CN107695345A - A kind of composite granule of refractory metal cladding zirconium diboride carborundum - Google Patents
A kind of composite granule of refractory metal cladding zirconium diboride carborundum Download PDFInfo
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- CN107695345A CN107695345A CN201711027523.5A CN201711027523A CN107695345A CN 107695345 A CN107695345 A CN 107695345A CN 201711027523 A CN201711027523 A CN 201711027523A CN 107695345 A CN107695345 A CN 107695345A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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Abstract
The present invention relates to a kind of composite granule of refractory metal cladding zirconium diboride carborundum, belong to composite powder material technical field.The composite granule is core shell structure, and zirconium diboride carborundum reunion powder is core, and the high melting point metal layer of its surface deposition is shell, the sphericity and good fluidity of the composite granule, meets requirement of the plasma spraying to powder.In addition, on the one hand the high melting point metal layer in the composite granule can suppress volatilization of the carborundum in high temperature, the loss of carborundum is reduced;On the other hand, because metal level has excellent ductility, in coating preparation process, because metal has excellent ductility, the defects of gap in coating, room can be filled, the compactness of coating is improved.
Description
Technical field
The present invention relates to zirconium diboride-carborundum reunion powder that a kind of surface is modified, more particularly to a kind of high-melting-point gold
Category coats the composite granule of spherical zirconium diboride-carborundum, belongs to composite powder material technical field.
Background technology
With the development of aeronautical and space technology, the speed of aircraft is more and more faster, engine interior and matrix surface institute
The temperature more and more higher born, conventional high-temperature alloy can not meet requirement already.High speed engine requires that material has height
Intensity, low-density, excellent heat shock resistance stability, corrosion-resistant and anti-oxidant etc. performance.
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, but resulting spherical powder, typically than more loose, coarse, bond strength is relatively low, mobility
It is poor with transport capacity.In addition, ZrB2Original washing powder body is due to its high-melting-point, oxidizable characteristic, it is difficult to is carried out with the technique of routine
Sintering densification;And in coating preparation process, zirconium diboride-silicon carbide powder is insufficient due to melting, it is difficult to has been formed
, there is the defects of a large amount of in whole lamellar structure so that coating compactness declines, and influences the performance of coating between lamella and lamella.
In view of this, there is an urgent need to develop a kind of Zirconium boride-silicon carbide composite powder used for plasma spraying of new structure, with overcome with
Upper shortcoming, meet the requirement of coating.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of refractory metal to coat two boronations
The composite granule of zirconium-carborundum, the composite granule are core shell structure, and zirconium diboride-carborundum reunion powder is core, its surface
The high melting point metal layer of deposition is shell, and grain diameter is controllable, sphericity and good fluidity, meets plasma spraying to powder
It is required that;In addition, on the one hand the presence of high melting point metal layer can suppress volatilization of the carborundum in high temperature, the damage of carborundum is reduced
Lose, on the other hand, because metal level has excellent ductility, in coating preparation process, because metal has excellent prolong
Malleability, the defects of gap in coating, room can be filled, improve the compactness of coating.
The purpose of the present invention is achieved through the following technical solutions.
A kind of composite granule of refractory metal cladding zirconium diboride-carborundum, the composite granule are core shell structure, two
Zirconium boride-carborundum reunion powder is core, and high melting point metal layer is shell;
The metallic element of the high melting point metal layer is nickel, cobalt, molybdenum, tungsten, tantalum, niobium or hafnium;The thickness of high melting point metal layer
It is preferred that 1 μm~10 μm;
The preparation method step of the composite granule is as follows:
(1) zirconium diboride, carborundum, polyvinyl alcohol (PVA) and deionized water are well mixed, obtain suspension;
In the suspension, the mass percent sum of zirconium diboride and carborundum is 35%~60%, zirconium diboride with
The mass ratio of carborundum is 4.8~9.5:1, quality and the zirconium diboride and the ratio of the quality sum of carborundum of polyvinyl alcohol are 3
~5:100;
Preferably, carry out being mixed with suspension using ball milling method, ratio of grinding media to material is 3~5:1, rotational speed of ball-mill 100r/
Min~400r/min, Ball-milling Time 2h~6h;
(2) suspension is transferred in spray drying granulation tower and carries out agglomeration granulation, and cross test sieve, obtain particle diameter as 20
μm~70 μm of zirconium diboride-carborundum reunion powder;
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;
(3) using magnetically controlled DC sputtering, electroless plating method or sol-gel process by refractory metal deposit to zirconium diboride-
On carborundum reunion powder, zirconium diboride-carborundum reunion powder of refractory metal cladding is obtained;
Direct current magnetron sputtering process is applied to tantalum, niobium, molybdenum or hafnium, comprises the following steps that:In magnetic control sputtering device, with the height
Zirconium diboride-carborundum reunion powder is placed on the high-frequency vibration sample stage in vacuum chamber by melting point metals as target;Take out
Argon gas is passed through after vacuum to 0.2Pa~1.0Pa, 20 DEG C~400 DEG C of temperature for controlling sample stage to add, sputtering power 2000W~
3000W, sputter gas flow 20SCCM~200SCCM, sputtering time are 60min~600min, by the rotation of sample stage and
High-frequency vibration realizes the uniform cladding to reunion powder, makes refractory metal uniform deposition in zirconium diboride-carborundum reunion powder
On body;
Electroless plating method is applied to nickel or cobalt, comprises the following steps that:By zirconium diboride-carborundum reunion powder, sulfate with
And surfactant is added in autoclave, and the hydrogen that pressure is 2MPa~3MPa is passed through, then at 150 DEG C~170 DEG C
Reduction reaction occurs for lower stirring, and ammoniacal liquor is added after reacting 1h~2h, is further continued for reacting 0.5h~2h, is deposited on refractory metal
Zirconium diboride-carborundum reunion powder surface;Wherein, the ratio between the amount of the material of ammoniacal liquor and the amount of material of sulfate preferably 2.1
~2.3:1, surfactant is anthraquinone and its derivative, and the quality of surfactant and the mass ratio of refractory metal are 0.2
~0.4:100, the speed of stirring is 800r/min~1000r/min, and the sulfate is cobaltous sulfate or nickel sulfate;
Sol-gel process is applied to tungsten, comprises the following steps that:Tungsten powder is added in hydrogen peroxide and reacted, whole process
Temperature control is obtained into milky white solution after 5 DEG C~30 DEG C, tungsten powder reaction completely, removes unnecessary hydrogen peroxide, then second is added dropwise
Acid and ethanol, burin-in process is carried out in closed stand of 40 DEG C~100 DEG C mechanical agitation 1h~24h or room temperature, is filtrated to get light
The tungsten colloidal sol of yellow transparent;Zirconium boride-carborundum reunion powder is immersed in tungsten colloidal sol, after sonic oscillation, filters tungsten colloidal sol,
Powder is put into 300 DEG C~350 DEG C of drying box and dries 2h~5h;By dried powder again in a hydrogen atmosphere in 760
DEG C~800 DEG C of reductase 12 h~3h, cooling, obtain the ZrB of tungsten cladding2- SiC powder;Wherein, per (0.5~1) g tungsten powder with
The hydrogen peroxide that (2.5~5) mL concentration is more than 30% is reacted, and 2mL absolute ethyl alcohol and 0.75mL acetic acid are added after reaction.
(4) high-temperature calcination or induction plasma are carried out to zirconium diboride-carborundum reunion powder of refractory metal cladding
Spheroidising, high melting point metal layer is densified, obtains the composite powder of the refractory metal cladding zirconium diboride-carborundum
Body;
Under the protective atmosphere of hydrogen or argon gas, in the high-melting-point less than zirconium diboride-carborundum reunion powder surface deposition
1h~3h is calcined at 100 DEG C~500 DEG C of melting point metal;
The parameter of induction plasma spheroidising is as follows:Plasma power is 28kW~30kW, carrier gas (preferably argon gas)
Flow is 5slpm~7slpm, and working gas is the mixed gas of hydrogen and argon gas, and hydrogen flowing quantity is 6slpm~7slpm, argon gas
Flow is 50slpm~65slpm, and chamber pressure is 8psia~12psia, and powder feeder rotating speed is 6r/min~8r/min.
Beneficial effect:
There is core using the spherical zirconium diboride-carborundum reunion powder of refractory metal cladding the invention provides a kind of
The NEW TYPE OF COMPOSITE powder body material of shell structure, the presence of refractory metal clad can suppress the carborundum in coating preparation process
Constituent element volatilizees sublimation problem at high temperature, reduces the loss of carborundum, reduces the mismatch problems of zirconium diboride and carborundum, carry
High coating and powder Design consistency;Because refractory metal clad has good high temperature plastic deformability, in coating
In deposition process, refractory metal clad can utilize the sky between itself excellent ductility filling coating splat and lamella
Gap, so as to improve the compactness of coating;In addition, refractory metal can aoxidize in high-temperature oxidation environment, reaction produces
Oxide can be with ZrB2Oxide ZrO2Reaction, reduces the logical oxygen ability of coating, improves the high-temperature oxidation resistant ablation of coating
Performance.The preparation method of composite granule of the present invention is simple to operate, easy to spread suitable for large-scale production.
Brief description of the drawings
Fig. 1 is that the Co that embodiment 1 is prepared coats ZrB2The high power SEM of-SiC composite granule
(SEM) figure.
Fig. 2 is that the Co that embodiment 1 is prepared coats ZrB2The different zones of-SiC composite granule carry out section member
Element analysis, (a) ZrB2- SiC core regions, (b) Co metal-backs region.
Fig. 3 is that the Co that embodiment 2 is prepared coats ZrB2The section high power scanning electron microscopy of-SiC composite granule
Mirror (SEM) figure.
Fig. 4 is that the Co that embodiment 2 is prepared coats ZrB2The distribution diagram of element of-SiC composite granule.
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:
The information of main agents used refers to table 1, and the information of key instrument equipment used refers to table 2.
Table 1
Table 2
Energy disperse spectroscopy (X-ray Energy Dispersive are carried using S-4800 type cold field emission SEM
Spectrometer, EDS) carry out Elemental redistribution detection;Mobility-detected, with refractory metal prepared in 50g embodiments
The composite granule of cladding zirconium diboride-carborundum flows through the time required for Hall flow meter to represent.
Embodiment 1
(1) 500g zirconium diborides, 100g carborundum, 18g PVA and 600g deionized waters are added in ball grinder, ball
Material is than being 4:1, the ball milling 3h under 250r/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 passes through test sieve, obtains the ZrB that particle diameter is 20 μm~70 μm2- SiC reunion powders;
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) by 400g ZrB2- SiC reunions powder, 620g CoSO4The height by hydrogen gas washing is added to 0.71g anthraquinones
Press in reactor, the temperature control of autoclave is passed through the hydrogen that pressure is 2MPa, then 800r/min's at 150 DEG C
Carry out reduction reaction under mixing speed, reaction add after 1h ammoniacal liquor that 587mL concentration is 14.30mol/L to remove sulfuric acid
Root ensures that reduction reaction is fully carried out, and is further continued for reacting 1h, and reaction carries out decompression and filtered to exclude waste liquid after terminating, and by collection
Solid, which is placed in 100 DEG C of vacuum drying chambers, dries 10h, obtains the ZrB of Co claddings2- SiC reunion powders;
(4) under argon atmosphere, by the ZrB of Co claddings2- SiC reunion powders are placed at 1350 DEG C and calcine 2h, make
ZrB2The Co metal levels densification of-SiC reunions powder surface cladding, obtain Co claddings ZrB2- SiC composite granule.
Fig. 1 is that the SEM of prepared composite granule schemes, from the figure, it can be seen that light is presented in powder after cladding is handled
Slip close surface topography, and the molecule on surface is the zirconium diboride-silicon carbide powder adhesion crushed during cladding
On powder surface.Fig. 2 (a) is to ZrB2One region of-SiC cores carries out elementary analysis, the element species detected and
The atomic percentage conc of each element refers to table 3;Fig. 2 (b) is to carry out elementary analysis to a region of Co metal-backs, is detected
The atomic percentage conc of element species and each element refers to table 4.It can be seen from the data of table 3 and table 4, shell is mainly Co elements,
Core is mainly Zr, B, Si, C element.Understood by mobility-detected, prepared Co claddings ZrB2The stream of-SiC composite granule
Dynamic performance is 40s/50g.
Table 3
Element | Percentage by weight | Atomic percent |
B K | 31.62 | 44.49 |
C K | 34.68 | 43.93 |
O K | 5.70 | 5.42 |
Si K | 0.90 | 0.49 |
Cl K | 0.23 | 0.10 |
Co K | 11.98 | 3.09 |
Zr L | 14.90 | 2.48 |
Total amount | 100.00 | 100.00 |
Table 4
Element | Percentage by weight | Atomic percent |
B K | 4.86 | 16.99 |
C K | 9.08 | 28.61 |
O K | 2.03 | 4.79 |
Si K | 2.44 | 3.29 |
Co K | 54.98 | 35.29 |
Zr L | 26.60 | 11.03 |
Total amount | 100.00 | 100.00 |
Embodiment 2
(1) 420g zirconium diborides, 60g carborundum, 14.4g PVA and 720g deionized waters are added in ball grinder,
Ratio of grinding media to material is 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 passes through test sieve, obtains the ZrB that particle diameter is 20 μm~70 μm2- SiC reunion powders;
Wherein, spray drying granulation parameter is:300 DEG C of inlet temperature, 110 DEG C, rotating speed of shower nozzle 29Hz of outlet temperature, wriggle
Revolution speed 35rpm;
(3) by 400g ZrB2- SiC reunions powder, 636g CoSO4It is added to 0.726g anthraquinones by hydrogen gas washing
In autoclave, the temperature control of autoclave is passed through the hydrogen that pressure is 2MPa, then in 800r/min at 150 DEG C
Mixing speed under carry out reduction reaction, reaction add after 1h ammoniacal liquor that 631mL concentration is 14.30mol/L with except desulfuration
Acid group ensures that reduction reaction is fully carried out, and is further continued for reacting 1h, reaction carries out decompression suction filtration and excludes waste liquid after terminating, and will collect
Solid be placed in 100 DEG C of vacuum drying chambers dry 10h, obtain Co cladding ZrB2- SiC reunion powders;
(4) ZrB coated using induction plasma nodularization equipment to Co2- SiC reunions powder is carried out at nodularization and densification
Reason, obtain Co claddings ZrB2- SiC composite granule;
Wherein, plasma power 29kW;Carrier gas (argon gas) flow is 5slpm;Working gas is hydrogen and argon gas
Mixed gas, hydrogen flowing quantity 7slpm, argon flow amount 60slpm;Chamber pressure is 11psia;Powder feeder rotating speed is 7r/
min。
Prepared Co claddings ZrB2The Cross Section Morphology of-SiC composite granule is as shown in figure 3, powder sphericity is preferable, again
It is in core shell structure to close powder interface, and outside metal carbonyl coat is fine and close, internal ZrB2/ SiC reunion powder structures are more loose;
Diameter of particle is distributed as particle diameter as 20 μm~100 μm, meets thermal spraying requirement.Prepared Co claddings ZrB2- SiC composite powder
The distribution diagram of element of body, as shown in figure 4, Co elements are mainly distributed on the shell region in powder section, inside powder mainly
The elements such as Zr, Si.Understood by mobility-detected, prepared Co claddings ZrB2The mobile performance of-SiC composite granule is
45s/50g。
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 (9)
- A kind of 1. composite granule of refractory metal cladding zirconium diboride-carborundum, it is characterised in that:The composite granule is core Shell structure, zirconium diboride-carborundum reunion powder is core, and high melting point metal layer is shell;The metallic element of the high melting point metal layer is nickel, cobalt, molybdenum, tungsten, tantalum, niobium or hafnium.
- 2. a kind of composite granule of refractory metal cladding zirconium diboride-carborundum according to claim 1, its feature exist In:The thickness of high melting point metal layer is 1 μm~10 μm.
- A kind of 3. preparation side of the composite granule of refractory metal cladding zirconium diboride-carborundum as claimed in claim 1 or 2 Method, it is characterised in that:Methods described step is as follows,(1) zirconium diboride, carborundum, polyvinyl alcohol and deionized water are well mixed, obtain suspension;Wherein, two boronation The mass ratio of zirconium and carborundum is 4.8~9.5:1;(2) suspension is transferred in spray drying granulation tower and carries out agglomeration granulation, and cross test sieve, obtain particle diameter for 20 μm~ 70 μm of zirconium diboride-carborundum reunion powder;(3) when refractory metal is tantalum, niobium, molybdenum or hafnium, refractory metal is deposited into two boronations using direct current magnetron sputtering process On zirconium-carborundum reunion powder, zirconium diboride-carborundum reunion powder of refractory metal cladding is obtained;When refractory metal is nickel or cobalt, refractory metal is deposited into zirconium diboride-carborundum reunion powder using electroless plating method On body, zirconium diboride-carborundum reunion powder of refractory metal cladding is obtained;When refractory metal is tungsten, refractory metal is deposited into zirconium diboride-carborundum reunion powder using sol-gel process On, obtain zirconium diboride-carborundum reunion powder of refractory metal cladding;(4) high-temperature calcination or induction plasma nodularization are carried out to zirconium diboride-carborundum reunion powder of refractory metal cladding Processing, obtain the composite granule of the refractory metal cladding zirconium diboride-carborundum;The technological parameter of high-temperature calcination:Under the protective atmosphere of hydrogen or argon gas, less than refractory metal fusing point 100 DEG C~500 1h~3h is calcined at a temperature of DEG C;The parameter of induction plasma spheroidising:Plasma power is 28kW~30kW;Carrier gas is argon gas, and carrier gas flux is 5slpm~7slpm;Working gas is the mixed gas of hydrogen and argon gas, and hydrogen flowing quantity is 6slpm~7slpm, and argon flow amount is 50slpm~65slpm;Chamber pressure is 8psia~12psia;Powder feeder rotating speed is 6r/min~8r/min.
- A kind of 4. preparation side of the composite granule of refractory metal cladding zirconium diboride-carborundum according to claim 3 Method, it is characterised in that:In the suspension, the mass percent sum of zirconium diboride and carborundum is 35%~60%, poly- second The quality of enol is 3~5 with zirconium diboride and the ratio of the quality sum of carborundum:100.
- A kind of 5. preparation side of the composite granule of refractory metal cladding zirconium diboride-carborundum according to claim 3 Method, it is characterised in that:Step (1) carries out being mixed with suspension using ball milling method;Wherein, ratio of grinding media to material is 3~5:1, ball milling Rotating speed is 100r/min~400r/min, Ball-milling Time 2h~6h.
- A kind of 6. preparation side of the composite granule of refractory metal cladding zirconium diboride-carborundum according to claim 3 Method, it is characterised in that:Step (2) spray drying granulation parameter is:210 DEG C~350 DEG C of inlet temperature, 100 DEG C of outlet temperature~ 130 DEG C, rotating speed of shower nozzle 25Hz~45Hz, wriggling revolution speed 35rpm~50rpm.
- A kind of 7. preparation side of the composite granule of refractory metal cladding zirconium diboride-carborundum according to claim 3 Method, it is characterised in that:Step (3) direct current magnetron sputtering process comprises the following steps that,Magnetic control sputtering device is vacuumized and is passed through 0.2Pa~1.0Pa argon gas, the temperature of sample stage is 20 DEG C~400 DEG C, sputtering Power 2000W~3000W, sputter gas flow 20SCCM~200SCCM, is sputtered using the refractory metal as target 60min~600min, make refractory metal uniform deposition on zirconium diboride-carborundum reunion powder;The refractory metal For tantalum, niobium, molybdenum or hafnium.
- A kind of 8. preparation side of the composite granule of refractory metal cladding zirconium diboride-carborundum according to claim 3 Method, it is characterised in that:Step (3) electroless plating method comprises the following steps that,Zirconium diboride-carborundum reunion powder, sulfate and surfactant are added in autoclave, and are passed through pressure For 2MPa~3MPa hydrogen, then reduction reaction occurs for stirring at 150 DEG C~170 DEG C, and ammoniacal liquor is added after reacting 1h~2h, It is further continued for reacting 0.5h~2h, refractory metal is deposited on zirconium diboride-carborundum reunion powder surface;Wherein, the ratio between the amount of the material of ammoniacal liquor and the amount of material of sulfate are 2.1~2.3:1;Surfactant be anthraquinone and Its derivative, the quality of surfactant and the mass ratio of refractory metal are 0.2~0.4:100;The refractory metal is Nickel or cobalt, the sulfate are cobaltous sulfate or nickel sulfate.
- A kind of 9. preparation side of the composite granule of refractory metal cladding zirconium diboride-carborundum according to claim 3 Method, it is characterised in that:Step (3) sol-gel process comprises the following steps that,Tungsten powder is reacted with hydrogen peroxide at 5 DEG C~30 DEG C, after tungsten powder reaction completely, then acetic acid and ethanol is added dropwise, and 40 DEG C~100 DEG C of mechanical agitation 1h~24h or room temperature it is closed stand carry out burin-in process, be filtrated to get tungsten colloidal sol;By zirconium boride- Carborundum reunion powder is immersed in tungsten colloidal sol, sonic oscillation, and filters tungsten colloidal sol, then powder is placed at 300 DEG C~350 DEG C Dry 2h~5h;Again in a hydrogen atmosphere, dried powder is placed in reductase 12 h~3h at 760 DEG C~800 DEG C, cools down, obtain To the ZrB of tungsten cladding2- SiC powder;Wherein, the tungsten powder per (0.5~1) g reacts with the hydrogen peroxide that (2.5~5) mL concentration is more than 30%, is added after reaction 2mL absolute ethyl alcohol and 0.75mL acetic acid.
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