JP7171523B2 - LAMINATED BODY HAVING ALUMINUM-MAGNESIUM ALLOY SPRAYED LAYER AND METHOD FOR MANUFACTURING THE SAME METAL SPRAYED LAYER - Google Patents

Description

The present invention relates to a laminate having an aluminum-magnesium alloy sprayed layer and a method for producing the metal sprayed layer.

When performing metal thermal spraying for the purpose of anticorrosion of steel structures, it is necessary to roughen the surface of the base material in order to ensure adhesion to the base material. One of the roughening treatment methods is blasting, but blasting (ISO 8501-1) with a rust removal level of Sa3 is required to perform aluminum thermal spraying and aluminum-magnesium alloy thermal spraying directly on the base material. As a result, the blasting treatment requires a large amount of money and time, and the generated dust adversely affects the safety and health of the work and the environment. Therefore, a roughening treatment method that does not require Sa3 blasting is being studied.

As a method that does not require Sa3 blasting, there is a method of applying a roughening material. By applying this method, it becomes possible to lower the grade of blasting to Sa2 1/2 or less, and the construction time and cost required for blasting can be greatly reduced. For example, adhesion can be ensured by applying a rough surface forming material comprising inorganic particles and a binder onto the base material to form an uneven resin layer on the base material surface.

However, when the surface temperature of the base material exceeds 70°C immediately after thermal spraying, the method of applying the rough surface forming material is likely to cause degeneration and deterioration of the uneven resin layer due to heat and peeling due to the accumulation of stress in the uneven resin layer. Therefore, it is used only when the substrate surface temperature immediately after thermal spraying is 70° C. or lower (normal temperature metal thermal spraying).

As an example of normal temperature metal spraying, a method is known in which a pure zinc wire rod and a pure aluminum wire rod are simultaneously sprayed onto a base material to form a zinc-aluminum quasi-alloy (zinc:aluminum=50:50) thermal spray coating. Application of roughening materials is possible.

On the other hand, an aluminum-magnesium alloy is known as a metal thermal spray material that has excellent corrosion resistance against salt water. alloys are widely used. However, unlike the zinc-aluminum pseudo-alloy, a normal temperature metal spraying method has not been established, and a thermal spraying method is used in which the surface temperature of the base material exceeds 70° C. immediately after thermal spraying. For this reason, aluminum-magnesium alloy thermal spraying cannot use a rough surface forming material, and Sa3 blasting is necessary. has been desired.

Japanese Patent Publication No. 2-56424 Japanese Patent Publication No. 3-28507

Aluminum-magnesium alloy with a magnesium content in the mass ratio of 90:10 to 99.5:0.5 initially has a low magnesium content, so the melting point, latent heat of fusion, etc. are considered when metal spraying. The properties of the metal are close to those of pure aluminum (melting point 660°C, specific heat 917J/kg°C, latent heat of fusion 397kJ/kg), and the thermal spraying conditions are also similar.

Incidentally, pure magnesium has a melting point of 649° C., a specific heat of 1038 J/kg° C., and a latent heat of fusion of 368 kJ/kg (JWES Joint Welding Technology Q&A1000 (Japan Welding Society, 2004 data)).

However, it was found that aluminum-magnesium alloy cannot be thermally sprayed because the wire does not melt under the same voltage conditions as for pure aluminum thermal spraying. When the arc voltage was increased to melt the wire, the melting temperature rose and even the leader tip for introducing the wire melted, making it impossible to carry out continuous thermal spraying for more than 30 minutes.

An object of the present invention is to find conditions for aluminum-magnesium alloy thermal spraying that enable continuous thermal spraying at room temperature, and to provide a laminate that is protected against corrosion by the alloy.

The inventors of the present invention have found conditions under which such an aluminum-magnesium alloy (mass ratio of 90:10 to 99.5:0.5) can be arc-sprayed in a reduced pressure, and have found a method for obtaining a laminate containing a resin layer. Found it.

1. A laminate comprising at least a substrate, a resin layer containing particles having an average particle size of 10 to 150 μm, and an aluminum-magnesium alloy (mass ratio of 90:10 to 99.5:0.5) sprayed layer in this order.
2. A method for producing a metal sprayed layer of an aluminum-magnesium alloy (mass ratio of 90:10 to 99.5:0.5), wherein the temperature of the substrate surface immediately after spraying the alloy is above the atmospheric temperature and below 70 ° C. A method for producing a metal sprayed layer, comprising thermal spraying.
3. 2. The above-mentioned metal spraying is characterized in that, in the metal spraying, a wire feed speed at which a pure aluminum wire having the same diameter can be sprayed is used as a reference, and metal spraying is performed under a wire feed speed that is slower than the feed speed. A method for producing a metal thermal spray layer.
4. 4. The method for producing a metal sprayed layer according to 2 or 3 above, wherein in the metal spraying, the metal is a wire having a diameter of 0.8 to 2.0 mm.

According to the present invention, an aluminum-magnesium alloy can be arc-sprayed in reduced pressure by applying the conditions even if the apparatus for thermal spraying is different.

Embodiments of the present invention are described in detail below.

<Thermal spraying conditions>
The present invention is characterized in that the feed amount of the wire rod per unit time for arc spraying of pure aluminum under reduced pressure is used as a reference, and the feed rate is made slower than the feed rate.

Since the thermal spraying conditions are not always the same for each thermal spraying apparatus, the proper thermal spraying conditions for aluminum-magnesium alloys can be known by using the thermal spraying conditions for pure aluminum as a reference.

Generally, in order to melt a metal that does not melt, it is conceivable to increase the amount of heat input and raise the temperature, and the conditions for thermal spraying include adjustment of the feeding speed of the wire and the voltage. However, the adjustment of the voltage naturally raises the temperature of the molten metal, greatly restricting the thermal spraying equipment and the thermal spraying base material, and thermal spraying to the uneven resin layer instead of blasting cannot be performed.

On the other hand, in the method in which the feeding speed of the wire rod is slower than that of the pure aluminum wire rod, the temperature rise of the molten metal is suppressed, and thermal spraying onto the uneven resin layer becomes possible. In the present invention, by performing thermal spraying under the above conditions, the surface temperature of the base material immediately after thermal spraying can be made higher than the ambient temperature (meaning the air temperature at the working place during work) and lower than 70°C. Here, "immediately after thermal spraying" means within 10 seconds after thermal spraying on the substrate. Further, normal temperature means a temperature higher than the atmospheric temperature and lower than 70°C.

In the present invention, the reason why the behavior of the aluminum-magnesium alloy differs from that of pure aluminum under thermal spraying conditions is presumed to be the difference in thermal conductivity. Since the aluminum-magnesium alloy wire has a lower thermal conductivity than the aluminum wire, it is assumed that when the same degree of heat is applied, the aluminum-magnesium wire is less likely to conduct heat to the core than the aluminum wire.

Therefore, it is thought that the amount of heat applied to the wire per unit volume was increased by lowering the feed rate, and as a result, the heat could be transferred to the core even in the aluminum-magnesium alloy. It is also known that magnesium segregates on the surface of an aluminum-magnesium alloy, and the possibility that this is the cause cannot be denied.

Since the thermal spraying conditions for aluminum-magnesium alloys differ depending on the thermal spraying equipment, it is reasonable to use the thermal spraying conditions for pure aluminum as a standard. The wire has a diameter of 0.8-2.0 mm, preferably 1.1-1.6 mm. The wire may be substantially circular, and if the cross-sectional area is the same, the effect can be obtained with the same diameter.

The feeding speed of the wire rod is 1 to 18 m/min. It is preferable that both the cathode and the anode be fed at the same speed, and the arc voltage is preferably 15 to 45V.
It is preferable that the spray distance is 100 to 300 mm and the thickness of the spray layer is 10 to 400 μm.

The feeding speed of the wire is preferably 0.5 to 5 m/min when the pure aluminum is 8 m/min, and 1 to 10 m/min when the pure aluminum is 12 m/min. It can be appropriately determined depending on the thermal spraying model within the range of 5 to 95% of the feed rate.

<Base material>
The substrate used in the present invention refers to all substrates that can be thermally sprayed, such as steel plates, non-ferrous metals, inorganic building materials, wood materials, plastics, ceramics, glass, and paper. For example, steel plates include black steel plates, dull steel plates, cold-rolled steel plates, stainless steel plates, and cast steel plates, as well as surface-treated steel plates such as tin plates, galvanized steel plates, painted steel plates, and laminated steel plates, and non-metals such as aluminum and copper. and their alloy plates. Inorganic building materials can be applied to slate board, silica glass board, gypsum slag board, extruded cement board, GRC board, gypsum board, mortar board, lightweight cellular concrete board, rock wool board, glass board and ceramic board.

As the wood-based material, in addition to natural wood boards such as beech, lauan, and agathis, veneer plywood, particle board, hard board, tep board, decorative plywood, and the like can be used. Examples of plastics that can be used include acrylic resin, polyvinyl chloride, polystyrene, ABS, nylon, polypropylene, phenol resin, glass fiber-reinforced epoxy resin, and polyphenyleoxide (PPO).

As for the shape of the base material, in addition to the flat plate, it is preferable to have a three-dimensional pattern such as embossing or stucco pattern, so that the metallic luster of the thermal spray layer and the recessed part of the thermal spray layer ( The contrast with the colored non-metallic glossy part of the colored paint film remaining on the non-polished part) can be provided to create a design appearance.

Substrates obtained by combining the above materials, for example, plastic foam and decorative plywood, or substrates in which paper, plastic, cloth, etc. are bonded to an inorganic substrate are also included in the scope of the substrate of the present invention.

<Resin layer>
Since the metal sprayed layer adheres to the base material by the anchor effect, if the base material is smooth, a resin layer (hereinafter also referred to as an uneven resin layer) is formed by applying a roughening material to the surface of the base material. RSm (average distance between irregularities)/Rz _JIS (ten-point average roughness) of the layer should be ≤5.0, preferably RSm/Rz _JIS ≤3.5.

Blasting itself requires a high level of skill and takes a long time, and the large amount of dust generated by blasting poses not only safety and health problems, but also environmental pollution. , it is preferable to form an uneven resin layer.

On the substrate, a coating composition containing 25 to 400% by volume of particles with a particle diameter of 10 to 150 μm with respect to the resin is applied at a ratio of 10 to 400 g / m ² to obtain an uneven resin layer RSm (average of unevenness spacing)/Rz _JIS (ten-point average roughness)≦5.0.

If the base material is an inorganic building material with strong alkalinity such as a slate plate, the metal sprayed layer may be discolored by the alkali. In addition, if the substrate is a steel plate, electrical corrosion may occur depending on the type of thermal spray layer. preferable.

The resin layer of the present invention contains particles having an average particle diameter of 10 to 150 μm. Nitrides, carbides and the like can be mentioned. Specific examples include aluminum oxide, silicon oxide, iron oxide, silicon carbide, and boron nitride.

Powders of acrylic resin, styrene resin, epoxy resin, polyethylene, etc. may be used depending on the solvent composition of the coating composition for forming the resin layer. These particles can be used singly or as a mixture of two or more. The use of silica sand, alumina, silicon carbide and the like is particularly preferred.

The average particle size of the particles in the present invention is in the range of 10-150 μm, preferably 30-100 μm. In addition, the average particle size in the present invention is a volume particle size measured by a laser diffraction scattering method.

In the present invention, the particles are 25 to 400% by volume [20 to 80% in pigment volume concentration (PVC)], preferably 65 to 150% by volume [in terms of pigment volume concentration (PVC)], based on the resin described later. 40 to 60%].

The resin used in the present invention is not particularly limited as long as it has a certain degree of dryness, hardness, adhesion, water resistance and durability. Specific examples include thermoplastic acrylic resins, vinyl resins, chlorinated rubbers, alkyd resins, which are one-liquid resins that dry at room temperature, unsaturated polyester resins, which are two-liquid curing resins, acrylic-urethane resins, polyester-urethane resins, and epoxy resins. Resins, thermosetting resins such as melamine-alkyd resins, melamine-acrylic resins, melamine-polyester resins, acrylic resins, and acrylic-urethane resins. These can be used singly or as a mixture of two or more.

Especially preferred are epoxy resins (in combination with curing agents such as polyamide resins and amine adducts), acrylic-urethane resins, acrylic resins, etc., which are thermoplastic during metal spraying and which allow the sprayed metal particles to enter the film and cure after spraying. .

To the coating composition of the present invention, an organic solvent, water, etc. for dissolving or dispersing the resin are added, if necessary, as components other than the resin. Additives such as dyes, pigments, dispersants, anti-foaming agents and anti-sagging agents (thixotropic agents) can also be used in combination.

In the present invention, the coating composition is prepared by adding a solvent or dispersion medium, various additives, etc., to the resin and particles, if necessary, and mixing them by a usual dispersing and mixing method.

The coating composition of the present invention is applied onto a substrate by a conventional method. In particular, it is preferable to employ the air spray method because it enables the formation of a discontinuous film.

In the present invention, the coating amount of the coating composition should be 10 to 400 g/m ² . It is preferably 25-300 g/m ² , particularly preferably 20-150 g/m ² .

In the present invention, Rsm (average spacing of unevenness)/Rz _JIS (ten-point average roughness) of the uneven resin layer after application of the composition is within the range of ≤ 5.0, preferably Rsm/Rz _JIS ≤ 3.5. It is necessary. In the present invention, Rsm and Rz _JIS are defined in JIS B-0601 (2001), and were measured under an atmosphere of 23° C. and 50 RH% with Surftest SJ-301 manufactured by Mitutoyo Corporation.

<Overcoat layer>
In the present invention, it is preferable to form an overcoat layer by further coating at least one layer of synthetic resin paint on the metal sprayed layer for sealing pores. It is known that a metal sprayed layer usually has irregularities with a surface roughness of about 100 μm in Rz _JIS , and many pores (the pores often reach the underlying surface).

Therefore, in the present invention, in order to protect the metal sprayed layer, it is necessary to close the recesses and pores with a synthetic resin paint, thereby remarkably improving the protective effect of the metal sprayed layer. Moreover, depending on the conditions of use, it is also possible to apply a surface coating.

The application of the synthetic resin paint in the present invention includes not only covering the entire surface of the metal sprayed layer, but also filling and applying (sealing) only the recesses and pores of the metal sprayed layer.

In the method of the present invention, the surface of the metal sprayed layer can be coated as it is. It is preferable to apply an intermediate coating and a top coating as necessary. It is also a preferred method to polish the metal sprayed layer before coating in order to minimize the unevenness of the metal sprayed layer.

This treatment eliminates protrusions on the surface of the metal sprayed layer, prevents the sprayed metal from being exposed on the surface after the surface is coated, and makes it possible to completely protect the surface with a thinner coating film. It can be greatly improved. As a polishing method, any means commonly used for polishing metal surfaces, such as abrasive paper, abrasive cloth, wire brush, belt sander, and sand grinder, can be used.

As the synthetic resin paint used in the method for producing the overcoat layer of the present invention, any known synthetic resin paint generally available on the market can be used.

For example, bisphenol-type epoxy resin, phenol novolac-type epoxy resin, polyglycol-type epoxy resin, ester-type epoxy resin, etc. are used as a vehicle, or bituminous-modified or urethane-modified, amine adduct, polyamine. Epoxy resin paints containing amino-based curing agents such as polyamide resins or polyisocyanate curing agents; Chlorinated rubber paints mixed with rosin, coumarone-indene resins, phenolic resins, petroleum resins, plasticizers, etc.; Chlorinated rubber paints; Vinyl chloride resin paints using vinyl homopolymers or copolymers of vinyl chloride and vinyl acetate, vinylidene chloride, etc. as the binder; monomers such as acrylic acid or methacrylic acid, their alkyl esters, styrene, vinyltoluene, etc. Acrylic resin paint with selected two or more copolymers as a vehicle; a reaction product obtained by condensation reaction of polybasic acids such as phthalic acid, polyhydric alcohols such as glycerin, and fatty acids as a vehicle Alkyd resin paints; Polyester resin paints that use products obtained by the condensation reaction of polybasic acids and polyhydric alcohols as a binder; Polyester polyols, polyether polyols, acrylic polyols, etc. (including bituminous modification) with a curing agent; Room-temperature curing or heat-curing type fluorine, fluorinated, with polyisocyanate or melamine resin as a curing agent, with hydroxyl-containing fluorine copolymer as the main component Fluorocarbon resin paints using vinylidene resins, etc. as colorants; Silicone resin paints, other silicone resins, silicone-modified alkyd resins, silicone-modified acrylic resins, etc. as colorants; Phenol resins, melamine resins, etc. mentioned.

If necessary, the synthetic resin paint of the present invention may be mixed with various additives such as coloring pigments, extender pigments, dyes, leveling agents, ultraviolet absorbers and dispersion stabilizers. The synthetic resin paint used in the present invention may be solvent-based, water-soluble, water-dispersed or non-solvent-based. Furthermore, the synthetic resin paint may be either of the normal temperature drying type or the forced drying (including heating) type.

(Experimental example 1-1)
After grit blasting an SS400 steel plate of 300 × 300 × 3.2 mm with a rust removal degree of Sa3, an aluminum-magnesium alloy layer was formed using a reduced pressure arc spraying apparatus A1 (SX-200 manufactured by Sunmeta Co., Ltd.) as follows. It was prepared as follows.

First, a pure zinc wire rod and a pure aluminum wire rod having a diameter of 1.3 mm were thermally sprayed by the above apparatus (reference 1-1). The conditions under which continuous thermal spraying was possible for 30 minutes were a feed rate of 8 m/min, an arc voltage of 15 V, an arc current of 120 A, an air pressure of 7 kg/cm ² , and an air flow rate of 1 m ³ /min (spraying distance of 200 mm).

Under the conditions of this standard 1-1, the result of spraying a pure zinc wire rod (Zn wire rod), a pure aluminum wire rod (Al wire rod) and an aluminum-magnesium alloy (95:5) wire rod (AlMg alloy wire rod) with a diameter of 1.3 mm is shown. Table 1 shows. Whether thermal spraying was possible was judged according to the following criteria.
○: Continuous thermal spraying possible for 30 minutes or more △: Thermal spraying possible, but continuous thermal spraying impossible for 30 minutes or more ×: Thermal spraying impossible The applicability to the uneven resin layer was also evaluated.
○: Substrate temperature immediately after thermal spraying is 70 ° C. or less ×: Substrate temperature immediately after thermal spraying exceeds 70 ° C. (Possibility of peeling due to deterioration and deterioration of the uneven resin layer due to heat and stress accumulation in the uneven resin layer (evaluated as not applicable due to

As shown in Table 1, thermal spraying at room temperature became possible when the feeding speed of the wire rod was slowed with respect to the thermal spraying conditions of the pure zinc wire rod and the pure aluminum wire rod. It should be noted that simply increasing the voltage does not enable room-temperature thermal spraying, and the effect of the feed rate of the wire has been clarified.

(Experimental example 1-2)
Aluminum-magnesium alloy (95:5) wires with different diameters were thermally sprayed under the conditions of Experimental Example 1-1. Table 2 shows the results.

When a wire with a diameter of 2.0 mm is thermally sprayed under the conditions of Reference 1-1 and Example 1, the amount of heat per unit volume of the wire is small and the wire cannot be melted. gone. As a result, in the aluminum-magnesium alloy wire rod, when the feeding speed of the wire rod is slowed down with respect to the thermal spraying conditions of the pure zinc wire rod and the pure aluminum wire rod, similar to the tendency of the thermal spraying conditions of the 1.3 mm diameter wire rod, The surface temperature of the base material became room temperature, and thermal spraying onto the uneven resin layer became possible.

(Experimental example 2-1)
In Experimental Example 2-1, grit blasting was performed with Sa2 1/2 instead of Sa3 in Experimental Example 1, and then the following resin layer was provided.
80 g of xylene, 60 g of methyl ethyl ketone, and 25 g of butanol were added to 100 g of an epoxy resin (Epicron 4051, manufactured by Dainippon Ink and Chemicals, epoxy equivalent of 950) and dissolved, and then 10 g of a polyamide resin (Epicure 892, manufactured by Celanese, active hydrogen equivalent of 133) was added to prepare. 275 g of epoxy-polyamide resin B having a heating residue of 40% (resin solid content volume of 100 cm ³ ) and 221 g of silicon carbide having an average particle diameter of 48 μm (green silicon carbide CG320 manufactured by Nagoya Grinding Equipment Industry, specific gravity 3.16) (particle volume of 70 cm ³ , PVC41) %) were sufficiently stirred to prepare a resin composition A.

Then, 60 g/m ² of this resin composition A was applied to a 300 × 300 × 3.2 mm SS400 steel plate with an air spray, and the average spacing of unevenness on the surface (RSm) was 280 µm, and the ten-point average roughness (Rz _JIS ) was set to 120 μm. At this time, the surface roughness (RSm/Rz _JIS ) is 2.3.

A pure zinc wire rod and a pure aluminum wire rod with a diameter of 1.3 mm were sprayed onto this uneven resin layer using a reduced pressure arc spraying apparatus A2 (manufactured by Daihen Co., Ltd. AS-400) in the same manner as in Experimental Example 1. (Standard 2-1).
A pure zinc wire rod, a pure aluminum wire rod and an aluminum-magnesium alloy (95:5) wire rod having a diameter of 1.3 mm were thermally sprayed under the conditions of this standard 2-1. Table 3 shows the results.

As shown in Table 3, thermal spraying onto the resin layer at room temperature became possible when the feeding speed of the wire rod was slowed with respect to the thermal spraying conditions of pure zinc and pure aluminum. It should be noted that thermal spraying is not possible simply by increasing the voltage, and the effect of the feed rate of the wire has been clarified.

(Experimental example 2-2)
Aluminum-magnesium alloy (95:5) wires with different diameters were thermally sprayed under the conditions of Experimental Example 2-1. Table 4 shows the results.

When a wire with a diameter of 2.0 mm is thermally sprayed under the conditions of Reference 2-1 and Example 3, the amount of heat per unit volume of the wire is small and the wire cannot be melted. did As a result, similar to the tendency of the thermal spraying conditions for the wire rod with a diameter of 1.3 mm, in the aluminum-magnesium alloy wire rod, when the feeding speed of the wire rod is slowed down with respect to the thermal spraying conditions for pure zinc and pure aluminum, the uneven resin layer at room temperature It became possible to thermal spray to

Claims (1)

A method for producing a laminate having at least a base material, a resin layer and a thermal spray layer,
the thermal spray layer is made of an aluminum-magnesium alloy with a mass ratio of aluminum to magnesium in the range of 90:10 to 99.5:0.5;
A ratio of 10 to 400 g/m ² of a coating composition in which the resin layer contains 25 to 400% by volume of metal, alloy, oxide, nitride, or carbide particles with a particle diameter of 10 to 150 μm with respect to the resin. is applied, and the surface roughness is RSm (average spacing of unevenness) / RzJIS (ten-point average roughness) ≤ 5.0.
The thermal spray layer is an aluminum-magnesium alloy wire having a diameter of 0.8 to 2.0 mm, fed at a feed rate of 1 to 5 m/min, an arc voltage of 15 to 45 V, and a spray distance of 100 to 300 mm. A method for producing a laminate, wherein the thickness of the layer is 10 to 400 μm, and the surface temperature of the base material immediately after thermal spraying is above the atmospheric temperature and below 70° C.