CN105714235B - A kind of TiO used for hot spraying2The preparation method of-CNTs composite nano-powders and its coating - Google Patents
A kind of TiO used for hot spraying2The preparation method of-CNTs composite nano-powders and its coating Download PDFInfo
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Abstract
A kind of TiO used for hot spraying2The preparation method of CNTs composite nano-powders and its coating belongs to field of thermal spray.The present invention is to overcome conventional Ti O2The shortcomings that hot-spraying coating, the excellent properties of antifriction and wear resistance based on CNTs are prepared for a kind of completely new hot spray powder system and coating system --- TiO2CNTs nano composite powders and its plasma sprayed coating.Finally, TiO compared by friction-wear test23wt%CNTs nano-composite coatings (abbreviation TiO2CNTs coatings) and introducing 12wt%Al2O3Second phase strengthens TiO2Composite coating (abbreviation TiO2‑Al2O3Coating) friction coefficient and wear extent, it was demonstrated that new coating of the present invention have more excellent tribological property.
Description
Technical field
A kind of TiO used for hot spraying2The preparation method of-CNTs composite nano-powders and its coating, belongs to field of thermal spray.
Background technology
Plasma spraying technology have that heat source temperature is high, sprayable material category is more, effluxvelocity is fast, deposition efficiency is high and
Many advantages, such as small to workpiece heat affecting.Ceramic coating prepared by it has wear-resisting, high temperature resistant, corrosion-resistant, anti-oxidant etc. excellent
Performance has in the manufacture and reparation of hundreds of parts in the fields such as aerospace, equipment remanufacturing, light industry and auto industry
It and is widely applied.Wherein, TiO2Coating hardness is moderate, wear-resistant, corrosion resistance is preferable, is commonly used for machine under medium load
The protection of tool component surface, such as bearing holder (housing, cover), reinforcing and reparation of pump seal and engine cylinder inner wall etc..But with its
Its ceramic coating (example aluminium oxide) is compared, TiO2The performances such as hardness, fracture toughness and the elasticity modulus of coating are poor, brittleness compared with
Greatly.
It is 1.8TPa that carbon nanotube (CNTs), which has high draw ratio and superpower mechanical property, elasticity modulus average value, is
100 times of steel, bending strength 14.2GPa, deposited strain energy is up to 100keV, and density is only the 1/6 of steel.It can also lead to
It crosses adjustment self structure and pentagon and heptagon occurs to discharge stress, show good self-lubricating property.Currently,
As the enhancing ideal candidate material of coating performance。
In field of thermal spray, more deep grind is had been obtained for improve coating military service performance using CNTs as reinforced phase
Study carefully.Currently, this coating system is broadly divided into two major classes：CNTs reinforced metal bases nano-composite coating (i.e. MMC-CNTs coatings)
Strengthen ceramic base nano-composite coating (i.e. CMC-CNTs coatings) with CNTs.
(1) MMC-CNTs coatings.In existing research, pass through ball-milling method, spray drying or chemical vapor deposition (CVD) mostly
The nano composite powders preparation process such as growth in situ, and with atmospheric plasma spraying technology, supersonic flame spraying technology and
Cold spray technique prepares Al-CNTs, Al-Si-CNTs, Cu-CNTs nano-composite coating, and then significantly improves the numerous of coating
Mechanical property (yield strength, tensile strength, heat conductivility, elasticity modulus etc.).
(2) CMC-CNTs coatings.That the type coating most study is Al at present2O3- CNTs coatings, mainly by ball-milling method,
Spray drying process or CVD growth in situ prepare powder, and are prepared with plasma spraying technology, and the fracture toughness of coating is made
It gets a promotion with performances such as tribology.Wang Liuying etc. prepares powder using ultrasonic blending method or mechanical milling method, then by micro-
Arc plasma spraying technology is prepared for Al2O3(/SiC)-TiO2- CNTs coatings, to improve its high temperature resistant, absorbing property or electricity
Magnetic characteristic etc..
In addition, CNTs can also be used for improving biocompatibility and the friction of hydroxyapatite coating layer (i.e. HA-CNTs coatings)
Performance is learned, the absorbing property etc. of MAS (cordierite)-CNTs coatings is improved.
These researchs, which all fully demonstrate CNTs, to be had important research value and is applied in hot-spraying coating is strengthened and is modified
Background.
Invention content
However, up to the present, there are no related patents or document report to cross TiO2The nano combined hot spraying powders of-CNTs
And its preparation of coating.The present invention is to overcome conventional Ti O2The shortcomings that hot-spraying coating, the excellent anti-friction wear-resistant based on CNTs
Can, it is prepared for a kind of completely new hot spray powder system and coating system --- TiO2- CNTs nano composite powders and its wait from
Sub- sprayed coating.Finally, TiO compared by friction-wear test2- 3wt%CNTs nano-composite coatings (abbreviation TiO2- CNTs is applied
Layer) and introducing 12wt% Al2O3Second phase strengthens TiO2Composite coating (abbreviation TiO2-Al2O3Coating) friction coefficient and mill
Damage amount, it was demonstrated that new coating of the present invention has more excellent tribological property.
TiO2The preparation flow of-CNTs nano-composite coatings includes mainly two steps：The first step is successively to use ultrasonic disperse
TiO is prepared with spray drying process2- CNTs composite nano-powders；Obtained TiO2The particle size range master of-CNTs composite nano-powders
It concentrates between 20 to 80 μm.
Second step is to prepare TiO with plasma spraying technology2- CNTs nano-composite coatings.
A kind of thermal spray powder, it is characterised in that：By TiO2With CNTs powder constituents, the weight percent of two kinds of substances
Respectively 97wt.%, 3wt.%.
A kind of preparation method of hot-spraying coating first prepares slurry with ultrasonic disperse technology, then is prepared with spray drying process
Composite nano-powder used for hot spraying finally uses plasma spraying technology prepares coating, it is characterised in that：
The weight percent of mixed-powder, deionized water and binder PVA is respectively 30wt.% in slurry,
68.5wt.% and 1.5wt.%；Mixed-powder is by TiO2Weight percent with CNTs powder constituents, two kinds of substances is respectively
97wt.%, 3wt.%；Slurry containing mixed-powder disperses 3 hours, frequency 45Hz in ultrasonic reactor continuous ultrasound, temperature 50
℃；In ultrasonic procedure, the dispersant SND 6800 that content is gross weight 0.5wt.% is added in the slurry；
Spray drying parameters are as follows：
Plasma spray coating process parameter is as follows：
The present invention is compared to traditional Al2O3The TiO of second-phase strength2Base composite coating, TiO2The nano combined paintings of-CNTs
Layer has more excellent tribological property (i.e. lower friction coefficient and higher wearability).
Description of the drawings
Fig. 1 nano-TiO2Scheme with the SEM of MWCNT
Fig. 2 (a) TiO2The SEM figures of CNTs distributions inside-CNTs composite nano-powders and its SEM in section figure (b) powders
(c)TiO2The laser particle distribution map of-CNTs composite nano-powders
Fig. 3 TiO2The SEM of-CNTs nano-composite coatings section and partial enlargement schemes
Fig. 4 (a) conventional melt breaking types TiO2-Al2O3The SEM of powder schemes (b) TiO2-Al2O3The SEM of coating cross sections schemes
(c)TiO2-Al2O3The laser particle distribution map of powder
Two kinds of coating friction coefficient curves of Fig. 5 change with time relationship
Fig. 6 TiO2-Al2O3Coating and TiO2The contour curve figure of-CNTs coating polishing scratch
Fig. 7 TiO2-Al2O3The SEM in coating polishing scratch region schemes
Fig. 8 TiO2The SEM in-CNTs coating polishing scratch region schemes
Specific implementation mode
1 ultrasonic disperse and spray drying process prepare TiO2- CNTs composite nano-powders
Nano-TiO2Average grain diameter be 60nm, the caliber of multi wall CNTs (MWCNTs) is 40~60nm, and length is less than 2 μm
(such as Fig. 1).
Ultrasonic disperse technology prepares slurry：
(1) by nano oxidized titanium powder and MWCNTs according to 97wt.%, the weight percent of 3wt.% is doped mixed
It closes, obtains the mixed-powder of two kinds of substances；
(2) by the mixed-powder, deionized water and binder PVA (polyvinyl alcohol) respectively according to 30wt.%,
The weight percent of 68.5wt.% and 1.5wt.%, which is stirred, is made slurry；
(3) in order to ensure that CNTs is evenly dispersed in the slurry, slurry is placed in ultrasonic reactor.Continuous ultrasound dispersion 3
Hour, frequency 45Hz, temperature 50 C；
(4) during ultrasonic disperse, to be further reduced the agglomeration of CNTs, dispersant SND is added in the slurry
6800 (anionic polycarboxylate's salt electrolytes), content accounts for the 0.5wt.% of slurry gross weight.
Spray drying process prepares thermal spraying composite granule：
Select LGZ-25 types centrifugal spray dryer that slurry obtained by ultrasonic disperse is carried out mist projection granulating.The spraying of selection
Drying parameter is：
| Temperature of inlet air | 230℃ | Slurry gives rate | 60g/min |
| Cavity air themperature | 151℃ | Atomization air flow | 12m3/h |
| Air exit temp | 130℃ | High-pressure air pressure | 0.4Mpa |
| Nozzle rotary speed | 13000r/min |
In addition, by observing inside the composite powder after being granulated (Fig. 2 (b)), we can clearly be observed that CNTs quilts
It is dispersed in powder, CNTs is mutually wound, cluster is less.In this way in thermal spray process, CNTs inside powder can be with
It is protected well, reduces excessively high heat source temperature (up to 10000 DEG C) to the greatest extent and CNTs (about 3680 DEG C of fusing point) structure is made
At destruction, to ensure that coating quality.
2 plasma spraying technologies prepare TiO2- CNTs nano-composite coatings
Spraying workpiece used is 42CrMo steel, sample dimensions 30*60*5mm.
Polished surface of test piece with the sand paper of 400 mesh first, then derusted, oil removing, the pretreatments such as sandblasting.
Then use plasma spraying method, by the composite nano-powder prepared in upper step by powder feeder be transported to etc. from
Before the rifle mouth of sub- spraying equipment, using the higher heat source temperature of plasma flame flow (up to 10000 DEG C or more), powder is made to reach
Molten condition is simultaneously ejected into the surface of test piece by blasting treatment with high speed (average speed is more than 340m/s), cooling
After obtain TiO2- CNTs nano-composite coatings (Fig. 3).
Specific spraying parameter：The flow of Ar gases is 42L/min, H2The flow of gas is 10 L/min；Voltage
For 72V, electric current 550A, powder feed rate 20g/min, spray distance 80mm.
It can be seen from the figure that CNTs can preferably keep its structural intergrity in the coating, tubular structure is by firmly
Ground is embedded in coat inside, shows " bridge joint " structure.
3 conventional Ti O2-Al2O3The preparation of coating (reference pair is than coating)
Contrast experiment uses TiO2-Al2O3Powder buys (such as Fig. 4 (a) and figure from Anyang Tian Chuan thermal spraying materials Co., Ltd
4 (c)), it is common TiO in the industrial production of spraying field2-Al2O3Powder.It is made, is had fine by melting crushing process
Spraying process, powder deposition efficiency is higher.
The technical process and parameter and TiO of spraying2- CNTs nano-composite coatings are essentially identical.
The tribological property contrast experiment of 4 two kinds of coatings and Analysis on Mechanism
UsingThe friction of micro-moving frictional wear testing machine (production of Germany OPTIMOL companies) testing coating
Learn performance.Using the shuttle friction type of ball disk, in atmospheric environment, under room temperature.Wherein, load 20N, frequency
20Hz, reciprocating stroke 1.5mm, time 60min.Mating plate is chromium plating ball, diameter 10mm.
Measured coating friction coefficient curve changes with time relationship such as Fig. 5.
As can be observed from Figure, TiO2-Al2O3Coating friction coefficient is higher than TiO2- CNT coating friction coefficient.
The wear extent of coating is evaluated by the depth and width of abrasion, as shown in Figure 6.As can be seen that being doped into
The TiO of CNTs2Its wear extent of composite coating reduces about 4.3 times.
SEM pictures such as Fig. 7 after two kinds of coating fretting wears, shown in Fig. 8：
Think, TiO2- CNTs coatings are compared to TiO2The reason of coating tribologic performance improves has at following 4 points：
1) from Fig. 7 and Fig. 8 as can be seen that surface after abrasion, all there are crackles.But for TiO2- CNT is applied
Layer makes the wear extent of coating reduce since the bridge joint effect of CNT limits the generation of crackle and further expands (Fig. 8 (b))；
2) as can be seen that several CNTs, which mutually winds, becomes longer tube-like materials and substantially vertical from Fig. 8 (c)
Rolling friction is reformed into the forms of motion along fretting wear direction, the in this way region, so that friction coefficient reduces；
3) enable the spraying molten drop after its solidification nearby close as can be seen that the bridge joint of CNTs acts on from Fig. 8 (d)
Connect, be not easy to be pulled away in (region I) in process of friction and wear, and the TiO apart from the CNTs farther out2(region II)
Then since lower cohesive strength is by more serious abrasion, become abrasive dust；
4) in process of friction and wear, it is present in the CNTs of wear surface, using its excellent self-lubricating property, that is, passes through
There is pentagon and heptagon to discharge stress in adjustment self structure, so that friction coefficient reduces.
Claims (1)
1. a kind of TiO2The nano combined hot-spraying coating preparation processes of-CNTs first use physics supersonic synergic chemical modification to be modified and realize
The uniform compounding of zero-dimension nano ceramics and one-dimensional carbon nanotube, then the nano composite slurry obtained by previous step is spray-dried and is prepared
Composite nano-powder feeding used for hot spraying is obtained, it is evenly dispersed that CNTs finally is prepared using plasma spraying technology
TiO2- CNTs coatings, it is characterised in that：
The weight percent of mixed-powder, deionized water and binder PVA is respectively 30wt.% in slurry, 68.5wt.% and
1.5wt.%；Mixed-powder is by TiO2Weight percent with CNTs powder constituents, two kinds of substances is respectively 97wt.%,
3wt.%；Slurry containing mixed-powder disperses 3 hours, frequency 45Hz in ultrasonic reactor continuous ultrasound, temperature 50 C；Ultrasonic mistake
Dispersant SND 6800 is added in slurry by Cheng Zhong, and content is the 0.5wt.% of slurry gross weight；
Spray drying parameters are as follows：
Plasma spray coating process parameter is as follows：
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| CN106048494A (en) * | 2016-07-05 | 2016-10-26 | 上海航天设备制造总厂 | Micro/nano-structured TiO2 coating with self-cleaning function and preparation method thereof |
| CN106399910A (en) * | 2016-11-18 | 2017-02-15 | 无锡明盛纺织机械有限公司 | Preparation method for composite abrasion-resistant coating |
| CN107737916A (en) * | 2017-09-07 | 2018-02-27 | 杭州萧山红旗摩擦材料有限公司 | Nano-material modified copper based powder metallurgy friction material and preparation method thereof |
| CN107856540B (en) * | 2017-10-27 | 2020-08-04 | 中国人民解放军装甲兵工程学院 | Trolley bus pantograph slide plate with long service life and preparation method thereof |
| CN107839487B (en) * | 2017-10-27 | 2019-12-06 | 中国人民解放军装甲兵工程学院 | Novel high-performance repairable pantograph slide plate of electric locomotive and preparation method thereof |
| CN107794486B (en) * | 2017-10-27 | 2020-03-27 | 中国人民解放军装甲兵工程学院 | High-performance long-life space equipment precision conductive slip ring and preparation method thereof |
| CN107815634B (en) * | 2017-10-27 | 2019-12-06 | 中国人民解放军装甲兵工程学院 | High-performance long-service-life remanufacturable life-prolonging collecting ring and preparation method thereof |
| CN108165921B (en) * | 2018-01-27 | 2019-09-20 | 辽东学院 | A kind of preparation method of the hot water supply pipe of high-temperature corrosion resistance |
| CN108716574B (en) * | 2018-06-19 | 2020-05-19 | 广汉华气防腐工程有限公司 | Production process of high-weather-resistance anticorrosive pipe |
| CN113913721B (en) * | 2021-09-14 | 2023-01-24 | 河海大学 | Composite powder for supersonic flame spraying, preparation and application |
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| CN102731101A (en) * | 2012-05-29 | 2012-10-17 | 苏州大学 | Method for manufacturing superhigh temperature ceramic special-shape member through plasma spraying near-net-forming |
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