CN101435032A - Corrosion resistant multi-aluminum bronze material for pipe - Google Patents
Corrosion resistant multi-aluminum bronze material for pipe Download PDFInfo
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Abstract
The invention provides a pipe corrosion-resistant multielement aluminium bronze alloy material and the ingredients are as follows: 4.0 to 10.0wt percent of Al, 1.0 to 4.5wt percent of Fe, 1.0 to 4.5wt percent of Mn, 0.8 to 4.0wt percent of Ni, 0.05 to 0.5wt percent of Cr and the balance of Cu and unavoidable impurities; in casting state, the tensile strength is more than 385MPa, the yield strength is more than 180MPa, the yield ratio is more than 0.48, and the specific elongation is more than 27 percent; in annealing state, the tensile strength is more than 525MPa, the yield strength is more than 285MPa, the yield ratio is more than 0.55, the specific elongation is more than 42 percent and the complete immersion uniform corrosion rate is 0.01 to 0.035mm/a; the copper alloy has excellent performance, is particularly suitable for the environment with high flow rate of seawater and is an ideal material for manufacturing sea water desalinating condenser equipment, shipping sea water condenser equipment and seashore power plant condensers.
Description
Technical field
The present invention relates to an Albatra metal-, relate in particular to a kind of corrosion resistant multi-aluminum bronze material for pipe, belong to the non-ferrous metal technical field.
Background technology
McGill metals has excellent physical chemistry, mechanical property, anticorrosive wear-resistant performance, it is the engineering materials of a class high comprehensive performance, in civilian, military industry, occupy important status, be widely used in structural parts, wearing piece and the corrosion barrier etc. of working in the occasions such as mechanical industry, boats and ships and ocean industry, household electrical appliances industry, petrochemical industry, electrical industry and building industry.
The corrosion resistant material that present countries in the world are used for condenser adopts the copper-nickel alloy that adds the As one-ton brass, adds the As aluminum brass and contain 10% and 30% nickel always, and the titanium alloy of use and stainless steel etc. are also arranged.
Continuous deterioration along with seawater quality, the corrosion resistant material of existing condenser can not meet the demands fully, intensity is on the low side, the shortcoming of the poor-performing of anti-the erosion corrosion as now existing with copper alloy, and titanium alloy and stainless steel then exist the serious problem of marine biological polution.In addition, sea water desalting equipment, boats and ships and Coastal Power Plant exist urgent requirement to the good copper pipe of high strength anti-corrosion performance always.China has developed the HSn70-1A-0.05 one-ton brass that adds Al at present, adds the HA177-2A-0.5 aluminum brass of Ni and B etc., has also developed the HSn-70-1B alloy of the fresh water generation station-service that pollutes simultaneously.U.S. Olin company develops Zn, and (((0.03～0.06wt%) surplus is the nickeliferous arsenical brass of copper to 2.5～3.5wt%)-As to 25～35wt%)-Ni.Japan develops Zn (10～40wt%)-P (0.005～0.07wt%)-Sn (0.05～1.0wt%)-Al (0.05～1.0wt%)-As (0.005～1.0wt%)-Sb (copper alloy of 0.005～1.0wt%), add one or more elements among B, Ni, Co, Cr, Mn, Te, In, Be, the Ti, it adds total amount is 0.005～2.0wt%, and surplus is a copper.Poland non-ferrous metal research institute has developed the aluminum brass that Ni, Cr, Mn improve.
Above-mentioned disclosed copper alloy though can adapt to certain Working environment, with regard to alloy seawater corrosion resistance, anti-erosion corrosion, still exists some problems.For example, one-ton brass and aluminum brass exist that intensity is on the low side, the problem of the poor-performing of anti-the erosion corrosion, and this has just limited the flow velocity of seawater in condenser and will use below 3m/s, greatly reduces the efficient of equipment.
(typical case's representative is: C68700 and the tube bank material that uses in briny environment at present mainly contains aluminum brass, its composition is 76～79wt%Cu, 1.8～2.5wt%Al, surplus is Zn), (typical case's representative is one-ton brass: C44300, its composition is 70～73wt%Cu, 0.8～1.2wt%Sn, 0.06wt%Fe, 0.02～0.06As, surplus is Zn), (typical case's representative is Alpaka: C70600, its composition is 9.0～11wt%Ni, 1.0～1.8wt%Fe, 1.0wt%Mn, 1.0wt%Zn, and surplus is Cu; C71500, its composition is 29～33wt%Ni, 0.4～0.7wt%Fe, 1.0wt%Mn, 1.0wt%Zn, surplus is Cu), stainless steel (typical case's representative is 1Cr18Ni9Ti, 0Cr18Ni9Ti, 00Cr19Ni10 and 00Cr18Ni12Mo2) and titanium alloy (typical case's representative is TA2) etc.
Limitation and deficiency that above-mentioned tube bank material uses in corrosive environment of sea water are: aluminum brass and one-ton brass exist that intensity is on the low side, dealloying (dezincify, dealuminzation) and the serious problem of erosion corrosion; There is the comparatively defective of difficulty of cost height, processing in Alpaka; There are the problem that cost is higher, marine biological polution is serious in titanium alloy and stainless steel.
Summary of the invention
The objective of the invention is to overcome the existing deficiency that exists, the novel corrosion resistant multi-aluminum bronze material for pipe of a kind of low cost, high strength, high-yield-ratio is provided.
Purpose of the present invention is achieved through the following technical solutions:
Corrosion resistant multi-aluminum bronze material for pipe, the quality percentage composition of composition is following-
Al 4.0～10.0wt％，
Fe 1.0～4.5wt％，
Mn 1.0～4.5wt％，
Ni 0.8～4.0wt％，
Cr 0.05～0.5wt％，
All the other components of this copper alloy are Cu and unavoidable impurities.
Further, above-mentioned corrosion resistant multi-aluminum bronze material for pipe, the tensile strength of described copper alloy under as cast condition is more than the 385MPa, yield strength is more than the 180MPa, yield tensile ratio is more than 0.48, unit elongation is more than 27%.
Further, above-mentioned corrosion resistant multi-aluminum bronze material for pipe, the tensile strength of described copper alloy under annealed state are more than the 525MPa, yield strength is more than the 285MPa, yield tensile ratio is more than 0.55, unit elongation is more than 42%, soaks uniform corrosion speed at 0.01～0.035mm/a entirely.
Substantive distinguishing features and obvious improvement that technical solution of the present invention is outstanding are mainly reflected in:
Copper alloy of the present invention has good intensity, high yield tensile ratio and excellent corrosion resistant performance, tensile strength under its as cast condition is that 385MPa is above, yield strength 180MPa above, yield tensile ratio 0.48 or more, unit elongation be more than 27%, the tensile strength 525MPa under the annealed state is above, more than the yield strength 285MPa, yield tensile ratio more than 0.55, unit elongation more than 42%, soak uniform corrosion speed at 0.01～0.035mm/a entirely; This alloy is the same with aluminum brass, one-ton brass and Alpaka, has the ability of the resisting contamination from marine organism stronger than stainless steel and titanium alloy; The existence of cupric ion etc. has suppressed halobiontic grows and grows, and has reduced the frequency of maintenance of equipment, has reduced working strength of workers, has improved usage ratio of equipment; This copper alloy production cost is low, tube wall thin, good heat conductivity, is particularly suitable for high seawater velocity environment, is the suitable material of making sea water desaltination condenser apparatus, boats and ships sea water condenser equipment, power station, strand condenser.
Embodiment
Sea water desaltination condenser apparatus, boats and ships sea water condenser equipment, power station, strand condenser apparatus work characteristics that the present invention works down according to high seawater velocity environment, develop a kind of novel tube bank Cu alloy material, this copper alloy has favorable mechanical performance and sea water corrosion resistant, also possesses high strength, high-yield-ratio and superior corrosion resistance energy simultaneously.
The component content of corrosion resistant multi-aluminum bronze material for pipe is, Al:4.0～10.0wt%, and Fe:1.0～4.5wt%, Mn:1.0～4.5wt%, Ni:0.8～4.0wt%, Cr:0.05～0.5wt%, all the other components are Cu and unavoidable impurities.
Adopted multi-element alloyed principle: the Al element solid solution forms alumina protective layer at alloy surface in copper, improve the corrosion resistance nature of alloy, in addition, and the flowability when interpolation Al element also improves alloy casting and the surface quality of foundry goods.The Mn element is improved the intensity of bell metal, and when containing Mn amount and increase, intensity increases considerably and plasticity reduces few.When the Fe in the bell metal reaches certain value, will form K phase compound, K is a crystallization nuclei with tiny particle when solidifying, and in crystal grain thinning, has improved intensity, hardness and the solidity to corrosion of bell metal.The effect of Ni is the raising solidity to corrosion, prevents " slow cooling fragility " and crystal grain thinning.A small amount of Cr purifies the alloy liquation, can also improve the mechanical property of alloy, the grain growth when suppressing alloy annealing, the intensity and the hardness of raising annealed material.Just because of multi-element alloyed effect, make on the copper alloy matrix of the present invention the disperse particle of multiple high strength phase that distributing, thereby make the mechanical property of this copper alloy be better than general xantal greatly, under briny environment, show higher corrosion resistance nature especially.
The strand of this Cu alloy material can obtain on the melting of routine and casting equipment.Adopt the method for " casting-hot rolling-cold rolling " on conventional equipment, to obtain sheet material, also can adopt the method for " casting-hot extrude-cold rolling-stretching " on conventional equipment, to obtain tubing, the material of two kinds of different sizes that technology obtained, its performance unanimity.
It is the good α phase of plasticity that the annealed state of copper alloy is organized matrix, and the K phase particle of the extreme hardness that distributing equably again on it has formed good corrosion-resistant tissue, so alloy of the present invention just can make its performance obtain adjusting and improving by thermomechanical treatment comprehensively.
The as-cast characteristic of alloy of the present invention, the performance after the thermal treatment and one-ton brass (heat treatment state), aluminum brass (heat treatment state), Alpaka (heat treatment state) performance compare, and be as shown in table 1.
Table 1
| Tensile strength Rm/MPa | Yield strength Rm/MPa | Yield tensile ratio | Unit elongation A/% | Uniform corrosion speed mm/a | |
| The present invention's (as cast condition) | 385 | 180 | 0.48 | 27 | —— |
| The present invention's (heat treatment state) | 525 | 285 | 0.55 | 42 | 0.01～0.035 |
| Aluminum brass | 392 | 150 | 0.38 | 40 | 0.02～0.18 ② |
| One-ton brass | 365 | 152 | 0.42 | 65 | 0.0075～0.10 ① |
| Alpaka (B10-1-1) | 290 | 90 | 0.31 | 30 | 0.01～0.0164 ① |
| Alpaka (B30-1-1) | 360 | 120 | 0.33 | 30 | 0.03～0.13 ① |
In the table: 1. subscript is represented data from " engineering materials application manual " (the 2nd edition);
2. subscript is represented data from " material corrosion and protection ".
As can be seen from Table 1, tensile strength of alloys of the present invention is 1.34 times of aluminum brass, is 1.44 times of one-ton brass, is 1.81 times of Alpaka (B10-1-1), is 1.46 times of Alpaka (B30-1-1).The yield strength of alloy of the present invention is 1.9 times of aluminum brass, is 1.88 times of one-ton brass, is 3.17 times of Alpaka (B10-1-1), is 2.38 times of Alpaka (B30-1-1).The yield tensile ratio of alloy of the present invention is 1.45 times of aluminum brass, is 1.31 times of one-ton brass, is 1.77 times of Alpaka (B10-1-1), is 1.67 times of Alpaka (B30-1-1).The unit elongation of alloy of the present invention is 1.05 times of aluminum brass, is 0.65 times of one-ton brass, is 1.4 times of Alpaka (B10-1-1), is 1.4 times of Alpaka (B30-1-1).Corrosion resistance nature in Mare Tranquillitatis water of alloy of the present invention and used aluminum brass, one-ton brass, Alpaka (B10-1-1) and Alpaka (B30-1-1) are suitable.
In addition, alloy of the present invention is the same with aluminum brass, one-ton brass and Alpaka, has the ability of the resisting contamination from marine organism stronger than stainless steel and titanium alloy.Grow and grow because the existence of cupric ion etc. has suppressed halobiontic, can reduce the frequency of maintenance of equipment like this, reduce working strength of workers, the raising efficiency of equipment.Adopt this material, can reduce the cost of condenser tube beam material, improve plant factor, alleviate working strength of workers, produce good economical, societal benefits.
Below by specific embodiment technical scheme of the present invention is further described.
Embodiment 1:
With raw material according to mass percent: Al 7.3wt%, Fe 4.4wt%, Mn 1.1wt%, Ni 2.6wt%, Cr 0.05wt%, all the other components are Cu and unavoidable impurities.It should be noted that in the fusion process of alloy, each element all has scaling loss in various degree, its burn out rate Al:7%, Fe:4%, Mn:3.5%, Ni:1.5%, Cr:1.8% should supply in the process of batching.Melting in medium-frequency induction furnace, vertical D.C.casting is cast as ingot blank.In process furnace, be heated to 900 ℃ after milling face, on hot rolls, carry out hot rolling behind the insulation certain hour and handle, make and roll the attitude slab.Surface treatment is carried out final state thermal treatment subsequently after multi-pass is cold-rolled to the thick sheet material of 2mm, obtains the high strength anti-corrosion alloy material of structure property excellence.
Material after present embodiment alloy casting state and the thermal treatment is carried out performance test, the results are shown in Table 2.
Table 2
| Tensile strength Rm/MPa | Yield strength Rm/MPa | Yield tensile ratio | Unit elongation A/% | Erosion rate mm/a | |
| As cast condition | 386 | 193 | 0.5 | 29 | —— |
| Heat treatment state | 531 | 297 | 0.56 | 42.6 | 0.01 |
Embodiment 2:
With raw material according to the quality percentage: Al 5.9wt%, Fe 1.1wt%, Mn 4.2wt%, Ni 3.0wt%, Cr 0.25wt%, all the other components are Cu and unavoidable impurities.It should be noted that in the fusion process of alloy, each element all has scaling loss in various degree, its burn out rate Al:8%, Fe:3%, Mn:3.2%, Ni:1.7%, Cr:1.8% should supply in the process of batching.Melting in medium-frequency induction furnace, vertical D.C.casting is cast as ingot blank.In process furnace, be heated to 900 ℃ after milling face, on hot rolls, carry out hot rolling behind the insulation certain hour and handle, make and roll the attitude slab.Surface treatment is carried out final state thermal treatment subsequently after multi-pass is cold-rolled to the thick sheet material of 2mm, obtains the high strength anti-corrosion alloy material of structure property excellence.
Material after present embodiment alloy casting state and the thermal treatment is carried out performance test, the results are shown in Table 3.
Table 3
| Tensile strength Rm/MPa | Yield strength Rm/MPa | Yield tensile ratio | Unit elongation A/% | Erosion rate mm/a | |
| As cast condition | 398 | 195 | 0.49 | 28.5 | —— |
| Heat treatment state | 528 | 290 | 0.55 | 42.5 | 0.02 |
Embodiment 3:
With raw material according to the quality percentage: Al 10.0wt%, Fe 3.3wt%, Mn 2.4wt%, Ni 0.8wt%, Cr 0.5wt%, all the other components are Cu and unavoidable impurities.It should be noted that in the fusion process of alloy, each element all has scaling loss in various degree, its burn out rate Al:7.4%, Fe:3.5%, Mn:3.9%, Ni:1.4%, Cr:1.8% should supply in the process of batching.Melting in medium-frequency induction furnace, vertical D.C.casting is cast as ingot blank.In process furnace, be heated to 900 ℃ after milling face, on hot rolls, carry out hot rolling behind the insulation certain hour and handle, make and roll the attitude slab.Surface treatment is carried out final state thermal treatment subsequently after multi-pass is cold-rolled to the thick sheet material of 2mm, obtains the high strength anti-corrosion alloy material of structure property excellence.
Material after present embodiment alloy casting state and the thermal treatment is carried out performance test, the results are shown in Table 4.
Table 4
| Tensile strength Rm/MPa | Yield strength Rm/MPa | Yield tensile ratio | Unit elongation A/% | Erosion rate mm/a | |
| As cast condition | 392 | 192 | 0.49 | 28.7 | —— |
| Heat treatment state | 526 | 295 | 0.56 | 42.2 | 0.025 |
Embodiment 4:
With raw material according to the quality percentage: Al 4.0wt%, Fe 3.6wt%, Mn 2.4wt%, Ni 4.0wt%, Cr 0.2wt%, all the other components are Cu and unavoidable impurities.It should be noted that in the fusion process of alloy, each element all has scaling loss in various degree, its burn out rate Al:7.9%, Fe:3.6%, Mn:3.2%, Ni:1.3%, Cr:1.8% should supply in the process of batching.Melting in medium-frequency induction furnace, vertical D.C.casting is cast as ingot blank.In process furnace, be heated to 900 ℃ after milling face, on hot rolls, carry out hot rolling behind the insulation certain hour and handle, make and roll the attitude slab.Surface treatment is carried out final state thermal treatment subsequently after multi-pass is cold-rolled to the thick sheet material of 2mm, obtains the high strength anti-corrosion alloy material of structure property excellence.
Material after present embodiment alloy casting state and the thermal treatment is carried out performance test, the results are shown in Table 5.
Table 5
| Tensile strength Rm/MPa | Yield strength Rm/MPa | Yield tensile ratio | Unit elongation A/% | Erosion rate mm/a | |
| As cast condition | 398 | 199 | 0.5 | 28.2 | —— |
| Heat treatment state | 525 | 289 | 0.55 | 42 | 0.035 |
In sum, this copper alloy has good intensity, high yield tensile ratio and excellent corrosion resistant performance, and production cost is low, tube wall is thin, good heat conductivity; Being specially adapted to high seawater velocity environment, is the best materials of making sea water desaltination condenser apparatus, boats and ships sea water condenser equipment, power station, strand condenser, better is implemented in safety in the seawater, stable, long term operation.
Below only be concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the rights protection scope of the present invention.
Claims (3)
1. corrosion resistant multi-aluminum bronze material for pipe, it is characterized in that: the quality percentage composition of its composition is as follows---
Al 4.0～10.0wt％，
Fe 1.0～4.5wt％，
Mn 1.0～4.5wt％，
Ni 0.8～4.0wt％，
Cr 0.05～0.5wt％，
All the other components of this copper alloy are Cu and unavoidable impurities.
2. corrosion resistant multi-aluminum bronze material for pipe according to claim 1 is characterized in that: the tensile strength of described copper alloy under as cast condition is more than the 385MPa, yield strength is more than the 180MPa, yield tensile ratio is more than 0.48, unit elongation is more than 27%.
3. corrosion resistant multi-aluminum bronze material for pipe according to claim 1 is characterized in that: the tensile strength of described copper alloy under annealed state is more than the 525MPa, yield strength is more than the 285MPa, yield tensile ratio is more than 0.55, unit elongation is more than 42%, soaks uniform corrosion speed at 0.01～0.035mm/a entirely.
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| CN101643867B (en) * | 2009-08-28 | 2011-11-23 | 镇江汇通金属成型有限公司 | High performance copper casting alloy and preparation method thereof |
| CN102554190A (en) * | 2011-12-08 | 2012-07-11 | 巢湖市兴裕铸造有限公司 | Marine side plate capable of resisting seawater corrosion and ocean environment corrosion |
| CN102773253A (en) * | 2012-07-06 | 2012-11-14 | 常州大学 | Steel-aluminum bronze bimetal material compounding method |
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| CN101643867B (en) * | 2009-08-28 | 2011-11-23 | 镇江汇通金属成型有限公司 | High performance copper casting alloy and preparation method thereof |
| CN103088231B (en) * | 2011-11-04 | 2016-03-09 | 天津市三条石有色金属铸造有限公司 | Sand casting pump head xantal |
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| CN102773253A (en) * | 2012-07-06 | 2012-11-14 | 常州大学 | Steel-aluminum bronze bimetal material compounding method |
| CN102773253B (en) * | 2012-07-06 | 2014-05-21 | 常州大学 | Steel-aluminum bronze bimetal material compounding method |
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| CN104614215A (en) * | 2015-01-30 | 2015-05-13 | 中国船舶重工集团公司第十二研究所 | High-manganese aluminum bronze standard substance and preparation method thereof |
| CN104614215B (en) * | 2015-01-30 | 2017-06-16 | 中国船舶重工集团公司第十二研究所 | High manganic aluminum bronze standard substance and preparation method thereof |
| CN105861874A (en) * | 2016-06-18 | 2016-08-17 | 张阳康 | Alloy material for lightening propeller and preparing method of alloy material |
| CN110629064A (en) * | 2018-06-25 | 2019-12-31 | 南京理工大学 | Chromium micro-alloyed multi-element complex cast aluminum bronze alloy |
| CN110724849A (en) * | 2019-10-16 | 2020-01-24 | 徐州木牛流马机器人科技有限公司 | Robot alloy skeleton |
| CN112301254A (en) * | 2020-11-28 | 2021-02-02 | 杭州富阳星宇铜业有限公司 | Copper alloy special-shaped material for new energy automobile wiring terminal and production method |
| CN112301254B (en) * | 2020-11-28 | 2022-01-14 | 杭州富阳星宇铜业有限公司 | Production method of copper alloy special-shaped material for new energy automobile wiring terminal |
| CN113584343A (en) * | 2021-07-28 | 2021-11-02 | 宁波博威合金材料股份有限公司 | Corrosion-resistant high-manganese aluminum bronze alloy and preparation method thereof |
| CN114395710A (en) * | 2021-12-29 | 2022-04-26 | 昆明冶金研究院有限公司北京分公司 | High-strength corrosion-resistant copper alloy and preparation method thereof |
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Effective date of registration: 20171121 Address after: 102209 Changping District City, Beiqijia, the future of science and technology in the south area of the town of Beijing Patentee after: China Aluminum Material Applied Research Institute Co Ltd Address before: Suzhou City, Jiangsu province 215021 Industrial Park No. 200 Shen Hu Road Patentee before: Suzhou Non-ferrous Metal academy Co., Ltd. |