A method of manufacturing a corrosion-resistant antifouling material

 

(57) Abstract:

The invention relates to the production of multilayer metallic materials and can be used in the production of corrosion-resistant and antifouling materials for ships, fixed and floating structures. The method involves coating the surface of the steel porous layer of titanium alloy by a method of cladding a Bang, and rolled, of a thickness not less than 1 mm and the subsequent deposition of a layer of copper or its alloy with volumetric porosity of 0.5 - 20% with the cathode or anode additives. 3 C. p. F.-ly, 2 tab.

The invention relates to the field of protection against corrosion and fouling of steel facilities marine equipment General-purpose vessels, floating and fixed structures.

There are various methods of protection against corrosion and fouling of steel offshore technology provided through a combination of: anti-corrosion anti-corrosion paint, metal, non-metallic and inorganic coatings; electrochemical methods (protective and cathodic protection); anti-fouling anti-fouling coatings, antifouling metal mA protection against corrosion. Guide, L. Shipbuilding, 1987; Gurevich, E. C., and others Protection from fouling. M. Nauka, 1989, S. 271; J. Soc. Nav. Archit. Jap. 1990-168, dec. p. 471).

Fundamentally by various combinations of these remedies effectively prevent corrosion and fouling of marine vessels and structures.

However, these remedies have the following major drawbacks: anti-corrosive coatings have a limited lifetime (3-4 years), and in ice conditions is not more than 1 year; antifouling coatings have a limited lifetime (1-3 years) and low efficiency (KIP) biocides (20-30%); electrochemical methods of protection are effective mainly in combination with paints in ice conditions subject to mechanical damage, and after the ice conditions in the fracture coatings protection efficiency is sharply reduced; physico-chemical protection against fouling reliable and effective mainly for closed volumes; terms of service anticorrosive and antifouling protection cannot be reconciled; without drydocking and repair of means of protection may not be reliable in operation offshore technology is truncated securable sheets of copper or copper alloys (for example, copper-Nickel alloy) using a bolt or adhesive bonding, and a method of cladding (J. Soc. Nav. Archit. Jap. 1990-168, dec. p. 471, prototype).

However, this method has some significant drawbacks, which does not spread. First, in practice this method is most commonly not only provides protection from corrosion due to the impossibility of a complete insulation of steel from sea water, but also lead to contact corrosion in places insulation. Secondly, effective protection against fouling is provided only in areas with an average intensity of fouling. In areas with high intensity of fouling (for example, the South-Eastern part of the World ocean) provided partial protection against fouling, and in areas with low intensity of fouling (e.g. the North sea) is increased (excessive) consumption of biocide. Thirdly, the method is very time-consuming and costly, associated with the use of sheets of copper-based thickness, 10-30 times greater than necessary to protect from fouling the equipment in operation, practically unusable. In this regard, this method has received very limited use, mainly education is nkiye (2-4 mm) and soft plating of copper or copper-Nickel alloy is often not withstand mechanical impacts, for example, facilities operation in ice conditions, which leads to intensive contact corrosion of steel.

The aim of the invention is the provision of virtually unlimited or regulated term of protection, protection from mechanical damage, including in the conditions of influence of ice, preventing contact corrosion, ensuring optimal efficiency of protection against fouling in marine basins with different biological activity.

The aim is achieved in that the bottom of the objects made from Tremella steel-titanium alloy, copper or copper alloy, with steel protects against corrosion by the application of a titanium alloy, and titanium alloy protect against fouling by applying to a coating of copper or copper alloy. For exceptions, contact steel corrosion and mechanical damage of the titanium layer is applied porous layer of thickness not less than 1.0 mm

Effective adjustable protection from fouling in marine basins with different biological activity provide a change in the intensity of ionization of copper, first, by changing the volumetric porosity of the coating on the base of copper from 0.5 to 20 the second alloy coating on the base of copper from 80 to 230 mV, provide an introduction to copper alloy cathode (for example, of Nickel, from 1 to 30 wt.) and (or) anode (for example, aluminum, from 0.5 to 15 wt.) additives. One method of regulating the rate of ionization of copper may be supplemented by others.

Criterion protective ability of the coating from fouling is the ionization rate of copper, suitable for basins with low biological activity 4-10 µg/cm2day, and for pools with high biological activity 30 µg/cm2day (Protection from fouling. M. Nauka, 1989).

P R I m e R using explosion and subsequent rolling produced sheets bimetal steel-titanium alloy that meets the requirements for mechanical strength, hardness, ductility) and technological (weldability, flexible, straightening, cutting to the properties and corrosion resistance, including when operating in ice conditions. Titanium layer carry a thickness of not less than 1.0 mm In this case must be excluded porosity and cracks.

On the surface of the titanium layer bimetal steel-titanium alloy applied thermal spray coating of copper or copper alloy, for example, flame method. By changing process conditions provide optimal is respectively the intensity of leaching of copper in the range from 10 to 30 ág/cm2day.

Depending on the potential of the selected titanium alloy in seawater pick up a coating composition based on copper so that the potential difference titanium alloy copper alloy was in the range of from 80 to 230 mV. When it for each specific porosity choose the amount of potential difference, which provides the desired optimal intensity of leaching of copper in the range from 10 to 30 ág/cm2day.

Using the opportunities provided by changing the porosity and potential difference, for almost all sea basins is possible to regulate the rate of leaching in the range of 10-30 ág/cm2day.

O p s t 1. Using explosion and subsequent rolling of manufactured samples of the bimetal steel (10HSND) titanium alloy (W 1-0). The thickness of the sheets of steel were selected from 4 to 30 mm when the thickness of the coating of titanium from 0.3 to 4.0 mm, the results of the experiments showed that when the thickness of the titanium layer is 1.0 mm or more, regardless of the thickness of the steel sheet, reliable steel-titanium. Mechanical properties of metals after plating match the original from the properties prior to plating. Provides a firm grip prachara impact held by the applicable governing documents, revealed the identity of the material properties in the initial state and after cladding. It was not observed cases, the formation of pores and cracks in the titanium layer, its detachment. The obtained results are fully consistent with the known data from the literature and experience in the application of bimetals steel-titanium.

However, when the thickness of the titanium layer is less than 1.0 mm and the steel sheet is more than 12 mm when bending and straightening was observed cases of cracking, the thickness of the titanium layer was up to 80% of the specified thickness. When the thickness of the titanium layer of 0.5 mm in some areas she was 0.1 mm. High reliability of the bimetal when the thickness of the titanium layer is less than 1.0 mm may be provided technological methods. However, high demands on the bimetal, the danger of contact corrosion of steel in the formation of pores or cracks in the titanium layer, the need to develop new technologies cladding dictates to set the thickness of the titanium layer is not less than 1.0 mm

O p s t 2. To assess the impact of volumetric porosity used samples of the steel-titanium, made in experiment 1. As the coating material used copper brand M 1 to see changed by changing the mode of deposition, including by regulating the speed of the spraying, the distance from the nozzle to the surface of the sample, the number of layers of coatings with the same thickness. Experiments were performed in artificial seawater with salinity of 35% Criterion protective ability of the coating to determine the optimal interval porosity was the minimum required protective ionization rate (leaching) of copper equal to 10 µg/cm2day. Most of the necessary protective ionization rate of copper for the most biologically active environments has been taken equal to 30 mg/cm2day.

The research results are summarized in table. 1.

With increasing porosity of the copper coating from 1 to 20% manage to achieve all the required interval protective copper concentrations. With less porosity minimum protective concentration (10 µg/cm2d) cannot be achieved, and at most it is certainly higher than the practical.

For example, an alloy of copper with 5 wt. Nickel shows that the interval protective concentration (13-30 g/cm2d) increasing with porosity 1-17%

Due to changes in porosity can reach the same optimal protective concentration in the range of speed leaching from 10 to 30 ág/cm2the mg/cm2day and effective mainly in marine basins with low biological activity. However, as a 20-year service life protection is provided when the thickness of the coating of copper 240 μm and alloy 265 μm, KPI prototype is only 8-10%

O p s t 3. To assess the impact of potential difference ( ) between the titanium and the coating on the rate of leaching and the effectiveness of protection from fouling the basis of samples taken from the bimetal steel-titanium, made in experiment 1.

To change the potential difference used alloys based on copper, having different potentials. Were used copper cathode additives (from 1 to 30 wt. Ni, Pb, Si) and the anode additives (from 0.5 to 15 wt. Al, Zn, Mn, Fe). And used different ratios of binary, ternary and multicomponent alloys. Regardless of the composition of the alloys and the content of additives ionization rate is determined only attainable by a potential difference for each specific volumetric porosity. The results of the experiments are given in table. 2.

By changing the potential difference is provided a speed change of ionization of copper in a wide range. Moreover, for any salinity may be provided with a protective concentrationbased, the use of the proposed method of protection against corrosion and fouling in comparison with existing methods provides the following key benefits: unlimited and strictly specified service life protection against corrosion and fouling; effectively managed the prevention of biofouling in marine basins with different biological activity; in relation to the vessel's underwater hull, the design service life of up to 25 years, compared to existing anti-fouling paints, 8-15 times longer life is 2-3 times greater efficiency of biocide (copper); in relation to the underwater part of the stationary and floating structures, with a design life of 50 years, compared with the existing paint antifouling coatings in 15-30 times greater service life; compared with plating of copper or copper alloys 2-3 times greater biocidal activity, does not cause the danger of contact corrosion of steel and 8-10 times reduces the consumption of copper; eliminates the need for drydocking of vessels and structures due to corrosion and fouling for an indefinite period; in the case of obsolescence of vessels or facilities trimetall can be IWAOBETSU MATERIAL, comprising coating the surface of the steel layer, a titanium alloy, characterized in that the layer of titanium alloy is applied porous with a minimum thickness of 1 mm, and then on the layer of titanium alloy additionally put a layer with a volume porosity of 0.5 - 20% of the copper or copper alloy cathode additives in quantities of 1 to 30 wt.% and/or anode additives in the amount of 0.5 - 15 wt.%.

2. The method according to p. 1, wherein the titanium alloy is applied by a method of cladding a blast and rolling.

3. The method according to p. 1, characterized in that the copper (copper alloy) with a given volumetric porosity of the applied electric arc, flame and plasma methods.

4. The method according to p. 1, characterized in that the cathode additives injected Nickel, lead, silicon and anodic aluminum, zinc, manganese, iron.

 

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