CN1687485A - High corrosion resisting and high wearable non-crystalline iron based nano crystal cost for plasma spraying and preparation method - Google Patents
High corrosion resisting and high wearable non-crystalline iron based nano crystal cost for plasma spraying and preparation method Download PDFInfo
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- CN1687485A CN1687485A CN 200510011484 CN200510011484A CN1687485A CN 1687485 A CN1687485 A CN 1687485A CN 200510011484 CN200510011484 CN 200510011484 CN 200510011484 A CN200510011484 A CN 200510011484A CN 1687485 A CN1687485 A CN 1687485A
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Abstract
Preparation of iron base amorphous nanocrystalline alloy coatings by plasma spraying which is wearable and anti-corrosive relates to iron base alloy coatings by plasma spraying, especially for the preparation of amorphous and nanocrystalline alloy coatings. The present invention aims at the problem of amorphous alloy coatings and nanocrystalline alloy coatings by thermal spraying. We use iron base multi- elements amorphous alloy as the coatings. We cool the substrate by carrying water or top injection method in spraying. The method can accelerate the cooling. The iron base amorphous alloy powder deposits on substrate, so we can get amorphous and nanocrystalline alloy coatings which contains the structure of amorphous and nanocrystalline. The coatings have the wearable and anti-corrosive capability.
Description
Technical field
The present invention relates to the plasma spraying iron alloy coating, particularly relate to the preparation of amorphous nanocrystalline composite coating.
Background technology
Non-crystalline material, nanocrystalline material have the performance more unique and more excellent than traditional material, are rising type materials.But in practice, so far, these materials are not still also applied on a large scale, and its principal element is that its preparation process is difficult to control, be difficult to large block amorphous, the nanocrystalline material of preparation in practice, its application mainly is limited in low dimensions such as strip, filament, powder in shape.Comparatively speaking, the preparation process of amorphous, nanocrystalline coating just realizes than being easier to, in numerous methods that prepare coating, hot-spraying techniques is a kind of technology that has competitive power, also be very promising technology simultaneously, in hot-spraying techniques, mainly adopt plasma spraying technology and hypersonic flame spraying technology to prepare non-crystal structure or nano-structured coating.
A tree name United States Patent (USP) U.S.P.5,939,146 reports, people such as E.J.Lavernia at first become nano-sized powders with high-energy ball milling with the micron powder ball milling, carry out hypersonic flame spraying then, just can be prepared into the more meticulous nano-structured coating of microstructure, the thickness of coating can reach several millimeters.This method also can spray 3 D workpiece, can obtain high-quality coating equally.
Nanostructured Materials, 1998,10 (2): the 169-178 report, people such as H.G.Jiang are that medium carries out the powder that high-energy ball milling is prepared into nanostructure respectively to the Inconel718 alloy with methyl alcohol and liquid nitrogen respectively, powder through the laggard capable hypersonic flame spraying of super-dry, obtained nano-structured coating.The powder of two kinds of methods (methyl alcohol and liquid nitrogen medium) preparations and the thermostability of thermally sprayed coating have been studied with isothermal heat treatment method, all nanocrystalline Inconel718 powdered alloy and coatings have all shown good thermostability, handled 60 minutes under the temperature of 1273K, crystal grain still remains on about 100nm.
J.Thermal Spray Technology, 2000,9 (3): the 399-406 report, people such as B.H.Kear compare the microstructure of the nanostructure WC/Co hard coat of air plasma spraying and hypersonic flame spraying preparation and conventional coatings and discover that the raising of nanostructure WC/Co hot spray coating wear resistance is its microstructural variation.
What above method prepared is single nano-structured coating, have good abrasion resistance properties, but corrosion resistance nature is general.
J.Thermal Spray Technology, 1999,8 (3): the 399-404 report, Mccartney D.J. sprays two kinds of Ni-Cr-Mo-B powdered alloys with supersonic flame spraying method, prepare the amorphous coating of these two kinds of alloys, and having studied their corrosion resistance characteristic, the result shows: two kinds of alloy coats are at 0.5mol/LH
2SO
4All have good solidity to corrosion in the solution, the corrosion potential of two kinds of alloy coats is about-300mV (relative saturation mercurous chloride electrode), and passivation current density is about 1mA/cm
2But because this coating is single non-crystal structure, though have excellent corrosion resisting performance, wear resisting property is not ideal enough.
In a word, nanocrystalline coating has the excellent abrasive energy, and amorphous coating then has good corrosion resistance nature, and in the above method, coatings prepared all is single structure.Be amorphous coating, have excellent corrosion resisting performance, but wear resisting property is general; Be nano-structured coating, have good wear resisting property, but corrosion resistance nature be general.So, needing to seek a kind of suitable way utilizes the nanometer technology to improve the characteristics of material wear-resistant performance, amorphization techniques raising material corrosion resisting property, the nanometer technology is combined with amorphization techniques, prepare the amorphous nano compound coating of corrosion-resistant and wear-resisting excellent combination property.
Summary of the invention
The present invention is directed to over and utilize hot-spraying techniques to prepare the problem of single amorphous coating or nano-structured coating existence, proposition by amorphous alloy powder as dusty spray, utilize the air plasma spraying method, in spraying process, matrix is cooled off, prepared the amorphous nanocrystalline composite coating that not only contains non-crystal structure but also contain nanostructure, this coating has excellent corrosion-resistant and wear-resisting over-all properties.
The present invention selects the plain amorphous alloy powder of Fe-base multielement as spray material, its composition is by weight percentage: 0.2～1.5%wtC, 2～8%wt Si, 3～9%wt B, 2～10%wt Cr, 4～17%wt W, 2～13%wtMo, 2～11%wtNi, 0～2%wtY, remaining be Fe, the size range of powder is 160 orders～400 orders.
The present invention adopts common air plasma spraying method to prepare coating, and spraying parameter is: arc voltage 60～80V, flame current 350～600A, main gas (Ar gas) 40～90L/min, secondary gas (H
2Gas) 25～50L/min, powder feed rate 15～100g/min, spray distance 80～135mm.In spraying process, adopt air blowing method or recirculated water cooling method to cool off matrix, the flow of cooling gas is 100～2000L/min, the flow of water coolant is 10～500L/min.
Compared with prior art, plasma spraying technology provided by the present invention prepares the method for iron-based amorphous nanocrystalline composite coating, cool off matrix with air blowing method or recirculated water cooling method, improved the speed of cooling of matrix, the amorphous Fe base alloy powder that has melted is deposited on the quick refrigerative matrix, crystallization has taken place in some in the formed coating, obtained the crystal grain of nano-scale, another part also keeps the amorphous structure of original iron-based dusty spray, finally obtained not only containing amorphous but also contain nanocrystalline compound coating, this coating has excellent anticorrosive wear-resistant and decreases over-all properties.And the coating that original technology is prepared or be single non-crystal structure, or be single nanostructure.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of iron-based dusty spray (a) and coating (b)
Fig. 2 is a plasma spraying iron-based coating TEM shape appearance figure (100000 *)
Fig. 3 is plasma spraying iron-based coating micro-area diffraction figure
Fig. 4 is differential thermal analysis (DSC) curve of plasma spraying iron-based coating
Embodiment
Embodiment selects the composition of the plain amorphous alloy powder of Fe-base multielement to be by weight percentage: 0.9%wtC, 3.8%wt Si, 4.1%wt B, 6.5%wt Cr, 11.5%wt W, 6.7%wt Mo, 4.5%wtNi, 0.2%wt Y, remaining be Fe, the size range of powder is 160 orders～400 orders.Be coated on the 0Cr13Ni5Mo stainless steel base with plasma spray and prepare coating, the plasma spraying parameter is: arc voltage 60V, flame current 550A, main gas (Ar gas) 60L/min, secondary gas (H
2Gas) 30L/min, powder feed rate 45g/min, spray distance 120mm.In spraying process, adopt air blowing method to cool off matrix, the flow of cooling gas is 300L/min.
The crystalline structure of dusty spray and coating
Fig. 1 is the X ray diffracting spectrum of iron-based dusty spray and respective coatings, and as can be seen from the figure: dusty spray is typical amorphous powder, and in the coating except containing amorphous, also contain crystalline material.The reference standard diffracting spectrum can be found coating and contain Ni
6Mo
6C
1.06And Fe
3Two kinds of materials of C.Calculated the average grain size of these two kinds of materials: Ni respectively through Scherrer formula (wherein constant gets 0.89, and λ gets 1.542 ) with the halfwidth of diffraction peak
6Mo
6C
1.06Average crystal grain is 72.2nm, Fe
3The C average crystal grain is 39.7nm.Adopt method of the present invention to prepare iron-based amorphous nanocrystalline composite coating.
The heterogeneous microstructure of coating
With transmission electron microscope observing the heterogeneous microstructure of coating, and carried out the microzone electron diffraction analysis, the results are shown in accompanying drawing 2.Therefrom as can be seen: the microtexture of coating is more even, disperse is distributed with the polycrystalline composition of variable grain size in the coating, measure the size of these polycrystalline compositions, measure its distribution of sizes between 10～60nm, identical substantially with the halfwidth of the diffraction peak of using the X diffraction through the grain-size that the Scherrer formula calculates.The micro-area diffraction figure of right figure has also shown also contained crystalline material in the coating except containing amorphous, and crystalline material is a nano-scale, as seen adopts method of the present invention to prepare iron-based amorphous nanocrystalline composite coating.
The hardness of coating
The present invention has measured the gained coating hardness with the large-scale microhardness tester of Leica, and the highest microhardness reaches 1331.8HV
50, minimum hardness is 852.3 HV
50, average microhardness is 1019.4HV
50
The thermostability of coating
With the DSC curve of having measured coating on the NETZSCH STA409C thermal analyzer, selecting argon gas for use is protective gas, and the flow velocity of argon gas is 50ml/min, and heat-up rate is 10.0K/min, and the scope of intensification is 23 ℃ to 800 ℃.Experimental data is seen accompanying drawing 3, and therefrom as can be seen: initial crystallization temperature is about 582.3 ℃, and this shows that 582.3 ℃ of following coatings be stable, crystallization process can not take place.The prepared iron-based amorphous nanocrystalline composite coating of the present invention has very high thermostability.
Coating corrosion-resistant
Adopt U.S. home-made Potentionstat/Galvanostat Model 273 type potentiostats to measure the electrochemical properties of coating, the size of sample is 25mm * 12mm, coating is carried out the scanning of electrochemistry electrokinetic potential soak 10min in 3.5% NaCl solution after, sweep velocity is 1mv/s, and reference electrode is a saturated calomel electrode.Control sample is the 0Cr13Ni5Mo stainless steel.Measure three parallel samples, testing data sees attached list 1, can find: the prepared iron-based amorphous nanometer crystalline coat of the present invention has very high solidity to corrosion.
The electrochemical parameter of subordinate list 1 plasma spraying base coating
| Sample | Specimen coding | Mean value | Corrosion speed (mm/a) | |||
| 1# | 2# | 3# | ||||
| Coating | ?E(I＝0)(mv) | -527.2 | -484.2 | -502.0 | ?-504.4 | ?-- |
| ?Icorr(R)(uA/cm 2) | 7.396 | 4.920 | 5.094 | ?5.803 | ?0.596 | |
| 0Cr13Ni5M o stainless steel | ?E(I＝0)(mv) | -350.4 | -404.3 | -382.1 | ?-378.9 | ?-- |
| ?Icorr(R)(uA/cm 2) | 7.529 | 9.522 | 9.123 | ?8.724 | ?0.896 | |
Abrasion property
Carry out room temperature unlubricated friction wearing test on the SRV high temperature wear trier that West Germany OPTIMEL company produces, mode of motion is to-and-fro movement, and contact form is the point type contact.Cylinder sample is of a size of Φ 24mm * 7.88mm, and its working face is Φ 24mm, is the G8 Wimet of Φ 10mm to the abrading-ball sample, and hardness 80～90HRC, amplitude are 0.8mm, and load is 20N, and frequency is 10Hz, and the time is 5min.Control sample is the 0Cr13Ni5Mo stainless steel.The concrete numerical value of wear volume and wear weight loss amount sees attached list 2.Can find that the iron-based amorphous nanometer crystalline coat that the present invention prepares has very high wear resisting property.
The friction and wear characteristic of subordinate list 2 plasma spray iron-based coatings
| Sample | Load (N) | Wear volume (* 10 -6mm 3) | Wear weight loss amount (ug) |
| The 0Cr13Ni5Mo stainless steel | 20 | 5110.5376 | 39.9 |
| Coating | 20 | 823.7072 | 6.4 |
Claims (2)
1, a kind of high corrosion resistant plasma spraying iron-based amorphous nanometer crystalline coat, it is characterized in that, the composition of spray material is by weight percentage: 0.2～1.5%wtC, 2～8%wtSi, 3～9%wtB, 2～10%wtCr, 4～17%wtW, 2～13%wtMo, 2～11%wtNi, 0～2%wtY, remaining be Fe, the size range of powder is 160 orders～400 orders.
2, a kind of preparation method of high corrosion resistant plasma spraying iron-based amorphous nanometer crystalline coat is characterized in that, spraying parameter is: arc voltage 60～80V, flame current 350～600A, main gas (Ar gas) 40～90L/min, secondary gas (H
2Gas) 25～50L/min, powder feed rate 15～100g/min, spray distance 80～135mm, in spraying process, adopt air blowing method or recirculated water cooling method to cool off matrix, the flow of cooling gas is 100～2000L/min, and the flow of water coolant is 10～500L/min.
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Cited By (16)
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|---|---|---|---|---|
| CN100360703C (en) * | 2005-12-29 | 2008-01-09 | 西安理工大学 | Process for preparing iron base non crystal state alloy by bar material plasma spraying |
| CN100432277C (en) * | 2006-11-13 | 2008-11-12 | 安泰科技股份有限公司 | High corrosion resistant antiwear iron base heat spray coating layer material and its preparation method |
| CN100554484C (en) * | 2007-04-12 | 2009-10-28 | 北京科技大学 | Fe based amorphous nano dusty spray and argon gas atomization production thereof |
| CN101298654B (en) * | 2008-06-30 | 2010-04-14 | 钢铁研究总院 | Ceramic-phase-containing iron-based amorphous nanocrystalline composite coating and preparation thereof |
| CN101191225B (en) * | 2006-11-22 | 2011-05-11 | 宝山钢铁股份有限公司 | Antiseptic wearable coat and coating method thereof |
| CN102181817A (en) * | 2011-04-28 | 2011-09-14 | 西安理工大学 | Method for preparing polycrystal wear-resistant coating by plasma spraying |
| CN101698940B (en) * | 2009-10-21 | 2012-04-11 | 河海大学 | High-cavitation-resistance composite coating and preparation method thereof |
| CN102534435A (en) * | 2010-12-20 | 2012-07-04 | 北京有色金属研究总院 | Iron-based amorphous alloy powder, iron-based amorphous alloy coating and preparation method thereof |
| CN102120263B (en) * | 2010-01-08 | 2012-07-25 | 三河市科大博德粉末有限公司 | Method for preparing wear-resistance coating |
| CN102650027A (en) * | 2011-12-19 | 2012-08-29 | 天津大学 | Production of carbon nanotube reinforced Fe-based amorphous alloy thermal spray coating and method |
| CN103045984A (en) * | 2013-01-21 | 2013-04-17 | 江西恒大高新技术股份有限公司 | Special high-temperature fly ash wear resistant arc spraying wire for amorphous nanocrystal |
| CN104480462A (en) * | 2014-12-12 | 2015-04-01 | 南京理工大学 | Iron-based amorphous coating and laser preparation method thereof |
| CN105081321A (en) * | 2015-08-24 | 2015-11-25 | 大连交通大学 | Cooling system for amorphous metal member formed in laser 3D printed manner and cooling method of cooling system |
| CN105648384A (en) * | 2016-01-14 | 2016-06-08 | 北京工业大学 | Cored wire used for preparing iron-based coating and coating preparation method of cored wire |
| CN113416910A (en) * | 2021-06-16 | 2021-09-21 | 南京工程学院 | Wear-resistant and corrosion-resistant high-entropy amorphous alloy powder, coating thereof, preparation method of coating and application of coating |
| CN115961206A (en) * | 2021-09-14 | 2023-04-14 | 泰尔(安徽)工业科技服务有限公司 | Laser cladding rolling mill sliding plate and machining method thereof |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100360703C (en) * | 2005-12-29 | 2008-01-09 | 西安理工大学 | Process for preparing iron base non crystal state alloy by bar material plasma spraying |
| CN100432277C (en) * | 2006-11-13 | 2008-11-12 | 安泰科技股份有限公司 | High corrosion resistant antiwear iron base heat spray coating layer material and its preparation method |
| CN101191225B (en) * | 2006-11-22 | 2011-05-11 | 宝山钢铁股份有限公司 | Antiseptic wearable coat and coating method thereof |
| CN100554484C (en) * | 2007-04-12 | 2009-10-28 | 北京科技大学 | Fe based amorphous nano dusty spray and argon gas atomization production thereof |
| CN101298654B (en) * | 2008-06-30 | 2010-04-14 | 钢铁研究总院 | Ceramic-phase-containing iron-based amorphous nanocrystalline composite coating and preparation thereof |
| CN101698940B (en) * | 2009-10-21 | 2012-04-11 | 河海大学 | High-cavitation-resistance composite coating and preparation method thereof |
| CN102120263B (en) * | 2010-01-08 | 2012-07-25 | 三河市科大博德粉末有限公司 | Method for preparing wear-resistance coating |
| CN102534435A (en) * | 2010-12-20 | 2012-07-04 | 北京有色金属研究总院 | Iron-based amorphous alloy powder, iron-based amorphous alloy coating and preparation method thereof |
| CN102181817B (en) * | 2011-04-28 | 2013-03-13 | 西安理工大学 | Method for preparing polycrystal wear-resistant coating by plasma spraying |
| CN102181817A (en) * | 2011-04-28 | 2011-09-14 | 西安理工大学 | Method for preparing polycrystal wear-resistant coating by plasma spraying |
| CN102650027A (en) * | 2011-12-19 | 2012-08-29 | 天津大学 | Production of carbon nanotube reinforced Fe-based amorphous alloy thermal spray coating and method |
| CN103045984A (en) * | 2013-01-21 | 2013-04-17 | 江西恒大高新技术股份有限公司 | Special high-temperature fly ash wear resistant arc spraying wire for amorphous nanocrystal |
| CN104480462A (en) * | 2014-12-12 | 2015-04-01 | 南京理工大学 | Iron-based amorphous coating and laser preparation method thereof |
| CN104480462B (en) * | 2014-12-12 | 2017-08-11 | 南京理工大学 | A kind of iron-based amorphous coating and its laser preparation method |
| CN105081321A (en) * | 2015-08-24 | 2015-11-25 | 大连交通大学 | Cooling system for amorphous metal member formed in laser 3D printed manner and cooling method of cooling system |
| CN105081321B (en) * | 2015-08-24 | 2017-04-12 | 大连交通大学 | Cooling system for amorphous metal member formed in laser 3D printed manner and cooling method of cooling system |
| CN105648384A (en) * | 2016-01-14 | 2016-06-08 | 北京工业大学 | Cored wire used for preparing iron-based coating and coating preparation method of cored wire |
| CN105648384B (en) * | 2016-01-14 | 2018-07-13 | 北京工业大学 | A kind of powder cored filament material and its coating production being used to prepare iron-based coating |
| CN113416910A (en) * | 2021-06-16 | 2021-09-21 | 南京工程学院 | Wear-resistant and corrosion-resistant high-entropy amorphous alloy powder, coating thereof, preparation method of coating and application of coating |
| CN113416910B (en) * | 2021-06-16 | 2022-02-15 | 南京工程学院 | Wear-resistant and corrosion-resistant high-entropy amorphous alloy powder, coating thereof, preparation method of coating and application of coating |
| CN115961206A (en) * | 2021-09-14 | 2023-04-14 | 泰尔(安徽)工业科技服务有限公司 | Laser cladding rolling mill sliding plate and machining method thereof |
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