KR100371128B1 - Cu-Ni-Sn-Al, Si, Sr, Ti, B alloys for high strength wire or plate - Google Patents

Abstract

The present invention relates to a copper (Cu)-nickel (Ni)-tin (Sn)-aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti), boron (B) alloy for high strength wire and plate Its purpose is to reduce nickel and tin as a main alloying element in copper-nickel-tin alloys, but to reduce some of the expensive nickel (Ni) and tin and to control the material strength and microstructure. The addition of elements provides a new high strength alloy.

The composition of the present invention is 1.0 to 8.0 wt% (wt%) nickel (Ni), 1.0 to 6.0 wt% (wt%) tin (Sn), and the total amount of 0.1 to 5.0 wt% (wt%) At least two kinds of elements selected from the group consisting of aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti) and boron (B), and the remainder are alloys composed of copper (Cu).

Description

Copper (nick) -nickel (tin)-aluminum (A), silicon (Si), strontium (Sr), titanium (Ti), boron alloys {Cu-Ni- for high strength wire rod and board Sn-Al, Si, Sr, Ti, B alloys for high strength wire or plate}

The present invention relates to a copper (Cu)-nickel (Ni)-tin (Sn)-aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti), boron (B) alloy for high strength wire and plate will be.

Among the existing copper alloys, copper (Cu) -nickel (Ni) -tin (Sn) -based ternary alloys exhibit high strength as a spinodal decomposition strengthening effect. The typical composition of this alloy is 9% nickel by weight. (Ni) and 6% tin (Sn), with the remaining 85% composed of copper (Cu).

85% copper (Cu)-9% nickel (Ni)-6% tin (Sn) -based ternary alloy can obtain tensile strength of 1,000 MPa or more through processing heat treatment using spinodal decomposition strengthening effect. It is used for the purpose high strength spring.

However, in the case of copper (Cu) -nickel (tin) -tin (Sn) -based spinodal decomposition-reinforced alloys, when the tin content is 6% or more, the ingot is not available for hot working due to the precipitation of the columnar grain boundary of the tin. Plate, bar and wire by the production of some, but there are problems in the manufacturing process, the stability of the quality, high cost and mass production, there is an economic problem that the unit price is very expensive.

An object of the present invention for solving the above problems is to reduce the portion of nickel (Ni) and tin, which is nickel and tin as the main alloying element in the copper-nickel-tin alloy, thereby reducing the material strength and fine It is to provide a new high strength alloy by adding elements having a function to control the structure.

In the present invention as described above, the alloy composition range is 1.0 to 8.0 wt% (weight percent) nickel (Ni), 1.0 to 6.0 wt% (weight percent) tin (Sn), and the total amount is 0.1 to 5.0 wt% (weight). Tensile strength by forming two or more elements selected from the group consisting of aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti) and boron (B), and the remainder of copper (Cu). It is attained by providing a high strength copper alloy having 1,000 Mpa or more and an elongation of 5 to 10%, and having an electrical resistivity of 10 to 14 mu OMEGA cm.

When explaining the configuration and the operation of the embodiment of the present invention to accomplish the object as described above and to perform the task for compensating the conventional drawbacks in detail as follows.

In the alloy of the present invention, in the copper-nickel-tin alloy, 1.0 to 8.0 wt% (wt%) nickel (Ni), 1.0 to 6.0 wt% (wt%) tin (Sn), and the total amount of 0.1 to 2 or more elements selected from the group consisting of aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti) and boron (B) at 5.0 wt% (weight percent), and the rest are copper (Cu) It is created.

The precipitation strengthening effect was obtained by adding aluminum and silicon in addition to the spinodal decomposition strengthening effect.

In the above, strontium, titanium, boron, and the like were added to achieve microstructure.

In addition, the aluminum and silicon are added for the purpose of precipitation strengthening, but the refining effect by the strong deoxidation effect in the molten metal improves the fluidity of the molten metal, and the addition of a small amount of strontium, titanium, and boron is inoculated to refine the columnar tissue. In addition, it exhibits the effect of miniaturizing the matrix structure by inhibiting crystal growth during annealing heat treatment after plastic working in the manufacturing process.

According to the results of the experiment, aluminum has excellent refining effect among the elements having excellent aging enhancing effect.

In addition, strontium, titanium, and boron, which have excellent crystal refining effect, are inexpensive and easy to obtain as mother alloys such as aluminum-strontium, aluminum-titanium-boron, and the like.

And these elements are good to alloy when composited in this way, and the component loss is small.

In the case of the present invention, it is necessary to finely control the grains from the casting structure of the ingot to the processing structure in order to improve the workability up to thin plates and thin wires, and for this purpose, the effect from the casting ingot stage to the inoculation treatment Are the elements that can be obtained.

In addition, the reason for limiting the numerical value of each component has little effect under the limited range, and moreover, the numerical value is limited since it adversely affects the mechanical properties. More specifically, it is as follows. The reason for limiting (Ni) to 1.0 to 8.0 wt% (weight percentage) is that it is difficult to hot and cold work over the limited composition range, and this requires the use of equipment comparable to that of steel, which requires a large force. In the composition range of the present invention, the numerical value is limited to 1.0 to 6.0 wt% (% by weight) in the composition of the present invention. The reason for the limitation is that the price of the material rises above the limited composition range, a problem occurs in plastic working, and the material properties tend to deteriorate. In the composition of the present invention, the numerical value is limited to aluminum (Al), silicon (Si), and strontium (Sr). ), The element selected by mixing two or more elements from the group consisting of titanium (Ti) and boron (B) is limited to 0.1 to 5.0 wt% (percent by weight). There is a disadvantage that problems occur in plastic working, there is a disadvantage in that the addition effect is less than the composition range, the numerical range was limited to the composition range of the present invention.

The material strength of the copper-nickel-tin alloy may depend only on the spinodal decomposition strengthening effect, but in the present invention, precipitation, strengthening, and microstructure were introduced by adding aluminum, silicon, and titanium in addition to the spinodal decomposition strengthening effect. Strontium and boron act to spheroidize or finely and uniformly disperse the shape of the precipitates, i.e. aluminum, silicon, and titanium are added for the purpose of strengthening precipitation, but the flowability of the melt with the refining effect of strong deoxidation in the melt In addition, the addition of trace amounts of strontium and boron rounds and refines the shape of aging precipitates generated during processing heat treatment, and suppresses crystal growth during annealing heat treatment after plastic working in the manufacturing process, thereby miniaturizing matrix structures. .

In the manufacturing process, the production of ingots is performed by continuous casting or mold casting in the case of an alloy method that can be hot worked and tin alloy is 4% or less, with a thick sheet of ingot having a thickness of 70 mm or more or a large diameter rod having a diameter of Φ100 mm or more. Make an ingot,

In the case of an alloy scheme having 4% or more of tin, which is advantageous in cold working, the ingot was manufactured by continuous casting with a thin plate having an ingot thickness of 30 mm or less or a small diameter rod having a diameter of Φ 20 mm or less.

In the case of the plate or small diameter rod manufactured by cold rolling or extrusion, after homogenization to completely remove the casting structure by plastic processing of 85% or more, it is cooled by holding water at a temperature of 850 ± 50 ° C. for 0.5 to 1.0 hours. An emulsification process is performed.

Also, in the case of a plate or a wire rod produced by hot rolling or extrusion, the solution is subjected to solution cooling after holding at a temperature of 850 ± 50 ° C. for 0.5 to 1.0 hours, followed by water cooling.

The bar or plate in the intermediate state, which is solvated, is rolled or drawn as much as the cold working amount according to the target physical properties, and then maintained at 300 to 550 ° C. for 1 to 10 hrs as an aging treatment. Enhancement and Copper (Cu)-Nickel (Ni)-Aluminum (Al) and Silicon () of (Cu _x Ni _y ) _z Sn-type Spinoidal Decomposition Products in Nickel-Ni-Sn-based Alloys Since the reinforcement effect by Cu _x Al, Cu _y Ni _z Al, Ni _x Al, Cu _x Si, Cu _y Ni _z Si, and Ni _x Si type precipitates appearing in Si) alloy is obtained, a high strength copper alloy can be obtained.

These results show that even when the expensive nickel (Ni) and tin are reduced to 8% or less and tin (Sn) to 6% or less, respectively, the tensile strength is 1,000 Mpa or more and the elongation is 5 to 10%. A high strength copper alloy exhibiting 14 μΩcm can be produced.

Hereinafter, the production method of the present invention in more detail.

Copper alloy for high-strength wire and sheet, with alloy composition range of 1.0 to 8.0 wt% (weight percentage) nickel (Ni), 1.0 to 6.0 wt% (weight percentage) tin (Sn), and total amount of 0.1 to 5.0 wt% ( Weight percent) of at least two elements selected from the group consisting of aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti) and boron (B), and the basis weight so that the remainder is composed of copper (Cu) To do that,

After the basis weight is reached to the desired composition ratio, a part of the total weight of copper (Cu) weighted is laid on the bottom of the furnace, and a part of the total weight of nickel (Ni) weighted on it is covered again, and a part of the weighted copper (Cu) is again covered. The method of laminating nickel (Ni) and covering with copper (Cu) is repeatedly charged, and finally, covered with copper (Cu), and then started dissolving. When both copper and nickel are dissolved, slag is removed and then When the temperature reaches 1,250 ° C, the heating is stopped or a heat source lower than 1,250 ° C is used, including tin (Sn), aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti), boron ( A dissolution alloy step of continuously adding and stirring the elements selected as additional elements in B),

When alloying elements are dissolved and the melt temperature is 1100 ~ 1250 ℃, the flowability of the melt is improved.In the case of alloying method where the tin can be hot-processed to 4% or less, the thick plate of ingot having a thickness of 70 mm or more or a diameter of Φ100 mm Ingots are manufactured by continuous casting or mold casting with large diameter rods as described above, and in the case of an alloy scheme having 4% or more of tin, which is advantageous for cold working, a thin plate having an ingot thickness of 30 mm or less or a small diameter of Φ20 mm or less Continuous casting with a small diameter rod to make an ingot, and in the case of the plate or small diameter rod manufactured by the cold rolling or extrusion, after homogenization to completely remove the casting structure by plastic processing of 85% or more, it is 850 ± 50 ℃ After holding for 0.5 to 1.0 hours at the temperature, the solution is cooled and subjected to solution treatment. In the case of a plate or wire produced by hot rolling or extrusion, 0.5 to 1.0 hour is maintained at a temperature of 850 ± 50 ° C. After the step of cooling by water and performing a solution treatment, the bar or plate in the intermediate state of this solution solution is rolled or drawn as much as the cold working amount according to the target properties of the target, and then aged at 300 to 550 ° C. as an aging treatment. When air-cooled after holding for ~ 10hr, the reinforcing effect of (Cu _x Ni _y ) _z Sn-type spinoidal decomposition products and copper (Cu) -nickel (Cu) -nickel (Ni) -tin (Sn) alloy Reinforcement effect by Cu _x Al, Cu _y Ni _z Al, Ni _x Al, Cu _x Si, Cu _y Ni _z Si, Ni _x Si type precipitates in Ni) -Aluminum (Al) and Silicon (Si) alloys The aging step is obtained.

The following Table 1 is an example of the alloys presented in the present invention, Tables 2 and 3 are changes in tensile strength and elongation according to the processing heat treatment, Table 4 is a change in the electrical resistivity value according to the processing heat treatment.

In Table 2, Table 3 and Table 4, when 85% copper (Cu) -9% nickel (Ni) -6% tin (Sn) ternary alloy is aged for 3 hours at 300 to 400 ° C, tensile The strength is 1,043 to 1,195 MPa and the elongation is 7 to 9%, and the electrical resistivity value is 10 to 14 µΩcm.

However, the addition of only aluminum (Al), silicon (Si) and titanium (Ti) to copper (Cu) -9% nickel (Ni) -6% tin (Sn) -based steels did not add tensile strength up to 1250 MPa. Compared to 1,195 MPa, which is the highest tensile strength in the case, the increase is not very remarkable, and in some cases, it is rather lowered to 1,000 MPa or less, and the elongation is greatly reduced to 5% or less, and the electrical resistivity is 2 to 5 An increase in μΩcm has been shown to compromise conductivity.

Meanwhile, in the case of the present invention, in the copper (Cu) -nickel (Ni) -tin (Sn) -aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti), and boron (B) -based alloys As a result, a portion of nickel (Ni) and tin (Sn) is reduced and a small amount of two or more elements of aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti) and boron (B) is added thereto. In the alloy system in one case, a high strength copper alloy having a tensile strength of 1,000 Mpa or more and an elongation of 5 to 10% is obtained, and an electrical resistivity of 10 to 14 µΩcm can be produced.

In particular, when alloying elements such as aluminum (Al), silicon (Si), strontium (Sr), titanium (Ti), and boron (B) are added together, many alloys are subjected to high temperature aging at 450 ° C. It maintains high strength of 900 MPa or more.

The above results show that new high strength materials such as copper (Cu) -nickel (Ni) -tin (Sn) -aluminum (Al), silicon (Si), strontium (Sr), and titanium (Ti) can obtain tensile strengths of 1000 MPa or more. ), Has the effect of developing a boron (B) alloy, in particular, it has the advantage of maintaining high strength without deterioration even when exposed to a temperature of 450 ℃ or more high temperature aging temperature. The comparative table which shows the Example and the Example of a comparative composition. '*' Corresponds to the composition range corresponding to the object of the present invention.

Table 1 Types of Alloys and Alloy Components (wt%)

Alloy type Ni Sn Al Si Sr Ti B Cu N9S6 9 6 - - - - - Remainder N9S6Al.5 9 6 0.5 - - - - Remainder N9S6Si.5 9 6 - 0.5 - - - Remainder N9S6Ti.5 9 6 - - - 0.5 - Remainder N9S6Al1 9 6 1.0 - - - - Remainder N9S6Si1 9 6 - 1.0 - - - Remainder N9S6Ti1 9 6 - - - 1.0 - Remainder N9S6Al2 9 6 2.0 - - - - Remainder N9S6Si2 9 6 - 2.0 - - - Remainder N9S6Ti2 9 6 - - - 2.0 - Remainder N6S4Al1 6 4 1.0 - - - - Remainder N6S4Al2 6 4 2.0 - - - - Remainder * N6S4Al.5Si.5 6 4 0.5 0.5 - - - Remainder * N6S4Al.5Ti.5 6 4 0.5 - - 0.5 - Remainder * N6S4Si.5Ti.5 6 4 - 0.5 - 0.5 - Remainder * N6S4Al.5Si.5Ti.5 6 4 0.5 0.5 - 0.5 - Remainder * N4S2Al2Si.5 4 2 2.0 0.5 - - - Remainder * N6S2Al2Si.5 6 2 2.0 0.5 - - - Remainder * N6S4Al1Si1 6 4 1.0 1.0 - - - Remainder * N8S2Al2Si.5 8 2 2.0 0.5 - - - Remainder * N8S4Al1Si1 8 4 1.0 1.0 - - - Remainder * N6S2Al1.8Sr.2 6 2 1.8 - 0.2 - - Remainder * N6S2Al1.8Sr.2Si.5 6 2 1.8 0.5 0.2 - - Remainder * N6S2Al4.5Sr.5 6 2 4.5 - 0.5 - - Remainder * N6S2Al1.8Ti.1B.02Si.5 6 2 1.8 0.5 - 0.1 0.02 Remainder * N6S2Al1.8Sr.1Ti.05B.01Si.5 6 2 1.8 0.5 0.1 0.05 0.01 Remainder * N6S2Al4.6Sr.25Ti.13B.03 6 2 4.6 - 0.25 0.13 0.03 Remainder * N6S2Al4.6Sr.25Ti.13B.03Si.5 6 2 4.6 0.5 0.25 0.13 0.03 Remainder

Table 2 Change in Tensile Strength by Heat Treatment (Unit: MPa)

Sample Name Solvent state Cold working condition 73% 3 hours aging 300 ℃ 350 ℃ 400 ℃ 450 ℃ N9S6 413 896 1,089 1,195 1,043 687 N9S6Al.5 418 - 1,007 1,093 1,123 1,062 N9S6Si.5 508 - 1,151 1,202 1,175 1,029 N9S6Ti.5 492 - 1,102 1,181 1,210 975 N9S6Al1 308 984 1,104 1,179 1,154 1,063 N9S6Si1 551 1,001 1,065 1,158 1,056 914 N9S6Ti1 561 1,004 1,120 1,250 1,036 896 N9S6Al2 472 933 1,104 1,156 1,190 1,140 N9S6Si2 365 951 1,067 970 998 925 N9S6Ti2 413 841 865 859 837 702 N6S4Al1 - - 1,023 - - - N6S4Al2 - - 1,033 - - - * N6S4Al.5Si.5 - 823 1,012 1,046 1,052 987 * N6S4Al.5Ti.5 - 872 871 941 886 880 * N6S4Si.5Ti.5 - 850 891 918 919 861 * N6S4Al.5Si.5Ti.5 - 830 882 914 923 932 * N4S2Al2Si.5 364 745 845 944 973 890 * N6S2Al2Si.5 436 804 926 946 1,027 877 * N6S4Al1Si1 489 845 971 1,040 1,032 823 * N8S2Al2Si.5 603 737 843 971 1,000 1,061 * N8S4Al1Si1 434 872 990 1,032 1,106 1,044 * N6S2Al1.8Sr.2 370 632 671 720 779 870 * N6S2Al1.8Sr.2Si.5 401 688 845 922 985 961 * N6S2Al4.5Sr.5 331 796 870 909 939 853 * N6S2Al1.8Ti.1B.02Si.5 486 730 833 922 961 926 * N6S2Al1.8Sr.1Ti.05B.01Si.5 401 745 880 978 1,022 981 * N6S2Al4.6Sr.25Ti.13B.03 - 543 595 668 708 801 * N6S2Al4.6Sr.25Ti.13B.03Si.5 353 789 1,022 1,057 1,081 949

Table 3 Change in elongation due to heat treatment (Unit:%)

Sample Name Solvent state Cold working condition 73% 3 hours aging 300 ℃ 350 ℃ 400 ℃ 450 ℃ N9S6 50 6 7 - 9 15 N9S6Al.5 56 - 9 6 4 5 N9S6Si.5 26 - One One 2 2 N9S6Ti.5 24 - 3 3 5 10 N9S6Al1 20 6 3 3 2 2 N9S6Si1 22 4 One One 2 3 N9S6Ti1 26 5 2 2 3 5 N9S6Al2 - - - - - - N9S6Si2 - - One One One One N9S6Ti2 - - One One One One N6S4Al1 - - - 11 - - N6S4Al2 - - - 3 - - * N6S4Al.5Si.5 - 7 5 4 5 7 * N6S4Al.5Ti.5 - 4 7 5 6 8 * N6S4Si.5Ti.5 - 6 7 7 7 9 * N6S4Al.5Si.5Ti.5 - 5 5 5 5 9 * N4S2Al2Si.5 56 12 8 4 5 12 * N6S2Al2Si.5 38 7 2 2 4 11 * N6S4Al1Si1 37 5 2 3 4 9 * N8S2Al2Si.5 29 8 7 6 6 9 * N8S4Al1Si1 37 3 One 2 3 4 * N6S2Al1.8Sr.2 31 7 6 4 3 4 * N6S2Al1.8Sr.2Si.5 29 5 7 6 6 7 * N6S2Al4.5Sr.5 28 4 5 3 3 3 * N6S2Al1.8Ti.1B.02Si.5 34 6 7 3 3 5 * N6S2Al1.8Sr.1Ti.05B.01Si.5 29 6 10 6 7 8 * N6S2Al4.6Sr.25Ti.13B.03 14 3 One 2 2 2 * N6S2Al4.6Sr.25Ti.13B.03Si.5 13 6 2 2 2 5

Table 4 Variation of Electrical Resistivity by Heat Treatment (Unit: μΩcm)

Sample Name Solvent state Cold working condition 73% 3 hours aging 300 ℃ 350 ℃ 400 ℃ 450 ℃ N9S6 18 18 14 12 10 9 N9S6Al.5 17 - 16 15 14 14 N9S6Si.5 19 - 14 13 10 8 N9S6Ti.5 22 - 15 15 11 6 N9S6Al1 25 20 18 17 15 11 N9S6Si1 19 18 14 13 11 9 N9S6Ti1 18 17 13 11 9 6 N9S6Al2 - - - - - - N9S6Si2 - - 15 14 13 - N9S6Ti2 12 - 11 10 10 10 N6S4Al1 - - - 14 - - N6S4Al2 - - - 17 - - * N6S4Al.5Si.5 - 16 14 13 11 10 * N6S4Al.5Ti.5 - 14 12 11 10 9 * N6S4Si.5Ti.5 - 14 12 10 10 9 * N6S4Al.5Si.5Ti.5 - 14 12 12 10 9 * N4S2Al2Si.5 8 9 8 7 7 6 * N6S2Al2Si.5 9 10 9 8 8 6 * N6S4Al1Si1 8 9 8 7 7 7 * N8S2Al2Si.5 8 10 9 10 9 7 * N8S4Al1Si1 10 10 9 8 7 7 * N6S2Al1.8Sr.2 8 9 9 9 9 7 * N6S2Al1.8Sr.2Si.5 9 10 9 9 8 7 * N6S2Al4.5Sr.5 9 10 10 10 10 7 * N6S2Al1.8Ti.1B.02Si.5 9 10 9 9 8 7 * N6S2Al1.8Sr.1Ti.05B.01Si.5 9 10 9 9 8 6 * N6S2Al4.6Sr.25Ti.13B.03 10 11 11 11 10 7 * N6S2Al4.6Sr.25Ti.13B.03Si.5 10 11 10 9 8 7

The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.

As described above, the present invention provides cost reduction and hot plasticity by reducing a part of expensive Ni and Sn in the existing Cu-9Ni-6Sn alloy, and has economic feasibility in mass production. It is a high-strength alloy with a fine structure, and has improved strength at high temperature to obtain tensile strength of 1,000 Mpa or more, elongation of 5 to 10%, and electrical resistivity of 10 to 14 μΩcm. This is greatly expected.

Claims (2)

In the copper-nickel-tin alloy for high strength wire and plate, 1.0 to 8.0 wt% (wt%) nickel (Ni), 1.0 to 6.0 wt% (wt%) tin (Sn), and aluminum (Al) and silicon (total amount of 0.1 to 5.0 wt% (wt%)). High-strength wire and plate copper (Cu), characterized in that at least two elements selected from the group consisting of Si), strontium (Sr), titanium (Ti) and boron (B), and the remainder is composed of copper (Cu) -Nickel (Ni)-Tin (Sn)-Aluminum (Al), Silicon (Si), Strontium (Sr), Titanium (Ti), Boron (B) alloys. delete