CN109868443A - A kind of nickel-based aluminum oxide high-temperature self-lubrication wear-resistant coating and preparation method thereof - Google Patents
A kind of nickel-based aluminum oxide high-temperature self-lubrication wear-resistant coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of nickel-based aluminum oxide high-temperature self-lubrication wear-resistant coating and preparation method thereof, the present invention prepares NiCoCrAlY/Al using supersonic flame spraying technology2O3‑CaF2.BaF2High temperature solid self-lubricants abrasion-resistant coating material structure is finer and close, has lower high temperature friction coefficient, at 800 DEG C, coefficient of friction only has 0.27, this is primarily due to CaF at high temperature2.BaF2Soften, the CaF after softening2.BaF2One layer of lubricating film is generated in coating surface under the action of shear stress, to reduce coefficient of friction.
Description
Technical field
This patent disclosure relates generally to wear-resistant coating fields, and in particular to prepares Ni-based oxidation using supersonic flame spraying technology
Aluminium high-temperature self-lubrication wear-resistant coating.
Background technique
The antirust of high temperature alloy used in aerospace, electric power, nuclear energy and field of metallurgy, anti-corrosion, wear-resisting and lubrication problem
It is critical issue urgently to be resolved at present, it directly affects the service life of high temperature alloy.Especially in high-speed resistance and heat
The high-temperature alloy material used under corrosive environment, under this harsh environment, lubricant grease is helpless, commonly uses solid lubrication
Agent such as graphite, MoS2Deng easily oxidation deactivation, it is wear-resisting to develop the solid lubrication that can be used for a long time under high temperature, high oxidation environment
Coating is effective solution approach.
Solid lubrication wear-resistant coating is by matrix phase, lubrication phase and wear-resisting phase composition.Wherein matrix mutually mainly by metal and its
Alloy material composition, there are commonly Ni-based, cobalt-based and ferrous alloy materials, primarily serve the effect of Binder Phase in the coating；Profit
It is sliding mutually mainly to have metal sulfide, inorganic simple substance, metal oxide and rare earth compound, inorganic borate etc. and the resistance to height in part
The high molecular material of temperature, such as PI, PTFE, PEEK, primarily serve the effect of lubrication in the coating；Wear phase is mainly by ceramic material
Material composition, including oxide, silicide, carbide and nitride etc., what is primarily served in the coating improves the wear-resisting of coating
Property and extend coating service life effect.
Currently, there are many research about high-temperature solid lubrication abrasion-resistant coating material, but with Al2O3For the coating of wear phase
Material report is less.Cheng Guoan et al. is prepared for NiCr/Al using powder thermospraying method2O3Composite coating analyzes the aobvious of coating
Micro-structure and object phase composition, and spraying process is had studied to the shadow of metal/ceramic system composite coating microstructure and object phase composition
It rings, but the not performance of testing coating in text.Zhang Tianming is prepared for Ni/Al using supersonic flame spraying technique2O3Compound painting
Layer, and the performance of coating is had studied, find Al2O3The wearability that can effectively improve coating is added in particle.Zhao Xiaobing is sprayed using flame
Painting technology is prepared for different Al2O3Ni nanoparticle/Al of content2O3Composite coating, and have studied the structure and performance of coating.
A.S.Hamdy et al. is prepared for Ni-P-Al using chemical plating2O3, Ni-P-W and Ni-P coating, have studied coating in 3.5%NaCl
Hot corrosion behavior in solution.Feng Q.Y. et al. is prepared for Ni/Al by coprecipitation2O3Composite coating has studied coating
High temperature corrosion and oxidation behavior.Research is found: nanometer Al2O3Particle has refined the crystallization of Ni, changes most preferably taking for coating
To, while the anticorrosive and antioxygenic property of coating is also improved.This seminar uses air plasma spraying and Supersonic
Fast flame spray technique is prepared for NiCoCrAlY/Al2O3-B4C coating material, research find that the coating is anti-with good high temperature
Oxidation susceptibility, but its high temperature lubrication property is poor, in order to further increase the high temperature lubrication property of coating, the present invention is in coating
In joined CaF2.BaF2As high temperature solid lubricant, NiCoCrAlY/ is prepared for using supersonic flame spraying technology
Al2O3-CaF2.BaF2High temperature solid self-lubricants abrasion-resistant coating material.
Summary of the invention
The object of the present invention is to provide a kind of nickel-based aluminum oxide high-temperature self-lubrication wear-resistant coating and preparation method thereof, the coatings
The high temperature such as aerospace, electric power, metallurgy are mainly used in respect on running gear.
A kind of NiCoCrAlY/Cr according to the present invention2O3-Ag-CaF2.BaF2The preparation method of composite coating, including with
Lower step:
(1) by certain metering score also known as amount Al2O3And CaF2.BaF2Powder is put into tempering tank, and deionization is added
Water is uniformly mixed by electric mixer, and proper quantity of defoaming agent is added to remove the bubble in mixed slurry, is sprayed by high speed centrifugation
Mist granulating and drying machine carries out centrifugal spray granulation to mixed slurry, obtains spherical Al2O3-CaF2.BaF2Composite granule.
(2) composite granule obtained is sieved, takes the particle between 20~45 μm compound for subsequent supersonic speed
The preparation of powder.
(3) using high pressure Process of Hydrogen Reduction in Al2O3-CaF2.BaF2Ni/Al is made in particle surface nickel plating2O3-
CaF2.BaF2Composite granule.
(4) by Ni/Al2O3-CaF2.BaF2Composite granule is sufficiently mixed with Co, Cr, Al, Y powder, under reducing atmosphere into
NiCoCrAlY/Al is made in row alloying2O3-CaF2.BaF2Composite granule.
(5) matrix is put and is cleaned by ultrasonic in acetone, to remove the grease stain and other materials of matrix surface；After drying, adopt
Sandblasting pretreatment is carried out to matrix surface with suction-type dry blasting machine.
(6) supersonic velocity flame plating equipment prepares coating is used, optimized spray parameters are as follows: oxygen flow 50m3/
H, spray distance 350mm, 30~40g/min of powder sending quantity, aviation kerosine 21L/h.
Under concrete condition, the weight of each component is formed are as follows: Ni:Co:Cr:Al:Y=74:2.5:17.5:5.5:0.5；
NiCoCrAlY:40%~50%；Al2O3: 40%~50%；CaF2.BaF2: 5%~15%.
Under preferable case, step (3) specifically: take a certain amount of Al2O3-CaF2.BaF2Powder granule and surfactant
It is sufficiently mixed uniformly；Then, by required nickel and Al2O3-CaF2.BaF2The mass ratio of particle is by nickel sulfate, buffer, catalysis
Agent and Al2O3-CaF2.BaF2Particle is fitted into autoclave jointly and seals；After the air in hydrogen displacement kettle, heating
To 150~180 DEG C, it is filled with the hydrogen of 2~5MPa, and adjusts stirring rate, hydrogen make-up as needed；Hydrogen is filled with to be gone back
Original reaction, until hydrogen pressure is constant in pressure gauge；Powder is taken out after cooling and is dried, as Ni/Al2O3-CaF2.BaF2It is multiple
Close powder.Wherein surfactant is specifically as follows polyacrylamide, and buffer is specifically as follows ammonium chloride, and catalyst specifically may be used
Think palladium chloride.It can be in Al using the high pressure Process of Hydrogen Reduction2O3-CaF2.BaF2One layer of the uniform plating in powder granule surface cause
Close nickel film.
With the supersonic flame spraying NiCoCrAlY/Al prepared before seminar2O3-B4C coating material is compared, the present invention
The NiCoCrAlY/Al of preparation2O3-CaF2.BaF2High temperature solid self-lubricants abrasion-resistant coating material structure is finer and close, has lower
High temperature friction coefficient, at 800 DEG C, coefficient of friction only has 0.27, this is primarily due to CaF at high temperature2.BaF2Occur soft
Change, the CaF after softening2.BaF2One layer of lubricating film is generated in coating surface under the action of shear stress, to reduce friction
Coefficient.
Detailed description of the invention
Fig. 1 is the present invention using supersonic flame spraying preparation NiCoCrAlY/Al2O3-CaF2.BaF2Composite coating technique
Flow chart.
Fig. 2 is temperature to supersonic flame spraying NiCoCrAlY/Al2O3-CaF2.BaF2The shadow of composite coating coefficient of friction
It rings.
Fig. 3 is temperature to supersonic flame spraying NiCoCrAlY/Al2O3-CaF2.BaF2The shadow of composite coating wear rate
It rings.
Specific embodiment
The present invention is described in detail with reference to embodiments, and the present invention is not limited by these manufacture embodiments.
The present invention prepares NiCoCrAlY/Al using supersonic flame spraying technology2O3-CaF2.BaF2Composite coating, system
Standby process flow is as shown in Figure 1.
Specific preparation process is divided into two parts:
1. the preparation of powder
(1) Al is stoichiometrically weighed respectively2O3And CaF2.BaF2Powder is put into plastic barrel, and certain ratio is added
The deionized water of example is uniformly mixed by JJ-1 type reinforcement electric mixer, and proper quantity of defoaming agent is added to remove in mixed slurry
Bubble, by LGZ high speed centrifugation Spray Grain-make Drier to mixed slurry carry out centrifugal spray granulation, obtain spherical
Al2O3-CaF2.BaF2Composite granule.
The weight of each component forms are as follows: Ni:Co:Cr:Al:Y=74:2.5:17.5:5.5:0.5；NiCoCrAlY:40%
~50%；Al2O3: 40%~50%；CaF2.BaF2: 5%~15%.Wherein CaF2.BaF2For CaF2And BaF2Mixed powder,
Molar ratio between the two is 1:1.
(2) composite granule obtained is sieved, takes the particle between 20~45 μm compound for subsequent supersonic speed
The preparation of powder.
(3) firstly, taking a certain amount of Al2O3-CaF2.BaF2Powder granule and surfactant are sufficiently mixed uniformly.So
Afterwards, by required nickel and Al2O3-CaF2.BaF2The mass ratio of particle is by nickel sulfate, ammonium chloride, palladium chloride and Al2O3-
CaF2.BaF2Particle is fitted into autoclave jointly and seals.After the air in hydrogen displacement kettle, it is heated to 150~180
DEG C, it is filled with the hydrogen of 2~5MPa, and adjust stirring rate, hydrogen make-up as needed.It is filled with hydrogen and carries out reduction reaction, directly
Into pressure gauge, hydrogen pressure is constant.Powder is taken out after cooling and is dried, as Ni/Al2O3-CaF2.BaF2Composite granule.
(4) by Ni/Al2O3-CaF2.BaF2Composite granule is sufficiently mixed with Co, Cr, Al, Y powder, under reducing atmosphere into
NiCoCrAlY/Al is made in row alloying2O3-CaF2.BaF2Composite granule.
2. the preparation of coating
(1) matrix is put and is cleaned by ultrasonic 10min in acetone, to remove the grease stain and other materials of matrix surface.It is dry
Afterwards, sandblasting pretreatment is carried out to Ni based high-temperature alloy matrix surface using GS-943 type suction-type dry blasting machine.
(2) T is usedⅠ-Ⅱ3200CY type supersonic velocity flame plating equipment prepares coating, optimized spray parameters are as follows: oxygen
Throughput 50m3/ h, spray distance 350mm, 30~40g/min of powder sending quantity, aviation kerosine 21L/h.
Embodiment 1
NiCoCrAlY/Al2O3-CaF2.BaF2Composite coating, consisting of: Ni:Co:Cr:Al:Y=74:2.5:17.5:
5.5:0.5；NiCoCrAlY:50%；Al2O3: 40%；CaF2.BaF2: 10%.Al is prepared for through spray granulation2O3-
CaF2.BaF2Composite granule, and cladded type NiCoCrAlY/ is prepared for using High Pressure Hydrogen reduction technique and solid phase alloying process
Al2O3-CaF2.BaF2Composite granule is prepared for NiCoCrAlY/Al using supersonic flame spraying technology2O3-CaF2.BaF2It is multiple
Coating material is closed, its coefficient of friction and wear rate are tested.
Fig. 2 show temperature to supersonic flame spraying NiCoCrAlY/Al2O3-CaF2.BaF2Composite coating coefficient of friction
Influence.As shown, the coefficient of friction of coating first has increased slightly and reduces afterwards as the temperature increases, rub system at 200 DEG C
Number is up to 0.81 or so, 800 DEG C of coefficient of frictions minimum 0.27 or so, this is primarily due to CaF at high temperature2.BaF2Occur
Softening, the CaF after softening2.BaF2One layer of lubricating film is generated in coating surface under the action of shear stress, is rubbed to reduce
Wipe coefficient.
Fig. 3 is temperature to supersonic flame spraying NiCoCrAlY/Al2O3-CaF2.BaF2The shadow of composite coating wear rate
It rings.It can be seen from the figure that the wear rate first increases and then decreases of coating as the temperature rises.At 400 DEG C, wear rate is maximum,
About 9.8 × 10-4mm3/ Nm, this may be because one side coating and surface of friction pair are adhered, separately at 400 DEG C
On the one hand as the temperature rises, the intergranular bond strength of coat inside reduces, and coating surface not yet generates at a temperature of this
Lubricating film, coating surface abrasion is relatively more serious under the action of shear stress；And at 800 DEG C, wear rate reaches minimum, about
5.0×10-4mm3/Nm.This may be because generating CaF at high temperature2.BaF2The reason of solid lubricant film.
Conclusion: when by testing its 800 DEG C, coefficient of friction and wear rate are minimum, respectively may be about 0.27 and 5.0 × 10- 4mm3/Nm。
Embodiment 2
NiCoCrAlY/Al2O3Composite coating, consisting of: Ni:Co:Cr:Al:Y=74:2.5:17.5:5.5:0.5；
NiCoCrAlY:45%；Al2O3: 50%；CaF2.BaF2: 5%.Al is prepared for through spray granulation2O3Powder, and using high
Pressure hydrogen reduction technology and solid phase alloying process are prepared for cladded type NiCoCrAlY/Al2O3Composite granule, using supersonic flame
Spraying technology is prepared for NiCoCrAlY/Al2O3Composite coating material tests its coefficient of friction and wear rate.
Conclusion: wear rate minimum 4.8 × 10 when by testing its room temperature-4mm3/Nm.At 800 DEG C, coefficient of friction is minimum,
About 0.4.
Embodiment 3
NiCoCrAlY/Al2O3-CaF2.BaF2Composite coating, consisting of: Ni:Co:Cr:Al:Y=74:2.5:17.5:
5.5:0.5；NiCoCrAlY:40%；Al2O3: 45%；CaF2.BaF2: 15%.Al is prepared for through spray granulation2O3-
CaF2.BaF2Composite granule, and cladded type NiCoCrAlY/ is prepared for using High Pressure Hydrogen reduction technique and solid phase alloying process
Al2O3-CaF2.BaF2Composite granule is prepared for NiCoCrAlY/Al using supersonic flame spraying technology2O3-CaF2.BaF2It is multiple
Coating material is closed, its coefficient of friction and wear rate are tested.
Conclusion: when by testing its 800 DEG C, coefficient of friction and wear rate are minimum, respectively may be about 0.35 and 3.8 × 10- 4mm3/Nm。
It will be appreciated by those skilled in the art that above embodiments are only presently preferred embodiments of the present invention, it is not used to
It limits the scope of protection of the present invention, all within principle and spirit of the invention, any modification, equivalent replacement or the improvement made
Deng should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of preparation method of nickel-based aluminum oxide high-temperature self-lubrication wear-resistant coating, comprising the following steps:
(1) by certain metering score also known as amount Al2O3And CaF2.BaF2Powder is put into tempering tank, and deionized water is added, and is led to
It crosses electric mixer to be uniformly mixed, proper quantity of defoaming agent is added to remove the bubble in mixed slurry, is made by spraying by high speed centrifugation
Grain drying machine carries out centrifugal spray granulation to mixed slurry, obtains spherical Al2O3-CaF2.BaF2Composite granule；
(2) composite granule obtained is sieved, takes the particle between 20~45 μm for subsequent supersonic speed composite granule
Preparation；
(3) using high pressure Process of Hydrogen Reduction in Al2O3-CaF2.BaF2Ni/Al is made in particle surface nickel plating2O3-CaF2.BaF2It is multiple
Close powder；
(4) by Ni/Al2O3-CaF2.BaF2Composite granule is sufficiently mixed with Co, Cr, Al, Y powder, is closed under reducing atmosphere
NiCoCrAlY/Al is made in aurification2O3-CaF2.BaF2Composite granule；
(5) matrix is put and is cleaned by ultrasonic in acetone, to remove the grease stain and other materials of matrix surface；After drying, using suction
Enter formula dry blasting machine and sandblasting pretreatment is carried out to matrix surface；
(6) supersonic velocity flame plating equipment prepares coating is used, optimized spray parameters are as follows: oxygen flow 50m3/ h, spraying
Distance 350mm, 30~40g/min of powder sending quantity, aviation kerosine 21L/h.
2. preparation method according to claim 1, the weight composition of each component are as follows: Ni:Co:Cr:Al:Y=74:2.5:
17.5:5.5:0.5；NiCoCrAlY:40%~50%；Al2O3: 40%~50%；CaF2.BaF2: 5%~15%.
3. the high temperature solid self-lubricants wear-resistant coating prepared by preparation method described in claim 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724803A (en) * | 2008-10-16 | 2010-06-09 | 北京有色金属研究总院 | Preparation method of composite powder for high-temperature wear-resisting self-lubricating coating |
| CN101736279A (en) * | 2008-11-05 | 2010-06-16 | 沈阳黎明航空发动机(集团)有限责任公司 | Hypersonic flame spraying process for self-lubricating wear-resistant coating |
| CN102528049A (en) * | 2010-12-20 | 2012-07-04 | 北京有色金属研究总院 | Composite powder for air bearing and rotor coating and preparation method of composite powder |
| CN104278226A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院兰州化学物理研究所 | Preparation technology for wide-temperature-range self-lubricating coating |
| CN106917059A (en) * | 2015-12-28 | 2017-07-04 | 王海斗 | A kind of thermal spraying composite granule and its production and use |
-
2019
- 2019-03-12 CN CN201910182714.1A patent/CN109868443B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724803A (en) * | 2008-10-16 | 2010-06-09 | 北京有色金属研究总院 | Preparation method of composite powder for high-temperature wear-resisting self-lubricating coating |
| CN101736279A (en) * | 2008-11-05 | 2010-06-16 | 沈阳黎明航空发动机(集团)有限责任公司 | Hypersonic flame spraying process for self-lubricating wear-resistant coating |
| CN102528049A (en) * | 2010-12-20 | 2012-07-04 | 北京有色金属研究总院 | Composite powder for air bearing and rotor coating and preparation method of composite powder |
| CN104278226A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院兰州化学物理研究所 | Preparation technology for wide-temperature-range self-lubricating coating |
| CN106917059A (en) * | 2015-12-28 | 2017-07-04 | 王海斗 | A kind of thermal spraying composite granule and its production and use |
Non-Patent Citations (3)
| Title |
|---|
| 张甜甜等: ""镍基耐高温自润滑刷式封严涂层研究"", 《航空制造技术》 * |
| 曹玉霞: ""超音速火焰喷涂 NiCoCrAlY/Al2O3复合涂层的抗氧化性能"", 《金属热处理》 * |
| 黄传兵等: ""NiCr/Cr3C2-BaF2•CaF2高温自润滑耐磨涂层的制备与摩擦磨损特性"", 《摩擦学学报》 * |
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