CN101709404B - Lead-free environment-friendly bismuth brass alloy rod or alloy ingot and preparation method thereof - Google Patents

Lead-free environment-friendly bismuth brass alloy rod or alloy ingot and preparation method thereof Download PDF

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CN101709404B
CN101709404B CN2009102001597A CN200910200159A CN101709404B CN 101709404 B CN101709404 B CN 101709404B CN 2009102001597 A CN2009102001597 A CN 2009102001597A CN 200910200159 A CN200910200159 A CN 200910200159A CN 101709404 B CN101709404 B CN 101709404B
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copper
bismuth
lead
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CN101709404A (en
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蒋明川
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TIANSHEN COPPER IND CO Ltd ZHEJIANG
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TIANSHEN COPPER IND CO Ltd ZHEJIANG
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Abstract

The invention relates to a lead-free environment-friendly bismuth brass alloy rod or an alloy ingot, which comprises the following chemical elements in percentage by weight: 57 to 68 percent of copper, 0.4 to 2.5 percent of bismuth, less than or equal to 0.25 percent of lead, 0.4 to 0.8 percent of aluminum, 0.02 to 0.5 percent of iron, 0.02 to 0.5 percent of tin, 0.01 to 0.5 percent of nickel, less than or equal to 0.02 percent of phosphorus, less than or equal to 0.02 percent of arsenic, less than or equal to 0.02 percent of manganese, less than or equal to 0.02 percent of sulfur, less than or equal to 0.005 percent of chromium, and the balance of zinc. The lead content of the bismuth brass alloy materials is greatly reduced, and accords with the requirements of environmental protection and health; and meanwhile, the bismuth brass alloy materials have excellent casting performance, are applicable to casting, in particular large-scale gravity casting, and have wide application prospect in sanitary appliance industry.

Description

A kind of bismuth brass alloy rod of leadless environment-friendly or alloy pig and preparation method thereof
Technical field
The present invention relates to a kind of lead-free brass alloys, relate in particular to a kind of lead-free free-cutting environment friendly bismuth brass alloy material with excellent castability, corrosion resistance nature, follow-up machinability, its profile manifestation is alloy bar or alloy pig.
Background technology
Leaded brass has excellent mechanical property and physicals and advantages of good casting and cutting ability; And it is cheap; Thereby be widely used in instrument, electronics, electrical equipment, haberdashery and hardware, potable water system etc., wherein maximum with production, the application quantity of Hpb59-1 especially.
Yet lead and compound thereof are one of chemical substances of 17 kinds of serious harm human longevities and physical environment; Lead in the alloy is in use very easily invaded out from matrix or is deviate from; Lead in the industrial gaseous waste article water system that then permeates the ground; Various forms of lead get into animal or human's food chain by all means, and harm humans is healthy, influences environment.Developing leaded brass and the leaded bronze that no leaded brass and no lead bronze substitute purposes such as water tap in the drinking-water system, water meter becomes the key subjects that current metallic substance industry is faced, and also is the important process that responds world's recycling economy (EHS plan) requirement.
To above-mentioned situation, developed no lead brass alloy in the prior art.The no lead brass alloy that relates in the prior art mainly contains one Chinese patent application 200410004292.2; A kind of " Pb-free copper-alloy and application thereof " wherein disclosed; Relate to Pb-free copper-alloy based on copper-zinc-Xi; Its component mainly comprises 60% to 70% copper, 0.5 to 3.5% tin and other cohesiveness elements: 0.01% to 0.5% iron and/or cobalt, 0.01% to 0.5% nickel, 0.01 to 0.5% manganese and/or silicon, surplus is a zinc.Also optionally add in addition and be up to 3% magnesium, silver, aluminium, arsenic, antimony, titanium, the zirconium that is up to 0.2% phosphorus and is up to 0.5%.Such Pb-free copper-alloy is mainly used in contact, pin and the tightening member in the Elektrotechnik and the communication technology.Container or the pipeline in the sanitary engineering, water fitting, the tap that can also be used in transportation or storage of liquids or the gas containers, particularly Refrigeration Technique prolong pipe, pipe connector and valve.Above-mentioned alloy material has been taken into account the many purposes as plastic metal, rolled alloy or casting alloy, but causes the real drawback in the practical application process.For example not good because of flowability in castingprocesses, if be applied in the middle of the gravitational casting, crackle can occur, water less than more casting flaws such as, shrinkage cavities, cause casting yield to descend, influence casting cost and foundry goods are as the application of expensive goods.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency that prior art exists, a kind of bismuth brass alloy rod or alloy pig of leadless environment-friendly and the method for preparing above-mentioned bar or alloy pig are provided.Utilize leadless environment-friendly brass alloy material of the present invention to reach the reduction lead content; Meet the requirement of environment protection health; Will make copper ingot possess good castability simultaneously, copper rod possesses fast cutting ability, particularly meets the performance and the requirement of automatic machine tool cut of large-scale gravitational casting.
The technical scheme that the present invention proposes is following:
A kind of bismuth brass alloy rod of leadless environment-friendly or alloy pig is characterized in that, the chemical constitution of this alloy material is following:
The element mass percent
Copper: 57%~68%
Bismuth: 0.4%~2.5%
Plumbous :≤0.25%
Aluminium: 0.4%~0.8%
Iron: 0.02%~0.5%
Tin: 0.02%~0.5%
Nickel: 0.01%~0.5%
Phosphorus :≤0.02%
Arsenic :≤0.02%
Manganese :≤0.02%
Sulphur :≤0.02%
Chromium :≤0.005%
Surplus is a zinc.
As the prescription scheme of optimization design more, the bismuth brass alloy rod of leadless environment-friendly or the chemical constitution of alloy pig are following:
The element mass percent
Copper: 58%~63%
Bismuth: 0.5%~0.9%
Plumbous :≤0.2%
Aluminium: 0.4%~0.6%
Iron: 0.02%~0.3%
Tin: 0.02%~0.3%
Nickel: 0.01%~0.2%
Phosphorus :≤0.02%
Arsenic :≤0.02%
Manganese :≤0.02%
Sulphur :≤0.02%
Chromium :≤0.005%
Surplus is a zinc.
A kind of method for preparing the bismuth brass alloy rod or the alloy pig of above-mentioned leadless environment-friendly is characterized in that this method comprises the steps:
Copper+charcoal → fusing → interpolation copper bismuth master alloy → fusing → zinc → stirring → P-Cu → refining → sampling, on-the-spot sample analysis, slag is adjusted → dragged for to composition, leaves standstill → come out of the stove cast,
The first step, the preheating line frequency induction furnace is selected cathode copper for use, and is reinforced in line frequency induction furnace;
In second step, progressively heat line frequency induction furnace, melting copper;
In the 3rd step, add copper bismuth master alloy;
In the 4th step, fusing is fully stirred and is added 0# zinc, fully stirs to make the alloy liquation mix;
The 5th step, add P-Cu and carry out deoxidation, add refining agent and stirring once more, described refining agent is the Tsi-1 refining agent, its composition consists of: fluorite 50%, sodium aluminum fluoride 20%, borax 10%, cupric oxide 20%;
The 6th step, fully stir the back at sampling analysis, the composition adjustment is until meeting above-mentioned castability requirement;
The 7th step, leave standstill, drag for slag, be incubated 1000~1100 ℃, voltage 210V leaves standstill and made contamination precipitation in 20 minutes or floated the purpose that reaches the purification of alloy liquation;
In the 8th step, be warmed up to 1150~1160 ℃ and come out of the stove and pour into bar or alloy pig.
The content of analyzing in above-mentioned the 6th step comprises:
1. back adjustment element ratio is analyzed in composition analysis;
2. metallographic crystal grain detects and fluidity test, adds refining agent as not reaching requirement;
3. minute surface detects, and searches and write down hard point number.
With respect to prior art, technique scheme has been brought following technique effect:
The first, bismuth-brass alloy material of the present invention has reduced copper content, in the sanitary equipment industry, makes the castability of alloy improve, and the consumption of yield rate and copper is provided, and has reduced the manufacturing cost of sanitary equipment.
The second, on the basis that meets the environment protection health standard; The present invention utilizes bismuth element to replace lead element; Reduced lead content, made its lead content meet the Compulsory Feature of country, the control lead content and with the use level of other elements; Make it possess good castability, be mobile, or the surface smoothness of foundry goods and grain size and degree of uniformity all meet the particularly quality requirements of high-grade sanitary appliance of sanitary equipment.
Three, bismuth-brass alloy of the present invention is more conducive to gravitational casting than the brass alloys of prior art; Flowability to the alloy liquation in the gravitational casting requires more much higher than conventional cast; Represented the trend of sanitary equipment industry casting; Bismuth-brass alloy of the present invention is the most outstanding is that the flowability of alloy liquation improves greatly, has guaranteed the quality and the yield rate of brass gravitational casting.
Embodiment
Come the bismuth brass alloy rod of leadless environment-friendly of the present invention or alloy pig and preparation method thereof are done further detailed description below in conjunction with concrete embodiment, but can not limit protection scope of the present invention with this.
The total composition of the bismuth brass alloy rod of the leadless environment-friendly that the present invention relates to or alloy pig constitutes to be wanted
Ask as follows:
The element mass percent
Copper: 57%~68%
Bismuth: 0.4%~2.5%
Plumbous :≤0.25%
Aluminium: 0.4%~0.8%
Iron: 0.02%~0.5%
Tin: 0.02%~0.5%
Nickel: 0.01%~0.5%
Phosphorus :≤0.02%
Arsenic :≤0.02%
Manganese :≤0.02%
Sulphur :≤0.02%
Chromium :≤0.005%
Surplus is a zinc.
Under the prerequisite that above-mentioned composition requires, reach better technique effect as a kind of distributing rationally,
Following scheme is proposed:
The element mass percent
Copper: 58%~63%
Bismuth: 0.5%~0.9%
Plumbous :≤0.2%
Aluminium: 0.4%~0.6%
Iron: 0.02%~0.3%
Tin: 0.02%~0.3%
Nickel: 0.01%~0.2%
Phosphorus :≤0.02%
Arsenic :≤0.02%
Manganese :≤0.02%
Sulphur :≤0.02%
Chromium :≤0.005%
Surplus is a zinc.
The method for preparing the leadless environment friendly bismuth brass alloy material of above-mentioned suitable gravitational casting, this method comprises the steps:
Copper+charcoal → fusing → interpolation copper bismuth master alloy → fusing → zinc → stirring → P-Cu → refining → sampling, on-the-spot sample analysis, slag is adjusted → dragged for to composition, leaves standstill → come out of the stove cast,
The first step, the preheating line frequency induction furnace is selected cathode copper for use, and is reinforced in line frequency induction furnace;
In second step, progressively heat line frequency induction furnace, melting copper;
In the 3rd step, add copper bismuth master alloy;
In the 4th step, fusing is fully stirred and is added zinc No. 0, fully stirs to make the alloy liquation mix;
The 5th step, add P-Cu and carry out deoxidation, add refining agent and stir once more, described refining agent is the Tsi-1 refining agent, above-mentioned refining agent consist of fluorite 50%, sodium aluminum fluoride 20%, borax 10%, cupric oxide 20%.
The 6th step, fully stir the back at sampling analysis, the composition adjustment is until meeting above-mentioned castability requirement; The content of analyzing in this step comprises:
1. back adjustment element ratio is analyzed in composition analysis;
2. metallographic crystal grain detects and fluidity test, adds refining agent as not reaching requirement;
3. minute surface detects, and searches and write down hard point number.
The 7th step, leave standstill, drag for slag, be incubated 1000~1100 ℃, voltage 210V leaves standstill and made contamination precipitation in 20 minutes or floated the purpose that reaches the purification of alloy liquation.
In the 8th step, be warmed up to 1150~1160 ℃ and come out of the stove and pour into alloy bar or alloy pig.Alloy bar or alloy pig be as the work in-process of bismuth-brass alloy, and then above-mentioned bar or alloy pig are processed into finished product through casting and other means.
In concrete practice, selected for use following several outstanding proportioning components to produce and met the no lead brass alloy ingot that water tap is cast usefulness.Constituent content is a mass percent in the form.
Element Copper Bismuth Plumbous Aluminium Iron Tin Nickel Phosphorus Arsenic Manganese Sulphur Chromium Zinc
Embodiment one 57 0.4 0.25 0.8 0.5 0.5 0.5 0.02 0.02 0.02 0.02 0.005 39.965
Embodiment two 68 2.5 0.20 0.6 0.3 0.3 0.3 0.02 0.01 0.01 0.01 0.005 27.755
Embodiment three 58 0.5 0.2 0.6 0.3 0.3 0.2 0.02 0.02 0.02 0.02 0.005 39.815
Embodiment four 63 0.9 0.1 0.5 0.2 0.3 0.1 0.02 0.02 0.01 0.02 0.005 34.845
Embodiment five 60 0.8 0.2 0.6 0.3 0.3 0.2 0.02 0.02 0.02 0.02 0.005 37.515
Compare with the castability of brass alloys of the prior art, test-results is following:
Figure G2009102001597D00071
Through above-mentioned test-results and actual production practice; Bismuth brass alloy rod or the alloy pig that can know leadless environment-friendly of the present invention possess good castability are arranged; Greatly reduce the defective that produces in the castingprocesses, and the content of copper reduces further, practiced thrift production cost; Existing simultaneously brass has reduced plumbous content, meets the requirement of environment protection health.Bismuth brass of the present invention is specially adapted to cast waterworks foundry goods, valve member etc., is the metallic substance that helps human health and environment protection, also is the meeting of present widespread use causes has the leaded brass of baneful influence to human body and environment good substitute.

Claims (3)

1. bismuth brass alloy rod or alloy pig is characterized in that the chemical constitution of this alloy bar or alloy pig is following:
Figure FSB00000705194100011
Surplus is a zinc.
2. a method for preparing described bismuth brass alloy rod of claim 1 or alloy pig is characterized in that this method comprises the steps:
Copper+charcoal → fusing → interpolation copper bismuth master alloy → fusing → zinc → stirring → P-Cu → refining → sampling, on-the-spot sample analysis, slag is adjusted → dragged for to composition, leaves standstill → come out of the stove cast,
The first step, the preheating line frequency induction furnace is selected cathode copper for use, and reinforced in line frequency induction furnace, feed in raw material is copper and charcoal;
In second step, progressively heat line frequency induction furnace, melting copper;
In the 3rd step, add copper bismuth master alloy;
In the 4th step, fusing is fully stirred and is added 0# zinc, fully stirs to make the alloy liquation mix;
The 5th step, add P-Cu and carry out deoxidation, add refining agent and stirring once more, described refining agent is the Tsi-1 refining agent, its composition consists of: fluorite 50%, sodium aluminum fluoride 20%, borax 10%, cupric oxide 20%;
The 6th step, fully stir back resampling analysis, the composition adjustment is until meeting the castability requirement;
The 7th step, leave standstill, drag for slag, be incubated 1000~1100 ℃, the voltage of line frequency induction furnace is 210V during insulation, leaves standstill to make contamination precipitation or floated in 20 minutes to reach the purpose that the alloy liquation purifies;
In the 8th step, be warmed up to 1150~1160 ℃ and come out of the stove and pour into alloy bar material or alloy pig.
3. the bismuth brass alloy rod of preparation leadless environment-friendly according to claim 2 or the method for alloy pig is characterized in that, the content of analyzing in said the 6th step comprises:
1. back adjustment element ratio is analyzed in composition analysis;
2. metallographic crystal grain detects and fluidity test, adds refining agent as not reaching requirement;
3. minute surface detects, and searches and write down hard point number.
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