Method for producing a coated metal substrate by laser metal deposition
阅读说明：本技术 用于通过激光金属沉积制造经涂覆的金属基材的方法 (Method for producing a coated metal substrate by laser metal deposition ) 是由 马科斯·佩雷斯罗德里格斯 阿尔瓦罗·曼洪费尔南德斯 米格尔·佩雷斯皮克拉斯 何塞·洛佩斯弗雷斯 于 2020-04-16 设计创作，主要内容包括：本发明涉及：预涂覆的金属基材,其中在0.5μm至5.0μm的所有波长处具有高于或等于60％的反射率的裸金属基材涂覆有包含至少一种钛酸盐和至少一种纳米颗粒的预涂层；用于制造这种预涂覆的金属基材的方法；用于制造经涂覆的金属基材的方法和经涂覆的金属基材。(The present invention relates to: a pre-coated metal substrate, wherein a bare metal substrate having a reflectance of greater than or equal to 60% at all wavelengths from 0.5 μ ι η to 5.0 μ ι η is coated with a pre-coating comprising at least one titanate and at least one nanoparticle; a method for manufacturing such a pre-coated metal substrate; a method for manufacturing a coated metal substrate and a coated metal substrate.)
1. A pre-coated metal substrate wherein a bare metal substrate having a reflectance of greater than or equal to 60% at all wavelengths from 0.5 μ ι η to 5.0 μ ι η is coated with a pre-coating comprising at least one titanate and at least one nanoparticle.
2. The pre-coated metal substrate according to claim 1, wherein the at least one titanate is selected from the group consisting of: na (Na)2Ti3O7、NaTiO3、K2TiO3、K2Ti2O5、MgTiO3、SrTiO3、BaTiO3、CaTiO3、FeTiO3And ZnTiO4Or mixtures thereof.
3. The pre-coated metal substrate according to any one of claims 1 or 2, wherein the at least one nanoparticle is selected from the group consisting of: TiO 22、SiO2Yttria Stabilized Zirconia (YSZ), Al2O3、MoO3、CrO3、CeO2Or mixtures thereof.
4. The pre-coated metal substrate according to any one of claims 1 to 3, wherein the thickness of the pre-coating layer is from 10 μm to 140 μm.
5. The pre-coated metal substrate according to any one of claims 1 to 4, wherein the bare metal substrate has a reflectance higher than or equal to 70% at all wavelengths from 0.5 μm to 5.0 μm.
6. The pre-coated metal substrate according to any one of claims 1 to 5, wherein the bare metal substrate is selected from the group consisting of: copper, aluminum, magnesium, platinum, rhodium, tantalum, silver, and gold.
7. The pre-coated steel substrate according to any one of claims 1 to 6, wherein the pre-coating layer further comprises a binder.
8. The pre-coated steel substrate according to claim 7, wherein the percentage of binder in the pre-coating layer is from 1 to 20 wt%.
9. A method for manufacturing a pre-coated metal substrate according to any one of claims 1 to 8, comprising the sequential steps of:
A. providing a bare metal substrate having a reflectance higher than or equal to 60% at all wavelengths from 0.5 μm to 5.0 μm,
B. depositing a pre-coating comprising at least one titanate and at least one nanoparticle,
C. optionally, drying the coated metal substrate obtained in step B).
10. The method according to claim 9, wherein in step B) the deposition of the pre-coating is performed by spin coating, spray coating, dip coating or brush coating.
11. The method according to any one of claims 9 or 10, wherein in step B, the pre-coating layer further comprises an organic solvent.
12. The method of claim 11, wherein the organic solvent is selected from the group consisting of: acetone, methanol, ethyl ethanolate, ethylene glycol and water.
13. The method according to any one of claims 9 to 12, wherein in step B) the pre-coating comprises 1 to 200g/L of at least one nanoparticle.
14. The method according to any one of claims 9 to 11, wherein in step B) the pre-coating comprises 100 to 500g/L of titanate.
15. The method according to any one of claims 9 to 14, wherein in step B) the pre-coating layer further comprises a binder precursor.
16. A method for manufacturing a coated metal substrate comprising the sequential steps of:
I. providing a pre-coated metal substrate, wherein a bare metal substrate having a reflectance of greater than or equal to 60% at all wavelengths from 0.5 μm to 5.0 μm is coated with a pre-coating comprising at least one titanate and at least one nanoparticle, and
depositing at least one metal coating by laser deposition, the laser having a wavelength of 0.5 μm to 5.0 μm.
17. The method according to claim 16, wherein in step II) the laser deposition is carried out with a protective gas being an inert gas and/or a reactive gas.
18. The method according to any one of claims 16 or 17, wherein in step II) the power of the laser is 0.2kW to 17 kW.
19. The method of any one of claims 16 to 18, wherein the at least one metal coating is selected from the group consisting of: inconel, 316L stainless steel, 42C martensitic stainless steel, and cobalt chromium based alloys.
20. A coated metal substrate comprising a bare metal substrate having a reflectivity higher than or equal to 60% at all wavelengths from 0.5 μ ι η to 5.0 μ ι η and coated with at least one metallic coating, wherein the interface between the metal substrate and the at least one metallic coating comprises a dissolved and/or precipitated pre-coating comprising at least one titanate and at least one nanoparticle.
21. The coated metal substrate of claim 20, wherein the at least one metal coating has a thickness of 0.3mm to 10 mm.
22. The coated metal substrate of any one of claims 20 or 21, wherein the metal substrate is coated with at least two metal coatings.
23. Use of the coated metal substrate according to any one of claims 20 to 22 for the manufacture of cooled parts for pyrometallurgical furnaces, cooling rolls, blast furnaces.
Examples
The following examples and tests are non-limiting in nature and must be considered for illustrative purposes only. They will illustrate the advantageous features of the invention, the importance of the parameters chosen by the inventors after a large number of experiments and further determine the characteristics that can be achieved by the invention.
For the tests, a copper substrate having the chemical composition in the following table 1 in weight percent was used:
Ag
Bi
Co
Cr
Fe
Ni
S
Si
Sn
Zn
Cu
0.0020
0.0002
0.0001
0.0005
0.0002
0.0001
<0.002
0.0007
0.0006
0.0003
balance of
The reflectance of the copper base material at a wavelength of 1.030 μm to 1.064 μm was 85%. These wavelengths are commonly used as laser sources in laser metal deposition.
Example 1:
by mixing acetone with MgTiO3(diameter: 2 μm), SiO2(diameter: 10nm) and TiO2(straight)Diameter: 50nm) to prepare an acetone solution containing the elements. In acetone solution, MgTiO3Has a concentration of 175g.L-1。SiO2Has a concentration of 25g.L-1。TiO2Has a concentration of 50g.L-1。
Then, test 1 was coated with an acetone solution by spraying. The acetone was evaporated. MgTiO 23The percentage in the coating was 70% by weight, SiO2In a percentage of 10% by weight and TiO2The percentage of (B) is 20% by weight. Run 2 was not coated with this solution.
A metal coating comprising 2 layers of Inconel 625 was then deposited on trials 1 and 2 by laser metal deposition. The chemical composition of Inconel 625 in weight percent is in table 2 below.
Mo
Fe
Mn
Cr
Si
O
N
Al
Nb
Ni
9.0
0.38
0.38
21.0
0.46
0.06
0.10
0.02
3.61
Balance of
The first layer was deposited with a laser power of 3.8 kW. The second time was deposition with 1.2kW of laser power. The protective gas is argon.
After deposition of Inconel 625 on trials 1 and 2, the thickness of the layer and the depth of penetration of the coating in the copper substrate were measured by Scanning Electron Microscopy (SEM). The test was bent up to 180 ° according to standard ISO 15614-7. The results are in table 3 below:
*: according to the invention
In the case of test 1, the Inconel 625 metal coating was thicker than in test 2. Furthermore, in the case of test 1, the coating penetration depth was higher than that of test 2. In fact, the reflectivity of test 1 has decreased, resulting in an improvement in laser deposition.
The hardness of both tests was then determined on the metal coating and the copper substrate using a microhardness tester. The results are in table 4 below, where "a" represents the hardness of the second layer of the coating; "b" represents the hardness of the first layer of the coating; "c" represents the hardness at the interface between the copper substrate and the first layer of the coating; and "d" represents the thickness of the copper substrate:
test of
a
b
c
d
1*
246
255
261
56
2
263
274
203
55
*: according to the invention
The hardness values of test 1 were more uniform on the metal coating than test 2, with a softened interface observed in test 2.
Example 2:
for test 3, a bag was preparedAn aqueous solution comprising: 363g.L-1MgTiO of3(diameter: 2 μm) 77.8g.L-1SiO of (2)2(diameter range: 12nm to 23nm), 77.8g.L-1Of TiO 22(diameter range: 36nm to 55nm) and 238g.L-13-aminopropyltriethoxysilane (fromMade ofAMEO). The solution is applied to a steel substrate and dried by 1) IR and 2) NIR. The dried coating was 40 μm thick and contained 62 wt.% MgTiO313% by weight of SiO213% by weight of TiO2And 12% by weight of a binder obtained from 3-aminopropyltriethoxysilane.
For run 4, an aqueous solution was prepared comprising the following components: 330g.L-1MgTiO of3(diameter: 2 μm) 70.8g.L-1SiO of (2)2(diameter range: 12nm to 23nm), 70.8g.L-1Of TiO 22(diameter range: 36nm to 55nm), 216g.L-13-aminopropyltriethoxysilane (fromMade ofAMEO) and 104.5g.L-1Organofunctional silanes and functionalized nano-sized SiO2Composition of particles (manufactured by Evonik)Sivo 110). The solution is applied to a steel substrate and dried by 1) IR and 2) NIR. The dried coating was 40 μm thick and contained 59.5 wt.% of MgTiO313.46% by weight of SiO212.8% by weight of TiO2And 14.24 wt% of a binder obtained from 3-aminopropyltriethoxysilane and an organofunctional silane.
In all cases, the adhesion of the precoat to the metal substrate is greatly improved.