CN103276377A - Preparation method of ultra-black coating with nano-pore structure - Google Patents
Preparation method of ultra-black coating with nano-pore structure Download PDFInfo
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- CN103276377A CN103276377A CN2013102006667A CN201310200666A CN103276377A CN 103276377 A CN103276377 A CN 103276377A CN 2013102006667 A CN2013102006667 A CN 2013102006667A CN 201310200666 A CN201310200666 A CN 201310200666A CN 103276377 A CN103276377 A CN 103276377A
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Abstract
The invention discloses a preparation method of an ultra-black coating with a nano-pore structure. The preparation method comprises the following steps of: cleaning and activating a metal matrix material, plating the cleaned and activated metal matrix material in a chemical plating solution to deposit a nickel phosphorus carbon alloy coating on the metal matrix material, wherein the chemical plating solution comprises nickel sulfate, sodium hypophosphite, a buffer agent, a complexing agent and a carbon black, and the particle size of the carbon black is 20-60mm, and chemically etching the nickel phosphorus carbon alloy coating on the surface of the metal matrix material using an etching acid solution. A plurality of nanometer conical pores different in sizes are uniformly distributed in the surface of the ultra-black coating prepared by the preparation method, nano-pores which are smaller in pore diameters are filled in the inner surfaces of the nanometer conical pores and in the plane areas between the adjacent conical pores, the light reflectivity of the ultra-black coating within a 400-2000 light wavelength range is less than 0.12%, and the ultra-black coating has light absorption performance better than that of the light absorbing coating obtained by carrying out conventional chemical etching on a Ni-P alloy.
Description
Technical field
The present invention relates to a kind of blacker-than-black coating production with nano-pore structure, belong to blacker-than-black light-absorbing coating technical field.
Background technology
Black coating is widely used in fields such as solar energy converting, heat-light-electric generation, infrared acquisition, microscope imaging, celestial observation.For example, glass tube with vacuum outer wall of inner tube surface-coated one deck blackwash that need be in solar water heater improves the specific absorption to sunlight.The lens barrel inwall of various opticinstruments needs blacking, to improve shining the absorption of the light on the inwall, reduces the reflection of light on inwall, reduces the light that reflects from inwall to the interference of imaging, improves the sharpness of imaging.
A certain amount of light all can be reflected in the surface of general solid material (as pottery, metal, plastics etc.).Desirable black material has zero specific refractory power, can absorb 100% light color, and general black pigment light reflectance is between 5% to 10%.At present knownly the Ni-P alloy coat is carried out chemical etching can obtain porous surface structure.Document (S. Kodama, M. Horiuchi, T. Kunii, K. Kuroda. Ultra-Black Nickel-Phosphorus Alloy Optical Absorber. IEEE Transactions On Instrumentation And Measurement. 1990,39,230-232.) report, this Ni-P alloy coat energy efficient absorption light with porous surface structure, its light reflectance can be low to moderate 0.16-0.18%.But be subjected to preparation method's restriction, present this porous Ni-P alloy coat has the tapered hole shape characteristic, and surface apertures belongs to the micron order size category.In this nano/micron pore structure, the wide aperture has increased the pore wall thickness between the adjacent holes, and internal surface of hole is more smooth in addition, causes quite a few light still to be reflected.For further reducing the light reflectance of above-mentioned porous Ni-P alloy coat, a kind of novel blacker-than-black coating of research and design and preparation method thereof is very necessary.
Summary of the invention
At the prior art above shortcomings, the object of the present invention is to provide a kind of blacker-than-black coating production with nano-pore structure, this blacker-than-black coating can improve material to the absorption of light, reduces object to reflection of light.
The present invention realizes that the technical solution of above-mentioned purpose is as follows:
A kind of blacker-than-black coating production with nano-pore structure, its preparation process is:
(1) pre-treatment: the metal matrix material surface is cleaned and activated, be beneficial to adhering to of the compound coated coating of subsequent chemistry;
(2) chemical composite nickel-plating phosphorus carbon: it is even earlier the chemical plating fluid for preparing to be carried out ultrasonic concussion, under 75-90 ℃ the plating temperature condition body material after the processing of (1) step is being put into the chemical plating fluid plating then, plating time is 1-3h, chemical plating fluid pH is 3-6, make metal matrix material surface deposition nickel phosphorus carbon alloy coating, then washing, drying; Each component of described chemical plating fluid and concentration are respectively single nickel salt 25-40g/L, inferior sodium phosphate 20-30g/L, buffer reagent 10-20g/L, complexing agent 25-35g/L, carbon black 0.5-3g/L, all the other are deionized water or distilled water, and wherein the particle diameter of carbon black is 20-60 nm;
Described buffer reagent is any in acetic acid or the sodium acetate; Described complexing agent is the mixture of any or two kinds of arbitrary proportions in citric acid, the lactic acid;
(3) chemical etching: with the etching acid solution metal matrix material surface nickel phosphorus carbon alloy coating is carried out chemical etching, washing, drying namely prepare the blacker-than-black coating with nano-pore structure; Wherein the etching acid solution is nitric acid, and concentration of nitric acid is 6-9mol/L, and etching temperature is 20-50 ℃, etching time 10-120s.
Compared to existing technology, the present invention has following beneficial effect:
1, the invention provides the blacker-than-black coating, in 400-2000nm wavelength of light scope, less than 0.12%, the light-absorbing coating that obtains than conventional chemical etching N i-P alloy has better light absorptive to the reflectivity of light.
2, preparation method's involved in the present invention unique distinction is, utilize chemically composited coating technology in Ni-P coating, to introduce the nano carbon black particle, these nano carbon black particles that are uniformly distributed in Ni-P coating can preferentially corrode in chemical etching process subsequently, and form nano-pore structure at the coating tissue surface.In addition, nano carbon black itself has good light absorptive, and the introducing of carbon black particle helps to reduce the blacker-than-black coating to the reflectivity of light.
3, the prepared blacker-than-black coating of the present invention has unique surface tissue, its surface is uniform-distribution with micron tapered hole (aperture is 1-20 μ m) not of uniform size, and is full of the littler nanoporous in aperture (aperture＜100nm) at the internal surface of micron tapered hole and the plane domain between the adjacent conical hole.
Description of drawings
Fig. 1 is 2000 times of field emission scanning electron microscope pictures of embodiment 1 gained blacker-than-black coating.
Fig. 2 is 20000 times of field emission scanning electron microscope pictures of embodiment 1 gained blacker-than-black coating.
Fig. 3 is 50000 times of field emission scanning electron microscope pictures of embodiment 1 gained blacker-than-black coating.
Embodiment
Blacker-than-black coating of the present invention, be on the metal matrix material surface evenly coated with the Ni-P-C composite deposite, with the etching acid solution Ni-P-C composite deposite on metal matrix material surface is carried out chemical etching again and is prepared from.Above-mentioned blacker-than-black coating, its surface are uniform-distribution with micron tapered hole (aperture is 1-20 μ m) not of uniform size, and are full of the littler nanoporous in aperture (aperture＜100nm) at the internal surface of micron tapered hole and the plane domain between the adjacent conical hole.
The present invention has the blacker-than-black coating production of nano-pore structure, and its preparation process is specially:
(1) pre-treatment: the metal matrix material surface is cleaned and activated, be beneficial to adhering to of the compound coated coating of subsequent chemistry;
(2) chemical composite nickel-plating phosphorus carbon: it is even earlier the chemical plating fluid for preparing to be carried out ultrasonic concussion, and the sonic oscillation time is 10-60min; Under 75-90 ℃ the plating temperature condition metal matrix material after the processing of (1) step is being put into the chemical plating fluid plating then, plating time is 1-3h, chemical plating fluid pH is 3-6, makes metal matrix material surface deposition nickel phosphorus carbon alloy coating, and washing is clean and dry then; Each component of described chemical plating fluid and concentration are respectively single nickel salt 25-40g/L, inferior sodium phosphate 20-30g/L, buffer reagent 10-20g/L, complexing agent 25-35g/L and carbon black 0.5-3g/L, all the other are deionized water or distilled water, and wherein the particle diameter of carbon black is 20-60 nm.Described buffer reagent is any in acetic acid or the sodium acetate; Described complexing agent is the mixture of any or two kinds of arbitrary proportions in citric acid, the lactic acid;
(3) chemical etching: with the etching acid solution metal matrix material surface nickel phosphorus carbon alloy coating is carried out chemical etching, washing, drying namely prepare the blacker-than-black coating with nano-pore structure; Wherein the etching acid solution is nitric acid, and concentration of nitric acid is 6-9mol/L, and etching temperature is 20-50 ℃, etching time 10-120s.
Pre-treatment of the present invention both can clean and activate according to the metal matrix material method routinely of reality, also can carry out pre-treatment by following method provided by the invention: remove the greasy dirt on metal matrix material surface and wash clean with heat alkali liquid earlier, acid-wash activation again is about to that body material after the oil removing is put into the hydrochloric acid soln etch and washing is clean.Described alkali lye is the mixed aqueous solution of being made up of the yellow soda ash of the tertiary sodium phosphate of the sodium hydroxide of 15-40g/L, 15-40g/L and 20-40g/L, and except oil temperature is 40-70 ℃, the oil removing time is 10-20min.Described acid-wash activation at room temperature carries out, and wherein concentration of hydrochloric acid is 5-30%, and the acid liquor etching time is 0.5-2min.
Blacker-than-black coating of the present invention, in 400-2000nm wavelength of light scope, less than 0.12%, the light-absorbing coating that obtains than conventional chemical etching N i-P alloy has better light absorptive to the reflectivity of light.
Preparation method to blacker-than-black coating of the present invention is described further below by specific embodiment.
Embodiment 1
(10 * 10 * 1.5mm) carry out oil removing 10min, washing to No. 20 steel matrix in 40 ℃ with the mixed solution of 15g/L sodium hydroxide, 40g/L tertiary sodium phosphate and 30g/L yellow soda ash; At room temperature use 5% hydrochloric acid etching 2min then, washing; Then steel substrate is put into the chemical plating fluid that disperses through the 10min sonic oscillation in 75 ℃ of plating 3h, plating bath pH is 4.5, chemical plating fluid is made up of single nickel salt 30g/L, inferior sodium phosphate 22g/L, sodium acetate 15g/L, lactic acid 30g/L, carbon black 1.5g/L, solvent is deionized water, particle size carbon black is 20-60nm, treat to wash immediately after plating is finished, drying obtains nickel phosphorus carbon alloy coating; Use the salpeter solution of 6mol/L to the nickel phosphorus carbon alloy coating chemical etching 90s of matrix surface at last, washing, drying obtains the blacker-than-black coating.Fig. 1, Fig. 2 and Fig. 3 are respectively the field emission scanning electron microscope picture of embodiment 1 gained blacker-than-black coating under 2000 times, 20000 times and 50000 times.
Embodiment 2
(20 * 20 * 3mm) carry out oil removing 20min, washing to No. 45 steel matrix in 40 ℃ with the mixed solution of 40g/L sodium hydroxide, 30g/L tertiary sodium phosphate and 20g/L yellow soda ash; At room temperature use 30% hydrochloric acid etching 0.5min then, washing; Then steel substrate is put into the chemical plating fluid that disperses through the 30min sonic oscillation in 82 ℃ of plating 2h, plating bath pH is 3, chemical plating fluid is made up of single nickel salt 40g/L, inferior sodium phosphate 28g/L, acetic acid 20g/L, lactic acid 30g/L, carbon black 3g/L, solvent is deionized water, particle size carbon black is 20-60nm, treat to wash immediately after plating is finished, drying obtains nickel phosphorus carbon alloy coating; Use the salpeter solution of 8mol/L to the nickel phosphorus carbon alloy coating chemical etching 40s of matrix surface at last, washing, drying obtains the blacker-than-black coating.
Embodiment 3
(20 * 20 * 3mm) soak oil removing 30min, washing to QAl7 McGill metals matrix in room temperature with acetone; At room temperature use 8% sulfuric acid etch 1min then, washing; Then copper alloy matrix is put into the chemical plating fluid that disperses through the 60min sonic oscillation in 85 ℃ of plating 1.5 h, plating bath pH is 5.2, chemical plating fluid is made up of single nickel salt 25g/L, inferior sodium phosphate 20g/L, acetic acid 10g/L, citric acid 25g/L, carbon black 0.5g/L, solvent is distilled water, particle size carbon black is 20-60nm, treat to wash immediately after plating is finished, drying obtains nickel phosphorus carbon alloy coating; Use the salpeter solution of 10mol/L to the nickel phosphorus carbon alloy coating chemical etching 20s of matrix surface at last, washing, drying obtains the blacker-than-black coating.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (4)
1. blacker-than-black coating production with nano-pore structure, it is characterized in that: its preparation process is:
(1) pre-treatment: the metal matrix material surface is cleaned and activated, be beneficial to adhering to of the compound coated coating of subsequent chemistry;
(2) chemical composite nickel-plating phosphorus carbon: it is even earlier the chemical plating fluid for preparing to be carried out ultrasonic concussion, under 75-90 ℃ the plating temperature condition body material after the processing of (1) step is being put into the chemical plating fluid plating then, plating time is 1-3h, chemical plating fluid pH is 3-6, make metal matrix material surface deposition nickel phosphorus carbon alloy coating, then washing, drying; Each component of described chemical plating fluid and concentration are respectively single nickel salt 25-40g/L, inferior sodium phosphate 20-30g/L, buffer reagent 10-20g/L, complexing agent 25-35g/L, carbon black 0.5-3g/L, all the other are deionized water or distilled water, and wherein the particle diameter of carbon black is 20-60 nm;
(3) chemical etching: with the etching acid solution metal matrix material surface nickel phosphorus carbon alloy coating is carried out chemical etching, washing, drying namely prepare the blacker-than-black coating with nano-pore structure; Wherein the etching acid solution is nitric acid, and concentration of nitric acid is 6-9mol/L, and etching temperature is 20-50 ℃, etching time 10-120s.
2. the blacker-than-black coating production with nano-pore structure according to claim 1 is characterized in that: buffer reagent is any in acetic acid or the sodium acetate in the described step (2).
3. the blacker-than-black coating production with nano-pore structure according to claim 1 is characterized in that: complexing agent is the mixture of any or two kinds of arbitrary proportions in citric acid, the lactic acid in the described step (2).
4. the blacker-than-black coating production with nano-pore structure according to claim 1, it is characterized in that: the blacker-than-black coating that present method prepares, its surface is uniform-distribution with the micron tapered hole not of uniform size that the aperture is 1-20 μ m, the nanoporous that is full of aperture＜100nm at internal surface and the plane domain between the adjacent conical hole of micron tapered hole.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861868A (en) * | 2015-06-17 | 2015-08-26 | 哈尔滨工业大学 | Preparation method of ultra-black coating |
| CN106556171A (en) * | 2015-09-29 | 2017-04-05 | 淄博环能海臣环保技术服务有限公司 | A kind of etching generates high temperature resistant selective absorbing functional membrane |
| CN106555177A (en) * | 2015-09-29 | 2017-04-05 | 淄博环能海臣环保技术服务有限公司 | One kind thermally decomposes to generate high temperature resistant selective absorbing functional membrane |
| CN107053787A (en) * | 2017-04-12 | 2017-08-18 | 广东欧珀移动通信有限公司 | A kind of composite and preparation method thereof, electronic equipment |
| CN112882137A (en) * | 2019-11-29 | 2021-06-01 | 大立光电股份有限公司 | Imaging lens, camera module and electronic device |
| CN114231874A (en) * | 2022-02-24 | 2022-03-25 | 潍坊工程职业学院 | Composite plating method for carbon steel surface |
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| US4361630A (en) * | 1979-04-20 | 1982-11-30 | The United States Of America As Represented By The Secretary Of The Commerce | Ultra-black coating due to surface morphology |
| US4897164A (en) * | 1989-04-24 | 1990-01-30 | Olin Hunt Specialty Products Inc. | Process for preparing the through hole walls of a printed wiring board for electroplating |
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Patent Citations (4)
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| US4361630A (en) * | 1979-04-20 | 1982-11-30 | The United States Of America As Represented By The Secretary Of The Commerce | Ultra-black coating due to surface morphology |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861868A (en) * | 2015-06-17 | 2015-08-26 | 哈尔滨工业大学 | Preparation method of ultra-black coating |
| CN106556171A (en) * | 2015-09-29 | 2017-04-05 | 淄博环能海臣环保技术服务有限公司 | A kind of etching generates high temperature resistant selective absorbing functional membrane |
| CN106555177A (en) * | 2015-09-29 | 2017-04-05 | 淄博环能海臣环保技术服务有限公司 | One kind thermally decomposes to generate high temperature resistant selective absorbing functional membrane |
| CN106556171B (en) * | 2015-09-29 | 2018-11-23 | 淄博环能海臣环保技术服务有限公司 | A kind of etching generation high temperature resistant selective absorbing functional membrane |
| CN107053787A (en) * | 2017-04-12 | 2017-08-18 | 广东欧珀移动通信有限公司 | A kind of composite and preparation method thereof, electronic equipment |
| CN112882137A (en) * | 2019-11-29 | 2021-06-01 | 大立光电股份有限公司 | Imaging lens, camera module and electronic device |
| CN114231874A (en) * | 2022-02-24 | 2022-03-25 | 潍坊工程职业学院 | Composite plating method for carbon steel surface |
| CN114231874B (en) * | 2022-02-24 | 2022-05-03 | 潍坊工程职业学院 | Composite plating method for carbon steel surface |
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