic wave existent condition, then carry out the reaction of hydro-thermal two pulse electrophoretic deposition; By dry for the style of taking out, coatingsurface flawless prepared by the present invention, the anchoring strength of coating being incorporated into matrix is large, and the present invention can obtain structure-controllable and C-AlPO of good performance at low temperatures 4-MoSi 2compound external coating (EC), preparation technology is simple, and easy to operate, raw material is easy to get, and preparation cost is lower.

Description

The crystal whisker toughened C-AlPO of carbon/carbon composite mullite 4-MoSi 2the preparation method of compound coating
Technical field
The invention belongs to C/C technical field of composite materials, relate to a kind of preparation method of C/C matrix material compound coating, be specifically related to a kind of ultrasonic-magnetic control-hydro-thermal two pulse electrophoretic deposition method prepares the crystal whisker toughened C-AlPO of carbon/carbon composite mullite 4-MoSi 2the method of compound coating.
Background technology
Carbon/carbon (C/C) matrix material has the excellent properties such as thermal expansivity is low, density is low, high temperature resistant, resistance to ablation, high strength, high-modulus, particularly within 2200 DEG C of inert atmosphere, under condition, its strength and modulus raises and the excellent properties of increase with temperature, makes it have broad application prospects at aerospace field.But C/C matrix material will be oxidized at the aerobic environment more than 370 DEG C, oxidation quality loss causes its strength degradation, limits its practical application.Therefore, solving C/C matrix material high-temp antioxidizing problem is the key making full use of its performance.
Improve C/C compound material antioxygenic property and mainly contain two kinds of approach: one is matrix modification technology; One is surface-coating technology.Research shows, matrix modification technology is only applicable to the oxidation protection of low-temperature zone to C/C material.Coating technology then can solve the high temperature oxidation problem of C/C material.
The more C/C matrix material high-temperature oxidation resistant coating of current research has SiC [Y.L.Zhang, H.J.Li, Q.G.Fu.AC/SiCgradientoxidationprotectivecoatingforcarbon/carboncomposites.Surf.Coaf.Techol., 2006, 201:3491-3495.], Si-MoSi2 [Yu-LeiZhang, He-JunLi, Xi-YuanYao.OxidationprotectionofC/SiCcoatedcarbon/carbon compositeswithSi-Mocoatingathightemperature, Corros.Sci., 2011, 53:2075-2079.], Mo-Si-N [Z.H.Lai, J.C.Zhu, J.H.Jeon.PhaseconstitutionsofMo-Si-Nanti-oxidationmulti-layercoatingsonC/Ccompositesbyfusedslurry.Mater.Sci.Eng. A, 2009, 499:267-270.] and Si-Mo-SiO 2[Z.Q.Yan, X.Xiong, P.Xiao, etal.Si-Mo-SiO 2oxidationprotectivecoatingspreparedbyslurrypaintingforC/ C-SiCcomposites.Surf.Coaf.Techol., 2008,202:4734-4740.] etc., it is other compound coating of transition layer that Huang Jianfeng etc. are investigated with SiC, as SiC/MoSi 2-CrSi 2-Si [Li-He-Jun, FengTao, FuQian-Gang.OxidationanderosionresistanceofMoSi 2-CrSi 2-Si/SiCcoatedC/Ccompositesinstaticandaerodynamicoxidation environment, Carbon, 2012,48:1636-1642.] etc.But above-mentioned coating does not also reach the application request under 1600-2500 DEG C of Fast ion flow Scouring Condition, the high-temperature oxidation resistant ceramic coating of carbon/carbon compound material easily come off under high-speed fuel gas washes away environment and the oxidation protection time short.
In order to solve SiC and MoSi 2due to defect problem that expansion coefficient difference causes between inside and outside coating, use for reference the thought [XWYin of Whisker-Reinforced Ceramics, LFCheng, LTZhang, etal.MicrostructureandoxidationresistanceofCarbon/silico ncarbidecompositesinfiltratedwithchromiumsilicide [J] .MaterialsScienceandEngineeringA, 2000, 290:89-94.], the coefficient of expansion utilizing mullite lower and the physical chemistry consistency good with SiC are passed through to introduce mullite crystal whisker in the coating, inside and outside coating can be strengthened, bonding force between matrix and undercoat, effectively reduce C-AlPO 4-MoSi 2because of stress that coefficient of thermal expansion mismatch and weave construction are suddenlyd change and caused between external coating (EC) and SiC undercoat, reduce coating cracking and trend [the once mediate banyan peeled off to a certain extent, Li Hejun, Yang Zheng, Deng. surface siliconization is on the impact [J] of C/C microstructure of composite structure. metal heat treatmet journal, 2000,21 (2): 64-67.].
Because mullite, SiC have good materialization consistency, wettability and close thermal expansivity [C.Friedrich, R.Gadow, M.Speicher.Protectivemultilayercoatingsforcarbon-carbonc omposites, Surf.Coat.Technol., 2002,151-152:405-411.].Therefore can fully sprawl each other, packing defect.The coefficient of expansion of mullite crystal whisker is 4.4 ~ 5.5 × 10 – 6/ DEG C, fusing point is 2000 DEG C, and still very stable 1800 DEG C time, 1810 DEG C are decomposed into corundum and liquid phase.Mullite crystal whisker, as the activeness and quietness material of a kind of potential ceramic base, metal matrix, polymer matrix composite, can be widely used in the field such as high-temperature structural material, friction materials.There is good high high-temp stability and high-temperature oxidation resistance.And mullite crystal whisker can strengthen inside and outside coating, bonding force between matrix and undercoat as toughening material, effectively prevent the problem that coating high-temp ftractures and comes off, adopt the coated designs of crystal whisker toughened composite material type simultaneously, it effectively can utilize composite principle, have complementary advantages, while raising antiscour shear stress, also greatly can improve antioxidant property.
Up to the present the preparation method of external coating (EC) is varied, mainly contains following several: supercritical fluid technology, chemical vapour deposition, entrapping method, formed in situ, sol-gel method, molten slurry coating reaction, detonation flame spraying and ultrasonic spray method etc.Adopt supercritical fluid technology to prepare C/C composite coating due to the process implementing of preparation to need to carry out at high temperature under high pressure, higher to the requirement of equipment, and the external coating (EC) formed will be heat-treated under an inert atmosphere, long [the BemeburgPL of preparation cycle, KrukonisVJ.Processingofcarbon/carboncompositesusingsuper criticalfluidtechnology [P] .UnitedStatesPatentUS5035921, 1991], the coating adopting formed in situ legal system standby needs pyroprocessing at 1500 DEG C, and can not once prepare [HuangJian-Feng, LiHe-Jun, ZengXie-Rong, LiKe-Zhi.Surf.coat.Technol.2006, 200, 5379.], easily ftracture and coat-thickness deficiency [HuangJian-Feng in the external coating (EC) surface adopting sol-gel method to prepare, ZengXie-Rong, LiHe-Jun, XiongXin-Bo, SunGuo-ling.Surf.coat.Technol.2005, 190, 255.], and adopt molten slurry coating reaction method to prepare coating still to exist and repeatedly will brush and can not once prepare, need the drawback [FuQian-Gang of Post isothermal treatment, LiHe-Jun, WangYong-Jie, LiKe-Zhi, TaoJun.Surface & CoatingTechnology.2010, 204, 1832.], although same employing detonation flame spraying and ultrasonic spray method have prepared alloy part coating, but, this technique also has a lot of incomplete place, prepared high-temp antioxidizing performance is still needed and will further be improved [TerentievaVS, BogachkovaOP, GoriatchevaEV.Methodforprotectingproductsmadeofarefracto rymaterialagainstoxidation, andresultingproducts [p] .US5677060, 1997.], and adopt ultrasonic-magnetic control-hydro-thermal two pulse electrophoretic deposition method to prepare the toughness reinforcing C-AlPO of mullite crystal whisker 4-MoSi 2the method of compound external coating (EC) have not been reported.
Summary of the invention
The object of the present invention is to provide the crystal whisker toughened C-AlPO of a kind of carbon/carbon composite mullite 4-MoSi 2the preparation method of compound coating.
For achieving the above object, present invention employs following technical scheme.
1) first by mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4powder is scattered in 3 ~ 3.5L propylene glycol and obtains mixture A, mullite crystal whisker, molybdenum disilicide powder and C-AlPO in mixture A 4the total concn of powder is 60 ~ 65g/L, and the content of mullite crystal whisker is mullite crystal whisker, molybdenum disilicide powder and C-AlPO 410 ~ 30% of powder total mass, the content of molybdenum disilicide powder is 10 ~ 40%, C-AlPO of described total mass 4the content of powder is 50 ~ 60% of described total mass, and by mixture A ultrasonic vibration 30 ~ 50min, then magnetic agitation 2 ~ 4h obtains suspending liquid A;
2) in suspending liquid A, add elemental iodine and obtain mixture B, in mixture B, the concentration of elemental iodine is 6.0 ~ 7.0g/L, and 30 ~ 60min is swung in the acoustic shock of mixture B ultrasonic, and then limit heating edge magnetic agitation 2 ~ 4h obtains suspension B, and Heating temperature is 80 ~ 90 DEG C;
3) pouring suspension B into one with Graphite Electrodes is anode, conducting base is in the water heating kettle of negative electrode, by the carbon/carbon compound material sample holder with SiC coating on negative electrode, then seal water heating kettle and the water heating kettle after sealing is put into ultrasonic generator, again ultrasonic generator is put into magnetic field generator and (provide directional magnetic field, in order to strengthen the particle of positively charged in suspension to movable cathode) in, then the anode and cathode of water heating kettle is received on the pulse power respectively, then under magnetic field and ultrasonic wave existent condition, carry out the reaction of hydro-thermal two pulse electrophoretic deposition, the magneticstrength of magnetic field generator controls at 200 ~ 300A/m, hydrothermal temperature controls at 240 ~ 360 DEG C of (water heating kettles, magnetic field generator and ultrasonic generator all put into electric drying oven with forced convection, hydrothermal temperature is controlled by electric drying oven with forced convection), the power of ultrasonic generator controls at 1600 ~ 2000W, pulse power voltage control is at 220V, pulse power periodic Control is at 1500 ~ 3500ms, pulse power peak value comparison method is at 80 ~ 110A, pulse power direct impulse working time control is at 400 ~ 800ms, pulse power reverse impulse working time control is at 350 ~ 550ms, the positive and negative pulse width control of the pulse power is at 200 ~ 400 μ s, pulse power group working time control is at 5 ~ 15min, pulse power net cycle time controls at 15 ~ 35min, room temperature is naturally cooled to after question response terminates,
4) through step 3) after, open water heating kettle and take out sample, the style of taking-up is put into electric drying oven with forced convection and at 50 ~ 90 DEG C dry 1 ~ 3h.
The length-to-diameter ratio of described mullite crystal whisker is 50 ~ 100.
Described molybdenum disilicide powder median size controls at 4 ~ 7 μm.
Described C-AlPO 4raw powder's production technology is: aluminum phosphate powder is carried out ball milling after 1400 DEG C of calcining 20min, obtains the C-AlPO that median size controls at 4 ~ 7 μm 4powder.
Purity >=99.7% of described elemental iodine, purity >=99.8% of propylene glycol.
The ultrasonic power of described ultrasonic vibration is 1500 ~ 2000W.
The compactedness of described water heating kettle is 50 ~ 60%.
Beneficial effect of the present invention is embodied in:
1) the crystal whisker toughened C-AlPO of carbon/carbon composite mullite for preparing of the present invention 4-MoSi 2compound external coating (EC) surface flawless, it is better that the carbon base body coated with SiC is combined;
2) the present invention can obtain structure-controllable and carbon/carbon composite mullite of good performance is crystal whisker toughened at low temperatures
C-AlPO 4-MoSi 2compound external coating (EC);
3) preparation technology of the present invention is simple, and easy to operate, raw material is easy to get, and preparation cost is lower.
Accompanying drawing explanation
Fig. 1 is the toughness reinforcing C-AlPO of mullite crystal whisker prepared by the embodiment of the present invention 1 4the XRD figure of-MoSi compound external coating (EC);
Fig. 2 is the toughness reinforcing C-AlPO of mullite crystal whisker prepared by the embodiment of the present invention 1 4-MoSi 2the surperficial SEM figure of compound external coating (EC).
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
Embodiment 1:
1) commercially available mullite crystal whisker (length-to-diameter ratio is 50 ~ 100) is selected, C-AlPO 4(commercially available aluminum phosphate powder through Overheating Treatment, after namely calcining 20min at 1400 DEG C, ball milling prepares C-AlPO to powder 4powder, median size controls at 4 ~ 7 μm), (commercially available molybdenum disilicide powder is through dry ball milling 20h for molybdenum disilicide powder, median size controls at 4 ~ 7 μm), elemental iodine (purity>=99.7%), and propylene glycol (purity>=99.8%) is raw material;
2) first by mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4powder is scattered in 3L propylene glycol that (content of mullite crystal whisker is mullite crystal whisker, molybdenum disilicide powder and C-AlPO 410% of powder total mass, the content of molybdenum disilicide powder is 40%, C-AlPO of described total mass 4the content of powder is 50% of described total mass), be mixed with mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4the total concn of powder is the suspension of 60g/L, by suspension ultrasonic vibration (ultrasonic power is 1600W) 50min, is then placed on magnetic stirring apparatus and stirs 2h, obtain suspending liquid A;
3) in suspending liquid A, add elemental iodine (concentration controlling elemental iodine is 6.2g/L) ultrasonic vibration (ultrasonic power is 1600W) 50min afterwards, then be placed on magnetic stirring apparatus and stir 2h (carrying out in whipping process heating and controlling Heating temperature is 80 DEG C), obtain suspension B;
4) suspension B is poured into one be anode with Graphite Electrodes, in the conducting base water heating kettle that is negative electrode (compactedness is 50%), by on the negative electrode of the carbon/carbon compound material sample holder with SiC coating in water heating kettle, style is immersed in suspension B, then seal water heating kettle and put it in ultrasonic generator, then ultrasonic generator is put into magnetic field generator, again the anode and cathode of water heating kettle is received respectively on the corresponding the two poles of the earth of SMD-P type intelligence multipulse electroplating power supply (great Shun electroplating device company limited of Handan City), then under magnetic field and ultrasonic wave existent condition, the reaction of hydro-thermal two pulse electrophoretic deposition is carried out: the magneticstrength of magnetic field generator controls at 200A/m, hydrothermal temperature controls at 240 DEG C, the power of ultrasonic generator controls at 1600W, voltage of supply controls at 220V, pulse power periodic Control is at 1500ms, peak value comparison method is at 80A, direct impulse working time control is at 400ms, reverse impulse working time control is at 350ms, positive and negative pulse width control is at 200 μ s, group working time control is at 5min, net cycle time controls at 15min, room temperature is naturally cooled to after question response terminates,
5) open water heating kettle, take out sample, then the style of taking-up is put into electric drying oven with forced convection and at 50 DEG C dry 3h, obtain the toughness reinforcing C-AlPO of final product mullite crystal whisker 4-MoSi 2the SiC – C/C sample of compound external coating (EC) protection.
Embodiment 2:
1) commercially available mullite crystal whisker (length-to-diameter ratio is 50 ~ 100) is selected, C-AlPO 4(commercially available aluminum phosphate powder through Overheating Treatment, after namely calcining 20min at 1400 DEG C, ball milling prepares C-AlPO to powder 4powder, median size controls at 4 ~ 7 μm), (commercially available molybdenum disilicide powder is through dry ball milling 20h for molybdenum disilicide powder, median size controls at 4 ~ 7 μm), elemental iodine (purity>=99.7%), and propylene glycol (purity>=99.8%) is raw material;
2) first by mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4powder is scattered in 3.1L propylene glycol that (content of mullite crystal whisker is mullite crystal whisker, molybdenum disilicide powder and C-AlPO 415% of powder total mass, the content of molybdenum disilicide powder is 35%, C-AlPO of described total mass 4the content of powder is 50% of described total mass), be mixed with mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4the total concn of powder is the suspension of 62g/L, by suspension ultrasonic vibration (ultrasonic power is 1700W) 45min, is then placed on magnetic stirring apparatus and stirs 2.5h, obtain suspending liquid A;
3) in suspending liquid A, add elemental iodine (concentration controlling elemental iodine is 6.4g/L) ultrasonic vibration (ultrasonic power is 1700W) 45min afterwards, then be placed on magnetic stirring apparatus and stir 2.5h (carrying out in whipping process heating and controlling Heating temperature is 80 DEG C), obtain suspension B;
4) suspension B is poured into one be anode with Graphite Electrodes, in the conducting base water heating kettle that is negative electrode (compactedness is 50%), by on the negative electrode of the carbon/carbon compound material sample holder with SiC coating in water heating kettle, style is immersed in suspension B, then seals water heating kettle and puts it in ultrasonic generator, then ultrasonic generator is put into magnetic field generator, again the anode and cathode of water heating kettle is received respectively on SMD-P type intelligence corresponding the two poles of the earth of multipulse electroplating power supply, then under magnetic field and ultrasonic wave existent condition, the reaction of hydro-thermal two pulse electrophoretic deposition is carried out: the magneticstrength of magnetic field generator controls at 220A/m, hydrothermal temperature controls at 280 DEG C, the power of ultrasonic generator controls at 1700W, voltage of supply controls at 220V, pulse power periodic Control is at 2000ms, peak value comparison method is at 90A, direct impulse working time control is at 500ms, reverse impulse working time control is at 400ms, positive and negative pulse width control is at 250 μ s, group working time control is at 10min, net cycle time controls at 20min, room temperature is naturally cooled to after question response terminates,
5) open water heating kettle, take out sample, then the style of taking-up is put into electric drying oven with forced convection and at 60 DEG C dry 2.5h, obtain the toughness reinforcing C-AlPO of final product mullite crystal whisker 4-MoSi 2the SiC – C/C sample of compound external coating (EC) protection.
Embodiment 3:
1) commercially available mullite crystal whisker (length-to-diameter ratio is 50 ~ 100) is selected, C-AlPO 4(commercially available aluminum phosphate powder through Overheating Treatment, after namely calcining 20min at 1400 DEG C, ball milling prepares C-AlPO to powder 4powder, median size controls at 4 ~ 7 μm), (commercially available molybdenum disilicide powder is through dry ball milling 20h for molybdenum disilicide powder, median size controls at 4 ~ 7 μm), elemental iodine (purity>=99.7%), and propylene glycol (purity>=99.8%) is raw material;
2) first by mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4powder is scattered in 3.3L propylene glycol that (content of mullite crystal whisker is mullite crystal whisker, molybdenum disilicide powder and C-AlPO 420% of powder total mass, the content of molybdenum disilicide powder is 25%, C-AlPO of described total mass 4the content of powder is 55% of described total mass), be mixed with mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4the total concn of powder is the suspension of 63g/L, by suspension ultrasonic vibration (ultrasonic power is 1800W) 40min, is then placed on magnetic stirring apparatus and stirs 3h, obtain suspending liquid A;
3) in suspending liquid A, add elemental iodine (concentration controlling elemental iodine is 6.6g/L) ultrasonic vibration (ultrasonic power is 1800W) 40min afterwards, then be placed on magnetic stirring apparatus and stir 3h (carrying out in whipping process heating and controlling Heating temperature is 85 DEG C), obtain suspension B;
4) suspension B is poured into one be anode with Graphite Electrodes, in the conducting base water heating kettle that is negative electrode (compactedness is 55%), by on the negative electrode of the carbon/carbon compound material sample holder with SiC coating in water heating kettle, style is immersed in suspension B, then seals water heating kettle and puts it in ultrasonic generator, then ultrasonic generator is put into magnetic field generator, again the anode and cathode of water heating kettle is received respectively on SMD-P type intelligence corresponding the two poles of the earth of multipulse electroplating power supply, then under magnetic field and ultrasonic wave existent condition, the reaction of hydro-thermal two pulse electrophoretic deposition is carried out: the magneticstrength of magnetic field generator controls at 240A/m, hydrothermal temperature controls at 280 DEG C, the power of ultrasonic generator controls at 1800W, voltage of supply controls at 220V, pulse power periodic Control is at 2500ms, peak value comparison method is at 100A, direct impulse working time control is at 600ms, reverse impulse working time control is at 450ms, positive and negative pulse width control is at 300 μ s, group working time control is at 15min, net cycle time controls at 25min, room temperature is naturally cooled to after question response terminates,
5) open water heating kettle, take out sample, then the style of taking-up is put into electric drying oven with forced convection and at 70 DEG C dry 2h, obtain the toughness reinforcing C-AlPO of final product mullite crystal whisker 4-MoSi 2the SiC – C/C sample of compound external coating (EC) protection.
Embodiment 4:
1) commercially available mullite crystal whisker (length-to-diameter ratio is 50 ~ 100) is selected, C-AlPO 4(commercially available aluminum phosphate powder through Overheating Treatment, after namely calcining 20min at 1400 DEG C, ball milling prepares C-AlPO to powder 4powder, median size controls at 4 ~ 7 μm), (commercially available molybdenum disilicide powder is through dry ball milling 20h for molybdenum disilicide powder, median size controls at 4 ~ 7 μm), elemental iodine (purity>=99.7%), and propylene glycol (purity>=99.8%) is raw material;
2) first by mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4powder is scattered in 3.4L propylene glycol that (content of mullite crystal whisker is mullite crystal whisker, molybdenum disilicide powder and C-AlPO 425% of powder total mass, the content of molybdenum disilicide powder is 15%, C-AlPO of described total mass 4the content of powder is 60% of described total mass), be mixed with mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4the total concn of powder is the suspension of 64g/L, by suspension ultrasonic vibration (ultrasonic power is 1900W) 35min, is then placed on magnetic stirring apparatus and stirs 3.5h, obtain suspending liquid A;
3) in suspending liquid A, add elemental iodine (concentration controlling elemental iodine is 6.8g/L) ultrasonic vibration (ultrasonic power is 1900W) 35min afterwards, then be placed on magnetic stirring apparatus and stir 3.5h (carrying out in whipping process heating and controlling Heating temperature is 90 DEG C), obtain suspension B;
4) suspension B is poured into one be anode with Graphite Electrodes, in the conducting base water heating kettle that is negative electrode (compactedness is 60%), by on the negative electrode of the carbon/carbon compound material sample holder with SiC coating in water heating kettle, style is immersed in suspension B, then seals water heating kettle and puts it in ultrasonic generator, then ultrasonic generator is put into magnetic field generator, again the anode and cathode of water heating kettle is received respectively on SMD-P type intelligence corresponding the two poles of the earth of multipulse electroplating power supply, then under magnetic field and ultrasonic wave existent condition, the reaction of hydro-thermal two pulse electrophoretic deposition is carried out: the magneticstrength of magnetic field generator controls at 260A/m, hydrothermal temperature controls at 300 DEG C, the power of ultrasonic generator controls at 1900W, voltage of supply controls at 220V, pulse power periodic Control is at 3000ms, peak value comparison method is at 110A, direct impulse working time control is at 700ms, reverse impulse working time control is at 500ms, positive and negative pulse width control is at 350 μ s, group working time control is at 15min, net cycle time controls at 30min, room temperature is naturally cooled to after question response terminates,
5) open water heating kettle, take out sample, then the style of taking-up is put into electric drying oven with forced convection and at 80 DEG C dry 1.5h, obtain the toughness reinforcing C-AlPO of final product mullite crystal whisker 4-MoSi 2the SiC – C/C sample of compound external coating (EC) protection.
Embodiment 5:
1) commercially available mullite crystal whisker (length-to-diameter ratio is 50 ~ 100) is selected, C-AlPO 4(commercially available aluminum phosphate powder through Overheating Treatment, after namely calcining 20min at 1400 DEG C, ball milling prepares C-AlPO to powder 4powder, median size controls at 4 ~ 7 μm), (commercially available molybdenum disilicide powder is through dry ball milling 20h for molybdenum disilicide powder, median size controls at 4 ~ 7 μm), elemental iodine (purity>=99.7%), and propylene glycol (purity>=99.8%) is raw material;
2) first by mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4powder is scattered in 3.5L propylene glycol that (content of mullite crystal whisker is mullite crystal whisker, molybdenum disilicide powder and C-AlPO 430% of powder total mass, the content of molybdenum disilicide powder is 10%, C-AlPO of described total mass 4the content of powder is 60% of described total mass), be mixed with mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4the total concn of powder is the suspension of 65g/L, by suspension ultrasonic vibration (ultrasonic power is 2000W) 30min, is then placed on magnetic stirring apparatus and stirs 4h, obtain suspending liquid A;
3) in suspending liquid A, add elemental iodine (concentration controlling elemental iodine is 7.0g/L) ultrasonic vibration (ultrasonic power is 2000W) 30min afterwards, then be placed on magnetic stirring apparatus and stir 4h (carrying out in whipping process heating and controlling Heating temperature is 90 DEG C), obtain suspension B;
4) suspension B is poured into one be anode with Graphite Electrodes, in the conducting base water heating kettle that is negative electrode (compactedness is 60%), by on the negative electrode of the carbon/carbon compound material sample holder with SiC coating in water heating kettle, style is immersed in suspension B, then seals water heating kettle and puts it in ultrasonic generator, then ultrasonic generator is put into magnetic field generator, again the anode and cathode of water heating kettle is received respectively on SMD-P type intelligence corresponding the two poles of the earth of multipulse electroplating power supply, then under magnetic field and ultrasonic wave existent condition, the reaction of hydro-thermal two pulse electrophoretic deposition is carried out: the magneticstrength of magnetic field generator controls at 300A/m, hydrothermal temperature controls at 320 DEG C, the power of ultrasonic generator controls at 2000W, voltage of supply controls at 220V, pulse power periodic Control is at 3500ms, peak value comparison method is at 110A, direct impulse working time control is at 800ms, reverse impulse working time control is at 550ms, positive and negative pulse width control is at 400 μ s, group working time control is at 15min, net cycle time controls at 35min, room temperature is naturally cooled to after question response terminates,
5) open water heating kettle, take out sample, then the style of taking-up is put into electric drying oven with forced convection and at 90 DEG C dry 1h, obtain the toughness reinforcing C-AlPO of final product mullite crystal whisker 4-MoSi 2the SiC – C/C sample of compound external coating (EC) protection.
The present invention has successfully prepared mullite crystal whisker-C-AlPO as seen from Figure 1 4-MoSi 2compound external coating (EC), the as seen from Figure 2 mullite crystal whisker-C-AlPO for preparing of the present invention 4-MoSi 2compound external coating (EC) surface is comparatively fine and close, uniform particles and have the phenomenon of spark sintering.
Ultrasonic-magnetic control-its feature of hydro-thermal two pulse electrophoretic deposition method, first be the sedimentation rate accelerating suspended particle under hydro-thermal supercritical environment, suspended particle can be reacted at matrix surface rapidly, and the localized hyperthermia simultaneously utilizing ultrasonic wave to produce in reaction system and high pressure effectively reduce mullite and C-AlPO 4, MoSi 2the Activation energy of suspended particles, it is made to react more completely with abundant in water heat electrophoresis deposition process, thus obtain the coating of compact structure, and suspended particle charged in magnetic field can orientation movement, can control movement velocity and the direction of particle, thus control the microstructure of coating, therefore dense coating can be prepared, can deposit on complex-curved, efficiency is high, and speed is fast simultaneously.Secondly, be under dual-pulse power supply, the intermittence electric discharge of negative and positive the two poles of the earth, makes suspended particle be deposited on matrix surface, avoids the coating non-uniform phenomenon that the electric discharge of traditional continuous arcing produces, thus obtains the coating of compact structure.Adopt this method can avoid adopting conventional high-temperature coating and the phase transformation that causes and embrittlement, solve the thermal damage to matrix in coating preparation process to a certain extent; Simultaneously because deposition process is non-streamlined process, uniform settled layer can be formed at matrix surface that is complex-shaped or porous surface, and can accurately control coated component, thickness and porosity, make the heterogeneous compound coating of simple efficient preparation and gradient ceramic coating become possibility; Moreover electrophoretic deposition is the displacement of charged particle, can not because of the bonding force of a large amount of gases affect coating of producing during brine electrolysis solvent and matrix.In addition, direct impulse controls coated grains size and impurity level, and reverse impulse controls sedimentation velocity and thickness distribution, achieves and obtains the toughness reinforcing C-AlPO of mullite crystal whisker fine and close, that have micro-flaw, different thickness in controlled conditions 4-MoSi 2coating.Ultrasonic-magnetic control-hydro-thermal two pulse electrophoretic deposition also has the features such as simple to operation, cost is low, depositing operation is easy to control.
The present invention prepares densification, the toughness reinforcing C-AlPO of mullite crystal whisker that force of cohesion is good 4-MoSi 2compound coating; be expected to improve under dynamic environment is washed away in combustion gas the temperature of the protection against oxidation of C/C matrix material; be expected to the new breakthrough obtaining C/C composite coating high-temperature oxidation resistance, significant in the application of high-temperature field to expansion C/C matrix material.

Claims (7)

1. the crystal whisker toughened C-AlPO of carbon/carbon composite mullite 4-MoSi 2the preparation method of compound coating, is characterized in that: comprise the following steps:
1) first by mullite crystal whisker, molybdenum disilicide powder and C-AlPO 4powder is scattered in propylene glycol and obtains mixture A, mullite crystal whisker, molybdenum disilicide powder and C-AlPO in mixture A 4the total concn of powder is 60 ~ 65g/L, and the content of mullite crystal whisker is mullite crystal whisker, molybdenum disilicide powder and C-AlPO 410 ~ 30% of powder total mass, the content of molybdenum disilicide powder is 10 ~ 40%, C-AlPO of described total mass 4the content of powder is 50 ~ 60% of described total mass, and by mixture A ultrasonic vibration 30 ~ 50min, then magnetic agitation 2 ~ 4h obtains suspending liquid A;
2) in suspending liquid A, add elemental iodine and obtain mixture B, in mixture B, the concentration of elemental iodine is 6.0 ~ 7.0g/L, and 30 ~ 60min is swung in the acoustic shock of mixture B ultrasonic, and then limit heating edge magnetic agitation 2 ~ 4h obtains suspension B, and Heating temperature is 80 ~ 90 DEG C;
3) pouring suspension B into one with Graphite Electrodes is anode, conducting base is in the water heating kettle of negative electrode, by the carbon/carbon compound material sample holder with SiC coating on negative electrode, then seal water heating kettle and the water heating kettle after sealing is put into ultrasonic generator, again ultrasonic generator is put into magnetic field generator, then the anode and cathode of water heating kettle is received on the pulse power respectively, then under magnetic field and ultrasonic wave existent condition, carry out the reaction of hydro-thermal two pulse electrophoretic deposition, the magneticstrength of magnetic field generator controls at 200 ~ 300A/m, hydrothermal temperature controls at 240 ~ 360 DEG C, the power of ultrasonic generator controls at 1600 ~ 2000W, pulse power voltage control is at 220V, pulse power periodic Control is at 1500 ~ 3500ms, pulse power peak value comparison method is at 80 ~ 110A, pulse power direct impulse working time control is at 400 ~ 800ms, pulse power reverse impulse working time control is at 350 ~ 550ms, the positive and negative pulse width control of the pulse power is at 200 ~ 400 μ s, pulse power group working time control is at 5 ~ 15min, pulse power net cycle time controls at 15 ~ 35min, room temperature is naturally cooled to after question response terminates,
4) through step 3) after, open water heating kettle and take out sample, the sample of taking-up is put into electric drying oven with forced convection and at 50 ~ 90 DEG C dry 1 ~ 3h.
2. the crystal whisker toughened C-AlPO of a kind of carbon/carbon composite mullite according to claim 1 4-MoSi 2the preparation method of compound coating, is characterized in that: the length-to-diameter ratio of described mullite crystal whisker is 50 ~ 100.
3. the crystal whisker toughened C-AlPO of a kind of carbon/carbon composite mullite according to claim 1 4-MoSi 2the preparation method of compound coating, is characterized in that: described molybdenum disilicide powder median size controls at 4 ~ 7 μm.
4. the crystal whisker toughened C-AlPO of a kind of carbon/carbon composite mullite according to claim 1 4-MoSi 2the preparation method of compound coating, is characterized in that: described C-AlPO 4raw powder's production technology is: aluminum phosphate powder is carried out ball milling after 1400 DEG C of calcining 20min, obtains the C-AlPO that median size controls at 4 ~ 7 μm 4powder.
5. the crystal whisker toughened C-AlPO of a kind of carbon/carbon composite mullite according to claim 1 4-MoSi 2the preparation method of compound coating, is characterized in that: purity>=99.7% of described elemental iodine, purity>=99.8% of propylene glycol.
6. the crystal whisker toughened C-AlPO of a kind of carbon/carbon composite mullite according to claim 1 4-MoSi 2the preparation method of compound coating, is characterized in that: the ultrasonic power of described ultrasonic vibration is 1500 ~ 2000W.
7. the crystal whisker toughened C-AlPO of a kind of carbon/carbon composite mullite according to claim 1 4-MoSi 2the preparation method of compound coating, is characterized in that: the compactedness of described water heating kettle is 50 ~ 60%.
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