TW201433451A - Composite material with improved adhesive force and manufacturing method thereof - Google Patents

Abstract

In a composite material with improved adhesive force and a manufacturing method thereof according to the present invention, the composite material mainly comprises a metal substrate containing iron or copper, an aluminum-contained coating, and an aluminum-contained ceramic layer. To improve the adhesive force of the ceramic layer to the metal substrate, metal particles of thermal spraying of metal aluminum or aluminum alloy or hot dipping or anhydrous aluminum plating is applied to form an aluminum-contained coating on the metal substrate. Then, micro arc oxidation is applied to the aluminum-contained coating, so as to form the aluminum-contained ceramic layer on the surface of the aluminum-contained coating. Thus, by utilizing the better adhesive force between the metal substrate and the aluminum-contained coating and utilizing the better adhesive force of the ceramic layer formed by the phase transition of the aluminum-contained coating, the effect of improving the adhesive force is achieved.

Description

Composite material for improving adhesion and manufacturing method thereof

The present invention relates to a composite material and a method of manufacturing the same; and more particularly to a composite material having a ceramic layer on a steel or copper substrate and a method of manufacturing the same.

In many industrial process environments, mechanical parts are required to be resistant to corrosion and wear, and conventional steels do not meet these requirements. If stainless steel is used, it can only be used for a few months in a corrosive environment.

In contrast, ceramics have good corrosion resistance and wear resistance, so forming a ceramic layer on a mechanical workpiece is an effective method to solve the problem of corrosion resistance and wear resistance. However, the traditional method is due to the poor bonding degree between the ceramic layer and the steel mechanical workpiece, and it is easy to cause the ceramic layer to fall off under the impact of external force, resulting in the loss of corrosion, wear resistance, or being broken and damaged.

In general, if you want to improve the coverage of the ceramic layer on the surface of the metal material, it is not the use of Micro Arc Qxidization (MAO) ceramic technology, or the use of spray ceramic coating technology. However, if the micro-arc oxidation ceramic technology is used alone, the molten ceramic coating technology is used to form the ceramic layer, which is not a high manufacturing cost, or a lack of bonding force, and even a problem in industrial mass production.

In the prior art, there has been a micro-arc oxidation ceramic technique, that is, a ceramic film formed on the surface of a base of a light metal such as aluminum, titanium, magnesium, and alloys thereof by micro-arc oxidation treatment. The principle of micro-arc oxidation ceramic technology is to create an anodized film on the surface of the workpiece while polarizing it by micro-arc instantaneous 7000K high temperature. The membrane is converted to a ceramic phase. The ceramic layer has high hardness, high wear resistance, good toughness, strong adhesion to the substrate, corrosion resistance, high temperature oxidation resistance, good insulation, and is particularly suitable for high speed sports and high wear resistance, corrosion resistance and high temperature impact resistance of light metal alloys. Parts. The micro-arc oxidation technology has the following characteristics: (1) The surface hardness of the material is greatly improved, and the microhardness is 1000 to 2000 HV, which is comparable to that of the hard alloy, which greatly exceeds the high carbon steel, high alloy steel and high speed after heat treatment. Tool steel hardness; (2) good wear resistance; (3) good heat resistance and corrosion resistance; (4) good insulation performance, insulation resistance up to 100M Ω; (5) substrate in situ The ceramic membrane is grown and bonded firmly, and the ceramic membrane is dense and uniform.

However, if the micro-arc oxidation treatment is performed directly on a mechanical workpiece made of iron or copper, the required ceramics cannot be formed on a mechanical workpiece made of iron or copper due to the lack of aluminum atoms required for the formation of ceramics. Floor. Therefore, micro-arc oxidation ceramic technology is mostly used in electronic device housings with light metals or other applications, and is not suitable for mechanical parts containing iron or copper.

In order to solve this problem, a method of performing micro-arc oxidation on a steel or stainless steel surface has been proposed, but it cannot be applied in industrial mass production. This type of method also requires a very large current density (30A ~ 150A / dm ² ), but the excessive power supply will cause problems, and the pulse must be used in the process, in addition to the high cost, energy use Low efficiency (a large proportion of the cycle is the reverse operating voltage, and the power consumption is no longer produced). In addition, in this method, in order to form a ceramic layer directly on the iron material, it is necessary to provide an aluminum atom which generates an oxide layer (and a ceramic layer) from sodium aluminate in the electrolyte, and thus the alumina hardening film must contain an elemental state. The iron, the outer loose layer has more uncrystallized iron element, which will cause the iron of the future hardened film to be oxidized into loose and poorly insulated ferric oxide, which has a certain influence on the insulation demand and reliability. In order to overcome the problems caused by the iron content of the ceramic film formed, it is necessary to additionally consider the problem of insulation, and it is also necessary to form a very thick film layer (100 μm ), but in forming the above thick film, since it is directly Large current density is formed, and the stress is very large, and it is not feasible to operate in a large area.

In contrast, when the ceramic coating technology is used to form the ceramic layer, the plasma flame is generated by using high-electric energy as a heat source, and the ceramic material is melted, and the spray material is accelerated and atomized by a high-speed air stream to melt. The spray particles collide at high speed onto the surface of the workpiece and are leveled and cured to produce the desired spray coating. The application of the plasma spray coating is to provide the desired shape and strength characteristics of the workpiece from the substrate, while the coating provides the interface characteristics required between the workpiece and the environment in which it is used. This technology is an advanced surface modification processing technology, which has been widely used in special applications such as anti-wear, regenerative repair, gap control, high temperature anti-corrosion, biomedical, thermal insulation, ablation, conductive and anti-conductive coating. With the advancement of the times, various functional coatings have emerged, such as dielectric coatings, conductive coatings, radiation-resistant coatings, etc., and coatings often require the formation of characteristic or irregular geometries to meet Usage requirements.

However, with ceramic as the molten material, the required melting temperature is quite high, and the requirements and costs for the entire process are relatively significantly improved, while the ceramic layer formed by the spray ceramic coating technology is still iron or copper with the substrate. There are problems such as poor bonding.

If the micro-arc oxidation ceramic technology or the molten ceramic coating technology of the known technology is used alone to form the ceramic layer, the manufacturing cost is not high, that is, the bonding strength is still insufficient, and even the industrial mass production is fundamentally unshaped.

Therefore, it is necessary to develop a condition of good bonding force, process temperature and the like. The requirements are lower, and it is feasible in industrial production, while the manufacturing cost is low.

In the composite material for improving adhesion and the method for producing the same according to the present invention, the composite material mainly comprises a metal substrate made of iron or copper, an aluminum-containing film and an aluminum-containing ceramic layer. In order to improve the adhesion of the ceramic layer of the metal substrate, firstly, the metal film of the aluminum or aluminum alloy is sprayed, or the aluminum-containing film is formed on the metal substrate by hot dip or waterless aluminum plating, and then the micro arc is used. The aluminum-containing coating is oxidized, and an aluminum-containing ceramic layer is formed on the surface of the aluminum-containing coating.

Thus, the composite material for improving the adhesion of the present invention mainly utilizes a metal substrate and a metal-containing coating, and a ceramic layer formed by a phase transition of the aluminum-containing film is also preferably used. In turn, the effect of improving the adhesion is achieved.

The advantages and spirit of this creation can be further understood by the following new detailed description and the accompanying drawings.

10‧‧‧Metal substrate

10a‧‧‧bonding layer

12‧‧‧Aluminum covered film

14‧‧‧Aluminum-containing ceramic layer

The first A to B drawings are schematic views of the manufacturing method of the composite material for improving the adhesion of the present invention.

The second A to C diagram is a schematic view of another manufacturing method of the composite material for improving adhesion according to the present invention.

Please refer to the first A~B diagram. The first A~B diagram is a schematic diagram of the manufacturing method of the composite material for improving the adhesion of the present invention. As shown in FIG. A, in the method for manufacturing a composite material for improving adhesion according to the present invention, first, a spray (for example, plasma spray, arc spray, flame spray, high-speed flame spray) is used. The metal particles of aluminum metal or aluminum alloy (the aluminum alloy may be zinc aluminum, tin aluminum, bismuth aluminum), or the aluminum-containing film 12 is formed on the metal substrate 10 by hot dip or anhydrous aluminum plating. Among them, the metal substrate 10 is made of iron or copper. Next, as shown in FIG. B, the aluminum-containing ceramic film 14 is formed on the surface of the aluminum-containing film 12 by micro-arc oxidation of the aluminum-containing film 12. If the metal particles of the molten metal aluminum or aluminum alloy are used, or the hot-dip or water-free aluminum plating is used, the roughness of the aluminum-containing film 12 formed on the metal substrate 10 is too high, and the mechanical polishing can be performed. Then, the aluminum-containing coating 12 is micro-arc oxidized to form the aluminum-containing ceramic layer 14, and can be processed in accordance with the shape of the original metal substrate 10.

Before using metal particles of molten aluminum or aluminum alloy, metal particles of metal aluminum or aluminum alloy having a particle diameter of 1 μm to 1000 μm must be prepared, and then the metal substrate 10 is sprayed with specific melting operation parameters. On the metal substrate 10, an aluminum-containing coating 12 having a thickness of 1 μm to 1 mm is formed. The parameters of the spray operation are as follows: (i) spray distance: 10 cm; (ii) spray pressure: 2 MPa; (iii) compressed air pressure: 0.5 MPa; (iv) compressed air flow: 1 m ³ /h; v) acetylene pressure: 0.05 MPa; (vi) acetylene flow ^{rate: 1.2m 3 / h; (vii} ) oxygen pressure: 0.4 MPa; (viii) oxygen gas flow rate: 1.8m ³ / h. The tensile strength of the aluminum layer can reach 7 MPa.

In the case of hot-dip aluminizing, the metal substrate 10 to be plated is immersed in an alkaline bath, after degreasing, washed with water, and pre-treated by pickling; the pre-treated metal substrate 10 to be plated is immersed in zinc oxide. a flux treatment process of one or more fluxes of lanthanum chloride, an alkali metal lanthanum or an alkaline earth metal lanthanum and one or more of the aliphatic nitrogen derivative; the flux treated by the flux treatment The metal substrate 10 is immersed in a hot dip metal bath, and the immersion plating process of the immersion plating film is formed; and the plated metal substrate 10 forming the immersion coating film is immersed in cooling water or cooled by air cooling, and An aluminum-containing coating 12 having a thickness of 1 μm to 1 mm is formed on the metal substrate 10.

When aluminum is coated with anhydrous molten salt, AlCl ₃ -NaCl-KCl ternary inorganic molten salt system is used for aluminum plating on carbon steel substrate, AlCl ₃ is 80 wt%, and plating bath temperature is controlled at 200 ° C, input current The density is 3.3~4.0 A/dm ² , the plating time is 45~90 min, and the coating is silver-white aluminum coating.

After the aluminum-containing film 12 is formed on the metal substrate 10, it is necessary to form the thickness on the surface of the aluminum-containing film 12 by using a micro-arc oxidation of the aluminum-containing film 12 in accordance with a predetermined step and a desired process condition. An aluminum-containing ceramic layer 14 of 1 μm to 200 μm . In order to form the aluminum-containing ceramic layer 14, a portion of the arc-oxidized aluminum-containing film 12 is consumed during the micro-arc oxidation of the aluminum-containing film 12, so that the thickness of the arc-oxidized aluminum-containing film 12 is thinned, so that before the process The thickness of the formed aluminum-containing film 12 is the sum of the thicknesses of the predetermined aluminum-containing film 12 and the aluminum-containing ceramic layer 14 so as to have a sufficient source of aluminum atoms when the micro-arc oxidation forms the aluminum-containing ceramic layer 14.

In the predetermined steps and the required process conditions, the metal substrate 10 having the aluminum-containing film 12 is first fixed on a support and immersed in a micro-arc oxidation tank containing a weakly alkaline aqueous solution. In the micro-arc oxidation bath, the metal substrate 10 having the aluminum-containing film 12 serves as one electrode of the micro-arc oxidation, and the conductive rod serves as the other electrode. The above weakly alkaline aqueous solution may be an aqueous solution of sodium metasilicate, and wherein the concentration of sodium metasilicate is preferably 10 g/l, and the concentration of sodium hydroxide is preferably 2 g/l.

After immersing the metal substrate 10 having the aluminum-containing film 12 in a micro-arc oxidation tank containing a weakly alkaline aqueous solution, a DC power source is passed between the electrodes, and the operation is performed at a low current density (1 to 5 A/dm ² ). Or the positive pulse voltage of 0~500 volts and the negative pulse voltage of 0~150, the pulse frequency is 0~60 Hz, the pulse waveform is square, and the amplitude and width of the positive and negative pulses can be adjusted separately. Among them, adjusting the width of the positive pulse voltage can prolong the oxidation time and increase the growth rate of the ceramic film, while adjusting the negative pulse voltage can promote the penetration of oxygen ions into the ceramic film, increase the mass density of the ceramic film, and better corrosion resistance. .

In order to further strengthen the bonding force between the metal substrate 10 and the aluminum-containing film 12, it is also possible to Add a bonding layer between them.

Please refer to the second A~2C diagram, and the second A~2C diagram is a schematic diagram of the manufacturing method of the composite material for improving the adhesion of the present invention. In the manufacturing method of the composite material for improving adhesion according to the present invention, as shown in FIG. 2A, first, an alloy of nickel, copper, tin, zinc or metallic nickel, copper, tin, and zinc is electroplated, and on the metal substrate 10. A bonding layer 10a is formed. Next, as shown in FIG. 2B, the aluminum-containing coating film 12 is formed on the bonding layer 10a of the metal substrate 10 by sputtering or by hot dip or non-aqueous aluminum plating. Finally, as shown in FIG. 2C, the aluminum-containing ceramic film 14 is also formed on the surface of the aluminum-containing film 12 by micro-arc oxidation of the aluminum-containing film 12.

In this way, firstly, the metal particles of the molten metal aluminum or aluminum alloy, or the aluminum-containing film 12 formed on the metal substrate 10 by hot-dip or non-aqueous aluminum plating, between the metal substrate 10 and the aluminum-containing film 12 are used. It has better bonding, and no conventional technology utilizes the high temperature required for spraying ceramic particles, and there is no problem such as poor bonding between metal and ceramic. Meanwhile, in the method of the present invention, the aluminum-containing coating 12 can be used as a source of aluminum atoms required for the subsequent micro-arc oxidation ceramic technology, and the aluminum-containing ceramic layer 14 can be smoothly formed on the surface of the aluminum-containing coating 12, However, there is no insulation requirement or other problems caused by iron in the prior art.

The features and spirit of the present invention are more clearly described in the above detailed description of the preferred embodiments, and the scope of the present invention is not limited by the preferred embodiments disclosed herein. On the contrary, it is intended to cover all kinds of changes and equivalences within the scope of the patent application to which the present invention is intended.

10‧‧‧Metal substrate

12‧‧‧Aluminum covered film

14‧‧‧Aluminum-containing ceramic layer

Claims (10)

A composite material for improving adhesion, comprising: a metal substrate made of iron or copper; an aluminum-containing film, using metal particles of molten aluminum or aluminum alloy, or using hot dip or waterless aluminum plating; Formed on the metal substrate; and an aluminum-containing ceramic layer formed on the surface of the aluminum-containing film by micro-arc oxidation of the aluminum-containing film. The composite material for improving adhesion according to the first aspect of the patent application, wherein the aluminum-containing coating has a thickness of 1 μm to 1 mm, and the aluminum-containing ceramic layer has a thickness of 1 μm to 300 μm . The composite material for improving adhesion according to the first aspect of the patent application, wherein the metal substrate and the aluminum-containing film further comprise: a bonding layer, using electroplated metal nickel, copper, tin, zinc or metallic nickel, copper, An alloy of tin and zinc is formed on the metal substrate; wherein the aluminum-containing film is formed on the bonding layer. A composite material for improving adhesion according to the first aspect of the patent application, wherein the aluminum alloy may be zinc aluminum, tin aluminum or bismuth aluminum. A method for manufacturing a composite material for improving adhesion, comprising: forming an aluminum-containing coating on a metal substrate by using metal particles of molten aluminum or aluminum alloy, the metal substrate is made of iron or copper; The aluminum-containing coating is micro-arc oxidized, and an aluminum-containing ceramic layer is formed on the surface of the aluminum-containing film. The method for producing a composite material for improving adhesion according to claim 5, wherein the aluminum-containing film has a thickness of 1 μm to 1 mm, and the aluminum-containing ceramic layer has a thickness of 1 μm to 300 μm . The method for manufacturing a composite material for improving adhesion according to claim 5, wherein before forming the aluminum-containing film, further comprising: using electroplated metal nickel, copper, tin, zinc or metallic nickel, copper, tin, zinc An alloy, and a bonding layer is formed on the metal substrate; wherein the aluminum-containing film is formed on the bonding layer. The method for producing a composite material for improving adhesion according to the fifth aspect of the patent application, wherein the metal particles of the metal aluminum or aluminum alloy have a particle diameter of from 1 μm to 1000 μm . The method for producing a composite material for improving adhesion according to the fifth aspect of the patent application, wherein the aluminum alloy may be zinc aluminum, tin aluminum or bismuth aluminum. A method of manufacturing a composite material for improving adhesion according to claim 5, wherein the thickness of the aluminum-containing film formed is a predetermined sum of thicknesses of the aluminum-containing film and the aluminum-containing ceramic layer, so that Microarc oxidation has sufficient source of aluminum atoms when forming the aluminum-containing ceramic layer.