CN105297032A - Method preventing marine organisms from adhering to surface of titanium or titanium alloy - Google Patents

Abstract

The invention discloses a method for preventing marine organisms from adhering to the surface of titanium or titanium alloy. The method is as follows: placing titanium material and copper material closely to obtain a galvanic corrosion structure, and then placing the galvanic corrosion structure in seawater Middle; the ratio of the surface area of the titanium material in the galvanic corrosion structure immersed in seawater to the surface area of the copper material in the galvanic corrosion structure immersed in seawater is (1-100): 1, the titanium material It is industrial pure titanium or titanium alloy, and the copper material is industrial pure copper or copper alloy. The invention utilizes the galvanic corrosion phenomenon of the titanium material and the copper material in seawater to accelerate the corrosion of the copper material and produce a large amount of copper ions and cuprous oxide, which diffuse to the surface of the adjacent titanium material and can Inhibit the adhesion of marine organisms on the surface of titanium materials.

Description

A method for preventing sea organisms from adhering to the surface of titanium or titanium alloy

technical field

The invention belongs to the technical field of application of titanium materials in the ocean, and in particular relates to a method for preventing the surface of titanium or titanium alloy from adhering to marine organisms.

Background technique

The problem encountered by marine equipment during its service is the attachment and fouling of marine organisms. Various marine organisms, such as barnacles, algae, oysters, mussels, limeworms, enteromorpha, etc., will adhere non-selectively to large areas on the surface of ship shells, marine structures, and breeding cages. The adhesion of marine organisms will increase the roughness of the bottom of the ship, which will increase the resistance of the ship's navigation, increase the energy consumption and emission of the ship, and bring great harm to the ship's navigation. According to statistics, if the hull below the waterline is fouled by 5%, the fuel consumption will increase by 10%, if the fouling is 10%, the fuel consumption will increase by 20%, if the fouling is greater than 50%, the fuel consumption will increase by more than 40%. The adhesion of marine organisms will accelerate the fouling and corrosion of structural parts such as marine facilities and buildings, and significantly shorten their lifespan. These sticky fouling organisms will cause the pH value, dissolved oxygen concentration and other solute concentrations in the attachment area to be unevenly distributed in space, thereby changing the rate and progress of metal material corrosion. Fouling organisms will also accelerate the process and speed of electrochemical corrosion. According to reports, due to anaerobic corrosion caused by marine biofouling, the United States causes losses of 5 to 6 billion US dollars per year. Faced with the serious harm of marine organisms, people have studied many methods to prevent marine organisms from sticking and reducing fouling.

Antifouling coatings are a method that has been adopted very early. The early toxic tin-containing coatings are gradually replaced by tin-free self-polishing antifouling coatings, such as cuprous oxide (Cu ₂ O) antifouling agents, heterocyclic bactericidal, anti Mold etc. Brushing antifouling coatings is complex in construction and short in life. Compared with the antifouling coating method, the electrolytic seawater antifouling method has the advantages of longer life and less pollution of seawater by the hypochlorite ions generated, but the structure is complex and requires an external electrolysis power supply, which is not suitable for environments without electric energy. People have found that copper ions and cuprous oxide can inhibit the adhesion of marine organisms through the study of the phenomenon that "the surface of copper materials placed in seawater will not or less adhere to marine organisms". Copper materials become copper ions through the reaction with seawater, and copper ions will reduce the activation of main enzymes in biological organisms to shorten the biological lifespan. Cuprous oxide kills larvae and spores of marine organisms. Further studies have shown that when the copper exudation rate is greater than 10 μg/(cm ² d), the attachment of barnacles can be inhibited; when the copper exudation rate is greater than 10-20 μg/(cm ² d), the attachment of hydra and jellyfish can be inhibited; The exudation rate of copper ions is greater than 20-40 μg/(cm ² d) can inhibit algae adhesion; when the exudation rate of copper ions is greater than 40 μg/(cm ² d) can prevent bacterial adhesion; when the exudation rate of copper ions is greater than 50 μg /(cm ² d), it can inhibit the attachment of most marine organisms. Therefore, by controlling the exudation rate of copper ions in seawater, the attachment of marine organisms can be effectively inhibited. When the exudation rate of copper ions is greater than 50 μg/(cm ² d), most of the attachment of marine organisms can be inhibited. According to these studies, people have developed electrolytic copper-aluminum (iron) antifouling and electrolytic chlorine-copper, aluminum antifouling methods, which contain cuprous oxide, Al(OH) ₃ , and available chlorine through electrolysis of seawater electrolytes to prevent marine organisms. The purpose of attachment, too, is that both methods are structurally complex and require electrical energy.

Titanium alloy has excellent properties such as low density, high strength and seawater corrosion resistance, and is widely used in marine engineering fields such as ocean temperature difference power generation, seawater desalination, oil and gas exploitation, ships, and aquaculture, and is known as "marine metal". Titanium alloy has good biocompatibility and is an ideal habitat for marine organisms. Therefore, the biofouling problem of titanium alloy in marine engineering is more serious than other metal materials.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preventing the surface of titanium or titanium alloy from adhering to marine organisms in view of the deficiencies in the above-mentioned prior art. Copper materials accelerate corrosion and produce a large amount of copper ions and cuprous oxide. These copper ions and cuprous oxide diffuse to the surface of adjacent titanium materials, which can inhibit the adhesion of marine organisms on the surface of titanium materials.

In order to solve the above technical problems, the technical solution adopted by the present invention is: a method for preventing the surface of titanium or titanium alloy from adhering to marine organisms, which is characterized in that the method is: place the titanium material and the copper material closely to obtain a galvanic couple corrosion structure, and then place the galvanic corrosion structure in seawater; the difference between the surface area of the titanium material in the galvanic corrosion structure immersed in seawater and the surface area of the copper material in the galvanic corrosion structure immersed in seawater The ratio is (1-100):1, the titanium material is industrial pure titanium or titanium alloy, and the copper material is industrial pure copper or copper alloy.

The above-mentioned method for preventing the surface of titanium or titanium alloy from adhering to marine organisms is characterized in that the surface area of the titanium material in the galvanic corrosion structure immersed in seawater is the same as the surface area of the copper material in the galvanic corrosion structure immersed in seawater. The surface area ratio is (1-40):1.

The above-mentioned method for preventing marine organisms from adhering to the surface of titanium or titanium alloy is characterized in that the surfaces of the titanium material and the copper material are smooth and smooth.

The above-mentioned method for preventing the surface of titanium or titanium alloy from adhering to marine organisms is characterized in that the industrial pure titanium is TA1 industrial pure titanium or TA2 industrial pure titanium, and the titanium alloy is TC4 titanium alloy, Ti80 titanium alloy, Ti75 Titanium alloy or Ti90 titanium alloy.

The above-mentioned method for preventing the surface of titanium or titanium alloy from adhering to marine organisms is characterized in that the industrial pure copper is T1 red copper, T2 red copper, TU1 oxygen-free copper, TUP deoxidized copper or TU2 oxygen-free copper, and the copper alloy It is HSi3-1 silicon bronze or HA177-2A brass.

Compared with the prior art, the present invention has the following advantages:

1. The present invention utilizes the galvanic corrosion phenomenon of titanium materials and copper materials in seawater to accelerate the corrosion of copper materials and produce a large amount of copper ions and cuprous oxide, which diffuse to the adjacent titanium material surface , can inhibit the adhesion of marine organisms on the surface of titanium materials.

2. The theoretical basis of the present invention is: in a corrosive medium, the corrosion that occurs when a metal contacts another metal with a higher potential is galvanic corrosion, and the self-corrosion potential of titanium in 25°C flowing seawater is about 0.1V (SCE) , while the self-corrosion potential of brass in 25°C flowing seawater is about -0.4V (SCE). When titanium and copper are in contact with each other and in seawater, due to the potential difference between titanium and copper, they form a galvanic couple, which occurs Galvanic corrosion is eliminated, copper with low potential is subject to accelerated corrosion, and titanium with high potential is protected, that is, no corrosion occurs. Copper is subjected to accelerated corrosion to produce copper ions and cuprous oxide that can inhibit the growth of marine organisms. These copper ions and Cuprous oxide diffuses to the titanium surface, effectively inhibiting the formation of marine organisms on the titanium surface, and the reactions that occur are as follows:

Cu+2Cl ^— ＝CuCl ₂ ^— +e

2CuCl ₂ ^— +H ₂ O＝Cu ₂ O+4Cl ^— +2H ⁺

2Cu+O ₂ +2H ₂ O+Cl ^— ＝Cu ₂ (OH) ₃ Cl+OH ^—

Copper reacts with chloride ions in seawater to generate soluble CuCl ₂ ^— , CuCl ₂ ^— hydrolyzes to generate Cu ₂ O, which has an inhibitory effect on the formation of marine organisms, and copper reacts with water and chloride ions in seawater to generate basic chloride Copper oxide and basic copper chloride continuously release copper ions in seawater. Since the accelerated corrosion of copper caused by galvanic corrosion will continue, Cu ₂ O and copper ions can be continuously generated. Therefore, the corrosion of titanium can be achieved. Long-term protection of the material, the condition for the termination of the reaction is that the copper material is completely corroded, but the reaction can be restarted by replacing the copper material;

Copper has good corrosion resistance in seawater, that is to say, less copper ions are released through corrosion of seawater in seawater. Scholars have found that in the South China Sea, the annual corrosion rate of copper and copper alloys in seawater is relatively low. Low, one-year test result: 5.6～44×10 ^-3 mm/a, four-year test result: 2.2～19×10 ^-3 mm/a, eight-year test result: 2.4～15×10 ^-3 mm /a, it can be seen that not only the corrosion rate is low, but also the corrosion rate is decreasing with the prolongation of time; adopt the galvanic corrosion structure of the present invention, the corrosion of copper has been accelerated, and under the test conditions of the present invention, the acceleration of copper The average result of the corrosion test is: the average result of the half-year test is 11.2mm/a, the average result of the one-year test is 12.8mm/a, the average result of the one-and-a-half-year test is 11.5mm/a, the average result of the two-year test is 13.2mm/a, The average result of the two-and-a-half-year test is 14.6mm/a, and the average result of the three-year test is 18.2mm/a. It can be seen that the galvanic corrosion structure accelerates the corrosion rate of copper, and the corrosion rate of copper continues to remain above 11.2mm/a , is more than 200 times the corrosion rate of copper materials in seawater, and it tends to increase with time. In this state of accelerated copper corrosion, the maximum exudation rate of copper ions is greater than 27mg/cm ² d, far greater than The minimum copper ion leaching rate that inhibits the attachment of most marine organisms is 50μg/cm ² d.

3. In the present invention, the titanium material and the copper material are closely bonded and placed in seawater. Due to the potential difference between the titanium material and the copper material, the two form a galvanic couple, and galvanic corrosion occurs. On the surface of the copper material with low potential A copper corrosion zone is formed, and seawater corrodes copper to form copper ions and cuprous oxide, which diffuse to the surface of titanium materials, inhibiting the adhesion of marine organisms on the surface of titanium materials, and achieving the purpose of protecting titanium materials , by adjusting the ratio of the surface area of the titanium material immersed in seawater to the surface area of the copper material immersed in seawater, the corrosion rate of the copper material is controlled, which can effectively control the amount of copper corrosion products (copper ions and cuprous oxide) to achieve The purpose of effectively inhibiting the growth of marine organisms on the surface of the titanium material is that the method has a simple structure, does not require an external power supply, is convenient to use, and is safe and reliable.

The technical solutions of the present invention will be described in further detail below with reference to the accompanying drawings and embodiments.

Description of drawings

Fig. 1 is a schematic cross-sectional view of the close joint of titanium material and copper material in the galvanic corrosion structure of the present invention.

Fig. 2 is a schematic cross-sectional view of a galvanic corrosion structure of the present invention after the copper material is corroded after being immersed in seawater.

detailed description

Example 1

In this embodiment, the method for preventing sea organisms from adhering to the surface of titanium or titanium alloys is as follows: place the titanium material and the copper material in close contact to obtain a galvanic corrosion structure, and then place the galvanic corrosion structure in seawater; The ratio of the surface area of the titanium material immersed in seawater in the corrosion structure to the surface area of the copper material in the galvanic corrosion structure immersed in seawater is 5:1, the titanium material is TA1 industrial pure titanium, and the copper material It is T1 red copper. Preferably, the titanium material and the copper material are smooth and flat plates; in this embodiment, the titanium material and the copper material are preferably placed in close contact by binding.

As shown in Figure 1 and Figure 2, in this embodiment, the titanium material and the copper material are closely bonded and placed in seawater. Due to the potential difference between the titanium material and the copper material, the two form a galvanic couple, and galvanic corrosion occurs , a copper corrosion zone is formed on the surface of the copper material with low potential, and the seawater corrodes copper to generate copper ions and cuprous oxide, which diffuse to the surface of the titanium material, inhibiting the adhesion of marine organisms on the surface of the titanium material , to achieve the purpose of protecting the titanium material.

Tests show that the galvanic corrosion structure of this embodiment has a copper seepage rate greater than 8 mg/cm ² d in seawater at 20 ° C, and the minimum amount of copper diffused to the surface of the titanium material reaches 0.2 mg/cm ² d, and the titanium material There is no attachment of marine organisms on the surface.

Example 2

In this embodiment, the method for preventing sea organisms from adhering to the surface of titanium or titanium alloys is as follows: place the titanium material and the copper material in close contact to obtain a galvanic corrosion structure, and then place the galvanic corrosion structure in seawater; The ratio of the surface area of the titanium material in the corrosion structure immersed in seawater to the surface area of the copper material in the galvanic corrosion structure immersed in seawater is 10:1, the titanium material is TC4 titanium alloy, and the copper material is TU1 Oxygen-free copper, preferably, the titanium material and the copper material are smooth and flat plates; in this embodiment, the titanium material and the copper material are preferably placed in close contact by binding.

Tests show that the galvanic corrosion structure of this embodiment has a copper seepage rate greater than 22 mg/cm ² d in seawater at 20 ° C, and the minimum amount of copper diffused to the surface of the titanium material reaches 0.5 mg/cm ² d, and the titanium material There is no attachment of marine organisms on the surface.

Example 3

In this embodiment, the method for preventing sea organisms from adhering to the surface of titanium or titanium alloys is as follows: place the titanium material and the copper material in close contact to obtain a galvanic corrosion structure, and then place the galvanic corrosion structure in seawater; The ratio of the surface area of the titanium material immersed in seawater in the corrosion structure to the surface area of the copper material in the galvanic corrosion structure immersed in seawater is 30:1, the titanium material is Ti80 titanium alloy, and the copper material is For TUP deoxidized copper, preferably, the titanium material and the copper material are smooth and flat plates; in this embodiment, the titanium material and the copper material are preferably placed in close contact by bundling.

Tests show that the galvanic corrosion structure of this embodiment has a copper seepage rate greater than 26 mg/cm ² d in seawater at 20 ° C, and the minimum amount of copper diffused to the surface of the titanium material reaches 0.8 mg/cm ² d, and the titanium material There is no attachment of marine organisms on the surface.

Example 4

In this embodiment, the method for preventing sea organisms from adhering to the surface of titanium or titanium alloys is as follows: place the titanium material and the copper material in close contact to obtain a galvanic corrosion structure, and then place the galvanic corrosion structure in seawater; The ratio of the surface area of the titanium material in the corrosion structure immersed in seawater to the surface area of the copper material in the galvanic corrosion structure immersed in seawater is 20:1, the titanium material is Ti75 titanium alloy, and the copper material is HSi3-1 silicon bronze, preferably, the titanium material and the copper material are smooth and flat plates; in this embodiment, the titanium material and the copper material are preferably placed in close contact by binding.

Tests show that the galvanic corrosion structure of this embodiment has a copper seepage rate greater than 15 mg/cm ² d in seawater at 20°C, and the minimum amount of copper diffused to the surface of the titanium material reaches 0.6 mg/cm ² d, and the titanium material There is no attachment of marine organisms on the surface.

Example 5

In this embodiment, the method for preventing sea organisms from adhering to the surface of titanium or titanium alloys is as follows: place the titanium material and the copper material in close contact to obtain a galvanic corrosion structure, and then place the galvanic corrosion structure in seawater; The ratio of the surface area of the titanium material immersed in seawater in the corrosion structure to the surface area of the copper material in the galvanic corrosion structure immersed in seawater is 40:1, the titanium material is Ti90 titanium alloy, and the copper material is HA177-2A brass, preferably, the titanium material and the copper material are smooth and flat plates; in this embodiment, the titanium material and the copper material are preferably placed in close contact by binding.

Tests show that the galvanic corrosion structure of this embodiment has a copper seepage rate greater than 32 mg/cm ² d in seawater at 20 ° C, and the minimum amount of copper diffused to the surface of the titanium material reaches 0.9 mg/cm ² d, and the titanium material There is no attachment of marine organisms on the surface.

Example 6

In this embodiment, the method for preventing sea organisms from adhering to the surface of titanium or titanium alloys is as follows: place the titanium material and the copper material in close contact to obtain a galvanic corrosion structure, and then place the galvanic corrosion structure in seawater; The ratio of the surface area of the titanium material immersed in seawater in the corrosion structure to the surface area of the copper material in the galvanic corrosion structure immersed in seawater is 1:1, the titanium material is TA2 industrial pure titanium, and the copper material It is T2 red copper. Preferably, the titanium material and the copper material are smooth and flat plates; in this embodiment, the titanium material and the copper material are preferably placed in close contact by binding.

Tests show that the galvanic corrosion structure of this example has a copper seepage rate greater than 1.2 mg/cm ² d in seawater at 20 ° C, and the minimum amount of copper diffused to the surface of the titanium material reaches 0.5 mg/cm ² d, and the titanium There is no attachment of marine organisms on the surface of the material.

Example 7

In this embodiment, the method for preventing sea organisms from adhering to the surface of titanium or titanium alloys is as follows: place the titanium material and the copper material in close contact to obtain a galvanic corrosion structure, and then place the galvanic corrosion structure in seawater; The ratio of the surface area of the titanium material immersed in seawater in the corrosion structure to the surface area of the copper material in the galvanic corrosion structure immersed in seawater is 100:1, the titanium material is Ti80 titanium alloy, and the copper material is TU2 Oxygen-free copper, preferably, the titanium material and the copper material are smooth and flat plates; in this embodiment, the titanium material and the copper material are preferably placed in close contact by bundling.

Tests show that the galvanic corrosion structure of this embodiment has a copper seepage rate greater than 63 mg/cm ² d in seawater at 20°C, and the minimum amount of copper diffused to the surface of the titanium material reaches 0.07 mg/cm ² d, and the titanium material There is no attachment of marine organisms on the surface.

The above are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent structural changes made to the above embodiments according to the technical essence of the present invention still belong to the technical aspects of the present invention. within the scope of protection of the scheme.

Claims (5)

1. prevent a method for titanium or titanium alloy surface attachment marine life, it is characterized in that, the method is: titanium material and copper product are fitted tightly placement, obtains galvanic corrosion structure, then described galvanic corrosion structure is placed in seawater; The ratio that titanium material in described galvanic corrosion structure immerses the surface area that the surface area in seawater immerses in seawater with the copper product in described galvanic corrosion structure is (1 ~ 100): 1, described titanium material is industrially pure titanium or titanium alloy, and described copper product is industrial pure copper or copper alloy.

2. according to a kind of method preventing titanium or titanium alloy surface attachment marine life according to claim 1, it is characterized in that, the ratio that the titanium material in described galvanic corrosion structure immerses the surface area that the surface area in seawater immerses in seawater with the copper product in described galvanic corrosion structure is (1 ~ 40): 1.

3. according to a kind of method preventing titanium or titanium alloy surface attachment marine life according to claim 1, it is characterized in that, described titanium material and the equal any surface finish of copper product and smooth.

4. according to a kind of method preventing titanium or titanium alloy surface attachment marine life according to claim 1, it is characterized in that, described industrially pure titanium is TA1 industrially pure titanium or TA2 industrially pure titanium, and described titanium alloy is TC4 titanium alloy, Ti80 titanium alloy, Ti75 titanium alloy or Ti90 titanium alloy.

5. according to a kind of method preventing titanium or titanium alloy surface attachment marine life according to claim 1, it is characterized in that, described industrial pure copper is T1 red copper, T2 red copper, TU1 oxygen free copper, TUP deoxidized copper or TU2 oxygen free copper, and described copper alloy is HSi3-1 silicon bronze or HA177-2A brass.