CN103255315B - A kind of without nickel lead-free free-cutting copper-nickel alloy and preparation method thereof - Google Patents
A kind of without nickel lead-free free-cutting copper-nickel alloy and preparation method thereof Download PDFInfo
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- CN103255315B CN103255315B CN201310161306.0A CN201310161306A CN103255315B CN 103255315 B CN103255315 B CN 103255315B CN 201310161306 A CN201310161306 A CN 201310161306A CN 103255315 B CN103255315 B CN 103255315B
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Abstract
The invention discloses a kind of without nickel lead-free free-cutting copper-nickel alloy, the weight percent of described White brass alloy consists of: manganese 10 ~ 15%, zinc 8 ~ 13%, silicon 0.5 ~ 0.8%, aluminium 0.5 ~ 1.5%, rare-earth element cerium 0.03 ~ 0.08%? " calcium+magnesium " 1 ~ 1.5%, surplus is copper and inevitable impurity.In White brass alloy of the present invention, manganese, zinc, aluminium are added in copper the phase same-action had with nickel, can put forward heavy alloyed intensity and elasticity, and keep the silvery white color and luster of alloy; The interpolation of silicon, calcium, magnesium and trace rare-earth cerium, can improve machining property and the cutting ability of alloy.
Description
Technical field
The present invention relates to a kind of cupronickel alloy material, be specifically related to a kind of pollution-free, Cutting free, machining property good without nickel Unleaded white brass alloy, the invention still further relates to the preparation method of this alloy.
Background technology
In copper alloy, add nickel element can put forward heavy alloyed intensity and corrosion stability, and increase substantially the elasticity of copper alloy, but in alloy, nickel content is higher, usually more than 16%.Copper-nickel alloy take nickel as the copper alloy of main alloy element, copper-nickel alloy is German silver (Cu-Ni-Zn) alloy particularly, not only there is argenteous outward appearance, and there is excellent corrosion resistance nature, higher elasticity and good processing performance, therefore German silver is except using as structured material, is also widely used for making the metal products with human contact.But German silver cutting ability is poor, can have a strong impact on the mechanical workout of alloy, in order to improve German silver processing characteristics, people add lead (Pb) 1-3% of trace in White brass alloy, to improve its cutting ability, as Cu
43ni
12zn
38mn
5pb
2alloys etc., plumbous owing to containing in alloy, significantly can improve cutting ability, and be widely used in the spare and accessory parts manufacturings such as pen core, frame, instrument, electronic apparatus, clock and watch, copper containing white lead at home and abroad market consumption is all larger.
Recent studies have found that, human body contacts with nickeliferous metallic substance for a long time, can produce sensitivity response and carcinogenic impact, day by day cause the attention of world medical circle and material engineering circle to human body.Countries in the world are more and more stricter to the nickel content restriction in daily and medical metal material, European Union had with human body the metal product contacted to all from 2000, implement the regulations management of nickel content and emission thereof, specify that manufacturers and importor must not release product against regulation at EU market, must not sales to consumers or product against regulation is provided.And nickel resources is limited, price is high, alloy manufacturing cost is remained high.
Moreover, have also appeared the trend of forbidding with nickel-containing alloys manufacture and human contact's product in the world.Germany, in 21 days July in 2000, forbids the product containing nickel element of production and import and human body Long contact time.In addition, there is potential threat to the health of human body and environment in the heavy metal-lead in copper alloy.Along with the development of human society and people are to the attention increasingly of improving the ecological environment, improving the quality of living; environmental protection consciousness is constantly strengthened; 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; as European Parliament and EU Committee require in the electronics of newly putting on market, electrical equipment, plant and instrument, strict restriction uses leaded objectionable impurities." waste household appliances and electronic product recycling management rules " and " electronics and IT products prevention and cure of pollution management method " that National Development and Reform Committee, the Ministry of Information Industry promulgate, have done strict restriction to objectionable impuritiess such as lead.Above-mentioned regulation is subject to great restriction to the application of copper alloy containing lead series of products in every profession and trade, and product comprises: household electrical appliance, communication equipment, set lights, medical equipment, detection and control instrument, toy, sports equipment etc.Therefore, related production enterprise of China must adjust corresponding Product Specifications, to adapt to the environmental requirement both at home and abroad to related products.
Because countries in the world are to common concern that is plumbous, nickel harmful effect, German silver material is faced with stern challenge, and development of new is unleaded seems particularly important without Alpaka alloy.Can estimate, due to nickel and the plumbous harm to human body and environment, both at home and abroad to the use of leaded and nickel goods by more and more stricter restriction, Development of New Generation is imperative without nickel Lead free cutting copper alloys material.
Recent domestic is researched and developed a series of without Alpaka material and lead-free free-cutting cupronickel alloy material, as: Cu-Mn-Zn-Al-Fe, CuMn
15zn
15al
1, the nickel-free copper alloy such as Cu-Mn-Zn, and lead-free free-cutting White brass alloy " a kind of containing secret lead-free easy-to-cut zinc-white copper alloy " (patent No. 200710118018.1), " a kind of lead-free easy-to-cut zinc-white copper alloy " (patent No. CN200510061720.X) etc., but the unleaded patent without nickel Cutting free White brass alloy there is not yet report.
Summary of the invention
The object of the present invention is to provide a kind of without nickel lead-free free-cutting White brass alloy, the present invention take copper as base, adopt that Domestic Resources enriches cheap zinc, manganese, aluminium are main adding elements, nickel and lead element is replaced with elements such as micro-calcium, magnesium, silicon, research and development have the unleaded without nickel Cutting free White brass alloy of the comprehensive mechanical such as good elasticity, Cutting free processing characteristics, reach and fall low-alloyed production cost, meet the mechanical cutting performance of alloy and the requirement of safety and environmental protection.
Another object of the present invention is to provide the preparation method without nickel lead-free free-cutting White brass alloy.
To achieve these goals, the present invention adopts following technical scheme to realize:
A kind of without nickel lead-free free-cutting copper-nickel alloy, the weight percent of described White brass alloy consists of: manganese 10 ~ 15%, zinc 8 ~ 13%, silicon 0.5 ~ 0.8%, aluminium 0.5 ~ 1.5%, rare-earth element cerium 0.03 ~ 0.08%, " calcium+magnesium " 1 ~ 1.5%, surplus is copper and inevitable impurity.
Further, the consisting of " 30%Ca+Mg " of described " calcium+magnesium ".
The above-mentioned preparation method without nickel lead-free free-cutting copper-nickel alloy, described method is specially:
1) first electrolytic copper is added smelting furnace, dry material 15 ~ 20min;
2) add after borax makes insulating covering agent, be warming up to 1250 ~ 1350 DEG C and carry out electrolytic copper fusing;
3) " copper-manganese " master alloy, " copper-silicon " master alloy after copper to be electrolysed melts completely, is added, melting 20 ~ 30min;
4) be cooled to 1250 ~ 1300 DEG C, add " calcium-magnesium " alloy, " copper-cerium " master alloy, add fine aluminium after stirring, melting 10 ~ 15min;
5) add pure zinc, after stirring, be incubated 5 ~ 10min;
6) be cooled to 1100 ~ 1200 DEG C to cast, form alloy cast ingot.
Further, in described step 3), the addition of manganese is 10 ~ 15%, and the addition of silicon is 0.5 ~ 0.8%.The addition of manganese and silicon calculates according to proportion in alloy total amount herein.
Further, in described step 4), the addition of " calcium+magnesium " is 1 ~ 1.5%, and the addition of cerium is 0.03 ~ 0.08%, and the addition of aluminium is 0.5 ~ 1.5%.The addition of " calcium+magnesium ", cerium and aluminium calculates according to proportion in alloy total amount herein.
Further, in described step 5), the addition of zinc is 8 ~ 13%.The addition of zinc calculates according to proportion in alloy total amount herein.
Further, hot rolling, cold rolling and annealing are carried out to described alloy cast ingot, implements machining deformation process.
Further, described hot-rolled temperature 850 DEG C, hot rolling rate is 75 ~ 78%.
Further, described cold processing ratio is 64 ~ 73%.
Further, described annealing temperature and time are: 750 DEG C × 2h.
The present invention is by adding appropriate alloying element manganese, zinc, aluminium, silicon, calcium, magnesium and trace rare-earth element cerium in copper, prepares without nickel lead-free free-cutting White brass alloy.In alloy, manganese, zinc, aluminium are added in copper the phase same-action had with nickel, can put forward heavy alloyed intensity and elasticity, and keep the silvery white color and luster of alloy; The interpolation of silicon, calcium, magnesium and trace rare-earth cerium, can improve machining property and the cutting ability of alloy.
The present invention has the following advantages without nickel lead-free free-cutting White brass alloy:
1. machinability is good.Owing to the addition of the alloying elements such as the cerium of silicon, calcium, magnesium and trace, in alloy substrate, form fine particle and be uniformly distributed in alloy substrate, can play and cut chip breaking effect, of the present invention have good machinability without the unleaded easy White brass alloy of nickel, and the stock removal rate of the stock removal rate of alloy and leaded brass (C36000) is close.
2. mechanical property and processing forming good.Due in alloy containing silicon, rare-earth element cerium, can crystal grain thinning improve the distribution of alloy phase, suppress the hot crackability tendency of alloy, without cracking phenomena in preparation process, cold and hot working stable performance, hot-work rate reaches 75 ~ 78%, and cold processing ratio reaches 64 ~ 73%.
3. preparation cost is low.Not containing expensive alloying element nickel in alloy of the present invention, compared with nickel content 17 ~ 19% in nickel silver alloy, there is good preparation cost advantage.
4. pollution-free, safety and environmental protection.Calcium, magnesium etc. is adopted to replace in White brass alloy of the present invention plumbous, thoroughly avoid the pollution that lead causes, the present invention is without nickel lead-free free-cutting cupronickel alloy material, can be used for preparing plate, band, rod, wire rod, be widely used in precision component, eye fittings, slide fastener, key and instrument and horological industry etc.
Accompanying drawing explanation
Fig. 1 is the alloy cast ingot photo of the present invention without nickel lead-free free-cutting copper-nickel alloy;
Fig. 2 is the chip photo of the alloy cast ingot of the embodiment of the present invention 1;
Fig. 3 is the chip photo of the alloy cast ingot of the embodiment of the present invention 2;
Fig. 4 is the chip photo of the alloy cast ingot of the embodiment of the present invention 3;
Fig. 5 is the chip photo of the alloy cast ingot of the embodiment of the present invention 4;
Fig. 6 is the chip photo of the alloy cast ingot of the embodiment of the present invention 5;
Embodiment
For further setting forth the present invention for the technique means that reaches predetermined goal of the invention and take and effect, below in conjunction with accompanying drawing and preferred embodiment, structure of the present invention, feature and effect are described in detail as follows.
In the preparation method of the present invention without nickel lead-free free-cutting copper-nickel alloy, charge calculation needs to select alloying element and consumption thereof according to White brass alloy performance requriements and alloy property, carries out design of alloy and charge calculation, alloyage furnace charge.
The present invention casts without being cooled to 1100 ~ 1200 DEG C after the melting of nickel lead-free free-cutting copper-nickel alloy, and alloy cast ingot as shown in Figure 1, has silvery white gloss.
Alloy ingot casting carries out cutting ability test analysis, and alloy sample analysis is as shown in Fig. 2-Fig. 6, and result shows that alloy prepared by the inventive method has good cutting ability.
Embodiment 1
By testing program described in table 1, in smelting furnace, first the electrolytic copper added is dried material 15 ~ 20min; Add after borax makes insulating covering agent, be warming up to 1250 ~ 1350 DEG C; After copper to be electrolysed melts completely, add the Mn of 10%, the Si of 0.5%, wherein Mn, Si add with master alloy form; Melting 20 ~ 30 minutes, is cooled to 1250 ~ 1300 DEG C, and add " 30%Ca+Mg " of 1%, the Ce of 0.03%, wherein Ce adds with Cu-Ce master alloy form; The fine aluminium of 0.5% is added after stirring; Melting 10 ~ 15 minutes, adds the pure zinc of 8%, insulation 5 ~ 10min; Be cooled to 1100 ~ 1200 DEG C to cast, ingot casting; Alloy hot-rolled temperature is 850 DEG C, and hot rolling rate is 75%; Cold processing ratio 73%; Be annealed into 750 DEG C × 2h.
Table 1 testing program example of the present invention (alloying element and content %)
Embodiment 2
By testing program described in table 2, in smelting furnace, first the electrolytic copper added is dried material 15 ~ 20min; Add after borax makes insulating covering agent, be warming up to 1250 ~ 1350 DEG C; After electrolytic copper melts completely, add the Mn of 12%, the Si of 0.6%, wherein Mn, Si add with master alloy form; Melting 20 ~ 30 minutes, is cooled to 1250 ~ 1300 DEG C, and add " 30%Ca+Mg " of 1.2%, the Ce of 0.05%, wherein Ce adds with Cu-Ce master alloy form; The fine aluminium of 0.5% is added after stirring; Melting 10 ~ 15 minutes, adds the pure zinc of 10%, insulation 5 ~ 10min; Be cooled to 1100 ~ 1200 DEG C to cast, ingot casting; Alloy hot-rolled temperature is 850 DEG C, and hot rolling rate is 78%; Cold processing ratio 70%; Be annealed into 750 DEG C × 2h.
Table 2 testing program example of the present invention (alloying element and content %)
Embodiment 3
By testing program described in table 3, in smelting furnace, first the electrolytic copper added is dried material 15 ~ 20min; Add after borax makes insulating covering agent, be warming up to 1250 ~ 1350 DEG C; After electrolytic copper melts completely, add the Mn of 10%, the Si of 0.5%, wherein Mn, Si add with master alloy form; Melting 20 ~ 30 minutes, is cooled to 1250 ~ 1300 DEG C, and add " 30%Ca+Mg " of 1.5%, the Ce of 0.06%, wherein Ce adds with Cu-Ce master alloy form; The fine aluminium of 0.5% is added after stirring; Melting 10 ~ 15 minutes, adds the pure zinc of 12%, insulation 5 ~ 10min; Be cooled to 1100 ~ 1200 DEG C to cast, ingot casting; Alloy hot-rolled temperature is 850 DEG C, and hot rolling rate is 78%; Cold processing ratio 64%; Be annealed into 750 DEG C × 2h.
Table 3 testing program example of the present invention (alloying element and content %)
Embodiment 4
By testing program described in table 4, in smelting furnace, first the electrolytic copper added is dried material 15 ~ 20min; Add after borax makes insulating covering agent, be warming up to 1250 ~ 1350 DEG C; After electrolytic copper melts completely, add the Mn of 13%, the Si of 0.7%, wherein Mn, Si add with master alloy form; Melting 20 ~ 30 minutes, is cooled to 1250 ~ 1300 DEG C, and add " 30%Ca+Mg " of 1%, the Ce of 0.04%, wherein Ce adds with Cu-Ce master alloy form; The fine aluminium of 1% is added after stirring; Melting 10 ~ 15 minutes, adds the pure zinc of 12%, insulation 5 ~ 10min; Be cooled to 1100 ~ 1200 DEG C to cast, ingot casting; Alloy hot-rolled temperature is 850 DEG C, and hot rolling rate is 75%; Cold processing ratio 64%; Be annealed into 750 DEG C × 2h.
Table 4 testing program example of the present invention (alloying element and content %)
Embodiment 5
By testing program described in table 5, in smelting furnace, first the electrolytic copper added is dried material 15 ~ 20min; Add after borax makes insulating covering agent, be warming up to 1250 ~ 1350 DEG C; After electrolytic copper melts completely, add the Mn of 15%, the Si of 0.8%, wherein Mn, Si add with master alloy form; Melting 20 ~ 30 minutes, is cooled to 1250 ~ 1300 DEG C, and add " 30%Ca+Mg " of 1.5%, the Ce of 0.08%, wherein Ce adds with Cu-Ce master alloy form; The fine aluminium of 1.5% is added after stirring; Melting 10 ~ 15 minutes, adds the pure zinc of 13%, insulation 5 ~ 10min; Be cooled to 1100 ~ 1200 DEG C to cast, ingot casting; Alloy hot-rolled temperature is 850 DEG C, and hot rolling rate is 75%; Cold processing ratio 70%; Be annealed into 750 DEG C × 2h.
Table 5 testing program example of the present invention (alloying element and content %)
In preparation method without nickel lead-free free-cutting copper-nickel alloy described in the invention, the alloy cast ingot that can obtain embodiment 1-5 carries out hot rolling, cold rolling and annealing, and implement machining deformation process, being out of shape the product obtained is sheet material.
Described just in order to the present invention is described above, be construed as the present invention and be not limited to above embodiment, meet the various variants of inventive concept all within protection scope of the present invention.
Claims (5)
1. the preparation method without nickel lead-free free-cutting copper-nickel alloy, it is characterized in that, the weight percent of described White brass alloy consists of: manganese 10 ~ 15%, zinc 8 ~ 13%, silicon 0.5 ~ 0.8%, aluminium 0.5 ~ 1.5%, rare-earth element cerium 0.03 ~ 0.08%, " calcium+magnesium " 1 ~ 1.5%, surplus is copper and inevitable impurity;
Described method is specially:
1) first electrolytic copper is added smelting furnace, dry material 15 ~ 20min;
2) add after borax makes insulating covering agent, be warming up to 1250 ~ 1350 DEG C and carry out electrolytic copper fusing;
3) " copper-manganese " master alloy, " copper-silicon " master alloy after copper to be electrolysed melts completely, is added, melting 20 ~ 30min;
4) be cooled to 1250 ~ 1300 DEG C, add " calcium-magnesium " alloy, " copper-cerium " master alloy, add fine aluminium after stirring, melting 10 ~ 15min;
5) add pure zinc, after stirring, be incubated 5 ~ 10min;
6) be cooled to 1100 ~ 1200 DEG C to cast, form alloy cast ingot;
Carry out hot rolling, cold rolling and annealing to described alloy cast ingot, implement machining deformation process, described hot-rolled temperature 850 DEG C, hot rolling rate is 75 ~ 78%, and described cold processing ratio is 64 ~ 73%.
2. preparation method as claimed in claim 1, it is characterized in that, in described step 3), the addition of manganese is 13 ~ 15%, and the addition of silicon is 0.5 ~ 0.8%.
3. preparation method as claimed in claim 1, it is characterized in that, in described step 4), the addition of " calcium+magnesium " is 1 ~ 1.5%, and the addition of cerium is 0.05 ~ 0.08%, and the addition of aluminium is 0.5 ~ 1.5%.
4. preparation method as claimed in claim 1, it is characterized in that, in described step 5), the addition of zinc is 10 ~ 13%.
5. preparation method as claimed in claim 1, it is characterized in that, described annealing temperature and time are: 750 DEG C × 2h.
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| CN201310161306.0A CN103255315B (en) | 2013-05-03 | 2013-05-03 | A kind of without nickel lead-free free-cutting copper-nickel alloy and preparation method thereof |
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| CN201310161306.0A CN103255315B (en) | 2013-05-03 | 2013-05-03 | A kind of without nickel lead-free free-cutting copper-nickel alloy and preparation method thereof |
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| CN103255315B true CN103255315B (en) | 2016-04-13 |
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| JP3750897B2 (en) * | 1999-04-16 | 2006-03-01 | Ｙｋｋ株式会社 | Nickel-free white copper alloy |
| JP2001003125A (en) * | 1999-06-17 | 2001-01-09 | Ykk Corp | Nickel-free white copper alloy material |
| CN101899588B (en) * | 2010-08-25 | 2011-09-21 | 江西理工大学 | Nickel-free white copper alloy containing rare earth additional elements and method for manufacturing plates made of same |
| CN103074516A (en) * | 2013-01-28 | 2013-05-01 | 江西理工大学 | Low-nickel leadless free-cutting cupronickel and preparation method thereof |
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