CN101476056A - Leadless free-cutting silicon-phosphorous-copper alloy - Google Patents
Leadless free-cutting silicon-phosphorous-copper alloy Download PDFInfo
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- CN101476056A CN101476056A CNA2008101632431A CN200810163243A CN101476056A CN 101476056 A CN101476056 A CN 101476056A CN A2008101632431 A CNA2008101632431 A CN A2008101632431A CN 200810163243 A CN200810163243 A CN 200810163243A CN 101476056 A CN101476056 A CN 101476056A
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Abstract
The invention discloses a leadless silicon-phosphorous-copper alloy that is easy to cut and is characterized in that the alloy consists of Cu of 65-70% by weight, Si of 2.0-3.5% by weight and P of 0.02-0.15% by weight, and the rest are Zn and ineluctable foreign matters, preferably, the alloy consists of Cu of 65% by weight, Si of 3% by weight and P of 0.15% by weight, and the rest are Zn and ineluctable foreign matters.The invention has advantages of excellent cutting ability, favorable welding performance, excellent wear-resistant and corrosion-resistance performances and high temperature oxidation resistance performance. The leadless silicon-phosphorous-copper alloy of the invention is especially suitable for making elements for machine-shaping, forgeable pieces, casting parts and the element materials for other manufacturing.
Description
Technical field
The present invention relates to an Albatra metal-, relate in particular to a kind of the have mechanical property of advantage and the leadless free-cutting silicon-phosphorous-copper alloy of wear resistant corrosion resistant.
Background technology
Leaded brass has fabulous cutting ability and self lubricity, and cold-forming property is good, can satisfy the mechanical workout of all kinds of shape component, so Winn bronze is widely applied to the fields such as fastening piece of valve member, bathroom alloy, machinery and the automobile manufacture industry of domestic water supply system at present.
In recent years, medical expert all over the world has been found that leaded brass has constituted threat to human health and ecotope, thereby national governments have put into effect in succession to ordering within a certain time that copper alloy containing lead is used.On September 22nd, 2003, Americanologist is crossed " waste and old electric product innovation is recycled method " (california 65 is proposed); On February 16th, 2005, kyoto, Japan protocol " employing environment tax " comes into force; On July 1st, 2006, European Union instructs by ROHS, throws in the electrical equipment of European Union and electronic product from now on to leaded, and objectionable impuritiess such as cadmium have strict control; China National Development and Reform Committee, the Ministry of Information Industry also unite and have put into effect " waste household appliances and electronic product recycling management rules " and " electronics and IT products prevention and cure of pollution management method " two rules.Application in every profession and trade is subjected to great restriction to the leaded brass series of products for this.With regard to " WEEE " and " RoHS " instruction, related products reach totally 123 kinds of 10 big classes.Comprising: large household appliance, small household appliance, IT and communication equipment, user equipment (sound equipment, image), set lights, electronic apparatus instrument, toy, leisure and sports equipment, medical equipment, detection and monitoring instrument.Wherein the first seven series products all is electronics, electrical equipment and the device product of China's main exit, and these products use the copper alloy containing lead material to occupy quite great proportion, estimates to account for 3 ~ 5% of its export amount, reaches 12 ~ 2,000,000,000 dollars approximately.Therefore, the relevant export enterprise of China proposes the supply requirement of leadless environment-friendly type Cu alloy material one after another, and adjusts corresponding product technology standard, to adapt to the environmental requirement to related products of area such as European Union and country.China's leaded brass just has tube, rod section, line, plate, foundry goods in widely used kind, amounts to about 800,000 tons, presses for the environment-friendly type alloy replacing.
Some lead-free copper alloys have also been invented at present both at home and abroad, disclosed a kind of patent of invention " Unleaded And Cutting Antimony Brass Alloy " in Chinese patent 200410015836.5 specification sheetss for example, it is not leaded, by the copper of weight %: 55-65%, antimony: 0.3-2.0%, manganese: 0.4-1.6%, other element: 0.1-1.0%.Described other element comprises at least two kinds of elements in titanium, zirconium, boron, iron, magnesium, silicon, the rare earth material.All the other are zinc and inevitable impurity; Manufacture method is that above-mentioned alloy composition is carried out the large extrusion ratio extruding under 630-720 ℃ of temperature, and intermediate heat treatment is carried out under 420-700 ℃ of temperature by the cold working condition.Be lower than the annealing that eliminates stress under 400 ℃ the temperature.This invention has excellent cutting ability, good welding property, and superior corrosion resistance and high temperature oxidation resistance are applicable to the component material of component, forging, foundry goods and other manufacture method of machining moulding.But the subject matter that present domestic research and development leadless environment-friendly alloy exists is:
In alloy, add element such as Di , Antimony and be rare your element, be difficult to form industrialization produce in batches to substitute a large amount of leaded brasss that use;
Add bismuth at present, merimee's yellow copper performance is bad, so lumber recovery is very low, has improved material cost;
For substituting a large amount of leaded brasss that use, the most promising material is to add silicon, phosphoric in brass, and reason is that element is abundant, adds the flowability that phosphorus can improve liquid metal, and hard phase can appear in the adding of silicon in alloy, improve cutting ability.
Summary of the invention
The objective of the invention is for a kind of lead-free good machinability that has is provided, easy cold and hot moulding and excellent wear-corrosion resistance, and can substitute the leadless free-cutting silicon-phosphorous-copper alloy of copper alloy containing lead.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals: a kind of leadless free-cutting silicon-phosphorous-copper alloy, it is characterized in that: alloy composition and weight part are: 65-70%Cu, 2.0-3.5%Si, 0.02-0.15%P, all the other are Zn and unavoidable impurities.
As preferably, alloy composition and weight part are 65-70%Cu, 2.0-3.0%Si, and 0.02-0.15%P, all the other are Zn and unavoidable impurities.
As further preferred, alloy composition and weight part are 65%Cu, 3%Si, and 0.15%P, all the other are Zn and unavoidable impurities.
The selection principle of alloy compositions of the present invention is: add the tissue behind 1% silicon in the Cu-Zn alloy, promptly be equivalent to increase the alloy structure of 10% zinc in the Cu-Zn alloy.So " the zinc equivalent " of silicon is 10." zinc equivalent coefficient " maximum of silicon, make α/(alpha+beta) phase boundary in the Cu-Zn system significantly shift to the copper side, promptly dwindle alpha phase zone strongly, be used for the alloy deoxidation simultaneously, transform metal casting welding flowability, generate intermetallic compound, gain in strength and wear resisting property, rather than make alloy generate the hard crisp phase of γ of high silicon, help the raising of cutting ability and welding property, when welding, can also suppress zinc evaporation and oxide inclusion simultaneously, thereby improve the processing performance of welding greatly.Phosphorus mainly plays deoxidation and increases casting fluidity, prevention dezincify in alloy, help the raising of cutting ability, and general add-on is 0.02-0.15%.
Leadless free-cutting silicon-phosphorous-copper alloy of the present invention, its alloy melting and complete processing can adopt two kinds of schemes, i.e. iron mould casting and horizontal casting.
Leadless free-cutting silicon-phosphorous-copper alloy of the present invention, it is a spot of hard mutually crisp with other mutually to contain α phase β, hard crisp mutually tinyly be evenly distributed on crystal boundary and intracrystalline and the precipitation strength effect is arranged, improve the cutting ability of alloy, also strengthened anti-corrosion, the wear-resisting mechanical property and the cold and hot processability of alloy simultaneously.
Leadless free-cutting silicon-phosphorous-copper alloy of the present invention, though described lead as unavoidable impurities, its content should not surpass 0.03 weight %.
Described alloy manufacture method is with weight %:65-70%Cu, 2.0-3.5%Si, and 0.02-0.15%P, all the other are Zn and unavoidable impurities.Carry out large extrusion ratio extruding under 580～720 ℃ of temperature, intermediate heat treatment is carried out under 420～550 ℃ of temperature by cold worked condition, is being lower than the annealing that eliminates stress under 400 ℃ the temperature.
Therefore, compared with prior art, the invention has the advantages that:
1. have excellent cutting ability, good welding property, good wear resistance and corrosion resistance and high temperature oxidation resistance are specially adapted to the component, forging, foundry goods of machining moulding and as the component material of other manufacture method;
2. low cost of manufacture only is equivalent to the manufacturing cost of the leaded brass of prior art, thereby has market competition advantage;
3. can make full use of the extremely abundant advantage of China's silicon, phosphor resource, drive the downstream industry development.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment:
The present invention is a basic raw material with copper, silicon, zinc, phosphorus, feed by following loading sequence: melt in copper-silicon-zinc-adding slag-cleaning agent-phosphor copper (adding of graphite bell-jar)-skim-flame casting, charcoal covering, slag-cleaning agent (sodium aluminum fluoride) the adding intermediate frequency furnace, with the method for swage casting, or make the extruding ingot blank in the mode of D.C.casting casting; Excellent base or line base are processed in hot extrusion in 580 ~ 720 ℃ of temperature ranges, make required excellent wire product with tensile cold deformation method then.Intermediate heat treatment behind the stretching cold deformation is carried out under 400～550 ℃ of temperature by cold worked condition, is being lower than the annealing that eliminates stress under 420 ℃ the temperature.Certainly, alloy of the present invention also can use the low frequency induction furnace fusing to produce.
Foregoing copper also can be regeneration brass material, and described regeneration brass material is through cleaning, go-no-go, classification, with the ratio batching of standard compliant recovery brass in shared copper.
The composition of leadless free-cutting silicon-phosphorous-copper alloy of the present invention is formed example (unit: weight %)
| The numbering element | Cu | Si | P | Impurity | Zn |
| 1 | 65.0 | 3.0 | 0.15 | Pb0.0060 | Surplus |
| 2 | 67.3 | 2.21 | 0.06 | Pb0.0050 | Surplus |
| 3 | 69.5 | 2.87 | 0.075 | Pb0.0056 | Surplus |
| 4 | 66.8 | 3.11 | 0.045 | Pb0.0063 | Surplus |
Leadless free-cutting silicon-phosphorous-copper alloy bar according to last routine component is made all adheres to specification through performance test.Now the test situation with the 1st group of copper alloy bar is listed as follows:
Table 1 specific conductivity and thermal conductivity
| State | Specific conductivity (%IACS) | Thermal conductivity * (w/mK) | |
| Leadless free-cutting silicon-phosphorous-copper alloy | Semihard | 100.6~102.1 | 437~447 |
| The T1 red copper | Semihard | 95~101.5 | 391~395 |
| Pure copper wire | Semihard | ≥95.8 | — |
| TUAg0.06 | Semihard | 97.5~98.5 | — |
By table 1 as seen, the specific conductivity of leadless free-cutting silicon-phosphorous-copper alloy and thermal conductivity all are better than T1 red copper, pure copper wire, TUAg0.06 respectively.
Table 2 tensile strength and unit elongation
By table 2 as seen, leadless free-cutting silicon-phosphorous-copper alloy intensity and plasticity all are better than T1 red copper and pure copper wire under various states.
The arc resisting ultimate compression strength of table 3
| Discharge inception voltage (kv) | Voltage breakdown (kv) | Arc light length (mm) | |
| Leadless free-cutting silicon-phosphorous-copper alloy | 17.0 | 19.5 | 2-10 |
| 0.3AgCu* | 16.0 | 19.0 | 2-12 |
* the 0.3AgCu alloy is available from Chongqing instrument material factory product.
As shown in Table 3: the reactance voltage intensity of leadless free-cutting silicon-phosphorous-copper alloy and 0.3AgCu alloy phase are worked as, and get the upper hand.
Table 4 ROHS limits element determination
| Pb(％) | Cd(％) | As(％) | |
| Leadless free-cutting silicon-phosphorous-copper alloy | 0.0060 | 0.0003 | 0.002 |
As shown in Table 4: it is atomic to contain the ROHS constraint element in the leadless free-cutting silicon-phosphorous-copper alloy, has reached the requirement of the two green instructions of European Union.
Table 5 tensile strength, unit elongation, hardness and cutting ability are measured
| State | Tensile strength Rm (MPa) | Unit elongation A% | Hardness (HRS) | Cutting ability | |
| Leadless free-cutting silicon-phosphorous-copper alloy | Semihard | 380~450 | 10~16 | 115~125 | 90~100 |
| HPb59-1 | Semihard | 390~420 | 10~12 | — | 80 |
| HPb63-3* | Semihard | 360~390 | 10~14 | — | 100 |
The cutting ability standard code is 100% with the cutting ability of HPb63-3, and other copper alloy is then done relatively.
By data contrast in table 4 and the table 5 as seen, the mechanical property of leadless free-cutting silicon-phosphorous-copper alloy is better than leaded brass, particularly cutting ability comprehensively can surpass HPb63-3, and harmful element all is lower than the regulation of ROHS instruction.
Claims (3)
1, a kind of leadless free-cutting silicon-phosphorous-copper alloy is characterized in that:
Alloy composition and weight part are::
65-70%Cu, 2.0-3.5%Si, 0.02-0.15%P, all the other are Zn and unavoidable impurities.
2, leadless free-cutting silicon-phosphorous-copper alloy according to claim 1 is characterized in that:
Alloy composition and weight part are 65-70%Cu, 2.0-3.0%Si, and 0.02-0.15%P, all the other are Zn and unavoidable impurities.
3, leadless free-cutting silicon-phosphorous-copper alloy according to claim 1 is characterized in that:
Alloy composition and weight part are 65%Cu, 3%Si, and 0.15%P, all the other are Zn and unavoidable impurities.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101632431A CN101476056A (en) | 2008-12-10 | 2008-12-10 | Leadless free-cutting silicon-phosphorous-copper alloy |
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| CNA2008101632431A CN101476056A (en) | 2008-12-10 | 2008-12-10 | Leadless free-cutting silicon-phosphorous-copper alloy |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103114221A (en) * | 2013-03-01 | 2013-05-22 | 南通大学 | Lead-free free-cutting silicon brass alloy and preparation method thereof |
| CN103261458A (en) * | 2010-09-10 | 2013-08-21 | 赖于福斯水及气有限公司 | Improved brass alloy and a method of manufacturing thereof |
| CN113348261A (en) * | 2019-06-25 | 2021-09-03 | 三菱综合材料株式会社 | Free-cutting copper alloy and method for producing free-cutting copper alloy |
-
2008
- 2008-12-10 CN CNA2008101632431A patent/CN101476056A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261458A (en) * | 2010-09-10 | 2013-08-21 | 赖于福斯水及气有限公司 | Improved brass alloy and a method of manufacturing thereof |
| US9217191B2 (en) | 2010-09-10 | 2015-12-22 | Raufoss Water & Gas As | Brass alloy comprising silicon and arsenic and a method of manufacturing thereof |
| CN103114221A (en) * | 2013-03-01 | 2013-05-22 | 南通大学 | Lead-free free-cutting silicon brass alloy and preparation method thereof |
| CN103114221B (en) * | 2013-03-01 | 2015-03-11 | 南通大学 | Lead-free free-cutting silicon brass alloy and preparation method thereof |
| CN113348261A (en) * | 2019-06-25 | 2021-09-03 | 三菱综合材料株式会社 | Free-cutting copper alloy and method for producing free-cutting copper alloy |
| CN113348261B (en) * | 2019-06-25 | 2022-09-16 | 三菱综合材料株式会社 | Free-cutting copper alloy and method for producing free-cutting copper alloy |
| US11479834B2 (en) | 2019-06-25 | 2022-10-25 | Mitsubishi Materials Corporation | Free-cutting copper alloy and method for manufacturing free-cutting copper alloy |
| US11512370B2 (en) | 2019-06-25 | 2022-11-29 | Mitsubishi Materials Corporation | Free-cutting copper alloy and method for producing free-cutting copper alloy |
| US11788173B2 (en) | 2019-06-25 | 2023-10-17 | Mitsubishi Materials Corporation | Free-cutting copper alloy, and manufacturing method of free-cutting copper alloy |
| US11814712B2 (en) | 2019-06-25 | 2023-11-14 | Mitsubishi Materials Corporation | Free-cutting copper alloy and method for producing free-cutting copper alloy |
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