CN105779811A - Good-formability environment-friendly brass alloy and manufacturing method thereof - Google Patents
Good-formability environment-friendly brass alloy and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to good-formability environment-friendly brass alloy and a manufacturing method thereof. The brass alloy contains 35wt% or more of Zn, 0.1-1.0wt% of Si, 0.01- 0.28wt% of Mn, and the balance Cu and inevitable impurities. The brass alloy has good cold processing formability, hot processing formability, castability, anti-dezincification-corrosion performance, excellent polishing performance and welding performance, and is suitable for parts, of bathroom plumbing, electric products, automobiles and the like, used for forging, casting and direct processing.
Description
Technical field
The invention belongs to technical field of alloy, be specifically related to a kind of environment-friendly yellow brass alloy, particularly relate to environment-friendly yellow brass alloy and the manufacture method thereof of a kind of thermoforming performance and casting character excellence.
Background technology
Ledrite usually contains the lead of 1wt%～4wt% so that it is obtain excellent cutting ability, good decay resistance, simultaneously with low cost.Ledrite has been taken as a kind of important basic material for every field such as electric, mechanical, hot-water heatings.But, Winn bronze can to environment in production, use procedure, the health of the harm mankind.The developed countries and regions such as the U.S., European Union successively formulates standard and decree, as S.3874, NSF372, AB1953, RoHS etc., progressively forbid producing and selling and using products containing lead.
At present, the unleaded of pyrite has been cooked substantial amounts of research work both at home and abroad, mainly through plumbous with bismuth generation, plumbous with antimony generation, with the silicon generation plumbous cutting ability realizing brass alloys, and by adding other appropriate element to improve the combination property of brass alloys.
But, on the one hand, Bi brass thermo forming poor performance, thermoforming process is easily generated defect, molding complex product difficulty, and Bi brass welding performance is poor；On the other hand, the safety of bismuth not yet obtains medical science and confirms, Bi brass material has a definite limitation in the application of European countries.
Recent domestic-developed lead-free free-cutting Stibium Brass, but antimony itself has toxicity, in use, the very easily dissolution of antimony in Stibium Brass, its tap, valve waited aquatic products to test antimony element stripping quantity in water through NSF and exceeded well over 0.6 μ g/L of standard regulation, there is environmental pollution and the hidden danger of harm human health, it is impossible to be applied to hot-water heating parts.
Silizin is to study non-leaded easily-cutting brass the most widely at present, at present existing a considerable amount of patents.nullIn existing published silizin patent, major part is the cutting ability that the bismuth by interpolation 0.1-5.0wt% or the antimony of 0.1-3.0wt% or the magnesium of 0.01-3.0wt% improve alloy，Such as Chinese patent application 200610005689.2、200910042723.7、200810084184.9，But owing to alloy with the addition of welding performance and the thermoforming degradation of product after bismuth，And the flagship product that the brass alloys that with the addition of antimony produce is tested antimony element through NSF and is exceeded standard，Additionally，Due to the oxidizable slag making of magnesium，To substantially drop low-alloyed mobility and produce substantial amounts of oxidizing slag after silizin adds magnesium，Thus causing that alloy is easily generated crackle when hot-working or casting，There are a large amount of material point and crackle in product polishing rear surface.
Except above several classes are for the research and development of ledrite, existing market more common without lead bronze and simple pyrite, such as CuZn40, it is reduction lead content on the basis of C36000, namely the alloy being made up of Cu, Zn and a small amount of Pb (less than 0.25wt%), it is less costly, but thermoforming and casting character are poor, and machining difficulty.
Summary of the invention
In order to overcome the defect of prior art, the present invention provides a kind of thermoforming and the leadless easy cutting corrosion resistant brass alloys of casting character excellence.The high comprehensive performance of brass alloys of the present invention, can be used for producing the parts such as faucet, pipe joint, electronic apparatus, automobile, machinery.
It is an object of the invention to be achieved through the following technical solutions.
The environment-friendly yellow brass alloy that a kind of processability is excellent, this alloy contains the Mn of the Si of the Zn of more than 35wt%, 0.1～1.0wt%, 0.01～0.28wt%, and surplus is Cu and inevitable impurity.
Preferably, in described alloy, the content of Si is 0.2～0.8wt%, more preferably 0.3～0.7wt%.Preferably, in described alloy, the content of Mn is 0.01～0.09wt%, it is preferred to 0.02～0.09wt%, more preferably 0.02～0.08wt%.
Preferably, described alloy is possibly together with the Pb of below 0.25wt%, it is preferable that in described alloy, the content of Pb is 0.15～0.25wt%.
Preferably, described alloy is possibly together with at least one element in Fe, P, Sn, Al and Ni, wherein, the content of Fe is the content of below 0.25wt%, P be the content of below 0.1wt%, Sn is below 0.8wt%, the content of Al is the content of below 0.8wt%, Ni is below 0.4wt%.
Preferably, in described alloy, the content that the content that content is 0.11～0.8wt%, Al is 0.1～0.8wt%, Ni that content is below 0.1wt%, Sn that content is 0.12～0.25wt%, P of Fe is 0.2～0.4wt%.
Preferably, described alloy is possibly together with at least one element in B, Zr, Ti and RE, wherein, the content of B is 0.001～0.03wt%, the content of Zr is the content that content is 0.001～0.5wt%, RE of 0.001～0.05wt%, Ti is 0.001～0.3wt%.
The present invention manufactures the method for the excellent environment-friendly yellow brass alloy of described processability and includes: dispensing, melting, horizontal casting, strip off the skin and heats forged, and the temperature of wherein said horizontal casting is 990～1060 DEG C, and the temperature of described heats forged is 680～760 DEG C.
The present invention manufactures the technological process of the excellent environment-friendly yellow brass alloy of described processability as shown in Figure 1.
Zn content is controlled to be above the cost of raw material in order to control alloy at 35wt% by the present invention, because can cause that the cost of raw material of goods is too high when Zn content is lower than 35wt%, additionally, when Zn content is lower than 35wt%, forgeability also begins to reduce.
Alloy of the present invention adds a certain amount of silicon, owing to the zinc equivalent coefficient of silicon is 10, β phase region can be expanded, thus improving the cutting ability of pyrite.When the content of silicon is more than 1.0wt%, the plasticity of alloy reduces, and cutting resistance increases severely；And when the content of silicon is lower than 0.1wt%, cutting ability, forgeability are undesirable, therefore the content of silicon is controlled in the scope of 0.1～1.0wt% by the application.
Alloy of the present invention adds a small amount of manganese simultaneously, manganese and silicon can form the manganese silicon compound that fusing point is higher, and this compound is uniformly distributed in matrix with graininess, on the one hand, the cutting ability of alloy can be promoted, and substantially crystal grain thinning improves thermoforming performance and casting character；On the other hand, when manganese silicon compound can stop hot-working, the recrystallization of crystal grain is grown up rapidly, thus further improving the thermoforming performance of alloy；Make the premium properties that alloy of the present invention does not have when being provided with simply single interpolation manganese or silicon.The Fe content of alloy of the present invention controls at below 0.28wt%, when the content of manganese is more than 0.1wt%, the polishing performance of alloy starts to be deteriorated, product is more difficult meets high standard polishing requirement, when the content of manganese is more than 0.28wt%, it is easily formed thick manganese silicon compound, drops low-alloyed cutting ability and plasticity, have a strong impact on the polishing performance of product, be suitable only for making non-polished part.
Adding lead, partly in order to be easy to the recycling of free-cutting brass waste material, on the other hand, plumbous addition can improve cutting ability further, and wherein, plumbous content should control at below 0.25wt%.
Optionally adding ferrum, it is possible to crystal grain thinning, promote the thermoforming performance of alloy, wherein, the content of ferrum should control within 0.25wt%.
Optionally adding phosphorus, deoxidation can improve casting character and the welding performance of alloy on the one hand, the addition of phosphorus can improve the Dezincification corrosion resistant performance of alloy on the other hand, and wherein, the content of phosphorus should control at below 0.1wt%.
Optionally adding the one in stannum, al and ni is to put forward heavy alloyed intensity and corrosion resistance.Wherein, the addition of Sn controls within 0.8wt%, and the addition of Al controls within 0.8wt%, and the addition of Ni controls within 0.4wt%, if content is too low, improves corrosion proof DeGrain, if too high levels is unfavorable to mechanical property.
Optionally adding the one in B, Zr, Ti and RE is for deoxidation crystal grain thinning, to improve hot-working character further.Wherein the addition of B controls is 0.001～0.03wt%, it is 0.001～0.05wt% that the addition of Zr controls, the addition that addition control is 0.001～0.5wt%, RE of Ti controls to be 0.001～0.3wt%, if low-alloyed fluidity of molten can drop in too high levels.
The environmental protection pyrite of the present invention is using Si, Mn as main adding elements; wherein; Mn and Si can form the manganese silicon compound that fusing point is higher; this compound is uniformly distributed in matrix with graininess; promote cutting ability and the thermoforming performance of alloy; meanwhile, when manganese silicon compound can stop hot-working, the recrystallization of crystal grain is grown up rapidly, and the thermoforming performance of alloy is further improved.Secondly, alloy of the present invention selectivity on the basis of interpolation Si, Mn adds Fe with crystal grain thinning, improves molding and the casting character of alloy further；On above basis, selectivity add in B, Zr, Ti, RE at least one can further thinning microstructure to realize promoting substantially the hot-working character of alloy；Optionally add at least one in P, Sn, Al and Ni, it is achieved that the LEAD-FREE BRASS ALLOY that a kind of thermoforming excellent performance, casting character are excellent, corrosion resisting property is good；On above basis, selectivity adds a small amount of Pb, it is achieved that a kind of processability is excellent, cutting ability is good and is easy to the lead-free alloy that waste recovery utilizes.
Specifically, the brass alloys of the present invention compared with prior art, at least have the advantages that
The present invention adds element silicon and manganese element simultaneously, the alloy obtained has thermoforming performance and the casting character of excellence, is particularly suitable for the product that molding is complicated, does not need to extrude, adopt horizontal casting ingot just can direct hot forging product, reduce production cost and simplify technique.
The brass alloys of the present invention are without toxic elements such as lead, cadmiums, make alloying element amount of precipitation in water meet NSF/ANSI61-2008 standard simultaneously, it is leadless environment-friendly type alloy, only allows the existence of micro Pb in alloy, solve the problem that waste recovery utilizes preferably.
The brass alloys of the present invention have excellent serviceability (such as corrosion resisting property, mechanical property etc.) and processing performance (such as processability, cutting ability, welding performance etc.), can be used for producing the parts such as faucet, pipe joint, electronic apparatus, automobile, it is particularly suitable for casting, forging and extruding and produces drinking water supply system parts, such as faucet product etc..
The thermoforming performance of alloy of the present invention is better than Bi brass, simple pyrite and tradition ledrite C36000, plastic complex-shaped product, does not implement hot extrusion and can meet demand, thus having market competition advantage.
Additionally, the anti-Dezincification corrosion performance of alloy of the present invention is substantially better than simple pyrite, ledrite C36000；Welding performance is substantially better than Bi brass, and cutting ability is better than simple pyrite.And with low cost, with simple pyrite and have lead bronze suitable, excellent combination property.Meanwhile, in the water of alloy of the present invention, poisoning metal element amount of precipitation meets the requirement of NSF examination criteria, belongs to environmental friendliness shaped material.Therefore alloy of the present invention has market application foreground widely.
Accompanying drawing explanation
Fig. 1 is the process chart manufacturing alloy of the present invention and comparative alloy.
Detailed description of the invention
Below in conjunction with specific embodiments and the drawings, the present invention is described in further detail.
Embodiment
The composition of alloy of the present invention and comparative alloy is as shown in table 1, and wherein comparative alloy 10 is bismuth-containing silizin, and comparative alloy 11 is simple pyrite CuZn40, and comparative alloy 12 is C36000 alloy.
Alloy of the present invention all casts, by technique shown in Fig. 1, the circular rod base that specification is identical with comparative alloy after smelting.Concrete preparation technology is: dispensing, melting, horizontal casting, strip off the skin and heats forged, and the temperature of wherein said horizontal casting is 990～1060 DEG C, and the temperature of described heats forged is 680～760 DEG C.
Hereinafter alloy of the present invention and comparative alloy being carried out performance detection, specific performance detection project and foundation are as follows:
1. cutting ability
After invention alloy and comparative alloy are processed into the excellent base of diameter 34mm, every kind of composition alloy intercepts the parallel sample of 3 root length degree respectively 200mm, all of alloy is adopted identical cutter, identical cutting speed and the identical depth of cut, measures the cutting resistance of invention alloy and comparative alloy respectively.
The foundation of cutting ability evaluation is cutting force numerical values recited, with the C36000 of generally acknowledged cutting ability excellence for standard, namely according to formula:
X=(cutting force of the cutting force/technic metal of C36000) × 100%
If ratio " X " >=85%, it is believed that the cutting ability of technic metal is excellent, represents with " ⊙ "；If 85% > " X " >=75%, it is believed that the cutting ability of technic metal is medium, represent with " "；If 75% > " Δ " >=65%, it is believed that the cutting ability of technic metal is general, represents with " Δ "；If ratio " X " < 65%, it is believed that the cutting ability of technic metal is poor, represents by "×", and concrete outcome is as shown in table 2.
2. polishing performance
Each alloy intercepts the copper rod one section of Φ 50mm, its cross section being polished by " 80#-240#-400#-800#-cloth wheel " glossing, then with the naked eye observes, Hard Inclusion quantity is less than 3, and each Hard Inclusion diameter is then excellent less than 0.3mm, represent with " "；Hard Inclusion quantity is less than 3, and each Hard Inclusion diameter is then good less than 0.5mm, represents with " Δ "；Hard Inclusion quantity, represents by "×" then for poor more than 3, and result is as shown in table 2.
3. anti-Dezincification corrosion performance
Dezincification test carries out according to GB/T10119-2008, prepares different parts 3 parallel samples of cutting rod base from invention alloy and comparative alloy, and sectional dimension is 10mm × 10mm.Sample through having inlayed is placed in copper chloride solution constant temperature and corrodes 24 hours, then experimental slides is made metallographic specimen, in electronics metallography microscope Microscopic observation the mean depth demarcating dezincification layer.Result is as shown in table 2.
4. hot-working character
The sample of length (highly) 40mm is cut from the horizontal casting rod of diameter 29mm, forge hot axial crushing deformation at 680 DEG C, 750 DEG C two temperature, and adopt following jumping-up rate, observe situation about cracking, the warm and hot forging performance of alloy of the present invention and comparative alloy is evaluated.
Jumping-up rate (%)=[(40-h)/40] × 100% (h is the height of sample after hot upsetting)
Specimen surface is bright and clean and flawless in forging, and jumping-up rate is more than 85%, then be excellent, with " ◎ " expression；Specimen surface is bright and clean and flawless in forging, and jumping-up rate is 75%～85%, then be good, with " " expression；Specimen surface has rougher but without obvious crackle, then, in being, use " Δ " represents；Specimen surface has macroscopic crackle then for poor, represents by "×".Result is as shown in table 2.
5. welding performance
Invention alloy and comparative alloy are processed into the standard tensile specimen that diameter is 8mm, then from middle, sample is sawed-off, melting welding and two kinds of welding manners of solder brazing are adopted to weld, tension test is carried out by GB/T228-2010 method after having welded thermally treated annealing, welding performance according to its postwelding polished surface quality and the tensile strength alloy of solder joint carries out Comprehensive Assessment, postwelding surface is without the visible pore of naked eyes and crackle, and mechanical properties is then excellent higher than 200MPa, represent with " ◎ "；Postwelding surface is without naked eyes visible crack, but has 1～2 pore, and pore spacing is more than 20mm, and single stomatal size is less than 0.3mm2, mechanical properties is then good higher than 200MPa simultaneously, represents by "○"；There are naked eyes visible crack or more than 2 pores in postwelding surface, or pore is smaller than 20mm, or single stomatal size is more than 0.3mm2, or mechanical properties lower than 200MPa then for poor, represent by "×", result is as shown in table 3.
6. underwater gold belongs to amount of precipitation
The underwater gold of invention alloy and comparative alloy belongs to the mensuration of amount of precipitation and performs by NSF/ANSI61-2008 standard, and laboratory sample is that detecting instrument is: Inductively coupled plasma mass spectrometry, and the time is 19 days, and assay is in Table 4 by the valve of rod base forging molding.
Table 1 alloy of the present invention and comparative alloy composition (wt%)
Table 2 present invention and the anti-Dezincification corrosion performance of comparative alloy, polishing performance, warm and hot forging performance, cutting ability
From result above, the average dezincification layer depth of alloy of the present invention is respectively less than 400 μm, it is substantially better than the comparative alloy 2,3 without Si and comparative alloy 7,9-12, alloy of the present invention has good Dezincification corrosion resistant performance, it is adaptable to water quality is faintly acid or the higher environment of chloride salt content.
Polishing and the cutting ability of alloy of the present invention 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 excellent performance of alloy of the present invention, it is significantly better than that comparative alloy 1～12, invention alloy is because adding Si and Mn element simultaneously, and warm and hot forging performance is substantially better than the comparative alloy 2～6 individually adding Mn or Si.Visible alloy of the present invention relatively comparative alloy, its warm and hot forging performance is more excellent, is more suitable for the product that forming shape is complicated, and market competition advantage is obvious.
Table 3 welding performance test result
Result shows, alloy of the present invention is equally suitable for melting welding and two kinds of welding methods of soldering with comparative alloy 11, but comparative alloy 10 and comparative alloy 12 are only suitable for soldering, alloy of the present invention has the welding performance that relatively Bi brass and ledrite are more excellent, it is applicable to more various welding method, there is certain market competition advantage.
Table 4 underwater gold belongs to amount of precipitation test result
Data above shows, the alloy of the present invention Pb amount of precipitation in water is far below the comparative alloy 12 i.e. amount of precipitation of C36000 alloy, other element amount of precipitation in water also meets the requirement of NSF/ANSI61-2008 drinking water standard, it is applicable to manufacture potable water system parts, and the scorification output that alloy C36000 is in water is far above NSF/ANSI61-2008 drinking water standard, be not suitable for manufacturing potable water system parts.
Comprehensive above performance test results is known: alloy excellent combination property of the present invention, the silizin that its cutting ability is better than simple pyrite CuZn40 and bismuth-containing is suitable, and corrosion resisting property and thermo forming performance are substantially better than bismuth-containing silizin, simple pyrite and ledrite C36000；Meanwhile, in the water of alloy of the present invention, poisoning metal element amount of precipitation meets the requirement of NSF examination criteria, belongs to environmental friendliness shaped material, has market application foreground widely.
Above-described embodiment is used for explaining the present invention, rather than limits the invention, in the spirit and claims of the present invention, and any amendment that the present invention is made and change, both fall within protection scope of the present invention.
Claims (8)
1. the environment-friendly yellow brass alloy that a processability is excellent, it is characterised in that these brass alloys contain the Mn of the Si of the Zn of more than 35wt%, 0.1～1.0wt%, 0.01～0.28wt%, and surplus is Cu and inevitable impurity.
2. brass alloys according to claim 1, it is characterised in that in described brass alloys, the content of Si is 0.2～0.8wt%, more preferably 0.3～0.7wt%.
3. brass alloys according to claim 1 and 2, it is characterised in that in described brass alloys, the content of Mn is 0.01～0.09wt%, it is preferred to 0.02～0.09wt%, more preferably 0.02～0.08wt%.
4. brass alloys according to any one of claim 1 to 3, it is characterised in that described brass alloys are possibly together with the Pb of below 0.25wt%；Preferably, described brass alloys are possibly together with the Pb of 0.15～0.25wt%.
5. brass alloys according to any one of claim 1 to 4, it is characterized in that, described brass alloys are possibly together with at least one element in Fe, P, Sn, Al and Ni, wherein, the content of Fe is the content of below 0.25wt%, P be the content of below 0.1wt%, Sn is below 0.8wt%, the content of Al is the content of below 0.8wt%, Ni is below 0.4wt%.
6. brass alloys according to any one of claim 1 to 5, it is characterized in that, in described brass alloys, the content of Fe is 0.12～0.25wt%, the content of P is below 0.1wt%, the content of Sn is 0.11～0.8wt%, the content of Al is the content of 0.1～0.8wt%, Ni is 0.2～0.4wt%.
7. environment-friendly yellow brass alloy according to any one of claim 1 to 6; it is characterized in that; described alloy is possibly together with at least one element in B, Zr, Ti and RE; wherein; the content of B is 0.001～0.03wt%; the content of Zr is the content that content is 0.001～0.5wt%, RE of 0.001～0.05wt%, Ti is 0.001～0.3wt%.
8. the method for the brass alloys according to any one of a manufacturing claims 1 to 7, the method includes: dispensing, melting, horizontal casting, strip off the skin and heats forged, the temperature of wherein said horizontal casting is 990～1060 DEG C, and the temperature of described heats forged is 680～760 DEG C.
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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 |
| CN107974573A (en) * | 2017-11-29 | 2018-05-01 | 九牧厨卫股份有限公司 | A kind of silicon brass alloy containing manganese easy cutting and its preparation method and application |
| 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 |
| CN111788321A (en) * | 2018-01-09 | 2020-10-16 | 奥托福克斯两合公司 | Copper-zinc alloy |
| 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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| 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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| CN105779811B (en) | 2018-10-09 |
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