CN107814589A - A kind of method of oxide in-situ cladding zirconium diboride carborundum reunion powder - Google Patents

A kind of method of oxide in-situ cladding zirconium diboride carborundum reunion powder Download PDF

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CN107814589A
CN107814589A CN201711027516.5A CN201711027516A CN107814589A CN 107814589 A CN107814589 A CN 107814589A CN 201711027516 A CN201711027516 A CN 201711027516A CN 107814589 A CN107814589 A CN 107814589A
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carborundum
powder
zirconium diboride
oxide
reunion
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柳彦博
马壮
郭嘉仪
孙世杰
王皓
张贺
王乙瑾
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Beijing Institute of Technology BIT
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Abstract

The present invention relates to a kind of method of oxide in-situ cladding zirconium diboride carborundum reunion powder, belong to composite powder material technical field.Methods described is to be realized using the zirconium diboride carborundum reunion powder oxide that autoxidation generates under high-temperature oxidation environment to zirconium diboride carborundum reunion powder in-stiu coating, and the composite granule with core shell structure is prepared.The sphericity and consistency of the cladding zirconium diboride carborundum of the oxide with core shell structure prepared using methods described are high, meet requirement of the plasma spraying for powder；The oxide cladding layers of autoxidation generation can suppress the volatilization of carborundum in Plasma Spraying Process Using, reduce the loss of carborundum, and the fusing point of oxide is less than zirconium boride, powder can melt more abundant, caused by further lamella overlaps in filling coating the defects of gap, room, the compactness of coating is improved.

Description

A kind of method of oxide in-situ cladding zirconium diboride-carborundum reunion powder
Technical field
The present invention relates to a kind of preparation of zirconium diboride-carborundum core-shell structured powder, and in particular to one kind utilizes high temperature The oxide that autoxidation generates under oxidation environment realizes the method to zirconium diboride-carborundum reunion powder in-stiu coating, belongs to Composite powder material technical field.
Background technology
Carbon fiber reinforced carbon matrix composite material (C/C) density is small, and thermal coefficient of expansion is low under high temperature and has good power Performance is learned, is considered as most being hopeful to apply the aerobic environment in one of material of aircraft hot-end component, but more than 400 DEG C In be oxidized easily, cause its performance reduction, it is one of effective method that anti-oxidant ablative coating is prepared on its surface.
Zirconium diboride (ZrB2) it is a kind of hexagonal crystal system metalloid structural compounds, there is high-melting-point (3040 DEG C) high rigidity And the advantages that superior chemical stability；Carborundum (SiC) has the advantages that high intensity, high rigidity, low thermal coefficient of expansion.So Carborundum is added in zirconium diboride can effectively improve as composite coating made of coating material, its inoxidizability.
At present, the method for preparing zirconium diboride-carborundum micron reunion powder used for plasma spraying mainly passes through ball milling Mixed powder and atomizing granulating technology.And in the powder obtained by above-mentioned PROCESS FOR TREATMENT without calcining densification, spherical powder Typically than more loose, coarse, intensity is relatively low on surface, and in coating preparation process, powder is easily broken in conveying and is difficult to melt Melt；And space to be present more for the anti-oxidant ablative coating prepared using air plasma spraying system, it is loosely organized the problems such as. In consideration of it, there is an urgent need to develop a kind of preparation method of compound zirconium diboride-silicon carbide powder suitable for plasma spray, with Overcome disadvantage mentioned above, meet that coating prepares demand.
The content of the invention
For defect present in prior art, it is an object of the invention to provide a kind of oxide in-situ to coat two boronations The method of zirconium-carborundum reunion powder, methods described technique is simple, suitable commercial introduction；It is prepared that there is core shell structure The sphericity and consistency of oxide cladding zirconium diboride-carborundum are high, meet requirement of the plasma spraying for powder；From oxygen Metaplasia into oxide cladding layers can suppress the volatilization of carborundum in Plasma Spraying Process Using, reduce the loss of carborundum, and And the fusing point of oxide is less than zirconium boride, powder can melt more abundant, further fill lamella overlap joint in coating and cause Gap, room the defects of, improve the compactness of coating.
The purpose of the present invention is achieved through the following technical solutions.
A kind of method of oxide in-situ cladding zirconium diboride-carborundum reunion powder, methods described step are as follows：
Zirconium diboride, carborundum, polyvinyl alcohol (PVA) and absolute ethyl alcohol are well mixed by step 1., obtain suspension；
In the suspension, the mass percent of binding agent polyvinyl alcohol is 0.24%~0.55%, zirconium diboride and carbon The mass percent sum of SiClx is 35%~60%, and the mass ratio of zirconium diboride and carborundum is 3~5:1；
Preferably, mixed using ball milling method, ball milling 2h~6h under 100r/min~400r/min, ratio of grinding media to material is 3~5:1, each composition is well mixed, obtains suspension；
Suspension is transferred in spray drying granulation tower and carries out agglomeration granulation by step 2., and the powder after granulation is dried Dry-cure simultaneously passes through test sieve, obtains zirconium diboride-carborundum reunion powder that particle diameter is 20 μm~90 μm；
Wherein, spray drying granulation parameter is：210 DEG C~350 DEG C of inlet temperature, 100 DEG C~130 DEG C of outlet temperature, spray Head rotating speed 25Hz~45Hz, wriggling revolution speed 35rpm~50rpm；
Preferably, 20h~30h is dried at 80 DEG C~150 DEG C；
Zirconium diboride-carborundum reunion powder is sent into atmospheric plasma nodularization equipment and carries out spheroidising by step 3., Powder after nodularization is subjected to drying and processing and passes through test sieve, obtains nodularization zirconium diboride-carbon that particle diameter is 10 μm~60 μm SiClx powder；
Wherein, atmospheric plasma spheroidising parameter is：Main gas (argon gas) flow 85SCFH~95SCFH, auxiliary gas (helium) Flow 50SCFH~60SCFH, carrier gas (argon gas) flow 10SCFH~15SCFH, electric current 900A~1000A, powder feeding rate 1.5RPM ~2.5RPM, spray gun distance is 45mm~55mm；
Preferably, 20h~30h is dried at 80 DEG C~200 DEG C；
Nodularization zirconium diboride-silicon carbide powder is placed in the tube furnace of logical oxygen by step 4., at 800 DEG C~1000 DEG C 1h~3h is incubated, automatic oxidation reaction generation oxide cladding layers in situ occur on the surface of zirconium diboride-carborundum, are had Oxide cladding zirconium diboride-silicon carbide powder of core shell structure.
Preferably, the flow of oxygen is 50mL~150mL/min in tube furnace.
Beneficial effect：
(1) the invention provides a kind of method of oxide in-situ cladding zirconium diboride-carborundum reunion powder, using this The powder body material with core shell structure is prepared in method, and shell component is with ZrO2Based on oxide, nuclear composition ZrB2/SiC Composite granule；It is well combined between shell and core, and it is comparatively dense, there is certain bond strength, methods described can improve powder The consistency of itself and cohesive force of body, meet the requirement of plasma spraying.
(2) the core shell structure powder of the oxide in-situ cladding zirconium diboride-carborundum prepared using the method for the invention Body material, because the oxide ester mp of autoxidation generation is less than zirconium boride, powder can melt more abundant, carry out coating Caused by lamella overlap joint can be filled in coating during preparation the defects of gap, room, the compactness of coating is improved；And The oxide shell layer that autoxidation is formed can suppress the volatilization of the carborundum in Plasma Spraying Process Using, reduce the damage of carborundum Lose.
Brief description of the drawings
Fig. 1 is that the surface Scanning Electron for oxide cladding zirconium diboride-silicon carbide powder that embodiment 1 is prepared is micro- Mirror (SEM) figure.
Fig. 2 is that the cross sectional scanning electron for oxide cladding zirconium diboride-silicon carbide powder that embodiment 1 is prepared is micro- Mirror (SEM) figure.
Fig. 3 is the X-ray diffraction (XRD) that the oxide that embodiment 1 is prepared coats zirconium diboride-silicon carbide powder Figure.
Fig. 4 is the cross sectional scanning electron microscope figure for the coating that embodiment 1 is prepared.
Embodiment
The present invention is described in further detail below by example, wherein, methods described is normal unless otherwise instructed Rule method, the raw material can obtain from open commercial sources unless otherwise instructed.
In following examples：
SEM is characterized：Observed using Japanese new and high technology Co., Ltd. S-4800 type cold field emissions SEM real Apply oxide cladding zirconium diboride-silicon carbide powder pattern prepared in example and prepared coating morphology；
X-ray diffraction analysis：X ' the Pert PRO MPD type polycrystal X rays produced using Dutch PANalytical companies Diffraction analysis instrument is analyzed oxide cladding zirconium diboride-carborundum prepared in embodiment；Test condition：Cu Kα Ray, Ni filter plates, tube voltage 40kv, tube current 40mA, DS=0.957 °, PSD=2.12 of slit sizes, 4 ° of sweep speed/ min；
Spray drying granulation tower：Wuxi east rises the LGZ-8 drying machine with centrifugal spray of Spray Grain-make Drier tool factory；
Atmospheric plasma nodularization equipment：Patent CN201410320466.X reports " control atmosphere under air open environment Atmospheric plasma gun system described in the method for the oxidizable coating of plasma spraying ".
PVA：Purity >=97%, produced by Beijing Yili Fine Chemicals Co., Ltd..
Oxide prepared in embodiment is coated by ZrB using plasma spray coating process2- SiC powder is prepared into thickness For 0.2mm ZrB2- SiC coatings；Wherein, spray distance 65mm, electric current 950A, main gas (argon gas) flow is 90SCFH, auxiliary Gas (helium) flow is 55SCFH, and carrier gas (argon gas) flow is 30SCFH, and powder feeding rate is 2.0RPM.
Embodiment 1
(1) 75g zirconium diborides, 25g carborundum, 0.8g PVA and 100g absolute ethyl alcohols are added in ball grinder, ball Material is than being 4:1, the ball milling 6h under 100r/min, each composition is well mixed, obtains the suspension of presoma powder；
(2) suspension that step (1) obtains is transferred in spray drying granulation tower and carries out agglomeration granulation, after granulation Powder, which is first placed in 80 DEG C of baking ovens, dries 30h, then by test sieve, obtains the ZrB that particle diameter is 20 μm~90 μm2- SiC reunion powder Body；
Wherein, spray drying granulation parameter is：210 DEG C of inlet temperature, 100 DEG C, rotating speed of shower nozzle 25Hz of outlet temperature, wriggle Revolution speed 35rpm；
(3) ZrB for obtaining step (2)2- SiC reunions powder is sent into atmospheric plasma nodularization equipment and carried out at nodularization Reason, the powder after nodularization is collected by deionized water, the powder of collection is placed in 100 DEG C of baking oven after drying 30h, then pass through Test sieve, obtain the nodularization ZrB that particle diameter is 10 μm~60 μm2- SiC powder；
Wherein, atmospheric plasma spheroidising parameter is：Electric current 900A, main gas (argon gas) flow 90SCFH, auxiliary gas (helium Gas) flow 50SCFH, carrier gas (argon gas) flow 10SCFH, powder feeding rate 2.0RPM, spray gun distance 50mm；
(4) the nodularization ZrB for obtaining step (3)2- SiC powder is placed in tube furnace, and it is 100mL/min's to be passed through flow Oxygen, it is heated to 800 DEG C and is incubated 2h, in ZrB2Automatic oxidation reaction generation oxide cladding layers in situ occur for-SiC surface, Obtain the oxide cladding ZrB with core shell structure2- SiC powder.
It can be seen from Fig. 1, the prepared composite granule with core shell structure is in smooth spherical, the particle diameter point of surface compact Cloth is 10 μm~60 μm.It can be seen from Fig. 2, the section of prepared composite granule has obvious core shell structure to occur, shell with Kernel is well combined.
The X ray diffracting spectrum of prepared composite granule is as shown in figure 3, there is zirconium diboride, carborundum, zirconium oxide Characteristic peak, it follows that oxidation shell component is based on zirconium oxide.
It can be seen from Fig. 4, the coating almost flawless that is prepared using the composite granule prepared by the present embodiment is present a small amount of Space, it is comparatively dense.
Embodiment 2
(1) 80g zirconium diborides, 20g carborundum, 0.7g PVA and 100g absolute ethyl alcohols are added in ball grinder, ball Material is than being 4:1, the ball milling 2h under 400r/min, each composition is well mixed, obtains the suspension of presoma powder；
(2) suspension that step (1) obtains is transferred in spray drying granulation tower and carries out agglomeration granulation, after granulation Powder, which is first placed in 150 DEG C of baking ovens, dries 20h, then by test sieve, obtains the ZrB that particle diameter is 20 μm~90 μm2- SiC reunites Powder；
Wherein, spray drying granulation parameter is：350 DEG C of inlet temperature, 130 DEG C, rotating speed of shower nozzle 45Hz of outlet temperature, wriggle Revolution speed 50rpm；
(3) ZrB for obtaining step (2)2- SiC reunions powder is sent into atmospheric plasma nodularization equipment and carried out at nodularization Reason, the powder after nodularization is collected by deionized water, the powder of collection is placed in 200 DEG C of baking oven after drying 20h, then pass through Test sieve, obtain the nodularization ZrB that particle diameter is 10 μm~60 μm2- SiC powder；
Wherein, atmospheric plasma spheroidising parameter is：Electric current 950A, main gas (argon gas) flow 95SCFH, auxiliary gas (helium Gas) flow 50SCFH, carrier gas (argon gas) flow 10SCFH, powder feeding rate 2.0RPM, spray gun distance 50mm；
(4) the nodularization ZrB for obtaining step (3)2- SiC powder is placed in tube furnace, is passed through the oxygen that flow is 60mL/min Gas, it is heated to 1000 DEG C and is incubated 1h, in ZrB2Automatic oxidation reaction generation oxide cladding layers in situ occur for-SiC surface, obtain ZrB is coated to the oxide with core shell structure2- SiC powder.
SEM signs are carried out to prepared composite granule, it can be seen from characterization result, prepared composite granule is in surface Fine and close smooth spherical, particle diameter distribution is 10 μm~60 μm；It can be seen from the SEM characterization results of section, prepared composite granule Occur with obvious core shell structure, shell is well combined with kernel.Occur two boron in the XRD spectra of prepared composite granule Change zirconium, carborundum, the characteristic peak of zirconium oxide, illustrate to aoxidize shell component based on zirconium oxide.Using answering prepared by the present embodiment Flawless and comparatively dense coating can be prepared by closing powder.
Embodiment 3
(1) 82g zirconium diborides, 18g carborundum, 0.9g PVA and 100g absolute ethyl alcohols are added in ball grinder, ball Material is than being 4:1, the ball milling 4h under 300r/min, each composition is well mixed, obtains the suspension of presoma powder；
(2) suspension that step (1) obtains is transferred in spray drying granulation tower and carries out agglomeration granulation, after granulation Powder, which is first placed in 120 DEG C of baking ovens, dries 25h, then by test sieve, obtains the ZrB that particle diameter is 20 μm~90 μm2- SiC reunites Powder；
Wherein, spray drying granulation parameter is：270 DEG C of inlet temperature, 120 DEG C, rotating speed of shower nozzle 30Hz of outlet temperature, wriggle Revolution speed 40rpm；
(3) ZrB for obtaining step (2)2- SiC reunions powder is sent into atmospheric plasma nodularization equipment and carried out at nodularization Reason, the powder after nodularization is collected by deionized water, the powder of collection is placed in 150 DEG C of baking oven after drying 25h, then pass through Test sieve, obtain the nodularization ZrB that particle diameter is 10 μm~60 μm2- SiC powder；
Wherein, atmospheric plasma spheroidising parameter is：Electric current 930A, main gas (argon gas) flow 92SCFH, auxiliary gas (helium Gas) flow 57SCFH, carrier gas (argon gas) flow 12SCFH, powder feeding rate 2.3RPM, spray gun distance 55mm；
(4) the nodularization ZrB for obtaining step (3)2- SiC powder is placed in tube furnace, and it is 150mL/min's to be passed through flow Oxygen, it is heated to 900 DEG C and is incubated 3h, in ZrB2Automatic oxidation reaction generation oxide cladding layers in situ occur for-SiC surface, Obtain the oxide cladding ZrB with core shell structure2- SiC powder.
SEM signs are carried out to prepared composite granule, it can be seen from characterization result, prepared composite granule is in surface Fine and close smooth spherical, particle diameter distribution is 10 μm~60 μm；It can be seen from the SEM characterization results of section, prepared composite granule Occur with obvious core shell structure, shell is well combined with kernel.Occur two boron in the XRD spectra of prepared composite granule Change zirconium, carborundum, the characteristic peak of zirconium oxide, illustrate to aoxidize shell component based on zirconium oxide.Using answering prepared by the present embodiment Flawless and comparatively dense coating can be prepared by closing powder.
In summary, presently preferred embodiments of the present invention is these are only, is not intended to limit the scope of the present invention. Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's Within protection domain.

Claims (6)

  1. A kind of 1. method of oxide in-situ cladding zirconium diboride-carborundum reunion powder, it is characterised in that：Methods described step It is as follows,
    Zirconium diboride, carborundum, polyvinyl alcohol and absolute ethyl alcohol are well mixed by step 1., obtain suspension；Wherein, two boron The mass ratio for changing zirconium and carborundum is 3~5:1；
    Suspension is transferred in spray drying granulation tower and carries out agglomeration granulation by step 2., and the powder after granulation is carried out at drying Manage and pass through test sieve, obtain zirconium diboride-carborundum reunion powder that particle diameter is 20 μm~90 μm；
    Zirconium diboride-carborundum reunion powder is sent into atmospheric plasma nodularization equipment and carries out spheroidising by step 3., by ball Powder after change carries out drying and processing and passes through test sieve, obtains nodularization zirconium diboride-carborundum that particle diameter is 10 μm~60 μm Powder；
    Nodularization zirconium diboride-silicon carbide powder is placed in the tube furnace of logical oxygen by step 4., is incubated at 800 DEG C~1000 DEG C 1h~3h, obtain the oxide cladding zirconium diboride-silicon carbide powder with core shell structure.
  2. 2. a kind of method of oxide in-situ cladding zirconium diboride-carborundum reunion powder according to claim 1, it is special Sign is：In suspension described in step 1, the mass percent of polyvinyl alcohol is 0.24%~0.55%, zirconium diboride and carbon The mass percent sum of SiClx is 35%~60%.
  3. 3. a kind of method of oxide in-situ cladding zirconium diboride-carborundum reunion powder according to claim 1, it is special Sign is：Mixed in step 1 using ball milling method, ball milling 2h~6h under 100r/min~400r/min, ratio of grinding media to material 3 ~5:1, each composition is well mixed, obtains suspension.
  4. 4. a kind of method of oxide in-situ cladding zirconium diboride-carborundum reunion powder according to claim 1, it is special Sign is：Spray drying granulation parameter is in step 2：210 DEG C~350 DEG C of inlet temperature, 100 DEG C~130 DEG C of outlet temperature, spray Head rotating speed 25Hz~45Hz, wriggling revolution speed 35rpm~50rpm.
  5. 5. a kind of method of oxide in-situ cladding zirconium diboride-carborundum reunion powder according to claim 1, it is special Sign is：Atmospheric plasma spheroidising parameter is in step 3：Primary air amount 85SCFH~95SCFH, auxiliary throughput 50SCFH ~60SCFH, carrier gas flux 10SCFH~15SCFH, electric current 900A~1000A, powder feeding rate 1.5RPM~2.5RPM, spray gun distance For 45mm~55mm, main gas and carrier gas are argon gas, and auxiliary gas is helium.
  6. 6. a kind of method of oxide in-situ cladding zirconium diboride-carborundum reunion powder according to claim 1, it is special Sign is：In step 4, the flow of oxygen is 50mL~150mL/min in tube furnace.
CN201711027516.5A 2017-10-27 2017-10-27 Method for in-situ coating of zirconium diboride-silicon carbide agglomerated powder by oxide Active CN107814589B (en)

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CN109437911A (en) * 2018-12-04 2019-03-08 合肥睿涌陶瓷材料科技有限公司 A kind of flame heat spray carbide composite ceramic stick and preparation method thereof
CN112194506A (en) * 2020-08-26 2021-01-08 北京理工大学 Preparation of oxide in-situ coated ZrB by using oxyacetylene fuel flow2Method for agglomerating powder by using-SiC
CN113248261A (en) * 2021-06-16 2021-08-13 北京理工大学 Molybdenum disilicide coated tantalum boride-hafnium carbide spherical powder and preparation method thereof
CN113248261B (en) * 2021-06-16 2022-05-10 北京理工大学 Molybdenum disilicide coated tantalum boride-hafnium carbide spherical powder and preparation method thereof
CN113880586A (en) * 2021-07-29 2022-01-04 北京理工大学 Hafnium diboride-tantalum disilicide composite powder and preparation method thereof
CN116425566A (en) * 2023-04-26 2023-07-14 北京理工大学 LaSi 2-modified ZrB 2-SiC-doped composite powder and preparation method thereof, and thermal protection coating and preparation method thereof
CN116425566B (en) * 2023-04-26 2024-07-12 北京理工大学 LaSi 2-modified ZrB 2-SiC-doped composite powder and preparation method thereof, and thermal protection coating and preparation method thereof
CN117026154A (en) * 2023-07-19 2023-11-10 北京金轮坤天特种机械有限公司 Preparation method of zirconium diboride compact coating

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