CN102912181B - Scandium-zirconium-strontium composite micro-alloyed nickel-aluminum bronze and method for manufacturing same - Google Patents
Scandium-zirconium-strontium composite micro-alloyed nickel-aluminum bronze and method for manufacturing same Download PDFInfo
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Abstract
The invention discloses scandium-zirconium-strontium composite micro-alloyed nickel-aluminum bronze and a method for manufacturing the same. The scandium-zirconium-strontium composite micro-alloyed nickel-aluminum bronze is characterized by comprising scandium (Sc) (0.025-0.078%), zirconium (Zr) (0.028-0.082%), strontium (Sr) (0.012-0.057%) and the balance nickel-aluminum bronze. The method for manufacturing the scandium-zirconium-strontium composite micro-alloyed nickel-aluminum bronze includes firstly, melting the nickel-aluminum bronze, and then sequentially adding Al-Sr master alloy, Al-Zr master alloy and the pure Sc into the melted nickel-aluminum bronze to obtain a mixture; secondly, adding slag removing agents into the mixture and feeding high-purity nitrogen to refine the mixture; and thirdly, pouring the refined mixture into a casting ladle, allowing the mixture to stand, then removing slag and casting the mixture into ingots. Compared with conventional nickel-aluminum bronze, the scandium-zirconium-strontium composite micro-alloyed nickel-aluminum bronze is fine and compact in structure, the hardness of the scandium-zirconium-strontium composite micro-alloyed nickel-aluminum bronze is improved by 13.4%, the uniform corrosion rate is reduced by 5.2% when the scandium-zirconium-strontium composite micro-alloyed nickel-aluminum bronze is placed in 3.5% NaCl solution, the friction coefficient is obviously reduced, and the scandium-zirconium-strontium composite micro-alloyed nickel-aluminum bronze has wide application prospects in fields of propellers of marine ships, seawater pumps, offshore oil platforms, seawater pipeline systems and mechanical molds, fields of bearings, bushings and turbines which work under conditions of high speed, high pressure and high temperature, and the like.
Description
Technical field
The present invention relates to a kind of Aluminum-bronze alloy and its preparation method, especially a kind of New Nickel xantal and preparation method thereof, specifically a kind of scandium, zirconium and strontium compound microalloyed nickelaluminium bronze and preparation method thereof.
Background technology
Nickelaluminium bronze has good tribological property, anti-high speed seawater scouring performance, corrosion resistance and good forming property (founding performance, plastic making, weldability), being widely used in many fields such as machinery, naval vessel, offshore oil platform, is the material of main part of manufacturing the mechanical component such as marine ship propeller, sea-water pump, offshore oil platform, seawater pipe, machine die and the bearing of working, lining, turbine under high speed, high pressure and high temperature.Along with maximization, the deep water of naval vessel, ocean, offshore oil platform, and the be on active service prolongation in cycle and the further harshness of Service Environment, in the urgent need to the higher nickelaluminium bronze of performance.
As everyone knows, alloying and microalloying are the effective means that improves alloy structure and performance.From composition (copper (Cu) 77 ~ 82%, manganese (Mn) 0.5 ~ 4.0%, the aluminium (Al) 7.0 ~ 11.0% of nickelaluminium bronze, iron (Fe) 2.0 ~ 6.0%, nickel (Ni) 3.0 ~ 6.0%, zinc (Zn) ￡ 1.0%, surplus is impurity element), this alloy not yet carries out microalloying.Zirconium (Zr) or scandium (Sc) join in McGill metals, and zirconium in alloy graining process (Zr) or scandium (Sc) element and Al form A1
31580 DEG C of Zr(fusing points), Al
31320 DEG C of Sc(fusing points) etc. high-melting-point thing phase, the Heterogeneous Nucleation effect of playing is solidified in copper alloy follow-up, refinement alloy structure, in follow-up process of cooling after alloy graining, zirconium (Zr) or scandium (Sc) element also can be separated out from copper alloy, and form intermetallic compound (b equates) with Cu element, form intermetallic compound A1 with Al element
3zr or Al
3sc etc., alloy plays strengthening effect, and stops grain growth.And compound the adding of zirconium (Zr) and scandium (Sc) can form and compare Al
3zr or Al
3the ternary thing phase A1 that Sc size is less
3(Sc
l-x,zr
x), make the Microalloying Effect of zirconium (Zr) and scandium (Sc) more remarkable.Strontium (Sr) is a kind of active element, and solid solubility in xantal is minimum.In high manganic aluminum bronze, add micro strontium (Sr) can not only effectively purify the distributing homogeneity of melt, raising element, in addition the scaling loss of scandium (Sc), zirconium (Zr) is played a protective role.
Up to the present, China not yet have a kind of scandium with independent intellectual property right, zirconium and strontium compound microalloyed nickelaluminium bronze available, this restricted to a certain extent the marine ship propeller of China, sea-water pump, offshore oil platform, seawater pipe, machine die and at a high speed, the high speed development of the mechanical component such as the bearing of working under high pressure and high temperature, lining, turbine.
Summary of the invention
The object of the invention is on the basis of nickelaluminium bronze principal constituent, by adding Microamounts of Scandium, zirconium and strontium element, invent a kind of high performance nickelaluminium bronze and preparation method thereof, to meet the demand in the fields such as mechanical component such as the marine ship propeller of China, sea-water pump, offshore oil platform, seawater pipe, mould and the bearing of working, lining, turbine under high speed, high pressure and high temperature.
One of technical scheme of the present invention is:
Scandium, zirconium and a strontium compound microalloyed nickelaluminium bronze, is characterized in that it comprises:
Scandium (Sc), mass percent is 0.025 ~ 0.078%;
Zirconium (Zr), mass percent is 0.028 ~ 0.082%;
Strontium (Sr), mass percent is 0.012 ~ 0.057%;
Nickelaluminium bronze, surplus;
The mass percent sum of each component is 100%;
Described scandium, zirconium and strontium compound microalloyedly can purify melt, thinning microstructure, obstruction grain growth, generate reinforced alloys; Described nickelaluminium bronze is mainly made up of copper (Cu), nickel (Ni), aluminium (Al), manganese (Mn), zinc (Zn), iron (Fe), wherein, the mass percent of nickel (Ni) is 3.0 ~ 6.0%, the mass percent of aluminium (Al) is 7.0 ~ 11.0%, the mass percent of manganese (Mn) is 0.5 ~ 4.0%, the mass percent of zinc (Zn) is ￡ 1.0%, the mass percent of iron (Fe) is 2.0 ~ 6.0%, the mass percent of scandium (Sc) is 0.025 ~ 0.078%, and the mass percent sum of each component is 100%.
Two of technical scheme of the present invention is:
A preparation method for scandium, zirconium and strontium compound microalloyed nickelaluminium bronze, is characterized in that:
First, by after nickelaluminium bronze fusing, add successively Al-Sr master alloy, Al-Zr master alloy and pure Sc, in adding procedure, must add by listed order, add again rear a kind of master alloy or metal to be added after must waiting front a kind of master alloy to melt; Secondly, after all melting, add into Cheongju slag agent (removing impurity), then pass into high pure nitrogen refining; Finally, pour casting ladle into, after leaving standstill, remove the gred and be cast into ingot; Can obtain scandium, zirconium and strontium compound microalloyed nickelaluminium bronze.
In described Al-Sr master alloy, the mass percent of Sr is that the mass percent of Zr in 8.901%～10.879%, Al-Zr master alloy is 3.699%～4.521%.
In described Al-Sr master alloy, the best in quality per-cent of Sr is that the best in quality per-cent of Zr in 9.89%, Al-Zr master alloy is 4.11%.
The invention has the beneficial effects as follows:
(1) scandium of the present invention, zirconium and strontium compound microalloyed nickelaluminium bronze, the feature such as there is dense structure, crystal grain is tiny, hardness is high, erosion resistance is good, frictional coefficient is low.As scandium of the present invention, zirconium and strontium compound microalloyed nickelaluminium bronze (taking embodiment mono-as example), its hardness (HV) is 240.7HV, has improved 13.4% than hardness 212.125 HV of conventional nickelaluminium bronze (taking comparative example one as example); For another example, by GB GB 10124-88(uniform corrosion test method), it is 20 DEG C in 3.5% NaCl(test temperature) uniform corrosion rate in solution is that 0.02298 mm/a(is taking embodiment mono-as example), reduce by 5.2% than uniform corrosion rate 0.02424 mm/a of conventional nickelaluminium bronze (taking comparative example one as example).
(2) scandium of the present invention, zirconium and strontium compound microalloyed nickelaluminium bronze (taking embodiment mono-as example), and on high-frequency reciprocating friction wear testing machine (frequency 20Hz, load 1N, time 10min, stroke 0.8 ~ 1mm, friction pair part is the Si of diameter 4 mm
3n
4ball) dry friction coefficient be 0.023, reduced by 15.4% than the dry friction coefficient 0.0272 of conventional nickelaluminium bronze (taking comparative example one as example); Wet friction coefficient in 3.5%NaCl solution is that 0.022(is taking embodiment mono-as example), reduce by 12.35% than the wet friction coefficient 0.0251 of conventional nickelaluminium bronze (taking comparative example one as example), frictional coefficient significantly reduces.
(3) the present invention has obtained desirable preparation method by a large amount of tests, especially add in order the method for each master alloy and pure metal to control each component content by adopting, can easily obtain the nickelaluminium bronze material of satisfactory microalloying by technique of the present invention.
(4) the invention discloses the preparation method of a kind of scandium, zirconium and strontium compound microalloyed nickelaluminium bronze, broken to a certain extent the external blockade on new techniques to high-performance nickelaluminium bronze, can meet Chinese large-sized ship propeller, water pump
,the demand in the field such as valve, sea water desalting equipment.
Brief description of the drawings
Fig. 1 is scandium, zirconium and the strontium compound microalloyed nickelaluminium bronze metallographic structure of the embodiment of the present invention one.
Fig. 2 is the conventional nickelaluminium bronze metallographic structure of comparative example one of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated.
embodiment mono-.
As shown in Figure 1.
A kind of scandium, zirconium and strontium compound microalloyed nickelaluminium bronze are prepared from by the following method
Be formulated as example by 7.2268kg.
First, by nickelaluminium bronze commercially available or prefabricated 7.1kg (copper (Cu) 77 ~ 82%, manganese (Mn) 0.5 ~ 4.0%, aluminium (Al) 7.0 ~ 11.0%, iron (Fe) 2.0 ~ 6.0%, nickel (Ni) 3.0 ~ 6.0%, zinc (Zn) ￡ 1.0%, surplus is impurity element) fusing after add successively 35.9gAl-Sr master alloy (89.85%Al, the content of 9.89%Sr(strontium can float between 8.901%～10.879%, lower same), 0.16%Fe, 0.10%Si) (rate of loss of Sr is about 40%), 86.4g Al-Zr master alloy (95.69%Al, the content of 4.11%Zr(zirconium can float between 3.699%～4.521%, lower same), 0.20%Fe, 0.10%Si) (rate of loss of Zr is about 8%), the pure Sc of 4.5g (rate of loss of Sc is about 8%), described master alloy can directly be purchased from the market, also can adopt ordinary method to prepare voluntarily, after the medium front a kind of master alloy fusing of melting process, add again rear a kind of master alloy or metal, after all melting, add into Cheongju slag agent (removing impurity), then pass into high pure nitrogen refining 3min, finally, pour casting ladle into, leave standstill after insulation 1 ~ 5min, remove the gred and be cast into ingot, obtain scandium, zirconium and strontium compound microalloyed nickelaluminium bronze.
The nickelaluminium bronze of the present embodiment through spectrum actual measurement composition is: 4.52% Ni, and 9.97%Al, 1.05% Mn, 5.4% Fe, 0.62%Zn, 0.057% Sc, 0.045% Zr, 0.029% Sr, surplus is copper and a small amount of impurity element.
The nickelaluminium bronze fine microstructures of the present embodiment, densification (Fig. 1), its hardness (HV) is 240.7HV, by GB GB 10124-88(uniform corrosion test method), it is 20 DEG C in 3.5% NaCl(test temperature) uniform corrosion rate in solution is 0.02298 mm/a, under high-frequency reciprocating friction-wear test condition, with Si
3n
4ball is when rubbing, and aerial dry friction coefficient is 0.023, and the wet friction coefficient in 3.5%NaCl solution is 0.022.
embodiment bis-.
A kind of scandium, zirconium and strontium compound microalloyed nickelaluminium bronze are prepared from by the following method
Be formulated as example by 7.2268kg.
First, to after the fusing of 7.1kg nickelaluminium bronze, add successively 30.9gAl-Sr master alloy (89.85%Al, 9.89%Sr, 0.16%Fe, 0.10%Si) (rate of loss of Sr is about 40%), 91.9g Al-Zr master alloy (95.69%Al, 4.11%Zr, 0.20%Fe, 0.10%Si) (rate of loss of Zr is about 8%), the pure Sc of 4g (rate of loss of Sc is about 8%), described master alloy can directly be purchased from the market, also can adopt ordinary method to prepare voluntarily, after the medium front a kind of master alloy fusing of melting process, add again rear a kind of master alloy or metal, after all melting, add into Cheongju slag agent (removing impurity), then pass into high pure nitrogen refining 3min, finally, pour casting ladle into, leave standstill after insulation 1 ~ 5min, remove the gred and be cast into ingot, obtain scandium, zirconium and strontium compound microalloyed nickelaluminium bronze.
The nickelaluminium bronze of the present embodiment through spectrum actual measurement composition is: 4.52% Ni, and 10.34% Al, 1.06 % Mn, 5.18% Fe, 0.41%Zn, 0.055% Sc, 0.048% Zr, 0.025% Sr, surplus is copper and a small amount of impurity element.
embodiment tri-.
As shown in Figure 1.
A kind of scandium, zirconium and strontium compound microalloyed nickelaluminium bronze are prepared from by the following method
Be formulated as example by 7.2268kg.
First, by nickelaluminium bronze commercially available or prefabricated 7.157kg (copper (Cu) 77 ~ 82%, manganese (Mn) 0.5 ~ 4.0%, aluminium (Al) 7.0 ~ 11.0%, iron (Fe) 2.0 ~ 6.0%, nickel (Ni) 3.0 ~ 6.0%, zinc (Zn) ￡ 1.0%, surplus is impurity element) fusing after add successively 14.61gAl-Sr master alloy (89.85%Al, 9.89%Sr, 0.16%Fe, 0.10%Si) (rate of loss of Sr is about 40%), 53.51g Al-Zr master alloy (95.69%Al, 4.11%Zr, 0.20%Fe, 0.10%Si) (rate of loss of Zr is about 8%), the pure Sc of 1.96g (rate of loss of Sc is about 8%), described master alloy can directly be purchased from the market, also can adopt ordinary method to prepare voluntarily, after the medium front a kind of master alloy fusing of melting process, add again rear a kind of master alloy or metal, after all melting, add into Cheongju slag agent (removing impurity), then pass into high pure nitrogen refining 3min, finally, pour casting ladle into, leave standstill after insulation 1 ~ 5min, remove the gred and be cast into ingot, obtain scandium, zirconium and strontium compound microalloyed nickelaluminium bronze.
The nickelaluminium bronze of the present embodiment through spectrum actual measurement composition is: 4.52% Ni, and 9.97%Al, 1.05% Mn, 5.4% Fe, 0.62%Zn, 0.025% Sc, 0.028% Zr, 0.012% Sr, surplus is copper and a small amount of impurity element.
embodiment tetra-.
As shown in Figure 1.
A kind of scandium, zirconium and strontium compound microalloyed nickelaluminium bronze are prepared from by the following method
Be formulated as example by 7.2268kg.
First, by nickelaluminium bronze commercially available or prefabricated 6.995kg (copper (Cu) 77 ~ 82%, manganese (Mn) 0.5 ~ 4.0%, aluminium (Al) 7.0 ~ 11.0%, iron (Fe) 2.0 ~ 6.0%, nickel (Ni) 3.0 ~ 6.0%, zinc (Zn) ￡ 1.0%, surplus is impurity element) fusing after add successively 69.42gAl-Sr master alloy (89.85%Al, the content of 9.89%Sr(strontium can float between 8.901%～10.879%, lower same), 0.16%Fe, 0.10%Si) (rate of loss of Sr is about 40%), 156.7g Al-Zr master alloy (95.69%Al, the content of 4.11%Zr(zirconium can float between 3.699%～4.521%, lower same), 0.20%Fe, 0.10%Si) (rate of loss of Zr is about 8%), the pure Sc of 6.127g (rate of loss of Sc is about 8%), described master alloy can directly be purchased from the market, also can adopt ordinary method to prepare voluntarily, after the medium front a kind of master alloy fusing of melting process, add again rear a kind of master alloy or metal, after all melting, add into Cheongju slag agent (removing impurity), then pass into high pure nitrogen refining 3min, finally, pour casting ladle into, leave standstill after insulation 1 ~ 5min, remove the gred and be cast into ingot, obtain scandium, zirconium and strontium compound microalloyed nickelaluminium bronze.
The nickelaluminium bronze of the present embodiment through spectrum actual measurement composition is: 4.52% Ni, and 9.97%Al, 1.05% Mn, 5.4% Fe, 0.62%Zn, 0.078% Sc, 0.082% Zr, 0.057% Sr, surplus is copper and a small amount of impurity element.
The metallographic structure of the combined microalloying nickelaluminium bronze of embodiment bis-～tetra-changes not quite compared with embodiment mono-, all present tiny, compact structure, its hardness (HV) and be 20 DEG C in 3.5% NaCl(test temperature) uniform corrosion rate in solution etc. is far away higher than the requirement of national Specification.
comparative example one
As shown in Figure 1.
A kind of conventional nickelaluminium bronze can directly be bought from market, also can be prepared from by the following method
Be formulated as example by 7.2268kg.
First, by after 7.2268 kg nickelaluminium bronze fusings, add into Cheongju slag agent (removing impurity), then pass into high pure nitrogen refining 3min; Finally pour casting ladle into, leave standstill after 1 ~ 5min, remove the gred and be cast into ingot; Obtain conventional nickelaluminium bronze.
The nickelaluminium bronze of this comparative example through spectrum actual measurement composition is: 4.54% Ni, and 8.84%Al, 1.20% Mn, 5.05% Fe, 0.44%Zn, surplus is copper and a small amount of impurity element.
The nickelaluminium bronze of this comparative example is organized thick (Fig. 2), its hardness (HV) is 212.125HV, by GB GB 10124-88(uniform corrosion test method), it is 20 DEG C in 3.5% NaCl(test temperature) uniform corrosion rate in solution is 0.02424 mm/a, under high-frequency reciprocating friction-wear test condition, with Si
3n
4ball is when rubbing, and aerial dry friction coefficient is 0.0272, and the wet friction coefficient in 3.5%NaCl solution is 0.0251.
Below proportioning and the manufacture method of several common scandiums, zirconium and strontium compound microalloyed nickelaluminium bronze have only been listed, those skilled in the art can be according to above-described embodiment, suitably adjust the proportioning of each component and strictly manufacture by above-mentioned steps, can obtain desirable scandium, zirconium and strontium compound microalloyed nickelaluminium bronze.
The part that the present invention does not relate to all prior art that maybe can adopt same as the prior art is realized.
Claims (2)
1. scandium, zirconium and a strontium compound microalloyed nickelaluminium bronze, is characterized in that it comprises:
Scandium (Sc), mass percent is 0.025 ~ 0.078%;
Zirconium (Zr), mass percent is 0.028 ~ 0.082%;
Strontium (Sr), mass percent is 0.012 ~ 0.057%;
Nickelaluminium bronze, surplus;
The mass percent sum of each component is 100%;
Described scandium, zirconium and strontium compound microalloyedly can purify melt, thinning microstructure, obstruction grain growth, generate reinforced alloys.
2. a preparation method for nickelaluminium bronze described in claim 1, is characterized in that:
First, by after nickelaluminium bronze fusing, add successively Al-Sr master alloy, Al-Zr master alloy and pure Sc, in adding procedure, must add by listed order, add again rear a kind of master alloy or metal to be added after must waiting front a kind of master alloy to melt;
Secondly, after all melting, add into Cheongju slag agent (removing impurity), then pass into high pure nitrogen refining;
Finally, pour casting ladle into, after leaving standstill, remove the gred and be cast into ingot;
Can obtain scandium, zirconium and strontium compound microalloyed nickelaluminium bronze; In described Al-Sr master alloy, the mass percent of Sr is that the mass percent of Zr in 8.901%～10.879%, Al-Zr master alloy is 3.699%～4.521%;
In described Al-Sr master alloy, the mass percent of Sr is that the mass percent of Zr in 9.89%, Al-Zr master alloy is 4.11%.
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| KR20000059365A (en) * | 1999-03-03 | 2000-10-05 | 황해웅 | Cu-Zn-Al, Sr, Ti, B alloys for EDM(Energy Discharge Machine) wire and its manufacturing method |
| CN1492064A (en) * | 2003-09-05 | 2004-04-28 | 中国船舶重工集团公司第七二五研究所 | Cast copper alloy for producing sea water pump valve and its preparing method |
| CN101629254A (en) * | 2009-06-25 | 2010-01-20 | 中南大学 | Multi-element composite micro-alloying copper alloy with high strength and high conductivity and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000059365A (en) * | 1999-03-03 | 2000-10-05 | 황해웅 | Cu-Zn-Al, Sr, Ti, B alloys for EDM(Energy Discharge Machine) wire and its manufacturing method |
| CN1492064A (en) * | 2003-09-05 | 2004-04-28 | 中国船舶重工集团公司第七二五研究所 | Cast copper alloy for producing sea water pump valve and its preparing method |
| CN101629254A (en) * | 2009-06-25 | 2010-01-20 | 中南大学 | Multi-element composite micro-alloying copper alloy with high strength and high conductivity and preparation method thereof |
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