CN105779811B - A kind of environment-friendly yellow brass alloy that processability is excellent and its manufacturing method - Google Patents
A kind of environment-friendly yellow brass alloy that processability is excellent and its manufacturing method Download PDFInfo
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Abstract
The present invention relates to a kind of environment-friendly yellow brass alloy that processability is excellent and its manufacturing method, brass alloys of the invention contain the Zn of 35wt% or more, the Mn of the Si of 0.1~1.0wt%, 0.01~0.28wt%, and surplus is Cu and inevitable impurity.The alloy has good cold working and thermo forming performance, casting character, good anti-Dezincification corrosion performance, excellent polishing performance and welding performance, the parts such as water heating bathroom, electronic apparatus, automobile suitable for forging, casting and direct processing.
Description
Technical field
The invention belongs to technical field of alloy, and in particular to a kind of environment-friendly yellow brass alloy, more particularly to a kind of thermoforming
Performance and the excellent environment-friendly yellow brass alloy and its manufacturing method of casting character.
Background technology
Ledrite usually contains the lead of 1wt%~4wt%, it is made to obtain excellent cutting ability, good corrosion resistance
Can, while it is of low cost.Ledrite is used for the every field such as electrical, machinery, hot-water heating as a kind of important basic material.
However, Winn bronze can cause environmental pollution during production, use, the health of the mankind is endangered.The prosperities such as the U.S., European Union
Standard and decree are successively formulated in countries and regions, such as S.3874, NSF 372, AB1953, RoHS, gradually forbid production, sell
Sell and use products containing lead.
Currently, done a large amount of research work to the unleaded of brass both at home and abroad, mainly by with bismuth for lead, with antimony generation
Lead, the cutting ability for realizing brass alloys for lead with silicon, and by adding suitable other elements to improve brass alloys
Comprehensive performance.
However, on the one hand, Bi brass thermo forming poor performance is also easy to produce defect during thermoforming, and molding is complicated
Product is difficult, and Bi brass welding performance is poor；On the other hand, medicine confirmation, Bi brass material is not yet received in the safety of bismuth
It is had certain limitations in the application of European countries.
Recent domestic-developed lead-free free-cutting Stibium Brass, but antimony itself has toxicity, in use, in Stibium Brass
Antimony easily dissolve out, tap, valve waited aquatic products to be provided far more than standard through NSF test antimony element stripping quantities in water
0.6 μ g/L, there are environmental pollution and endanger the hidden danger of human health, may not apply to hot-water heating parts.
Silizin is to study widest non-leaded easily-cutting brass at present, has a considerable amount of patents at present.It is public
It is largely the antimony or 0.01- by the bismuth or 0.1-3.0wt% that add 0.1-5.0wt% in the silizin patent opened
The magnesium of 3.0wt% improves the cutting ability of alloy, as Chinese patent application 200610005689.2,200910042723.7,
200810084184.9, but welding performance and thermoforming degradation due to being added to product after bismuth in alloy, and be added to
The flagship product of the brass alloys production of antimony is exceeded through NSF test antimony elements, in addition, due to the oxidizable slag making of magnesium, in silizin
It will be substantially reduced the mobility of alloy after middle addition magnesium and generate a large amount of oxidizing slag, so as to cause alloy in hot-working or casting
Crackle is also easy to produce when molding, product polishing rear surface has a large amount of material points and crackle.
In addition to above several classes are for the research and development of ledrite, the more common no lead bronze of existing market, that is, simple brass, such as CuZn40,
It is that lead content is reduced on the basis of C36000, i.e., the alloy being made of Cu, Zn and a small amount of Pb (being less than 0.25wt%), at
This is relatively low, but thermoforming and casting character are poor, and machining is difficult.
Invention content
In order to overcome the deficiencies of existing technologies, the present invention provides a kind of thermoforming and the excellent lead-free free-cutting of casting character
Inhibited brass alloy.The high comprehensive performance of brass alloys of the present invention, can be used for produce tap, pipe joint, electronic apparatus,
The parts such as automobile, machinery.
The purpose of the present invention is achieved through the following technical solutions.
A kind of environment-friendly yellow brass alloy that processability is excellent, the alloy contain the Zn of 35wt% or more, 0.1~1.0wt%
Si, the Mn of 0.01~0.28wt%, surplus be Cu and inevitable impurity.
Preferably, the content of Si is 0.2~0.8wt%, more preferably 0.3~0.7wt% in the alloy.Preferably,
In the alloy content of Mn be 0.01~0.09wt%, preferably 0.02~0.09wt%, more preferably 0.02~
0.08wt%.
Preferably, the alloy also contains 0.25wt% Pb below, it is preferable that the content of Pb is 0.15 in the alloy
~0.25wt%.
Preferably, the alloy also contains selected from least one of Fe, P, Sn, Al and Ni element, wherein the content of Fe
For 0.25wt% hereinafter, the content of P be 0.1wt% hereinafter, the content of Sn be 0.8wt% hereinafter, the content of Al be 0.8wt% with
Under, the content of Ni is 0.4wt% or less.
Preferably, the content of Fe is 0.12~0.25wt% in the alloy, and the content of P is 0.1wt% hereinafter, Sn's contains
Amount is 0.11~0.8wt%, and the content of Al is 0.1~0.8wt%, and the content of Ni is 0.2~0.4wt%.
Preferably, the alloy also contains selected from least one of B, Zr, Ti and RE element, wherein the content of B is
The content of 0.001~0.03wt%, Zr are 0.001~0.05wt%, and the content of Ti is 0.001~0.5wt%, and the content of RE is
0.001~0.3wt%.
The method that the present invention manufactures the excellent environment-friendly yellow brass alloy of the processability includes：Dispensing, melting, level are even
It casts, strip off the skin and heats forged, wherein the temperature of the horizontal casting is 990~1060 DEG C, the temperature of the heats forged is 680
~760 DEG C.
The technological process that the present invention manufactures the excellent environment-friendly yellow brass alloy of the processability is as shown in Figure 1.
It is in order to control the cost of raw material of alloy, because working as Zn content that the present invention, which controls Zn content in 35wt% or more,
The cost of raw material of product can be caused excessively high when less than 35wt%, in addition, when Zn content is less than 35wt%, forgeability is also opened
Begin to reduce.
A certain amount of silicon is added in alloy of the present invention, since the zinc equivalent coefficient of silicon is 10, β phase regions can be expanded, to change
The cutting ability of kind brass.When the content of silicon is more than 1.0wt%, the plasticity of alloy reduces, and cutting resistance increases severely；And when silicon
When content is less than 0.1wt%, cutting ability, forgeability are undesirable, thus the application by the control of the content of silicon 0.1~
In the range of 1.0wt%.
Add a small amount of manganese simultaneously in alloy of the present invention, manganese can form higher melting-point manganese silicon compound, the change with silicon
It closes object and matrix is uniformly distributed in graininess, on the one hand, the cutting ability of alloy can be promoted, and apparent crystal grain thinning improves
Hot formability energy and casting character；On the other hand, manganese silicon compound can prevent the recrystallization of crystal grain when hot-working from growing up rapidly, from
And further improve the hot formability energy of alloy；So that alloy of the present invention does not have when being provided with only single addition manganese or silicon
Some excellent performances.The manganese content of alloy of the present invention is controlled in 0.28wt% hereinafter, when the content of manganese is more than 0.1wt%, is closed
The polishing performance of gold starts to be deteriorated, and product is more difficult to meet high standard polishing requirement, when the content of manganese is more than 0.28wt%, easy shape
At coarse manganese silicon compound, low-alloyed cutting ability and plasticity are dropped, seriously affects the polishing performance of product, is suitable only for making
Non-polished part.
Lead is added, is on the one hand to the recycling convenient for free-cutting brass waste material, on the other hand, the addition of lead can be with
Further improve cutting ability, wherein the content of lead should be controlled in 0.25wt% or less.
Iron is selectively added, the hot formability energy of alloy with crystal grain thinning, can be promoted, wherein the content of iron should control
Within 0.25wt%.
Selectively add phosphorus, on the one hand can deoxidation improve alloy casting character and welding performance, another aspect phosphorus
The Dezincification corrosion resistant performance of alloy can be improved by being added, wherein the content of phosphorus should be controlled in 0.1wt% or less.
Selectively add tin, in al and ni one is in order to improve the intensity and corrosion resistance of alloy.Wherein, Sn plus
Enter amount control within 0.8wt%, the addition of Al controls within 0.8wt%, the addition control of Ni 0.4wt% with
It is interior, corrosion proof effect unobvious are improved if content is too low, if too high levels are unfavorable to mechanical property.
Selectively add in B, Zr, Ti and RE one is for deoxidation and crystal grain thinning, with further improve heat plus
Work performance.The addition control of wherein B is 0.001~0.03wt%, and the addition control of Zr is 0.001~0.05wt%, Ti
Addition control be 0.001~0.5wt%, RE addition control be 0.001~0.3wt%, if too high levels can reduce
The fluidity of molten of alloy.
The environmentally friendly brass of the present invention is using Si, Mn as main adding elements, wherein Mn and Si can form higher melting-point manganese
Silicon compound, the compound are uniformly distributed in matrix with graininess, promote the cutting ability and hot formability energy of alloy, meanwhile,
Manganese silicon compound can prevent the recrystallization of crystal grain when hot-working from growing up rapidly, and the hot formability of alloy can be further improved.
Secondly, alloy of the present invention selectively adds Fe with crystal grain thinning on the basis of adding Si, Mn, further improves the molding of alloy
And casting character；On the basis of above, selectivity adds at least one of B, Zr, Ti, RE can further refinement group
It knits to realize the hot-working character for maximumlly promoting alloy；Selectively at least one of addition P, Sn, Al and Ni, is realized
A kind of thermoforming is had excellent performance, casting character is excellent, the good LEAD-FREE BRASS ALLOY of corrosion resisting property；On the basis of above,
Selectivity adds a small amount of Pb, realizes that a kind of processability is excellent, cutting ability is good and is utilized convenient for waste recovery unleaded
Alloy.
Specifically, the brass alloys of the present invention are compared with prior art, at least have the advantages that：
The present invention adds element silicon and manganese element simultaneously, and obtained alloy has excellent hot formability energy and castability
Can, the product complicated particularly suitable for molding is not required to be squeezed, using horizontal casting ingot can direct hot forging product, reduce
Production cost and simplify technique.
The brass alloys of the present invention do not add the toxic elements such as lead, cadmium, while making the amount of precipitation symbol of alloying element in water
NSF/ANSI61-2008 standards are closed, are leadless environment-friendly type alloys, only allows the presence of micro Pb in alloy, preferably solves
The problem of waste recovery utilizes.
The brass alloys of the present invention have excellent performance (such as corrosion resisting property, mechanical property) and processing performance
(such as processability, cutting ability, welding performance) can be used for producing tap, pipe joint, electronic apparatus, automobile etc. zero
Component is particularly suitable for casting, forging and squeezes production drinking water supply system parts, such as tap product.
The hot formability of alloy of the present invention can be better than Bi brass, simple brass and traditional ledrite C36000, plastic shape
The product of shape complexity, unreal applying heat squeeze can meet demand, to have market competition advantage.
In addition, the anti-Dezincification corrosion performance of alloy of the present invention is substantially better than simple brass, ledrite C36000；Welding performance
It is substantially better than Bi brass, cutting ability is better than simple brass.And it is of low cost, and simple brass and have that lead bronze is suitable, it is comprehensive
It can be excellent.Meanwhile poisoning metal element amount of precipitation meets the requirement of NSF examination criterias in the water of alloy of the present invention, belongs to environment
Friendly material.Therefore alloy of the present invention has wider market application prospect.
Description of the drawings
Fig. 1 is manufacture alloy of the present invention and the process flow chart of comparative alloy.
Specific implementation mode
With reference to specific embodiments and the drawings, the present invention is described in further detail.
Embodiment
Alloy of the present invention and the ingredient of comparative alloy are as shown in table 1, and wherein comparative alloy 10 is bismuth-containing silizin, and comparison is closed
Gold 11 is simple brass CuZn40, and comparative alloy 12 is C36000 alloys.
Alloy of the present invention and comparative alloy cast the identical round bar stock of specification after technique is smelting as shown in Figure 1.Tool
Preparation process is：Dispensing, horizontal casting, strips off the skin and heats forged at melting, wherein the temperature of the horizontal casting be 990~
1060 DEG C, the temperature of the heats forged is 680~760 DEG C.
Below by alloy of the present invention and comparative alloy progress performance detection, specific performance detection project and according to as follows：
1. cutting ability
After invention alloy and comparative alloy are processed into the bar stock of diameter 34mm, each composition alloy intercepts 3 root long degree point
Not Wei 200mm parallel sample, to all alloys use identical cutter, identical cutting speed and the identical depth of cut,
The cutting resistance of invention alloy and comparative alloy is measured respectively.
The foundation of cutting ability evaluation is cutting force numerical values recited, using the excellent C36000 of generally acknowledged cutting ability as standard,
I.e. according to formula：
X=(cutting force of cutting force/technic metal of C36000) × 100%
If ratio " X " >=85%, it is believed that the cutting ability of technic metal is excellent, is indicated with " ⊙ "；If 85%>“X”≥
75%, it is believed that the cutting ability of technic metal is medium, is indicated with " 〇 "；If 75%>" Δ " >=65%, it is believed that technic metal
Cutting ability is general, is indicated with " Δ "；If ratio " X "<65%, it is believed that the cutting ability of technic metal is poor, uses "×"
It indicates, concrete outcome is as shown in table 2.
2. polishing performance
One section of the copper rod of each alloy interception Φ 50mm, by " 80#-240#-400#-800#- cotton piece buffs " polishing process to its cross
Section is polished, and is then with the naked eye observed, Hard Inclusion quantity no more than 3, and each hard spot diameter is less than 0.3mm
It is then excellent, is indicated with " 〇 "；Hard Inclusion quantity no more than 3, and it is good that each hard spot diameter, which is less than 0.5mm then, with " Δ "
It indicates；It is then poor that Hard Inclusion quantity, which is more than 3, is indicated with "×", the results are shown in Table 2.
3. anti-Dezincification corrosion performance
Dezincification experiment is carried out according to GB/T 10119-2008, and the difference in bar stock is made from invention alloy and comparative alloy
3 parallel samples are cut at position, and sectional dimension is 10mm × 10mm.It is rotten that sample through having inlayed is placed in constant temperature in copper chloride solution
Then metallographic specimen is made in experimental slides by erosion 24 hours, and under the microscope and the average depth of dezincification layer is demarcated in electronics metallography microscope
Degree.The results are shown in Table 2.
4. hot-working character
The sample that length (height) 40mm is cut from the horizontal casting stick of diameter 29mm, in 680 DEG C, 750 DEG C of two temperature
The case where degree is lower to be hot-forged axial crushing deformation, and uses following jumping-up rates, and observation cracks, to alloy of the present invention and comparison
The warm and hot forging performance of alloy is evaluated.
Jumping-up rate (%)=[(40-h)/40] × 100% (h is the height of sample after hot upsetting)
Forge that specimen surface is bright and clean and flawless, jumping-up rate is 85% or more, then to be excellent, is indicated with " ◎ "；Forge sample
Any surface finish and flawless, jumping-up rate is 75%~85%, then to be good, is indicated with " 〇 "；Specimen surface has rougher but without bright
Aobvious crackle is indicated then in " Δ "；It is poor that specimen surface, which has macroscopic crackle then, is indicated with "×".As a result such as 2 institute of table
Show.
5. welding performance
Invention alloy and comparative alloy are processed into the standard tensile specimen of a diameter of 8mm, then from middle by sample
It is sawed-off, it is welded, has been welded after thermally treated annealing by GB/T228-2010 using two kinds of welding manners of melting welding and solder brazing
Method carries out tension test, is carried out to the welding performance of alloy according to its postwelding polished surface quality and the tensile strength of solder joint comprehensive
Evaluation is closed, postwelding surface is visible by naked eyes stomata and crackle, and mechanical properties are then excellent higher than 200MPa, with " ◎ " table
Show；Postwelding surface is visible by naked eyes crackle, but has 1~2 stomata, and stomata spacing is more than 20mm, and single stomatal size is less than
0.3mm2, while mechanical properties are then good higher than 200MPa, are indicated with "○"；There are naked eyes visible crack or 2 in postwelding surface
A above stomata or stomata are smaller than 20mm, or single stomatal size is more than 0.3mm2Or mechanical properties are less than
200MPa is then poor, is indicated with "×", the results are shown in Table 3.
6. underwater gold category amount of precipitation
The measurement of the underwater gold category amount of precipitation of invention alloy and comparative alloy is executed by NSF/ANSI 61-2008 standards, real
It is by the valve of bar stock forging molding to test sample, and detecting instrument is：Inductively coupled plasma mass spectrometry, time are 19 days, are examined
It the results are shown in Table 4.
1 alloy of the present invention of table and comparative alloy ingredient (wt%)
Anti- Dezincification corrosion performance, polishing performance, warm and hot forging performance, the cutting ability of 2 present invention of table and comparative alloy
It can be seen from the above result that the average dezincification layer depth of alloy of the present invention is respectively less than 400 μm, hence it is evident that better than not adding Si
Comparative alloy 2,3 and comparative alloy 7,9-12, alloy of the present invention have good Dezincification corrosion resistant performance, be in suitable for water quality
Faintly acid or the higher environment of chloride salt content.
The polishing of alloy of the present invention and cutting ability are excellent, and cutting ability is substantially better than comparative alloy 1-3,7,9 and 11, can
Meet production application.
Under same forging temperature, the warm and hot forging of alloy of the present invention is had excellent performance, and is significantly better than that comparative alloy 1~12,
Invention alloy is substantially better than the comparative alloy 2~6 of individually addition Mn or Si because adding Si and Mn elements, warm and hot forging performance simultaneously.
It can be seen that for alloy of the present invention is compared with comparative alloy, warm and hot forging performance is better, is more suitable for the product of forming shape complexity, city
Field competitive advantage is apparent.
3 welding performance test result of table
The results show that alloy of the present invention is suitble to two kinds of welding methods of melting welding and soldering as comparative alloy 11, but compare
Alloy 10 and comparative alloy 12 are only suitable for being brazed, and alloy of the present invention has compared with Bi brass and the superior weldability of ledrite
Can, it is applicable to welding method with a greater variety, there is certain market competition advantage.
4 underwater gold category amount of precipitation test result of table
Data above shows the Pb amount of precipitations of alloy of the present invention in water far below the i.e. C36000 alloys of comparative alloy 12
Amount of precipitation, the amount of precipitation of other elements in water also meet the requirement of NSF/ANSI 61-2008 drinking water standards, are suitable for system
Potable water system parts are made, and the scorification outputs of alloy C36000 in water drink water gauge far above NSF/ANSI 61-2008
Standard is not suitable for manufacturing potable water system parts.
In summary known to performance test results：Alloy excellent combination property of the present invention, cutting ability are yellow better than simple
It is copper CuZn40, suitable with the silizin of bismuth-containing, and corrosion resisting property and thermo forming performance are substantially better than bismuth-containing silizin, simple
Brass and ledrite C36000；Meanwhile poisoning metal element amount of precipitation meets wanting for NSF examination criterias in the water of alloy of the present invention
It asks, belongs to environmentally friendly material, there is wider market application prospect.
Above-described embodiment limits the invention for explaining the present invention, in the spirit and right of the present invention
In claimed range, to any modifications and changes that the present invention makes, protection scope of the present invention is both fallen within.
Claims (14)
1. a kind of environment-friendly yellow brass alloy that processability is excellent, which is characterized in that the group of the brass alloys becomes：35wt% or more
Zn, the Mn of the Si of 0.3~0.7wt%, 0.02~0.09wt%, surplus be Cu and inevitable impurity.
2. brass alloys according to claim 1, which is characterized in that in the brass alloys content of Mn be 0.02~
0.08wt%.
3. brass alloys according to claim 1, which is characterized in that it is below that the brass alloys also contain 0.25wt%
Pb。
4. brass alloys according to claim 1, which is characterized in that the brass alloys also contain 0.15~0.25wt%
Pb.
5. the method for the brass alloys described in a kind of any one of manufacturing claims 1 to 4, this method include：Dispensing, melting,
Horizontal casting strips off the skin and heats forged, wherein the temperature of the horizontal casting is 990~1060 DEG C, the temperature of the heats forged
Degree is 680~760 DEG C.
6. a kind of environment-friendly yellow brass alloy that processability is excellent, which is characterized in that the group of the brass alloys becomes：35wt% or more
Zn, the Mn of the Si of 0.3~0.45wt%, 0.02~0.09wt%, surplus be Cu and inevitable impurity.
7. brass alloys according to claim 6, which is characterized in that in the brass alloys content of Mn be 0.02~
0.08wt%.
8. brass alloys according to claim 6, which is characterized in that it is below that the brass alloys also contain 0.25wt%
Pb。
9. brass alloys according to claim 6, which is characterized in that the brass alloys also contain 0.15~0.25wt%
Pb.
10. brass alloys according to claim 6, which is characterized in that the brass alloys also contain selected from Fe, P, Sn,
At least one of Al and Ni element, wherein the content of Fe is 0.12~0.25wt%, and the content of P is 0.1wt% hereinafter, Sn
Content be 0.11~0.34wt%, the content of Al is 0.1~0.8wt%, and the content of Ni is 0.2~0.4wt%.
11. the environment-friendly yellow brass alloy according to any one of claim 6 to 10, which is characterized in that the alloy also contains
Have selected from least one of B, Zr, Ti and RE element, wherein the content of B is 0.001~0.03wt%, and the content of Zr is
The content of 0.001~0.05wt%, Ti are 0.001~0.5wt%, and the content of RE is 0.001~0.3wt%.
12. a kind of environment-friendly yellow brass alloy that processability is excellent, which is characterized in that the group of the brass alloys becomes：61.27wt%
Cu, the Pb of the Sn of the Al of the Mn of the Si of 0.70wt%, 0.02wt%, 0.30wt%, 0.34wt%, 0.10wt%, surplus is
Zn and inevitable impurity.
13. a kind of environment-friendly yellow brass alloy that processability is excellent, which is characterized in that the group of the brass alloys becomes：61.55wt%
Cu, the Ti of the Ni of the Fe of the Mn of the Si of 0.30wt%, 0.08wt%, 0.20wt%, 0.05wt%, 0.02wt%, surplus is
Zn and inevitable impurity.
14. a kind of environment-friendly yellow brass alloy that processability is excellent, which is characterized in that the group of the brass alloys becomes：58.39wt%
Cu, the Sn of the Mn of the Si of 0.38wt%, 0.05wt%, 0.26wt%, surplus be Zn and inevitable impurity.
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| CN106636732A (en) * | 2016-12-12 | 2017-05-10 | 余姚市庆达机械有限公司 | High-plasticity brass alloy material and preparation method thereof |
| CN107974573B (en) * | 2017-11-29 | 2020-06-09 | 九牧厨卫股份有限公司 | Manganese-containing free-cutting silicon brass alloy and preparation method and application thereof |
| DE202018100075U1 (en) * | 2018-01-09 | 2019-04-10 | Otto Fuchs - Kommanditgesellschaft - | Copper-zinc alloy |
| 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 |
| CN112962002A (en) * | 2021-02-02 | 2021-06-15 | 宁波长振铜业有限公司 | Dezincification-resistant high-plasticity easy-to-process H62 simple brass alloy and preparation method thereof |
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| 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 |
| CN102443716A (en) * | 2010-09-30 | 2012-05-09 | 路达(厦门)工业有限公司 | Low cost brass alloy and its manufacture method |
| CN102618747A (en) * | 2011-01-26 | 2012-08-01 | 摩登岛股份有限公司 | Free cutting brass alloy |
| CN102220514B (en) * | 2011-06-13 | 2012-12-12 | 苏州撼力铜合金材料有限公司 | Special low-lead copper alloy using silicon to replace lead for bathroom |
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