CN104392767A - Graphene-based conductive pearlescent pigment and preparation method thereof - Google Patents
Graphene-based conductive pearlescent pigment and preparation method thereof Download PDFInfo
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- CN104392767A CN104392767A CN201410520211.8A CN201410520211A CN104392767A CN 104392767 A CN104392767 A CN 104392767A CN 201410520211 A CN201410520211 A CN 201410520211A CN 104392767 A CN104392767 A CN 104392767A
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Abstract
The invention relates to a graphene-based conductive pearlescent pigment and a preparation method thereof. The graphene-based conductive pearlescent pigment comprises a pearlescent pigment and graphene wrapping the surface of the pearlescent pigment, wherein the thickness of the graphene is 0.3 to 100nm, and the mass percentage content of the graphene in the composite material is 0.01 to 5%.
Description
Technical field
The present invention relates to and a kind of there is pigment of conductivity and pearl effect and preparation method thereof, belong to pearlescent pigment and New function field of material technology.
Background technology
Pearlescent pigment refers to and is coated on mica, aluminium flake, glass sheet surface by quasi-metal oxides such as metal oxide or silicon dioxide such as the higher titanium dioxide of refractive index, make it a kind of functional material presenting pearly-lustre characteristic, be widely used in the aspects such as coating, cosmetics, anti-forgery ink, printing and dyeing.In recent years, along with the continuous expansion of the pearlescent pigment scope of application, except the primary demand meeting attractive, decorative, market to be applicable to the conduction of specific environment, magnetic, the functional pearlescent pigment of heat conduction demand constantly increasing (reference literature 1-2).Wherein, Electro-conductive pearlescent pigment is widely used in the various field such as plastic products, electronics plastic cement products, electronic devices and components of conduction terrace, bumper, auto parts and components as a kind of functional pigment.In it is prepared, traditional Electro-conductive pearlescent pigment by tin ash doping metals (indium and antimony) and nonmetalloid (fluorine and phosphorus) obtained, expensive, complex process, and the coordination in color and conductivity two is difficult to take into account.The product colour that conductivity is better is darker, can not simultaneously satisfactory (reference literature 3-5).Therefore, exploitation color and the adjustable novel conductive pearlescent pigment of conductivity, prepare high connductivity light color system pearlescent pigment, widen the scope of application of Electro-conductive pearlescent pigment, become the focus of current Electro-conductive pearlescent pigment development field.
Graphene is by the two dimensional surface carbon nanomaterial of monolayer carbon atomic arrangement, owing to having high carrier mobility and extremely low resistivity, is one of current electric conductivity best material.Its theoretical specific surface area reaches 2630m
2/ g, intrinsic mobility is up to 200000cm
2/ Vs, Young's modulus can reach ~ 1.0TPa, and thermal conductivity is up to ~ 5000W/mK, and conductivity reaches 10
6s/cm.In addition, Graphene visible light wave range up to ~ 97.7% excellent photopermeability, and the advantage of no color differnece, makes Graphene obtain extensive investigation and application (reference literature 6-8) in the field such as transparency electrode, energy storage device.Therefore, how to utilize conductivity and the optical property of Graphene excellence, preparation color and conductivity coordinate controlled novel conductive pearlescent pigment, made an addition in coating, plastics, rubber, adhesive, ink, cement, fiber, pottery, be applied to the conduction of each industrial departments such as oil, chemical industry, building materials, electronics, electromechanics, communication, automobile, medicine, papermaking, weaving, packaging, printing, boats and ships, pottery, Aero-Space, weapons and people's daily life, antistatic field, meet the need of market, there is important using value.
Prior art document:
Document 1
Frank J.Maile,Gerhard Pfaff,Peter Reynders,Progress in Organic Coatings 54(2005)150–163.
Document 2
Gerhard Pfaff and Peter Reynders,Chem.Rev.99(1999)1963-1981.
Document 3
Junru Tan,Lazhen Shen,Xiansong Fu,Wenxiang Hou,Xiuzeng Chen.Dyes and Pigments 62(2004)107-114.
Document 4
Shen Lazhen, Tan Junru, Fu Xiansong, Hou Wenxiang, Chen Xiuzeng, silicate is circulated a notice of, 4 (2004) 36-39.
Document 5
Fu Xiansong, Tan Junru, Hou Wenxiang, Chen Xiuzeng, Huang Caicai, color stuffing, 1 (2003) 29-31.
Document 6
Geim,A.K.and Novoselov,K.S.Nature Materials,6(2007)183-191.
Document 7
Castro Neto,AH；Guinea,F.；Peres,N.M.R.；Novoselov,K.S.；Geim,A.K.,Reviews of ModernPhysics.81(2009)109-162.
Document 8
Stankovich,S；Dikin,D.A.；Dommett,G.H.B.；Kohlhaas,K.M.；Zimney,E.J.；Stach,E.A.；Piner,R.D.；Nguyen,S.T.；Ruoff,R.S.,Nature,442(2006),282-286.。
Summary of the invention
In the face of prior art Problems existing, the object of the present invention is to provide a kind of graphene-based pearlescent pigment composite material and preparation method thereof, thus in lower doping, under lower Color influences, give the electric conductivity that pearlescent pigment is higher.
At this, on the one hand, the invention provides a kind of graphene-based pearlescent pigment composite material, described composite material comprises the Graphene being coated on pearlescent pigment surface, the thickness of described Graphene is 0.3 ~ 100nm, and in described composite material, the mass percentage of Graphene is 0.01 ~ 5%.
In the present invention, adopt there is good conductivity, transmitance is high, aberration is little and the Graphene of structural integrity as the conductive of pearlescent pigment, thus the pearlescent pigment of higher electric conductivity can be obtained with lower doping (0.01 ~ 5wt%).In the present invention, the resistivity of described composite material is less than 10
5Ω cm, is preferably 10 ~ 10
4Ω cm.
In composite material described in the present invention, pearlescent pigment comprises dielectric base layer and metal oxide layer or quasi-metal oxides layer, described dielectric base layer can comprise mica, aluminium flake, sheet glass one or more described in metal oxide layer comprise at least one of titanium dioxide, di-iron trioxide, tri-iron tetroxide, tin ash, described quasi-metal oxides layer comprises silicon dioxide.
Preferably, the diameter of described dielectric base layer can be 10-300 μm, and thickness can be 50-500nm, and the diameter of described oxide skin(coating) can be 10-300 μm, and thickness can be 0.01 ~ 1 μm.
Preferably, described Graphene utilizes graphite through the standby graphite oxide of chemical stripping legal system, then obtain after vapour phase reduction or liquid-phase reduction.
In the present invention, be coating layer material by the graphite oxide adopting chemical stripping legal system standby, be conducive to dispersed and efficiently coated in basis material of Graphene on the one hand, thus the electric conductivity of raising composite material; Be easy on the other hand reduce production cost, thus realize the large-scale production of composite material.
Preferably, described pearlescent pigment be with the mica of laminated structure, surfacing, high radius-thickness ratio, aluminium flake, sheet glass for substrate, utilize the composite material with special color effect of the coated preparation of slaine technology for hydrolyzing.
Graphene-based pearlescent pigment composite material of the present invention has the outstanding advantages such as Color tunable, high conduction performance, high stability, to the development and application of Electro-conductive pearlescent pigment and the development of conductive interface material significant.
On the other hand, the present invention also provides the preparation method of above-mentioned graphene-based pearlescent pigment composite material, comprising:
A () chemical stripping legal system is for graphite oxide solution;
(b) preparation pearlescent pigment dispersion liquid;
(c) mixed oxidization graphite solution and pearlescent pigment dispersion soln, gained mixed liquor in 20 ~ 100 DEG C add thermal agitation 1 hour ~ 1 week to prepare graphite oxide based pearlescent pigments;
D () utilizes vapor phase method or chemical method reduction-oxidation graphite-based pearlescent pigment to obtain graphene-based pearlescent pigment.
Preferably, in step (a): in described graphite oxide solution, the mass percentage of graphene oxide is 0.1-20%, solvent is water or organic solvent, and pH can be 0 ~ 11, and described organic solvent is at least one in methyl alcohol, ethanol, acetone, butanone, benzene, toluene.
In step (b): in described delustering pigment dispersion liquid, the mass percentage of pearlescent pigment is 0.1-20%, solvent is water or organic solvent, pH can be 0 ~ 11, and described organic solvent is at least one in methyl alcohol, ethanol, acetone, butanone, benzene, toluene.
Preferably, in step (b), described delustering pigment dispersion liquid contains the dispersant of 0.1-5wt%.But a kind of or several combination in described dispersant cationic dispersing agent, anionic dispersing agent, non-ionic dispersing agent.Cationic dispersing agent can be softex kw, hexadecyltrimethylammonium chloride, neopelex; Non-ionic dispersing agent can be Triton X-100, nonylphenol polyoxyethylene ether emulsifier, Arabic gum, ethylene oxide adduct (Tween-20, Tween-40, Tween-60 and Tween-80), ethoxylated dodecyl alcohol, lauric acid amide of ethanol; Anionic dispersing agent can be poly-propionic acid, poly-(methyl) acrylic acid ammonia, poly-(methyl) PAA, fatty acid soaps, lauryl sodium sulfate; Described dispersant concentration is 0.1 ~ 5wt%.
In step (b), described pearlescent pigment be with described dielectric base layer for substrate, utilize the coated described oxide skin(coating) of slaine technology for hydrolyzing to prepare.
Preferably, in step (c), the mass ratio of graphite oxide and described pearlescent pigment described in described mixed liquor is 1:(20 ~ 100), pH is 0.1 ~ 7.
In the present invention, in step (d), described graphite oxide based pearlescent pigments utilizes gas phase reduction process to reduce, and atmosphere is argon gas atmosphere, and temperature is 300 ~ 800 DEG C, and calcination time is 0.5 ~ 10 hour.
In the present invention, in step (d), described graphite oxide based pearlescent pigments utilizes chemical reduction method to reduce, and reducing agent is hydrazine hydrate solution, and temperature is room temperature ~ 100 DEG C, and the reaction time is 0.5 ~ 24 hour.
Preparation method's technique of the present invention is simple, and controllability is strong, and reproducible, cost is low, and electric conductivity is excellent, large-scale production easy to implement.
Accompanying drawing explanation
Fig. 1 is mica sheet SEM photo, and show that raw material mica sheet size is relatively more even, surface smoothness is higher;
Fig. 2 is the TEM photo of self-control graphite oxide/mica titanium nacreous material, shows mica titanium coated with uniform aluminum oxide/graphite layer;
Fig. 3 be self-control Graphene/Titania-mica Composites TEM photo, what show graphene uniform is distributed in mica titanium material surface, and in the process of vapour phase reduction TiO
2the degree of crystallinity of layer improves;
Fig. 4 is the Raman collection of illustrative plates of Graphene/Titania-mica Composites, and before and after reduction, the peak area ratio at D peak and G peak is increased to 1.528 from 1.294, shows to be reduced to Graphene through reduction rear oxidation graphite.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following execution mode, should be understood that accompanying drawing and following execution mode are only for illustration of the present invention, and unrestricted the present invention.
The invention provides a kind of graphene-based pearlescent pigment composite material, adopt the high graphene coated of conductivity to have the pearlescent pigment of special color effect, can under lower Color influences, give pearlescent pigment higher electric conductivity.In obtained composite material, the mass percentage of Graphene can be 0.01 ~ 5%.
Described Graphene is obtained through reducing after can being coated on pearlescent pigment by the graphite oxide that chemical stripping legal system is standby.
(1) graphite, sodium nitrate are joined in the concentrated sulfuric acid in ice bath, slowly add potassium permanganate afterwards, stirred at ambient temperature, add hot water, be placed in oil bath and be incubated, finally add hydrogen peroxide and terminate oxidation reaction.By solution centrifugal washing to neutral, ultrasonicly obtain the dispersion liquid of graphite oxide in water.
(2) by mica powder dispersion in an acidic solution, 80 DEG C add thermal agitation, the TiCl of dilution
4dropwise joins in suspension, drips NaOH solution simultaneously and stablizes pH value, is added dropwise to complete rear continuation heating and stirs 2h, suction filtration, washing, dries and obtains mica titanium nacreous material, Fig. 1 is shown in by its mica powder SEM photo, and show that raw material mica sheet size is relatively more even, surface smoothness is higher.
(3) by pearlescent pigment dispersed with stirring in aqueous dispersant, drip the graphite oxide aqueous solution simultaneously, after being added dropwise to complete, temperature rising reflux a period of time, suction filtration, washing, dries and obtains graphite oxide/pearlescent pigment powder, Fig. 2 is shown in by its TEM photo, shows mica titanium coated with uniform aluminum oxide/graphite layer.
(4) by graphite oxide/pearlescent pigment composite material through reductive heat treatment, such as under an ar atmosphere, 300-800 DEG C, calcining 0.5-10h; Hydrazine hydrate solution return stirring 0.5-24h, can obtain Graphene/pearlescent pigment composite material, and Fig. 3 is shown in by its TEM photo, and what show graphene uniform is distributed in mica titanium material surface, and in the process of vapour phase reduction TiO
2the degree of crystallinity of layer improves.
By prepared Graphene/pearlescent pigment composite material, utilize Raman spectrometer to study its graphite oxide reducing degree, its test result can, see Fig. 4, show to be reduced to Graphene through reduction rear oxidation graphite.
By prepared Graphene/pearlescent pigment composite material, utilize powder resistivity instrument to study its electric conductivity, its test result can see table 1:
Table 1
| Sequence number | Graphene content wt | Resistivity Ω cm (100kg/cm2) |
| 1 | 0.1 | 8.33×10 4 |
| 2 | 0.5 | 1.99×10 4 |
| 3 | 1.0 | 5.21×10 3 |
| 4 | 2.0 | 799.4 |
| 5 | 3.0 | 235.1 |
| 6 | 5.0 | 10.7 |
Experiment proves that the Graphene/pearlescent pigment composite material of the present invention's synthesis has good electric conductivity, can be used for preparing antistatic coating etc.
Graphene provided by the invention/pearlescent pigment composite material and preparation method thereof has following features:
(1) adopt Graphene as the novel conductive dopant material of pearlescent pigment;
(2) electricity of Graphene excellence, chemistry, Physical and mechanical properties can give pearlescent pigment multifunctionality;
(3) graphene-based pearlescent pigment composite material preparation process technique is simple, and cost is low, can realize large-scale production;
(4) the graphene-based pearlescent pigment composite material resistance rate prepared by is at 10 more than Ω cm, and continuously adjustabe, be expected to the range of application expanding Electro-conductive pearlescent pigment further.
The present invention using the conductive of Graphene as pearlescent pigment, achieves object material conductivity significantly being improved with low-doped amount first.Graphene-based pearlescent pigment composite material of the present invention has the outstanding advantages such as Color tunable, high conduction performance, high stability, to the extensive use of Electro-conductive pearlescent pigment and the development of conductive interface material significant.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The technological parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
The 500mL concentrated sulfuric acid, 10g sodium nitrate, 60g potassium permanganate and 10g graphite is added successively in reactor, stirring at room temperature 5 days, 100mL80 DEG C of hot water is at the uniform velocity dropped in reactor, after heat release completely, centrifuge washing to solution is neutral, be diluted to 1000mL, obtain the graphite oxide aqueous solution that concentration is 10mg/mL, pH=6.Mica powder is configured to the aqueous suspension of 10%, adjusts pH=2.0 with concentrated hydrochloric acid, 80 DEG C add thermal agitation, 2mol/L TiCl
4the aqueous solution dropwise joins in suspension, and dropping NaOH solution stablizes pH value is simultaneously 2, and be added dropwise to complete rear continuation heating and stir 2h, filtering and washing obtains mica titanium perlatolic material.Be 5% be dispersed in the aqueous hydrochloric acid solution of pH=2.0 by obtained mica titanium perlatolic material by mass concentration, drip a certain amount of graphite oxide aqueous solution wherein, 50 DEG C add thermal agitation 3 days, suction filtration, washing, 120 DEG C of oven dry.By gained powder under an ar atmosphere, 500 DEG C, calcining 3h, obtain graphene-based Titania-mica Composites, in composite material, the content of Graphene is 0.5%.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity is 1.99 × 10
4Ω cm, this composite material is electric conducting material.
Embodiment 2
The 500mL concentrated sulfuric acid, 10g sodium nitrate, 60g potassium permanganate and 10g graphite is added successively in reactor, stirring at room temperature 5 days, 100mL80 DEG C of hot water is at the uniform velocity dropped in reactor, after heat release completely, centrifuge washing to solution is neutral, be diluted to 1000mL, obtain the graphite oxide aqueous solution that concentration is 10mg/mL, pH=5.Mica powder is configured to the aqueous suspension of 10%, adjusts pH=2.0 with concentrated hydrochloric acid, 80 DEG C add thermal agitation, 2mol/L TiCl
4the aqueous solution dropwise joins in suspension, and dropping NaOH solution stablizes pH value is simultaneously 1.5, and be added dropwise to complete rear continuation heating and stir 2h, filtering and washing obtains mica titanium perlatolic material.Be 5% be dispersed in the aqueous hydrochloric acid solution of pH=2.0 by obtained mica titanium perlatolic material by mass concentration, drip a certain amount of graphite oxide aqueous solution 80 DEG C wherein and add thermal agitation 3 days, suction filtration, washing, 120 DEG C of oven dry.By gained powder under an ar atmosphere, 500 DEG C, calcining 3h, obtains graphene-based Titania-mica Composites.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity is 1.45 × 10
4Ω cm, this composite material is electric conducting material.
Embodiment 3
Except the calcining of Ar atmosphere is changed into except 2% hydrazine hydrate solution, 180 DEG C of hydro-thermal 24h, to prepare Graphene/Titania-mica Composites with the identical mode described in embodiment 1.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity is 2.75 × 10
4Ω cm, this composite material is electric conducting material.
Embodiment 4
Except graphite oxide solution addition is reduced except five times, to prepare Graphene/Titania-mica Composites with the identical mode described in embodiment 1.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity is 3.99 × 10
4Ω cm, this composite material is electric conducting material.In composite material, the content of Graphene is 0.1%.
Embodiment 5
Except graphite oxide solution addition is increased except twice, to prepare Graphene/Titania-mica Composites with the identical mode described in embodiment 1.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity is 5.21 × 10
3Ω cm, this composite material is electric conducting material.In composite material, the content of Graphene is 1.0%.
Embodiment 6
Except graphite oxide solution addition is increased except four times, to prepare Graphene/Titania-mica Composites with the identical mode described in embodiment 1.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity is 799.4 Ω cm, and this composite material is electric conducting material.In composite material, the content of Graphene is 2.0%.
Embodiment 7
Except graphite oxide solution addition is increased except six times, to prepare Graphene/Titania-mica Composites with the identical mode described in embodiment 1.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity is 235.1 Ω cm, and this composite material is electric conducting material.In composite material, the content of Graphene is 3.0%.
Embodiment 8
Except graphite oxide solution addition is increased except ten times, to prepare Graphene/Titania-mica Composites with the identical mode described in embodiment 1.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity is 10.7 Ω cm, and this composite material is electric conducting material.In composite material, the content of Graphene is 5.0%.
Comparative example 1
Except removing Ar atmosphere calcination process, prepare graphene-based Titania-mica Composites in the same manner as example 1.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity cannot read, and this composite material is insulating material.
Comparative example 2
Mica powder is configured to the aqueous suspension of 10%, adjusts pH=2.0 with concentrated hydrochloric acid, 80 DEG C add thermal agitation, 2mol/L TiCl
4the aqueous solution dropwise joins in suspension, and dropping NaOH solution stablizes pH value is simultaneously 2, and be added dropwise to complete rear continuation heating and stir 2h, filtering and washing obtains mica titanium perlatolic material.When testing with the resistance of powder resistivity instrument to this composite material, 100kgcm
-2under pressure, resistivity cannot read, and this composite material is insulating material.
Industrial applicability: graphene-based pearlescent pigment material of the present invention has the outstanding advantages such as Color tunable, high conduction performance, high stability, to the extensive use of Electro-conductive pearlescent pigment and the development of conductive interface material significant.
Claims (13)
1. a graphene-based pearlescent pigment composite material, it is characterized in that, described composite material comprises pearlescent pigment and is coated on pearlescent pigment surface Graphene, and the thickness of described Graphene is 0.3-100nm, and in described composite material, the mass percentage of Graphene is 0.01-5%.
2. graphene-based pearlescent pigment composite material according to claim 1, it is characterized in that, the resistivity of described composite material is less than 10
5Ω cm, is preferably 10 ~ 10
4Ω cm.
3. graphene-based pearlescent pigment composite material according to claim 1 and 2, it is characterized in that, in described composite material, pearlescent pigment comprises dielectric base layer and oxide skin(coating), described oxide skin(coating) is metal oxide layer or quasi-metal oxides layer, described dielectric base layer comprises at least one of mica, aluminium flake, sheet glass, described metal oxide layer comprises at least one of titanium dioxide, di-iron trioxide, tri-iron tetroxide, tin ash, and described quasi-metal oxides layer comprises silicon dioxide.
4. graphene-based pearlescent pigment composite material according to claim 3, is characterized in that, the diameter of described dielectric base layer is 10-300 μm, and thickness is 50-500nm, and the diameter of described oxide skin(coating) is 10-300 μm, and thickness is 0.01-1 μm.
5. the graphene-based pearlescent pigment composite material according to any one of claim 1-4, is characterized in that, described Graphene is obtained through reducing after being coated on pearlescent pigment by the graphite oxide that chemical stripping legal system is standby.
6. a preparation method for the graphene-based pearlescent pigment composite material according to any one of claim 1 to 5, is characterized in that, comprising:
A () chemical stripping legal system is for graphite oxide solution;
(b) preparation pearlescent pigment dispersion liquid;
(c) mixed oxidization graphite solution and pearlescent pigment dispersion soln, gained mixed liquor in 20 ~ 100 DEG C add thermal agitation 1 hour ~ 1 week to prepare graphite oxide based pearlescent pigments;
D () utilizes vapor phase method or chemical method reduction-oxidation graphite-based pearlescent pigment to obtain graphene-based pearlescent pigment.
7. preparation method according to claim 6, it is characterized in that, in step (a).: in described graphite oxide solution, the mass percentage of graphene oxide is 0.1-20%, solvent is water or organic solvent, pH is 0 ~ 11, and described organic solvent is at least one in methyl alcohol, ethanol, acetone, butanone, benzene, toluene.
8. preparation method according to claim 6, it is characterized in that, in step (b): in described delustering pigment dispersion liquid, the mass percentage of pearlescent pigment is 0.1-20%, solvent is water or organic solvent, pH is 0 ~ 11, and described organic solvent is at least one in methyl alcohol, ethanol, acetone, butanone, benzene, toluene.
9. preparation method according to claim 8, is characterized in that, in step (b), described delustering pigment dispersion liquid contains the dispersant of 0.1-5wt%.
10. the preparation method according to any one of claim 6-9, is characterized in that, in step (b), described pearlescent pigment be with described dielectric base layer for substrate, utilize the coated described oxide skin(coating) of slaine technology for hydrolyzing to prepare.
11. preparation methods according to any one of claim 6-10, it is characterized in that, in step (c), the mass ratio of graphite oxide and described pearlescent pigment described in described mixed liquor is 1:(20-100), pH is 0.1 ~ 7.
12. preparation methods according to any one of claim 6-10, is characterized in that, in step (d), described graphite oxide based pearlescent pigments utilizes gas phase reduction process to reduce, atmosphere is argon gas atmosphere, and temperature is 300-800 DEG C, and calcination time is 0.5-10 hour.
13. preparation methods according to any one of claim 6-10, is characterized in that, in step (d), described graphite oxide based pearlescent pigments utilizes chemical reduction method to reduce, reducing agent is hydrazine hydrate solution, and temperature is room temperature-100 DEG C, and the reaction time is 0.5-24 hour.
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