EP3649272B1 - A steel substrate bearing a cold sprayed coating - Google Patents
A steel substrate bearing a cold sprayed coating Download PDFInfo
- Publication number
- EP3649272B1 EP3649272B1 EP18737726.2A EP18737726A EP3649272B1 EP 3649272 B1 EP3649272 B1 EP 3649272B1 EP 18737726 A EP18737726 A EP 18737726A EP 3649272 B1 EP3649272 B1 EP 3649272B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- anyone
- metallic substrate
- gas
- sprayed coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims description 77
- 239000011248 coating agent Substances 0.000 title claims description 73
- 239000000758 substrate Substances 0.000 title claims description 73
- 229910000831 Steel Inorganic materials 0.000 title claims description 40
- 239000010959 steel Substances 0.000 title claims description 40
- 239000007789 gas Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- 239000007921 spray Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 230000001133 acceleration Effects 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000005422 blasting Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000005488 sandblasting Methods 0.000 claims description 2
- 238000009718 spray deposition Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 19
- 239000002245 particle Substances 0.000 description 15
- 230000004224 protection Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005246 galvanizing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
- 229910015392 FeAl3 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229940105847 calamine Drugs 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 238000010288 cold spraying Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000004503 fine granule Substances 0.000 description 1
- 229910052864 hemimorphite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
Definitions
- the present invention relates to a steel substrate bearing a cold sprayed coating and a method for the manufacture of this cold sprayed coated steel substrate.
- the invention is particularly well suited for the industry, civil engineering and construction fields.
- metallic substrates are often use in order to produce metallic parts, in particular for marine metallic structures.
- the metallic parts can be steel pilings, bearing piles, combined walls, moles, parts of offshore wind powers or plates and beams for offshore structures.
- the main problem of these parts is their resistance to corrosion. Indeed, the parts are used in corrosive areas, i.e. in sea area. Due to these corrosive areas, the lifetime of such parts can be divided by 5 when compared to the use of such parts on earth.
- metallic substrates having a higher resistance to corrosion in order to improve their lifetime especially in corrosive atmospheres.
- Some protections can be used to protect these parts. For example, it is known to produce these parts with a sacrificial thickness, the lifetime depending on the thickness of the part. However, even if the sacrificial thicknesses improve the lifetime of these parts, they do not really improve the corrosion resistance. It is also know to deposit paints or metallic coatings such as a zinc coating by hot-dip galvanizing. However, these deposition processes are very expensive and difficult to implement at industrial scale especially for long and heavy products.
- a coil is firstly annealed and then hot-dipped in a zinc bath in the hot-dip galvanizing line.
- a zinc bath in the hot-dip galvanizing line.
- the steel pilings are produced by hot-rolling at about 1250°C.
- the semi-finished products called "beam blank” pass through walking beam furnace that are mobile. Then, oxides formed during the reheating are removed from the beam blank. The blanks pass through rolling mills. After, the length of the steel piling is about 100m. The steel piling is then cut in order to obtain a final length around 20m. The steel piling is finally cooled and can be implementing in the soil in the sea. Due to the length and the shape of the steel piling, it cannot be hot-dipped in continuous hot-dip galvanizing lines.
- Cold spray also called as “Cold Gas Dynamic Spray”.
- Cold spray can be classified into two categories depending on different spraying pressures: low-pressure cold spray and high-pressure cold spray.
- Cold spray process mainly refers to a process in which tiny solid particles are sprayed onto the surface of a metallic or insulating substrate using a compressed gas flow with a supersonic speed, and deposited following strong plastic deformation, to form a coating.
- the spraying since the spraying is performed under a low temperature (below 600°C), phenomena such as oxidation, grain growth and phase transition are difficult to occur for spraying materials such that the properties of original materials can be well maintained.
- the coating manufactured by a cold spray process has a denser microstructure, a lower heat-affected residual stress and a better long-acting protection for superstructures of the marine oil and gas equipments as compared to conventional thermally sprayed coatings, because during the cold spray, the process temperature is reduced, and solid particles is deposited mainly depending on the plastic deformation due to improvement in kinetic energy, and the particles are deformed more fully.
- the cold spray method can be used for covering metallic substrate in industry, civil engineering and construction field.
- a metallic zinc coating can be used as an anti-corrosive coating of metallic components, wherein the metallic zinc coating is used as a sacrificial anode material, providing a cathodic protection to protect metallic substrates from corrosion.
- the metallic zinc coating does not provide a sufficient barrier effect.
- the patent application JP200730873A discloses an anti-corrosion coating of Al-Zn alloy with Al 2 O 3 hard particles to be applied on steel plate substrate by cold spray.
- the patent application CN104946930 discloses a composite-structure aluminum-zinc protective coating and a preparation method thereof.
- the preparation method comprises the following steps: preparing a Zn-AI alloy composition, wherein the Zn-AI alloy composition comprises 5-35 wt.% of Al and the balance of Zn and inevitable impurities; preparing a Zn-AI alloy powder by atomization shock cooling to obtain dendritic structure powder with fine granule inside; and by using high-speed inert gas and/or reducing gas as carrier gas, carrying out high-speed injection on a steel structural member surface to deposit the Zn-AI alloy coating which is 100-500 mu m thick.
- the anticorrosion properties of the aluminum-zinc metallic coating are not sufficient. Indeed, the high amount of zinc in the coating allows a sacrificial protection allowing a decrease or a prevention of red rust. Nevertheless, especially for metallic substrates used in very corrosive atmospheres, they have to be protected by a coating having a sacrificial protection and a barrier effect in order to significantly reduce the corrosion problems and therefore to greatly increase the life time of the metallic substrate.
- the object of the invention is to provide a coated steel substrate having an improved resistance to corrosion, in particular having a barrier effect and a sacrificial protection.
- the object is also to provide a coated steel substrate having a longer life time especially in corrosive atmosphere.
- it also makes available an easy to implement method for the manufacture of such coated steel substrates.
- electrochemical potential has to be at least 50mV more negative than the potential of the metallic substrate.
- a maximum potential of -0.78V with respect to a saturated calomel electrode (SCE) is needed. It is preferable not to decrease the potential at a value of -1.4V/SCE, even -1.25V/SCE which would involve a fast consumption and would finally decrease the period of protection of steel.
- the steel substrate bearing a cold sprayed coating can also comprise any characteristics of claims 2 to 8.
- Another object is achieved by providing a method for the manufacture of a steel substrate bearing a cold sprayed coating according to claim 9.
- the method can also comprise any characteristics of claims 10 to 20.
- the object is achieved by providing the use of a steel substrate bearing a cold sprayed coating according to claim 21.
- the thickness of the layers represented is exclusively for purposes of illustration and cannot be considered to be a representation of the different layers to scale.
- the invention relates to a metallic substrate bearing a cold sprayed coating comprising:
- the cold sprayed coated metallic substrate according to the present invention has a sacrificial protection and a barrier effect mainly due to the presence of zinc, Al 2 O 3 and aluminum in the above specific amounts. Indeed, it is believed that Zn having a low electrochemical potential in addition to Al having a high barrier effect with specific proportions will provide a higher corrosion protection in corrosive areas Thus, the metallic substrate is well protected against corrosion, the appearance of the red rust is prevented or at least significantly delayed. Moreover, it seems that Al 2 O 3 can improve the hardness of the coating so as to obtain a better adhesion of the coating on the metallic substrate. Finally, it is believed that the presence of magnesium will not provide a sufficient resistance corrosion.
- the coating can comprise unavoidable impurities.
- the optionally impurities are chosen from Fe, Si, Cu, the content by weight of each additional element being inferior to 0.3% by weight.
- the coating comprises from 2.0 to 8.0, more preferably from 3.0 to 6.0% by weight of zinc.
- the coating has a porosity between 3.0 and 7.0%.
- the microstructure of the coating does not comprise an intermetallic diffusion layer made of Fe and Al. More preferably, the microstructure of the coating does not comprise an intermetallic diffusion layer made of FeAl 3 and Fe 2 Al 5 . More preferably, the coating microstructure does not include an intermetallic layer between the coating and the metallic substrate. Without willing bound by any theory, it seems that the specific microstructure of the present invention prevents the risks of coating brittleness and therefore improves the adherence of the coating on the metallic substrate.
- the thickness of the coating is between 100 and 350 ⁇ m, more preferably between 150 and 250 ⁇ m.
- the coating hardness is between 40 and 80HV(0.1) and more preferably between 50 and 70HV(0.1).
- the hardness of the coating is between of 60HV(0.1).
- the metallic substrate is a steel substrate.
- the metallic substrate is a part chosen from: a piling, a wire, a plate, a tube and a beam.
- the method for the manufacture of a steel substrate bearing a cold sprayed coating according to the present invention comprises the following step:
- the surface treatment is chosen from: shot blasting, pickling polishing, sand blasting and grinding.
- the surface preparation step is performed so as to obtain a surface roughness of the metallic substrate above 5 ⁇ m, more preferably between 5 and 30 ⁇ m and advantageously between 10 and 20 ⁇ m. Indeed, without willing to be bound by any theory, it is believed that the surface preparation modified the surface texture of the metallic substrate allowing an increase of the coating adhesion.
- the surface treatment is preferably shot basting.
- the steel substrate can comprise an oxide layer on its surface originating from the elaboration route of the metallic substrate.
- the surface preparation can remove oxides present on the metallic substrate to further improve the coating adhesion on the metallic substrate.
- the metallic substrate is a steel substrate
- a layer of calamine is generally formed after the hot-rolling.
- the surface preparation can remove the millscale layer.
- step C) comprises the following sub-steps:
- Figure 1 illustrates a typical cold spray device wherein preferably, in step C), at least one gas under pressure is injected in the cold spray device.
- the gas is chosen among: nitrogen, argon, helium, air or a mixture thereof.
- the pressure of the gas is between 1 and 10 MPa.
- the pressure of the gas is between 2 and 7 MPa.
- step C.ii) a first part of the gas is heated in the heating section 1 at a temperature 200 and 600°C, more preferably between 300 and 500°C and for example of 400°C.
- the second part of the gas navigates through the powder the feeder section 2 in order to carrier the powder mixture.
- steps C.ii) and C.iii) are performed simultaneously.
- the first part represents above 60% by volume of the gas and the second part represents below 40% by volume of the gas. More preferably, the first part represents above 70% by volume of the gas and the second part represents below 30% by volume of the gas.
- the first part represents above 80% by volume of the gas and the second part represents below 20% by volume of the gas.
- step C.v the first and the second parts of gas are mixed before the ejector of the supersonic nozzle 3.
- the mixing gases comprising the powder mixture crosses the ejector of the supersonic nozzle 4 resulting in an acceleration of the gases at supersonic speed.
- the supersonic nozzle is a tube that is pinched in the middle, making a carefully balanced, asymmetric hourglass shape.
- the powder mixture particles impact the metallic substrate 4 to create a coating.
- the supersonic speed is between 350 and 1200m.s -1 , preferably between 400 and 1000m.s -1 and more preferably between 400 and 850m.s -1 .
- the distance projection between the ejector supersonic and the metallic substrate is between 10 and 50mm, more preferably between 20 and 40mm and for example of 30mm.
- the projection angle between the supersonic nozzle and the metallic substrate is between 70 and 110°.
- the powder mixture comprises from 2.0 to 8.0, more preferably from 3.0 to 6.0% by weight of zinc.
- the coating comprises between 10 and 20% by weight of Al 2 O 3 .
- the powder particles shape is spherical, spheroidal or angular.
- Figure 2 illustrates a spherical powder particle.
- Figure 3 illustrates an example of angular powder particle.
- an angular particle can have a hexagonal shape, a cubic shape or a triangular shape
- Figure 4 illustrates a spheroidal powder particle.
- the powder particles have a size above 10 ⁇ m, more preferably between 10 and 150 ⁇ m and more preferably between 10 and 100 ⁇ m.
- the hardness of the powder mixer is between 30 and 50HV(0.01).
- the cold spray method according to the present invention can be used locally on the metallic substrate.
- the productivity of the cold spray method increases.
- it can be used on piling products in order to protect preferentially at least one specific area, the one subjected to the corrosion medium.
- the coating of a metallic substrate can be damaged. It can be due to scratches for example during the transport or during the building of metallic structures.
- the method according to the present invention it is possible to repair the metallic coating by depositing the cold sprayed coating on the damaged area(s).
- the local deposition of the coating on the metallic substrate with the method according to the present invention is easy to implement and quick improving the productivity.
- the cold sprayed metallic substrate can be used for the manufacture offshore structure, offshore wind power, Marine current power, hull of a boat, coastal and port infrastructure, quay wall and, underground structure, rail and anchorage.
- the metallic substrate is a steel substrate having the following composition according to the EN 10248-1 norm: C (wt.%) Si(wt.%) Mn(wt.%) S(wt.%) P(wt.%) 0.18 0.21 1.32 0.003 0.013
- Trial 1 is a cold sprayed coated steel sheet wherein the coating comprising 3.9% by weight of Zn, the balance being Al.
- Trial 2 is a cold sprayed coated steel sheet wherein the coating comprising Al.
- Trial 3 is a cold sprayed coated steel sheet wherein the coating comprising 15% by weight of Al 2 O and Al.
- the steel sheet was first shot blasted to obtain a surface roughness of 14.5 ⁇ m. Then, the powder mixture was deposited by cold spray process.
- the parameter of the cold spray process was as follows:
- a test consisting in measuring the electrochemical potential of the coated steel surface sheet was realized. Steel sheets and coatings were separated and dipped in a solution comprising 5% by weight of sodium chloride at pH 7. A saturated calomel electrode (SCE) was also immersed into the solution. The coupling potential of the surface was measured over time.
- SCE saturated calomel electrode
- Trial 1 according to the present invention is highly sacrificial compared to Trials 1 to 3. Coupling potential of Trial 1 is under -0.78V/SCE as required.
- Trials 1 to 3 were prepared and subjected to a corrosion test to evaluate the protection of the coated steel sheets.
- the salt fog comprises 5% by weight of NaCl.
- the salt fog had the following characteristics:
- Trial 1 shows excellent protection against corrosion when compared to Trials 2 and 3. Moreover, Trial 2 shows red rust after 15 days of salt spray test.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating By Spraying Or Casting (AREA)
Description
- The present invention relates to a steel substrate bearing a cold sprayed coating and a method for the manufacture of this cold sprayed coated steel substrate. The invention is particularly well suited for the industry, civil engineering and construction fields.
- In industry, civil engineering and construction fields, metallic substrates are often use in order to produce metallic parts, in particular for marine metallic structures. For example, the metallic parts can be steel pilings, bearing piles, combined walls, moles, parts of offshore wind powers or plates and beams for offshore structures. The main problem of these parts is their resistance to corrosion. Indeed, the parts are used in corrosive areas, i.e. in sea area. Due to these corrosive areas, the lifetime of such parts can be divided by 5 when compared to the use of such parts on earth. Thus, there is a need to provide metallic substrates having a higher resistance to corrosion in order to improve their lifetime especially in corrosive atmospheres.
- Some protections can be used to protect these parts. For example, it is known to produce these parts with a sacrificial thickness, the lifetime depending on the thickness of the part. However, even if the sacrificial thicknesses improve the lifetime of these parts, they do not really improve the corrosion resistance. It is also know to deposit paints or metallic coatings such as a zinc coating by hot-dip galvanizing. However, these deposition processes are very expensive and difficult to implement at industrial scale especially for long and heavy products.
- Indeed, for example for the hot-dip galvanizing process, usually, a coil is firstly annealed and then hot-dipped in a zinc bath in the hot-dip galvanizing line. With the actual lines, it is difficult to cover parts such as marine metallic structures.
- Indeed, for example, the steel pilings are produced by hot-rolling at about 1250°C. The semi-finished products called "beam blank" pass through walking beam furnace that are mobile. Then, oxides formed during the reheating are removed from the beam blank. The blanks pass through rolling mills. After, the length of the steel piling is about 100m. The steel piling is then cut in order to obtain a final length around 20m. The steel piling is finally cooled and can be implementing in the soil in the sea. Due to the length and the shape of the steel piling, it cannot be hot-dipped in continuous hot-dip galvanizing lines.
- It is possible to cover these parts by a technique called "Cold spray", also called as "Cold Gas Dynamic Spray". Cold spray can be classified into two categories depending on different spraying pressures: low-pressure cold spray and high-pressure cold spray. Cold spray process mainly refers to a process in which tiny solid particles are sprayed onto the surface of a metallic or insulating substrate using a compressed gas flow with a supersonic speed, and deposited following strong plastic deformation, to form a coating. In the cold spray process, since the spraying is performed under a low temperature (below 600°C), phenomena such as oxidation, grain growth and phase transition are difficult to occur for spraying materials such that the properties of original materials can be well maintained. Meanwhile, the coating manufactured by a cold spray process has a denser microstructure, a lower heat-affected residual stress and a better long-acting protection for superstructures of the marine oil and gas equipments as compared to conventional thermally sprayed coatings, because during the cold spray, the process temperature is reduced, and solid particles is deposited mainly depending on the plastic deformation due to improvement in kinetic energy, and the particles are deformed more fully. The cold spray method can be used for covering metallic substrate in industry, civil engineering and construction field.
- It is known to use some metallic coatings as a protection coating against corrosion using cold spray process. Metallic aluminum particles are generally recognized as relatively ideal cold spraying materials due to their low yield strength, good plastic deformation capacity and excellent corrosion-resistance property. A metallic zinc coating can be used as an anti-corrosive coating of metallic components, wherein the metallic zinc coating is used as a sacrificial anode material, providing a cathodic protection to protect metallic substrates from corrosion. However, the metallic zinc coating does not provide a sufficient barrier effect.
- The
patent application JP200730873A CN104946930 discloses a composite-structure aluminum-zinc protective coating and a preparation method thereof. The preparation method comprises the following steps: preparing a Zn-AI alloy composition, wherein the Zn-AI alloy composition comprises 5-35 wt.% of Al and the balance of Zn and inevitable impurities; preparing a Zn-AI alloy powder by atomization shock cooling to obtain dendritic structure powder with fine granule inside; and by using high-speed inert gas and/or reducing gas as carrier gas, carrying out high-speed injection on a steel structural member surface to deposit the Zn-AI alloy coating which is 100-500 mu m thick. - However, the anticorrosion properties of the aluminum-zinc metallic coating are not sufficient. Indeed, the high amount of zinc in the coating allows a sacrificial protection allowing a decrease or a prevention of red rust. Nevertheless, especially for metallic substrates used in very corrosive atmospheres, they have to be protected by a coating having a sacrificial protection and a barrier effect in order to significantly reduce the corrosion problems and therefore to greatly increase the life time of the metallic substrate.
- Thus, the object of the invention is to provide a coated steel substrate having an improved resistance to corrosion, in particular having a barrier effect and a sacrificial protection. The object is also to provide a coated steel substrate having a longer life time especially in corrosive atmosphere. Finally, it also makes available an easy to implement method for the manufacture of such coated steel substrates.
- In terms of sacrificial protective corrosion, electrochemical potential has to be at least 50mV more negative than the potential of the metallic substrate. For example, in case of steel substrate, a maximum potential of -0.78V with respect to a saturated calomel electrode (SCE) is needed. It is preferable not to decrease the potential at a value of -1.4V/SCE, even -1.25V/SCE which would involve a fast consumption and would finally decrease the period of protection of steel.
- This object is achieved by providing a steel substrate bearing a cold sprayed coating according to
claim 1. The steel substrate bearing a cold sprayed coating can also comprise any characteristics ofclaims 2 to 8. - Another object is achieved by providing a method for the manufacture of a steel substrate bearing a cold sprayed coating according to claim 9. The method can also comprise any characteristics of claims 10 to 20. Finally, the object is achieved by providing the use of a steel substrate bearing a cold sprayed coating according to claim 21.
- Other characteristics and advantages of the invention will become apparent from the following detailed description of the invention.
- To illustrate the invention, various embodiments and trials of non-limiting examples will be described, particularly with reference to the following Figures:
-
Figure 1 is a schematic illustration of a cold spray device. -
Figure 2 is a schematic illustration of a powder particle having a spherical shape. -
Figure 3 is a schematic illustration of a powder particle having an angular shape. -
Figure 4 is a schematic illustration of a powder particle having a spheroidal shape. - In all the figures, the thickness of the layers represented is exclusively for purposes of illustration and cannot be considered to be a representation of the different layers to scale.
- The following terms will be defined:
- "Porosity" is a measure of the void (i.e. "empty") spaces in a material, and is a fraction of the volume of voids over the total volume, as a percentage between 0 and 100% by volume,
- the hardness can be defined by HV(0.1) or HV(0.01) according to the norm ISO 6507-1 and
- "wt.%" means the percentage by weight.
- The invention relates to a metallic substrate bearing a cold sprayed coating comprising:
- from 1.0 to 10.0% by weight of zinc,
- between 10 and 20% by weight of Al2O3,
- the balance being aluminum,
- the coating not comprising magnesium,
- said coating having a porosity between 0.9 and 8.0% and
- wherein the microstructure of the coating does not comprise an intermetallic diffusion layer made of Fe and Al.
- Without willing to be bound by any theory, it seems that the cold sprayed coated metallic substrate according to the present invention has a sacrificial protection and a barrier effect mainly due to the presence of zinc, Al2O3 and aluminum in the above specific amounts. Indeed, it is believed that Zn having a low electrochemical potential in addition to Al having a high barrier effect with specific proportions will provide a higher corrosion protection in corrosive areas Thus, the metallic substrate is well protected against corrosion, the appearance of the red rust is prevented or at least significantly delayed. Moreover, it seems that Al2O3 can improve the hardness of the coating so as to obtain a better adhesion of the coating on the metallic substrate. Finally, it is believed that the presence of magnesium will not provide a sufficient resistance corrosion.
- The coating can comprise unavoidable impurities. For example, the optionally impurities are chosen from Fe, Si, Cu, the content by weight of each additional element being inferior to 0.3% by weight.
- Preferably, the coating comprises from 2.0 to 8.0, more preferably from 3.0 to 6.0% by weight of zinc.
- Preferably, the coating has a porosity between 3.0 and 7.0%.
- On the contrary to conventional deposition processes, in particular the hot-dip deposition, the microstructure of the coating does not comprise an intermetallic diffusion layer made of Fe and Al. More preferably, the microstructure of the coating does not comprise an intermetallic diffusion layer made of FeAl3 and Fe2Al5. More preferably, the coating microstructure does not include an intermetallic layer between the coating and the metallic substrate. Without willing bound by any theory, it seems that the specific microstructure of the present invention prevents the risks of coating brittleness and therefore improves the adherence of the coating on the metallic substrate.
- Advantageously, the thickness of the coating is between 100 and 350µm, more preferably between 150 and 250µm.
- Preferably, the coating hardness is between 40 and 80HV(0.1) and more preferably between 50 and 70HV(0.1). For example, the hardness of the coating is between of 60HV(0.1).
- The metallic substrate is a steel substrate.
- In a preferred embodiment, the metallic substrate is a part chosen from: a piling, a wire, a plate, a tube and a beam.
- The method for the manufacture of a steel substrate bearing a cold sprayed coating according to the present invention comprises the following step:
- A. The provision of a metallic substrate,
- B. Optionally, a surface preparation step of the metallic substrate,
- C. The cold spray deposition of a powder mixture comprising from 1.0 to 10.0% by weight of zinc, between 10 and 20% by weight of Al2O3, the powder not comprising magnesium, the balance being aluminum, on the metallic substrate, said deposition being performed in a cold spray device comprising a heating section, a powder feeder and a supersonic nozzle.
- Preferably, when step B) is performed, the surface treatment is chosen from: shot blasting, pickling polishing, sand blasting and grinding. In this case, preferably, the surface preparation step is performed so as to obtain a surface roughness of the metallic substrate above 5µm, more preferably between 5 and 30µm and advantageously between 10 and 20µm. Indeed, without willing to be bound by any theory, it is believed that the surface preparation modified the surface texture of the metallic substrate allowing an increase of the coating adhesion. In this embodiment, the surface treatment is preferably shot basting.
- Additionally, usually, the steel substrate can comprise an oxide layer on its surface originating from the elaboration route of the metallic substrate. In this case, it is believed that the surface preparation can remove oxides present on the metallic substrate to further improve the coating adhesion on the metallic substrate. For example, when the metallic substrate is a steel substrate, a layer of calamine is generally formed after the hot-rolling. In this case, the surface preparation can remove the millscale layer.
- Advantageously, the step C) comprises the following sub-steps:
- i. The injection of at least one gas in the cold spray device, said gas being under pressure,
- ii. The heat treatment of a first part of the gas at a temperature between 200 and 600°C in a heating section,
- iii. the transport of the second part of the gas through the powder feeder section so as to carrier the powder mixture,
- iv. The mixing of the first and the second parts of gas before the ejector of the supersonic nozzle and
- v. The acceleration of the mixing gases comprising the powder mixture at supersonic speed through the ejector of the supersonic nozzle so as to deposit the powder mixer on the metallic substrate.
-
Figure 1 illustrates a typical cold spray device wherein preferably, in step C), at least one gas under pressure is injected in the cold spray device. - Preferably in step C.i), the gas is chosen among: nitrogen, argon, helium, air or a mixture thereof.
- Advantageously, the pressure of the gas is between 1 and 10 MPa. For example, the pressure of the gas is between 2 and 7 MPa.
- Then, advantageously, in step C.ii), a first part of the gas is heated in the
heating section 1 at a temperature 200 and 600°C, more preferably between 300 and 500°C and for example of 400°C. - Preferably, in step C.iii), the second part of the gas navigates through the powder the
feeder section 2 in order to carrier the powder mixture. - In a preferred embodiment, steps C.ii) and C.iii) are performed simultaneously.
- Preferably, the first part represents above 60% by volume of the gas and the second part represents below 40% by volume of the gas. More preferably, the first part represents above 70% by volume of the gas and the second part represents below 30% by volume of the gas. Advantageously, the first part represents above 80% by volume of the gas and the second part represents below 20% by volume of the gas.
- Then, advantageously in step C.v), the first and the second parts of gas are mixed before the ejector of the
supersonic nozzle 3. - After, preferably, the mixing gases comprising the powder mixture crosses the ejector of the
supersonic nozzle 4 resulting in an acceleration of the gases at supersonic speed. Usually, the supersonic nozzle is a tube that is pinched in the middle, making a carefully balanced, asymmetric hourglass shape. Thus, the powder mixture particles impact themetallic substrate 4 to create a coating. - Advantageously, the supersonic speed is between 350 and 1200m.s-1, preferably between 400 and 1000m.s-1 and more preferably between 400 and 850m.s-1.
- In a preferred embodiment, the distance projection between the ejector supersonic and the metallic substrate is between 10 and 50mm, more preferably between 20 and 40mm and for example of 30mm.
- Preferably, the projection angle between the supersonic nozzle and the metallic substrate is between 70 and 110°.
- Preferably, the powder mixture comprises from 2.0 to 8.0, more preferably from 3.0 to 6.0% by weight of zinc.
- The coating comprises between 10 and 20% by weight of Al2O3.
- Preferably, the powder particles shape is spherical, spheroidal or angular.
Figure 2 illustrates a spherical powder particle.Figure 3 illustrates an example of angular powder particle. For example, an angular particle can have a hexagonal shape, a cubic shape or a triangular shapeFigure 4 illustrates a spheroidal powder particle. - Advantageously, the powder particles have a size above 10µm, more preferably between 10 and 150µm and more preferably between 10 and 100µm.
- Advantageously, the hardness of the powder mixer is between 30 and 50HV(0.01).
- The cold spray method according to the present invention can be used locally on the metallic substrate. In other words, it is possible to deposit the coating according to the present invention only on specific areas in order to obtain a metallic substrate having at least one coated area, the reminder being none coated. In this case, the productivity of the cold spray method increases. For example, it can be used on piling products in order to protect preferentially at least one specific area, the one subjected to the corrosion medium.
- Moreover, it is also possible to deposit an additional coating on at least one specific area of a metallic substrate being already coated in order to highly improve the corrosion resistance in area(s) that will be subjected to very corrosive atmospheres.
- Finally, sometimes, the coating of a metallic substrate can be damaged. It can be due to scratches for example during the transport or during the building of metallic structures. In this case, with the method according to the present invention, it is possible to repair the metallic coating by depositing the cold sprayed coating on the damaged area(s). The local deposition of the coating on the metallic substrate with the method according to the present invention is easy to implement and quick improving the productivity.
- According to the present invention, the cold sprayed metallic substrate can be used for the manufacture offshore structure, offshore wind power, Marine current power, hull of a boat, coastal and port infrastructure, quay wall and, underground structure, rail and anchorage.
- The disclosure will now be explained in trials carried out for information only.
- The examples and trials are not according to the invention.
- For all samples, the metallic substrate is a steel substrate having the following composition according to the EN 10248-1 norm:
C (wt.%) Si(wt.%) Mn(wt.%) S(wt.%) P(wt.%) 0.18 0.21 1.32 0.003 0.013 -
Trial 1 is a cold sprayed coated steel sheet wherein the coating comprising 3.9% by weight of Zn, the balance being Al. -
Trial 2 is a cold sprayed coated steel sheet wherein the coating comprising Al. -
Trial 3 is a cold sprayed coated steel sheet wherein the coating comprising 15% by weight of Al2O and Al. - For all Trials, the steel sheet was first shot blasted to obtain a surface roughness of 14.5µm. Then, the powder mixture was deposited by cold spray process. The parameter of the cold spray process was as follows:
- gas: nitrogen at a pressure of 2.5MPa,
- heat treatment at a temperature of 400°C,
- second part of the carrier gas: 7% by volume,
- projection distance: 30mm,
- projection angle: 90°,
- supersonic speed: between 450 and 800m.s-1.
-
Trials 1 to 3 were prepared and subjected to an electrochemical potential test. - A test consisting in measuring the electrochemical potential of the coated steel surface sheet was realized. Steel sheets and coatings were separated and dipped in a solution comprising 5% by weight of sodium chloride at pH 7. A saturated calomel electrode (SCE) was also immersed into the solution. The coupling potential of the surface was measured over time. Results are shown in the following Table 1 :
Trials Composition Powder mixture Coating Al Zn Al2O3 size (µm) shape Hardness (HV) Thickness (µm) Porosity (%) Hardness (HV) Coupling potential (V/SCE) 1 95 3.9 - Between 15-55 spherical 40 200 1.9 60 -1.01 2 >99 - - Between 15-55 spherical 28 200 5.2 60 -0.73 3 85 - 15 Between 15-55 spherical ND 200 2.7 63 -0.76 ND: Not Done. -
Trial 1 according to the present invention is highly sacrificial compared toTrials 1 to 3. Coupling potential ofTrial 1 is under -0.78V/SCE as required. -
Trials 1 to 3 were prepared and subjected to a corrosion test to evaluate the protection of the coated steel sheets. - Firstly, all trials were scratched through the coating till the metallic substrate on a width of 2mm. Then, a test, consisting in submitting coated steel sheet to corrosion cycles according to the norm ATSM-B-117, was realized. All Trials were incorporated in an enclosure wherein a salt fog was sprayed. The salt fog comprises 5% by weight of NaCl. The salt fog had the following characteristics:
- pH = 7,
- temperature = 35°C and
-
debit flow 1,5ml/h. - The presence of corrosion on coated steel sheet around scratches was observed by naked eyes: 0 means excellent, in other words, there is little or no corrosion around scratch and 5 means very bad, in other words, there is a lot of corrosion around scratch. Results are shown in the following Table 2:
Number of days Trials 1 3 8 1 0 0 0 2 0 1 2 3 0 1 2 -
Trial 1 shows excellent protection against corrosion when compared toTrials Trial 2 shows red rust after 15 days of salt spray test.
Claims (21)
- A metallic substrate bearing a cold sprayed coating comprising:- from 1.0 to 10.0% by weight of zinc,- between 10 and 20% by weight of Al2O3,- the balance being aluminum,- the coating not comprising magnesium,- said coating having a porosity between 0.9 and 8.0%,- wherein the microstructure of the coating does not comprise an intermetallic diffusion layer made of Fe and Al and- wherein the metallic substrate is a steel substrate.
- A metallic substrate bearing a cold sprayed coating according to claim 1, wherein the coating comprises from 2.0 to 8.0% by weight of zinc.
- A metallic substrate bearing a cold sprayed coating according to claim 2, wherein the coating comprises from 3.0 to 6.0% by weight of zinc.
- A metallic substrate bearing a cold sprayed coating according to anyone of claims 1 to 3, wherein the coating has a porosity between 3.0 and 7.0%.
- A metallic substrate bearing a cold sprayed coating according to anyone of claims 1 to 4, wherein the microstructure of the coating does not comprise an intermetallic diffusion layer.
- A metallic substrate bearing a cold sprayed coating according to anyone of claims 1 to 5, wherein the thickness of the coating is between 100 and 350µm.
- A metallic substrate bearing a cold sprayed coating according to anyone of claims 1 to 6, wherein the coating hardness is between 40 and 80 HV(0.1).
- A metallic substrate bearing a cold sprayed coating according to claims 1 to 7, wherein the metallic substrate is a part chosen from: a piling, a wire, a plate, a tube and a beam.
- A method for the manufacture of a steel substrate bearing a cold sprayed coating comprising the following step:a. The provision of a steel substrate,b. Optionally, a surface preparation step of the steel substrate,c. The cold spray deposition of a powder mixture, comprising from 1.0 to 10.0% by weight of zinc, between 10 and 20% by weight of Al2O3, the coating not comprising magnesium, the balance being aluminum, on a steel substrate, said deposition being performed in a cold spray device comprising a heating section, a powder feeder and a supersonic nozzle.
- A method according to claim 9, wherein step C) comprises the following sub-steps:i. The injection of at least one gas in the cold spray device, said gas being under pressure,ii. The heat treatment of a first part of the gas at a temperature between 200 and 600°C in a heating section,iii. the transport of the second part of the gas through the powder feeder section so as to carrier the powder mixture,iv. The mixing of the first and the second parts of gas before the ejector of the supersonic nozzle andv. The acceleration of the mixing gases comprising the powder mixture at supersonic speed through the ejector of the supersonic nozzle so as to deposit the powder mixer on the steel substrate.
- Method according to claim 9 or 10, wherein when step B) is performed, the surface treatment is chosen from: shot blasting, pickling polishing, sand blasting and grinding.
- Method according to claim 10 or 11, wherein in step C.i), the gas is chosen among: nitrogen, argon, helium, air or a mixture thereof.
- Method according to anyone of claims 10 to 12, wherein in step C.i), the pressure of the gas is between 1 and 10 MPa.
- Method according to anyone of claims 10 to 13, wherein in step C.ii), the first part represents above 60% by volume of the gas and the second part represents below 40% by volume of the gas.
- Method according to anyone of claims 10 to 14, wherein in step C.v), the supersonic speed is between 350 and 1200m.s-1.
- Method according to anyone of claims 10 to 15, wherein in step C.v), the distance projection between the ejector supersonic and the metallic substrate is between 10 and 50mm.
- Method according to anyone of claims 10 to 16, wherein in step C.v), the projection angle between the ejector supersonic and the metallic substrate is between 70 and 110°.
- Method according to anyone of claims 9 to 17, wherein the powder mixture shape is spherical, spheroidal or angular.
- Method according to anyone of claims 9 to 18, wherein the powder mixture has a size above 10µm.
- Method according to anyone of claims 9 to 19, wherein the hardness of the powder mixer is between 30 and 50HV (0.01).
- Use of a metallic substrate bearing a cold sprayed coating according to anyone of claims 1 to 8 or obtainable according to anyone of claims 9 to 20, for the manufacture of offshore structure, Offshore wind power, Marine current power, hull of a boat, coastal and port infrastructure, quay wall and, underground structure, rail and anchorage.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IB2017/000818 WO2019008405A1 (en) | 2017-07-04 | 2017-07-04 | A metallic substrate bearing a cold sprayed coating |
PCT/IB2018/054907 WO2019008501A1 (en) | 2017-07-04 | 2018-07-02 | A metallic substrate bearing a cold sprayed coating |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3649272A1 EP3649272A1 (en) | 2020-05-13 |
EP3649272B1 true EP3649272B1 (en) | 2021-08-25 |
Family
ID=59523188
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18737726.2A Active EP3649272B1 (en) | 2017-07-04 | 2018-07-02 | A steel substrate bearing a cold sprayed coating |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP3649272B1 (en) |
WO (2) | WO2019008405A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9335296B2 (en) | 2012-10-10 | 2016-05-10 | Westinghouse Electric Company Llc | Systems and methods for steam generator tube analysis for detection of tube degradation |
US11935662B2 (en) | 2019-07-02 | 2024-03-19 | Westinghouse Electric Company Llc | Elongate SiC fuel elements |
US11662300B2 (en) | 2019-09-19 | 2023-05-30 | Westinghouse Electric Company Llc | Apparatus for performing in-situ adhesion test of cold spray deposits and method of employing |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2205897C1 (en) * | 2001-12-26 | 2003-06-10 | Общество С Ограниченной Ответственностью Обнинский Центр Порошкового Напыления | Coating method |
JP2007308737A (en) * | 2006-05-16 | 2007-11-29 | Toyota Motor Corp | Corrosion protection method for welded part |
FI124667B (en) * | 2011-07-06 | 2014-11-28 | Rautaruukki Oyj | Method and raw material for the manufacture of metal coating and steel product |
ITCO20130018A1 (en) * | 2013-05-17 | 2014-11-18 | Nuovo Pignone Srl | METHOD FOR THE TREATMENT OF A COMPONENT TO PREVENT THE EROSION OF SUCH A COMPONENT |
CN104946930B (en) | 2014-03-28 | 2017-10-31 | 宝山钢铁股份有限公司 | A kind of uniform composite structure zinc-aluminium protective coating and its manufacture method |
CN105624665B (en) * | 2016-03-09 | 2018-09-21 | 广州供电局有限公司 | Steel structural part surface protection coating and preparation method thereof |
-
2017
- 2017-07-04 WO PCT/IB2017/000818 patent/WO2019008405A1/en active Application Filing
-
2018
- 2018-07-02 EP EP18737726.2A patent/EP3649272B1/en active Active
- 2018-07-02 WO PCT/IB2018/054907 patent/WO2019008501A1/en active Search and Examination
Also Published As
Publication number | Publication date |
---|---|
WO2019008405A1 (en) | 2019-01-10 |
EP3649272A1 (en) | 2020-05-13 |
WO2019008501A1 (en) | 2019-01-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3649273B1 (en) | A metallic substrate bearing a cold sprayed coating | |
EP3649272B1 (en) | A steel substrate bearing a cold sprayed coating | |
US9302449B2 (en) | High corrosion resistant hot dip Zn alloy plated steel sheet | |
CN107761035A (en) | A kind of corrosion resistant fine and close thermal spray metal alloy coat and preparation method thereof completely | |
KR101819381B1 (en) | Zn ALLOY PLATED STEEL SHEET HAVING EXCELLENT BENDABILITY AND METHOD FOR MANUFACTURING SAME | |
CN107164716B (en) | Powder core wire and method for preparing high-speed electric arc spraying coating | |
CN108026625B (en) | Zn alloy coated steel material containing Mg | |
KR101746974B1 (en) | Method for preparing metal-coated steel sheet and metal-coated steel sheet prepared by the same | |
JP5640312B2 (en) | Zinc-based alloy-plated steel with excellent corrosion resistance and weldability and painted steel with excellent corrosion resistance | |
EP3359704A1 (en) | Steel sheet coated with a metallic coating based on aluminum and comprising titanium | |
KR102010078B1 (en) | Galvannealed steel sheet having exellent hydrogen crack resistance and method for producing the same | |
JP2012092403A (en) | Steel for ship having excellent coating corrosion resistance | |
CN113832372B (en) | Alloy powder, and preparation method, application and application method thereof | |
Bobzin et al. | Investigation on the cold rolling and structuring of cold sprayed copper-coated steel sheets | |
EP4079923A1 (en) | Hot dip alloy coated steel material having excellent anti-corrosion properties and method of manufacturing same | |
CN211036060U (en) | Thermal spraying rare earth alloy composite coating reinforcing steel bar | |
CN104943269B (en) | A kind of local strengthening hot rolling zinc/aluminum-plated steel plate and its manufacture method | |
CN108588625B (en) | ZnAlMgSiB anticorrosive coating for steel structure and preparation method thereof | |
JP2002080952A (en) | Home building material excellent in corrosion resistance, and home building member | |
JP2017047459A (en) | Plating welded h-shaped steel and manufacturing method of the same | |
JPS63149386A (en) | Coated steel material having superior corrosion resistance after painting | |
US20220154326A1 (en) | A coated steel substrate, a method for the manufacture of a coated steel substrate, a method for manufacture of a steel product and a steel product | |
CN108893698B (en) | ZnAlMgTiSiB anticorrosive coating for steel structure and preparation method thereof | |
JPH01283388A (en) | Blast material and highly corrosion-resistant metallic material and their production | |
KR101325400B1 (en) | Semi-alloyed hot-rolled hot-dip galvanizing steel sheet and method for manufacturing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20200204 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20210222 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602018022420 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Ref country code: AT Ref legal event code: REF Ref document number: 1423882 Country of ref document: AT Kind code of ref document: T Effective date: 20210915 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1423882 Country of ref document: AT Kind code of ref document: T Effective date: 20210825 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211125 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211227 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211125 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211126 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602018022420 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 |
|
26N | No opposition filed |
Effective date: 20220527 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20220731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220731 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230427 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220702 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230621 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230620 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20180702 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210825 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240620 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20240619 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20240619 Year of fee payment: 7 |