CN101565784B - Lead-free free-cutting calcium-yellow brass alloy - Google Patents
Lead-free free-cutting calcium-yellow brass alloy Download PDFInfo
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Abstract
The invention discloses a lead-free free-cuting calcium-yellow brass alloy, comprising the following components with weight percentage: 57 percent-65.0 percent of Cu, 0.3 percent-2.5 percent of Ca, 0.2 percent-2.0 percent of Mg, 0.1 percent-2.0 percent of Si, 0.01-0.5 percent of Al, 0.01 percent-0.3 percent of lanthanum-cerium alloy, 0.01 percent-2.0 percent of X, and the balance of zinc and unavoidable impurities; wherein X is at least one of three elements of Fe, P, Sn. The lead-free free-cutting calcium-yellow brass alloy has no negative effect on human body and environment, is lead-free, does not need to add expensive metals of bismuth, stibium, nickel and the like, and has low production cost and easy recovery. Moreover, the lead-free free-cutting calcium-yellow brass alloy has highercutting property, high corrosion resisting property, hot-working character and mechanical property, and can be widely used in the products of water faucet fittings, valve rods and the like.
Description
Technical field
The present invention relates to a kind of lead-free free-cutting calcium-yellow brass alloy.
Background technology
Easily the cutting leaded brass is to be main component with copper, zinc, adds plumbous traditional copper alloy, and the alloy designations that all there is series countries in the world is as JISH3100 C3601, JISH3100 C3604, JISH3100 C3771; ASTMB36C36000, ASTMB36 C37700; GB/T5231 Hpb62-3, Hpb60-2, Hpb59-1.These lead brass alloys are to guarantee cutting ability by the lead that interpolation contains 1.0%～3.7% (weight).Plumbiferous brass alloy material is because good cutting performance is widely used in the water tap accessory that pipe arrangement is used, and valve rod etc. use as structured material.In addition as the parts that contact with water under service condition, have the problem of Dezincification corrosion.For this reason, use anti-dezincify copper alloy in recent years gradually, it is the alloy that improves the corrosion resistance of free-cutting brass that publication number is respectively the patent application of TW5097276, EP0903416, JP719152, US5445687 disclosed; Also have in the public clear 61-58540 communique of spy, delivered the anti dezincification character energy that in the Cu-Zn-Sn series copper alloy, adds Pb, Fe, Ni, Sb raising alloy.
Owing to contain the lead of 1.0%～3.7% (weight), the metallic vapor that produces when high temperature operations such as alloy melting casting contains plumbous composition in the existing lead brass alloy, and plumbous composition is also arranged in the dust when machining and ground finish.Have from dissolving plumbous problem when having goods such as water tap accessory and valve rod to use again, human body and environment are caused negative impact with the water contact site.
In view of lead has negative influence to human body and environment, in recent years, there is strict restriction countries in the world to the lead content in the metallic substance.People carry out energetically with the alternative leaded brass of non-leaded easily-cutting brass for this reason.Put into production use with bismuth (Bi), antimony (Sb), nickel (Ni) the plumbous existing a plurality of trades mark of free-cutting copper alloy of generation, but since price costlinesses such as bismuth, antimony, nickel, the production cost height, and recovery difficult is big, has hindered the use of these trade mark alloys.In view of the foregoing, it is a kind of unleaded and do not add expensive bismuth, antimony, nickel to be badly in need of exploitation, has high cutting ability, the leadless free-cutting brass alloy of corrosion resisting property, hot workability and mechanical property.
Summary of the invention
The technical problem to be solved in the present invention is the above-mentioned deficiency at prior art, provides a kind of high cutting ability that has, the lead-free free-cutting calcium-yellow brass alloy that corrosion resisting property, hot workability and mechanical property and production cost are low.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: a kind of lead-free free-cutting calcium-yellow brass alloy, its weight percent consists of: Cu 57%～65.0%, Ca 0.3%～2.5%, and Mg 0.2%～2.0%, and Si 0.1%～2.0%, Al0.01%～0.5%, lanthanum cerium alloy 0.01%～0.3%, X0.01%～2.0%, surplus is zinc and unavoidable impurities; Wherein X is at least a in Fe, P, three kinds of elements of Sn.
Lead-free free-cutting calcium-yellow brass alloy of the present invention, its weight percent component is preferably: Cu59%～65.0%, Ca0.3%～2.0%, Mg0.35%～2.0%, Si0.1%～1.5%, Al0.03%～0.35%, lanthanum cerium alloy 0.03%～0.2%, X0.05%～2.0%, surplus are zinc and unavoidable impurities.
Lead-free free-cutting calcium-yellow brass alloy of the present invention, its weight percent component is further preferably: Cu60.0%～65%, Ca0.4%～1.8%, Mg0.35%～1.5%, Si0.1%～1.2%, Al0.03%～0.25%, lanthanum cerium alloy 0.05%～0.15%, X0.05%～1.5%, surplus are zinc and unavoidable impurities.
The weight percent content of the lead in the above-mentioned unavoidable impurities is no more than 0.01%, even the lead content of this degree is dissolved in the tap water and in the water of discharging, can bring what negative impact to environment and human body.
The weight percent content of cerium is 40% in the above-mentioned lanthanum cerium alloy.
The reason that limits metallic element kind and addition in the lead-free free-cutting calcium-yellow brass alloy of the present invention is:
Ca: add in order to improve cutting ability.Calcium solid solution hardly exists with the molecule of disperse in matrix, so can play the effect that generates smear metal when disconnecting machining, improves cutting ability.Calcium can not cause damage to human body, and therefore the fusing point of calcium, can be avoided as bismuth at 842 ℃, because fusing point is low, when brass hot-work, exists and is easy to generate red brittleness with molten state.Obtaining good cutting ability calcium must be more than 0.4% (weight).The calcium contents preferable range is controlled at 0.4%～1.8%.
Mg: add in order to improve cutting ability, also be distributed with the second phase particle of disperse in the magniferous brass, the magnesium-containing compound particle has crisp and not hard characteristic, is easy to fragmentation when contacting with blade under the shear pressure effect.Magnesium copper zinc ternary compound distributes at intragranular, and intragranular germinating crackle can effectively reduce the size of cutting under the effect of cutting force.Improve the cutting ability of material.Magnesium content is too high, and the processing characteristics of alloy descends greatly, therefore, is limited to 1.5% on the Mg content.Cross that low to improve cutting ability not obvious, so lower limit is not less than 0.35%.
Si: add in order to improve corrosion resisting property and castability.Silicon is lower than 0.1% DeGrain.Greater than 1.2% material ductility is reduced greatly.The preferred span of control of silicone content should be 0.1%～1.2%.
Al: add in order to improve hot workability.A small amount of interpolation can also improve the corrosion resisting property of material.Aluminium content does not have effect less than 0.03%, too much reduces the plasticity of cutting ability and material, on be defined as 0.25% (weight).
Lanthanum cerium alloy: mainly be the mechanical property that crystal grain thinning improves material, influence the material castability greater than 0.15%, cross low inoperatively, be limited to 0.05% (weight) down.The suitable preferred add-on of lanthanum cerium alloy is 0.05%～0.15%.
Cu: from solidity to corrosion and mechanical properties, the mutually corrosion resisting properties that improve of the α that copper content height obtains more, alloy material plasticity is better, but intensity, hardness descend, the hot workability variation, in order to take into account the hot workability of material, mechanical property and corrosion resistance copper content optimum scope are 60%～65%.
X represents at least a in Fe, P, three kinds of elements of Sn in the described alloy of the present invention, its weight percent content and composition are at least a among Fe 0.05%～0.3%, P 0.05%～0.3%, the Sn 0.1%～1.0%, and the total amount of X is no more than 1.5%.
X represents at least a in Fe, P, three kinds of elements of Sn, and working is respectively:
Fe: small amounts of iron energy refinement cast structure and recrystallized structure, improve processing characteristics.Iron is 0.05%～0.3% in the alloy of the present invention.
P: be generally used for the deoxidation of copper alloy, increase fluidity of molten, improving the preferred usual amounts of cutting ability and Dezincification corrosion is 0.05%～0.3%.
Sn: improve corrosive nature, gain in strength and wear resistance, preferred 0.1%～1.0%.
As mentioned above, calcium in the alloy material of the present invention, magnesium, silicon, lead, iron, phosphorus, tin, lanthanum cerium alloy guarantee that by selecting optimal addition to obtain accumulative effect alloy material has good cutting performance, corrosion resisting property, hot workability and mechanical property.
Compared with prior art, lead-free free-cutting calcium-yellow brass alloy of the present invention did not both have negative impact to human body and environment, and was unleaded again, do not add expensive metal such as bismuth, antimony, nickel, and production cost is low, be easy to reclaim; And lead-free free-cutting calcium-yellow brass alloy of the present invention has higher cutting ability, and corrosion resisting property, hot workability and mechanical property can extensively be used in goods such as water tap accessory and valve rod.
Embodiment
Below in conjunction with embodiment the present invention is done to describe in further detail, but the present invention not only is confined to following examples.
Embodiment of the invention alloy sample preparation method is: batching, and---------ingot casting is in 550～650 ℃ of insulations annealing in 1～4 hour---hot extrusion (620～700 ℃) φ 17mm rod base---, and stretching φ 15mm pole, its flow process the brass alloys production technique with conventional substantially are identical for the ingot casting of semicontinuous casting φ 163mm in the line frequency furnace melting.
Comparative sample (table 2) also adopts same processing condition to process, and wherein HB60-2 is our factory's bismuth brass.
The concrete component content tabulation of each embodiment of free-cutting calcium-yellow brass alloy of the present invention (table 1).
Table 1 embodiment of the invention alloy compositions (wt%)
| Embodiment | Cu | Ca | Mg | Si | The lanthanum cerium alloy | Al | Pb | X | Zn |
| 1 | 62.50 | 0.63 | 0.85 | 0.24 | 0.083 | 0.06 | 0.0022 | P0.08 Fe0.08 | Surplus |
| 2 | 61.75 | 0.65 | 0.88 | 0.21 | 0.082 | 0.05 | 0.0031 | P0.11 | Surplus |
| Sn0.17 | |||||||||
| 3 | 61.82 | 0.74 | 0.87 | 0.25 | 0.093 | 0.06 | 0.0024 | P0.2 Fe0.11 | Surplus |
| 4 | 62.20 | 0.63 | 0.85 | 0.23 | 0.054 | 0.05 | 0.0024 | P0.21 Sn0.3 | Surplus |
| 5 | 63.40 | 0.78 | 0.89 | 0.26 | 0.065 | 0.07 | 0.0016 | P0.17 Sn0.35 | Surplus |
| 6 | 62.83 | 0.61 | 0.91 | 0.23 | 0.055 | 0.08 | 0.0045 | P0.23 | Surplus |
| 7 | 62.50 | 0.67 | 0.86 | 0.25 | 0.045 | 0.065 | 0.0063 | P0.18 Fe0.07 | Surplus |
| 8 | 62.15 | 0.75 | 0.92 | 0.28 | 0.056 | 0.055 | 0.0050 | Fe0.1 | Surplus |
| 9 | 61.90 | 0.72 | 0.87 | 0.27 | 0.057 | 0.07 | 0.0020 | P0.15 Sn0.2 | Surplus |
| 10 | 62.40 | 0.63 | 0.93 | 0.26 | 0.062 | 0.08 | 0.0050 | P0.18 Fe0.12 | Surplus |
| 11 | 62.35 | 0.68 | 0.87 | 0.24 | 0.070 | 0.06 | 0.0029 | P0.2 Fe0.09 | Surplus |
| 12 | 61.85 | 0.69 | 0.86 | 0.23 | 0.071 | 0.07 | 0.0033 | P0.08 Sn0.25 | Surplus |
| 13 | 62.92 | 0.65 | 0.89 | 0.21 | 0.073 | 0.07 | 0.0027 | P0.13 Sn0.5 | Surplus |
| 14 | 63.10 | 0.62 | 0.92 | 0.22 | 0.082 | 0.08 | 0.0030 | P0.22 Fe0.08 | Surplus |
| 15 | 63.20 | 0.64 | 0.93 | 0.24 | 0.085 | 0.06 | 0.0084 | P0.16 Sn0.25 | Surplus |
| 16 | 62.75 | 0.65 | 0.91 | 0.23 | 0.089 | 0.065 | 0.0073 | P0.17 Sn0.24 | Surplus |
Table 2 Comparative Examples alloy compositions (wt%)
| Comparative Examples | Cu | Zn | Bi | Al | Sn | P | Pb | Remarks | |
| 20 | 60.2 | Surplus | 0.008 | 0.1 | 3.01 | C3601 | |||
| 21 | 60.1 | Surplus | 0.03 | 0.03 | 2.55 | C3604 | |||
| 22 | 58.7 | Surplus | 0.007 | 0.12 | 2.32 | C3771 | |||
| 23 | 60.18 | Surplus | 2.01 | 0.04 | 0.05 | (Si)0.244 | HB60-2 | ||
| 24 | 60.57 | Surplus | 2.05 | 0.03 | 0.039 | (Si)0.343 | HB60-2 | ||
| 25 | 59.5 | Surplus | 1.70 | 0.015 |
| 26 | 21.1 | Surplus | 1.90 | 0.03 | 0.55 | 0.05 | |||
| 27 | 59.8 | Surplus | 2.0 | 0.02 | Lanthanum cerium alloy 0.35 |
The cutting ability test method that is evaluated as general copper alloy of cutting ability (prepare graduated cylinder, collect cutting, utilize nature to fall and fill graduated cylinder) is promptly carried out with so-called smear metal form test method.The speed of mainshaft is 950rpm/min, and the amount of feed is 0.18mm/rev, and the depth of cut is 0.5mm, and wherein " zero " represents excellent cutting performance, and " △ " expression is good, and " X " expression cutting ability is poor.
Secondly in order to observe the forge hot performance, the pole of φ 15mm is cut into 15mm length, at 600 ℃, under 650 ℃ of heating conditions, with 70% rate of compression, compression (length of sample is compressed to 8.2mm from 15mm) is judged specimen surface state after the compression with range estimation at axis direction.Be expressed as " * " that is expressed as " △ ", the big crackle of generation that is expressed as " zero ", generation crackle that specimen surface does not crack.
In order to observe the Dezincification corrosion resistant performance, carried out the Dezincification corrosion test with the method for " ISO6509 " regulation.It is long to be cut into 10mm with external diameter 15mm pole, imbeds in the resol, and the specimen surface of exposure and the axis direction of pole meet at right angles.With sand paper specimen surface is ground to after No. 1200, uses ultrasonic cleaning in pure water, use for test dry back.The Dezincification corrosion degree of depth is less than be expressed as " zero " of 100 μ m, and the Dezincification corrosion degree of depth is at be expressed as " △ " of 100-200 μ m, the Dezincification corrosion degree of depth being expressed as more than 200 μ m " * ".
Above-mentioned each performance test results is listed in table 3:
Table 3 test-results
| Embodiment | Hot workability | Mechanical property | Cutting ability | Corrosion resisting property |
| Sample | 600℃ | 650℃ | Tensile strength (MPa) | The smear metal form | The Dezincification corrosion degree of depth |
| 1 | ○ | ○ | 465 | ○ | ○ |
| 2 | ○ | ○ | 485 | ○ | ○ |
| 3 | ○ | ○ | 486 | ○ | ○ |
| 4 | ○ | ○ | 465 | ○ | ○ |
| 5 | ○ | ○ | 467 | ○ | ○ |
| 6 | ○ | ○ | 470 | ○ | ○ |
| 7 | ○ | ○ | 471 | ○ | ○ |
| 8 | ○ | ○ | 480 | ○ | ○ |
| 9 | ○ | ○ | 475 | ○ | ○ |
| 10 | ○ | ○ | 481 | ○ | ○ |
| 11 | ○ | ○ | 471 | ○ | ○ |
| 12 | ○ | ○ | 468 | ○ | ○ |
| 13 | ○ | ○ | 470 | ○ | ○ |
| 14 | ○ | ○ | 465 | ○ | ○ |
| 15 | ○ | ○ | 468 | ○ | ○ |
| 16 | ○ | ○ | 469 | ○ | ○ |
| 20 | ○ | ○ | 360 | ○ | × |
| 21 | ○ | ○ | 372 | ○ | × |
| 22 | ○ | △ | 345 | ○ | × |
| 23 | ○ | △ | 418 | ○ | ○ |
| 24 | ○ | ○ | 425 | ○ | ○ |
| 25 | ○ | ○ | 410 | ○ | △ |
| 26 | ○ | ○ | 420 | ○ | ○ |
| 27 | ○ | ○ | 406 | ○ | × |
Above-mentioned various test-results proves, the cutting ability of lead-free free-cutting calcium-yellow brass alloy of the present invention, hot workability, corrosion resisting property, the leaded brass that mechanical property is equal and traditional are suitable, can extensively use in goods such as water tap accessory and valve rod.
Claims (6)
1. lead-free free-cutting calcium-yellow brass alloy, it is characterized in that: its weight percent consists of: Cu 57%～65.0%, Ca 0.3%～2.5%, Mg 0.2%～2.0%, Si 0.1%～2.0%, and Al 0.01%～0.5%, lanthanum cerium alloy 0.01%～0.3%, X 0.01%～2.0%, and surplus is zinc and unavoidable impurities; Wherein X is at least a in Fe, P, three kinds of elements of Sn.
2. lead-free free-cutting calcium-yellow brass alloy according to claim 1, it is characterized in that: the weight percent of each element consists of in the described alloying element: Cu 59%～65.0%, Ca 0.3%～2.0%, Mg 0.35%～2.0%, Si0.1%～1.5%, Al 0.03%～0.35%, lanthanum cerium alloy 0.03%～0.2%, X 0.05%～2.0%, surplus is zinc and unavoidable impurities.
3. lead-free free-cutting calcium-yellow brass alloy material according to claim 2, it is characterized in that: the weight percent of each element consists of in the described alloy: Cu 60.0%～65%, Ca 0.4%～1.8%, Mg 0.35%～1.5%, Si0.1%～1.2%, Al 0.03%～0.25%, lanthanum cerium alloy 0.05%～0.15%, X 0.05%～1.5%, surplus is zinc and unavoidable impurities.
4. according to right 1 or 2 described lead-free free-cutting calcium-yellow brass alloys, it is characterized in that: the weight percent content of described alloying constituent X is at least a among Fe 0.05%～0.3%, P 0.05%～0.3%, the Sn 0.1%～1.0%, and the total amount of X is no more than 1.5%.
5. lead-free free-cutting calcium-yellow brass alloy according to claim 1 is characterized in that: described unavoidable impurities, wherein the content of Qian weight percent is no more than 0.01%.
6. lead-free free-cutting calcium-yellow brass alloy according to claim 1 is characterized in that: the weight percent content of cerium is 40% in the described lanthanum cerium alloy.
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| CN101824561B (en) * | 2010-05-06 | 2012-04-18 | 安徽九华金润铜业有限公司 | Lead-free corrosion-resistant phosphorosilicate brass |
| CN102400010A (en) * | 2011-11-15 | 2012-04-04 | 广东华金合金材料实业有限公司 | Lead-free free-cutting phosphorus-magnesium-calcium yellow brass alloy |
| CN102543312B (en) * | 2012-02-27 | 2013-03-27 | 江阴市电工合金有限公司 | Method for manufacturing high-conductivity high-ductility copper alloy bus for motor |
| CN102628120B (en) * | 2012-04-25 | 2013-11-27 | 苏州金仓合金新材料有限公司 | Antimony-added high-tin bronze alloy rod for high-speed railway equipment and manufacturing method thereof |
| CN102690973B (en) * | 2012-06-07 | 2014-03-12 | 宁波天业精密铸造有限公司 | Lead-free free-cutting brass alloy and preparation method thereof |
| CN104232985A (en) * | 2014-09-25 | 2014-12-24 | 江苏鑫成铜业有限公司 | High-corrosion-resistance copper alloy |
| CN105624463B (en) * | 2015-12-29 | 2018-02-27 | 宁波会德丰铜业有限公司 | A kind of leadless free-cutting brass alloy and preparation method thereof |
| CN112239824A (en) * | 2019-07-19 | 2021-01-19 | 启东市荣盛铜业有限公司 | High-nickel lead-containing free-cutting material and grain structure densification production process thereof |
| CN110747369A (en) * | 2019-11-26 | 2020-02-04 | 华南理工大学 | Lead-free-cutting silicon-magnesium-calcium brass alloy and preparation method thereof |
| CN113106289B (en) * | 2021-03-19 | 2022-03-25 | 宁波金田铜业(集团)股份有限公司 | Free-cutting copper alloy with excellent hot forging performance and preparation method thereof |
| DE102022120122A1 (en) | 2022-08-10 | 2024-02-15 | Diehl Brass Solutions Stiftung & Co. Kg | Lead-free brass alloy |
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Inventor after: Feng Bin Inventor after: Zhang Lu Inventor after: Huang Min Inventor after: He Guanbing Inventor before: Peng Feng Inventor before: Hu Shitie Inventor before: Xia Baoping Inventor before: Liu Jianping Inventor before: Liu Wenjian |
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Effective date of registration: 20160204 Address after: Yuyao City, Lin Shan Zhen Lincheng Cun 315460 Zhejiang city of Ningbo Province Patentee after: Ningbo Xing'aodao Metal New Material Co., Ltd. Address before: 315174, 557 Feng Feng Road, Gaoqiao village, Gaoqiao Town, Ningbo, Zhejiang, Yinzhou District Patentee before: Ningbo Aoda Copper Products Co., Ltd. |