CN109266075B - Method for improving marine organism corrosion and pollution resistance of stainless steel plate - Google Patents
Method for improving marine organism corrosion and pollution resistance of stainless steel plate Download PDFInfo
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Abstract
The invention provides a method for improving marine organism corrosion and pollution resistance of a stainless steel plate. The method adopts a linear or cross-linked polymer material to modify the surface of the stainless steel, wherein the polymer material is polymethyl methacrylate dimethyl amino ethyl ester (P) (DMAEMA) and derivatives thereof introduced with quaternary ammonium groups. Dopamine is self-polymerized on the surface of the stainless steel to anchor an alkyl bromine atom transfer radical polymerization initiator, then methacrylic acid dimethyl aminoethyl ester is subjected to atom transfer radical polymerization on the surface of the stainless steel, and linear or cross-linked polymethyl methacrylate dimethyl aminoethyl ester is grafted on the surface of the stainless steel. The functionalized stainless steel has good antifouling and anti-biological corrosion functions in marine environment. Compared with the prior art, the method has low cost and long service life, can efficiently and environmentally prevent fouling and biological corrosion of the stainless steel, and does not generate any by-product, so that the method for functionally modifying the stainless steel has good application prospect in the field of oceans.
Description
Technical Field
The invention belongs to the field of stainless steel antifouling and biological corrosion prevention, and particularly relates to a method for achieving antifouling and biological corrosion prevention in a marine environment by utilizing polymer functionalized stainless steel.
Background
Stainless Steel (SS) is the most widely used engineering material in marine applications because of its resistance to corrosion over other materials. However, the original stainless steel surface is still easily polluted by marine organism attachments, algae such as barnacles, bacteria and other marine organisms easily scale on the stainless steel surface, and a biofilm is formed in the process, and once the biofilm is formed, the physical degradation and the biological degradation of the stainless steel surface are caused. Bioerosion is a delicate problem in the marine industry, resulting in severe structural damage to stainless steel, increasing fuel consumption and maintenance costs. Therefore, stainless steel is the most widely used material in the marine industry, and the improvement of the antifouling and biological corrosion resistance of stainless steel has hidden huge social wealth, and the antifouling and biological corrosion prevention technology of stainless steel has become the sunward industry of the marine ship industry at home and abroad nowadays.
At present, the surface property of stainless steel is changed mainly by physical and chemical treatment or surface modification, wherein the chemical treatment method is mainly acid pickling passivation. The method specifically comprises the following steps: firstly, wiping off oil dirt on the surface of stainless steel; then the stainless steel pickling passivation paste is evenly stirred, and a protective layer is formed outside the stainless steel, which is generally chromium salt formed by chromium in the passivation solution. The problems of the method are that: the passivation solution contains toxic reagents such as heavy metal salts and the like, and generates a large amount of acid-base waste liquid, which causes serious pollution and harm to the ecological environment and human health if the passivation solution is not treated by a proper method. The most commonly used antifouling surface polymers in the surface modification method are polyethylene glycol and its derivatives, but polyethylene glycol is easily oxidized in a complex medium, and thus its long-term use is limited.
Therefore, how to perform surface functionalization modification on stainless steel and realize effective utilization of resources is one of the important problems facing human society.
Disclosure of Invention
Aiming at the defects of the existing stainless steel protection technology, the invention provides a method for grafting a polymer on the surface of stainless steel for modification, and the method has the advantages of safety, no toxicity, high efficiency and environmental protection.
The present invention provides a method for enhancing resistance to biological corrosion and contamination using a polymer functionalized stainless steel substrate. The method adopts a linear or cross-linked polymer material to modify the surface of the stainless steel, wherein the polymer material is polymethyl methacrylate dimethyl amino ethyl ester (P) (DMAEMA) and derivatives thereof introduced with quaternary ammonium groups. Dopamine is self-polymerized on the surface of the stainless steel to anchor an alkyl bromine atom transfer radical polymerization initiator, then methacrylic acid dimethyl aminoethyl ester is subjected to atom transfer radical polymerization on the surface of the stainless steel, and linear or cross-linked polymethyl methacrylate dimethyl aminoethyl ester is grafted on the surface of the stainless steel. The method has the advantages that the functionalized stainless steel has good antifouling and biological corrosion prevention functions in the marine environment.
A method for improving marine organism corrosion and pollution resistance of a stainless steel plate is characterized by comprising the following steps:
(1) preparation of Polymer functionalized stainless Steel
Firstly, anchoring an alkyl bromine atom transfer radical polymerization initiator on the surface of stainless steel with a polydopamine coating, and then grafting linear or crosslinked polymethyl methacrylate dimethyl aminoethyl methacrylate on the surface of the stainless steel through atom transfer radical polymerization to obtain polymer functionalized stainless steel;
(2) simulation application of polymer functionalized stainless steel to marine environment
Respectively carrying out a coffee double-eyebrow algae attachment experiment, a barnacle venus larva settlement experiment, an antibacterial activity experiment on pseudomonas and a corrosion experiment on the surface functionalized stainless steel on the polymer functionalized stainless steel prepared in the step (1); the culture broth used in the bacterial corrosion experiments was based on filtered seawater.
According to the method for improving the marine organism corrosion and pollution resistance of the stainless steel plate, linear or cross-linked polydimethylaminoethyl methacrylate is grafted on the surface of the stainless steel through atom transfer radical polymerization in the step (1), and then the polymer on the surface of the stainless steel after the polymer functionalization is further treated and quaternized.
Further, the method for preparing the polymer functionalized stainless steel in the step (1) comprises the following steps:
1) the process of anchoring alkyl bromine atom transfer radical polymerization initiator is: the polydopamine coated stainless steel SS-PDA substrate is immersed in 10-20mL of dichloromethane containing 1.0-1.3mL (about 7.2mmol) of triethylamine and cooled in an ice-water mixture; 5mL of methylene chloride containing 0.9-1.2mL (about 7.2mmol) of 2-bromoisobutyryl bromide was added dropwise to the mixture; then, the reaction mixture is stirred for 24 hours at room temperature, and then is washed by a large amount of acetone, ethanol and deionized water and dried;
2) grafting linear polymethyl methacrylate dimethyl amino ethyl ester on the surface of the stainless steel in the step 1) through atom transfer radical polymerization, wherein the process is as follows: [ DMAEMA]：[CuCl]：[CuCl2]：[Bpy]The molar charge ratio is 100: 1:0.2:1, carrying out surface-initiated atom transfer radical polymerization in a high-boron silicon tube; stirring and degassing for 20-40 minutes under argon, and introducing an SS-PDA-Br substrate into the reaction mixture; the reaction tube is sealed and stored for 24 hours under the condition of 35-40 ℃ water bath to prepare the linear polymer functionalized stainless steel;
or the like, or, alternatively,
2) the process of grafting and crosslinking the polymethyl methacrylate dimethyl amino ethyl acrylate on the surface of the stainless steel in the step 1) by atom transfer radical polymerization comprises the following steps: surface-initiated atom transfer radical polymerization in a high boron silicon tube, [ DMAEMA ]: [ PEGDMA polyethylene glycol dimethacrylate ]: [ CuCl ]: [ CuCl2 ]: the molar charge ratio of [ Bpy2, 2-bipyridine ] is 100:10:1:0.2:1, and the reaction is carried out in 3-5mL of methanol; after stirring and degassing for 20-40 minutes under argon, a sample of SS-PDA-Br was introduced into the reaction mixture; the tube was hermetically stored at 35-40 ℃ in a water bath for 24 hours to produce a cross-linked polymer functionalized stainless steel.
Further, preparation of quaternized linear or crosslinked polymer functionalized stainless steels: immersing an SS-g-P or SS-g-CP substrate in 10-20mL 2-propanol solution containing 20% bromohexane in volume fraction and 0.1-0.3mL triethylamine in a high-boron silicon tube at 70 ℃ for 48 hours to prepare an SS-g-QP substrate or an SS-g-QCP surface; after quaternization, washing with acetone and deionized water, and drying to obtain the quaternized linear or crosslinked polymer functionalized stainless steel.
According to the method for improving the marine organism corrosion and pollution resistance of the stainless steel plate, the polymer is one of linear or cross-linked polymethyl methacrylate dimethyl amino ethyl ester and a ring substituted derivative or a heteroatom substituted derivative thereof, and a quaternization product and a derivative thereof.
According to the method for improving the marine organism corrosion and pollution resistance of the stainless steel plate, the bacterial types of the corrosion resistance experiment are not limited, the bacterial types include the Codiobolus coffea, the Stachys japonica larvae and the pseudomonas and have certain corrosion resistance effect on other marine bacteria.
The invention provides a method for preparing polymer functionalized stainless steel, which comprises the following steps:
1) the process of anchoring alkyl bromine atom transfer radical polymerization initiator is: the polydopamine coated stainless steel SS-PDA substrate is immersed in 10-20mL of dichloromethane containing 0.1-0.3mL (about 7.2mmol) of triethylamine and cooled in an ice-water mixture; 5-10mL of methylene chloride containing 0.9-1.3mL (about 7.2mmol) of 2-bromoisobutyryl bromide was added dropwise to the mixture; then, the reaction mixture is stirred for 24 hours at room temperature, and then is washed by a large amount of acetone, ethanol and deionized water and dried;
2) grafting linear polymethyl methacrylate dimethyl amino ethyl ester on the surface of the stainless steel in the step 1) through atom transfer radical polymerization, wherein the process is as follows: [ DMAEMA]：[CuCl]：[CuCl2]：[Bpy]The molar charge ratio is 100: 1:0.2:1, carrying out surface-initiated atom transfer radical polymerization in a high-boron silicon tube; stirring and degassing for 20-40 minutes under argon, and introducing an SS-PDA-Br substrate into the reaction mixture; the reaction tube is sealed and stored for 24 hours under the condition of 35-40 ℃ water bath to prepare the linear polymer functionalized stainless steel;
or the like, or, alternatively,
2) the process of grafting and crosslinking the polymethyl methacrylate dimethyl amino ethyl acrylate on the surface of the stainless steel in the step 1) by atom transfer radical polymerization comprises the following steps: surface-initiated atom transfer radical polymerization in a high boron silicon tube, [ DMAEMA ]: [ PEGDMA ]: [ CuCl ]: [ CuCl2 ]: [ Bpy ] the molar charge ratio is 100:10:1:0.2:1, and the reaction is carried out in 4-6mL of methanol; after stirring and degassing for 20-40 minutes under argon, a sample of SS-PDA-Br was introduced into the reaction mixture; the tube was hermetically stored at 35-40 ℃ in a water bath for 24 hours to produce a cross-linked polymer functionalized stainless steel.
According to the method for preparing the polymer functionalized stainless steel, the surface polymer of the stainless steel after the polymer functionalization is further treated to be quaternized: immersing an SS-g-P or SS-g-CP substrate in 10-20mL 2-propanol solution containing 20% bromohexane in volume fraction and 0.1-0.3mL triethylamine in a high-boron silicon tube at 70 ℃ for 48 hours to prepare an SS-g-QP substrate or an SS-g-QCP surface; after quaternization, washing with acetone and deionized water, and drying to obtain the quaternized linear or crosslinked polymer functionalized stainless steel.
The present invention also provides a polymer functionalized stainless steel prepared by the above method of preparing a polymer functionalized stainless steel.
1mg of the final reaction product in the preparation method of the present invention may be modified by 2 x 2cm2Stainless steel surface.
Detailed description of the invention:
a method for improving marine organism corrosion and pollution resistance of a stainless steel plate specifically comprises the following steps:
(1) preparation of Polymer functionalized stainless Steel
Firstly, anchoring an alkyl bromine atom transfer radical polymerization initiator on the surface of stainless steel with a polydopamine coating, and then grafting linear or crosslinked polymethyl methacrylate dimethyl amino ethyl ester on the surface of the stainless steel through atom transfer radical polymerization. And the further treatment is to quaternize the polymer on the surface of the stainless steel after the polymer is functionalized.
(2) Simulation application of polymer functionalized modified stainless steel in marine environment
Respectively carrying out a coffee double-eyebrow algae attachment experiment, a barnacle venus larva settlement experiment, an antibacterial activity experiment on pseudomonas and a corrosion experiment on the surface functionalized stainless steel on the functionalized stainless steel prepared in the step (1). In order to simulate the marine environment in the bacterial corrosion experiment and quantitatively detect the biological corrosion resistance effect of certain bacteria, the culture solution is based on filtered seawater. The bacteria selected in the experiment are typical bacterial strains which widely exist in the sea and corrode the ship body.
The polymer is linear or cross-linked polymethyl methacrylate dimethyl amino ethyl ester and one of ring substitution derivatives or heteroatom substitution derivatives thereof, including quaternization products and derivatives thereof.
The bacteria species of the biological corrosion resistance experiment are not limited, and the bacteria species not only comprise the coffee double eyebrow algae, the barnacle cyprids and the pseudomonas, but also have certain corrosion resistance to other marine bacteria.
The specific experimental procedure for the preparation of polymer functionalized stainless steel is shown in fig. 7:
introduction of alkyl bromides into stainless steel substrates as ATRP initiators
The polydopamine coated stainless steel (SS-PDA) substrate was immersed in a solution of 1.0mL (7.2mmol) triethylamine in 10mL dichloromethane and cooled to 0 ℃ in a mixture of ice and water. Then a solution of 0.9mL (7.2mmol) of 2-bromoisobutyryl bromide in 5mL of methylene chloride was added dropwise to the mixture, and the mixture was stirred at room temperature for 24 hours. The alkyl bromide modified stainless steel surface (SS-PDA-Br) was washed with copious amounts of acetone, ethanol and deionized water. Finally, the mixture was dried under reduced pressure in a vacuum drying oven.
Surface-initiated methyl methacrylate (DMAEMA) atom transfer radical polymerization [ DMAEMA ]: [ CuCl ]: [ CuCl2 ]: [ Bpy ] molar feed ratio 100: 1:0.2:1 surface initiated atom transfer radical polymerization in a high boron silicon tube. After stirring and evacuation under argon for 20 minutes, a sample of SS-PDA-Br was added to the reaction mixture. The reaction tube was hermetically stored at 35 ℃ in a water bath for 24 hours to cause polymeric grafting of DMAEMA on the stainless steel surface. The product is SS-g-P for short.
Preparation of crosslinked P (DMAEMA) brush on surface of 3, SS-PDA-Br
Polyethylene glycol dimethacrylate (PEGDMA) was used as a crosslinker. Surface-initiated atom transfer radical polymerization in a high boron silicon tube, [ DMAEMA ]: [ PEGDMA ]: [ CuCl ]: [ CuCl2 ]: [ Bpy ] molar feed ratio 100:10:1:0.2:1, in 4mL of methanol. After stirring and evacuation under argon for 20 minutes, SS-PDA-Br was added to the reaction mixture. The reaction tube is sealed and stored for 24 hours under the condition of 35 ℃ water bath, thereby preparing the stainless steel surface with crosslinked P (DMAEMA), namely SS-g-CP surface for short.
Quaternary amination of 4, SS-g-P and SS-g-CP surfaces
In a high-boron silicon tube at 70 ℃, the SS-g-P and SS-g-CP substrates were immersed in 10mL 2-propanol solution containing 20% volume fraction bromohexane and 0.1mL triethylamine for 48 hours to produce quaternized stainless steel surfaces, respectively referred to as SS-g-QP and SS-g-QCP surfaces. After quaternization, the sample was washed sequentially with copious amounts of acetone and deionized water to remove unreacted bromohexane, and then dried in a vacuum oven overnight.
Compared with the prior art, the method for improving the biological corrosion resistance and the pollution resistance by utilizing the polymer functionalized stainless steel substrate has the following beneficial effects:
(1) the polymer functionalized modified stainless steel substrate is utilized to improve the capability of resisting biological corrosion, and the stainless steel material on the surface of the ship body of ocean and other water areas can be effectively protected without energy consumption and environment friendliness; and the method for modifying the stainless steel by the polymer can effectively prevent bacterial microorganisms in the ocean from inhabitation and has good anti-pollution effect.
(2) The polymer has simple synthesis method and is easy to be widely used for mass production.
Drawings
FIG. 1 is a fluorescence microscopic image of Coffea bicolor on the surface of each sample: (A) raw stainless steel (B) SS-PDA-Br (C) SS-g-P (D) SS-g-CP (E) SS-g-QP (F) SS-g-QCP.
FIG. 2 is a graph showing the relative degree of adhesion of Coffea amabilis on the surface of pristine stainless steel and the surface of functionalized stainless steel.
Figure 3 is the percentage of settled and dead cyprids on the surface of virgin and functionalized stainless steel.
FIG. 4 shows fluorescence micrographs of Pseudomonas on the surface of each sample (viable cells: a, c, e, g; dead cells: b, d, f, h) (a, b) raw stainless steel, (c, d) SS-PDA-Br, (e, f) SS-g-QP, (g, h) SS-g-QCP.
FIG. 5 shows the survival of Pseudomonas adhered to the surface of a specimen.
Fig. 6 is a tafel polarization curve.
FIG. 7 is a schematic flow diagram of the preparation of a polymer functionalized stainless steel.
Detailed Description
The following provides a specific embodiment of the method for improving the marine corrosion and pollution resistance of the stainless steel plate.
Example 1:
in this example, the preparation process of the polymer functionalized modified stainless steel is as follows:
(1) the process of anchoring alkyl bromine atom transfer radical polymerization initiator is: the polydopamine coated stainless steel (SS-PDA) substrate was immersed in 10mL of dichloromethane containing 1.0mL (7.2mmol) of triethylamine and cooled in an ice-water mixture. 5mL of methylene chloride containing 0.9mL (7.2mmol) of 2-bromoisobutyryl bromide was added dropwise to the mixture. Thereafter, the reaction mixture was stirred at room temperature for 24 hours. The stainless steel (SS-PDA-Br substrate for short) anchored with initiator was washed with a large amount of acetone, ethanol and deionized water. Finally, the mixture was dried under reduced pressure in a vacuum drying oven.
(2) Grafting linear polymethyl methacrylate dimethyl amino ethyl ester on the surface of the stainless steel in the step (1) through atom transfer radical polymerization, wherein the process is as follows: [ DMAEMA]：[CuCl]：[CuCl2]：[Bpy]The molar charge ratio is 100: 1:0.2:1 surface initiated atom transfer radical polymerization in a high boron silicon tube. After stirring and degassing for 20 minutes under argon, the SS-PDA-Br substrate was introduced into the reaction mixture. The reaction tube is sealed and stored for 24 hours under the condition of 35 ℃ water bath, and a linear polymer functionalized stainless steel surface (SS-g-P surface for short) is prepared.
In order to verify the antifouling and anti-biofouling capabilities of the linear polymer functionalized stainless steel prepared as described above, the following steps (3) to (6) were carried out:
(3) a culture solution of Coffea bisporus was prepared, and a fluorescence microscope image of Coffea bisporus cells attached to a sample after soaking in an algae suspension for 24 hours was obtained on the sample using a microscope equipped with an excitation filter of 535nm and an emission filter of 617 nm.
(4) Transferring each precipitated substrate from step (3) to 2mL of 30% salinity, 0.22 μm filtered seawater. The ultrasonic bath was immersed for 10 minutes to strip settled coffee brow algae. Subsequently, 200 μ L aliquots were transferred to 96-well microplates (polysulfone substrate). At an excitation wavelength (lambda) of 440nmex) The fluorescence intensity of each well was measured at 690nm on a microplate reader. The fluorescence intensity of the filtered seawater of 30% salinity and 0.22 μm is set as blank. Each measurement was averaged in triplicate.
Observing the fluorescence microscopic image of the SS-g-P substrate surface in the figure 1 obtained in the step (3), comparing with the original stainless steel fluorescence microscopic image, the great reduction of the attached coffee double eyebrow algae cells can be visually seen. As can be seen from the figure, the SS-g-P surface was effective in reducing adhesion of cells of Coffea elata.
The above step (4) resulted in the relative degree of adhesion of the Coffea brevicornus on the original stainless steel surface and the functionalized stainless steel surface of FIG. 2. The adhesion of Cowberries on the SS-g-P substrate surface was reduced to 38% compared to the original stainless steel surface. It can also be seen from this figure that the SS-g-P substrate surface is effective in reducing the adhesion of cells of Coffea brows.
(5) 0.5mL of filtered seawater containing about 40 cyprids of Stauntonia barnacii was added to 2cm by 2cm samples of the original or modified stainless steel substrate, respectively. The culture was carried out in the dark at room temperature for 24 hours. The total number of colonized larvae was observed under a microscope. And taking an average value by three times of detection.
The above step (5) resulted in the percentage of settled and dead cyprids on the original and functionalized stainless steel surfaces of figure 3. As can be seen from the figure, about 68% of the balanus venomous larvae settle on the original stainless steel surface, indicating their high susceptibility to biofouling. In contrast, the surface settling fraction of the stainless steel after polymer grafting was substantially reduced, 15% of the SS-g-P substrate surface.
(6) Pseudomonas was used to observe the adhesion characteristics and bactericidal effect of the antimicrobial polymer coating. The pseudomonads are cultured in seawater rich in nutrients. After incubation, the bacterial suspension was centrifuged again at 2700 cycles and the supernatant was separated. The bacterial cells were washed twice with artificial seawater and resuspended at a concentration of 107 cells per square centimeter. Each substrate was cut into 1cm X1 cm, immersed in 1mL of bacterial suspension under static conditions at 37 ℃ for 4 hours, and then rinsed three times with pure water to remove non-sticky bacteria. To determine the number of viable bacterial cells on the functionalized stainless steel surface, quantitative in vitro antibacterial assays were performed using the extended plate method.
The survival of the Pseudomonas adhered to the surface of the sample obtained in FIG. 5 was expressed by the number of cells per square centimeter of the sample in the above step (6). The number of living cells per square centimeter of the original stainless steel surface is higher than 106While the SS-g-P surface was reduced to 4X 105. This indicates that in SS-g-The survival rate of the bacteria on the surface of the P is reduced, so that the biological corrosion is effectively reduced.
Experiments show that the linear polymer functionalized stainless steel has better performance of preventing living beings inhabitation and biological corrosion, and can effectively reduce the corrosion loss of a ship body when being applied to a marine ship, thereby effectively saving resources and maintenance cost.
Example 2:
the functionalized stainless steel of this example uses the same SS-PDA-Br substrate as in example 1, except that the graft cross-linked polydimethylaminoethyl methacrylate is prepared as follows:
the process of grafting and crosslinking the polymethyl methacrylate dimethyl amino ethyl ester on the surface of the stainless steel through atom transfer radical polymerization comprises the following steps: surface-initiated atom transfer radical polymerization in a high boron silicon tube, [ DMAEMA ]: [ PEGDMA ]: [ CuCl ]: [ CuCl2 ]: [ Bpy ] the molar charge ratio was 100:10:1:0.2:1, and the reaction was carried out in 4mL of methanol. After stirring and degassing for 20 minutes under argon, a sample of SS-PDA-Br was introduced into the reaction mixture. The reaction tube was sealed and stored for 24 hours at 35 ℃ in a water bath to produce a cross-linked polymer functionalized stainless steel (SS-g-CP substrate for short).
To verify the antifouling and anti-biofouling capabilities of the cross-linked polymer functionalized stainless steel prepared as described above, the procedure was exactly the same as in example 1.
The cross-linked polymer functionalized stainless steel is tested in the coffee eyebrow growth medium to obtain a fluorescence microscopic image of the SS-g-CP substrate surface in figure 1, and compared with the original stainless steel fluorescence microscopic image, the fluorescent microscopic image can visually show that a great amount of attached coffee eyebrow growth cells are reduced. As can be seen from the figure, the SS-g-CP basal surface was also effective in reducing adhesion of cells of Coffea elata.
Experiments with cross-linked polymer functionalized stainless steel in the culture of coffee brow algae gave the relative degree of adhesion of coffee brow algae on the surface of the original stainless steel and the functionalized stainless steel in FIG. 2. The adhesion of Cowberries on the SS-g-CP substrate surface was reduced to 33% compared to the original stainless steel surface. As can be seen from the figure, the SS-g-CP basal surface was also effective in reducing adhesion of cells of Coffea elata.
Cross-linked polymer functionalized stainless steel the percentage of settled and dead cyprids on the raw and functionalized stainless steel surfaces of figure 3 was obtained in the barnacle cyprid larvae experiment. From this figure, it can be seen that the fraction of stainless steel surface settlement after cross-linked polymer grafting is substantially reduced compared to about 68% of the barnacle venus larvae settling on the original stainless steel surface, 4% of the SS-g-CP substrate surface.
Cross-linked polymer functionalized stainless steels in the Pseudomonas experiments gave FIG. 5 the survival of Pseudomonas adhered to the surface of the samples, the survival being expressed in number of cells per square centimeter of sample. The number of living cells per square centimeter of the original stainless steel surface is higher than 106While the surface of the SS-g-CP substrate is reduced to 2X 105. This indicates that bacterial survival is also reduced on the surface of the SS-g-CP substrate, which is effective in reducing bio-erosion.
Example 3:
the SS-g-P substrate used in this example was exactly the same as the procedure used in example 1. Except that the SS-g-P substrate was then quaternized by the following specific steps:
(1) in a high-boron silicon tube at 70 ℃, the SS-g-P substrate was immersed in 10mL 2-propanol solution containing 20% bromohexane by volume fraction and 0.1mL triethylamine for 48 hours to prepare SS-g-QP substrate, respectively. After quaternization, the sample was washed sequentially with copious amounts of acetone and deionized water to remove unreacted bromohexane, and then dried in a vacuum oven overnight.
To verify the antifouling and anti-bioerosion capabilities of the cross-linked polymer functionalized stainless steel prepared as described above, the previous experimental procedure was the same as in example 1, except that the Tafel polarization curve was examined after exposure to the Pseudomonas inoculation medium to obtain the Tafel slope (. beta.)cAnd betaa) Corrosion potential (E)corr) And corrosion current density (i)corr) The results of the analysis are shown in Table 1.
The fluorescence microscopic image of the SS-g-CP substrate surface in the figure 1 is obtained by the experiment of the quaternized linear polymer functionalized stainless steel in the coffee eyebrow growth medium, and compared with the original stainless steel fluorescence microscopic image, the attached coffee eyebrow growth cell is greatly reduced. As can be seen from the figure, the SS-g-QP substrate surface was also effective in reducing adhesion of cells of Coffea bifida.
Experiments with quaternized linear polymer functionalized stainless steel in the culture broth of coffee brow algae gave the relative degree of adherence of coffee brow algae on the raw stainless steel surface and the functionalized stainless steel surface in fig. 2. The SS-g-QP substrate surface adhesion of the coffee brow was reduced to 24% compared to the original stainless steel surface. As can be seen from the figure, the SS-g-QP substrate surface was also effective in reducing adhesion of cells of Coffea bifida.
Quaternized linear polymer functionalized stainless steels the percentage of settled and dead cyprids on the raw and functionalized stainless steel surfaces of fig. 3 was obtained in the barnacle cyprid larvae experiment. From this figure, it can be seen that the fraction of settled on the surface of the stainless steel after grafting of the cross-linked polymer is much reduced compared to about 68% of the barnacle venus larvae settled on the original stainless steel surface, 8% of the SS-g-QP substrate surface.
Quaternized linear polymer functionalized stainless steel fluorescence microscopy images of pseudomonas adhesion to the surface of the test specimens were obtained in pseudomonas experiments as shown in fig. 4. As can be seen visually in the figure, the SS-g-QP basal surface has a large reduction in viable cells and an increase in dead cells. Indicating that quaternized linear polymer functionalized stainless steels are effective in preventing bacterial colonization.
Quaternized linear polymer functionalized stainless steels in the pseudomonas experiment gave the survival status of pseudomonas adhered to the surface of the sample of fig. 5, the survival rate is expressed in number of cells per square centimeter of the sample. The number of living cells per square centimeter of the original stainless steel surface is higher than 106While the surface of the SS-g-QP substrate is reduced to 4X 104. This indicates that the bacterial survival rate is also reduced on the surface of the SS-g-QP substrate, which is effective in reducing the biological corrosion.
The Tafel polarization curves of FIG. 6, the original and surface functionalized samples exposed to sterile and Pseudomonas inoculation media, were obtained in a Pseudomonas experiment and analyzed to obtain the Tafel slope (. beta.)cAnd betaa) Corrosion potential (E)corr) And corrosion current density (i)corr) The values of (A) and (B) are shown in Table 1. The corrosion potential of the original sample remains relatively constant with the exposure time in sterile medium, whereas in pseudomonas inoculation medium the negative direction is actively shifted, which is generally due to the anodic dissolution process in mixed potential theory. For the polymer grafted samples, the corrosion potential undergoes a significant shift relative to the original samples inoculated with pseudomonas. The corrosion potential is enhanced, indicating enhanced corrosion resistance. Corrosion current density (i) of the original sample due to passivation of the surface filmcorr) Still small, and even slightly degraded in sterile media. However, corrosion current density (i) of the original stainless steel couponcorr) The value increased gradually with the exposure time in the inoculation medium and reached about 12.85. mu.A-cm after 35 days of exposure-2Indicating that the corrosion rate is significantly increased under the action of Pseudomonas. As for the polymer coating samples, the corrosion current density was significantly reduced. This also indicates that the corrosion resistance of stainless steel is well strengthened. I of SS-g-QP sample compared to the original sample after 21 days exposure of Pseudomonas inoculation MediumcorrAre reduced by about 6 times, respectively. The results show that the polymer coating has good protective properties against bio-corrosion by pseudomonas. The Inhibition Efficiency (IE) of the SS-g-QP samples was higher than 83% after 21 days of exposure.
Example 4:
the SS-g-CP substrate used in this example was exactly the same as that used in example 2. Except that the SS-g-CP substrate was then quaternized by the following specific steps:
(1) the SS-g-CP substrate was immersed in 10mL 2-propanol solution containing 20% volume fraction bromohexane and 0.1mL triethylamine in a high-boron silicon tube at 70 deg.C for 48 hours to prepare SS-g-QCP surfaces, respectively. After quaternization, the sample was washed sequentially with copious amounts of acetone and deionized water to remove unreacted bromohexane, and then dried in a vacuum oven overnight.
To verify the antifouling and anti-biofouling capabilities of the cross-linked polymer functionalized stainless steels prepared as described above, the foregoing experimental methods and examples2 same, only different from the previous step, detecting the Tafel polarization curve of the strain after the strain is exposed in the pseudomonas inoculation culture medium to obtain the Tafel slope (beta)cAnd betaa) Corrosion potential (E)corr) And corrosion current density (i)corr) The results of the analysis are shown in Table 1.
The fluorescence microscopic image of the SS-g-CQP substrate surface in figure 1 obtained by the experiment of the quaternized cross-linked polymer functionalized stainless steel in the coffee agrimonia pilosa culture solution can be compared with the original stainless steel fluorescence microscopic image, and the great reduction of the attached coffee agrimonia pilosa cells can be visually seen. As can be seen from the figure, the SS-g-CQP substrate surface was also effective in reducing the adhesion of cells of Coffea elata.
Experiments with quaternized cross-linked polymer functionalized stainless steel in the culture broth of coffee brow yielded the relative degree of adherence of coffee brow algae on the raw stainless steel surface and the functionalized stainless steel surface in fig. 2. The adherence of Cowbergia was reduced to 20% on the SS-g-CQP substrate surface compared to the original stainless steel surface. As can be seen from the figure, the SS-g-CQP substrate surface was also effective in reducing the adhesion of cells of Coffea elata.
Quaternized cross-linked polymer functionalized stainless steel the percentage of settled and dead cyprids on the raw and functionalized stainless steel surfaces of figure 3 was obtained in the barnacle cyprid larvae experiment. From this figure, it can be seen that the fraction of stainless steel surface settlement after cross-linked polymer grafting is substantially reduced compared to about 68% of the barnacle cyprid larvae settling on the original stainless steel surface, which is 0% for the SS-g-CQP substrate surface.
Quaternized linear polymer functionalized stainless steel fluorescence microscopy images of pseudomonas adhesion to the surface of the test specimens were obtained in pseudomonas experiments as shown in fig. 4. As can be seen visually in the figure, the SS-g-QP basal surface was greatly reduced in viable cells, while the dead cells were not increased. The quaternized linear polymer functionalized stainless steel can effectively prevent bacteria from inhabitation and has no influence on the environment.
Quaternary ammonium crosslinked Polymer functionalized stainless steels in Pseudomonas experiments the survival of Pseudomonas adhered to the surface of the test specimens was obtained in FIG. 5, survival in terms of Per SquareThe number of cells in a centimeter sample. The number of living cells per square centimeter of the original stainless steel surface is higher than 106While the surface of the SS-g-CQP substrate is reduced to 103. This indicates that the amount of bacteria surviving on the surface of the SS-g-CQP substrate is greatly reduced, which is effective in reducing the bio-corrosion.
The Tafel polarization curves of FIG. 6, the original and surface functionalized samples exposed to sterile and Pseudomonas inoculation media, were obtained in a Pseudomonas experiment and analyzed to obtain the Tafel slope (. beta.)cAnd betaa) Corrosion potential (E)corr) And corrosion current density (i)corr) The values of (A) and (B) are shown in Table 1. The corrosion potential of the original sample remains relatively constant with the exposure time in sterile medium, whereas in pseudomonas inoculation medium the negative direction is actively shifted, which is generally due to the anodic dissolution process in mixed potential theory. For the polymer grafted samples, the corrosion potential undergoes a significant shift relative to the original samples inoculated with pseudomonas. The corrosion potential is enhanced, indicating enhanced corrosion resistance. Corrosion current density (i) of the original sample due to passivation of the surface filmcorr) Still small, and even slightly degraded in sterile media. However, corrosion current density (i) of the original stainless steel couponcorr) The value increased gradually with the exposure time in the inoculation medium and reached about 12.85. mu.A-cm after 35 days of exposure-2Indicating that the corrosion rate is significantly increased under the action of Pseudomonas. As for the polymer coating samples, the corrosion current density was significantly reduced. This also indicates that the corrosion resistance of stainless steel is well strengthened. I of SS-g-CQP sample compared to the original sample after 21 days of Pseudomonas inoculation Medium ExposurecorrAre reduced by about 12 times, respectively. The results show that the polymer coating has good protective properties against bio-corrosion by pseudomonas. The SS-g-CQP samples had an Inhibitory Efficiency (IE) of greater than 92% after 21 days of exposure. The quaternized cross-linked polymer functionalized stainless steel has very obvious antifouling and biological corrosion prevention effects, has great use value and great commercial value, and is also beneficial to resource saving and marine environment protection.
βc: the tafel slope of the cathodic polarization curve.
βa: the tafel slope of the anodic polarization curve.
Ecorr: corrosion potential when the polarization current is zero.
CR: the rate of corrosion.
IE: suppression efficiency
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for improving marine organism corrosion and pollution resistance of a stainless steel plate is characterized by comprising the following steps:
(1) preparation of Polymer functionalized stainless Steel
Firstly, anchoring an alkyl bromine atom transfer radical polymerization initiator on the surface of stainless steel with a polydopamine coating, and then grafting linear or crosslinked polymethyl methacrylate dimethyl aminoethyl methacrylate on the surface of the stainless steel through atom transfer radical polymerization to obtain polymer functionalized stainless steel;
(2) simulation application of polymer functionalized stainless steel to marine environment
Respectively carrying out a coffee double-eyebrow algae attachment experiment, a barnacle venus larva settlement experiment, an antibacterial activity experiment on pseudomonas and a corrosion experiment on the surface functionalized stainless steel on the polymer functionalized stainless steel prepared in the step (1); the culture solutions used in the bacterial corrosion experiments were all based on filtered seawater;
the method for preparing the polymer functionalized stainless steel in the step (1) comprises the following steps:
1) the process of anchoring alkyl bromine atom transfer radical polymerization initiator is: immersing a stainless steel substrate with a polydopamine coating on the surface into 10-20mL of dichloromethane containing 1.0-1.3mL of triethylamine, and cooling in an ice-water mixture; 5mL of methylene chloride containing 0.9-1.2mL of 2-bromoisobutyryl bromide was added dropwise to the mixture; then, the reaction mixture is stirred for 24 hours at room temperature, and then is washed by a large amount of acetone, ethanol and deionized water and dried;
2) grafting linear polymethyl methacrylate dimethyl amino ethyl ester on the surface of the stainless steel in the step 1) through atom transfer radical polymerization, wherein the process is as follows: [ dimethylaminoethyl methacrylate ]: [ cuprous chloride ]: [ copper chloride ]: [ 2' 2-bipyridine ] molar feed ratio is 100: 1:0.2:1, carrying out surface-initiated atom transfer radical polymerization in a high-boron silicon tube; stirring and degassing for 20-40 min under argon gas condition, and introducing a stainless steel substrate with an alkyl bromine atom transfer radical polymerization initiator on the surface into the reaction mixture; the reaction tube is sealed and stored for 24 hours under the condition of 35-40 ℃ water bath to prepare the linear polymer functionalized stainless steel;
or the like, or, alternatively,
2) the process of grafting and crosslinking the polymethyl methacrylate dimethyl amino ethyl acrylate on the surface of the stainless steel in the step 1) by atom transfer radical polymerization comprises the following steps: surface-initiated atom transfer radical polymerization in a high-boron silicon tube, [ dimethylaminoethyl methacrylate ]: [ polyethylene glycol dimethacrylate ]: [ cuprous chloride ]: [ copper chloride ]: the molar charge ratio of [ 2' 2-bipyridyl ] is 100:10:1:0.2:1, and the reaction is carried out in 3-5mL of methanol; after stirring and degassing for 20-40 minutes under argon, introducing a stainless steel sample with an alkyl bromine atom transfer radical polymerization initiator on the surface into the reaction mixture; the tube was hermetically stored at 35-40 ℃ in a water bath for 24 hours to produce a cross-linked polymer functionalized stainless steel.
The species of the corrosion-resistant bacteria are Coffea biennis, Staphyloccocus pulmonarius larvae and Pseudomonas sp.
2. The method for improving the marine organism corrosion and pollution resistance of the stainless steel plate according to claim 1, wherein in the step (1), after grafting linear or crosslinked polydimethylaminoethyl methacrylate on the surface of the stainless steel through atom transfer radical polymerization, the polymer on the surface of the stainless steel after polymer functionalization is further treated and quaternized.
3. A method of improving the marine corrosion and pollution resistance of stainless steel sheets according to claim 2, wherein the preparation of the quaternized linear or crosslinked polymer functionalized stainless steel: immersing a stainless steel substrate with a surface grafted with a linear polymer or a stainless steel substrate with a surface grafted with a crosslinked polymer in 10-20mL of 2-propanol solution containing 20% of bromohexane in volume fraction and 0.1-0.3mL of triethylamine for 48 hours in a high-boron silicon tube at 70 ℃ to prepare the stainless steel substrate with the surface grafted with the linear polymer or the stainless steel substrate with the surface grafted with the crosslinked polymer; after quaternization, washing with acetone and deionized water, and drying to obtain the quaternized linear or crosslinked polymer functionalized stainless steel.
4. The method of claim 1, wherein the polymer is one of linear or cross-linked polydimethylaminoethyl methacrylate and their ring-substituted or heteroatom-substituted derivatives, including quaternized products and derivatives thereof.
5. A method of making a polymer functionalized stainless steel comprising the steps of:
1) the process of anchoring alkyl bromine atom transfer radical polymerization initiator is: immersing a stainless steel substrate with a polydopamine coating on the surface into 10-20mL of dichloromethane containing 0.1-0.3mL of triethylamine, and cooling in an ice-water mixture; 5-10mL of methylene chloride containing 0.9-1.3mL of 2-bromoisobutyryl bromide was added dropwise to the mixture; then, the reaction mixture is stirred for 24 hours at room temperature, and then is washed by a large amount of acetone, ethanol and deionized water and dried;
2) grafting linear polymethyl methacrylate dimethyl amino ethyl ester on the surface of the stainless steel in the step 1) through atom transfer radical polymerization, wherein the process is as follows: [ dimethylaminoethyl methacrylate ]: [ cuprous chloride ]: [ copper chloride ]: [ 2' 2-bipyridine ] molar feed ratio is 100: 1:0.2:1, carrying out surface-initiated atom transfer radical polymerization in a high-boron silicon tube; stirring and degassing for 20-40 min under argon gas condition, and introducing a stainless steel substrate with an alkyl bromine atom transfer radical polymerization initiator on the surface into the reaction mixture; the reaction tube is sealed and stored for 24 hours under the condition of 35-40 ℃ water bath to prepare the linear polymer functionalized stainless steel;
or the like, or, alternatively,
2) the process of grafting and crosslinking the polymethyl methacrylate dimethyl amino ethyl acrylate on the surface of the stainless steel in the step 1) by atom transfer radical polymerization comprises the following steps: surface-initiated atom transfer radical polymerization in a high-boron silicon tube, [ dimethylaminoethyl methacrylate ]: [ polyethylene glycol dimethacrylate ]: [ cuprous chloride ]: [ copper chloride ]: the molar charge ratio of [ 2' 2-bipyridyl ] is 100:10:1:0.2:1, and the reaction is carried out in 4-6mL of methanol; after stirring and degassing for 20-40 minutes under argon, introducing a stainless steel sample with an alkyl bromine atom transfer radical polymerization initiator on the surface into the reaction mixture; the tube was hermetically stored at 35-40 ℃ in a water bath for 24 hours to produce a cross-linked polymer functionalized stainless steel.
6. A method of making a polymer functionalized stainless steel according to claim 5 wherein the surface of the polymer functionalized stainless steel is further treated to quaternize: immersing a stainless steel substrate surface-grafted with a linear polymer or a stainless steel substrate surface-grafted with a crosslinked polymer in a 10-20mL of 2-propanol solution containing 20% by volume of bromohexane and 0.1-0.3mL of triethylamine for 48 hours in a high-boron silicon tube at 70 ℃ to obtain a stainless steel substrate surface-grafted with a quaternized linear polymer or a stainless steel substrate surface-grafted with a quaternized crosslinked polymer; after quaternization, washing with acetone and deionized water, and drying to obtain the quaternized linear or crosslinked polymer functionalized stainless steel.
7. A polymer functionalized stainless steel produced by the method of producing a polymer functionalized stainless steel of claim 5 or 6.
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| CN102119192A (en) * | 2008-08-13 | 2011-07-06 | 阿克佐诺贝尔国际涂料股份有限公司 | Polymer with salt groups and antifouling coating composition comprising said polymer |
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| CN101891867A (en) * | 2010-04-30 | 2010-11-24 | 中国科学院长春应用化学研究所 | Method for preparing SiO2-poly(dimethylaminoethyl methacrylate) (PDMAEMA) nanoparticles having core-shell structure |
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