CN114231963B - Method for controlling carbon steel corrosion and preparing nano material based on biomineralization principle - Google Patents
Method for controlling carbon steel corrosion and preparing nano material based on biomineralization principle Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention belongs to the technical field of metal corrosion protection and nano material preparation, and particularly relates to a method for controlling carbon steel corrosion and preparing nano material based on a biomineralization principle. The biomineralization coating disclosed by the invention can realize self-repair by utilizing the activity of bacteria, can be prepared in a large scale under mild conditions, and has low cost. In addition, the nano functional material with special morphology can also be prepared by utilizing the principle of biomineralization. Therefore, the invention not only can inhibit metal corrosion by forming a biological coating, but also has the function of nano material synthesis, and has important application prospect in the fields of corrosion control of ocean engineering equipment, synthesis and application of functional nano materials.
Description
Technical Field
The invention belongs to the technical field of metal corrosion protection and nano material preparation, and particularly relates to a method for controlling carbon steel corrosion and preparing a nano material based on a biomineralization principle.
Background
Carbon steel is widely used in production and life because of its advantages of abundant raw materials, easy processing, low price, good technological properties, etc. Among them, X80 steel has wide application in petroleum and natural gas industries due to its superior mechanical strength and toughness. However, X80 steel still has serious corrosion problems, especially localized corrosion problems. Localized corrosion is one of the key causes of corrosion perforation and subsequent service failure of the X80 steel, and causes huge economic loss and serious safety accidents. The X80 pipeline steel can spontaneously corrode in a natural state, and particularly in a complex marine environment, the X80 steel can inevitably corrode more severely. In marine environments, high concentrations of chloride ions and high salt environments provide a favorable condition for the development and extension of electrochemical corrosion, while also being subject to the presence of a large number of organisms and microorganisms. In seawater, more than half of the corrosion of steel is associated with microbial corrosion. Microbial corrosion (Microbiologically Influenced Corrosion, MIC) refers to the phenomenon in which microorganisms directly or indirectly affect metal corrosion through their own vital activities or metabolites. The corrosion behavior and mechanism of metals are closely related to the kind of microorganisms, biological activity, metabolism, growth and death of microorganisms, formation of biofilms, and the like. The structure and composition of the biofilm, including Extracellular Polymer (EPS), corrosion products, cell numbers, and the degree of densification or porosity of the biofilm, can affect the corrosion behavior of metals. And differences in the structure and composition of the biofilm may even lead to opposite corrosion results.
Biomineralization (Biomineralization) refers to the process of producing inorganic minerals from organisms through the regulation of biological macromolecules. The maximum difference from the general mineralization is that the biological macromolecules, organism metabolism, cells and organic matrixes participate, and the ions in the solution are converted into solid-phase minerals under the control or influence of biological organic substances at specific positions and under certain physicochemical conditions. Microbial corrosion of carbon steel results in a process of corrosion product film formation, which may also be referred to as biomineralization. The structure of the biomineralization film determines the corrosion behavior of steel, the compact biomineralization film has good protection effect on a substrate, and the porous loose passivation film can promote the corrosion of metal materials. The traditional corrosion control method mainly uses a coating, but the coating is easy to damage and lose efficacy due to various factors in the service process, and the coating has a good self-repairing function. In addition, the coating is more susceptible to peeling failure in environments of high ocean temperature, high salt, high humidity and microbiological diversity. Therefore, how to improve the service life of ocean engineering equipment and build a controllable anti-corrosion coating are one of the development directions in the future. And a compact anti-corrosion coating is constructed on the surface of the metal material in situ under the action of biomineralization, so that the biological activity is expected to realize dynamic repair, and a long-term protection effect is achieved. In addition, the functional nanomaterial is widely applied to various disciplines, and how to realize controllable large-scale preparation of the nanomaterial is still a research challenge.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for controlling carbon steel corrosion and preparing nano materials based on a biomineralization principle, which utilizes the biomineralization principle of microorganisms to directly construct a nano biomineralization coating on the surface of a metal material in situ, thereby playing a good corrosion control effect, prolonging the service life of a protective coating and simultaneously synthesizing the nano materials.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
on the one hand, the invention provides a method for controlling carbon steel corrosion based on a biomineralization principle, namely, a layer of compact biomineralization film is formed on the surface of metal by utilizing the mineralization principle of microorganisms, so that the aim of inhibiting metal corrosion is fulfilled, and the biomineralization film consists of nano particles with the particle size smaller than 10 nm.
Preferably, the method for controlling carbon steel corrosion based on the biomineralization principle comprises the following specific steps: the metal is soaked in the solution containing the microorganism, a layer of compact biomineralization film is formed on the surface of the metal by utilizing the biomineralization principle of the microorganism, so that the aim of inhibiting metal corrosion is fulfilled, and the biomineralization film consists of nano particles with the particle size smaller than 10 nm.
The invention utilizes a strain of bacteria (pseudomonas stutzeri) separated in marine environment, utilizes a biomineralization principle to directly participate in a metal corrosion protection process, constructs a compact biomineralization membrane in situ, utilizes the activity of bacteria to achieve the purpose of self-repairing, thereby realizing durable and efficient protection effect, prepares nano materials through biomineralization, and simultaneously prepares nano materials through biomineralization, the mineralization membrane constructed through biological and abiotic methods is composed of nano iron oxide materials, thereby providing a new idea for preparing functional nano materials, realizing large-scale rapid synthesis of nano materials and laying a good foundation for corrosion control and further development of nano materials.
Preferably, the microorganism is a marine bacterium including, but not limited to, pseudomonas stutzeri (Pseudomonas Stutzeri) which is autotrophic. Further, the preservation number of the chemolithoautotrophic pseudomonas stutzeri is CGMCC No.8521, and the chemolithoautotrophic pseudomonas stutzeri is specifically referred to patent CN 103789232B.
Preferably, the metal comprises carbon steel. Specifically, the metal is X80 steel.
Preferably, the biomineralization film is comprised of a metal oxide, including but not limited to iron oxide.
Preferably, the biomineralization coating (i.e., biomineralization film) has good compactness, has good corrosion control effect, and is capable of self-healing.
Preferably, the concentration of bacteria in the microorganism-containing solution is 10 3 -10 7 cells/mL. Further, the higher the concentration of bacteria is, the more compact the biomineralization coating is, and the better the protection effect is.
Preferably, the biomineralization medium used to prepare the microorganism-containing solution includes, but is not limited to, seawater, with a specific solution composition of NaCl, KCl, mgCl 2 ,CaCl 2 ,Na 2 SO 4 ,NaHCO 3 ,KBr,H 3 BO 3 ,SrCl 2 ,NaF。
Further, the mineralization medium for preparing the microorganism-containing solution comprises 24.53g/L NaCl,0.695g/L KCl and 5.2g/L MgCl 2 ，1.16g/L CaCl 2 ，4.09g/LNa 2 SO 4 ，0.201g/LNaHCO 3 ，0.101g/L KBr，0.027g/L H 3 BO 3 ， 0.025g/L SrCl 2 ，0.003g/LNaF。
Preferably, the time of soaking (i.e., biomineralization time) is 7-30 days. Specifically, the soaking time was 14 days.
Preferably, the enrichment method of pseudomonas stutzeri is as follows: inoculating bacteria in a culture medium containing 0.5g/L K, culturing at 37deg.C for not less than 10 days, centrifuging to remove metabolic corrosion products, and filtering with 0.22 μm filter membrane 2 HPO 4 ，0.5g/LNaNO 3 ，0.2g/L CaCl 2 ，0.5g/L MgSO 4 ·7H 2 O，0.5g/L(NH 4 ) 2 SO 4 10g/L ferric ammonium citrate, pH 6.5.
The second aspect of the invention provides a method for preparing a nanomaterial based on the biomineralization principle, namely synthesizing the nanomaterial by utilizing the mineralization principle of microorganisms.
Preferably, the nanomaterial includes, but is not limited to, nanoribbons and nanoparticles composed of iron oxide. Further, the nano particles are nano materials with particle size smaller than 10nm formed by abiotic growth of nano belts and biomineralization.
A third aspect of the present invention provides applications of the above nanomaterials in fields including, but not limited to, protection against metal corrosion, catalysis, environmental treatments, energy materials.
A fourth aspect of the invention provides the use of the above method of controlling metal corrosion based on biomineralization principles in marine metal corrosion and protection.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for controlling carbon steel corrosion and preparing the nano material based on the biomineralization principle, provided by the invention, a compact biomineralization film is formed on the surface of metal by utilizing bacteria to influence the mineralization process of metal ions, so that the corrosion of the metal is inhibited, and the corrosion rate of the metal in seawater is obviously reduced. Unlike the marine metal corrosion protection technology, such as surface coating protection, electrochemical protection, etc., the present invention uses the corrosion product film produced by microbial corrosion as a protection layer to separate the metal surface from corrosion factors, and the metabolic product, cell body, organic matrix, etc. of the microbe participate in the corrosion protection technology, so that the microbe plays an important role. The biomineralization coating disclosed by the invention can realize self-repair by utilizing the activity of bacteria, can be prepared in a large scale under mild conditions, and has low cost. In addition, the nano functional material with special morphology can be prepared by utilizing the principle of biomineralization, and a good preparation strategy of the functional nano material is further provided. The invention is a novel metal corrosion protection method by utilizing biological control metal marine corrosion, and has important application prospects in the fields of corrosion and protection of metals such as oil and gas field industry gathering pipelines, marine engineering equipment and the like, and the fields of synthesis and application of functional nano materials.
Drawings
FIG. 1 is a graph showing the corrosion rate of a test specimen after 14 days of testing in simulated seawater containing different bacteria concentrations;
FIG. 2 is an SEM image of corrosion product film after 14 days of test of samples in simulated seawater containing different bacterial concentrations (a is non-biological control; b is 10 7 cells/mL of test solution of bacteria; c is 10 5 cells/mL of test solution of bacteria; d is 10 3 cell/mL test solution of bacteria);
FIG. 3 is an XRD analysis of corrosion products after 14 days of testing of the sample in simulated seawater containing different bacterial concentrations;
FIG. 4 is a TEM morphology of a nano iron oxide material of the X80 steel surface under abiotic action;
FIG. 5 is a TEM topography of a nanomaterial for X80 steel surface under biomineralization.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Example 1 method for controlling carbon steel corrosion and preparing nanomaterials based on biomineralization principle
In the following examples, the test solution was simulated seawater (i.e., mineralized medium) comprising 24.53g/LNaCl,0.695g/LKCl, 5.2g/L MgCl 2 ，1.16g/L CaCl 2 ，4.09g/LNa 2 SO 4 ，0.201g/LNaHCO 3 ，0.101g/L KBr，0.027g/L H 3 BO 3 ，0.025g/L SrCl 2 0.003g/LNaF; the bacterial culture medium included 0.5g/L K 2 HPO 4 ，0.5g/LNaNO 3 ，0.2 g/L CaCl 2 ，0.5g/L MgSO 4 ·7H 2 O，0.5g/L(NH 4 ) 2 SO 4 10g/L ferric ammonium citrate, pH 6.5. The solid medium used for plate counting was 2% agar added to the medium. All high temperature resistant glass instruments, simulated seawater, culture mediums and the like are sterilized under high pressure for more than 20 minutes at 121 ℃ before the test, and a working electrode, a reference electrode, a counter electrode and the like are sterilized under an ultraviolet lamp for more than 30 minutes. High-purity CO is introduced after simulated seawater sterilization 2 1 hour was used as the test solution.
The method for controlling metal corrosion based on biomineralization principle is established by the following steps
(1) Enrichment of bacteria (chemolithoautotrophic Pseudomonas stutzeri (P. Stutzeri))
Bacteria were inoculated in fresh medium and cultured in an incubator at 37 ℃ for 10 days, metabolic corrosion products were removed by centrifugation, and the bacteria were enriched by filtration using a 0.22 μm filter. The collected bacterial cells were transferred to 100mL of simulated seawater by ultrasonic dispersion to obtain a concentrated solution of high cell concentration. The concentrate was then diluted by simulated seawater for use in the experiment.
(2) Construction of in-situ constructed biomineralization membrane test device
Comprises a sterile operation table and a glass bottle, wherein the sterile operation table is provided with simulated seawater and concentrated solution with high cell concentration, the total test solution is controlled to be 250mL, and the initial cell concentration of the test solution is controlled to be 10 7 cells/mL、10 5 cells/mL、10 3 cells/mL and 0cells/mL.
(3) Weight loss method for calculating corrosion rate test
X80 steel polished by 400# SiC sand paper, 800# SiC sand paper and 1200# SiC sand paper are respectively placed in the 4 bacteria concentration systems, and an analytical balance is used for weighing corrosion samples before placing. After 14 days of testing, the corrosion samples were removed and the corrosion products on the surface were removed using an acid wash solution containing an imidazoline derivative corrosion inhibitor. And then cleaning the bare sample with alkali washing solution containing corrosion inhibitor, water, acetone and absolute ethyl alcohol respectively. Finally, all samples were dried using nitrogen and weighed. And calculating the corrosion rate according to the weight loss result.
(4) Analysis of surface topography
Samples after 14 days of testing were surface analyzed using a Scanning Electron Microscope (SEM) and an x-ray diffractometer (XRD). Samples for SEM observation were first soaked in phosphate buffer containing 2.5% (w/w) glutaraldehyde for 8h to kill the fixed p.stutzeri, then dehydrated stepwise with ethanol of different concentrations (50%, 60%, 70%, 80%, 90%, 100%,) and dried with nitrogen. Before observation, a thin gold film is coated on the surface of the glass to improve the conductivity of the glass. The corrosion products of the different samples were subjected to component analysis using TEM and XRD.
FIG. 1 shows the calculated corrosion rate based on the weight loss of the samples after soaking in simulated seawater containing different P.Stutzeri bacterial concentrations for 14 days, showing that the corrosion rate of the non-biological control samples was maximum at (0.141.+ -. 0.005) mm/y and increased significantly with decreasing initial cell number. The corrosion rate of the p.stutzeri-containing system was lower than the control group, indicating that the presence of p.stutzeri was able to inhibit steel corrosion and that inhibition was related to the initial cell concentration.
Figure 2 shows SEM images of corrosion product films after 14 days of immersion of the samples in simulated seawater containing different p.stutzeri bacterial concentrations. For the non-biological control samples, the surface corrosion product film was loosely porous (fig. 2 a). When the initial cell number is 10 7 At cells/mL, the surface film of the sample was very dense, and the visible portion of the sample surface was covered with P.stutzeri cells, with some cracks (FIG. 2 b). Surface film cracking may be due to dehydration drying prior to scanning electron microscopy. The compact mineralized film layer is used as a barrier to separate the surface of the carbon steel from corrosion factors, and has a good protection effect on the carbon steel, so that the corrosion rate of the carbon steel in simulated seawater is remarkably reduced. For an initial cell number of 10 5 cells/mL and 10 3 The surface film of the cell/mL sample was similar to that of the control sample, but a partially denser product film was still visible at the bottom.
FIG. 3 shows corrosion products of samples after 14 days of immersion in simulated seawater containing different P.Stutzeri bacterial concentrationsXRD analysis shows that the main corrosion products of each sample are similar and mainly Fe 3 O 4 And FeOOH. Fe (Fe) 3 O 4 And FeOOH is the main corrosion product in the presence of oxygen. But when the initial cell number is 10 7 At cells/mL, the x-ray diffraction peak was weaker, indicating that the crystal structure of the corrosion product was poor, the content was lower, and for other samples, a more typical peak could be found.
FIG. 4 is a TEM topography of mineralized products formed on the surface of a sample under abiotic conditions, where it can be seen that the abiotic mineralized products consist of nanoribbons and have smaller particle size.
FIG. 5 is a TEM topography of biomineralization products formed on sample surfaces under biological conditions, where it can be seen that biomineralization products consist of particles with particle size less than 10nm and severe agglomeration occurs.
In summary, the carbon steel is placed in a simulated seawater environment containing different P.Stutzeri bacteria concentrations, a compact biomineralization film can be formed on the surface of the carbon steel in situ by utilizing the biomineralization principle of the bacteria, and the function of the nano biomineralization coating is achieved, so that the purpose of inhibiting carbon steel corrosion is achieved, a good corrosion control effect is achieved, and the service life of the protective coating is prolonged. Meanwhile, the invention utilizes the effect of bacteria to regulate and control the conversion of metal ions into nano materials with the particle size smaller than 10nm, thereby laying a foundation for the formation of compact mineralized films. Therefore, the invention not only can prepare the biological coating, but also has the synthesis of the nano material, and has important application prospect in the fields of corrosion control of ocean engineering equipment, synthesis and application of the functional nano material.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (1)
1. A method for controlling carbon steel corrosion based on a biomineralization principle is characterized by comprising the following steps: immersing metal in a solution containing microorganisms, and forming a layer of compact biomineralization film on the surface of the metal by utilizing the biomineralization principle of the microorganisms so as to achieve the aim of inhibiting metal corrosion, wherein the biomineralization film consists of nano particles with the particle size of less than 10 nm;
the metal is carbon steel;
the microorganism is chemolithotrophic pseudomonas stutzeri;
the biomineralization film is comprised of metal oxides, including iron oxides;
in the microorganism-containing solution, the concentration of the bacteria was 10 7 cells/mL；
The mineralization medium for preparing the microorganism-containing solution comprises 24.53g/L NaCl,0.695g/L KCl and 5.2g/L MgCl 2 ，1.16g/LCaCl 2 ，4.09g/L Na 2 SO 4 ，0.201g/L NaHCO 3 ，0.101g/L KBr，0.027g/L H 3 BO 3 ，0.025g/L SrCl 2 ，0.003g/L NaF。
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| US4461684A (en) * | 1981-02-13 | 1984-07-24 | The Marine Resources Company | Accretion coating and mineralization of materials for protection against biodegradation |
| CN1559664A (en) * | 2004-03-02 | 2005-01-05 | 武汉理工大学 | Preparation and Application of Bacterial Mineralized Nano-goethite |
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| US4461684A (en) * | 1981-02-13 | 1984-07-24 | The Marine Resources Company | Accretion coating and mineralization of materials for protection against biodegradation |
| CN1559664A (en) * | 2004-03-02 | 2005-01-05 | 武汉理工大学 | Preparation and Application of Bacterial Mineralized Nano-goethite |
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| "微生物EPS对碳钢和黄铜腐蚀影响与机理研究";习伟进;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第01期);第B022-730页 * |
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