CN105838115A - Method for preparing graphene-based conductive pearlescent pigment - Google Patents
Method for preparing graphene-based conductive pearlescent pigment Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2220/00—Methods of preparing the interference pigments
- C09C2220/10—Wet methods, e.g. co-precipitation
Abstract
The invention relates to a method for preparing graphene-based conductive pearlescent pigment .The method comprises the steps of mixing oxidized graphene solution with pearlescent pigment dispersion liquid, and heating and stirring the mixed solution for one hour to one week at 20-100 DEG C to obtain oxidized graphene-based pearlescent pigment; preparing oxidized graphene-based pearlescent pigment dispersion liquid, adding a metallic reducing agent, conducting uniform mixing, and then conducting heating and stirring for 10 seconds to 24 hours at 10-100 DEG C, so that the graphene-based conductive pearlescent pigment is obtained .The method is convenient to operate, high in efficiency, environmentally friendly, free of pollution, low in cost and capable of achieving large-scale production.
Description
Technical field
The present invention relates to the preparation method of a kind of graphene-based Electro-conductive pearlescent pigment, belong to pearlescent pigment and New function material
Material technical field.
Background technology
Graphene-based Electro-conductive pearlescent pigment is a kind of New function type composite bead delustering pigment.This composite pigment is at existing pearly-lustre
On the basis of pigment, by introducing high transparency, the grapheme material of high connductivity, thus keeping original pearlescent pigment rich colors
On the basis of, give pearlescent pigment certain conducting function, can be used for each industrial departments such as coating, plastics, weaving, pottery and
Conduction in people's daily life, antistatic field (reference literature 1).
The synthetic method of this composite pigment is broadly divided into two steps: (1) selects graphite oxide prepared by Hummers method
Alkene is combined with pearlescent pigment, it is achieved the preparation of pearlescent pigment@graphene oxide composite pigment；(2) utilize hydrazine hydrate reduction method and
High-temperature calcination technique redox graphene, obtains graphene-based composite bead delustering pigment.But, it is understood that gold in pearlescent pigment
Genus oxide skin(coating) particle diameter, thickness, valence state are the important means of regulation and control pearlescent pigment extinction amount, are to make pearlescent pigment present abundant color
The basic reason (list of references 2-4) of color effect.Meanwhile, in pearlescent pigment, metal-oxide is nano-scale, has reaction position
The feature that point is many, activity is high, is the essential condition preparing pearlescent pigment@graphene oxide composite pigment.But, graphene-based lead
In high-temperature calcination used in the existing preparation method of small electric bulb delustering pigment and hydrazine hydrate reduction technique, reducing power is strong, easily
Making metal-oxide, while graphene oxide reduces, reduction reaction also occur, metal ion loses electronics, produces Lacking oxygen,
There is the change of extinction amount in the color causing composite pigment, reduce composite pigment color owing to oxygen loss and metal ion valence state reduce
Effect, finally makes the using value of composite pigment decline to a great extent (list of references 5-8).Although shortening redox graphene work
The response time of skill and reduction reaction temperature, can weaken the reducing degree of metal ion to a great extent, but can not
Fundamentally solve problems.Therefore, how to utilize electric conductivity and the optical property of Graphene excellence, solve reducing process pair
The impact of graphene-based Electro-conductive pearlescent pigment photoelectric properties, preparation color and antistatic property coordinate controlled compound pearly-lustre face
Material, is made an addition to, in coating, plastics, rubber, binding agent, ink, fiber, pottery, be applied to electronics, electromechanics, communication, vapour
Car, papermaking, weave, pack, print, each industrial department such as pottery, Aero-Space, weapons and the conduction of people's daily life,
Antistatic field, meets the market demand, has important using value.
Prior art literature:
Document 1
Wang Yan, Sun Jing, Luo Jianqiang, Liu Miaomiao, graphene-based Electro-conductive pearlescent pigment and preparation method thereof, apply for Chinese invention patent
No.201410520211.8.；
Document 2
Gerhard Pfaff and Peter Reynders,Chem.Rev.99(1999)1963-1981.；
Document 3
Frank J.Maile,Gerhard Pfaff,Peter Reynders.Prog.Org.Coat.54(2005)150-63.；
Document 4
Gerhard Pfaff.Viley-VCH Verlag Gmh&Co KGaA.(2009)75-104.；
Document 5
Hiroshi Irie,Yuka Watanabe,Kazuhito Hashimoto.J.Phys.Chem.B.107(2003)
5483–6.；
Document 6
Eunae Kang,Yoon Seok Jung,Andrew S.Cavanagh,et al.Adv.Mater.11(2011)2430-
8.；
Document 7
Rongjun Xie,Hintzen Hubertus T,J.Am.Ceram.Soc.96(2013)665-87.；
Document 8
Gao Q,Wu X,Fan Y.Dyes and Pigments.109(2014)90-5.。
Summary of the invention
The problem existed in the face of prior art, it is an object of the invention to provide a kind of optical property original to pearlescent pigment
Affect graphene-based Electro-conductive pearlescent pigment little, that composite pigment conducts electricity very well, simple to operate, pollution-free, energy consumption is low, efficiency is high
Preparation method, solve prior art be used for preparing graphene-based Electro-conductive pearlescent pigment have that absorbance increases, reaction temperature is high,
Time length, pollute weight and the high problem of equipment requirements, it is achieved in same Graphene doping and pearlescent pigment optical property not
Under conditions of change, composite pigment electric conductivity is obviously improved.
The present invention is achieved through the following technical solutions.
Graphene oxide solution and pearlescent pigment dispersion liquid being mixed, gained mixed solution heats at 20～100 DEG C and stirs
Mix 1 hour～1 week, obtain graphene oxide based pearlescent pigments；
Preparation graphene oxide based pearlescent pigments dispersion liquid, adds after metallic reducing agent uniformly mixes and heats at 10～100 DEG C
Stir 10 seconds～24 hours, obtain described graphene-based Electro-conductive pearlescent pigment.
The present invention utilizes metal as reducing agent, and reducing condition gentleness is controlled, and reaction temperature is low, and speed is fast, and side reaction is few,
And optionally graphene oxide can be reduced to Graphene without the metal-oxide in reduction pearlescent pigment, thus keep away
Exempt from preparation technology to change metal-oxide valence state and make former pearlescent pigment color change.
It is preferred that the weight/mass percentage composition of graphene oxide is 0.1～20% in described graphene oxide solution, solvent is
Water or organic solvent, described organic solvent is methanol, ethanol, propanol, isopropanol, acetone, butanone, benzene, toluene, N, N-dimethyl
At least one in Methanamide (DMF), dimethyl sulfoxide (DMSO), ethylene glycol.
It is preferred that the weight/mass percentage composition of pearlescent pigment is 0.1～20% in described pearlescent pigment dispersion liquid, solvent is water
Or organic solvent, described organic solvent is methanol, ethanol, propanol, isopropanol, acetone, butanone, benzene, toluene, N, N-dimethyl methyl
At least one in amide (DMF), dimethyl sulfoxide (DMSO), ethylene glycol.
It is preferred that graphene oxide is 1:(20～100 with the mass ratio of pearlescent pigment in described mixed solution), preferably 1:
(20～50).
It is preferred that described pearlescent pigment includes that core reflector layer and refracting layer, described core reflector layer include Muscovitum, aluminum
At least one in sheet, sheet glass, described refracting layer includes titanium dioxide, iron sesquioxide, zirconium dioxide, lead oxide, four oxygen
Change at least one in three-iron, silicon dioxide, tin ash.
It is preferred that the refracting layer of described pearlescent pigment a diameter of 1～300 μm, thickness is 0.001 μm～1 μm, and thickness is preferred
It is 1～500nm.
It is preferred that described pearlescent pigment dispersion liquid contains the dispersant of 0.1～5wt%.But described dispersant cation
A kind of or several combination in type dispersant, anionic dispersing agent, non-ionic dispersing agent.Cationic dispersing agent
Can be at least one in cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecylbenzene sodium sulfonate；Non-
Ionic dispersant can be that Triton X-100, nonylphenol polyoxyethylene ether emulsifier, arabic gum, oxirane add
Become in thing (tween 20, Tween-40, Tween-60 and tween 80), polyoxyethylene lauryl ether, lauric acid amide of ethanol
At least one；Anionic dispersing agent can be poly-propanoic acid, poly-(methyl) acrylic acid ammonia, poly-(methyl) sodium acrylate, fatty acid soaps,
At least one in sodium lauryl sulphate.
It is preferred that described metallic reducing agent is at least in lithium, sodium, magnesium, aluminum, calcium, nickel, ferrum, copper, zinc, lead, stannum, manganese
Kind.
Also, it is preferred that described metallic reducing agent is powder or block, particle diameter is distributed as 10-7～102Cm, preferably 0.1
～10 μm.
It is preferred that the mass ratio of described metallic reducing agent and graphene oxide based pearlescent pigments is 1:(0.01～100), excellent
Elect 1:(0.1～10 as).
The graphene-based pearlescent pigment composite process of preparing that the present invention provides has a characteristic that
(1) this method is easy and simple to handle, and efficiency is high, and environmental protection is pollution-free, low cost, it is possible to achieve large-scale production；
(2) on the basis of not affecting the original optical property of pearlescent pigment, composite pigment electric conductivity is substantially improved；
(3) the graphene-based pearlescent pigment conductivity of composite material prepared by is good and continuously adjustabe, is expected to expand further conduction
The range of application of pearlescent pigment.
Accompanying drawing explanation
Fig. 1 is the TEM photo of the mica titanium@Graphene composite bead delustering pigment of embodiment 1 preparation；
Fig. 2 is the Raman collection of illustrative plates before and after the mica titanium@Graphene composite bead delustering pigment reduction of embodiment 1 preparation；
Fig. 3 is the XPS collection of illustrative plates before and after the mica titanium@Graphene composite bead delustering pigment reduction of embodiment 1 preparation；
Fig. 4 is the Ti 2p collection of illustrative plates before and after the mica titanium@Graphene composite bead delustering pigment reduction of embodiment 1 preparation；
Fig. 5 is the Ti 2p collection of illustrative plates after the mica titanium@Graphene composite bead delustering pigment reduction of comparative example 2 preparation；
Fig. 6 is the Raman collection of illustrative plates after the mica titanium@Graphene composite bead delustering pigment reduction of comparative example 2 preparation.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment below in conjunction with accompanying drawing and following embodiment
It is merely to illustrate the present invention, and the unrestricted present invention.
The present invention utilizes metal deoxidization can give the electric conductivity that pearlescent pigment is higher under relatively low Color influences.Reference
Table 1 (the photoelectric properties tables of data before and after the reduction of mica titanium Graphene composite bead delustering pigment), data show original pearly-lustre after reduction
Pigment has certain electric conductivity, absorbance change ＜ 0.5%；Under the conditions of identical Graphene content, prepared by this method
Graphene-based Electro-conductive pearlescent pigment electric conductivity improves 4-8 times, and absorbance change is relatively small.
The preparation method of the graphene-based Electro-conductive pearlescent pigment composite that the explanation present invention in following exemplary ground provides.
Hummers method prepares graphene oxide solution.Graphite, sodium nitrate are joined in concentrated sulphuric acid in ice bath, afterwards
It is slowly added to potassium permanganate, stirs under room temperature, add hot water, be placed in oil bath insulation, be eventually adding hydrogen peroxide and terminate oxidation instead
Should.Solution centrifugal is washed, ultrasonic obtains graphene oxide dispersion liquid in water.Oxygen in graphene oxide solution after dilution
The weight/mass percentage composition of functionalized graphene can be 0.1～20%, and solvent is water or organic solvent.Described organic solvent can be methanol,
At least one in ethanol, propanol, isopropanol, acetone, butanone, benzene, toluene, DMF, DMSO, ethylene glycol.
Slaine Hydrolyze method prepares pearlescent pigment, and prepares dispersion liquid.Heretofore described pearlescent pigment is the base that insulate
Bottom (core reflector layer) is that substrate does not utilizes slaine technology for hydrolyzing to be coated with described oxide, forms oxide skin(coating) (namely
Refracting layer) wherein, core reflector layer can include at least one in Muscovitum, aluminium flake, sheet glass.Refracting layer include titanium dioxide,
At least one in iron sesquioxide, zirconium dioxide, lead oxide, ferroso-ferric oxide, silicon dioxide, tin ash, described pearly-lustre
Refracting layer a diameter of 1～300 μm of pigment, thickness is 0.001～1 μm (thickness is preferably 1～500nm).As one in detail
Example, disperses mica powder in an acidic solution, 80 DEG C of heated and stirred, the TiCl of dilution4Solution is added dropwise in suspension,
It is simultaneously added dropwise NaOH solution and stablizes pH value, continue heated and stirred 2h, sucking filtration, washing after being added dropwise to complete, dry and obtain mica titanium pearl
Delustering pigment.Preparation pearlescent pigment dispersion liquid, wherein the weight/mass percentage composition of pearlescent pigment can be 0.1～20%, and solvent can be water
Or organic solvent, described organic solvent can be methanol, ethanol, propanol, isopropanol, acetone, butanone, benzene, toluene, DMF, DMSO,
At least one in ethylene glycol.
Reunite to prevent pearlescent pigment from occurring, affect the graphene oxide uniformity at pearlescent pigment external sheath,
Pearlescent pigment dispersion liquid adds the dispersant of 0.1～5wt%.Described dispersant can be but be not limited only to cationic dispersing agent,
A kind of or several combination in anionic dispersing agent, non-ionic dispersing agent.Cationic dispersing agent can be 16
At least one in alkyl trimethyl ammonium bromide, hexadecyltrimethylammonium chloride, dodecylbenzene sodium sulfonate.Nonionic divides
Powder can be that Triton X-100, nonylphenol polyoxyethylene ether emulsifier, arabic gum, ethylene oxide adduct (are told
Temperature-20, Tween-40, Tween-60 and tween 80), polyoxyethylene lauryl ether, in lauric acid amide of ethanol at least one
Kind.Anionic dispersing agent can be poly-propanoic acid, poly-(methyl) acrylic acid ammonia, poly-(methyl) sodium acrylate, fatty acid soaps, dodecane
At least one in base sodium sulfate.
Graphene oxide solution and pearlescent pigment dispersion liquid being mixed, gained mixed solution heats at 20～100 DEG C and stirs
Mix 1 hour～1 week.Owing to graphene oxide is contrary with pearlescent pigment surface electronegativity, utilize electrostatic adsorption between the two
And the π of graphene oxide～pi-conjugated system, it is achieved graphene oxide is coated on pearlescent pigment surface, obtains having nucleocapsid knot
The graphene oxide based pearlescent pigments of structure.Wherein, if the mass ratio of graphene oxide and pearlescent pigment in described mixed solution
Meet graphene oxide can be coated with pearlescent pigment surface, such as mass ratio completely can be 1:(20～100), preferably 1:
50。
Preparation graphene oxide based pearlescent pigments dispersion liquid, adds after metallic reducing agent uniformly mixes at 10～100 DEG C
Lower heated and stirred 10 seconds～24 hours, the graphene oxide being now coated on pearlescent pigment surface is reduced into stone by metallic reducing agent
Ink alkene, obtains graphene-based Electro-conductive pearlescent pigment.(Fig. 1 is that the mica titanium Graphene of embodiment 1 preparation is combined pearly-lustre to see Fig. 1
The TEM photo of pigment), show mica titanium coated with uniform graphene layer, i.e. graphene uniform is distributed in mica titanium material
Material surface.Wherein, described metallic reducing agent purity ＞ 99.0%, can be such as lithium, sodium, magnesium, aluminum, calcium, nickel, ferrum, copper, zinc, lead,
At least one in stannum, manganese.Described metallic reducing agent can be powder or block, preferably powder, and particle diameter is distributed as 10-7~
102Cm, preferably 0.1～10 μm.Metallic reducing agent in this particle size distribution range has higher reactivity, and can lead to
Cross Filtration to remove, little to composite pigment impurities affect.As long as the consumption of metallic reducing agent meets 1:(0.01～100),
Preferably 1:(0.1～10), so can ensure that graphene oxide is fully reduced, the metallic reducing agent impact of excess can be avoided again
The purity of composite pigment.As a detailed example, graphene oxide based pearlescent pigments composite is disperseed in the solution, use
Concentrated hydrochloric acid is adjusted to acidity, addition metal dust, stirs to metal dust reaction completely, and sucking filtration, washing, drying obtains graphene-based
Pearlescent pigment powder body.
The present invention utilize mineral acid or inorganic base to regulate solution ph.Described mineral acid can be hydrochloric acid, sulphuric acid, nitre
At least one in acid, phosphoric acid.Described inorganic base can be at least one in ammonia, sodium hydroxide, potassium hydroxide.
By prepared graphene-based pearlescent pigment composite, utilize Raman spectrometer to its graphene oxide reduction journey
Degree study, its test result can be found in Fig. 2 (Fig. 2 be embodiment 1 preparation mica titanium@Graphene composite bead delustering pigment also
Raman collection of illustrative plates before and after former), I before and after reductionDWith IGRatio increases to 1.02 from 0.98, shows through reduction rear oxidation Graphene
It is reduced to Graphene.
By prepared graphene-based pearlescent pigment composite, utilize XPS spectrum instrument to its graphene oxide reduction journey
Degree study, its test result can be found in Fig. 3 (Fig. 3 be embodiment 1 preparation mica titanium@Graphene composite bead delustering pigment also
XPS collection of illustrative plates before and after former), before and after reduction, the increase of C/O shows to be reduced to Graphene through reduction reaction rear oxidation Graphene.
By prepared graphene-based pearlescent pigment composite, utilize XPS spectrum instrument that the chemical valence state of its titanium is carried out
Research, its test result can be found in Fig. 4 (before and after Fig. 4 is mica titanium@Graphene composite bead delustering pigment reduction prepared by embodiment 1
Ti 2p collection of illustrative plates), before and after reduction, peak position shows that Ti does not occurs valence state to change after reduction reaction.
By prepared graphene-based pearlescent pigment composite, utilize powder resistivity instrument and ultraviolet spectrometer to its light
Electrical property is studied, and its test result can be found in table 1:
Table 1: the photoelectric properties tables of data before and after the reduction of mica titanium@Graphene composite bead delustering pigment
Experiment proves that graphene-based pearlescent pigment composite prepared by the inventive method has good electric conductivity, can
For preparing antistatic coating etc..
The preparation method technique of the present invention is simple, environmental protection, and side effect is little, and controllability is strong, reproducible, low cost,
Excellent product performance, it is easy to implement large-scale production.
Metal deoxidization is used for the preparation of graphene-based Electro-conductive pearlescent pigment by the present invention first, it is achieved at same Graphene
Doping and pearlescent pigment optical property constant on the premise of, the purpose that composite pigment electric conductivity is obviously improved.Side of the present invention
Method have easy and simple to handle, environmental protection, efficiently, the feature of low cost, prepared conducing composite material has Color tunable, high connductivity
The outstanding advantage such as performance, high stability, the development to extensively application and the conductive interface material of Electro-conductive pearlescent pigment has important
Meaning.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this
Invention is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential improvement and adjustment that bright foregoing is made belong to protection scope of the present invention.Following example is concrete
Technological parameters etc. are the most only that an example in OK range, i.e. those skilled in the art can be done properly by explanation herein
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
In reactor, it is sequentially added into 500mL concentrated sulphuric acid, 10g sodium nitrate, 60g potassium permanganate and 10g graphite, is stirred at room temperature 5 days,
At the uniform velocity being dropped in reactor by 80 DEG C of hot water of 100mL, after heat release completely, centrifuge washing to solution is neutrality, is diluted to
1000mL, obtains the graphene oxide water solution that concentration is 10mg/mL, pH=6.Mica powder is configured to 10% suspension water-soluble
Liquid, adjusts pH=2.0 with concentrated hydrochloric acid, 80 DEG C of heated and stirred, 2mol/L TiCl4Aqueous solution is added dropwise in suspension, drips simultaneously
Add NaOH solution stablizing pH value is 2, continues heated and stirred 2h after being added dropwise to complete, and filtering and washing obtains mica titanium nacreous material.Will
Obtained mica titanium nacreous material is 5% to be dispersed in the aqueous hydrochloric acid solution of pH=2.0 by mass concentration, drips one wherein
Quantitative graphene oxide water solution, 50 DEG C of heated and stirred 3 days, sucking filtration, washing, 120 DEG C of drying.By ultrasonic for gained powder 10g
Being dispersed in the aqueous hydrochloric acid solution of pH=2.0,400 mesh Zn powder 2g, to entering in reaction solution, stir 5min, sucking filtration, wash, 200
DEG C drying to obtain graphene-based Titania-mica Composites, in composite, the content of Graphene is 0.5%.With ultraviolet spectrometer to this
The absorbance change of composite is tested, and before and after reduction, absorbance is changed to 0.40%, and the original pearly-lustre of this composite is imitated
Fruit and color keep constant.With powder resistivity instrument, the resistance of this composite is tested, 100kg cm-2Electricity under pressure
Resistance rate is 1.1 × 104Ω cm, this composite is conductive material.
Embodiment 2
In reactor, it is sequentially added into 500mL concentrated sulphuric acid, 10g sodium nitrate, 60g potassium permanganate and 10g graphite, is stirred at room temperature 5 days,
At the uniform velocity being dropped in reactor by 80 DEG C of hot water of 100mL, after heat release completely, centrifuge washing to solution is neutrality, is diluted to
1000mL, obtains the graphene oxide water solution that concentration is 10mg/mL, pH=5.Mica powder is configured to 10% suspension water-soluble
Liquid, adjusts pH=2.0 with concentrated hydrochloric acid, 80 DEG C of heated and stirred, 2mol/L TiCl4Aqueous solution is added dropwise in suspension, drips simultaneously
Add NaOH solution stablizing pH value is 1.5, continues heated and stirred 2h after being added dropwise to complete, and filtering and washing obtains mica titanium nacreous material.
By gained powder 10g ultrasonic disperse in the aqueous solution of pH=2,200 mesh Zn powder 0.5g add in reaction solution, stir 1min,
Sucking filtration, washing, dry to obtain graphene-based Titania-mica Composites for 200 DEG C, in composite, the content of Graphene is 0.1%.With
The absorbance of this composite is changed by ultraviolet spectrometer to be tested, and before and after reduction, absorbance is changed to 0.46%, and this is combined
The original pearl effect of material and color keep constant.With powder resistivity instrument, the resistance of this composite is tested,
100kg·cm-2Under pressure, resistivity is 3.6 × 104Ω cm, this composite is conductive material.
Embodiment 3
In addition to changing Zn powder into iron powder, in the way of identical with described in embodiment 1, prepare graphene-based pearlescent pigment.With purple
The absorbance of this composite is changed by external spectrum instrument to be tested, and before and after reduction, absorbance is changed to 0.49%, this composite wood
Expect that original pearl effect and color keep constant.With powder resistivity instrument, the resistance of this composite is tested, 100kg
cm-2Under pressure, resistivity is 2.1 × 104Ω cm, this composite is conductive material.
Embodiment 4
In addition to changing Zn powder into metallic sodium and reaction solution pH=7, in the way of identical with described in embodiment 1, prepare graphite
Thiazolinyl pearlescent pigment.With ultraviolet spectrometer, the absorbance change of this composite is tested, absorbance change before and after reduction
Being 0.39%, the original pearl effect of this composite and color keep constant.With the powder resistivity instrument electricity to this composite
Resistance is tested, 100kg cm-2Under pressure, resistivity is 1.7 × 104Ω cm, this composite is conductive material.
Embodiment 5
In addition to graphene oxide mica titanium nacreous material reacting solution pH value is adjusted to 12, with the phase described in embodiment 1
Same mode prepares graphene-based pearlescent pigment.With ultraviolet spectrometer, the absorbance change of this composite is tested, also
Before and after former, absorbance is changed to 0.30%, and the original pearl effect of this composite and color keep constant.Use powder resistivity instrument
The resistance of this composite is tested, 100kg cm-2Under pressure, resistivity is 2.5 × 104Ω cm, this composite
For conductive material.
Embodiment 6
In addition to graphene oxide solution addition is increased twice, in the way of identical with described in embodiment 1, prepare graphite
Thiazolinyl pearlescent pigment.With ultraviolet spectrometer, the absorbance change of this composite is tested, absorbance change before and after reduction
Being 0.34%, the original pearl effect of this composite and color keep constant.With the powder resistivity instrument electricity to this composite
Resistance is tested, 100kg cm-2Under pressure, resistivity is 1.8 × 103Ω cm, this composite is conductive material.Composite wood
In material, the content of Graphene is 1.0%.
Embodiment 7
In addition to graphene oxide solution addition is increased by four times, in the way of identical with described in embodiment 1, prepare graphite
Thiazolinyl pearlescent pigment.With ultraviolet spectrometer, the absorbance change of this composite is tested, absorbance change before and after reduction
Being 0.31%, the original pearl effect of this composite and color keep constant.With the powder resistivity instrument electricity to this composite
Resistance is tested, 100kg cm-2Under pressure, resistivity is 320.7 Ω cm, and this composite is conductive material.Composite
The content of middle Graphene is 2.0%.
Embodiment 8
In addition to graphene oxide solution addition is increased by six times, in the way of identical with described in embodiment 1, prepare graphite
Thiazolinyl pearlescent pigment.With ultraviolet spectrometer, the absorbance change of this composite is tested, absorbance change before and after reduction
Being 0.48%, the original pearl effect of this composite and color keep constant.With the powder resistivity instrument electricity to this composite
Resistance is tested, 100kg cm-2Under pressure, resistivity is 105.2 Ω cm, and this composite is conductive material.Composite
The content of middle Graphene is 3.0%.
Embodiment 9
In addition to graphene oxide solution addition is increased by ten times, in the way of identical with described in embodiment 1, prepare graphite
Thiazolinyl pearlescent pigment.With ultraviolet spectrometer, the absorbance change of this composite is tested, absorbance change before and after reduction
Being 0.35%, the original pearl effect of this composite and color keep constant.With the powder resistivity instrument electricity to this composite
Resistance is tested, 100kg cm-2Under pressure, resistivity is 8.8 Ω cm, and this composite is conductive material.In composite
The content of Graphene is 5.0%.
Comparative example 1
In addition to removing metal recovery process, prepare graphene-based Titania-mica Composites in the same manner as example 1.With
When the resistance of this composite is tested by powder resistivity instrument, 100kg cm-2Under pressure, resistivity is+∞, this composite wood
Material is insulant.
Comparative example 2
In addition to metal recovery process is changed into Ar atmosphere calcining reduction, prepare graphene-based in the same manner as example 1
Titania-mica Composites.Testing the absorbance change of this composite with ultraviolet spectrometer, before and after reduction, absorbance becomes
Turning to 4.80%, this composite darkens.When the resistance of this composite being tested with powder resistivity instrument,
100kg·cm-2Under pressure, resistivity is 8.33 × 104Ω cm, this conductivity of composite material declines 8 times.By prepared stone
Mertenyl pearlescent pigment composite, utilizes XPS spectrum instrument to study the chemical valence state of its titanium, and its test result can be found in
Fig. 5 (Fig. 5 is the Ti 2p collection of illustrative plates before and after the mica titanium@Graphene composite bead delustering pigment high-temperature calcination reduction of comparative example 2 preparation).
In Fig. 5, two peaks of 459.1eV and 462.0eV are Ti4+Characteristic peak；Newly-increased two peaks of 454.6eV and 456.3eV are Ti3+'s
Characteristic peak, shows the metal-oxide Ti in high-temperature calcination reduction process composite pigment4+Part is reduced to Ti3+.By institute
The graphene-based pearlescent pigment composite of preparation, utilizes Raman spectrometer to study its graphene oxide reducing degree,
Its test result can be found in Fig. 6 (before and after Fig. 6 is mica titanium@Graphene composite bead delustering pigment reduction prepared by comparative example 2
Raman collection of illustrative plates), I before and after reductionDWith IGRatio increases to 1.04 from 0.97, shows through high-temperature calcination reduction rear oxidation Graphene
It is reduced to Graphene.
Comparative example 3
In addition to metal recovery process is changed into hydrazine hydrate backflow reduction, prepare graphene-based in the same manner as example 1
Titania-mica Composites.Testing the absorbance change of this composite with ultraviolet spectrometer, before and after reduction, absorbance becomes
Turning to 6.52%, this composite darkens.When the resistance of this composite being tested with powder resistivity instrument,
100kg·cm-2Under pressure, resistivity is 3.85 × 104Ω cm, this conductivity of composite material declines about 4 times.
Industrial applicability:
Graphene-based Electro-conductive pearlescent pigment method that what the present invention provided prepare have easy and simple to handle, environmental protection, efficiently, side reaction little,
The advantage of low cost, and prepared composite has the outstanding advantages such as Color tunable, high conduction performance, high stability, right
The development of extensively application and the conductive interface material of Electro-conductive pearlescent pigment is significant.
Claims (10)
1. the preparation method of a graphene-based Electro-conductive pearlescent pigment, it is characterised in that including:
Graphene oxide solution and pearlescent pigment dispersion liquid being mixed, gained mixed solution heated and stirred 1 at 20～100 DEG C is little
Time～1 week, obtain graphene oxide based pearlescent pigments；
Preparation graphene oxide based pearlescent pigments dispersion liquid, adds after metallic reducing agent uniformly mixes and heats at 10～100 DEG C
Stir 10 seconds～24 hours, obtain described graphene-based Electro-conductive pearlescent pigment.
Preparation method the most according to claim 1, it is characterised in that graphene oxide in described graphene oxide solution
Weight/mass percentage composition is 0.1～20%, and solvent is water or organic solvent, and described organic solvent is methanol, ethanol, propanol, isopropyl
In alcohol, acetone, butanone, benzene, toluene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethylene glycol at least one
Kind.
Preparation method the most according to claim 1 and 2, it is characterised in that pearlescent pigment in described pearlescent pigment dispersion liquid
Weight/mass percentage composition be 0.1～20%, solvent is water or organic solvent, and described organic solvent is methanol, ethanol, propanol, isopropyl
In alcohol, acetone, butanone, benzene, toluene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethylene glycol at least one
Kind.
4. according to the preparation method according to any one of claim 1-3, it is characterised in that graphite oxide in described mixed solution
Alkene is 1:(20～100 with the mass ratio of pearlescent pigment).
5. according to the preparation method according to any one of claim 1-4, it is characterised in that described pearlescent pigment includes that core is anti-
Penetrating layer and refracting layer, described core reflector layer includes that at least one in Muscovitum, aluminium flake, sheet glass, described refracting layer include two
At least one in titanium oxide, iron sesquioxide, zirconium dioxide, lead oxide, ferroso-ferric oxide, silicon dioxide, tin ash.
Preparation method the most according to claim 5, it is characterised in that the refracting layer of described pearlescent pigment a diameter of 1～
300 μm, thickness is 0.001～1 μm, preferably 1～500nm.
7. according to the preparation method according to any one of claim 1-6, it is characterised in that described pearlescent pigment dispersion liquid contains
The dispersant of 0.1～5wt%.
8. according to the preparation method according to any one of claim 1-7, it is characterised in that described metallic reducing agent be lithium, sodium,
At least one in magnesium, aluminum, calcium, nickel, ferrum, copper, zinc, lead, stannum, manganese.
Preparation method the most according to claim 8, it is characterised in that described metallic reducing agent is powder or block, grain
Footpath is distributed as 10-7～102cm。
10. according to the preparation method according to any one of claim 1-9, it is characterised in that described metallic reducing agent and oxidation
The mass ratio of graphene-based pearlescent pigment is 1:(0.01～100), preferably 1:(0.1～10).
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