CN104862520B - Brass alloy as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses a brass alloy as well as a preparation method and an application thereof. The brass alloy comprises elements of Cu, Mn, Al, Si and Zn; a microstructure of the brass alloy comprises a CuMn solid solution, an AlCuZn solid solution, a CuMnAl solid solution and a MnSi intermetallic compound. The brass alloy meets the lead-free demand and solves the problems of poor cutting properties and wear-resisting properties of the brass alloy in the prior art, and the brass alloy has excellent strength, hardness and plasticity.

Description

A kind of brass alloys, preparation method and applications

Technical field

The present invention relates to a kind of alloy material, more particularly, to a kind of brass alloy material with solid solution structure and its system Preparation Method and application.

Background technology

Lead element is not solid-solution in copper, is distributed on copper and copper alloy matrix with dispersed part point-like, and lead quality is very soft, can Significantly improve cutting ability and the self-lubricating property of copper and copper alloy, extensively should therefore in machining copper and copper alloy With.Complex brass has excellent mechanical performance and anti-wear performance, in engineering machinery, automobile engine, turbocharger, speed change Case etc. is widely used as wear resistant alloy material, in order to increase cutting ability and the anti-wear performance of complex brass alloy, one As can add a small amount of lead element in complex brass alloy.But because lead has carcinogenic, teratogenesis, mutagenic danger to human body Evil, particularly infant are taken in lead element and nervous system can be caused to destroy and intelligent development decline, and therefore lead element is international Environmental protection organization lists the row of banned substance in, and the ELV of European Union instructs the copper alloy lead content that also clear stipulaties are used for auto parts and components 0.1wt% need to be less than, due to seriously reducing cutting ability and the application performance of copper alloy without lead element, therefore ELV instructs Lead element is implemented to exempt, maximum can add and be less than 3wt%, but this exemption clauses expired in 2017.Therefore how not Ensure that the cutting ability of alloy and anti-wear performance become alloy material hot research topic on the basis of adding lead element.

At present in plumbing field, the unleaded research of copper alloy of the industry such as bathroom makes great progress, but resistance to Mill copper alloy field is unleaded to be studied also in the starting stage, due to the self-lubricating property that lead element is excellent, in engineering machinery, vapour The interpolation of the wear-resisting field such as car engine, turbocharger, change speed gear box lead element can improve the anti-wear performance of material, therefore wear-resisting The unleaded cutting ability not only needing to ensure alloy material of copper alloy is in addition it is also necessary to ensure the wearability of material after removal lead element Energy.A lot of research worker it is also proposed respective improvement project, such as Chinese patent application (application number CN201410375285.7) It is related to copper alloy ring gear material and preparation method thereof.This patent of invention is leaded in order to solve automobile gear shifting box synchronizer gear ring material And the problem of high cost, copper alloy alligatoring ring matrix material a kind of nontoxic, inexpensive and that intensity is higher and preparation method thereof is provided, The component of this alloy is as follows：Cu：55-61wt%；Al：3.5-4.5wt%；Mn：1.2-2.0wt%；Si：0.7-1.3wt%； Fe：0.5-1.1wt%；Ni：3.6-4.5wt%；Balance of Zn.Recorded according to this its description, by special production technology Prepare above alloy material and can obtain nontoxic, inexpensive and intensity and the higher material of hardness, intensity reaches 750MPa, and hardness will Nearly 100HRB, has an excellent mechanical performance, but this patent application do not embody unleaded in the case of the cutting ability of material improve Problem.For another example to be related to one kind leaded and have good mechanical for Chinese patent application (application number CN201210361578.0) The complex brass of energy, anti-wear performance and machinability, this proprietary alloy composition：Cu59-63wt%；Mn1.2-4.0wt%；Si0.2- 2.8wt%；Al1.0-2.5wt%；Sn0.1-0.5wt%；Balance of Zn.Recorded according to this patent application specification, by γ Phase Proportion and Mn, Al, Si element relation control, and can obtain the complex brass alloy of preferable mechanical performance and cutting ability, but should Patent application fails to solve to bring because self-lubricating property reduces asking of friction and wear behavior reduction in the case of lead element removes Topic.

Content of the invention

First purpose of the present invention is not only to provide a kind of brass alloys meeting unleaded demand, and this pyrite closes Gold also solves cutting ability present in prior art, the not enough problem of anti-wear performance, and has excellent intensity, hardness and good Good plasticity.

The above-mentioned purpose of the present invention can be achieved through the following technical solutions：A kind of brass alloys include Cu, Mn, Al, Si, Zn, includes in the microstructure of brass alloys between CuMn solid solution, AlCuZn solid solution, CuMnAl solid solution and MnSi metal Compound.

In brass alloys, copper and zinc can form CuZn solid solution, and CuZn solid solution is stood with face-centred cubic structure, body-centered First structure cell form of square structure exists.The CuZn solid solution of face-centred cubic structure has excellent processing characteristics at normal temperatures, and The CuZn solid solution of body-centered cubic structure is hard and crisp at normal temperatures but has excellent processing characteristics under high temperature.Huang in the present invention Add Al element in copper alloy, form the AlCuZn solid solution with super cell's structure, super cell's structure of AlCuZn is by two kinds Form forms, and one kind is that Al atom replaces Zn atom with displacement format on the basis of face-centred cubic structure CuZn solid solution, is formed AlCuZn super cell's solid solution of similar face-centred cubic structure, this solid solution hardness is relatively low, and has good plastic working Performance.Another kind is that Al atom is existed with displacement format replacement Zn atom simultaneously on the basis of the CuZn solid solution of body-centered cubic structure First structure cell is internally embedded Cu, and Al, Zn atom forms AlCuZn super cell's solid solution of similar body-centered cubic structure, and this super cell is solid Solution on inheriting the body-centered cubic structure CuZn unit hard and crisp performance basis of structure cell solid solution, because Cu, Al, Zn atom is with right Linea angulata mode is distributed, and greatly improves machining stress distribution arrangement, forms the stress concentration performance being beneficial to machining, significantly The machinability improving product of degree, AlCuZn super cell's solid solution ratio such as less than 30 in brass alloys of the present invention (v/v) % (volumn concentration in alloy structure for the respective organization, similarly hereinafter), the intensity of material can reduce it is impossible to meet resistance to The requirement to material high intensity for the mill field, and cutting ability poor it is impossible to meet batch machining require, higher than 85 (v/v) %, Although cutting ability is preferably, fragility increases, and is equally unfavorable for the application of material.AlCuZn solid solution body weight therefore in brass alloys Amount percentage ratio controls in 30-85 (v/v) %, preferably 45-70 (v/v) %, more preferably 48-65 (v/v) %.AlCuZn solid solution There is large effect to the cutting ability of brass alloys and anti-wear performance in body particle diameter, particle diameter is less than 5nm, due to its stress distribution The particular orientation in direction, leads to brass alloys matrix hardness too high, is unfavorable for inlaying of anti-abrasive hard tissue, in friction subtask During anti-abrasive hard tissue come off thus scratching the surface of part, and AlCuZn solid solution particle diameter be more than 25nm, then can not be formed Effectively stress concentration point, so that working angles cutting swarf not easy fracture, causes to twine knife problem, affects piece surface fineness, Therefore AlCuZn solid solution size controlling is in 5-25nm, preferably 9-18nm, more preferably 10-18nm.

Add manganese element can form CuMn solid solution in brass alloys, in Cu unit cell configuration, Mn atomic substitutions Cu The CuMn cellular solid solution that atom is formed remains Cu high-ductility, high elongation, and excellent in cold workability can wait, in brass alloys The CuMn solid solution of 5 (v/v) more than % need to be contained it is ensured that brass alloys have good cold-forming property to meet brass alloys Plasticity in the application, prevents material embrittlement, but too high CuMn solid solution body burden, especially more than 30 (v/v) % although Huang The plasticity of copper alloy has larger lifting, but in its working angles, cutting swarf easily occurs twining the problem of knife and intensity and hardness Low.The ratio of therefore CuMn solid solution controls in 5-30 (v/v) %, preferably 8-20 (v/v) %, more preferably 10-18 (v/ V) %.CuMn solid solution particle diameter more than 24nm, its intensity decreases, less than 8nm, then brass alloys plasticity reduces, and therefore CuMn is solid Solution size controlling is in 8-24nm, preferably 11-19nm, more preferably 12-18nm.

It is solid that the Cu atom that manganese element has been replaced in CuAl body-centered cubic structure cellular solid solution defines CuMnAl super cell Solution, CuMnAl super cell's solid solution that this reaction generates inherits the high-strength high hard feature of CuAl solid solution, is brass alloys Matrix provide enough mechanical strengths to ensure the application in wear-resisting field for the brass alloys, and this CuMnAl super cell is solid Solution surrounding is Al atom, and body-centered is Cu or Mn atom, and this atom composition structure can lower the coefficient of friction of friction pair due to it, Improve the anti-wear performance of brass alloys.On the other hand, Al atomic substitutions CuMn face-centred cubic structure cellular in brass alloys Cu atom in solid solution, forms CuMnAl super cell's solid solution, and it is solid that this CuMnAl super cell's solid solution inherits CuMn cellular The feature of solution simultaneously increased intensity and hardness and wear resistance on this basis.Good resistance in order to ensure that material has Mill performance and mechanical performance, CuMnAl super cell's solid solution is no less than 5 (v/v) %, but more than 40 (v/v) %, the machinery of material Poor-performing is it is impossible to fully meet application requirement.Therefore CuMnAl solid solution ratio controls in 5-40 (v/v) %, preferably 8- 38 (v/v) %, more preferably 10-26 (v/v) %.CuMnAl solid solution particle diameter is less than 5nm, leads to the coefficient of friction of brass alloys Increase, thus reducing the anti-wear performance of brass alloys, and CuMnAl solid solution particle diameter is more than 25nm, the intensity fall of brass alloys Low it is impossible to meet its application requirement, the CuMnAl solid solution size controlling of therefore brass alloys is in 5-25nm, preferably 6- 19nm, more preferably 7-18nm.

The MnSi compound of manganese and silicon formation has very excellent stability and very high hardness.MnSi compound exists Formed in Mushy Zone in casting process, pattern and atom composition do not change upon formation, this compound hardness energy Reach more than HV650, be not solid-solution in brass base, with graininess or spot distribution on brass base, in brass alloys When forming friction pair with other materials, MnSi compound plays the effect of the strong point, can prevent because it has high hardness number Body portion is only caused to wear and tear in application process, and the supporting role due to MnSi, decrease the contact surface of friction pair material Long-pending, reduce frictional resistance, improve energy utilization.MnSi compound ratio is less than 1 (v/v) %, and above control effect is failed to understand Aobvious, higher than 12 (v/v) % although improve the hardness of brass alloys and the support effect of frictional contact surface, but it is unfavorable for rubbing The reduction of resistance, therefore MnSi compound ratio control in 1-12 (v/v) %, preferably 1.2-10 (v/v) %, more preferably 1.5-5 (v/v) %.

Preferably, brass alloys are also included selected from one or more of Ni, Fe, Ti, P, Sn, Co, Bi, Te, Re element And the inevitable impurity of other, the wherein total content of Ni, Fe, Ti, P, Sn, Co, Bi, Te, Re element are by weight percentage Less than or equal to 2%, the content of impurity is less than 0.5% by weight percentage.

Ferrum element forms FeMnSi compound with Mn, Si in brass alloys, and this compound is the peritectoid with Fe as nucleus Compound, increased the strong point of rubbing surface, decreases the wear extent in application process, improves the anti-wear performance of material.And Fe element as nucleating agent, increases the quantity of forming core, hinders growing up of crystal grain, play the effect of crystal grain thinning in casting process Really, improve the combination property of material, and ferrum element non-solid solution part is distributed on brass base so that star is flower-shaped, can promote to cut The fracture of bits, improves the cutting ability of brass alloys.But the ferrum element of excess, especially more than 1wt% it may appear that ferrum segregation The problem assembled, leads to the combination property of material to be deteriorated.Therefore iron content≤1wt%, preferably 0.02wt%- 0.8wt%, more preferably 0.1wt%-0.7wt%.

Nickel element and cobalt element have larger solid solubility in brass alloys, can strengthen the matrix of brass alloys, improve yellow The intensity of copper alloy and plasticity, are conducive to the raising of materials application stability, and can be with Mn in brass alloys of the present invention, Si Element forms the compound such as NiSi, NiMnSi, CoSi, CoMnSi, can increase the strong point of rubbing surface, reduces the friction of friction pair Coefficient, decreases the wear extent in application process, improves the anti-wear performance of material.NiSi simultaneously, CoSi compound closes in pyrite In gold, there is certain solid solubility, and solid solubility drastically declines with the reduction of temperature, therefore can be by the side of the timeliness that quenches Formula improves NiSi, the pattern of CoSi compound and distributing homogeneity, and NiSi in the brass alloys after timeliness, CoSi compound Surrounding forms stress concentration point, is conducive to the raising of brass alloys cutting ability.But Ni, Co element belongs to valuable rare metal Element, too high amount can improve the cost of raw material, therefore Ni, and Co constituent content controls in≤1wt%, and Ni element is preferably 0.1- 0.9wt%, more preferably 0.3-0.8wt%.Co element is preferably 0.05-0.8wt%, more preferably 0.1-0.5wt%.

Titanium elements form CuTi compound with Cu, can increase the strong point of rubbing surface, reduce the coefficient of friction of friction pair, subtract Lack the wear extent in application process, improve the anti-wear performance of material.And CuTi compound has the effect of Solid solution precipitation strengthening Really, the CuTi compound after precipitation is evenly distributed on whole matrix with small and dispersed form, can further improve material Mechanical performance and anti-wear performance, but the Ti element of excess, cause fusion process oxidization burning loss to be seriously unfavorable for economic effect, because This Ti constituent content controls in below 1wt%, preferably 0.005-0.8wt%, more preferably 0.1-0.5wt%.

P elements can play intensity, hardness and the plasticity that crystal grain thinning improves brass alloys, and P elements and copper form CuP simultaneously Compound, increased the strong point of rubbing surface, decreases the wear extent in application process, improves the anti-wear performance of material.And Brass alloys matrix forms " void effect ", increases the chip breaking ability in working angles for the brass alloys, improve cutting of material Cut performance, but the mechanical performance that P elements then make material more than 1wt% drastically declines, therefore phosphorus element content≤1wt%, preferably For 0.001wt%-0.5wt%, more preferably 0.01wt%-0.2wt%.

Bismuth element is distributed on matrix with lamellar in brass alloys, can significantly improve the chip-breaking performance of brass alloys and subtract Few cutting resistance.But bismuth element is distributed on crystal boundary in a large number, reduce the grain-boundary strength of brass alloys more than 1wt%, then bismuth element, The mechanical performance making brass alloys reduces.Therefore bismuth element content≤1wt%, preferably 0.1wt%-0.8wt%, more preferably For 0.3wt%-0.8wt%.

Second purpose of the present invention is to provide the preparation method of above-mentioned brass alloys, and the method includes smelting, casting, heat Extrusion process, cold working and heat treatment step obtain finished product, and it is in extruding that described hot extrusion obtains pyrite blank for casting At a temperature of row cold working again after extruding, 200-500 DEG C of mold preheating temperature, extrusion temperature is 600 DEG C～850 DEG C, and extruding is flat All speed 5-15mm/s.

In above-mentioned preparation method preferably, smelting temperature be 1050 DEG C～1350 DEG C, casting temperature be 1000 DEG C～ 1250 DEG C, cold worked cold working rate is between 0～50%.

Brass alloys ductility disclosed by the invention is good, has excellent abrasive resistance and corrosion resistance, and mechanical performance is strong, processing Convenient formation, in manufacturing wear-resisting spare part and anticorrosion parts, there is good application performance.

Brief description

Fig. 1, a kind of schematic diagram of the AlCuZn solid solution of brass alloys disclosed by the invention；

Fig. 2, a kind of schematic diagram of the CuMnAl solid solution of brass alloys disclosed by the invention；

Fig. 3, another kind of schematic diagram of the AlCuZn solid solution of brass alloys disclosed by the invention；

Fig. 4, another kind of schematic diagram of the CuMnAl solid solution of brass alloys disclosed by the invention；

Fig. 5, the schematic diagram of the CuMn solid solution of brass alloys disclosed by the invention.

Specific embodiment

For a further understanding of the present invention, with reference to embodiment and accompanying drawing, embodiment of the present invention is described, It is understood that these descriptions are intended merely to further illustrate technical characteristic and the advantage of the present invention, rather than to the present invention The restriction of the protection domain requiring.

Raw material in embodiments of the present invention is all nonmetallic using conventional industrial simple metal or technical pure.Composition detection side Method according to all parts of GB/T5121-2008, mechanical property test method according to GB/T228-2010, hardness measuring method according to GB/T231.1-2009.Solid solution ratio and particle diameter test equipment Germany Brooker X-ray diffractometer, testing result is by general number Read according to storehouse, simulation schematic diagram is referring to accompanying drawing 1-5.

Cutting force meansurement equipment is the good Cutting Force Test System of Chongqing enlightening, and test condition is：The amount of feeding 0.078, cutting speed Degree 31.5674, back engagement of the cutting edge 0.5.Test the tangential force obtaining in material removal process, axial force, radial force, test obtains Tangential force, axial force, radial force and according to cutting force computing formula calculate.

Frictional factor test device is friction wear testing machine, and test condition is：Shake pair:5mm；Frequency：60HZ；Load： 100N；Linear velocity：0.15m/s；Friction mode：Reciprocal linear；Couple material:45# steel；Friction environment：Hydraulic pressure oil lubrication；Test Temperature：Room temperature.

Section Example of the present invention is referring to such as following table 1-4

Table 1

Table 2

Table 3

Table 4

Include, without being limited to above example 1-23 in the concrete application embodiment scheme of the interior present invention, can also add Plus include, without being limited to if following table 5-7 is in interior other addition element.Embodiment 14-26 then shows the Huang that the present invention program obtains In copper alloy, its tissue can be CuMn solid solution, AlCuZn solid solution, CuMnAl solid solution, MnSi intermetallic compound, and The presence of other compositions or element is negligible.

The selection scheme of the other addition element embodiments including Ni, Fe, Ti, P, Sn, Co, Bi, Te, Re can be Following any (referring to such as following table 5-7), and the other interpolation units including Ni, Fe, Ti, P, Sn, Co, Bi, Te, Re The adding technique scheme of element in alloy gross mass it suffices that 100% requirement, but it should be noted that in a certain interpolation Embodiment wherein in a technical scheme beyond 100% when, the percentage value not affecting element in this interpolation embodiment is at this Application in bright technical scheme.

Table 5

Addition element	1	2	3	4	5	6	7	8	9	10
											Ni (wt%)						0.1	0.9	0.3	0.8
Fe (wt%)	1	0.02	0.8	0.1	0.7
											Co (wt%)										0.05

Table 6

Addition element	11	12	13	14	15	16	17	18	19	20
											Ti (wt%)				1	0.005	0.8	0.1	0.5
P (wt%)									1	0.001
											Co (wt%)	0.8	0.1	0.5

Table 7

Addition element	21	22	23	24	25	26	27	28	19	30
											P (wt%)	0.5	0.01	0.2
Sn (wt%)								0.02	0.2	0.1
											Bi (wt%)				1	0.1	0.8	0.3

Table 8

Addition element	31	32	33	34	35	36	37	38	39	40
											Ni (wt%)									0.5
Fe (wt%)										0.7
											Co (wt%)									0.08	0.25
Te (wt%)	0.005	0.1	0.05	0.08

Re (wt%)

0.01

0.001

0.03

0.05

Table 9

Addition element	41	42	43	44	45	46	47	48	49	50
											Ni (wt%)								0.4	0.75
Fe (wt%)	0.08								0.3
											Ti (wt%)	0.2	0.4								0.25
P (wt%)		0.1	0.08							0.15
											Sn (wt%)					0.15	0.08			0.06
Bi (wt%)			0.4	0.7						0.7
											Te (wt%)						0.07	0.008
Re (wt%)							0.04	0.008

Table 10

Addition element	51	52	53	54	55	56	57	58	59	60
											Ni (wt%)		0.17			0.4		0.34		0.47	0.31
Fe (wt%)			0.56		0.09		0.55	0.13		0.45
											Ti (wt%)		0.34			0.007	0.23		0.7	0.008	0.22
P (wt%)		0.04		0.09		0.11		0.06	0.002	0.13
											Sn (wt%)	0.13		0.17		0.13		0.15	0.16	0.02	0.06
Co (wt%)			0.43	0.32		0.07	0.06	0.37	0.06	0.14
											Bi (wt%)		0.42		0.63		0.2	0.72	0.11	0.13	0.29
Te (wt%)	0.07		0.06		0.009		0.03		0.09	0.03
											Re (wt%)	0.04			0.007		0.02		0.03	0.04	0.05

The technical scheme of all alloys in all embodiments of the invention, in the host element including Cu, Mn, Al, Si, Zn Afterwards, then add or without other elements (include Ni, Fe, Ti, P, Sn, Co, Bi, Te, Re arbitrary or multiple when, add Segmentation scheme referring to aforementioned) when, its balance includes in copper, zinc element, element silicon, aluminium element and manganese element a kind of Or multiple and impurity element.

The all technical schemes of the present invention include, without being limited to aforementioned all embodiments, and the copper alloy of its gained is satisfied by tension Intensity 600MPa, compression ratio 10%, hardness 170HB, coefficient of friction 0.06, cutting force 120KN, and can be widely used for wear-resisting The manufacture of anti-corrosion parts, continuous service life is average more than 1000h.

In place of this place embodiment is to the claimed non-limit of technical scope midrange, equally all will in the present invention Ask in the range of protection.

Technological means disclosed in the present invention program are not limited only to the technological means disclosed in above-mentioned technological means, also include The technical scheme being made up of above technical characteristic combination in any.The above is the specific embodiment of the present invention it should refer to Go out, for those skilled in the art, under the premise without departing from the principles of the invention, can also make some Improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (5)

1. a kind of brass alloys, described brass alloys element include Cu, Mn, Al, Si, Zn it is characterised in that：Described brass alloys Microstructure in include CuMn solid solution, AlCuZn solid solution, CuMnAl solid solution, MnSi intermetallic compound, with body Long-pending percentage composition meter, in the microstructure of described brass alloys, CuMn solid solution is 5-30%；AlCuZn solid solution is 30- 85%；CuMnAl solid solution is 5-40%；MnSi intermetallic compound is 1-12%；In the microstructure of described brass alloys , in 8-24nm, in 5-25nm, the particle diameter of CuMnAl solid solution is in 2- for the particle diameter of AlCuZn solid solution for the particle diameter of CuMn solid solution 25nm.

2. brass alloys according to claim 1 it is characterised in that described brass alloys also include selected from Ni, Fe, One or more of Ti, P, Sn, Co, Bi, Te, Re element and other inevitably impurity, described Ni, Fe, Ti, P, Sn, The total content of Co, Bi, Te, Re element is less than or equal to 2% by weight percentage, and the content of described impurity is by weight percentage Less than 0.5%.

3. a kind of preparation method of described brass alloys as arbitrary in claim 1-2, the method includes smelting, casting, hot extrusion Pressure is processed, cold working and heat treatment step obtain finished product, and described hot extrusion obtains pyrite blank in extrusion temperature for casting Lower row cold working again after extruding, 200-500 DEG C of mold preheating temperature, extrusion temperature is 600 DEG C～850 DEG C, extruding averagely speed Degree 5-15mm/s.

4. brass alloys according to claim 3 preparation method it is characterised in that described smelting temperature be 1050 DEG C～ 1350 DEG C, described casting temperature is 1000 DEG C～1250 DEG C, and described cold worked cold working rate is between 0～50%.

5. a kind of described brass alloys as arbitrary in claim 1-2 answering in manufacturing wear-resisting spare part and anticorrosion parts With.