CN109112350A - High tough corrosion resistant alumin(i)um yellow brass web pre fetching and preparation method thereof - Google Patents

High tough corrosion resistant alumin(i)um yellow brass web pre fetching and preparation method thereof Download PDF

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Publication number
CN109112350A
CN109112350A CN201810998830.6A CN201810998830A CN109112350A CN 109112350 A CN109112350 A CN 109112350A CN 201810998830 A CN201810998830 A CN 201810998830A CN 109112350 A CN109112350 A CN 109112350A
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alumin
corrosion resistant
web pre
yellow brass
alloy
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冯斌
章建炜
黄敏
贺官兵
张路
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NINGBO XING'AODAO METAL NEW MATERIAL CO Ltd
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NINGBO XING'AODAO METAL NEW MATERIAL CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/004—Copper alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/045—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds for horizontal casting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)

Abstract

The present patent application discloses a kind of high tough corrosion resistant alumin(i)um yellow brass web pre fetching, the weight percent composition of the material are as follows: Cu 60~72%, Sn 2.0~3.0%, Al 0.8~2%, X10.002~0.2%, X20.02~0.5%, surplus is Zn and inevitable impurity；Wherein X1For at least one of tri- kinds of elements of La, Ce, Y, X2For at least one of two kinds of elements of B, P.The material have both intensity height, good toughness, corrosion resistance and good multiple advantage, can apply in sea-farming well.The present patent application also discloses the preparation method of the tough corrosion resistant alumin(i)um yellow brass web pre fetching of above-mentioned height, using tensile strength >=450MPa of alumin(i)um yellow brass web pre fetching made of electromagnetism-ULTRASONIC COMPLEX technique, elongation >=35%, 100 μm of Dezincification corrosion depth <.

Description

High tough corrosion resistant alumin(i)um yellow brass web pre fetching and preparation method thereof
Technical field
The invention belongs to etting technologies and copper alloy technical field, and in particular to a kind of high tough corrosion resistant aldubra conjunction Golden web pre fetching and preparation method thereof.
Background technique
In mariculture industry, usually using net cage come cultured fishes, and web pre fetching is the base stock for making net cage. Traditional web pre fetching is made of synthetic fibers, such as nylon, polyethylene, polypropylene, although synthetic fibers have preferably Corrosion resistance and toughness, but traditional web pre fetching has the following deficiencies: 1, since net cage need to submerge in the seawater for a long time, and There are the microorganisms, i.e. marine fouling organism such as algae spores, the animal larva of a large amount of fast-growths in seawater, is attached to etting table Face is easy for blocking mesh in this way, then reduces dissolved oxygen, leads to infection of marine fishes disease, deteriorates water quality, so needing frequent Cleaning and draping；2, synthetic fibers sole mass is light, intensity is small, so the web pre fetching wind and wave resistance being made from it, Anti-erosion energy Power is poor, just suffers heavy losses once meeting the attack of the strong storms such as typhoon.
In view of the defect of above-mentioned traditional web pre fetching, technical staff is highly desirable, which can be developed to have, prevents marime fouling The adhewsive action while the high web pre fetching of intensity of biology, and copper just meets such performance requirement.Since copper is in marine environment In can ionize out copper ion, and copper ion has natural anti-microbial property, so copper as etting energy made of main component Enough prevent the adhewsive action of marine fouling organism；Moreover, because copper is heavy metal, it is natural than the quality weight of synthetic fibers, intensity It is high.Specifically, HA177-2 alumin(i)um yellow brass is because of its excellent mechanical property, antibacterial, antibiont adhesion, advantage at low cost And become cage netting ideal material.But because Zn content is greater than 20wt% in HA177-2 alumin(i)um yellow brass, and Zn is in seawater In be easily dissolved, leave a large amount of hole, cause material heavy corrosion, so the alloy is in sea-farming use process, Haves the defects that Dezincification corrosion, this corrosion is the main failure mode of brass, eventually makes the strength reduction of brass, contracts significantly The service life of short etting.In order to improve corrosion resistance, traditional method is that suitable arsenic is added into brass, manufactured in this way Although web pre fetching can be improved corrosion resistance, but the amplitude improved is very limited, far from meeting etting in sea-farming The needs of Anti-erosion corrosion, and the toxicity of arsenic element is fatal to cultivation.
Intensity height, good toughness, corrosion resistance and good, nontoxic multiple advantage are had both so lacking in the prior art The web pre fetching of high tough fine corrosion resistance, the alumin(i)um yellow brass of the prior art cannot be applied well in sea-farming In.
Summary of the invention
The technical problem to be solved by the invention is to provide one kind to have both intensity height, good toughness, corrosion resistance and good, nothing The tough corrosion resistant alumin(i)um yellow brass web pre fetching of height of the harmless multiple advantage of poison, can apply in sea-farming well.
Technical solution of the invention is as follows: a kind of high tough corrosion resistant alumin(i)um yellow brass web pre fetching, the material Weight percent composition are as follows: Cu 60~72%, Sn 2.0~3.0%, Al 0.8~2%, X10.002~0.2%, X2 0.02~0.5%, surplus is Zn and inevitable impurity；Wherein X1For at least one of tri- kinds of elements of La, Ce, Y, X2For B, at least one of two kinds of elements of P.
Preferably, the weight percent composition of the alumin(i)um yellow brass web pre fetching are as follows: Cu 65~70%, Sn 2.2~ 2.8%, Al 1~1.8%, X10.005~0.15%, X20.05~0.2%, surplus is Zn and inevitable impurity；Its Middle X1For at least one of tri- kinds of elements of La, Ce, Y, X2For at least one of two kinds of elements of B, P.
Preferably, the X1Weight percent content be La 0.005~0.185%, Ce 0.005~0.150%, Y At least one of 0.01~0.18%, and X1Total amount be no more than 0.2%.That is, the X1For in La, Ce, Y extremely Few one kind, corresponding weight percent are La 0.005~0.185%, Ce 0.005~0.150%, Y 0.01~0.18%.
Preferably, the X2Weight percent content be B 0.1~0.5%, P 0.02~0.4% at least one Kind, and X2Total amount be no more than 0.5%.That is, the X2For at least one of B, P, corresponding weight percent is B 0.1~0.5%, P 0.02~0.4%.
Preferably, which is used to make etting and net cage.It is further preferred that using the material production etting and Net cage is applied in sea-farming.After the copper alloy netting, can 100% recycling, realize all recycle.
Preferably, the X1Weight percent composition are as follows: La 0.005~0.1%, Ce 0.005~0.05%, Y 0.01~0.05%.
Preferably, the X2Weight percent composition are as follows: B 0.15~0.3%, P 0.05~0.2%.
The reason of element species and additive amount are limited in alumin(i)um yellow brass web pre fetching of the present invention is:
On the one hand the addition of tin element Sn enhances the crystal boundary of Cu-Zn solid solution alloy, greatly reduce the corrosion of crystal boundary Sensibility, it is therefore prevented that be the composition of this micro cell of anode using the crystal grain of low energy as the crystal boundary of cathode, high-energy, to improve Corrosion resisting property；On the other hand, in alloy surface the oxidation film that passivation reaction generates densification can occur for tin, which can effectively prevent Brass base continues that corrosion reaction occurs.Sn content can not form oxidation film lower than 2.0%, not increase corrosion resistance, and contain Measure more than 3.0% pair of material performance without further improvement, most preferably preferably 2.0~3.0%.
Aluminium element Al, the intensity and corrosion resistance of material can be improved significantly by adding suitable aluminium element in the alloy.Al contains Amount can not form complete layer oxide film in alloy material surface lower than 0.8%, so that alloy is easy to be corroded, i.e., not mention The corrosion resistance of high material；And Al content is more than 2% intensity and hardness that can significantly improve alloy material, is occurred in alloy at this time Hard but also crisp γ phase not only, so that the plasticity of alloy is greatly lowered, degraded toughness, so best preferably 0.8~2%.
Copper Cu, copper content is high, and α phase is more, and corrosion resistance, the toughness of material are preferable, and the too low degraded toughness of copper content is excellent Selecting scheme one is 60~72%, and preferred embodiment two is 65~70%.
Zn-ef ficiency Zn is added in the form of spelter, since the fusing point (419.58 DEG C) of Zn is lower, it is easy to it is dissolved in Cu, Spelter ensure that the chemical component of alloy, improve the intensity of material.Zn too high levels, material corrosion resistance are deteriorated, and content is too low, The intensity of material is inadequate.Zn content is limited in the form of surplus according to other elements content, due to limiting containing for other elements Amount so that the strength of materials is high, good toughness, corrosion resistance and good, then shows Zn content also in preferred scope in preferred scope.
X1And X2It is micro alloying element, wherein X1For at least one of tri- kinds of elements of La, Ce, Y, X2It is two kinds of B, P At least one of element, working is respectively:
X1Middle La, Ce, Y are rare earth element, are on the one hand elements for inhibiting the mechanism of action of brass dezincification corrosion La, Ce, Y are more active, easily aoxidize, as Al can alloy surface generate one layer of sull protect inner base from Corrosion；On the other hand, due in CuCl2In solution, the current potential of brass is between Cu2+/Cu+And Cu2+/Cu(Cu+/ Cu) between, make The copper ion for obtaining monovalence needs indirectly from Cu2Cl2The Cu of formation2+It can just restore, be deposited on brass afterwards, and La, Ce, Y It can be by Cu2+Restore Cu+, and then inhibit Cu2Cl2Decomposition, to inhibit dezincification.In addition, rare earth element La and Ce, Y are also Good deslagging refining agent, impurity element and Pb, As that can effectively with the electronegativity such as O, S, H in melt in fusion process Equal impurity, which combine, forms compound, generates slag and floats, and to purify copper alloy, enhances alloy corrosion resistance.The study found that this hair Bright alumin(i)um yellow brass is fabricated to web pre fetching when applying in sea-farming, X1Intensity, but toughness can be improved in too high levels Declined；X1Content is too low, and the corrosion resistance of material reduces, and the optimum amount range of different rare earth elements is different, Specific best preferred respectively La 0.005~0.185%, Ce 0.005~0.150%, Y 0.01~0.18%.
B has significant Grain refinement, further increases the strength of materials, hardness and corrosion resistance, content is lower than The intensity, hardness of 0.1% not no reinforcing material, will be precipitated more than 0.5% in the form of boride is mingled with, and deteriorate plasticity, corrosion resistant Reduced performance is lost, most preferred range is 0.1~0.5%.
P is good smelting copper alloy deoxidier, since P has lower fusing point (44.1 DEG C) and boiling point (280 DEG C), energy Increase fluidity of molten, necessarily causes the violent boiling of copper melts if being directly added into copper melts, splashes, red phosphorus largely evaporates and oxygen Change, can not only operate, but also impair one's health, therefore phosphor bronze alloy is added into alloy melt and carries out deoxidation treatment.Phosphorus content is low It is unobvious to material flowability and deoxidation effect in 0.02%, more than 0.4% pair of material performance without further improvement, Most preferred range is 0.02~0.4%.
The advantages of the present invention:
1) present invention is developed from the web pre fetching in sea-farming with intensity height, good toughness, erosion resistance The material of height, corrosion resistance and good, nontoxic multiple advantage: it by copper as main component, can be ionized in marine environment The copper ion for providing natural antibacterial performance prevents the adhewsive action of marine fouling organism；Meanwhile various ingredients phase of the invention Mutually cooperation, content overcomes the defect of brass dezincification corrosion in optimum range, can increase substantially intensity, toughness and corrosion-resistant Property, the needs that etting Anti-erosion corrodes in sea-farming are fully met, the copper alloy netting cage thus prepared can be fish Growth and breeding provide more a cleaning, healthier water body environment；
2) optimum addition of the invention by adjusting optimization each component is to obtain accumulative effect, so that the tension of material Intensity >=450MPa, elongation >=35%, 100 μm of Dezincification corrosion depth <, so having both intensity height, good toughness, Anti-erosion energy Power height, corrosion resistance and good, nontoxic multiple advantage；
3) fusing point of tri- kinds of elements of Zn, Sn, Al is all relatively low, larger with the different melting points of Cu, so preparing material mistake It is easy to that dendritic segregation and inverse segregation occurs in journey, to this technical problem, using X1(rare earth element La and Ce, Y) and X2(B, P) two The mode of kind micro alloying element joint addition, can significantly refine grain structure, effectively refinement crystal grain, inhibit to greatest extent The dendritic segregation and inverse segregation of Zn, Sn, Al, and then improve the performance of material.
Another technical problem to be solved by this invention is to provide a kind of high tough corrosion resistant alumin(i)um yellow brass etting The preparation method of material, can obtain intensity height, good toughness, corrosion resistance and good alumin(i)um yellow brass web pre fetching.
The technical solution of above-mentioned technical problem is as follows: a kind of high tough corrosion resistant alumin(i)um yellow brass web pre fetching Preparation method, it the following steps are included:
1) alloy melting: weighing each component by weight percentage, in N2Under atmosphere successively by copper, aluminium, micro alloying element, Tin, spelter, which are added in the crucible of induction melting furnace, is heated to molten condition, and molten alloy surface covers charcoal, and it is molten to obtain alloy Body；The micro alloying element is X1And X2, by X1And X2It is added in the form of intermediate alloy；It is every add a kind of component before, first Slag former is added, then stirs, fish out slag, and cover dry crystalline flake graphite；
2) horizontal casting: alloy melt being added in 1200~1300 DEG C of holding furnace, and Ultrasonic probe is inserted into copper Alloy liquid level is drawn hereinafter, unlatching supersonic generator, electromagnetic induction coil using the anti-process flow pushed away of stretching-pause- Casting, obtains slab；
3) slab is successively subjected to homogenizing annealing, cold rolling, recrystallization annealing, obtains high tough corrosion resistant aldubra and closes Golden web pre fetching.
Preferably, the smelting temperature before aluminium is added is 1150~1200 DEG C, and the smelting temperature after addition aluminium is 1200 ~1400 DEG C, aluminium is added before copper is unfused.Since aluminium fusing point (660.32 DEG C) is lower, can be added with form of pure metal, but aluminium Addition can release a large amount of heat, so being added before copper is unfused, to prevent hot-spot.Specifically, smelting temperature 1150 is set After~1200 DEG C, copper is first added, then take advantage of copper it is unfused when be homogeneously added into aluminium, at this time smelting temperature be 1200~1400 DEG C, This makes it possible to guarantee thermally equivalent.
Preferably, the maximal input of induction melting furnace is 15kW, and voltage of intermediate frequency is 70~520V, electric current of intermediate frequency 3 ~22A, frequency of oscillation are 1~20Hz.
Preferably, the exportable frequency of induction melting furnace is the alternating current of l~10kHz, and frequency is passed through in electromagnetic inductor Rate be 2.5kHz alternating current and generate alternating electromagnetic field.
Preferably, 2~5cm below Ultrasonic probe insertion copper alloy liquid level, holding oscillating current are 1.5~2.5A, vibration The dynamic time is 100~150s.In general, the time that Ultrasonic probe vibrates in copper alloy melt is longer, to copper alloy net The performance improvement of clothing material is more significant, but in order to extend the service life of Ultrasonic probe, time of vibration is limited to 100~ 150s。
Specifically, it pulling-casting process parameter: rises and draws 1220 DEG C of temperature；The drawing of stretching is away from 10mm, and anti-advance is from 1.3mm, cast Time 0.3s is arrheaed in 100 times/min of frequency, pause；When cast, melt liquid level is that 700mm is crystallized away from crystallizer entrance distance Device.
Specifically, cold-rolling process parameter: inflow temperature: 20 DEG C, water feeding pressure: 0.5Mpa；Made-up belt outlet temperature: 350 DEG C. Specifically, secondary water cooling technological parameter: inflow temperature: 25 DEG C, water feeding pressure: 0.5Mpa.
Preferably, the temperature of homogenizing annealing is 950~1050 DEG C, and annealing time is 1~5h.
Preferably, the temperature of recrystallization annealing is 400~600 DEG C, and annealing time is 1~3h.
The preparation method of tough corrosion resistant alumin(i)um yellow brass web pre fetching of the invention high compared with prior art, have with Lower remarkable advantage and the utility model has the advantages that
1) alumin(i)um yellow brass web pre fetching is prepared using above-mentioned electromagnetism-ULTRASONIC COMPLEX technique and belongs to domestic and international related fields head Wound, tensile strength >=450MPa of manufactured material, elongation >=35%, 100 μm of Dezincification corrosion depth <, so above-mentioned technique Intensity height, good toughness, erosion resistance height, corrosion resistance and good, nontoxic alumin(i)um yellow brass web pre fetching, energy can be made It is enough to apply in sea-farming well；
2) induction coil generates highdensity magnetic induction line in induction melting furnace, and magnetic induction line constantly changes with alternating current, feels The alloy raw material cutting magnetic induction line to be melted in coil in graphite crucible is answered, very big vortex is generated in alloy raw material, there is whirlpool The mobile generation thermal energy for flowing existing alloy raw material therein electronics, with can be by melting alloy raw to molten condition, this Sample can reduce melt temperature gradient, and homogeneous heating reduces macroscopic segregation of cast ingot, and then improve the performance of alloy, Er Qiejie It saves thermal energy, reduce energy consumption, conducting self-heating is more thorough, and faster, electromagnetic agitation is more uniform for heating speed；
3) generation for the defects of electromagnetic agitation can reduce pin hole, bubble, surface are mingled with and slag inclusion, it is final to obtain internal group Knit the high quality ingot casting of the defects of fine and close, without stomata.Compared with common continuous casting ingot casting, continuous casting electromagnetic ingot casting cross-section center etc. Axialite area range is larger and crystal grain is tiny；Electromagnetic field effect forms the effect of stirring and convection current in alloy melt, can inhibit melt The growth of middle dendrite can be fractureed by electromagnetic force forming dendrite, smash and become new nucleus, it is solidifying to improve slab Gu the equiaxial crystal ratio of tissue, achievees the purpose that refined crystalline strengthening；
4) ultrasonic tool head generates high-energy ultrasonic and forms a large amount of cavitation bubble, and cavitation bubble promotes alloy melt inner clip The gas collisions of sundries fault location, aggregation become larger, and when bubble floating captures field trash, by alloy melt inclusion and stomata one Discharge is played, impurity and purification melt is played the role of；Ultrasonic vibration can be such that ingot casting crystallite dimension obviously refines, organize in solidification It is even, remove stomata, be clipped in slag etc., improve segregation, improves material property；
5) electromagnetism-ULTRASONIC COMPLEX technique has apparent refining effect, effectively refinement continuous casting process to the solidified structure of alloy In arborescent structure, overcome the defect that Zn, Sn, Al are easy to happen dendritic segregation and inverse segregation, to greatest extent inhibit Zn, Sn, The dendritic segregation and inverse segregation of Al, and pollution-free to melt, it is easy to operate, it is environmentally protective, energy-saving, production cost is low；
6) horizontal continuous casting process can reduce Zn, Sn, Al in the inverse segregation of casting billet surface, improve the surface quality of slab, High-densit tissue has been taken into account again while guaranteeing high efficiency production, has been taken into account again while guaranteeing mechanical property high intensity Comparable toughness, investment of production are few.
Specific embodiment
The present invention is described in further details with specific embodiment below, but the present invention is not only limited in detail below in fact Apply example.
Plurality of raw materials involved in the present invention, including Cu, Al, Zn, Sn, Cu, La, Ce, Y, B, P can be purchased by commercially available It arrives.
This field all know chemical element title and corresponding symbol specifically: copper-Cu, aluminium-Al, zinc-Zn, tin-Sn, Lanthanum-La, cerium-Ce, yttrium-Y, boron-B, phosphorus-P.
Occur multiple parameters in the present invention, such as weight percent, temperature, voltage, electric current, frequency, time, unit (such as %, DEG C, V, A, Hz, s) be unified in the upper limit after mark, such as 60~72%, 1200~1300 DEG C, 70~520V, 3~22A, 1~ 20Hz, 100~150s.It is, of course, also possible to using unit is marked after upper limit value and lower limit value, such as 60%~72%, 1200 DEG C ~1300 DEG C, 70V~520V, 3A~22A, 1Hz~20Hz, 100s~150s.The expression way of both parameter areas, It, all can tape unit after numerical value in embodiment to the upper limit of parameter, two endpoint values of lower limit and intermediate value.
Material electromagnetic process is the technical process for combining materials processing technology with magnetohydrodynamics, and the present invention uses Electromagnetic field is applied to material for SPZ-15 small-sized hand turnover type intermediate frequency furnace.Graphite crucible and electricity are equipped in induction melting furnace Magnetic induction coil, when melting, due to electromagnetic induction, alloy raw material cutting magnetic induction line in graphite crucible, alloy raw material is generated very Big vortex has the mobile generation thermal energy for being vortexed existing alloy raw material therein electronics, with can be by melting alloy raw To molten condition.When horizontal casting, electromagnetic induction coil is opened, electromagnetic field effect forms the effect of stirring and convection current in alloy melt Fruit.
Ultrasound typically refers to frequency in the sound wave of 20kHz or more, and because of its frequency height, wavelength is short, therefore good with beam, Energy collection neutralizes the features such as penetration power is strong.Ultrasonic coagulation effect mechanism is passed through before metal freezing or in metal solidification process Power ultrasound is applied to improve metal solidification texture to metal bath, reaches refinement crystal grain, the method for improving alloy property.Ultrasound Wave producer is equipped with Ultrasonic probe, and Ultrasonic probe is first inserted into copper alloy liquid level hereinafter, be then turned on supersonic generator, It can be realized and power ultrasound is applied to alloy melt.
Embodiment provided below is not intended to limit the invention covered range, and described step is also not use Sequence is executed to limit its.Those skilled in the art combine existing common knowledge to do conspicuous improvement to the present invention, also fall Enter the present invention claims protection scope within.
Product embodiments
Table 1 is the embodiment of the present invention and comparative example material component (wt%), and surplus is Zn and inevitable impurity.Table 2 It is embodiment alloy compared with comparative example material property.
Tensile strength >=450MPa of alumin(i)um yellow brass web pre fetching of the present invention it can be seen from table 1, table 2, elongation >= 35%, 100 μm of Dezincification corrosion depth <, it is high, corrosion resistance and good multiple excellent with intensity height, good toughness, erosion resistance Gesture fully meets the needs that etting Anti-erosion corrodes in sea-farming.For prove material of the present invention component and content with upper Excellent properties are stated, multiple groups comparative test is carried out.On the one hand, reference implementation example 9 cancels the wherein addition of certain or certain elements, That is comparative example 12~15 tests comparative example performance related with component.On the other hand, reference implementation example 9, will wherein certain component Content be located at except content range of the present invention, i.e. comparative example 16~25 tests comparative example performance relevant to content.Comparison can To find out, lack in material of the present invention the content of any component or certain component not material in content range of the present invention Material, performance has decline, far away from the performance of material of the present invention.
1 product of the present invention embodiment of table and comparative example material component (wt%)
2 product of the present invention embodiment of table is compared with the performance of comparative example material
No Tensile strength (MPa) Elongation (%) Dezincification corrosion depth (μm)
1 450 35 99
2 473 42 90
3 462 35 95
4 485 37 82
5 472 36 90
6 459 39 93
7 450 44 96
8 469 43 88
9 503 36 85
10 510 41 79
11 501 42 95
12 (comparative examples) 372 34 210
13 (comparative examples) 439 23 225
14 (comparative examples) 379 31 196
15 (comparative examples) 407 31 159
16 (comparative examples) 430 29 220
17 (comparative examples) 495 35 100
18 (comparative examples) 490 33 200
19 (comparative examples) 500 22 110
20 (comparative examples) 450 35 125
21 (comparative examples) 480 28 110
22 (comparative examples) 420 36 98
23 (comparative examples) 460 25 130
24 (comparative examples) 420 33 195
25 (comparative examples) 430 34 170
Preparation method embodiment
Material rate is added referring to product embodiments.
Embodiment 1
A kind of preparation method of high tough corrosion resistant alumin(i)um yellow brass web pre fetching, it the following steps are included:
1) alloy melting: each component is weighed by the weight percent of product embodiments, in N2Under atmosphere successively by copper, aluminium, Micro alloying element, tin, spelter, which are added in the crucible of induction melting furnace, is heated to molten condition, molten alloy surface covering wood Charcoal obtains alloy melt；The micro alloying element is added in the form of intermediate alloy；It is every add a kind of component before, first plus Enter slag former, then stirs, fishes out slag, and cover dry crystalline flake graphite；Smelting temperature before aluminium is added is 1150 DEG C, is added Smelting temperature after aluminium is 1200 DEG C, and aluminium is added before copper is unfused；
2) horizontal casting: alloy melt being added in 1200 DEG C of holding furnace, and making alloy copper liquid is more than crystallizer section Height, then by Ultrasonic probe be inserted into copper alloy liquid level below 2cm, open supersonic generator, electromagnetic induction coil, adopt Cast is carried out with the anti-process flow pushed away of stretching-pause-, obtains slab；It is 1.5A, vibration that supersonic generator, which keeps oscillating current, The dynamic time is 100s；
3) slab is successively subjected to homogenizing annealing, cold rolling, recrystallization annealing, obtains high tough corrosion resistant aldubra and closes Golden web pre fetching.
The maximal input of induction melting furnace is 15kW, voltage of intermediate frequency 70V, electric current of intermediate frequency 3A, and frequency of oscillation is 1Hz；The exportable frequency of induction melting furnace is the alternating current of l kHz, and the friendship that frequency is 2.5kHz is passed through in electromagnetic inductor Time-dependent current and generate alternating electromagnetic field.
Pulling-casting process parameter: it rises and draws 1220 DEG C of temperature；The drawing of stretching is away from 10mm, and anti-advance is from 1.3mm, cast frequency 100 Time 0.3s is arrheaed in secondary/min, pause；When cast, melt liquid level is 700mm crystallizer away from crystallizer entrance distance.
Cold-rolling process parameter: inflow temperature: 20 DEG C, water feeding pressure: 0.5Mpa；Made-up belt outlet temperature: 350 DEG C.Specifically, Secondary water cooling technological parameter: inflow temperature: 25 DEG C, water feeding pressure: 0.5Mpa.
The temperature of homogenizing annealing is 950 DEG C, annealing time 5h.
The temperature of recrystallization annealing is 400 DEG C, annealing time 3h.
Embodiment 2
A kind of preparation method of high tough corrosion resistant alumin(i)um yellow brass web pre fetching, it the following steps are included:
1) alloy melting: each component is weighed by the weight percent of product embodiments, in N2Under atmosphere successively by copper, aluminium, Micro alloying element, tin, spelter, which are added in the crucible of induction melting furnace, is heated to molten condition, molten alloy surface covering wood Charcoal obtains alloy melt；The micro alloying element is added in the form of intermediate alloy；It is every add a kind of component before, first plus Enter slag former, then stirs, fishes out slag, and cover dry crystalline flake graphite；Smelting temperature before aluminium is added is 1200 DEG C, is added Smelting temperature after aluminium is 1400 DEG C, and aluminium is added before copper is unfused；
2) horizontal casting: alloy melt being added in 1300 DEG C of holding furnace, and making alloy copper liquid is more than crystallizer section Height, then by Ultrasonic probe be inserted into copper alloy liquid level below 5cm, open supersonic generator, electromagnetic induction coil, adopt Cast is carried out with the anti-process flow pushed away of stretching-pause-, obtains slab；It is 2.5A, vibration that supersonic generator, which keeps oscillating current, The dynamic time is 150s；
3) slab is successively subjected to homogenizing annealing, cold rolling, recrystallization annealing, obtains high tough corrosion resistant aldubra and closes Golden web pre fetching.
The maximal input of induction melting furnace is 15kW, voltage of intermediate frequency 520V, electric current of intermediate frequency 22A, frequency of oscillation For 20Hz；The exportable frequency of induction melting furnace is the alternating current of 10kHz, and it is 2.5kHz's that frequency is passed through in electromagnetic inductor Alternating current and generate alternating electromagnetic field.
Pulling-casting process parameter: it rises and draws 1220 DEG C of temperature；The drawing of stretching is away from 10mm, and anti-advance is from 1.3mm, cast frequency 100 Time 0.3s is arrheaed in secondary/min, pause；When cast, melt liquid level is 700mm crystallizer away from crystallizer entrance distance.
Cold-rolling process parameter: inflow temperature: 20 DEG C, water feeding pressure: 0.5Mpa；Made-up belt outlet temperature: 350 DEG C.Specifically, Secondary water cooling technological parameter: inflow temperature: 25 DEG C, water feeding pressure: 0.5Mpa.
The temperature of homogenizing annealing is 1050 DEG C, annealing time 1h.
The temperature of recrystallization annealing is 600 DEG C, annealing time 1h.
Embodiment 3
A kind of preparation method of high tough corrosion resistant alumin(i)um yellow brass web pre fetching, it the following steps are included:
1) alloy melting: each component is weighed by the weight percent of product embodiments, in N2Under atmosphere successively by copper, aluminium, Micro alloying element, tin, spelter, which are added in the crucible of induction melting furnace, is heated to molten condition, molten alloy surface covering wood Charcoal obtains alloy melt；The micro alloying element is added in the form of intermediate alloy；It is every add a kind of component before, first plus Enter slag former, then stirs, fishes out slag, and cover dry crystalline flake graphite；Smelting temperature before aluminium is added is 1180 DEG C, is added Smelting temperature after aluminium is 1300 DEG C, and aluminium is added before copper is unfused；
2) horizontal casting: alloy melt being added in 1250 DEG C of holding furnace, and making alloy copper liquid is more than crystallizer section Height, then by Ultrasonic probe be inserted into copper alloy liquid level below 4m, open supersonic generator, electromagnetic induction coil, adopt Cast is carried out with the anti-process flow pushed away of stretching-pause-, obtains slab；It is 2A, vibration that supersonic generator, which keeps oscillating current, Time is 120s；
3) slab is successively subjected to homogenizing annealing, cold rolling, recrystallization annealing, obtains high tough corrosion resistant aldubra and closes Golden web pre fetching.
The maximal input of induction melting furnace is 15kW, voltage of intermediate frequency 220V, electric current of intermediate frequency 15A, frequency of oscillation For 10Hz；The exportable frequency of induction melting furnace is the alternating current of 5kHz, and it is 2.5kHz's that frequency is passed through in electromagnetic inductor Alternating current and generate alternating electromagnetic field.
Pulling-casting process parameter: it rises and draws 1220 DEG C of temperature；The drawing of stretching is away from 10mm, and anti-advance is from 1.3mm, cast frequency 100 Time 0.3s is arrheaed in secondary/min, pause；When cast, melt liquid level is 700mm crystallizer away from crystallizer entrance distance.
Cold-rolling process parameter: inflow temperature: 20 DEG C, water feeding pressure: 0.5Mpa；Made-up belt outlet temperature: 350 DEG C.Specifically, Secondary water cooling technological parameter: inflow temperature: 25 DEG C, water feeding pressure: 0.5Mpa.
The temperature of homogenizing annealing is 1000 DEG C, annealing time 3h.
The temperature of recrystallization annealing is 500 DEG C, annealing time 2h.
Comparative example 1
Difference from example 1 is that common heating method melting does not have electromagnetism sense without induction melting furnace yet Coil is answered, does not apply electromagnetic field.
Comparative example 2
Difference from example 1 is that not applying ultrasonic field in step 2) without supersonic generator.
Comparative example 3
Difference from example 1 is that the frequency of oscillation of induction melting furnace is 0.5Hz；Induction melting furnace can be defeated Frequency is the alternating current of 0.5kHz out, and the alternating current that frequency is 1kHz is passed through in electromagnetic inductor and generates alternating electromagnetism ?.
Comparative example 4
Difference from example 1 is that the frequency of oscillation of induction melting furnace is 30Hz；Induction melting furnace it is exportable Frequency is the alternating current of 30kHz, and the alternating current that frequency is 5kHz is passed through in electromagnetic inductor and generates alternating electromagnetic field.
Comparative example 5
Difference from example 1 is that it is 1A, time of vibration 50s that supersonic generator, which keeps oscillating current,.
Comparative example 6
Difference from example 1 is that it is 3A, time of vibration 200s that supersonic generator, which keeps oscillating current,.
Comparative example 7
Difference from example 1 is that both without applying electromagnetic field, also without applying ultrasonic field.
Compared with material property made from 3 preparation method embodiment of table and comparative example
No Tensile strength (MPa) Elongation (%) Dezincification corrosion depth (μm)
1 480 46 99
2 500 42 90
3 520 40 95
Comparative example 1 405 27 102
Comparative example 2 422 33 119
Comparative example 3 419 32 105
Comparative example 4 400 30 102
Comparative example 5 410 30 120
Comparative example 6 402 28 100
Comparative example 7 385 25 128
As can be seen from Table 3, the alloy of melting is carried out horizontal casting, energy by present invention combination electromagnetism-ULTRASONIC COMPLEX technique Be made intensity height, good toughness, erosion resistance height, corrosion resistance and good alumin(i)um yellow brass web pre fetching.And do not apply electromagnetism And/or ultrasonic field or induction melting furnace, supersonic generator parameter setting not in the scope of protection of the invention, tension Intensity, elongation and corrosion resistance all sharp falls obtain alumin(i)um yellow brass net far away from using preparation method of the present invention The performance of clothing material.

Claims (10)

1. a kind of high tough corrosion resistant alumin(i)um yellow brass web pre fetching, which is characterized in that the weight percent of the material forms Are as follows: Cu 60~72%, Sn 2.0~3.0%, Al 0.8~2%, X10.002~0.2%, X20.02~0.5%, surplus is Zn and inevitable impurity；Wherein X1For at least one of tri- kinds of elements of La, Ce, Y, X2For in two kinds of elements of B, P at least It is a kind of.
2. the tough corrosion resistant alumin(i)um yellow brass web pre fetching of height according to claim 1, which is characterized in that the aluminium is yellow The weight percent of copper alloy netting material forms are as follows: Cu 65~70%, Sn 2.2~2.8%, Al 1~1.8%, X1 0.005~0.15%, X20.05~0.2%, surplus is Zn and inevitable impurity；Wherein X1For tri- kinds of elements of La, Ce, Y At least one of, X2For at least one of two kinds of elements of B, P.
3. the tough corrosion resistant alumin(i)um yellow brass web pre fetching of height according to claim 1, which is characterized in that the X1's Weight percent content is La 0.005~0.185%, Ce 0.005~0.150%, at least one in Y 0.01~0.18% Kind, and X1Total amount be no more than 0.2%.
4. the tough corrosion resistant alumin(i)um yellow brass web pre fetching of height according to claim 1, which is characterized in that the X2's Weight percent content is at least one of B 0.1~0.5%, P 0.02~0.4%, and X2Total amount be no more than 0.5%.
5. the tough corrosion resistant alumin(i)um yellow brass web pre fetching of height according to claim 1, which is characterized in that use the material The etting and net cage for expecting production are applied in sea-farming.
6. based on the preparation method of the described in any item high tough corrosion resistant alumin(i)um yellow brass web pre fetchings of Claims 1 to 5, It is characterized in that, it the following steps are included:
1) alloy melting: weighing each component by weight percentage, in N2Successively by copper, aluminium, micro alloying element, tin, zinc under atmosphere Block, which is added in the crucible of induction melting furnace, is heated to molten condition, and molten alloy surface covers charcoal, obtains alloy melt；It is described Micro alloying element is X1And X2, by X1And X2It is added in the form of intermediate alloy；It is every add a kind of component before, be first added and make Then slag agent stirs, fishes out slag, and covers dry crystalline flake graphite；
2) horizontal casting: alloy melt is added in 1200~1300 DEG C of holding furnace, Ultrasonic probe is then inserted into copper Alloy liquid level is drawn hereinafter, unlatching supersonic generator, electromagnetic induction coil using the anti-process flow pushed away of stretching-pause- Casting, obtains slab；
3) slab is successively subjected to homogenizing annealing, cold rolling, recrystallization annealing, obtains high tough corrosion resistant alumin(i)um yellow brass net Clothing material.
7. the preparation method of the tough corrosion resistant alumin(i)um yellow brass web pre fetching of height according to claim 6, feature exist In the smelting temperature before aluminium is added is 1150~1200 DEG C, and the smelting temperature after addition aluminium is 1200~1400 DEG C, and aluminium exists It is added before copper is unfused.
8. the preparation method of the tough corrosion resistant alumin(i)um yellow brass web pre fetching of height according to claim 6, feature exist In the maximal input of induction melting furnace is 15kW, and voltage of intermediate frequency is 70~520V, and electric current of intermediate frequency is 3~22A, oscillation frequency Rate is 1~20Hz.
9. the preparation method of the tough corrosion resistant alumin(i)um yellow brass web pre fetching of height according to claim 6, feature exist In the exportable frequency of induction melting furnace is the alternating current of l~10kHz, and it is 2.5kHz's that frequency is passed through in electromagnetic inductor Alternating current and generate alternating electromagnetic field.
10. the preparation method of the tough corrosion resistant alumin(i)um yellow brass web pre fetching of height according to claim 6, feature exist In Ultrasonic probe is inserted into 2~5cm of copper alloy liquid level or less, and it is 1.5~2.5A, vibration that supersonic generator, which keeps oscillating current, The dynamic time is 100~150s.
CN201810998830.6A 2018-08-29 2018-08-29 High tough corrosion resistant alumin(i)um yellow brass web pre fetching and preparation method thereof Pending CN109112350A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109868371A (en) * 2019-01-29 2019-06-11 大连交通大学 The guard method of ultrasonic probe
CN112410604A (en) * 2020-11-17 2021-02-26 宁波长振铜业有限公司 Method for reducing impurity aluminum in brass melt

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CN102352452A (en) * 2011-11-02 2012-02-15 中铝洛阳铜业有限公司 Processing process method of corrosion-resistant copper-zinc-aluminum alloy material
WO2015046421A1 (en) * 2013-09-26 2015-04-02 三菱伸銅株式会社 Discoloration-resistant copper alloy and copper alloy member
CN108188362A (en) * 2017-12-15 2018-06-22 中南大学 CuNiSn systems alloy and made-up belt combination outfield horizontal casting preparation method and device

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Publication number Priority date Publication date Assignee Title
CN101244451A (en) * 2008-03-19 2008-08-20 大连理工大学 Method and apparatus for improving horizontal continuous casting billet quality by applying composite field
CN102352452A (en) * 2011-11-02 2012-02-15 中铝洛阳铜业有限公司 Processing process method of corrosion-resistant copper-zinc-aluminum alloy material
WO2015046421A1 (en) * 2013-09-26 2015-04-02 三菱伸銅株式会社 Discoloration-resistant copper alloy and copper alloy member
CN108188362A (en) * 2017-12-15 2018-06-22 中南大学 CuNiSn systems alloy and made-up belt combination outfield horizontal casting preparation method and device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109868371A (en) * 2019-01-29 2019-06-11 大连交通大学 The guard method of ultrasonic probe
CN112410604A (en) * 2020-11-17 2021-02-26 宁波长振铜业有限公司 Method for reducing impurity aluminum in brass melt

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