CN105143479A - Copper alloy seamless tube for heat transfer tube - Google Patents
Copper alloy seamless tube for heat transfer tube Download PDFInfo
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- CN105143479A CN105143479A CN201480013709.3A CN201480013709A CN105143479A CN 105143479 A CN105143479 A CN 105143479A CN 201480013709 A CN201480013709 A CN 201480013709A CN 105143479 A CN105143479 A CN 105143479A
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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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- 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
- C22C9/02—Alloys based on copper with tin 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
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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Abstract
A copper alloy seamless tube for a heat transfer tube, obtained by processing a copper alloy and characterized in that: the copper alloy contains Sn and, by mass, 0.01 to 0.08% of Zr and 0.004 to 0.04% of P, with the remainder being made up by Cu and unavoidable impurities; the amount of Sn and Zr contained in the copper alloy satisfies the following relationship (1): (1) 0.4 <= A + 2B <= 0.85 (where A represents the Sn content (mass%) and B represents the Zr content (mass%)); and the electrical conductivity of the copper alloy seamless tube for a heat transfer tube satisfies the following relationship (2): (2) [rho]2-[rho]1 >= 0.3 (%IACS)(where [rho]1 represents the electrical conductivity (%IACS) after solution treatment and [rho]2 represents the electrical conductivity (%IACS) after aging treatment). According to the present invention, it is possible to provide a copper alloy seamless tube for a heat transfer tube having high strength, little decrease in strength caused by brazing, high creep deformation resistance characteristics, and a high effect of suppressing intermediate temperature brittleness.
Description
Technical field
The present invention relates to the seamless tube of the copper alloy used in the heat pipe of use in refrigeration system interchanger, use in refrigerator interchanger etc. or refrigerant piping.
Background technology
All the time, the heat pipe of the interchanger used in air conditioning machinery, the refrigerators etc. such as room conditioning, integrated air-conditioning system (packageairconditioner) adopts the seamless tube of copper alloy mostly, has employed the phosphorous deoxidize copper tube (JISC1220T) that the various physical property such as intensity, processibility, thermal conductivity and material and tooling cost achieve balance.
In recent years, for these interchanger, reduce or cost reduction, be necessary so the thin-walled property of seamless tube becomes owing to requiring weight, existing phosphorous deoxidize copper tube is low due to intensity, so be difficult to thin-walled property, requires that exploitation replaces the seamless tube of its copper alloy.
Therefore, as the copper alloy of solution strengthening type, in patent documentation 1, propose the copper alloy being added with Sn.In addition, as solution strengthening and precipitation strength type copper alloy, in patent documentation 2 and patent documentation 3, the copper alloy being added with Sn and Zr is proposed.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-268467 publication (claims)
Patent documentation 2:WO2008/041777 publication (claims)
Patent documentation 3: Japanese Unexamined Patent Publication 2011-94174 publication (claims)
Summary of the invention
the problem that invention will solve
For the copper alloy seamless pipe used in the heat pipe of use in refrigeration system interchanger, use in refrigerator interchanger etc. or refrigerant piping, due to the thermal fatigue along with hot exapnsion and thermal contraction repeatedly, so there is the danger that fatigue cracking occurs.In addition, with hot exapnsion, seamless tube produces tension force, has the danger producing creep strain according to use temperature.
Therefore, the copper alloy seamless pipe used in the heat pipe of use in refrigeration system interchanger, use in refrigerator interchanger etc. or refrigerant piping, on the basis of " intensity is high " and " intensity caused by brazing reduces few ", also requires to possess heat-resistant anti-fatigue be full of cracks occurrence features and creep resistant deforming characteristic.
But, for documents 1 such, the seamless tube of the copper alloy of the solution strengthening type that is added with Sn, there is medium temperature fragility, in temperature limit of brittleness region, easily produce thermal fatigue, creep fracture.When manufacturing interchanger, under the state that tension force is applied to seamless tube, carry out the heating such as brazing, therefore produce medium temperature fragility, easily produce brittle crack.
As the factor of promoting medium temperature fragility, there is S and H, by the content of S and H is reduced to the limit, thus medium temperature fragility to a certain degree can be suppressed, but insufficient.In addition, in order to the content of S is reduced to the limit, highly purified raw gold must be used, not preferred from cost aspect.In addition, in order to the content of H is reduced to the limit, need long liquation process, need the melting casting etc. having carried out control climate, not preferred in cost.
Therefore, even if the content of S and H for common level (not being reduced to the level of the limit), also expect effectively to suppress medium temperature fragility.It should be noted that, the content of S and H of common level (not being reduced to the level of the limit) refers to, S is about 0.0005 ~ 0.0008 quality %, H is about 0.0002 ~ 0.0010 quality %.
On the other hand, for patent documentation 2 and patent documentation 3 such, the seamless tube of the copper alloy of the solution strengthening that is added with Sn and Zr and precipitation strength type, by adding Zr, in intensity, intensity that is high and that caused by brazing reduces on few basis, can also suppress the embodiment of medium temperature fragility to a certain degree.
But, require the heat-resistant anti-fatigue be full of cracks raising of occurrence features and the raising of creep resistant deforming characteristic further.
Therefore, the object of the invention is to, provide that intensity intensity that is high, that caused by brazing reduces less, the high and copper alloy seamless pipe of the heat pipe that inhibition that is medium temperature fragility is high of creep resistant deforming characteristic.
for the scheme of dealing with problems
The present inventor etc. are in order to solve above-mentioned the problems of the prior art, repeatedly further investigate, found that: by containing Sn and Zr with specific content in copper alloy, and then Zr is existed with suitable state in copper alloy, thus can obtain that intensity intensity that is high, that caused by brazing reduces less, the high and copper alloy seamless pipe of the heat pipe that inhibition that is medium temperature fragility is high of creep resistant deforming characteristic, thus complete the present invention.
That is, the present invention (1) provides a kind of heat pipe copper alloy seamless pipe, it is characterized in that, its heat pipe copper alloy seamless pipe obtained for worked copper alloy,
This copper alloy contains Sn, the Zr of 0.01 ~ 0.08 quality % and the P of 0.004 ~ 0.04 quality %, and surplus is made up of Cu and inevitable impurity, and the content of Sn and Zr in this copper alloy meets following formula (1):
(1)0.4≤A+2B≤0.85
(in formula, A represents the content (quality %) of Sn, and B represents the content (quality %) of Zr.)
The electric conductivity of this heat pipe copper alloy seamless pipe meets following formula (2):
(2)ρ2-ρ1≥0.3(％IACS)
(in formula, ρ 1 refers to the electric conductivity (%IACS) after solution treatment, and ρ 2 refers to the electric conductivity (%IACS) after ageing treatment.)。
In addition, the present invention (2) provides a kind of heat pipe copper alloy seamless pipe, it is characterized in that, its heat pipe copper alloy seamless pipe obtained for worked copper alloy,
This copper alloy contains Sn, the Zr of 0.01 ~ 0.08 quality % and the P of 0.004 ~ 0.04 quality %, and surplus is made up of Cu and inevitable impurity, and the content of Sn and Zr in this copper alloy meets following formula (1):
(1)0.4≤A+2B≤0.85
(in formula, A represents the content (quality %) of Sn, and B represents the content (quality %) of Zr.)
The electric conductivity of this heat pipe copper alloy seamless pipe meets following formula (3):
(3)ρ4-ρ3≥0.3(％IACS)
(in formula, ρ 3 refers to the electric conductivity (%IACS) after the heating-water-cooled test of at 950 DEG C 10 minutes, and ρ 4 refers to the electric conductivity (%IACS) after the heating-water-cooled test of at 550 DEG C 60 minutes.)。
the effect of invention
According to the present invention, can provide that intensity intensity that is high, that caused by brazing reduces less, the high and copper alloy seamless pipe of the heat pipe that inhibition that is medium temperature fragility is high of creep resistant deforming characteristic.
Embodiment
The heat pipe copper alloy seamless pipe of first scheme of the present invention is (following, also heat pipe copper alloy seamless pipe (1) of the present invention is denoted as) be a kind of heat pipe copper alloy seamless pipe, it is characterized in that, its heat pipe copper alloy seamless pipe obtained for worked copper alloy
This copper alloy contains Sn, the Zr of 0.01 ~ 0.08 quality % and the P of 0.004 ~ 0.04 quality %, and surplus is made up of Cu and inevitable impurity, and the content of Sn and Zr in this copper alloy meets following formula (1):
(1)0.4≤A+2B≤0.85
(in formula, A represents the content (quality %) of Sn, and B represents the content (quality %) of Zr.)
The electric conductivity of this heat pipe copper alloy seamless pipe meets following formula (2):
(2)ρ2-ρ1≥0.3(％IACS)
(in formula, ρ 1 refers to the electric conductivity (%IACS) after solution treatment, and ρ 2 refers to the electric conductivity (%IACS) after ageing treatment.)。
The heat pipe copper alloy seamless pipe of alternative plan of the present invention is (following, also heat pipe copper alloy seamless pipe (2) of the present invention is denoted as) be a kind of heat pipe copper alloy seamless pipe, it is characterized in that, its heat pipe copper alloy seamless pipe obtained for worked copper alloy
This copper alloy contains Sn, the Zr of 0.01 ~ 0.08 quality % and the P of 0.004 ~ 0.04 quality %, and surplus is made up of Cu and inevitable impurity, and the content of Sn and Zr in this copper alloy meets following formula (1):
(1)0.4≤A+2B≤0.85
(in formula, A represents the content (quality %) of Sn, and B represents the content (quality %) of Zr.)
The electric conductivity of this heat pipe copper alloy seamless pipe meets following formula (3):
(3)ρ4-ρ3≥0.3(％IACS)
(in formula, ρ 3 refers to the electric conductivity (%IACS) after the heating-water-cooled test of at 950 DEG C 10 minutes, and ρ 4 refers to the electric conductivity (%IACS) after the heating-water-cooled test of at 550 DEG C 60 minutes.)。
Except the electric conductivity of heat pipe copper alloy seamless pipe (1) of the present invention meets formula (2), and the electric conductivity of heat pipe copper alloy seamless pipe (2) of the present invention meets outside formula (3), heat pipe copper alloy seamless pipe (1) of the present invention is identical with heat pipe copper alloy seamless pipe (2) of the present invention.
Heat pipe copper alloy seamless pipe (1) of the present invention and heat pipe copper alloy seamless pipe of the present invention (2) are the seamless tube used as the heat pipe of use in refrigeration system interchanger, use in refrigerator interchanger, natural gas refrigerant heat-pump-type interchanger etc. or refrigerant piping, are the seamless tube of the copper alloy of seamless tube, the i.e. heat pipe of copper alloy formed by copper alloy.
The copper alloy of heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2) is: containing Sn, Zr and P as necessary element, the copper alloy that surplus is made up of Cu and inevitable impurity.
In heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2), Sn has: the effect being improved the effect of the intensity of copper alloy and the ductility under improving normal temperature by solution strengthening.In addition, when these elements, can carry out alloying at a lower temperature, be therefore favourable in manufacture.
In heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2), Zr has: the effect being improved the intensity of copper alloy by precipitation strength.In addition, Zr has: under the prerequisite that brazing temperature unduly uprises, Zr precipitate remains, and suppresses the coarsening of crystal grain, thus reduces the effect of intensity reduction.
In the copper alloy of heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2), the content of Zr is 0.01 ~ 0.08 quality %.When the content of the Zr in copper alloy is less than 0.01 quality %, suppress the effect of coarse grains little, the intensity caused by brazing reduces and becomes large, and in addition, even if meet the solution strengthening based on Sn and the precipitation strength based on Zr, the strengthening of copper alloy also becomes insufficient.On the other hand, when the content of the Zr in copper alloy is more than 0.08 quality %, cause superfluous precipitation-hardening, become the reason reducing processibility.Particularly, cold roll-forming processibility is deteriorated.Its result, the transfer printing of the spiral slot shape of pipe inner face becomes insufficient, is difficult to obtain the such heat conductivility obtained by C1220.
The content of the Sn in the copper alloy of heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2) is set to A (quality %), the content of Zr is when being set to B (quality %), in the copper alloy of heat pipe copper alloy seamless pipe of the present invention, A+2B is more than 0.4 and less than 0.85, that is, following formula (1) is met:
(1)0.4≤A+2B≤0.85，
Preferred A+2B is more than 0.42 and less than 0.83, that is, meet following formula (1a):
(1a)0.42≤A+2B≤0.83。
Be in above-mentioned scope by making A+2B and make the content of Zr be 0.01 ~ 0.08 quality %, thus when needing strict processibility, also can maintain the intensity of seamless tube by minimally.On the other hand, when A+2B is less than above-mentioned scope, the undercapacity of seamless tube, and when exceeding above-mentioned scope, the obvious step-down of cold-workability.
The content of the P in the copper alloy of heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2) is 0.004 ~ 0.04 quality %, is preferably 0.015 ~ 0.030 quality %.Copper alloy is by the P element containing more than 0.004 quality %, thus the deoxidation in material is presented as fully.And when the content of the P in copper alloy is too much, the thermal conductivity step-down of copper alloy, the content of the P therefore in copper alloy is below 0.040 quality %.
For the electric conductivity of heat pipe copper alloy seamless pipe (1) of the present invention, ρ 2-ρ 1 is more than 0.3, that is, meet following formula (2):
(2)ρ2-ρ1≥0.3(％IACS)
(in formula, ρ 1 refers to the electric conductivity (%IACS) after solution treatment, and ρ 2 refers to the electric conductivity (%IACS) after ageing treatment.)，
Preferred ρ 2-ρ 1 is more than 0.5 and less than 20, that is, meet following formula (2a):
(2a)0.5≤ρ2-ρ1≤20。
In addition, for the electric conductivity of heat pipe copper alloy seamless pipe (2) of the present invention, ρ 4-ρ 3 is more than 0.3, that is, meet following formula (3):
(3)ρ4-ρ3≥0.3(％IACS)
(in formula, ρ 3 refers to the electric conductivity (%IACS) after the heating-water-cooled test of at 950 DEG C 10 minutes, and ρ 4 refers to the electric conductivity (%IACS) after the heating-water-cooled test of at 550 DEG C 60 minutes.)，
Preferred ρ 4-ρ 3 is more than 0.5 and less than 20, namely meets following formula (3a):
(3a)0.5≤ρ4-ρ3≤20。
In the present invention, solution treatment refers to, the process of the Zr series intermetallic compound solid solution fully in the process of cooling of the ingot casting melted and in casting process, crystallization being gone out, in addition, ageing treatment refers to, makes the process that Zr series intermetallic compound is separated out.Heat pipe copper alloy seamless pipe of the present invention manufactures according to the order of " melt and the process annealing process of casting process → hot-extrudable operation → cold working operation → as required and rollforming operation → ageing treatment ".And in such manufacturing process, the heating in hot-extrudable operation becomes the solution treatment of the Zr series intermetallic compound solid solution fully making crystallization in the process of cooling of the ingot casting in melting and casting process go out.
In copper alloy seamless tube, melt and ingot casting in casting process process of cooling in the Zr that goes out of crystallization when not having an abundant solid solution in solution treatment, in order to obtain the intensity of the content meeting Zr, amount and the distribution of the fine precipitate of separating out in ageing treatment become inappropriate.In addition, in solution treatment, do not have the Zr system crystal thing of complete solid solution to improve not only bad for intensity, also hinder the processibility in the bending machining operation when follow-up cold working operation, rollforming operation, interchanger make.And then, in process of setting when casting of the Zr of solid solution or solution treatment, generating compound with S, thus catching S, and when hot-extrudable, catch the H forming crystal boundary space, thus improving creep resistant deforming characteristic, suppression medium temperature fragility.So, after solution treatment, the Zr of solid solution is not only conducive to the precipitation strength of the ageing treatment based on subsequent handling, also helps the suppression of the raising of creep resistant deforming characteristic, medium temperature fragility.In addition, by making the precipitation state of the Zr in ageing treatment suitable, thus the inhibition of medium temperature fragility uprises.
But, be difficult to quantitative for the precipitation state of the Zr in the solid solution condition of the Zr in solution treatment and ageing treatment.Therefore, the present inventor etc. further investigate repeatedly, found that: by the difference (ρ 2-ρ 1) of the electric conductivity after solution treatment and the electric conductivity after ageing treatment, the precipitation state of the Zr in the solid solution condition of the Zr in solution treatment and ageing treatment can be held, ρ 2-ρ 1 is limited in specific scope, thus creep resistant deforming characteristic can be improved, suppress medium temperature fragility.That is, for the electric conductivity of heat pipe copper alloy seamless pipe (1) of the present invention, ρ 2-ρ 1 is more than 0.3, that is, meet following formula (2):
(2)ρ2-ρ1≥0.3(％IACS)，
Preferred ρ 2-ρ 1 is more than 0.5 and less than 20, that is, meet following formula (2a):
(2a)0.5≤ρ2-ρ1≤20。
Be in above-mentioned scope by ρ 2-ρ 1, thus creep resistant deforming characteristic can be improved, suppress medium temperature fragility.
In addition, the discoveries such as the present inventor: the difference (ρ 4-ρ 3) of the electric conductivity after being tested by the heating-water-cooled of 60 minutes at the electric conductivity after heating-water-cooled test of 10 minutes at 950 DEG C and 550 DEG C, the precipitation state of the Zr in the solid solution condition of the Zr in solution treatment and ageing treatment can be held, ρ 4-ρ 3 is limited in specific scope, thus high creep-resistant property distortion can be proposed, suppress medium temperature fragility.That is, for the electric conductivity of heat pipe copper alloy seamless pipe (2) of the present invention, ρ 4-ρ 3 is more than 0.3, that is, meet following formula (3):
(3)ρ4-ρ3≥0.3(％IACS)，
Preferred ρ 4-ρ 3 is more than 0.5 and less than 20, that is, meet following formula (3a):
(3a)0.5≤ρ4-ρ3≤20。
Be in above-mentioned scope by ρ 4-ρ 3, thus creep resistant deforming characteristic can be improved, suppress medium temperature fragility.
It should be noted that, in the present invention, at 950 DEG C, the heating-water-cooled test of 10 minutes refers to, using as the test carrying out water-cooled after the copper alloy seamless pipe of subjects carries out the heating of 10 minutes at 950 DEG C ± 25 DEG C, first, at nitrogen atmosphere, be set as in the electric furnace of 950 ± 25 DEG C, load subjects, in-furnace temperature returns to 950 DEG C, then keeps 10 minutes at 950 DEG C ± 25 DEG C, then carries out water-cooled immediately from 950 DEG C thus carry out.Then, the electric conductivity (%IACS) of the subjects at measuring 950 DEG C after heating-water-cooled test in 10 minutes, obtains ρ 3.
In addition, in the present invention, at 550 DEG C, the heating-water-cooled test of 60 minutes refers to, after the heating of carrying out 10 minutes as the copper alloy seamless pipe of subjects at 950 DEG C and water-cooled, then the test of water-cooled is carried out after carrying out the heating of 60 minutes at 550 DEG C ± 10 DEG C, first, in the same manner as subjects is tested with the heating-water-cooled of 10 minutes at 950 DEG C, water-cooled is carried out immediately from 950 DEG C carry out heating in 10 minutes at 950 DEG C ± 25 DEG C after, then at 950 DEG C, carry out heating and the water-cooled of 10 minutes, gained subjects is loaded in salt bath furnace, keep 60 minutes at 550 DEG C ± 10 DEG C, then carry out water-cooled immediately thus carry out.Then, the electric conductivity (%IACS) of the subjects at measuring 550 DEG C ± 10 DEG C after heating-water-cooled test in 60 minutes, obtains ρ 4.
The copper alloy of heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2) also can contain S atom.When the copper alloy of heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2) is also containing S, the content of the S in copper alloy is 0.0005 ~ 0.0010 quality %.In addition, the copper alloy of heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2) also can contain H.When the copper alloy of heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2) is also containing H, the content of the H in copper alloy is 0.0002 ~ 0.0020 quality %.When the content of the S in copper alloy or the content of H exceed above-mentioned scope, S or H cannot be supplemented fully by the Zr of solid solution, the effect of suppression of the raising of creep resistant deforming characteristic, medium temperature fragility cannot be obtained.On the other hand, when the content of the S in copper alloy or the content of H are less than above-mentioned scope, although can obtain the effect of the raising of creep resistant deforming characteristic, the suppression of medium temperature fragility, cost easily uprises.
Heat pipe copper alloy seamless pipe of the present invention according to melting, the process annealing process of casting and cooling → hot-extrudable and cooling → cold working → as required and the order of rollforming → ageing treatment manufacture successively.
First, carry out melting, cast and cooling.Melt and in casting, carry out melting and casting according to ordinary method, the content obtaining specifying coordinates the steel billet of the element of regulation.Such as, the mode of content being regulation with the content in heat pipe copper alloy seamless pipe of the present invention coordinate the raw gold containing element of the raw gold of copper and heat pipe copper alloy seamless pipe of the present invention, maybe should alloy containing element and copper, carry out composition adjustment, then high frequency melting furnace etc. is used, casting steel billet.Then, after casting, steel billet is cooled.
Then, hot-extrudable and cooling is carried out.In hot-extrudable, heat by casting the steel billet obtained at an established temperature and carry out hot-extrudable.By plug extrude carry out hot-extrudable.That is, with to before heating by the steel billet of cold piercing in advance or before extrusion by the state of the steel billet insertion plug of hot piercing, carry out hot-extrudable.Then, carry out hot-extrudable, then cool rapidly, obtain hot-extrudable pipe.
Then, cold working is carried out.In cold working, to being carried out the cold working such as cold rolling, cold-drawn by the hot-extrudable hot-extrudable pipe obtained, reduce external diameter and the wall thickness of pipe, obtain seamless tube blank.
When not formed inner face smooth tubes (light pipe) of inner surface slot, and then cold working, is heated the seamless tube blank obtained by cold working, then carries out the ageing treatment cooled at 400 ~ 600 DEG C.Then, by carrying out ageing treatment, thus obtain heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2).
When obtaining the pipe of the band inner surface slot being formed with inner surface slot, and then cold working, is carried out the process annealing of being carried out by the seamless tube blank obtained by cold working heating at 400 ~ 600 DEG C, then, carries out rollforming.Rollforming carries out as follows: in seamless tube blank, configuration implements the rollforming plug of spiral helicine slot machining to outside surface, utilize multiple rollforming balls of high speed rotating, extrude from the outside of pipe, the groove of rollforming plug is transferred to the internal surface of pipe, thus carries out.Then, ageing treatment is carried out to the seamless tube implementing rollforming.Ageing treatment is carried out as follows: carried out heating at 400 ~ 600 DEG C by the seamless tube implementing rollforming and cool thus carry out.Then, by carrying out ageing treatment, thus obtain heat pipe copper alloy seamless pipe (1) of the present invention or heat pipe copper alloy seamless pipe of the present invention (2).
And, as in heat pipe copper alloy seamless pipe (1) of the present invention, electric conductivity is made to be formula (2): ρ 2-ρ 1 >=0.3 (%IACS), preferred formula (2a): the method for 0.5≤ρ 2-ρ 1≤20, and in heat pipe copper alloy seamless pipe (2) of the present invention, electric conductivity is made to be formula (3): ρ 4-ρ 3 >=0.3 (%IACS), preferred formula (3a): the method for 0.5≤ρ 4-ρ 3≤20, such as can enumerate: melt and in cooling after casting, regulate the method for speed of cooling of steel billet.The discoveries such as the present inventor: be pursuant to and melt different with the existence of the difference of speed of cooling of steel billet in cooling after casting and the Zr in copper alloy, to melt and the value of difference to " ρ 2-ρ 1 " and " ρ 4-ρ 3 " of existence of Zr after casting has an impact.It should be noted that, according to the difference such as cooling conditions, solution treatment condition, Ageing conditions after the diameter of steel billet, casting, in order to electric conductivity being adjusted to formula (2), preferred formula (2a) and suitable speed of cooling or in order to electric conductivity being adjusted to formula (3), preferred formula (3a) and suitable speed of cooling is different, therefore to melt and the speed of cooling of steel billet in cooling after casting suitably can be selected according to the cooling conditions, solution treatment condition, Ageing conditions etc. after the diameter of steel billet, casting.In addition, by suitably regulate steel billet diameter, casting after cooling conditions, solution treatment condition, Ageing conditions etc., meet formula (2) with the electric conductivity of heat pipe copper alloy seamless pipe (1) of the present invention, the mode of preferred formula (2a) regulates, in addition, meet formula (3) with the electric conductivity of heat pipe copper alloy seamless pipe (2) of the present invention, the mode of preferred formula (3a) regulates.
For heat pipe copper alloy seamless pipe of the present invention, as the heat pipe of interchanger, batch the making for coil shape comes for interchanger (crossing current fin-and-tube type heat exchanger (CrossFinnedTubetypeheatexchanger)).The heat pipe of the aluminum fin-stock of air side and refrigeration agent side is assembled and is formed by crossing current fin-and-tube type heat exchanger integratedly.
For crossing current fin-and-tube type heat exchanger, first by press process etc., make the aluminum plate fin being formed with the assembly hole of multiple regulation, then, by stacked for gained aluminum plate fin, then heat pipe copper alloy seamless pipe (1) of the present invention or the heat pipe copper alloy seamless pipe of the present invention (2) to having carried out fixed ruler cutting and the processing of hair clip bend pipe is inserted to the inside of assembly hole, then, seamless tube expander is bonded to aluminum plate fin, U-bend be brazing in and implement the seamless tube end that side that hair clip bend pipe processes is opposition side, thus making.
Embodiment
Then, enumerate embodiment, further illustrate the present invention, but it is merely example, does not limit the present invention.
(embodiment and comparative example)
< heat pipe copper alloy seamless pipe >
(melt, cast and cooling)
By semicontinuous casting, the steel billet of the external diameter 254mm of casting containing chemical composition shown in table 1, then cools.The water yield of the water coolant of steel billet is now set to following.It should be noted that, in table 1, surplus is Cu and inevitable impurity.
Cooling conditions A: cooling water inflow 1000L/ minute
Cooling conditions B: cooling water inflow 600L/ minute
(hot-extrudable and cooling)
The steel billet obtained as described above is kept more than 10 minutes in continuous furnace, in 950 DEG C (± 25 DEG C), thus heat, then at extrusion temperature 950 DEG C, extrude the pipe of external diameter 81mm × wall thickness 8mm, drop in water immediately after extruding and cool, obtain hot-extrudable pipe.Now, carry out with taking into account solution treatment.
From the head of the hot-extrudable pipe of gained and the test sample (sample 1) of afterbody sampling electric conductivity.
(cold working)
The hot-extrudable pipe obtained as described above is carried out cold rolling and cold-drawn, obtains the seamless tube blank of external diameter 9.52mm × wall thickness 0.8mm.
(ageing treatment)
The seamless tube blank obtained as described above is carried out in batch furnace, in non-oxidizing atmosphere, in 550 DEG C the heating of 60 minutes, obtain heat pipe copper alloy seamless pipe.
Sample 2 is sampled for electric conductivity measuring from gained heat pipe copper alloy seamless pipe.In addition, sampling sample 3 and sample 4 are tested for heating-water-cooled.
< heating-water-cooled test >
At 950 DEG C, the heating-water-cooled test of 10 minutes refers to, using as the test carrying out water-cooled after the copper alloy seamless pipe of subjects carries out the heating of 10 minutes at 950 DEG C ± 25 DEG C, first, at nitrogen atmosphere, be set as in the electric furnace of 950 ± 25 DEG C, load subjects, after in-furnace temperature returns to 950 DEG C, keep 10 minutes at 950 DEG C ± 25 DEG C, then carry out water-cooled immediately from 950 DEG C, thus carry out.Then, the electric conductivity (%IACS) of the subjects at measuring 950 DEG C after heating-water-cooled test in 10 minutes, obtains ρ 3.
In addition, at 550 DEG C, the heating-water-cooled test of 60 minutes refers to, after the heating of carrying out 10 minutes as the copper alloy seamless pipe of subjects at 950 DEG C and water-cooled, then the test of water-cooled is carried out after carrying out the heating of 60 minutes at 550 DEG C ± 10 DEG C, first, in the same manner as subjects is tested with the heating-water-cooled of 10 minutes at 950 DEG C, carry out heating in 10 minutes at 950 DEG C ± 25 DEG C after, from 950 DEG C of water-cooleds immediately, then at 950 DEG C, carry out heating and the water-cooled of 10 minutes, gained subjects is loaded in salt bath furnace, keep 60 minutes at 550 DEG C ± 10 DEG C, then water-cooled is carried out immediately, thus carry out.Then, the electric conductivity (%IACS) of the subjects at measuring 550 DEG C ± 10 DEG C after heating-water-cooled test in 60 minutes, obtains ρ 4.
(heating-water-cooled test 1) 950 DEG C ± 25 DEG C × 10 minutes
First, sample 3 is encased in nitrogen atmosphere, is set in the electric furnace of 950 ± 25 DEG C, after temperature return to 950 in stove DEG C, keep 10 minutes at 950 ± 25 DEG C, then from 950 DEG C of water-cooleds immediately, carry out heating-water-cooled test 1.
(heating-water-cooled test 2) 550 DEG C ± 10 DEG C × 60 minutes
First, sample 4 and heating-water-cooled are tested heating and the water-cooled of to carry out at 950 ± 25 DEG C in the same manner as 1 10 minutes, then the sample 4 having carried out testing with heating-water-cooled 1 same heating and water-cooled is loaded in salt bath furnace, keep 60 minutes at 550 DEG C ± 10 DEG C, then water-cooled immediately, carries out heating-water-cooled test 2.
< evaluates >
(mechanical properties)
Use solder (JISZ3264BCuP-2) and oxygen-propane mixture body, implement torch brazing, make the compressive strength measurement sample after brazing.Now, brazing is implemented until solder flows into connector portions.Cooling is set to air cooling, after cooling, carries out the bursting test based on hydraulic pressure, uses following formula * 1 according to strength at break, infers tensile strength, evaluates the mechanical properties (tensile strength and elongation) before and after brazing.
Evaluate the mechanical properties before brazing by tension test, according to JISZ2241, measure tensile strength and elongation.The results are shown in table 3.
< formula * 1 > KHK formula: parting pressure=2 × tensile strength × wall thickness/(external diameter-0.8 × wall thickness)
(electric conductivity)
For electric conductivity measuring, utilize based on the method for JISH0505, i.e. four-terminal method, measure resistance, its value divided by 0.15328 gained is represented with percentage.
(medium temperature friability test)
To copper alloy seamless pipe at 350 DEG C with rate of straining 10
-4draw speed carry out tension test.Be that the situation of more than 30% is as qualified using elongation (δ).
(thermal fatigue test)
In the thermostatic bath of 100 DEG C, press 100,000 times in the repetition of copper alloy seamless pipe load 0 to 15MPa, carry out thermal fatigue test.The situation of be full of cracks is not produced as qualified using in test.
[table 1]
| Alloy is numbered | Sn | Zr | P | S | H |
| 1-a | 0.65 | 0.02 | 0.024 | 00007 | 0.0004 |
| 1-b | 0.65 | 0.02 | 0.024 | 0.0002 | 0.0001 |
| 2 | 0.65 | 0.04 | 0.023 | 0.0007 | 0.0004 |
| 3 | 0.65 | 0.075 | 0.007 | 0.0008 | 0.0004 |
| 4 | 0.50 | 0.02 | 0.021 | 0.0008 | 0.0005 |
| 5 | 0.50 | 0.04 | 0.018 | 0.0009 | 0.0018 |
| 6 | 0.40 | 0.01 | 0.025 | 0.0005 | 0.0004 |
| 7 | 0.35 | 0.04 | 0.015 | 0.0009 | 0.0008 |
| 8 | 0.28 | 0.07 | 0.008 | 0.0008 | 0.0005 |
| 9 | 0.78 | 0.03 | 0.024 | 0.0007 | 0.0003 |
| 10 | 0.50 | 0.085 | 0.007 | 0.0007 | 0.0017 |
| 11 | 0.30 | 0.09 | 0.009 | 0.0009 | 0.0005 |
| 12 | 0.65 | 0.09 | 0.007 | 0.0010 | 0.0004 |
| 13 | 0.50 | 0.005 | 0.024 | 0.0007 | 0.0008 |
| 14 | 0.35 | 0.01 | 0.038 | 0.0006 | 0.0003 |
| 15 | 0.30 | 0.04 | 0.014 | 0.0009 | 0.0004 |
| 16 | 0.75 | 0.06 | 0.015 | 0.0007 | 0.0004 |
[table 2]
[table 3]
Claims (3)
1. a heat pipe copper alloy seamless pipe, is characterized in that, its heat pipe copper alloy seamless pipe obtained for worked copper alloy,
This copper alloy contains Sn, the Zr of 0.01 ~ 0.08 quality % and the P of 0.004 ~ 0.04 quality %, and surplus is made up of Cu and inevitable impurity, and the content of Sn and Zr in this copper alloy meets following formula (1):
(1)0.4≤A+2B≤0.85
In formula, A represents the content (quality %) of Sn, and B represents the content (quality %) of Zr,
The electric conductivity of this heat pipe copper alloy seamless pipe meets following formula (2):
(2)ρ2-ρ1≥0.3(％IACS)
In formula, ρ 1 refers to the electric conductivity (%IACS) after solution treatment, and ρ 2 refers to the electric conductivity (%IACS) after ageing treatment.
2. a heat pipe copper alloy seamless pipe, is characterized in that, its heat pipe copper alloy seamless pipe obtained for worked copper alloy,
This copper alloy contains Sn, the Zr of 0.01 ~ 0.08 quality % and the P of 0.004 ~ 0.04 quality %, and surplus is made up of Cu and inevitable impurity, and the content of Sn and Zr in this copper alloy meets following formula (1):
(1)0.4≤A+2B≤0.85
In formula, A represents the content (quality %) of Sn, and B represents the content (quality %) of Zr,
The electric conductivity of this heat pipe copper alloy seamless pipe meets following formula (3):
(3)ρ4-ρ3≥0.3(％IACS)
In formula, ρ 3 refers to the electric conductivity (%IACS) after the heating-water-cooled test of at 950 DEG C 10 minutes, and ρ 4 refers to the electric conductivity (%IACS) after the heating-water-cooled test of at 550 DEG C 60 minutes.
3. heat pipe copper alloy seamless pipe according to claim 1 and 2, is characterized in that, described copper alloy is also containing the S of 0.0005 ~ 0.0010 quality % and the H of 0.0002 ~ 0.0020 quality %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-048038 | 2013-03-11 | ||
| JP2013048038A JP6244588B2 (en) | 2013-03-11 | 2013-03-11 | Copper alloy seamless pipe for heat transfer tubes |
| PCT/JP2014/056110 WO2014142049A1 (en) | 2013-03-11 | 2014-03-10 | Copper alloy seamless tube for heat transfer tube |
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| Publication Number | Publication Date |
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| CN105143479A true CN105143479A (en) | 2015-12-09 |
| CN105143479B CN105143479B (en) | 2017-05-17 |
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| JP (1) | JP6244588B2 (en) |
| KR (1) | KR20150122664A (en) |
| CN (1) | CN105143479B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107109531A (en) * | 2014-11-05 | 2017-08-29 | 株式会社Uacj | Heat exchanger inner face grooved pipe and its manufacture method |
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| KR101698718B1 (en) | 2016-04-29 | 2017-01-20 | 엘지디스플레이 주식회사 | Organic light emitting display device |
| JP6822889B2 (en) | 2017-04-13 | 2021-01-27 | 株式会社Ｓｈカッパープロダクツ | Copper alloy material, manufacturing method of copper alloy material and cage rotor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518176A (en) * | 2003-01-23 | 2004-08-04 | 日矿金属加工株式会社 | High intensity high conduction property copper alloy of good fatigue and middle temprature property |
| JP2008255381A (en) * | 2007-03-30 | 2008-10-23 | Kobelco & Materials Copper Tube Inc | Heat resistant and high strength copper alloy tube for heat exchanger |
| JP2010222692A (en) * | 2009-03-25 | 2010-10-07 | Sumitomo Light Metal Ind Ltd | Copper alloy seamless pipe for supplying water and hot water |
| CN102191402A (en) * | 2010-03-10 | 2011-09-21 | 株式会社神户制钢所 | High-strength high-heat-resistance copper alloy |
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| JP3303778B2 (en) * | 1998-06-16 | 2002-07-22 | 三菱マテリアル株式会社 | Seamless copper alloy tube for heat exchanger with excellent 0.2% proof stress and fatigue strength |
| JP5534777B2 (en) * | 2009-10-28 | 2014-07-02 | 株式会社Ｕａｃｊ | Copper alloy seamless pipe |
| JP5713230B2 (en) * | 2010-04-28 | 2015-05-07 | 住友電気工業株式会社 | Cu-Ag alloy wire and method for producing Cu-Ag alloy wire |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518176A (en) * | 2003-01-23 | 2004-08-04 | 日矿金属加工株式会社 | High intensity high conduction property copper alloy of good fatigue and middle temprature property |
| JP2008255381A (en) * | 2007-03-30 | 2008-10-23 | Kobelco & Materials Copper Tube Inc | Heat resistant and high strength copper alloy tube for heat exchanger |
| JP2010222692A (en) * | 2009-03-25 | 2010-10-07 | Sumitomo Light Metal Ind Ltd | Copper alloy seamless pipe for supplying water and hot water |
| CN102191402A (en) * | 2010-03-10 | 2011-09-21 | 株式会社神户制钢所 | High-strength high-heat-resistance copper alloy |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107109531A (en) * | 2014-11-05 | 2017-08-29 | 株式会社Uacj | Heat exchanger inner face grooved pipe and its manufacture method |
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| CN105143479B (en) | 2017-05-17 |
| JP2014173156A (en) | 2014-09-22 |
| MY181920A (en) | 2021-01-14 |
| TWI608110B (en) | 2017-12-11 |
| TW201446982A (en) | 2014-12-16 |
| JP6244588B2 (en) | 2017-12-13 |
| WO2014142049A1 (en) | 2014-09-18 |
| KR20150122664A (en) | 2015-11-02 |
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