CN102899522B - Zirconium micro-alloyed nickel-aluminum bronze - Google Patents
Zirconium micro-alloyed nickel-aluminum bronze Download PDFInfo
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Abstract
The invention relates to zirconium micro-alloyed nickel-aluminum bronze and a preparation method thereof. The zirconium micro-alloyed nickel-aluminum bronze is characterized in that the alloy mainly comprises nickel-aluminum bronze and zirconium (Zr) with mass percentage of 0.03 to 0.1%. The preparation process flow of alloy comprises the following steps of: firstly, after melting the nickel-aluminum bronze, and then adding Al-Zr intermediate alloy; after completely melting, adding a deslagging agent, and then introducing a high-purity nitrogen gas to refine for 3min; and finally, pouring into a ladle, keeping stand and keeping the temperature for 1-5min, deslagging and casting into ingots. Compared with the conventional nickel-aluminum bronze, the alloy provided by the invention has a fine microstructure, the hardness is increased by 8.1%, the uniform corrosion rate in 3.5% NaCl solution is reduced to 5.3%, and the coefficient of friction is obviously reduced; and the alloy has wide application prospects in fields such as marine ship propellers, seawater pumps, marine oil platforms, seawater piping systems, mechanical molds and bearings, bushings and turbines which work at high speed, high pressure and high temperature.
Description
Technical field
The present invention relates to a kind of Aluminum-bronze alloy and its preparation method, especially a kind of nickel aluminum bronze and preparation method thereof, specifically a kind of Zirconium-micro-alloyed nickelaluminium bronze and preparation method thereof.
Background technology
Nickelaluminium bronze has excellent anti-high speed seawater scouring performance, corrosion resistance and tribological property, and relative to super-duplex stainless steel, its forming property is good, the prices of raw and semifnished materials and low cost of manufacture.But it is when for the manufacture of heavy parts, because foundry goods speed of cooling is slow, causes cast structure thick, seriously inhibit the raising of cast properties.
As everyone knows, alloying and microalloying are the effective means improving copper alloy microstructure and property.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) element joins in McGill metals, and first zirconium (Zr) and Al form A1 in alloy graining process
3zr(fusing point 1580 DEG C) etc. high-melting-point thing phase, Heterogeneous Nucleation effect of playing is solidified in the follow-up of alloy, refining alloy tissue, improves " the slow cooling fragility " of alloy.
Up to the present, China not yet has a kind of Zirconium-micro-alloyed nickelaluminium bronze with independent intellectual property right available, this constrain to a certain extent China's marine vessel water screw, sea-water pump, offshore oil platform, seawater pipe, mould and at a high speed, the high speed development of the mechanical component such as bearing, lining, turbine that works under high pressure and high temperature.
Summary of the invention
The object of the invention is on the basis of nickel aluminum bronze main component, by adding trace zirconium element, inventing a kind of high performance nickelaluminium bronze and preparation method thereof.
One of technical scheme of the present invention is:
A Zirconium-micro-alloyed nickelaluminium bronze, is characterized in that: it forms primarily of with zirconium (Zr), and wherein the mass percent of zirconium is 0.03 ~ 0.1%, and surplus is nickelaluminium bronze.Described nickelaluminium bronze is primarily of copper (Cu), nickel (Ni), aluminium (Al), manganese (Mn), zinc (Zn), iron (Fe) composition, 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%, and the mass percent of zinc (Zn) is 1.0%, and the mass percent of iron (Fe) is 2.0 ~ 6.0%, surplus is copper (Cu) and a small amount of impurity element, and the mass percent sum of each component is 100%.
Two of technical scheme of the present invention is:
A preparation method for Zirconium-micro-alloyed nickelaluminium bronze, is characterized in that:
First, after being melted by nickelaluminium bronze, Al-Zr master alloy is then added; After all melting, add slag-cleaning agent (removing impurity), then pass into high pure nitrogen refining; Finally, pour casting ladle into, after leaving standstill insulation 1 ~ 5min, remove the gred and be cast into ingot; Zirconium-micro-alloyed nickelaluminium bronze can be obtained.
In described Al-Zr master alloy, the mass percent of Zr is 3.699 ~ 4.521%.
In described Al-Zr master alloy, the best in quality per-cent of Zr is 4.11%.
The invention has the beneficial effects as follows:
(1) nickelaluminium bronze that the present invention is Zirconium-micro-alloyed, has and organizes the features such as crystal grain is tiny, hardness is high, erosion resistance is good, frictional coefficient is low.Nickelaluminium bronze (for embodiment one) as Zirconium-micro-alloyed in the present invention, its hardness (HV) is 229.3HV, improves 8.1% than hardness 212.125 HV of conventional nickelaluminium bronze (for comparative example one); 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 0.02295 mm/a(is for embodiment one), reduce 5.3% than uniform corrosion rate 0.02424 mm/a of conventional nickelaluminium bronze (for comparative example one).
(2) nickelaluminium bronze (for embodiment one) that the present invention is Zirconium-micro-alloyed, on high-frequency reciprocating friction wear testing machine, (friction pair part is the Si of diameter 4 mm for frequency 20Hz, load 1N, time 10min, stroke 0.8 ~ 1mm
3n
4ball) dry friction coefficient be 0.0238, reduce 12.5% than the dry friction coefficient 0.0272 of conventional nickelaluminium bronze (for comparative example one); Wet friction coefficient in 3.5%NaCl solution is that 0.0243(is for embodiment one), reduce 3.19 % than the wet friction coefficient 0.0251 of conventional nickelaluminium bronze (for comparative example one), frictional coefficient significantly reduces.
(3) the present invention obtains desirable preparation method by a large amount of tests, easily can obtain satisfactory Zirconium-micro-alloyed nickelaluminium bronze material by processing parameter of the present invention.
(4) the invention discloses a kind of preparation method of Zirconium-micro-alloyed nickelaluminium bronze, broken the external blockade on new techniques to high-performance nickelaluminium bronze to a certain extent, Chinese large-sized ship propeller, water pump can be met
,the demand in the field such as valve, sea water desalting equipment.
Accompanying drawing explanation
Fig. 1 is the Zirconium-micro-alloyed 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 one.
As shown in Figure 1.
A Zirconium-micro-alloyed nickelaluminium bronze, its preparation method is:
Example is formulated as by 8.9577kg.
First, make 8.85kg by oneself (see comparative example one) or commercially available nickelaluminium bronze (composition: 79.77Cu, 1.1Mn, 8.84Al, 5.05Fe, 4.54Ni, 0.58Zn, numeral in embodiment before all elements symbol all represents mass percent, lower with) fusing after add 107.7g Al-Zr master alloy (content of 95.69%Al, 4.11%Zr(zirconium is good with 3.699 ~ 4.521%), 0.20%Fe, 0.10%Si) (rate of loss of Zr is about 8%), described master alloy can directly be purchased from the market, and ordinary method also can be adopted to prepare voluntarily; After all melting, add slag-cleaning agent (removing impurity), then pass into high pure nitrogen refining 3min; Finally, pour casting ladle into, after leaving standstill insulation 1 ~ 5min, remove the gred and be cast into ingot; Namely Zirconium-micro-alloyed nickelaluminium bronze is obtained.
Nickelaluminium bronze after the combined microalloying of the present embodiment through spectrum actual measurement composition is: 4.43% Ni, 9.92% Al, 1.07% Mn, 5.24% Fe, 0.52%Zn, 0.045% Zr, and surplus is copper and a small amount of impurity element.
The present embodiment Zirconium-micro-alloyed after nickelaluminium bronze fine microstructures (Fig. 1), its hardness (HV) is 229.3HV, 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 0.02295 mm/a, under high-frequency reciprocating friction-wear test condition, with Si
3n
4ball is to when rubbing, and aerial dry friction coefficient is 0.0238, and the wet friction coefficient in 3.5%NaCl solution is 0.0243.
embodiment two.
A Zirconium-micro-alloyed nickelaluminium bronze, its preparation method is:
Example is formulated as by 8.9577kg.
First, by 8.855kg nickelaluminium bronze (composition: 78.34Cu, 1.30Mn, 9.94Al, 5.52Fe, 4.30Ni, 0.43Zn, numeral in embodiment before all elements symbol all represents mass percent, lower with) fusing after add 102.7g Al-Zr master alloy (95.69%Al, 4.11%Zr, 0.20%Fe, 0.10%Si) (rate of loss of Zr is about 8%), described master alloy can directly be purchased from the market, and ordinary method also can be adopted to prepare voluntarily; After all melting, add slag-cleaning agent (removing impurity), then pass into high pure nitrogen refining 3min; Finally, pour casting ladle into, after leaving standstill insulation 1 ~ 5min, remove the gred and be cast into ingot; Namely Zirconium-micro-alloyed nickelaluminium bronze is obtained.
The present embodiment Zirconium-micro-alloyed after nickelaluminium bronze through spectrum actual measurement composition be: 4.29 % Ni, 10.91% Al, 1.28 % Mn, 5.69% Fe, 0.40%Zn, 0.0434% Zr, surplus is copper and a small amount of impurity element.
Embodiment three.
A Zirconium-micro-alloyed nickelaluminium bronze, its preparation method is:
Example is formulated as by 8.9577kg.
First, make 8.887kg by oneself (see comparative example one) or commercially available nickelaluminium bronze (composition: 79.77Cu, 1.1Mn, 8.84Al, 5.05Fe, 4.54Ni, 0.58Zn, numeral in embodiment before all elements symbol all represents mass percent, lower with) fusing after add 71.07g Al-Zr master alloy (content of 95.69%Al, 4.11%Zr(zirconium is good with 3.699 ~ 4.521%), 0.20%Fe, 0.10%Si) (rate of loss of Zr is about 8%), described master alloy can directly be purchased from the market, and ordinary method also can be adopted to prepare voluntarily; After all melting, add slag-cleaning agent (removing impurity), then pass into high pure nitrogen refining 3min; Finally, pour casting ladle into, after leaving standstill insulation 1 ~ 5min, remove the gred and be cast into ingot; Namely Zirconium-micro-alloyed nickelaluminium bronze is obtained.
The present embodiment Zirconium-micro-alloyed after nickelaluminium bronze through spectrum actual measurement composition be: 4.43% Ni, 9.92% Al, 1.07% Mn, 5.24% Fe, 0.52%Zn, 0.03% Zr, surplus is copper and a small amount of impurity element.
embodiment four.
A Zirconium-micro-alloyed nickelaluminium bronze, its preparation method is:
Example is formulated as by 8.9577kg.
First, make 8.721kg by oneself (see comparative example one) or commercially available nickelaluminium bronze (composition: 79.77Cu, 1.1Mn, 8.84Al, 5.05Fe, 4.54Ni, 0.58Zn, numeral in embodiment before all elements symbol all represents mass percent, lower with) fusing after add 236.9g Al-Zr master alloy (content of 95.69%Al, 4.11%Zr(zirconium is good with 3.699 ~ 4.521%), 0.20%Fe, 0.10%Si) (rate of loss of Zr is about 8%), described master alloy can directly be purchased from the market, and ordinary method also can be adopted to prepare voluntarily; After all melting, add slag-cleaning agent (removing impurity), then pass into high pure nitrogen refining 3min; Finally, pour casting ladle into, after leaving standstill insulation 1 ~ 5min, remove the gred and be cast into ingot; Namely Zirconium-micro-alloyed nickelaluminium bronze is obtained.
The present embodiment Zirconium-micro-alloyed after nickelaluminium bronze through spectrum actual measurement composition be: 4.43% Ni, 9.92% Al, 1.07% Mn, 5.24% Fe, 0.52%Zn, 0.1% Zr, surplus is copper and a small amount of impurity element.
Metallographic structure shows, embodiment two ~ tetra-Zirconium-micro-alloyed after the weave construction of nickelaluminium bronze and mechanical property close with embodiment one.
comparative example one.
As shown in Figure 2.
A kind of conventional nickelaluminium bronze, is prepared from by the following method
Example is formulated as by 7.2268kg.
First, after 7.2268 kg nickelaluminium bronze fusings, add slag-cleaning agent (removing impurity), then pass into high pure nitrogen refining 3min; Finally, pour casting ladle into, after leaving standstill 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, 8.84%Al, 1.20% Mn, 5.05% Fe, 0.44%Zn, and 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 to 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 Zirconium-micro-alloyed nickelaluminium bronze is only listed, those skilled in the art can according to above-described embodiment, suitably adjust the proportioning of each component and strictly manufacture by above-mentioned steps, desirable Zirconium-micro-alloyed nickelaluminium bronze can be obtained.
The part that the present invention does not relate to prior art that maybe can adopt all same as the prior art is realized.
Claims (2)
1. a Zirconium-micro-alloyed nickelaluminium bronze, it is primarily of nickelaluminium bronze and zirconium (Zr) composition, and wherein the mass percent of zirconium is 0.03 ~ 0.1%, and surplus is nickelaluminium bronze; Described nickelaluminium bronze is primarily of copper (Cu), nickel (Ni), aluminium (Al), manganese (Mn), zinc (Zn), iron (Fe) composition, 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%, and the mass percent of zinc (Zn) is 1.0%, and the mass percent of iron (Fe) is 2.0 ~ 6.0%, surplus is copper (Cu) and a small amount of impurity element, and the mass percent sum of each component is 100%; Its feature its adopt following methods manufacture and obtain: first, after nickelaluminium bronze fusing, add Al-Zr master alloy; In described Al-Zr master alloy, the mass percent of Zr is 3.699 ~ 4.521%;
Secondly, after all melting, add slag-cleaning agent to remove impurity, then pass into high pure nitrogen refining;
Finally, pour casting ladle into, remove the gred and be cast into ingot after leaving standstill;
Can obtain Zirconium-micro-alloyed nickelaluminium bronze, described zirconium is formed with the form of Al-Zr master alloy.
2. Zirconium-micro-alloyed nickelaluminium bronze according to claim 1, is characterized in that the mass percent of Zr in described Al-Zr master alloy is 4.11%.
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| EP3187605A1 (en) * | 2015-12-28 | 2017-07-05 | Casa Maristas Azterlan | Method for obtaining hybrid aluminium bronze alloy |
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| RU2560391C2 (en) * | 2013-11-18 | 2015-08-20 | Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) | Production of aluminium alloy with content of zirconium over 30% from zirconium-bearing oxide material (versions) |
| CN104313365B (en) * | 2014-10-14 | 2016-09-07 | 上海交通大学 | A kind of preparation method of nickel-aluminum bronze |
| CN105671397A (en) * | 2016-01-23 | 2016-06-15 | 中山百鸥医药科技有限公司 | Worm gear of grain packing machine for processing omega-3 fish oil soft capsules |
| CN110629068A (en) * | 2018-06-25 | 2019-12-31 | 南京理工大学 | Zirconium microalloyed multi-element complex cast aluminum bronze alloy |
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| 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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| 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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| EP3187605A1 (en) * | 2015-12-28 | 2017-07-05 | Casa Maristas Azterlan | Method for obtaining hybrid aluminium bronze alloy |
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