CN102690972A - Copper alloy tube for heat exchange - Google Patents
Copper alloy tube for heat exchange Download PDFInfo
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- CN102690972A CN102690972A CN2012100621031A CN201210062103A CN102690972A CN 102690972 A CN102690972 A CN 102690972A CN 2012100621031 A CN2012100621031 A CN 2012100621031A CN 201210062103 A CN201210062103 A CN 201210062103A CN 102690972 A CN102690972 A CN 102690972A
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Abstract
The invention provides a copper alloy tube used for heat exchange. The advantage of high strength of the copper alloy tube is maintained, and simultaneously, the process performance is enhanced, and the production performance is enhanced by inhibitaing the pressure increase in heat extrusion. The copper alloy tube used for heat exchange is formed by tubular copper alloy, wherein the contents are provided as following: 0.1 to 1.0 mas% of Mn, 0.05 to 0.5 mas% of Fe and 0.01 to 0.1 mas% of P, with the remaining being Cu and unavoided impurity, and the mass ratio of Fe to P is about 2 to 8.
Description
Technical field
The present invention relates to the copper alloy tube for heat exchanger that in the heat exchanger of air-conditioning instrument such as box air-conditioning or heat pump water heater or its pipe arrangement, uses, when particularly having excellent intensity, the copper alloy tube for heat exchanger of excellent in workability such as hot extrusion.
Background technology
For the copper pipe that in heat exchanger, uses, desired strength is high, processibility is good, excellent corrosion resistance, heat conductivity is good, solderability good and characteristic such as fatigue strength height, as the material of the actual service conditions that satisfies these, generally uses phosphorized copper.
And on the other hand,, carrying out because of the restriction of freon refrigerant being used the conversion that substitutes freonll-11 and with CO from the problem of corresponding global warming
2As popularizing of the heat pump water heater of refrigeration agent.Condensing pressure becomes higher than in the past when operating owing to it for such new refrigerant, and is therefore withstand voltage fully in order in the copper pipe that uses phosphorized copper, to obtain, and need the wall thickness of pipe be become thicker than in the past.But,, in addition,, also be disadvantageous from practicing thrift viewpoint as the copper product of resource if the wall thickness thickening owing to increased the copper amount of using, therefore is accompanied by the surging of copper valency in recent years and brings the surging of product price.
Developing material as the such problem of correspondence has following copper alloy tube: use the Cu-Co-P that improves intensity through the compound that disperses to separate out Co and P at material internal be alloy (for example; With reference to patent documentation 1); Or use is alloy (for example, with reference to a patent documentation 2) through the Cu-Sn-P that solid solution Sn in Cu improves intensity.These copper alloys are because higher than phosphorized copper intensity, though therefore the pressure of refrigeration agent rise also can use with in the past on an equal basis or more the pipe of thin wall thickness come corresponding.
Patent documentation 1: No. 3303778 communique of Japanese Patent
Patent documentation 2: No. 3794971 communique of Japanese Patent
Patent documentation 3: No. 3878640 communique of Japanese Patent
Summary of the invention
But Cu-Co-P is that the compound of alloy Co and P disperses to separate out in the parent phase of Cu, obtains high intensity through its precipitation strength.But,,, thereby have the such problem of reduction high strength performance because necessary soldering when heat exchanger is assembled promotes the solid solution again of such precipitate when high temperature heats for this material.
Cu-Sn-P is the situation of alloy, and Sn helps strengthening under solid solution condition, even at high temperature heat the performance that also can keep high strength.But, when strengthening, compare the addition that is necessary to increase alloying constituent with precipitation strength through the solid solution composition, if it is many to add quantitative change, can produce the problem that heat conductivity reduces or processibility worsens.
Be heated under the situation of high-temperature even Cu-P-Co-Sn-Zn is an alloy, also be difficult to because of thickization of heating crystal grain, thereby after heating, still can keep HS.But the mechanical characteristics after the annealing is compared firmly, extends little with phosphorized copper, the groove processing that therefore can be created in the heat-transfer pipe inner face problem of difficulty that becomes.
In addition; In the processing of copper pipe, after generally the extrusion processing cast material is configured as the preliminary shaping pipe in hot rolling, process the size that is processed into regulation through cold rolling drawing; If but the addition of increase alloying constituent, the problem that the resistance to deformation when extrusion processing is arranged uprises.Consequently, if do not apply higher squeeze pressure, just can not be configured as the preliminary shaping pipe, therefore the restriction condition to processing units becomes stricter.
The objective of the invention is to, a kind of copper alloy tube for heat exchanger is provided, when keeping the high-intensity advantage of having of copper alloy tube, improve its processibility, particularly realize productive raising through the rising that suppresses squeeze pressure in the hot extrusion.
As previously mentioned, when using precipitation strength as the strengthening mechanism of copper alloy tube, surpassing when soldering has the problem that reduces the high strength performance under 750 ℃ of such heat.In addition, when using solution strengthening as strengthening mechanism, the resistance to deformation rising when causing extrusion processing because of the increase of addition, heat conductivity reduces becomes problem.For the merits and demerits that makes these strengthening mechanisms realizes good on realistic scale and deposits, hope that balance mixes precipitation strength composition and solution strengthening composition well, can apply flexibly both advantages together.That is, we can say, add the solution strengthening element not producing because of the resistance to deformation rising causes in the addition scope of unfavorable condition, further corresponding interpolation precipitation strength element with it, it is effective attempting to replenish intensity.For the above result who discusses repeatedly, present inventors have found can solve above-mentioned problem through following means.
In order to achieve the above object; An embodiment of the invention are to provide a kind of copper alloy tube for heat exchanger; Be the Mn that will contain 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %; The mass ratio of Fe and P (Fe/P) is 2～8, and remainder is that the copper alloy of Cu and unavoidable impurities is configured as tubulose and forms.
The copper alloy that will contain the Mn of 0.1～1.0 quality % uses as material.Mn is present in the copper with solid solution condition, is the composition that helps improving intensity.In addition, through coexisting with P, a part is converted into P-compound and separates out, and therefore, is the composition that also can expect precipitating reinforcing effect.
Except the Mn of specified amount, Fe, P, be that 2～8 scope contains the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality % at mass ratio (Fe/P).Fe separates out in material as P-compound through adding with P, is that purpose is added Fe to replenish intensity through precipitation strength therefore.In the present invention, through the precipitation strength that balance makes up the solution strengthening added because of Mn well and adds because of Fe, can obtain the superperformance of target.In addition, the interpolation of Fe makes the crystal grain granular, and the effect of thickization of crystal grain when suppressing heat is also arranged.If thickization of crystal grain, becoming is easy to generate grain-boundary crack, reduces processibility, therefore we can say that the interpolation of Fe also has the effect of keeping good processibility.Here, if the addition of Fe too is less than the addition of P, it is insufficient that precipitation strength becomes, and can not expect effect.In addition, if too much, owing to Fe quantitative change residual under solid solution condition is many, unfavorable conditions such as being easy to generate the heat conductivity reduction becomes.
In addition; In order to achieve the above object; An embodiment of the invention are to provide a kind of copper alloy tube for heat exchanger, are with the Fe of the Mn that contains 0.1～1.0 quality %, 0.05～0.5 quality % and the P of 0.01～0.1 quality %, and contain the Ni that adds up to 0.01～0.25 quality % and among the Co one or both; The total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P} is 2～8, and remainder is that the copper alloy of Cu and unavoidable impurities is configured as tubulose and forms.
For Fe, its part can be replaced into Ni and Co.At this moment, the addition of Ni and Co adds up to 0.01～0.25 quality %.In addition, be necessary with the total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P} is defined as 2～8 scope.
In addition; In order to achieve the above object; An embodiment of the invention are to provide a kind of copper alloy tube for heat exchanger, are with the Fe of the Mn that contains 0.1～1.0 quality %, 0.05～0.5 quality % and the P of 0.01～0.1 quality %, and contain the composition of from Sn, Zn, In, Mg, selecting more than a kind that adds up to 0.01～0.3 quality %; The mass ratio of Fe and P (Fe/P) is 2～8, and remainder is that the copper alloy of Cu and unavoidable impurities is configured as tubulose.
Except the composition of Mn, Fe, P,, also can obtain good characteristic even in the scope that adds up to 0.01～0.3 quality %, further add the composition of from Sn, Zn, In, Mg, selecting more than a kind.These are mainly and can replenish the composition of intensity because of solution strengthening.
In addition; In order to achieve the above object; An embodiment of the invention are to provide a kind of copper alloy tube for heat exchanger; To contain the Mn of 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %, and contain the Ni that adds up to 0.01～0.25 quality % and among the Co one or both, further contain the composition of from Sn, Zn, In, Mg, selecting more than a kind that adds up to 0.01～0.3 quality %; The total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P} is 2～8, and remainder is that the copper alloy of Cu and unavoidable impurities is configured as tubulose.
In above-mentioned copper alloy tube for heat exchanger, the addition of above-mentioned Mn is 0.2～0.8 quality % more preferably.The addition of above-mentioned Fe is 0.05～0.4 quality % more preferably.The addition of above-mentioned P is 0.02～0.08 quality % more preferably.The total of above-mentioned Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P} more preferably 3～6.
For example for more than the 240MPa, further is more than the 270MPa through the tensile strength after will annealing, and can guarantee HS.In addition, for example be more than 40% through the unit elongation after will annealing, further be more than 43%, grain fineness number for example is below the 30 μ m, further is below the 22 μ m, can keep the excellent in vending workability as copper alloy tube for heat exchanger.
In addition, through for example being below 1.5, can suppress the rising of squeeze pressure, keep good productivity with the resistance to deformation evaluation of estimate." resistance to deformation evaluation of estimate " be meant, with the stress determination value of compression testing sheet of the present invention value divided by the stress determination value of the compression testing sheet that is made up of comparative material.The stress determination value of compression testing sheet of the present invention is; The diameter that making is made up of copper alloy of the present invention is that 12mm, length are the compression testing sheet of 15mm; Use mechanical type high speed compression testing device (カ system プ ラ ス ト メ one タ one), under 800 ℃, with Deformation velocity 1s
-1Carry out compression set, the stress when measuring 25% compression and the value that obtains.The stress determination value of the compression testing sheet that is made up of comparative material does; Constitute by the phosphorized copper that contains P:0.03 quality % as comparative material; Make and the same compression testing sheet of the present invention, with the same condition of the present invention under, the stress when measuring 25% compression and the value that obtains.
According to copper alloy tube for heat exchanger of the present invention, when keeping the high-intensity advantage of having of copper alloy tube, improve its processibility, particularly attempt to improve productivity through the rising that suppresses squeeze pressure in the hot extrusion.
Description of drawings
Fig. 1 shows the schematic cross-section of processing unit (plant) of pipe of the band inner face groove of the heat-transfer pipe method of manufacture be used to explain band inner face groove.
Fig. 2 shows an example of intersection fin (Network ロ ス Off ィ Application チ ュ one Block) type heat exchanger.
Fig. 3 shows an example of intersection fin-type heat exchanger method of manufacture.
Nomenclature
1 metal tube
2 floating mandrels
3 connecting rods
The stopper of 4 with grooves
5 grooves
6 pressing mechanisms
7 drawing dies
8 grooves
The heat-transfer pipe of 9 band inner face grooves
10 drawing dies
The heat-transfer pipe of 11 band inner face grooves
30 splitters
31 aluminium fins
The heat-transfer pipe end of 32 band inner face grooves
The heat-transfer pipe of 101 band inner face grooves
102 (inner face) groove
The 103 fin collars
104 aluminium fins
105 expander iron cores
The heat-transfer pipe of the band inner face groove behind 106 expanders
Embodiment
The copper alloy tube for heat exchanger that relates in the embodiment of the present invention does; Be Mn, Fe and the P that will contain the regulation addition; And remainder is that the copper alloy of Cu and unavoidable impurities is configured as the copper alloy tube for heat exchanger that tubulose forms, and in the copper alloy of use, the addition of Mn is 0.1～1.0 quality %; The addition of Fe is 0.05～0.5 quality %; The addition of P is 0.01～0.1 quality %, and the mass ratio of Fe and P (Fe/P) is 2～8, and remainder is Cu and unavoidable impurities.
The 1st embodiment
The copper alloy tube for heat exchanger that relates in the present invention's the 1st embodiment is with the Fe of the Mn that contains 0.1～1.0 quality %, 0.05～0.5 quality % and the P of 0.01～0.1 quality %; The mass ratio of Fe and P (Fe/P) is 2～8, and remainder is that the copper alloy of Cu and unavoidable impurities is configured as tubulose and forms.
The copper alloy that will contain the Mn of 0.1～1.0 quality % uses as material.Mn is present in the copper with solid solution condition, is to help the composition that intensity improves.In addition, through coexisting with P, a part is converted into P-compound and separates out, and is the composition that also can expect precipitating reinforcing effect therefore.
Except the Mn of specified amount, Fe, P, be that 2～8 scope contains the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality % at mass ratio (Fe/P).Fe separates out in material as P-compound through adding with P, is that purpose is added Fe to replenish intensity through precipitation strength therefore.In this embodiment,, can obtain the superperformance of target through the precipitation strength that balance makes up the solution strengthening added because of Mn well and adds because of Fe.In addition, the interpolation of Fe makes the crystal grain granular, and the effect of thickization of crystal grain when suppressing heat is also arranged.If thickization of crystal grain, becoming is easy to generate grain-boundary crack, reduces processibility, therefore we can say that the interpolation of Fe also has the effect of keeping good processibility.Here, if the addition of Fe too is less than the addition of P, it is insufficient that precipitation strength becomes, and can not expect effect.In addition, if too much, owing to Fe quantitative change residual under solid solution condition is many, unfavorable conditions such as being easy to generate the heat conductivity reduction becomes.
Next, the numerical definiteness of above-mentioned copper alloy composition below is described.
The addition of Mn is the reasons are as follows of 0.1～1.0 quality %.The addition of Mn can not be expected solution strengthening fully during less than 0.1 quality %, can not reach the purpose of high strength of the present invention.In addition, if when adding Mn and surpassing 1.0 quality %, the problem that the resistance to deformation rising in the time of can might extrusion processing occurring, heat conductivity reduce.Therefore, the compositing range of Mn is defined as 0.1～1.0 quality %.In addition, the addition of Mn also may be prescribed as 0.2～0.8 quality %.
The addition of P is the reasons are as follows of 0.01～0.1 quality %.The addition of P has promoted not the formation of P-compound during less than 0.01 quality %, can not obtain the additional intensity because of precipitation strength.In addition, if when adding P and surpassing 0.1 quality %, when casting, during hot extrusion, become and be easy to generate the cracking that causes by the segregation of P-compound.Therefore, the addition of P is defined as 0.01～0.1 quality %.In addition, the addition of P also may be prescribed as 0.02～0.08 quality %.
The addition of Fe is the reasons are as follows of 0.05～0.5 quality %.For compositing range with respect to above-mentioned P, form compound effectively and precipitation strength, the compositing range of Fe is necessary to be defined as 0.05～0.5 quality %.The addition of Fe is during less than 0.05 quality %, and the formation quantitative change of P-compound gets insufficient, can not expect to add the effect of bringing.In addition, if when adding Fe and surpassing 0.5 quality %, Fe quantitative change residual under solid solution condition is many, produces unfavorable conditions such as heat conductivity reduction.In addition, the addition of Fe also may be prescribed as 0.05～0.4 quality %.
The mass ratio of Fe and P (Fe/P) is 2～8 the reasons are as follows.Even the compositing range of Fe and P is in above-mentioned scope, if both balanced differences can not form P-compound effectively.Here, in this embodiment, the mass ratio of Fe and P (Fe/P) is defined as 2～8.Because the mass ratio of Fe and P is less than 2, P becomes too much, and the mass ratio of Fe and P surpasses at 8 o'clock, and Fe becomes too much, and therefore, which kind of situation all is difficult to separate out P-compound respond wellly.In addition, the mass ratio of Fe and P also may be prescribed as 3～6.
The 2nd embodiment
The copper alloy tube for heat exchanger that relates in the present invention's the 2nd embodiment does, with respect to the composition of the copper alloy of the 1st embodiment, uses to be added with the Ni of specified amount and one or both the copper alloy tube of copper alloy among the Co.
Promptly, the copper alloy tube for heat exchanger of this embodiment is with the Fe of the Mn that contains 0.1～1.0 quality %, 0.05～0.5 quality % and the P of 0.01～0.1 quality %; And contain the Ni that adds up to 0.01～0.25 quality % and among the Co one or both; The total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P} is 2～8, and remainder is that the copper alloy of Cu and unavoidable impurities is configured as tubulose and forms.
Next, the following reason of numerical definiteness of the composition of the above-mentioned copper alloy of explanation.In addition, because addition and the Fe of Mn, P, Fe are identical with the 1st embodiment with the qualification reason of the mass ratio of P, therefore omit its explanation here.
Among Ni and the Co one or both add up to the reasons are as follows of 0.01～0.25 quality %.Ni and Co and Fe are similarly through separating out P-compound and expect to produce the composition that active strength is replenished because of precipitation strength.Therefore, promptly use the part of these element substitutions Fe, also can obtain target property of the present invention.At this moment, the compositing range of Ni and Co is defined as and adds up to 0.01～0.25 quality %.These addition can not form P-compound during less than 0.01 quality % fully, can not expect to add the effect of bringing.In addition, add when surpassing 0.25 quality %, since many with solid solution condition residual Ni and Co quantitative change, with the identical meeting of situation of Fe unfavorable conditions such as heat conductivity reduction take place therefore.In addition, also can among Ni and the Co one or both be defined as and add up to 0.02～0.15 quality %.
Here, hope the addition of Ni and Co is made as the scope below the isodose with respect to the addition of Fe.The relative ratio step-down of Fe if this is, the effect of the crystal grain miniaturization that Fe had dies down.
The total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P} is 2～8 the reasons are as follows.When adding Ni and Co with Fe, in order to form P-compound effectively, the total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P} is defined as 2～8 scope.Because the total of Fe, Ni, Co and the mass ratio of P are less than 2, P becomes too much, surpasses at 8 o'clock, and Fe, Ni, Co become too much, and therefore, which kind of situation all can not be separated out P-compound respond wellly.In addition, the mass ratio of the total of Fe, Ni, Co and P also may be prescribed as 3～6.
In the selection of Ni, Co, when thinking further to obtain stable on heating situation etc., can use Co.
The 3rd embodiment
The copper alloy tube for heat exchanger that relates in the present invention's the 3rd embodiment does, with respect to the composition of the copper alloy of the 1st embodiment, uses the copper alloy tube of from Sn, Zn, In, Mg, selecting of the copper alloy of composition more than a kind that is added with specified amount.
Promptly; The copper alloy tube for heat exchanger of this embodiment is with the Fe of the Mn that contains 0.1～1.0 quality %, 0.05～0.5 quality % and the P of 0.01～0.1 quality %; And contain the composition of from Sn, Zn, In, Mg, selecting more than a kind that adds up to 0.01～0.3 quality %; The mass ratio of Fe and P (Fe/P) is 2～8, and remainder is that the copper alloy of Cu and unavoidable impurities is configured as tubulose and forms.
Next, the following reason of numerical definiteness of the composition of the above-mentioned copper alloy of explanation.In addition, because addition and the Fe of Mn, P, Fe are identical with the 1st embodiment with the qualification reason of the mass ratio of P, therefore omit its explanation here.
The composition of from Sn, Zn, In, Mg, selecting more than a kind add up to the reasons are as follows of 0.01～0.3 quality %.Sn, Zn, In, Mg are the big composition of solid solution strengthening effect.When adding these, can expect that effective intensity is additional with Mn.At this moment, the compositing range of Sn, Zn, In, Mg is defined as and adds up to 0.01～0.3 quality %.These addition is during less than 0.01 quality %, and the effect of interpolation is insufficient, adds when surpassing 0.3 quality %, is increased and the resistance to deformation rising can cause extrusion processing time the, the problem that heat conductivity reduces by the total amount of added ingredients.In addition, also can the compositing range of Sn, Zn, In, Mg be defined as total 0.03～0.2 quality %.
In addition; Do not use Mn and during through Sn, Zn, In and Mg adjustment intensity; The danger such than the about-face electric conductivity is obviously arranged; And as this embodiment, add the Mn of 0.1～1.0 quality %, when further using Sn, Zn, In and Mg, can not can cancel out each other because of the characteristic that do not have the electric conductivity reduction that Mn causes with because of the characteristic of Sn, Zn, In and the caused strength reinforcing of Mg.
The 4th embodiment
The copper alloy tube for heat exchanger that relates in the present invention's the 4th embodiment does; Composition with respect to the copper alloy of the 1st embodiment; Use is added with the Ni of specified amount and among the Co one or both, further is added with the copper alloy tube of from Sn, Zn, In, Mg, selecting of the copper alloy of composition more than a kind of specified amount.
Promptly; The copper alloy tube for heat exchanger of this embodiment is with the Fe of the Mn that contains 0.1～1.0 quality %, 0.05～0.5 quality % and the P of 0.01～0.1 quality %; And contain the Ni that adds up to 0.01～0.25 quality % and among the Co one or both; Further contain the composition of from Sn, Zn, In, Mg, selecting more than a kind that adds up to 0.01～0.3 quality %; The total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P} is 2～8, and remainder is that the copper alloy of Cu and unavoidable impurities is configured as tubulose and forms.
One or both addition and the numerical definiteness reason of the addition of composition more than a kind from Sn, Zn, In, Mg, selected among mass ratio, Ni and the Co of the addition of above-mentioned Mn, P, Fe, Fe and P is identical with the 1st to the 3rd embodiment, therefore omits its explanation here.
The effect of each embodiment
Copper alloy tube for heat exchanger according to relating in as above so above-mentioned each embodiment can obtain following effect.
(1), can realize intensity and hot workability and deposit through using Mn as becoming main added ingredients.Promptly; When fully keeping copper alloy tube and having high-intensity advantage; For its processibility, particularly hang down the rising that suppresses squeeze pressure, thereby can process with productivity no less than in the past phosphorized copper through the thermal distortion resistance is suppressed to.
Know from above that (2) each embodiment has promoted the conversion to the high new refrigerant of condensing pressure, in addition, also can expect unusual effect as the viewpoint of the copper product of resource from saving.
(3) in addition, for the interpolation of Mn, except having improved intensity, good effect is also arranged with respect to the raising of pitting corrosion resistance.Therefore, copper alloy tube of the present invention also can expect to realize simultaneously the raising of pitting corrosion resistance except high strength.
Embodiment
Next, enumerating embodiment for the present invention carries out bright specifically.Here, embodiment 1～6 is corresponding to the 1st embodiment, and embodiment 7～11 is corresponding to the 2nd embodiment, and embodiment 12～15 is corresponding to the 3rd embodiment, and embodiment 16,17 is corresponding to the 4th embodiment.
Embodiment 1
Through in the fused solution of oxygen free copper, add Mn, Fe and Cu-P mother alloy and cast, make as raw material contain Mn:0.3 quality %, Fe:0.1 quality %, P:0.03 quality % and remainder be Cu and unavoidable impurities, diameter is 20mm, the long diameter that uses ingot bar and same composition for the test of 100mm as 250mm, grows to process as the copper pipe of 400mm and use the copper base.
Copper pipe processing with the copper base 900 ℃, keep homogenizing in 1 hour handle after, 830 ℃ of heating, process and hot extrusion through boring a hole at copper base center with iron core (mandrel), being processed into external diameter is that 80mm, wall thickness are the extruding preliminary shaping pipe of 8mm.Cold rollingly should push the preliminary shaping pipe to be processed into external diameter be after 40mm, wall thickness are 2mm through what undertaken by cold reducing mill (tube reducer), and use cold drawing bench to carry out drawing processing through cold working, processing external diameter is that 10mm, wall thickness are the smooth tubes of 0.5mm.This smooth tubes carries out being annealed in 10 minutes the copper pipe sample at 450 ℃.
When carrying out the evaluation of thermal distortion resistance, measure tensile strength, unit elongation and the grain fineness number of copper pipe sample for the foregoing description 1.The mensuration of tensile strength and unit elongation is undertaken by the stretching test method of JIS 2241.Grain fineness number is the median size of the crystal grain of constituent material, and its mensuration is carried out through the process of chopping of JISH0501, observes and the vertical cross section of length direction of managing, and measures grain fineness number.
Carry out the evaluation of thermal distortion resistance with following method.Use the test of embodiment 1 to use ingot bar, processing diameter is that 12mm, length are the compression testing sheet of 15mm, uses mechanical type high speed compression testing device, under 800 ℃, with Deformation velocity 1s
-1Carry out compression set, the stress when measuring 25% compression.Next, the phosphorized copper that contains P:0.03 quality % as comparative material is also processed same compression testing sheet, under identical condition, carry out compression set, the stress when measuring 25% compression.Here, with the stress determination value of embodiment 1 stress determination value, with the resistance to deformation evaluation of estimate of this value as embodiment 1 divided by phosphorized copper.
Above result, the resistance to deformation evaluation of estimate of embodiment 1 is 1.20, and tensile strength is 272MPa, and unit elongation is 55%, and grain fineness number is 18 μ m.Here, in order to suppress the rising of squeeze pressure, keep good productivity, we can say that the resistance to deformation evaluation of estimate for example is is effective below 1.5 as one of the object of the invention.In addition, from guaranteeing the high-intensity point as another purpose, the tensile strength after the annealing for example is more than the 240MPa, further is to be necessary more than the 270MPa.Further, in order to keep the excellent in vending workability of the copper alloy tube of using as heat exchanger, the unit elongation after the annealing need further be more than 43% for for example more than 40%, and grain fineness number for example is below the 30 μ m, further is below the 22 μ m.Be based on this point, embodiments of the invention 1 can be described as the copper alloy tube with the superperformance that satisfies the object of the invention.
Then; With the copper pipe sample after the above-mentioned annealing (smooth tubes of external diameter 10mm, wall thickness 8mm) as former pipe, the making external diameter be 7mm, diapire thick for 0.6mm, fin high for 0.15mm, fin number are 60, the fin drift angle is that 60 °, torsion(al)angle are the pipe of 18 ° band inner face groove.
The working method of the heat-transfer pipe of band inner face groove is described with reference to Fig. 1.In addition, the working method that here discloses is an example of general method, and it is also no problem to use other method to process.The sectional view that the heat-transfer pipe of the band inner face groove that Fig. 1 forms for the working method that shows the pipe through band inner face groove and the summary of the heat-transfer pipe processing unit (plant) of band inner face groove constitute.
In the pipe of metal tube 1, be configured to be connected with floating mandrel 2 through connecting rod 3 with the state that rotates freely at the stopper 4 of with groove with groove 5.Through metal tube 1 is carried out drawing on the drawing direction shown in the arrow, floating mandrel 2 is fixing through drawing die 10, and thus, the stopper 4 of with groove also is fixed on the position of drawing direction.With the periphery of corresponding metal tube 1 in the position of the stopper 4 of this with groove through pressing mechanism 6; For example ball or roll; Extrusion metal pipe 1 revolves round the sun the circumference of metal tube 1 on one side on one side; At the inner face formation of metal tube 1 and the corresponding fin of shape of the groove 5 of the stopper 4 of with groove, simultaneously, processing has the pipe 9 of the band inner face groove of groove 8.
At this moment, in order to obtain the height of desirable fin, use the means such as periphery that strengthen extrusion metal pipe 1, till the degree of the material that is full of metal tube in the groove 5 at the stopper 4 of with groove.Through strengthening extruding, though the degree of depth of groove deepens the thick attenuation of diapire.Even do not strengthen extruding, in the time of obtaining desirable fin height, promptly yet; When the base thickness degree when obtaining desirable fin height is big, can judge processibility good (even processing for maybe, but processibility is during for difference; Have to pressing mechanism 6 is produced burden, accelerate abrasion, production rate reduces).
Thereafter, the drawing die 7 of the external diameter through being processed into regulation is processed into the heat-transfer pipe 11 of the band inner face groove of predetermined outside diameter.
Example as a reference, the phosphorized copper smooth tubes and the Cu-P-Co-Sn-Zn that prepare identical external diameter and be 10mm, wall thickness and be 0.8mm are alloy, likewise implement to be with the processing of inner face groove.Table 1 display result.
Even with the processing of the copper alloy tube of embodiment 1, likewise can obtain desirable fin height with in the past phosphorous deoxidize copper tube with the inner face groove.In addition, can know, the thick equal extent that also is almost of diapire, processibility is good identically with phosphorized copper.And on the other hand, even Cu-P-Co-Sn-Zn is the extruding that alloy strengthens periphery, material can not be full of the groove of the stopper of with groove yet, can not obtain desirable fin height.
Table 1
In Fig. 2,, show the intersection fin-type heat exchanger as an example of the heat exchanger in air conditioning machinery, the Teat pump boiler.
This intersection fin-type heat exchanger is made up of the heat-transfer pipe 32 of a plurality of plate fins 31 with the band inner face groove that connects these, and wherein, a plurality of plate fin 31 is made up of aluminium.Through in the heat-transfer pipe 32 of band inner face groove, getting involved splitter 30 refrigeration agent is flowed into, thereby carry out heat exchange between the heat-transfer pipe 32 of this refrigeration agent and band inner face groove and the air between the plate fin 31.
When making the intersection fin; At first; Aluminum fin upward pressure process and assemble hole being made up of aluminium sheet makes above-mentioned plate fin 31, and this pilot hole has the fin collar portion (one one of Off ィ Application カ ラ) of height about the slotting 1～4mm that leads to the heat-transfer pipe 32 of above-mentioned band inner face groove and be used for fixing.
Then, after range upon range of resulting this plate fin 31, insert the heat-transfer pipe 32 of the logical band inner face groove of making in addition in the inside of pilot hole.The heat-transfer pipe 32 of band inner face groove uses has implemented fixed ruler cutting, U type (ヘ ァ ピ Application) bending machining.
The heat-transfer pipe 32 of expander adhesion zone inner face groove on aluminium sheet fin 31, to the end of the heat-transfer pipe 32 of the band inner face groove of the opposition side of having implemented U type bending machining side operation through brazing processing U curved tube, make and intersect fin-type heat exchanger.
Suppose the heat-transfer pipe of the embodiment of table 11 record is processed as former pipe and the heat-transfer pipe of the band inner face groove made is supplied with heat-transfer pipe as intersecting fin-type heat exchanger, implement expander.Heat-transfer pipe for the band inner face groove of processing as former pipe as the heat-transfer pipe that is made up of phosphorized copper of the table 1 of comparative example and making is also implemented expander.Table 2 shows the result of expander.
The expander multiplying power of the heat-transfer pipe external diameter of the band inner face groove of the heat-transfer pipe external diameter that in table 2, has shown the band inner face groove behind heat-transfer pipe 32 external diameters, fin height, expander of the band inner face groove behind the heat-transfer pipe external diameter, fin height, expander of maximum outside diameter (put down in writing into expander iron core footpath), the band inner face groove before the expander of expander iron core 105 before divided by expander.
Expander is owing to be the method for manufacture of expanding caliber from the inner face of the heat-transfer pipe 32 of band inner face groove; The fin front end of the heat-transfer pipe 32 of band inner face groove is to a certain degree flattened by the expander iron core, fin step-down (when the material condition in addition of the shape of the external diameter of shapes such as the size of pipe, fin height, expander iron core etc. and expander speed, lubricated wet goods is identical).Because reasons such as the extensibility of heat-transfer pipe material are little, when caliber was difficult to expand, the resistance to deformation during owing to expander was big, and therefore, it is big that the flattening of fin front end becomes, and it is big that the reduction of fin height also becomes.At this moment, the reduction that becomes the mathematical expectation of the refrigerant side thermal conductivity that causes greatly because of the reduction of fin height just becomes problem.In addition, if the resistance to deformation during expander is big, also there is the expander iron core to overwhelm the phenomenon of fin (inclination).At this moment, even the reduction of fin height is constant big, the external diameter behind the expander can not fully be expanded, and the increase by the contact thermal resistance that causes with the adaptation variation of aluminum plate fins 31 is arranged.Here, the object of 7.3mm is used in the aperture of supplying with the aluminum plate fins 31 of expander, if be more than the 7.3mm, then also expands with the heat-transfer pipe aluminum plate fins of band inner face groove, therefore, becomes and carries out driving fit.In addition, the general many uses of expander multiplying power are more than 5%, below 7%.
Can know by table 2; The fin height of " heat-transfer pipe of the band inner face groove that the heat-transfer pipe of embodiment 1 record is processed as former pipe " and " heat-transfer pipe of the band inner face groove that phosphorized copper is processed as former pipe " diminishes before than expander; Its degree much at one, the fin of the formed copper alloy tube of copper alloy that successfully will relate to by present embodiment flatten be suppressed to phosphorized copper be equal extent.
In addition, the external diameter behind the expander all expands to more than the aperture of aluminum plate fins, has all obtained desirable expander multiplying power.
In addition, under any condition, all do not see the phenomenon that the fin by expander strikes the beam.
Table 2
Embodiment 2～17
Next, the copper alloy of the embodiment 2～17 that forms shown in the fusion casting table 3 is used with embodiment 1 identical operation and is processed, and processes separately test with ingot bar and copper pipe sample.
Use the method identical for these, carry out the evaluation of thermal distortion resistance, and measure the characteristic value of copper pipe sample with embodiment 1.
Result separately is shown in table 4 and the table 5.All embodiment are suppressed at the resistance to deformation evaluation of estimate below 1.5, have obtained the above intensity of 240MPa simultaneously.In addition, unit elongation or grain fineness number also are in order to obtain the sufficient value of excellent in vending workability, and all embodiment can say so and have the copper alloy tube of the superperformance that satisfies the object of the invention.
In addition, in the above embodiments, 450 ℃, the smooth tubes after the drawing processing is carried out 10 minutes annealing, this annealing temperature exerts an influence to tensile strength, extensibility, the grain fineness number of sample.Promptly, if annealing temperature is for to be higher than 600 ℃ of such high temperature, then reduces tensile strength, it is big that crystal grain becomes.In addition, if annealing temperature is for being lower than 400 ℃ of such low temperature, the value step-down of extensibility.Further, when under being higher than 600 ℃ of such high temperature, annealing, the situation that is reduced heat conductivity by the solid solution again of separating out composition is arranged.In order to avoid such problem; Need in suitable TR, anneal; The optimum range of annealing temperature can be set at 400 ℃ of the equal TR of said and phosphorized copper, copper alloy tube in the past to 600 ℃ (in addition; Owing to make crystal grain significantly be out of shape by cold rolling, drawing processing, therefore can ignore the influence of hot-rolled temperature for grain fineness number.For the characteristic of final heat-transfer pipe, owing to, therefore can ignore in fact by about final annealing temperature institute.)
Table 3
Table 4
Table 5
Comparative example
For copper alloy tube of the present invention, enumerate the qualification reason of its alloy composition of comparative example explanation.For the copper alloy of the comparative example of forming shown in the table 3 1～18, likewise carry out the fusion casting with aforesaid embodiment, it is processed diameter separately is that 20mm, length are used ingot bar for the test of 100mm.Process the compression testing sheet same by these tests with ingot bar, use with the same method of embodiment and carry out the evaluation of thermal distortion resistance with embodiment.
The result is shown in the above-mentioned table 4.Further, for the resistance to deformation evaluation of estimate is suppressed at the comparative example below 1.5, the copper base is used in the same copper pipe processing of fusion casting and embodiment, uses with the same operation of embodiment and is processed into the copper pipe sample.The characteristic value of the copper pipe sample of processing is shown in the above-mentioned table 5.
The addition of the Mn of comparative example 1～8, Fe, P is the addition that departs from specialized range of the present invention.Comparative example 1～3 is the low excessively example of addition of Mn.Comparative example 4～6 is the low excessively example of addition of Fe and P.At this moment, though the thermal distortion resistance is suppressed to lower, the tensile strength of copper pipe sample does not reach 240MPa, should high strength be inadequate.In addition, grain fineness number is also significantly grown into and is surpassed about 30 μ m, and the worry that when bending machining, cracks from the crystal crystal boundary is arranged.
Comparative example 7 is the too much example of addition of Mn, and comparative example 8 is the too much example of addition of Fe and P.In these comparative examples, it is very high that the thermal distortion resistance becomes, and is about 2 times value of phosphorized copper.If such degree is brought up in resistance to deformation,, produce impossible situation that is processed as for the equipment that in the hot extrusion of common copper pipe, uses.
Comparative example 9 and comparative example 10 depart from the example of specialized range for the mass ratio of Fe and P.Comparative example 9 is with respect to P, and Fe is insufficient example, at this moment, though the thermal distortion resistance is suppressed to lower, for the tensile strength of copper pipe sample or unit elongation are insufficient result.Comparative example 10 is with respect to P, and Fe is too much example, and at this moment, the thermal distortion resistance uprises than present embodiment.
Comparative example 11 and comparative example 12 are the example that departs from specialized range for the Ni that cooperates Fe and add or the addition of Co.This kind situation thermal distortion resistance also uprises than present embodiment, becomes big owing to be applied to the hot extrusion equipment load, and therefore the problem that causes productivity to reduce is arranged.
Comparative example 13 is the example that departs from specialized range with comparative example 14 for Fe, Ni, the total of Co and the mass ratio of P.These examples we can say that also the addition of Ni and Co is too much state, and it is higher than present embodiment that the thermal distortion resistance becomes.
Comparative example 15～18 is the example that departs from specialized range for the addition of Sn, Zn, In, Mg.If the addition of these compositions is too much, because the interpolation element quantitative change of solid solution condition is many, so the thermal distortion resistance becomes very high, and producing and using the extrusion processing of common equipment is impossible situation.
More than, the comparative example that departs from compositing range given to this invention all can not satisfy the object of the invention, can only obtain inadequate result.
In addition, the present invention does not receive the restriction that limited above-mentioned each embodiment and above-mentioned each embodiment, in the scope shown in the claim, can apply suitable the change and implement, and these are included in the technical scope of the present invention.
Applicability in the industry
The present invention goes for the heat exchanger of use in refrigerator, air conditioning machinery, heat pump, water-heater, bathing pool pot, air-conditioning etc.Such a heat exchanger, liquid or steam through becoming thermal medium in the copper alloy tube of this embodiment or present embodiment through making thermal medium evaporation or condensation, carry out heat exchange.For example, the air conditioning apparatus that constitutes the heat-pump-type freeze cycle becomes and possesses outdoor heat converter, indoor heat converter, the compressor that is connected with these, changes the mobile four-way valve and the expansion valve of thermal medium in cold, the heating installation.When cold air, indoor heat converter plays a role as vaporizer, and outdoor heat converter plays a role as condensing surface, and when heating installation, indoor heat converter plays a role as condensing surface, and outdoor heat converter plays a role as vaporizer.
Claims (16)
1. copper alloy tube for heat exchanger; Being configured as tubulose by copper alloy forms; It is characterized in that said copper alloy contains the Mn of 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %, remainder is Cu and unavoidable impurities; And the mass ratio Fe/P of Fe and P is 2～8.
2. copper alloy tube for heat exchanger; Be configured as tubulose by copper alloy and form, it is characterized in that, said copper alloy contains the Mn of 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %; Also contain the Ni that adds up to 0.01～0.25 quality % and among the Co one or both; Remainder is Cu and unavoidable impurities, and the total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P are 2～8.
3. copper alloy tube for heat exchanger; Be configured as tubulose by copper alloy and form, it is characterized in that, said copper alloy contains the Mn of 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %; Also contain the composition of from Sn, Zn, In, Mg, selecting more than a kind that adds up to 0.01～0.3 quality %; Remainder is Cu and unavoidable impurities, and the mass ratio Fe/P of Fe and P is 2～8.
4. copper alloy tube for heat exchanger; Being configured as tubulose by copper alloy forms; It is characterized in that said copper alloy contains the Mn of 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %, also contain the Ni that adds up to 0.01～0.25 quality % and among the Co one or both; Further contain the composition of from Sn, Zn, In, Mg, selecting more than a kind that adds up to 0.01～0.3 quality %; Remainder is Cu and unavoidable impurities, and the total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P are 2～8.
5. copper alloy tube for heat exchanger according to claim 4, wherein, the addition of said Mn is 0.2～0.8 quality %.
6. copper alloy tube for heat exchanger according to claim 4, wherein, the addition of said Fe is 0.05～0.4 quality %.
7. copper alloy tube for heat exchanger according to claim 4, wherein, the addition of said P is 0.02～0.08 quality %.
8. copper alloy tube for heat exchanger according to claim 4, wherein, the total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P are 3～6.
9. copper alloy tube for heat exchanger according to claim 4; Wherein, The addition of said Mn is 0.2～0.8 quality %; The addition of said Fe is 0.05～0.4 quality %, and the addition of said P is 0.02～0.08 quality %, and the total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P are 3～6.
10. an Albatra metal-; For the heat-transfer pipe that in heat exchanger, uses is used copper alloy; It is characterized in that; Contain the Mn of 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %, the mass ratio Fe/P of Fe and P is 2～8, and remainder is made up of Cu and unavoidable impurities.
A 11. Albatra metal-; For the heat-transfer pipe that in heat exchanger, uses is used copper alloy; It is characterized in that, contain the Mn of 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %, also contain the Ni that adds up to 0.01～0.25 quality % and among the Co one or both; The total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P are 2～8, and remainder is made up of Cu and unavoidable impurities.
A 12. Albatra metal-; For the heat-transfer pipe that in heat exchanger, uses is used copper alloy; It is characterized in that, contain the Mn of 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %, also contain the composition of from Sn, Zn, In, Mg, selecting more than a kind that adds up to 0.01～0.3 quality %; The mass ratio Fe/P of Fe and P is 2～8, and remainder is made up of Cu and unavoidable impurities.
A 13. Albatra metal-; For the heat-transfer pipe that in heat exchanger, uses is used copper alloy; It is characterized in that; Contain the Mn of 0.1～1.0 quality %, the Fe of 0.05～0.5 quality % and the P of 0.01～0.1 quality %, also contain the Ni that adds up to 0.01～0.25 quality % and among the Co one or both, further contain the composition of from Sn, Zn, In, Mg, selecting more than a kind that adds up to 0.01～0.3 quality %; The total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P are 2～8, and remainder is made up of Cu and unavoidable impurities.
14. heat exchanger according to claim 4 is used copper alloy; Wherein, The addition of said Mn is 0.2～0.8 quality %; The addition of said Fe is 0.05～0.4 quality %, and the addition of said P is 0.02～0.08 quality %, and the total of Fe, Ni, Co and the mass ratio of P (Fe+Ni+Co)/P are 3～6.
15., wherein, the pipe inner face is carried out groove processing according to the described copper alloy tube for heat exchanger of claim 1～9.
16. a heat exchanger is characterized in that, uses the copper alloy tube for heat exchanger of claim 15 record.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-062052 | 2011-03-22 | ||
| JP2011062052 | 2011-03-22 | ||
| JP2011287089A JP2012211384A (en) | 2011-03-22 | 2011-12-28 | Copper alloy for heat transfer tube, copper alloy tube for heat exchanger using the same, and heat exchanger using the copper alloy tube for heat exchanger |
| JP2011-287089 | 2011-12-28 |
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|---|---|
| CN102690972A true CN102690972A (en) | 2012-09-26 |
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| CN2012100621031A Pending CN102690972A (en) | 2011-03-22 | 2012-03-09 | Copper alloy tube for heat exchange |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015027975A3 (en) * | 2013-09-02 | 2015-11-12 | Kme Germany Gmbh & Co. Kg | Copper alloy containing iron and phosphorus |
| CN113388753A (en) * | 2021-06-22 | 2021-09-14 | 沈伟 | Alloy with capillary structure and preparation method thereof |
| CN114085978A (en) * | 2021-10-15 | 2022-02-25 | 福建捷思金属科技发展有限公司 | Ultrahigh-pressure-resistant copper-iron alloy pipe fitting for refrigeration system and preparation method |
-
2012
- 2012-03-09 CN CN2012100621031A patent/CN102690972A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015027975A3 (en) * | 2013-09-02 | 2015-11-12 | Kme Germany Gmbh & Co. Kg | Copper alloy containing iron and phosphorus |
| CN113388753A (en) * | 2021-06-22 | 2021-09-14 | 沈伟 | Alloy with capillary structure and preparation method thereof |
| CN113388753B (en) * | 2021-06-22 | 2022-01-04 | 沈伟 | Alloy with capillary structure and preparation method thereof |
| CN114085978A (en) * | 2021-10-15 | 2022-02-25 | 福建捷思金属科技发展有限公司 | Ultrahigh-pressure-resistant copper-iron alloy pipe fitting for refrigeration system and preparation method |
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Application publication date: 20120926 |