CN102925744B - Leadless brass alloy and preparation method thereof - Google Patents
Leadless brass alloy and preparation method thereof Download PDFInfo
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- CN102925744B CN102925744B CN201210412904.6A CN201210412904A CN102925744B CN 102925744 B CN102925744 B CN 102925744B CN 201210412904 A CN201210412904 A CN 201210412904A CN 102925744 B CN102925744 B CN 102925744B
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Abstract
The invention discloses a leadless brass alloy and a preparation method thereof. The leadless brass alloy comprises the following components in percentage by weight: 59-65% of copper, 32-35% of zinc, 0.2-1% of silicon, 0.03-0.1% of phosphorus, 0.1-1% of magnesium, 0.02-0.1% of aluminum, 0.1-1% of nickel, 0.1-1% of tin and 0.0001-0.001% of lanthanum-cerium mixed rare earth element. The preparation method comprises the following steps: 1) alloy smelting: adding recovered brass, white copper and tin-phosphor bronze waste, adding a covering agent, and smelting at 1100-1200 DEG C; 2) alloy refining: after melting the raw materials, adding copper-silicon alloy, lanthanum-cerium mixed rare earth element (La+Ce) and aluminum, alloying and refining; 3) alloy degassing: adding copper-phosphorus alloy and magnesium, evenly stirring, adding zinc while keeping the temperature of the melt; and 4) alloy casting: casting the alloy at 1030-1080 DEG C. The preparation method adopts recovered copper alloy waste as well as cheap silicon, phosphorus and the like as the raw materials, so the alloy preparation cost is low.
Description
Technical field
The present invention relates to a kind of LEAD-FREE BRASS ALLOY and preparation method thereof, espespecially a kind of preparation method utilizing waste and old copper material to prepare LEAD-FREE BRASS ALLOY.
Background technology
Tradition brass alloys add the plumbous low melting point element for representative in the alloy, thus make alloy have excellent processing characteristics and higher intensity and plasticity.It is generally acknowledged that the machinability of brass is improved along with the increase of lead, the most effective at the lead approximately containing 3%.Because leaded brass has excellent cutting ability, be applied in multiple manufacturing widely, as the various parts etc. of machinery, electronic apparatus, building and mechanical precision cutting process, but containing heavy metal-lead human body being had to high risks in leaded brass, though its content is not high, but potential threat is existed to the health of people.Along with the development of human sciences's technology and people are to the attention increasingly of improving the ecological environment, improving the quality of living; environmental protection consciousness is constantly strengthened; therefore, the application of copper alloy containing lead is subject to the restriction of domestic and international various countries environmental protection policy, especially restricted more strict in developed country.
Replacing plumbous with nontoxic or low harmful toxic matter, is the main path reducing Lead contamination.Abandoning pollution on the environment to reduce after production medium leaded brass is scrapped, lead-free brass alloy material must be adopted.But lead-free general brass alloys, its processing characteristics extreme difference, discomfort meets precision machined requirement.Not only lead-free reflow is exactly that the element adding appropriate toxicological harmless in brass replaces plumbous function, makes it reach its performance, meets industrial needs but also protect ecotope.The LEAD-FREE BRASS ALLOY patent of research and development both at home and abroad at present, mainly in brass, add tellurium, bismuth, the elements such as antimony, as: patent 200910154951, 200810188263, 200910044085, 200810042416, 200910044798, 200410089150, 200780048880, 02121991, 200810090868 etc., but bismuth-containing, the lead-free reflow processing characteristics of the elements such as antimony is poor, lumber recovery is low, and tellurium, bismuth, the elements such as antimony are your element rare, resource-constrained, compared with lead brass alloy, production cost is high, be difficult to form industrialization batch production with the leaded brass used a large amount of on alternative market.
Summary of the invention
For prior art Problems existing, an object of the present invention be to provide a kind of cost low, utilize lead-free waste and old copper material to prepare the method for LEAD-FREE BRASS ALLOY.Another object of the present invention is to provide one to have excellent machinability and use properties, according to LEAD-FREE BRASS ALLOY prepared by aforesaid method.
For achieving the above object, LEAD-FREE BRASS ALLOY of the present invention, according to weight percent meter, comprises following composition: copper 59% ~ 65%, zinc 32% ~ 35%, silicon 0.2% ~ 1%, phosphorus 0.03% ~ 0.1%, magnesium 0.1% ~ 1%, aluminium 0.02% ~ 0.1%, nickel 0.1% ~ 1%, tin 0.1% ~ 1%, mixed rare earth of lanthanum and cerium metal 0.0001% ~ 0.001%.
The preparation method of LEAD-FREE BRASS ALLOY of the present invention, comprises the following steps: 1) alloy melting: first add the brass of recovery, German silver, tin-phosphor bronze waste material, add insulating covering agent melting, and smelting temperature is 1100 ~ 1200 DEG C; 2) refining and modifying: after melting sources, adds copper-silicon alloy, mixed rare earth of lanthanum and cerium metal (La+Ce), aluminium, carries out alloying and refining; 3) alloy degasification: add copper-phosphorus alloy, magnesium, uniform stirring, melt insulation zincification; 4) alloy casting: carry out alloy casting at 1030 ~ 1080 DEG C.
Further, also raw materials pretreatment is comprised before described alloy melting: classification, go-on-go, pre-treatment are carried out to the brass reclaimed, German silver, tin-phosphor bronze waste material.
Further, also alloy preparation is comprised: carry out proportioning according to the gross weight of copper in alloy between described alloy melting and described raw materials pretreatment, brass 75-85%, tin-phosphor bronze 10-15%, German silver 5-10%, all the other alloys melt after composition analysis at waste material, then by alloying constituent weight percent batching.
Further, described insulating covering agent is borax, graphite flake or calcium chloride.
The preparation method of LEAD-FREE BRASS ALLOY of the present invention utilizes the copper alloy waste material and inexpensive silicon, phosphorus etc. of selecting starting material to be recovery, and far below the LEAD-FREE BRASS ALLOY material that additive method is produced, reasonable offer cost is low.Each alloying element in lead-free reflow has following effect: copper and zinc are the fundamental element of alloy; Add the mobility that element silicon can improve alloy; Add phosphoric and can improve alloy flowability and degasification; Interpolation magnesium elements can remove the gas in melt; Add aluminium element and can form protective membrane on alloy melt surface, isolated melt and atmosphere prevent air-breathing; Nickel and Xi Ke improve the processing characteristics of alloy; Add mixed rare earth of lanthanum and cerium metal (La+Ce), there is degasification, removal of impurities, refining, Grain refinement.The crystal grain of prepared according to the methods of the invention LEAD-FREE BRASS ALLOY is tiny, there is good hot and cold processing characteristics, and good cutting ability and corrosion resisting property, be applicable to other component materials such as the shaping various component of mechanical workout, forging, foundry goods, valve, tube stub.
Accompanying drawing explanation
Fig. 1 a is the schematic diagram of display lead brass alloy cutting ability;
Fig. 1 b is the schematic diagram of the LEAD-FREE BRASS ALLOY cutting ability of the display embodiment of the present invention 1;
Fig. 1 c is the schematic diagram of the LEAD-FREE BRASS ALLOY cutting ability of the display embodiment of the present invention 2;
Fig. 1 d is the schematic diagram of the LEAD-FREE BRASS ALLOY cutting ability of the display embodiment of the present invention 3;
Fig. 1 e is the schematic diagram of the LEAD-FREE BRASS ALLOY cutting ability of the display embodiment of the present invention 4;
Fig. 1 f is the schematic diagram of the LEAD-FREE BRASS ALLOY cutting ability of the display embodiment of the present invention 5;
Fig. 2 measures the schematic diagram that alloy flowability graphite used waters mold in the present invention;
Fig. 3 a is the schematic diagram of display lead brass alloy mobility;
Fig. 3 b is the schematic diagram of the LEAD-FREE BRASS ALLOY mobility of the display embodiment of the present invention 1;
Fig. 3 c is the schematic diagram of the LEAD-FREE BRASS ALLOY mobility of the display embodiment of the present invention 2;
Fig. 3 d is the schematic diagram of the LEAD-FREE BRASS ALLOY mobility of the display embodiment of the present invention 3;
Fig. 3 e is the schematic diagram of the LEAD-FREE BRASS ALLOY mobility of the display embodiment of the present invention 4;
Fig. 3 f is the schematic diagram of the LEAD-FREE BRASS ALLOY mobility of the display embodiment of the present invention 5.
Embodiment
The preparation method of LEAD-FREE BRASS ALLOY of the present invention, comprises the steps:
1, raw materials pretreatment: classification, go-on-go, pre-treatment (oil removing, dedusting, dewater) are carried out to the brass reclaimed, German silver, tin-phosphor bronze waste material;
2, alloy preparation: by alloying constituent composition described in table 1, carry out alloying ingredient calculating, prepared furnace charge;
Alloying ingredient method: carry out proportioning according to the gross weight of copper in alloy, brass 75-85%, tin phosphorus blue or green 10-15%, German silver 5-10%, all the other alloys, prepare burden by alloying constituent weight percent in old material fusing after composition analysis;
3, alloy melting: first add the brass of recovery, German silver, tin-phosphor bronze waste material during melting, then add other alloy; Alloy melting temp is 1100 ~ 1200 DEG C, adds insulating covering agent melting (borax, graphite flake, calcium chloride etc.);
4, refining and modifying: after melting sources, adds mixed rare earth of lanthanum and cerium metal (La+Ce), copper-silicon alloy, aluminium, carries out alloying and refining, removal of impurities;
5, alloy degasification: add copper-phosphorus alloy, magnesium etc., uniform stirring degasification, removal of impurities, melt insulation zincification;
6, alloy casting: after alloy component analysis detection is qualified, carries out alloy casting at 1030 ~ 1080 DEG C and become ingot casting.
Table 1 LEAD-FREE BRASS ALLOY of the present invention becomes to be grouped into example (% by weight)
In order to verify the performance of the LEAD-FREE BRASS ALLOY that method of the present invention is prepared, by the test of alloy cutting ability, Dezincification corrosion performance test, alloy cast ingot and fluidity testing above-mentioned five kinds of LEAD-FREE BRASS ALLOYs and HPb59-1 being compared and drawing.
1) alloy cutting ability test: comparative sample is the HPb59-1 alloy (100%) that cutting ability is excellent is reference, unified lathe tool and turning mode is adopted during turning, the chip of Pb-free copper-alloy of the present invention is the short chip of fine powder, HPb59-1 alloy is the straight chip of fine acicular slightly grown, as Fig. 1 a-1f.
2) Dezincification corrosion performance test: carry out in water bath with thermostatic control, carries out the contrast of Dezincification corrosion layer thickness with leaded brass (HPb59-1).Experimental technique: sample is vertically put into the 1.0%CuCl that normal content is housed
2in the beaker of solution (amount of solution is directly proportional to Area of Sample, every square centimeter of 240ml), bath temperature is 75 DEG C, and etching time is 24 hours.After corrosion, sample is taken out, cleans, dries up, be placed in moisture eliminator dry.Sample is cut from central symmetry axes, polishes smooth, survey its corrosion layer thickness under the microscope.
3) alloy cast ingot and fluidity testing: adopt linear pattern graphite mo(u)ld as shown in Figure 2, measures mobility and the alloy cast ingot of alloy; Fluidity testing result as illustrated in figs. 3 a-f.
Table 2 LEAD-FREE BRASS ALLOY of the present invention is cast with HPb59-1, corrosive nature compares
| Comparative alloy | Casting properties (mm) | Dezincification corrosion layer depth (μm) |
| HPb59-1 | 220 | 511.5 |
| Embodiment 1 | 378 | 154.4 |
| Embodiment 2 | 383 | 186.8 |
| Embodiment 3 | 416 | 264.5 |
| Embodiment 4 | 422 | 276.2 |
| Embodiment 5 | 453 | 281.6 |
LEAD-FREE BRASS ALLOY of the present invention is owing to adding the alloying elements such as silicon, phosphorus, nickel, tin, aluminium, magnesium, rare earth, effectively improve the processing characteristics of alloy, compared with lead brass alloy HPb59-1, improve mobility and the corrosion resistance nature of alloy, there is good cutting ability.
It is to be noted that above-described embodiment is exemplary being illustrated the present invention, the random variation that spirit according to the present invention is made, all should not think disengaging protection scope of the present invention.
Claims (5)
1. a LEAD-FREE BRASS ALLOY, it is characterized in that, according to weight percent meter, comprise following composition: copper 59% ~ 65%, zinc 32% ~ 35%, silicon 0.2% ~ 1%, phosphorus 0.03% ~ 0.1%, magnesium 0.6% ~ 1%, aluminium 0.04% ~ 0.1%, nickel 0.3% ~ 1%, tin 0.6% ~ 1%, mixed rare earth of lanthanum and cerium metal 0.0001% ~ 0.001%.
2. the preparation method of a LEAD-FREE BRASS ALLOY as claimed in claim 1, it is characterized in that, comprise the following steps: 1) alloy melting: first add the brass of recovery, German silver, tin-phosphor bronze waste material, add insulating covering agent melting, smelting temperature is 1100 ~ 1200 DEG C; 2) refining and modifying: after melting sources, adds copper-silicon alloy, mixed rare earth of lanthanum and cerium metal (La+Ce), aluminium, carries out alloying and refining; 3) alloy degasification: add copper-phosphorus alloy, magnesium, uniform stirring, melt insulation zincification; 4) alloy casting: carry out alloy casting at 1030 ~ 1080 DEG C.
3. preparation method as claimed in claim 2, is characterized in that, also comprise raw materials pretreatment before described alloy melting: carry out classification, go-on-go, pre-treatment to the brass reclaimed, German silver, tin-phosphor bronze waste material.
4. preparation method as claimed in claim 3, it is characterized in that, also alloy preparation is comprised: carry out proportioning according to the gross weight of copper in alloy between described alloy melting and described raw materials pretreatment, brass 75-85%, tin-phosphor bronze 10-15%, German silver 5-10%, all the other alloys melt after composition analysis at waste material, then by alloying constituent weight percent batching.
5. preparation method as claimed in claim 2, it is characterized in that, described insulating covering agent is borax, graphite flake or calcium chloride.
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| CN201210412904.6A CN102925744B (en) | 2012-10-25 | 2012-10-25 | Leadless brass alloy and preparation method thereof |
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| CN201210412904.6A CN102925744B (en) | 2012-10-25 | 2012-10-25 | Leadless brass alloy and preparation method thereof |
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| CN102925744A CN102925744A (en) | 2013-02-13 |
| CN102925744B true CN102925744B (en) | 2015-04-15 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104109773A (en) * | 2013-04-18 | 2014-10-22 | 鹤山市金洲铜材实业有限公司 | Casting brass ingot and preparation method thereof |
| CN104480344B (en) * | 2014-11-21 | 2017-03-29 | 九牧厨卫股份有限公司 | A kind of phosphorous easily-cut silicon brass alloy and preparation method thereof |
| CN104711450A (en) * | 2015-04-03 | 2015-06-17 | 北京金鹏振兴铜业有限公司 | High-strength and high-ductility magnesium brass alloy |
| CN104775042A (en) * | 2015-04-16 | 2015-07-15 | 新疆大学 | Low-metal-loss smelting method of copper alloy |
| CN105886806A (en) * | 2016-05-17 | 2016-08-24 | 安徽九华金润铜业有限公司 | Smelting method of silicon phosphorus brass |
| CN106591676A (en) * | 2016-12-09 | 2017-04-26 | 钦州市钦南区科学技术情报研究所 | Lead-free copper alloy and preparation method thereof |
| CN108220619B (en) * | 2018-01-26 | 2020-01-03 | 宁波华成阀门有限公司 | High-purity red copper and manufacturing method thereof |
| CN109266900A (en) * | 2018-12-07 | 2019-01-25 | 宁波艾维洁具有限公司 | A kind of Anti-dezincificationyellow yellow brass alloy of lead-free corrosion resistant and preparation method thereof |
| CN109468488A (en) * | 2018-12-24 | 2019-03-15 | 广州海鸥住宅工业股份有限公司 | Low lead Anti-dezincificationyellow yellow brass alloy and preparation method thereof |
| CN112410604A (en) * | 2020-11-17 | 2021-02-26 | 宁波长振铜业有限公司 | Method for reducing impurity aluminum in brass melt |
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| JP2002003967A (en) * | 2000-06-26 | 2002-01-09 | Sumitomo Light Metal Ind Ltd | Lead-free free cutting brass excellent in dezincification corrosion resistance and its production method |
| CN101440444B (en) * | 2008-12-02 | 2010-05-12 | 路达(厦门)工业有限公司 | Leadless free-cutting high-zinc silicon brass alloy and manufacturing method thereof |
| CN101435034A (en) * | 2008-12-05 | 2009-05-20 | 浙江科宇金属材料有限公司 | Leadless free-cutting tin-magnesium brass alloy |
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