CN103866332A - High-temperature resistant metal surface coating with high absorbing capacity and manufacturing method thereof - Google Patents
High-temperature resistant metal surface coating with high absorbing capacity and manufacturing method thereof Download PDFInfo
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- CN103866332A CN103866332A CN201210537931.6A CN201210537931A CN103866332A CN 103866332 A CN103866332 A CN 103866332A CN 201210537931 A CN201210537931 A CN 201210537931A CN 103866332 A CN103866332 A CN 103866332A
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Abstract
The invention discloses a manufacturing method of a high-temperature resistant metal surface coating with a high absorbing capacity. The method comprises the following steps: step A, providing a metal base material, carrying out a cleaning pretreatment on the metal base material; step B, carrying out a polishing treatment on the metal base material; and step C, carrying out a positive electrode treatment on the metal base material, wherein the nominal voltage of the positive electrode treatment is controlled in a range of 40 to 60 volts and the nominal temperature of the positive electrode treatment is controlled in a range of 0 to 10 DEG C so as to form a porous oxidation layer with fine pores on the metal base material. During the positive electrode treatment, the nominal temperature is controlled in a low temperature range so as to ensure the stable growth of a porous structure; the nominal voltage is controlled in a low voltage range so as to slow the dissolution speed, and finally the finished product of high-temperature resistant metal surface coating with a high absorbing capacity is obtained.
Description
Technical field
The present invention relates to a kind of metallic surface plated film and manufacture method thereof, refer in particular to a kind of metallic surface plated film and manufacture method thereof of high temperature resistant and high absorbing power.
Background technology
The extinction structure with anti-reflective film coating is a kind of structure that photoelectricity and photo-thermal industry are often used, its industry development is not only in green energy industry, be seen everywhere especially in daily life, as glasses, the camera lens of camera, indicating meter etc. has its related application, its function is mainly the absorption increasing sunlight, and reduce its energy and lose because of reflection, the application of the market of general normal temperature mainly taking can increase that sunlight penetrates and the antireflective anti-reflection film that reduces reflection as main flow, its main raw is with plastic cement cheaply, glass material is main, in the application of middle high temperature taking the high temperature resistant anti-reflective film of low reflection as main, its main raw is using resistant to elevated temperatures metal or ceramic as its material, to obtain more energy, both have several hundred million output values on market, and its development for photoelectricity and photo-thermal industry is of crucial importance.
Correlation technique at present, as the solar selective absorbing film of TaiWan, China patent publication No. I318200, it comprises metal-ceramic composite bed more than one deck, by thin metal layer on arbitrary metal-ceramic composite bed plated surface, do not affect the characteristic of low radiation to increase the specific absorption of solar selective absorbing film, the structure of solar selective absorbing film comprises bottom metal reflecting layer, multiple layer metal-ceramic thin film, single/multiple thin metal layer and top anti-reflecting layer, the stacking metal-ceramic composite bed in surface, bottom metal reflecting layer, each thin metal layer correspondence is coated in arbitrary film surface, top anti-reflecting layer is covered in overall rete top.
But the structure that this front case is multi-layer cladding, is difficult for forming firm combination, and easily produces the phenomenon of peeling off between each rete, practicality is comparatively not enough.
Separately have correlation technique, as apparatus structure of the thin-film solar cells of TaiWan, China patent publication No. 201123467 and preparation method thereof, wherein this board structure includes a stratum basale; And an anodization, be formed on this stratum basale, and there are multiple pores arrays; Wherein in the plurality of hole, have more an alkali halide metal precursor, with in the processing procedure of follow-up formation absorption layer, make the quantitative alkali halide metal precursor of inserting in advance stratum basale diffuse to this absorption layer, and then provide and control alkali metal content required in this absorption layer, and effectively block possibility source of pollution.
But above-mentioned prior art still has not enough place, and reason is:
1. the process temperatures of anodizing is being played the part of important role, generally speaking, treatment process all with room temperature as process temperatures, but its variation cannot be monitored, when temperature rise meeting causes the increase rapidly of joule heating, the dissolution rate of barrier layer and hole is accelerated, and the hole of cannot effectively growing.
2. should be using fine aluminium as stratum basale, though fine aluminium has advantages of light weight, it is good to extend, conduct electricity, but mechanical properties is poor, therefore in industrial application, there is its weak point, but when by mechanical properties, preferably alloy imposes anodizing, other elements that this alloy mixes will increase the uncertainty of research, and are difficult for controlling porous oxidation film quality.
In view of this, the inventor does not attain perfect caused many disappearances and inconvenience in above-mentioned metallic surface coating structure design, and deeply design, and active research improvement has a fling at and development and Design goes out this case.
Summary of the invention
The object of the present invention is to provide a kind of metallic surface plated film and manufacture method thereof of high temperature resistant and high absorbing power, it can guarantee the stabilized growth of vesicular structure, and produce the metallic surface plated film finished product of high-absorbility, and promote surperficial mechanical properties and its photo-thermal conversion efficiency.
In order to reach above-mentioned purpose, solution of the present invention is:
A metallic surface film-plating method for high temperature resistant and high absorbing power, it comprises the following steps:
A., one metal base is provided, and aforementioned metal base material is bestowed to a clean processing before;
B. aforementioned metal base material is bestowed to a polished finish;
C. aforementioned metal base material is bestowed to anodizing, the voltage rating of aforesaid anode processing is controlled at 40 volts to 60 volts, and the temperature rating of processing is controlled at 0 ° of C to 10 ° of C, to form a porous oxide coatings with fine hole on aforementioned metal base material.
Aforementioned metal base material is any of aluminium, aluminium alloy, iron, iron alloy, nickel, nickelalloy, copper, copper alloy, tin, tin alloy.
The electrolytic solution of aforesaid anode processing be a sulfuric acid liquid, an oxalic acid liquid, a chromic acid liquor, a phosphoric acid liquid any or mix.
The electrolytic solution of aforesaid anode processing is the sulfuric acid liquid of 0.3 volumetric molar concentration.
The time length of aforesaid anode processing is 60 minutes ± 5 minutes.
The temperature rating of the processing of aforesaid anode processing is controlled at 0 ° of C, and voltage rating is controlled at 50 volts.
The thickness of aforementioned porous oxide coatings between 86um to 128um, porosity between 2.7% to 4.2%, average bore hole size is between 8.2nm to 9nm.
An alkali cleaning processing, a neutralizing treatment and a degrease processing are sequentially carried out in aforementioned pre-treatment.
Aforementioned polished finish is electrochemical polishing treatment, and treatment temp is controlled at 25 ° of C to 30 ° of C, and voltage rating is controlled at 10 volts, and polishing fluid is the mixed solution of chloric acid and ethanol, and lasting 5min.
With a metallic surface plated film for the made high temperature resistant and high absorbing power of the metallic surface film-plating method of high temperature resistant and high absorbing power, it comprises:
One metal base;
On aforementioned metal base material, be provided with a porous oxide coatings with fine hole, the thickness of aforementioned porous oxide coatings is between 86um to 128um, and average bore hole size is between 8.2nm to 9nm.
The porosity of aforementioned porous oxide coatings is between 2.7% to 4.2%.
Adopt after said structure, effect of the present invention is:
1. the present invention is just first controlled at low temperature by temperature rating in the time of anodizing, to guarantee the stabilized growth of vesicular structure, and also set lower voltage rating and slow down dissolution rate, and produce the finished product of high-absorbility, particularly, specific absorption can reach 92% to 93%, and promotes surperficial mechanical properties and its photo-thermal conversion efficiency.
2. the present invention utilizes electrochemical means to generate one deck in metallic substrate surface to adhere to good porous oxide coatings, and sees through voltage rating and temperature, allows porous oxide coatings stable growth, and therefore structure is very firm, is difficult for causing the situation of peeling off.
3. the method for this case is not limited to plane, also can be applied to curved surface, so that the product application of various shape.Present method can be applicable to dystectic various pure metal or alloy as aluminium, copper, nickel, iron ... Deng, refer in particular to the Aludur among aluminium alloy, also can be used for tin.
Brief description of the drawings
Fig. 1 is schematic flow sheet of the present invention.
Fig. 2 A is that the temperature rating of metal base anodizing of the present invention is controlled at 5 ° of C, and voltage rating is controlled at scanning type electron microscope (SEM) figure of 30 volts.
Fig. 2 B is that the temperature rating of metal base anodizing of the present invention is controlled at 5 ° of C, and voltage rating control is scanning type electron microscope (SEM) figure of 40 volts.
Fig. 2 C is that the temperature rating of metal base anodizing of the present invention is controlled at 5 ° of C, and voltage rating is scanning type electron microscope (SEM) figure of 50 volts.
Fig. 2 D is that the temperature rating of metal base anodizing of the present invention is controlled at 5 ° of C, and voltage rating is scanning type electron microscope (SEM) figure of 60 volts.
Fig. 3 A is that the temperature rating of metal base anodizing of the present invention is controlled at 0 ° of C, and voltage rating is scanning type electron microscope (SEM) figure of 30 volts.
Fig. 3 B is that the temperature rating of metal base anodizing of the present invention is controlled at 0 ° of C, and voltage rating is scanning type electron microscope (SEM) figure of 40 volts.
Fig. 3 C is that the temperature rating of metal base anodizing of the present invention is controlled at 0 ° of C, and voltage rating is scanning type electron microscope (SEM) figure of 50 volts.
Fig. 3 D is that the temperature rating of metal base anodizing of the present invention is controlled at 0 ° of C, and voltage rating is scanning type electron microscope (SEM) figure of 60 volts.
Fig. 4 A be metal base anodizing of the present invention through different temperature rating conditions, and voltage rating is the reflectance varies experiment comparison diagram of 30 volts.
Fig. 4 B be metal base anodizing of the present invention through different temperature rating conditions, and voltage rating is the reflectance varies experiment comparison diagram of 50 volts.
Fig. 5 is metal base of the present invention anode specific absorption comparison diagram after treatment under different voltage ratings and different temperature rating condition.
Fig. 6 be metal substrate anodizing of the present invention through different voltage ratings, and temperature rating is fixed as the reflectance varies comparison diagram of 0 ° of C.
Fig. 7 be metal substrate anodizing of the present invention through different voltage ratings, and temperature rating is fixed as the specific absorption comparison diagram of 0 ° of C.
Embodiment
In order further to explain technical scheme of the present invention, below by specific embodiment, the present invention will be described in detail.
The present invention is high temperature resistant and main effect of the metallic surface film-plating method of high-absorbility can present in following embodiment is clear.
The present invention please first consults shown in Fig. 1, comprises:
A., one metal base is provided, the Aludur of aforementioned metal base material among in the present embodiment using aluminium alloy is as illustration, but not as limit, also can be aluminium, iron, iron alloy, nickel, nickelalloy, copper, copper alloy, tin, any of tin alloy, then aforementioned metal base material is bestowed to a clean processing before, aforementioned pre-treatment comprises an alkali cleaning processing, one degrease is processed and a neutralizing treatment, aforementioned alkali cleaning is processed aforementioned metal base material is soaked in to the action of carrying out alkali cleaning in sodium hydroxide solution, remove whereby surperficial impurity, aforementioned degrease processing is to see through acetone soln to remove the existing greasy dirt of aforementioned metal base material itself, aforementioned neutralizing treatment is to see through the action that salpeter solution neutralizes aforementioned metal base material, and remove hydroxide layer that aforementioned metal substrate surface generates to complete the action of pre-treatment.
The correlation parameter that [table one] is pre-treatment
| Item | Parameter |
| Solution composition (alkali cleaning) | Sodium hydroxide and deionized water do and mix with 20g/ |
| Time | |
| 30 min | |
| Solution composition (degrease) | Taking |
| Time | |
| 1 hr | |
| Solution composition (neutralization) | Nitric acid and deionized water do and mix with the volume ratio of 1:3 |
| |
30 min |
B. aforementioned metal base material is bestowed to a polished finish, aforementioned polished finish is electrochemical polishing treatment, and the temperature rating of processing is controlled at 25 ° of C to 30 ° of C, and voltage rating is controlled at 10V, and polishing fluid is the mixed solution of chloric acid and ethanol, and lasting 5min.
[table two] is the correlation parameter of electrochemical polishing treatment
| Title | Parameter |
| Solution composition | Chloric acid: ethanol does and mixes with the volume ratio of 1:4 |
| Voltage | 10 |
| Time | |
| 5 min | |
| Temperature | 25-30 ℃ |
C. aforementioned metal base material is placed in to positive terminal as pre-treatment thing, to bestow anodizing, the voltage rating of aforesaid anode processing is controlled at 30 volts to 60 volts, the temperature rating of processing is controlled at 0 ° of C to 15 ° of C, and the time length is 60 minutes ± 5 minutes, to form a porous oxide coatings with fine hole on aforementioned metal base material, the thickness that makes whereby aforementioned porous oxide coatings between 7.8nm to 151nm, porosity between 2.7% to 7%, average bore hole size is between 8.2 nm to 11.6nm, and the hole degree of depth is equivalent to the thickness of aforementioned porous oxide coatings;
Further illustrate: the generation of aforementioned porous oxide coatings is not limited in plane, also can be applied to curved surface, so that the product application of various shape, aforementioned voltage rating is preferably controlled at 50 volts, and the temperature rating of processing is controlled at 0 ° of C, and place magnetite below positive terminal and cathode terminal centre, make stable being distributed in solution of ionic concn of electrolytic solution by stirring, the electrolytic solution of aforesaid anode processing is a sulfuric acid liquid again, one oxalic acid liquid, one chromic acid liquor, any of one phosphoric acid liquid or mixing, wherein, preferably the sulfuric acid liquid of 0.3 volumetric molar concentration, use the advantage of sulfuric acid liquid to be: operating voltage is less compared with low power consumption, operational condition is easy and production cost is lower, add that in addition sulfuric acid liquid processing procedure gained film corrosion stability is good, and attrition resistance is good,
Another better selection of aforementioned electrolyte is the mixed nitration mixture of use oxalic acid and sulfuric acid phase again, when this can effectively improve anodizing, porous oxide coatings is because the excessive slight crack problem causing of stress, the different hole size characteristic of two acid can reduce cumulative stress speed and avoid slight crack to produce and heat energy generation, can further promote the abrasion resisting effect of metal base.
The surface tissue parameter list of 30 volts of [table three] voltage ratings and 50 volts of anodizing
| 30V/50V | The size (nm) of average hole | Hole distribution scope (nm) | Porosity (%) | Thickness (um) |
| 0℃ | 8.9/8.2 | 6～10/6～10 | 2.7/3.9 | 7.8/103 |
| 5℃ | 14/5.8 | 5～25/3～7 | 6.6/--- | 11/136 |
| 10 |
15/11.16 | 10～30/5～25 | 7/--- | 19/151 |
The surface tissue parameter list that [table four] obtains in 0 DEG C of anodizing of temperature rating
| 0℃ | The size (nm) of average hole | Hole distribution scope (nm) | Porosity (%) | Thickness (um) |
| 30V | 8.9 | 6～10 | 2.7 | 7.8 |
| 40V | 8.3 | 6～10 | 3.6 | 86 |
| 50V | 8.2 | 6～10 | 3.9 | 103 |
| 60V | 9 | 7～11 | 4.2 | 128 |
Fig. 2 A to Fig. 2 D is that temperature rating condition of the present invention control is 5 ° of C, scanning type electron microscope (SEM) figure after anodizing, be 0 ° of C and Fig. 3 A to Fig. 3 D is temperature rating condition of the present invention control, scanning type electron microscope (SEM) figure after anodizing, learn that by observation metal base is in 0 ° of C and 5 ° of surface topographies that C obtains, change to some extent along with the change of voltage rating.
Fig. 4 A is that anodizing of the present invention is through different temperature ratings, and voltage rating is under the condition of 30 volts, carry out the comparison of reflectance varies with ultraviolet spectrometer, in figure, can find the surface obtaining after the anodizing of 30 volts, along with the lifting of temperature rating, its overall reflectivity decreases its overall wave band.
Fig. 4 B is that anodizing of the present invention is through different temperature ratings, and voltage rating is under the condition of 50 volts, carry out the comparison of reflectance varies with ultraviolet spectrometer, due to suitable complete of the structure of metallic substrate surface, the high aspect ratio pore space structure of this metal base, by the effect of its multiple reflections, makes overall reflectivity lower than 10%.
Fig. 5 is the specific absorption comparison diagram of metal base of the present invention after different voltage ratings and different temperature rating condition anodizing, via can spectrogram the reflectivity of 30 volts and 50 volts being done to the specific absorption after weighting, voltage rating is that specific absorption and the temperature rating of 30 volts presents proportional relation, and 50 volts of voltage rating present inverse relation with temperature rating.
Fig. 6 is that metal substrate anodizing of the present invention is through different voltage ratings, and temperature rating is fixed as the reflectance varies comparison diagram of 0 ° of C, learn in temperature rating and be fixed as 0 DEG C, the structure obtaining all obtains lower than the reflectivity below 10% under the voltage rating of 40 volts to 60 volts, and 40 volts of scopes in visible ray have lower reflectivity, but the reflectivity in Yu Jinwaiguang district is higher.
Fig. 7 be metal substrate anodizing of the present invention through different voltage ratings, and temperature rating is fixed as the specific absorption comparison diagram of 0 ° of C, learns when temperature rating is fixed on 0 ° of C, the voltage rating condition of 40 volts to 60 volts, specific absorption can reach 92% to 93%.
Above-described embodiment and accompanying drawing non-limiting product form of the present invention and style, suitable variation or modification that any person of an ordinary skill in the technical field does it, all should be considered as not departing from patent category of the present invention.
Claims (11)
1. a metallic surface film-plating method for high temperature resistant and high absorbing power, is characterized in that, comprises the following steps:
A., one metal base is provided, and aforementioned metal base material is bestowed to a clean processing before;
B. aforementioned metal base material is bestowed to a polished finish;
C. aforementioned metal base material is bestowed to anodizing, the voltage rating of aforesaid anode processing is controlled at 40 volts to 60 volts, and the temperature rating of processing is controlled at 0 ° of C to 10 ° of C, to form a porous oxide coatings with fine hole on aforementioned metal base material.
2. the metallic surface film-plating method of high temperature resistant and high absorbing power as claimed in claim 1, is characterized in that: aforementioned metal base material is any of aluminium, aluminium alloy, iron, iron alloy, nickel, nickelalloy, copper, copper alloy, tin, tin alloy.
3. the metallic surface film-plating method of high temperature resistant and high absorbing power as claimed in claim 1, is characterized in that: the electrolytic solution of aforesaid anode processing be a sulfuric acid liquid, an oxalic acid liquid, a chromic acid liquor, a phosphoric acid liquid any or mix.
4. the metallic surface film-plating method of high temperature resistant and high absorbing power as claimed in claim 3, is characterized in that: the electrolytic solution of aforesaid anode processing is the sulfuric acid liquid of 0.3 volumetric molar concentration.
5. the metallic surface film-plating method of high temperature resistant and high absorbing power as claimed in claim 1, is characterized in that: the time length of aforesaid anode processing is 60 minutes ± 5 minutes.
6. the metallic surface film-plating method of high temperature resistant and high absorbing power as claimed in claim 1, is characterized in that: the temperature rating of the processing of aforesaid anode processing is controlled at 0 ° of C, and voltage rating is controlled at 50 volts.
7. the metallic surface film-plating method of high temperature resistant and high absorbing power as claimed in claim 1, is characterized in that: the thickness of aforementioned porous oxide coatings between 86um to 128um, porosity between 2.7% to 4.2%, average bore hole size is between 8.2nm to 9nm.
8. the metallic surface film-plating method of high temperature resistant and high absorbing power as claimed in claim 1, is characterized in that: an alkali cleaning processing, a neutralizing treatment and a degrease processing are sequentially carried out in aforementioned pre-treatment.
9. the metallic surface film-plating method of high temperature resistant and high absorbing power as claimed in claim 1, it is characterized in that: aforementioned polished finish is electrochemical polishing treatment, treatment temp is controlled at 25 ° of C to 30 ° of C, and voltage rating is controlled at 10 volts, and polishing fluid is the mixed solution of chloric acid and ethanol, and lasting 5min.
10. with a metallic surface plated film for the made high temperature resistant and high absorbing power of the metallic surface film-plating method of the high temperature resistant and high absorbing power of claim 1, it is characterized in that, comprise:
One metal base;
On aforementioned metal base material, be provided with a porous oxide coatings with fine hole, the thickness of aforementioned porous oxide coatings is between 86um to 128um, and average bore hole size is between 8.2nm to 9nm.
The 11. metallic surface plated films of high temperature resistant and high absorbing power as claimed in claim 10, is characterized in that: the porosity of aforementioned porous oxide coatings is between 2.7% to 4.2%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114108050A (en) * | 2021-12-14 | 2022-03-01 | 江南大学 | Preparation method of nano-porous alumina plate for solar energy absorption |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201219607A (en) * | 2010-11-04 | 2012-05-16 | Hon Hai Prec Ind Co Ltd | Aluminium productor and method for making same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201219607A (en) * | 2010-11-04 | 2012-05-16 | Hon Hai Prec Ind Co Ltd | Aluminium productor and method for making same |
Non-Patent Citations (1)
| Title |
|---|
| 丁大伟: "基于多孔Al2O3的太阳光吸收/转化涂层的研究", 《中国博士学位论文全文数据库 工程科技II辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114108050A (en) * | 2021-12-14 | 2022-03-01 | 江南大学 | Preparation method of nano-porous alumina plate for solar energy absorption |
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Application publication date: 20140618 |