CN1876365A - Cu-Al2O3 gradient composite material coating and its preparation method - Google Patents
Cu-Al2O3 gradient composite material coating and its preparation method Download PDFInfo
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- CN1876365A CN1876365A CN 200610043097 CN200610043097A CN1876365A CN 1876365 A CN1876365 A CN 1876365A CN 200610043097 CN200610043097 CN 200610043097 CN 200610043097 A CN200610043097 A CN 200610043097A CN 1876365 A CN1876365 A CN 1876365A
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Abstract
The invention discloses a Cu-Al2O3 gradient composite material coating layer, comprising five layers of material, which from bottom layer to outer with percent by weight are: the first layer: NiAl 100%; the second layer: NiAl 30%-80%, Cu 20%-70%; the third layer: Cu 75%-90%, Al2O3 10%-25%; the fourth layer: Cu 55%-70%, Al2O3 30%-45%; and the fifth layer: Cu 35%-50%, Al2O3 50%-65%. Said powder is coated on basic material separately with plasma spraying method to get gradient coating material, which is characterized by compact structure, low factor of porosity, high bonding property with basic material, and good thermal shock resistance and abrasion resistance.
Description
Technical field
The present invention relates to a kind of composite coating, be specifically related to by Cu-Al
2O
3The gradient composite material coating that forms the invention still further relates to the preparation method of this material coating.
Background technology
The metal-ceramic coating material can combine the pottery and the excellent properties of metal, thereby obtains the intensity and the toughness of existing metal, and the composite of advantages such as pottery is high temperature resistant, wear-resistant, corrosion-resistant is arranged again.But ceramic material has the crisp intrinsic weakness of matter, and thermophysical property (as the coefficient of expansion, the thermal conductivity etc.) difference of it and metal material is bigger, causes thermal stress to concentrate easily; In addition, ceramic coating and combining of matrix material are mainly that machinery is chimeric, and coating is layer structure, and compactness is relatively poor, often contains 10%～15% pore in the coating, is prone to micro-crack, causes coating and high base strength lower.
Introduce functionally gradient thought, coating composition and structural element are changed gradually along its thickness direction, coating performance also is continuous gradient to be changed, and this is to slow down coating stress to concentrate, improve one of anchoring strength of coating efficient ways.Up to the present, prior art is more used Ni-Al/Al
2O
3, Fe-Al/Al
2O
3Deng functionally gradient coating.Mainly be the special construction that utilizes Ni-Al, Fe-Al series intermetallic compound to have long-range order, its performance is between metal and pottery, with Al
2O
3Preferably Adapter Property is arranged, and is desirable buffer layer material.But, adopt price far below Cu and the Al of Ni-Al, Fe-Al
2O
3The Gradient Coating Materials that forms, in the process of thermal spraying, Cu and Al
2O
3Between have stronger atom diffusion, form intermetallic compound, can significantly improve hardness and the wearability of coating, the wearability of its coating even be higher than the coating of ceramic powders preparation, nobody relates to so far in research in this respect.
Summary of the invention
The purpose of this invention is to provide a kind of by Cu-Al
2O
3The gradient composite material coating that forms is compared with the material that prior art adopts, and low price, hardness and wearability improve, the problem that solved well that coating stress is concentrated, the bond strength of coating and matrix is low.
Another object of the present invention provides the preparation method of above-mentioned material coating.
The technical solution adopted in the present invention is Cu-Al
2O
3Gradient composite material coating is made up of five layer materials, and from the bottom to the outer by mass percentage, its composition is respectively:
Ground floor: NiAl 100%;
The second layer: NiAl 30%～80%, Cu 20%～70%;
The 3rd layer: Cu 75%～90%, Al
2O
310%～25%;
The 4th layer: Cu 55%～70%, Al
2O
330%～45%;
Layer 5: Cu 35%～50%, Al
2O
350%～65%;
More than the total amount of each layer be respectively 100%.
Another technical scheme of the present invention is, the preparation method of above-mentioned gradient composite material coating, and this method is carried out according to the following steps:
Mix respectively at first, in proportion powder
NiAl powder with 30%～80% and 20%～70% Cu powder are put into ball mill and are added mixed pulvis and carry out ball milling, make powder even, again the above-mentioned powder that mixes is put into drying baker and carry out drying, 110 ℃～150 ℃ of temperature, be incubated 2～4 hours, make respectively as stated above again 75%～90%Cu powder and 10%～25%Al
2O
3The mixed-powder of powder, 55%～70%Cu powder and 30%～45%Al
2O
3The mixed-powder of powder, 35%～50%Cu powder and 50%～65%Al
2O
3The mixed-powder of powder, above-mentioned Cu powder, Al
2O
3The particle diameter of powder, NiAl powder is respectively 200 orders～400 orders, 10 μ m～38 μ m, 200 orders～400 orders;
Then spray preliminary treatment
Matrix surface is carried out oil removing, rust cleaning etc. and sandblast roughening treatment;
Last spray-on coating
Adopt plasma spraying method, on matrix, spraying is followed successively by in proper order with the above-mentioned powder spray that mixes: ground floor NiAl powder, the second layer are the mixed powder of 30%～80%NiAl and 20%～70%Cu, and the 3rd layer is 75%～90%Cu and 10%～25%Al
2O
3Mixed powder, the 4th layer is 55%～70%Cu and 30%～45%Al
2O
3Mixed powder, layer 5 is 35%～50%Cu and 50%～65%Al
2O
3Mixed powder.
Mixed pulvis is an alcohol.
The mass ratio of alcohol and powder is 1: 10.
Adopt the technological parameter of plasma spraying method to be: Hydrogen Vapor Pressure is 0.30Mpa～0.40Mpa, argon pressure is 0.70Mpa～0.90Mpa, voltage 50V～70V, electric current 500A～700A, spray distance is 80mm～150mm, 85 °～95 ° of spray angles, and spraying rate is 10cm/s～20cm/s, 100 ℃～200 ℃ of preheat temperatures, total coating thickness is 0.8mm～1.6mm.
The present invention has following advantage compared with the prior art:
(1) the coating microstructure is even, fine and close, and hole is few;
(2) Zhi Bei gradient coating and substrate combinating strength height, good thermal shock, have higher hardness and wearability;
(3) preparation technology of coating is simple, favorable repeatability, and cost is low.
Description of drawings
Fig. 1 organizes photo (* 60) for coating material of the present invention longitudinal section;
Fig. 2 is the metallograph (* 400) at coating material of the present invention and matrix bond place;
Fig. 3 is coating material of the present invention surface SEM photo.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Cu-Al of the present invention
2O
3The gradient coating composite is made up of five layer materials, and from the bottom to the outer by mass percentage, its composition is respectively: ground floor: NiAl 100%; The second layer: NiAl30%～80%, Cu 20%～70%; The 3rd layer: Cu 75%～90%, Al
2O
310%～25%; The 4th layer: Cu 55%～70%, Al
2O
330%～45%; Layer 5: Cu 35%～50%, Al
2O
350%～65%; The total amount of each layer is respectively 100%.
Because fine copper has face-centered cubic lattice, no ppolymorphism changes, and plasticity is fabulous, and fusing point is relatively low, in oxide ceramic surface wetability is preferably arranged during molten state.Therefore, adopt Cu and Al
2O
3Form Cu-Al
2O
3Gradient coating utilizes plasma spraying method to apply, and makes the composition of coating gently carry out the transition in gradient the surface by matrix, avoid matrix to arrive the tissue of coating, the sudden change of performance, can reach and reduce the coating thermal stress and concentrate, reduce micro-crack and produce, improve the effect of anchoring strength of coating.And the price of pure copper powder is far below powder such as Ni-Al, Fe-Al; In the process of thermal spraying, Cu and Al
2O
3Between have stronger atom diffusion, form intermetallic compound, can significantly improve hardness and the wearability of coating.Make the wearability of its coating be higher than Al
2O
3The coating of powder preparation.
The invention provides a kind of Cu-Al of preparation
2O
3The method of gradient coating,
The use material is: technical pure copper powder, particle diameter are 200 orders～400 orders, industrial Al
2O
3Powder, particle diameter are 10 μ m～38 μ m, industrial NiAl powder, and particle diameter is 200 orders～400 orders.
This method is carried out according to the following steps:
Mix respectively at first, in proportion powder
With Cu and Al
2O
3Powder mixes in predetermined several ratios (as shown in table 1), putting into respectively ball mill adds mixed pulvis and carries out ball milling, make powder even, the mass ratio of mixed pulvis and powder is 1: 10, then the powder that mixes is put into drying baker, temperature is controlled to be 110 ℃～150 ℃, be incubated 2～4 hours and carry out drying, remove moisture and increase the flowability of powder, bake out temperature is unsuitable too high, in case Cu and NiAl Powder Oxidation, make respectively the mixed-powder of following ratio;
Table 1 gradient coating powder proportioning (mass fraction, %)
GC
1GC
2GC
3GC
4GC
5Numbering
The 100%NiAl ground floor
NiAl (30%～80%)+Cu (20%～70%) second layer
Cu (75%～90%)+Al
2O
3(10%～25%) the 3rd layer
Cu (55%～70%)+Al
2O
3(30%～45%) the 4th layer
Cu (35%～50%)+Al
2O
3(50%～layer 5
65％)
Then spray preliminary treatment
Matrix is removed surface oil, impurity such as rust, the surface sand-blasting roughening treatment, sandblast angle (being the angle of sand grains injection direction and substrate surface) is 60 °～80 °, avoid 90 ° of direction sandblasts, to prevent that sand grains from embedding surface of the work, clean sand blasted surface with acetone after the sandblast, should spray as early as possible after the matrix surface sandblast, before dusty spray, adopt plasma gun to carry out moisture and the moisture that matrix surface is removed in preheating, and the interface temperature when improving spraying particle and contacting with matrix, the coating stress that minimizing causes because of the matrix thermal expansion, avoid coating cracking, improve coating and high base strength;
Last spray-on coating
The above-mentioned powder that mixes is respectively charged into fine powder feeder, open successively the switches such as main power source, dc source, water cooler, argon gas and hydrogen, the fine powder feeder of unlatching was regulated the powder feeding gas flow after preheating was finished, during spraying sample sequenced in order successively and be fixed on the workbench, spraying is followed successively by in proper order: ground floor NiAl powder, the second layer is the mixed powder of 30%～80%NiAl and 20%～70%Cu, and the 3rd layer is 75%～90%Cu and 10%～25%Al
2O
3Mixed powder, the 4th layer is 55%～70%Cu and 30%～45%Al
2O
3Mixed powder, layer 5 is 35%～50%Cu and 50%～65%Al
2O
3Mixed powder as working lining, can also spray layer 6 is 15%～30%Cu and 70%～85%Al
2O
3Mixed powder as working lining.The control technological parameter: Hydrogen Vapor Pressure is 0.30Mpa～0.40Mpa, argon pressure is 0.70Mpa～0.90Mpa, voltage 50V～70V, electric current 400A～700A, spray distance is 80mm～150mm, 85 °～95 ° of spray angles, and spraying rate is 10cm/s～20cm/s, 100 ℃～200 ℃ of preheat temperatures, total coating thickness is 0.8mm～1.6mm.
Embodiment 1
Material is chosen as: industrial electrolysis pure copper powder, particle diameter are 200～220 orders, copper content＞99.5%;
Commercially available NiAl powder, particle diameter are 280～300 orders, and wherein mass percent is Ni:80%, Al:20%;
Commercially available Al
2O
3Powder, particle diameter are 30 μ m, purity＞99.5%.
Mix respectively at first, in proportion powder
NiAl powder with 50% and 50% Cu powder are put into ball mill and are added alcohol and carry out ball milling, alcohol is 1: 10 with the powder quality ratio, mixed powder 2 hours, make powder even, again the above-mentioned powder that mixes is put into drying baker and carry out drying, 110 ℃ of temperature insulation 4 hours is removed moisture and is increased the flowability of powder.Make respectively as stated above again 80%Cu powder and 20%Al
2O
3The mixed-powder of powder, 60%Cu powder and 40%Al
2O
3The mixed-powder of powder, 40%Cu powder and 60%Al
2O
3The mixed-powder of powder;
Then spray preliminary treatment
Matrix adopting Q235 steel, specimen size are Φ 110mm * 150mm cylinder, with 16 order emergy blasting treatments, clean with acetone after handling again;
Spray-on coating then
Adopt plasma spraying method, on matrix, spraying is followed successively by in proper order with the above-mentioned powder spray that mixes: ground floor NiAl powder bottoming, and the second layer is the mixed powder of 50%NiAl and 50%Cu, the 3rd layer is 80%Cu and 20%Al
2O
3Mixed powder, the 4th layer is 60%Cu and 40%Al
2O
3Mixed powder, layer 5 is 40%Cu and 60%Al
2O
3Mixed powder be working lining, totally five layers, thickness is about 1.0mm, the process parameter control of plasma spraying is: Hydrogen Vapor Pressure 0.32MPa, argon pressure 0.85MPa, voltage 55V, electric current 600A, spray distance 100mm, 90 ° of spray angles, spraying rate 15cm/s, 150 ℃ of preheat temperatures.
Embodiment 2
Material is chosen as: particle diameter is 350 orders～400 purpose pure copper powder, and particle diameter is 200 orders～250 purpose NiAl powder, and particle diameter is the Al of 18 μ m～30 μ m
2O
3Powder.
Mix respectively at first, in proportion powder
NiAl powder with 30% and 70% Cu powder are put into ball mill and are added alcohol and carry out ball milling, alcohol is 1: 10 with the powder quality ratio, mixed powder 2 hours, make powder even, again the above-mentioned powder that mixes is put into drying baker and carry out drying, 130 ℃ of temperature insulation 3 hours is removed moisture and is increased the flowability of powder.Make respectively as stated above again 90%Cu powder and 10%Al
2O
3The mixed-powder of powder, 70%Cu powder and 30%Al
2O
3The mixed-powder of powder, 50%Cu powder and 50%Al
2O
3The mixed-powder of powder, 30%Cu powder and 70%Al
2O
3The mixed-powder of powder;
Then spray preliminary treatment
Matrix adopting 45# steel, specimen size are Φ 120mm * 500mm cylinder, and spraying is preceding with 16 order emergy blasting treatments;
Spray-on coating then
Adopt plasma spraying method, on matrix, spraying is followed successively by in proper order with the above-mentioned powder spray that mixes: ground floor NiAl powder bottoming, and the second layer is the mixed powder of 30%NiAl and 70%Cu, the 3rd layer is 90%Cu and 10%Al
2O
3Mixed powder, the 4th layer is 70%Cu and 30%Al
2O
3Mixed powder, layer 5 is 50%Cu and 50%Al
2O
3Mixed powder, layer 6 is 30%Cu and 70%Al
2O
3Mixed powder be working lining, totally six layers, thickness is about 1.6mm, the process parameter control of plasma spraying is: Hydrogen Vapor Pressure 0.4MPa, argon pressure 0.9MPa, voltage 70V, electric current 700A, spray distance 150mm, 90 ° of spray angles, spraying rate 20cm/s, 200 ℃ of preheat temperatures.
Embodiment 3
Material is chosen as: particle diameter is 280 orders～350 purpose pure copper powder, 300 orders～350 purpose NiAl powder, and particle diameter is the Al of 30 μ m～40 μ m
2O
3Powder.
Mix respectively at first, in proportion powder
NiAl powder with 80% and 20% Cu powder are put into ball mill and are added alcohol and carry out ball milling, alcohol is 1: 10 with the powder quality ratio, mixed powder 2 hours, make powder even, again the above-mentioned powder that mixes is put into drying baker and carry out drying, 150 ℃ of temperature insulation 2 hours is removed moisture and is increased the flowability of powder.Make respectively as stated above again 75%Cu powder and 25%Al
2O
3The mixed-powder of powder, 55%Cu powder and 45%Al
2O
3The mixed-powder of powder, 35%Cu powder and 65%Al
2O
3The mixed-powder of powder;
Then spray preliminary treatment
Matrix adopting casting pig, specimen size are Φ 100mm * 120mm cylinder, with 16 order corundum sand blasting treatments, clean with acetone after handling before the spraying again;
Spray-on coating then
Adopt plasma spraying method, on matrix, spraying is followed successively by in proper order with the above-mentioned powder spray that mixes: ground floor NiAl powder bottoming, and the second layer is the mixed powder of 80%NiAl and 20%Cu, the 3rd layer is 75%Cu and 25%Al
2O
3Mixed powder, the 4th layer is 55%Cu and 45%Al
2O
3Mixed powder, layer 5 is 35%Cu and 65%Al
2O
3Mixed powder be working lining, totally five layers, thickness is about 0.8mm, the process parameter control of plasma spraying is: Hydrogen Vapor Pressure 0.3MPa, argon pressure 0.7MPa, voltage 50V, electric current 500A, spray distance 80mm, 90 ° of spray angles, spraying rate 10cm/s, 100 ℃ of preheat temperatures.
In order to investigate Cu-Al of the present invention
2O
3Gradient coating is different from non-gradient double-layer ceramic coating performance, the coating material of the present invention that obtains with embodiment 1 respectively and matrix with the NiAl bottoming after direct spraying Al
2O
3Coating, bond strength, hardness, thermal shock resistance, the wearability of two kinds of coatings are tested and are compared, and observed the gradient coating section structure.
Adopting the bonding pulling method to test the bond strength of two kinds of coatings, find gradient coating of the present invention and substrate combinating strength height, is the twice of double-layer ceramic coating; Gradient coating has higher hardness, and two kinds of coating hardness are respectively 87.9 (HR15N) and 90.9 (HR15N); Measured the thermal shock resistance of two kinds of coatings with cyclic heating method, matrix is the Q235 steel plate that is of a size of 5cm * 5cm * 3mm, the thermal cycling test condition is as follows: the stove of the sample of coating being put into 800 ℃ of conditions is incubated 20min, take out then the blowing compressed air cooling, so iterative cycles is until crackle, peeling occur, and the result shows that the thermal shock resistance of gradient coating of the present invention approximately is about 4 times of double-layer ceramic coating; Utilize the wearability of self-control abrasive test machine testing gradient coating of the present invention, its wearability has improved 3 times than matrix approximately; Than pure Al
2O
3Ceramic thermal spray coating improves 40%, the utilized observation by light microscope section structure of gradient coating of the present invention and the faying face of coating and matrix, as shown in Figure 1 and Figure 2, can find that its composition through-thickness is continuous gradient and changes, coating is combined with matrix closely; From Fig. 3, the surface topography SEM photo of coating material can find out that coating structure densification, porosity are low.
Claims (5)
1. Cu-Al
2O
3Gradient composite material coating is characterized in that, is made up of five layer materials, and from the bottom to the outer by mass percentage, its composition is respectively:
Ground floor: NiAl 100%;
The second layer: NiAl 30%～80%, Cu 20%～70%;
The 3rd layer: Cu 75%～90%, Al
2O
310%～25%;
The 4th layer: Cu 55%～70%, Al
2O
330%～45%;
Layer 5: Cu 35%～50%, Al
2O
350%～65%;
More than the total amount of each layer be respectively 100%.
2. according to the preparation method of the described gradient composite material coating of claim 1, it is characterized in that this method is carried out according to the following steps:
Mix respectively at first, in proportion powder
NiAl powder with 30%～80% and 20%～70% Cu powder are put into ball mill and are added mixed pulvis and carry out ball milling, make powder even, again the above-mentioned powder that mixes is put into drying baker and carry out drying, 110 ℃～150 ℃ of temperature, be incubated 2～4 hours, make respectively as stated above again 75%～90%Cu powder and 10%～25%Al
2O
3The mixed-powder of powder, 55%～70%Cu powder and 30%～45%Al
2O
3The mixed-powder of powder, 35%～50%Cu powder and 50%～65%Al
2O
3The mixed-powder of powder, above-mentioned Cu powder, Al
2O
3The particle diameter of powder, NiAl powder is respectively 200 orders～400 orders, 10 μ m～38 μ m, 200 orders～400 orders;
Then spray preliminary treatment
Matrix surface is carried out oil removing, rust cleaning etc. and sandblast roughening treatment;
Last spray-on coating
Adopt plasma spraying method, on matrix, spraying is followed successively by in proper order with the above-mentioned powder spray that mixes: ground floor NiAl powder, the second layer are the mixed powder of 30%～80%NiAl and 20%～70%Cu, and the 3rd layer is 75%～90%Cu and 10%～25%Al
2O
3Mixed powder, the 4th layer is 55%～70%Cu and 30%～45%Al
2O
3Mixed powder, layer 5 is 35%～50%Cu and 50%～65%Al
2O
3Mixed powder.
3. preparation method according to claim 2 is characterized in that, described mixed pulvis is an alcohol.
4. preparation method according to claim 3 is characterized in that, the mass ratio of described alcohol and powder is 1: 10.
5. preparation method according to claim 2, it is characterized in that, the technological parameter of described employing plasma spraying method is: Hydrogen Vapor Pressure is 0.30Mpa～0.40Mpa, and argon pressure is 0.70Mpa～0.90Mpa, voltage 50V～70V, electric current 500A～700A, spray distance is 80mm～150mm, 85 °～95 ° of spray angles, and spraying rate is 10cm/s～20cm/s, 100 ℃～200 ℃ of preheat temperatures, total coating thickness is 0.8mm～1.6mm.
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|---|---|---|---|
| CN200610043097A CN100588536C (en) | 2006-07-05 | 2006-07-05 | Cu-Al2O3 gradient composite material coating and its preparation method |
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|---|---|---|---|
| CN200610043097A CN100588536C (en) | 2006-07-05 | 2006-07-05 | Cu-Al2O3 gradient composite material coating and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1876365A true CN1876365A (en) | 2006-12-13 |
| CN100588536C CN100588536C (en) | 2010-02-10 |
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ID=37509005
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255537B (en) * | 2007-07-02 | 2011-04-13 | 兰州理工大学 | Method for preparing fibre reinforced metal-based gradient composite material |
| CN115283664A (en) * | 2022-07-13 | 2022-11-04 | 哈尔滨工业大学（深圳） | Cu-Al 2 O 3 Cold spraying composite powder and preparation method and application thereof |
-
2006
- 2006-07-05 CN CN200610043097A patent/CN100588536C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255537B (en) * | 2007-07-02 | 2011-04-13 | 兰州理工大学 | Method for preparing fibre reinforced metal-based gradient composite material |
| CN115283664A (en) * | 2022-07-13 | 2022-11-04 | 哈尔滨工业大学（深圳） | Cu-Al 2 O 3 Cold spraying composite powder and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100588536C (en) | 2010-02-10 |
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