CN108914113B - A kind of method of ultrasonic wave assisted plasma beam cladding high entropy alloy coating - Google Patents
A kind of method of ultrasonic wave assisted plasma beam cladding high entropy alloy coating Download PDFInfo
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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Abstract
The invention discloses a kind of methods of ultrasonic wave assisted plasma beam cladding high entropy alloy coating; the mixed-powder of a certain proportion of nickel chromium triangle borosilicate powder of heating cladding, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder composition in the case where surface of low-carbon steel is using the protection of plasma beam argon gas; since major components are five yuan or more; the high-entropy alloy based on solid solution can be formed; with the hesitation of high-entropy alloy in cladding process; and powder is mostly prealloy powder; lower with fusing point, hesitation advantageously forms tiny Cr7C3With tiny crystal grain, the good high entropy alloy coating of wearability is obtained.
Description
Technical field
The invention belongs to high energy beam field of surface treatment, in particular to it is wear-resisting multiple to prepare high-entropy alloy using plasma cladding
The method for closing coating.
Background technique
In the industry such as engineering machinery, aerospace, automobile, geological prospecting, a large amount of components are in the items such as abrasion, corrosion
Under part, to improve its wearability, corrosion resistance, generally use that surface is modified or the method for prepares coating.Wherein Fe-Cr-B-Si,
Ni-Cr-B-Si, Co-Cr-B-Si etc. are common thermal spraying or cladding alloy material, and reinforced phase is (Cr, Fe)7C3, resistance to
Preferably, solid solution has a large amount of Cr that coating is made to have preferable corrosion resistance for mill property, craftsmanship etc..High-entropy alloy is by five or more
Element constituent element composition have some conventional alloys incomparable and according to the alloy close to equal atomic ratio alloys
Very good mechanical properties, such as high rigidity, high tenacity, high abrasion, corrosion resistance, high intensity, particularly suitable for prepares coating.Using
The face-centred cubic structure high-entropy alloy for being dissolved Cr has good corrosion resistance and toughness, adds Cr7C3As reinforced phase, have good
Good corrosion resistance and wearability, to further decrease nascent Cr7C3Size, using ultrasonic wave auxiliary cladding make Cr7C3Solidifying
Gu smashing established dendrite in the process, the viscosity effect of a large amount of nucleus and high-entropy alloy is generated in the coating, can be dropped
Cr in low process of setting7C3With the size of face-centred cubic structure crystal grain, be conducive to the toughness and wearability that improve coating.Plasma
Beam is a kind of high energy beam of arc energy high concentration low cost, by the way that by electric arc mechanical compression, arc column temperature is up to 10000-
24000K, and the matrix for treating cladding has certain " excavation " effect, is conducive to the uniform of coating, but simultaneously also can melting end
Steel splitting matrix causes to dilute original coating composition, has advantage at low cost using plasma cladding.
Summary of the invention
The disadvantage of present invention solution surface of low-carbon steel coating abrasion performance difference, it is therefore an objective to improve surface of low-carbon steel wearability, resistance to
Corrosion, the production method of use include following processing steps:
Step 1: choosing using the mild steel piece surface that need to strengthen as matrix, and its surface is pre-processed, that is, used
Grinding wheel or sand paper polishing surface are derusted, and the greasy dirt on surface is removed with alcohol or acetone.
Step 2: nickel chromium triangle borosilicate powder, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder are carried out with ball mill by a certain percentage
Ball milling mixing forms mixed-powder；Wherein the mass percent of nickel chromium triangle borosilicate meal component is Cr:14-17, B:2.5-4.5, Si:
3-4.5, C:0.6-1.0, remaining is Ni, and granularity is 30-300 μm；The purity of copper powder is 99.5-100%, and granularity is 30-300 μm；
The mass percent of low-carbon ferrochromium meal component is C:0.1-0.2%, Cr:50-70%, remaining is Fe, and granularity is 30-300 μm；High-carbon
The mass percent of ferromanganese powder is Mn:62-85；C:7.0-8.0；Si:1.5-2.5, remaining is iron, and granularity is 30-300 μm；It is mixed
Close the mass percent of nickel chromium triangle borosilicate powder, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder in powder are as follows: 10-12:10-12:8-10:
10-12.Ball milling mixing therein is to carry out ball milling mixing using steel ball grinder, and abrading-ball therein is with metal powder mass ratio
2.5-3.2: 1, vacuum valve is opened after sealing and is vacuumized 20-30 minutes, ball grinder is put into planetary ball mill, revolving speed is
260-300 r/min swings to frequency 30-45 Hz, and carrying out the ball mill mixing time is 60-80 minutes.
Cladding powder is made Step 3: mixed-powder and pressure sensitive adhesive are mixed in a certain ratio, is coated to low-carbon base steel
Body surface face, coating thickness is 0.8-1.2 cm, in 100-120 DEG C of drying 1.5-2h.
Cladding is carried out Step 4: heating under ultrasonic wave auxiliary to cladding powder using plasma beam, it is as wear-resisting after cooling
Coating.Wherein plasma beam cladding technological parameter are as follows: for argon gas as protection gas and ionized gas, cladding electric current is 100-160 A,
Operating voltage 20-40 V, scanning speed are 3-6 mm/s, and argon gas is 0.9-1.5m as the flow of protection gas3/ h, argon gas conduct
The flow of ionization is 0.7-1.3m3/ h, distance of the nozzle away from surface to be treated are 0.7-1.3cm.Ultrasonic wave assists cladding apparatus,
Ultrasonic transducer is disposed on low carbon steel substrate；Plasma beam be heated to cladding powder start melt when, ultrasonic wave transducer
Device starting, low carbon steel substrate vibrate with ultrasonic transducer, assist forming cladding coating, Zhi Daorong by ultrasonic activation
Cover completion.Ultrasonic transducer is connected with supersonic generator, and the output power of ultrasonic transducer is 0.2-2kW, ultrasonic wave
Energy converter working frequency is 20-100kHz, and it is 1-30 μm that ultrasonic transducer, which exports amplitude,.
Beneficial effects of the present invention:
(1) process of the invention uses matrix of the high-entropy alloy as wear-resistant coating, and it is peculiar to can make full use of its
Diffusion velocity is slow, the characteristic insensitive to composition transfer, make coating that there is higher toughness, intensity and wearability.
(2) problem to be solved by this invention is that had using the high entropy alloy coating of solid solution Cr compared with high corrosion-resistant, as
The Cr of reinforced phase7C3With good wearability.
(3) it carries out auxiliary cladding using ultrasonic wave and has to form uniformly tiny Cr7C3The tiny feature with crystal grain.
(4) in view of the ingredient of steel matrix is mainly Fe, can increase in coating because of the fusing of steel matrix in cladding process
Fe content, in conjunction with melting and coating process parameter, it is wear-resisting to realize coating so as to suitably reduce the additive amount of Fe in cladding powder
The good advantage of property, corrosion resistance.
Specific embodiment
Embodiment 1:
Step 1: choosing using the Q235 piece surface that need to strengthen as matrix, and its surface is pre-processed, that is, uses sand
Wheel or sand paper polishing surface are derusted, and the greasy dirt on surface is removed with alcohol or acetone；
Step 2: nickel chromium triangle borosilicate powder, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder are carried out with ball mill by a certain percentage
Ball milling mixing forms mixed-powder；Wherein the mass percent of nickel chromium triangle borosilicate meal component is Cr:14-17, B:2.5-4.5, Si:
3-4.5, C:0.6-1.0, remaining is Ni, and granularity is 30-300 μm；The purity of copper powder is 99.5-100%, and granularity is 30-300 μm；
The mass percent of low-carbon ferrochromium meal component is C:0.1-0.2%, Cr:50-70%, remaining is Fe, and granularity is 30-300 μm；High-carbon
The mass percent of ferromanganese powder is Mn:62-85；C:7.0-8.0；Si:1.5-2.5, remaining is iron, and granularity is 30-300 μm；Nickel
The mass percent of chromium borosilicate powder, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder are as follows: 10:10:8:10.Ball milling mixing therein
It is that ball milling mixing is carried out using steel ball grinder, abrading-ball therein and metal powder mass ratio are 2.5: 1, open vacuum valve after sealing
It vacuumizes 30 minutes, ball grinder is put into planetary ball mill, revolving speed is 260 r/min, swings to 45 Hz of frequency, carries out ball milling
Mixing time is 80 minutes.
Cladding powder is made Step 3: mixed-powder and pressure sensitive adhesive are mixed in a certain ratio, is coated to low-carbon base steel
Body surface face, coating thickness is 0.8 cm, in 100 DEG C of drying 1.5h.
Cladding is carried out Step 4: heating under ultrasonic wave auxiliary to cladding powder using plasma beam, it is as wear-resisting after cooling
Coating.Wherein plasma beam cladding technological parameter are as follows: for argon gas as protection gas and ionized gas, cladding electric current is 160 A, work
40 V of voltage, scanning speed are 6 mm/s, and argon gas is 1.5m as the flow of protection gas3/ h, argon gas are as the flow of ionization
1.3m3/ h, distance of the nozzle away from surface to be treated are 1.3cm.Ultrasonic wave assists cladding apparatus, disposes on low carbon steel substrate super
Acoustic wave transducer；When plasma beam is heated to cladding powder and starts to melt, ultrasonic transducer starting, low carbon steel substrate is with super
Acoustic wave transducer vibrates together, carries out ultrasonic activation and assists cladding coating, until cladding is completed.Ultrasonic transducer is connected with
Supersonic generator, the output power of ultrasonic transducer are 2kW, and ultrasonic transducer working frequency is 100kHz, ultrasonic wave
It is 30 μm that energy converter, which exports amplitude,.
Our experiments show that the defects of plasma cladding coating morphology is smooth, basic pore-free, crackle, coating structure is crystalline substance
Tiny, the uniform dendrite tissue of ingredient of grain, and tiny Cr is dispersed in the high-entropy alloy matrix of FCC7C3.Coating
Wearability is 4.5 times of Q235 steel.
Embodiment 2:
The mild steel Q195 piece surface that need to strengthen is pre-processed as matrix, and to its surface Step 1: choosing,
It is derusted with grinding wheel or sand paper polishing surface, the greasy dirt on surface is removed with alcohol or acetone；
Step 2: nickel chromium triangle borosilicate powder, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder are carried out with ball mill by a certain percentage
Ball milling mixing forms mixed-powder；Wherein the mass percent of nickel chromium triangle borosilicate meal component is Cr:14-17, B:2.5-4.5, Si:
3-4.5, C:0.6-1.0, remaining is Ni, and granularity is 30-300 μm；The purity of copper powder is 99.5-100%, and granularity is 30-300 μm；
The mass percent of low-carbon ferrochromium meal component is C:0.1-0.2%, Cr:50-70%, remaining is Fe, and granularity is 30-300 μm；High-carbon
The mass percent of ferromanganese powder is Mn:62-85；C:7.0-8.0；Si:1.5-2.5, remaining is iron, and granularity is 30-300 μm；Nickel
The mass percent of chromium borosilicate powder, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder are as follows: 12:12:8:10.Ball milling mixing therein
It is that ball milling mixing is carried out using steel ball grinder, abrading-ball therein and metal powder mass ratio are 3.2: 1, open vacuum valve after sealing
It vacuumizes 20 minutes, ball grinder is put into planetary ball mill, revolving speed is 260 r/min, swings to frequency 30Hz, carries out ball milling
Mixing time is 60 minutes.
Cladding powder is made Step 3: mixed-powder and pressure sensitive adhesive are mixed in a certain ratio, is coated to low-carbon base steel
Body surface face, coating thickness 0.8cm, in 100 DEG C of drying 1.5h.
Cladding is carried out Step 4: heating under ultrasonic wave auxiliary to cladding powder using plasma beam, it is as wear-resisting after cooling
Coating.Wherein plasma beam cladding technological parameter are as follows: for argon gas as protection gas and ionized gas, cladding electric current is 100A, work
40 V of voltage, scanning speed are 3 mm/s, and argon gas is 0.9m as the flow of protection gas3/ h, argon gas are as the flow of ionization
0.7m3/ h, distance of the nozzle away from surface to be treated are 0.7cm.Ultrasonic wave assists cladding apparatus, disposes on low carbon steel substrate super
Acoustic wave transducer；When plasma beam is heated to cladding powder and starts to melt, ultrasonic transducer starting, low carbon steel substrate is with super
Acoustic wave transducer vibrates together, carries out ultrasonic activation and assists cladding coating, until cladding is completed.Ultrasonic transducer is connected with
Supersonic generator, the output power of ultrasonic transducer are 0.2kW, and ultrasonic transducer working frequency is 20kHz, ultrasonic wave
It is 1 μm that energy converter, which exports amplitude,.
Our experiments show that the defects of plasma cladding coating morphology is smooth, basic pore-free, crackle, coating is substantially uniform,
With do not use ultrasonic wave auxiliary phase ratio, using the tissue more fine uniform of coating after ultrasonic wave, Cr therein7C3It is uniformly distributed
In high-entropy alloy matrix.About 3.6 times of hardness are improved, wearability improves 4.2 times.
Embodiment 3:
The mild steel Q275 piece surface that need to strengthen is pre-processed as matrix, and to its surface Step 1: choosing,
It is derusted with grinding wheel or sand paper polishing surface, the greasy dirt on surface is removed with alcohol or acetone；
Step 2: nickel chromium triangle borosilicate powder, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder are carried out with ball mill by a certain percentage
Ball milling mixing forms mixed-powder；Wherein the mass percent of nickel chromium triangle borosilicate meal component is Cr:14-17, B:2.5-4.5, Si:
3-4.5, C:0.6-1.0, remaining is Ni, and granularity is 30-300 μm；The purity of copper powder is 99.5-100%, and granularity is 30-300 μm；
The mass percent of low-carbon ferrochromium meal component is C:0.1-0.2%, Cr:50-70%, remaining is Fe, and granularity is 30-300 μm；High-carbon
The mass percent of ferromanganese powder is Mn:62-85；C:7.0-8.0；Si:1.5-2.5, remaining is iron, and granularity is 30-300 μm；Nickel
The mass percent of chromium borosilicate powder, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder are as follows: 11:12:10:11.Ball milling mixing therein
It is that ball milling mixing is carried out using steel ball grinder, abrading-ball therein and metal powder mass ratio are 3: 1, and vacuum valve is opened after sealing and is taken out
Vacuum 25 minutes, ball grinder is put into planetary ball mill, revolving speed is 280 r/min, swings to 40 Hz of frequency, carries out ball milling
Mixing time is 70 minutes.
Cladding powder is made Step 3: mixed-powder and pressure sensitive adhesive are mixed in a certain ratio, is coated to low-carbon base steel
Body surface face, coating thickness 1cm, in 100 DEG C of drying 1.8h.
Cladding is carried out Step 4: heating under ultrasonic wave auxiliary to cladding powder using plasma beam, it is as wear-resisting after cooling
Coating.Wherein plasma beam cladding technological parameter are as follows: for argon gas as protection gas and ionized gas, cladding electric current is 120 A, work
30 V of voltage, scanning speed are 4 mm/s, and argon gas is 1.2m as the flow of protection gas3/ h, argon gas are as the flow of ionization
1m3/ h, distance of the nozzle away from surface to be treated are 1cm.Ultrasonic wave assists cladding apparatus, and ultrasonic wave is disposed on low carbon steel substrate
Energy converter；Plasma beam be heated to cladding powder start melt when, ultrasonic transducer starting, low carbon steel substrate is with ultrasonic wave
Energy converter vibrates together, carries out ultrasonic activation and assists cladding coating, until cladding is completed.Ultrasonic transducer is connected with ultrasound
Wave producer, the output power of ultrasonic transducer are 1kW, and ultrasonic transducer working frequency is 80kHz, ultrasonic transducer
Exporting amplitude is 20 μm.
Our experiments show that the defects of plasma cladding coating morphology is smooth, basic pore-free, crackle, coating is substantially uniform,
With do not use ultrasonic wave auxiliary phase ratio, tissue more fine uniform, Cr therein7C3It is uniformly distributed in high-entropy alloy matrix, it is resistance to
Mill property improves 5 times, and corrosion resistance is preferable.
Claims (3)
1. a kind of method of ultrasonic wave assisted plasma beam cladding high entropy alloy coating, which is characterized in that the production method
Including following processing steps:
Step 1: choosing using the mild steel piece surface that need to strengthen as matrix, and its surface is pre-processed, that is, uses grinding wheel
Or sand paper polishing surface is derusted, and the greasy dirt on surface is removed with alcohol or acetone；
Step 2: nickel chromium triangle borosilicate powder, copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder are carried out ball milling with ball mill by a certain percentage
Mixing, wherein the mass percent of nickel chromium triangle borosilicate meal component be Cr:14-17, B:2.5-4.5, Si:3-4.5, C:0.6-1.0,
Remaining is Ni, and granularity is 30-300 μm；The purity of copper powder is 99.5-100%, and granularity is 30-300 μm；The matter of low-carbon ferrochromium meal component
Measuring percentage is C:0.1-0.2%, Cr:50-70%, remaining is Fe, and granularity is 30-300 μm；The mass percent of high carbon ferromanganese powder
For Mn:62-85；C:7.0-8.0；Si:1.5-2.5, remaining is iron, and granularity is 30-300 μm；Nickel chromium triangle borosilicate powder in mixed-powder,
The mass percent of copper powder, low-carbon ferrochromium powder and high carbon ferromanganese powder are as follows: 10-12:10-12:8-10:10-12 forms mixed powder
End；
Cladding powder is made Step 3: mixed-powder and pressure sensitive adhesive are mixed in a certain ratio, is coated to low carbon steel substrate table
Face, coating thickness is 0.8-1.2 cm, and is dried；
Cladding, melting and coating process parameter are as follows: argon gas are carried out Step 4: heating under ultrasonic wave auxiliary to cladding powder using plasma beam
As protection gas and ionized gas, cladding electric current is 100-160 A, and operating voltage 20-40 V, scanning speed is 3-6 mm/s,
Argon gas is 0.9-1.5m3/h as the flow of protection gas, and argon gas is 0.7-1.3m3/h as the flow of ionization, and nozzle is away from wait locate
The distance for managing surface is 0.7-1.3cm, is wear-resistant coating after cooling；Wherein ultrasonic auxiliary device is on low carbon steel substrate
Ultrasonic transducer is disposed, the output power of ultrasonic transducer is 0.2-2kW, and ultrasonic transducer working frequency is 20-
100kHz, it is 1-30 μm that ultrasonic transducer, which exports amplitude,；Plasma beam be heated to cladding powder start melt when, ultrasonic wave
Energy converter starting, low carbon steel substrate are vibrated with ultrasonic transducer, are carried out ultrasonic activation and are assisted cladding coating, Zhi Daorong
Cover completion.
2. a kind of method of ultrasonic wave assisted plasma beam cladding high entropy alloy coating according to claim 1, feature
Be: the ball milling mixing is to carry out ball milling mixing using steel ball grinder, and abrading-ball therein is with metal powder mass ratio
2.5-3.2: 1, vacuum valve is opened after sealing and is vacuumized 20-30 minutes, and ball grinder is put into planetary ball mill, revolving speed 260-
300 r/min swing to frequency 30-45 Hz, and carrying out the ball mill mixing time is 60-80 minutes.
3. a kind of method of ultrasonic wave assisted plasma beam cladding high entropy alloy coating according to claim 1, feature
It is: the stoving process are as follows: in 100-120 DEG C of drying 1.5-2h.
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| CN110106501B (en) * | 2019-06-21 | 2020-05-01 | 阳江市五金刀剪产业技术研究院 | Cutter manufactured by micro-beam plasma additive manufacturing and preparation method thereof |
| CN113265652A (en) * | 2020-12-02 | 2021-08-17 | 兆山科技（北京）有限公司 | Method for preparing high-entropy borosilicate ceramic surface material by utilizing cold spraying |
| CN114393341B (en) * | 2022-01-11 | 2023-08-15 | 西安理工大学 | High-entropy alloy reinforced copper-based wear-resistant corrosion-resistant coating and preparation method thereof |
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