CN106167903B - A kind of method that copper corrosion inhibition film is prepared based on 4 phenyl pyrimidines - Google Patents
A kind of method that copper corrosion inhibition film is prepared based on 4 phenyl pyrimidines Download PDFInfo
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- CN106167903B CN106167903B CN201610629402.7A CN201610629402A CN106167903B CN 106167903 B CN106167903 B CN 106167903B CN 201610629402 A CN201610629402 A CN 201610629402A CN 106167903 B CN106167903 B CN 106167903B
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- copper
- corrosion inhibition
- phenyl
- copper electrode
- inhibition film
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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
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to a kind of method that copper corrosion inhibition film is prepared based on 4 phenyl pyrimidines, comprise the following steps：Pretreated copper electrode is taken, is inserted in the 4 phenyl pyrimidine solution for removing dissolved oxygen, under air-proof condition, corrosion inhibition film is formed on copper electrode surface.Compared with prior art, inhibitor molecular is self-assembled to copper surface by the present invention, forms self-assembled monolayers, and method is more green, and 4 PPM corrosion inhibiter are more environmentally friendly, and raw material is inexpensive, and corrosion mitigating effect is more preferable etc..
Description
Technical field
The present invention relates to copper inhibitor field, more particularly, to a kind of side that copper corrosion inhibition film is prepared based on 4- phenyl pyrimidines
Method.
Background technology
Copper has the performances such as excellent intensity, machining property, thermal conductivity, electric conductivity, weldability and corrosion resistance,
Extensively using the related industry in ocean.But the chlorine ion concentration in marine environment is higher, therefore copper corrosion is tight in marine environment
Weight.Slow down the corrosion of copper usually using corrosion inhibiter, conventional organic inhibitor such as BTA (BTA), have to copper slow well
Effect is lost, but the molecule is noxious material, pollutes environment.Therefore, new favorable rust preventing effect is sought, inhibition efficiency is high,
Inexpensive corrosion inhibiter is significant.
Chinese patent 201010147254.8 discloses a kind of high-performance copper, nickel protective agent, for protecting copper, nickel, prevents
Copper or copper alloy, nickel or nickel alloy are oxidized or change colour or be corroded.It contain triazole, tetrazole, iso-indoles, indoles,
BTA, imidazoles pyridazine, purine, C4~C12 long-chain derivatives of pyrazolopyrimidine and/or triazolo pyrimidine, can be
Copper or nickel and its alloy surface form organic protective film, effectively protects copper or nickel and its alloy to prevent oxidation discoloration and not shadow
Ring its conductive and welding performance.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind is phonetic based on 4- phenyl
The method that pyridine prepares copper corrosion inhibition film.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method that copper corrosion inhibition film is prepared based on 4- phenyl pyrimidines, is comprised the following steps：Pretreated copper electrode is taken,
Insert in 4- phenyl pyrimidines (4-PPM) solution for removing dissolved oxygen, under air-proof condition, self assembly, i.e., formed on copper electrode surface
Corrosion inhibition film.
Described 4- phenyl pyrimidines solution is 0.1~5mM of the concentration 4- phenyl pyrimidine aqueous solution.
The time that copper electrode soaks in 4- phenyl pyrimidine solution is 1-10h, and temperature is room temperature.
The copper electrode of pretreatment refers to：Through polishing, clean, polish, the copper electrode after acid soak.
Further, the step of pretreatment is specially：
(1) copper electrode is taken, polishing removes copper oxide surface, cleaning, then is polished to form bright mirror surface with aluminum oxide, so
Clean up again afterwards；
(2) copper electrode that step (1) obtains is quickly entered in salpeter solution and soaked, remove the cupric oxide generated again,
Clean up, i.e. pretreatment is completed.
As further scheme, the concentration of the salpeter solution in step (2) is 6-8M.
Compared with prior art, the present invention has advantages below：
(1) 4- phenyl pyrimidines are incorporated into copper inhibitor field by the invention, by the method for self assembly, can
To form copper corrosion inhibition film on copper surface.
(2) through electrochemistry, optical microphotograph sign and Raman Characterization, it is found that on the N in 4- phenyl pyrimidine molecules
There are lone pair electrons, can be with N6Acted on for adsorption site and copper, and complex is formed with Cu unoccupied orbitals, so as to form the absorption of densification
Film, simultaneously as 4- phenyl pyrimidine molecules are to form this unique structure by coplanar pyrimidine ring and phenyl ring, so being formed
Corrosion inhibition film marshalling and also densification, therefore the corrosion inhibition film has very high inhibition efficiency.Though and BTA molecule and
Nitrogen-atoms in molecule acts on copper, but whole molecule is not copline, and in practical application, generally only by BTA
It is added in corrosion system, has no correlative study of the BTA on copper after first film forming for inhibition and report.
(3) 4-PPM corrosion inhibiter is more environmentally friendly, and raw material is inexpensive, and cost is low, is particularly suitable for large-scale production and application.
Brief description of the drawings
Fig. 1 is the electrochemical impedance figure of the Cu electrodes of the 4-PPM films formed under different assembling concentration；
Fig. 2 is the electrochemical impedance figure of the Cu electrodes of the 4-PPM films formed under different built-up times；
Fig. 3 is the optics after the Cu electrodes of blank Cu electrodes and surface-assembled 4-PPM films soak in identical corrosive medium
Micro- phenogram；
Fig. 4 is the Raman collection of illustrative plates of 4-PPM powder and the 4-PPM films of Cu electrode surface self assemblies；
Fig. 5 is absorption schematic diagram of the 4-PPM molecules on copper surface.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Raman spectrogram in following embodiments tests the SuperLabram II type confocal microscopy laser in Dilor companies
Carried out in Raman system.He-Ne lasers using wavelength as 632.8nm are excitation source, liquid nitrogen cooling type CCD-detector
(1024 × 256pixels), 50 times of long-focal length lens of Olympus, 1800 lines/mm gratings, the preposition slit of grating (Slit) are
100 μm, pinhole diaphragm aperture (hole) is 1000 μm, notch filter piece.The sweep time of each spectrogram is 8 seconds, integration time
For 3 times.Electrochemical workstation model CHI660C (Shanghai Chen Hua instrument company).
Embodiment 1
(1) pre-treatment of copper：Polished respectively on coarse sandpaper and fine sandpaper electrode, remove the electrode surface cupric oxide,
Then it is cleaned by ultrasonic respectively in water, second alcohol and water respectively 8~10 minutes, is then polished with 0.5 micron of alchlor, treat copper
Surface is respectively cleaned by ultrasonic 8~10 minutes in water, second alcohol and water again after forming the minute surface of light；
(2) copper electrode that step (1) obtains is immersed into rapidly 7M HNO3Solution soaks 10~15 seconds, removes copper surface and exists
The cupric oxide of pretreatment process generation, then with water and alcohol flushing.
(3) preparation of copper surface 4- phenyl pyrimidines (4-PPM) film：Inhibition molecule 4-PPM has unique molecular structure, point
Have lone pair electrons in son on N, complex can be formed with Cu unoccupied orbitals and can be adsorbed onto copper surface, formed one layer of fine and close adsorbed film from
And it can effectively prevent metal erosion.Before self-assembling technique is carried out, 4-PPM solution (5mM~0.1mM) is required to logical high pure nitrogen
Or so half an hour is with except the oxygen being dissolved in assembles concentration.The copper electrode obtained through step (2) is immersed in the 4- for removing oxygen
In PPM assembles concentration beakers, beaker is sealed, at room temperature self assembly certain time (1~10 hour), be prepared for respectively different dense
The 4-PPM self-assembled films spent under (5mM~0.1mM) and the 4-PPM self assemblies under the different self assembly times (1~10 hour)
Film.
Embodiment 2
(1) pre-treatment of copper：Polished respectively on coarse sandpaper and fine sandpaper electrode, remove electrode surface cupric oxide, so
It is cleaned by ultrasonic respectively in water, second alcohol and water respectively afterwards 8 minutes, is then polished with 0.5 micron of alchlor, treat copper surface shape
It is each in water, second alcohol and water again after into the minute surface of light to be cleaned by ultrasonic 8 minutes；
(2) copper electrode that step (1) obtains is immersed into rapidly 7M HNO3Solution soaks 10 seconds, removes copper surface in Qian Chu
The cupric oxide of reason process generation, then with water and alcohol flushing.
(3) preparation of copper surface 4- phenyl pyrimidines (4-PPM) film：Before self assembly is carried out, 4-PPM solution (0.1mM) is logical
Or so high pure nitrogen half an hour is with except the oxygen being dissolved in assembles concentration.The copper electrode obtained through step (2) is immersed in again and removed
Go in the 4-PPM assembles concentration beakers of oxygen, beaker is sealed, at room temperature self assembly 6h, you can obtain self-assembly corrosion inhibition film.
Embodiment 3
(1) pre-treatment of copper：Polished respectively on coarse sandpaper and fine sandpaper electrode, remove electrode surface cupric oxide, so
It is cleaned by ultrasonic respectively in water, second alcohol and water respectively afterwards 10 minutes, is then polished with 0.5 micron of alchlor, treat copper surface
Form each in water, second alcohol and water again after bright minute surface be cleaned by ultrasonic 10 minutes；
(2) copper electrode that step (1) obtains is immersed into rapidly 7M HNO3Solution soaks 15 seconds, removes copper surface in Qian Chu
The cupric oxide of reason process generation, then with water and alcohol flushing.
(3) preparation of copper surface 4- phenyl pyrimidines (4-PPM) film：Before self assembly is carried out, the logical height of 4-PPM solution (5mM)
Or so pure nitrogen gas half an hour is with except the oxygen being dissolved in assembles concentration.Obtained copper electrode will be handled through step (2) again to be immersed in
In the 4-PPM assembles concentration beakers for removing oxygen, beaker is sealed, at room temperature self assembly 1h, you can obtain self-assembly corrosion inhibition film.
Embodiment 4
(1) pre-treatment of copper：Polished respectively on coarse sandpaper and fine sandpaper electrode, remove electrode surface cupric oxide, so
It is cleaned by ultrasonic respectively in water, second alcohol and water respectively afterwards 9 minutes, is then polished with 0.5 micron of alchlor, treat copper surface shape
It is each in water, second alcohol and water again after into the minute surface of light to be cleaned by ultrasonic 9 minutes；
(2) copper electrode that step (1) obtains is immersed into rapidly 7M HNO3Solution soaks 12 seconds, removes copper surface in Qian Chu
The cupric oxide of reason process generation, then with water and alcohol flushing.
(3) preparation of copper surface 4- phenyl pyrimidines (4-PPM) film：Before self assembly is carried out, the logical height of 4-PPM solution (1mM)
Or so pure nitrogen gas half an hour is with except the oxygen being dissolved in assembles concentration.Obtained copper electrode will be handled through step (2) again to be immersed in
In the 4-PPM assembles concentration beakers for removing oxygen, beaker is sealed, at room temperature self assembly 4h, you can obtain self-assembly corrosion inhibition film.
Embodiment 5
(1) pre-treatment of copper：Polished respectively on coarse sandpaper and fine sandpaper electrode, remove electrode surface cupric oxide, so
It is cleaned by ultrasonic respectively in water, second alcohol and water respectively afterwards 9 minutes, is then polished with 0.5 micron of alchlor, treat copper surface shape
It is each in water, second alcohol and water again after into the minute surface of light to be cleaned by ultrasonic 9 minutes；
(2) copper electrode that step (1) obtains is immersed into rapidly 7M HNO3Solution soaks 12 seconds, removes copper surface in Qian Chu
The cupric oxide of reason process generation, then with water and alcohol flushing.
(3) preparation of copper surface 4- phenyl pyrimidines (4-PPM) film：Before self assembly is carried out, 4-PPM solution (0.1mM) is logical
Or so high pure nitrogen half an hour is with except the oxygen being dissolved in assembles concentration.Obtained copper electrode will be handled through step (2) again to impregnate
In the 4-PPM assembles concentration beakers for removing oxygen, beaker is sealed, at room temperature self assembly 10h, you can obtain self-assembly corrosion inhibition
Film.
Embodiment 6
The inhibition of the 4-PPM films under different self assembly conditions (assembling concentration and built-up time) is investigated using electrochemistry experiment
Performance.The corrosive medium that experiment is selected is 3% salting liquid, and the OCP of one hour or so is first run before impedance experiment,
Impedance take-off potential is OCP.Wherein, Fig. 1 and Fig. 2 is respectively various concentrations (5mM~0.1mM) and different built-up times
Under 4-PPM self-assembled films impedance diagram, it can be seen that assembling concentration is 0.1mM, built-up time is when being 6h, the resistance of copper electrode
The radius of anti-arc is maximum, illustrates that the 4-PPM films of now Cu electrode surfaces are most fine and close.It can be found after after testing, assembling concentration is
When 0.1mM, built-up time are 6h, inhibition efficiency can reach 83.2% or so.
Embodiment 7
Take and the copper electrode after 6h is assembled in 0.1mM 4-PPM, itself and blank copper electrode are contrasted.Both pass through light
Microscope is learned to be detected in real time.As shown in Figure 3, the results showed that, the Cu electrodes (Fig. 3 b) of surface self-organization 4- phenyl pyrimidine films
The situation of being corroded with respect to blank Cu electrodes (Fig. 3 a) is obviously improved, and 4-PPM corrosion inhibition films have very high delay for Cu
Lose efficiency.
Embodiment 8
Determine the copper electrode surface 4- phenyl pyrimidine films in 4-PPM powder and embodiment 2 respectively using Raman spectrum
Raman collection of illustrative plates, as shown in Figure 4.According to Raman surface melody and SERS mechanism, in SERS spectra, the group close to metal surface
Peak compared with solid summit strengthen, the molecule can be drawn with N6Acted on for adsorption site and copper.The adsorptive behavior of 4-PPM molecules is as schemed
Shown in 5.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel do not depart from improvement that scope made and modification all should be the present invention's according to the announcement of the present invention
Within protection domain.
Claims (4)
- A kind of 1. method that copper corrosion inhibition film is prepared based on 4- phenyl pyrimidines, it is characterised in that comprise the following steps：After taking pretreatment Copper electrode, insert remove dissolved oxygen 4- phenyl pyrimidine solution in, under air-proof condition, copper electrode surface formed corrosion inhibition film；Described 4- phenyl pyrimidines solution is 0.1~5mM of the concentration 4- phenyl pyrimidine aqueous solution；The time that copper electrode soaks in 4- phenyl pyrimidine solution is 1-10h, and temperature is room temperature.
- A kind of 2. method that copper corrosion inhibition film is prepared based on 4- phenyl pyrimidines according to claim 1, it is characterised in that pre- place The copper electrode of reason refers to：Through polishing, clean, polish, the copper electrode after acid soak.
- A kind of 3. method that copper corrosion inhibition film is prepared based on 4- phenyl pyrimidines according to claim 2, it is characterised in that pre- place The step of reason is specially：(1) copper electrode is taken, polishing removes copper oxide surface, cleaning, then is polished to form bright mirror surface with aluminum oxide, Ran Houzai It is secondary to clean up；(2) copper electrode that step (1) obtains is quickly entered in salpeter solution and soaked, remove the cupric oxide generated again, cleaning Totally, i.e., pretreatment is completed.
- A kind of 4. method that copper corrosion inhibition film is prepared based on 4- phenyl pyrimidines according to claim 3, it is characterised in that step (2) concentration of the salpeter solution in is 6-8M.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0845438A1 (en) * | 1996-11-28 | 1998-06-03 | Kurita Water Industries Ltd. | Oxygen scavenger and boiler water treatment chemical |
| CN101100754A (en) * | 2006-07-05 | 2008-01-09 | 中国科学院海洋研究所 | Uracil carbon steel pickling corrosion inhibitor and application thereof |
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2016
- 2016-08-03 CN CN201610629402.7A patent/CN106167903B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0845438A1 (en) * | 1996-11-28 | 1998-06-03 | Kurita Water Industries Ltd. | Oxygen scavenger and boiler water treatment chemical |
| CN101100754A (en) * | 2006-07-05 | 2008-01-09 | 中国科学院海洋研究所 | Uracil carbon steel pickling corrosion inhibitor and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 3种吡啶甲酰腙席夫碱自组装分子膜对铜的缓蚀作用;刘峥等;《功能材料》;20111231;实验部分2.2的内容 * |
| 有机类铜缓蚀剂的现状研究与发展;赵小能;《科教前沿》;20081115(第21期) * |
| 铜表面甲基咪唑自组装单分子层的表面增强拉曼光谱及电化学研究;潘英骋等;《第十六届全国光散射学时会议论文摘要集》;20111125;第94页第1-3段 * |
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