CN110230015A - A kind of composite wave-suction material and its preparation method and application suitable for marine environment - Google Patents
A kind of composite wave-suction material and its preparation method and application suitable for marine environment Download PDFInfo
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- CN110230015A CN110230015A CN201910525662.3A CN201910525662A CN110230015A CN 110230015 A CN110230015 A CN 110230015A CN 201910525662 A CN201910525662 A CN 201910525662A CN 110230015 A CN110230015 A CN 110230015A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/129—Flame spraying
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
The composite wave-suction material and its preparation method and application that the invention discloses a kind of suitable for marine environment, the material include the hexagonal BCN ceramics of the Fe-based amorphous and 5-15 wt% of 85-95 wt%；The Fe-based amorphous ingredient comprising following weight percent: 27wt%Cr, 4wt%B, 4wt%Si, 5wt%Cu, 7wt%Ni, 8wt%Mo, surplus Fe；Single layer or few layer structure hexagonal BCN is prepared by pyrolysismethod in the hexagonal BCN.Fe-based amorphous raw material will be prepared first progress melting, atomization in vacuum aerosolization furnace is added and sieves powder, then iron-based amorphous powder and hexagonal BCN are sufficiently mixed, obtain powdered composite wave-suction material.The microwave absorbing coating suitable for marine environment is prepared using supersonic flame spraying technology in the composite wave-suction material.Microwave absorbing coating of the present invention can get the good, excellent anti-corrosion performance with good absorbing property and substrate combinating strength, suitable for rough seas.
Description
Technical field
The invention belongs to the field of thermal spray of Materials Processing Engineering, and in particular to a kind of compound suction suitable for marine environment
Wave material and its preparation method and application.
Background technique
With the development of science and technology, a large amount of military equipments face the multi-platform multiple spectra investigation of space base, ground, sea base and visit
The task environment of survey is increasingly complicated, and it is currently used for coating one layer of microwave absorbing coating on military equipment surface to reach radar invisible
Technological means.And the microwave absorbing coating (such as microwave absorbing coating on ship housing surface) being on active service under marine environment its suction under corrosiveness
Wave performance can be gradually reduced, thus the Stealth Fighter of ship is caused to decline.To solve the above-mentioned problems, the fast of military crafts is adapted to
Speed development, studying the strong coating system of corrosion-resistant, suction wave frequency Duan Guang, ability has important practical significance.
Non-crystalline material compared to crystalline state as closing without microdefects such as lattice, crystal boundary, dislocations present in conventional alloys
Gold is more uniform in structure and ingredient, therefore typically exhibits excellent corrosion resistance.It is iron-based in all kinds of non-crystalline materials
Amorphous due to its cheap cost, excellent soft magnet performance and be considered as one of direction of following absorbing material development.But
Existing Fe-based amorphous in order to obtain higher content of amorphous, Cr constituent content is usually less than 20wt.%, and lower Cr element
Content is unfavorable to the corrosion resistance of ferrous alloy material.When Fe-based amorphous alloy is used as absorbing material, it is difficult to comply with suction wave
The development trend of material " thin, light, wide, strong ".Therefore, it is necessary to design one kind there is " thin, light, wide, strong " characteristic to be applicable to
The absorbing material of marine environment.
Summary of the invention
In view of the above-mentioned problems, the present invention provide a kind of composite wave-suction material suitable for marine environment and preparation method thereof and
Using in the coating of preparation, hexagonal BCN ceramic particle is evenly distributed in noncrystal substrate, and the coating of spraying has both iron-based non-
The features such as anti-corrosion, the inexpensive and hexagonal BCN wave-sucking performance of brilliant height is strong, frivolous.
To achieve the goals above, the technical solution adopted by the present invention are as follows: the present invention provides a kind of applicable Yu Haiyang's rings
The composite wave-suction material in border, the hexagonal BCN of the Fe-based amorphous and 5-15 wt% including 85-95 wt%；It is described Fe-based amorphous to include
The ingredient of following weight percent: 27wt% Cr, 4wt% B, 4wt% Si, 5wt% Cu, 7wt% Ni, 8wt% Mo, surplus are
Fe；The hexagonal BCN is at least one of single layer structure hexagonal BCN, double-layer structure hexagonal BCN and three-decker hexagonal BCN.
Further preferably, above-mentioned a kind of composite wave-suction material suitable for marine environment, including the Fe-based amorphous of 90 wt%
With the hexagonal BCN of 10 wt%.
The present invention also provides a kind of preparation method of above-mentioned composite wave-suction material suitable for marine environment, this method
The following steps are included:
(1) according to above-mentioned Fe-based amorphous ingredient and weight ratio, low-carbon ferrochromium, high carbon ferro-chrome, ferro-boron, ferrosilicon, cathode copper, electricity are weighed
Nickel, molybdenum-iron and pure iron are solved, the principle being eventually adding according to low melting point after first high-melting-point, containing easy scaling loss element material is successively by molybdenum
Iron, high carbon ferro-chrome, low-carbon ferrochromium, pure iron, electrolytic nickel, cathode copper, ferro-boron, ferrosilicon are put into vacuum induction electromagnetic oven, are then risen
Temperature melts it all；
(2) vacuum aerosolization processing is carried out to melt liquid, aerosolization pressure is 3MPa, is then dried, Sieving and casing 15-45
μm powder to get arrive iron-based amorphous powder；
(3) by boric acid and melamine in N2Hexagonal BCN is obtained in 1300 DEG C of 5 h of reaction under atmosphere protection, is separated through ultrasound
Hexagonal BCN, the hexagonal BCN be single layer structure hexagonal BCN, double-layer structure hexagonal BCN and three-decker hexagonal BCN in extremely
Few one kind；
(4) above-mentioned iron-based powder is uniformly mixed with hexagonal BCN material using double movement batch mixers to get composite wave-absorbing material is arrived
Material.
Application the present invention also provides above-mentioned composite wave-suction material as the antiradar coatings in marine environment.
The present invention also provides the construction methods of above-mentioned composite wave-suction material, include the following steps:
(1) matrix surface is pre-processed: after matrix surface derusting oil removing, in the case where air pressure is 0.7-0.8 MPa, using grain
Degree is the corundum sand of 5-35 mesh, carries out sandblasting roughening to matrix surface；
(2) it carries out spraying composite wave-absorbing material of any of claims 1 or 2 in matrix surface using supersonic flame spraying technology
Material, solidification obtain microwave absorbing coating, wherein the technological parameter setting sprayed are as follows: 2000 scfh of oxygen flow, kerosene oil flow 6.8
Gph, 330 mm of spray distance, 23 scfh of carrier gas flux, 5.5 rpm of powder feeder revolving speed, 280 mm/s of spray gun movement speed.
The bond strength of above-mentioned microwave absorbing coating >=70 MPa, 1 mm thick coating is in 8 GHz -18 GHz wave band absorption maximums
Value reaches -30 dB.
The utility model has the advantages that
1. the ratio between the type and each atom that pass through allotment addition atom, so that having largely atom between atom
Mispairing realizes raising corrosion resistance so that the ferrous alloy system of design has good amorphous formation ability and stability
It ensure that content of amorphous with higher in Fe-based amorphous while energy；
2. by compound Fe-based amorphous and single layer or the hexagonal BCN ceramic particle of few layer structure, acquisition has both Fe-based amorphous and six
The composite wave-suction material of both square BCN advantage；
3. the composite wave-suction material is by supersonic flame spraying, so that microwave absorbing coating performance is more excellent, bond strength >=
70 MPa, seawater corrosion resistance rate≤0.1 mm/, 1 mm thick coating reaches in 8 GHz -18 GHz wave band obtained the maximum absorption -
30 dB。
Detailed description of the invention
Fig. 1 is the XRD spectrum of iron-based amorphous powder made from the embodiment of the present invention 1.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that
Specific material proportion, process conditions and its result described in embodiment are merely to illustrate the present invention, without should will not
Limit the present invention described in detail in claims.
Embodiment 1
A kind of composite wave-suction material suitable for marine environment, including Fe-based amorphous and hexagonal BCN, wherein Fe-based amorphous content is
95 wt%, hexagonal BCN content are 5 wt%；Described Fe-based amorphous comprising following component, specific weight percent is as follows: 27wt%
Cr, 4wt% B, 4wt% Si, 5wt% Cu, 7wt% Ni, 8wt% Mo, surplus Fe；The hexagonal BCN is six side of single layer structure
At least one of BCN, double-layer structure hexagonal BCN and three-decker hexagonal BCN.
Composite wave-suction material is made by following steps:
(1) according to above-mentioned Fe-based amorphous ingredient and weight ratio, certain low-carbon ferrochromium, high carbon ferro-chrome, ferro-boron, ferrosilicon, electricity are weighed
Solving copper, electrolytic nickel, molybdenum-iron and pure iron, (content of its middle-low-carbon ferrochrome and high carbon ferro-chrome ratio is corresponding only for obtaining without influence
Constituent content), the principle being eventually adding according to low melting point after first high-melting-point, containing easy scaling loss element material is successively by molybdenum-iron, high-carbon
Ferrochrome, low-carbon ferrochromium, pure iron, electrolytic nickel, cathode copper, ferro-boron, ferrosilicon be put into vacuum induction electromagnetic oven (by this be put into it is suitable
For sequence to reduce the scaling loss of easy scaling loss element, high-melting-point melts system faster, increases melting efficiency), then heat up
Melt it all；
(2) vacuum aerosolization processing is carried out to melt liquid, aerosolization pressure is 3MPa, is then dried, Sieving and casing 15-45
μm powder to get arrive iron-based amorphous powder；
(3) by boric acid and melamine in N2Hexagonal BCN is obtained in 1300 DEG C of 5 h of reaction under atmosphere protection, then is removed through ultrasound
(Hielscher UIP2000-HD processor for ultrasonic wave) obtains hexagonal BCN, the hexagonal BCN can for single layer structure hexagonal BCN or
Both any mixture or three's mixture between double-layer structure hexagonal BCN or the hexagonal BCN or three of three-decker；
(4) use the bis- movement batch mixers of JHT-20 of Zhengzhou Jin He device fabrication Co., Ltd production by above-mentioned iron-based powder and six
Square BCN material is sufficiently mixed uniformly to get the compound suction for arriving Fe-based amorphous/hexagonal BCN ceramics suitable for marine environment
Wave material.
It is above-mentioned it is a kind of suitable for the composite wave-suction material of marine environment as the tool in the microwave absorbing coating marine environment
Body application is as follows:
(1) matrix surface is pre-processed: after matrix surface derusting oil removing, in the case where air pressure is 0.7-0.8 MPa, using grain
Degree is the corundum sand of 5-35 mesh, carries out sandblasting roughening to matrix surface；
(2) it is sprayed using supersonic flame spraying technology (HVOF) in matrix surface, the technological parameter setting of spraying are as follows: oxygen
2000 scfh of throughput, 6.8 gph of kerosene oil flow, 330 mm of spray distance, 23 scfh of carrier gas flux, powder feeder revolving speed 5.5
Rpm, 280 mm/s of spray gun movement speed.
Iron-based amorphous powder is made to step in the present embodiment (2) and carries out XRD test, test map is as shown in Figure 1.From iron
As can be seen that map only has the steamed bun peak of a widthization at about 45 ° of 2 θ or so in base amorphous powder XRD test map, this illustrates this
The Fe-based amorphous of invention preparation has good amorphous formation ability, and amorphous content basically reaches 100%.
Embodiment 2
A kind of composite wave-suction material suitable for marine environment, including Fe-based amorphous and hexagonal BCN, wherein Fe-based amorphous content is
90 wt%, hexagonal BCN ingredient are 10 wt%；Described Fe-based amorphous comprising following component, specific weight percent is as follows: 27wt%
Cr, 4wt% B, 4wt% Si, 5wt% Cu, 7wt% Ni, 8wt% Mo, surplus Fe；The hexagonal BCN is six side of single layer structure
At least one of BCN, double-layer structure hexagonal BCN and three-decker hexagonal BCN.
In the present embodiment the application in the coating of Fe-based amorphous preparation method, composite wave-suction material and construction method with
Embodiment 1 is identical.
Embodiment 3
A kind of composite wave-suction material suitable for marine environment, including Fe-based amorphous and hexagonal BCN, wherein Fe-based amorphous content is
85 wt%, hexagonal BCN ingredient are 15 wt%；Described Fe-based amorphous comprising following component, specific weight percent is as follows: 27wt%
Cr, 4wt% B, 4wt% Si, 5wt% Cu, 7wt% Ni, 8wt% Mo, surplus Fe；The hexagonal BCN is six side of single layer structure
At least one of BCN, double-layer structure hexagonal BCN and three-decker hexagonal BCN.
In the present embodiment the application in the coating of Fe-based amorphous preparation method, composite wave-suction material and construction method with
Embodiment 1 is identical.
Embodiment 4
The microwave absorbing coating suitable for marine environment with a thickness of 1 mm is prepared respectively according to embodiment 1 ~ 3, and phase is carried out to it
The test (bond strength, seawater corrosion resistance and in 8 GHz -18 GHz wave band obtained the maximum absorption) for closing performance, is surveyed using pulling method
The bond strength of coating is measured, selection E-7 glue is binder；Using the resistance to sea of Gastec CS350H electrochemical workstation testing coating
Aqueous corrosion rate；It is required according to GJB2038-1994 " radar absorbing reflectivity test method ", utilizes HP8722ET vector
Network Analyzer, using the wave-sucking performance of arched reflective method testing coating.Its testing result is as follows:
Summarize: for traditional Fe-based amorphous material in order to obtain high content of amorphous, Cr constituent content is usually lower, therefore its corrosion resistant
Corrosion can be to be improved.And the absorbing material suitable for marine environment that the present invention designs, it is designed by ingredient, is contained improving Cr
The material with completely amorphous structure is obtained under the premise of amount.This is Fe-based amorphous to be made of seven kinds of elements, medium and small atom B,
Si can increase with system mainly interatomic size mismatch degree, improve system amorphous formation ability, Cr element can be effective
The corrosion resistance of coating is improved, Mo element can be improved material corrosion resistance, and what Cu element can be improved material resists micro- life
Object corrosive nature, Ni element can improve the toughness of ferrous alloy.Therefore, it is this it is Fe-based amorphous have than tradition it is Fe-based amorphous more
Excellent corrosion resistance is suitble to be used as absorbing material in harsh environment.Hexagonal BCN ceramics are as known most light ceramic material
Material, density is only 15 milligrams per cubic centimeter；By single layer or few layer (less than 3 layers) structure hexagonal BCN ceramics with it is Fe-based amorphous
Compound, unique micro-nano structure and ingredient designability have microwave absorbing coating in different electromagnetic wave bands (wave bands such as S, K)
There is very excellent absorbing property, and it inhales wave frequency section with controllability.Institute is sprayed in combination with supersonic flame (HVOF)
With high speed and relatively low the two features of temperature, composite material can be made to keep for a long time under the strong corrosive environments such as ocean
Good suction intensity of wave and suction wave width, breaking through existing absorbing material, service life is short under marine environment or wave-sucking performance is weak
Limitation.The coating good, excellent anti-corrosion performance with good absorbing property and substrate combinating strength, is suitble to be coated on severe
In the military equipment to work under environment.
Claims (6)
1. a kind of composite wave-suction material suitable for marine environment, it is characterised in that: the Fe-based amorphous and 5- including 85-95 wt%
The hexagonal BCN of 15 wt%；The Fe-based amorphous ingredient comprising following weight percent: 27wt% Cr, 4wt% B, 4wt% Si,
5wt% Cu, 7wt% Ni, 8wt% Mo, surplus Fe；The hexagonal BCN is single layer structure hexagonal BCN, double-layer structure hexagonal BCN
At least one of with the hexagonal BCN of three-decker.
2. a kind of composite wave-suction material suitable for marine environment according to claim 1, it is characterised in that: including 90
Fe-based amorphous and 10 wt% the hexagonal BCN of wt%.
3. a kind of preparation method of composite wave-suction material suitable for marine environment according to claim 1 or 2, feature
It is: method includes the following steps:
(1) according to above-mentioned Fe-based amorphous ingredient and weight ratio, low-carbon ferrochromium, high carbon ferro-chrome, ferro-boron, ferrosilicon, cathode copper, electricity are weighed
Nickel, molybdenum-iron and pure iron are solved, the principle being eventually adding according to low melting point after first high-melting-point, containing easy scaling loss element material is successively by molybdenum
Iron, high carbon ferro-chrome, low-carbon ferrochromium, pure iron, electrolytic nickel, cathode copper, ferro-boron, ferrosilicon are put into vacuum induction electromagnetic oven, are then risen
Temperature melts it all；
(2) vacuum aerosolization processing is carried out to melt liquid, aerosolization pressure is 3MPa, is then dried, Sieving and casing 15-45
μm powder to get arrive iron-based amorphous powder；
(3) by boric acid and melamine in N2Hexagonal BCN is obtained in 1300 DEG C of 5 h of reaction under atmosphere protection, is separated through ultrasound
Hexagonal BCN, the hexagonal BCN be single layer structure hexagonal BCN, double-layer structure hexagonal BCN and three-decker hexagonal BCN at least
It is a kind of；
(4) above-mentioned iron-based powder is uniformly mixed with hexagonal BCN using double movement batch mixers to get composite wave-suction material is arrived.
4. application of the composite wave-suction material according to claim 1 or 2 as the microwave absorbing coating in marine environment.
5. application according to claim 4, which is characterized in that the construction method of the composite wave-suction material includes following step
It is rapid:
(1) matrix surface is pre-processed: after matrix surface derusting oil removing, in the case where air pressure is 0.7-0.8 MPa, using grain
Degree is the corundum sand of 5-35 mesh, carries out sandblasting roughening to matrix surface；
(2) it carries out spraying composite wave-absorbing material of any of claims 1 or 2 in matrix surface using supersonic flame spraying technology
Material, solidification obtain microwave absorbing coating, wherein the technological parameter setting sprayed are as follows: 2000 scfh of oxygen flow, kerosene oil flow 6.8
Gph, 330 mm of spray distance, 23 scfh of carrier gas flux, 5.5 rpm of powder feeder revolving speed, 280 mm/s of spray gun movement speed.
6. application according to claim 5, it is characterised in that: the bond strength of the microwave absorbing coating >=70 MPa, 1 mm
Thick coating reaches -30 dB in 8 GHz -18 GHz wave band obtained the maximum absorption.
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| CN201910525662.3A CN110230015B (en) | 2019-06-18 | 2019-06-18 | Composite wave-absorbing material suitable for marine environment and preparation method and application thereof |
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| CN201910525662.3A CN110230015B (en) | 2019-06-18 | 2019-06-18 | Composite wave-absorbing material suitable for marine environment and preparation method and application thereof |
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| CN110230015B CN110230015B (en) | 2021-06-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4205548A4 (en) * | 2020-10-08 | 2024-10-16 | Kolon Inc | Alloy, alloy powder, and alloy coated body having antimicrobial activity |
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| CN1336793A (en) * | 2000-04-10 | 2002-02-20 | 株式会社日立制作所 | Electromagnetic wave absorber, its mfg. method, and articles equipped with said absorber |
| CN106191711A (en) * | 2016-07-07 | 2016-12-07 | 河海大学 | A kind of iron-based amorphous powder and its preparation method and application |
| CN109825900A (en) * | 2019-01-23 | 2019-05-31 | 中国人民解放军国防科技大学 | Preparation method of BCN nano ceramic fiber |
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2019
- 2019-06-18 CN CN201910525662.3A patent/CN110230015B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1336793A (en) * | 2000-04-10 | 2002-02-20 | 株式会社日立制作所 | Electromagnetic wave absorber, its mfg. method, and articles equipped with said absorber |
| CN106191711A (en) * | 2016-07-07 | 2016-12-07 | 河海大学 | A kind of iron-based amorphous powder and its preparation method and application |
| CN109825900A (en) * | 2019-01-23 | 2019-05-31 | 中国人民解放军国防科技大学 | Preparation method of BCN nano ceramic fiber |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4205548A4 (en) * | 2020-10-08 | 2024-10-16 | Kolon Inc | Alloy, alloy powder, and alloy coated body having antimicrobial activity |
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