TWI568890B - A method of forming a composite metal oxide film on the surface of a substrate - Google Patents

Description

Method for forming a composite metal oxide film layer on a surface of a substrate

The invention relates to a micro-arc oxidation treatment (Micro-ARC Oxidation) with a pulse-reverse current mode with a pulse-reverse current pattern after forming a metal film on different substrates to form an insulation. , anti-corrosion, scratch-resistant or specific functional composite metal oxide film technology.

According to the metal oxide material (or ceramic material) due to its high hardness, wear resistance, weather resistance, corrosion resistance, non-contamination or long-term bacteria, easy to clean and other characteristics, the selection of materials is highly valued; In view of the fact that in addition to the mechanical properties, the overall properties of the substrate are required to be the main body, and the other properties affecting the physical properties are determined by the composition and structure of the film having a thickness of several tens of nanometers to several hundreds of meters on the surface of the substrate; It is said that as long as a metal oxide film having a thickness of several tens of nanometers to several hundreds meters is formed on the surface of the substrate, the physical property improvement effect can be attained, and the composite metal oxide film is more recognized for its special physical properties. However, in the prior art, there are the following problems: First, glass and plastic materials can be chemically evaporated or sputtered to form a metal oxide film on the surface thereof, but the equipment investment amount is large and the output speed is low, and There are a limited variety of metal oxide films that can be formed (eg, cerium oxide/titanium dioxide/zirconia, etc.), in which a composite metal oxide film is less (currently only ITO is mass-produced), but the formed film There are often problems of large porosity and poor hardness, so it is often necessary to carry out further post-treatment, including sealing and sintering, but sintering often requires high temperature (above 250 ° C) and long time (more than 3 hours), not only The formation of energy waste and cost problems, some components are also unable to withstand long-term high temperatures, but also form production constraints.

Secondly, the metal oxide film of the metal substrate has many growth modes, including: (1) a metal oxide film formed on the surface by chemical vapor deposition or sputtering, and the equipment investment amount is large. The output speed is low, and problems such as sealing and sintering are still present. The only advantages are: sintering can be carried out at a high temperature for a short period of time (for example, 600 ° C / 60 minutes); (2) if the metal oxide film composition is The oxide of the metal can be anodized to directly form a metal oxide film on the surface of the metal substrate, such as an aluminum substrate or an aluminum-magnesium alloy substrate to form an aluminum oxide (Al2O3) insulating layer, titanium and a titanium alloy. Titanium dioxide (TiO2) insulating layers are all such, and corrosion resistance and high hardness properties are the main processing purposes. However, the anode treatment generally has a problem that the growth rate of the film layer is low and the treatment liquid is highly polluting, and the composite metal oxide film cannot be formed, and the problems of post-treatment such as sealing and sintering still exist; and (3) in recent years, the micro-arc Micro arc oxidation (MAO) is gaining more and more attention. The advantage is that the treatment liquid has low pollution, but the membrane still has the disadvantage of large porosity/low density (see: Republic of China Patent No. I297041 and China) Republic of China Patent No. I342901), so it still needs to be sealed and sintered after treatment; the improved micro-arc oxidation treatment method (see: Republic of China Patent No. I477656 and Republic of China Patent No. I479503) can effectively reduce its porosity and eliminate The necessity of sealing and sintering treatment, but the formation of a composite metal oxide film layer cannot be formed.

Finally, the ceramic material can be directly sintered with metal oxide powder or multi-component mixed metal oxide powder under certain conditions to form a single or composite metal oxide; however, the temperature required for this process is very high (700 ° C, 800 ° C to Above 1000 °C), the energy consumption is very large, and the direction of energy saving and carbon reduction is not suitable; and the post-processing of the formed ceramic material is not easy, and its use is more limited; especially for components that only require the function or characteristics of the surface film, if , glass or plastic materials and the use of ceramic components, will result in material waste, processing difficulties and cost increases; for the original physical properties (such as: metal conduction / heat transfer, glass transmission, etc.) is not feasible .

In view of the above phenomenon, the present invention has a pulse-reverse current mode in combination with a selected chemical solution for micro-arc oxidation surface treatment (Micro-ARC Oxidation) to form a composite having insulation, corrosion resistance, scratch resistance or specific functions. The technology of metal oxide film layers.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a composite metal oxide film layer on a surface of a substrate, which has advantages such as being unrestricted by substrate characteristics, saving energy, reducing pollution, and reducing cost.

In order to achieve the foregoing object, the present invention provides a treatment technology for forming a composite metal oxide film layer on a surface of a substrate, which comprises the following steps: (1) firstly on the surface of a substrate (including a glass material, a plastic material or a metal material) Chemical vapor deposition or sputtering of a metal film layer formed on one of aluminum (Al), magnesium (Mg), titanium (Ti) or an alloy thereof; if the metal material is aluminum (Al) or magnesium (Mg) And one of titanium (Ti) or an alloy thereof, only the decontamination/deoxidation layer is required; (2) the substrate having the metal film layer is used as the anode; the electrolyte solution and the conductive metal plate are selected as the cathode, To establish a reaction system, wherein the electrolyte solution includes a modifier and insoluble nanoparticles: (3) selecting an appropriate current and voltage, wherein the current is pulsed with a reverse pulse current pattern, and the reaction system is set After the reaction is carried out at temperature and time, a composite metal oxide film layer is formed on the surface of the substrate, and has high hardness, insulation, abrasion resistance, weather resistance, corrosion resistance, non-staining or growth of bacteria, and easy cleaning.

The electrolyte solution used in the present invention comprises sodium citrate, ammonium citrate, sodium phosphate, ammonium phosphate, sodium sulfate, ammonium sulfate, sodium fluoride, potassium fluoride, ammonium hydrogen fluoride, sodium hydroxide, potassium hydroxide or a composition thereof. The concentration is different depending on the need, and the solid content is 0.1 to 100 g/liter.

The modifier of the present invention comprises: boric acid, sodium borate, manganese sulfate, potassium vanadate, sodium vanadate, ammonium vanadate, ammonium molybdate, sodium molybdate, etc., and the addition amount is 0.05-50 g/liter. And the modified agent contains nano particles including: carbon, aluminum oxide, cerium oxide, titanium dioxide, molybdenum oxide, cerium oxide, cerium oxide, tungsten oxide, zirconium oxide, copper oxide, zinc oxide, chromium oxide or cerium oxide. Nanoparticles, wherein the nanoparticles have a particle size of 1 to 400 nm and a loading of 0.05 to 50 g/liter.

Another object of the present invention is to use a stainless steel plate or a copper plate as a cathode, and the current is pulsed-reverse pulse current type, and the pulse-time of each pulse current is 0.05 to 10 milliseconds (ms); the range of the pulse voltage The system is between 400 volts and 2000 volts. The reverse pulse voltage ranges from 200 volts to 800 volts. The pulse current is pulse-time. 0.05~10 milliseconds (ms), the intermediate power-off time (off-time) between the pulse current and the reverse pulse current is 1~20 times of the pulse-current pulse-time. The reaction time of the reaction system depends on the film layer. It is 10 seconds to 60 minutes, and the reaction temperature is 5 to 60 ° C. Thus, after the reaction system is set at a temperature and time, the substrate is formed to have high hardness, insulation, abrasion resistance, weather resistance, corrosion resistance, and difficulty. Stained or long-lasting bacteria, easy to clean, etc. Functional membrane layer.

For your convenience, the review committee can make a further understanding and understanding of the purpose, technical features and effects of the present invention. The embodiments are combined with the drawings, and the details are as follows:

The invention relates to a method for forming a composite metal oxide film layer on a surface of a substrate, which first selects a metal material or a material having a metal film layer on the surface as an anode substrate, wherein when the metal material is aluminum (Al , one of magnesium (Mg), titanium (Ti) or an alloy thereof, only the process of decontaminating or deoxidizing the metal material; when the material is a glass material, a plastic material or a metal material (non-aluminum) (Al), magnesium (Mg), titanium (Ti) or alloys thereof, first form aluminum (Al), magnesium (Mg), titanium (Ti) or its surface by chemical vapor deposition or sputtering A metal film layer of one of the alloys; thus, the manufacturer can select an appropriate material as the anode substrate according to the demand, without being limited to the metal material of the substrate, but only the corresponding metal. Membrane layer.

Thereafter, the method selects an electrolyte solution and a conductive metal plate as a cathode to establish a reaction system, wherein the electrolyte solution includes a modifier and insoluble nanoparticles to enable the nanoparticle to be attached to the metal film. The surface layer of the layer, in turn, the particle size of the nanoparticle is 1 to 400 nm (optimally 1 to 30 nm), and finally, an appropriate current and voltage are applied to the reaction system, wherein the current is pulsed-reverse Pulse current type, the current of each pulse current is 0.05~10 milliseconds, the range of pulse voltage is between 400 volts and 2000 volts (optimally 600 volts to 1400 volts), and the range of reverse pulse voltage is between Between 200 volts and 800 volts, the reverse pulse current energization time is 0.05-10 milliseconds, and the intermediate power-off time between the pulse current and the reverse pulse current is 1-20 times of the pulse current energization time. Moreover, the reaction system is at the reaction temperature (eg, After 5~60 ° C) and reaction time (such as 10 seconds to 60 minutes, preferably 10 seconds to 60 seconds), a composite metal oxide film layer is formed on the surface of the substrate to have high hardness. , insulation, wear resistance, weather resistance, corrosion resistance, not easy Staining or growing bacteria, easy to clean, etc., thus, since the electrolyte solution of the present invention includes insoluble nanoparticles, the film produced by the present invention is compared with the dissociative particles contained in the conventional electrolyte solution. The layer properties are better.

Hereinafter, the examples are given to illustrate the contents of the present invention, but the scope of the present invention is not limited to such examples:

Example 1: A pure aluminum plate (30 x 30 (cm2)) was immersed in 2% sodium hydroxide for 1 minute to remove surface oil and washed with water to ensure a clean surface. The washed aluminum plate is immersed in the alkaline treatment liquid of the micro-arc plasma; the alkaline treatment liquid contains sodium hydroxide 3 g/L, sodium citrate 5 g/L, and titanium dioxide nano particles (particle size is 1-20 nm, The amount added was 0.5 g/liter), and a stainless steel plate was used as a cathode. The operating conditions of the micro-arc plasma are: set the pulse voltage to 600 volts, the pulse-time of each pulse is 1 millisecond (ms), and the off-time is 2 milliseconds. Ms), between the reverse pulse voltage of 200 volts, the pulse-time of the reverse pulse current is 2 milliseconds (ms), and the intermediate power-off time (off-time) of the reverse pulse current is 1 millisecond (ms). After 3 minutes of working time, the finished product can be produced, and the surface of the finished product is a dense film of alumina/titanium dioxide, which has the characteristics of softness, smoothness, easy cleanness and corrosion resistance.

Example 2: After washing a titanium metal plate (30×30 (cm 2 )), it is immersed in a neutral treatment liquid of micro-arc plasma; the treatment liquid contains trisodium phosphate 5 g/L, sodium hydroxide 3 g/ L and cerium oxide nanoparticles (particle size of 10 to 50 nm, added in an amount of 2 g / liter). The working condition of the micro-arc plasma is: set the pulse voltage between 800 volts, the pulse-time of each pulse is 0.5 milliseconds (ms), and the off-time is 2 milliseconds. (ms), between the reverse pulse voltage of 200 volts, the pulse-time of the reverse pulse current is 0.5 milliseconds (ms), and the intermediate power-off time (off-time) of the reverse pulse current is 1 millisecond (ms). After 2 minutes of working time, the finished product can be produced, and the surface of the finished product is a composite film of titanium dioxide/cerium oxide, which has the characteristics of smooth, hydrophilic, easy to clean, antibacterial, corrosion resistant and golden yellow luster.

Embodiment 3: After washing a titanium metal plate (30×30 (cm 2 )), it is immersed in a neutral treatment liquid of micro-arc plasma; the treatment liquid contains trisodium phosphate 5 g/L, sodium hydroxide 3 g/ L and tungsten oxide nanoparticles (particle size 30~70nm, added in 1g/liter). The operating conditions of the micro-arc plasma are: set the pulse voltage between 800 volts, each pulse current-pulse-time is 3 milliseconds (ms), and the intermediate power-off time (off-time) is 6 milliseconds ( Ms), between the reverse pulse voltage of 400 volts, the pulse current of the reverse pulse current (pulse-time) is 3 milliseconds (ms), and the reverse power of the reverse pulse current (off-time) is 1 millisecond (ms). After 2 minutes of working time, the finished product can be produced, and the surface of the finished product is a complex of titanium dioxide/tungsten oxide. The film layer has the characteristics of high hardness, high wear resistance, high corrosion resistance and the like.

The components and method steps disclosed in the foregoing embodiments are merely illustrative and are not intended to limit the scope of the present invention. The scope of the present application should be based on the scope of the patent application, and other equivalent elements or steps. Alternatives or changes should also be covered by the scope of the patent application in this case.

Claims (7)

A method for forming a composite metal oxide film layer on a surface of a substrate, comprising the steps of: selecting a metal material or a material having a metal film layer on the surface as an anode substrate; selecting an electrolyte solution and a conductive metal plate as a cathode to establish a reaction system, wherein the electrolyte solution includes a modifier and insoluble nanoparticles, wherein the material of the nanoparticle is different from the material of the metal material or the metal film layer; and the reaction system is applied An appropriate current and an appropriate voltage, wherein the appropriate current is pulsed-reverse pulse current type; and the reaction system is reacted at a set temperature and for a set time, the surface of the anode substrate can form a composite The metal oxide film layer has high hardness, insulation, abrasion resistance, weather resistance, corrosion resistance, non-staining, and is not easy to grow bacteria and easy to clean. The method of claim 1, wherein the metal film layer on the surface of the material is one of aluminum, magnesium, titanium or an alloy thereof, and is formed on the surface of the material by chemical vapor deposition or sputtering. The cathode is a stainless steel plate or a copper plate. The method of claim 1, wherein the metal material is one of aluminum, magnesium, titanium or an alloy thereof, and the decontamination or deoxidation layer is performed, and the cathode is a stainless steel plate or a copper plate. The method of claim 1, wherein the electrolyte solution comprises sodium citrate, ammonium citrate, sodium phosphate, ammonium phosphate, sodium sulfate, ammonium sulfate, sodium fluoride, and fluorine. Potassium, ammonium hydrogen fluoride and sodium hydroxide, potassium hydroxide or a combination thereof, and the solid concentration of the component concentration of the electrolyte solution is 0.1 to 100 grams per liter. The method of claim 1, wherein the modifier comprises a component comprising at least boric acid, sodium borate, manganese sulfate, potassium vanadate, sodium vanadate, ammonium vanadate, ammonium molybdate or sodium molybdate. In one type, the modifier is added in an amount of 0.05 to 50 grams per liter. The method of claim 5, wherein the modifier comprises nano particles of carbon, alumina, ceria, titania, molybdenum oxide, cerium oxide, cerium oxide, tungsten oxide, zirconium oxide, copper oxide. , a zinc oxide, a chromium oxide or a cerium oxide nanoparticle, and the nanoparticle has a particle diameter of 1 to 400 nm, and the amount thereof is 0.05 to 50 g per liter. The method of claim 1, wherein the energization time of each pulse current is 0.05 to 10 milliseconds, the range of the pulse voltage is between 400 volts and 2000 volts, and the range of the reverse pulse voltage is between 200 volts and 800 volts. Between volts, the reverse pulse current energization time is 0.05~10 milliseconds, and the middle power failure time between the pulse current and the reverse pulse current is 1~20 times of the pulse current energization time, and the reaction time of the reaction system is 10 seconds to 60 minutes, and The reaction temperature is 5 to 60 °C.