CN102925743A - Lead-free wear-resistant copper alloy and preparation method thereof - Google Patents
Lead-free wear-resistant copper alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses lead-free wear-resistant copper alloy comprising, by weight, 55%-56% of copper, 0.01%-6.0% of aluminum, 0.5%-5.0% of manganese, 0.3%-3.0% of silicon, 0.0001%-0.01% of cerium, and/or 0.001%-2.0% of cobalt, and/or 0.001%-2.0% of chromium, less than 0.01% of lead, and the balance of zinc and inevitable impurities. The lead-free wear-resistant copper alloy has the advantages of being good in wear-resistant performance, low in friction coefficient, high in mechanical performance, and good in heat stability. Besides, the weight ratio of the lead to the copper alloy is less than or equal to 0.01%, so the copper alloy meets the lead-free requirements of raw materials in the whole manufacturing industry. The invention further discloses a preparation method thereof. Finished products are produced after scalping, stretching and annealing, so the method reduces the number of a plurality of stretching and annealing processes, shortens production periods, improves efficiency, and has the advantages of being low in casting cost and simple in production process and the like.
Description
Technical field
The present invention relates to a kind of unleaded wear-resistant copper alloy and preparation method thereof.
Background technology
Existing wear-resistant copper alloy is (such as the CuZn40Al2 of German standard, the C67420 of USS, the C86300 alloy of USS) because of its good mechanical property, wear resisting property, hot workability, be widely used in the manufacturings such as engineering machinery, automobile component, hydraulic pressure, wear-resistant copper alloy at home and abroad market consumption is all larger.As everyone knows, leaded component can cause serious environmental pollution in production or use procedure, are detrimental to health, and the U.S., European Union etc. in succession put into effect relevant laws and regulations lead content in the component is controlled.Now more to the research without leaded brass both at home and abroad, and also obtained significant progress.But the research to unleaded wear-resistant copper alloy is less.Promulgation along with ROSH instruction (parliament of European Union and EU Council " about special harmful substance illegal instruction in electronic apparatus ") and California, USA bill, more and more urgent to the unleaded demand of whole manufacturing starting material, the industry leading enterprises such as lot of domestic and international engineering machinery, hydraulic pressure, automobile component have proposed requirement to copper alloy is unleaded.Therefore it is extremely urgent to study a kind of unleaded wear-resistant copper alloy.
In recent years, both at home and abroad the research of unleaded wear-resistant copper alloy also had made some progress, for example disclose environment-friendly manganese brass alloy and manufacture method thereof on the Intellectual Property Right Bureau of the RPC website, its alloy composition (weight percent) contains the Cu of 55 ~ 65wt%, the Mn of 1.0 ~ 6.5wt%, 0.2 the Al of ~ 3.0wt%, the Fe of 0 ~ 3.0wt%, the Sn of 0.3 ~ 2.0wt%, the Mg of 0.01 ~ 0.3wt%, the Bi of 0 ~ 0.3wt% and/or the Pb of 0 ~ 0.2wt%, all the other are Zn and other inevitable impurity.This alloy has excellent mechanical property, castability, machinability and solidity to corrosion, especially anticorrosion stress-resistant performance, also has the casting cost low, the advantages such as production technique is simple, be suitable for forging, the component of casting and machining and the processing of other manufacture method, be particularly suitable for forging, faucet body and the valve of casting and machining.But this alloy has added bismuth element, because the cost of bismuth is higher, and world resource closes on exhaustion in the making processes, and competitive power is not strong.And along with the appearance of the relevant laws and regulations regulations of manufacturing, require lead amount≤0.01wt% in the alloy, and the lead content of above-mentioned alloy is controlled at 0 ~ 0.2wt%, do not satisfy the requirement of regulations.
Summary of the invention
The technical problem to be solved in the present invention is for above-mentioned deficiency of the prior art, and a kind of unleaded wear-resistant copper alloy with excellent mechanical property, low-friction coefficient, high wear resistance performance, good thermostability and excellent hot workability is provided.
Technical scheme of the present invention is: a kind of unleaded wear-resistant copper alloy, described alloy comprises the component of following weight percent: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, and/or cobalt 0.001% ~ 2.0%, and/or chromium 0.001% ~ 2.0%, plumbous≤0.01%, surplus is zinc and inevitable impurity.
Further, described alloy also comprises one or more in iron, tin, the nickel, and its weight percent is iron 0.3% ~ 2.0%, tin 0.2% ~ 1.2%, nickel 1.0% ~ 4.0%.
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, cobalt 0.001% ~ 2.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, cobalt 0.001% ~ 2.0%, iron 0.3% ~ 2.0%, tin 0.2% ~ 1.2%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, cobalt 0.001% ~ 2.0%, nickel 1.0% ~ 4.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, cobalt 0.001% ~ 2.0%, nickel 1.0% ~ 4.0%, iron 0.3% ~ 2.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55% ~ 65%, and aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, chromium 0.001% ~ 2.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, chromium 0.001% ~ 2.0%, iron 0.3% ~ 2.0%, tin 0.2% ~ 1.2%,, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, chromium 0.001% ~ 2.0%, cobalt 0.0001% ~ 2.0%, nickel 1.0% ~ 4.0%, iron 0.3% ~ 2.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
Another technical problem that the present invention will solve provides the preparation method of above-mentioned unleaded wear-resistant copper alloy, the method comprises: batching, melting, horizontal casting billet or D.C.casting billet, push, strip off the skin, stretch, annealing, alignment, heat-treat at last and obtain finished product, wherein said smelting temperature is 1050 ~ 1150 ℃, described horizontal casting temperature is 920 ~ 980 ℃, described D.C.casting temperature is 980 ~ 1050 ℃, described extrusion temperature is 600 ~ 720 ℃, thermal treatment temp is 260 ~ 340 ℃, and heat treatment time is 2 ~ 6h.
The metallographic structure of above-mentioned unleaded wear-resistant copper alloy for mixing, its phase composite is: take β mutually as main, the Compound Phases such as 1 ~ 20% α phase and 1 ~ 6% silicomanganese, ferro-aluminum, nisiloy.Because β is mutually hard and crisp, in working angles, easily form chip breaking, make material in machining process, not be prone to problems such as twining cutter, therefore increase the machinability that β can improve material mutually.
Add aluminium in the unleaded wear-resistant copper alloy of the present invention and by solution strengthening its intensity and hardness are improved, and can promote the flowability of alloy, be conducive to the Foundry Production of alloy.The virtual zinc equivalent coefficient of aluminium is 6, can enlarge significantly the β phase region, effectively alleviate the unleaded cutting ability that causes of material and descend, aluminium can form fine and close aluminium sesquioxide film at material surface simultaneously, can effectively improve the material atmospheric corrosion resistance.But too high aluminium content can cause material the γ phase to occur, make the material fragility increase be unfavorable for that subsequent applications and too high aluminium content can cause casting stress excessive in castingprocesses, cause ingot casting centre burst to occur, so the weight percent of aluminium content is controlled at 0.01% ~ 6.0% and is advisable.
Manganese and zinc in a large number solid solution play solution strengthening effect in copper, in certain compositional range, can form the Cu-Mn-Zn ternary solid solution, make alloy have good hot and cold processing characteristics and higher yield point temperature, put forward heavy alloyed thermostability.The weight percent of manganese content is controlled at 0.5% ~ 5.0%, cross the low manganese silicon compound that forms very few, be unfavorable for the wear-resisting of material, too highly then can form too much manganese silicon compound, cause the frictional coefficient of material to raise and cause with the friction pair material of its pairing and cross quick-wearing.
Silicon is as main alloy element, and itself and manganese, nickel etc. all can form hard point compound, improves the abrasion resistance properties of material and reduces frictional coefficient between the pairing friction pair.The virtual zinc equivalent coefficient of silicon is 10, effectively enlarges the β phase region, and the microtexture that makes alloy mutually as main, is conducive to the machining of alloy take β.Silicone content excessively hangs down and is unfavorable for bringing into play its effect, and too high then can causing increases the stress cracking tendency of alloy and cause alloy fragility to increase, so the weight percent of silicone content is controlled at 0.3% ~ 3.0%.
Manganese and silicon can form Vickers' hardness (HV) value and reach manganese silicon compound hard point more than 700 in brass, in friction process, play a supporting role, reduce friction contact surface between the pair, thereby reduce the frictional coefficient of pairing friction pair, because the high rigidity characteristic of manganese silicon compound can effectively promote again the abrasion resistance properties of copper alloy.
Effect of Ce mainly is desulfurization, deoxidation, crystal grain thinning, refining and the high-temperature behavior of improving material, but along with the increase of cerium content, the fragility of material increases.Because the activity of cerium is very large, very easily voloxidation, so the weight percent of cerium content is controlled at 0.0001% ~ 0.01% and is advisable, and too much adds and causes material cost to increase lower then DeGrain.
The effect of cobalt mainly is to play by solution strengthening to improve alloy substrate hardness, strengthen the mechanical property of alloy, cobalt contents is too high, fully solid solution under the alloy casting temperature, form the simple substance point of cobalt, affect the moulding of alloy, cross that low then strengthening effect is not obvious, so the weight percent of cobalt contents is controlled at 0.0001% ~ 2.0% and is advisable.
The chromium effect mainly is to play by solution strengthening to improve alloy substrate hardness, strengthen the mechanical property of alloy, the chromium too high levels, fully solid solution under the alloy casting temperature, form the simple substance point of chromium, affect the moulding of alloy, cross that low then strengthening effect is not obvious, so the weight percent of chromium content is controlled at 0.001% ~ 2.0% and is advisable.
The Main Function of nickel and silicon add the wear-resisting particle of formation nisiloy simultaneously; improve the abrasion resistance properties of material; nickel can enlarge alpha phase zone simultaneously; increase α phase ratio; wear-resisting particle is played a protective role, prevent the phenomenon that wear-resisting particle comes off in a large number in friction process, but too high nickel content can cause α mutually too much; cause the mechanical property of material to descend, so the weight percent of nickel content is controlled at 1.0% ~ 4.0% and is advisable.
Iron act as crystal grain thinning, improve the mechanical property of material, and form the irony point, around irony point, form a small amount of loose, formation " hole effect ", the cutting ability of raising material that can be suitable.The weight percent of iron level is controlled at 0.3% ~ 2.0%, cross low to material property without castering action, the rich iron phase segregation of too high easy formation and reduce the moulding of material.
Compared with prior art, unleaded wear-resistant copper alloy of the present invention has the following advantages: have excellent abrasion resistance properties and lower frictional coefficient, and have high mechanical property and good thermostability, and the weight percent of this alloy lead content contains≤and 0.01%, satisfied the unleaded requirement of whole manufacturing starting material.
The preparation method of the unleaded wear-resistant copper alloy that the present invention adopts has the following advantages: by stripping off the skin, stretch, anneal out finished product, reduced middle multi-drawing, annealing operation, reduced the production cycle, raised the efficiency, has the casting cost low, the advantage such as production technique is simple.
Figure of description
Fig. 1-4 is respectively the photo of the metallographic sample that embodiment 7,21,17,2 unleaded mill copper alloys make;
Fig. 5-8 is respectively that Fig. 1-4 is through the photo of 300 ℃ of metallographic samples of making after annealing 12 hours.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
It is the elements such as rare earth that raw material among embodiments of the invention 1～embodiment 32 all adopts conventional industrial pure copper, industrial-purity zinc, technical pure manganese, commercial-purity aluminium, industrial pure silicon, technically pure iron, industrial pure ni, technical pure cobalt, industrial pure tin, technical pure chromium, cerium, under the industrially scalable condition, adopt electrosmelting, D.C.casting billet, push, strip off the skin, stretch, annealing, alignment, heat-treat at last and obtain finished product.
The concrete Chemical Composition content of each embodiment of wear-resistant copper alloy of the present invention and comparative alloy sees Table shown in one.
The operational path of unleaded wear-resistant copper alloy of the present invention is as follows:
------------electrosmelting strips off the skin---cold-drawn---alignment---thermal treatment---check---finished product packing in hot extrusion for horizontal continuous-casting or semicontinuous casting in the starting material preparation.
The production technique of each embodiment of wear-resistant copper alloy of the present invention is carried out founding, extruding, stretching and thermal treatment by table two, finally obtains the excellent base of Ф 30.0mm.Comparative alloy is that the German trade mark is that CuZn40Al2 and U.S.'s trade mark are the leaded manganese brass of C67420.
Mechanics Performance Testing sample preparation: the excellent base of usually taking from the Ф 30.0mm half-hard state of each embodiment alloy of the present invention and comparative alloy in the above-mentioned drawing process, preparation and the mechanical property of carrying out sample according to the GB/T228 standard detect, carry out at universal testing machine, the detected result of its tensile strength sees Table 1.
Frictional coefficient and the preparation of abrasion loss specimen and test: the excellent base of getting the Φ 30.0mm of above-mentioned production, the sample that is prepared into Φ 30.0mm*10mm carries out frictional coefficient and abrasion loss test in the surperficial division department of Ningbo material of the Chinese Academy of Sciences, and test condition is: the pair of shaking: 5mm; Frequency: 60HZ; Load: 100N; Linear velocity: 0.15m/s; Friction mode: reciprocal linear; Couple material: 45# steel; Friction environment: two kinds of dry grinding and oil abrasions; Test temperature: room temperature.Test result sees Table 1.
The test of thermostability: metallographic sample preparation, for the ease of sanding and polishing, get Φ 30.0mm rod base and be lathed Φ 15.0*10mm sample, polish by the metallographic sander, in the analysis of metallographic sensing chamber of inspection center of Bo Wei group metallurgical microstructrue, accompanying drawing 1 ~ accompanying drawing 4 is respectively embodiment 7,21,17,2 metallurgical microstructrue photo, after analysis is finished sample is carried out 300 ℃ of annealing 12 hours, be prepared into metallographic sample tissues observed changing conditions, detected result is seen accompanying drawing 5 ~ accompanying drawing 8 again.From figure, draw through carrying out up to 300 ℃ of annealing after 12 hours, the metallographic of sample form and grain size without considerable change, illustrate that it has good thermostability.
Above-described embodiment performance test proves, compare with comparative alloy, alloy of the present invention has excellent abrasion resistance properties and lower frictional coefficient, and have high mechanical property and good thermostability, be suitable for rotor, oil distribution casing, piston shoes and the component such as automotive engine valves conduit and floating bearing of turbo-charger of hydro-pump.
Subordinate list one:
Subordinate list two
Claims (10)
1. unleaded wear-resistant copper alloy, it is characterized in that, described alloy comprises the component of following weight percent: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, and/or cobalt 0.001% ~ 2.0%, and/or chromium 0.001% ~ 2.0%, plumbous≤0.01%, surplus are zinc and inevitable impurity.
2. unleaded wear-resistant copper alloy according to claim 1 is characterized in that, described alloy also comprises one or more in iron, tin, the nickel, and its weight percent is iron 0.3% ~ 2.0%, tin 0.2% ~ 1.2%, nickel 1.0% ~ 4.0%.
3. unleaded wear-resistant copper alloy according to claim 1, it is characterized in that, the weight percent of described alloying constituent consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, cobalt 0.001% ~ 2.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
4. unleaded wear-resistant copper alloy according to claim 1 and 2, it is characterized in that, the weight percent of described alloying constituent consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, cobalt 0.001% ~ 2.0%, iron 0.3% ~ 2.0%, tin 0.2% ~ 1.2%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
5. unleaded wear-resistant copper alloy according to claim 1 and 2, it is characterized in that, the weight percent of described alloying constituent consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, cobalt 0.001% ~ 2.0%, nickel 1.0% ~ 4.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
6. unleaded wear-resistant copper alloy according to claim 1 and 2, it is characterized in that, the weight percent of described alloying constituent consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, cobalt 0.001% ~ 2.0%, nickel 1.0% ~ 4.0%, iron 0.3% ~ 2.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
7. unleaded wear-resistant copper alloy according to claim 1, it is characterized in that, the weight percent of described alloying constituent consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, chromium 0.001% ~ 2.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
8. unleaded wear-resistant copper alloy according to claim 1 and 2 is characterized in that, the weight percent of described alloying constituent consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, chromium 0.001% ~ 2.0%, iron 0.3% ~ 2.0%, tin 0.2% ~ 1.2%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
9. unleaded wear-resistant copper alloy according to claim 1 and 2 is characterized in that, the weight percent of described alloying constituent consists of: copper 55% ~ 65%, aluminium 0.01% ~ 6.0%, manganese 0.5% ~ 5.0%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, chromium 0.001% ~ 2.0%, cobalt 0.0001% ~ 2.0%, nickel 1.0% ~ 4.0%, iron 0.3% ~ 2.0%, lead is not more than 0.01%, and surplus is zinc and inevitable impurity.
10. method for preparing the unleaded wear-resistant copper alloy of the described any one of claim 1 to 9, it is characterized in that, the method comprises: batching, melting, horizontal casting billet or D.C.casting billet, push, strip off the skin, stretch, annealing, alignment, heat-treat at last and obtain finished product, wherein said smelting temperature is 1050 ~ 1150 ℃, described horizontal casting temperature is 920 ~ 980 ℃, described D.C.casting temperature is 980 ~ 1050 ℃, described extrusion temperature is 600 ~ 720 ℃, thermal treatment temp is 260 ~ 340 ℃, and heat treatment time is 2 ~ 6h.
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