CN109440179A - A kind of metal tantalum matrix of roughing in surface and preparation method thereof - Google Patents
A kind of metal tantalum matrix of roughing in surface and preparation method thereof Download PDFInfo
- Publication number
- CN109440179A CN109440179A CN201910006207.2A CN201910006207A CN109440179A CN 109440179 A CN109440179 A CN 109440179A CN 201910006207 A CN201910006207 A CN 201910006207A CN 109440179 A CN109440179 A CN 109440179A
- Authority
- CN
- China
- Prior art keywords
- tantalum
- matrix
- spot corrosion
- preparation
- anodization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/08—Etching of refractory metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/14—Etching locally
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention belongs to electrochemical corrosion technical fields, the present invention provides a kind of preparation methods of the metal tantalum matrix of roughing in surface, the following steps are included: using inert material as cathode, metal tantalum matrix is anode, carries out anodization spot corrosion processing to metal tantalum matrix using the ethanol solution of etamon chloride as electrolyte；Obtain the metal tantalum matrix of roughing in surface；The distance between the cathode and anode are 0.5~3.0cm, and the voltage of the anodization spot corrosion processing is 8~20V, and the time of anodization spot corrosion processing is 5~40min.The present invention is handled using Anodicization, and in the organic system containing chloride ion, chloride ion penetrates tantalum surface passivating film under the action of electric field and corrodes anode metal tantalum, forms a large amount of intensive point corrosion pits in metal tantalum matrix surface.The roughness for improving tantalum primary surface also improves the specific surface area of tantalum matrix.
Description
Technical field
The present invention relates to electrochemical corrosion technical field, in particular to the metal tantalum matrix of a kind of roughing in surface and its preparation
Method.
Background technique
Tantalum is a kind of refractory metal that corrosion resistance is strong, is always occurred in the form of compound in nature.Tantalum and tantalum
Alloy have high-melting-point, good electrical and thermal conductivity, higher chemical stability, excellent elevated temperature strength, good processability,
Solderability and low moulding crisp transition temperature, excellent dynamic mechanical and aoxidized rear surface form fine and close, stable, Gao Jie electricity
The features such as unformed oxidation film of constant and be widely used in electronics, chemical industry, aerospace, military weapon, health care etc.
Field.Metal tantalum is mainly used in electronics industry, in tantalum in use, being mainly used to make capacitor, including various tantalum capacitors
And supercapacitor, capacitor is because its capacity is big, high reliablity, the service life is long, resistance to pressure is good, function-stable, in communication, computer
Integrated circuit, Auto Electronic Controlled System, digital electrical apparatus etc. have obtained extremely wide application.
However the oxidation film of the smooth densification of tantalum surface has seriously affected the active material of tantalum surface preparation and the knot of tantalum matrix
It closes, in order to solve this problem, Many researchers are attempted to change the surface state of tantalum matrix, tantalum piece is roughened,
Surface film oxide is removed simultaneously.Chinese patent CN101728084A, which is disclosed, polishes to smooth tantalum foil with fine sandpaper, on surface
The consistent uniform scratch in direction is formed, while also eliminating oxidation film, then using thermal decomposition method in roughened tantalum surface
Ruthenic oxide thin-film material is prepared, adhesive force is improved, meanwhile, rough surface increases surface area, electrode material
Capacitance is also improved.In addition, researcher also changing to tantalum surface state caused by the chemical attack in some systems
Change is studied.Chinese patent CN101667492A, which is disclosed, immerses a certain amount of sulfuric acid, nitric acid or hydrofluoric acid etc. for tantalum foil
30min progress chemical attack is boiled in heating in inorganic acid solution, is made its surface roughening and is removed oxidation film layer；Chinese patent
The patent of CN106356200A disclose by tantalum outer casing inner wall be placed in 80 DEG C mass concentration be 35~40% sodium hydroxide it is molten
It is taken out after 20min in liquid, discovery improves the roughness of its inner wall on the basis of not influencing tantalum outer cover quality, while also increasing
The specific surface area of inner wall；In " corrosion behavior of tantalum and surface ion nitriding layer in lye " (Zhang Deyuan etc., China YouSe gold
Belong to journal, 2001,11 (z2)) corrode examination before and after 96h in a text in 50 DEG C be sufficiently stirred of 6.5% sodium hydroxide to tantalum
Sample surface is studied, and disclosing tantalum specimen surface after sodium hydroxide solution corrodes is homogeneous corrosion.In summary, tantalum is through sand
The homogeneous corrosion of paper polishing or acid, aqueous slkali can a degree of increase surface roughness and specific surface area.But existing skill
There are not through control electrochemistry point etching technique the related technology reports for increasing tantalum piece roughness and specific surface area in art also.
Summary of the invention
In view of this, it is an object of that present invention to provide metal tantalum matrix of a kind of roughing in surface and preparation method thereof, this hair
It is bright to have obtained the metal tantalum of roughing in surface by controlling electrochemistry point etching technique.
The present invention provides a kind of preparation methods of the metal tantalum matrix of roughing in surface, comprising the following steps:
Using inert material as cathode, metal tantalum matrix anode, the ethanol solution of etamon chloride is electrolyte to metal
Tantalum matrix carries out anodization spot corrosion processing, obtains the metal tantalum matrix of roughing in surface；
The distance between the cathode and anode are 0.5~3.0cm, the voltage of anodization spot corrosion processing is 8~
20V, the time of anodization spot corrosion processing are 5~40min.
Preferably, the distance between the cathode and anode are 1.5~2.5cm.
Preferably, the voltage of anodization spot corrosion processing is 12~16V, the time of anodization spot corrosion processing is 5~
40min。
Preferably, the concentration of etamon chloride is 0.05~0.5mol/ in the ethanol solution of the etamon chloride
L。
Preferably, the metal tantalum matrix is handled before further including before carrying out anodization spot corrosion processing, the pre-treatment packet
It includes and metal tantalum matrix is successively subjected to organic solvent washing, alkali cleaning and washing.
Preferably, the detergent of the organic solvent washing is acetone, ethyl alcohol, benzene, toluene or carbon tetrachloride.
Preferably, the lye of the alkali cleaning is NaOH, Na3PO4、Na2SiO4And Na2CO3Mixed aqueous solution.
Preferably, the concentration of NaOH is 1~10g/L, Na in mixed aqueous solution3PO4Concentration be 20~100g/L,
Na2SiO4Concentration be 5~50g/L, Na2CO3Concentration be 5~30g/L.
Preferably, the temperature of the alkali cleaning is 60~85 DEG C, and the time of alkali cleaning is 5~15min.
The present invention also provides the metal tantalum matrix for the roughing in surface that above-mentioned preparation method is prepared, the roughing in surface
The surface pitting region area of tantalum metallic matrix account for the 50~98% of entire metal surface area, the point corrosion pit in the spot corrosion region
Diameter is 5~25um.
Advantageous effects: the present invention provides a kind of preparation method of the metal tantalum matrix of roughing in surface, including it is following
Step: using inert material as cathode, metal tantalum matrix is anode, and the ethanol solution of etamon chloride is electrolyte to metal tantalum
Matrix carries out anodization spot corrosion processing；Obtain the metal tantalum matrix of roughing in surface；The distance between the cathode and anode are 0.5
~3.0cm, the voltage of the anodization spot corrosion processing are 8~20V, and the time of anodization spot corrosion processing is 5~40min.This hair
Bright to be handled using Anodicization, in the organic system containing chloride ion, chloride ion penetrates anode under the action of electric field
Tantalum piece surface passivated membrane simultaneously corrodes metal tantalum, forms a large amount of intensive point corrosion pits in metal tantalum matrix surface.By specific embodiment
Experimental data it is found that the ratio that the present invention treated tantalum metal watch matrix millet cake erosion region area accounts for entire metal surface area can
Up to 50~98%, point corrosion pit diameter is 5~25 μm, and average point corrosion pit diameter is 20.8 μm, and tantalum matrix surface greatly improved
Roughness also improves the specific surface area of tantalum piece.
Detailed description of the invention
Fig. 1 is the schematic diagram of anodization Pitting Mechanism of the present invention；
Fig. 2 is anode tantalum piece surface topography map before the polarization spot corrosion of 1 middle-jiao yang, function of the spleen and stomach of embodiment is handled；
Fig. 3 is anode tantalum piece surface topography map after the polarization spot corrosion processing of 1 middle-jiao yang, function of the spleen and stomach of embodiment；
Fig. 4 is anode tantalum piece surface topography magnified partial view after the polarization spot corrosion processing of 1 middle-jiao yang, function of the spleen and stomach of embodiment；
Fig. 5 is tantalum piece surface topography map after the polarization spot corrosion processing of 2 middle-jiao yang, function of the spleen and stomach of embodiment；
Fig. 6 is tantalum piece surface topography map after the polarization spot corrosion processing of 3 middle-jiao yang, function of the spleen and stomach of embodiment；
Fig. 7 is tantalum piece surface topography map after the polarization spot corrosion processing of 4 middle-jiao yang, function of the spleen and stomach of embodiment；
Fig. 8 is tantalum piece surface topography map after the polarization spot corrosion processing of 5 middle-jiao yang, function of the spleen and stomach of embodiment；
Fig. 9 is tantalum piece surface topography map after the polarization spot corrosion processing of 6 middle-jiao yang, function of the spleen and stomach of embodiment.
Specific embodiment
The present invention provides a kind of preparation methods of the metal tantalum matrix of roughing in surface, comprising the following steps:
Using inert material as cathode, metal tantalum matrix is anode, and the ethanol solution of etamon chloride is electrolyte to gold
Belong to tantalum matrix and carry out anodization spot corrosion processing, obtains the metal tantalum matrix of roughing in surface；
The distance between the cathode and anode are 0.5~3.0cm, the voltage of anodization spot corrosion processing is 8~
20V, the time of anodization spot corrosion processing are 5~40min.
For the present invention using inert material as cathode, metal tantalum matrix is anode, and the ethanol solution of etamon chloride is electrolysis
Liquid carries out anodization spot corrosion processing to metal tantalum, obtains the metal tantalum matrix of roughing in surface.
The present invention is not particularly limited the source of metal tantalum matrix, selects commercial goods well known to those skilled in the art
?.It is in the present invention preferably the metal tantalum matrix that purity is greater than 98%.In the present invention, the inert material is preferably gold
Belong to tantalum, titanium or graphite.
The distance between cathode and anode of the present invention be 0.5~3.0cm, preferably 1.5~2.5cm, more preferably
2.0cm；The voltage of anodization spot corrosion processing of the present invention is 8~20V, preferably 10~18V, more preferably 12~16V；This
The time for inventing the anodization spot corrosion processing is 5~40min, preferably 15~35min, more preferably 25~30min.
In the present invention, in the ethanol solution of the etamon chloride concentration of etamon chloride be preferably 0.05~
0.5mol/L, more preferably 0.1~0.15mol/L.
In the present invention, chloride ion penetrates the passivating film of tantalum base metal surface under electric field action and corrodes metal tantalum,
When anode potential is more than a critical potential Eb(disruptive potential), current density increase, and cathode surface generates a large amount of bubble (H2), sun
Pole surface does not have gas evolution, and aggressivity chloride ion penetrates surface passivated membrane under the action of electric field, forms small etch pit, becomes a little
Lose core；Under the action of voltage, current density continues to increase, and point borrosion hole interior metal dissolves, and metal ion is continuous in hole
Increase, the outer anion of borrosion hole is migrated into hole under the action of electric field, is enriched with, and chlorine ion concentration increases in hole, so that in borrosion hole
Metal is in active dissolution state, and spot corrosion growth rate increases, and point borrosion hole is grown up, to keep anode metal tantalum matrix surface thick
Change.
In the present invention, the reaction that cathode and anode occur during the spot corrosion is as follows:
Anode: Ta+mCl-+nC2H5O-=Ta (OC2H5)nClm+5e-
Cathode: Ta (OC2H5)nClm+5e-+mC2H5OH+5H+=Ta (OC2H5)5+mCl-+5/2H2
Overall reaction: Ta+5C2H5OH=Ta (OC2H5)5+5/2H2
The schematic diagram of its anodization Pitting Mechanism is as shown in Figure 1, by above-mentioned reactional equation and Fig. 1 it is found that tantalum is in anode quilt
Oxidation forms intermediate product, is then transmitted to cathode, is replaced under cathode potential by ethoxy anion and generates ethanol tantalum, simultaneously
Hydrogen is released, the Cl sloughed-With the quaternary ammonium root cation C in electrolyte8H20N+Season is combined by salt C8H20NCl continues to undertake
The function of ionic conduction.
In the present invention, the metal tantalum matrix is handled before further including before carrying out anodization spot corrosion processing, is located before described
Reason includes that metal tantalum matrix is successively carried out organic solvent washing, alkali cleaning and washing.
In the present invention, the detergent of the organic solvent washing is preferably acetone, ethyl alcohol, benzene, toluene or carbon tetrachloride,
More preferably acetone.The present invention is not particularly limited the method for organic solvent washing, selects well known to those skilled in the art
Deoiling method.Preferably by metal tantalum matrix, ultrasonic vibration washs the present invention in organic solvent.The present invention shakes excusing from death
Velocity and time be not particularly limited, select velocity and time well known to those skilled in the art.
In the present invention, the lye of the alkali cleaning is preferably NaOH, Na3PO4、Na2SiO4And Na2CO3Mixed aqueous solution.
In the present invention, the concentration of NaOH is preferably 1~10g/L in the mixed aqueous solution, more preferably 3~5g/L；The Na3PO4
Concentration be preferably 20~100g/L, more preferably 40~80g/L, most preferably 50~60g/L；The Na2SiO4Concentration it is excellent
It is selected as 5~50g/L, more preferably 10~40g/L, most preferably 20~30g/L；The Na2CO3Concentration be preferably 5~30g/
L, more preferably 10~25g/L, most preferably 15~20g/L.
In the present invention, the temperature of the alkali cleaning is preferably 60~85 DEG C, and more preferably 65~80 DEG C, most preferably 75~
80℃；The time of the alkali cleaning is preferably 5~15min, more preferably 10~12min.Specific side of the present invention to alkali liquid washing
Method is not particularly limited, and selects washing methods well known to those skilled in the art.The present invention preferably washes organic solvent
Metal tantalum matrix after washing immerses in lye impregnates the time at said temperatures.
It in the present invention, further include washing after the alkali cleaning.The present invention is not particularly limited the method for washing, selects this
Method for washing known to the technical staff of field.In the present invention, it is preferred to for ultrasound washing.Side of the present invention to ultrasound washing
Method is not particularly limited, and selects ultrasonic method for washing well known to those skilled in the art.
The present invention passes through organic solvent washing, the oil of alkali cleaning and washing removal metal tantalum matrix surface.
The present invention also provides the metal tantalum matrix for the roughing in surface that above-mentioned preparation method is prepared, the roughing in surface
Metal tantalum matrix surface spot corrosion region area account for the 50~98% of entire metal surface area, point corrosion pit diameter is 5~25um.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
1) pretreatment of tantalum matrix: by tantalum piece, ultrasonic vibration 10min carries out electrochemical deoiling in acetone first；Then 80
DEG C heat alkali liquid in impregnate 10min and carry out alkali liquor oil removing, wherein NaOH, Na in lye3PO4、Na2SiO4And Na2CO3Quality it is dense
Degree is respectively 5g/L, 50g/L, 20g/L and 15g/L, and solvent is water；Then it is cleaned by ultrasonic completely with deionized water, is finally immersed in
It is spare in dehydrated alcohol.
2) 1.657g etamon chloride is weighed, a certain amount of absolute ethyl alcohol and stirring dissolution is added and is configured to the dense of 100ml
Spend the etamon chloride solution of 0.1mol/L.
3) under normal temperature and pressure, using tantalum as anode, graphite is cathode, and the distance of yin-yang interpolar is 2.0cm, is configured with step 2)
0.1mol/L etamon chloride solution make electrolyte, adjusting voltage is that 14V carries out anodization spot corrosion processing to tantalum piece
30min。
4) by anodization spot corrosion, treated that anode tantalum piece spends ionized water cleans up.
Fig. 2 and Fig. 3 is respectively 1 middle-jiao yang, function of the spleen and stomach of embodiment polarization spot corrosion anode tantalum piece surface topography before and after the processing, compared with Fig. 2,
It can be seen that the most surfaces of tantalum piece are all dispersed with point corrosion pit in Fig. 3, and it is for statistical analysis to point corrosion pit, it can be found that tantalum is golden
Metal surface spot corrosion region area accounts for the 95% of entire metal surface area, and point corrosion pit diameter is 5~25 μm.
Fig. 4 is anode tantalum piece surface topography magnified partial view after the polarization spot corrosion processing of 1 middle-jiao yang, function of the spleen and stomach of embodiment.It can be seen by Fig. 4
Anodicization treated tantalum metal surface is dispersed with nearly hemispheric point corrosion pit out, and part point corrosion pit is connected with each other shape
The etch pit of Cheng Geng great.Compared with Fig. 2, which handles the roughness and specific surface area for being added significantly to tantalum surface.
Embodiment 2
1) pretreatment of tantalum piece: by tantalum piece, ultrasonic vibration 10min carries out electrochemical deoiling in acetone first；Then at 85 DEG C
Heat alkali liquid in impregnate 15min and carry out alkali liquor oil removing, wherein NaOH, Na in lye3PO4、Na2SiO4And Na2CO3Mass concentration
Respectively 10g/L, 100g/L, 50g/L and 30g/L, solvent are water；Then it is cleaned by ultrasonic completely with deionized water, is finally immersed in
It is spare in dehydrated alcohol.
2) 1.657g etamon chloride is weighed, a certain amount of absolute ethyl alcohol and stirring dissolution is added and is configured to the dense of 100ml
Degree is the etamon chloride solution of 0.1mol/L；
3) at normal temperature under normal pressure, using the tantalum piece cleaned up in step (1) as anode, graphite is cathode, yin-yang interpolar
Distance be 2.0cm, the etamon chloride solution of the 0.1mol/L configured with step (2) makees electrolyte, adjusts DC power supply
Voltage is 20V, carries out anodization spot corrosion to tantalum piece and handles 40min；
4) by anodization spot corrosion, treated that anode tantalum piece spends ionized water cleans up.
Fig. 5 is anode tantalum piece surface topography after the polarization spot corrosion processing of 2 middle-jiao yang, function of the spleen and stomach of embodiment, it can be found that tantalum surface base after spot corrosion
This is corroded completely, and point corrosion pit profile can not be identified, and spot corrosion region area accounts for the 98% of entire metal surface area.The embodiment
Spot corrosion processing is excessively violent, and tantalum matrix surface exists compared with multiple punching.
Embodiment 3
1) pretreatment of tantalum piece: by tantalum piece, ultrasonic vibration 10min carries out electrochemical deoiling in acetone first；Then at 60 DEG C
Heat alkali liquid in impregnate 5min and carry out alkali liquor oil removing, wherein NaOH, Na in lye3PO4、Na2SiO4And Na2CO3Mass concentration
The respectively mixed aqueous solution of 1g/L, 20g/L, 5g/L and 5g/L；Then it is cleaned by ultrasonic completely with deionized water, is finally immersed in nothing
It is spare in water-ethanol；
2) 1.657g etamon chloride is weighed, a certain amount of absolute ethyl alcohol and stirring dissolution is added and is configured to the dense of 100ml
Degree is the etamon chloride solution of 0.1mol/L；
3) at normal temperatures and pressures, using the tantalum piece cleaned up in step 1) as anode, graphite is cathode, yin-yang interpolar away from
From for 3.0cm, the etamon chloride solution of the 0.1mol/L configured with step 2) makees electrolyte, adjusts direct current power source voltage and is
12V carries out anodization spot corrosion to tantalum piece and handles 5min；
4) by anodization spot corrosion, treated that anode tantalum piece spends ionized water cleans up.
Fig. 6 is anode tantalum piece surface topography map after the polarization spot corrosion processing of 3 middle-jiao yang, function of the spleen and stomach of embodiment, it can be found that 3 middle-jiao yang, function of the spleen and stomach of embodiment
After polarization spot corrosion processing tantalum surface point fragmentary cloth some point corrosion pits, tantalum metal surface spot corrosion region area account for entire metal surface
Long-pending 18%, point corrosion pit diameter are 3~12 μm, and average point corrosion pit diameter is 6.2 μm.
Embodiment 4
1) pretreatment of tantalum piece: by tantalum piece, ultrasonic vibration 10min carries out electrochemical deoiling in acetone first；Then at 80 DEG C
Heat alkali liquid in impregnate 10min and carry out alkali liquor oil removing, wherein NaOH, Na in lye3PO4、Na2SiO4And Na2CO3Mass concentration
The respectively mixed aqueous solution of 5g/L, 50g/L, 20g/L and 15g/L；Then it is cleaned by ultrasonic completely with deionized water, is finally immersed in
It is spare in dehydrated alcohol；
2) 0.829g etamon chloride is weighed, a certain amount of absolute ethyl alcohol and stirring dissolution is added and is configured to the dense of 100ml
Degree is the etamon chloride solution of 0.05mol/L；
3) at normal temperature under normal pressure, using the tantalum piece cleaned up in step (1) as anode, graphite is cathode yin-yang interpolar
Distance is 0.5cm, and the etamon chloride solution of the 0.05mol/L configured with step 2) makees electrolyte, adjusts DC power supply electricity
Pressure is 8V, carries out anodization spot corrosion to tantalum piece and handles 5min；
4) anodization spot corrosion treated tantalum piece is cleaned up with deionized water.
Fig. 7 is tantalum piece surface topography map after the polarization spot corrosion processing of 4 middle-jiao yang, function of the spleen and stomach of embodiment, it can be found that tantalum metal in embodiment 4
The point corrosion pit that seldom diameter is 1~5.5 μm, these point corrosion pit area surfaces are only distributed by Anodicization processing rear surface
Product only accounts for the 3% of entire metal surface area.
Embodiment 5
1) pretreatment of tantalum matrix: by tantalum piece, ultrasonic vibration 10min carries out electrochemical deoiling in acetone first；Then 80
DEG C heat alkali liquid in impregnate 10min and carry out alkali liquor oil removing, wherein NaOH, Na in lye3PO4、Na2SiO4And Na2CO3Quality it is dense
Degree is respectively the mixed aqueous solution of 5g/L, 50g/L, 20g/L and 15g/L；Then it is cleaned by ultrasonic completely with deionized water, is finally soaked
Enter spare in dehydrated alcohol；
2) 1.657g etamon chloride is weighed, a certain amount of absolute ethyl alcohol and stirring dissolution is added and is configured to the dense of 100ml
Degree is the etamon chloride solution of 0.1mol/L；
3) at normal temperature under normal pressure, using the tantalum piece cleaned up in step (1) as anode, graphite is cathode yin-yang interpolar
Distance is 2.0cm, and the etamon chloride solution of the 0.1mol/L configured with step 2) makees electrolyte, adjusts direct current power source voltage
For 16V, anodization spot corrosion is carried out to tantalum piece and handles 15min；
4) anodization spot corrosion treated tantalum piece is cleaned up with deionized water.
Fig. 8 is tantalum piece surface topography map after the polarization spot corrosion processing of 5 middle-jiao yang, function of the spleen and stomach of embodiment, it can be found that tantalum metal in embodiment 5
The point corrosion pit that more diameter is 3~23 μm, these point corrosion pit region areas are distributed by Anodicization processing rear surface
Account for the 79% of entire metal surface area.
Embodiment 6
1) pretreatment of tantalum matrix: by tantalum piece, ultrasonic vibration 10min carries out electrochemical deoiling in acetone first；Then 80
DEG C heat alkali liquid in impregnate 10min and carry out alkali liquor oil removing, wherein NaOH, Na in lye3PO4、Na2SiO4And Na2CO3Quality it is dense
Degree is respectively the mixed aqueous solution of 5g/L, 50g/L, 20g/L and 15g/L；Then it is cleaned by ultrasonic completely with deionized water, is finally soaked
Enter spare in dehydrated alcohol；
2) 1.657g etamon chloride is weighed, a certain amount of absolute ethyl alcohol and stirring dissolution is added and is configured to the dense of 100ml
Degree is the etamon chloride solution of 0.1mol/L；
3) at normal temperature under normal pressure, using the tantalum piece cleaned up in step (1) as anode, graphite is cathode yin-yang interpolar
Distance is 2.0cm, and the etamon chloride solution of the 0.1mol/L configured with step 2) makees electrolyte, adjusts direct current power source voltage
For 12V, anodization spot corrosion is carried out to tantalum piece and handles 20min；
4) anodization spot corrosion treated tantalum piece is cleaned up with deionized water.
Fig. 9 is tantalum piece surface topography map after the polarization spot corrosion processing of 6 middle-jiao yang, function of the spleen and stomach of embodiment, it can be found that tantalum metal in embodiment 6
It is dispersed with the point corrosion pit that diameter is 3~19 μm by Anodicization processing rear surface, these point corrosion pit region areas account for whole
The 33% of a metal surface area.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the metal tantalum matrix of roughing in surface, comprising the following steps:
Using inert material as cathode, metal tantalum matrix is anode, and the ethanol solution of etamon chloride is electrolyte to metal tantalum
Matrix carries out anodization spot corrosion processing, obtains the metal tantalum matrix of roughing in surface；
The distance between the cathode and anode are 0.5~3.0cm, and the voltage of the anodization spot corrosion processing is 8~20V, sun
The time of polarization spot corrosion processing is 5~40min.
2. preparation method according to claim 1, which is characterized in that the distance between the cathode and anode be 1.5~
2.5cm。
3. preparation method according to claim 1, which is characterized in that the voltage of anodization spot corrosion processing is 12~
16V, the time of anodization spot corrosion processing are 15~35min.
4. preparation method according to claim 1, which is characterized in that tetrem in the ethanol solution of the etamon chloride
The concentration of ammonium chloride is 0.05~0.5mol/L.
5. preparation method according to claim 1, which is characterized in that the metal tantalum matrix is carrying out at anodization spot corrosion
It further include pre-treatment before reason, the pre-treatment includes that metal tantalum matrix is successively carried out organic solvent washing, alkali cleaning and washing.
6. preparation method according to claim 5, which is characterized in that the detergent of the organic solvent washing be acetone,
Ethyl alcohol, benzene, toluene or carbon tetrachloride.
7. preparation method according to claim 5, which is characterized in that the lye of the alkali cleaning is NaOH, Na3PO4、
Na2SiO4And Na2CO3Mixed aqueous solution.
8. preparation method according to claim 7, which is characterized in that in the mixed aqueous solution concentration of NaOH be 1~
10g/L, Na3PO4Concentration be 20~100g/L, Na2SiO4Concentration be 5~50g/L, Na2CO3Concentration be 5~30g/L.
9. according to preparation method described in claim 5~8 any one, which is characterized in that the temperature of the alkali cleaning be 60~
85 DEG C, the time of alkali cleaning is 5~15min.
10. the metal tantalum matrix for the roughing in surface that preparation method described in claim 1~10 any one is prepared, described
The surface pitting region area of the tantalum metallic matrix of roughing in surface accounts for the 50~98% of entire metal surface area, the spot corrosion region
Point corrosion pit diameter be 5~25 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910006207.2A CN109440179A (en) | 2019-01-04 | 2019-01-04 | A kind of metal tantalum matrix of roughing in surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910006207.2A CN109440179A (en) | 2019-01-04 | 2019-01-04 | A kind of metal tantalum matrix of roughing in surface and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109440179A true CN109440179A (en) | 2019-03-08 |
Family
ID=65542418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910006207.2A Pending CN109440179A (en) | 2019-01-04 | 2019-01-04 | A kind of metal tantalum matrix of roughing in surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109440179A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110957138A (en) * | 2019-11-18 | 2020-04-03 | 湖南华冉科技有限公司 | Inner wall treatment method of tantalum capacitor shell |
| CN111238908A (en) * | 2020-04-01 | 2020-06-05 | 中国大唐集团科学技术研究院有限公司华中电力试验研究院 | Preparation method of pitting sample |
| CN113745007A (en) * | 2021-08-24 | 2021-12-03 | 西安交通大学 | Electrochemical corrosion dilatation process of anode foil of tantalum electrolytic capacitor |
| CN114964987A (en) * | 2022-05-27 | 2022-08-30 | 北京航空航天大学 | Metal sample small-size pitting pit prefabricating method based on pitting mechanism |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1521288A (en) * | 2002-12-20 | 2004-08-18 | H.C.ʩ���˹ɷ�����˾ | Process for the production of niobium or tantalum parts by electrochemical etching |
| CN108456917A (en) * | 2018-04-19 | 2018-08-28 | 湖南工业大学 | A kind of preparation method of porous tantalum piece |
-
2019
- 2019-01-04 CN CN201910006207.2A patent/CN109440179A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1521288A (en) * | 2002-12-20 | 2004-08-18 | H.C.ʩ���˹ɷ�����˾ | Process for the production of niobium or tantalum parts by electrochemical etching |
| CN108456917A (en) * | 2018-04-19 | 2018-08-28 | 湖南工业大学 | A kind of preparation method of porous tantalum piece |
Non-Patent Citations (4)
| Title |
|---|
| HAI-PING YANG ET AL: ""Corrosion Study on Tantalum in Anhydrous Ethanol"", 《CHINESE JOURNAL OF CHEMICAL PHYSICS》 * |
| 实用技工技术教材编写组编: "《实用清洗技术》", 31 December 2007, 广东科技出版社 * |
| 张剑波等: "《清洗技术基础教程》", 31 July 2004, 中国环境科学出版社 * |
| 梁治齐: "《实用清洗技术手册》", 31 January 2000, 化学工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110957138A (en) * | 2019-11-18 | 2020-04-03 | 湖南华冉科技有限公司 | Inner wall treatment method of tantalum capacitor shell |
| CN110957138B (en) * | 2019-11-18 | 2024-04-16 | 湖南华冉科技有限公司 | Inner wall treatment method of tantalum capacitor shell |
| CN111238908A (en) * | 2020-04-01 | 2020-06-05 | 中国大唐集团科学技术研究院有限公司华中电力试验研究院 | Preparation method of pitting sample |
| CN113745007A (en) * | 2021-08-24 | 2021-12-03 | 西安交通大学 | Electrochemical corrosion dilatation process of anode foil of tantalum electrolytic capacitor |
| CN114964987A (en) * | 2022-05-27 | 2022-08-30 | 北京航空航天大学 | Metal sample small-size pitting pit prefabricating method based on pitting mechanism |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109440179A (en) | A kind of metal tantalum matrix of roughing in surface and preparation method thereof | |
| CN105088309B (en) | A kind of energy-efficient anode oxidative treatment method of pack alloy | |
| CN101425390B (en) | Medium high voltage anode aluminum foil corrosion method | |
| US3779877A (en) | Electrolytic etching of aluminum foil | |
| US3085950A (en) | Electrolytic etching of aluminum foil | |
| JPH0581677B2 (en) | ||
| CN107604168A (en) | The method of recovering copper, nickel, cobalt from the sludge containing non-ferrous metal | |
| CN108441918A (en) | A kind of aluminum alloy surface treatment process | |
| CA1331578C (en) | Conversion of manganese dioxide to permanganate | |
| CN104975336A (en) | Preparation method of porous silicon used in lithium ion battery anode material | |
| WO2019041797A1 (en) | Etching method for electrode foil for low-contact resistance low-voltage aluminum electrolytic capacitor | |
| CN102634805A (en) | Method for preparing magnesium alloy with super-hydrophobic layer on surface | |
| CN108456917A (en) | A kind of preparation method of porous tantalum piece | |
| CN103409785B (en) | A kind of titanium alloy surface reduces the nano coating preparation method of sea organism attachment | |
| CN105648502B (en) | A kind of Mg alloy surface hydrophobic composite membrane layer and preparation method thereof | |
| CN107937920B (en) | For ocean platform cathodic protection reparation oxide anode material and preparation process | |
| CN106676619A (en) | Method for preparing metal glass nano porous structure | |
| CN103762081A (en) | Manufacturing method for aluminum base ferroelectric thin film | |
| CN108893760A (en) | A kind of production method of lithium ion collector corronil foil | |
| Yang et al. | A new electrolytic method for on-site regeneration of acidic copper (II) chloride etchant in printed circuit board production | |
| CN100442406C (en) | Etching technique of hard foil | |
| KR100489640B1 (en) | Electrolyte solution for anodizing and corrosion-resisting coating method of magnesium alloy using the same | |
| JP4426383B2 (en) | Method for forming oxide film on aluminum or aluminum alloy | |
| RU2007105880A (en) | METHOD FOR PRODUCING SURFACES OF NICKEL OXIDE WITH INCREASED CONDUCTIVITY | |
| CN107227485A (en) | A kind of etching process method of hard state optical aluminum foil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190308 |