CN109609804B - A kind of Cu-Ni-Si-Mn alloy and preparation method thereof - Google Patents
A kind of Cu-Ni-Si-Mn alloy and preparation method thereof Download PDFInfo
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- CN109609804B CN109609804B CN201811608202.9A CN201811608202A CN109609804B CN 109609804 B CN109609804 B CN 109609804B CN 201811608202 A CN201811608202 A CN 201811608202A CN 109609804 B CN109609804 B CN 109609804B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/10—Alloys based on copper with silicon as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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Abstract
The present invention relates to copper alloy fields, in particular to a kind of Cu-Ni-Si-Mn alloy and preparation method thereof.The Cu-Ni-Si-Mn alloy, chemical component include: the Cu of Ni 5-25%, Si 5-10%, Mn 4-8%, P 0.1-0.3%, S 0.01-0.02%, Sn 0.01-0.03%, Zn 0.05-0.09%, Fe 0.06-0.1% and surplus by mass percentage.Proportion by suitable metal component and the control to impurity in the present embodiment, can be obviously improved the wearability and heating conduction of copper alloy.The preparation method processing step is few, easy to operate, it is easy to accomplish, the Cu-Ni-Si-Mn alloy prepared has excellent wearability and thermal conductivity.
Description
Technical field
The present invention relates to copper alloy fields, in particular to a kind of Cu-Ni-Si-Mn alloy and preparation method thereof.
Background technique
Due to its excellent electric conductivity and thermal conductivity, corrosion resistance, produceability, good intensity and fatigue durability are pure
Copper can be applied to various industry and automobile product, such as heat exchanger, automobile radiators, domestic heating system, bearing and bushing,
Sleeve, electronic contact and resistance welding electrode.
So far, the Cu-Ni-Si system developed, Cu-Fe system, Cu-Ag system etc., wherein Cu-Ni-Si system has simultaneously
High intensity and high thermal conductivity, extensively largely study it by domestic and foreign scholars, achieve significant progress.It is copper-based
Composite material is as the hot spot studied instantly, in consideration of it, special propose the application.
Summary of the invention
The purpose of the present invention is to provide a kind of Cu-Ni-Si-Mn alloy, wearability and excellent thermal conductivity.
Another object of the present invention is to provide a kind of preparation method of above-mentioned Cu-Ni-Si-Mn alloy, the preparation methods
Processing step is few, easy to operate, it is easy to accomplish, the Cu-Ni-Si-Mn alloy prepared has excellent wearability and thermally conductive
Property.
The embodiment of the present invention is achieved in that
A kind of Cu-Ni-Si-Mn alloy, chemical component include: by mass percentage Ni5-25%, Si 5-10%,
Mn 4-8%, P 0.1-0.3%, S 0.01-0.02%, Sn 0.01-0.03%, Zn 0.05-0.09%, Fe 0.06-
0.1% and surplus Cu.
A kind of preparation method of Cu-Ni-Si-Mn alloy comprising using cathode copper, nickel, silicon, manganese as raw material it is smelting at
The chemical component of melt, detection Cu-Ni-Si-Mn alloy includes: Ni 5-25%, Si 5-10%, Mn by mass percentage
4-8%, P 0.1-0.3%, S0.01-0.016%, Sn 0.01-0.03%, Zn 0.05-0.09%, Fe 0.06-0.1% with
And the Cu of surplus；Then melt is carried out being cast into ingot casting, solution treatment and ageing treatment is carried out to ingot casting.
The beneficial effect of the embodiment of the present invention for example, in the present embodiment, by increasing manganese, Neng Gouqi in copper alloy
To the effect of deoxidation, be conducive to the improvement of the mechanical property and processing performance of copper.Ni is added simultaneously can be improved and golden obdurability；
Add Si that the intensity, hardness, casting fluidity of alloy can be improved.By the proportion of suitable metal component and right in the present embodiment
The control of impurity can be obviously improved the wearability and heating conduction of copper alloy.The preparation method processing step is few, operation letter
It is single, it is easy to accomplish, the Cu-Ni-Si-Mn alloy prepared has excellent wearability and thermal conductivity.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 be the Cu-Ni-Si-Mn alloy that provides of comparative experiments of the present invention after different heat treatment metallographic structure figure (a~
And matrix and mutually area percentage after different solid solution agings g)；
Fig. 2 is alloy SEM/ of the Cu-Ni-Si-Mn alloy that provides of comparative experiments of the present invention after different heat treatment
Mapping figure and linear sweep graph；
Fig. 3 is the abrasion quantitative change for Cu-Ni-Si-Mn alloy alloy after different heat treatment that comparative experiments of the present invention provides
Change figure and its wear surface SEM figure；
Fig. 4 is that Brinell hardness, Vickers are hard at different conditions for the Cu-Ni-Si-Mn alloy that provides of comparative experiments of the present invention
Degree；
Fig. 5 is thermal conductivity of the Cu-Ni-Si-Mn alloy that provides of comparative experiments of the present invention under Different Heat Treatment Conditions；
Fig. 6 is thermal diffusion figure of the Cu-Ni-Si-Mn alloy that provides of comparative experiments of the present invention under Different Heat Treatment Conditions.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Cu-Ni-Si-Mn alloy of the embodiment of the present invention and preparation method thereof is specifically described below.
This application provides a kind of Cu-Ni-Si-Mn alloy, chemical component includes: Ni 5- by mass percentage
25%, Si 5-10%, Mn 4-8%, P 0.1-0.3%, S 0.01-0.02%, Sn 0.01-0.03%, Zn 0.05-
0.09%, the Fe 0.06-0.1% and Cu of surplus.
Micro Mn is added in copper, can not only play the role of deoxidation, but also is conducive to the mechanical property and technique of copper
The improvement of performance.Ni is added to can be improved and golden obdurability；Add Si that the intensity, hardness, casting fluidity of alloy can be improved.
Manganese brass is since its casting character is good, tissue stabilization when being heated, and corrosion-proof wear can weld, be widely used in steaming
All kinds of parts to work in vapour and liquid fuel.It has however been found that addition Mn research it is few, and rarely document report about
The wearability of such alloy and the research in terms of thermal conductivity, so middle addition Mn on the basis of Cu-Ni-Si alloy, exploitation
The Cu-Ni-Si-Mn alloy that wearability and heating conduction are taken into account.In addition, Ni, Si, Mn constituent content added in alloy is more existing
Most of Cu-Ni-Si alloys be raised.For example, in the prior art, total additive amount of Ni, Si, Mn are less than in alloy
10%, more very this is less than < 5%.It that is to say, Ni, Si and the Mn being added in Cu in the application are larger, this is conducive to opposite improve
The wearability of Cu-Ni-Si-Mn alloy.
And other compositions (S, Sn, Zn, Fe) are used as impurity, its content need to be controlled, through inventor the study found that working as S
When 0.01-0.02%, Sn 0.01-0.03%, Zn 0.05-0.09%, Fe0.06-0.1%, properties of product are more preferably.
Preferably, the chemical component of Cu-Ni-Si-Mn alloy include: by mass percentage Ni8-20%, Si 6-9%,
Mn 4-7%, P 0.14-0.21%, S 0.01-0.016%, Sn0.018-0.026%, Zn 0.055-0.083%, Fe
The Cu of 0.063-0.095% and surplus；
Preferably, the chemical component of Cu-Ni-Si-Mn alloy includes: Ni10-17%, Si 6- by mass percentage
8%, Mn 4-6%, P 0.158-0.193%, S 0.012-0.014%, Sn0.020-0.024%, Zn 0.062-
0.076%, the Fe 0.071-0.087% and Cu of surplus.
In addition, present invention also provides a kind of preparation methods of Cu-Ni-Si-Mn alloy comprising following steps:
S1, melting
Cathode copper, nickel, silicon, manganese is smelting at melt as raw material, and the chemical component for detecting Cu-Ni-Si-Mn alloy is pressed
Mass percent meter includes: Ni 5-25%, Si 5-10%, Mn 4-8%, P 0.1-0.3%, S 0.01-0.016%, Sn
0.01-0.03%, Zn 0.05-0.09%, Fe0.06-0.1% and surplus Cu.
Specifically, first melting intermediate alloy Cu-Ni, intermediate alloy Cu-Si and intermediate alloy Cu-Mn respectively, then will
Intermediate alloy Cu-Ni, intermediate alloy Cu-Si and intermediate alloy Cu-Mn carry out the final alloy of melting simultaneously.
In fusion process, cause expendable metal loss scaling loss.In melting production process, the scaling loss of metal
It is inevitable problem.Iron loss not only makes alloy melt generate slag inclusion, causes the quality problems of alloy-steel casting, simultaneously
It also will increase alloy production cost.And the fusing point difference of each component of Cu, Ni, Si and Mn in the application is larger, in melting
The case where component of low melting point is easy to happen scaling loss.In the application, each component is first smelted into intermediate alloy, intermediate alloy
Fusing point is the median of the fusing point of two raw alloys, then carries out melting with each intermediate alloy and forms final alloy, each
The fusing point gap of intermediate alloy reduces, and advantageously reduces scaling loss amount during subsequent melt.
Next the specific steps of each intermediate alloy of melting will be specifically described:
Melting intermediate alloy Cu-Ni includes: to be risen cathode copper under the protection of protective gas using being electrolysed copper and mickel as raw material
Temperature makes cathode copper be molten into copper liquid to 1000-1300 DEG C, after copper liquid clarification, proportioned nickel is added, is continuously heating to
It 1350-1450 DEG C, until completely melted, is cast in graphite jig, is taken out after natural cooling molding；Preferably, intermediate alloy
The content of Ni is 20-40% in Cu-Ni.
Melting intermediate alloy Cu-Si includes: to rise cathode copper under the protection of protective gas using cathode copper and silicon as raw material
Temperature makes cathode copper be molten into copper liquid to 1000-1300 DEG C, after copper liquid clarification, proportioned silicon is added, is continuously heating to
It 1350-1450 DEG C, until completely melted, is cast in graphite jig, is taken out after natural cooling molding；Preferably, intermediate alloy
The content of Si is 20-40% in Cu-Si.
Melting intermediate alloy Cu-Mn includes: to rise cathode copper under the protection of protective gas using cathode copper and manganese as raw material
Temperature makes cathode copper be molten into copper liquid to 1000-1300 DEG C, after copper liquid clarification, proportioned manganese is added, is continuously heating to
It 1250-1350 DEG C, until completely melted, is cast in graphite jig, is taken out after natural cooling molding；Preferably, intermediate alloy
The content of Mn is 20-40% in Cu-Mn.
In the present embodiment, various intermediate alloys are formed by preparatory melting, according to the specific raw material of various intermediate alloys
The selection for carrying out smelting temperature, can reduce disposable melting bring scaling loss.
Preferably, in intermediate alloy Cu-Ni, intermediate alloy Cu-Si and intermediate alloy Cu-Mn three Cu content phase
Deng.
The final alloy of melting includes: that intermediate alloy Cu-Ni, intermediate alloy Cu-Si and intermediate alloy Cu-Mn exist simultaneously
It is warming up to 1350-1450 DEG C under protective gas protection, after alloy is completely melt, phosphor-copper is put into Xiang Suoshu melt and is removed
Oxygen.
In the present embodiment, protective gas is inert gas, for example including but be not limited to, one of nitrogen and argon gas or more
Kind.
S2, casting
Diameter is cast to as 85mm, in the cast iron die of a height of 180mm, natural cooling demoulds after 1 hour.
S3, peeling
The alloy cast is subjected to finishing processing, the upper and lower surface vehicle of alloy is put down, side peeling.
S4, solid solution
Solution treatment be in solid solubility temperature be 900-950 DEG C under conditions of be dissolved 1-10h；Preferably, solid solubility temperature 925-
950℃。
S5, timeliness
Directly carry out ageing treatment after solid solution, ageing treatment be 400-550 DEG C in aging temp under conditions of timeliness 2-
24h；Preferably, aging temp is 450-550 DEG C；Preferably, aging temp is 450-500 DEG C.
After ageing treatment, to alloy cooled to room temperature scale removal again, and polished with fine sandpaper.
In the present embodiment, by increasing manganese in copper alloy, deoxidation can be played the role of, be conducive to the mechanical property of copper
With the improvement of processing performance.Ni is added simultaneously can be improved and golden obdurability；Add Si that the intensity, hardness, casting of alloy can be improved
Make mobility.Proportion by suitable metal component and the control to impurity in the present embodiment, can be obviously improved copper alloy
Wearability and heating conduction.The preparation method processing step is few, easy to operate, it is easy to accomplish, the Cu-Ni-Si- prepared
Mn alloy has excellent wearability and thermal conductivity.
Cu-Ni-Si-Mn alloy of the invention and preparation method thereof further progress is illustrated with reference to embodiments.
Embodiment 1
A kind of Cu-Ni-Si-Mn alloy is present embodiments provided, chemical component includes: Ni by mass percentage
12%, Si 7%, Mn 5%, P 0.2%, S 0.01%, Sn 0.01%, Zn 0.07%, Fe 0.08% and surplus
Cu。
Preparation method includes:
S1, ingredient
Raw material is cathode copper, nickel plate, silicon grain, manganese piece, purity is followed successively by 99.985%, 99.96%, 99.85%,
99.7%.The quality of raw material needed for calculating melting three intermediate alloys Cu-30Ni, Cu-30Si, Cu-30Mn first, to centre
After the completion of alloy melting, calculating weighing is carried out to intermediate alloy, the quality of three alloys needed for calculating the final alloy of melting, if
The content of some component is insufficient, and useful raw materials are cathode copper, nickel plate, silicon grain, manganese piece are supplied.
S2, melting
Melting intermediate alloy Cu-30Ni includes: to be electrolysed copper and mickel as raw material, by cathode copper under the protection of protective gas
1150 DEG C are warming up to, cathode copper is made to be molten into copper liquid, after copper liquid clarification, proportioned nickel is added, is continuously heating to 1400 DEG C,
Until completely melted, it is cast in graphite jig, is taken out after natural cooling molding.
Melting intermediate alloy Cu-30Si includes: using cathode copper and silicon as raw material, by cathode copper under the protection of protective gas
1150 DEG C are warming up to, cathode copper is made to be molten into copper liquid, after copper liquid clarification, proportioned silicon is added, is continuously heating to 1400 DEG C,
Until completely melted, it is cast in graphite jig, is taken out after natural cooling molding.
Melting intermediate alloy Cu-30Mn includes: using cathode copper and manganese as raw material, by cathode copper under the protection of protective gas
1150 DEG C are warming up to, cathode copper is made to be molten into copper liquid, after copper liquid clarification, proportioned manganese is added, is continuously heating to 1300 DEG C,
Until completely melted, it is cast in graphite jig, is taken out after natural cooling molding.
The final alloy of melting includes: by intermediate alloy Cu-30Ni, intermediate alloy Cu-30Si and intermediate alloy Cu-30Mn
1400 DEG C are warming up under protective gas protection simultaneously, after alloy is completely melt, phosphor-copper is put into melt and carries out deoxygenation.
S3, casting
Diameter is cast to as 85mm, in the cast iron die of a height of 180mm, natural cooling demoulds after 1 hour.
S4, peeling
The alloy cast is subjected to finishing processing, the upper and lower surface vehicle of alloy is put down, side peeling.
S5, solid solution
Solution treatment be in solid solubility temperature be 950 DEG C under conditions of be dissolved 1h.
S6, timeliness
Directly carry out ageing treatment after solid solution, ageing treatment be 500 DEG C in aging temp under conditions of timeliness 2h.
Embodiment 2
A kind of Cu-Ni-Si-Mn alloy is present embodiments provided, chemical component includes: Ni by mass percentage
20%, Si 5%, Mn 5%, P 0.1%, S 0.02%, Sn 0.03%, Zn 0.06%, Fe 0.07% and surplus
Cu。
Preparation method includes:
S1, ingredient
Raw material is cathode copper, nickel plate, silicon grain, manganese piece, purity is followed successively by 99.985%, 99.96%, 99.85%,
99.7%.The quality of raw material needed for calculating melting three intermediate alloys Cu-23Ni, Cu-23Si, Cu-23Mn first, to centre
After the completion of alloy melting, calculating weighing is carried out to intermediate alloy, the quality of three alloys needed for calculating the final alloy of melting, if
The content of some component is insufficient, and useful raw materials are cathode copper, nickel plate, silicon grain, manganese piece are supplied.
S2, melting
Melting intermediate alloy Cu-23Ni includes: to be electrolysed copper and mickel as raw material, by cathode copper under the protection of protective gas
1050 DEG C are warming up to, cathode copper is made to be molten into copper liquid, after copper liquid clarification, proportioned nickel is added, is continuously heating to 1350 DEG C,
Until completely melted, it is cast in graphite jig, is taken out after natural cooling molding.
Melting intermediate alloy Cu-23Si includes: using cathode copper and silicon as raw material, by cathode copper under the protection of protective gas
1050 DEG C are warming up to, cathode copper is made to be molten into copper liquid, after copper liquid clarification, proportioned silicon is added, is continuously heating to 1350 DEG C,
Until completely melted, it is cast in graphite jig, is taken out after natural cooling molding.
Melting intermediate alloy Cu-23Mn includes: using cathode copper and manganese as raw material, by cathode copper under the protection of protective gas
1050 DEG C are warming up to, cathode copper is made to be molten into copper liquid, after copper liquid clarification, proportioned manganese is added, is continuously heating to 1250 DEG C,
Until completely melted, it is cast in graphite jig, is taken out after natural cooling molding.
The final alloy of melting includes: by intermediate alloy Cu-23Ni, intermediate alloy Cu-23Si and intermediate alloy Cu-23Mn
1350 DEG C are warming up under protective gas protection simultaneously, after alloy is completely melt, phosphor-copper is put into melt and carries out deoxygenation, inspection
Survey the chemical component of Cu-Ni-Si-Mn alloy.
S3, casting
Diameter is cast to as 85mm, in the cast iron die of a height of 180mm, natural cooling demoulds after 1 hour.
S4, peeling
The alloy cast is subjected to finishing processing, the upper and lower surface vehicle of alloy is put down, side peeling.
S5, solid solution
Solution treatment be in solid solubility temperature be 925 DEG C under conditions of be dissolved 6h.
S6, timeliness
Directly carry out ageing treatment after solid solution, ageing treatment be 450 DEG C in aging temp under conditions of timeliness 12h.
Embodiment 3
A kind of Cu-Ni-Si-Mn alloy is present embodiments provided, chemical component includes: Ni by mass percentage
8%, the Cu of Si 9%, Mn 7%, P 0.3%, S 0.02%, Sn 0.03%, Zn 0.07%, Fe 0.09% and surplus.
Preparation method includes:
S1, ingredient
Raw material is cathode copper, nickel plate, silicon grain, manganese piece, purity is followed successively by 99.985%, 99.96%, 99.85%,
99.7%.The quality of raw material needed for calculating melting three intermediate alloys Cu-37Ni, Cu-37Si, Cu-37Mn first, to centre
After the completion of alloy melting, calculating weighing is carried out to intermediate alloy, the quality of three alloys needed for calculating the final alloy of melting, if
The content of some component is insufficient, and useful raw materials are cathode copper, nickel plate, silicon grain, manganese piece are supplied.
S2, melting
Melting intermediate alloy Cu-37Ni includes: to be electrolysed copper and mickel as raw material, by cathode copper under the protection of protective gas
1250 DEG C are warming up to, cathode copper is made to be molten into copper liquid, after copper liquid clarification, proportioned nickel is added, is continuously heating to 1450 DEG C,
Until completely melted, it is cast in graphite jig, is taken out after natural cooling molding.
Melting intermediate alloy Cu-37Si includes: using cathode copper and silicon as raw material, by cathode copper under the protection of protective gas
1250 DEG C are warming up to, cathode copper is made to be molten into copper liquid, after copper liquid clarification, proportioned silicon is added, is continuously heating to 1450 DEG C,
Until completely melted, it is cast in graphite jig, is taken out after natural cooling molding.
Melting intermediate alloy Cu-37Mn includes: using cathode copper and manganese as raw material, by cathode copper under the protection of protective gas
1250 DEG C are warming up to, cathode copper is made to be molten into copper liquid, after copper liquid clarification, proportioned manganese is added, is continuously heating to 1350 DEG C,
Until completely melted, it is cast in graphite jig, is taken out after natural cooling molding.
The final alloy of melting includes: by intermediate alloy Cu-37Ni, intermediate alloy Cu-37Si and intermediate alloy Cu-37Mn
1350 DEG C are warming up under protective gas protection simultaneously, after alloy is completely melt, phosphor-copper is put into melt and carries out deoxygenation, inspection
Survey the chemical component of Cu-Ni-Si-Mn alloy.
S3, casting
Diameter is cast to as 85mm, in the cast iron die of a height of 180mm, natural cooling demoulds after 1 hour.
S4, peeling
The alloy cast is subjected to finishing processing, the upper and lower surface vehicle of alloy is put down, side peeling.
S5, solid solution
Solution treatment be in solid solubility temperature be 900 DEG C under conditions of be dissolved 1h.
S6, timeliness
Directly carry out ageing treatment after solid solution, ageing treatment be 550 DEG C in aging temp under conditions of timeliness 20h.
Comparative experiments
The Cu-Ni-Si-Mn alloy that comparative example 1-6 is provided and preparation method thereof is substantially same as Example 1, and distinctive points exist
It is different in solution treatment parameter or ageing treatment parameter:
In comparative example 1,1h is dissolved under conditions of being 975 DEG C in solid solubility temperature.
In comparative example 2, timeliness 2h under conditions of being 400 DEG C in aging temp.
Test example
A series of performance test is carried out to above-described embodiment 1 and comparative example 1-2.
After the completion of different heat treatment sample is by corase grinding, fine grinding, polishing, corroded with 3g iron chloride, 15ml hydrochloric acid, In
Metallographic structure observation is carried out under optical microscopy (OM) (Axio Imager, Zeiss, Germany) and is taken pictures.Object phase area is
The continuous metallurgical microscopic clapped under five 200 times under an optical microscope, then passes through object phase area proportion software network analysis
Gained.
Hardness measurement is using FM-810 type Vickers (Japan) (surveying five points under 100gf, be averaged) and HB-
3000 type Brinell hardness testers.
When measuring thermal conductivity, the sample of previously processed mistake is divided with electric spark wire cutting machine (TPCW-2535E type, domestic)
Not being cut into diameter is 13mm, the disk with a thickness of 2mm.Polished it, the processing such as descale.Finally use thermal diffusion
Instrument (LFA427, NETZSCH, Germany) carries out the test of room temperature to 300 ° of thermal diffusion coefficient, and wherein temperature gradient is 50
℃。
Wearability experiment, preferred dimension are 50mm × 50mm × 4mm sample, are polished with sand paper so that experimental material has
Then identical abrasive conditions are equipped with 180# sand paper with SUGA-type abrasion tester and carry out wear test, apply load and be
19.6N respectively does three groups to each Cu-Ni-Si-Mn alloy sample, is then respectively averaged.
Tissue topography's analysis is also carried out to sample using scanning electron microscope (JCM600, JEOL, Japan) in experiment；X-ray is spread out
Instrument (D-MAX-2500-PC type Japan) is penetrated mutually to detect sample progress object.
(1) Metallographic Analysis of alloy
Fig. 1 shows the metallographic structure figures after the as cast condition of Cu-12Ni-7Si-5Mn alloy and different fixation rates.From figure
In as can be seen that as cast condition under have matrix (46%), there is (Fig. 1 (a, h)) in bone-shaped phase (38%) and sheet phase (16%).Sample point
Not after 900 DEG C, 925 DEG C and 950 DEG C solution treatment, matrix area is with the raising of solid solubility temperature and first increase reduces afterwards；Piece
Shape phase area gradually rises substantially；Bone-shaped accompany solid solubility temperature raising and reduce.
Sample is after being dissolved 950 DEG C again respectively in 400 DEG C, 450 DEG C, 500 DEG C and 550 DEG C of at a temperature of timeliness 2h.
From Fig. 1 (e, f, j) as can be seen that thering are a large amount of bone-shaped mutually to exist in 500 DEG C of timeliness；And bone-shaped is opposite at 450 DEG C, 550 DEG C
It is less.By Fig. 1 (h) it is found that when solid solubility temperature is 950 DEG C, sheet phase and bone-shaped phase area and maximum.Solid solution plus ageing treatment
When, it is dissolved 950 DEG C of 1h added-time area and close both when imitating 450 DEG C of 2h timeliness, but the area of bone-shaped phase is in 500 DEG C of maximums.
(2) sem analysis
In order to determine the composition of phase, SEM/Mapping has been carried out, line is swept and XRD analysis.Under as cast condition have Cu,
Mn27Si47、Cu3.8Ni、Cu4Si；And there is cenotype Cu after being dissolved 900 DEG C6.69There is illustrating the incomplete of solid solution in Si, there is a large amount of the
Two-phase does not dissolve into matrix；In 925 DEG C of solid solutions, the second phase Cu4Si dissolves into matrix；In 950 DEG C of solid solutions, the second phase only has
Cu3.8Ni、Mn27Si47Illustrate that the comparison of solid solution is abundant.Then respectively directly in 450 DEG C, 500 after 950 DEG C of solid solubility temperature processing
DEG C and 550 DEG C of progress ageing treatments after, phase Cu6.69Si、Cu3.8Ni is always existed；Phase Cu6.69Si 500 DEG C of timeliness exist and
It disappears again at 550 DEG C of timeliness；Phase Mn after timeliness27Si47It disappears, there is cenotype Mn4Si7Occur.
The as cast condition and SEM/Mapping, line after different fixation rates that Fig. 2 indicates Cu-12Ni-7Si-5Mn alloy
Sweep analysis.By Fig. 2 (As-cast) it is found that Cu is mainly distributed in matrix；It is a small amount of exist in two-phase；Si, Mn, Ni exist
In two-phase.After 900 DEG C of solid solution, Cu is primarily present in matrix；Si is present in two-phase；Mn, Ni are primarily present in bone-shaped phase.In
When 925 DEG C of solid solution, 950 DEG C of solid solution, Cu is primarily present in matrix；Si, Mn, Ni are present in two-phase.At 450 DEG C, Ni is only
It is present in sheet phase, so sheet is mutually mainly Cu3.8Ni.At 500 DEG C, 550 DEG C, Ni, Si, Mn are present in two-phase.Have
Linear sweep graph can be seen that matrix is mainly Cu, and there are also a small amount of Ni, Si, Mn.The sheet phase of sample under as cast condition and after solution treatment
Each element line sweeps that peak value is descending to be followed successively by Ni, Si, Mn, Cu；Solid solution the added-time effect after peak value it is descending be followed successively by Si, Ni,
Mn,Cu.It is successively Si, Ni, Mn, Cu that it is descending, which to sweep peak value, for the line of dendroid bone-shaped phase after different heat treatment.
Fig. 3 it is found that matrix based on Cu；Sheet is mutually mainly with Cu3.8Based on Ni, but there are Mn27Si47、Cu3.8Ni、
Cu4Si、Cu6.69Si；And bone-shaped is mutually mainly with Cu4Si、Cu6.69Based on Si, Mn27Si47、Cu3.8Ni exists on a small quantity.
(3) wear test
The as cast condition and the abrasion analysis after different fixation rates that Fig. 3 is Cu-12Ni-7Si-5Mn alloy.Fig. 3 (a, b)
Indicate wear cumulation amount with abrasion number variation diagram.It can be with the wear cumulation amount of the sample after as cast condition and solution treatment all in figure
Stablize and increase, in a linear relationship with abrasion number, this illustrates that matrix and hardening constituent play good wear-resistant effect.From Fig. 4
In, it is evident that the abrasion of sample after solution treatment is all smaller than the abrasion of as-cast specimen, in 950 DEG C of solution treatment, sample
Wearability is best.By abrasion of 950 DEG C of solution treatment samples after different timeliness as shown in figure 4, wherein wearability is most
It is in aging temp is well 500 DEG C, and wear curve is substantially the same at other two temperature, and abrasion loss is essentially identical.
Wear surface is all substantially ditch dug with a plow pattern, is that scratch surface is made in wear process by the SiC abrasive grain on sand paper
At, so the main wear mechanisms of two body abrasion are micro- cuttings, abrasive grain is in sliding process by tissue plow to groove two
Side or front end, be tissue deform, management volume.Finally wear surface is detached from the form of chip or plough bits.From Fig. 3 (c-i)
It can be seen that wear surface is along glide direction, there are ditch dug with a plows, apparent Abrasive Wear Characteristics are presented, there are abrasive grains, mill for wear surface
The pit considered to be worth doing and differed in size, this is because abrasive grain moves under compression and shearing stress effect along glide direction, thus opposite grinding
It damages surface and generates ditch dug with a plow or micro mechanics effect.As cast condition undertissue surface is mostly based on chip, and there is crackle appearance on surface.From solid solution place
Fig. 3 (d, e, f) after reason is as can be seen that the surface light that solid solubility temperature is in 900 DEG C, 925 DEG C than solid solubility temperature at 950 DEG C
It is sliding, without big chip, peel off；And in 950 DEG C of solid solution added-time effect treated specimen surface, such as Fig. 3 (g, h, i) institute
Show, the sample wear surface in 500 in Fig. 3 (g) DEG C aging samples ratio Fig. 3 (h, i) wants smooth, and ditch dug with a plow is than more visible, peeling
It is less；Fig. 3 (h, i) wear surface ditch dug with a plow is criss-cross, peeling pit occurs, adhesion tearing occurs.Wear mechanism becomes adhesion mill
Damage.
In order to analyze above-mentioned wear results, analyzed in terms of metallurgical structure and material surface hardness two.
First to three samples after solution treatment, it is dissolved added-time effect treated three samples and as-cast specimen carries out Brinell hardness survey
Amount, result are as shown in Figure 4.When nonageing processing, the hardness of sample increases with the raising of solid solubility temperature, at 950 DEG C
It is up to 221HB, plays preferable solution strengthening effect.In the sample for carrying out ageing treatment after 950 DEG C of solid solutions, at 500 DEG C
The effect of effect is best, and hardness reaches 278HB.
Also occurrence law changes the abrasion loss of sample after difference solid solution and fixation rates, this is not only whole with sample
Body hardness (Brinell hardness) is related, it is often more important that, it is related from the percentage of different phase compositions and hardness.So utilizing dimensional microstructure
The hardness of each phase of family name.Its result is as shown in Figure 4.In sample under the conditions of seven kinds, the hardness of the sheet phase under the conditions of every kind
Value is all the largest, this is attributed to sheet phase ni content nearly 50%.Ni have face-centred cubic structure, lattice constant α=
0.3523nm, fusing point is higher (1455 DEG C), and corrosion resistance is good, high mechanical properties.This effectively raises its hardness number.Three kinds of phases
Variation tendency under different heat treatment is not quite similar.For matrix after solid solution compared under as cast condition, hardness number is decline,
It is enhanced after solid solution added-time effect.Mutually after solid solution and after solid solution plus ageing treatment, hardness number has sheet again
Biggish raising；It first increases with solid solubility temperature after reaching 586HV and is reduced with temperature.The hardness number of dendroid phase is with solid solution
The raising of temperature and increase；Reach maximum at 500 DEG C of timeliness, is then reduced with the raising of temperature.From metallographic microscope it can be found that
As the raising bone-shaped of solid solubility temperature mutually gradually decreases compared with as cast condition, while sheet mutually has certain reduction；Also from XRD diagram
It knows with the raising of solid solubility temperature, the second phase to be to reduce.This shows the raising with solid solubility temperature, and the second phase starts to dissolve into base
Body, the higher dissolution of temperature it is more abundant, sample integral hardness just will increase；But it is wear-resisting due to the reduction of alloy surface hardening constituent
Property will reduce.So the integral hardness of alloy can uprush, but after different heat treatment from the point of view of the area of phase, it is dissolved at added-time effect
After reason, sheet phase and bone-shaped phase Vickers hardness number and area are all on a declining curve, thus alloy integral hardness and wearability can under
Drop.
(4) thermal conductivity is analyzed
As shown in Figure 5 and Figure 6, under room temperature, the thermal diffusion coefficient of as-cast specimen is minimum, is dissolved 950 DEG C of 500 DEG C of added-time effects
Sample is maximum；For thermal diffusion coefficient curve entirety under seven different conditions with temperature in monotonic increase trend, research finds that this is
Because as the temperature increases, the thermal resistance of sample interface reduces as the temperature increases, heating conduction will be improved.For thermally conductive
Property, with the raising of solid solubility temperature, alloy grain roughening, then crystal boundary is reduced, and crystal boundary is the transition zone of neighboring die, grain boundaries
Atomic arrangement more disorder, reduce the degree that grain boundary area causes alloy lattice to distort and reduce, lead to the flat of electronics in alloy
Equal free path increases, to improve the thermal conductivity of alloy.The second phase area of alloy after timeliness constantly declines with aging temp, closes
The distortion of lattice degree of auri body also just increases accordingly, and the heating conduction of alloy is caused to decline.Two kinds of mechanism pass through solid metal
Transmit heat: vibration wave (referred to as phonon) and free electron in lattice.Thermal diffusivity is carried by such as lattice defect or dislocation
Flow the influence of the factors such as interaction between sub- concentration and carrier and lattice wave.As the temperature rises, free electron is transported
Dynamic aggravation, thermal conductivity just will increase.But lattice vibration aggravates simultaneously, and phonon increases the resistance that free electron moves, and reduces and closes
The thermal conductivity of gold.And solute atoms reduces the scattering process of free electron with the raising of temperature.Therefore in certain temperature
In range, when influence of the temperature to solute atoms thermal resistivity plays a leading role, the thermal conductivity of alloy rises with the raising of temperature
It is high.
The thermal conductivity of metal can with two items and come approximate, i.e. residual components and thermal component.Herein, metal is residual
Remaining ingredient is such as dislocation, crystal boundary, hole and foreign atom as caused by fault of construction, almost temperature independent.The fortune of electronics
It is dynamic to be influenced by fault of construction present in composite material or alloy.If providing thermal energy to composite material, pass through heat
Electronics can be increased and pass through the quantity of the jump probability and free electron of defect.It is therefore contemplated that shadow of the electronics to heat transfer
Ring than be up to 500 DEG C phonon it is more dominant, and the thermal conductivity for the sample studied herein also with temperature raising and increase.
From above data analysis as can be seen that in the application, best solid solubility temperature is 950 DEG C, and best aging temp is 500
DEG C, when solid solubility temperature is 975 DEG C, wearability is poor, while aging temp is lower than 450 DEG C, and performance is bad.
In conclusion in the present embodiment, by increasing manganese in copper alloy, deoxidation can be played the role of, be conducive to copper
Mechanical property and processing performance improvement.Ni is added simultaneously can be improved and golden obdurability；Add Si that the strong of alloy can be improved
Degree, hardness, casting fluidity.Proportion by suitable metal component and the control to impurity in the present embodiment, can be significant
Promote the wearability and heating conduction of copper alloy.The preparation method processing step is few, easy to operate, it is easy to accomplish, it prepares
Cu-Ni-Si-Mn alloy have excellent wearability and thermal conductivity.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of Cu-Ni-Si-Mn alloy, which is characterized in that it includes using cathode copper, nickel, silicon, manganese as original
Expect smelting at melt, the chemical component for detecting the Cu-Ni-Si-Mn alloy includes: Ni 5- by mass percentage
25%, Si 5-10%, Mn 4-8%, P 0.1-0.3%, S 0.01-0.016%, Sn 0.01-0.03%, Zn 0.05-
0.09%, the Fe 0.06-0.1% and Cu of surplus；Then the melt is carried out being cast into ingot casting, the ingot casting is carried out
Solution treatment and ageing treatment；
Chemical component melting by the Cu-Ni-Si-Mn alloy includes:
Melting intermediate alloy Cu-Ni, intermediate alloy Cu-Si and intermediate alloy Cu-Mn are first distinguished, then by the intermediate alloy
Cu-Ni, the intermediate alloy Cu-Si and the intermediate alloy Cu-Mn carry out the final alloy of melting simultaneously；
Wherein, intermediate alloy Cu-Ni described in melting includes: to be electrolysed copper and mickel as raw material, by the cathode copper in protective gas
Protection under be warming up to 1000-1300 DEG C, so that the cathode copper is molten into copper liquid, after the copper liquid clarification after, addition match
The nickel, be continuously heating to 1350-1450 DEG C, until completely melted, be cooled and shaped after casting；
Intermediate alloy Cu-Si described in melting include: using cathode copper and silicon as raw material, by the cathode copper protective gas protection
Under be warming up to 1000-1300 DEG C, so that the cathode copper is molten into copper liquid, after copper liquid clarification, be added proportioned described
Silicon is continuously heating to 1350-1450 DEG C, until completely melted, is cooled and shaped after casting；
Intermediate alloy Cu-Mn described in melting include: using cathode copper and manganese as raw material, by the cathode copper protective gas protection
Under be warming up to 1000-1300 DEG C, so that the cathode copper is molten into copper liquid, after copper liquid clarification, be added proportioned described
Manganese is continuously heating to 1250-1350 DEG C, until completely melted, is cooled and shaped after casting.
2. the preparation method of Cu-Ni-Si-Mn alloy according to claim 1, which is characterized in that after the solution treatment
It is directly entered the ageing treatment.
3. the preparation method of Cu-Ni-Si-Mn alloy according to claim 1 or 2, which is characterized in that the solution treatment
Be in solid solubility temperature be 900-950 DEG C under conditions of be dissolved 1-10h.
4. the preparation method of Cu-Ni-Si-Mn alloy according to claim 3, which is characterized in that the solid solubility temperature
925-950℃。
5. the preparation method of Cu-Ni-Si-Mn alloy according to claim 1 or 2, which is characterized in that the ageing treatment
Be in aging temp be 450-550 DEG C under conditions of timeliness 2-24h.
6. the preparation method of Cu-Ni-Si-Mn alloy according to claim 5, which is characterized in that the aging temp is
450-500℃。
7. the preparation method of Cu-Ni-Si-Mn alloy according to claim 1, which is characterized in that the intermediate alloy Cu-
It is 20-40% that the content of Ni, which accounts for the mass percent of the intermediate alloy Cu-Ni, in Ni；
It is 20-40% that the content of Si, which accounts for the mass percent of the intermediate alloy Cu-Si, in the intermediate alloy Cu-Si；
It is 20-40% that the content of Mn, which accounts for the mass percent of the intermediate alloy Cu-Mn, in the intermediate alloy Cu-Mn.
8. the preparation method of Cu-Ni-Si-Mn alloy according to claim 7, which is characterized in that the intermediate alloy Cu-
The content of Cu is equal in Ni, the intermediate alloy Cu-Si and the intermediate alloy Cu-Mn three.
9. the preparation method of Cu-Ni-Si-Mn alloy according to claim 1, which is characterized in that the final alloy packet of melting
It includes: the intermediate alloy Cu-Ni, the intermediate alloy Cu-Si and the intermediate alloy Cu-Mn is protected in protective gas simultaneously
It is warming up to 1350-1450 DEG C under shield, after alloy is completely melt, detects the chemical component of the Cu-Ni-Si-Mn alloy.
10. the preparation method of Cu-Ni-Si-Mn alloy according to claim 1, which is characterized in that by the melt into
Before row casting, it is first put into phosphor-copper into the melt and carries out deoxygenation, then casts again.
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