Corrosion-resistant sprayed coating, method for forming same and spraying device for forming same

Abstract

[Problem] To provide a corrosion-resistant coating that exhibits greater corrosion protection in saltwater environments and the like than was conventional, a method for forming the same, and a device for forming the same. [Solution] A corrosion-resistant alloy coating is formed on a substrate surface by: a) using a thermal spray gun, having a function wherein a flame including melted material particles is jetted toward a substrate, and the flame is partitioned from the open air in an upstream region on said jet path (which is to say the region in which the material particles are melted), and a function wherein, in a downstream region (the area continuing from the upstream region), the material particles and the flame are forcibly cooled by a jet-gas or jet-mist before reaching the substrate; and b) using a corrosion-resistant alloy material comprising aluminum, for the material particles.

Claims

1. A method for forming a corrosion-resistant sprayed coating, wherein a corrosion-resistant alloy sprayed coating comprising aluminum that has a porosity of 1% or less, with the surface thereof unsealed, and that forms a microstructure with a grain size of 10 m or less, is formed on a substrate surface, using a thermal spray gun having a function wherein a flame including melted material particles is jetted toward a substrate, and the flame is partitioned from the open air in an upstream region on said jet path, and a function wherein, in a downstream region, the material particles and the flame are forcibly cooled by a jet-gas or jet-mist before reaching the substrate, and although thermal spraying is performed with a corrosion-resistant alloy material comprising aluminum as the material particles, neither laser irradiation nor extrusion processing are performed, wherein at least some of the microstructure includes a nanostructure with a submicron grain size, and wherein the corrosion-resistant alloy sprayed coating comprises magnesium of 0.3 to 15 mass %, oxygen of 0.2 mass % or less, and a remaining balance of aluminum.

2. The method for forming a corrosion-resistant coating according to claim 1, wherein the corrosion-resistant alloy coating is formed on the surface of a substrate made from aluminum or an aluminum alloy.

3. The method for forming a corrosion-resistant sprayed coating according to claim 1, wherein the amount of oxygen supplied to the flame in the upstream region where the flame is partitioned from the open air is less than the amount of oxygen necessary for complete combustion.

4. The method for forming a corrosion-resistant sprayed coating according to claim 1, wherein the corrosion-resistant alloy material is supplied to the thermal spray gun in the form of a powder or a wire.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 This is a side view showing a wire-type coating formation device 1.

(2) FIG. 2 This is an enlarged assembly view showing the vicinity of the tip-nozzle of the wire-type coating formation device 1.

(3) FIG. 3 This shows the results of combined cycle tests.

(4) FIG. 4 This shows the results of polarization measurement tests.

(5) FIG. 5 This is an SEM sectional view of a sample wherein AlMg was sprayed on an iron substrate.

(6) FIG. 6 This shows the results of ferroxyl tests.

(7) FIG. 7 These are EBSP analysis maps.

(8) FIG. 8 This is a sectional view with a metallurgical microscope of a sample wherein AlMg was sprayed on an aluminum substrate.

(9) FIG. 9 This is a side view showing a powder-type coating formation device 2.

DESCRIPTION OF EMBODIMENTS

(10) Hereinafter, the present invention will be described in detail. A corrosion-resistant alloy sprayed coating is formed on a surface of a steel structure, steel plate or the like, by spraying with a coating formation device, which is a special thermal spray gun, using a material principally comprising AlMg.

(11) The wire-type coating formation device 1 used is shown in FIG. 1 and FIG. 2.

(12) In the illustrated wire-type coating formation device 1, as an external cooling means, a double nozzle comprising a tip-nozzle inner cylinder 15 and a tip-nozzle outer cylinder 16, from which a jet-gas (or mist) is output for external cooling of a flame or the like, is mounted on the forward end of a flame-type thermal spray gun 10, to which a material for coating is supplied as a wire.

(13) While omitted in the drawings, the wire-type flame spray gun 10 is connected to a material-wire supply pipe 11, in which the material-wire that will be thermally sprayed is supplied by way of a gas turbine (for example, using nitrogen), an acetylene supply pipe 12a that serves as fuel, an oxygen supply pipe 12b, and a supply pipe 13, for an internal cooling gas (for example nitrogen). A gas cap 14 is provided at the front end of the wire-type flame spray gun 10, from which, as shown in FIG. 2, the flame 17 and the molten material (resulting from melting the aforementioned material wire) are jetted. The aforementioned internal cooling gas is expelled from a position bordering the inside of the gas cap 14, so as to cool the gas cap 14 and regulate the temperature of the flame 17. The gas cap 14 is fixed on the wire-type flame spray gun 10 in the vicinity of the forward end thereof, for example by way of threading, on the tip-nozzle inner cylinder 15, and the tip-nozzle outer cylinder 16 is mounted on the wire-type flame spray gun 10 by way of this tip-nozzle inner cylinder 15.

(14) Jet-gas (or jet-mist) for external cooling is supplied to the conical gap between the tip-nozzle inner cylinder 15 and the tip-nozzle outer cylinder 16, and is ejected from an annular jet opening at the front, in the direction of the forward centerline of the flame 17. Thus, the coating formation device 1, which includes the tip-nozzle outer cylinder 16 and the like, performs the characteristic functions of; a) supplying corrosion-resistant alloy material by wire; b) supplying the aforementioned jet-gas or jet-mist that cools the melted material particles and the flame so as to produce a gradually narrowing cylindrical flow from the outer periphery of the tip-nozzle, directed toward the forward (downstream) center; and c) supplying the jet-gas or jet-mist as an annular jet, concentric with the jetted flame (forming a circle that is concentric with the flame, at outside the flame, in a cross-sectional view) at an angle such as to intersect the centerline of the flame at a distance from the flame jet opening that is 3 to 7 times the diameter of the flame.

(15) The tip-nozzle outer cylinder 16 shown in FIG. 1 expels a jet-gas (for example nitrogen) or a jet-mist (for example water mist) as described above, whereby the forward half of the flame 17 (see FIG. 2) that is jetted from the wire-type flame spray gun 10, which is to say the flame 17 in a melting region in which the material-wire is melted, can be partitioned from the open air. A stainless steel double nozzle is used in this embodiment, and, as described above, the tip-nozzle inner cylinder 15 and the tip-nozzle outer cylinder 16 are arranged concentrically, so that a gap is provided between the two, and this gap serves as a flow path for the jet-gas or jet-mist, and also as a jet opening for this gas. A cooling gas flows between the cylinders of the double nozzle (tip-nozzle inner cylinder 15 and tip-nozzle outer cylinder 16), whereby temperature rises in the tip-nozzle inner cylinder 15 and the like are prevented. The gap between the cylinders of the double nozzle (tip-nozzle inner cylinder 15 and tip-nozzle outer cylinder 16) is provided oriented toward the centerline of the flame 17, and the jet-gas or jet-mist is positively jetted in the direction of the center of the flame 17. The intersection of the jet-gas or jet-mist with the centerline of the flame 17 is positioned forward from the jet opening for the flame 17 by a distance that is 3 to 7 times the diameter of the flame 17, whereby the jet-gas or jet-mist rapidly cools the fully melted material at the forward end region of the flame 17, which has the effect of making the structure thereof more fine.

(16) When the wire-type coating formation device 1 in FIG. 1 is used, a sprayed coating 18 can be formed on the surface of a substrate 19, as shown to the right in FIG. 2. The flame 17 that is jetted from the gas cap 14 of the wire-type flame spray gun 10 reaches the substrate 19 surrounded by jet-gas or jet-mist that is jetted from the tip-nozzle outer cylinder 16 (the jet opening described above), and therefore the amount of oxides present in the sprayed coating 18 is small. Furthermore, as described above, the grain size of the sprayed coating 18 is also reduced due to the rapid cooling.

(17) In place of the coating formation device 1 shown in FIG. 1 and FIG. 2, the coating formation device 2 shown in FIG. 9 may also be used. The coating formation device 2 is one wherein a cylindrical member 21 or the like, which may also be referred to as an outer cooling device, is mounted at the front of a powder-type flame spray gun 20. While illustration of the main unit of the thermal spray gun 20 is omitted, this is connected to a pipe that supplies a powdered material to be sprayed together with a transport gas (for example nitrogen) and supply pipes for oxygen and acetylene, which serves as the fuel, as well as a supply pipe for an internal cooling gas (for example nitrogen). The flame and the molten material (the melted powder) are jetted from the thermal spray gun 20.

(18) The cylindrical member 21, serves to partition the flame from the open air, at the forward half of the flame that is jetted by the thermal spray gun 20, which is to say, in the melting region in which the powder material is melted, and to discharge a jet-mist or jet-gas from the forward end to the rear half (the forward part) of the flame. In this embodiment, a double cylindrical pipe made from stainless steel is used as the cylindrical member 21, in which an outer pipe 22 and an inner pipe 23 are arranged concentrically, with a gap between the two. A jet-mist or a jet-gas for providing external cooling of the flame and the molten material is supplied to this gap, and is ejected from the forward end 24. In this regard, if water is dripped from fine holes 22a that are provided in the outer pipe 22, a jet-mist will be formed by way of the nitrogen gas ejector effect, and the jet-mist will flow between the outer pipe 22 and the inner pipe 23 so as to be jetted from the forward end 24.

(19) Using either the coating formation device 1 shown in FIG. 1 and FIG. 2, or the coating formation device 2 in FIG. 9, a good AlMg coating, which has excellent corrosion resistance, can be formed on the surface of a steel structure. Furthermore, a good coating can also be formed on the surfaces of substrates made from aluminum, aluminum alloys or the like, rather than steel structures. This is because the use of the formation device 1 or 2 in which the molten material and the flame are cooled by the jet-gas or jet-mist results in reduced thermal impact on the substrate.

WORKING EXAMPLES

(20) The sprayed coating is formed by way of the following procedure.

(21) First, the surface of a steel plate (substrate) is blasted with alumina grit or steel grit. Next, an AlMg material is sprayed onto the surface of the substrate with the coating formation device 1 (wire type) or 2 (powder type). Specifically, the AlMg material is melted in a reducing atmosphere by adjusting the ratio of oxygen to acetylene, which is the combustion gas, and a jet-gas or jet-mist is caused to flow along the double nozzle so as to partition the melted material from the open air, so as to form a sprayed coating on the steel plate (substrate) at a cooling rate of approximately 1,000,000 C. per second or greater.

(22) Note that, unless otherwise stated, the present invention is that wherein spraying is performed according to the conditions in Working Examples 1 to 3, and the prior art is that wherein spraying is performed according to the conditions in Comparative Examples 1 and 2. The conditions are shown in Table 1.

(23) TABLE-US-00001 TABLE 1 Working Working Working Comparative Comparative Example 1 Example 2 Example 3 Example 1 Example 2 Acetylene/oxygen 6:5 6:5 7:6 1:1 2:3 ratio Material supply Powder Wire type Powder Wire type Powder type method type type Thermal Al- Al- Al- Al- Al- spraying 5 mass % 5 mass % 5 mass % 5 mass % Mg 5 mass % Mg material Mg Mg Mg Internal cooling Nitrogen Nitrogen Nitrogen Air Air gas 70 L/min 900 L/min 70 L/min 900 L/min 70 L/min External cooling Nitrogen Nitrogen + Nitrogen + none none gas 400 L/min mist mist 900 L/min 680 L/min

(24) The properties of the AlMg coating formed on the surface of the steel plate (substrate) as described above were found by way of the following tests.

(25) 1. Combined Cycle Test

(26) Plate corrosion resistance was evaluated for a steel plate on which the sprayed coatings were provided by performing an accelerated corrosion test in accordance with JASO M 609, 610, in which cycles were repeated consisting of: saline spraying (5% aqueous solution of NaCl/35 C./100% humidity/2 hours).fwdarw.drying (65 C./25% humidity/4 hours).fwdarw.wet (high temperature) (50 C./98% humidity/2 hours), so as to evaluate Working Example 1 and Comparative Example 1. The film thicknesses of the sprayed coating on the test pieces in these tests were 150 to 200 m. Note that the test described above was performed after making scratches, that reached the steel base, on the steel plate provided with the sprayed coating by using a cutter. The coatings after the test are shown in photographs in FIG. 3. The white rusts in the Comparative Example 1 are oxides of aluminum or magnesium, suggesting that the coating was degraded early, while in Working Example 1, the results were good, with neither red rust nor white rust forming, even after 1000 hours (125 cycles).

(27) 2) CASS Test (Copper Accelerated Acetic Acid Salt Spray Test)

(28) The spray test was conducted over 48 hours, in accordance with JIS H 8502, in which a pH 3.0 test solution of 40 g/liter sodium chloride and 0.205 g/liter of copper(II) chloride was sprayed at an air saturator temperature of 63 C., and a test tank temperature of 50 C., at a spray rate of 2.0 mL/80 cm.sup.2/hour, and a compressed air pressure of 0.098 MPa. Working Example 1 and Comparative Example 1 were evaluated. In these tests, the film thicknesses of the test pieces were 250 to 300 m. Changes in the surface conditions such as discoloration, stains, corrosion, surface degradation, peeling and the like, and changes in the weight of the test pieces after the tests are shown in the following Table 2. An Al(OH).sub.3 corrosion product was formed as a result of an aluminum dissolution reaction and weight was lost as a result of the gel-like Al(OH).sub.3 running off.

(29) TABLE-US-00002 TABLE 2 Working Example 1 Comparative Example 1 Coating AlMg AlMg type Surface Good Discoloration condition Weight 1.7% 9.6% change

(30) 3) Elemental Analysis Tests

(31) The results of analysis produced by ICP emission spectrography and inert gas fusion are shown in Table 3. As per Table 3, there was no difference in the ratio of oxygen in the sprayed materials in Working Example 1 and Comparative Example 1, but in the sprayed coatings, the oxygen content in Working Example 1 was less than 0.2 mass %, while in Comparative Example 1 the oxygen content was more than 0.2 mass %. Accordingly, it can be said that oxidization of aluminum and magnesium is better prevented in Working Example 1 than in Comparative Example 1.

(32) TABLE-US-00003 TABLE 3 (mass %) Thermal spraying material Sprayed Coating Al Mg O Al Mg O Working 94.86 5.14 <0.00* 93.3 3.75 0.17 Example 1 Comparative 94.66 5.34 <0.00* 94.4 4.58 0.24 Example 1 *Below measurement limit

(33) 4) Electrochemical Measurement Tests

(34) Polarization measurements were performed for the coatings in Working Example 1 and Comparative Example 1, and the results are shown in FIG. 4. The natural potential in Working Example 1 was 1.161 V, while the natural potential in Comparative Example 1 was 1.277 V. The AlMg coating is less noble than steel, and thus provides a sacrificial corrosion protection function. Note that the natural potential of steel is from 0.4 V to 0.6 V. Since Working Example 1 is more noble than Comparative Example 1 and the protection current is suppressed more than in Comparative Example 1, diffusion of oxygen in the AlMg sprayed coating is limited, and thus improved corrosion protection life in salt water can be expected.

(35) 5) SEM Images

(36) SEM observation was performed for Working Examples 1 to 3 and Comparative Example 1, and the SEM images are shown in FIG. 5. The porosity in Working Examples 1 to 3 was 1% or less, and thus it could be confirmed that there were less pores and cracks than in Comparative Example 1.

(37) Note that a ferroxyl test was performed on Working Example 1, in accordance with JIS K 8617, in which pure water was added to 10 g of potassium hexacyanoferrate trihydrate, 10 g of potassium hexacyanoferrate and 60 g of sodium chloride, and this was brought to 1000 ml. Defects reaching the substrate can be observed as blue spots, but there were no spots in Working Example 1. The results of the ferroxyl test for Working Example 1 are shown in FIG. 6.

(38) 6) EBSP Analysis

(39) EBSP (electron back scattering pattern) analysis was performed for the coatings in Working Example 1 and Comparative Example 2, and the results are shown in FIG. 7. It was confirmed that the grain size in Working Example 1 was 10 m or less, which was a much finer grain size than that in Comparative Example 2.

(40) When spraying is performed using the coating formation device 1 or 2 in FIG. 1 and FIG. 2 or FIG. 9, the thermal impact on the substrate is low, due to the rapid cooling of the melted material and the flame by the external cooling using the jet-gas or jet-mist, and thus there will be no problems, even on substrates with low melting points (aluminum or aluminum alloys or the like).

(41) Here, with aluminum as a substrate, a sprayed coating was formed on the surface of said substrate using the same conditions as in Working Example 1. The cross-section thereof taken with a metallurgic microscope is shown in FIG. 8.