KR20160025786A - Copper alloy for use in sea water with high abrasion resistance, method for producing the same and sea water structrue made therefrom - Google Patents

Abstract

The present invention relates to copper alloy for seawater, a manufacturing method, and a seawater structure manufactured therefrom. More specifically, the copper alloy for seawater comprises: 25-40 wt% of zinc (Zn); 0.15-10 wt% of manganese (Mn); 0.1-4.0 wt% of nickel (Ni); 0.01-3.0 wt% of silicon (Si); 0.01-3.0 wt% of tin (Sn); and the remainder including copper and inevitable impurities, wherein the range of the weight ratio (Ni/Si) of the nickel and silicon is 2-7, and the range of the weight ratio (Mn/Sn) of the manganese and tin is 0.05-10, a manufacturing method thereof, and the seawater structure manufactured therefrom.

Description

TECHNICAL FIELD [0001] The present invention relates to a copper alloy material for high abrasion resistant seawater, a method for producing the same, and a seawater structure manufactured therefrom. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a seawater copper alloy material, a method for producing the same, and a seawater structure manufactured therefrom. More particularly, the present invention relates to a process for the preparation of a catalyst composition comprising 25 to 40 wt.% Zinc (Zn), 0.15 to 10 wt.% Manganese (Mn), 0.1 to 4.0 wt.% Nickel, (Si), 0.01 to 3.0% by weight of tin (Sn), the remaining amount of copper (Cu) and inevitable impurities, and the weight ratio of nickel to silicon (Ni / Si) (Mn / Sn) of from 0.05 to 10, a method for producing the same, and a seawater structure made therefrom.

Conventional fishery materials are predominantly made of synthetic resins such as nylon, such as agricultural materials and industrial materials. The synthetic resin fishing nets described above are called synthetic resin fishing nets or chemical fiber fishing nets.

On the other hand, in the case of using the synthetic resin fishing net including the fishing net made of a material such as nylon, polyester, or polypropylene, when the synthetic resin net is installed in the water, Or biofouling of microorganisms, it blocks the flow of the surrounding seawater and lowers the oxygen concentration in the water as well as deteriorates the flowability in water. Therefore, it is easily contaminated by various residue of feed such as fungus and disease causing bacteria And parasites such as bacteria or anchor worms (Lernaea elegans) may become parasitic on the fish surface, The productivity of the cultured fish is decreased and the yield of the culture is lowered. In order to solve the above-described problems, the fishing nets are sometimes replaced or cleaned by a predetermined time unit, for example, every several months in order to prevent adhesion of aquatic organisms to synthetic resin fishing nets. In this case, it takes a lot of time and money to replace or clean the fishing net.

On the other hand, another drawback of the synthetic resin fishing nets is that such synthetic resin nets can be dumped or lost to the oceans by natural or anthropogenic factors. Such dumping or loss of synthetic resin fishing nets can cause ghost fishing phenomena to continue in the ocean, killing marine life, including fish, and even destroying marine ecosystems, including spawning grounds and habitats, .

In addition, the fishing gear including the synthetic resin fishing net often breaks some of its use and is no longer usable. Specifically, the synthetic resin fishing net used for the gill net or fish trap used in the coastal waters is mainly used for partial repair and is disposed of for about 6 to 12 months. Trawl and dragnet are used for about a year and then the surrounding net is used for about 20 months and replaced with a new net. Therefore, in order to increase the period of use of the fishing net, it is required that the fishing net has sufficient strength at a certain level or higher.

In order to overcome the disadvantages of the synthetic resin fishing net described above, a metal net (metal net) has been constantly being developed. In the past, wire mesh has been widely used as a metal net, but corrosion has been severely caused in the case of long contact with seawater, resulting in poor durability and poor environmental compatibility.

As a recent example of another metal network, a fishing net of a copper alloy material has been developed. Since the copper alloy fishing net does not adhere underwater to the net due to the antibacterial property of the copper itself, it is possible to smooth the flow of seawater and to provide enough oxygen and food to fish to provide an environment in which fish can grow healthy . In addition, copper alloy fishing nets are more resistant to corrosion and stronger than conventional synthetic resin fishing nets, thereby preventing the attack of external creatures and preventing the fish from escaping, resulting in improved productivity and lower maintenance costs, Effect was obtained.

However, although the copper alloy material has excellent seawater corrosion resistance and antibacterial properties, it has a problem in that it has a weak strength compared to a wire net, and that fish caught can be detached and the stability of fishing nets is insufficient.

In recent years, the importance of abrasion resistance as a main feature in fishing nets has been increasing, It was found that the thickness of the mesh decreases rapidly as the friction between the mangy and the mangy occurs continuously due to the influence of the waves. The reduction of the net thickness not only makes it difficult to maintain the shape of the fishing net against the wave, but also directly relates to the economic cost such as the maintenance cost and the life of the net.

Accordingly, it is necessary to develop a copper alloy reclaimed mesh material that achieves high strength and high abrasion resistance at the same time.

Korean Patent Laid-Open No. 10-2011-0009997 discloses a Cu-Zn-Ni-Mn based copper alloy material as an example of a fishing net of a copper alloy material for seawater as described above. However, since the strength and abrasion resistance It is necessary to improve it as a material for cultivation.

Therefore, there is a demand for development of a copper alloy material having improved abrasion resistance and sufficiently improving the strength so as to prevent the change of the external shape and the preservation of the mesh while having water-repellency equal to or more than that of existing materials, as compared with conventionally developed copper- .

In order to solve the above-mentioned problems, the present invention provides a seawater copper alloy material having seawater corrosion resistance equal to or higher than that of existing seawater copper alloy materials, at the same time having excellent processability and wear resistance, and having excellent mechanical properties including excellent strength do. The present invention also provides a method of manufacturing the copper alloy material and a seawater structure made of the copper alloy material for seawater.

The copper alloy material for seawater according to the present invention may contain 25 wt% to 40 wt% zinc (Zn), 0.15 wt% to 10 wt% manganese (Mn), 0.1 wt% to 4.0 wt% nickel, 0.01 wt% (Si), 0.01 to 3.0% by weight of tin (Sn), the remaining amount of copper (Cu) and inevitable impurities, and the weight ratio of nickel to silicon (Ni / Si) 2 to 7, and the weight ratio of manganese to tin (Mn / Sn) is 0.05 to 10. Wherein the copper alloy material contains one or more elements selected from the group consisting of aluminum (Al), cobalt (Co), iron (Fe), phosphorus (P), magnesium (Mg), lead (Pb), and calcium % ≪ / RTI > The intermetallic compound and the precipitates having an average diameter of 0.1 to 1 ㎛ range in the copper alloy material is a copper base and dispersed, the intermetallic compound is _{Cu 2 MnSn, Cu 4 MnSn,} Cu 5 Mn 4 Si, Cu 8 Mn 9 Si 3 thereof is selected from a mixture, it said precipitate is selected from NiSi, Ni ₂ Si, or a mixture thereof.

A method for producing a seawater copper alloy material according to the present invention comprises the steps of: preparing a mixture of 25 wt% to 40 wt% zinc, 0.15 wt% to 10 wt% manganese, 0.1 wt% to 4.0 wt% nickel, (Si), 0.01 to 3.0% by weight of tin (Sn), the balance of copper (Cu) and unavoidable impurities in a content ratio of 0.01 to 3.0% by weight and a weight ratio range of Ni / 7, and a weight ratio of Mn / Sn of 0.05 to 10, Hot extruding and drawing the obtained ingot at a temperature of 600 ° C to 900 ° C for 30 minutes to 12 hours, quenching the hot extruded and drawn product at room temperature, Cold drawing, heat-treating the cold drawn product at 500 ° C to 800 ° C for 30 minutes to 10 hours, and cold drawing the heat-treated product. Wherein the ingot contains at least one element selected from the group consisting of aluminum (Al), cobalt (Co), iron (Fe), phosphorus (P), magnesium (Mg), lead (Pb) and calcium (Ca) Or less. In addition, the final draw ratio is 10% to 90%.

The seawater structure according to the present invention is made of the copper alloy material for seawater according to the present invention described above. The seawater constructions are preferably aquaculture networks.

The seawater copper alloy material according to the present invention has excellent machinability and abrasion resistance while maintaining the seawater corrosion resistance of existing copper alloy materials, and has excellent mechanical properties including excellent strength.

FIG. 1 shows the results obtained by measuring the surface of a sample prepared according to Example 1 and Comparative Example 1 by 10,000 times and 40,000 magnifications, SEM, and EDS.
FIG. 2 shows results obtained by measuring the SEM and EDS analysis after 5,000 times and 15,000 times magnification, respectively, after aging the samples prepared according to Example 1 and Comparative Example 1 to produce precipitates.
FIG. 3 is a graph showing a change in hardness value according to the cold reduction rate (%) of the copper alloy material produced according to the examples and comparative examples of the present invention.

As used herein, the term "copper alloy material for seawater" refers to a copper alloy material that is a material of a seawater structure for use by immersing a part or all of the seawater in water for a long time and can be used as a material for fishing nets .

The copper alloy material for seawater according to the present invention may contain 25 wt% to 40 wt% zinc (Zn), 0.15 wt% to 10 wt% manganese (Mn), 0.1 wt% to 4.0 wt% nickel, 0.01 wt% (Si), 0.01 to 3.0 wt% of tin (Sn), and a balance of copper and inevitable impurities, wherein the nickel / silicon weight ratio (Ni / Si) ranges from 2 To 7, and the weight ratio of manganese and tin (Mn / Sn) is 0.05 to 10. The copper alloy material may further include at least one element selected from the group consisting of Al, Co, Fe, P, Mg, Pb, and Ca in an amount of 1 wt% or less.

In the copper alloy material according to the present invention, zinc (Zn) is contained in an amount of 25% by weight to 40% by weight based on the total weight of the copper alloy material. The zinc improves the strength and hardness characteristics of the copper alloy material obtained by alloying in the copper metal structure and improves the heat resistance. In the copper alloy material, when zinc is less than 25 wt%, it is difficult to secure sufficient hardness and the economical efficiency decreases as the amount of copper used for zinc increases. When the zinc content exceeds 40 wt%, the brittle material Beta phase, which is a two-phase phase, is increased, so that ductility is deteriorated, and cracking of the material occurs at the time of processing. In the copper alloy material according to the present invention, zinc may preferably be included in the range of 32 wt% to 38 wt%.

In the copper alloy material according to the present invention, manganese (Mn) is 0.15 wt% to 10 wt% based on the total weight of the copper alloy material, ≪ / RTI > The manganese serves to improve the corrosion resistance and wear resistance of the copper alloy material obtained by forming an intermetallic compound together with other components. Manganese (Mn) reacts with tin (Sn) to produce Cu ₂ MnSn or Cu ₄ MnSn to improve corrosion resistance and manganese (Mn) reacts with silicon (Si) to form Cu ₅ Mn ₄ Si, Cu ₈ Mn ₉ Si ₃ or the like to form an intermetallic compound, thereby improving abrasion resistance. If the content of manganese is less than 0.15% by weight, the above-mentioned effect of improving the corrosion resistance and wear resistance can not be sufficiently obtained, and if it exceeds 10% by weight, the brittleness of the material appears.

In the copper alloy material according to the present invention, nickel (Ni) is included in the range of 0.1 wt% to 4 wt% based on the weight of the copper alloy material. The nickel serves to improve hardness and corrosion resistance of the obtained copper alloy material. Nickel (Ni) is a homogeneous solid solution of copper (Cu), which improves the hardness and corrosion resistance without deterioration of ductility due to the addition of components. Particularly, precipitates (NiSi , Ni ₂ Si) and is dispersed and distributed in the copper matrix, thereby significantly increasing the hardness. When the content of nickel is less than 0.1% by weight, the effect of increasing hardness and corrosion resistance is not sufficiently exhibited. When the content of nickel is more than 4% by weight, the increase of hardness and corrosion resistance is slowed, . Also, as the amount of expensive nickel added increases, the economical efficiency remarkably decreases.

In the copper alloy material according to the present invention, silicon (Si) is contained in the range of 0.01 wt% to 3 wt% based on the total weight of the copper alloy material. The silicon (Si) serves to improve abrasion resistance and hardness of the obtained copper alloy material. Silicon (Si) acts to generate the manganese (Mn) and the reaction to the intermetallic compound in the copper (Cu) base _{(Cu 5 Mn 4 Si, Cu} 8 Mn 9 Si 3 , etc.) increase the abrasion resistance, and nickel ( Ni) to generate precipitates (NiSi, Ni ₂ Si, etc.), thereby significantly improving the hardness. If the content of silicon is less than 0.01% by weight, the above-described effects of improving the abrasion resistance and strength can not be obtained. If the content of silicon is more than 5% by weight, adverse effects on hot workability are caused by addition of silicon. Also, as the amount of expensive Si added increases, the economical efficiency remarkably decreases.

In the copper alloy material according to the present invention, tin (Sn) is contained in the range of 0.01 wt% to 3.0 wt% based on the total weight of the copper alloy material. The tin serves to improve the corrosion resistance and hardness of the obtained copper alloy material. Tin (Sn) reacts with manganese (Mn) to form an intermetallic compound in the copper matrix to improve abrasion resistance, and as the degree of processing increases, the degree of hardness increases. When the content of tin (Sn) is less than 0.01% by weight, the aforementioned seawater corrosion resistance and hardness improvement effect can not be obtained. When the content of tin (Sn) is more than 3% by weight, Phase is remarkably generated and the hot workability is deteriorated. Moreover, the wire is difficult to process due to the lack of ductility.

In the copper alloy material according to the present invention, copper (Cu) is the main component. Copper is contained as the remaining amount so as to make the content ratio of the above-mentioned other components. Copper is prevented from adhering marine organisms to the seawater structure due to the action of the eluted copper ions and at the same time the sea area in which the seawater structure is immersed is sterilized or sterilized, There is an improved feature. The general antifouling properties of the abovementioned copper ions are already known and can be obtained, for example, from the Copper Development Association's website ( http://www.copper.org/antimicrobial/homepage.html ) Antibacterial properties can be confirmed. On the other hand, it is known that the elution amount of copper ions in the copper alloy material should be at least 60% based on the copper ion elution amount in order to sufficiently secure the aforementioned antifouling property in the seawater structure made of the copper alloy material. If the elution amount of copper ions is less than 60% of the copper ion elution amount of pure copper, it can not prevent the contamination prevention function properly. Since the copper ion elution per day in pure sea water is 693mg / ㎡ / day, copper ion elution rate of 415.8mg / ㎡ / day per day in seawater of copper alloy can exhibit sufficient antibacterial characteristics. The copper alloy material according to the present invention has a copper ion elution amount of 60% or more of the copper copper ion elution amount, as will be seen in the following examples.

The copper alloy material according to the present invention may also contain a trace amount of impurities within a range that does not affect the characteristics of the copper alloy material. Therefore, the copper alloy material according to the present invention contains 0.1 wt% or more of at least one element selected from the group consisting of arsenic (As), titanium (Ti), sulfur (S), chromium (Cr), niobium (Nb) and antimony (Sb) And may further include the following trace amount. The impurities can be added in the conventional copper alloy manufacturing process and are included in a very small amount, so that the impurities will not significantly affect the characteristics of the copper alloy material according to the present invention.

In the copper alloy material according to the present invention, the weight ratio (Ni / Si) of nickel (Ni) and silicon (Si) ranges from 2 to 7. Within this range, fine particles of NiSi and Ni ₂ Si are precipitated, and when the weight ratio (Ni / Si) is less than 2, precipitates are formed less and it is difficult to secure required hardness. If the weight ratio (Ni / Si) exceeds 7, the effect of increasing the hardness is slowed down, and the economical efficiency is remarkably lowered due to the excessive addition of Ni, and wire roughening becomes difficult due to lack of ductility.

In the copper alloy material according to the present invention, the weight ratio of manganese (Mn) to tin (Sn) is 0.05 to 10. In the copper alloy material, manganese (Mn) and tin (Sn) react with each other to produce Cu ₂ MnSn or Cu ₄ MnSn to improve corrosion resistance. In the copper alloy material according to the present invention, . When the weight ratio (Mn / Sn) is less than 0.05, it is difficult to secure sufficient corrosion resistance. When the weight ratio (Mn / Sn) is more than 10, it is difficult to secure a sound billet due to excessive casting due to excessive manganese addition.

In the copper alloy material according to the present invention, an intermetallic compound (Cu ₂ MnSn, Cu ₄ MnSn, Cu ₅ Mn ₄ Si, Cu ₈ Mn ₉ Si _3, etc.) having an average diameter in the range of 0.1 탆 to 1 탆 is contained in the copper Precipitates (NiSi, Ni ₂ Si, etc.) are dispersed. If the average diameter of the intermetallic compound (Cu ₂ MnSn, Cu ₄ MnSn, Cu ₅ Mn ₄ Si, Cu ₈ Mn ₉ Si _3, etc.) or precipitates (NiSi, Ni ₂ Si, etc.) is less than 0.1 탆, It is difficult to secure sufficient strength, and cracking may occur during processing by Si or Sn remaining in the grain or grain boundaries. If the average particle size exceeds 1 탆, brass matrix and intermetallic compound and precipitate are coarsened in an overcooked state, and it is difficult to obtain the effect of improving the strength by dispersion distribution of the fine particles.

Further, in the seawater copper alloy material according to the present invention, it is preferable to use a group consisting of aluminum (Al), cobalt (Co), iron (Fe), phosphorus (P), magnesium (Mg), lead (Pb) The amount of one or more selected elements may be further included in an amount of 1 wt% or less, and the amount of copper added as the remaining amount by the amount of the element is reduced. The added element has no adverse effect on the hardness and softening resistance of the obtained copper alloy material, and at the same time, from the viewpoints of the seawater corrosion resistance and the ion elution amount, and exhibits an effect similar to that of the copper alloy material of the present invention.

The strength of the copper alloy material according to the present invention can be measured by hardness and softening resistance. The hardness of the copper alloy material differs depending on the percentage reduction in thickness after the heat treatment in the manufacturing process. The copper alloy material according to the present invention has a hardening rate of about 160 to 200 Hv . If it is included in the above-mentioned range, it can be regarded as having sufficient strength required for seawater structures such as aquaculture net. In the case of the softening resistance, the hardness is measured after charging the copper alloy material with the machining rate relatively higher by 70% at maximum and then holding the copper alloy material at 400 캜 for 30 minutes, and should be within the range of about 140 to 178 Hv.

A method for producing a seawater copper alloy material according to the present invention

The seawater copper alloy material according to the present invention is produced by a method comprising the steps of:

(Mn), 0.1 to 4.0% by weight of nickel (Ni), 0.01 to 3.0% by weight of silicon (Si), 0.1 to 10% ), 0.01 to 3.0% by weight of tin (Sn), and the balance of copper (Cu), and Ni / Si in a weight ratio of 2 to 7 and Mn / Sn in a weight ratio of 0.05 to 10 A step of making the ingot so as to become

Hot extruding and drawing the obtained ingot by heat treatment at 600 ° C to 900 ° C for 30 minutes to 12 hours,

Quenching the hot extruded and drawn product to room temperature and cold drawing the product,

Heat treating the cold drawn product at 500 ° C to 800 ° C for 30 minutes to 10 hours, and

Cold-drawing the heat-treated product.

In the method for producing a seawater copper alloy material according to the present invention, firstly, the ingot (billet or ingot) is formed by mixing 25 wt% to 40 wt% of zinc, 0.15 wt% to 10 wt% of manganese (Mn) (Si), 0.01 to 3.0% by weight of tin (Sn), and a balance of copper (Cu) in a total amount of 0.01 to 4.0% by weight of nickel (Ni), 0.01 to 3.0% The weight ratio of Ni / Si is 2 to 7, and the weight ratio of Mn / Sn is 0.05 to 10. The ingot may further contain at least one element selected from the group consisting of Al, Co, Fe, P, Mg, Pb and Ca in an amount of 1 wt% or less.

 The obtained ingot is heat-treated in a continuous annealing furnace at a temperature of 600 ° C to 900 ° C for 30 minutes to 12 hours, and then hot-extruded to be linearly or bar-shaped. If the heat treatment is carried out at a temperature lower than 600 ° C, sufficient heat treatment can not be obtained, and recrystallization in the metal structure becomes difficult and excessive heat load occurs. At a temperature higher than 900 ° C, Occurs. If the heat treatment is further performed for shorter than 30 minutes, the softening of the metal structure is not sufficiently performed, and if the heat treatment is performed for longer than 12 hours, the metal structure is excessively softened and the productivity is lowered.

 Thereafter, the obtained heat-treated product is cooled to room temperature (approximately 21 ° C to 30 ° C) by quenching, and then cold drawn.

Then, the product obtained from the above step is subjected to heat treatment at 500 ° C to 800 ° C for 30 minutes to 10 hours. The heat treatment step may be carried out in a bell-type annealing furnace or a batch annealing furnace. In the previous step, the already heat-treated product is recrystallized at a relatively low temperature, so that the heat treatment temperature is in the range of 500 ° C to 800 ° C. In the heat treatment step, recrystallization in the metal structure is difficult at 500 ° C or lower, and coarse texture growth occurs at an excessively high temperature above 800 ° C, resulting in abnormal texture and deteriorating productivity. If the heat treatment time is shorter than 30 minutes, the softening of the structure is not sufficient, and if the heat treatment time exceeds 12 hours, the metal structure becomes excessively soft and the productivity deteriorates.

 The obtained product is then cold drawn. The draw ratio in the cold drawing step is in the range of 10% to 90%. If the pulling rate is lower than 10%, it is difficult to secure a sufficient mechanical strength. If the pulling rate is higher than 90%, the cold rolling reduction reaches a limit due to an excessive processing rate. The heat treatment step and the cold drawing step may be repeatedly performed so as to reach the pulling rate or to reach a specifically desired pulling rate range according to the purpose of the final product to be manufactured.

Example

Example  1 to 11

In order to manufacture the copper alloy material according to the present invention, the ingot was prepared so as to have the chemical composition shown in Table 1, and then hot-extruded at 600 ° C for 6 hours to form a 1.5 mm- ). The resultant product was quenched to room temperature, cold drawn, heat treated at 600 ° C for 1 hour, and the resulting test piece was cut and cold drawn at a percentage reduction in thickness of up to 30% immediately after heat treatment to obtain a final sample . The obtained samples were designated Samples 1 to 11, respectively.

Comparative Example  1 to 10

The sample of Comparative Example 1 was selected as a material having excellent strength, abrasion resistance, dezinc corrosion resistance and seawater corrosion resistance in the seawater copper alloy material of Korean Patent Laid-Open No. 10-2011-0009997 and designated GB1, and the sample of Comparative Example 2 Is a 6: 4 ratio of brass, and the sample of Comparative Example 3 is pure copper. The copper alloy sample according to Comparative Example 4 has an excessively high silicon content when compared with the copper alloy sample according to the present invention. The sample of Comparative Example 5 is a copper alloy material having a too low weight ratio of nickel and silicon, and the sample of Comparative Example 6 is a copper alloy material having an excessively high nickel / silicon weight ratio. In addition, the sample of Comparative Example 7 is a copper alloy material having a too low weight ratio of manganese and tin, and the sample of Comparative Example 8 is a copper alloy material having an excessively high weight ratio of manganese and tin. The sample of Comparative Example 9 is a copper alloy having an average diameter of an intermetallic compound or precipitate of less than 0.1 占 퐉, and the sample of Comparative Example 10 is an average of intermetallic compounds or precipitates It is a copper alloy material having a diameter exceeding 1 탆.

division sample Alloy composition (% by weight) Weight ratio Average diameter
(탆) Remarks Cu Zn Mn Ni Si Sn Other Ni / Si Mn / Sn Example One Remainder 36 0.2 One 0.2 0.5 - 5 0.4 0.4 2 Remainder 36 5 One 0.2 0.5 - 5 10 0.3 3 Remainder 36 0.2 One 0.5 0.5 - 2 0.4 0.3 4 Remainder 36 0.2 0.5 0.2 0.5 - 2.5 0.4 0.4 5 Remainder 30 0.2 One 0.2 0.5 - 5 0.4 0.7 6 Remainder 36 0.2 One 0.2 3 - 5 1/15 0.6 7 Remainder 36 0.2 One 0.2 0.5 Al 0.1 5 0.4 0.5 8 Remainder 36 0.2 One 0.2 0.5 Fe 0.2 5 0.4 0.4 9 Remainder 36 0.2 One 0.2 0.5 Co 0.2 5 0.4 0.3 10 Remainder 36 0.2 One 0.2 0.5 P 0.05 5 0.4 0.4 11 Remainder 36 0.2 One 0.2 0.5 Ca 0.1 5 0.4 0.3 Comparative Example 1 (GB1) Remainder 36 6.0 One - - - 2
(64 brass) Remainder 40 - - - - - 3 (pure) 100 - - - - - - 4 Remainder 36 0.1 1.1 5.0 0.5 - 11/50 0.2 Hot crack 5 Remainder 36 0.2 One 3 0.5 1/3 0.4 Cold crack 6 Remainder 36 0.2 3 0.2 0.5 15 0.4 Hot crack 7 Remainder 36 0.2 One 0.2 3 5 0.06 Hot crack 8 Remainder 36 10 One 0.2 0.5 5 20 Unable to secure healthy ingot 9 Remainder 36 0.2 One 0.2 0.5 5 0.4 0.04 Low intensity
Hot crack 10 Remainder 36 0.2 One 0.2 0.5 5 0.4 2 Low intensity

Experimental Example

The specimens of Examples 1 to 11 and Comparative Examples 1 to 3 were taken as test specimens and the hardness, softening resistance, dezinc corrosion resistance and corrosion resistance were evaluated in order to confirm the mechanical properties, dezinc corrosion resistance, seawater corrosion resistance and abrasion resistance characteristics of the respective copper alloy materials , Seawater corrosion resistance and abrasion resistance test.

The hardness was tested using a micro Vickers hardness tester, and the results are shown in Table 2. In this connection, the graph of the change in the hardness value according to the reduction rate (%) of the material is shown in the graph shown in Fig. As a result of comparison with the hardness value of the sample GB1 of the comparative example 1, it can be confirmed that the hardness of the copper alloy re-samples according to the present invention is higher.

In the case of the softening resistance, the material having a maximum reduction of 70% by increasing the processing rate relatively was charged into a heat treatment furnace at 400 ° C, and then held for 30 minutes and taken out. The reduced hardness was measured using a micro Vickers hardness tester. Respectively. As can be seen from the following Table 2, the samples of Examples 1 to 11 have hardness values of about 144 to about 178 Hv based on the temperature of 400 ° C. From this, it can be confirmed that the copper alloy material according to the present invention exhibits remarkably excellent softening property than the copper alloy re-sample (represented by GB1) produced according to Comparative Example 1. [

The dezinc corrosion resistance was determined by etching each specimen after etching for 24 hours in a 75 ° C aqueous solution of CuCl _{2 for} 24 hours, polishing the cut surface to observe the depth of the corrosion, and measuring the corrosion depth with an optical microscope. Respectively. It can be confirmed that the samples according to Examples 1 to 11 are improved in dezinc corrosion resistance as compared with the samples according to Comparative Examples 1 and 2.

The seawater corrosion resistance was measured by KS D9502 salt spray test method and brine prepared by dissolving sodium chloride in distilled water was used. The specimens were mounted in a saline sprayer and sprayed at constant time intervals for 24 hours. The specimens were taken out to observe surface corrosion characteristics. The results are shown in Table 2. The notation was classified according to its own visual inspection standards as: good: good; poor: poor; poor: poor. As a result of the comparison, it was confirmed that the copper alloy re-samples according to the present invention had the same level of seawater corrosion resistance as the GB1 sample of Comparative Example 1. [

In order to evaluate the wear resistance, ASTM G99 pin-on-disk method was applied, and the abrasion resistance evaluation test conditions were carried out under a load of 5 kgf / 500 rpm / 3600 sec / wet environment (H ₂ O). The fin or other material to be polished was conducted under a fixed condition, and a method of measuring the amount of abrasion of the material to be polished, that is, the amount of decrease in weight, was carried out. The results are shown in Table 2. The abrasion resistance was compared with weight loss according to the weight change of disk. As a result of the comparison, it can be seen that the samples according to the examples have abrasion resistance four times higher than those of the comparative example 1. In other words, it was confirmed that the copper alloy material according to the present invention is superior in abrasion resistance to the GB1 sample of Comparative Example 1.

division Sample No. Hardness
(Hv) Fire resistance
(Hv) Dezinc corrosion
(Depth, 탆) Seawater corrosion Ion elution amount
(mg / m 2 / day) Abrasion resistance Example One 193 175 178 ○ 487 ↓ 0.1005g 2 195 173 183 ○ 471 ↓ 0.1255g 3 198 178 192 ○ 492 ↓ 0.1216g 4 192 168 295 ○ 465 ↓ 0.1305g 5 181 144 243 ○ 491 ↓ 0.1005g 6 186 161 254 ○ 473 ↓ 0.1114g 7 189 168 182 ○ 489 ↓ 0.1255g 8 191 171 210 ○ 491 ↓ 0.1321g 9 190 173 181 ○ 479 ↓ 0.1102g 10 187 171 198 ○ 482 ↓ 0.1078g 11 193 173 202 ○ 486 ↓ 0.2005g Comparative Example 1 (GB1) 147 128 327 ○ 488 ↓ 0.4219g 2 (64 brass) 126 85 716 △ 420 - 3 (pure) 110 70 - - 693 -

As a result of the above tests, the samples according to Examples 1 to 11 were superior in strength and abrasion resistance to the samples according to Comparative Examples 1 to 3, and exhibited both good dezinc corrosion resistance and seawater corrosion resistance.

On the other hand, SEM photographs and EDS component analysis results of the copper alloy re-samples according to Example 1 and the copper alloy re-samples according to Comparative Example 1 are shown in Figs. 1 and 2, respectively. Fig. 1 shows the result of SEM measurement at 10,000 times and 40,000 times of the sample surface in the hot rolled state of Example 1. Fig. Specifically, the EDS component analysis of the copper alloy re-sample of Example 1 produced according to the present invention showed that manganese reacted with silicon and tin to form an intermetallic compound, The reason why the wear resistance of the copper alloy material according to the present invention is improved is described below.

FIG. 2 is a graph showing the results obtained by measuring the cross-section of Example 1 and the cross-section of the copper alloy material according to Comparative Example 1 by SEM at 5,000 times and 15,000 times and the EDS component analysis, respectively. According to the results, it was confirmed that a precipitate was formed between nickel and silicon in the cross section of the copper alloy material according to the present invention. The above results explain why the hardness and strength of the copper alloy material according to the present invention are improved when compared with the cross section of the copper alloy re-sample according to Comparative Example 1. [

FIG. 3 is a graph showing a change in the hardness value according to the reduction rate (%) of the material as described above.

Claims (8)

(Mn), 0.1 to 4.0% by weight of nickel (Ni), 0.01 to 3.0% by weight of silicon (Si), 0.1 to 10% ), 0.01 to 3.0 wt% of tin (Sn), the balance copper (Cu) and inevitable impurities, the weight ratio of nickel to silicon (Ni / Si) is 2 to 7, (Mn / Sn) is in the range of 0.05 to 10 by weight. The method according to claim 1,
Wherein the copper alloy material comprises one or more elements selected from the group consisting of aluminum (Al), cobalt (Co), iron (Fe), phosphorus (P), magnesium (Mg), lead (Pb), and calcium % Or less of the total amount of the copper alloy. The method according to claim 1,
The intermetallic compound and the precipitates having an average diameter of 0.1 to 1 ㎛ range in the copper alloy material is a copper base and dispersed, the intermetallic compound is _{Cu 2 MnSn, Cu 4 MnSn,} Cu 5 Mn 4 Si, Cu 8 Mn 9 Si 3 thereof , And the precipitate is selected from NiSi, Ni ₂ Si or a mixture thereof. (Mn), 0.1 to 4.0% by weight of nickel (Ni), 0.01 to 3.0% by weight of silicon (Si), 0.1 to 10% ), 0.01 to 3.0% by weight of tin (Sn), the balance of copper (Cu) and inevitable impurities in a weight ratio range of 2 to 7 and a weight ratio of Mn / Sn of 0.05 ≪ / RTI > to 10,
Heat-treating the obtained ingot at 600 ° C to 900 ° C for 30 minutes to 12 hours, hot extruding and drawing,
Quenching and drawing the hot extruded and drawn product to room temperature and cold drawing,
Heat treating the cold drawn product at 500 ° C to 800 ° C for 30 minutes to 10 hours, and
And a step of cold drawing the heat-treated product. The method of claim 4, wherein
Wherein the ingot contains at least one element selected from the group consisting of aluminum (Al), cobalt (Co), iron (Fe), phosphorus (P), magnesium (Mg), lead (Pb) and calcium (Ca) By weight based on the total weight of the copper alloy. 5. The method of claim 4,
And the final draw ratio is 10% to 90%. A seawater structure made of a copper alloy material for seawater according to any one of claims 1 to 3. 8. The method of claim 7,
Wherein said seawater constructions are aquaculture systems.

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