CN106379906B - A kind of preparation method of blue pigment modelled after an antique - Google Patents
A kind of preparation method of blue pigment modelled after an antique Download PDFInfo
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- CN106379906B CN106379906B CN201610665535.XA CN201610665535A CN106379906B CN 106379906 B CN106379906 B CN 106379906B CN 201610665535 A CN201610665535 A CN 201610665535A CN 106379906 B CN106379906 B CN 106379906B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5024—Silicates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
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Abstract
The invention discloses a kind of preparation method of blue pigment modelled after an antique, using instant waterglass as silicon source, with calcium nitrate Ca (NO3)2, copper nitrate Cu (NO3)2, barium nitrate Ba (NO3)2Respectively calcium source, copper source and barium source, barium, calcium copper silicate presoma are first made under temperature constant magnetic stirring, cupric silicate calcium and the pre-crystallized body of cupric silicate barium is made in 16~20h of hydro-thermal reaction at a temperature of 160~180 DEG C again, finally 4~6h of crystallization sintering under 550~700 DEG C of lower temperature, you can two kinds of ancient pottery and porcelain pigment of Chinese blue and Egyptian blue that purity is high, crystalline condition is good are made.
Description
Technical field
The invention belongs to ancient pottery and porcelain pigment art, and in particular to a kind of preparation method of blue pigment modelled after an antique.
Background technology
In recent years, rare-earth ceramic pigment, the pigment such as pearlescent pigment, a variety of colors of spe-cial optical effects it is long-persistence luminous
Pigment is born in succession, and achieves practical application in industry.The preparation technology of various new ceramics pigment also produces in succession, such as changes
Learn coprecipitation, hydro-thermal method, sol-gal process, liquid phase microware heating method, wet-chemical mechanochemical synthesis etc..In addition,
Some new technology such as SHS process, chemical vapour deposition technique, shock wave synthesis etc. for preparing nano material also draw in succession
Enter for preparing ceramic paint so that ceramic paint progressively develops to the direction of high-performance, low energy consumption, fine grained, high Chromaticity rate.
With the development of science and technology and the raising of living standards of the people, people improve constantly to the demand of ceramic paint, therefore
Also need to study a greater variety of ceramic paints.The ceramic paint of seriation and the new ceramics pigment of number of mechanisms material into
For another important directions of current ceramic paint development.Come the ceramic paint of developing low-cost it is also ceramic face using natural minerals
Expect the important directions of development, and the water glass color of the copper used in the recovery to ancient china historical relic also quiet enters
Research field.
Due to blueness in nature and the shortage of purple inorganic pigment, since B.C. 2500, the skillful craftsman in ancient times
Just give full play to their intelligence and wisdom, start these artificial synthesized pigment.Egyptian blue is 1814 earliest in Italian wall
The blue pigment being found in picture, its composition are cupric silicate calcium (CaCuSi4O10), once it was considered as earliest synthetic dyestuff；But
Later archaeologist has found that ancient Egyptian just drew ornament early in B.C. 2600 or so with it, but they belong to green grass or young crops
The Counterfeit Item of metal and stone.Chinese blue is ancient times artificial synthesized blue compound, chemical molecular formula BaCuSi4O10, occur earliest
In Warring states' mid-term.U.S. Fo Lier research institutes Fitzhugh is by the pottery of the ancient Chinese Warring states to Han dynasty period, bronze ware colored drawing
And the prism historical relic of bluish violet eight is analyzed, discovery wherein has blueness and purple cupric silicate barium pigment, and they are named
For Chinese blue.
Chinese blue (BaCuSi4O10) and Egyptian blue (CaCuSi4O10) it is two kinds of indigo plants with important history and Cultural Significance
Color pigment.BaCuSi4O10And CaCuSi4O10Belong to copper silicon barium ore deposit, while be also found that their track in some natural mineral
Mark, such as copper silicoglaserite etc..Chinese blue and the chemical composition of Egyptian blue are very close, only difference is that alkaline earth element is not
Together, therefore, two kinds of compounds have identical basic structure and closely similar property.They all pass through [SiO]4Square layer
Shape structure forms framework, four ring-types [SiO]4Unit is formed new [SiO] by being condensed with new connection4Unit.By so
Unlimited connection, form the lattice that cubic ring element and all directions ring element are formed, and " gauffer " is formed in the ring element of all directions.
Two relative cubic ring elements are very close so that Si-O- groups end combines to form plane square structure with copper ion.
Copper ion is pigmentation element, their being bonded in stable silicate sturcture closely, it is not easy to by chemically and physically
Method removes, therefore Chinese blue and Egyptian blue are highly stable.
For the preparation of Chinese blue and Egyptian blue, some scholars have also carried out certain research.About B.C.
4000, Egyptian, Mesopotamia people and Persians just createed a kind of exquisite pottery with pure quartz sand
Device, here it is quartz to make pottery, can also translations Egypt antique pottery.It is the first synthetic material that man invented is created.About in public affairs
Member first three thousand, the craftsman and artist of early stage have developed production coloring earth " Egypt again from quartz pottery preparation method
Indigo plant ", the method for " Egyptian green ".Archaeological discovery, these pigment powder are mostly used for painting, and potting are rarely used for, so being handed down
" Egyptian blue " fictile it is very rare and precious.This top grade of wearing [A.Pabst, Structures of some
tetragonal she et silicates,Acta Crystallographica,1959(12):733-739.] super in research
When leading material, by BaCO3, CuO and amorphous Si O2By 1:1:After 4 ratio grinding, 10% borax of addition is fluxing agent, 850
After being heated 1 day at DEG C, Chinese blue has been prepared.If Bauer wait [S.Bouherour, H.Berke, H.G.Wiedemann,
Ancient man-made copper silicate pigments studied by Raman microscopy,Chimia,
2001,55(11):942-951.] to think, the preparation condition of Chinese blue is harsher than Egyptian blue, such as expects pure China
Indigo plant, the stoichiometric proportion of raw material is strictly controlled, and speculate that ancient times may be more using stable barite BaSO4Or witherite
BaCO3As the compound of baric, catalyst is used as using lead oxide or ceruse.[H.Berke, the The such as glycolylurea Ci Beike
invention of blue and purple pigments in ancient times,Chemical Society
Reviews,2007(36):15-30.] think, Chinese blue is typically to use barite BaSO4Or barium carbonate BaCO3Deng baric
Mineral are prepared with quartz, copper-bearing mineral and essential lead salt additive after 900-1000 DEG C of successive reaction several hours
's.On the one hand lead salt additive plays catalytic action, barium ore deposit is decomposed at a lower temperature；On the other hand fluxing agent is used as, just
Additive during as prepared Egyptian blue.
In these correlative study Notables, the preparation method of Chinese blue and Egyptian blue, most of is to add to help
The technique that flux or catalyst use high-temperature calcination.Such preparation technology has the shortcomings that apparent：First, as barium source
Barium sulfate property it is stable, water, acid, alkali or organic solvent are insoluble in, so with other reactants mostly using solid phase reaction
Mode, therefore harsher is required to reaction condition.Another barium source-barium carbonate has severe toxicity simultaneously, big to environmental hazard；
Second, auxiliary agent-the lead salt added is also larger to human body and environmental hazard in itself；Third, due to last calcining actually
It is solid phase reaction process, so high temperature of the calcining heat often beyond more than 900 DEG C, energy consumption are big；Fourth, solid phase reaction product is past
It is past impure, more dephasign be present.I.e. that is, such preparation technology, which has high energy consumption, product quality not high and environmentally friendly, etc. asks
Topic.
The content of the invention
It is an object of the invention to provide a kind of preparation method of blue pigment modelled after an antique, to overcome above-mentioned prior art to exist
The defects of, Chinese blue and two kinds of ancient pottery and porcelain pigment purities height, crystalline conditions of Egyptian blue prepared by the present invention is good.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of preparation method of blue pigment modelled after an antique, comprises the following steps：
Step 1：According to n (M)：n(Cu)：N (Si)=1:1:4 mol ratio design pigment composition, wherein as M=Ba
For Chinese blue, it is Egyptian blue during M=Ca, Ca (NO is weighed respectively according to the mol ratio of design3)2·4H2O、Ba(NO3)2And Cu
(NO3)2·3H2O, and deionized water dissolving is used respectively；
Step 2：Preparation of instant water glass solution, in the case where continuously stirring by Cu (NO3)2·3H2O solution adds dropwise
Enter in instant water glass solution, then proceed to that Ba (NO are added dropwise3)2Solution or Ca (NO3)2·4H2O solution, and adjust pH and be
Alkalescent, continue stirring and obtain cupric silicate barium or cupric silicate calcium copolymerization precipitation suspension；
Step 3：Gained cupric silicate barium or cupric silicate calcium copolymerization precipitation suspension are subjected to hydro-thermal reaction, then cooling is unloaded
Centrifugal filtration, washing, drying after pressure, obtain cupric silicate barium or the pre-crystallized powder of cupric silicate calcium；
Step 4：Cupric silicate barium or the pre-crystallized powder of cupric silicate calcium are fully ground, crystallization sintering is carried out after tabletting, most
Obtained Egyptian blue or Chinese blue pigment eventually.
Further, instant water glass solution is to use modulus as 2.0~2.3 instant waterglass and deionization in step 2
The concentration that water is prepared is the 0.55~0.65mol/L aqueous solution.
Further, whipping temp is 35~45 DEG C in step 2.
Further, by Cu (NO in step 23)2·3H25~10min in instant water glass solution is added dropwise in O solution
After continue that Ba (NO are added dropwise3)2Solution or Ca (NO3)2·4H2O solution；Adjust pH be alkalescent after, continue stirring 20~
30min obtains cupric silicate barium or cupric silicate calcium copolymerization precipitation suspension.
Further, molar concentration is used to adjust pH=8~9 for 1% NaOH solution in step 2.
Further, the temperature of hydro-thermal reaction is 160~180 DEG C in step 3, and the time is 16~20h.
Further, drying temperature is 80~90 DEG C in step 3.
Further, the temperature that sintering is crystallized in step 4 is 550~700 DEG C, and the time is 4~6h.
Compared with prior art, the present invention has technique effect beneficial below：
First：The raw material of Chinese blue and Egyptian blue is using the commercially available instant waterglass of industry as silicon source, with calcium nitrate Ca (NO3)2、
Copper nitrate Cu (NO3)2, barium nitrate Ba (NO3)2Respectively calcium source, copper source and barium source, this several raw material is all soluble in water, water-soluble
Sufficient reaction can be compared in liquid, the impurity of generation is just few.Instant waterglass is as a kind of alkaline silicate, Neng Gouwei
Whole reaction system provides a good alkaline environment, contributes to the formation of Chinese blue and Egyptian blue.Most of all, in the past
Prepare more introducing lead salts in the raw material of Chinese blue and Egyptian blue reduces reaction temperature as fluxing agent, and the present invention is not added with any
Fluxing agent, the influence to environment will not be caused.Therefore, the present invention is green, and low energy is efficient.
Second：It is co-precipitated a hydrothermal synthesis method to be combined chemical coprecipitation technique with hydrothermal technique, solution coprecipitation reaction
Obtained product carries out hydro-thermal reaction as hydro-thermal reaction predecessor.It is well known that hydro-thermal method is a kind of important Green Chemistry
Synthetic method, it is not only simple to operate, and the product of high-purity can be obtained.The method is carried out under high temperature, high pressure, is changed anti-
The solubility of thing is answered so as to promote the progress of reaction.Under high-temperature and high-pressure conditions, expired by controlling hydrothermal condition progressively to develop
The crystallite dimension and pattern of prestige, such crystal grain can fully be grown by hydro-thermal reaction, obtain that crystal development is good, it is few to reunite
Product, grown up so as to effectively prevent crystal grain, the phenomenon that defect is formed, powder hard aggregation and calcination impurity introduce.Everybody
Know, the water glass color for initially preparing copper uses solid sintering technology mostly, and not only purity is low, and need to add lead salt conduct and help
Agent reduces reaction temperature.For the presoma of the present invention after hydro-thermal, crystal progressively develops desired crystallite dimension and pattern,
The sintering temperature in subsequent experimental greatly reduces.In fact, the present invention crystallization sintering temperature below 700 DEG C, this
Compared with existing method is often beyond more than 900 DEG C of calcining heat, calcining heat is greatly lowered, has saved energy consumption.
3rd：Employ particularly suitable charging sequence.Charging sequence is critically important, and order is not required for often cannot get
Product.Other ackd salts must be added thereto based on instant sodium silicate solution in the present invention, and can not phase
Instead.When adding other nitrate, copper nitrate also should be first added, then adds calcium nitrate or barium nitrate.So it is for elder generation
Allow waterglass to form cupric silicate with copper nitrate, then cupric silicate calcium (cupric silicate barium) is formed with calcium nitrate (barium nitrate), enable reaction
It is enough more fully to carry out, avoid the formation of similar to calcium silicates, cupric silicate this kind of impurity.
Brief description of the drawings
Fig. 1 is the XRD test results for the Egyptian blue sample that the embodiment of the present invention 1 obtains；
Fig. 2 is the XRD test results for the Chinese blue sample that the embodiment of the present invention 2 obtains.
Embodiment
Embodiments of the present invention are described in further detail below：
(1) according to n (M)：n(Cu)：N (Si)=1:1:4 mol ratio (M=Ba is Chinese blue, and M=Ca is Egyptian blue) is set
Count pigment composition.It is 2.0~2.3 instant waterglass first to weigh certain hydromodule, with deionized water be configured to concentration for 0.55~
The 0.65mol/L aqueous solution.Calcium nitrate Ca (NO are weighed respectively according still further to the mol ratio of design3)2·4H2O, barium nitrate Ba (NO3)2
With copper nitrate Cu (NO3)2·3H2O chemical reagent, and dissolved with appropriate amount of deionized water.
(2) instant water glass solution is placed in constant temperature blender with magnetic force, continuously stirred at 35~45 DEG C and by nitric acid
Copper solution is added dropwise wherein, continues that barium nitrate or calcium nitrate solution is added dropwise after 5~10min, and be 1% with molar concentration
NaOH solution regulation pH=8~9, continue constant temperature and stir 20~30min, obtain cupric silicate barium or cupric silicate calcium copolymerization precipitation is outstanding
Supernatant liquid.
(3) gained copolymerization precipitation suspension is placed in hydrothermal reaction kettle, the hydro-thermal reaction 16 at a temperature of 160~180 DEG C
~20h.Centrifugal filtration, washing after cooling release, and moisture is sloughed in drying in 80~90 DEG C of baking ovens, obtains cupric silicate barium or silicon
The sour pre-crystallized powder of copper calcium.
(4) pre-crystallized powder is fully ground, is placed in after tabletting in electrothermal furnace, in 550~700 DEG C crystallization sintering 4~
6h, it is final that the Egyptian blue (CaCuSi that purity is high, bright-colored, crystalline condition is good is made4O10) and Chinese blue (BaCuSi4O10) face
Material.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
(1) according to n (Ca)：n(Cu)：N (Si)=1:1:4 mol ratio design Egyptian blue pigment composition.First weigh certain
Hydromodule is 2.3 instant waterglass, and the aqueous solution that concentration is 0.65mol/L is configured to deionized water.According still further to design
Mol ratio weighs calcium nitrate Ca (NO respectively3)2·4H2O and copper nitrate Cu (NO3)2·3H2O chemical reagent, and with appropriate deionization
Water dissolves.
(2) instant water glass solution is placed in constant temperature blender with magnetic force, continuously stirred at 45 DEG C and copper nitrate is molten
Liquid is added dropwise wherein, continues that calcium nitrate solution is added dropwise after 10min, and adjusted with the NaOH solution that molar concentration is 1%
PH=9, continue constant temperature stirring 30min, obtain cupric silicate calcium copolymerization precipitation suspension.
(3) gained copolymerization precipitation suspension is placed in hydrothermal reaction kettle, the hydro-thermal reaction 20h at a temperature of 180 DEG C.Cooling
Centrifugal filtration, washing after release, and moisture is sloughed in drying in 80 DEG C of baking ovens, obtains the pre-crystallized powder of cupric silicate calcium.
(4) pre-crystallized powder is fully ground, be placed in after tabletting in electrothermal furnace, in 600 DEG C of crystallization sintering 5h, final system
Obtain the Egyptian blue (CaCuSi that purity is high, bright-colored, crystalline condition is good4O10) pigment.
Embodiment 2
(1) according to n (Ba)：n(Cu)：N (Si)=1:1:4 mol ratio design Chinese blue pigment composition.First weigh certain
Hydromodule is 2.3 instant waterglass, and the aqueous solution that concentration is 0.65mol/L is configured to deionized water.According still further to rubbing for design
You weigh barium nitrate Ba (NO by ratio respectively3)2With copper nitrate Cu (NO3)2·3H2O chemical reagent, and dissolved with appropriate amount of deionized water.
(2) instant water glass solution is placed in constant temperature blender with magnetic force, continuously stirred at 45 DEG C and copper nitrate is molten
Liquid is added dropwise wherein, continues that barium nitrate solution is added dropwise after 10min, and adjusted with the NaOH solution that molar concentration is 1%
PH=9, continue constant temperature stirring 30min, obtain cupric silicate barium copolymerization precipitation suspension.
(3) gained copolymerization precipitation suspension is placed in hydrothermal reaction kettle, the hydro-thermal reaction 20h at a temperature of 180 DEG C.Cooling
Centrifugal filtration, washing after release, and moisture is sloughed in drying in 80 DEG C of baking ovens, obtains the pre-crystallized powder of cupric silicate barium.
(4) pre-crystallized powder is fully ground, be placed in after tabletting in electrothermal furnace, in 700 DEG C of crystallization sintering 5h, final system
Obtain the Chinese blue (BaCuSi that purity is high, bright-colored, crystalline condition is good4O10) pigment.
Embodiment 3
(1) according to n (Ca)：n(Cu)：N (Si)=1:1:4 mol ratio design Egyptian blue pigment composition.First weigh certain
Hydromodule is 2.0 instant waterglass, and the aqueous solution that concentration is 0.55mol/L is configured to deionized water.According still further to design
Mol ratio weighs calcium nitrate Ca (NO respectively3)2·4H2O and copper nitrate Cu (NO3)2·3H2O chemical reagent, and with appropriate deionization
Water dissolves.
(2) instant water glass solution is placed in constant temperature blender with magnetic force, continuously stirred at 35 DEG C and copper nitrate is molten
Liquid is added dropwise wherein, continues that calcium nitrate solution is added dropwise after 5min, and adjust pH with the NaOH solution that molar concentration is 1%
=8, continue constant temperature stirring 20min, obtain cupric silicate calcium copolymerization precipitation suspension.
(3) gained copolymerization precipitation suspension is placed in hydrothermal reaction kettle, the hydro-thermal reaction 16h at a temperature of 160 DEG C.Cooling
Centrifugal filtration, washing after release, and moisture is sloughed in drying in 90 DEG C of baking ovens, obtains the pre-crystallized powder of cupric silicate calcium.
(4) pre-crystallized powder is fully ground, be placed in after tabletting in electrothermal furnace, in 550 DEG C of crystallization sintering 6h, final system
Obtain the Egyptian blue (CaCuSi that purity is high, bright-colored, crystalline condition is good4O10) pigment.
Embodiment 4
(1) according to n (Ba)：n(Cu)：N (Si)=1:1:4 mol ratio design Chinese blue pigment composition.First weigh certain
Hydromodule is 2.0 instant waterglass, and the aqueous solution that concentration is 0.55mol/L is configured to deionized water.According still further to rubbing for design
You weigh barium nitrate Ba (NO by ratio respectively3)2With copper nitrate Cu (NO3)2·3H2O chemical reagent, and dissolved with appropriate amount of deionized water.
(2) instant water glass solution is placed in constant temperature blender with magnetic force, continuously stirred at 35 DEG C and copper nitrate is molten
Liquid is added dropwise wherein, continues that barium nitrate solution is added dropwise after 5min, and adjust pH with the NaOH solution that molar concentration is 1%
=8, continue constant temperature stirring 20min, obtain cupric silicate barium copolymerization precipitation suspension.
(3) gained copolymerization precipitation suspension is placed in hydrothermal reaction kettle, the hydro-thermal reaction 16h at a temperature of 160 DEG C.Cooling
Centrifugal filtration, washing after release, and moisture is sloughed in drying in 90 DEG C of baking ovens, obtains the pre-crystallized powder of cupric silicate barium.
(4) pre-crystallized powder is fully ground, be placed in after tabletting in electrothermal furnace, in 600 DEG C of crystallization sintering 6h, final system
Obtain the Chinese blue (BaCuSi that purity is high, bright-colored, crystalline condition is good4O10) pigment.
Embodiment 5
(1) according to n (Ca)：n(Cu)：N (Si)=1:1:4 mol ratio design Egyptian blue pigment composition.First weigh certain
Hydromodule is 2.2 instant waterglass, and the aqueous solution that concentration is 0.60mol/L is configured to deionized water.According still further to design
Mol ratio weighs calcium nitrate Ca (NO respectively3)2·4H2O and copper nitrate Cu (NO3)2·3H2O chemical reagent, and with appropriate deionization
Water dissolves.
(2) instant water glass solution is placed in constant temperature blender with magnetic force, continuously stirred at 40 DEG C and copper nitrate is molten
Liquid is added dropwise wherein, continues that calcium nitrate solution is added dropwise after 8min, and adjust pH with the NaOH solution that molar concentration is 1%
=8.5, continue constant temperature stirring 25min, obtain cupric silicate calcium copolymerization precipitation suspension.
(3) gained copolymerization precipitation suspension is placed in hydrothermal reaction kettle, the hydro-thermal reaction 18h at a temperature of 170 DEG C.Cooling
Centrifugal filtration, washing after release, and moisture is sloughed in drying in 80 DEG C of baking ovens, obtains the pre-crystallized powder of cupric silicate calcium.
(4) pre-crystallized powder is fully ground, be placed in after tabletting in electrothermal furnace, in 650 DEG C of crystallization sintering 4h, final system
Obtain the Egyptian blue (CaCuSi that purity is high, bright-colored, crystalline condition is good4O10) pigment.
Embodiment 6
(1) according to n (Ba)：n(Cu)：N (Si)=1:1:4 mol ratio design Chinese blue pigment composition.First weigh certain
Hydromodule is 2.2 instant waterglass, and the aqueous solution that concentration is 0.60mol/L is configured to deionized water.According still further to rubbing for design
You weigh barium nitrate Ba (NO by ratio respectively3)2With copper nitrate Cu (NO3)2·3H2O chemical reagent, and dissolved with appropriate amount of deionized water.
(2) instant water glass solution is placed in constant temperature blender with magnetic force, continuously stirred at 40 DEG C and copper nitrate is molten
Liquid is added dropwise wherein, continues that barium nitrate solution is added dropwise after 8min, and adjust pH with the NaOH solution that molar concentration is 1%
=8.5, continue constant temperature stirring 25min, obtain cupric silicate barium copolymerization precipitation suspension.
(3) gained copolymerization precipitation suspension is placed in hydrothermal reaction kettle, the hydro-thermal reaction 18h at a temperature of 170 DEG C.Cooling
Centrifugal filtration, washing after release, and moisture is sloughed in drying in 80 DEG C of baking ovens, obtains the pre-crystallized powder of cupric silicate barium.
(4) pre-crystallized powder is fully ground, be placed in after tabletting in electrothermal furnace, in 650 DEG C of crystallization sintering 4h, final system
Obtain the Chinese blue (BaCuSi that purity is high, bright-colored, crystalline condition is good4O10) pigment.
XRD test analysis
Test the Egyptian blue that respectively prepares embodiment 1 and Chinese blue Specimen Determination prepared by embodiment 2 XRD, gained
As a result Fig. 1 and Fig. 2 are seen respectively.Fig. 1 and Fig. 2 show respectively, Egyptian blue (CaCuSi4O10) and Chinese blue (BaCuSi4O10) pigment
Characteristic peak peak shape is sharp, intensity is high, without other dephasign peaks.Fully prove, the Egyptian blue prepared according to above-mentioned processing technology routine
It is good with Chinese blue pigment purity height, crystalline condition.
Claims (6)
1. a kind of preparation method of blue pigment modelled after an antique, it is characterised in that comprise the following steps：
Step 1：According to n (M)：n(Cu)：N (Si)=1:1:4 mol ratio design pigment composition, wherein in being as M=Ba
State is blue, is Egyptian blue during M=Ca, Ca (NO are weighed respectively according to the mol ratio of design3)2·4H2O、Ba(NO3)2And Cu
(NO3)2·3H2O, and deionized water dissolving is used respectively；
Step 2：Preparation of instant water glass solution, in the case where continuously stirring by Cu (NO3)2·3H2Speed is added dropwise in O solution
In molten water glass solution, then proceed to that Ba (NO are added dropwise3)2Solution or Ca (NO3)2·4H2O solution, and it is weak base to adjust pH
Property, continue stirring and obtain cupric silicate barium or cupric silicate calcium copolymerization precipitation suspension；
Step 3：Gained cupric silicate barium or cupric silicate calcium copolymerization precipitation suspension are subjected to hydro-thermal reaction, the temperature of hydro-thermal reaction
For 160~180 DEG C, the time is 16~20h, then cools down centrifugal filtration, washing, drying after release, obtains cupric silicate barium or silicon
The sour pre-crystallized powder of copper calcium；
Step 4：Cupric silicate barium or the pre-crystallized powder of cupric silicate calcium are fully ground, crystallization sintering is carried out after tabletting, is crystallized
The temperature of sintering is 550~700 DEG C, and the time is 4~6h, finally obtained Egyptian blue or Chinese blue pigment.
A kind of 2. preparation method of blue pigment modelled after an antique according to claim 1, it is characterised in that instant water in step 2
Glass solution is that the concentration for using modulus to be prepared for 2.0~2.3 instant waterglass and deionized water is 0.55~0.65mol/L's
The aqueous solution.
3. the preparation method of a kind of blue pigment modelled after an antique according to claim 1, it is characterised in that temperature is stirred in step 2
Spend for 35~45 DEG C.
4. the preparation method of a kind of blue pigment modelled after an antique according to claim 1, it is characterised in that by Cu in step 2
(NO3)2·3H2O solution, which is added dropwise in instant water glass solution after 5~10min, continues that Ba (NO are added dropwise3)2Solution or Ca
(NO3)2·4H2O solution；Adjust pH and obtain cupric silicate barium or the copolymerization of cupric silicate calcium after alkalescent, to continue 20~30min of stirring
Precipitation suspension.
5. the preparation method of a kind of blue pigment modelled after an antique according to claim 1, it is characterised in that use and rub in step 2
The NaOH solution that your concentration is 1% adjusts pH=8~9.
6. the preparation method of a kind of blue pigment modelled after an antique according to claim 1, it is characterised in that temperature is dried in step 3
Spend for 80~90 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610665535.XA CN106379906B (en) | 2016-08-12 | 2016-08-12 | A kind of preparation method of blue pigment modelled after an antique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610665535.XA CN106379906B (en) | 2016-08-12 | 2016-08-12 | A kind of preparation method of blue pigment modelled after an antique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106379906A CN106379906A (en) | 2017-02-08 |
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| US5888291A (en) * | 1994-02-11 | 1999-03-30 | Rhone-Poulenc Chimie | Alkaline-earth metal-, copper- and optionally titanium-based silicates, blue or violet pigments based on these silicates, process for their preparation and their use |
| CN103601202A (en) * | 2013-11-14 | 2014-02-26 | 吉林大学 | Method for preparing SrCuSi4O10 and BaCuSi4O10 blue pigments through hydrothermal technique |
| CN104876283A (en) * | 2015-05-12 | 2015-09-02 | 上海大学 | Preparation method of anti-counterfeiting cobalt blue pigment with infrared reflectance function and fluorescence emission function |
| CN105088348A (en) * | 2015-08-20 | 2015-11-25 | 浙江大学 | Method for preparing BaCuSi4O10 two-dimensional crystal |
| CN105098586A (en) * | 2015-08-27 | 2015-11-25 | 浙江大学 | Application of BaCuSi4O10 two-dimensional crystals and saturable absorber device constituted by BaCuSi4O10 two-dimensional crystals |
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| US5888291A (en) * | 1994-02-11 | 1999-03-30 | Rhone-Poulenc Chimie | Alkaline-earth metal-, copper- and optionally titanium-based silicates, blue or violet pigments based on these silicates, process for their preparation and their use |
| CN103601202A (en) * | 2013-11-14 | 2014-02-26 | 吉林大学 | Method for preparing SrCuSi4O10 and BaCuSi4O10 blue pigments through hydrothermal technique |
| CN104876283A (en) * | 2015-05-12 | 2015-09-02 | 上海大学 | Preparation method of anti-counterfeiting cobalt blue pigment with infrared reflectance function and fluorescence emission function |
| CN105088348A (en) * | 2015-08-20 | 2015-11-25 | 浙江大学 | Method for preparing BaCuSi4O10 two-dimensional crystal |
| CN105098586A (en) * | 2015-08-27 | 2015-11-25 | 浙江大学 | Application of BaCuSi4O10 two-dimensional crystals and saturable absorber device constituted by BaCuSi4O10 two-dimensional crystals |
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| "Chemistry in Ancient Times: The Development of Blue and Purple Pigments";Heinz Berke;《Angew. Chem. Int. Ed》;20020520;第41卷(第14期);第2483-2487页 * |
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