CN108956441A - The test method of sulfate reducing bacteria corrosion in a kind of simulating ocean environment - Google Patents
The test method of sulfate reducing bacteria corrosion in a kind of simulating ocean environment Download PDFInfo
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- CN108956441A CN108956441A CN201811023902.1A CN201811023902A CN108956441A CN 108956441 A CN108956441 A CN 108956441A CN 201811023902 A CN201811023902 A CN 201811023902A CN 108956441 A CN108956441 A CN 108956441A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
- G01N17/006—Investigating resistance of materials to the weather, to corrosion, or to light of metals
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
- G01N17/02—Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement
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Abstract
The present invention provides a kind of test methods of sulfate reducing bacteria corrosion in simulating ocean environment, sample to be tested surface is coated into composite high-molecular film first, pure polymeric membrane is coated in composite high-molecular film surface, the composite high-molecular film is made by the pure high molecular material aqueous gel containing corrosion product, sulfur-bearing metabolite predecessor, sample to be tested after coating is placed in simulated seawater, organic acid is added in the simulated seawater, later using weight-loss method or electrochemical process evaluation corrosion resistance or research corrosion mechanism.Simulation of the realization to sulfate reducing bacteria corrosion process under effect multifactor in marine environment that can be easy using test method of the present invention, can also realize the Fast Evaluation of SRB corrosive nature resistance to metal material.
Description
Technical field
The invention belongs to Corrosion Science fields, more particularly to one kind is for sulfate reducing bacteria corrosion process in marine environment
The test method simulated.
Background technique
Microbiologic(al) corrosion (microbiologically induced corrosion, MIC) is in microbial life activity
Lower corrosion process occurred is participated in, this process is widely present in petroleum industry, marine settings, fluid conveying and water process etc.
Field, caused corrosion failure problem are increasingly subject to the attention of engineering and research field.Due to influencing micro- life in actual environment
The factor of object corrosion process is complicated and changeable, while also uncontrollable and quantitative description, using the bioenvironmental experiment side of simulation
Effect of the method to biological factor in evaluation material seawater corrosion, the rule for disclosing biological corrosion are of great significance.
In various microorganisms related with corrosion, sulfate reducing bacteria (SRB) is main one kind.Existing research table
Bright, the corrosion mechanism of SRB mainly includes metabolite corrosion mechanism, concentration cell corrosion mechanism, corrosion product corrosion mechanism.Mesh
Before, usual microbiologic(al) corrosion process analogy method is to cultivate selected microorganism, and then form specific microorganism
Corrosive environment, then sample is placed in the environment carry out it is corrosion simulated.Sample is impregnated in bacteria-containing liquid culture medium
Method can be used for studying corrosion rate and corrosion product composition (Zhao Xiaodong, Duan Jizhou, Wu Su are eaten, Chinese corrosion and protection
Journal, 2008,28 (5): 299-302).But when needing to carry out home position observation to corrosion process, the above method is not applicable
's.
Invention " a kind of experimental provision that simulation microorganism/macromolecular film generates " (publication number: 2844899 Y of CN) is open
The device is equipped with the salable flow cell of the simulation microbiologic(al) corrosion environment with circulation fluid entrance, passes through control simulation liquid stream
Speed can make microorganism in the microbial film of the different shapes such as specimen surface formation " condition film ", " monofilm ", " mature film "；Flowing
Pond seals warehouse lid and the probe and scanning measurement system for being used for real-time photography, online microexamination is housed.
It invents " a kind of magnesium alloy microbial corrosion method based on solid medium " (publication number: 101226136 B of CN)
It discloses its method and is related to simulation to sulfate reducing bacteria corrosion process.Specific steps include sample processing and sterilizing, solid training
The configuration and sterilizing, the culture of bacterium and activation of feeding base carry out constant temperature corrosion in specimen surface using band bacterium culture medium.This method
The shortcomings that microbiologic(al) corrosion process is difficult to home position observation in liquid corrosive medium infusion method is overcome, this method implementation process is opposite
Simply, low to specimen surface processing requirement, convenient for carrying out home position observation to corrosion process.But either use liquid culture
The method that base still uses solid medium can not achieve the speeding-up simulation to microbiologic(al) corrosion process, thus can not be used to pair
The microbial corrosion resistance of material can be carried out Fast Evaluation, which is because, for microorganism growth in culture medium or culture solution
The amount of nutriment is fixed, thus the micro organism quantity that can be accommodated in culture medium or culture solution be it is certain, with battalion
The consumption of substance is supported, micro organism quantity necessarily undergoes the process by increasing to decaying, and metabolic process is also necessarily undergone by vigorous
To the process of stagnation, this also means that metabolite at specimen surface, corrosion product concentration are uncontrollable and cannot be always
Maintain higher level, thus cannot from metabolite corrosion mechanism and corrosion product corrosion mechanism angle to corrosion process into
Row speeding-up simulation.In addition, sterilizing, biochemical culture equipment and a variety of auxiliary need to be equipped with during the test by cultivating microorganism
Equipment, process is cumbersome, time-consuming.Since the factor for influencing microbiologic(al) corrosion process in true marine environment is complicated and changeable, and it is real
The cumbersome time-consuming of chamber microbiological incubation is tested, the method for simulation microbial film is used in some microbiologic(al) corrosion researchs.Such as
Sodium alginate gel is deposited on metal material surface, simulation microbial film is formed, metal material is studied in simulated seawater
Electrochemical behavior (Wang Qingfei, Sui Jing, ten thousand hill etc., Journal of Chemical Industry and Engineering, 2001,52 (9): 814-817).But this method is not
The influence of corrosion product and metabolite can be simulated, while also not consider the shadow of the outer Marine Environment Factors of microbial film
It rings.
Summary of the invention
A kind of simulation sulfate reducing bacteria corrosion process is provided it is an object of the invention to overcome the above problem and deficiency
Test method, various corrosion factors in SRB corrosion process can be accurately controlled, without carrying out cumbersome, time-consuming microorganism
Incubation can also realize the Fast Evaluation of SRB corrosive nature resistance to metal material.
What the object of the invention was realized in:
The test method of sulfate reducing bacteria (SRB) corrosion in a kind of simulating ocean environment, first by sample to be tested surface
Composite high-molecular film is coated, is coated with pure polymeric membrane in composite high-molecular film surface, the composite high-molecular film is by containing corruption
It is obtained to lose product, sulfur-bearing metabolite predecessor, the mixing pension gelation of pure high molecular material, the sample to be tested after coating is set
In simulated seawater, organic acid is added in the simulated seawater, corrosion resistance is evaluated using weight-loss method or electrochemical process later
Or research corrosion mechanism.
Further, the high molecular material is sodium alginate (SA).
Further, the corrosion product in the composite high-molecular film is FeS, and FeS concentration is 0.01mol/L~0.2mol/
L, the sulfur-bearing metabolite predecessor in the composite high-molecular film are thioacetamide, and the substance of thioacetamide and FeS
The ratio between amount be 0.5:1~1:3.
Further, the organic acid selects one of acetic acid, propionic acid, lactic acid or more, and the organic acid concentration is
0.1mol/L~0.5mol/L.
Composite high-molecular film is prepared by film forming matter of high molecular material, contains corrosion product, sulfur-bearing in composite high-molecular film
Metabolite predecessor is coated at steel substrate surface；Pure polymeric membrane is coated in composite high-molecular film surface.It is above-mentioned multiple
Close polymeric membrane and pure polymeric membrane and hinder extraneous oxygen to the diffusion at steel substrate surface, make steel substrate surface be in
The similar anaerobic condition of SRB growing environment.The sample to be tested for coating composite high-molecular film and pure polymeric membrane is placed in containing having
In the simulated seawater of machine acid, organic acid diffuses at composite high-molecular film through pure polymeric membrane, containing in composite high-molecular film
Sulphur metabolite predecessor and corrosion product hydrolyze under organic acid effect, in-situ preparation sulfur-bearing metabolite；Sulfur-bearing metabolism produces
Object and organic acid diffuse at steel substrate the corrosion process for participating in steel substrate jointly with corrosion product.
The high molecular material is sodium alginate (SA), when preparing pure polymeric membrane as film forming matter using SA, first by SA
It is prepared into certain density aqueous solution, SA solution is extended after film forming, uses calcium chloride water as gelling agent by SA liquid film
Gelation and be made SA gel mould.In SA solution concentration and gelling agent calcium chloride concentration be determine SA gel film properties it is main because
Element.SA and the too low then gel film-strength of calcium chloride concentration and water resistance are bad, and then gel film toughness is bad for excessive concentration.SA solution
Concentration be 3wt%~5wt%；Calcium chloride concentration is 5wt%~7wt% in gelling agent.
Composite high-molecular film is by the pure high molecular material aqueous gel containing corrosion product, sulfur-bearing metabolite predecessor
Change and be made, when preparing composite high-molecular film as film forming matter using SA, by corrosion product and sulfur-bearing metabolite predecessor and SA
Mixed liquor is made in aqueous solution blending, mixed liquor is coated on steel substrate surface, wet film is made, then coagulated wet film using gelling agent
Gelatinization, so that the composite S A gel mould containing corrosion product and sulfur-bearing metabolite predecessor be made；Heretofore described high score
Corrosion product in sub- film is FeS.The sulfur-bearing metabolite predecessor is thioacetamide (TAA), FeS in the mixed liquor
Concentration is that the ratio between the amount of substance of 0.01mol/L~0.2mol/L, TAA and FeS are 0.5:1~1:3.
Organic acid in the simulated seawater can be selected one of acetic acid, propionic acid, lactic acid, concentration be 0.1mol/L~
0.5mol/L.The hydrogen ion that organic acid ionizes out passes through sodium alginate gel membrane diffusion to sulfur-bearing metabolite predecessor and corrosion
At product FeS and react generation H2S, while the organic acid on steel substrate surface is diffused to as except H2It is another kind of except S
Metabolite participates in corrosion process.
Traditional microbiologic(al) corrosion research method need to carry out the cumbersome microculture of process, be unable to control microbial metabolism
Product, corrosion product concentration values, thus speeding-up simulation cannot be carried out to microbiologic(al) corrosion process, it can not be effectively used for micro-
The further investigation of biological corrosion mechanism.
The beneficial effects of the present invention are: test method of the present invention can accurately control each in SRB corrosion process
Plant corrosion factor, without carrying out cumbersome, time-consuming microbial cultivation process.It therefore, can letter using test method of the present invention
Just simulation of the realization to sulfate reducing bacteria (SRB) corrosion process under effect multifactor in marine environment, can also realize to gold
Belong to the Fast Evaluation of the resistance to SRB corrosive nature of material.
Detailed description of the invention
Fig. 1 is that sample to be tested of the present invention coats composite high-molecular film and pure polymeric film structure schematic diagram.
1 is body to be measured in figure, and 2 be composite high-molecular film, and 3 be pure polymeric membrane, and 4 be simulated seawater.
Specific embodiment
Below by embodiment, the present invention is further illustrated.
The test method of sulfate reducing bacteria (SRB) corrosion in a kind of simulating ocean environment, first by sample to be tested surface
Composite high-molecular film is coated, is coated with pure polymeric membrane in composite high-molecular film surface, the composite high-molecular film is by containing corruption
It is obtained to lose product, the pure high molecular material aqueous gelization of sulfur-bearing metabolite predecessor, the sample to be tested after coating is set
In simulated seawater, organic acid is added in the simulated seawater, corrosion resistance is evaluated using weight-loss method or electrochemical process later
Or research corrosion mechanism.
The high molecular material is sodium alginate.
Corrosion product in the polymeric membrane is FeS, and FeS concentration is 0.01mol/L~0.2mol/L, the macromolecule
Sulfur-bearing metabolite predecessor in film is thioacetamide, and the ratio between amount of substance of TAA and FeS is 0.5:1~1:3.
The organic acid selects one of acetic acid, propionic acid, lactic acid or more, the organic acid concentration be 0.1mol/L~
0.5mol/L。
Embodiment 1: the resistance to SRB Evaluation of Corrosion Resistance of steel material based on weight-loss method
To specimen geometry without particular/special requirement, specimen size is recommended as 50mm × 25mm × 5mm, top
The hole for boring a diameter 5mm, for hanging sample.When carrying out weight-loss corrosion test, every group of sample should at least have 3 Duplicate Samples.It adopts
Ungrease treatment is carried out to specimen surface with degreasing agent for metal or acetone and other organic solvent；Through degreasing and the sample that is rinsed with water immediately
It puts into dehydrated alcohol, taking-up after-blow dry doubling is placed in spare in drier.Sample is surveyed using preceding needing to carry out quality weighing and size
Amount, quality are accurate to 0.001g, accurate size to 0.1mm.
Composite high-molecular film is made by the mixing pension gelation containing FeS, sulfur-bearing metabolite predecessor, sodium alginate.
Wherein SA solution concentration is 3wt%, FeS 0.2mol/L in mixed liquor；The ratio between amount of substance of thioacetamide and FeS is 1:
1.CaCl is immersed in after mixed liquor is coated on sample to be tested surface2Solution gel film forming, the CaCl2Solution concentration is
7wt%.3 layers of composite high-molecular film are prepared on steel substrate, prepare 5 layers of pure sodium alginate gel in composite high-molecular film surface
Film, to guarantee the corrosion product, the sulfur-bearing metabolite precursor amounts that are attached on sample to be tested.
Simulated seawater is 3.5wt%NaCl aqueous solution, and it is 0.5mol/L acetic acid, simulated seawater flow velocity that concentration is added wherein
For 5m/s, temperature is 25 DEG C.
After sample is immersed in simulated seawater, the acetic acid in simulated seawater diffuses to compound high score by pure SA gel mould
At FeS and TAA in sub- film, the two and acetic acid effect generate sulfur-bearing metabolite H2S, H2S and acetic acid pass through composite high-molecular film
It diffuses at steel substrate, participates in steel corrosion process jointly with the FeS in composite high-molecular film herein.
Sample impregnates 72h (primary every replacement simulated seawater for 24 hours) in simulated seawater.After the test can to sample into
Row surface corrosion product, pattern research can also clean specimen surface corrosion product by national standard GB/T16545-1996, join
Corrosion rate is calculated according to national standard GB/T14165-1993.
Embodiment 2:
Steel material SRB corrosion process electrochemical research
Ungrease treatment is carried out to specimen surface using degreasing agent for metal or acetone and other organic solvent；Through degreasing and it is rinsed with water
Sample put into dehydrated alcohol immediately, take out after-blow dry doubling be placed in it is spare in drier.
Composite high-molecular film is made by the mixing pension gelation containing FeS, sulfur-bearing metabolite predecessor, sodium alginate.
Wherein SA solution concentration is 5wt% in mixed liquor.FeS is 0.1mol/L；The ratio between amount of substance of TAA and FeS is 0.5:1.It will
Mixed liquor is immersed in CaCl after being coated on sample to be tested surface2Solution gel film forming, the CaCl2Solution concentration is 6wt%.
2 layers of composite high-molecular film are prepared on steel substrate, are prepared 3 layers of pure sodium alginate gel mould in composite high-molecular film surface, are
Guarantee corrosion product, the sulfur-bearing metabolite precursor amounts being attached on sample to be tested.
Simulated seawater be 3.5wt%NaCl aqueous solution, temperature be 25 DEG C wherein be added concentration be 0.5mol/L acetic acid.It will
Sample, as electrolyte, carries out electrochemical impedance survey using electrochemical workstation as working electrode, the simulated seawater containing acetic acid
Examination.Test temperature is 25 DEG C, scanning range 10-2~105Hz, sine wave potential amplitude are 20mV.
Although the parameters such as the above binding reagents concentration, experimental condition have been described in detail implementation of the invention, this
Invention is not limited to above-mentioned specific embodiment, and above embodiment is not restrictive, the ordinary skill of this field
Personnel under the inspiration of the present invention, without breaking away from the scope protected by the purposes and claims of the present invention, can also make
The specific transformation of diversified forms, these should not be excluded except protection scope of the present invention.
Claims (4)
1. the test method of sulfate reducing bacteria corrosion in a kind of simulating ocean environment, it is characterised in that: by sample to be tested surface
Composite high-molecular film is coated first, is coated with pure polymeric membrane in composite high-molecular film surface, the composite high-molecular film is by containing
There is the pure high molecular material aqueous gelization of corrosion product, sulfur-bearing metabolite predecessor to be made, it will be to be tested after coating
Sample is placed in simulated seawater, and organic acid is added in the simulated seawater, corrosion-resistant using weight-loss method or electrochemical process evaluation later
Performance or research corrosion mechanism.
2. the test method of sulfate reducing bacteria corrosion, feature in a kind of simulating ocean environment according to claim 1
Be: the high molecular material is sodium alginate.
3. the test method of sulfate reducing bacteria corrosion, feature in a kind of simulating ocean environment according to claim 1
Be: the corrosion product in the composite high-molecular film is FeS, and FeS concentration is 0.01mol/L~0.2mol/L, described compound
Sulfur-bearing metabolite predecessor in polymeric membrane is thioacetamide, and the ratio between thioacetamide and the amount of substance of FeS are
0.5:1~1:3.
4. the test method of sulfate reducing bacteria corrosion, feature in a kind of simulating ocean environment according to claim 1
Be: the organic acid selects one of acetic acid, propionic acid, lactic acid or more, the organic acid concentration be 0.1mol/L~
0.5mol/L。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111551390A (en) * | 2020-03-26 | 2020-08-18 | 广东工业大学 | High-pressure seabed simulation system with in-situ sampling device and control method thereof |
| CN112394029A (en) * | 2019-08-13 | 2021-02-23 | 宝山钢铁股份有限公司 | Simulation liquid for evaluating film binding force on surface of coated iron and evaluation method thereof |
| CN113804613A (en) * | 2021-09-15 | 2021-12-17 | 鞍钢股份有限公司 | Test method for simulating corrosion of iron bacteria in water environment |
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