WO2004090181A1 - Copper base alloy - Google Patents

Abstract

A copper base alloy, characterized in that it comprises an added metal which forms an alloy or an intermetallic compound with Bi, Pb and a substance formed by the binding of Bi and Pb, and exhibits improved mechanical properties, in particular tensile strength, at a high temperature due to the incorporation of the added metal, wherein the added metal is preferably one or more metals selected from the group consisting of Te, P, Zr, Ti, Co, In, Ca, B and mish metal. The formation of an alloy or an intermetallic compound of the added metal with Bi, Pb and a substance formed by the binding of Bi and Pb in the structure of the copper alloy results in the improvement of the tensile strength at a high temperature, which leads to the preparation of a Pb-substantially free copper alloy having mechanical properties being further near to those of CAC406.

Description

 Description Copper-based alloy Technical field

 The present invention relates to a copper-based alloy suitable for, for example, plumbing, cocks, fittings, and other water-supply plumbing equipment and the like, and more particularly to a copper-based alloy having improved mechanical properties at high temperatures, particularly improved tensile strength. Background art

 In general, bronze material (CAC 406) is excellent in formability, corrosion resistance, machinability, and pressure resistance, and has a good flow of molten metal when melted. In general, it is widely used for plumbing equipment such as pulp, cook, and wed.

 However, recently, Pb (lead) contained in bronze has a serious social problem as it has an adverse effect on the human body, and the amount of Pb leached into tap water is being strictly regulated worldwide.

 Under such circumstances, it is urgently necessary to develop a new useful Pb-less copper alloy. Among them, various types of Bi-type, Bi_Sb-type, Bi-Se-type, etc. Materials are being developed. ,

 For example, Japanese Patent Publication No. Hei 5-63335 6 proposes a lead-free copper alloy in which Bi is added in place of lead in a copper alloy to improve machinability and prevent dezincification.

Also, in Japanese Patent No. 2888982, the lead-free bronze with increased mechanical strength, which suppresses the porosity generation at the time of fabrication due to the addition of Bi for improving machinability by adding Sb, is disclosed. Proposed. Further, in the specification of US Pat. No. 5,614,038, addition of Se and Bi precipitates a Zn—Se compound in particular, and reduces mechanical properties and machinability and formability by CAC4. A bronze alloy substantially equivalent to 06 has been proposed.

 In many cases, Pb-less copper alloys are manufactured using the same manufacturing equipment as conventional CAC 406 during mass production. Pb may be mixed.

 In addition, the above Pb-less copper alloys are manufactured using recycled materials such as scrap in consideration of commercially available ingots and costs and the environment. However, these materials contain Pb as inevitable impurities. Is inevitable.

 Therefore, at present, the above Pb-less copper alloy allows the content of Pb of 0.4% by weight or less at the unavoidable impurity level even if the production equipment is dedicated to the Pb-less copper alloy.

 As disclosed in Japanese Patent Publication No. 5-635953, Japanese Patent No. 2889829, U.S. Pat.No. 5,614,38, as an alternative element to Pb, B In the case of Pb-less bronze containing i, which contains a small amount of P as described above, if the material is exposed to a high temperature exceeding 100 ° C, the mechanical properties will increase. However, the tensile strength may be reduced.

 This is because, as a substitute for Pb, if Pb-less bronze containing Bi contains even a small amount of Pb, it does not form a solid solution with Cu. This is because it exists as a B i -P, b binary eutectic in the crystal grain boundary and in the crystal grains, which locally becomes a weak portion at high temperatures and decreases the tensile strength.

 Here, the eutectic is a structure formed by simultaneously crystallizing α and / 3 crystals from the melt, and the crystal grains are very fine, and α and are mixed.

The decrease in tensile strength affects the actual use of plumbing equipment for water supply ―

Although not three, the market demands the supply of Pb-less bronze materials that provide mechanical properties closer to CAC 406.

 The present invention has been developed in view of the above circumstances, and its object is to provide an alloy with B i, alone or combined with each other; an alloy with Pb, or an intermetallic compound in an alloy structure. Forming has improved the reduction in tensile strength at high temperatures and has further brought the mechanical properties closer to CAC 406: to provide a Pb-less copper-based alloy. Disclosure of the invention

 In order to achieve the above object, the present invention provides a mechanical property at a high temperature by adding Bi or Pb alone or in a state of being bonded to each other and an additive element forming an alloy or an intermetallic compound. In particular, it is a copper base alloy with improved tensile strength.

 The additive element is a copper-based alloy selected from one or more of the group consisting of Te, P, Zr, Ti, Co, In, Ca, B, and misch metal.

 The additive element is a copper-based alloy containing 0.01 to 2.0% by weight. This is a copper-based alloy that suppresses the formation of a Bi-Pb binary eutectic in the alloy structure.

 The copper-based alloy contains at least copper containing at least 2.8 to 6.0% by weight of Sn, 1.0 to 12.0% by weight of Zn, and 0.1 to 3.0% by weight of Bi. It is a base alloy.

 The above copper-based alloy weighs at least Sn 2.8-6.0. / 0, Zn 1.0-12.0% by weight, Bi 0.1-1.2.4% by weight, Se 0.05-1.

It is a copper-based alloy containing 2% by weight.

The content of Pb contained in the copper-based alloy was set to 0.25% by weight or less. It is a copper-based alloy. '' Brief description of the drawings

 FIG. 1 is a graph showing the test results of tensile test 1.

 FIG. 2 is a graph showing test results of the tensile test 2.

 FIG. 3 is a graph showing test results of the tensile test 3.

 FIG. 4 is a graph showing the test results of the tensile test 3.

 FIG. 5 is a graph showing the test results of the tensile test 3.

 FIG. 6 is a graph showing the test results of the tensile test 4.

 FIG. 7 is a graph showing the test results of the machinability test.

 FIG. 8 is a graph showing the results of the Charpy impact test of the samples No. 62 to No. 64 and the B i —P b area ratio.

 FIG. 9 is a graph showing the Charpy impact test results of samples No. 65 to No. 67 and the B i -P b area ratio.

 FIG. 10 is a metallographic photograph (magnification: 400 times) of a standard sample (comparative example).

 FIG. 11 is a mapping of each element in the metallographic photograph of FIG.

 FIG. 12 is a metallographic photograph (magnification 400 times) of a sample No. 63 containing 0.09% by weight of P. ,

 FIG. 13 is a mapping of each element in the metallographic photograph of FIG.

 FIG. 14 is a photograph of a metal structure of sample No. 66 containing 0.2% by weight of Te (magnification: 400 times).

FIG. 15 shows the matting of each element in the metallographic photograph of FIG. _

5 Fig. 16 shows tissue observation photographs (before and after image processing) in which the area ratio of sample No. 62 to No. 64 was measured.

 FIG. 17 shows tissue observation photographs (before and after image processing) in which the area ratio of the samples No. 65 to No. 67 was measured. BEST MODE FOR CARRYING OUT THE INVENTION

 In the copper-based alloy of the present invention, the meaning of Bi and Pb, which are present alone or in a state of being bonded to each other, and the meaning of addition of an additional element forming an alloy or an intermetallic compound will be described.

 When an additive element is added to the alloy, the alloy structure contains Bi-M intermetallic compound (or alloy), Pb-M intermetallic compound (or alloy), or Bi-Pb-M intermetallic compound (or alloy). Or alloy) to suppress the generation of Bi-Pb binary eutectic in the alloy structure. Here, M is an additive element, and one or two of the group consisting of Te, P ヽ Zr, Ti, Co, In, Ca, B, and mischmetal. More than one species was selected.

 This is because it contains one or more additional elements selected from the group consisting of Te, P, Zr, Ti, Co, In, Ca, B, and metal, etc. In the solidification process of solids, B i — P b Binary eutectic crystallizes faster than the eutectic crystallizes in the alloy structure and has a higher melting point than B i — P b binary eutectic. Intermetallic compounds (or alloys), Pb-M intermetallic compounds (or alloys), or Bi-Pb-M intermetallic compounds (or alloys), etc. are formed, and Bi-Pb This is because Bi and Pb that form the binary eutectic are reduced, and thereby the generation of the Bi—Pb binary eutectic is suppressed. As described above, by suppressing the generation of the Bi-Pb binary eutectic, the mechanical properties at high temperatures are improved.

In particular, preferred copper-based alloys are Cu-Sn-Zn_Bi-based and Cu-Sn-Zn-Bi-Se-based copper-based alloys. The following forms containing the component elements are adopted, and the range of each component and the reason thereof will be specifically described in detail. '

 Sn: 2.8 to 6.0% by weight

ο; contained as a solid solution in the phase to improve the wear resistance and corrosion resistance by improving strength and hardness, and forming a protective layer of Sn 保護₂ . Sn is an element that decreases the machinability as the content increases in the practical component range. Therefore, it is necessary to ensure the mechanical properties while keeping the content low, and within the range that does not lower the corrosion resistance. As a more preferable range, attention should be paid to the elongation characteristics that are easily affected by the content of Sn, and even if the manufacturing conditions are slightly different, the elongation around 4.0% by weight with the best characteristics can be reliably obtained. , 3.5-4.5% by weight.

 Zn: 1.0 to 12.0% by weight

 It is effective as an element that improves hardness and mechanical properties, especially elongation, without affecting machinability. The effective content for improving the high-temperature properties is 1.0% by weight or more, considering the content of additional elements such as Te that forms an alloy or an intermetallic compound with Bi and Pb and the content of Se. . In addition, Zn suppresses the generation of S11 oxide due to gas absorption into the molten metal, and is also effective for the soundness of the molten metal. Therefore, in order to exert this effect, the content of 4.0% by weight or more is effective. It is. More practically, the content is preferably 5.0% by weight or more from the viewpoint of compensating for the suppression of Bi and Se. On the other hand, since Z1! Has a high vapor pressure, it is desirable to contain 12.0% by weight or less in consideration of securing a working environment and mirroring. Considering the economics, about 8.0% by weight is optimal.

 B i: 0.1 to 3.0% by weight

A content of 0.1% by weight or more is effective for improving machinability. In order to prevent porosity generated in the product during the solidification process of the structure and to prevent the occurrence of shrinkage cavities and other structural defects, and to ensure the soundness of the product, the content should be at least 0.6% by weight. It is effective. On the other hand, in order to ensure the required mechanical properties, it is effective to set the content to 3.0% by weight or less, and in particular, to set the content to 1.7% by weight or less while suppressing the content. Sufficient confirmation of mechanical properties It is effective to keep. Practically, the content of Bi is preferably 0.1 to 2.4% by weight together with the content of Se, and about 1.3% by weight is optimal considering the optimum content of Se.

 Se: 0.05 to: L. 2% by weight

A component that exists as an intermetallic compound of Bi-Se, Zn-Se, and Cu-Se in the copper alloy, and contributes to ensuring the soundness of machinable materials, similar to Bi. is there. Therefore, the content of Se is effective for the mechanical properties and the soundness of animals while suppressing the content of Bi. The upper limit of the content was set at 1.2% by weight from the viewpoint of economy. Although a small amount of Se contributes to ensuring the soundness of foods, it is effective to contain 0.05% by weight or more in order to obtain its effect reliably. And Especially about 0.2 weight. / ₀ is optimal.

 Te: 0.01 to 1.0% by weight

 Te is a component that improves the machinability by dispersing without dissolving in the matrix. However, the effect of improving the machinability by Te is not exhibited at less than 0.01% by weight. Further, in order to crystallize the intermetallic compound Te Pb (melting point: about 917 ° C.) and to suppress the generation of Bi—Pb binary eutectic, 0.05% by weight or more is required. However, the content exceeding 1.0% by weight is not economical, and does not improve the decrease in tensile strength corresponding to the content. From these points, the content of the bat 6 is set to 0.01 to 1.0% by weight, preferably to 0.05 to 0.5% by weight.

 P: 0.01 to 0.5% by weight

Contains 0.01 to 0.5% by weight for the purpose of promoting deoxidation of the molten metal and producing sound foods. Excess content lowers the solidus and causes segregation. In addition, P has the function of refining crystal grains and improving mechanical properties. When P is added as a deoxidizing agent, the P content in the alloy is usually 0.015 to 0.03% by weight, but Bi—Pb binary eutectic (melting point about 1%) 2 5 ° C) crystallized intermetallic compound P b ₃ P ₂ is higher melting point than, B i - to suppress the formation of P b 2 ternary co Akirabutsu, the tensile strength at high temperatures under low -

8 In order to improve the following, the content is preferably 0.05 to 0.1% by weight.

 P b: 0.25% by weight or less

 Even at the impurity level, Pb may be contained in the range of 0.3 to 0.4% by weight. Therefore, the range of unavoidable impurities that do not actively contain Pb is set to 0.25% by weight or less.

 In addition to the above Te and Zr, in the steel-base alloy of the present invention, the additional elements contained for the purpose of suppressing the generation of the Bi—Pb binary eutectic are Te, P, It is possible to select one or more from the group consisting of Zr, Ti, Co, In, Ca, B, and misch metal, and the content is from 0.01 to 0.1 1.0% by weight is preferred. Also, with respect to a copper-based alloy containing Sb in an amount of 0.05 to 0.5% by weight, the addition of the above-mentioned additional element suppresses the generation of a Bi—Pb binary eutectic, It has the effect of improving high-temperature characteristics. In addition, inevitable impurities in the copper-based alloy of the present invention include Fe (0.3% by weight or less), A1 (0.01% by weight or less), and Si (0.01% by weight or less). Can be

Cu—Sn—Zn—Bi—Se-type Cu—Sn—Zn—B containing Te and Zr as additional elements in the leadless copper-based alloy of the present invention Perform a tensile test on i-type bronze material and explain the test results. The tensile test was performed using a CO ₂鎳 type mold at a temperature of 113 ° C, mirror-shaped into a JISA model, and then manufactured by cutting. The test was performed using an Amsula tensile tester. The tensile test was performed on each sample n = 4, and the test results are average values.

 The tensile test was performed under the following four conditions.

 (Test 1)

 Te content: 0 to: I, 48% by weight, Test temperature: room temperature (22 ° C), 100 ° C and 150 ° C. Table 1 shows the composition of the sample. In Test 1, the effect of Te content is confirmed.

table 1

(Test 2)

The content of Te: 0 to 0.17% by weight, the content of Se: 0 to 1.2% by weight, and the test temperature: 150 ° C. Table 2 shows the composition of the sample. In this test 2, the effect of Te content is confirmed for samples with different Se content.

Chemical component value (ί: wt%)

Sample U m U _n R! P `` hup (nnm T β

 O. 1 o π n t ^ tSil O Q. 1 o 1 ft .. 911 li << iJ 07 rito ^ CM Q

 0 0 つ 1 Π A Λ! “!” 1fi \ i Ω G nfill Mn 11 ος G

 Re 0 nOQfi o Totoki Ai T7 1 4 o Π OOQQ Q Tao 8th Mn 1 QA o

 ? o ς · 太 8th 1 o 1 ku 1 4 \ ku 0 Π11 001 oc

 JfcB 1 u 7 Q 4 Work o fin

 Tai B Bn 17 17 1 1 4 1 1 3

 n 1 Q

 ¾M * to> 00 01 0 Π1 n 00Q7 011 Honshu No.19 Zik A Zek Λ0 Invention No.20 86.0 8.16 4.02 1.3 0.43 0.0135 205 0.12 Invention Mo.21 86.2 7.99 3.96 1.22 0.58 0.0104 203 0.1 The present invention fto.22 84.9 8.38 4.09 1.36 1.20 0.0162 216 0.11 The present invention Mo.23 86.6 3 1.36 0.42 0.0144 207 0.5 Present invention No.26 85.5 8.25 4.08 1.43 0 „64 0.0141 213 0.17 Present invention Mo.27 85-0 0 17.17 4.16 1.41 1.18 0.0118 225 0.15

(Test 3)

Te content: 0-0.22% by weight, 36 content: 0-0.83 Weight ⁰ /. , Zn content: 1.02 to 8.53% by weight, Test temperature: 150 ° C. Table 3 shows the composition of the sample. This test 3 confirms application to low Z11.

Table 3

(Test 4)

 Zr content: 0 to 0.21% by weight, test temperature: room temperature (20 ° C), 100 ° C and 150 ° C. Table 4 shows the composition of the sample. In Test 4, the effect of Zr content is confirmed.

Table 4 Chemical value (■! Rank: wt%)

5 Material CuZnSnBiSePbZr Comparative Example No.55 86.9 7.47 4.00 1.31 0.17 0.054 212 0 Invention No.56 86.3 8.28 3.92 1.25 0.18 0.048 256 0.05 Invention No.57 86.4 8.00 4.05 1.21 0.17 0.052 239 0.12 Invention No. 58 86.2 7.87 4.05 1.37 0.18 0.057 253 0.21 The results of Test 1 are shown in Table 5 and FIG. From the results, Te was 0.04% by weight and 0.11% by weight. /. , 0.16% by weight, 0.50% by weight, 0.99% by weight, 1.48% by weight ° / _{0, the} content of 100 ° (in standard: 15.7 N / N compared to mm ^2, respectively ^{1 9 8. 3 N / mm 2} , 2 1 0. 1 N mm 2, 2 1 8. 6 N / mm 2, 2 1 5. 9 N / mm 2, 2 0 2 .3 N / mm ² _s 1 97.7 N / mm ² with improved tensile strength.Even at 150 ° C, compared to the standard 155.4 N / mm ² , each has 1 6 8 0 N / mm ² , 1 85.5 N / mm ² , 2 09.7 N / mm ² 2 0 8.

 _ ヽ ノ a

5 N / mm ² , 19 5 l N / mm ² , 194.8 NZmm ² and Q tensile strength improved. For this reason, by adding Te, sufficient tensile strength can be obtained at room temperature, and further, tensile strength at high temperatures can be improved. However, the content exceeding 1.0% by weight is not economical, so the content was set to 1% by weight or less. As shown in Table 5 and FIG. 1, the tensile strength at a high temperature is highest at TeO.16% by weight.

Table 5

試験 2の結果を表 6及び第 2図に示す。 なお、 S e = 0、 0. 2重量 %、 0. 4重量％、 0. 6重量％、 1 . 2重量％はいずれも狙い値であ る。 この結果から、 S e = 0のとき、 T eを 0、 0. 0 6重量⁰ /₀、 0 . 1 1重量％、 0. 1 4重量％含有させた試料 N o . 8、 1 3、 1 8、 2 3において、 引張強度は、 それぞれ 1 0 4. 7 N/ m 1 0 9. 1 N/mm 1 1 8. 9 N/mm², 1 2 4. 6 NZra m ²と引張強度が 若干向上した。 S e = 0. 2のとき、 T eを 0、 0. 0 6重量 °/₀、 0. 1 0重量⁰ /₀、 0. 1 4重量⁰ /。含有させた試料 N o . 9、 1 4、 1 9、 2 4において、 引張強度は、 それぞれ 1 5 0. 0 N/mm²、 1 5 0. 7 N/mm 1 6 1 . 8 N/mm 1 6 7. 3 NZmm ²と S e = 0の 場合より引張強度が向上した。 同様に S e = 0. 4のとき、 T eを 0、 0. 04重量％、 0. 1 2重量％、 0. 1 5重量 °/₀含有させた試料 N o . 1 0、 1 5、 2 0、 2 5において、 引張強度は、 それぞれ 1 4 6. 7 Nノ mm²ヽ 1 4 8. 2 N/mm², 1 8 5. 5 NZmm²、 2 0 4. 7 NZinm²であり、 S e = 0. 6のとき、 T eを 0、 0. 0 5重量。/₀、 0. 1 0重量％、 0. 1 7重量％含有させた試料 N o . 1 1、 1 6、 2 1、 2 6においては、 それぞれ 1 5 9. 6 N/ m 1 5 6. 4Nノ mm²、 1 8 8. 0 N/mm\ 2 04. 4 NZmm²であり、 S e = l . 2のとき、 T eを 0、 0. 0 6重量⁰ /₀、 0. 1 1重量％、 0. 1 5重 量⁰ /₀含有させた試料 N o . 1 2、 1 7、 2 2、 2 7においては、 それぞ れ 1 6 3. 5 N/mm²、 1 7 6. 6 N/mm²、 2 0 1. 2 N / m m ² 、 2 1 5. 3 N/mm²であり、 T eの含有量の増加に伴い引張強度が 向上した。 このことは、 T eの含有に加え、 S eの含有量を増すことに より、 高温での引張強度が改善されていることを示すものである。

The results of Test 2 are shown in Table 6 and FIG. Note that Se = 0, 0.2% by weight, 0.4% by weight, 0.6% by weight, and 1.2% by weight are all target values. The results, S when e = 0, the T e 0, 0. 0 6 wt _^0/0, 0.1 1 wt%, 0.1 4 samples were contained wt% N o. 8, 1 3, In 18 and 23, the tensile strength was 104.7 N / m 109.1 N / mm 1 18.9 N / mm ² and 1 24.6 NZra m ² respectively. Slightly improved. When S e = 0. 2, a T e 0, 0. 0 6 wt ° / _0, 0.1 0 wt _^0/0, 0.1 4 weight ⁰ /. In the contained samples No. 9, 14, 19, and 24, the tensile strengths were 150.0 N / mm ² and 150.7 N / mm 16 1.8 N / mm, respectively. 1 67.3 NZmm ² and S e = 0 The tensile strength improved as compared with the case. Similarly, when S e = 0.4, samples No. 10, 15 and 15 containing Te at 0, 0.04 wt%, 0.12 wt%, 0.15 wt ° / ₀ in 2 0, 2 5, the tensile strength are each 1 4 6. 7 N Roh mm ²ヽ^{1 4 8. 2 N / mm 2} , 1 8 5. 5 NZmm 2, 2 0 4. 7 NZinm 2, When S e = 0.6, Te is 0, 0.05 weight. For samples No. 11, 16, 21, and 26 containing / ₀ , 0.10% by weight, and 0.17% by weight, respectively, 159.6 N / m 15 6. 4N Bruno mm ^2, 1 8 8. was 0 N / mm \ 2 04. 4 NZmm 2, when the S e = l. 2, a T e 0, 0. 0 6 wt _^0/0, 0.1 1 wt%, 0.1 5 by weight _^0/0 sample was contained N o. 1 2, 1 7, 2 2, at 2 7, respectively is ^{1 6 3. 5 N / mm 2} , 1 7 6. 6 N / mm ² , 201.2 N / mm ² , 25.3 N / mm ² , and the tensile strength improved with an increase in the Te content. This indicates that the tensile strength at high temperatures was improved by increasing the content of Se in addition to the content of Te.

¾.

Tensile strength

 Ogi W, / mm

 104 7

 Mn Q 150 0

Mn 11

No 13 109 1

 Mo, 14 "! 50.7

 Mo 15 148.2

 Mn 16 156 A

 Mo, 1] 7 ΐ7β

 11 »Q

 M 1Q

 Mn 20

 Mo.21 188.0

 No.22 201.2

 Ha.23 124.6

 Mo.24 167.3

 No.25 204.7

 Mo.26 204.4

 o.27 "1

In particular, as shown in FIG. 2, the inclusion of 0.2% by weight of Se improves the tensile strength at high temperature by about 50% compared to a specimen containing no Se. When the content of Ding 6 is 0.05% by weight or more, the tensile strength at high temperatures is further improved. As the content of Se increases, the tensile strength at high temperatures also increases, but the increase tends to be gentle. In this example, the upper limit of the content of Se is set to 1.2% by weight from the viewpoint of economy, but considering the rate of improvement in tensile strength, it is preferable to set the upper limit to 0.4% by weight. In particular, 0.2% by weight is optimal.

The results of Test 3 are shown in Table 7 and FIGS. 3 to 5. Note that Z n == 2 ―

16 weight. /. , 4 wt% and 8 wt%, S e = 0, 0.3 wt. /. And 0.6% by weight are both target values. From this result, the level of Zeta eta == 2, if the S e = 0, the T e 0, 0. 1 2 wt%, 0.2 1 wt _^0/0 containing sample N o. 2. 8 to N o. tensile strength at 3 0 are each ^{1 2 1. 4 N / mm 2} , 1 5 0. 7 N / mm 2 N 1 5 5. 5 N / mni 2, the S e = 0. 3 when the T e 0, 0. 1 0 wt%, 0.2 1 wt _^0/0 containing sample N o. 3 1~N o. 3 tensile strength at 3, respectively 1 7 0. 4 N / mm '1 98.7 N / mm 2 0 0.4 N / mm ² and when S e = 0.6, Te is 0, 0.09% by weight, 0.22 weight ⁰ / ₀ containing samples N o. 3 4~N o. tensile strength at 3 6, respectively ^{1 5 4. l N / mm 2} , 1 9 8. 0 N / mm 2, 2 1 5. 8 NZmm 2 Yes, tensile strength improved with increasing Se and Te contents. Also, at the level of Zn = 4% by weight (Sample No. 37 to No. 45) and 8% by weight (Sample No. 46 to No. 54), S e = 0 Although the improvement in tensile strength with increasing Te content is less than when Se = 0.3% by weight and 0.6% by weight, the tensile strength increases with Se = 0.3% by weight and 0.6% by weight. %, The tensile strength improved with an increase in the content of Se and Te. This indicates that the tensile strength at high temperatures was improved by increasing the content of Se in addition to the content of Te, as in Test 2. As shown in Table 7 and FIGS. 3 to 5, even if the Zn content is low, the effect of the present invention can be obtained.

Table 7

Tensile strength

Sample N / mm ²

 No.28 121.4

 No.29 150.7

 No.30 155.5

 No.31 170.4

 No.32 198.7

 No.33 200.4

 No.34 154.1

 No.35 198.0

 No.36 215.8

 No.37 117.1

 No.38 161.1

 No.39 174.6

 Mo.40 144.2

 o.41 191.3

 Mo.42 206.9

 Mlo.43 162.3

 o.44 200.7

 No.45 220.4

 No. 46 120.5

 No.47 128.1

 No.48 156.1

 No.49 155.0

 No.50 163.8

 No. 51 196.9

 No.52 156.5

 No.53 187.0

 No.54 217.6

The results of Test 4 are shown in Table 8 and FIG. The Results Z r a 0.5 0 5 wt _^0/0, 0. 1 2 wt _^0/0, 0. By containing 2 1 wt%, 1 0 0 ° standard 1 7 0. 4 NZmm ² in C and in comparison, each ^{1 8 0. 1 N / mm 2} , 1 9 4. 7 N / mm 2 0 5. 6 NZmm 2 and has a tensile strength is improved, 1 5 0 ° standard 1 4 9 even C . Compared to 4 N / mm ² Were respectively ^{1 5 7. 8 N / mm 2} , 1 7 2. 0 N / 1 8 4. 2 N / mm 2 and tensile strength increase. At room temperature, similarly to Te, the tensile strength does not increase or decrease depending on the Zr content, and all have sufficient tensile strength. For this reason, even when Zr is contained, sufficient tensile strength can be obtained at room temperature, and further, tensile strength at high temperatures can be improved. From the above tests, it was found that the content of Te can improve the tensile strength at high temperature, and further, the interaction with Se can improve the tensile strength at high temperature. The content of Zr can also improve the tensile strength at high temperatures, but its effect is slightly lower than Te.

 Table 8

次に、 T e添加による切削性能を評価するため、 切削試験を行った。 切削試験は従来材、 T eを含有した本発明実施品、 CAC 4 0 6につ いて行った。 化学成分値を表 9に示す。

Next, a cutting test was performed to evaluate the cutting performance by adding Te. The cutting test was performed on a conventional material, a product according to the present invention containing Te, and CAC406. Table 9 shows the chemical component values.

Table 9 (Chemical value: wt%)

 Sample CuZnSnBiSePbP (ppm) Te Comparative Example No.59 85.9 8.28 4.36 1.25 0.20 0.006 193

 Invention No. 60 85.4 8.33 4.19 1.31 0.19 0.004 188 0.51

CAC406 No.61 84.6 5.75 4.26 5.38 202 Cutting test conditions are as follows: machining diameter Φ30, feed amount 0.2 mm / rev, depth of cut 3.0 mm, number of revolutions 180 rpm, cutting speed 170 m / min, the cutting state was dry, and the evaluation was made by setting the cutting resistance of CAC 406 to 100 and expressing the cutting resistance of each sample as a cutting index. The following shows how to calculate the machinability index.

 Machinability index = (Cutting resistance value of CAC406) Z (Cutting resistance value of each sample) X100

 The results of the machinability test are shown in Table 10 and FIG. From this result, the machinability index of the comparative example is 84.4, and the sample containing 0.51% by weight of Te is 95.1. The machinability is greatly improved by containing Te. It has been done.

 Table 10

Next, among the copper-based alloys of the present invention, examples including test examples of Cu-Sn-Zn-Bi-Se-based bronze alloys containing P as an additive element, and An example including a test example of a Cu—Sn—Zn—Bi—Se-based bronze alloy containing Te will be described.

Based on C-Sn-Zn-Bi-Se-based bronze alloy, bronze containing 0.05 to 0.09% by weight of P and 0.6% of 1 Prepare a bronze porcelain containing 0 to 21% by weight, perform a high-temperature Shallby impact test on this bronze porcelain, and explain the test results. The content of Pb contained in the bronze material was set to 0.2% by weight or less.

In the Charpy impact test, a test piece was manufactured using a CO _{2 type} mold at an inflow temperature of 110 ° C, and then a No. 3 test piece stipulated in JISZ 222 manufactured by cutting. Was carried out using a Charpy impact tester (300 J) specified in JISB 7722. In addition, an oil path was used for the test, the specimen was heated to 100 ° C. with high-temperature oil, held for 10 minutes, taken out of the oil bath, and subjected to a Charpy impact test within 5 seconds. . Table 11 shows the chemical component values of each test piece. Table 12 shows that the impact value of the standard sample (sample No. 64) was 100% and P was 0.05% by weight ( Shows the impact value (relative to the standard) of the sample containing Sample No. 62) and 0.09% by weight (Sample No. 63). FIG. 8 shows a graph of the data of these samples No. 62 to No. 64.

 Table 11

また、 表 1 2に、 標準サンプル （試料 N o . 6 7) の衝擊値を 1 0 0 %として、 丁 6を0. 1重量⁰ /₀ (試料 N o . 6 5) 、 0. 2 1重量⁰ /₀ ( 試料 N o . 6 6) 含有した試料の衝撃値を示す。 なお、 これら試料 N o . 6 5〜N o . 6 7のデータをグラフ化したものを第 9図に示す。

Further, Table 1 2, the standard sample as a 1 0 0%衝擊value (Sample N o. 6 7), 0. 1 wt Ding 6 _^0/0 (Sample N o. 6 5), 0. 2 1 weight _^0/0 (sample N o. 6 6) shows the impact values of the samples contained. FIG. 9 is a graph of the data of these samples No. 65 to No. 67.

Table 1 2 a: _ pu it

 Sample area ratio (%) to standard ratio (%)

 Invention No. 62 0.103 126

 Invention No. 63 0.104 273

 Comparative Example No. 64 0.268 100

 Invention No. 65 0.052 175

 Invention No. 66 0.035 248

 Comparative Example No. 67 0.212 100 As shown in Fig. 8, when 0.05% by weight of P is contained, the impact value is improved by 126% compared to the standard sample, and P is 0.09% by weight. %, The impact value was improved by 273% compared to the standard sample. Therefore, it was found that the impact value of the alloy was improved with the inclusion of P.

As shown in Fig. 9, when the content of 1: ₆ is 0.1% by weight, the impact value is improved by 1175% compared to the standard sample, and when the content of 0.16% is 0.21% by weight. The impact value was improved by 248% compared to the standard sample. Therefore, it was found that the impact value of the alloy was improved with the inclusion of Te, as with the inclusion of P.

 As a result of the high-temperature impact test, as compared with the standard sample, the content of P was improved by an average of 200%, and the content of Te was improved by an average of 212%. The area ratio of the Bi-Pb eutectic shown in the table and the figure will be described later.

 Further, each test piece was subjected to EDX quantitative analysis and mapping. Mapping is to analyze where a specific element is located, and to display the area where the element is concentrated in yellow. Each analysis was performed on the cut surface of the test piece after the Charpy impact test while avoiding the fracture surface. FIG. 10 shows a metallographic photograph (magnification: 400 ×) of the new standard sample (comparative example), and FIG. 11 shows the matting of each element in the metallographic photograph of FIG.

Table 13 shows the chemical component values of this standard sample (Comparative Example). Table 14 shows the results of the quantitative analysis of EDX in regions 1 to 3 shown in the metallographic photographs of FIG.

 Table 13

表 1 4

Table 14

As evident from Fig. 11 and Table 14, from the results of the mating of the standard sample shown in Fig. 11, Bi and Pb were found to coexist in region 1, and Table 14 From the results of the quantitative EDX analysis shown in (1), it was found that B i and P b were concentrated in region 1 to form a B 1 -P b binary eutectic.

 Next, FIG. 12 shows a metallographic photograph (magnification: 400 times) of the sample No. 63 containing 0.09% by weight of P, and each element in the metallic structure photograph of FIG. The mapping is shown in Figure 1'3. Table 15 shows the results of EDX quantitative analysis in regions 1 and 2 shown in the metallographic photographs of FIG.

 Table 15 Chemical component values (unit: wt%)

 C u Z n S n Β ί S e P b P

Area 1 2.69 45.98 0.02 0.00 51.01 0.24 0.06 Area 2 6.28 1.15 0.06 92.34 0.14 0.00 0.03 As is evident from Fig. 13 and Table 15, the mapping results shown in Fig. 13 show that P and Pb coexist in Region 1, and the EDX quantification shown in Table 15 From the analysis results, it was found that P and Pb concentratedly formed P—Pb intermetallic compounds in region 1.

 Here, an alloy refers to a state in which two or more metal elements are melted in a solid state. Further, an intermetallic compound refers to a compound formed by combining two or more component metals in an alloy with a relatively simple ratio of the number of atoms.

 Next, FIG. 14 shows a metallographic photograph (magnification: 400 times) of the sample No. 66 containing 0.21% by weight of the chopstick 6, and each element in the metallographic photograph of FIG. Figure 15 shows the mapping. Table 16 shows the results of quantitative analysis of EDX in regions 1 to 5 shown in the metallographic photographs of FIG.

 Table 16

第 1 5図及び表 1 6から明らかであるよ.うに、 第 1 5図に示すマツピ ング結果から、 T e と P bは領域 1、 3、 4、 5において共存している ことが判明し、 表 1 6に示す E D X定量分析結果から、 T eと； P bは上 記領域、 とりわけ、 領域 5において集中的に T e— P b金属間化合物を 作っていることが判明した。

As is evident from Fig. 15 and Table 16, it is clear from the mapping results shown in Fig. 15 that Te and Pb coexist in regions 1, 3, 4, and 5. From the results of the EDX quantitative analysis shown in Table 16, it was found that Te and Pb intensively form Te—Pb intermetallic compounds in the above-mentioned region, particularly in region 5.

 In addition, in order to measure the area ratio of the Bi-Pb binary eutectic, microstructure observation photographs were taken and analyzed using image analysis software.

The area ratio refers to the ratio of the area occupied by the target substance (Bi-Pb binary eutectic phase) to the area of the visual field captured as an image. The Bi-Pb binary eutectic phase was identified by comparing the EDX quantitative analysis results with the metallographic photographs. The metallographic photograph was taken at a magnification of 400 ×, and the area ratio was calculated from the average value of 20 visual fields in each sample.

 Microstructure of the standard sample (sample No. 64), the sample No. 62 containing 0.05% by weight of P, and the sample No. 63 containing 0.09% by weight of P. The observed photographs (before and after image processing) are shown in Fig. 16. Table 11 shows the results of measuring the area ratio of the Bi-Pb binary eutectic when P was contained as an additive element.

 The area of the standard sample (Sample No. 67), the sample No. 65 containing 1% by weight of TeO, and the sample No. 66 containing 1% by weight of TeO. Figure 17 shows the tissue observation photographs (before and after image processing) whose ratios were measured. Table 12 shows the results of measuring the area ratio of the Bi-Pb binary eutectic when Te was contained as an additive element.

 As shown in Table 12, the area ratio of the Bi-Pb phase of the standard sample (sample No. 64) was 0.268%, and the Bi_Pb phase when P was contained. The area ratio was 0.103% when P 0.05% by weight was contained, and 0.14% when P 0.09% by weight was contained. FIG. 8 shows a graph of the data of these samples No. 62 to No. 64.

As shown in Table 12, the standard sample (sample No. 67) had a Bi-Pb phase area ratio of 0.212%, and contained 0.1% by weight of TeO. 0 5 2%, T e O . was 0 3 5% 0.2 1 wt _^0/0 containing. FIG. 9 shows a graph of the data of these samples No. 65 to No. 67.

 As shown in Figs. 8 and 9, it was found that the inclusion of P and Te as additional elements suppressed the area ratio of Bi-; Pb phase to 0.2% or less. did. In particular, when the generation of the Bi-Pb binary eutectic was suppressed to 0.1% or less, it was found that the impact value was improved to about 130% in comparison with the standard sample.

High temperature impact test, EDX quantitative analysis, mapping, and Bi-P described above b From the measurement of the area ratio of the binary eutectic, by containing P and Te, it is possible to form P-Pb intermetallic compound, Te-Pb intermetallic compound, etc. in the alloy structure. It was found that the generation of B i-binary eutectic was suppressed, and the high melting point of these intermetallic compounds improved the high-temperature impact value.

The copper-based alloy of the present invention is not limited to the above-mentioned bronze alloy. Further, in the case of a brass-based alloy, for example, brass for hot forging, Cu 59.0 to 6 2.0% by weight, Sn 0.5 to 1.5% by weight, Bi 1.0 to 2.0% by weight, Se 0.03 to 0.20% by weight, Fe 0.05 It contains a component range of ~ 0.20% by weight, P 0.05 ~ 0.10% by weight, and in the case of brass for cutting, Cu 61.0 ~ 63.0 weight ⁰ /. , Sn O. 3~0. 7 wt%, B i 1. 5~2. 5 wt%, S e 0. 0 3~0. 2 0 wt%, F e 0. 1~0. 3 0 wt ⁰ /. A P 0. 0 5 to 0. Applicable to 1 0 weight _^0/0 leadless copper base alloys containing component range.

 Further, in the above embodiment, the addition of additional elements such as Te and P suppresses the generation of the Bi-Pb binary eutectic in the alloy structure. In the forging process, the amount of recycled materials such as scrap was reduced, and the content of Pb was suppressed by adjusting the content of Pb to be lower than the upper limit of 0.2% by weight as an inevitable impurity. I'm sorry.

Industrial CD availability

According to the present invention, a Bi-Pb binary eutectic is formed in an alloy structure by adding Bi and Pb, which are singly or bonded to each other, and an additive element that forms an alloy or an intermetallic compound. By suppressing the occurrence of cracks, it became possible to improve the mechanical properties at high temperatures, especially the decrease in tensile strength. Further, the copper-based alloy of the present invention can be used for processing and forming water contact products such as pulp, joints, pipes, faucets, water supply / hot water supply products, and electric / mechanical products such as gas appliances, washing machines, and air conditioners. It is suitable for processing and molding. Other suitable materials and parts using the copper-based alloy of the present invention as a material are, in particular, water contact parts such as pulp and faucet, that is, ball pulp, empty ponole in ball valve, pallet, taphrino knollep, gate pallet. , Globe panoleb, check valve, water supply, mounting fittings for water heaters and hot water flush toilet seats, water supply pipes, connection pipes and fittings, refrigerant pipes, electric water heater parts (casing, gas nozzle, pump parts, wrench etc. ), Strainers, parts for water meters, parts for underwater sewerage, drain plugs, elbow pipes, bellows, connecting flanges for toilet bowls, spindles, joints, headers, branch taps, hose nipples, faucet fittings, stopcocks , Plumbing supplies, sanitary ware fittings, shower hose connection fittings, gas appliances, building materials such as doors and knobs, home appliances, It can be widely applied to tubing header adapters, automotive cooler parts, fishing tackle parts, microscope parts, water meters. One part, weigher parts, railway pantograph parts, and other parts. Furthermore, toilet articles, kitchen articles, bathroom articles, toilet articles, furniture parts, living room articles, sprinkler parts, door parts, gate parts, vending machine parts, washing machine parts, air conditioner parts, gas welding machines Parts, heat exchanger parts, solar water heater parts, molds and their parts, bearings, gears, construction equipment parts, railcar parts, transportation equipment parts, materials, intermediate products, finished products and assemblies And so on.

Claims

The scope of the claims ' 1. By adding Bi or Pb, alone or bonded to each other, and an additive element that forms an alloy or an intermetallic compound, the mechanical properties at high temperatures, especially the tensile strength, are improved. Copper based alloy.  2. The additive element is selected from one or more of the group consisting of Te, P, Zr, Ti, Co, In, Ca, B, and misch metal. 2. The copper-based alloy according to item 1.  3. The copper-based alloy according to claim 1 or 2, wherein the additive element is contained in an amount of 0.01 to 2.0% by weight.  4. The copper-base alloy according to any one of claims 1 to 3, wherein the generation of a Bi-Pb binary eutectic in the alloy structure is suppressed.  5. The copper-based alloy contains at least Sn 2.8 to 6.0% by weight, Zn 1.0 to 12.0% by weight, and BiO. 1 to 3.0% by weight. The copper-based alloy according to any one of claims 1 to 4.  6. The above-mentioned copper-based alloy weighs at least S112.8 to 6.0. /. Claims 1 to 4 which contain 1.0 to 12.0% by weight of Zn, 0.1 to 2.4% by weight of Bi, and 0.1 to 1.2% by weight of Se. The copper-based alloy according to any one of the above items.  7. The copper-based alloy according to any one of claims 1 to 6, wherein the content of Pb contained in the copper-based alloy is 0.25% by weight or less.