CN105271796B - A kind of low angle dependence blueness zinc sulphide schemochrome film and preparation method thereof - Google Patents
A kind of low angle dependence blueness zinc sulphide schemochrome film and preparation method thereof Download PDFInfo
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- CN105271796B CN105271796B CN201510604283.5A CN201510604283A CN105271796B CN 105271796 B CN105271796 B CN 105271796B CN 201510604283 A CN201510604283 A CN 201510604283A CN 105271796 B CN105271796 B CN 105271796B
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Abstract
The invention discloses a kind of low angle dependence blueness zinc sulphide schemochrome film and preparation method thereof, belong to schemochrome technical field of material.Including first using the chemical homogeneous precipitation method; the zinc sulphide microsphere nano particle of uniform particle diameter is prepared, then film is prepared in glass or ceramic matrix surface, is calcined under protection of reducing atmosphere; carbonize micro-content organism, so as to obtain the equally distributed blue schemochrome film of carbon black.Preparation method of the present invention is simple, it is repeated strong, solves chemical organic compounds pigment fugitive color, harmful technical barrier, it is high to substrate requirement that photonic crystal of opals structure is overcome simultaneously, the problems such as plating conditions harshness, suitable for, without changeable colors along with angle schemochrome colorant, being had broad application prospects in various material surface construction.Obtained blue zinc sulphide schemochrome film carbon black is evenly distributed, non-angular dependence, good sphericity, uniform particle diameter.
Description
Technical field
The invention belongs to photon crystal material preparing technical field, and in particular to a kind of low angle dependence blueness zinc sulphide
Schemochrome film and preparation method thereof.
Background technology
The materials arranged in alternating of high low-refraction forms periodic structure, i.e. photonic crystal, and the light of specific wavelength can not
Photon band gap is produced by it, so as to generate schemochrome.Schemochrome is a kind of physics colour generation, have it is bright-colored, never take off
The advantages that color, environment-friendly, short preparation period.In the last few years by the orderly self-assembly method of colloid micro ball, albumen can be formed
Stone structure photonic crystal, last light the photon crystal surface with periodic structure formed by it is dry penetrate, diffraction, scattering etc.
Effect, so as to produce bright and colourful schemochrome, but because having rainbow effect, i.e., the color that different directions are observed is not
Together, so as to greatly limit schemochrome in FPD, the wide viewing angle such as printed medium and optical device show in terms of application.
There is researcher to propose that color saturation can be improved by adding micro black pigment, and can effectively reduce schemochrome to angle
Dependence, reach with viewing angle change schemochrome keep constant effect (CN 103173039A, 102702791A,
103788770A), but the above method is disadvantageous in that, photonic crystal structure color film prepare in, it is necessary to by powder with it is micro-
Carbon black or black pigment mixing film are measured, technique is more complicated, and opal structural requires very high to film coating environment, by extraneous ring
Border interference is big, and the environmental fluctuating of very little can all have a great impact to the quality of film, therefore is difficult to be widely used.Much grind
The person of studying carefully adds micro carbon black or melanin in silica either polystyrene colloidal liquid solution, is prepared using the methods of spin coating
Go out shortrange order, the schemochrome film of longrange disorder, the effect of wherein carbon black or melanin is can be in visible light wave range
Inside there is stronger absorption, so as to reduce incoherent scattering so that schemochrome film is in the state of shortrange order, longrange disorder
Higher color saturation, while this shortrange order can be shown, the structure of longrange disorder is because isotropism, tool
There is low angle dependence, i.e., as the change of viewing angle, color are basically unchanged, display, printing etc. can be applied to.But
It is that the ultrafine nanometer carbon black applied in the process has higher surface energy, therefore difficult scattered, easily reunion is present, and
The shortcomings of being difficult to dissolving in most solution, and organic black dyes needs to carry out the technical process such as colorant match, colour mixture, process is complicated
And organic black dyes for preparing it is unstable the shortcomings of.In the last few years, semiconductor sulfide (such as zinc sulphide) material because
There are many excellent performances such as to be received significant attention in sewage disposal, magneto-optic conversion, antibacterial, photonic crystal etc. for it.
So far, also no document is to preparing this short distance using materials such as inorganic semiconductor oxide, sulfide
Ordered structure color film carried out report.
The content of the invention
It is the defects of in order to overcome above-mentioned prior art to exist, blue it is an object of the invention to provide a kind of low angle dependence
Color zinc sulphide schemochrome film and preparation method thereof, this method is simple to operate, and repeatability is strong, is adapted to industrial-scale production；Through
Spherical zine sulfide photonic crystal is spherical made from this method spends, and uniform particle diameter, is widely used.
The present invention is to be achieved through the following technical solutions：
The invention discloses a kind of preparation method of low angle dependence blueness zinc sulphide photonic crystal structure color film, bag
Include following steps：
1) (3~5) are pressed:1 mass ratio takes Zn (NO3)2·6H2O and polyvinylpyrrolidone, then by polyvinylpyrrolidine
Ketone：Deionized water=(0.05~0.06) g：100mL ratio adds deionized water, is sufficiently mixed uniformly, obtains homogeneous solution；
2) (0.3~0.5) g is pressed：50mL ratio, thioacetamide is dissolved in deionized water, ultrasonic mixing processing, is obtained
To thioacetyl amine aqueous solution；
3) thioacetyl amine aqueous solution made from homogeneous solution made from step 1) and step 2) is pressed into (2~2.5)：1
After volume ratio mixes, at 70~85 DEG C, 5~8h of water-bath, the emulsion containing zinc sulphide microballoon is made, then by washing
And ultrasonic disperse, the ethanol solution of obtained monodisperse ZnS microballoon；
4) substrate is placed in the vacuum drying of monodisperse ZnS microballoon ethanol solution, zinc sulfide film is made, by zinc sulphide
Under protective atmosphere, through 300~500 DEG C of calcination processings, blue zinc sulphide photonic crystal structure color colorant is made in film.
It is uniformly to use 25~30min of magnetic stirrer that step 1), which is sufficiently mixed,.
Ultrasonic mixing processing time is 10~20min in step 2).
Washing described in step 3) is first to wash the emulsion containing zinc sulphide microballoon 2~4 times through deionization, then through nothing
Water-ethanol cleans 2~4 times.
Step 4) the protective atmosphere uses nitrogen or argon gas.
Step 4) the vacuum drying is carried out at 50~65 DEG C.
The invention also discloses using low angle dependence blueness zinc sulphide photonic crystal structure color made from the above method
Film, the low angle dependence blueness zinc sulphide photonic crystal structure color film carbon black are evenly distributed, and non-angular dependence is spherical
Spend, uniform particle diameter.
Compared with prior art, the present invention has technique effect beneficial below：
The preparation method of low angle dependence blueness zinc sulphide schemochrome film disclosed by the invention, first using chemical homogeneous
The precipitation method, by strictly controlling Zn (NO3)2·6H2O and polyvinylpyrrolidone reaction ratio (3~5：, and deionization 1)
The dosage of water, the zinc sulphide microsphere nano particle of uniform particle diameter is prepared, then the calcination processing under protective atmosphere, make micro to have
Machine thing carbonizes, so as to obtain the blue schemochrome film that carbon black is evenly distributed in microballoon, this carbon containing zinc sulphide microballoon film
The color of pigment will not change with the change of viewing angle, in colour-stable, not fugitive color.Preparation method of the present invention is simple, weight
Renaturation is strong, because the presence of C caused by micro organic carbon causes incoherent scattering luminous intensity to reduce, and coherent scattering
Intensity is more prominent, so as to which the non-protein stone structure in rough surface shortrange order still has higher color saturation.No
But solve chemical organic compounds pigment fugitive color, harmful technical barrier, while solve opal structural to substrate
It is required that strict, the skill problem such as film coating environment harshness.Semiconductor, sulfide (such as zinc sulphide) material have many excellent property
Can, it can apply in sewage disposal, magneto-optic conversion, antibacterial, photonic crystal etc., and multi-functional material can be prepared to
Material.So far, also no document is to preparing this shortrange order knot using materials such as inorganic semiconductor oxide, sulfide
Structure color film carried out report.
Carbon black point in blue zinc sulphide photonic crystal structure color film made from a kind of novel method is utilized through the present invention
Cloth is uniform, non-angular dependence, good sphericity, uniform particle diameter, on display material, sensing, catalysis and various types of materials surface
Color field has a wide range of applications.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the gained of embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the gained of embodiment 1；
Fig. 3 is EDS figure of the zinc sulphide microballoon after calcining；
Fig. 4 is the optical photograph of the schemochrome film of the gained of embodiment 1；
Fig. 5 is to amplify 30 times of photos under the schemochrome Film Optics microscope of the gained of embodiment 1.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1
The present invention is to be achieved through the following technical solutions：
A kind of preparation method of blue zinc sulphide schemochrome colorant, comprises the following steps：
1) it is 3 in mass ratio:1 weighs Zn (NO3)2·6H2O and some grams of polyvinylpyrrolidone (PVP), add beaker
In, proportionally 0.06g PVP:100mL deionized waters, total Water are that 100mL magnetic agitations fully dissolve and uniformly mixed, and are stirred
Mix 30min and obtain homogeneous solution；
2) precise thioacetamide 0.3g, add 50mL deionized water 10~20min of ultrasonic mixing, obtain thioacetyl
Amine aqueous solution；
3) 1) and after 2) two homogeneous solutions stir respectively, added above-mentioned in same beaker, magnetic agitation 80
Water-bath 6h under the conditions of DEG C, you can obtain the emulsion containing zinc sulphide microballoon, then wash through washing, alcohol and respectively pass through afterwards three times
Ultrasonic disperse obtains the ethanol solution of monodisperse ZnS microballoon.
4) ethanol solution that glass or ceramic substrate are positioned over to the monodisperse ZnS microballoon obtained by step 3) exists
Dried in 60 DEG C of vacuum drying chambers, short distance word order zinc sulfide film is made, film is then passed through into 300 DEG C of heat under nitrogen protection
Processing, you can obtain non-angular dependence, the equally distributed blue zinc sulphide photonic crystal structure color film of carbon black.
Sample through blue zinc sulphide schemochrome film made from the present embodiment as shown in Figure 4, Figure 5, is clear that
Blueness is presented in it.Its XRD analysis as shown in figure 1, its XRD analysis as shown in figure 1,2 θ=28.2 °, 47.7 °, 56.6 ° right respectively
ZnS (111), (220), (311) crystal face are answered, and in addition to ZnS characteristic peaks, occurs without other miscellaneous peaks, shows made
Standby sample is pure ZnS.；Scanning electron microscope (SEM) photograph is high as shown in Fig. 2 it can be seen that zinc sulphide microsphere surface is coarse
Spend single dispersing, uniform particle diameter (230 ± 10nm).Energy spectrum analysis as shown in figure 3, as can be seen from the figure except Zn and S peak it
The outer characteristic peak that have also appeared C element, show there be micro C element in ZnS microballoons, and from SEM it can be seen from the figure thats, C
Element is uniformly distributed in mono-dispersion microballoon, and soilless sticking phenomenon occurs.
Embodiment 2
1) it is 3.5 in mass ratio:1 weighs Zn (NO3)2·6H2O and some grams of polyvinylpyrrolidone (PVP), add and burn
In cup, proportionally 0.055g PVP:100mL deionized waters, total Water are that 100mL magnetic agitations fully dissolve and uniformly mixed
Close, stirring 30min obtains homogeneous solution；
2) precise thioacetamide 0.3g, add 50mL deionized water 10~20min of ultrasonic mixing, obtain thioacetyl
Amine aqueous solution；
3) 1) and after 2) two homogeneous solutions stir respectively, added above-mentioned in same beaker, magnetic agitation 80
Water-bath 7h under the conditions of DEG C, you can obtain the emulsion containing zinc sulphide microballoon.Washed through washing, alcohol each three times afterwards by super
Sound is scattered to obtain the ethanol solution of monodisperse ZnS microballoon；
4) ethanol solution that glass or ceramic substrate are positioned over to the monodisperse ZnS microballoon obtained by step 3) exists
Dried in 50 DEG C of vacuum drying chambers, then by film under nitrogen protection by 500 DEG C of heat treatments, you can obtain low angle dependence
Property, carbon black is uniformly distributed blue zinc sulphide schemochrome film.
Embodiment 3
1) it is 4 in mass ratio:1 weighs Zn (NO3)2·6H2O and some grams of polyvinylpyrrolidone (PVP), add beaker
In, proportionally 0.05g PVP:100mL deionized waters, total Water are that 100mL magnetic agitations fully dissolve and uniformly mixed, and are stirred
Mix 30min and obtain homogeneous solution；
2) precise thioacetamide 0.4g, add 50mL deionized water 10~20min of ultrasonic mixing, obtain thioacetyl
Amine aqueous solution；
3) 1) and after 2) two homogeneous solutions stir respectively, added above-mentioned in same beaker, magnetic agitation 85
Water-bath 5h under the conditions of DEG C, you can obtain the emulsion containing zinc sulphide microballoon.Washed through washing, alcohol each three times afterwards by super
Sound is scattered to obtain the ethanol solution of monodisperse ZnS microballoon；
4) ethanol solution that glass or ceramic substrate are positioned over to the monodisperse ZnS microballoon obtained by step 3) exists
Dried in 55 DEG C of vacuum drying chambers, then by film under nitrogen protection by 400 DEG C of heat treatments, you can obtain low angle dependence
Property, carbon black is uniformly distributed blue zinc sulphide schemochrome film.
Embodiment 4
1) it is 5 in mass ratio:1 weighs Zn (NO3)2·6H2O and some grams of polyvinylpyrrolidone (PVP), add beaker
In, proportionally 0.05g PVP:100mL deionized waters, total Water are that 100mL magnetic agitations fully dissolve and uniformly mixed, and are stirred
Mix 30min and obtain homogeneous solution；
2) precise thioacetamide 0.5g, add 50mL deionized water 10~20min of ultrasonic mixing, obtain thioacetyl
Amine aqueous solution；
3) 1) and after 2) two homogeneous solutions stir respectively, added above-mentioned in same beaker, magnetic agitation 75
Water-bath 6h under the conditions of DEG C, you can obtain the emulsion containing zinc sulphide microballoon.Washed through washing, alcohol each three times afterwards by super
Sound is scattered to obtain the ethanol solution of monodisperse ZnS microballoon；
4) ethanol solution that glass or ceramic substrate are positioned over to the monodisperse ZnS microballoon obtained by step 3) exists
Drying obtains shortrange order zinc sulfide film in 50 DEG C of vacuum drying chambers, and film is then passed through into 350 DEG C of heat under nitrogen protection
Processing, you can obtain low angle dependence, carbon black is uniformly distributed zinc sulphide blue powder pigment.
In summary, the preparation method of a kind of blue low angle dependence zinc sulphide schemochrome film disclosed by the invention,
Include the preparation of nano-zinc sulfide microballoon；The preparation of shot-range ordered structure color film, by zinc sulfide film under reducing atmosphere
Calcining；Finally give a kind of blue schemochrome film of no changeable colors along with angle.This method cost is cheap, simple and easy, suitable for
Various material surface construction is without changeable colors along with angle schemochrome colorant, and preparation method is simple, and repeatability is strong, is easy to prepare on a large scale.
By controlling the particle diameter of microballoon, the multiple colors such as bluish-green, royal purple, purplish blue can be obtained, display material, sensing, catalysis and
Various types of materials surface coloring field has a wide range of applications.
Claims (7)
- A kind of 1. preparation method of low angle dependence blueness zinc sulphide photonic crystal structure color film, it is characterised in that including Following steps：1) (3~5) are pressed:1 mass ratio takes Zn (NO3)2·6H2O and polyvinylpyrrolidone, then by polyvinylpyrrolidone：Go Ionized water=(0.05~0.06) g：100mL ratio adds deionized water, is sufficiently mixed uniformly, obtains homogeneous solution；2) (0.3~0.5) g is pressed：50mL ratio, thioacetamide is dissolved in deionized water, ultrasonic mixing processing, obtains sulphur For acetyl amine aqueous solution；3) thioacetyl amine aqueous solution made from homogeneous solution made from step 1) and step 2) is pressed into (2~2.5)：1 volume After mixing, at 70~85 DEG C, 5~8h of water-bath, the emulsion containing zinc sulphide microballoon is made, then by washing and surpass Sound disperses, and the ethanol solution of monodisperse ZnS microballoon is made；4) substrate is placed in the vacuum drying of monodisperse ZnS microballoon ethanol solution, zinc sulfide film is made, by zinc sulfide film Under protective atmosphere, through 300~500 DEG C of calcination processings, blue zinc sulphide photonic crystal structure color colorant is made.
- 2. the preparation method of low angle dependence blueness zinc sulphide photonic crystal structure color film according to claim 1, Characterized in that, it is uniformly to use 25~30min of magnetic stirrer that step 1), which is sufficiently mixed,.
- 3. the preparation method of low angle dependence blueness zinc sulphide photonic crystal structure color film according to claim 1, Characterized in that, ultrasonic mixing processing time is 10~20min in step 2).
- 4. the preparation method of low angle dependence blueness zinc sulphide photonic crystal structure color film according to claim 1, Characterized in that, the washing described in step 3) is first to wash the emulsion containing zinc sulphide microballoon 2~4 times through deionization, then Through washes of absolute alcohol 2~4 times.
- 5. the preparation method of low angle dependence blueness zinc sulphide photonic crystal structure color film according to claim 1, Characterized in that, the step 4) protective atmosphere uses nitrogen or argon gas.
- 6. the preparation method of low angle dependence blueness zinc sulphide photonic crystal structure color film according to claim 1, Characterized in that, the step 4) vacuum drying is carried out at 50~65 DEG C.
- It is 7. brilliant using low angle dependence blueness zinc sulphide photon made from the method described in any one in claim 1~6 Body schemochrome film, it is characterised in that low angle dependence blueness zinc sulphide photonic crystal structure color film carbon black distribution is equal It is even, non-angular dependence, good sphericity, uniform particle diameter.
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| CN105694085A (en) * | 2016-02-03 | 2016-06-22 | 陕西科技大学 | Method for lowering color generation angle dependency of PS colloidal crystal film |
| EP3627988B1 (en) | 2017-09-29 | 2021-01-13 | NIKE Innovate C.V. | Structurally-colored articles and methods for making and using structurally-colored articles |
| US11597996B2 (en) | 2019-06-26 | 2023-03-07 | Nike, Inc. | Structurally-colored articles and methods for making and using structurally-colored articles |
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| US11241062B1 (en) | 2020-08-07 | 2022-02-08 | Nike, Inc. | Footwear article having repurposed material with structural-color concealing layer |
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