CN105838115B - A kind of preparation method of graphene-based Electro-conductive pearlescent pigment - Google Patents
A kind of preparation method of graphene-based Electro-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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- 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 present invention relates to a kind of preparation method of graphene-based Electro-conductive pearlescent pigment, including：Graphene oxide solution and pearlescent pigment dispersion liquid are mixed, gained mixed solution heating stirring 1 hour~1 week at 20~100 DEG C, obtain graphene oxide based pearlescent pigments；Prepare graphene oxide based pearlescent pigments dispersion liquid, add metallic reducing agent uniformly mixing after at 10~100 DEG C heating stirring 10 seconds~24 hours, obtain the graphene-based Electro-conductive pearlescent pigment.This method is easy to operate, efficiency high, green, pollution-free, and cost is low, it is possible to achieve large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of graphene-based Electro-conductive pearlescent pigment, belong to pearlescent pigment and New function material
Expect technical field.
Background technology
Graphene-based Electro-conductive pearlescent pigment is a kind of compound pearlescent pigment of New function type.This composite pigment is in existing pearly-lustre
On the basis of pigment, by introducing high transparency, highly conductive grapheme material, so as to keep original pearlescent pigment rich colors
On the basis of, assign pearlescent pigment certain conducting function, available for each industrial department such as coating, plastics, weaving, ceramics and
Conduction, antistatic field (reference literature 1) in people's daily life.
The synthetic method of this composite pigment is broadly divided into two steps：(1) graphite oxide prepared from Hummers methods
Alkene is compound with pearlescent pigment, realizes the preparation of pearlescent pigment@graphene oxide composite pigments；(2) using hydrazine hydrate reduction method and
High-temperature calcination technique redox graphene, obtain graphene-based compound pearlescent pigment.It is but it is understood that golden in pearlescent pigment
Category oxide skin(coating) particle diameter, thickness, valence state are the important means for regulating and controlling pearlescent pigment extinction amount, are to make pearlescent pigment that abundant color be presented
The basic reason (bibliography 2-4) of color effect.Meanwhile metal oxide is nano-scale in pearlescent pigment, there is reaction position
The characteristics of point is more, activity is high, are the necessary conditions for preparing pearlescent pigment@graphene oxide composite pigments.However, graphene-based lead
In high-temperature calcination and hydrazine hydrate reduction technique used in the existing preparation method of small electric bulb delustering pigment, reducing power is strong, easily
Make metal oxide that reduction reaction also occur while graphene oxide reduces, metal ion loses electronics, produces Lacking oxygen,
The color of composite pigment is caused to reduce composite pigment color because oxygen loss and metal ion valence state reduce the change of generation extinction amount
Effect, the final application value for causing composite pigment decline to a great extent (bibliography 5-8).Although shorten redox graphene work
The reaction time of skill and reduction reaction temperature, it can largely weaken the reducing degree of metal ion, but can not
Fundamentally solve problems.Therefore, how using graphene excellent electric conductivity and optical property, solves reducing process pair
The influence of graphene-based Electro-conductive pearlescent pigment photoelectric properties, prepares color and antistatic property coordinates controllable compound pearly-lustre face
Material, made an addition in coating, plastics, rubber, adhesive, ink, fiber, ceramics, applied to electronics, electromechanics, communication, vapour
The conduction of each industrial department such as car, papermaking, weaving, packaging, printing, ceramics, Aero-Space, weapons and people's daily life,
Antistatic field, meets the market demand, has important application 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.。
The content of the invention
The problem of existing in face of prior art, it is an object of the invention to provide a kind of to the original optical property of pearlescent pigment
Influence that small, composite pigment conducts electricity very well, be simple to operate, be pollution-free, energy consumption is low, the graphene-based Electro-conductive pearlescent pigment of efficiency high
Preparation method, solve prior art be used to preparing graphene-based Electro-conductive pearlescent pigment exist absorbance increase, reaction temperature it is high,
The problem of time is long, pollution weight and equipment requirement is high, realizes 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 are mixed, gained mixed solution is heated at 20~100 DEG C and stirred
Mix 1 hour~1 week, obtain graphene oxide based pearlescent pigments；
Graphene oxide based pearlescent pigments dispersion liquid is prepared, is added after metallic reducing agent uniformly mixes at 10~100 DEG C
Heating stirring 10 seconds~24 hours, obtains the graphene-based Electro-conductive pearlescent pigment.
The present invention is by the use of metal as reducing agent, and reducing condition is gently controllable, and reaction temperature is low, and speed is fast, and side reaction is few,
And graphene oxide optionally can be reduced to graphene without reducing the metal oxide in pearlescent pigment, so as to keep away
Exempting from preparation technology change metal oxide valence state makes former pearlescent pigment color change.
It is preferred that the weight/mass percentage composition of graphene oxide is 0.1~20% in the graphene oxide solution, solvent is
Water or organic solvent, the organic solvent is methanol, ethanol, propyl alcohol, isopropanol, acetone, butanone, benzene, toluene, N, N- dimethyl
At least one of formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol.
It is preferred that the weight/mass percentage composition of pearlescent pigment is 0.1~20% in the pearlescent pigment dispersion liquid, solvent is water
Or organic solvent, the organic solvent is methanol, ethanol, propyl alcohol, isopropanol, acetone, butanone, benzene, toluene, N, N- dimethyl methyls
At least one of acid amides (DMF), dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol.
It is preferred that the mass ratio of graphene oxide and pearlescent pigment is 1 in the mixed solution:(20~100), preferably 1：
(20~50).
It is preferred that the pearlescent pigment includes core reflector layer and refracting layer, the core reflector layer includes mica, aluminium
At least one of piece, sheet glass, the refracting layer include titanium dioxide, di-iron trioxide, zirconium dioxide, lead oxide, four oxygen
Change at least one of three-iron, silica, tin ash.
It is preferred that a diameter of 1~300 μm of the refracting layer of the pearlescent pigment, thickness is 0.001 μm~1 μm, and thickness is preferred
For 1~500nm.
It is preferred that the pearlescent pigment dispersion liquid contains 0.1~5wt% dispersant.The dispersant can be 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 of cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, neopelex；It is non-
Ionic dispersant can add for Triton X-100, nonylphenol polyoxyethylene ether emulsifier, Arabic gum, oxirane
Into in thing (Tween-20, Tween-40, Tween-60 and Tween-80), ethoxylated dodecyl alcohol, lauric acid amide of ethanol
It is at least one；Anionic dispersing agent can be poly- propionic acid, poly- (methyl) acrylic acid ammonia, poly- (methyl) PAA, fatty acid soaps,
At least one of lauryl sodium sulfate.
It is preferred that the metallic reducing agent is at least one in lithium, sodium, magnesium, aluminium, calcium, nickel, iron, copper, zinc, lead, tin, manganese
Kind.
Also, it is preferred that the metallic reducing agent is powdered or block, particle diameter distribution 10-7~102Cm, preferably 0.1
~10 μm.
It is preferred that the mass ratio of the metallic reducing agent and graphene oxide based pearlescent pigments is 1：(0.01~100), it is excellent
Elect 1 as：(0.1~10).
It is provided by the invention to prepare graphene-based pearlescent pigment composite process there are following features：
(1) this method is easy to operate, efficiency high, green, pollution-free, and cost is low, it is possible to achieve large-scale production；
(2) on the basis of the original optical property of pearlescent pigment is not influenceed, 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 further expand
The application of Electro-conductive pearlescent pigment.
Brief description of the drawings
Fig. 1 is the TEM photos of the compound pearlescent pigment of mica titanium graphene prepared by embodiment 1；
Fig. 2 is the Raman collection of illustrative plates before and after the compound pearlescent pigment reduction of mica titanium graphene prepared by embodiment 1；
Fig. 3 is the XPS collection of illustrative plates before and after the compound pearlescent pigment reduction of mica titanium graphene prepared by embodiment 1；
Fig. 4 is the Ti 2p collection of illustrative plates before and after the compound pearlescent pigment reduction of mica titanium graphene prepared by embodiment 1；
Fig. 5 is the Ti 2p collection of illustrative plates after the compound pearlescent pigment reduction of mica titanium graphene prepared by comparative example 2；
Fig. 6 is the Raman collection of illustrative plates after the compound pearlescent pigment reduction of mica titanium graphene prepared by comparative example 2.
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
The present invention is merely to illustrate, is not intended to limit the present invention.
The present invention can assign pearlescent pigment higher electric conductivity using metal deoxidization under relatively low Color influences.With reference to
Table 1 (the front and rear photoelectric properties tables of data of the compound pearlescent pigment reduction of mica titanium graphene), original pearly-lustre after as shown by data 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.
Illustrate to following exemplary the preparation method of graphene-based Electro-conductive pearlescent pigment composite provided by the invention.
Hummers methods prepare graphene oxide solution.Graphite, sodium nitrate are added in the concentrated sulfuric acid in ice bath, afterwards
Potassium permanganate is slowly added to, is stirred at room temperature, hot water is added, is placed in oil bath and is incubated, hydrogen peroxide is eventually adding and terminates oxidation instead
Should.Solution centrifugal is washed, ultrasound obtains dispersion liquid of the graphene oxide in water.Oxygen in graphene oxide solution after dilution
The weight/mass percentage composition of graphite alkene can be 0.1~20%, and solvent is water or organic solvent.The organic solvent can be methanol,
At least one of ethanol, propyl alcohol, isopropanol, acetone, butanone, benzene, toluene, DMF, DMSO, ethylene glycol.
Metal salt Hydrolyze method prepares pearlescent pigment, and prepares dispersion liquid.Heretofore described pearlescent pigment is with the base that insulate
Bottom (core reflector layer) is that substrate does not coat the oxide using metal salt technology for hydrolyzing, forms oxide skin(coating) (namely
Refracting layer) wherein, core reflector layer may include at least one of mica, aluminium flake, sheet glass.Refracting layer include titanium dioxide,
At least one of di-iron trioxide, zirconium dioxide, lead oxide, ferroso-ferric oxide, silica, tin ash, the pearly-lustre
A diameter of 1~300 μm of the refracting layer of pigment, thickness are 0.001~1 μm (thickness is preferably 1~500nm).As one in detail
Example, mica powder is scattered in an acidic solution, 80 DEG C of heating stirrings, the TiCl of dilution4Solution is added dropwise in suspension,
The stable pH value of NaOH solution is added dropwise simultaneously, continues heating stirring 2h after being added dropwise to complete, filters, washing, drying obtains mica titanium pearl
Delustering pigment.Pearlescent pigment dispersion liquid is prepared, the wherein weight/mass percentage composition of pearlescent pigment can be 0.1~20%, and solvent can be water
Or organic solvent, the organic solvent can be methanol, ethanol, propyl alcohol, isopropanol, acetone, butanone, benzene, toluene, DMF, DMSO,
At least one of ethylene glycol.
In order to prevent pearlescent pigment from reuniting, uniformity of the graphene oxide in pearlescent pigment external sheath is influenceed,
Pearlescent pigment dispersion liquid adds 0.1~5wt% dispersant.The 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 of alkyl trimethyl ammonium bromide, hexadecyltrimethylammonium chloride, neopelex.Nonionic point
Powder (can be told for Triton X-100, nonylphenol polyoxyethylene ether emulsifier, Arabic gum, ethylene oxide adduct
Temperature -20, Tween-40, Tween-60 and Tween-80), ethoxylated dodecyl alcohol, at least one in lauric acid amide of ethanol
Kind.Anionic dispersing agent can be poly- propionic acid, poly- (methyl) acrylic acid ammonia, poly- (methyl) PAA, fatty acid soaps, dodecane
At least one of base sodium sulphate.
Graphene oxide solution and pearlescent pigment dispersion liquid are mixed, gained mixed solution is heated at 20~100 DEG C and stirred
Mix 1 hour~1 week.Because graphene oxide and pearlescent pigment surface electronegativity are on the contrary, utilize electrostatic adsorption between the two
And the π of graphene oxide~pi-conjugated system, realize that graphene oxide is coated on pearlescent pigment surface, obtain with nucleocapsid knot
The graphene oxide based pearlescent pigments of structure.Wherein, as long as the mass ratio of graphene oxide and pearlescent pigment in the mixed solution
Meet that graphene oxide can coat pearlescent pigment surface completely, such as mass ratio can be 1:(20~100), preferably 1:
50。
Graphene oxide based pearlescent pigments dispersion liquid is prepared, is added after metallic reducing agent uniformly mixes at 10~100 DEG C
Lower heating stirring 10 seconds~24 hours, the graphene oxide for being now coated on pearlescent pigment surface is reduced into stone by metallic reducing agent
Black alkene, obtain graphene-based Electro-conductive pearlescent pigment.Referring to Fig. 1, (Fig. 1 is the compound pearly-lustre of mica titanium graphene prepared by embodiment 1
The TEM photos of pigment), show mica titanium coated with uniform graphene layer, i.e. graphene uniform is distributed in mica titanium
Expect surface.Wherein, the metallic reducing agent purity ＞ 99.0%, for example, can be lithium, sodium, magnesium, aluminium, calcium, nickel, iron, copper, zinc, lead,
At least one of tin, manganese.The metallic reducing agent can be powdered or block, preferably powdered, particle diameter distribution 10-7~
102Cm, preferably 0.1~10 μm.Metallic reducing agent in the particle size distribution range has higher reactivity, and can lead to
Filtration method removal is crossed, it is small to composite pigment impurities affect.As long as the dosage of metallic reducing agent meets 1：(0.01~100),
It is preferred that 1：(0.1~10), it can so ensure that graphene oxide is fully reduced, and can avoid excessive metallic reducing agent from influenceing again
The purity of composite pigment.It is as a detailed example, graphene oxide based pearlescent pigments composite is scattered in the solution, use
Concentrated hydrochloric acid is adjusted to acidity, adds metal dust, stirs to metal dust reaction completely, filters, washing, drying obtains graphene-based
Pearlescent pigment powder.
In the present invention solution ph is adjusted using inorganic acid or inorganic base.The inorganic acid can be hydrochloric acid, sulfuric acid, nitre
At least one of acid, phosphoric acid.The inorganic base can be at least one of ammoniacal liquor, sodium hydroxide, potassium hydroxide.
By prepared graphene-based pearlescent pigment composite, journey is reduced to its graphene oxide using Raman spectrometer
Degree studied, its test result can be found in Fig. 2 (Fig. 2 be embodiment 1 prepare the compound pearlescent pigment of mica titanium graphene also
Raman collection of illustrative plates before and after original), I before and after reductionDWith IGRatio increases to 1.02 from 0.98, shows by reducing rear oxidation graphene
It is reduced to graphene.
By prepared graphene-based pearlescent pigment composite, journey is reduced to its graphene oxide using XPS spectrum instrument
Degree studied, its test result can be found in Fig. 3 (Fig. 3 be embodiment 1 prepare the compound pearlescent pigment of mica titanium graphene also
XPS collection of illustrative plates before and after original), before and after reduction C/O increase show to be reduced to graphene by reduction reaction rear oxidation graphene.
By prepared graphene-based pearlescent pigment composite, the chemical valence state of its titanium is carried out using XPS spectrum instrument
Research, its test result can be found in Fig. 4, and (Fig. 4 is before and after the compound pearlescent pigment of mica titanium graphene prepared by embodiment 1 reduces
Ti 2p collection of illustrative plates), peak position shows that after reduction reaction valence state change does not occur for Ti before and after reduction.
By prepared graphene-based pearlescent pigment composite, using 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 front and rear photoelectric properties tables of data of the compound pearlescent pigment reduction of mica titanium graphene
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, and green, Small side effects, controllability is strong, reproducible, and cost is low,
Excellent product performance, large-scale production easy to implement.
Metal deoxidization is used for the preparation of graphene-based Electro-conductive pearlescent pigment by the present invention first, realizes in same graphene
On the premise of doping and pearlescent pigment optical property are constant, purpose that composite pigment electric conductivity is obviously improved.Present invention side
Method has the characteristics of easy to operate, environmentally friendly, efficient, inexpensive, and prepared conducing composite material has Color tunable, highly conductive
The outstanding advantages such as performance, high stability, the development of extensive use and conductive interface material to Electro-conductive pearlescent pigment have important
Meaning.
Embodiment is enumerated 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 is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
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 an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
The 500mL concentrated sulfuric acids, 10g sodium nitrate, 60g potassium permanganate and 10g graphite are sequentially added into reactor, is stirred at room temperature
5 days, 80 DEG C of hot water of 100mL are at the uniform velocity added dropwise in reactor, after heat release is complete, centrifuge washing to solution is in neutrality, dilution
To 1000mL, the graphene oxide water solution that concentration is 10mg/mL, pH=6 are obtained.Mica powder is configured to 10% water in suspension
Solution, pH=2.0,80 DEG C of heating stirrings, 2mol/L TiCl are adjusted with concentrated hydrochloric acid4The aqueous solution is added dropwise in suspension, simultaneously
It is 2 that the stable pH value of NaOH solution, which is added dropwise, continues heating stirring 2h after being added dropwise to complete, filtering and washing obtains mica titanium nacreous material.
Obtained mica titanium nacreous material is dispersed in pH=2.0 aqueous hydrochloric acid solution by mass concentration for 5%, is added dropwise thereto
A certain amount of graphene oxide water solution, 50 DEG C of heating stirrings 3 days, filter, washing, 120 DEG C of drying.Gained powder 10g is surpassed
Sound is dispersed in pH=2.0 aqueous hydrochloric acid solution, and 400 mesh Zn powder 2g stir 5min to entering in reaction solution, filter, washing,
200 DEG C dry to obtain graphene-based Titania-mica Composites, and the content of graphene is 0.5% in composite.Use ultraviolet spectrometer
The absorbance change of this composite is tested, absorbance change is 0.40% before and after reduction, the original pearl of the composite
Light effect and color keep constant.The resistance of this composite is tested with powder resistivity instrument, 100kgcm-2Pressure
Lower resistivity is 1.1 × 104Ω cm, the composite are conductive material.
Embodiment 2
The 500mL concentrated sulfuric acids, 10g sodium nitrate, 60g potassium permanganate and 10g graphite are sequentially added into reactor, is stirred at room temperature
5 days, 80 DEG C of hot water of 100mL are at the uniform velocity added dropwise in reactor, after heat release is complete, centrifuge washing to solution is in neutrality, dilution
To 1000mL, the graphene oxide water solution that concentration is 10mg/mL, pH=5 are obtained.Mica powder is configured to 10% water in suspension
Solution, pH=2.0,80 DEG C of heating stirrings, 2mol/L TiCl are adjusted with concentrated hydrochloric acid4The aqueous solution is added dropwise in suspension, simultaneously
It is 1.5 that the stable pH value of NaOH solution, which is added dropwise, continues heating stirring 2h after being added dropwise to complete, filtering and washing obtains mica titanium perlatolic face
Material.By gained powder 10g ultrasonic disperses in the pH=2 aqueous solution, 200 mesh Zn powder 0.5g are added in reaction solution, stirring
1min, filter, washing, 200 DEG C dry to obtain graphene-based Titania-mica Composites, and the content of graphene is in composite
0.1%.The absorbance change of this composite is tested with ultraviolet spectrometer, absorbance change is before and after reduction
0.46%, the original pearl effect of the composite and color keep constant.Resistance with powder resistivity instrument to this composite
Tested, 100kgcm-2Resistivity is 3.6 × 10 under pressure4Ω cm, the composite are conductive material.
Embodiment 3
In addition to Zn powder is changed into iron powder, graphene-based pearlescent pigment is prepared in a manner of with the identical described in embodiment 1.
The absorbance change of this composite is tested with ultraviolet spectrometer, absorbance change is 0.49% before and after reduction, and this is multiple
The original pearl effect of condensation material and color keep constant.The resistance of this composite is tested with powder resistivity instrument,
100kg·cm-2Resistivity is 2.1 × 10 under pressure4Ω cm, the composite are conductive material.
Embodiment 4
In addition to Zn powder is changed into metallic sodium and reaction solution pH=7, prepared in a manner of with the identical described in embodiment 1
Graphene-based pearlescent pigment.The absorbance change of this composite is tested with ultraviolet spectrometer, absorbance before and after reduction
Change turns to 0.39%, and the original pearl effect of the composite and color keep constant.With powder resistivity instrument to this composite
Resistance tested, 100kgcm-2Resistivity is 1.7 × 10 under pressure4Ω cm, the composite are conductive material.
Embodiment 5
In addition to graphene oxide mica titanium nacreous material reacting solution pH value is adjusted into 12, with described in embodiment 1
Identical mode prepare graphene-based pearlescent pigment.The absorbance change of this composite is surveyed with ultraviolet spectrometer
Examination, absorbance change is 0.30% before and after reduction, and the original pearl effect of the composite and color keep constant.Use p owder resistivity
Rate instrument is tested the resistance of this composite, 100kgcm-2Resistivity is 2.5 × 10 under pressure4Ω cm, this is compound
Material is conductive material.
Embodiment 6
In addition to graphene oxide solution addition is increased by twice, prepared in a manner of with the identical described in embodiment 1
Graphene-based pearlescent pigment.The absorbance change of this composite is tested with ultraviolet spectrometer, absorbance before and after reduction
Change turns to 0.34%, and the original pearl effect of the composite and color keep constant.With powder resistivity instrument to this composite
Resistance tested, 100kgcm-2Resistivity is 1.8 × 10 under pressure3Ω cm, the composite are conductive material.It is multiple
The content of graphene is 1.0% in condensation material.
Embodiment 7
In addition to graphene oxide solution addition is increased into four times, prepared in a manner of with the identical described in embodiment 1
Graphene-based pearlescent pigment.The absorbance change of this composite is tested with ultraviolet spectrometer, absorbance before and after reduction
Change turns to 0.31%, and the original pearl effect of the composite and color keep constant.With powder resistivity instrument to this composite
Resistance tested, 100kgcm-2Resistivity is 320.7 Ω cm under pressure, and the composite is conductive material.It is compound
The content of graphene is 2.0% in material.
Embodiment 8
In addition to graphene oxide solution addition is increased into six times, prepared in a manner of with the identical described in embodiment 1
Graphene-based pearlescent pigment.The absorbance change of this composite is tested with ultraviolet spectrometer, absorbance before and after reduction
Change turns to 0.48%, and the original pearl effect of the composite and color keep constant.With powder resistivity instrument to this composite
Resistance tested, 100kgcm-2Resistivity is 105.2 Ω cm under pressure, and the composite is conductive material.It is compound
The content of graphene is 3.0% in material.
Embodiment 9
In addition to graphene oxide solution addition is increased into ten times, prepared in a manner of with the identical described in embodiment 1
Graphene-based pearlescent pigment.The absorbance change of this composite is tested with ultraviolet spectrometer, absorbance before and after reduction
Change turns to 0.35%, and the original pearl effect of the composite and color keep constant.With powder resistivity instrument to this composite
Resistance tested, 100kgcm-2Resistivity is 8.8 Ω cm under pressure, and the composite is conductive material.Composite wood
The content of graphene is 5.0% in material.
Comparative example 1
In addition to removing metal recovery process, graphene-based mica titanium composite wood is prepared in the same manner as example 1
Material.When being tested with powder resistivity instrument the resistance of this composite, 100kgcm-2Resistivity is+∞ under pressure, should
Composite is insulating materials.
Comparative example 2
In addition to metal recovery process to be changed to Ar atmosphere calcining reductions, graphite is prepared in the same manner as example 1
Alkenyl Titania-mica Composites.The absorbance change of this composite is tested with ultraviolet spectrometer, extinction before and after reduction
Degree change turns to 4.80%, and the composite darkens.When being tested with powder resistivity instrument the resistance of this composite,
100kg·cm-2Resistivity is 8.33 × 10 under pressure4Ω cm, the conductivity of composite material decline 8 times.By prepared stone
Mertenyl pearlescent pigment composite, the chemical valence state of its titanium is studied using XPS spectrum instrument, its test result can be found in
Fig. 5 (Fig. 5 is the Ti 2p collection of illustrative plates before and after the compound pearlescent pigment high-temperature calcination reduction of mica titanium graphene prepared by comparative example 2).
Two peaks of 459.1eV and 462.0eV are Ti in Fig. 54+Characteristic peak；Newly-increased two peaks of 454.6eV and 456.3eV are Ti3+'s
Characteristic peak, show by 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 prepared, is studied its graphene oxide reducing degree using Raman spectrometer,
Its test result can be found in Fig. 6, and (Fig. 6 is that the compound pearlescent pigment reduction of mica titanium graphene prepared by comparative example 2 is front and rear
Raman collection of illustrative plates), I before and after reductionDWith IGRatio increases to 1.04 from 0.97, shows to reduce rear oxidation graphene by high-temperature calcination
It is reduced to graphene.
Comparative example 3
In addition to metal recovery process to be changed to hydrazine hydrate backflow reduction, graphite is prepared in the same manner as example 1
Alkenyl Titania-mica Composites.The absorbance change of this composite is tested with ultraviolet spectrometer, extinction before and after reduction
Degree change turns to 6.52%, and the composite darkens.When being tested with powder resistivity instrument the resistance of this composite,
100kg·cm-2Resistivity is 3.85 × 10 under pressure4Ω cm, the conductivity of composite material decline about 4 times.
Industrial applicability：
It is provided by the invention to prepare graphene-based Electro-conductive pearlescent pigment method there is easy to operate, environmentally friendly, efficient, side reaction
Small, the advantages of cost is low, and prepared composite has the outstanding advantages such as Color tunable, high conduction performance, high stability,
The development of extensive use and conductive interface material to Electro-conductive pearlescent pigment is significant.
Claims (9)
- A kind of 1. preparation method of graphene-based Electro-conductive pearlescent pigment, it is characterised in that including：Graphene oxide solution and pearlescent pigment dispersion liquid are mixed, gained mixed solution heating stirring 1 at 20~100 DEG C is small When~1 week, graphene oxide based pearlescent pigments are obtained, wherein, the pearlescent pigment includes core reflector layer and refracting layer, described Core reflector layer includes mica, aluminium flake, at least one of sheet glass, the refracting layer include titanium dioxide, di-iron trioxide, At least one of zirconium dioxide, lead oxide, ferroso-ferric oxide, silica, tin ash；Graphene oxide based pearlescent pigments dispersion liquid is prepared, adds after metallic reducing agent uniformly mixes and is heated at 10~100 DEG C Stirring 10 seconds~24 hours, filter, washing, 200 DEG C of drying obtain the graphene-based Electro-conductive pearlescent pigment；The metal reduction The mass ratio of agent and graphene oxide based pearlescent pigments is 1：（5~10）.
- 2. preparation method according to claim 1, it is characterised in that graphene oxide in the graphene oxide solution Weight/mass percentage composition is 0.1~20%, and solvent is water or organic solvent, and the organic solvent is methanol, ethanol, propyl alcohol, isopropyl Alcohol, acetone, butanone, benzene, toluene, N,N-dimethylformamide（DMF）, dimethyl sulfoxide (DMSO)（DMSO）, in ethylene glycol at least one Kind.
- 3. preparation method according to claim 1, it is characterised in that the matter of pearlescent pigment in the pearlescent pigment dispersion liquid It is 0.1~20% to measure percentage composition, and solvent be water or organic solvent, the organic solvent be methanol, ethanol, propyl alcohol, isopropanol, Acetone, butanone, benzene, toluene, N,N-dimethylformamide（DMF）, dimethyl sulfoxide (DMSO)（DMSO）, at least one of ethylene glycol.
- 4. preparation method according to claim 1, it is characterised in that graphene oxide and pearly-lustre face in the mixed solution The mass ratio of material is 1:（20~100）.
- 5. preparation method according to claim 1, it is characterised in that a diameter of the 1 of the refracting layer of the pearlescent pigment~ 300 μm, thickness is 0.001~1 μm.
- 6. preparation method according to claim 5, it is characterised in that the thickness of the refracting layer of the pearlescent pigment be 1~ 500nm。
- 7. preparation method according to claim 1, it is characterised in that the pearlescent pigment dispersion liquid contains 0.1~5wt% Dispersant.
- 8. preparation method according to claim 1, it is characterised in that the metallic reducing agent be lithium, sodium, magnesium, aluminium, calcium, At least one of nickel, iron, copper, zinc, lead, tin, manganese.
- 9. preparation method according to claim 8, it is characterised in that the metallic reducing agent is powdered or block, grain Footpath is distributed as 10-7Cm~10 μm.
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| CN106380898B (en) * | 2016-08-31 | 2018-05-29 | 杭州华大海天科技有限公司 | Mica titanium golden pigment with blue effect and preparation method thereof |
| CN109251558B (en) * | 2017-07-13 | 2021-03-23 | 山东欧铂新材料有限公司 | Mica powder/graphene conductive composite material and preparation method thereof |
| CN108359272B (en) * | 2018-03-20 | 2020-06-16 | 常州大学 | Preparation method and application of conductive pearl powder with graphene as base material |
| CN108864790B (en) * | 2018-06-19 | 2020-09-22 | 多凌新材料科技股份有限公司 | Graphene composite antirust pigment and preparation method thereof |
| CN109021620B (en) * | 2018-07-26 | 2020-08-14 | 中国科学院上海硅酸盐研究所 | High-performance graphene-based conductive pearlescent pigment composite material and preparation method thereof |
| CN109894106A (en) * | 2019-03-18 | 2019-06-18 | 中国科学院上海硅酸盐研究所 | A kind of tri compound catalysis material and its preparation method and application |
| 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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