CN101298654B - Ceramic-phase-containing iron-based amorphous nanocrystalline composite coating and preparation thereof - Google Patents
Ceramic-phase-containing iron-based amorphous nanocrystalline composite coating and preparation thereof Download PDFInfo
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Abstract
The invention belongs to the field of thermal spraying and particularly relates to a composite amorphous and nano-crystalline coating layer with ceramic phase and ferrum base and a preparation method thereof. Carbide or oxide ceramics of Co or Ni ladles are firstly added into a flux core, a flux-cored wire is prepared together with the flux core and a ferrum-base alloy with amorphous ingredients and used as a spraying material, and the electric arc spraying method is adopted for leading the flux-cored wire to be melted, atomized into fused drops and finally deposited on a substrate, thus preparing the composite amorphous and nano-crystalline coating layer with ceramic-phase structure and ferrum base, which has the performance of high bond strength, good wear resistance, corrosion resistance and oxidation resistance as well as remarkably prolonged service life of the substrate, and the composite amorphous and nano-crystalline coating layer with ceramic phase and ferrum base can be widely applied to the restoration and the protection of device parts in the fields of metallurgy, electric power and petroleum, etc.
Description
Technical field
The invention belongs to field of thermal spray, particularly a kind of iron-based amorphous nanocrystalline composite coating that contains ceramic phase and preparation method thereof.
Background technology
The inefficacy pilosity of material is born in the surface, and wearing and tearing and corrosion are the common form that material or component of machine in use lost efficacy, and annually causes tremendous loss to national economy.Surface engineering technology is the important channel of improving the material surface performance, and wherein hot-spraying techniques is one of most important technology.Can deposit layer of metal or metal-ceramic coating at material surface by thermospray, make it have wear-resistant, protection against corrosion, performance such as anti-oxidant, thereby body material is played a protective role.The high development of current industrial technology, demands for higher performance to thermally sprayed coating, at under the severe environment (such as, the coal firing boiler tube wall of thermal power generation unit bears high temperature, high pressure, flue gas corrosion, and the turbine blade in power station bears sandstone wearing and tearing and cavitation erosion etc.) application and development corrosion-resistant, abrasion-resistant coatings becomes the research emphasis of field of thermal spray.
In the existing technology, stupalith is the important high-temperature corrosion resistance of a class, oxidation and wearing and tearing thermal spraying material.Thermospray pottery or cermet composite coating, it mainly is the compound coating of oxide compound and carbide ceramics and they and metal, because of it has good wear resistance and excellent high-temperature behavior, especially erosive wear resistance, can alleviate thermal etching and flue gas erosive wear effectively, be applied in many occasions.Yet, single ceramic coating because have higher porosity, lower fracture toughness property and and the matrix metal material have bigger thermal expansion coefficient difference, application is restricted; Cermet composite coating, as Cr3C2-(N iCr), cermet composite coatings such as WC-Co can obtain higher coating quality and good coating performance, use more extensive, in the high temperature erosion protection of boiler tubing, shortcoming is the material cost height, mainly adopts plasma spraying or HVOF (High Velocity Oxygen Fuel) as Cr3C2-(N iCr) coatings applications, complex process, construction cost height and site operation inconvenience.
Fe-based amorphous, nanocrystalline alloy coating is a kind of novel hot spray coating, because of it has over-all propertieies such as wear-resistant, corrosion-resistant, and cost is cheap relatively, obtains broad research in recent years, is applied in boiler " four pipes " protection such as studying its alternative 45CT both at home and abroad.Early stage main plasma spraying and the HVOF (High Velocity Oxygen Fuel) technology of adopting prepares amorphous, nanocrystalline coating, aspect construction convenience and construction cost, exist not enough, begun one's study at present and adopted arc spraying technology to prepare amorphous, nanocrystalline coating, a kind of preparation method of Fe-based amorphous, nanocrystalline coating just is provided as CN200610114516.4.Compare pottery or cermet composite coating, Fe-based amorphous, nanocrystalline coating advantage is that corrosion resisting property is better, bonding strength is high, cost is low, but hardness is not as good as the former height, on wear-resisting grain, slip or erosion property also not as good as some potteries or cermet composite coating.
Summary of the invention
Purpose of the present invention just provide a kind of bonding strength height, wear-resistant, corrosion-resistant, antioxidant property is good, long service life, cost are low contains iron-based amorphous nanocrystalline composite coating of ceramic phase and preparation method thereof.
According to above-mentioned purpose, the technical scheme of integral body of the present invention is:
Adopt Fe-based amorphous, nanocrystalline support substrate as ceramic phase, and use electrical arc spraying method for preparing coating, can bring into play amorphous, nanocrystalline matrix mutually and ceramic hard separately advantage mutually, and can significantly improve the use properties of metal in serious corrosive wear, increase the service life.
At first Co or Ni bag carbide or oxide ceramics are joined in the medicine core, prepare the patent medicine core-wire material together as spray material with ferrous alloy with amorphous formation composition, adopt arc spray process to be deposited on the matrix with the fusing of medicine core-wire material and after being atomized into molten drop, prepare the iron-based amorphous nanocrystalline composite coating that contains the ceramic phase structure, the anchoring strength of coating height, the hard ceramic phase is distributing on the iron-based amorphous nanometer crystalline matrix, advantages of good abrasion is arranged, corrosion-resistant, performance such as anti-oxidant, significant prolongation matrix work-ing life, can be widely used in metallurgy, electric power, in the reparation of the equipment part of industries such as oil and the protection.
According to above-mentioned purpose and overall technical architecture, the concrete technical scheme of the present invention is:
The medicine core-wire material that spray material is made up of coating and medicine core, its total composition weight percent is: Cr13～25%, Mn 0.2～5%, and B 0.2～5%, and C 0.05～1%, Si 0.1～0.5%, Mo 0.5～5%, and W 0.5～6%, and contains Co or Ni bag carbide ceramics powder 5～10% in the medicine core, perhaps contain Co or Ni bag oxide ceramic powder 6～12%, all the other are Fe.
Medicine core-wire material coating adopts carbon content≤0.04%, chrome content to be about 16～17% chromium steel band, has component X 1; The mixed powder that the medicine core is formed for metal, alloy and the pottery etc. of preparation, composition is X2, total composition X of coating and medicine core is in the mentioned component scope.
Above-mentioned carbide is WC, TiC, Cr
3C
2In any; Oxide compound is Al
2O
3, TiO
2, Cr
2O
3, ZrO
2In any.
Containing Co or Ni bag carbide ceramics powder in the medicine core is micron order, and particle diameter is 38 μ m～150 μ m.
Or to contain Co or Ni bag carbide ceramics powder in the medicine core be nano level, and original size is 30～100nm, and particle diameter is 38 μ m～150 μ m after the granulation.
Or to contain Co or Ni bag oxide ceramic powder in the medicine core be micron order, and particle diameter is 38 μ m～150 μ m.
Or to contain Co or Ni bag oxide ceramic powder in the medicine core be nano level, and original size is 30～100nm, and particle diameter is 38 μ m～150 μ m after the granulation.
The above-mentioned preparation method who contains the iron-based amorphous nanocrystalline composite coating of ceramic phase, adopt arc spraying technology to prepare coating, the preparation method adopts twin wire arc spray equipment to spray, quicken to be deposited on the matrix with utilizing pressurized air to be atomized into drop after the fusing of medicine core-wire material, utilize the quick cooling effect of matrix directly to form the amorphous nano crystal structure, the ceramic particle disperse of fusing is not distributed on the amorphous nano-crystalline structural matrix fully, preparation technology parameter is: arc voltage 28～34V, working current 190～250A, atomization pressure 0.6～0.8MPa, spray distance 150～200mm.
Compared with prior art, the present invention adds metal bag ceramic powder in the medicine core, and preparation patent medicine core-wire material, after adopting the electric arc spraying spraying, can form the iron-based amorphous nanometer crystalline structure composite coating that contains ceramic phase, the anchoring strength of coating height has advantages of good abrasion, performance such as corrosion-resistant, anti-oxidant, significant prolongation matrix work-ing life, can be widely used in the reparation and protection of equipment part of industries such as metallurgy, electric power, oil.
Description of drawings
Fig. 1 is the coatingsurface XRD diffracting spectrum of embodiment 2.
Fig. 2 is the coating TEM image of embodiment 2.
Fig. 3 is the coating DSC curve of embodiment 2.
Fig. 4 is the coating hardness distribution plan of embodiment 2.
Fig. 5 is the coated anode polarization curve of embodiment 2.
Embodiment
1. the composition weight percent of Xuan Zeing is Cr 16.99%, Mo 1.98%, W 3.80%, Mn 0.38%, and B 3.10%, and C 0.80%, Si 0.43%, Co bag WC powder weight accounts for gross weight 5.20% in the medicine core, and surplus is Fe, and mentioned component is prepared the patent medicine core-wire material, total composition of its coating and medicine core satisfies mentioned component, Co bag WC powder granularity is 44 μ m～124 μ m in the medicine core, and other powder size is that medicine core weight accounts for 37.07% between 26 μ m～150 μ m, the electric arc spraying process parameter is: arc voltage 34V, the about 200A of working current, atomization pressure 0.7MPa, spray distance 200mm.Sprayed coating and substrate combinating strength are more than 46MPa, and micro-vickers hardness has characteristics such as hardness height, wear resistance is good, abrasion-resistance is good greater than 900HV0.3kg, are applicable to coal-fired plant boiler " four pipes " high temperature wear resistant.
2. the composition weight percent of Xuan Zeing is Cr 17.10%, and Mo 1.20%, and W 1.20%, and Mn 0.38%, and B 3.10%, and C 0.60%, and Si 0.40%, Ni bag Cr in the medicine core
3C
2Powder weight accounts for gross weight 9.50%, and surplus is Fe, and mentioned component is prepared the patent medicine core-wire material, and total composition of its coating and medicine core satisfies mentioned component, Ni bag Cr in the medicine core
3C
2Powder size is 38 μ m～74 μ m, and other powder size is that medicine core weight accounts for 36.71% between 26 μ m～150 μ m, and the electric arc spraying process parameter is: arc voltage 32V, the about 180A of working current, atomization pressure 0.7MPa, spray distance 200mm.Sprayed coating and substrate combinating strength are more than 45MPa, and micro-vickers hardness has characteristics such as hardness height, wear resistance is good, abrasion-resistance is good greater than 950HV0.3kg, are applicable to that coal-fired plant boiler " four pipes " temperature is higher than 550 ℃ of position high temperature wear resistants.
3. the composition weight percent of Xuan Zeing is Cr 20.60%, Mo 1.20%, W 1.10%, Mn 1.02%, B 2.95%, C 0.55%, and Si 0.60%, and Co bag TiC powder weight accounts for gross weight 7.30% in the medicine core, surplus is Fe, mentioned component is prepared the patent medicine core-wire material, and total composition of its coating and medicine core satisfies mentioned component, and Co bag TiC powder is a nanometer powder in the medicine core, original size is 30～100nm, granularity is 38 μ m～150 μ m after the granulation, and other powder size is that medicine core weight accounts for 38.29% between 26 μ m～150 μ m, the electric arc spraying process parameter is: arc voltage 30V, the about 180A of working current, atomization pressure 0.7MPa, spray distance 200mm.Sprayed coating and substrate combinating strength are more than 50MPa, micro-vickers hardness is greater than 1000HV0.3kg, have characteristics such as hardness height, wear resistance is good, abrasion-resistance is good, shock-resistance is good, be applicable to coal-fired plant boiler " four pipes " high temperature wear resistant and the anti-sand erosion of turbine blade.
4. the composition weight percent of Xuan Zeing is Cr 19.20%, and Mo 2.03%, and W 1.90%, and Mn 0.60%, and B 3.01%, and C 0.73%, and Si 0.40%, Ni bag ZrO in the medicine core
2Powder weight accounts for gross weight 6.10%, and surplus is Fe, and mentioned component is prepared the patent medicine core-wire material, and total composition of its coating and medicine core satisfies mentioned component, Ni bag ZrO in the medicine core
2Powder size is 53 μ m～104 μ m, and other powder size is that medicine core weight accounts for 37.97% between 26 μ m～150 μ m, and the electric arc spraying process parameter is: arc voltage 30V, the about 190A of working current, atomization pressure 0.7MPa, spray distance 150mm.Sprayed coating and substrate combinating strength are more than 40MPa, and micro-vickers hardness has characteristics such as hardness height, wear resistance is good, high-temperature oxidation is good greater than 1000HV0.3kg, are applicable to coal-fired plant boiler " four pipes " high temperature wear resistant.
5. the composition weight percent of Xuan Zeing is Cr 16.10%, and Mo 3.03%, and W 3.90%, and Mn 0.60%, and B 2.81%, and C 0.73%, and Si 0.40%, Ni bag Cr in the medicine core
2O
3Powder weight accounts for gross weight 7.70%, and surplus is Fe, and mentioned component is prepared the patent medicine core-wire material, and total composition of its coating and medicine core satisfies mentioned component, Ni bag Cr in the medicine core
2O
3Powder size is 38 μ m～150 μ m, and other powder size is that medicine core weight accounts for 39.49% between 26 μ m～150 μ m, and the electric arc spraying process parameter is: arc voltage 32V, the about 190A of working current, atomization pressure 0.7MPa, spray distance 150mm.Sprayed coating and substrate combinating strength are more than 40MPa, and micro-vickers hardness has characteristics such as hardness height, wear resistance is good, high-temperature oxidation is good greater than 1000HV0.3kg, are applicable to that coal-fired plant boiler " four pipes " temperature is higher than 550 ℃ of position high temperature wear resistants.
6. the composition weight percent of Xuan Zeing is Cr 18.10%, and Mo 1.03%, and W 1.00%, and Mn 0.60%, and B 2.81%, and C 0.63%, and Si 0.40%, Co bag Al in the medicine core
2O
3Powder weight accounts for gross weight 11.20%, and surplus is Fe, and mentioned component is prepared the patent medicine core-wire material, and total composition of its coating and medicine core satisfies mentioned component, Co bag Al in the medicine core
2O
3Powder is a nanometer powder, original size is 30～100nm, granularity is 38 μ m～150 μ m after the granulation, other powder size is between 26 μ m～150 μ m, medicine core weight accounts for 38.06%, and the electric arc spraying process parameter is: arc voltage 32V, the about 180A of working current, atomization pressure 0.7MPa, spray distance 150mm.Sprayed coating and substrate combinating strength are more than 40MPa, micro-vickers hardness is greater than 1000HV0.3kg, have characteristics such as hardness height, wear resistance is good, high-temperature oxidation is good, be applicable to coal-fired plant boiler " four pipes " high temperature wear resistant and the anti-sand erosion of turbine blade.
Fig. 1 is the coating XRD diffracting spectrum of embodiment 2, has tangible crystallization peak, and crystallization product is mainly α-Fe (Cr) and Cr3C2 by analysis, has tangible broadening phenomenon.
Fig. 2 is the coating TEM pattern of embodiment 2, coating is crystalline state and amorphous mixed structure, nanocrystalline disperse is distributed in the amorphous phase, nanocrystalline phase size is about 100-250nm, do not see the micron order crystalline phase in the visual field, as seen there is melting process in Ni bag Cr3C2 powder in spraying, and what do not melt fully exists with submicron order even nano level crystalline phase.
Fig. 3 is the coating DSC curve of embodiment 2, has two exothermic peaks on the visible curve, and an especially significantly exothermic peak is arranged about 564 ℃, shows that the conversion of non-crystalline state to crystalline state taken place coating, and the beginning crystallization temperature is about 541 ℃; Near 817 ℃, also have an exothermic peak, illustrate in the remaining amorphous phase of this temperature secondary crystallization has taken place.Illustrate that coatings prepared of the present invention has good thermostability at 541 ℃.
Fig. 4 is that the coating of embodiment 2 is loading the coating microhardness distribution curve that records under 100g, the loading time 10s condition, and the hardness of visible coating is very high and distribution is more even, and its microhardness HV0.1 exceeds much than matrix in 1000～1400 scopes.
Fig. 5 is the electrokinetic potential anodic polarization curves of coating in 3.5%NaCl solution of embodiment 2, and corrosion potential is-0.54V, has tangible passivation region, and passivation current density is 0.00275mA/cm
2, as seen this coating has good corrosion resistance.
Adopt vertical omnipotent friction wear testing machine to carry out the unlubricated ball disc type frictional wear experiment of coating, ball material is Si3N4,1/4 inch of diameter, the dish sample is processed into after the specified dimension coating to be tested in the spraying of wearing test face for the Q235 steel, each embodiment coating test parameter after the wear weight loss rate see Table 1, can find that coating has the advantages of good abrasion performance.
Table 1
| Load (N) | Time (min) | Speed (r/min) | Wear weight loss rate % | |
| Embodiment 1 | 20 | 15 | 100 | 0.011 |
| Embodiment 2 | 20 | 15 | 100 | 0.001 |
| Embodiment 3 | 20 | 15 | 100 | 0.001 |
| Embodiment 4 | 20 | 15 | 100 | 0.003 |
| Load (N) | Time (min) | Speed (r/min) | Wear weight loss rate % | |
| Embodiment 5 | 20 | 15 | 100 | 0.001 |
| Embodiment 6 | 20 | 15 | 100 | 0.005 |
| Q235 | 20 | 15 | 100 | 1.624 |
Claims (9)
1. iron-based amorphous nanocrystalline composite coating that contains ceramic phase, it is characterized in that the medicine core-wire material that spray material is made up of coating and medicine core, its total composition weight percent is: Cr 13～25%, Mn0.2～5%, B 0.2～5%, C 0.05～1%, and Si 0.1～0.5%, and Mo 0.5～5%, W 0.5～6%, and contain Co or Ni bag carbide ceramics powder 5～10% in the medicine core, and perhaps containing Co or Ni bag oxide ceramic powder 6～12%, all the other are Fe.
2. according to the iron-based amorphous nanocrystalline composite coating that contains ceramic phase of claim 1, it is characterized in that medicine core-wire material coating employing carbon content≤0.04%, chrome content are 16～17% chromium steel band.
3. according to the iron-based amorphous nanocrystalline composite coating that contains ceramic phase of claim 1, it is characterized in that carbide is WC, TiC, Cr
3C
2In any.
4. according to the iron-based amorphous nanocrystalline composite coating that contains ceramic phase of claim 1, it is characterized in that oxide compound is Al
2O
3, TiO
2, Cr
2O
3, ZrO
2In any.
5. according to the iron-based amorphous nanocrystalline composite coating that contains ceramic phase of claim 1 or 3, it is characterized in that containing in the medicine core Co or Ni bag carbide ceramics powder is micron order, and particle diameter is 38～150 μ m.
6. according to the iron-based amorphous nanocrystalline composite coating that contains ceramic phase of claim 1 or 3, it is characterized in that containing in the medicine core Co or Ni bag carbide ceramics powder is nano level, and original size is 30～100nm, and particle diameter is 38～150 μ m after the granulation.
7. according to the iron-based amorphous nanocrystalline composite coating that contains ceramic phase of claim 1 or 4, it is characterized in that containing in the medicine core Co or Ni bag oxide ceramic powder is micron order, and particle diameter is 38～150 μ m.
8. according to the iron-based amorphous nanocrystalline composite coating that contains ceramic phase of claim 1 or 4, it is characterized in that containing in the medicine core Co or Ni bag oxide ceramic powder is nano level, and original size is 30～100nm, and particle diameter is 38～150 μ m after the granulation.
9. the preparation method who contains the iron-based amorphous nanocrystalline composite coating of ceramic phase according to claim 1, it is characterized in that adopting arc spraying technology to prepare coating, the preparation method adopts twin wire arc spray equipment to spray, quicken to be deposited on the matrix with utilizing pressurized air to be atomized into drop after the fusing of medicine core-wire material, utilize the quick cooling effect of matrix directly to form the amorphous nano crystal structure, the ceramic particle disperse of fusing is not distributed on the amorphous nano-crystalline structural matrix fully, preparation technology parameter is: arc voltage 28～34V, working current 190～250A, atomization pressure 0.6～0.8MPa, spray distance 150～200mm.
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