CN110453206A - Press from both sides metal layer crystalline flake graphite and its preparation method and application - Google Patents
Press from both sides metal layer crystalline flake graphite and its preparation method and application Download PDFInfo
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- CN110453206A CN110453206A CN201910730207.7A CN201910730207A CN110453206A CN 110453206 A CN110453206 A CN 110453206A CN 201910730207 A CN201910730207 A CN 201910730207A CN 110453206 A CN110453206 A CN 110453206A
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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
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
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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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- 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
The invention discloses a kind of preparation methods for pressing from both sides metal layer crystalline flake graphite, comprising the following steps: and layering crystalline flake graphite is successively sensitized and is activated, so that the surface of crystalline flake graphite and Inter layer adsorption metal Pd, and forming core site is formed on the metal Pd；And using chemical plating method it is described layering crystalline flake graphite surface and interlayer metal cladding to get arrive the folder metal layer crystalline flake graphite.The invention also discloses the folder metal layer crystalline flake graphite prepared by the above method and its applications.Folder metal layer crystalline flake graphite prepared by the present invention can be improved the bond strength of crystalline flake graphite and Copper substrate when being used for Cu-base composites.
Description
Technical field
The present invention relates to technical field of new material preparation, and in particular to a kind of folder metal layer crystalline flake graphite, preparation method
And application.
Background technique
Graphite is the allotrope of carbon, and color is grey black, there is soapy feeling, and hexagonal crystal system lamellar crystal structure is single
Binding force is stronger between atom in layer, and pi bond binding force between layers is lower, is easily broken off generation Relative sliding；It is light (close
Degree is 2.2-2.3g/cm3), fusing point is up to 3527 DEG C, and heat resisting temperature is 454 DEG C in air, does not occur with metal or rubber
Chemical reaction.At normal temperature, after the pi bond of graphite between layers is broken, splitting surface is formed, the gas that should be faced in air has
Certain adsorption capacity, this splitting surface are the support of graphite lubrication performance, temperature of the greasy property of splitting surface at up to 638 DEG C
Still maintain good under degree.
Graphite has many advantages, such as excellent lubricity, high-termal conductivity, damping capacity and high-temperature stability, and is considered as copper-based
The most common solid lubricant in friction material.Addition graphite can reduce the metal-between friction pair in copper base friction material
Metal contacts and is formed between friction pair the transfer layer of rich graphite directly to improve the job stability of friction material, anti-wiping
Wound, bite-resistant, anti stick and wearability.But the density difference of graphite and copper is more greatly different, with conventional method by two kinds of powder
Carry out uniformly mixed, graphite and copper are immiscible in solid phase, liquid phase, and this mutually non-wetted feature will will lead to sintering
Graphite and copper interface bond strength are poor in composite material, and the mechanical property and friction for reducing graphite-copper based composites are ground
Damage performance.It is reported according to pertinent literature, the current most common method solved these problems is graphite surface metallization, such as in graphite
Surface applies Cu layers, the coats of metal such as Ni layers.However, the often only combination to size lesser graphite and copper is improved of this method
Power is effective, such as ball-type graphite, graphite powder or graphite fibre.And after graphite size is greater than certain value, this method is not
Effective as metallizing small size graphite surface it can improve interface bond strength.Therefore need to the structure of crystalline flake graphite into
Row design, improves its bond strength with Copper substrate.
Summary of the invention
The purpose of the present invention is to provide a kind of folder metal layer crystalline flake graphites, to improve the combination of crystalline flake graphite and Copper substrate
Intensity.
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation methods for pressing from both sides metal layer crystalline flake graphite, including
Following steps:
Layering crystalline flake graphite is successively sensitized and is activated, so that the surface of crystalline flake graphite and Inter layer adsorption metal
Pd, and forming core site is formed on the metal Pd；And
Using the method for chemical plating on the surface of the layering crystalline flake graphite and interlayer metal cladding to get golden to the folder
Belong to layer crystalline flake graphite.
Further, the layering crystalline flake graphite is prepared through following steps:
Natural flake graphite is uniformly mixed with mixed acid, oxidant, is stirred to react 1~2h at 30~40 DEG C；Reaction
After, it will be dry after natural flake graphite washing, filtering, 1~2min is kept the temperature at 300~400 DEG C to get institute is arrived
State layering crystalline flake graphite.
Further, the size of the natural flake graphite is 100~300 μm.
Further, the mixed acid is mixed by perchloric acid and phosphoric acid, the volume ratio of the two be 3~6:0.5~
1.5；The oxidant is potassium permanganate.
Further, the content ratio of the mixed acid, potassium permanganate and natural flake graphite is (3.5~7.5ml): (0.2
~0.6g): (3~5g).
In the present invention, activation is to allow flake graphite's surface to adsorb one layer of metal Pd, and Pd is a kind of very strong catalysis work
Property metal, during chemical plating metal coating, the coat of metal as center forming core and will be grown up using Pd, thus make chemistry it is plated
Journey is smooth；The absorption of metal Pd is will by Sn (OH) the Cl colloid of the carbon fiber surface absorption after sensitized treatment
Pd2+Reduction gained.Further, the formula of sensitized solution are as follows: SnCl2, 20~30g/L；The HCl of 37wt%, 30~50mL/L；
Remaining as deionized water；The formula of activated solution are as follows: PdCl2, 0.1~0.3g/L；The HCl of 37wt%, 3~6mL/L；Remaining as
Deionized water.
Further, the material of the metal layer is a kind of in Cu, Ni, Co, Ag.
Further, the formula of Electroless Cu Plating solution are as follows: cupric sulfate pentahydrate, 14~18g/L；Disodium ethylene diamine tetraacetate,
20~30g/L；Sodium potassium tartrate tetrahydrate, 15~25g/L；Formalin, 12~16mL/L；Remaining is deionized water；PH adjusting agent is
The NaOH solution of 50wt.%, adjusting solution ph is 13.5~14；Electroless Cu Plating temperature is 30~45 DEG C；
Electroless Ni plating solution formula are as follows: nickel sulfate hexahydrate, 25~35g/L；Sodium hypophosphite, 18~22g/L；Citric acid
Sodium, 20~30g/L；Ammonium chloride, 18~22g/L；Remaining is deionized water；PH adjusting agent is ammonium hydroxide, adjust solution ph be 8~
9；Electroless Plating Ni temperature is 65~80 DEG C；
Electroless cobalt plating solution formula are as follows: cobaltous sulfate, 15~25g/L；Sodium hypophosphite, 20~40g/L；Sodium citrate, 20
~35g/L；Remaining is deionized water；PH adjusting agent is ammonium hydroxide, and adjusting solution ph is 8~13；Electroless cobalt plating temperature be 75~
85℃；
Chemical plating Ag solution formula are as follows: silver nitrate, 12~18g/L；Potassium hydroxide, 10~15g/L；Glucose, 15~
25g/L；Ethyl alcohol, 40~60mL/L；Sodium potassium tartrate tetrahydrate, 15~25g/L；Remaining is deionized water；PH adjusting agent is ammonium hydroxide, is adjusted
Solution ph is 13.5~14；Chemical plating Ag temperature is 30~40 DEG C.
It further, further include that the folder metal layer crystalline flake graphite that will be obtained after chemical plating cleans in alcoholic solution, is dry
Step.
Another aspect of the present invention provides the folder metal layer crystalline flake graphite being prepared by the method.
The present invention also provides the folder metal layer crystalline flake graphites to prepare the application in Cu-base composites.
Beneficial effects of the present invention:
Preparation method of the invention can apply metal layer in flake graphite's surface and crystalline flake graphite between layers, from
And solve the problems, such as that traditional crystalline flake graphite only applies the coat of metal on surface and coating is caused to be easy to separate with graphite；
Present invention process is simple simultaneously, and preparation cost expense is low, is suitable for commercial scale and uses.
Detailed description of the invention
Fig. 1 is the SEM shape appearance figure of raw material crystalline flake graphite；
Fig. 2 is the SEM shape appearance figure of layering crystalline flake graphite prepared by embodiment 1；
Fig. 3 is the SEM shape appearance figure of folder metal layer crystalline flake graphite prepared by embodiment 1；
Fig. 4 is the EDS figure of folder metal copper layer flake graphite's surface prepared by embodiment 1.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples, so that those skilled in the art can be with
It more fully understands the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
Present embodiment discloses a kind of preparation methods for pressing from both sides metallic copper crystalline flake graphite, comprising the following steps:
Step 1: the preparation of layering crystalline flake graphite
(1) under room temperature environment, by 5ml perchloric acid and 1ml phosphoric acid be put into glass beaker be uniformly mixed obtain mixed acid,
0.4g potassium permanganate is added, is slowly stirred, is dissolved in it in mixed acid, being eventually adding 4g crystalline flake graphite and being sufficiently stirred makes it
It is uniformly mixed.Glass beaker equipped with perchloric acid, phosphoric acid, potassium permanganate and crystalline flake graphite is placed into the constant temperature that water temperature is 40 DEG C
60min is reacted in water bath, should be stirred continuously during reaction to guarantee that reaction is uniform.After reaction, repeatedly washing, will precipitate
The crystalline flake graphite to get off filters out and the drying at 60 DEG C.Finally obtained crystalline flake graphite is being put into Muffle furnace, by horse
Not furnace rises to 300 DEG C, keeps the temperature 60s.Turn off Muffle furnace power supply, is down to 100 DEG C hereinafter, by crystalline flake graphite from Muffle to in-furnace temperature
It is taken out in furnace furnace, the crystalline flake graphite being layered.Crystalline flake graphite primary morphology is as shown in Figure 1, obtained layering crystalline flake graphite shape
Looks are as shown in Figure 2.
Step 2: the crystalline flake graphite sensitization of layering, activation processing
The crystalline flake graphite handled by the first step is put into sensitized solution and is stirred continuously, is taken out simultaneously after 15min
It is clean to spend Ion Cleaning, room temperature is dried.The proportion of sensitized solution are as follows: SnCl2, 20g/L；The HCl of 37wt%, 40mL/L；It is surplus
Remaining is deionized water.Crystalline flake graphite after sensitization is put into activated solution and is stirred continuously, is taken out after 15min and uses deionization
It cleans up, room temperature is dried；Activated solution proportion are as follows: PdCl2, 0.2g/L；The HCl of 37wt%, 5mL/L；Remaining as deionization
Water.
Step 3: the preparation of folder metallic copper crystalline flake graphite
Using the method for chemical plating, metal copper layer is plated between the flake graphite's surface and graphite linings of layering.Chemical plating
Cu solution formula are as follows: cupric sulfate pentahydrate, 16g/L；Disodium ethylene diamine tetraacetate, 25g/L；Sodium potassium tartrate tetrahydrate, 20g/L；Formaldehyde is molten
Liquid, 13mL/L, remaining is deionized water.Constant water bath box is heated to 35 DEG C, keeps the temperature 10 minutes, is then added 50wt.%'s
NaOH solution adjusts solution ph to 13.5~14, keeps the temperature 30min and is stirred continuously.
Step 4: plating posttreatment
By folder metal layer crystalline flake graphite that third step obtains from taking out and be put into ethanol solution at once ultrasonic in water bath
Wave cleaning, is dried in drying box.
Obtained folder metallic copper crystalline flake graphite pattern is as shown in figure 3, it can be seen from the figure that flake graphite's surface is by metal
Coating is coated.Referring to fig. 4, flake graphite's surface is analyzed by EDS it is found that the coat of metal of flake graphite's surface is copper plating
Layer.
Embodiment 2
Present embodiment discloses a kind of preparation methods for pressing from both sides metallic copper crystalline flake graphite, include the following steps:
Step 1: the preparation of layering crystalline flake graphite
(1) under room temperature environment, 3ml perchloric acid and 1.5ml phosphoric acid is put into glass beaker and mixed
Acid adds 0.5g potassium permanganate, is slowly stirred, is dissolved in it in mixed acid, is eventually adding 3g crystalline flake graphite and is sufficiently stirred
It is uniformly mixed it.Perchloric acid will be housed, phosphoric acid, it is 40 DEG C that the glass beaker of potassium permanganate and crystalline flake graphite, which is placed into water temperature,
60min is reacted in constant water bath box, should be stirred continuously during reaction to guarantee that reaction is uniform.After reaction, repeatedly washing, will
The crystalline flake graphite to precipitate filters out and the drying at 60 DEG C.Finally obtained crystalline flake graphite is being put into Muffle furnace,
Muffle furnace is risen to 300 DEG C, keeps the temperature 60s.Turn off Muffle furnace power supply, to in-furnace temperature be down to 100 DEG C hereinafter, by crystalline flake graphite from
It is taken out in Muffle furnace furnace, the crystalline flake graphite being layered.
Step 2: the crystalline flake graphite sensitization of layering, activation processing
The crystalline flake graphite handled by the first step is put into sensitized solution and is stirred continuously, is taken out simultaneously after 15min
It is clean to spend Ion Cleaning, room temperature is dried.Sensitized solution proportion are as follows: SnCl2, 20g/L；The HCl of 37wt%, 40mL/L；It is remaining
For deionized water.Crystalline flake graphite after sensitization is put into activated solution and is stirred continuously, is taken out after 15min and clear with deionization
Wash clean, room temperature are dried；Activated solution proportion are as follows: PdCl2, 0.2g/L；The HCl of 37wt%, 5mL/L；Remaining as deionized water.
Step 3: the preparation of folder metallic copper crystalline flake graphite
Using the method for chemical plating, metal copper layer is plated between the flake graphite's surface and graphite linings of layering.Chemical plating
Copper solution formula are as follows: cupric sulfate pentahydrate, 18g/L；Disodium ethylene diamine tetraacetate, 22g/L；Sodium potassium tartrate tetrahydrate, 20g/L；Formaldehyde is molten
Liquid, 15mL/L, remaining is deionized water.Constant water bath box is heated to 35 DEG C, keeps the temperature 10 minutes, is then added 50wt.%'s
NaOH solution adjusts solution ph to 13.5~14, keeps the temperature 30min and is stirred continuously.
Step 4: plating posttreatment
By folder metal layer crystalline flake graphite that third step obtains from taking out and be put into ethanol solution at once ultrasonic in water bath
Wave cleaning, is dried in drying box.
Embodiment 3
Present embodiment discloses a kind of preparation methods for pressing from both sides metallic nickel crystalline flake graphite, comprise the following steps that
Step 1: the preparation of layering crystalline flake graphite
(1) under room temperature environment, by 5ml perchloric acid and 1ml phosphoric acid be put into glass beaker be uniformly mixed obtain mixed acid,
0.4g potassium permanganate is added, is slowly stirred, is dissolved in it in mixed acid, being eventually adding 4g crystalline flake graphite and being sufficiently stirred makes it
It is uniformly mixed.Perchloric acid, phosphoric acid will be housed, the glass beaker of potassium permanganate and crystalline flake graphite is placed into the constant temperature that water temperature is 40 DEG C
60min is reacted in water bath, should be stirred continuously during reaction to guarantee that reaction is uniform.After reaction, repeatedly washing, will precipitate
The crystalline flake graphite to get off filters out and the drying at 60 DEG C.Finally obtained crystalline flake graphite is being put into Muffle furnace, by horse
Not furnace rises to 300 DEG C, keeps the temperature 60s.Turn off Muffle furnace power supply, is down to 100 DEG C hereinafter, by crystalline flake graphite from Muffle to in-furnace temperature
It is taken out in furnace furnace, the crystalline flake graphite being layered.
Step 2: the crystalline flake graphite sensitization of layering, activation processing
The crystalline flake graphite handled by the first step is put into sensitized solution and is stirred continuously, is taken out simultaneously after 15min
It is clean to spend Ion Cleaning, room temperature is dried.Sensitized solution proportion are as follows: SnCl2, 20g/L；The HCl of 37wt%, 40mL/L；It is remaining
For deionized water.Crystalline flake graphite after sensitization is put into activated solution and is stirred continuously, is taken out after 15min and clear with deionization
Wash clean, room temperature are dried；Activated solution proportion are as follows: PdCl2, 0.2g/L；The HCl of 37wt%, 5mL/L；Remaining as deionized water.
Step 3: the preparation of folder metallic nickel crystalline flake graphite
Using the method for chemical plating, metal nickel layer is plated between the flake graphite's surface and graphite linings of layering.Chemical plating
Nickel solution formula are as follows: nickel sulfate hexahydrate, 30g/L；Sodium hypophosphite, 20g/L；Sodium citrate, 25g/L；Ammonium chloride, 20g/L；Its
Remaining is deionized water.Constant water bath box is heated to 75 DEG C, keeps the temperature 10 minutes, ammonia spirit adjusting solution ph is then added and arrives
8~9, it keeps the temperature 30min and is stirred continuously.
Step 4: plating posttreatment
By folder metal layer crystalline flake graphite that third step obtains from taking out and be put into ethanol solution at once ultrasonic in water bath
Wave cleaning, is dried in drying box.
Embodiment 4
Present embodiment discloses a kind of preparation methods for pressing from both sides metallic cobalt crystalline flake graphite, comprising the following steps:
Step 1: the preparation of layering crystalline flake graphite
(1) under room temperature environment, by 5ml perchloric acid and 1ml phosphoric acid be put into glass beaker be uniformly mixed obtain mixed acid,
0.4g potassium permanganate is added, is slowly stirred, is dissolved in it in mixed acid, being eventually adding 4g crystalline flake graphite and being sufficiently stirred makes it
It is uniformly mixed.Perchloric acid, phosphoric acid will be housed, the glass beaker of potassium permanganate and crystalline flake graphite is placed into the constant temperature that water temperature is 40 DEG C
60min is reacted in water bath, should be stirred continuously during reaction to guarantee that reaction is uniform.After reaction, repeatedly washing, will precipitate
The crystalline flake graphite to get off filters out and the drying at 60 DEG C.Finally obtained crystalline flake graphite is being put into Muffle furnace, by horse
Not furnace rises to 300 DEG C, keeps the temperature 60s.Turn off Muffle furnace power supply, is down to 100 DEG C hereinafter, by crystalline flake graphite from Muffle to in-furnace temperature
It is taken out in furnace furnace, the crystalline flake graphite being layered.
Step 2: the crystalline flake graphite sensitization of layering, activation processing
The crystalline flake graphite handled by the first step is put into sensitized solution and is stirred continuously, is taken out simultaneously after 15min
It is clean to spend Ion Cleaning, room temperature is dried.Sensitized solution proportion are as follows: SnCl2, 20g/L；The HCl of 37wt%, 40mL/L；It is remaining
For deionized water.Crystalline flake graphite after sensitization is put into activated solution and is stirred continuously, is taken out after 15min and clear with deionization
Wash clean, room temperature are dried；Activated solution proportion are as follows: PdCl2, 0.2g/L；The HCl of 37wt%, 5mL/L；Remaining as deionized water.
Step 3: the preparation of folder metallic cobalt crystalline flake graphite
The method plated using chemical plating, plates layer of metal cobalt between the flake graphite's surface and graphite linings of layering.Chemistry
Nickel plating solution formula are as follows: cobaltous sulfate, 20g/L；Sodium hypophosphite, 30g/L；Sodium citrate, 28g/L；Remaining is deionized water.It will
Constant water bath box is heated to 85 DEG C, keeps the temperature 10 minutes, and ammonia spirit is then added and adjusts solution ph to 8~13, keeps the temperature 30min
And it is stirred continuously.
Step 4: plating posttreatment
By folder metal layer crystalline flake graphite that third step obtains from taking out and be put into ethanol solution at once ultrasonic in water bath
Wave cleaning, is dried in drying box.
Embodiment 5
Present embodiment discloses a kind of preparation methods for pressing from both sides metallic silver crystalline flake graphite, comprise the following steps that
Step 1: the preparation of layering crystalline flake graphite
(1) under room temperature environment, by 5ml perchloric acid and 1ml phosphoric acid be put into glass beaker be uniformly mixed obtain mixed acid,
0.4g potassium permanganate is added, is slowly stirred, is dissolved in it in mixed acid, being eventually adding 4g crystalline flake graphite and being sufficiently stirred makes it
It is uniformly mixed.Perchloric acid, phosphoric acid will be housed, the glass beaker of potassium permanganate and crystalline flake graphite is placed into the constant temperature that water temperature is 40 DEG C
60min is reacted in water bath, should be stirred continuously during reaction to guarantee that reaction is uniform.After reaction, repeatedly washing, will precipitate
The crystalline flake graphite to get off filters out and the drying at 60 DEG C.Finally obtained crystalline flake graphite is being put into Muffle furnace, by horse
Not furnace rises to 300 DEG C, keeps the temperature 60s.Turn off Muffle furnace power supply, is down to 100 DEG C hereinafter, by crystalline flake graphite from Muffle to in-furnace temperature
It is taken out in furnace furnace, the crystalline flake graphite being layered.
Step 2: the crystalline flake graphite sensitization of layering, activation processing
The crystalline flake graphite handled by the first step is put into sensitized solution and is stirred continuously, is taken out simultaneously after 15min
It is clean to spend Ion Cleaning, room temperature is dried.Sensitized solution proportion are as follows: SnCl2, 20g/L；The HCl of 37wt%, 40mL/L；It is remaining
For deionized water.Crystalline flake graphite after sensitization is put into activated solution and is stirred continuously, is taken out after 15min and clear with deionization
Wash clean, room temperature are dried；Activated solution proportion are as follows: PdCl2, 0.2g/L；The HCl of 37wt%, 5mL/L；Remaining as deionized water.
Step 3: the preparation of folder metallic silver crystalline flake graphite
Using the method for chemical plating, metal nickel layer is plated between the flake graphite's surface and graphite linings of layering.Chemical plating
Silver-colored solution formula are as follows: silver nitrate, 15g/L；Potassium hydroxide, 12g/L；Glucose, 20g/L；Ethyl alcohol, 30mL/L；Sodium potassium tartrate tetrahydrate,
20g/L；Remaining is deionized water.Constant water bath box is heated to 30 DEG C, keeps the temperature 10 minutes, it is molten that ammonia spirit adjusting is then added
Liquid pH value keeps the temperature 30min and is stirred continuously to 13.5~14.
Step 4: plating posttreatment
By folder metal layer crystalline flake graphite that third step obtains from taking out and be put into ethanol solution at once ultrasonic in water bath
Wave cleaning, is dried in drying box.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (11)
1. a kind of preparation method for pressing from both sides metal layer crystalline flake graphite, which comprises the following steps:
Layering crystalline flake graphite is successively sensitized and is activated, so that the surface of the layering crystalline flake graphite and Inter layer adsorption
Metal Pd, and forming core site is formed on the metal Pd；And
Using chemical plating method it is described layering crystalline flake graphite surface and interlayer metal cladding to get arrive the folder metal layer
Crystalline flake graphite.
2. the preparation method of folder metal layer crystalline flake graphite as described in claim 1, which is characterized in that the layering crystalline flake graphite
It is to be prepared through following steps:
Natural flake graphite is uniformly mixed with mixed acid, oxidant, is stirred to react 1~2h at 30~40 DEG C；Reaction terminates
Afterwards, will be dry after natural flake graphite washing, filtering, 1~2min is kept the temperature at 300~400 DEG C to get to described point
Layer crystalline flake graphite.
3. the preparation method of folder metal layer crystalline flake graphite as claimed in claim 2, which is characterized in that the natural flake graphite
Size be 100~300 μm.
4. the preparation method of folder metal layer crystalline flake graphite as claimed in claim 2, which is characterized in that the mixed acid is by high chlorine
Acid and phosphoric acid mix, and the volume ratio of the two is 3~6: 0.5~1.5；The oxidant is potassium permanganate.
5. the preparation method of folder metal layer crystalline flake graphite as claimed in claim 4, which is characterized in that the mixed acid, Gao Meng
The content of sour potassium and natural flake graphite ratio is (3.5~7.5ml): (0.2~0.6g): (3~5g).
6. the preparation method of folder metal layer crystalline flake graphite as described in claim 1, which is characterized in that the formula of sensitized solution
Are as follows: SnCl2, 20~30 g/L；The HCl of 37wt%, 30~50 mL/L；Remaining as deionized water；
The formula of activated solution are as follows: PdCl2, 0.1~0.3 g/L；The HCl of 37wt%, 3~6 mL/L；Remaining as deionized water.
7. the preparation method of folder metal layer crystalline flake graphite as described in claim 1, which is characterized in that the metal layer material choosing
From one of Cu, Ni, Co, Ag.
8. the preparation method of folder metal layer crystalline flake graphite as claimed in claim 7, which is characterized in that
The formula of Electroless Cu Plating solution are as follows: cupric sulfate pentahydrate, 14~18 g/L；Disodium ethylene diamine tetraacetate, 20~30 g/L；Wine
Stone acid potassium sodium, 15~25 g/L；Formalin, 12~16 mL/L；Remaining is deionized water；PH adjusting agent is 50wt.%'s
NaOH solution, adjusting solution ph is 13.5~14；Electroless Cu Plating temperature is 30~45 DEG C；
Electroless Ni plating solution formula are as follows: nickel sulfate hexahydrate, 25~35 g/L；Sodium hypophosphite, 18~22 g/L；Sodium citrate,
20~30 g/L；Ammonium chloride, 18~22 g/L；Remaining is deionized water；PH adjusting agent is ammonium hydroxide, adjust solution ph be 8~
9；Electroless Plating Ni temperature is 65~80 DEG C；
Electroless cobalt plating solution formula are as follows: cobaltous sulfate, 15~25 g/L；Sodium hypophosphite, 20~40 g/L；Sodium citrate, 20~
35 g/L；Remaining is deionized water；PH adjusting agent is ammonium hydroxide, and adjusting solution ph is 8~13；Electroless cobalt plating temperature be 75~
85℃；
Chemical plating Ag solution formula are as follows: silver nitrate, 12~18 g/L；Potassium hydroxide, 10~15 g/L；Glucose, 15~25g/
L；Ethyl alcohol, 40~60 mL/L；Sodium potassium tartrate tetrahydrate, 15~25 g/L；Remaining is deionized water；PH adjusting agent is ammonium hydroxide, is adjusted molten
Liquid pH value is 13.5~14；Chemical plating Ag temperature is 30~40 DEG C.
9. the preparation method of folder metal layer crystalline flake graphite as described in claim 1, which is characterized in that further including will be after chemical plating
The step that obtained folder metal layer crystalline flake graphite is cleaned in alcoholic solution, dried.
10. the folder metal layer crystalline flake graphite being prepared such as the described in any item methods of claim 1 ~ 9.
11. folder metal layer crystalline flake graphite described in any one of claim 10 is preparing the application in Cu-base composites.
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