CN100463987C - Free-cutting anticorrosive brass alloy and its prepn process - Google Patents
Free-cutting anticorrosive brass alloy and its prepn process Download PDFInfo
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Abstract
The present invention discloses one kind of free-cutting anticorrosive brass alloy and its preparation process. Chemically, the brass alloy consists of Cu 57-64 wt%, Bi 0.6-2.5 wt%, B 0.0003-0.025 wt%, Mn 0.01-0.2 wt%, Sb 0.002-0.02 wt% and Zn and inevitable impurities for the rest. The inevitable impurities has content within 0.3 wt%, and includes Pb within 0.1 wt% and Cd within 0.001 wt%; and the alloy contains Cu+Zn over 97 wt%. The brass alloy has high anticorrosive performance, excellent cutting performance and good welding performance.
Description
Technical field
The present invention relates to a kind of lead-free brass alloys, relate in particular to a kind of more free machining unleaded brass alloy with excellent Dezincification corrosion resistant performance.It is specially adapted to electronics telecommunication connector, domestic water supply system pipeline foundry goods, valve member, switch web member; Home electric; The optoelectronic components of light fixture and photographic apparatus; Fields such as component manufacturing in toy for children and machinery and the automobile industry.Being a kind of human health and eco-friendly metallic substance of helping, also is the meeting of present widespread use causes the leaded brass of baneful influence to human body and environment a kind of substitute.
Background technology
Leaded brass has characteristics such as good cold and hot working performance, fabulous cutting ability and self-lubricating, can satisfy the machining of different shape component, so Winn bronze is also just by the wide spectrums such as component manufacturing of optoelectronic components, automobile and the machinery manufacturing industry of universally acknowledged component, light fixture and the photographic apparatus that is widely applied to the pipeline foundry goods of electronics telecommunication, domestic water supply system and accessory, household electrical appliances and toy for children for important base mateiral.
Yet lead is a kind of to environment and harmful element, and lead particularly can cause irreversible damage to children's kidney and cranial nerve to blood of human body and neural system.The medical expert of countries in the world has found that Winn bronze has constituted threat to human health and environmental health in recent years, medical research institutes such as Northern Europe, the U.S., Japan and China have all made the report that leaded brass works the mischief to human environment, thereby the government that national governments have also put into effect in succession to the copper alloy containing lead application orders within a certain time, 2005, Japanese government was limited in 0.01mg/L with the leaching amount of lead in water.And Chinese Government has also put into effect in succession in the recent period with the world and has ordered the corresponding to mandatory rules of laws such as " electronics and IT products prevention and cure of pollution management methods " within a certain time.
In view of the foregoing, in recent years particularly since 2003, the U.S., the European Community, Japan, countries such as China have made ordering within a certain time of strict control respectively to the lead content in the copper alloy with in the leaching amount of Pb in Drinking Water, and will constantly reduce wherein lead content (wherein the content of electronics and IT products lead must less than 0.1%), thereby the application of Winn bronze will face strict restriction and challenge, therefore developing Lead free cutting copper alloys in succession substitutes copper alloy containing lead, be the key subjects that must solve that world today's metallic substance production is faced, also be the international EHS of enforcement plan (E: environmental protection, H: health, S: world's recycling economy safety) the key subjects that must solve.
At present both at home and abroad as China, the U.S., lead-free brass alloys have also been invented by Germany and Japan, wherein for example disclosed " lead-free free-cutting low antimony bismuth brass alloy and manufacture method thereof " in Chinese patent application number 200510050425.4 specification sheetss, it is the leadless free-cutting brass alloy material of Ningbo Powerway Group Co., Ltd's invention, consisting of of this alloy: copper: 55～65wt%, bismuth: 0.3～1.5wt%, antimony: 0.05～1.0wt%, boron: 0.0002～0.05wt%, other element: 0.2～1.2wt%, described other element is to be selected from titanium, nickel, iron, tin, phosphorus, at least two kinds of elements in the rare earth metal, all the other are zinc and unavoidable impurities, and content plumbous in the unavoidable impurities is less than 0.1wt%; The copper zincification adds bismuth and adds antimony and add boron greater than 97wt% in the described alloy composition, and wherein zinc greater than 35.5wt%.Its cutting ability is near the machinability level (its cutting coefficient is 86～95%) of leaded brass.Its manufacture method is: adopt Alloying Treatment and covering protection method melting low antimony bismuth brass alloys; making the quick solid solution in the brass liquation of boron, antimony is intermetallic compound; and make bismuth metal be uniformly distributed in intracrystalline and crystal boundary; and under 1040 ℃, be continuously cast into the brass ingot casting; under 680～760 ℃ of temperature, carry out the large extrusion ratio extruding; intermediate heat treatment is carried out under 500～700 ℃ of temperature by cold worked condition, is being lower than the annealing that eliminates stress under 400 ℃ the temperature.Another invention is the Chinese patent application 200410004293.7 disclosed " Pb-free copper-alloy and its application " of German Wieland company research and development, this alloy is made up of following ingredients: copper: 70.0～83.0%, silicon: 1～5%, tin: 0.01～2%, iron: 0.01～0.3% and/or cobalt: 0.01～0.3%, nickel: 0.01～0.3%, manganese: 0.01～0.3%, and surplus is zinc and unavoidable impurities.Its cutting ability is 75-85% only also, and the market price is higher.
Summary of the invention
The objective of the invention is in order to provide a kind of machinability more excellent, and have the no lead brass alloy of excellent Dezincification corrosion resistant performance, anticorrosion stress-resistant, cold and hot formability and good weldability and good mechanical property.
The objective of the invention is by providing easy-cutting lead-free brass alloy to realize with following chemical constitution:
The chemical constitution of lead-free free-cutting brass alloy of the present invention is: copper: 57～64wt%, bismuth: 0.6～2.5wt%, boron: 0.0003～0.025wt%, manganese: 0.01～0.2wt% and antimony: 0.002～0.02wt%, and all the other are zinc and unavoidable impurities; The content of the summation of unavoidable impurities in alloy is no more than 0.3wt%, and the content of the lead in the unavoidable impurities in alloy is no more than 0.1wt%, the cadmium content in alloy and is no more than 0.001wt%; And the copper zincification is greater than 97wt% in the described alloy composition.
The preferred group of these brass alloys becomes: copper: 57～63wt%, bismuth: 0.8～2.3wt%, boron: 0.0005～0.02wt%, manganese: 0.015～0.2wt% and antimony: 0.002～0.015wt% forms, and all the other are zinc and unavoidable impurities.
The further preferred group of these brass alloys becomes: 57.5～62.5wt%, bismuth: 0.8～2.4wt%, boron: 0.0010～0.02wt%, manganese: 0.012～0.18wt% and antimony: 0.003～0.02wt% forms, and all the other are zinc and unavoidable impurities.
These brass alloys further preferred group become: 58～62wt%, bismuth: 0.9～2.5wt%, boron: 0.0010～0.015wt%, manganese: 0.01～0.15wt% and antimony: 0.003～0.015wt% forms, and all the other are zinc and unavoidable impurities.
The free machining unleaded brass alloy of the present invention is to utilize bismuth to substitute the plumbous cutting ability that improves alloy; Improve simultaneously the Dezincification corrosion resistant performance of alloy, not only distinguished, but also substituted external like product and suppress dezincifys with tin, aluminium, phosphorus etc. with boron, manganese and antimony.
The free machining unleaded brass alloy of the present invention is to have excellent cutting ability (cutting coefficient is 96～115%), Dezincification corrosion resistant performance, anticorrosion stress-resistant performance, good mechanical property and cold and hot processability and good welding property help environmental protection, healthy leadless free-cutting brass alloy.Can be widely used in the casting of optoelectronic components, household electrical appliances, automobile component of electronics, telecommunication, computer, tap water engineering, five metals, machinery, photographic apparatus and thermoforming, easily cut the component production.
The copper content of the free machining unleaded brass alloy of the present invention is 57～64%.Copper content was less than 57% o'clock, though help the raising of cutting ability and the enhancing of wear resisting property, the cold forming capability and the intensity of alloy obviously reduce; And copper content can increase the manufacturing cost of alloy and reduce cutting ability greater than 64%.
The adding of bismuth can improve the machinability of alloy.The solid solubility of bismuth in copper is extremely low, even the solubleness in the time of 800 ℃ also only 0.01%, but the solubleness in the liquation is very big, bismuth precipitates in process of setting, form the second phase particle of disperse, the disperse phase fusing point of this bismuth lower (271.3 ℃), in the contact surface local heating of cutter head and bits and instant melting, this fuse effect helps to change the shape and the lubricated cutter of smear metal, make alloy in machining, easily form short chip breaking point thereby play, bonding between minimizing cutter head and the workpiece and seam and the effect that improves cutting speed, and then make alloy have satisfied cutting ability.Bi content was less than 0.6% o'clock in this alloy, do not satisfy the requirement of excellent in machinability, bi content was greater than 2.5% o'clock, though will further improve cutting ability but reduce the hot and cold processability of alloy and the mechanical property of alloy is sharply descended, and can obviously reduce the Dezincification corrosion resistant performance simultaneously and increase cost.For making full use of the characteristic that bismuth can improve cutting ability, also to prevent the tendency that excessive bismuth causes hot and cold processability and mechanical property to descend simultaneously, the content of bismuth is 0.6～2.5% in alloy.Such content control makes this alloy obtain more excellent cutting ability, Dezincification corrosion resistant performance and good cold and hot processability, mechanical property, and then reaches the requirement of environmental protection, alloy material good for health.
This alloy is based on boron, improves the Dezincification corrosion resistant performance of alloy with manganese and the auxiliary boron of antimony, not only distinguished, but also substituted external like product suppresses dezincifys with tin, aluminium, phosphorus etc. method.Though interpolation tin, aluminium, phosphorus can play the effect of certain inhibition dezincify, effect is obvious like that not as good as adding boron, manganese and antimony.Confirm according to ISO6509-1981 dezincify experimental technique: after adding element boron, manganese and the antimony of an amount of inhibition dezincify in the alloy of the present invention, Dezincification corrosion resistant obviously strengthens, the maximum Dezincification corrosion degree of depth is less than 150 μ m, be significantly less than the maximum dezincify degree of depth that suppresses the alloy of dezincify with tin, aluminium, phosphorus, also improved the cutting ability of alloy simultaneously.
Boron mainly has been the effect that suppresses dezincify, improves corrosion resisting property, and the function of deoxidation, crystal grain thinning, enhancing cutting ability is also arranged simultaneously.Because the boron atomic radius is littler than zinc atom radius; therefore the easier diffusion of boron atom ratio zinc atom when brass is corroded can preferentially be captured the room and then be stopped up the diffusion admittance of zinc atom, increases the resistance of zinc diffusion; form anti-corrosion protective membrane, thereby reach effect as the inhibition Dezincification corrosion of arsenic.The add-on of boron is 0.0003～0.025%.Boron content is less than 0.0003% o'clock, to suppressing dezincify and anti-corrosion DeGrain; Boron content was greater than 0.025% o'clock, and boride is easily separated out at crystal boundary, embrittlement, reduced the alloy processability.Manganese plays Dezincification corrosion resistant performance and deoxidation and the solution strengthening that auxiliary boron improves alloy, and manganese is of value to the raising of alloy Dezincification corrosion resistant performance, mechanical property and processing performance 0.01～0.2% in this alloy.The antimony of low levels all has certain solubleness in copper and zinc simultaneously, antimony is to exist with nontoxic solid solution attitude in the alloy, water insoluble, rather than resemble and be present in the alloy with deleterious free state the lead, can suppress dezincify equally, improve the effect of alloy Dezincification corrosion resistant performance thereby play with the auxiliary boron of manganese and with the boron acting in conjunction.When the interpolation content of antimony less than 0.002% the time, not obvious to the Dezincification corrosion resistant impact of performance that auxiliary boron improves alloy, and the auxiliary content that adds was greater than 0.02% o'clock, though it is bigger that auxiliary boron improves the Dezincification corrosion resistant performance, but it is also very obvious that the plasticity of this alloy reduces, also increased cost simultaneously, so the auxiliary content that adds antimony is 0.002～0.02%.Lead-free free-cutting brass alloy of the present invention is by after adding manganese and antimony, and the Dezincification corrosion resistant performance obviously improves, and has not only distinguished, but also has substituted external like product suppresses dezincifys with tin, aluminium, phosphorus etc. method.
The manufacture method of described alloy is with weight %: copper: 57～64wt%; bismuth: 0.6～2.5wt%; boron: 0.0003～0.025wt%; manganese: 0.01～0.2wt% and antimony: 0.002～0.02wt%; all the other are zinc and unavoidable impurities; adopt Alloying Treatment and covering protection method melting brass alloy; make bismuth metal; boron quick solid solution in the brass liquation is an intermetallic compound; and under 1020 ℃, be continuously cast into the brass ingot casting; under 680～770 ℃ of temperature, carry out the large extrusion ratio extruding; intermediate heat treatment is annealed under 430～700 ℃ of temperature by cold worked condition, is being lower than the annealing that eliminates stress under 400 ℃ the temperature.
Compared with prior art, the invention has the advantages that: 1. have more excellent cutting ability, cutting coefficient reaches 96～115%, also have excellent Dezincification corrosion resistant performance, good welding property, good solidity to corrosion, mechanical property and can polish the plating performance, be specially adapted to the component, forging, foundry goods of machining moulding and as the component material of other manufacture method; 2. improve the Dezincification corrosion resistant performance of alloy with boron, manganese and antimony, not only distinguished, but also substituted external like product suppresses dezincifys with tin, aluminium, phosphorus etc. method; 3. low cost of manufacture only is equivalent to the manufacturing cost of the leaded brass of prior art, thereby has market competition advantage.Particularly, its raw materials cost is close with the generic no lead brass alloy (Cu-Zn-Sb alloy) of China; The generic no lead brass alloy of Bhide state Wieland (Cu-Zn-Si alloy) is low more than 10%; But than traditional C36000 Winn bronze raw materials cost slightly high 2%.4. can reach international environmental protection, health, safety standards code requirement fully, and the more free machining lead-free anti-corrosion brass alloy material of another kind of environmental protection, health is provided for world's recycling economy.
Description of drawings
Fig. 1, be the car of alloy of the present invention bits pattern synoptic diagram, the turning back engagement of the cutting edge is 1.0mm, and the speed of mainshaft is 1120rpm/min, and the amount of feed is 0.1mm/rev.
Embodiment
Below in conjunction with specific embodiment invention is described in further detail:
The technological process of production of brass alloys is as follows in the embodiment of the invention:
Starting material are prepared and batching, and---------------stretching,------------aligning polishing---stress relieving---check finished product packing stretches in pickling in thermal treatment in extruding in the ingot casting heating in continuous casting in the Alloying Treatment melting.
Specifically can be expressed as follows: adopt Alloying Treatment and covering protection method melting brass alloy; making the quick solid solution in the brass liquation of bismuth metal, boron is intermetallic compound; and under 1020 ℃, be continuously cast into the brass ingot casting; under 680～770 ℃ of temperature, carry out the large extrusion ratio extruding; intermediate heat treatment is annealed under 430～700 ℃ of temperature by cold worked condition, is being lower than the annealing that eliminates stress under 400 ℃ the temperature.
Wherein changing process of thermal treatment flow implementation process over to proves, thermal treatment is lower than 400 ℃ stress relieving and can carries out, and intermediate heat treatment needs to anneal under 430～700 ℃ of temperature according to cold worked condition, but warm brittle zone annealing in should as far as possible avoiding (its flow process is produced identical with the lead brass alloy of routine substantially).
The free machining lead-free anti-corrosion brass alloy of the present invention is formed ingot casting, is pushed, is drawn into pole by the alloy ingredient in the table 1 among the embodiment; The contrast sample is that the trade mark of the U.S. is the Winn bronze alloy of C36000, and it is the universally acknowledged best Winn bronze of machinability (100%), also carries out same shaping.
It is of a size of Φ 170*400～500 millimeter each embodiment ingot casting of leadless easy cutting corrosion resistant low boron bismuth-brass alloy of the present invention, under 680 ℃～770 ℃ of identical appointed condition and different extrusion temperatures, be squeezed into the wire rod of 9 millimeters of Φ 8, Φ, its concrete component content is shown in Table 1.
Table 1: the composition of leadless easy cutting corrosion resistant low boron bismuth-brass alloy of the present invention is formed example: (weight %)
Estimate by turning that the experiment of machinability is performed such: under identical mechanical workout condition, adopt the cutting force experiment instrument to record the cutting force of each invention alloy, and calculate the machinability index of each invention alloy phase thus for C36000, C36000 is the universally acknowledged best Winn bronze of machinability, and its machinability is considered to 100%.Machinability exponential method of calculation are: cutting resistance * 100% of [machinability index]=[cutting resistance of C36000]/each invention alloy.The machinability index is greater than 96% be expressed as " zero ", and the machinability index is at 80～96% be expressed as " △ ", and the machinability index is less than 80% be expressed as " * ".
Carried out the dezincify experiment according to ISO 6509 dezincify experimental techniques, the contrast sample is the C36000 Winn bronze.The maximum Dezincification corrosion degree of depth that records is less than be expressed as " zero " of 150 μ m, and the maximum Dezincification corrosion degree of depth is at be expressed as " △ " of 150～250 μ m, the maximum Dezincification corrosion degree of depth being expressed as more than 250 μ m " * ".
In order to observe hot workability, extrude from the embodiment alloy and respectively to get Φ 9*20mm on the product and make sample, contrast sample C36000 in addition and also get same size, do the thermo compression test.Sample axially loads then 670 ℃ of heating 30 minutes, and deflection is 70%, and length is reduced to 6mm by 20mm, observes its distortion rear surface crackle situation under 5～10 times of magnifying glasses.Specimen surface does not crack is expressed as " zero ", produces be expressed as " △ " of fine crack, produces be expressed as " * " of big crackle.
According to the ISO6957 experimental technique, alloy of the present invention has been carried out stress etching experiment, the contrast sample is the C36000 Winn bronze.Experiment finishes, through the specimen surface situation behind 10 times the amplification observation experiment.Specimen surface does not crack is expressed as " zero ", produces be expressed as " △ " of fine crack, produces be expressed as " * " of big crackle.
The above test-results of leadless easy cutting corrosion resistant low boron bismuth-brass alloy of the present invention sees Table 2.
Table 2: the test-results of leadless easy cutting corrosion resistant low boron bismuth-brass alloy of the present invention
Claims (4)
1. free machining lead-free anti-corrosion brass alloy is characterized in that the chemical constitution of this alloy is:
Copper: 57～64wt%
Bismuth: 0.6～2.5wt%
Boron: 0.0003～0.025wt%
Manganese: 0.01～0.2wt%
Antimony: 0.002～0.02wt%
All the other are zinc and unavoidable impurities; The content of the summation of unavoidable impurities in alloy is no more than 0.3wt%, and the content of the lead in the unavoidable impurities in alloy is no more than 0.1wt%, the cadmium content in alloy and is no more than 0.001wt%; And the copper zincification is greater than 97wt% in the described alloy composition.
2. brass alloys according to claim 1 is characterized in that its chemical constitution is:
Copper: 57～63wt%
Bismuth: 0.8～2.3wt%
Boron: 0.0005～0.02wt%
Manganese: 0.015～0.2wt%
Antimony: 0.002～0.015wt%
All the other are zinc and unavoidable impurities.
3. brass alloys according to claim 1 is characterized in that its chemical constitution is:
Copper: 57.5～62.5wt%
Bismuth: 0.8～2.4wt%
Boron: 0.0010～0.02wt%
Manganese: 0.012～0.18wt%
Antimony: 0.003～0.02wt%
All the other are zinc and unavoidable impurities.
4. brass alloys according to claim 1 is characterized in that its chemical constitution is:
Copper: 58～62wt%
Bismuth: 0.9～2.5wt%
Boron: 0.0010～0.015wt%
Manganese: 0.01～0.15wt%
Antimony: 0.003～0.015wt%
All the other are zinc and unavoidable impurities.
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Families Citing this family (9)
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| CN101994024B (en) * | 2009-08-28 | 2012-11-07 | 摩登岛股份有限公司 | Anti-dezincification copper alloy and preparation method of objects made of same |
| CN102465216A (en) * | 2010-11-18 | 2012-05-23 | 浙江三瑞铜业有限公司 | Environment-friendly lead-free free-cutting brass |
| CN102634688B (en) * | 2011-02-10 | 2014-05-07 | 湖南特力新材料有限公司 | Leadless free-cutting copper alloy and preparation method |
| CN103667778B (en) * | 2013-11-27 | 2015-10-28 | 余姚市士森铜材厂 | A kind of leadless environment-friendly brass of rolling and forming |
| CN103667779B (en) * | 2013-11-27 | 2015-12-09 | 余姚市士森铜材厂 | A kind of preparation method of lead-free reflow |
| CN104722901A (en) * | 2013-12-24 | 2015-06-24 | 财团法人金属工业研究发展中心 | Welding method of lead-free brass |
| CN107699731A (en) * | 2017-08-15 | 2018-02-16 | 浙江中瀚合金材料有限公司 | A kind of antimony bismuth silizin shell of water flowmeter and alloy preparation method |
| CN107604204A (en) * | 2017-08-15 | 2018-01-19 | 浙江中瀚合金材料有限公司 | A kind of antimony bismuth silicon brass alloy material |
| CN111101017B (en) * | 2019-12-31 | 2021-04-27 | 黑龙江北鸥卫浴用品有限公司 | Corrosion-resistant low-lead brass alloy, brass casting and preparation method thereof |
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Owner name: NINGBO BOWEI ALLOY MATERIAL CO., LTD. Free format text: FORMER OWNER: NINGBO POWERWAY GROUP CO., LTD. Effective date: 20091002 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20091002 Address after: Zhejiang city of Ningbo province Yinzhou District Yunlong Town of Taiping Bridge Patentee after: Ningbo Powerway Alloy Materials Co., Ltd. Address before: Yunlong Town, Ningbo, Zhejiang, Yinzhou District Patentee before: Bowei Group Co., Ltd., Ningbo |