Embodiment
The method that forms colored decorative film in the metallic surface of the present invention comprises that this method is included in the metallic surface and forms coating, then with this coating oxidation, described coating forms by the method for vacuum ion plating, described coating is the coating of titanium or titanium alloy, and the average grain size of the described coating that vacuum ion plating forms is the 10-100 nanometer.The method of carrying out vacuum ion plating in the metallic surface is conventional method.Described vacuum ion plating method is included in the argon gas glow discharge that makes under the vacuum ion plating condition as working gas, thereby makes the ionization of target metal vapors, and the Ionized target metal of this steam quickens deposit at electric field and forms coating to the metallic surface.
The present invention is controlled in the scope of 10-100 nanometer by the average grain size of coated metal that described vacuum ion plating is formed, and then carries out oxidation, makes the colored decorative film that finally obtains have the color of homogeneous, and has high hardness.The measuring method of the average grain size of described coated metal is conventionally known to one of skill in the art, can obtain by transmissioning electric mirror determining, and described transmission electron microscope can be commercially available.
In order to make that the average grain size of the described coated metal that vacuum ion plating forms is the 10-100 nanometer, can realize according to the whole bag of tricks, for example the condition of vacuum ion plating can be controlled to be: with argon gas as working gas, the flow of described argon gas is the 40-80 ml/min, the bias voltage of grid bias power supply is the 100-300 volt, the dutycycle of grid bias power supply is 40-70%, and the power of grid bias power supply is 1500-2000 watt, and target is titanium or titanium alloy.In addition, the time of described vacuum ion plating can be carried out suitable adjustment according to needed thickness.Consider the sticking power of coating, the present invention preferably with the gauge control of described coating at the 0.1-3 micron.In order to obtain the coating of above-mentioned thickness, under the condition of above-mentioned vacuum ion plating, as long as the time of vacuum ion plating was controlled at 0.5-2 hour.In addition, described vacuum ion plating can be implemented by vaccum ion coater.Described vaccum ion coater can be commercially available.
Titanium alloy as described target can be the conventional various titanium alloys that use.Under the preferable case, described titanium alloy contains titanium and can form the metal of alloy with titanium, and the described metal that can form alloy with titanium is one or more in zinc, vanadium, aluminium, molybdenum and the chromium, and the content of the titanium in the described titanium alloy is more than the 80 weight %.
Under the preferable case, before forming described coating, the metallic surface earlier this metal is carried out pre-treatment.Described pre-treatment comprises mechanical polishing and oil removing.Described mechanical polishing can be undertaken by mechanical polisher.Described oil removing is that described metal is contacted with the electrochemical deoiling aqueous solution, as long as the amount of the described electrochemical deoiling aqueous solution can be cleaned out the greasy dirt of described metallic surface up hill and dale.The temperature of described contact can be 40-50 ℃, and the time of contact can be 5-30 minute.Described in the oil removing contact can be directly with metal impregnation in the electrochemical deoiling aqueous solution, also the electrochemical deoiling aqueous solution can be sprayed on the metal.The wherein said electrochemical deoiling aqueous solution contains the sodium hydroxide of 20-40 grams per liter, the yellow soda ash of 20-30 grams per liter and the Na of 50-70 grams per liter
3PO
412H
2O.In addition, described oil removing also described metal can be placed organic solvent for example acetone carry out supersound process.
In addition, after the metallic surface formed coating, before carrying out oxidation, preferred elder generation carried out oil removing once more with described metal, and carries out pickling.The method of described oil removing is narrated in the above.Described pickling is that described metal is contacted with acid washing water solution, as long as the consumption of described acid washing water solution can be removed the oxide compound of metallic surface.The temperature of described contact can be 10-40 ℃, and the time of described contact can be 5-30 minute.Described in the pickling contact can be directly with metal impregnation in acid washing water solution, also can be to metal with the acid washing water solution spraying.Described acid washing water solution contain the 20-50 milliliter/liter hydrofluoric acid and the 30-70 milliliter/liter ethylene glycol.
The present invention can be a whole bag of tricks with the method that described coating carries out oxidation, for example can be the method for chemical oxidation, the method for electrochemical oxidation.Consider that from the angle of oxidation efficiency the present invention preferably uses electrochemical oxidation.As long as described electrochemical oxidation can make the coating oxidation of metallic surface.Preferably according to the electrochemical oxidation that carries out as described below: with the acidic solution is electrolytic solution, and forming coated metal with the surface is anode, is that 2-200V, electrolyte temperature are under 10-80 ℃ the condition at voltage, electrochemical oxidation 1 minute-2 hours.Described acidic solution is to contain the phosphoric acid of 70-120 grams per liter and the organic acid aqueous solution of 20-70 grams per liter, and described organic acid is one or more in formic acid, acetate or the propionic acid.Material as the negative electrode of electrochemical oxidation in the described electrochemical oxidation is conventionally known to one of skill in the art.For example, described negative electrode can be a stainless steel etc.Need to prove that in addition the color of colored decorative film of the present invention is relevant with the degree of oxidation of described coating.Generally ascending according to degree of oxidation, that described color is followed successively by is dark brown, blue, cyan, green, yellow and orange.The size of the degree of the oxidation of described coating can be controlled by the voltage of electrochemical oxidation and the time of oxidation, and under same oxidization time, voltage is high more, and degree of oxidation is big more, and voltage is more little, and degree of oxidation is more little; Under identical voltage, oxidization time is long more, and degree of oxidation is big more, and oxidization time is short, and correspondingly degree of oxidation is just little.
Under the preferable case, this method is carried out the post bake processing after also being included in described oxide treatment, and described post bake is treated to the metal after the described overlay coating oxidation is contacted with hardening bath, and the consumption of described hardening bath makes described metallic surface fully contact with hardening bath and gets final product.Generally, the consumption of described hardening bath can be more than 1 times of described metal volume, the method for described contact can be directly with described metal impregnation in described hardening bath.The temperature of described contact is 10-50 ℃, and the time of contact is 10-30 minute, and described hardening bath is the acidic chromium acid salt aqueous solution, and the content of chromic salt is the 200-300 grams per liter in this solution, and described chromic salt for example can be Sodium chromate and/or potassiumchromate.In addition, described hardening bath can be regulated the pH value with various acid and makes it be acid to get final product.
Further under the preferable case, this method also is included in carries out sealing treatment after described post bake is handled, described sealing treatment is that the metal after described post bake is handled contacts with deionized water, and the consumption of described deionized water makes described metallic surface fully contact with deionized water and gets final product.Generally, the consumption of described deionized water can be more than 1 times of described metal volume, the method for described contact can be directly with described metal impregnation in described deionized water.The temperature of described contact is 70-100 ℃, and the time of contact is 5-30 minute.
In addition, the method that forms colored decorative film in the metallic surface of the present invention can all can form colored decorative film in various metallic surfaces.Described metal for example can be carbon steel, steel alloy, aluminium alloy, nickelalloy or cast iron etc.Above-mentioned metal all can be commercially available.
Below by embodiment method of the present invention is illustrated in greater detail.
Embodiment 1
The present embodiment explanation method that forms colored decorative film in the metallic surface of the present invention.
Carbon steel (trade mark ZG230-450, the Baosteel production) material of 20cm * 10cm * 3cm is carried out mechanical polishing, in acetone, carry out ultrasonic cleaning 20 minutes then, then oven dry.
This carbon steel material is placed vaccum ion coater (Shenzhen shake Hengchang produce JIL type vacuum plating unit), with argon gas as working gas, flow is 70 ml/min, the bias voltage of grid bias power supply is 180V, the power of grid bias power supply is 1700W, the dutycycle of grid bias power supply is 40%, and target is a titanium, and the ion plating time is 1.5 hours.Formation thickness is 1 micron titanium coating.(NEC JEOL2010) measures that to obtain average grain size be 50nm by transmission electron microscope with this coating that obtains.
To in 1 liter 40 ℃ the electrochemical deoiling aqueous solution, flood 20 minutes through the carbon steel material of ion plating then, contain the sodium hydroxide of 30 grams per liters, the yellow soda ash of 20 grams per liters and the Na of 50 grams per liters in the described electrochemical deoiling aqueous solution
3PO
412H
2O; With this carbon steel material of deionized water wash, flooded 10 minutes in 25 ℃ 1 liter acid washing water solution more then, described acid washing water solution contains 30 milliliters/liter hydrofluoric acid and 40 milliliters/liter ethylene glycol.
Above-mentioned carbon steel material after overpickling is placed electrolytic solution, under 30 ℃, is anode with this carbon steel material, with the stainless steel is negative electrode, be electrolytic oxidation 3 minutes under 3 volts the condition at voltage, wherein, described electrolytic solution contains the phosphoric acid of 70 grams per liters and the acetate of 30 grams per liters.
After above-mentioned oxide treatment, place 30 ℃ 10 liters hardening bath to flood 20 minutes this carbon steel material, described hardening bath contains the H of 200 grams per liter potassiumchromates and 270 grams per liters
2SO
4
This method also is included in carries out sealing treatment after described post bake is handled, and described sealing treatment is for being immersed in described metal in 10 liters the deionized water, and the temperature of described immersion is 70 ℃, and the time of contact is 5 minutes.
Finally obtain having the carbon steel material of purple decorating film, this purple decorating film color even.This carbon steel material is carried out the test of corrosion resistance nature, wear resisting property and hardness as follows, and the result is as shown in table 1.
1) erosion resistance test: in 35 ℃ salt fog cabinet, the above-mentioned carbon steel material with dark brown decorative film that obtains was sprayed 500 hours continuously with the sodium chloride solution of 5 weight %.Whether the coating of observing this material surface then has bubbles or obscission.If do not have be recorded as " qualified " of foaming or obscission, otherwise be recorded as " defective ".
2) wearability test: use the RCA paper tape wear resistant instrument of model as F350008, on the above-mentioned carbon steel material surface with dark brown decorative film of friction under 175 gram forces till expose body material, the number of turns that the record rubber wheel rotates.
3) hardness test: use the Shimazu microhardness tester to measure the Vickers' hardness of the colored decorative film that the metallic surface forms, wherein the loaded weight at mensuration process end is 50g, and the loading time is 10 seconds.
Comparative Examples 1
Method according to embodiment 1 is handled carbon steel material, and different is, in vacuum ion plating, the bias voltage of grid bias power supply is 130V, and the power of grid bias power supply is 500W, and the dutycycle of grid bias power supply is 40%.Formation thickness is 1 micron titanium coating.(NEC, JEOL2010) average grain size of measuring the coated metal that this Comparative Examples obtains is 150nm to use transmission electron microscope.Finally obtain having the carbon steel material of purple decorating film, but this purple decorating film surface color heterogeneity, and there is blueness the part.Measure this purple decorating film corrosion resistance nature, wear resisting property and hardness according to the method for embodiment 1, the result is as shown in table 1.
Embodiment 2
Method according to embodiment 1 forms colored decorative film, and different is that described metal is the low alloy steel (09Mn2V, Baosteel production) of 20cm * 10cm * 3cm.The ion plating of described metal is carried out according to as described below: in vaccum ion coater, with argon gas as working gas, flow is 50 ml/min, the bias voltage of grid bias power supply is 250V, the dutycycle of grid bias power supply is 50%, and the power of grid bias power supply is 2000W, and target is a titanium, the ion plating time is 0.5 hour, and formation thickness is 0.2 micron titanium coating.(NEC JEOL2010) measures that to obtain average grain size be 20nm by transmission electron microscope with this coating that obtains.
Described electrochemical oxidation carries out as follows: the carbon steel material after overpickling is placed electrolytic solution, be 50 ℃ in temperature, be anode with this aluminum alloy materials, with the stainless steel is negative electrode, it at voltage electrolytic oxidation 3 minutes under 10 volts the condition, wherein, described electrolytic solution contains the phosphoric acid of 70 grams per liters and the acetate of 30 grams per liters.
Finally obtain having the low alloy steel material of bright golden yellow decorating film.This low alloy steel material is carried out corrosion resistance nature, wear resisting property and hardness test according to the method for embodiment 1, and the result is as shown in table 1.
Embodiment 3
Method according to embodiment 1 forms colored decorative film, different is, described electrochemical oxidation carries out as follows: the carbon steel material after overpickling is placed electrolytic solution, be 60 ℃ in temperature, be anode with this alloy steel material, with the stainless steel is negative electrode, be electrolytic oxidation 2 hours under 2 volts the condition at voltage, wherein, described electrolytic solution contains the phosphoric acid of 120 grams per liters and the formic acid of 60 grams per liters.
After above-mentioned oxide treatment, place 50 ℃ 10 liters hardening bath to flood 15 minutes this carbon steel material, described hardening bath contains the H of 280 grams per liter potassiumchromates and 270 grams per liters
2SO
4
This method also is included in carries out sealing treatment after described post bake is handled, and described sealing treatment is for being immersed in described metal in 10 liters the deionized water, and the temperature of described immersion is 90 ℃, and the time of contact is 25 minutes.
Finally obtain having the carbon steel material of yellow decorating film.This carbon steel material is carried out corrosion resistance nature, wear resisting property and hardness test according to the method for embodiment 1, and the result is as shown in table 1.
Embodiment 4
Method according to embodiment 1 forms colored decorative film, and different is that described metal is the low alloy steel (09Mn2V, Baosteel production) of 20cm * 10cm * 3cm.The ion plating of described metal is carried out according to as described below: in vaccum ion coater, with argon gas as working gas, flow is 50 ml/min, the bias voltage of grid bias power supply is 100V, and the dutycycle of grid bias power supply is 40%, and the power of grid bias power supply is 1500W, target is titanium alloy (Ti-6Al-4V, the content of titanium is 90 weight % in the alloy), the ion plating time is 0.8 hour, formation thickness is 0.2 micron titanium alloy coating.(NEC JEOL2010) measures that to obtain average grain size be 90nm by transmission electron microscope with this coating that obtains.
Described electrochemical oxidation carries out as follows: the carbon steel material after overpickling is placed electrolytic solution, be 60 ℃ in temperature, be anode with this alloy steel material, with the stainless steel is negative electrode, it at voltage electrolytic oxidation 3 minutes under 50 volts the condition, wherein, described electrolytic solution contains the phosphoric acid of 100 grams per liters and the formic acid of 50 grams per liters.
Finally obtain having the low alloy steel material of yellow decorating film.This low alloy steel material is carried out corrosion resistance nature, wear resisting property and hardness test according to the method for embodiment 1, and the result is as shown in table 1.
Table 1
Numbering |
The average grain size of coated metal (nm) |
Erosion resistance |
Wear resistance (circle) |
Vickers' hardness |
Embodiment 1 |
50 |
Qualified |
220 |
400 |
Comparative Examples 1 |
150 |
Qualified |
101 |
200 |
Embodiment 2 |
20 |
Qualified |
250 |
450 |
Embodiment 3 |
50 |
Qualified |
215 |
390 |
Embodiment 4 |
90 |
Qualified |
200 |
350 |
As can be seen from Table 1, the Vickers' hardness of the colored decorative film that embodiment of the invention 1-4 obtains is all more than 350, and the Vickers' hardness of the colored decorative film that Comparative Examples 1 obtains only is 200.In addition, it is qualified that the corrosion resistance nature of the colored decorative film that embodiment of the invention 1-4 obtains is, and the wear resistance of these colored decorative films all 200 the circle more than, be much higher than Comparative Examples 1 101 the circle.