CN107130231B - The preparation method of nanometer metallic silver cladding synthetic fluoromica powder - Google Patents
The preparation method of nanometer metallic silver cladding synthetic fluoromica powder Download PDFInfo
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- CN107130231B CN107130231B CN201710534173.5A CN201710534173A CN107130231B CN 107130231 B CN107130231 B CN 107130231B CN 201710534173 A CN201710534173 A CN 201710534173A CN 107130231 B CN107130231 B CN 107130231B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
A kind of preparation method of nanometer metallic silver cladding synthetic fluoromica powder, includes the following steps: the pretreatment of (1) synthetic fluoromica powder, comprising: (1-1) roughening；(1-2) activation, first coats the first active layer with liquid-phase precipitation method on roughened synthetic fluoromica powder, and the chemical component of the first active layer is SnO2、SiO2Or ZnO；The second active layer is coated on the first active layer with liquid-phase precipitation method again, the chemical component of the second active layer is TiO2、CaO、Al2O3Or ZrO2；(2) silver ammino solution is prepared；(3) by silver mirror reaction, nano metal silver layer is coated on activated synthetic fluoromica powder.Nanometer metallic silver produced by the present invention cladding synthetic fluoromica powder has the excellent performances such as good good conductive and heat-conductive catalytic performance, excellent decorative performance, high intensity, high tenacity, chemical resistance, nontoxic free from admixture, quality be light, and it is low in cost, cost performance is high.
Description
Technical field
The present invention relates to the manufactures of powder, and in particular to a kind of system of nanometer metallic silver cladding synthetic fluoromica powder
Preparation Method.
Background technique
The advantages that silver powder is conductive good, oxidation resistance is strong, stable chemical performance, but it is expensive, limits
It is widely applied.As the price of international metallic silver rises, low cost becomes extravagant hope using silver powder.How metallic silver is reduced
Usage amount becomes a big problem of puzzlement the sector development to reduce cost.
Commonly powder surface is silver-plated saves silver-colored dosage, if surface cladding ratio is more complete, can replace in any case
Silver powder.Silver-plated to have plating, chemical plating, vapour deposition process etc. to plant multi-method, wherein chemical plating method has simple process, matrix material
Material should not derivation electricity, be suitable for irregular basis material, the advantages that cost is relatively low, and chemical deposit has high-compactness, thickness
The performances such as uniform, good corrosion resistance and wear resistance are spent, therefore, the metal of powder body material are realized by the method for chemical plating
Change, it has also become the research hotspot of the sector.
Present market has to be used as using the silver powder (non-metallic powder of electroplate) of non-metallic matrix material preparation
Conductive filler has many advantages, such as that light, electrical and thermal conductivity is good, but technical matters is immature, so that the silver powder of preparation is deposited
The problems such as impurity content is big, covering amount is few, clad is more crisp, clad is shaky；And use metal matrix material (such as copper)
The silver powder of preparation, although quality will generally be got well, price is still high, and quality weight.Therefore, how one is obtained
Kind of function admirable, silver powder low in cost, cost performance is high, it has also become the problem of urgent need to resolve.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of nanometer metallic silver cladding synthetic fluoromica powder
Preparation method, nanometer metallic silver obtained coats synthetic fluoromica powder function admirable in this way, low in cost,
Cost performance is high.The technical solution adopted is as follows:
A kind of preparation method of nanometer metallic silver cladding synthetic fluoromica powder, it is characterised in that including following steps
It is rapid:
(1) pretreatment of synthetic fluoromica powder
(1-1) roughening
(1-1-1) takes 100 parts by weight synthetic fluoromica powder (by dry weight), and it is dense to be added to 320-480 parts by weight
Degree is to disperse 25-35 minutes, then remove supernatant liquor after standing 0.8-1.2 hours in the hydrochloric acid of 6mol/L, leave and take lower layer
Sediment；
The sediment that step (1-1-1) obtains is washed and is dehydrated with water by (1-1-2), obtains roughened artificial conjunction
At fluorophologopite powder；
(1-2) activation
(1-2-1) coats the first active layer with liquid-phase precipitation method on roughened synthetic fluoromica powder, and first
The chemical component of active layer is SnO2、SiO2Or ZnO；
(1-2-2) coats the second active layer, the chemical component of the second active layer with liquid-phase precipitation method on the first active layer
For TiO2、CaO、Al2O3Or ZrO2, obtain activated synthetic fluoromica powder；
(2) silver ammino solution is prepared；
(3) silver mirror reaction
It is coated on activated synthetic fluoromica powder using prepared silver ammino solution by silver mirror reaction
Nano metal silver layer (nano metal silver layer is coated on the second active layer) is made nanometer metallic silver and coats artificial synthesized fluorine gold cloud
Female powder.
Above-mentioned steps (1-1) are roughened (also known as roughening treatment), are to make synthetic fluoromica by the light corrosion of acid
Powder surface generates uniform break chemical bonds, can preferably be combined with active layer.Above-mentioned steps (1-2) activate, and are
To the activation processing on synthetic fluoromica powder surface, by liquid-phase deposition technique, on synthetic fluoromica powder surface
Active layer is formed, generate powder surface more can make nanometer metallic silver combine more firm in conjunction with the group of metallic silver.Active layer
It is divided into two layers, wherein internal layer is generally SnO2、SiO2Or ZnO, pre- combination is primarily served, roughened artificial conjunction is assigned
At the transition zone that fluorophologopite powder is a thin layer of；Outer layer is generally TiO2、CaO、Al2O3Or ZrO2, primarily serve and build chemical bond
Effect, assign roughened synthetic fluoromica powder surface active chemical bond, adsorb nano silver preferably
Above.
It is preferred that in above-mentioned steps (1-1-1), the partial size of the synthetic fluoromica powder taken be 10 microns hereinafter, or
20-80 microns or 50-200 microns.
It is preferred that sediment is washed and is dehydrated using following methods in above-mentioned steps (1-1-2): adding into sediment
Enter 350-450 parts by weight of deionized water and be stirred, is then dehydrated with plate and frame filter press.Above-mentioned washing, dehydration process can
It carries out primary or repeats repeatedly.Also deionized water can be used to be cleaned during being dehydrated with plate and frame filter press.Sheet frame
The filter cake obtained after filter press dehydration is required roughened synthetic fluoromica powder.It is preferred that is obtained is roughened
The water content of synthetic fluoromica powder is 18-22%(weight).
In above-mentioned steps (1-2), using the first activating solution, by liquid-phase precipitation method in roughened artificial synthesized fluorine gold cloud
The first active layer is coated in female powder；Using the second activating solution, the second activation is coated on the first active layer by liquid-phase precipitation method
Layer.SnCl can be used in first activating solution4Solution, solution of sodium metasilicate through or ZnCl2Solution, the first active layer of formation are SnO2Layer,
SiO2Layer or ZnO layer.TiCl can be used in second activating solution4Solution, CaCl2Solution, AlCl3Solution or ZrCl4Solution, the of formation
Two active layers are TiO2Layer, CaO layers, Al2O3Layer or ZrO2Layer.
In a kind of preferred embodiment, in step (1-2-1) by following techniques on roughened synthetic fluoromica powder
Coat the first active layer: roughened synthetic fluoromica powder is added in activating container by (1-2-1-1), and to activation
250-350 parts by weight of deionized water is added in container, warming while stirring obtains feed liquid to 60-70 DEG C；Then it is kept in feed liquid
In the case where 60-70 DEG C of temperature, feed liquid is stirred 25-35 minutes；Again with pH adjusting agent (hydrochloric acid that such as concentration is 6mol/L)
The pH value of feed liquid is adjusted to 1.5-1.8；(1-2-1-2) feed liquid temperature be 60-70 DEG C under conditions of, by 80-120 parts by weight
The first activating solution that weight percent concentration is 2.5% is added drop-wise in feed liquid, while being added pH adjusting agent and being adjusted the pH value of feed liquid
Between 1.5-1.8；First activating solution is SnCl4Solution.In preferred steps (1-2-1-2), with test solution diaphragm pump by
One activating solution (i.e. SnCl4Solution) gradually it is added drop-wise in feed liquid, it completes to be added dropwise in 0.8-1.2 hours.
In another preferred embodiment, by following techniques in roughened synthetic fluoromica powder in step (1-2-1)
The first active layer of upper cladding: roughened synthetic fluoromica powder is added in activating container by (1-2-1-1), and to work
Change and 250-350 parts by weight of deionized water is added in container, warming while stirring obtains feed liquid to 80-85 DEG C；Then it is protected in feed liquid
In the case where holding 80-85 DEG C of temperature, feed liquid is stirred 25-35 minutes；With pH adjusting agent, (NaOH that such as concentration is 10% is molten again
Liquid) pH value of feed liquid is adjusted to 8.5-9.0；(1-2-1-2) feed liquid temperature be 80-85 DEG C under conditions of, by 20-30 weight
The first activating solution that part concentration is 1mol/L is added drop-wise in feed liquid, while being added pH adjusting agent and being adjusted the pH value of feed liquid in 8.5-
Between 9.0；First activating solution is solution of sodium metasilicate through.It is living by first with test solution diaphragm pump in preferred steps (1-2-1-2)
Change liquid (i.e. solution of sodium metasilicate through) to be gradually added drop-wise in feed liquid, completes to be added dropwise in 0.8-1.2 hours.
In another preferred embodiment, by following techniques in roughened synthetic fluoromica powder in step (1-2-1)
The first active layer of upper cladding: roughened synthetic fluoromica powder is added in activating container by (1-2-1-1), and to work
Change and 250-350 parts by weight of deionized water is added in container, warming while stirring obtains feed liquid to 80-85 DEG C；Then it is protected in feed liquid
In the case where holding 80-85 DEG C of temperature, feed liquid is stirred 25-35 minutes；Again with the pH adjusting agent (salt that such as concentration is 6mol/L
Acid) pH value of feed liquid is adjusted to 5.0-6.0；(1-2-1-2) is heavy by 80-120 under conditions of feed liquid temperature is 80-85 DEG C
The first activating solution that amount part weight percent concentration is 2.0% is added drop-wise in feed liquid, while adding pH value of the pH adjusting agent by feed liquid
It adjusts between 5.0-6.0；First activating solution is ZnCl2Solution.In preferred steps (1-2-1-2), with test solution diaphragm pump
By the first activating solution (i.e. ZnCl2Solution) gradually it is added drop-wise in feed liquid, it completes to be added dropwise in 0.8-1.2 hours.
In a kind of preferred embodiment, the second active layer is coated on the first active layer by following techniques in step (1-2-2):
After (1-2-2-1) first activating solution is added dropwise to complete, pH adjusting agent is added into activating container, and (such as weight percent concentration is 10%
NaOH solution), the pH value of feed liquid is adjusted to 2.0-2.2, while the temperature of feed liquid is adjusted to 75-85 DEG C；(1-2-2-2)
Under the adjusting of pH controller, while the second activating solution and pH adjusting agent that into activating container, addition concentration is 4mol/L are (such as
The NaOH solution that weight percent concentration is 10%), and it is maintained at the pH value of feed liquid between 2.0-2.2；When the second of addition
When activating solution reaches 75-85 parts by weight, stop that the second activating solution and pH adjusting agent is added；Then kept for 75-85 DEG C in feed liquid
Feed liquid is stirred 25-35 minutes in the case where temperature, then obtains activated synthetic fluoromica after being dehydrated to feed liquid
Powder；Second activating solution is TiCl4Solution.
In more preferable step (1-2-2-2), feed liquid is dehydrated using plate and frame filter press, needed for obtained filter cake is
Activated synthetic fluoromica powder.Deionized water also can be used to carry out clearly during being dehydrated with plate and frame filter press
It washes.The water content of activated synthetic fluoromica powder is usually 18-22%.
In more preferable step (1-2-2-2), while the second activating solution and pH are pumped into activating container with test solution diaphragm pump
Regulator is pumped into speed by the control of pH controller, is maintained at pH value between 2.0-2.2.Above-mentioned pH controller is adjusted as one
Control switch, it connects three lines；Wherein a line connects pH electrode, incudes the pH value in solution, shows current pH in digital display screen
Value；Another two lines connect two test solution diaphragm pumps, and one is sour pole test solution diaphragm pump (TiCl4), the other is alkali pole test solution every
Membrane pump (NaOH).Sour pole has been at addition state.PH value on pre-set digital display is in a range (2.0-
2.2), when being lower than pH value, controller automatically opens alkali pole pump, and NaOH is added, increase pH value, pH value is maintained 2.0-2.2
Between.
In another preferred embodiment, the second active layer is coated on the first active layer by following techniques in step (1-2-2):
After (1-2-2-1) first activating solution is added dropwise to complete, pH adjusting agent is added into activating container, and (such as weight percent concentration is 10%
NaOH solution or weight percent concentration be 10% hydrochloric acid), the pH value of feed liquid is adjusted to 11-12, while by the temperature of feed liquid
Degree is adjusted to 60-70 DEG C；(1-2-2-2) is under the adjusting of pH controller, while it is 4mol/L that concentration, which is added, into activating container
The second activating solution and pH adjusting agent (hydrochloric acid that such as weight percent concentration is 10%), and the pH value of feed liquid is made to be maintained at 11-
Between 12；When the second activating solution of addition reaches 40-50 parts by weight, stop that the second activating solution and pH adjusting agent is added；Then
Feed liquid is stirred 25-35 minutes in the case where feed liquid keeps 60-70 DEG C of temperature, then activated to being obtained after feed liquid dehydration
Synthetic fluoromica powder；Second activating solution is CaCl2Solution.
In more preferable step (1-2-2-2), feed liquid is dehydrated using plate and frame filter press, needed for obtained filter cake is
Activated synthetic fluoromica powder.Deionized water also can be used to carry out clearly during being dehydrated with plate and frame filter press
It washes.The water content of activated synthetic fluoromica powder is usually 18-22%.
In more preferable step (1-2-2-2), while the second activating solution and pH are pumped into activating container with test solution diaphragm pump
Regulator is pumped into speed by the control of pH controller, is maintained at pH value between 11-12.
In another preferred embodiment, the second active layer is coated on the first active layer by following techniques in step (1-2-2):
After (1-2-2-1) first activating solution is added dropwise to complete, pH adjusting agent is added into activating container, and (such as weight percent concentration is 10%
NaOH solution or weight percent concentration be 10% hydrochloric acid), the pH value of feed liquid is adjusted to 9-10, while by the temperature of feed liquid
Degree is adjusted to 80-85 DEG C；(1-2-2-2) is under the adjusting of pH controller, while it is 4mol/L that concentration, which is added, into activating container
The second activating solution and pH adjusting agent (hydrochloric acid that such as weight percent concentration is 10%), and the pH value of feed liquid is made to be maintained at 9-
Between 10；When the second activating solution of addition reaches 50-60 parts by weight, stop that the second activating solution and pH adjusting agent is added；Then
Feed liquid is stirred 25-35 minutes in the case where feed liquid keeps 80-85 DEG C of temperature, then activated to being obtained after feed liquid dehydration
Synthetic fluoromica powder；Second activating solution is AlCl3Solution.
In more preferable step (1-2-2-2), feed liquid is dehydrated using plate and frame filter press, needed for obtained filter cake is
Activated synthetic fluoromica powder.Deionized water also can be used to carry out clearly during being dehydrated with plate and frame filter press
It washes.The water content of activated synthetic fluoromica powder is usually 18-22%.
In more preferable step (1-2-2-2), while the second activating solution and pH are pumped into activating container with test solution diaphragm pump
Regulator is pumped into speed by the control of pH controller, is maintained at pH value between 9-10.
In another preferred embodiment, the second active layer is coated on the first active layer by following techniques in step (1-2-2):
After (1-2-2-1) first activating solution is added dropwise to complete, pH adjusting agent is added into activating container, and (such as weight percent concentration is 10%
NaOH solution or weight percent concentration be 10% hydrochloric acid), the pH value of feed liquid is adjusted to 1.3-2.3, while by feed liquid
Temperature is adjusted to 75-85 DEG C；(1-2-2-2) is under the adjusting of pH controller, while it is 4mol/ that concentration, which is added, into activating container
The second activating solution and pH adjusting agent (NaOH solution that such as weight percent concentration is 10%) of L, and keep the pH value of feed liquid
Between 1.3-2.3；When the second activating solution of addition reaches 70-80 parts by weight, stops that the second activating solution is added and pH is adjusted
Agent；Then feed liquid is stirred 25-35 minutes in the case where feed liquid keeps 75-85 DEG C of temperature, then is obtained after being dehydrated to feed liquid
Activated synthetic fluoromica powder；Second activating solution is ZrCl4Solution.
In more preferable step (1-2-2-2), feed liquid is dehydrated using plate and frame filter press, needed for obtained filter cake is
Activated synthetic fluoromica powder.Deionized water also can be used to carry out clearly during being dehydrated with plate and frame filter press
It washes.The water content of activated synthetic fluoromica powder is usually 18-22%.
In more preferable step (1-2-2-2), while the second activating solution and pH are pumped into activating container with test solution diaphragm pump
Regulator is pumped into speed by the control of pH controller, is maintained at pH value between 1.3-2.3.
In preferred steps (2), the method for preparing silver ammino solution are as follows: by 12-16 parts by weight AgNO3 With 200-300 parts by weight
The NaOH solution that weight percent concentration is 5% is mixed and stirred for uniformly, and the ammonia that weight percent concentration is 12.5% is then added dropwise
Water, until solution is clarified, then the nitre acid for adjusting pH value for being 15-16% with weight percent concentration obtains silver ammino solution to 12-13.Silver
Ammonia solution is usually now matched in process of production.
The process of silver mirror reaction in preferred steps (3) are as follows:
The activated synthetic fluoromica powder that (3-1) obtains step (1-2) is added in reaction vessel, then to
250-350 parts by weight of deionized water is added in reaction vessel；Then the temperature of charge in reaction vessel is adjusted to 20-30 DEG C,
0.04-0.06 parts by weight sodium thiosulfate is added, (purpose of stirring is to keep sodium thiosulfate abundant within 0.8-1.2 hours for stirring
Dissolution, and synthetic fluoromica powder is made to be uniformly dispersed in deionized water)；
Reducing solution is gradually added into reaction vessel by (3-2), and addition is completed in 1-2 hours, then stirs 0.8-1.2
Hour, then the pH value of material in reaction vessel is adjusted to 12-13；
Reducing solution used is prepared by following techniques: taking the anhydrous acetaldehyde of 7-9 parts by weight, 200-280 parts by weight weight percent
The ethanol solution that specific concentration is 30% mixes, and obtains reducing solution after mixing evenly；
Prepared silver ammino solution is added gradually in reaction vessel that (mixing speed can by (3-3) in the case of stirring
For 250-350rpm), (adding speed of silver ammino solution is controlled in 5ml/ silver ammino solution for addition completion in 0.8-1.2 hours
Min or so)；During adding silver ammino solution, the temperature of charge in reaction vessel is controlled at 20-30 DEG C, and use nitre
Acid adjusts the pH value of material in reaction vessel, and the pH value of material in reaction vessel is made to maintain 12-13；
After (3-4) has added silver ammino solution, insulated and stirred 0.8-1.2 hours (mixing speed can be 250-350rpm), so
After filter out powder and dried, obtain nanometer metallic silver cladding synthetic fluoromica powder.
The equation of above-mentioned steps (3) reaction are as follows:
R-CHO+2Ag(NH3)2OH→R-COONH4+H2O+2Ag↓+3NH3。
Above-mentioned steps (3) select reduction method in activated synthetic fluoromica powder coated with silver on surface, i.e., in solution
The reducing agent of middle addition can provide electronics after being oxidized, precipitate reduction goes out metallic silver and coats activated synthetic fluoromica
Powder.The technique of coated with silver is similarly liquid phase deposition, and key problem in technology is: firstly, to make the artificial synthesized fluorine being wrapped by golden
Mica powder is evenly spread in liquid；Secondly, passing through the process conditions (grain including synthetic fluoromica powder of control cladding
Degree, concentration, the pH value of solution coat the temperature and time etc. of process), to realize that it is activated that nanometer metallic silver is evenly coated at
On synthetic fluoromica powder.
It is suitble to the substance (solute) of configuration reducing solution the substance that formaldehyde, sodium potassium tartrate tetrahydrate etc. possess aldehyde radical also can be used.
Synthetic fluoromica powder used in above-mentioned steps (1-1-1) is commercially available.
Synthetic fluoromica powder used in preferred steps (1-1-1) is obtained by following techniques:
Synthetic mica piece after (1-1-1-1) fluffy, operating procedure are as follows: the first step, by synthetic fluoromica piece
It puts into electric furnace, boils 3 hours；Second step takes out synthetic fluoromica piece, puts into cold water, passes through heat expansion
The process of shrinkage makes the preparatory extruding of piece；Third step configures a certain amount of sodium carbonate liquor, puts into the artificial conjunction pre-processed
At fluorophologopite piece, impregnate 24 hours at room temperature；4th step will impregnate the synthetic fluoromica piece investment one of sodium carbonate
Determine the ammonium chloride solution of concentration, impregnates 1 hour；5th step takes out soaked synthetic fluoromica piece, merging 350
DEG C calcining, washing；
(1-1-1-2) hydraulic fracture: taking waterpower paper-making pulper, is slightly removed to synthetic fluoromica piece,
By the removal of impurities grading technology of ladder sieve, pure synthetic fluoromica slurry is obtained；
(1-1-1-3) delaminates grinding: grinding to synthetic fluoromica slurry, should make that the powder crystal come is ground
It is unilateral not by the loss of mechanical force, and can be levigate by powder, reach and be maximally maintained unilateral smooth of powder, after being conducive to
Continuous cladding；
(1-1-1-4) compound online classification: the powder obtained to grinding is classified；
(1-1-1-5) is pneumatically dehydrated.
Above-mentioned steps (1-1-1-1) are changed by the states of matter of chemical immersion synthetic fluoromica piece process, are made artificial
The cleavage surface of synthetic fluorophlogopite piece interlayer is effectively peeled off, and provides good premise to wet grinding, concrete operations can
Referenced patent number is " a kind of synthetic fluoromica piece disclosed in the Chinese invention patent specification of ZL201310355762.9
The method of fluffy ".
The Chinese utility model patent specification of patent No. ZL201620503450.7 can be used in above-mentioned steps (1-1-1-4)
Disclosed " the compound online grading plant of compound mica " carries out.
The Chinese utility model patent specification of patent No. ZL201620503454.5 can be used in above-mentioned steps (1-1-1-5)
Disclosed " the pneumatic dehydration device of synthetic fluorophlogopite powder " carries out.Since pretreated subsequent handling needs to add water, take off
The powder obtained after water does not need to dry, and keeps moisture content in 18-22%.
Synthetic fluoromica powder has the advantages such as high-purity, high-weatherability, high tenacity, resistance to acid and alkali, without containing pair
The harmful lead of human body, mercury, arsenic element, and smooth surface are in mirror surface, and nanometer metallic silver coats on it, will not influence gold
Belong to the performance (such as electrical and thermal conductivity) of silver itself；One layer of nano level metal silver is coated outside synthetic fluoromica powder, it will
It is changed into conductive material from insulating materials, while assigning the properties such as the metallic silver gloss of its silver, special catalytic property, then
The properties such as high intensity, high tenacity, good weatherability in conjunction with synthetic fluoromica powder, so that the functionality of the composite granule
By force.In brief, there is nanometer metallic silver cladding synthetic fluoromica powder produced by the present invention good conductive and heat-conductive to urge
Change the excellent performances such as good performance, excellent decorative performance, high intensity, high tenacity, chemical resistance, nontoxic free from admixture, quality be light, and
Low in cost, cost performance is high, is conducive to widen it in the application of many technical fields.
Nanometer metallic silver produced by the present invention cladding synthetic fluoromica powder can be widely applied to aerospace industry,
Daily anti-corrosion, daily decoration, organic chemical industry, marine paint, high-end electronic field the fields such as antistatic process, visitor can be lowered
Family use cost.
Specific embodiment
Embodiment 1
The preparation method of nanometer metallic silver cladding synthetic fluoromica powder includes the following steps: in the present embodiment
(1) pretreatment of synthetic fluoromica powder
(1-1) roughening
(1-1-1) takes 100 parts by weight synthetic fluoromica powder (by dry weight), is added to 400 parts by weight concentration and is
In the hydrochloric acid of 6mol/L, disperses 30 minutes, then remove supernatant liquor after standing 1 hour, leave and take the sediment of lower layer；
The sediment that step (1-1-1) obtains is washed and is dehydrated with water by (1-1-2), obtains roughened artificial conjunction
At fluorophologopite powder；
In this step (1-1-2), sediment is washed and is dehydrated using following methods: 400 being added into sediment
Parts by weight of deionized water is simultaneously stirred, and is then dehydrated and (may be used also during being dehydrated with plate and frame filter press with plate and frame filter press
It is cleaned with deionized water)；The filter cake obtained after plate and frame filter press dehydration is required roughened artificial synthesized fluorine gold
Mica powder (water content of obtained roughened synthetic fluoromica powder is 18-22%(weight))；
(1-2) activation
(1-2-1) coats the first active layer with liquid-phase precipitation method on roughened synthetic fluoromica powder, and first
The chemical component of active layer is SnO2；
The first activation of cladding on roughened synthetic fluoromica powder by following techniques in this step (1-2-1)
Layer: roughened synthetic fluoromica powder is added in activating container by (1-2-1-1), and is added into activating container
300 parts by weight of deionized water, warming while stirring obtain feed liquid to 60-70 DEG C；Then 60-70 DEG C of temperature is kept in feed liquid
In the case where, feed liquid is stirred 30 minutes；The pH value of feed liquid is adjusted with pH adjusting agent (hydrochloric acid that such as concentration is 6mol/L) again
To 1.5-1.8；(1-2-1-2) under conditions of feed liquid temperature is 60-70 DEG C, with test solution diaphragm pump by 100 parts by weight weight hundred
Dividing the first activating solution that specific concentration is 2.5%, (the first activating solution is SnCl4Solution) gradually it is added drop-wise in feed liquid, while adding pH
Regulator adjusts the pH value of feed liquid between 1.5-1.8, completes to be added dropwise in 1 hour；
(1-2-2) coats the second active layer, the chemical component of the second active layer with liquid-phase precipitation method on the first active layer
For TiO2, obtain activated synthetic fluoromica powder；
The second active layer is coated on the first active layer by following techniques in this step (1-2-2): (1-2-2-1) first is living
After change liquid is added dropwise to complete, pH adjusting agent (NaOH solution that such as weight percent concentration is 10%) is added into activating container, will expect
The pH value of liquid is adjusted to 2.0-2.2, while the temperature of feed liquid is adjusted to 75-85 DEG C；The adjusting of (1-2-2-2) in pH controller
Under, while (the second activating solution is TiCl to the second activating solution that addition concentration is 4mol/L into activating container4Solution) and pH tune
Agent (NaOH solution that such as weight percent concentration is 10%) is saved, and is maintained at the pH value of feed liquid between 2.0-2.2；When adding
When the second activating solution entered reaches 80 parts by weight, stop that the second activating solution and pH adjusting agent is added；Then 75-85 is kept in feed liquid
DEG C temperature in the case where to feed liquid stir 30 minutes, then to feed liquid dehydration after obtain activated synthetic fluoromica
Powder；
In step (1-2-2-2), feed liquid is dehydrated (in the process being dehydrated with plate and frame filter press using plate and frame filter press
In also deionized water can be used to be cleaned), obtained filter cake is required activated synthetic fluoromica powder；Through work
The water content of the synthetic fluoromica powder of change is usually 18-22%；
In step (1-2-2-2), while the second activating solution and pH adjusting agent are pumped into activating container with test solution diaphragm pump,
It is pumped into speed by the control of pH controller, is maintained at pH value between 2.0-2.2；
(2) silver ammino solution is prepared；
In this step (2), the method for preparing silver ammino solution are as follows: by 14 parts by weight AgNO3 With 250 parts by weight weight percents
The NaOH solution that specific concentration is 5% is mixed and stirred for uniformly, the ammonium hydroxide that weight percent concentration is 12.5% is then added dropwise, until solution
Clarification, then the nitre acid for adjusting pH value for being 15.5% with weight percent concentration obtain silver ammino solution to 12.5；
(3) silver mirror reaction
The process of silver mirror reaction in this step (3) are as follows:
The activated synthetic fluoromica powder that (3-1) obtains step (1-2) is added in reaction vessel, then to
300 parts by weight of deionized water are added in reaction vessel；Then the temperature of charge in reaction vessel is adjusted to 20-30 DEG C, then plus
Enter 0.05 parts by weight sodium thiosulfate, stirs 1 hour；
Reducing solution is gradually added into reaction vessel by (3-2), is added and is completed in 1.5 hours, is then stirred 1 hour,
The pH value of material in reaction vessel is adjusted to 12-13 again；
Reducing solution used is prepared by following techniques: taking the anhydrous acetaldehyde of 8 parts by weight, 242 parts by weight weight percent concentrations
It is mixed for 30% ethanol solution, obtains reducing solution after mixing evenly；
Prepared silver ammino solution is added gradually in reaction vessel that (mixing speed is by (3-3) in the case of stirring
300rpm), silver ammino solution adds completion in 1 hour (adding speed of silver ammino solution is controlled in 5ml/min or so)；It is adding
During silver ammino solution, the temperature of charge in reaction vessel is controlled at 20-30 DEG C, and is adjusted in reaction vessel with nitric acid
The pH value of material makes the pH value of material in reaction vessel maintain 12-13；
After (3-4) has added silver ammino solution, insulated and stirred 1 hour (mixing speed 300rpm) then filters out powder simultaneously
It is dried, obtains nanometer metallic silver cladding synthetic fluoromica powder (by above-mentioned silver mirror reaction, activated artificial
Nano metal silver layer is coated on synthetic fluorophlogopite powder).
Embodiment 2
The preparation method of nanometer metallic silver cladding synthetic fluoromica powder includes the following steps: in the present embodiment
(1) pretreatment of synthetic fluoromica powder
(1-1) roughening
(1-1-1) takes 100 parts by weight synthetic fluoromica powder (by dry weight), is added to 480 parts by weight concentration and is
In the hydrochloric acid of 6mol/L, disperses 25 minutes, then remove supernatant liquor after standing 0.8 hour, leave and take the sediment of lower layer；
The sediment that step (1-1-1) obtains is washed and is dehydrated with water by (1-1-2), obtains roughened artificial conjunction
At fluorophologopite powder；
In this step (1-1-2), sediment is washed and is dehydrated using following methods: 420 being added into sediment
Parts by weight of deionized water is simultaneously stirred, and is then dehydrated and (may be used also during being dehydrated with plate and frame filter press with plate and frame filter press
It is cleaned with deionized water)；The filter cake obtained after plate and frame filter press dehydration is required roughened artificial synthesized fluorine gold
Mica powder (water content of obtained roughened synthetic fluoromica powder is 18-22%(weight))；
(1-2) activation
(1-2-1) coats the first active layer with liquid-phase precipitation method on roughened synthetic fluoromica powder, and first
The chemical component of active layer is SiO2；
The first activation of cladding on roughened synthetic fluoromica powder by following techniques in this step (1-2-1)
Layer: roughened synthetic fluoromica powder is added in activating container by (1-2-1-1), and is added into activating container
350 parts by weight of deionized water, warming while stirring obtain feed liquid to 80-85 DEG C；Then 80-85 DEG C of temperature is kept in feed liquid
In the case where, feed liquid is stirred 25 minutes；The pH value of feed liquid is adjusted with pH adjusting agent (NaOH solution that such as concentration is 10%) again
To 8.5-9.0；30 parts by weight concentration are by (1-2-1-2) with test solution diaphragm pump under conditions of feed liquid temperature is 80-85 DEG C
The first activating solution (the first activating solution is solution of sodium metasilicate through) of 1mol/L is gradually added drop-wise in feed liquid, while adding pH adjusting agent
The pH value of feed liquid is adjusted between 8.5-9.0, completes to be added dropwise in 1.2 hours；
(1-2-2) coats the second active layer, the chemical component of the second active layer with liquid-phase precipitation method on the first active layer
For CaO, activated synthetic fluoromica powder is obtained；
The second active layer is coated on the first active layer by following techniques in this step (1-2-2): (1-2-2-1) first is living
After change liquid is added dropwise to complete, the pH adjusting agent (NaOH solution or weight that such as weight percent concentration is 10% is added into activating container
The hydrochloric acid that percent concentration is 10%), the pH value of feed liquid is adjusted to 11-12, while the temperature of feed liquid is adjusted to 60-70 DEG C；
(1-2-2-2) the second activating solution (second that concentration is 4mol/L is added into activating container under the adjusting of pH controller
Activating solution is CaCl2Solution) and pH adjusting agent (hydrochloric acid that such as weight percent concentration is 10%), and protect the pH value of feed liquid
It holds between 11-12；When the second activating solution of addition reaches 50 parts by weight, stop that the second activating solution and pH adjusting agent is added；
Then feed liquid is stirred 35 minutes in the case where feed liquid keeps 60-70 DEG C of temperature, then activated to being obtained after feed liquid dehydration
Synthetic fluoromica powder；
In step (1-2-2-2), feed liquid is dehydrated (in the process being dehydrated with plate and frame filter press using plate and frame filter press
In also deionized water can be used to be cleaned), obtained filter cake is required activated synthetic fluoromica powder；Through work
The water content of the synthetic fluoromica powder of change is usually 18-22%；
In step (1-2-2-2), while the second activating solution and pH adjusting agent are pumped into activating container with test solution diaphragm pump,
It is pumped into speed by the control of pH controller, is maintained at pH value between 11-12；
(2) silver ammino solution is prepared；
In this step (2), the method for preparing silver ammino solution are as follows: by 12 parts by weight AgNO3 With 300 parts by weight weight percent
The NaOH solution that concentration is 5% is mixed and stirred for uniformly, the ammonium hydroxide that weight percent concentration is 12.5% is then added dropwise, until solution is clear
Clearly, then with weight percent concentration the nitre acid for adjusting pH value for being 15% obtains silver ammino solution to 12-13；
(3) silver mirror reaction
The process of silver mirror reaction in this step (3) are as follows:
The activated synthetic fluoromica powder that (3-1) obtains step (1-2) is added in reaction vessel, then to
250 parts by weight of deionized water are added in reaction vessel；Then the temperature of charge in reaction vessel is adjusted to 20-30 DEG C, then plus
Enter 0.04 parts by weight sodium thiosulfate, stirs 0.8 hour；
Reducing solution is gradually added into reaction vessel by (3-2), is added and is completed in 2 hours, is then stirred 0.8 hour,
The pH value of material in reaction vessel is adjusted to 12-13 again；
Reducing solution used is prepared by following techniques: taking the anhydrous acetaldehyde of 9 parts by weight, 280 parts by weight weight percent concentrations
It is mixed for 30% ethanol solution, obtains reducing solution after mixing evenly；
Prepared silver ammino solution is added gradually in reaction vessel that (mixing speed is by (3-3) in the case of stirring
250rpm), silver ammino solution adds completion in 1.2 hours (adding speed of silver ammino solution is controlled in 5ml/min or so)；?
During adding silver ammino solution, the temperature of charge in reaction vessel is controlled at 20-30 DEG C, and adjusts reaction with nitric acid and holds
The pH value of material in device, makes the pH value of material in reaction vessel maintain 12-13；
After (3-4) has added silver ammino solution, insulated and stirred 1.2 hours (mixing speed 250rpm) then filters out powder
And dried, nanometer metallic silver cladding synthetic fluoromica powder is obtained (by above-mentioned silver mirror reaction, in activated people
Nano metal silver layer is coated on work synthetic fluorophlogopite powder).
Embodiment 3
The preparation method of nanometer metallic silver cladding synthetic fluoromica powder includes the following steps: in the present embodiment
(1) pretreatment of synthetic fluoromica powder
(1-1) roughening
(1-1-1) takes 100 parts by weight synthetic fluoromica powder (by dry weight), is added to 320 parts by weight concentration and is
In the hydrochloric acid of 6mol/L, disperses 35 minutes, then remove supernatant liquor after standing 1.2 hours, leave and take the sediment of lower layer；
The sediment that step (1-1-1) obtains is washed and is dehydrated with water by (1-1-2), obtains roughened artificial conjunction
At fluorophologopite powder；
In this step (1-1-2), sediment is washed and is dehydrated using following methods: 350 being added into sediment
Parts by weight of deionized water is simultaneously stirred, and is then dehydrated and (may be used also during being dehydrated with plate and frame filter press with plate and frame filter press
It is cleaned with deionized water)；The filter cake obtained after plate and frame filter press dehydration is required roughened artificial synthesized fluorine gold
Mica powder (water content of obtained roughened synthetic fluoromica powder is 18-22%(weight))；
(1-2) activation
(1-2-1) coats the first active layer with liquid-phase precipitation method on roughened synthetic fluoromica powder, and first
The chemical component of active layer is ZnO；
The first activation of cladding on roughened synthetic fluoromica powder by following techniques in this step (1-2-1)
Layer: roughened synthetic fluoromica powder is added in activating container by (1-2-1-1), and is added into activating container
280 parts by weight of deionized water, warming while stirring obtain feed liquid to 80-85 DEG C；Then 80-85 DEG C of temperature is kept in feed liquid
In the case where, feed liquid is stirred 28 minutes；The pH value of feed liquid is adjusted with pH adjusting agent (hydrochloric acid that such as concentration is 6mol/L) again
To 5.0-6.0；(1-2-1-2) under conditions of feed liquid temperature is 80-85 DEG C, with test solution diaphragm pump by 80-120 parts by weight weight
(the first activating solution is ZnCl to the first activating solution that percent concentration is 2.0%2Solution) gradually it is added drop-wise in feed liquid, it adds simultaneously
PH adjusting agent adjusts the pH value of feed liquid between 5.0-6.0, completes to be added dropwise in 1 hour；
(1-2-2) coats the second active layer, the chemical component of the second active layer with liquid-phase precipitation method on the first active layer
For ZrO2, obtain activated synthetic fluoromica powder；
The second active layer is coated on the first active layer by following techniques in this step (1-2-2): (1-2-2-1) first is living
After change liquid is added dropwise to complete, the pH adjusting agent (NaOH solution or weight that such as weight percent concentration is 10% is added into activating container
The hydrochloric acid that percent concentration is 10%), the pH value of feed liquid is adjusted to 1.3-2.3, while the temperature of feed liquid is adjusted to 75-85
℃；(1-2-2-2) the second activating solution that concentration is 4mol/L is added into activating container under the adjusting of pH controller
(the second activating solution is ZrCl4Solution) and pH adjusting agent (NaOH solution that such as weight percent concentration is 10%), and make feed liquid
PH value be maintained between 1.3-2.3；When the second activating solution of addition reaches 70 parts by weight, stop be added the second activating solution and
PH adjusting agent；Then feed liquid is stirred 32 minutes in the case where feed liquid keeps 75-85 DEG C of temperature, then to feed liquid dehydration after
Obtain activated synthetic fluoromica powder；
In this step (1-2-2-2), feed liquid is dehydrated (in the mistake being dehydrated with plate and frame filter press using plate and frame filter press
Also deionized water can be used to be cleaned in journey), obtained filter cake is required activated synthetic fluoromica powder；Through
The water content of the synthetic fluoromica powder of activation is usually 18-22%；
In this step (1-2-2-2), while the second activating solution and pH adjusting are pumped into activating container with test solution diaphragm pump
Agent is pumped into speed by the control of pH controller, is maintained at pH value between 1.3-2.3；
(2) silver ammino solution is prepared；
In this step (2), the method for preparing silver ammino solution are as follows: by 16 parts by weight AgNO3 With 270 parts by weight weight percents
The NaOH solution that specific concentration is 5% is mixed and stirred for uniformly, the ammonium hydroxide that weight percent concentration is 12.5% is then added dropwise, until solution
Clarification, then the nitre acid for adjusting pH value for being 16% with weight percent concentration obtain silver ammino solution to 12-13；
(3) silver mirror reaction
The process of silver mirror reaction in this step (3) are as follows:
The activated synthetic fluoromica powder that (3-1) obtains step (1-2) is added in reaction vessel, then to
350 parts by weight of deionized water are added in reaction vessel；Then the temperature of charge in reaction vessel is adjusted to 20-30 DEG C, then plus
Enter 0.06 parts by weight sodium thiosulfate, (purpose of stirring is to dissolve sodium thiosulfate sufficiently, and make artificial within 1.2 hours for stirring
Synthetic fluorophlogopite powder is uniformly dispersed in deionized water)；
Reducing solution is gradually added into reaction vessel by (3-2), is added and is completed in 1 hour, is then stirred 1.2 hours,
The pH value of material in reaction vessel is adjusted to 12-13 again；
Reducing solution used is prepared by following techniques: taking the anhydrous acetaldehyde of 7 parts by weight, 200 parts by weight weight percent concentrations
It is mixed for 30% ethanol solution, obtains reducing solution after mixing evenly；
Prepared silver ammino solution is added gradually in reaction vessel that (mixing speed is by (3-3) in the case of stirring
350rpm), silver ammino solution adds completion in 0.8 hour (adding speed of silver ammino solution is controlled in 5ml/min or so)；Adding
During adding silver ammino solution, the temperature of charge in reaction vessel is controlled at 20-30 DEG C, and adjusts reaction vessel with nitric acid
The pH value of middle material makes the pH value of material in reaction vessel maintain 12-13；
After (3-4) has added silver ammino solution, insulated and stirred 0.8 hour (mixing speed 350rpm) then filters out powder
And dried, nanometer metallic silver cladding synthetic fluoromica powder is obtained (by above-mentioned silver mirror reaction, in activated people
Nano metal silver layer is coated on work synthetic fluorophlogopite powder).
Embodiment 4
The preparation method of nanometer metallic silver cladding synthetic fluoromica powder includes the following steps: in the present embodiment
(1) pretreatment of synthetic fluoromica powder
(1-1) roughening
(1-1-1) takes 100 parts by weight synthetic fluoromica powder (by dry weight), is added to 420 parts by weight concentration and is
In the hydrochloric acid of 6mol/L, disperses 32 minutes, then remove supernatant liquor after standing 0.9 hour, leave and take the sediment of lower layer；
The sediment that step (1-1-1) obtains is washed and is dehydrated with water by (1-1-2), obtains roughened artificial conjunction
At fluorophologopite powder；
In this step (1-1-2), sediment is washed and is dehydrated using following methods: 450 being added into sediment
Parts by weight of deionized water is simultaneously stirred, and is then dehydrated and (may be used also during being dehydrated with plate and frame filter press with plate and frame filter press
It is cleaned with deionized water)；The filter cake obtained after plate and frame filter press dehydration is required roughened artificial synthesized fluorine gold
Mica powder (water content of obtained roughened synthetic fluoromica powder is 18-22%(weight))；
(1-2) activation
(1-2-1) coats the first active layer with liquid-phase precipitation method on roughened synthetic fluoromica powder, and first
The chemical component of active layer is SnO2；
The first activation of cladding on roughened synthetic fluoromica powder by following techniques in this step (1-2-1)
Layer: roughened synthetic fluoromica powder is added in activating container by (1-2-1-1), and is added into activating container
320 parts by weight of deionized water, warming while stirring obtain feed liquid to 60-70 DEG C；Then 60-70 DEG C of temperature is kept in feed liquid
In the case where, feed liquid is stirred 32 minutes；The pH value of feed liquid is adjusted with pH adjusting agent (hydrochloric acid that such as concentration is 6mol/L) again
To 1.5-1.8；(1-2-1-2) under conditions of feed liquid temperature is 60-70 DEG C, with test solution diaphragm pump by 90 parts by weight weight percents
(the first activating solution is SnCl to the first activating solution that specific concentration is 2.5%4Solution) gradually it is added drop-wise in feed liquid, while adding pH tune
It saves agent to adjust the pH value of feed liquid between 1.5-1.8, completes to be added dropwise in 1.1 hours；
(1-2-2) coats the second active layer, the chemical component of the second active layer with liquid-phase precipitation method on the first active layer
For Al2O3, obtain activated synthetic fluoromica powder；
The second active layer is coated on the first active layer by following techniques in this step (1-2-2): (1-2-2-1) first is living
After change liquid is added dropwise to complete, the pH adjusting agent (NaOH solution or weight that such as weight percent concentration is 10% is added into activating container
The hydrochloric acid that percent concentration is 10%), the pH value of feed liquid is adjusted to 9-10, while the temperature of feed liquid is adjusted to 80-85 DEG C；
(1-2-2-2) the second activating solution (second that concentration is 4mol/L is added into activating container under the adjusting of pH controller
Activating solution is AlCl3Solution) and pH adjusting agent (hydrochloric acid that such as weight percent concentration is 10%), and protect the pH value of feed liquid
It holds between 9-10；When the second activating solution of addition reaches 55 parts by weight, stop that the second activating solution and pH adjusting agent is added；So
Feed liquid is stirred 30 minutes in the case where feed liquid keeps 80-85 DEG C of temperature afterwards, then activated to being obtained after feed liquid dehydration
Synthetic fluoromica powder；
In step (1-2-2-2), feed liquid is dehydrated (in the process being dehydrated with plate and frame filter press using plate and frame filter press
In also deionized water can be used to be cleaned), obtained filter cake is required activated synthetic fluoromica powder；Through work
The water content of the synthetic fluoromica powder of change is usually 18-22%；
In step (1-2-2-2), while the second activating solution and pH adjusting agent are pumped into activating container with test solution diaphragm pump,
It is pumped into speed by the control of pH controller, is maintained at pH value between 9-10；
(2) silver ammino solution is prepared；
In this step (2), the method for preparing silver ammino solution are as follows: by 15 parts by weight AgNO3 With 200 parts by weight weight percents
The NaOH solution that specific concentration is 5% is mixed and stirred for uniformly, the ammonium hydroxide that weight percent concentration is 12.5% is then added dropwise, until solution
Clarification, then the nitre acid for adjusting pH value for being 15% with weight percent concentration obtain silver ammino solution to 12-13；
(3) silver mirror reaction
The process of silver mirror reaction in this step (3) are as follows:
The activated synthetic fluoromica powder that (3-1) obtains step (1-2) is added in reaction vessel, then to
300 parts by weight of deionized water are added in reaction vessel；Then the temperature of charge in reaction vessel is adjusted to 20-30 DEG C, then plus
Enter 0.045 parts by weight sodium thiosulfate, stirs 1 hour；
Reducing solution is gradually added into reaction vessel by (3-2), is added and is completed in 1.5 hours, and it is small then to stir 0.9
When, then the pH value of material in reaction vessel is adjusted to 12-13；
Reducing solution used is prepared by following techniques: taking the anhydrous acetaldehyde of 8 parts by weight, 250 parts by weight weight percent concentrations
It is mixed for 30% ethanol solution, obtains reducing solution after mixing evenly；
Prepared silver ammino solution is added gradually in reaction vessel that (mixing speed is by (3-3) in the case of stirring
300rpm), silver ammino solution adds completion in 1 hour (adding speed of silver ammino solution is controlled in 5ml/min or so)；It is adding
During silver ammino solution, the temperature of charge in reaction vessel is controlled at 20-30 DEG C, and is adjusted in reaction vessel with nitric acid
The pH value of material makes the pH value of material in reaction vessel maintain 12-13；
After (3-4) has added silver ammino solution, insulated and stirred 1 hour (mixing speed 300rpm) then filters out powder simultaneously
It is dried, obtains nanometer metallic silver cladding synthetic fluoromica powder (by above-mentioned silver mirror reaction, activated artificial
Nano metal silver layer is coated on synthetic fluorophlogopite powder).
In the step of above-described embodiment 1-4 (1-1-1), the partial size of the synthetic fluoromica powder taken be 10 microns with
Under or 20-80 microns or 50-200 microns, it is commercially available.
In addition, above-described embodiment 1-4 gives four kinds of examples of active layer composition, but the present invention is not limited to the above implementation
Example, that is to say, that the first active layer (SnO of any one chemical component2Layer, SiO2Layer or ZnO layer) it all can be with any one change
The the second active layer (TiO studied point2Layer, CaO layers, Al2O3Layer or ZrO2Layer) combine and form active layer, only need to activation step
Corresponding first activating solution, the second activating solution are selected in rapid.
Claims (9)
1. a kind of preparation method of nanometer metallic silver cladding synthetic fluoromica powder, it is characterised in that include the following steps:
(1) pretreatment of synthetic fluoromica powder
(1-1) roughening
(1-1-1) takes 100 parts by weight synthetic fluoromica powder, is added to the salt that 320-480 parts by weight concentration is 6mol/L
In acid, disperses 25-35 minutes, then remove supernatant liquor after standing 0.8-1.2 hours, leave and take the sediment of lower layer；
The sediment that step (1-1-1) obtains is washed and is dehydrated with water by (1-1-2), obtains roughened artificial synthesized fluorine
Phlogopite powder；
(1-2) activation
(1-2-1) coats the first active layer, the first activation with liquid-phase precipitation method on roughened synthetic fluoromica powder
The chemical component of layer is SnO2、SiO2Or ZnO；
(1-2-2) coats the second active layer with liquid-phase precipitation method on the first active layer, and the chemical component of the second active layer is
TiO2、CaO、Al2O3Or ZrO2, obtain activated synthetic fluoromica powder；
(2) silver ammino solution is prepared；
The method for preparing silver ammino solution are as follows: by 12-16 parts by weight AgNO3 It is 5% with 200-300 parts by weight weight percent concentration
NaOH solution be mixed and stirred for uniformly, the ammonium hydroxide that weight percent concentration is 12.5% is then added dropwise and then is used until solution is clarified
Weight percent concentration is the nitre acid for adjusting pH value of 15-16% to 12-13, obtains silver ammino solution；
(3) silver mirror reaction
Nanometer is coated on activated synthetic fluoromica powder by silver mirror reaction using prepared silver ammino solution
Metallic silver layer is made nanometer metallic silver and coats synthetic fluoromica powder；
The process of silver mirror reaction are as follows:
The activated synthetic fluoromica powder that (3-1) obtains step (1-2) is added in reaction vessel, then to reaction
250-350 parts by weight of deionized water is added in container；Then the temperature of charge in reaction vessel is adjusted to 20-30 DEG C, then plus
Enter 0.04-0.06 parts by weight sodium thiosulfate, stirs 0.8-1.2 hours；
Reducing solution is gradually added into reaction vessel by (3-2), and addition is completed in 1-2 hours, and it is small then to stir 0.8-1.2
When, then the pH value of material in reaction vessel is adjusted to 12-13；
Reducing solution used is prepared by following techniques: taking the anhydrous acetaldehyde of 7-9 parts by weight, 200-280 parts by weight weight percent dense
Degree mixes for 30% ethanol solution, obtains reducing solution after mixing evenly；
Prepared silver ammino solution is added gradually in reaction vessel by (3-3) in the case of stirring, and silver ammino solution is in 0.8-
It adds and completes in 1.2 hours；During adding silver ammino solution, the temperature of charge in reaction vessel is controlled in 20-30
DEG C, and with nitric acid adjust reaction vessel in material pH value, so that the pH value of material in reaction vessel is maintained 12-13；
After (3-4) has added silver ammino solution, insulated and stirred 0.8-1.2 hours, then filters out powder and dried, received
Rice metallic silver coats synthetic fluoromica powder.
2. the preparation method of nanometer metallic silver cladding synthetic fluoromica powder according to claim 1, feature exist
The first active layer: (1-2-1- is coated on roughened synthetic fluoromica powder by following techniques in step (1-2-1)
1) roughened synthetic fluoromica powder is added in activating container, and 250-350 weight is added into activating container
Part deionized water, warming while stirring obtain feed liquid to 60-70 DEG C；Then the case where feed liquid keeps 60-70 DEG C of temperature
Under, feed liquid is stirred 25-35 minutes；The pH value of feed liquid is adjusted to 1.5-1.8 with pH adjusting agent again；(1-2-1-2) is in feed liquid
Under conditions of temperature is 60-70 DEG C, the first activating solution that 80-120 parts by weight weight percent concentration is 2.5% is added drop-wise to material
In liquid, while adding pH adjusting agent and adjusting the pH value of feed liquid between 1.5-1.8；First activating solution is SnCl4Solution.
3. the preparation method of nanometer metallic silver cladding synthetic fluoromica powder according to claim 1, feature exist
The first active layer: (1-2-1- is coated on roughened synthetic fluoromica powder by following techniques in step (1-2-1)
1) roughened synthetic fluoromica powder is added in activating container, and 250-350 weight is added into activating container
Part deionized water, warming while stirring obtain feed liquid to 80-85 DEG C；Then the case where feed liquid keeps 80-85 DEG C of temperature
Under, feed liquid is stirred 25-35 minutes；The pH value of feed liquid is adjusted to 8.5-9.0 with pH adjusting agent again；(1-2-1-2) is in feed liquid
Under conditions of temperature is 80-85 DEG C, the first activating solution that 20-30 parts by weight concentration is 1mol/L is added drop-wise in feed liquid, simultaneously
PH adjusting agent is added to adjust the pH value of feed liquid between 8.5-9.0；First activating solution is solution of sodium metasilicate through.
4. the preparation method of nanometer metallic silver cladding synthetic fluoromica powder according to claim 1, feature exist
The first active layer: (1-2-1- is coated on roughened synthetic fluoromica powder by following techniques in step (1-2-1)
1) roughened synthetic fluoromica powder is added in activating container, and 250-350 weight is added into activating container
Part deionized water, warming while stirring obtain feed liquid to 80-85 DEG C；Then the case where feed liquid keeps 80-85 DEG C of temperature
Under, feed liquid is stirred 25-35 minutes；The pH value of feed liquid is adjusted to 5.0-6.0 with pH adjusting agent again；(1-2-1-2) is in feed liquid
Under conditions of temperature is 80-85 DEG C, the first activating solution that 80-120 parts by weight weight percent concentration is 2.0% is added drop-wise to material
In liquid, while adding pH adjusting agent and adjusting the pH value of feed liquid between 5.0-6.0；First activating solution is ZnCl2Solution.
5. according to the preparation method of the described in any item nanometer metallic silver cladding synthetic fluoromica powder of claim 2-4,
It is characterized in that the first activating solution is gradually added drop-wise in feed liquid with test solution diaphragm pump, in step (1-2-1-2) in 0.8-1.2
It completes to be added dropwise in hour.
6. the preparation method of nanometer metallic silver cladding synthetic fluoromica powder according to claim 1, feature exist
The second active layer is coated on the first active layer by following techniques in step (1-2-2): (1-2-2-1) first activating solution is added dropwise
After the completion, pH adjusting agent is added into activating container, the pH value of feed liquid is adjusted to 2.0-2.2, while by the temperature tune of feed liquid
Section is to 75-85 DEG C；(1-2-2-2) is under the adjusting of pH controller, while be added into activating container that concentration is 4mol/L the
Two activating solutions and pH adjusting agent, and it is maintained at the pH value of feed liquid between 2.0-2.2；When the second activating solution of addition reaches
When 75-85 parts by weight, stop that the second activating solution and pH adjusting agent is added；Then the case where feed liquid keeps 75-85 DEG C of temperature
Under to feed liquid stir 25-35 minute, then to feed liquid be dehydrated after obtain activated synthetic fluoromica powder；Described second
Activating solution is TiCl4Solution.
7. the preparation method of nanometer metallic silver cladding synthetic fluoromica powder according to claim 1, feature exist
The second active layer is coated on the first active layer by following techniques in step (1-2-2): (1-2-2-1) first activating solution is added dropwise
After the completion, pH adjusting agent is added into activating container, the pH value of feed liquid is adjusted to 11-12, while the temperature of feed liquid being adjusted
To 60-70 DEG C；Concentration is added under the adjusting of pH controller, while into activating container as the second of 4mol/L in (1-2-2-2)
Activating solution and pH adjusting agent, and it is maintained at the pH value of feed liquid between 11-12；When the second activating solution of addition reaches 40-50
When parts by weight, stop that the second activating solution and pH adjusting agent is added；Then in the case where feed liquid keeps 60-70 DEG C of temperature to material
Liquid stirs 25-35 minutes, then obtains activated synthetic fluoromica powder after being dehydrated to feed liquid；Second activating solution
It is CaCl2Solution.
8. the preparation method of nanometer metallic silver cladding synthetic fluoromica powder according to claim 1, feature exist
The second active layer is coated on the first active layer by following techniques in step (1-2-2): (1-2-2-1) first activating solution is added dropwise
After the completion, pH adjusting agent is added into activating container, the pH value of feed liquid is adjusted to 9-10, while the temperature of feed liquid being adjusted to
80-85℃；(1-2-2-2) is added concentration into activating container and lives for the second of 4mol/L under the adjusting of pH controller
Change liquid and pH adjusting agent, and is maintained at the pH value of feed liquid between 9-10；When the second activating solution of addition reaches 50-60 weight
When part, stop that the second activating solution and pH adjusting agent is added；Then feed liquid is stirred in the case where feed liquid keeps 80-85 DEG C of temperature
It mixes 25-35 minutes, then obtains activated synthetic fluoromica powder after being dehydrated to feed liquid；Second activating solution is
AlCl3Solution.
9. the preparation method of nanometer metallic silver cladding synthetic fluoromica powder according to claim 1, feature exist
The second active layer is coated on the first active layer by following techniques in step (1-2-2): (1-2-2-1) first activating solution is added dropwise
After the completion, pH adjusting agent is added into activating container, the pH value of feed liquid is adjusted to 1.3-2.3, while by the temperature tune of feed liquid
Section is to 75-85 DEG C；(1-2-2-2) is under the adjusting of pH controller, while be added into activating container that concentration is 4mol/L the
Two activating solutions and pH adjusting agent, and it is maintained at the pH value of feed liquid between 1.3-2.3；When the second activating solution of addition reaches
When 70-80 parts by weight, stop that the second activating solution and pH adjusting agent is added；Then the case where feed liquid keeps 75-85 DEG C of temperature
Under to feed liquid stir 25-35 minute, then to feed liquid be dehydrated after obtain activated synthetic fluoromica powder；Described second
Activating solution is ZrCl4Solution.
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