CN101717878A - Seawater scouring corrosion resistant nickel-copper alloy and tubular product and preparation method thereof - Google Patents
Seawater scouring corrosion resistant nickel-copper alloy and tubular product and preparation method thereof Download PDFInfo
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- CN101717878A CN101717878A CN200910241852A CN200910241852A CN101717878A CN 101717878 A CN101717878 A CN 101717878A CN 200910241852 A CN200910241852 A CN 200910241852A CN 200910241852 A CN200910241852 A CN 200910241852A CN 101717878 A CN101717878 A CN 101717878A
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Abstract
The invention relates to a seawater scouring corrosion resistant nickel-copper alloy and a tubular product and a preparation method thereof, belonging to the technical field of metallic material alloying and material corrosion prevention. The nickel-copper alloy tubular product consists of the nickel-copper alloy, and the nickel-copper alloy contains the following components in weight ratio: 5-15 percent of nickel, 2-8 percent of stannum, 1-6 percent of zinc, 0-3 percent of ferrum, 0-2 percent of rare earth elements, not more than 0.5 percent of impurities and the balance of copper. On one hand, the nickel-copper alloy improves the strength and the hardness of the alloy so as to ensure the seawater scouring corrosion resistance of the nickel-copper alloy, on the other hand improves the electrochemical corrosion resistance of the alloy; compared with the common nickel-copper alloy, the 4.5m/s seawater scouring corrosion resistance of the nickel-copper alloy tubular product is higher, and the corrosion rate is lower, thereby realizing that the material cost is reduced and the cost performance is improved, and enlarging the application of the nickel-copper alloy in the fields of condensation tubes and heat-exchanger tubes.
Description
Technical field
The present invention relates to a kind of cupronickel and tubing and preparation method of seawater scouring corrosion resistant, belong to metallic material alloyization and material antiseptic erosion technical field.
Background technology
Cupronickel is celebrated with seawater corrosion resistance, is the outstanding person in the copper alloy aspect oceanographic engineering.Though two main alloy element are for infinitely dissolving each other in the cupronickel, but exist spinodal decomposition (Spinodal Decomposition) in the Cu-Ni-Fe alloy system, under certain condition, intracrystalline or crystal boundary generation second in alloy are separated out mutually, thereby the mechanical property of remarkably influenced cupronickel, the corrosion resisting property to this material also has very big influence simultaneously.
Corrosion is two different performances with anti-Mare Tranquillitatis water logging bubble in the impingement corrosion of anti-flowing seawater, is the technical indicator that significance is all arranged in application.The former is based on mechanical wear, and the latter is controlled by galvanic corrosion.Two kinds of performances all need to pay close attention to.
In the last few years, the further investigation work of carrying out at the cupronickel CDA715 that is most widely used on the engineering (homemade trade mark BFe30-1-1) and CDA706 (homemade trade mark BFe30-1-1) both at home and abroad shows, second separates out mutually and occurs on the crystal boundary, sea water corrosion resistant that can the severe exacerbation alloy material.Also the someone thinks, second separates out the anti-seawater impingement corrosion performance that can strengthen cupronickel mutually.For CDA715 (copper nickel ratio is 70: 30) and two kinds of alloys of CDA706 (copper nickel ratio is 90: 10), in the processing of alloy material and heat treatment process, generate second partial crystallization that hands down and go out, need special processing condition.But when this alloy was on active service in briny environment, along with the generation of surface corrosion process, tangible structure timeliness had taken place in alloy equally, going out along partial crystallization of second phase occur, thereby made progressively variation of its corrosion resisting property.Because the timeliness effect of this microtexture and the sea-water corrosion process of this alloy have confidential relation, are called " sea-water corrosion induces going out along partial crystallization of second phase ".This phenomenon all can occur in CDA715 and two kinds of alloys of CDA706.CDA715 and CDA706 corrosion resisting property in seawater is very limited.In the inflation seawater, when the big 3m/s of seawater velocity, corrosion speed can reach about 160～200 μ m/a, and flow velocity increases again, the rising that is in line of the corrosion speed of CDA715 (copper nickel ratio is 70: 30), the corrosion speed of CDA706 (copper nickel ratio is 90: 10) then exponentially are risen.During to 4m/s, both reach the corrosion speed that 200 μ m/a are above and 700 μ m/a are above respectively.Such corrosion speed has determined the tubing that 1mm is thick, has only 1-4 work-ing life.This does not also consider the influence of its local corrosion behavior to the tubing life-span.In view of this fact, high or contain when using prolong in the big flowing seawater of quantity of sand and mud at flow velocity, mainly select the thin-wall pipes of titanium or titanium alloy, replace copper-alloy pipe-material commonly used.The result who does has like this strengthened on the one hand construction investment, also other problems can occur under certain occasion, such as the hydrogen-induced damage of titanium under the galvanic protection condition and fracture etc.
How to utilize the distinctive amplitude modulation tissue of cupronickel, it is maximized favourable factors and minimized unfavourable ones, have great importance for improving cupronickel sea water corrosion resistant (erosion corrosion and galvanic corrosion).The present invention utilizes this thinking just, has carried out the R﹠D work of the cupronickel of anti-the erosion corrosion, has very significantly improved cupronickel resistant to salt water impact corrosive performance, enlarges the flow rates of its resistant to salt water impact.
Summary of the invention
One of purpose of the present invention is, corroding with anti-Mare Tranquillitatis water logging bubble at the impingement corrosion of anti-flowing seawater is the focal issue of two different performances, a kind of cupronickel with comparatively ideal anti-erosion corrosion and anti-static sea-water corrosion is provided, enlarges the application of cupronickel in prolong and heat exchanger tube field.
For achieving the above object, the present invention takes following technical scheme:
A kind of cupronickel of seawater scouring corrosion resistant, its component and weight ratio are: nickel: 5～15%, tin: 2～8%, zinc: 1～6%, iron: 0～3%, rare earth element: 0～2%, foreign matter content is not more than 0.5%, and all the other are copper.
A kind of optimized technical scheme is characterized in that: described rare earth element is cerium and/or lanthanum.Cerium, lanthanum can add with single-element, also can two kinds of mixing add.
A kind of optimized technical scheme is characterized in that: when described rare earth element was cerium and lanthanum, the weight ratio of cerium and lanthanum was 1: 1～1: 3.
The cupronickel of seawater scouring corrosion resistant of the present invention adopts the ordinary method preparation, as vacuum consumable smelting, skull melting, beam-plasma melting, electron beam melting, shower furnace melting etc. or its combination.
Another object of the present invention provides the tubing of the cupronickel preparation of the above-mentioned seawater scouring corrosion resistant of a kind of usefulness.
For achieving the above object, the present invention takes following technical scheme:
A kind of cupronickel tubing of seawater scouring corrosion resistant, it is characterized in that: it is made up of cupronickel, the component of cupronickel and weight ratio are: nickel: 5～15%, tin: 2～8%, zinc: 1～6%, iron: 0～3%, rare earth element: 0～2%, foreign matter content is not more than 0.5%, and all the other are copper.
A kind of optimized technical scheme is characterized in that: described cupronickel tube outer diameter is 20～40mm, and thickness is 0.5～3mm.
The 3rd purpose of the present invention provides the preparation method of the cupronickel tubing of above-mentioned seawater scouring corrosion resistant.
For achieving the above object, the present invention takes following technical scheme:
A kind of preparation method of cupronickel tubing of seawater scouring corrosion resistant, comprise following concrete steps: pass through alloy designs earlier, in alloy compositions and ratio batching, prepare pipe behind the horizontal casting, through homogenizing thermal treatment, peeling repeatedly stretches and process annealing is softened, finished product stretches then, shear at last, pack and finished product.
The preparation method of the cupronickel tubing of seawater scouring corrosion resistant, its flow process is: alloy designs → batching → horizontal casting → homogenizing thermal treatment → stretching → process annealing → finish draw → shearing, packing.
A kind of optimized technical scheme is characterized in that: during in alloy compositions and ratio batching, described zinc uses the zinc-copper master alloy, realizes the zinc content in the alloy; Described rare earth element uses copper-rare earth intermediate alloy, realizes alloy middle-weight rare earths content.
A kind of optimized technical scheme is characterized in that: described homogenizing thermal treatment is preferably 4～10 hours for being incubated 4～15 hours down at 650 ℃, improves the tin element segregation status.
A kind of optimized technical scheme is characterized in that: described process annealing is meant that annealing temperature is 450～500 ℃, and annealing time is 1～10 hour, is preferably 4～5 hours.
A kind of optimized technical scheme is characterized in that: described stretching and process annealing remollescent number of times are 2～5 times.
Beneficial effect:
The cupronickel of a kind of seawater scouring corrosion resistant provided by the invention, problem at this material erosion corrosion and galvanic corrosion in seawater, realize that by alloying and complete processing crystal grain is tiny, bring out alloy and a large amount of amplitude modulation tissues in deformation process, occurs, the interpolation of rare earth element guaranteed the alloy structure grain refining with second mutually be evenly distributed on crystal grain inside, can improve the intensity of alloy and hardness so on the one hand to guarantee the anti-erosion corrosion performance of its resistant to salt water impact, improve the ability of alloy electrochemical corrosion resistant on the other hand, avoid only appearing at crystal boundary simultaneously and worsen electrochemically resistant corrosive phenomenon, help taking place the uniform corrosion form, with the chemical property that guarantees alloy material integral body and shock resistance corrode performance.
Copper-alloy pipe-material of the present invention, result of use is better in the seawater of 4.5m/s flow velocity high flow rate; With general cupronickel, comprise that (copper nickel ratio is 70: 30 to cupronickel CDA715, homemade trade mark BFe30-1-1) compares with CDA706 (homemade trade mark BFe30-1-1), the copper-alloy pipe-material seawater scouring of anti-4.5m/s corrosive nature of the present invention is higher, erosion rate is lower, thereby realize that material cost reduces, cost performance improves, and has enlarged the application of cupronickel in prolong and heat exchanger tube field.
The present invention will be further described below by the drawings and specific embodiments, but and do not mean that limiting the scope of the invention.
Description of drawings
Fig. 1 is the histogram of cupronickel tubing 30 days average erosion rates in the 4.5m/s seawater.
Embodiment
Embodiment 1
A kind of Niconmetal, each component be by weight, nickel 7%, and tin 6%, zinc 4%, foreign matter content is not more than 0.5%, and surplus is a copper.Its process of making tubing is as follows: pass through alloy designs earlier, prepare burden in the said components ratio, prepare external diameter 80mm behind the horizontal casting, the pipe of thick 20mm, through 650 ℃ of homogenizing thermal treatments of following 6 hours, obtain external diameter 79.5m after the peeling, the pipe of thickness 19mm stretches, and adopts the softening and stretching of 3 process annealing, annealing process is annealing temperature 450-500 ℃, annealing time 4.5 hours, finished product stretches then, finished product tube outer diameter 30mm, thickness 2mm shears at last, packs and form finished product.
Embodiment 2
A kind of Niconmetal, each component be by weight, nickel 10%, and tin 6%, zinc 2%, iron 2%, cerium 1%, foreign matter content is not more than 0.5%, and surplus is a copper.Its process of making tubing is as follows: earlier by alloy designs, in said components ratio batching, prepare external diameter 80mm behind the horizontal casting, the pipe of thick 20mm, through 650 ℃ of homogenizing thermal treatments of 6 hours, peeling back external diameter 79.5mm, the pipe of thickness 19mm stretches, and adopts the softening and stretching of 3 process annealing, annealing process is annealing temperature 450-500 ℃, annealing time 4.5 hours, finished product stretches then, finished product tube outer diameter 30mm, thickness 2mm shears at last, packs and form finished product.
Embodiment 3
A kind of Niconmetal, each component be by weight, nickel 5%, and tin 3%, zinc 6%, iron 2%, lanthanum 2%, foreign matter content is not more than 0.5%, and surplus is a copper.Its process of making tubing is as follows: earlier by alloy designs, in said components ratio batching, prepare external diameter 80mm behind the horizontal casting, the pipe of thick 20mm, through 650 ℃ of homogenizing thermal treatments of 6 hours, peeling back external diameter 79.5mm, the pipe of thickness 19mm stretches, and adopts the softening and stretching of 3 process annealing, annealing process is annealing temperature 450-500 ℃, annealing time 4.5 hours, finished product stretches then, finished product tube outer diameter 30mm, thickness 2mm shears at last, packs and form finished product.
Embodiment 4
A kind of Niconmetal, each component be by weight, nickel 15%, and tin 2%, zinc 6%, iron 3%, cerium 1%, lanthanum 1%, foreign matter content is not more than 0.5%, and surplus is a copper.Its process of making tubing is as follows: earlier by alloy designs, in said components ratio batching, prepare external diameter 80mm behind the horizontal casting, the pipe of thick 20mm, through 650 ℃ of homogenizing thermal treatments of 6 hours, peeling back external diameter 79.5mm, the pipe of thickness 19mm stretches, and adopts the softening and stretching of 3 process annealing, annealing process is annealing temperature 450-500 ℃, annealing time 4.5 hours, finished product stretches then, finished product tube outer diameter 30mm, thickness 2mm shears at last, packs and form finished product.
Embodiment 5
A kind of Niconmetal, each component be by weight, nickel 15%, and tin 8%, zinc 3%, iron 1%, cerium 0.5%, lanthanum 1.5%, foreign matter content is not more than 0.5%, and surplus is a copper.Its process of making tubing is as follows: earlier by alloy designs, in said components ratio batching, prepare external diameter 80mm behind the horizontal casting, the pipe of thick 20mm, through 650 ℃ of homogenizing thermal treatments of 6 hours, peeling back external diameter 79.5mm, the pipe of thickness 19mm stretches, and adopts the softening and stretching of 3 process annealing, annealing process is annealing temperature 450-500 ℃, annealing time 4.5 hours, finished product stretches then, finished product tube outer diameter 30mm, thickness 2mm shears at last, packs and form finished product.
Embodiment 6
A kind of Niconmetal, each component be by weight, nickel 15%, and tin 8%, zinc 1%, iron 3%, foreign matter content is not more than 0.5%, and surplus is a copper.Its process of making tubing is as follows: earlier by alloy designs, in said components ratio batching, prepare external diameter 80mm behind the horizontal casting, the pipe of thick 20mm, through 650 ℃, 4 hours homogenizing thermal treatment, peeling back external diameter 79.5mm, the pipe of thickness 19mm stretches, and adopts the softening and stretching of 5 process annealing, annealing process is annealing temperature 450-500 ℃, annealing time 5 hours, finished product stretches then, finished product tube outer diameter 25mm, thickness 0.5mm shears at last, packs and form finished product.
Embodiment 7
A kind of Niconmetal, each component be by weight, nickel 5%, and tin 2%, zinc 6%, iron 1%, cerium 0.5%, lanthanum 1.0%, foreign matter content is not more than 0.5%, and surplus is a copper.Its process of making tubing is as follows: earlier by alloy designs, in said components ratio batching, prepare external diameter 80mm behind the horizontal casting, the pipe of thick 20mm, through 650 ℃, 10 hours homogenizing thermal treatment, peeling back external diameter 79.5mm, the pipe of thickness 19mm stretches, and adopts the softening and stretching of 2 process annealing, annealing process is annealing temperature 450-500 ℃, annealing time 4 hours, finished product stretches then, finished product tube outer diameter 40mm, thickness 3mm shears at last, packs and form finished product.
Performance test
Comparative Examples: adopt the market to buy and obtain CDA715 (copper nickel ratio is 70: 30) tubing, tube outer diameter is 30mm, and thickness is 2mm.
Adopt rotating disc type erosion corrosion test set that the foregoing description and Comparative Examples are carried out erosion-corrosion experiment for same batch, experimental result sees Table 1.As shown in Figure 1, be the histogram of tubing 30 days average erosion rates in the 4.5m/s seawater of the cupronickel of embodiment 1-7 and Comparative Examples alloy.As shown in Table 1, cupronickel tubing of the present invention is compared with Comparative Examples cupronickel tubing, and its seawater scouring corrosion resistant performance improves a lot.
Table 1 cupronickel tubing average corrosion rate of 30 days in the 4.5m/s seawater
Claims (10)
1. the cupronickel of a seawater scouring corrosion resistant, its component and weight ratio are: nickel: 5～15%, tin: 2～8%, zinc: 1～6%, iron: 0～3%, rare earth element: 0～2%, foreign matter content is not more than 0.5%, and all the other are copper.
2. the cupronickel of seawater scouring corrosion resistant according to claim 1, it is characterized in that: described rare earth element is cerium and/or lanthanum.
3. the cupronickel of seawater scouring corrosion resistant according to claim 2, it is characterized in that: when described rare earth element was cerium and lanthanum, the weight ratio of cerium and lanthanum was 1: 1～1: 3.
4. the cupronickel tubing of a seawater scouring corrosion resistant, it is characterized in that: it is made up of cupronickel, the component of cupronickel and weight ratio are: nickel: 5～15%, tin: 2～8%, zinc: 1～6%, iron: 0～3%, rare earth element: 0～2%, foreign matter content is not more than 0.5%, and all the other are copper.
5. the cupronickel tubing of seawater scouring corrosion resistant according to claim 4, it is characterized in that: described cupronickel tube outer diameter is 20～40mm, thickness is 0.5～3mm.
6. the preparation method of the cupronickel tubing of a seawater scouring corrosion resistant, comprise following concrete steps: pass through alloy designs earlier, in alloy compositions and ratio batching, prepare pipe behind the horizontal casting, through homogenizing thermal treatment, peeling repeatedly stretches and process annealing is softened, finished product stretches then, shear at last, pack and finished product.
7. the preparation method of the cupronickel tubing of seawater scouring corrosion resistant according to claim 6 is characterized in that: during in alloy compositions and ratio batching, described zinc uses the zinc-copper master alloy, and described rare earth element uses copper-rare earth intermediate alloy.
8. the preparation method of the cupronickel tubing of seawater scouring corrosion resistant according to claim 6 is characterized in that: described homogenizing thermal treatment is for 650 ℃ of insulations 4～15 hours down.
9. the preparation method of the cupronickel tubing of seawater scouring corrosion resistant according to claim 6, it is characterized in that: described process annealing is meant that annealing temperature is 450～500 ℃, and annealing time is 1～10 hour.
10. the preparation method of the cupronickel tubing of seawater scouring corrosion resistant according to claim 6, it is characterized in that: described stretching and process annealing remollescent number of times are 2～5 times.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101948966A (en) * | 2010-10-27 | 2011-01-19 | 东南大学 | Titanium-containing low-nickel copper alloy with seawater corrosion resistance |
| CN102485925A (en) * | 2011-11-23 | 2012-06-06 | 厦门火炬特种金属材料有限公司 | Copper-nickel-tin alloy and preparation method for wires thereof |
| CN102690974A (en) * | 2011-03-24 | 2012-09-26 | 福州永锭铸业有限公司 | Copper alloy |
| CN102775047A (en) * | 2012-07-31 | 2012-11-14 | 苏州东方模具科技股份有限公司 | Bimetal opening mold for glass mold and preparation method of bimetal opening mold |
| CN103757480A (en) * | 2014-01-10 | 2014-04-30 | 滁州学院 | Seawater corrosion resistance complex cupronickel alloy material and preparation method thereof |
| CN104498768A (en) * | 2014-12-16 | 2015-04-08 | 江苏创兰太阳能空调有限公司 | Coil pipe stretching die material |
| CN104651661A (en) * | 2013-11-21 | 2015-05-27 | 青岛润鑫伟业科贸有限公司 | Novel iron-white copper alloy |
| CN105714148A (en) * | 2016-04-29 | 2016-06-29 | 华南理工大学 | Spinodal decomposition type high-strength copper nickel tin alloy and preparation method thereof |
| CN106086519A (en) * | 2016-08-31 | 2016-11-09 | 芜湖楚江合金铜材有限公司 | A kind of copper-nickel alloy silk of corrosion-resistant tension |
| CN106545708A (en) * | 2016-10-28 | 2017-03-29 | 无锡市永兴金属软管有限公司 | A kind of oil storage tank Antishocking metal hose and preparation method thereof |
| CN107186385A (en) * | 2017-07-31 | 2017-09-22 | 安徽华众焊业有限公司 | A kind of silverless Cu-base soldering material |
| US20180191038A1 (en) * | 2015-07-20 | 2018-07-05 | Microvast Power Systems Co., Ltd. | Battery pack and battery pack system |
| CN114395711A (en) * | 2021-12-28 | 2022-04-26 | 有研工程技术研究院有限公司 | Anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect and preparation method thereof |
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- 2009-12-10 CN CN200910241852A patent/CN101717878A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948966A (en) * | 2010-10-27 | 2011-01-19 | 东南大学 | Titanium-containing low-nickel copper alloy with seawater corrosion resistance |
| CN102690974A (en) * | 2011-03-24 | 2012-09-26 | 福州永锭铸业有限公司 | Copper alloy |
| CN102485925A (en) * | 2011-11-23 | 2012-06-06 | 厦门火炬特种金属材料有限公司 | Copper-nickel-tin alloy and preparation method for wires thereof |
| CN102775047A (en) * | 2012-07-31 | 2012-11-14 | 苏州东方模具科技股份有限公司 | Bimetal opening mold for glass mold and preparation method of bimetal opening mold |
| CN102775047B (en) * | 2012-07-31 | 2014-06-04 | 苏州东方模具科技股份有限公司 | Bimetal opening mold for glass mold and preparation method of bimetal opening mold |
| CN104651661A (en) * | 2013-11-21 | 2015-05-27 | 青岛润鑫伟业科贸有限公司 | Novel iron-white copper alloy |
| CN103757480A (en) * | 2014-01-10 | 2014-04-30 | 滁州学院 | Seawater corrosion resistance complex cupronickel alloy material and preparation method thereof |
| CN104498768A (en) * | 2014-12-16 | 2015-04-08 | 江苏创兰太阳能空调有限公司 | Coil pipe stretching die material |
| US20180191038A1 (en) * | 2015-07-20 | 2018-07-05 | Microvast Power Systems Co., Ltd. | Battery pack and battery pack system |
| CN105714148A (en) * | 2016-04-29 | 2016-06-29 | 华南理工大学 | Spinodal decomposition type high-strength copper nickel tin alloy and preparation method thereof |
| CN106086519A (en) * | 2016-08-31 | 2016-11-09 | 芜湖楚江合金铜材有限公司 | A kind of copper-nickel alloy silk of corrosion-resistant tension |
| CN106545708A (en) * | 2016-10-28 | 2017-03-29 | 无锡市永兴金属软管有限公司 | A kind of oil storage tank Antishocking metal hose and preparation method thereof |
| CN107186385A (en) * | 2017-07-31 | 2017-09-22 | 安徽华众焊业有限公司 | A kind of silverless Cu-base soldering material |
| CN114395711A (en) * | 2021-12-28 | 2022-04-26 | 有研工程技术研究院有限公司 | Anti-tarnishing and anti-corrosion copper alloy material with rapid bacteriostasis effect and preparation method thereof |
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Application publication date: 20100602 |