CN105002394A - Precipitation enhanced type brass alloy and preparation method thereof - Google Patents
Precipitation enhanced type brass alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to precipitation enhanced type brass alloy and a preparation method thereof. The precipitation enhanced type brass alloy is characterized by comprising, by weight, 68%-92% of copper, 6%-30% of zinc, 0.01%-3% of cobalt and 0.01%-0.35% of phosphorus. The weight sum of the copper and the zinc is larger than 96%, and the weight sum of inevitable impurities is smaller than 0.2%. The brass alloy can be used for preparing sheets, bars, plates and the like. The cost of the alloy can be lowered obviously. The precipitation enhanced type brass alloy is lower in stress relaxation rate, more resistant to creep, higher in yield ratio, higher in elasticity modulus and better in electric conductivity.
Description
Technical field
The alloy field that the present invention relates to, specifically refers to a kind of precipitation strength type brass alloys and preparation method.
Background technology
Take tin-phosphor bronze as the high strength of representative, snappiness, antifatigue, resistal be widely used on medical treatment, aviation, communication, automobile, the junctor of the industry such as electric, terminal, rly., spring, switching component.But first, it belongs to bronze series alloy, and copper content is high, and China belongs to copper resource scarcity country, smart copper consumption 8,720,000 tons in 2014, and wherein 3,590,000 tons is import, and the percentage of import reaches 41%, and copper valency continues to keep high-order.And containing high level, more expensive metal Sn in tin-phosphor bronze, the prices of raw and semifnished materials cause this product price to remain high.Along with China's economic enters new normality, market competition is day by day fierce, and enterprise enters the small profits epoch, and active demand reduces each side and becomes originally to improve the level of profitability, for the enterprise of above-mentioned industry, urgently a kind of low cost resilient material meeting service requirements reduces costs.
Brass has good processing performance, mechanical property and corrosion resisting property, is one of most widely used alloy material in non-ferrous metal.In copper zinc alloy, add some functional elements, come from different backgrounds and possess different abilities brass alloys, and it can be made to meet different user demand.And in zinc resource deposit, within 2010, rise, China's mines output increasing degree is comparatively large, and zinc ore deliverability strengthens, and from 2011, Chinese zinc ore concentrate market was in superfluous state, had overstock a large amount of zinc ore concentrate stock.And the raw-material price of zinc is only about 1/3rd of copper valency.Improved the performance of brass by corresponding scheme, to be inevitable trend with the demand meeting above-mentioned industry.
Vehicles Collected from Market there is a few money complex brass elasticity equivalent material, but in actual application, there is many problems.Although reach the service requirements of elasticity of substitution material in the index such as tensile strength, yield strength, but material base attribute causes corresponding stress relaxation resistance, creep-resistant property is worse than phosphor bronze, work-ing life and poor reliability are in phosphor bronze, and environment for use is restricted.In addition, along with lightweight, the miniaturization of above-mentioned industry device used in recent years, to phosphor bronze equivalent material, even phosphor bronze itself, has higher requirement and challenges.Such as, for elastic element, want holding force or screen resilience that miniaturization also keeps meeting service requirements, unique mode is exactly improve the Young's modulus of material, and this index is determined by the base attribute of material, and phosphor bronze Young's modulus is at about 110GPa, and brass class equivalent material is due to the increase of solution strengthening ratio, Young's modulus is reduced further, at about 105GPa, the miniaturization of resilient material Application Areas, light-weighted demand cannot be met.Secondly, in order to seek miniaturization, thin-walled property, require to form the balance that this components and parts material has higher intensity and intensity and unit elongation.As everyone knows, intensity and plasticity are conflicts, and material improves intensity by cold deformation work hardening and unit elongation can be caused to decline, and the plastic working ability of material is reduced, and use is restricted.In addition, the Application Areas of maximum operation (service) temperature is required at some big current, as power connector requires higher electric conductivity, current phosphor bronze electric conductivity, at about 16%IACS, objectively need the equivalent material of more high conductivity to occur, and current equivalent material is as one-ton brass, for the consideration of cost and mechanical property, make more alloying element be solid-solubilized in matrix phase, this makes the lifting of materials conductive rate be subject to great restriction, can only reach about 20%IACS.
As current a brass equivalent material, GB HSn70-1, American Standard C44300, its composition is Cu:70%-73%, Sn:0.9%-1.2%, surplus is Zn, mechanical property can be made to reach the service requirements of above-mentioned industry material by work hardening, but its 1000h stress relaxation-resistant rate under 100 DEG C of 50% yield strength initial stress is only less than 80%, is difficult to meet persistence requirements.
It is a by reducing the tin-phosphor bronze equivalent material that Sn content reduces costs that the Chinese patent application that and for example publication number is CN103088229A is announced.Its main component is Sn:0.01%-2.5%, P:0.01-0.3%, Fe:0.01-0.5, Ni:0.01-0.5%, Mn:0.01-0.1%, and surplus is Cu.According to its specification sheets, properties can meet above-mentioned industry requirement substantially, but electric conductivity is only 10%-16%IACS, and Application Areas is restricted.In addition, the cost range of decrease is little, and while reducing Sn content, Cu content brings up to more than 97%, and the comprehensive cost range of decrease is only 5%-10%.
Summary of the invention
Technical problem to be solved by this invention provides a kind of for the present situation of prior art significantly to reduce cost of alloy and have the precipitation strength type brass alloys of more low-stress relaxation rate, more resistance to creep, more high-yield-ratio, more high elastic coefficient and better electric conductivity.
Another technical problem to be solved by this invention provides a kind of for the present situation of prior art significantly to reduce cost of alloy and have the preparation method of precipitation strength type brass alloys of more low-stress relaxation rate, more resistance to creep, more high-yield-ratio, more high elastic coefficient and better electric conductivity.
The present invention solves the problems of the technologies described above adopted technical scheme: these precipitation strength type brass alloys, it is characterized in that comprising following weight composition:
Wherein copper, zinc two kinds of element sums are greater than 96%wt%, and wherein inevitably foreign matter content sum is less than 0.2%.
The weave construction of these brass alloys is matrix phase and the precipitated phase of Dispersed precipitate on described matrix phase, and wherein said matrix phase is copper zinc α type sosoloid, and described matrix phase area occupied is than>=95%, and described precipitated phase is Co
mp
n, described precipitated phase area occupied is than being 0.01%-5%, and 0.2≤M/N≤3.
Preferably, described Cu content is 69wt%-80.999wt%, and described Zn content is 21wt%-32wt%, and described cobalt contents is 0.05wt%-2.5wt%, and described phosphorus content is 0.01wt%-0.35wt%.
Or described Cu content is 80.9991wt%-92wt%, described Zn content is 10wt%-21wt%, and described cobalt contents is 0.05wt%-2.5wt%, and described phosphorus content is 0.01wt%-0.35wt%.
Further, the massfraction of described cobalt and phosphorus meets 0.45≤([Co]+1)/([P]+2)≤2.
Better, yield strength/tensile strength >=85% of these brass alloys, stress relaxation rate < 15% at 100 DEG C, under 50% yield strength initial stress, 1000H condition.
In above-mentioned each scheme, these brass alloys can also comprise the tin element of 0.01%-3.5wt%.
Further, these brass alloys can also comprise the X of 0.01wt%-4wt%, and described X is selected from least one in the Fe of Mn and 0.01wt%-1.5wt% of Al, 0.01wt%-3.5wt% of Ni, 0.01wt%-4wt% of 0.01wt%-3wt%.
Further, these brass alloys also comprise the Y of 0.0005wt%-1wt%, and selected Y is selected from least one in the RE of V and 0.0005wt%-0.1wt% of Li, 0.0005wt%-0.5wt% of Ca, 0.0005wt%-0.5wt% of B, 0.0005wt%-0.3wt% of Ti, 0.0005wt%-0.3wt% of Mg, 0.001wt%-0.8wt% of Zr, 0.001wt%-0.5wt% of Cr, 0.001wt%-0.2wt% of 0.001wt%-0.3wt%.
In above-mentioned each scheme, the preparation method of precipitation strength type brass alloys, is characterized in that comprising the steps:
Batching → horizontal casting or vertical semicontinuous casting → hot rolling or hot extrusion → solution treatment → once cold rolling or cold drawing → mono-time ageing treatment → secondary cold-rolling or cold drawing → secondary ageing process → tri-time cold rolling or cold drawing → finished product thermal treatment → cleaning;
The casting temperature of wherein said horizontal casting or vertical semicontinuous casting is 1060 DEG C-1260 DEG C; Described hot rolling or extrusion temperature are 700 DEG C-900 DEG C; Described solution treatment is on-line solution, and heat-eliminating medium is air or water, speed of cooling is 10 DEG C/and min-150 DEG C/S; Described once cold rolling or cold drawing working modulus are 5%-95%; A described aging strengthening model temperature is 350 DEG C-650 DEG C, and soaking time is 10min-10h, and rate of heating is 2-50 DEG C/min, and speed of cooling is 5-50 DEG C/min; Described two, three cold rolling or cold drawing working moduluses are 3%-95%, and described secondary ageing thermal treatment temp is 300 DEG C-600 DEG C, and soaking time is 10min-10h, and rate of heating is 2-50 DEG C/min, and speed of cooling is 5-50 DEG C/min; Described finished product thermal treatment temp is 100 DEG C-300 DEG C, and soaking time is 10min-10h, and rate of heating is 2-50 DEG C/min, and speed of cooling is 5-50 DEG C/min.Described cold rolling or cold drawing and aging strengthening model combination process number of times can increase according to product specification or reduce, but at least ensure more than twice.
Or comprise the steps:
Batching → horizontal casting or Continuous Up casting → solution treatment → cold rolling or cold drawing → mono-time ageing treatment → cold rolling or cold-drawn → secondary ageing process → cold drawn or cold-drawn → finished product thermal treatment;
Wherein casting temperature is 1060 DEG C-1260 DEG C, and solution treatment is on-line solution, and heat-eliminating medium is air or water, speed of cooling is 10 DEG C/and min-150 DEG C/S.Cold rolling or cold-drawn working modulus is 5%-95%.A described timeliness aging strengthening model temperature is 350 DEG C-650 DEG C, soaking time is 10min-10h, rate of heating is 2-50 DEG C/min, speed of cooling is 5-50 DEG C/min, described secondary ageing thermal treatment temp is 300 DEG C-600 DEG C, soaking time is 10min-10h, rate of heating is 2-50 DEG C/min, speed of cooling is 5-50 DEG C/min, described finished product destressing aging strengthening model temperature is 100 DEG C-300 DEG C, soaking time is 10min-10h, and rate of heating is 2-50 DEG C/min, and speed of cooling is 5-50 DEG C/min.Described cold rolling or cold drawing and aging strengthening model combination process number of times can increase according to product specification or reduce, but at least ensure more than twice.
The effect of Zn: Zn is solid-solution in Cu in a large number, and content, lower than 38%, all forms αsolidsolution, plays the effect of solution strengthening, forms the matrix of alloy structure.Patent of the present invention passes through control Zn at fine copper matrix solid solution capacity, change lattice distortion degree, to reach the solid solution condition of stable Co and P, it is made still to have larger solid solubility when higher temperature 600 DEG C-800 DEG C, thus realize the supersaturated solid solution that just can produce cobalt phosphorus compound under online water-cooled or air cooling condition, to meet the condition of Precipitation.Described Alloy zinc content is higher than 32%, matrix conductive rate is too low, Young's modulus is too low, use cannot be met, Zn content is lower than 6%, and the lattice distortion that solid solution causes is few, is solid-solution in the stability between lattice and strengthens the limited efficiency of matrix to cobalt phosphorus compound, effective supersaturated solid solution cannot be formed, thus the Precipitation of cobalt phosphorus compound phase cannot be realized.Preferred Zn constituent content is 6.5wt%-29.5wt%, and more preferably Zn constituent content is 7wt%-29wt%.
The effect of Co and P: when adding separately Co element, Co is solid-solution in matrix, only plays the effect of solution strengthening, cannot reach higher intensity, and can reduce Young's modulus, the electric conductivity of material.The effect of deoxygenation refining metal can be played when P element is added separately, increase the mobility of alloy melt, Cu can also be formed with Cu
3p-compound, but P reduces very remarkable to the electric conductivity of material.Co and P adds simultaneously, can form cobalt phosphorus compound, and by solid solution aging technique, compound is separated out, and itself, on matrix, solid solution to enter matrix and reduce Co and the P eliminating of electric conductivity outside matrix, improve the electric conductivity of material by Dispersed precipitate.The existence of Age-prrcipitation Phase, improves Young's modulus and the stress relaxation-resistant ability of material, can limit slippage and the movement of dislocation when cold deformation, forms Cottrell air mass, makes material obtain higher yield strength and yield tensile ratio.Co element worsens more than the hot workability of 3wt% material, lower than 0.01wt%, cannot improve material property by the enough precipitated phase of quantity of formation.P element can produce hot-short more than 0.35% material, the oxidation of aggravation matrix, and seriously reduces electric conductivity, cannot form enough precipitated phases improve material property lower than 0.01wt%.The massfraction wt% of cobalt and phosphorus need meet 0.45≤([Co]+1)/([P]+2)≤2, be less than 0.45 or be greater than 2 time, mechanical property can be caused on the low side, can not service requirements be met.Preferred: the massfraction wt% of cobalt and phosphorus meets 0.5≤([Co]+1)/([P]+2)≤1.75.
When the effect of Sn: Sn can slow down hot-work, dynamic and static state recrystallization process, can promote Zn 600 DEG C-800 DEG C time to the effect of cobalt phosphorus compound at Copper substrate stable existence.In addition, Sn can also pass through solution strengthening effect, improves intensity and the hardness of material.Tin can also suppress dezincify, improves material solidity to corrosion.Sn cannot function as described above lower than 0.01%, and Sn, higher than 3.5%, can produce the segregation of Sn, and there is cracking risk when hot rolling and hot extrusion.Preferred Sn constituent content is 0.05wt%-3.0wt%, and more preferably Sn constituent content is 0.1wt%-2.5wt%.
The effect of Ni, Al, Mn, Fe: wherein the zinc equivalent coefficient of Ni is negative value, can expand alpha phase zone, improves thermotolerance and the hot workability of material, plays the effect of solution strengthening simultaneously, improve material solidity to corrosion.Can also reduce the minimum solid solubility temperature of precipitated phase, Al zinc equivalent coefficient is high, reduces alpha phase zone, has good solution strengthening effect, improves the intensity of material.Ni and Al can also form NiAl hard phase, plays strengthening effect on the one hand, stablizes precipitated phase in addition on the one hand, suppresses the effect that it is grown up.Fe, due to its higher fusing point, when founding as the core of crystallization, plays the effect of crystal grain thinning, improves the mechanical property of material.Mn is a kind of reductor, reduces the oxygen level in melt, improves softening temperature and the stress relaxation resistance of material simultaneously.Ni, Al, Mn, Fe content is less than 0.01% and can not functions as described above, Ni is greater than 3%, Al is greater than 4%, Mn is greater than 3.5%, Fe is greater than 1.5%, seriously can reduce electric conductivity, reduces Young's modulus, cannot meet the user demand of this kind of material, Fe content can the serious corrosion resistance nature reducing material more than 1.5% simultaneously.Preferred: Ni:0.02wt%-2wt%, Al:0.02wt%-3.5wt%, Mn:0.02wt%-2.5wt%, Fe:0.015wt%-1.0wt%; More preferably: Ni:0.03wt%-1.5wt%, Al:0.03wt%-3.0wt%, Mn:0.03wt%-2.0wt%, Fe:0.02wt%-0.8wt%.
The effect of B, Mg, Ca, Li: wherein B, Mg can suppress crystal boundary to react, grain growth during obstruction alloy aging thermal treatment, crystal grain thinning, stablizes cobalt phosphorus precipitated phase, reduces the hardness after alloy solid solution process, road cold-forming property after improving.B, Ca can improve the anti-dezincify ability of brass, improve solidity to corrosion.B, Mg can improve the stress relaxation resistance of material, and improve the cold and hot working performance of material, Li, Ca can improve the machining property of material.Preferred B:0.001wt%-0.2wt%, Mg:0.005wt%-0.3wt%, Ca:0.001wt%-0.25wt%, Li:0.001wt%-0.4wt%; More preferably B:0.002wt%-0.15wt%, Mg:0.01wt%-0.2wt%, Ca:0.002wt%-0.2wt%, Li:0.005wt%-0.3wt%.
The effect of Cr, Zr: Cr can improve the corrosion stability of material in high temperature seawater, Cr and Zr can improve material softening temperature and hot strength, promotes the high-temperature stability of material, improves its stress relaxation resistance.Cr and Zr adds simultaneously, can form Cr
2zr compound, when adding separately both improvement result is better than, also can improve anti-caking and the welding property of material simultaneously.Cr content can not play corresponding effect lower than 0.001%, Zr content lower than 0.001, and Cr content can make the production cost of material and material cost significantly raise higher than 0.3%, Zr content higher than 0.2%.Preferred Cr:0.005wt%-0.25wt%, Zr:0.005wt%-0.15wt%; More preferably: Cr:0.008wt%-0.20wt%, Zr:0.008wt%-0.10wt%.
The effect of Ti, V, Re: Ti, V are added to crystal grain thinning in brass, improves intensity and unit elongation, can stablize the size of precipitation strength phase simultaneously, suppress it to grow up further in ag(e)ing process.Rare earth can removal of impurities when melting, deoxygenation, improves the purity of metal, crystal grain thinning.Content of rare earth, more than 0.1wt%, can form high-temperature oxide and be mingled with, and worsen metallicity, rare earth does not have above-mentioned effect lower than 0.0002wt%.Preferred: Ti:0.005wt%-0.6wt%, V:0.001wt%-0.4wt%, RE (rare earth): 0.0008wt%-0.08wt%; More preferably Ti:0.008wt%-0.5wt%, V:0.01wt%-0.35wt%, RE (rare earth): 0.001wt%-0.05wt%.
Fine copper has very high electric conductivity, but its low strength, in order to make the demand meeting different application direction, taking different schedule of reinforcements to improve its mechanical property, common are solution strengthening, work hardening, second-phase strength, Precipitation is strengthened, refined crystalline strengthening.For brass, conventional has solution strengthening, workhardness and refined crystalline strengthening, Precipitation strengthening is mainly used in bronze matrix, because brass self fusing point is low, and Precipitation strengthening needs higher solid solubility temperature to ensure, and the first solid solution of precipitated phase enters in matrix to form supersaturated solid solution, therefore be difficult on brass base, realize Precipitation strengthening, a kind of Cu-Co-P alloy as described in patent No. CN 103154285 A, need to heat hot rolling at 925 DEG C-1025 DEG C, then cool fast, guarantee forms supersaturated solid solution, can effectively separate out to meet next step precipitated phase.This patent is by adjustment copper zinc ratio, control the lattice distortion degree of copper zinc sosoloid, the stability of cobalt phosphorus compound between its lattice during solid solution can be improved, temperature precipitated phase being formed in the base supersaturated solid solution is reduced to 600 DEG C about-800 DEG C, its high temperature more than 600 DEG C is made still to have higher solid solubility, solve above-mentioned brass base mutually in cannot form the difficult problem of supersaturated solid solution, thus ensure Co
mp
ncompound be able in further aging technique brass base mutually on separate out formed.
A kind of precipitation strength type one-ton brass of the present invention, its microtexture has following characteristics: matrix phase is that the face-centered cubic αsolidsolution that copper and zinc are formed is formed, its area accounting >=95%, cobalt element and phosphoric demand fulfillment condition once in alloy: the massfraction wt% of cobalt and phosphorus meets 0.4≤([Co]+1)/([P]+2)≤2, such guarantee cobalt phosphorus compound is effectively separated out, and ensures that the mechanical property of material and physicals reach design objective.Cobalt element part be solid-solubilized in copper zinc solid solution matrix mutually in, another part and phosphoric form cobalt phosphorus compound Co
mp
n, separate out after solid-solution and aging heat treatment, Dispersed precipitate is on matrix phase, and compound Atom mol ratio meets 0.2≤M/N≤3, and compound shape is spherical, elliposoidal or bar shaped, and the area accounting of cobalt phosphorus compound is between 0.01%-5%.
A kind of precipitation strength type brass of the present invention, except adopting solution strengthening, outside cold deformation strengthening, also achieve Precipitation strengthening, contrast through great many of experiments, its mechanical property has following characteristics: the alloy that effective precipitated phase exists and the comparative group alloy existed without precipitated phase, under identical tensile strength, there is higher yield strength, higher unit elongation, as under 575MPa tensile strength, its yield strength of the group having precipitation strength to produce mutually can reach 565MPa, yield strength is 99.17% with tensile strength ratio, unit elongation can reach 19% simultaneously, and the comparative group not having precipitation strength to produce, under 564MPa tensile strength, yield strength is only 459MPa, yield strength is 80% with tensile strength ratio, and now unit elongation only has 5%.Meanwhile, material of the present invention has higher Young's modulus, and experimental data display Young's modulus can reach 110GPa-128GPa, and the comparative group Young's modulus not having precipitation strength to produce mutually only has about 105GPa.These characteristics precipitation strength of the present invention type brass has better elasticity, better zero defect deformability, and under equal requirement, material can be thinner thinner, can meet the lightweight of industry described in background, miniature requirement.
A kind of precipitation strength type alloy of the present invention is due to the generation of Age-prrcipitation Phase, make originally to be solid-solubilized in the Co element in matrix phase with the form Dispersed precipitate of precipitated phase on matrix phase, to purify matrix phase, reduce the lattice distortion that causes due to solid solution to the impact of electronic conduction, improve materials conductive rate, 5%-12%IACS can be improved on year-on-year basis, can reach 40%IACS, and only having 15%IACS with C51900 tin-phosphor bronze, the electric conductivity that patent No. CN 104232987 announces is 25%-32%IACS.
The stress relaxation of material is in fact applying the phenomenon lower than there is the distortion of compacted property during its proof stress to material, and it creating can not the viscous deformation that reverses of resilience, causes the screen resilience of material, holding force to decline, thus can not meet user demand.A kind of precipitation strength alloy of the present invention is due to the generation of precipitation strength phase, hindering expansion, the slippage of dislocation when there is creep, climbing, improve elastic limit of materials simultaneously, from the stress relaxation resistance improving material, reduce stress relaxation rate.As embodiment 87, material 100 DEG C, 1000h, relaxation rate is 5% under 50% yield strength initial stress, and the embodiment 83 not having precipitation strength to produce mutually, under similarity condition, stress relaxation rate is 15%.Introduce in background, it is low that current brass substitutes phosphor bronze material stress relaxation resistance, material as a kind of in patent No. TW201307585A1 cloth, and under H/2 state material 100 DEG C, 1000h, 50% yield strength initial stress, relaxation rate is 17%; Under C51900H/2 state material 100 DEG C, 1000h, 50% yield strength initial stress, relaxation rate is 10%.Can find out, separate out the precipitated phase of technique generation through solid solution aging, significantly improve the stress relaxation resistance of material, compensate for a significant deficiency of brass equivalent material.
In sum, precipitation strength type brass alloys of the present invention, there is excellent mechanical property, tensile strength and yield strength can reach more than 850MPa, yield tensile ratio can reach more than 95%, and electric conductivity can reach 40%IACS, and stress relaxation rate can lower than 10%, have the advantage of low cost concurrently, 8%-20% lower than existing C51900 tin-phosphor bronze simultaneously.
Accompanying drawing explanation
Fig. 1 makes the metallograph of 1000 times, sample for composition described in the embodiment of the present invention 11; Wherein yl moiety is matrix phase, and the dark-coloured pointing object (what have is black) in black box is Co
mp
nprecipitated phase, the part for precipitated phase marked in square frame.
Fig. 2 makes the stereoscan photograph of 10000 times, sample for composition described in the embodiment of the present invention 10; The light block (broken white) marked in black box is Co
mp
nprecipitated phase.
Fig. 3 makes the stereoscan photograph of 5000 times, sample for composition described in the embodiment of the present invention 11; The light block (broken white) marked in black box is Co
mp
nprecipitated phase.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1-45
Wherein the alloy of embodiment 1 is GB H70 (American Standard C26000), the alloy of embodiment 2 is GB HSn70-1 (American Standard C44300), the alloy of embodiment 26 is H80 (American Standard C24000), the alloy of embodiment 27 is QSn6.5-0.1 (American Standard C51900), the alloy of embodiment 35 is H85 (American Standard C23000), and the alloy of embodiment 44 is H90 (American Standard C22000).
Embodiment 3-17: each group is prepared burden according to design mix respectively, and wherein Mg and P is respectively with Cu-Mg master alloy, and Cu-P master alloy adds.Each assembly material is founding ingot casting in 10Kg intermediate frequency furnace respectively, is lathed Φ 50 and extrudes ingot casting, is squeezed into Φ 15 blank, blank water-cooled.As shown in Table 1 and Table 2, described composition is composition after stove to each case study on implementation composition, and the blank after having extruded samples.Extrusion billet is processed successively as follows: DEG C aging strengthening model 4h → 20% working modulus cold drawing → 280 DEG C aging strengthening model 3h → cleaning of DEG C aging strengthening model 5h → 30% working modulus cold drawing → 450,60% working modulus cold drawing → 550.Finished product is processed into Φ 7 standard pull tension sample, 10 tons of hydraulic drawbench carries out tensile test to sample, tests its tensile strength, yield strength, unit elongation, Young's modulus.Finished product is cut into 100cm length electric bridge tester and measures its electric conductivity.Embodiment 1-45 composition and performance test data are as shown in Table 1 and Table 2.
Table 1 embodiment 1-20 composition proportion and performance comparison table thereof
Table 2 embodiment 21-45 composition proportion and performance comparison table thereof
Embodiment 46-55
For the production of bar, comprise embodiment 46-55, each embodiment is prepared burden according to design mix, and P adds in CuP master alloy mode.Shown in each case study on implementation component list 3, described composition is composition after stove, and the blank after having extruded samples.
Wherein embodiment 46-50 is in main frequency furnace melting, and smelting temperature is 1080 DEG C-1180 DEG C, adopts vertical semi-continuous casting Φ 170mm ingot casting.Embodiment 51-55 is in intermediate frequency furnace melting, and smelting temperature 1150 DEG C-1250 DEG C, the stove that falls after alloying completes enters intermediate frequency holding furnace, adopts horizontal continuous-casting to produce Φ 170mm ingot casting.
At the straight rod of 1250T horizontal extruder double fluid water seal extruding Φ 15.Wherein the extrusion temperature of embodiment 46-50 is 700 DEG C-780 DEG C, the extrusion temperature of embodiment 51-55 780 DEG C-860 DEG C.
Extrusion billet is processed successively as follows: DEG C aging strengthening model 4h → 20% working modulus cold drawing → 280 DEG C aging strengthening model 3h → cleaning of DEG C aging strengthening model 5h → 30% working modulus cold drawing → 450,60% working modulus cold drawing → 550.Finished product is processed into Φ 7 standard pull tension sample, 10T hydraulic drawbench carries out tensile test to sample, tests its tensile strength, yield strength, unit elongation, Young's modulus.Finished product is cut into 100cm length electric bridge tester and measures its electric conductivity.Embodiment 46-55 composition and performance test data as shown in table 3.
Table 3 embodiment 46-55 composition proportion and performance comparison table thereof
Embodiment 56-65
For the production of wire rod, comprise embodiment 56-65, each embodiment is prepared burden according to design mix respectively, and wherein P adds in CuP master alloy mode.Wherein embodiment 56-58 adopts and carries out vertical semicontinuous casting mode with the identical processing parameter of embodiment 46-55 and produce Φ 170mm ingot casting, and embodiment 59-61 employing is carried out horizontal continuous-casting mode with the identical processing parameter of embodiment 46-55 and produced Φ 170mm ingot casting.Embodiment 62-65 adopts intermediate frequency furnace melting, smelting temperature 1150 DEG C-1250 DEG C, and the stove that falls after alloying completes enters power frequency holding furnace and carries out horizontal continuous-casting production Φ 8 continuous casting circle blank, and blank adopts secondary cooling water water-cooled after going out crystallizer.Each case study on implementation composition is as shown in table 4, and described composition is composition after stove, and case 56-61 blank after extrusion samples, and case 62-65 samples on continuously cast bloom.
In scheme 56-61, Φ 170 ingot casting is at 1250T horizontal extruder extruding Φ 8 astragal base.All line bases are prepared burden according to design mix, after stove, composition such as following technique manufactures a finished product: 50% cold working rate 1200 drawing of falling machine drawing-(continuously cast bloom, falling one 0.15mm is carried out in machine drawing to dig skin, removes surperficial casting flaw) → 550 DEG C aging strengthening model 5h → 30% working modulus 800 drawing of falling machine drawing → 450 DEG C aging strengthening model 4h → 50% working modulus in Large Scale and Continuous drawing aging strengthening model machine drawing → 50% working modulus in medium-sized continuous drawing aging strengthening model machine drawing-30% working modulus at small-sized continuous drawing aging strengthening model machine drawing final product.Finished product intercepts 50cm in its mechanical property of the raw test of the special 5T hydraulic drawbench of wire rod, intercepts 1m and test its electric conductivity on bridge test instrument.Embodiment 56-65 composition and performance test data as shown in table 4.
Table 4 embodiment 56-65 composition proportion and performance comparison table thereof
Embodiment 66-80
For the production of band.Wherein embodiment 66 is QSn6.5-0.1 (American Standard C51900).All the other each embodiments are prepared burden according to design mix, and wherein P, Cr, Zr, B, Mg add in CuP, CuCr, CuZr, CuB, CuMg master alloy mode respectively.Above-mentioned materials is carried out melting at intermediate frequency furnace respectively, smelting temperature 1080 DEG C-1280 DEG C, pours holding furnace into after alloying completes, and carries out horizontal continuous-casting and produces the thick made-up belt of 15mm, casting temp 1060 DEG C-1260 DEG C, made-up belt carries out online water-cooled in crystallizer outlet.Each case study on implementation composition is as shown in table 5, and described composition is composition after stove, and the made-up belt of continuous casting samples.Each group of made-up belt carries out finished product production with following technique.Milling face → 80% working modulus is cold rolling → and 550 DEG C of aging strengthening model → 60% working moduluses are cold rolling → and 500 DEG C of aging strengthening model → 20% working moduluses are cold rolling → 280 DEG C of finished products → cleanings.Finished product is cut into 50mm wide, the sample that 250mm is long, is cut into standard dog bone sample in hydraulic press upper punch, tests its mechanical property with 10T hydraulic drawing trier.Finished product is cut into 20mm × 20mm square sample, tests its electric conductivity with eddy current conductivity apparatus.Embodiment 66-80 composition and properties as shown in table 5.
Table 5 embodiment 66-80 composition proportion and performance comparison table thereof
Embodiment 81-95
Be applied to band to produce.Wherein embodiment 81 is CuSn3Zn9 (American Standard C42500).Embodiment 82 is GB H70 (American Standard C26000), embodiment 83 is GB HSn70-1 (American Standard C44300), embodiment 84 is H80 (American Standard C24000), embodiment 85 is each embodiment of H90 (American Standard C22000) 86 for CuSn2P0.1 (American Standard C50715) is comparative example, prepare burden according to design mix for each group, wherein P, Cr, Zr, Ti, Mg add in CuP, CuCr, CuZr, CuTi, CuMg master alloy mode respectively, melting is carried out respectively, smelting temperature 1080 DEG C-1280 DEG C at intermediate frequency furnace.Vertical semicontinuous casting is adopted to produce 220mm × 400mm ingot casting.Each group of ingot casting carries out hot rolling cogging, sotck thinkness 15mm respectively, hot-rolled temperature 750 DEG C-880 DEG C, and hot rolling blank carries out on-line solution, directly cools with water.Each case study on implementation composition is as shown in table 6, and described composition is composition after stove, and the blank after hot rolling completes samples.
Each assembly material is processed according to technique below: and milling face → 80% working modulus is cold rolling → 550 DEG C of aging strengthening model → 60% working moduluses are cold rolling → and 500 DEG C of aging strengthening model → 20% working moduluses are cold rolling → 280 DEG C of finished products → cleanings.Finished product is cut into 50mm wide, the sample that 250mm is long, is cut into standard dog bone sample in hydraulic press upper punch, tests its mechanical property with 10T hydraulic drawing trier.Finished product is cut into 20mm × 20mm square sample, tests its electric conductivity with eddy current conductivity apparatus.Embodiment 81-95 composition and properties as shown in table 6.
Table 6 embodiment 81-95 composition proportion and performance comparison table thereof
Choose the alloy of different embodiment group, the stress relaxation resistance of test material.Test is carried out according to ASTME328-2002 (2008) standard, to the initial stress of socle girder loading 50% this sample yield strength that respective samples is formed, and its draught of survey record.Then at 100 DEG C and 125 DEG C, be incubated 1000h respectively, measure its springback capacity.According to test data, the stress relaxation rate of Calculating material, calculation formula is: stress relaxation rate=(draught-springback capacity)/draught × 100%, result is as shown in table 7.
Table 7 different comparative example stress relaxation resistance data sheet
As above table 7, case study on implementation 66 is conventional tin-phosphor bronze C51900, case study on implementation 67,68,71,72,80 is heterogeneity alloy described in patent of the present invention, containing CoxPy precipitation strength phase in matrix, contrast can find that its stress relaxation rate is less than the case 66 of contrast, and resistance to persistence can obviously be promoted.Contrast 67 and 69,70, contrasts 71 and 72, in the case having precipitated phase to produce equally, because Cr, Zr, Mg, B trace alloying element adds, reduce further stress relaxation rate, improve the durability performance of material.Case study on implementation 82 is conventional H 70 brass, stress relaxation rate is greater than 30%, case study on implementation 83 is GB HSn70-1, stress relaxation rate is greater than 15%, case study on implementation 86 is American Standard C50715, its stress relaxation rate is greater than 10%, and case study on implementation 87,88,89,91,92,94,95 is alloy described in patent of the present invention, containing Co in its matrix
mp
nprecipitation strength phase, stress relaxation rate is generally lower than contrast case, and endurance quality gets a promotion.
Claims (13)
1. precipitation strength type brass alloys, is characterized in that comprising following weight composition:
Wherein copper, zinc two kinds of element sums are greater than 96%wt%, and wherein inevitably foreign matter content sum is less than 0.2%.
2. precipitation strength type brass alloys according to claim 1, it is characterized in that the weave construction of these brass alloys is matrix phase and the precipitated phase of Dispersed precipitate on described matrix phase, wherein said matrix phase is copper zinc α type sosoloid, described matrix phase area occupied is than>=95%, and described precipitated phase is Co
mp
n, described precipitated phase area occupied is than being 0.01%-5%, and 0.2≤M/N≤3.
3. precipitation strength type brass alloys according to claim 2, it is characterized in that described Cu content is 69wt%-80.8wt%, described Zn content is 21wt%-32wt%, and described cobalt contents is 0.05wt%-2.5wt%, and described phosphorus content is 0.01wt%-0.35wt%.
4. precipitation strength type brass alloys according to claim 2, it is characterized in that described Cu content is 80.9wt%-92wt%, described Zn content is 10wt%-21wt%, and described cobalt contents is 0.05wt%-2.5wt%, and described phosphorus content is 0.01wt%-0.35wt%.
5. precipitation strength type brass alloys according to claim 2, is characterized in that the massfraction of described cobalt and phosphorus meets 0.45≤([Co]+1)/([P]+2)≤2.
6. precipitation strength type brass alloys according to claim 2, it is characterized in that yield strength/tensile strength >=85% of these brass alloys, stress relaxation rate < 15% at 100 DEG C, under 50% yield strength initial stress, 1000H condition.
7. the precipitation strength type brass alloys according to the arbitrary claim of claim 1 to 6, is characterized in that these brass alloys also comprise the tin element of 0.01%-3.5wt%.
8. the precipitation strength type brass alloys according to the arbitrary claim of claim 1 to 6, it is characterized in that these brass alloys also comprise the X of 0.01wt%-4wt%, described X is selected from least one in the Fe of Mn and 0.01wt%-1.5wt% of Al, 0.01wt%-3.5wt% of Ni, 0.01wt%-4wt% of 0.01wt%-3wt%.
9. precipitation strength type brass alloys according to claim 7, it is characterized in that these brass alloys also comprise the X of 0.01wt%-4wt%, described X is selected from least one in the Fe of Mn and 0.01wt%-1.5wt% of Al, 0.01wt%-3.5wt% of Ni, 0.01wt%-4wt% of 0.01wt%-3wt%.
10. the precipitation strength type brass alloys according to the arbitrary claim of claim 1 to 6, it is characterized in that these brass alloys also comprise the Y of 0.0005wt%-1wt%, selected Y is selected from least one in the RE of V and 0.0005wt%-0.1wt% of Li, 0.0005wt%-0.5wt% of Ca, 0.0005wt%-0.5wt% of B, 0.0005wt%-0.3wt% of Ti, 0.0005wt%-0.3wt% of Mg, 0.001wt%-0.8wt% of Zr, 0.001wt%-0.5wt% of Cr, 0.001wt%-0.2wt% of 0.001wt%-0.3wt%.
11. precipitation strength type brass alloys according to claim 9, it is characterized in that these brass alloys also comprise the Y of 0.0005wt%-1wt%, selected Y is selected from least one in the RE of V and 0.0005wt%-0.1wt% of Li, 0.0005wt%-0.5wt% of Ca, 0.0005wt%-0.5wt% of B, 0.0005wt%-0.3wt% of Ti, 0.0005wt%-0.3wt% of Mg, 0.001wt%-0.8wt% of Zr, 0.001wt%-0.5wt% of Cr, 0.001wt%-0.2wt% of 0.001wt%-0.3wt%.
The preparation method of the precipitation strength type brass alloys as described in 12. claims as arbitrary in claim 1 to 11, is characterized in that comprising the steps:
Batching → horizontal casting or vertical semicontinuous casting → hot rolling or hot extrusion → solution treatment → once cold rolling or cold drawing → mono-time ageing treatment → secondary cold-rolling or cold drawing → secondary ageing process → tri-time cold rolling or cold drawing → finished product thermal treatment → cleaning;
The casting temperature of wherein said horizontal casting or vertical semicontinuous casting is 1060 DEG C-1260 DEG C; Described hot rolling or extrusion temperature are 700 DEG C-900 DEG C; Described solution treatment is on-line solution, and heat-eliminating medium is air or water, speed of cooling is 10 DEG C/and min-150 DEG C/S; Described once cold rolling or cold drawing working modulus are 5%-95%; A described aging strengthening model temperature is 350 DEG C-650 DEG C, and soaking time is 10min-10h, and rate of heating is 2-50 DEG C/min, and speed of cooling is 5-50 DEG C/min; Described two, three cold rolling or cold drawing working moduluses are 3%-95%, and described secondary ageing thermal treatment temp is 300 DEG C-600 DEG C, and soaking time is 10min-10h, and rate of heating is 2-50 DEG C/min, and speed of cooling is 5-50 DEG C/min; Described finished product thermal treatment temp is 100 DEG C-300 DEG C, and soaking time is 10min-10h, and rate of heating is 2-50 DEG C/min, and speed of cooling is 5-50 DEG C/min.
The preparation method of the precipitation strength type brass alloys as described in 13. claims as arbitrary in claim 1 to 11, is characterized in that comprising the steps:
Batching → horizontal casting or Continuous Up casting → solution treatment → cold rolling or cold drawing → mono-time ageing treatment → cold rolling or cold-drawn → secondary ageing process → cold drawn or cold-drawn → finished product thermal treatment;
Wherein casting temperature is 1060 DEG C-1260 DEG C, and solution treatment is on-line solution, and heat-eliminating medium is air or water, speed of cooling is 10 DEG C/and min-150 DEG C/S; Cold rolling or cold-drawn working modulus is 5%-95%; A described aging strengthening model temperature is 350 DEG C-650 DEG C, soaking time is 10min-10h, rate of heating is 2-50 DEG C/min, speed of cooling is 5-50 DEG C/min, described secondary ageing thermal treatment temp is 300 DEG C-600 DEG C, soaking time is 10min-10h, rate of heating is 2-50 DEG C/min, speed of cooling is 5-50 DEG C/min, described finished product destressing aging strengthening model temperature is 100 DEG C-300 DEG C, soaking time is 10min-10h, and rate of heating is 2-50 DEG C/min, and speed of cooling is 5-50 DEG C/min.
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