CN100510132C - Copper/zinc/silicon alloy, use and production thereof - Google Patents
Copper/zinc/silicon alloy, use and production thereof Download PDFInfo
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- C22C9/04—Alloys based on copper with zinc as the next major constituent
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Abstract
A Cu-Zn-Si alloy includes, in % by weight, 70 to 80% of copper, 1 to 5% of silicon, 0.0001 to 0.5% of boron, up to 0.2% of phosphorus and/or up to 0.2% of arsenic, a remainder of zinc, plus inevitable impurities. Products using the alloy and processes for producing the alloy are also provided. The alloy is distinguished by an improved resistance to oxidation and by uniform mechanical properties.
Description
Technical field
The present invention relates to the purposes and the preparation of copper/zinc/silicon alloy and this copper/zinc/silicon alloy.
Background technology
But the critical requirement to copper/zinc/silicon alloy is their anti-dezincifys and is mechanical workout.So far, realized the favorable mechanical processing characteristics of these type of brass alloys, for example described in EP 1 045 041 A1 by adding lead.Yet, recently, also developed unleaded brass alloys, for example described in EP 1 038 981 A1 and DE103 08 778 B3 with favorable mechanical processing characteristics.Unleaded and plumbiferous Cu-Zn-Si alloy all tends to oxidation and forms the oxidation cortex under the temperature between 300 ℃ and 800 ℃.This oxidation cortex is loose ground and metal adhesion and can easily peels off, and is distributed in the whole production equipment, and this result who causes is these disturbed property ground contaminations.Clean this production unit very expensive and effort, production cost height thus.Another shortcoming of present known Cu-Zn-Si alloy is that the mechanical property of this material changes along long workpiece direction, and reason is that this material is inhomogeneous.
Summary of the invention
Consider these facts, the present invention therefore based on technical problem provide obtain aspect its homogeneity to improve and in addition than low propensity in the copper/zinc/silicon alloy that forms oxide skin, and provide the purposes and the preparation of these type of brass alloys.
First task that relates to alloy solves by copper/zinc/silicon alloy according to the present invention, this copper/zinc/silicon alloy comprises (% meter by weight): 70-80% copper, 1-5% silicon, 0.0001-0.5% boron, the zinc of 0-0.2% phosphorus and/or arsenic and surplus is together with unavoidable impurities.
Copper content is between 70% and 80%, because less than 70% or will have disadvantageous effect to the machining property of alloy greater than 80% copper content.If depart from the silicon concentration scope of pointed 1%-5%, also be identical situation.Boron concentration is between 0.0001-0.5% in alloy.Surprisingly, have now found that, realize on the one hand that corresponding to the boron of concentration range required for protection the formation of oxidation cortex is few, improve of the adhesion of remaining oxide skin simultaneously significantly material by adding.On the other hand, also surprisingly, add the fluctuation that boron has caused improving the homogeneity of weave construction and therefore avoided mechanical property.Phosphorus and arsenic can be separately be present in the alloy with the concentration content of as many as 0.2%, and can the phase trans-substitution.Phosphorus and arsenic have favorable influence to the formation and the corrosive nature of initial cast structure structure, improve the flow capacity of melt here in addition, reduce counter stress cracking sensitivity of corrosion.Remaining major portion is a zinc in the alloy.
Avoid the oxidation cortex of segregative increase production cost and improve mechanical property except listed above, and also provide outside favorable mechanical processing characteristics and the good advantage of processability together with high erosion resistance, also especially be apparent that anti dezincification character and anti-stress cracking corrodibility in the present invention.The dezincify test of carrying out according to ISO 6509 only obtains the dezincify degree of depth of as many as 26 μ m.
Second task of purposes that relates to this copper/zinc/silicon alloy is by being used for the electrotechnology member, the sanitary engineering member is used for carrying or storing liquid or gas containers, is subjected to the member of torsional load, but recycle member, the die forging parts, work in-process, band, sheet material, profiled material, sheet material, or solve as the purposes of plastic metal, rolled alloy or casting alloy.
This Cu-Zn-Si alloy can be used for contact, pin or tightening member in electrotechnology, for example as rest(ing) contact or stationary contact, they also comprise clamping and socket connection or plug contacts.
This alloy has high erosion resistance for liquid and gaseous medium.In addition, its extremely anti-dezincify and stress crack corrosion.Therefore, this alloy especially is suitable for carrying or stores liquid or gas containers, the especially container in Refrigeration Technique, or the pipeline in the sanitary engineering, water fitting, tap prolong parts, pipe jointer and valve.
Low erosion rate is also guaranteed, the metal leakage loss because the performance of alloying constituent is discharged in the effect of liquid state or gaseous medium, self is low promptly.At this on the one hand, this material is suitable for the Application Areas of the low discharge of poisonous waste of requirement with the protection environment.Therefore, but alloy according to the present invention can be used for the field of recycle member.
Counter stress cracking corrosive insensitivity recommends this alloy to be used for spiral or to clamp connecting, in such connection, because technology has been stored high elastic energy with determining.Therefore, especially suitable is, and this alloy is used for that all stand to stretch and/or member, the especially screw bolt and nut of torsional load.After cold deformation, this material obtains high yield-point (Dehngrenze) value.Therefore, in connecting, the spiral that does not allow viscous deformation can realize bigger screw-down torque.The yield-point ratio of this Cu-Zn-Si alloy (
) than low under the situation of free-cutting brass.Therefore, that only once tighten and in this process overtighten wittingly spiral connect and obtain extra high fastening force.
The possible purposes of this Cu-Zn-Si alloy is to be used for tubular and band shape parent material.This alloy also is highly suitable for and can be particularly useful for key, carved pattern, ornamental purpose or punching press graticule mesh (Stanzgitter) and uses by the band of milling or punching press, sheet material and sheet material.
Relate to the 3rd the following solution of task of the preparation of this copper/zinc/silicon alloy: routine casts continuously and carry out hot rolling between 600 ℃ and 760 ℃, and is especially cold rolling with after strain, preferably adds further annealing and deforming step.
Relate to the also following solution of task of the preparation of such copper/zinc/silicon alloy: carry out the routine continuous casting and be up to 760 ℃, preferably extruding between 650 ℃ and 680 ℃, and in air, cool off.
In a favourable improvement of Cu-Zn-Si alloy, this alloy comprises: 75-77% copper, 2.8-4% silicon and 0.001-0.1% boron, and 0.03-0.1% phosphorus and/or arsenic are except zinc and the unavoidable impurities as surplus element.
In a preferred alternatives, copper/zinc/silicon alloy comprises that (in weight %) is at least a to be selected from following element: 0.01-2.5% lead, 0.01-2% tin, 0.01-0.3% iron, 0.01-0.3% cobalt, 0.01-0.3% nickel and 0.01-0.3% manganese.Plumbous interpolation can have favorable influence to machining property.
In this case, this alloy comprises advantageously that (in weight %) is at least a to be selected from following element: 0.01-0.1% lead, 0.01-0.2% tin, 0.01-0.1% iron, 0.01-0.1% cobalt, 0.01-0.1% nickel and 0.01-0.1% manganese.
In preferred an improvement, the Cu-Zn-Si alloy comprises in addition that (in weight %) is at least a to be selected from following element: the silver of as many as 0.5%, the aluminium of as many as 0.5%, the magnesium of as many as 0.5%, the antimony of as many as 0.5%, the zirconium of the titanium of as many as 0.5% and as many as 0.5%, and be preferably selected from 0.01-0.1% silver, 0.01-0.1% aluminium, 0.01-0.1% magnesium, 0.01-0.1% antimony, 0.01-0.1% titanium and 0.01-0.1% zirconium.
In a favourable alternatives, the Cu-Zn-Si alloy comprises in addition that (in weight %) is at least a to be selected from following element: the cadmium of as many as 0.3%, the chromium of as many as 0.3%, the selenium of as many as 0.3%, the bismuth of the tellurium of as many as 0.3% and as many as 0.3% is preferably selected from the 0.01-0.3% cadmium, 0.01-0.3% chromium, 0.01-0.3% selenium, 0.01-0.3% tellurium and 0.01-0.3% bismuth.
Embodiment
To illustrate in greater detail an embodiment with following description with reference to the accompanying drawings.In this accompanying drawing:
Description of drawings
Fig. 1 shows and is not adding the CuZn21Si3P alloy (a) of boron, contains the CuZn21Si3P alloy (b) of 0.0004% boron, and the CuZn21Si3P alloy (c) that contains 0.009% boron go up 600 ℃ down after the annealing 2 hours the formation of oxidation cortex and
Fig. 2 shows the CuZn21Si3P alloy (a) that does not add boron, contains the CuZn21Si3P alloy (b) of 0.0004% boron, and the formation of cast structure's structure that contains the CuZn21Si3P alloy (c) of 0.009% boron.
This embodiment based on the CuZn21Si3P alloy have the change in concentration of component, wherein copper is 75.8-76.1%, silicon is 3.2-3.4%, phosphorus is 0.07-0.1%, together with as the zinc of all the other components and inevitable impurity. This examples of alloys have 0%, 0.004% with 0.009% different boron content. This alloy is prepared as follows: continuous casting, then in the temperature that is lower than 760 ℃, preferably under the temperature between 650 ℃ and 680 ℃, push, and fast cooling.
All alloys have excellent anti dezincification character. Only disclose the dezincify degree of depth less than 26 μ m according to the dezincify of ISO 6509 test.
If with the CuZn21Si3P alloy, for example during thermal distortion, be exposed under 300-800 ℃ the temperature, then form oxide skin, this oxide skin is peeled off easily and is polluted production unit.The surface of the degree of depth scaling of no boron CuZn21Si3P alloy is shown in Fig. 1 a.In Fig. 1 a, the major portion of this sample surfaces manifests grey.This gray colored illustrates the scaling surface of this CuZn21Si3P alloy.Only can see the bright spot of the discrete of several minorities on this alloy surface without any regular distribution.In contrast, the CuZn21Si3P alloy ratio that contains 0.0004% boron among Fig. 1 b does not have the spot that boron alloy shows more much more quantity on alloy surface white manifests.These white dots are represented the metal bright area of alloy.These metal bright area promptly do not have the zone of scaling, are evenly distributed on the surface of alloy.Compare with the situation of no boron alloy, the ratio on the surface of scaling reduces significantly and the oxide skin that stays adheres on the metal more firmly.Fig. 1 c shows the CuZn21Si3P alloy that contains 0.009% boron.Be clear that the bright surface of metal from this figure, promptly the quantity of white dot further increases.In some zone, exist bright gold to belong to the bigger successive zone of material, and also can see fairly regular distribution on this alloy surface from this figure.The ratio on the surface of scaling further reduces, and remaining oxide skin adheres on the metal securely.Therefore, show astoundingly, the low boron concentration limit of 0.0001-0.5% the oxide skin of Cu-Zn-Si alloy form, increased the adhesion of oxide skin significantly simultaneously, thereby avoided undesirable pollution of production unit metal.
For having different lead contents, for example 0.01%, 0.05%, 0.1% or 2.5% Cu-Zn-Si-P alloy has also been found similar result.
Tend to the tendency of scaling except reducing the Cu-Zn-Si alloy, boron also has positive effect to mechanical property, and structure is more even because boron makes alloy organizing.This change of alloy microstructure is shown in Figure 2 as the function of boron concentration.Though not adding the CuZn21Si3P alloy of boron has coarse, uneven weave construction (Fig. 2 a), the CuZn21Si3P alloy that contains 0.0004% boron has significantly more uniform tissue structure, and this weave construction has had particle diameter (Fig. 2 b) very uniformly.Boron content further is increased to 0.009% and causes CuZn21Si3P alloy even more even or homogeneity to become even bigger, and wherein the particles no longer of this weave construction can be seen (Fig. 2 c) by naked eyes.
Except the vision change of weave construction, the interpolation of boron also has favorable influence to mechanical property.This is to apparent especially by the bar of Cu-Zn-Si alloy compacting.In order to measure mechanical property, extract sample at the section start and the place, end of this bar.The tensile strength of the bar of being made by the CuZn21Si3P alloy that does not add boron is compared with the place, end of bar at the section start of bar and is differed 60N/mm
2More than.Under the contrast, the alloy that has 0.0004% boron content accordingly only has the 40N/mm of being lower than between the tensile strength at the section start of bar and place, end
2Difference.By 0.009% boron is added in the CuZn21Si3P alloy, the deviation between the tensile strength at the section start of bar and place, end is lower than 5N/mm
2
Therefore, this material has the mechanical property that runs through integrally identical.Correspondingly, in whole compacting length, obtain uniform intensity.Its reason is the grain refine effect of boron.
The homogeneity of increase of the boron content of Cu-Zn-Si alloy and alloy microstructure or the relation between the intensity difference that in a compacting workpiece, reduces have been summed up in the table.
| Alloy | The position | Tensile strength (N/mm 2) |
| CuZn21Si3P | Place, compacting section start compacting end | 514578 |
| The CuZn21Si3P that contains 0.0004% boron | Place, compacting section start compacting end | 507545 |
| The CuZn21Si3P that contains 0.009% boron | Place, compacting section start compacting end | 508512 |
Claims (18)
1.Cu-Zn-Si alloy, it comprises the copper in weight % 70-80%, 1-5% silicon, and 0.0001-0.5% boron, the aluminium of as many as 0.5%, and the phosphorus of 0.03-0.2% and/or arsenic, and the zinc of surplus is together with unavoidable impurities.
2. according to the Cu-Zn-Si alloy of claim 1, it is characterized in that comprising 75-77% copper 2.8-4% silicon in weight %, 0.0001-0.01% boron, the aluminium of as many as 0.5%, and 0.03-0.1% phosphorus and/or arsenic, and the zinc of surplus is together with unavoidable impurities.
3. according to the Cu-Zn-Si alloy of claim 1 or 2, it is characterized in that additionally comprising at least a following element that is selected from: 0.01-2.5% lead, 0.01-2% tin in weight %, 0.01-0.3% iron, the 0.01-0.3% cobalt, 0.01-0.3% nickel, 0.01-0.3% manganese.
4. according to the Cu-Zn-Si alloy of claim 3, it is characterized in that additionally comprising at least a following element that is selected from: 0.01-0.1% lead, 0.01-0.2% tin, 0.01-0.1% iron in weight %, 0.01-0.1% cobalt, 0.01-0.1% nickel and 0.01-0.1% manganese.
5. according to the Cu-Zn-Si alloy of claim 1 or 2, it is characterized in that additionally comprising at least a following element that is selected from: the silver of as many as 0.5% in weight %, the magnesium of as many as 0.5%, the antimony of as many as 0.5%, the zirconium of the titanium of as many as 0.5% and as many as 0.5%.
6. according to the Cu-Zn-Si alloy of claim 5, it is characterized in that additionally comprising at least a following element that is selected from: 0.01-0.1% silver, 0.01-0.1% magnesium, 0.01-0.1% antimony, 0.01-0.1% titanium and 0.01-0.1% zirconium in weight %.
7. according to the Cu-Zn-Si alloy of claim 3, it is characterized in that additionally comprising at least a following element that is selected from: the silver of as many as 0.5% in weight %, the magnesium of as many as 0.5%, the antimony of as many as 0.5%, the zirconium of the titanium of as many as 0.5% and as many as 0.5%.
8. according to the Cu-Zn-Si alloy of claim 7, it is characterized in that additionally comprising at least a following element that is selected from: 0.01-0.1% silver, 0.01-0.1% magnesium, 0.01-0.1% antimony, 0.01-0.1% titanium and 0.01-0.1% zirconium in weight %.
9. according to the Cu-Zn-Si alloy of claim 1 or 2, it is characterized in that additionally comprising at least a following element that is selected from: the cadmium of as many as 0.3% in weight %, the chromium of as many as 0.3%, the selenium of as many as 0.3%, the bismuth of the tellurium of as many as 0.3% and as many as 0.3%.
10. according to the Cu-Zn-Si alloy of claim 9, it is characterized in that additionally comprising at least a following element that is selected from: 0.01-0.3% cadmium, 0.01-0.3% chromium, 0.01-0.3% selenium, 0.01-0.3% tellurium and 0.01-0.3% bismuth in weight %.
11. Cu-Zn-Si alloy according to claim 3, it is characterized in that additionally comprising at least a following element that is selected from: the cadmium of as many as 0.3% in weight %, the chromium of as many as 0.3%, the selenium of as many as 0.3%, the bismuth of the tellurium of as many as 0.3% and as many as 0.3%.
12., it is characterized in that additionally comprising at least a following element that is selected from: 0.01-0.3% cadmium, 0.01-0.3% chromium, 0.01-0.3% selenium, 0.01-0.3% tellurium and 0.01-0.3% bismuth in weight % according to the Cu-Zn-Si alloy of claim 11.
13. be used for the electrotechnology member according to each Cu-Zn-Si alloy among the claim 1-12, the sanitary engineering member is used for carrying or storing liquid or gas containers, is subjected to the member of torsional load, but recycle member, the die forging parts, work in-process, band, sheet material, profiled material, sheet material, or as the purposes of plastic metal, rolled alloy or casting alloy.
14. preparation is according to the method for each Cu-Zn-Si alloy among the claim 1-12, it comprises conventional continuous casting and 600-760 ℃ of following hot rolling, with after strain.
15., it is characterized in that described distortion is cold rolling according to the method for claim 14.
16., it is characterized in that adding further annealing and deforming step according to the method for claim 14.
17. preparation is according to the method for each Cu-Zn-Si alloy among the claim 1-12, it comprises conventional continuous casting and being up to 760 ℃ of extruding down, then cools off in air.
18., it is characterized in that 650-680 ℃ of extruding down according to the method for claim 17.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| DE102004049468 | 2004-10-11 | ||
| DE102004049468.1 | 2004-10-11 |
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| CN101023191A CN101023191A (en) | 2007-08-22 |
| CN100510132C true CN100510132C (en) | 2009-07-08 |
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| US (2) | US20060078458A1 (en) |
| EP (1) | EP1812612B1 (en) |
| JP (1) | JP5148279B2 (en) |
| KR (1) | KR101010906B1 (en) |
| CN (1) | CN100510132C (en) |
| AT (1) | ATE466965T1 (en) |
| BR (1) | BRPI0516067B1 (en) |
| CA (1) | CA2582972C (en) |
| DE (1) | DE502005009545D1 (en) |
| ES (1) | ES2343532T3 (en) |
| MY (1) | MY145376A (en) |
| PL (1) | PL1812612T3 (en) |
| PT (1) | PT1812612E (en) |
| TW (1) | TWI369405B (en) |
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| JP3917304B2 (en) * | 1998-10-09 | 2007-05-23 | 三宝伸銅工業株式会社 | Free-cutting copper alloy |
| US6413330B1 (en) * | 1998-10-12 | 2002-07-02 | Sambo Copper Alloy Co., Ltd. | Lead-free free-cutting copper alloys |
| JP3734372B2 (en) * | 1998-10-12 | 2006-01-11 | 三宝伸銅工業株式会社 | Lead-free free-cutting copper alloy |
| JP3898619B2 (en) * | 2002-10-15 | 2007-03-28 | 大同メタル工業株式会社 | Copper-based alloy for sliding |
| JP4296344B2 (en) * | 2003-03-24 | 2009-07-15 | Ｄｏｗａメタルテック株式会社 | Copper alloy material |
| EP1777305B1 (en) * | 2004-08-10 | 2010-09-22 | Mitsubishi Shindoh Co., Ltd. | Copper-base alloy casting with refined crystal grains |
-
2005
- 2005-05-13 PL PL05747601T patent/PL1812612T3/en unknown
- 2005-05-13 KR KR1020077007251A patent/KR101010906B1/en active IP Right Grant
- 2005-05-13 DE DE502005009545T patent/DE502005009545D1/en active Active
- 2005-05-13 JP JP2007535030A patent/JP5148279B2/en active Active
- 2005-05-13 PT PT05747601T patent/PT1812612E/en unknown
- 2005-05-13 EP EP05747601A patent/EP1812612B1/en active Active
- 2005-05-13 AT AT05747601T patent/ATE466965T1/en active
- 2005-05-13 ES ES05747601T patent/ES2343532T3/en active Active
- 2005-05-13 CA CA2582972A patent/CA2582972C/en active Active
- 2005-05-13 BR BRPI0516067-7A patent/BRPI0516067B1/en active IP Right Grant
- 2005-05-13 WO PCT/EP2005/005238 patent/WO2006039951A1/en active Application Filing
- 2005-05-13 CN CNB2005800317665A patent/CN100510132C/en active Active
- 2005-05-27 MY MYPI20052420A patent/MY145376A/en unknown
- 2005-05-30 TW TW094117687A patent/TWI369405B/en not_active IP Right Cessation
- 2005-10-11 US US11/247,544 patent/US20060078458A1/en not_active Abandoned
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2009
- 2009-06-03 US US12/477,612 patent/US20090280026A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR900006105B1 (en) * | 1987-06-13 | 1990-08-22 | 풍산금속 공업주식회사 | Cu-alloy and method for cu-alloy sheet |
| CN1167162A (en) * | 1997-05-08 | 1997-12-10 | 华南理工大学 | Beta brass shape-memory alloy and preparation method |
| CN1524970A (en) * | 2003-02-28 | 2004-09-01 | ������-�ֿ˹����ɷ�����˾ | A lead-free copper alloy and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101010906B1 (en) | 2011-01-25 |
| WO2006039951A1 (en) | 2006-04-20 |
| US20090280026A1 (en) | 2009-11-12 |
| MY145376A (en) | 2012-01-31 |
| PT1812612E (en) | 2010-06-28 |
| TW200611985A (en) | 2006-04-16 |
| KR20070060100A (en) | 2007-06-12 |
| DE502005009545D1 (en) | 2010-06-17 |
| TWI369405B (en) | 2012-08-01 |
| CN101023191A (en) | 2007-08-22 |
| ES2343532T3 (en) | 2010-08-03 |
| EP1812612A1 (en) | 2007-08-01 |
| BRPI0516067A (en) | 2008-08-19 |
| CA2582972A1 (en) | 2006-04-20 |
| BRPI0516067B1 (en) | 2014-10-14 |
| EP1812612B1 (en) | 2010-05-05 |
| JP2008516081A (en) | 2008-05-15 |
| JP5148279B2 (en) | 2013-02-20 |
| PL1812612T3 (en) | 2010-10-29 |
| ATE466965T1 (en) | 2010-05-15 |
| CA2582972C (en) | 2014-02-04 |
| US20060078458A1 (en) | 2006-04-13 |
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