CN110219005A - Copper-based material inhibiting solution and preparation method thereof, corrosion inhibition method - Google Patents
Copper-based material inhibiting solution and preparation method thereof, corrosion inhibition method Download PDFInfo
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- CN110219005A CN110219005A CN201910617642.9A CN201910617642A CN110219005A CN 110219005 A CN110219005 A CN 110219005A CN 201910617642 A CN201910617642 A CN 201910617642A CN 110219005 A CN110219005 A CN 110219005A
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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Abstract
A kind of copper-based material inhibiting solution and preparation method thereof, corrosion inhibition method, the inhibiting solution include that mass ratio is (1~100): (2~11): 1000 hydrophobically modified nanoparticle, corrosion inhibiter and organic solvent.A kind of slow rotten method is also provided, an air boundary is formed between copper-based material surface, the microstructure and corrosion inhibiter of hydrophobically modified nanoparticle surface by spraying above-mentioned inhibiting solution, while playing corrosion inhibition, does not influence copper-based electric conductivity.
Description
Technical field
The invention belongs to copper-based material corrosion and protection technical field more particularly to a kind of copper-based material inhibiting solution and its systems
Preparation Method, corrosion inhibition method.
Background technique
Copper is one of the metal material that the mankind use earliest.Fine copper (red copper) has good ductility, thermally conductive, electric conductivity
Can, it is widely used in the fields such as electrical, light industry, machine-building.Be obtain preferably with particular characteristic copper product, often to
The elements such as silicon, zinc are wherein added, obtain a series of copper-based material.
One key property of copper-based material is electric conductivity, but under natural atmosphere state, copper can in air
Oxygen occur oxidation reaction influence its electrical contact performance.It is anti-to be typically necessary progress surface for copper-based oxidation process in order to prevent
Shield processing.Since the coating that conventional coating is formed mostly is using resin film former, coating is thicker and non-conductive, for being not intended to
Changing the application field of copper-based sill electric conductivity, there are clearly disadvantageous.
Summary of the invention
In view of this, the main purpose of the present invention is to provide a kind of copper-based material inhibiting solutions and preparation method thereof, inhibition
Method, at least be partially solved at least one of above-mentioned the technical issues of referring to.
As one aspect of the present invention, a kind of copper-based material inhibiting solution is provided, including mass ratio is (1~100): (2
~11): 1000 hydrophobically modified nanoparticle, corrosion inhibiter and organic solvent.
As another aspect of the present invention, a kind of preparation method of copper-based material inhibiting solution as described above is provided,
The following steps are included:
Hydrophobically modified nanoparticle is ground and is distributed in organic solvent, dispersion liquid is obtained, wherein the hydrophobically modified
The mass ratio of nanoparticle and organic solvent is 1: 10~1: 1000；
Corrosion inhibiter is added in dispersion liquid, the copper-based material inhibiting solution is obtained, wherein the corrosion inhibiter and dispersion liquid
Mass ratio be 1: 100~1: 500.
As another aspect of the invention, a kind of corrosion inhibition method of copper-based material is provided, comprising the following steps:
Copper-based material inhibiting solution as described above is sprayed at copper-based material surface, is formed on the copper-based material surface slow
Lose layer；
Wherein, the corrosion-inhibiting layer includes the hydrophobically modified nanoparticle for being scattered in copper-based material surface, is adsorbed in Copper base material
The air boundary expecting the corrosion inhibiter on surface and being formed between the hydrophobically modified nanoparticle and corrosion inhibiter.
As it is still another aspect of the present invention to provide a kind of conductive materials, comprising:
Copper-based material；And
Corrosion-inhibiting layer, including being scattered in the hydrophobically modified nanoparticle on copper-based material surface, being adsorbed in copper-based material surface
Corrosion inhibiter and the air boundary formed between the hydrophobically modified nanoparticle and corrosion inhibiter.
As it is still another aspect of the present invention to provide a kind of conductive materials as described above in electrical contact component
Using.
Based on the above-mentioned technical proposal, the present invention has the advantages that
(1) modified Nano particle diameter 20-200nm provided by the invention, monodispersity is good, micro- with certain surface
Structure, surface-active is big, and a small amount of nano-dispersed can promote corrosion inhibiter quickly to be formed on copper-based material surface slow in copper-based surfaces
Layer is lost, the corrosion mitigating effect of corrosion inhibiter is improved.
(2) copper-based material inhibiting solution provided by the invention, can be painted on copper-based material and component surface, and modification is received
An air boundary is formed between the microstructure and corrosion inhibiter on rice corpuscles surface, can be played corrosion inhibition, is formed by slow
It is very thin while not influencing copper-based electric conductivity to lose layer, certain protective action is provided.
Detailed description of the invention
Fig. 1 (a) is hydrophobically modified SiO prepared by the embodiment of the present invention 12Nanoparticle microscopic appearance scanning electron microscope (SEM) photograph；
Fig. 1 (b) is hydrophobically modified SiO prepared by the embodiment of the present invention 12The FTIR spectrum (FTIR) of nanoparticle
Figure；
Fig. 2 is that there is the present invention hydrophobically modified nanoparticle of surface microstructure to disperse schematic diagram in copper-based surfaces；
Fig. 3 is hydrophobically modified SiO prepared by the embodiment of the present invention 12The facilitation that nanoparticle adsorbs corrosion inhibiter is opened
Road current potential-time diagram；
Fig. 4 (a) is the electrochemical AC impedance curve of the H62 brass of the embodiment of the present invention 1 before and after the processing using inhibiting solution
(EIS)；
Fig. 4 (b), which is the embodiment of the present invention 1, utilizes the electrochemical AC impedance curve of inhibiting solution treated H62 brass
(EIS) it is fitted equivalent circuit；
Fig. 5 is Ta Feier (Tafel) curve of the H62 brass of 1 inhibiting solution of the embodiment of the present invention before and after the processing；
Fig. 6 is the microscopic appearance of H62 brass surfaces and wetting after 1 inhibiting solution spray treatment difference number of the embodiment of the present invention
Angular measurement figure (0 time, 1 time, 5 times, 10 times, 15 times, 20 times).
In above-mentioned attached drawing, appended drawing reference meaning is as follows:
1- copper-based material；2- corrosive medium；3- hydrophobically modified nanoparticle；
4- corrosion inhibiter；5- air boundary.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The present invention is configured to dispersion liquid using hydrophobically modified nanoparticle and corrosion inhibiter, directly by spraying method copper-based
Material surface, realization rapidly, is synergistically protected, and does not influence the electric conductivity of copper-based material.Further use the molten of environmental protection
Agent ethyl alcohol is dispersed, and sprays use, can also be sprayed number by control, be made copper-based material surface that hydrophobicity be presented.
According to some embodiments of the present invention, a kind of copper-based material inhibiting solution is provided, is (1~100) comprising mass ratio:
(2~11): 1000 hydrophobically modified nanoparticle, corrosion inhibiter and solvent.When a small amount of hydrophobically modified nano-dispersed is in copper-based material
Surface can promote corrosion inhibiter Quick uniform to be adsorbed on copper-based material surface；Using modified Nano particle surface microstructure with
Corrosion inhibiter forms an air boundary, while not influencing copper-based electric conductivity, plays the role of hindering corrosive medium, into
And improve the protective action to copper-based material.Air boundary can slow down electrochemical corrosion, including in wet condition, seawater
Corrosion under environment, acidity or alkaline medium environment.
Preferably, the partial size of the hydrophobically modified nanoparticle is 20~200nm, is hydrophobically modified SiO2Nanoparticle
Son, TiO2Nanoparticle, Al2O3Nanoparticle or ZnO nanoparticle etc..It, can heap if the hydrophobically modified nanoparticle dosage is excessive
Product will affect substrate surface physicochemical characteristics on copper-based material surface, such as copper-based connection characteristic；And dosage then rises not less excessively
To effect, auxiliary absorption cannot be provided and improve the effect of inhibition.
Preferably, which is modifying agent to receiving using the straight chain alcohol of silane coupling agent or C6~C10
Rice corpuscles hydrophobically modified and be made；Wherein silane coupling agent is, for example, phenyl triethoxysilane, hexadecyl trimethoxy silicon
Alkane, three second of dodecyltrimethoxysilane, γ-methacryloxypropyl trimethoxy silane (KH-570) or vinyl
Oxysilane.
Preferably, corrosion inhibiter is benzotriazole, triazole derivatives or 2- mercaptobenzoxazole.
Preferably, organic solvent is toluene or ethyl alcohol.
According to some embodiments of the present invention, a kind of preparation method of above-mentioned copper-based material inhibiting solution is additionally provided, including
Following steps:
Hydrophobically modified nanoparticle is ground and is distributed in organic solvent, dispersion liquid is obtained, wherein the hydrophobically modified
The mass ratio of nanoparticle and organic solvent is 1: 10~1: 1000；
Corrosion inhibiter is added in dispersion liquid, the copper-based material inhibiting solution is obtained, wherein the corrosion inhibiter and dispersion liquid
Mass ratio be 1: 100~1: 500.
Preferably, which can for example be prepared by following steps:
Nanoparticle precursor is added into the solution A comprising alkali and solvent, obtains solution B；
It is added modifying agent into solution B, and heating stirring 12~for 24 hours, it is centrifugated and is dried to obtain hydrophobically modified nanometer
Particle.
Specifically, nanoparticle precursor is, for example, esters of silicon acis, titanate esters, zinc salt or aluminium salt etc., is respectively used to preparation warp
The SiO of hydrophobically modified2Nanoparticle, TiO2Nanoparticle, Al2O3Nanoparticle or ZnO nanoparticle etc..Certain dewatering nano
The preparation method of particle is not limited thereto, and can also be prepared by other well known methods.
According to some embodiments of the present invention, a kind of corrosion inhibition method of copper-based material is additionally provided, comprising the following steps:
Above-mentioned copper-based material inhibiting solution is sprayed at copper-based material surface, forms corrosion-inhibiting layer on copper-based material surface；Wherein,
The corrosion-inhibiting layer include the hydrophobically modified nanoparticle for being scattered in copper-based material surface, be adsorbed in the corrosion inhibiter on copper-based material surface with
And the air boundary formed between hydrophobically modified nanoparticle and corrosion inhibiter.
Preferably, spraying number is 1~15 time, and with the increase of spraying number, the hydrophobic performance on copper-based material surface is got over
It is good, be conducive to hinder inhibition medium.
According to some embodiments of the present invention, a kind of conductive material handled by above-mentioned corrosion inhibition method is additionally provided, is wrapped
It includes:
Copper-based material；And
Corrosion-inhibiting layer, including being scattered in the hydrophobically modified nanoparticle on copper-based material surface, being adsorbed in copper-based material surface
Corrosion inhibiter and the air boundary formed between hydrophobically modified nanoparticle and corrosion inhibiter.
According to some embodiments of the present invention, it additionally provides a kind of above-mentioned conductive material and is such as in electrical contact member in electrical contact field
Application in device.
It is tested below by way of comparative example, embodiment and dependence test to further illustrate the present invention.It is retouched in detail in following
In stating, to elaborate many concrete details to provide the comprehensive understanding to the embodiment of the present invention convenient for explaining.However it is obvious
Ground, one or more embodiments can also be carried out without these specific details.Moreover, the case where not conflicting
Under, the details in following embodiment can be other possible embodiments in any combination.
Embodiment 1:
The preparation of copper-based material inhibiting solution:
A kind of copper-based material inhibiting solution, specific preparation process is as follows:
5g deionized water, 1g ammonium hydroxide are added in 50g ethyl alcohol by the first step, are stirred 15 minutes, are uniformly mixed it, are obtained
To solution A；
The solution A mixed is added in the there-necked flask with condenser pipe, the positive silicon of 3.5g is added into solution A by second step
Acetoacetic ester quickly stirs 20 minutes at room temperature, obtains solution B；
The Nano-meter SiO_2 of 0.4g is slowly added dropwise to solution B for third step2Modifying agent-phenyl triethoxysilane (PTES),
Continue stirring 18 hours at room temperature.Product centrifuge washing is dried into hydrophobically modified SiO after reaction2Nanoparticle.
Step 4: by 0.1g hydrophobically modified SiO2Nanoparticle grinds redisperse into 100g ethyl alcohol, prepares dispersion liquid D；
Step 5: 0.5g benzotriazole (BTA) is added in above-mentioned dispersion liquid D, it is configured to copper-based material inhibiting solution.
Performance test: hydrophobically modified SiO is measured using Malvern Zetasizer Nano granularity potentiometer2Nanoparticle seed
Diameter is 100 ± 25nm；Using scanning electron microscope (Japanese JSM-7500F scanning electron microscope) to hydrophobically modified SiO2The surface of nanoparticle
Pattern is observed, as a result as shown in Fig. 1 (a), the hydrophobically modified SiO2Nanoparticle surface has the more of micro-rough
Level structure, and monodispersity is good.Hydrophobically modified SiO2Shown in FTIR infared spectrum such as Fig. 1 (b) of nanoparticle, there are Si- benzene
Base, it was demonstrated that be grafted successfully.
The corrosion inhibition method of copper-based material:
H62 brass surfaces, which are sprayed on, by above-mentioned copper-based material inhibiting solution 1 time forms corrosion-inhibiting layer.As shown in Fig. 2, the corrosion-inhibiting layer
Including be scattered in the hydrophobically modified nanoparticle 3 on 1 surface of copper-based material, be adsorbed in copper-based material surface corrosion inhibiter 4 and
The air boundary 5 formed between hydrophobically modified nanoparticle 3 and corrosion inhibiter 4, can be to corrosive medium 2 such as fresh water, seawater, acid
Property or the formation such as alkaline medium hinder.Fig. 3 is hydrophobically modified SiO prepared by the embodiment of the present invention 12Nanoparticle inhales corrosion inhibiter
Attached facilitation open circuit potential-time diagram, it can be seen that spraying hydrophobically modified SiO2The brass open circuit potential of nanoparticle becomes
Change faster, degree is bigger, illustrates to spray modified SiO2Nanoparticle has facilitation to the absorption of corrosion inhibiter.
Chemical property is carried out to the H62 brass of 1 copper-based material inhibiting solution of H62 brass and spraying without slow corrosion treatment
Test, using three-electrode system, saturated calomel electrode is as reference electrode, and platinized platinum is as auxiliary electrode, using Shanghai Chen Hua electricity
Chem workstation CHI 660e carries out electro-chemical test；At (open circuit potential) OCP, frequency range is AC impedance (EIS)
100kHz-0.01Hz, 5mV/s；Tafel voltage range OCP ± 300mV, 5mV/s.Fig. 4 (a) is before inhibiting solution of the present invention is handled
The electrochemical AC impedance curve of H62 brass afterwards is fitted using the circuit of Fig. 4 (b), and wherein Rs is solution resistance, and Rc is table
Facial mask resistance, Rt are air boundary resistance, and CPEc and CPEd respectively indicate skin covering of the surface and Air Interface layer capacitance, as a result table
Bright, the air boundary resistance Rt between nanometer and corrosion inhibiter is 3901 Ω.Fig. 5 be invention inhibiting solution before and after the processing
H62 brass Tafel curve, the results showed that, after inhibiting solution is handled, the corrosion electric current density Icorr of brass surfaces by
4.27μA·cm-2Lowering is 0.74 μ Acm- 2,.It is generally believed that corrosion current reduction illustrates corrosion rate reduction, wherein nanometer
Air boundary between corrosion inhibiter is obvious for improving corrosion mitigating effect.The nanometer of dispersion does not have influence brass surfaces to lead substantially
Electrical characteristics test spraying inhibiting solution H62 brass surfaces resistance before and after the processing using JK2511 type Estimate of Resistance for DC Low Resistance tester, are
0.08mΩ。
Using the 20 video contact angle measuring instrument of DSA of German Kr ü ss Instruments GmbH, at spraying inhibiting solution
H62 brass carries out angle of wetting test after reason.As a result see Fig. 6, with the increase of spraying number, angle of wetting is by there are original 89.2 °
133.2 ° are risen to, certain hydrophobic performance is shown, illustrates to handle through inhibiting solution of the invention, it is anti-can not only to form inhibition
Effect is protected, the hydrophobic property of substrate surface can also be improved.
Embodiment 2:
The preparation of copper-based material inhibiting solution:
A kind of copper-based material inhibiting solution, specific preparation process is as follows:
6g deionized water, 3g ammonium hydroxide are added in 100g ethyl alcohol by the first step, are stirred 15 minutes, are uniformly mixed it, are obtained
To solution A；
The solution A mixed is added in the there-necked flask with condenser pipe, the positive silicon of 4.5g is added into solution A by second step
Acetoacetic ester quickly stirs 20 minutes at room temperature, obtains solution B；
The Nano-meter SiO_2 of 0.6g is slowly added dropwise to solution B for third step2Modifying agent vinyltriethoxysilane, at room temperature
Continue stirring 12 hours.Product centrifuge washing is dried into hydrophobically modified SiO after reaction2Nanoparticle.
Step 4: by 2g hydrophobically modified SiO2Nanoparticle grinds redisperse into 100g ethyl alcohol, prepares dispersion liquid D；
Step 5: 0.5g benzotriazole (BTA) is added in above-mentioned dispersion liquid D, it is configured to copper-based material inhibiting solution；
Performance test: hydrophobically modified SiO is measured using Malvern Zetasizer Nano granularity potentiometer2Nanoparticle seed
Diameter is 65 ± 15nm.
The corrosion inhibition method of copper-based material:
The red copper of 1 copper-based material inhibiting solution of red copper and spraying without slow corrosion treatment is carried out similar to Example 1
Electrochemical property test, the results showed that, after inhibiting solution is handled, air boundary resistance Rt is 3871 Ω, corrosion electric current density
For by 4.55 original μ Acm-2Lowering is 0.54 μ Acm-2.The hydrophobically modified nanoparticle of dispersion does not have to influence purple substantially
Copper surface conductance characteristic tests spraying inhibiting solution red copper surface electricity before and after the processing using JK2511 type Estimate of Resistance for DC Low Resistance tester
Resistance, is 0.06m Ω.
Angle of wetting test similar to Example 1 is carried out to red copper after spraying inhibiting solution processing, with the increasing of spraying number
Add, angle of wetting is by there are original 85.2 ° that can rise to 138.5 °.
Embodiment 3:
The preparation of copper-based material inhibiting solution:
A kind of copper-based material inhibiting solution, specific preparation process is as follows:
8g deionized water, 2.5g ammonium hydroxide are added in 100g ethyl alcohol by the first step, are stirred 15 minutes, it is uniformly mixed,
Obtain solution A；
The solution A mixed is added in the there-necked flask with condenser pipe, the positive silicic acid of 5g is added into solution A by second step
Ethyl ester quickly stirs 20 minutes at room temperature, obtains solution B；
The Nano-meter SiO_2 of 0.5g is slowly added dropwise to solution B for third step2Modifying agent hexadecyl trimethoxy silane, in room temperature
Under continue stirring 24 hours.Product centrifuge washing is dried into hydrophobically modified SiO after reaction2Nanoparticle.
Step 4: by 1.5g hydrophobically modified SiO2Nanoparticle grinds redisperse into 100g toluene, prepares dispersion liquid D；
Step 5: 0.35g2- mercaptobenzoxazole (MBO) is added in above-mentioned dispersion liquid D, it is slow to be configured to copper-based material
Lose liquid；
Performance test: modified SiO is measured using Malvern Zetasizer Nano granularity potentiometer2Nano particle diameter is
175±25nm。
The corrosion inhibition method of copper-based material:
To the Cu-40Zn alloy of 1 copper-based material inhibiting solution of Cu-40Zn alloy and spraying without slow corrosion treatment carry out with
The similar electrochemical property test of embodiment 1, the results showed that, after inhibiting solution is handled, air boundary resistance Rt is 4650 Ω,
Corrosion electric current density is by 4.32 original μ Acm-2Lowering is 0.48 μ Acm-2.The hydrophobically modified nanoparticle of dispersion is basic
Cu-40Zn surface conductance characteristic is not influenced, before testing spraying inhibiting solution processing using JK2511 type Estimate of Resistance for DC Low Resistance tester
Cu-40Zn sheet resistance afterwards is 0.09m Ω.
Angle of wetting test similar to Example 1 is carried out to Cu-40Zn alloy after spraying inhibiting solution processing, with spraying time
Several increases, angle of wetting is by there is original 88.9 ° that can rise 142.3 °.
Embodiment 4:
The preparation of copper-based material inhibiting solution:
A kind of copper-based material inhibiting solution, specific preparation process is as follows:
6g deionized water, 3g ammonium hydroxide are added in 100g ethyl alcohol by the first step, are stirred 15 minutes, are uniformly mixed it, are obtained
To solution A；
The solution A mixed is added in the there-necked flask with condenser pipe, the positive silicon of 4.5g is added into solution A by second step
Acetoacetic ester quickly stirs 20 minutes at room temperature, obtains solution B；
The Nano-meter SiO_2 of 0.5g is slowly added dropwise to solution B for third step2It is small to continue stirring 12 at room temperature for modifying agent n-octyl alcohol
When.Product centrifuge washing is dried into hydrophobically modified SiO after reaction2Nanoparticle.
Step 4: by 2g hydrophobically modified SiO2Nanoparticle grinds redisperse into 100g ethyl alcohol, prepares dispersion liquid D；
Step 5: 0.5g benzotriazole (BTA) is added in above-mentioned sub- dispersion liquid D, it is configured to copper-based material inhibition
Liquid；
Performance test: modified SiO is measured using Malvern Zetasizer Nano granularity potentiometer2Nano particle diameter is
80±15nm。
The corrosion inhibition method of copper-based material:
The brass of 1 copper-based material inhibiting solution of brass and spraying without slow corrosion treatment is carried out similar to Example 1
Electrochemical property test, the results showed that, after inhibiting solution is handled, air boundary resistance Rt is 3959 Ω, corrosion electric current density
For by 4.27 original μ Acm-2Lowering is 0.53 μ Acm-2.The hydrophobically modified nanoparticle of dispersion does not have to influence yellow substantially
Copper surface conductance characteristic tests spraying inhibiting solution brass surfaces electricity before and after the processing using JK2511 type Estimate of Resistance for DC Low Resistance tester
Resistance, sheet resistance is 0.08m Ω.
Embodiment 5:
The preparation of copper-based material inhibiting solution:
A kind of copper-based material inhibiting solution, specific preparation process is as follows:
5.5g deionized water, 2g ammonium hydroxide are added in 100g ethyl alcohol by the first step, are stirred 15 minutes, it is uniformly mixed,
Obtain solution A；
The solution A mixed is added in the there-necked flask with condenser pipe, the positive silicic acid of 5g is added into solution A by second step
Ethyl ester quickly stirs 20 minutes at room temperature, obtains solution B；Solution B is divided into two parts, a portion continue to stir 12h from
Heart washing and drying obtains unmodified SiO2Nanoparticle, another part carry out step 3.
The Nano-meter SiO_2 of 0.5g is slowly added dropwise to solution B for third step2Modifying agent phenyl triethoxysilane, at room temperature after
Continuous stirring 12 hours.Product centrifuge washing is dried into modified SiO after reaction2Nanoparticle.
Step 4: by 2g is unmodified and hydrophobically modified SiO2Nanoparticle is ground respectively, then is distributed to 100g second respectively
In alcohol, dispersion liquid D and dispersion liquid F is prepared；
Step 5: 0.5g benzotriazole (BTA) is added separately in above-mentioned dispersion liquid D and dispersion liquid F, it is configured to copper
Sill inhibiting solution；
Performance test: using Malvern Zetasizer Nano granularity potentiometer measurement hydrophobically modified and unmodified
SiO2Nano particle diameter is 45 ± 15nm.
The corrosion inhibition method of copper-based material:
Contain unmodified SiO to being coated with2It the brass of the copper-based material inhibiting solution of nanoparticle and is coated with containing hydrophobically modified
SiO2The brass of the copper-based material inhibiting solution of nanoparticle carries out electrochemical property test, the results showed that, through containing unmodified SiO2It receives
After the copper-based material inhibiting solution processing of rice corpuscles, between the ac impedance spectroscopy hydrophobically modified nanoparticle fitted and corrosion inhibiter
Interface resistance Rt is that 1459 Ω (since unmodified nanoparticle surface is smooth, do not form obvious air circle between corrosion inhibiter
Surface layer, Rt are smaller)；Corrosion electric current density is by 4.27 original μ Acm-2Become 2.77 μ Acm-2, hydrophobically modified SiO2
Inhibiting solution processing after, the interface resistance Rt of air boundary is 4145 Ω, and corrosion electric current density is by 4.27 original μ A
cm-2Become 0.87 μ Acm-2.Spraying inhibiting solution brass table before and after the processing is tested using JK2511 type Estimate of Resistance for DC Low Resistance tester
Surface resistance, sheet resistance are 0.08m Ω.
Embodiment 6:
The preparation of copper-based material inhibiting solution:
A kind of copper-based material inhibiting solution, specific preparation process is as follows:
5.8g deionized water, 2.5g ammonium hydroxide are added in 100g ethyl alcohol by the first step, are stirred 15 minutes, keep its mixing equal
It is even, obtain solution A；
The solution A mixed is added in the there-necked flask with condenser pipe, 5g metatitanic acid fourth is added into solution A by second step
Ester quickly stirs 15 minutes at room temperature, obtains solution；
The nano-TiO of 0.75g is slowly added dropwise to solution B for third step2Modifying agent Silane coupling reagent KH-570, at room temperature
Continue stirring 12 hours.Product centrifuge washing is dried into modified TiO after reaction2Nanoparticle.
Step 4: by 2g hydrophobically modified TiO2Nanoparticle is ground respectively, then is distributed in 100g ethyl alcohol respectively, is prepared and is divided
Dispersion liquid D；
Step 5: 0.45g benzotriazole (BTA) is added separately in above-mentioned dispersion liquid D and dispersion liquid F, it is configured to
Copper-based material inhibiting solution；
Performance test: using the TiO of Malvern Zetasizer Nano granularity potentiometer measurement hydrophobically modified2Nanoparticle
Partial size is 25 ± 5nm.
The corrosion inhibition method of copper-based material:
To being coated with TiO containing hydrophobically modified2The brass of the copper-based material inhibiting solution of nanoparticle carries out chemical property survey
Examination, the results showed that, hydrophobically modified TiO2Inhibiting solution processing after, the interface resistance Rt of air boundary is 4013 Ω, corrosion
Current density is 0.79 μ Acm-2.Spraying inhibiting solution brass before and after the processing is tested using JK2511 type Estimate of Resistance for DC Low Resistance tester
Sheet resistance, sheet resistance are 0.08m Ω.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (12)
1. a kind of copper-based material inhibiting solution is (1~100): (2~11) including mass ratio: 1000 hydrophobically modified nanoparticle,
Corrosion inhibiter and organic solvent.
2. copper-based material inhibiting solution according to claim 1, which is characterized in that the hydrophobically modified nanoparticle is through dredging
The modified SiO of water2Nanoparticle, TiO2Nanoparticle, Al2O3Nanoparticle or ZnO nanoparticle；
Preferably, the partial size of the hydrophobically modified nanoparticle is 20~200nm.
3. copper-based material inhibiting solution according to claim 1, which is characterized in that the hydrophobically modified nanoparticle is with silicon
The straight chain alcohol of alkane coupling agent or C6~C10 are that nanoparticle hydrophobically modified is made in modifying agent；
Preferably, the silane coupling agent is phenyl triethoxysilane, hexadecyl trimethoxy silane, dodecyl three
Methoxy silane, γ-methacryloxypropyl trimethoxy silane or vinyltriethoxysilane.
4. copper-based material inhibiting solution according to claim 1, which is characterized in that the corrosion inhibiter is benzotriazole, three
Nitrogen Zole derivatives or 2- mercaptobenzoxazole.
5. copper-based material inhibiting solution according to claim 1, which is characterized in that the organic solvent is toluene or ethyl alcohol.
6. a kind of preparation method of the copper-based material inhibiting solution as described in claim 1 to 5 any one, comprising the following steps:
Hydrophobically modified nanoparticle is ground and is distributed in organic solvent, dispersion liquid is obtained, wherein the hydrophobically modified nanometer
The mass ratio of particle and organic solvent is 1: 10~1: 1000；
Corrosion inhibiter is added in dispersion liquid, the copper-based material inhibiting solution is obtained, wherein the matter of the corrosion inhibiter and dispersion liquid
Amount is than being 1: 100~1: 500.
7. preparation method according to claim 6, which is characterized in that the hydrophobically modified nanoparticle passes through following steps
Preparation:
Nanoparticle precursor is added into the solution A comprising alkali and solvent, obtains solution B；
It is added modifying agent into solution B, and heating stirring 12~for 24 hours, it is centrifugated and is dried to obtain the hydrophobically modified nanometer
Particle.
8. preparation method according to claim 7, it is characterised in that:
The nanoparticle precursor is esters of silicon acis, titanate esters, zinc salt or aluminium salt.
9. a kind of corrosion inhibition method of copper-based material, which comprises the following steps:
Copper-based material inhibiting solution as described in claim 1 to 5 any one is sprayed at copper-based material surface, described copper-based
Material surface forms corrosion-inhibiting layer；
Wherein, the corrosion-inhibiting layer includes the hydrophobically modified nanoparticle for being scattered in copper-based material surface, is adsorbed in copper-based material table
The corrosion inhibiter in face and the air boundary formed between the hydrophobically modified nanoparticle and corrosion inhibiter.
10. corrosion inhibition method according to claim 9, which is characterized in that spraying number is 1~15 time.
11. a kind of conductive material, comprising:
Copper-based material；And
Corrosion-inhibiting layer, including the hydrophobically modified nanoparticle for being scattered in copper-based material surface, the inhibition that is adsorbed in copper-based material surface
Agent and the air boundary formed between the hydrophobically modified nanoparticle and corrosion inhibiter.
12. a kind of application of conductive material as claimed in claim 11 in electrical contact component.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154470A (en) * | 2020-02-21 | 2020-05-15 | 四川振邦石油科技有限公司 | Slow-release solid corrosion inhibitor, preparation method and application |
| CN111850568A (en) * | 2020-06-30 | 2020-10-30 | 中国石油天然气集团有限公司 | Corrosion inhibitor for preventing scale corrosion of oilfield ground gathering and transportation pipeline and preparation method thereof |
| CN113755829A (en) * | 2021-08-16 | 2021-12-07 | 深圳市志凌伟业光电有限公司 | Blackening-treated copper film surface anticorrosion protective liquid medicine |
| CN115874186A (en) * | 2022-12-05 | 2023-03-31 | 诺泰生物科技(合肥)有限公司 | Preparation method and application of water-based siloxane aluminum copper corrosion inhibitor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368273A (en) * | 2007-08-15 | 2009-02-18 | 江苏海迅实业集团股份有限公司 | Copper alloy antirust agent |
| US9660277B2 (en) * | 2005-06-24 | 2017-05-23 | Prestone Products Corporation | Methods for inhibiting corrosion in brazed metal surfaces and coolants and additives for use therein |
| CN106928806A (en) * | 2017-03-14 | 2017-07-07 | 中国船舶重工集团公司第七二五研究所 | A kind of intelligent nano container for preventing copper and corrosion of copper alloy, its preparation and application process |
| CN107083102A (en) * | 2017-04-19 | 2017-08-22 | 蒋冠吾 | A kind of combined oxidation cerium nano-sized hydrophobic particle of multilevel hierarchy and its preparation method and application |
| CN107163844A (en) * | 2017-05-16 | 2017-09-15 | 江南大学 | A kind of antirust agent and preparation method and application |
| CN108796489A (en) * | 2018-06-08 | 2018-11-13 | 浙江工业大学 | A kind of chrome-free tanning agent and its preparation process fine and close suitable for copper and copper alloy nanometer selfreparing multistage |
-
2019
- 2019-07-09 CN CN201910617642.9A patent/CN110219005B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9660277B2 (en) * | 2005-06-24 | 2017-05-23 | Prestone Products Corporation | Methods for inhibiting corrosion in brazed metal surfaces and coolants and additives for use therein |
| CN101368273A (en) * | 2007-08-15 | 2009-02-18 | 江苏海迅实业集团股份有限公司 | Copper alloy antirust agent |
| CN106928806A (en) * | 2017-03-14 | 2017-07-07 | 中国船舶重工集团公司第七二五研究所 | A kind of intelligent nano container for preventing copper and corrosion of copper alloy, its preparation and application process |
| CN107083102A (en) * | 2017-04-19 | 2017-08-22 | 蒋冠吾 | A kind of combined oxidation cerium nano-sized hydrophobic particle of multilevel hierarchy and its preparation method and application |
| CN107163844A (en) * | 2017-05-16 | 2017-09-15 | 江南大学 | A kind of antirust agent and preparation method and application |
| CN108796489A (en) * | 2018-06-08 | 2018-11-13 | 浙江工业大学 | A kind of chrome-free tanning agent and its preparation process fine and close suitable for copper and copper alloy nanometer selfreparing multistage |
Non-Patent Citations (1)
| Title |
|---|
| 黄月文: "纳米杂化有机硅溶胶在金属防腐中的应用", 《电镀与涂饰》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154470A (en) * | 2020-02-21 | 2020-05-15 | 四川振邦石油科技有限公司 | Slow-release solid corrosion inhibitor, preparation method and application |
| CN111850568A (en) * | 2020-06-30 | 2020-10-30 | 中国石油天然气集团有限公司 | Corrosion inhibitor for preventing scale corrosion of oilfield ground gathering and transportation pipeline and preparation method thereof |
| CN113755829A (en) * | 2021-08-16 | 2021-12-07 | 深圳市志凌伟业光电有限公司 | Blackening-treated copper film surface anticorrosion protective liquid medicine |
| CN113755829B (en) * | 2021-08-16 | 2024-05-07 | 深圳市志凌伟业技术股份有限公司 | Blackening-treated copper film surface anti-corrosion protection liquid medicine |
| CN115874186A (en) * | 2022-12-05 | 2023-03-31 | 诺泰生物科技(合肥)有限公司 | Preparation method and application of water-based siloxane aluminum copper corrosion inhibitor |
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