CN102925743B - A kind of unleaded wear-resistant copper alloy - Google Patents
A kind of unleaded wear-resistant copper alloy Download PDFInfo
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Abstract
The invention discloses a kind of unleaded wear-resistant copper alloy, described alloy comprises the component of following percentage by weight: 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. Unleaded wear-resistant copper alloy of the present invention has the following advantages: have excellent abrasion resistance properties and lower coefficient of friction, and there is high mechanical performance and good heat endurance, and the percentage by weight of this alloy lead content, containing≤0.01%, has met the unleaded requirement of whole manufacturing raw material; The present invention also discloses a kind of preparation method of above-mentioned unleaded wear-resistant copper alloy, and this preparation method, by stripping off the skin, stretch, anneal out finished product, has reduced middle multi-drawing, annealing operation, reduce the production cycle, raise the efficiency, there is casting cost low, the advantage such as production technology is simple.
Description
Technical field
The present invention relates to a kind of unleaded wear-resistant copper alloy.
Background technology
Existing wear-resistant copper alloy (as the CuZn40Al2 of DIN, the C67420 of Unite States Standard, U.S.'s markAccurate C86300 alloy) because of its good mechanical property, anti-wear performance, hot-working character, is widely used inThe manufacturings such as engineering machinery, auto parts and components, hydraulic pressure, wear-resistant copper alloy at home and abroad market consumption all thanLarger. As everyone knows, leaded parts can cause serious environmental pollution in production or use procedure,Be detrimental to health, the U.S., European Union etc. in succession puts into effect relevant laws and regulations lead content in parts is carried outControl. Now more to the research without ledrite both at home and abroad, and also obtained significant progress. But to unleadedThe research of wear-resistant copper alloy is less. Along with ROSH instruction, (parliament of European Union and EU Council are " about at electricitySpecial harmful substance illegal instruction in sub-electrical equipment ") and the promulgation of California, USA bill, to whole manufacturing formerThe unleaded demand of material is more and more urgent, the industries such as lot of domestic and international engineering machinery, hydraulic pressure, auto parts and componentsLeading enterprise has 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 is also had made some progress, for example middle ChineseOn people republic intellectual property board web, environment-friendly manganese brass alloy and manufacture method thereof are disclosed, its group of alloysThe Cu that becomes (percentage by weight) to contain 55～65wt%, the Mn of 1.0～6.5wt%, the Al of 0.2～3.0wt%,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/orThe Pb of 0～0.2wt%, all the other are Zn and other inevitable impurity. This alloy has excellent mechanical propertyEnergy, casting character, machinability and corrosion resistance, especially anticorrosion stress-resistant performance, also have casting cost low,The advantages such as production technology is simple, are suitable for forging, casting and machining and other manufacture methods processingParts, are particularly suitable for faucet body and the valve of forging, casting and machining. But this alloyAdded bismuth element, the cost due to bismuth in manufacturing process is higher, and world resource closes on exhaustion, competitivenessNot strong. And along with the appearance of the relevant laws and regulations regulations of manufacturing, require content plumbous in alloy≤ 0.01wt%, and the lead content of above-mentioned alloy is controlled at 0～0.2wt%, does not meet 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, provides one to haveExcellent mechanical property, low-friction coefficient, high wear resistance performance, good heat endurance and excellent heatThe unleaded wear-resistant copper alloy of processing characteristics.
Technical scheme of the present invention is: a kind of unleaded wear-resistant copper alloy, described alloy comprises following weight percentThe component of ratio: copper 55%～65%, aluminium 0.01%～6.0%, manganese 0.5%～5.0%, silicon 0.3%～3.0%, cerium0.0001%～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, nickel, and its percentage by weight isIron 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%, aluminium0.01%～6.0%, manganese 0.5%～5.0%, silicon 0.3%～3.0%, cerium 0.0001%～0.01%, cobalt0.001%～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%, aluminium0.01%～6.0%, manganese 0.5%～5.0%, silicon 0.3%～3.0%, cerium 0.0001%～0.01%, cobalt0.001%～2.0%, iron 0.3%～2.0%, tin 0.2%～1.2%, lead is not more than 0.01%, surplus be zinc andInevitably impurity.
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55%～65%, aluminium0.01%～6.0%, manganese 0.5%～5.0%, silicon 0.3%～3.0%, cerium 0.0001%～0.01%, cobalt0.001%～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%, aluminium0.01%～6.0%, manganese 0.5%～5.0%, silicon 0.3%～3.0%, cerium 0.0001%～0.01%, cobalt0.001%～2.0%, nickel 1.0%～4.0%, iron 0.3%～2.0%, lead is not more than 0.01%, and surplus is zinc and notEvitable impurity.
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55%～65%, aluminium0.01%～6.0%, manganese 0.5%～5.0%, silicon 0.3%～3.0%, cerium 0.0001%～0.01%, chromium0.001%～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%, aluminium0.01%～6.0%, manganese 0.5%～5.0%, silicon 0.3%～3.0%, cerium 0.0001%～0.01%, chromium0.001%～2.0%, iron 0.3%～2.0%, tin 0.2%～1.2%,, lead is not more than 0.01%, surplus be zinc andInevitably impurity.
As preferably, the weight percent of this wear-resistant copper alloy composition consists of: copper 55%～65%, aluminium0.01%～6.0%, manganese 0.5%～5.0%, silicon 0.3%～3.0%, cerium 0.0001%～0.01%, chromium0.001%～2.0%, cobalt 0.0001%～2.0%, nickel 1.0%～4.0%, iron 0.3%～2.0%, lead is not more than 0.01%,Surplus is zinc and inevitable impurity.
Another technical problem that the present invention will solve is to provide 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, finally heat-treat and obtain finished product, and wherein said smelting temperature is 1050～1150 DEG C,Described horizontal casting temperature is 920～980 DEG C, and described D.C.casting temperature is 980～1050 DEG C, and described squeezesPressing temperature is 600～720 DEG C, and heat treatment temperature is 260～340 DEG C, and heat treatment time is 2～6h.
Above-mentioned unleaded wear-resistant copper alloy be mix metallographic structure, its phase composition is: taking β mutually as main, 1～20%α phase and the Compound Phase such as silicomanganese of 1～6%, ferro-aluminum, nisiloy. Crisp because β is mutually hard, cuttingIn journey, easily form chip breaking, make material in machining process, not be prone to problems such as twining cutter, therefore increase βCan improve mutually the machinability of material.
In unleaded wear-resistant copper alloy of the present invention, add aluminium and by solution strengthening, its intensity and hardness are improved, andAnd can promote the mobility of alloy, be conducive to the Foundry Production of alloy. The virtual zinc equivalent coefficient of aluminium is 6,Can expand significantly β phase region, effectively alleviate the unleaded cutting ability causing of material and decline, aluminium simultaneouslyCan form fine and close alundum (Al2O3) film at material surface, can effectively improve material atmospheric corrosion resistancePerformance. But too high aluminium content can cause material to occur γ phase, make material fragility increase be unfavorable for follow-up answeringWith and too high aluminium content can in casting process, cause casting stress excessive, cause ingot casting occur in heart shakeLine, therefore the percentage by weight of aluminium content is controlled at 0.01%～6.0% and is advisable.
Manganese and zinc in a large number solid solution, in copper, play solution strengthening effect, in certain compositional range, and can shapeBecome Cu-Mn-Zn ternary solid solution, make alloy there is good hot and cold processing characteristics and higher surrenderPoint temperature, puies forward heavy alloyed heat endurance. The percentage by weight of manganese content is controlled at 0.5%～5.0%, too lowThe manganese silicon compound forming is very few, is unfavorable for the wear-resisting of material, too highly can form too much manganese silicon compound,Cause the coefficient of friction of material raise and cause with the friction pair material of its pairing and cross quick-wearing.
Silicon is as main alloy element, itself and manganese, nickel etc. all can form hard point compound, improves materialAbrasion resistance properties also reduces the coefficient of friction between pairing friction pair. The virtual zinc equivalent coefficient of silicon is 10, hasThe expansion β phase region of effect, the microstructure that makes alloy mutually as main, is conducive to the machining of alloy taking β. SiliconContent is too low is unfavorable for bringing into play its effect, and too high can causing increases the stress cracking tendency of alloy and cause and closeGold fragility increases, and therefore the percentage by weight of silicone content is controlled at 0.3%～3.0%.
Manganese and silicon can form Vickers hardness (HV) value and reach more than 700 manganese silicon compound hard in brassPoint is played a supporting role in friction process, reduces the contact-making surface between friction pair, rubs thereby reduce pairingWipe secondary coefficient of friction, because the high rigidity characteristic of manganese silicon compound can effectively promote again the resistance to of copper alloyPolishing machine.
The effect of cerium is mainly desulfurization, deoxidation, crystal grain thinning, refining and the high-temperature behavior of improving material, butAlong with the increase of cerium content, the fragility of material increases. Because the activity of cerium is very large, very easily voloxidation, because ofThe percentage by weight of this cerium content is controlled at 0.0001%～0.01% and is advisable, and too much adds and causes the cost of raw materialIncrease lower DeGrain.
The effect of cobalt is mainly to be played and improved alloy substrate hardness by solution strengthening, strengthens the mechanicalness of alloyCan, cobalt content is too high, solid solution completely at Alloys Casting temperature, and the simple substance point of formation cobalt, impact is closedGolden is moulding, and too low strengthening effect is not obvious, and therefore the percentage by weight of cobalt content is controlled at0.0001%～2.0% is advisable.
Chromium effect is mainly to be played and improved alloy substrate hardness by solution strengthening, strengthens the mechanical performance of alloy,Chromium too high levels, solid solution completely at Alloys Casting temperature, form the simple substance point of chromium, affects alloyMoulding, too low strengthening effect is not obvious, and therefore the percentage by weight of chromium content is controlled at 0.001%～2.0%Be 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 expand alpha phase zone simultaneously, increases α phase ratio, and wear-resisting particle is played a protective role, and prevents wear-resisting matterThe phenomenon that point comes off in a large number in friction process, but too high nickel content can cause α mutually too much, causes materialMechanical performance decline, therefore the percentage by weight 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 irony point, all at irony pointEnclose and form a small amount of loosening, form " void effect " cutting ability of raising material that can be suitable. Iron containsAmount percentage by weight be controlled at 0.3%～2.0%, too low to material property without castering action, too high easy shapeCheng Futie phase segregation and reduce material moulding.
Compared with prior art, unleaded wear-resistant copper alloy of the present invention has the following advantages: have the resistance to of excellencePolishing machine and lower coefficient of friction, and there is high mechanical performance and good heat endurance, and shouldThe percentage by weight of alloy lead content, containing≤0.01%, has met the unleaded requirement of whole manufacturing raw material.
The preparation method of unleaded wear-resistant copper alloy that the present invention adopts has the following advantages: by stripping off the skin, stretch,The finished product of annealing out, has reduced middle multi-drawing, annealing operation, has reduced the production cycle, raise the efficiency,There is casting cost low, the advantage such as production technology is simple.
Figure of description
Fig. 1-4 are respectively the photo of the metallographic sample that embodiment 7,21,17,2 unleaded mill copper alloys make;
Fig. 5-8 are respectively the photos of Fig. 1-4 through 300 DEG C of metallographic samples of making after annealing 12 hours.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Raw material in embodiments of the invention 1～embodiment 32 all adopt conventional industrial pure copper, industrial-purity zinc,Technical pure manganese, commercial-purity aluminium, industrial pure silicon, ingot iron, industrial pure ni, technical pure cobalt, industrial pure tin,Technical pure chromium, cerium are the elements such as rare earth, under industrially scalable condition, adopt electro-smelting, D.C.casting circleIngot, push, strip off the skin, stretch, annealing, alignment, finally heat-treat and obtain finished product.
The concrete chemical analysis content of each embodiment of wear-resistant copper alloy of the present invention and comparative alloy is in table oneShow.
The process route of unleaded wear-resistant copper alloy of the present invention is as follows:
Raw material are prepared---electric furnace smelting---horizontal continuous-casting or semi-continuous casting---hot extrusion------cold-drawn---alignment---heat treatment---inspection---finished product packing strips off the skin.
The production technology of each embodiment of wear-resistant copper alloy of the present invention by table two carry out founding, extruding, stretching andHeat treatment, finally obtains the excellent base of Ф 30.0mm. Comparative alloy is that the German trade mark is CuZn40Al2 and U.S.State's trade mark is the leaded manganese brass of C67420.
Mechanics Performance Testing sample preparation: conventionally take from above-mentioned drawing process each embodiment alloy of the present invention andThe excellent base of the Ф 30.0mm half-hard state of comparative alloy, carries out preparation and the power of sample according to GB/T228 standardLearn Performance Detection, on universal testing machine, carry out, the testing result of its tensile strength is in table 1.
Coefficient of friction and wear extent test sample preparation and test: get the excellent base of the Φ 30.0mm of above-mentioned production,The sample that is prepared into Φ 30.0mm*10mm carries out coefficient of friction in the Ningbo surperficial division department of material of the Chinese Academy of SciencesWith wear extent test, 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 is in table 1.
The test of heat endurance: metallographic sample preparation, for the ease of sanding and polishing, get Φ 30.0mm rod base carBe whittled into Φ 15.0*10mm sample, by the polishing of metallographic sander, detect at inspection center of Bo Wei group metallographicThe analysis of chamber metallurgical microstructrue, accompanying drawing 1～accompanying drawing 4 is respectively that the metallographic of embodiment 7,21,17,2 is micro-Photo is organized in sight, after analysis completes, sample is carried out to 300 DEG C of annealing 12 hours, then is prepared into metallographic sampleTissues observed situation of change, testing result is shown in accompanying drawing 5～accompanying drawing 8. From figure, draw through carrying out up to 300 DEG CAnneal after 12 hours, the metallographic composition of sample and grain size, without significant change, illustrate that it has goodHeat endurance.
Above-described embodiment performance test proves, compared with comparative alloy, alloy of the present invention has excellent wear-resistingDamage performance and lower coefficient of friction, and there is high mechanical performance and good heat endurance, be suitable forRotor, oil distribution casing, piston shoes and automotive engine valves conduit and the floating bearing of turbo-charger of hydraulic pumpDeng parts.
Subordinate list one:
Subordinate list two
Claims (3)
1. a unleaded wear-resistant copper alloy, it is characterized in that, described alloy comprises the component of following percentage by weight: copper 55% ~ 65%, aluminium 1.02% ~ 6.0%, manganese 0.5% ~ 2.65%, 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; Described alloy also comprises one or more in iron, tin, nickel, and its percentage by weight is iron 0.3% ~ 2.0%, tin 0.2% ~ 1.2%, nickel 1.0% ~ 4.0%; The phase composition of alloy comprises: taking β mutually as main, the Compound Phases such as 1 ~ 20% α phase and the silicomanganese of 1-6%, ferro-aluminum, nisiloy.
2. unleaded wear-resistant copper alloy according to claim 1, it is characterized in that, the weight percent of described alloying component consists of: copper 55% ~ 65%, aluminium 1.02% ~ 6.0%, manganese 0.5% ~ 2.65%, 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.
3. unleaded wear-resistant copper alloy according to claim 1, is characterized in that, the weight percent of described alloying component consists of: copper 55% ~ 65%, aluminium 1.02% ~ 6.0%, manganese 0.5% ~ 2.65%, silicon 0.3% ~ 3.0%, cerium 0.0001% ~ 0.01%, chromium 0.001% ~ 2.0%, 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.
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| CN115261668B (en) * | 2022-06-30 | 2023-02-28 | 宁波金田铜业(集团)股份有限公司 | Brass alloy strip and preparation method thereof |
| CN115198139B (en) * | 2022-08-31 | 2023-06-09 | 宁波金田铜业(集团)股份有限公司 | Wear-resistant brass alloy bar and preparation method thereof |
| DE102022122831A1 (en) * | 2022-09-08 | 2024-03-14 | Diehl Brass Solutions Stiftung & Co. Kg | Lead-free brass alloy and machine element made therefrom |
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| DE102005015467C5 (en) * | 2005-04-04 | 2024-02-29 | Diehl Brass Solutions Stiftung & Co. Kg | Using a copper-zinc alloy |
| DE102005059391A1 (en) * | 2005-12-13 | 2007-06-14 | Diehl Metall Stiftung & Co.Kg | Copper-zinc alloy and synchronizer ring made from it |
| CN102383004A (en) * | 2010-08-30 | 2012-03-21 | 宁波金田铜业(集团)股份有限公司 | Manganiferous lead-free forgeable easy-cutting brass and preparation method thereof |
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