CN104392767B - 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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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 a kind of pigment with electric conductivity and pearl effect and preparation method thereof, belong to pearlescent pigment and
New function field of material technology.
Background technology
Pearlescent pigment is referred to and aoxidized with the metal-oxide or silicon dioxide etc. such as refractive index higher titanium dioxide metalloid
Thing is coated on Muscovitum, aluminium flake, glass sheet surface, is allowed to present a kind of functional material of pearly-lustre characteristic, is widely used in applying
The aspects such as material, cosmetics, anti-forgery ink, printing and dyeing.In recent years, with the continuous expansion of pearlescent pigment use range, except meeting
Outside the primary demand of attractive, decorative, market is to suitable for conduction, magnetic, the demand of heat conduction feature pearlescent pigment of specific environment
In constantly increase (reference literature 1-2).Wherein, Electro-conductive pearlescent pigment is widely used in conductively as a kind of functional pigment
The various fields such as level ground, bumper, the plastic of auto parts and components, electronics plastic cement products, electronic devices and components.In its preparation
Aspect, traditional Electro-conductive pearlescent pigment is obtained by tin ash doping metals (indium and antimony) and nonmetalloid (fluorine and phosphorus)
, expensive, complex process, and coordinating to be difficult to take into account of both color and electric conductivity.The better product face of electric conductivity
Color is deeper, it is impossible to while satisfactory (reference literature 3-5).Therefore, color and the adjustable novel conductive pearly-lustre of electric conductivity are developed
Pigment, prepares high connductivity light color system pearlescent pigment, widens the scope of application of Electro-conductive pearlescent pigment, becomes current Electro-conductive pearlescent pigment
The focus of development field.
Graphene is by the two dimensional surface carbon nanomaterial of monolayer carbon atom arrangement, due to migrating with high carrier
Rate and extremely low resistivity, are one of best materials of current electric conductivity.Its theoretical specific surface area reaches 2630m2/ g, originally relocates residents from locations to be used for construction of new buildings or factories
Shifting rate is up to 200000cm2/ Vs, Young's moduluss are reachable～1.0TPa, thermal conductivity up to～5000W/mK, electrical conductivity reaches 106S/
cm.Additionally, Graphene is up to～97.7% excellent photopermeability, and the advantage of no color differnece in visible light wave range so that graphite
Alkene has been obtained widely studied and has applied (reference literature 6-8) in fields such as transparency electrode, energy storage devices.Therefore, how using stone
The excellent electric conductivity of black alkene and optical property, prepare color and electric conductivity coordinates controllable novel conductive pearlescent pigment, are added
In being added on coating, plastics, rubber, binding agent, ink, cement, fiber, ceramics, oil, chemical industry, building materials, electronics, machine are applied to
Each industrial department such as electricity, communication, automobile, medicine, papermaking, weaving, packaging, printing, ship, ceramics, Aero-Space, weapons and
The conduction of people's daily life, antistatic field, meet the market demand, with important using value.
Prior art literature：
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 circular, 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 Modern Physics.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..
The content of the invention
In the face of the problem that prior art is present, it is an object of the invention to provide a kind of graphene-based pearlescent pigment composite wood
Material and preparation method thereof, so as to give pearlescent pigment higher electric conductivity under relatively low doping, relatively low Color influences.
Here, on the one hand, the present invention provides a kind of graphene-based pearlescent pigment composite, the composite includes bag
It is overlying on the Graphene on pearlescent pigment surface, the thickness of the Graphene is 0.3～100nm, Graphene in the composite
Weight/mass percentage composition is 0.01～5%.
In the present invention, adopt and there is good conductivity, transmitance height, little and structural integrity the Graphene of aberration as pearly-lustre face
The conductive of material, so as to the pearly-lustre face of higher electric conductivity can be obtained with relatively low doping (0.01～5wt%)
Material.In the present invention, the resistivity of the composite is less than 105Ω cm, preferably 10～104Ω·cm。
Pearlescent pigment includes dielectric base layer and metal oxide layer or metalloid oxygen in heretofore described composite
Compound layer, the dielectric base layer may include that one or more described metal oxide layers of Muscovitum, aluminium flake, sheet glass include two
Titanium oxide, iron sesquioxide, ferroso-ferric oxide, at least one of tin ash, the quasi-metal oxides layer includes titanium dioxide
Silicon.
It is preferred that the diameter of the dielectric base layer can be 10-300 μm, thickness can be 50-500nm, the oxide skin(coating)
Diameter can be 10-300 μm, thickness can be 0.01～1 μm.
It is preferred that the Graphene is the graphite oxide prepared using graphite Jing chemical strippings method, then through vapour phase reduction
Or obtain after liquid-phase reduction.
In the present invention, stone is conducive to for coating layer material, on the one hand by the graphite oxide for adopting chemical stripping method to prepare
Dispersed and efficient cladding of the black alkene in matrix material, so as to improve the electric conductivity of composite；On the other hand it is easy to
Production cost is reduced, so as to realize the large-scale production of composite.
It is preferred that the pearlescent pigment is to be with laminated structure, surfacing, the Muscovitum of high radius-thickness ratio, aluminium flake, sheet glass
Substrate, the composite with special color effect for preparing is coated using slaine technology for hydrolyzing.
There is the graphene-based pearlescent pigment composite of the present invention Color tunable, high conduction performance, high stability etc. to dash forward
Go out advantage, the development of development and application and conductive interface material to Electro-conductive pearlescent pigment is significant.
On the other hand, the present invention also provides the preparation method of above-mentioned graphene-based pearlescent pigment composite, including：
A () chemical stripping method prepares graphite oxide solution；
B () prepares pearlescent pigment dispersion liquid；
C () mixed oxidization graphite solution and pearlescent pigment dispersion soln, gained mixed liquor is in 20～100 DEG C of heated and stirred 1
Hour～1 week preparing graphite oxide based pearlescent pigments；
D () is obtained graphene-based pearlescent pigment using vapor phase method or chemical method reduction-oxidation graphite based pearlescent pigments.
It is preferred that in step (a)：The weight/mass percentage composition of graphene oxide is 0.1- in the graphite oxide solution
20%, solvent is water or organic solvent, and pH can be 0～11, and the organic solvent is methanol, ethanol, acetone, butanone, benzene, toluene
In at least one.
In step (b)：The weight/mass percentage composition of pearlescent pigment is 0.1-20% in the delustering pigment dispersion liquid, and solvent is
Water or organic solvent, pH can be 0～11, and the organic solvent is at least in methanol, ethanol, acetone, butanone, benzene, toluene
Kind.
It is preferred that in step (b), the delustering pigment dispersion liquid contains the dispersant of 0.1-5wt%.The dispersant can
It is the one kind in cationic dispersing agent, anionic dispersing agent, non-ionic dispersing agent or several combinations.Cation
Type dispersant can be cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecylbenzene sodium sulfonate；Nonionic
Type dispersant can be Triton X-100, nonylphenol polyoxyethylene ether emulsifier, arabic gum, ethylene oxide adduct
(tween 20, Tween-40, Tween-60 and tween 80), polyoxyethylene lauryl ether, lauric acid amide of ethanol；Anionic
Dispersant can be poly- propanoic acid, poly- (methyl) acrylic acid ammonia, poly- (methyl) sodium acrylate, fatty acid soaps, sodium lauryl sulphate；Institute
Dispersant concentration is stated for 0.1～5wt%.
In step (b), the pearlescent pigment is with the dielectric base layer as substrate, using slaine technology for hydrolyzing bag
Cover what the oxide skin(coating) was prepared.
It is preferred that in step (c), the mass ratio of graphite oxide and the pearlescent pigment described in the mixed liquor is 1:
(20～100), pH is 0.1～7.
In the present invention, in step (d), the graphite oxide based pearlescent pigments are reduced using gas phase reduction process, and atmosphere is
Argon gas atmosphere, temperature is 300～800 DEG C, and calcination time is 0.5～10 hour.
In the present invention, in step (d), the graphite oxide based pearlescent pigments are reduced using chemical reduction method, also
Former agent is hydrazine hydrate solution, and temperature is room temperature～100 DEG C, and the response time is 0.5～24 hour.
The preparation method process is simple of the present invention, controllability is strong, and reproducible, low cost, electric conductivity is excellent, it is easy to real
Apply large-scale production.
Description of the drawings
Fig. 1 is mica sheet SEM photograph, shows that raw material Muscovitum chip size is more uniform, and surface smoothness is higher；
Fig. 2 is the TEM photos for making graphite oxide/mica titanium nacreous material by oneself, shows mica titanium coated with uniform oxygen
Fossil layer of ink；
Fig. 3 is the TEM photos for making Graphene/Titania-mica Composites by oneself, and show graphene uniform is distributed in mica titanium
Material surface, and the TiO during vapour phase reduction2The degree of crystallinity of layer is improved；
Fig. 4 for Graphene/Titania-mica Composites Raman collection of illustrative plates, before and after reduction the peak area ratio at D peaks and G peaks from
1.294 increase to 1.528, show to be reduced to Graphene through reducing rear oxidation graphite.
Specific embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments
It is merely to illustrate the present invention, and the unrestricted present invention.
The present invention provides a kind of graphene-based pearlescent pigment composite, has spy using the high graphene coated of electric conductivity
The pearlescent pigment of different color effects, can give pearlescent pigment higher electric conductivity under relatively low Color influences.It is obtained compound
In material, the weight/mass percentage composition of Graphene can be 0.01～5%.
The graphite oxide that the Graphene can be prepared by chemical stripping method is coated on Jing reduction after pearlescent pigment and is obtained.
(1) graphite, sodium nitrate are added in concentrated sulphuric acid in ice bath, are slowly added to be stirred under potassium permanganate, room temperature afterwards
Mix, add hot water, be placed in oil bath and be incubated, be eventually adding hydrogen peroxide and terminate oxidation reaction.Solution centrifugal is washed to neutrality, is surpassed
Sound obtains dispersion liquid of the graphite oxide in water.
(2) mica powder is disperseed in an acidic solution, 80 DEG C of heated and stirred, the TiCl of dilution4Solution is added dropwise to hang
In supernatant liquid, while the stable pH value of Deca NaOH solution, continues heated and stirred 2h after being added dropwise to complete, sucking filtration, washing, drying obtains cloud
Female titanium nacreous, its mica powder SEM photograph is shown in Fig. 1, shows that raw material Muscovitum chip size is more uniform, and surface smoothness is higher.
(3) by pearlescent pigment dispersed with stirring in aqueous dispersant, while Deca graphite oxide aqueous solution, is added dropwise to complete
Afterwards, for a period of time, sucking filtration, washing, drying obtains graphite oxide/pearlescent pigment powder body to temperature rising reflux, and its TEM photo is shown in Fig. 2, table
Bright mica titanium coated with uniform aluminum oxide/graphite layer.
(4) by graphite oxide/pearlescent pigment composite Jing reductive heat treatments, for example under an ar atmosphere, 300-800 DEG C,
Calcining 0.5-10h；Hydrazine hydrate solution is refluxed 0.5-24h, and Graphene/pearlescent pigment composite is obtained, its TEM photo
See Fig. 3, show graphene uniform is distributed in mica titanium material surface, and the TiO during vapour phase reduction2The crystallization of layer
Degree is improved.
By prepared Graphene/pearlescent pigment composite, using Raman spectrometer to its graphite oxide reducing degree
Studied, its test result can be found in Fig. 4, show to be reduced to Graphene through reducing rear oxidation graphite.
By prepared Graphene/pearlescent pigment composite, its electric conductivity is ground using powder resistivity instrument
Study carefully, its test result can be found in table 1：
Table 1
| Sequence number | Graphene content wt | Resistivity Ω cm (100kg/cm2) |
| 1 | 0.1 | 8.33×104 |
| 2 | 0.5 | 1.99×104 |
| 3 | 1.0 | 5.21×103 |
| 4 | 2.0 | 799.4 |
| 5 | 3.0 | 235.1 |
| 6 | 5.0 | 10.7 |
Experiment proves that the Graphene/pearlescent pigment composite of present invention synthesis has good electric conductivity, can be used for
Prepare antistatic coating etc..
Graphene/pearlescent pigment composite that the present invention is provided and preparation method thereof has following features：
(1) using Graphene as pearlescent pigment novel conductive dopant material；
(2) the excellent electricity of Graphene, chemistry, Physical and mechanical properties can give pearlescent pigment multifunctionality；
(3) graphene-based pearlescent pigment composite preparation process process is simple, low cost, it is possible to achieve extensive raw
Produce；
(4) the graphene-based pearlescent pigment composite material resistance rate prepared by is in more than 10 Ω cm, and continuously adjustabe, has
Hope the range of application for further expanding Electro-conductive pearlescent pigment.
The present invention first using Graphene as pearlescent pigment conductive, realize leads material with low-doped amount
The purpose for electrically greatly improving.The graphene-based pearlescent pigment composite of the present invention has Color tunable, high conduction performance, height
The outstanding advantages such as stability, the development of extensive application and conductive interface material to Electro-conductive pearlescent pigment is significant.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
500mL concentrated sulphuric acids, 10g sodium nitrates, 60g potassium permanganate and 10g graphite are sequentially added in reactor, is stirred at room temperature
5 days, 100mL80 DEG C of hot water is at the uniform velocity dropped in reactor, after heat release is complete, centrifuge washing to solution is in neutrality, dilution
To 1000mL, the graphite oxide aqueous solution that concentration is 10mg/mL, pH=6 are obtained.The suspension that mica powder is configured to into 10% is water-soluble
Liquid, with concentrated hydrochloric acid pH=2.0,80 DEG C of heated and stirred, 2mol/L TiCl are adjusted4Aqueous solution is added dropwise in suspension, while drop
Plus the stable pH value of NaOH solution is 2, and heated and stirred 2h is continued after being added dropwise to complete, filtering and washing obtains mica titanium perlatolic material.Will
Obtained mica titanium perlatolic material is 5% to be dispersed in the aqueous hydrochloric acid solution of pH=2.0 by mass concentration, thereto Deca one
Quantitative graphite oxide aqueous solution, 50 DEG C of heated and stirred 3 days, sucking filtration, washing, 120 DEG C of drying.By gained powder in Ar atmosphere
Under, 500 DEG C, 3h is calcined, graphene-based Titania-mica Composites are obtained, the content of Graphene is 0.5% in composite.Use powder
When resistivity meter is tested the resistance of this composite, 100kgcm-2Resistivity is 1.99 × 10 under pressure4Ω cm,
The composite is conductive material.
Embodiment 2
500mL concentrated sulphuric acids, 10g sodium nitrates, 60g potassium permanganate and 10g graphite are sequentially added in reactor, is stirred at room temperature
5 days, 100mL80 DEG C of hot water is at the uniform velocity dropped in reactor, after heat release is complete, centrifuge washing to solution is in neutrality, dilution
To 1000mL, the graphite oxide aqueous solution that concentration is 10mg/mL, pH=5 are obtained.The suspension that mica powder is configured to into 10% is water-soluble
Liquid, with concentrated hydrochloric acid pH=2.0,80 DEG C of heated and stirred, 2mol/L TiCl are adjusted4Aqueous solution is added dropwise in suspension, while drop
Plus the stable pH value of NaOH solution is 1.5, and heated and stirred 2h is continued after being added dropwise to complete, filtering and washing obtains mica titanium perlatolic material.
By mass concentration it is 5% to be dispersed in the aqueous hydrochloric acid solution of pH=2.0 by obtained mica titanium perlatolic material, Deca thereto
80 DEG C of a certain amount of graphite oxide aqueous solution heated and stirred 3 days, sucking filtration, washing, 120 DEG C of drying.By gained powder in Ar atmosphere
Under, 500 DEG C, 3h is calcined, obtain graphene-based Titania-mica Composites.The resistance of this composite is carried out with powder resistivity instrument
During test, 100kgcm-2Resistivity is 1.45 × 10 under pressure4Ω cm, the composite is conductive material.
Embodiment 3
Except by Ar atmosphere calcining be changed to 2% hydrazine hydrate solution, 180 DEG C of hydro-thermals 24h in addition to, with it is identical described in embodiment 1
Mode prepare Graphene/Titania-mica Composites.When being tested the resistance of this composite with powder resistivity instrument,
100kg·cm-2Resistivity is 2.75 × 10 under pressure4Ω cm, the composite is conductive material.
Embodiment 4
In addition to graphite oxide solution addition is reduced into five times, to prepare stone with the identical mode described in embodiment 1
Black alkene/Titania-mica Composites.When being tested the resistance of this composite with powder resistivity instrument, 100kgcm-2Pressure
Lower resistivity is 3.99 × 104Ω cm, the composite is conductive material.The content of Graphene is 0.1% in composite.
Embodiment 5
In addition to graphite oxide solution addition is increased into twice, to prepare stone with the identical mode described in embodiment 1
Black alkene/Titania-mica Composites.When being tested the resistance of this composite with powder resistivity instrument, 100kgcm-2Pressure
Lower resistivity is 5.21 × 103Ω cm, the composite is conductive material.The content of Graphene is 1.0% in composite.
Embodiment 6
In addition to graphite oxide solution addition is increased into four times, to prepare stone with the identical mode described in embodiment 1
Black alkene/Titania-mica Composites.When being tested the resistance of this composite with powder resistivity instrument, 100kgcm-2Pressure
Lower resistivity is 799.4 Ω cm, and the composite is conductive material.The content of Graphene is 2.0% in composite.
Embodiment 7
In addition to graphite oxide solution addition is increased into six times, to prepare stone with the identical mode described in embodiment 1
Black alkene/Titania-mica Composites.When being tested the resistance of this composite with powder resistivity instrument, 100kgcm-2Pressure
Lower resistivity is 235.1 Ω cm, and the composite is conductive material.The content of Graphene is 3.0% in composite.
Embodiment 8
In addition to graphite oxide solution addition is increased into ten times, to prepare stone with the identical mode described in embodiment 1
Black alkene/Titania-mica Composites.When being tested the resistance of this composite with powder resistivity instrument, 100kgcm-2Pressure
Lower resistivity is 10.7 Ω cm, and the composite is conductive material.The content of Graphene is 5.0% in composite.
Comparative example 1
In addition to removing Ar atmosphere calcination process, graphene-based mica titanium is prepared in the same manner as example 1 and is combined
Material.When being tested the resistance of this composite with powder resistivity instrument, 100kgcm-2Resistivity cannot be read under pressure
Go out, the composite is insulant.
Comparative example 2
Mica powder is configured to into 10% aqueous suspension, with concentrated hydrochloric acid pH=2.0,80 DEG C of heated and stirred, 2mol/L are adjusted
TiCl4Aqueous solution is added dropwise in suspension, while the stable pH value of Deca NaOH solution is 2, continues to heat after being added dropwise to complete
Stirring 2h, filtering and washing obtains mica titanium perlatolic material.When being tested the resistance of this composite with powder resistivity instrument,
100kg·cm-2Resistivity cannot read under pressure, and the composite is insulant.
Industrial applicability：The graphene-based pearlescent pigment material of the present invention has Color tunable, high conduction performance, high stable
The outstanding advantages such as property, the development of extensive application and conductive interface material to Electro-conductive pearlescent pigment is significant.
Claims (10)
1. a kind of graphene-based pearlescent pigment composite, it is characterised in that the composite includes pearlescent pigment and cladding
In pearlescent pigment surface Graphene, the thickness of the Graphene is 0.3-100nm, the quality hundred of Graphene in the composite
Content is divided to be 0.01-5%, pearlescent pigment includes dielectric base layer and oxide skin(coating) in the composite, the oxide skin(coating) is
Metal oxide layer or quasi-metal oxides layer, the dielectric base layer includes Muscovitum, aluminium flake, at least one of sheet glass, institute
Metal oxide layer is stated including titanium dioxide, iron sesquioxide, ferroso-ferric oxide, at least one of tin ash, the eka-gold
Category oxide skin(coating) includes silicon dioxide,
The Graphene is coated on Jing vapor phase methods reduction after pearlescent pigment and is obtained by graphite oxide prepared by chemical stripping method, wherein
Atmosphere is argon gas atmosphere, and temperature is 300～800 DEG C, and calcination time is 0.5～10 hour.
2. graphene-based pearlescent pigment composite according to claim 1, it is characterised in that the resistance of the composite
Rate is less than 105Ω·cm。
3. graphene-based pearlescent pigment composite according to claim 2, it is characterised in that the resistance of the composite
Rate is 10～104Ω·cm。
4. graphene-based pearlescent pigment composite according to claim 1, it is characterised in that the dielectric base layer
A diameter of 10-300 μm, thickness is 50-500nm, a diameter of 10-300 μm of the oxide skin(coating), and thickness is 0.01-1 μm.
5. the preparation method of the graphene-based pearlescent pigment composite any one of a kind of Claims 1-4, its feature
It is, including：
（a）Chemical stripping method prepares graphite oxide solution；
（b）Prepare pearlescent pigment dispersion liquid；
（c）Mixed oxidization graphite solution and pearlescent pigment dispersion soln, gained mixed liquor was in 20～100 DEG C of heated and stirred 1 hour
～1 week preparing graphite oxide based pearlescent pigments；
（d）Graphene-based pearlescent pigment is obtained using the vapor phase method reduction-oxidation graphite based pearlescent pigments.
6. preparation method according to claim 5, it is characterised in that in step（a）In：Oxygen in the graphite oxide solution
The weight/mass percentage composition of graphite alkene is 0.1-20%, and solvent is water or organic solvent, and pH is 0～11, and the organic solvent is first
At least one in alcohol, ethanol, acetone, butanone, benzene, toluene.
7. preparation method according to claim 5, it is characterised in that in step（b）In：In the pearlescent pigment dispersion liquid
The weight/mass percentage composition of pearlescent pigment is 0.1-20%, and solvent is water or organic solvent, and pH is 0～11, and the organic solvent is first
At least one in alcohol, ethanol, acetone, butanone, benzene, toluene.
8. preparation method according to claim 7, it is characterised in that in step（b）In, the pearlescent pigment dispersion liquid contains
There is the dispersant of 0.1-5wt%.
9. the preparation method according to any one of claim 5-8, it is characterised in that in step（b）In, the pearly-lustre face
Material is, with the dielectric base layer as substrate, to coat what the oxide skin(coating) was prepared using slaine technology for hydrolyzing.
10. the preparation method according to any one of claim 5-8, it is characterised in that in step（c）In, the mixing
The mass ratio of graphite oxide described in liquid and the pearlescent pigment is 1:（20-100）, pH is 0.1～7.
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| CN113214679A (en) * | 2021-05-08 | 2021-08-06 | 河南凌宝新材料科技有限公司 | Production process of graphene-based pearlescent pigment |
| CN113292868A (en) * | 2021-05-13 | 2021-08-24 | 江苏贝丽得新材料有限公司 | Layered carbon material modified pearlescent pigment compound and preparation method thereof |
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