CN108950312A

CN108950312A - A kind of transformer conductive material

Info

Publication number: CN108950312A
Application number: CN201810584356.2A
Authority: CN
Inventors: 朱红彬; 毛忠来; 汤彬富
Original assignee: Jiangsu Hengxuan Electrical Co Ltd
Current assignee: NANTONG SUYUAN HENGXUAN ELECTRIC CO., LTD.
Priority date: 2018-06-08
Filing date: 2018-06-08
Publication date: 2018-12-07

Abstract

The present invention provides a kind of transformer conductive material, pass through the combined microalloying of the elements such as Yb, Zr, Hf, Fe, cooperate Compound Heat Treatment system, electric conductivity and heat resistance to alloy carry out comprehensive regulation, obtain the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance, it is able to maintain certain conductivity and intensity at relatively high temperatures, that is, there is preferable high-temperature electric conduction performance and heat resistance.The aluminium alloy that the present invention is developed and designed, in higher temperature in use, since the amplitude of conductivity decline is relatively small electric energy loss can be substantially reduced, this is of great significance for energy-saving and emission-reduction.

Description

A kind of transformer conductive material

The present invention relates to a kind of field transformers, and in particular to a kind of transformer conductive material.

Background technique

With science and technology, the development of electronics market, electronic transformer is widely used, various forms of Electronic transformer continues to bring out, and piezoelectric ceramic transformer also gradually grows up as a kind of novel electronic transformer.Due to Piezoelectric ceramic transformer is a kind of integrated solid transformer, have high step-up ratio, it is small in size, light-weight, be not afraid of high pressure and hit It wears and is burnt with short circuit, humidity, do not cause without copper and iron material and the specific performances such as electromagnetic interference, especially adaptation electronic circuit The trend developed to integrated, flaking, causes the great interest of people.Currently, traditional transformer conductive material exists Even compactness is poor, and mechanical strength is low, and piezoelectric activity is undesirable, and energy consumption is high, at high cost, lead volatility causes environment when high temperature sintering Pollution and component deviation simultaneously influence piezoelectric property, and the reduced deficiency of piezoelectric property is caused in low-temperature sintering.

Aluminium has preferable electric conductivity, as conductor material in fields such as transmission line of electricity, substation, aluminium electroloysis, buildings It is widely applied.Fine aluminium although conductivity with higher, but intensity is not high, heat resistance is poor, microalloying can change It is apt to its heat resistance and intensity, still, very detrimental effect can be generated to its electric conductivity.

Conductor during current-carrying can due to ohm effect generate heat, and make conductor generate temperature rise, cause its intensity and Conductivity decline.For electrician's aluminium, national standard " GB/T30552-2014 " proposes the requirement of conductivity and intensity, and wants It is asked to be greater than 90% in the intensity survival rate of service temperature.But influence of the temperature to conductivity cannot be ignored, for The conductor material that higher temperature is on active service should also require it to keep certain conductivity other than it should be required to keep sufficient intensity, I.e. resistivity is increased with temperature and the amplitude of rising is little.In engineering, temperature-coefficient of electrical resistance α is commonly used to characterize temperature to resistivity Influence, electricalresistivityρ (T)=ρ (T0) [1+ α (T~T0)] of some temperature T, wherein ρ (T0) is some reference temperature T0 (logical Often be 20 DEG C) resistivity.Temperature-coefficient of electrical resistance α is smaller, and resistivity is lower to the sensibility of temperature, is able to maintain in certain temperature Higher conductivity can reduce its electric energy loss in high-temperature service.

Inventor's early period has carried out more good try, such as patent in terms of developing high conductivity and heat heat resistance aluminium alloy conductor Disclose a kind of lightweight high conductivity and heat heat resistance aluminum conductor of plus iron in CN201610177708.3, the aluminum conductor mainly by Al, B, Zr, Fe, La composition, have both higher room-temperature conductivity and intensity, heat resisting temperature has reached 230 DEG C in short-term, and still, which does not have It is related to high-temperature electric conduction performance, does not grasp the raised changing rule of its conductivity with temperature, it is difficult to it is higher is applied to service temperature Occasion.

The present invention cooperates Compound Heat Treatment system, to alloy by the combined microalloying of the elements such as Yb, Zr, Hf, Fe Electric conductivity and heat resistance carry out comprehensive regulation, obtain the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance, at relatively high temperatures It is able to maintain certain conductivity and intensity, that is, there is preferable high-temperature electric conduction performance and heat resistance.The present invention is developed and is set The aluminium alloy of meter, in higher temperature in use, electric energy loss can be substantially reduced since the amplitude of conductivity decline is relatively small, This is of great significance for energy-saving and emission-reduction.

Summary of the invention

It is sensitive that in view of the deficiencies of the prior art, the present invention provides a kind of reasonable mixture ratio of components, high conductivity and heat heat resistance and resistance temperatures The lower aluminium alloy of property and its preparation process and application.

A kind of transformer conductive material of the present invention, the aluminium alloy are made of the alloying element of following mass percent: Zr: 0.02~0.15%；Hf:0.02~0.15%；Yb:0.06~0.22%；Fe:0.05~0.15%；In the aluminium alloy, Yb The content summation for being greater than 1, Zr and Hf element with the mass ratio of Zr element is less than or equal to 0.15%, and the content of impurity Si is less than The content summation of 0.05%, Fe are less than 0.18%, and the content summation of impurity Ti, V, Cr, Mn are less than 0.01%, surplus Al.

Preferably, the aluminium alloy is by mass percentage, composed of the following components: Zr:0.05~0.10%； Hf:0.01~0.05%；Yb:0.10~0.20%；Fe:0.08~0.15%；The mass ratio of Yb and Zr element is greater than 1, Zr It is less than or equal to 0.15% with the content summation of Hf element, content summation of the content less than 0.05%, Fe of impurity Si is less than 0.18%, the content summation of impurity Ti, V, Cr, Mn etc. are less than 0.01%, surplus Al.

Scheme as a further preference, the aluminium alloy are by mass percentage, composed of the following components: Zr:0.05 ~0.10%；Hf:0.01~0.03%；Yb:0.10~0.20%；Fe:0.09~0.12%；The mass ratio of Yb and Zr element It is less than or equal to 0.13% greater than the content summation of 1, Zr and Hf element, content summation of the content less than 0.05%, Fe of impurity Si Less than 0.18%, the content summation of impurity Ti, V, Cr, Mn etc. are less than 0.01%, surplus Al.

Zr, Hf, Fe are to damage very big transition element to the conductivity of alloy, especially when it is to be dissolved state presence When.The present invention passes through the compound addition of trace alloying element and is aided with special two-stage time effect process, give full play to Yb, Zr, Hf, The synergistic effect of Fe element produces unexpected effect reducing resistance.

In the present invention, the total content of Zr and Hf is in 0.06~0.15wt% range, preferably 0.06~013wt%；Yb It is greater than 1 with the mass ratio of Zr, is preferably greater than equal to 1.5, further preferably 1.5-5, is still more preferably 1.5-2. By rationally controlling the ratio of Yb and Zr and the total content of Zr and Hf, in conjunction with the two-stage time effect process of high temperature after first low temperature, sufficiently It plays the induction precipitation between element and inhibits roughening effect, as shown in Fig. 1 (a)-Fig. 1 (c), form the Al that partial size is less than 50nm₃ (Hf, Zr, Yb) compound particle, kernel Al₃Yb phase, Zr, Hf enrichment of element are in Al₃Yb phase outer layer.Yb has in aluminium alloy The Al of small and dispersed distribution can be precipitated when lower temperature range is heat-treated in higher diffusion rate₃Yb phase, with Become Al during high-temperature aging afterwards₃The core of (Hf, Zr, Yb) compound particle, lower Zr, Hf enrichment of element of diffusion rate In Al₃Yb phase outer layer.Al₃Yb promotes Zr, Hf element precipitation, is preferably minimized the solid solution degree of Zr, Hf in alloy substrate, from And achieve the purpose that improve alloy conductivity, Zr, Hf inhibit Al₃Yb particle coarsening, and then reach improvement alloy heat resistance Purpose.In addition, matching proper amount of Zr element by suitable Hf element, the lower diffusion rate of Hf and smaller atom half are utilized Diameter reduces solute atoms caused distortion of lattice and the mismatch being precipitated on phase interface in aluminum substrate, when the temperature rises, Effectively precipitated phase can be inhibited to be roughened, and reduce resistance caused by atom thermal vibration and increase effect, improve the high-temperature electric conduction of alloy Performance.

A kind of preparation process of transformer conductive material of the present invention, taking purity is 99.7% technical pure aluminium ingot remelting, or Intermediate alloy is added in 760 DEG C of -780 DEG C of meltings as silicon source using electrolytic aluminium liquid in person, after intermediate alloy fusing, stirring, Refining, stokehold fast analyzing constituent carry out composition adjustment by the material component proportion of design, stand in 710 DEG C of -730 DEG C of heat preservations, Then it casts, be heat-treated, obtain aluminium alloy ingot.

In the present invention, silicon source used is commercial-purity aluminium.Preferably, the present invention a kind of transformer conductive material Preparation process matches by the 0.02~0.10% of commercial-purity aluminium gross mass used and takes B element, and the B element is with Al-B intermediate alloy Form and be added prior to other intermediate alloys, stirring adds Al-Zr, Al-Hf, Al-Yb after standing.When the industry When the content of Fe element designs content lower than it in fine aluminium, Al-Fe intermediate alloy is added.It is compared it can be seen from Fig. 2 (a) (b) Add the alloy of the embodiment 1 of Al-B intermediate alloy when melting, does not contain more visible matter plus in 6 alloy of comparative example of B element It puts and crystal grain is coarseer.

A kind of preparation process of transformer conductive material of the present invention, it is described to be cast into rapid cooling casting, the fast quickly cooling But it casts including but not limited to water cooling casting；The cooling velocity for being quickly cooled down casting is 20-100 DEG C/min；The ingot blank Including semicontinuous ingot casting or continuous casting billet.

A kind of preparation process of transformer conductive material of the present invention, the heat treatment are two-stage time effect, the two-stage time effect First order aging temp be 250~350 DEG C, soaking time is 4~8h, and the second level aging temp of the two-stage time effect is 400 DEG C~450 DEG C, soaking time is 24~48h.

The precipitated phase size that comparison diagram 1 (a) and Fig. 3 can be seen that not using the alloy of two-stage time effect is extremely uneven, and And having coarsening phenomenon, precipitated phase partial size is greater than 50nm.

Of the invention designed and preparation the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance, tensile strength are greater than 70MPa, is greater than 60%IACS in 20 DEG C of conductivities, is greater than 40%IACS in 150 DEG C of conductivities, in 200 DEG C of conductivity Greater than 36%IACS.

Of the invention designed and preparation the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance, by the cold of 80% deflection Deformation, the intensity survival rate after 400h is kept the temperature at 200 DEG C are not less than 90%, i.e., heat resisting temperature is not less than 200 DEG C when long, 250 DEG C heat preservation 1h after intensity survival rate be not less than 90%, i.e., in short-term heat resisting temperature be not less than 250 DEG C.

The application of of the invention designed and preparation the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance, the application include It is used as at least one of guide rod, bus, conducting wire；The guide rod is aluminum electrolyzing cell used anode rod.

Detailed description of the invention

Attached drawing 1 (a) is the TEM photograph via bright field of 2 alloy of embodiment, and attached drawing 1 (b) is the energy of the second phase of 2 alloy of embodiment Spectrogram, attached drawing 1 (c) are the TEM dark field photo of 2 alloy of embodiment；

Attached drawing 2 (a), attached drawing 2 (b) are respectively the metallograph of comparative example 6, embodiment 1；

Attached drawing 3 is the TEM photo of comparative example 5；

A large amount of small and dispersed distributions have been precipitated it can be seen from the TEM bright field image shown in Fig. 1 (a) in 2 alloy of embodiment Second phase particles, the second phase particles of Dispersed precipitate are answering containing Al, Hf, Zr, Yb it can be seen from the power spectrum shown in Fig. 1 (b) Phase is closed, it is compound to form the Al3 (Hf, Zr, Yb) with ectonexine contrast it can be seen from the TEM dark field image shown in Fig. 1 (c) Particle, partial size are less than 50nm.

The alloy for having added the embodiment 1 of Al-B intermediate alloy when melting is compared it can be seen from Fig. 2 (a), Fig. 2 (b), not Add that 6 alloy of comparative example of B element contains more visible particle and crystal grain is coarseer.

As seen from Figure 3, the precipitated phase size not using the alloy of two-stage time effect is extremely uneven, and has roughening existing As precipitated phase partial size is greater than 50nm.

Specific embodiment

Technical pure aluminium ingot, Al-2.5%B intermediate alloy, Al- in embodiment and comparative example, with purity greater than 99.7% 5%Zr intermediate alloy, Al-5%Hf intermediate alloy, Al-10%Yb intermediate alloy, Al-9.3%Fe intermediate alloy are raw material.Its Preparation process are as follows: by commercial-purity aluminium after 780 DEG C of fusings, 740 DEG C of heat preservations are cooled to, aluminium boron intermediate alloy is added, by stirring, After standing, aluminium zirconium hardener, aluminium hafnium intermediate alloy, aluminium ytterbium intermediate alloy is added, when the Fe element in the commercial-purity aluminium contains Amount lower than its design content when, add ferro-aluminum intermediate alloy, after intermediate alloy is completely melt, be stirred, refine, stokehold at Divide quickly analysis and composition adjustment, after 720 DEG C of heat preservations stand 10~15min, with the cooling velocity water cooling casting of 30 DEG C/min.

In embodiment 1-3 and comparative example 1-5, in smelting process, the additional amount of B element is commercial-purity aluminium quality used 0.06%.

In the comprehensive performance evaluation table of embodiment and comparative example, the tensile strength is cast alloy after Overheating Treatment It measures；The heat resisting temperature is that heat treatment blank measures after the cold deformation of 80% deflection；Described 20 DEG C of conductivity root It is tested according to GB/T 12966-2008, the conductivity for being higher than 20 DEG C is measured using four-point method, and sample is heated to test temperature Degree, measures and calculates resistivity and be converted into conductivity.

In the embodiment of the present invention and comparative example 1-5 in resulting product, the content of impurity Si is less than 0.05wt%, impurity Ti, V, the equal size summation of Cr, Mn are less than 0.01wt%.The summation of impurity content is less than 0.06wt%.

Embodiment 1:

The mass percent of each element after composition adjustment are as follows: zirconium 0.10%, hafnium 0.03%, ytterbium 0.20%, iron are 0.11%, surplus is that Al and inevitable impurity element are warming up to 400 DEG C after 250 DEG C of heat preservation 8h after being quickly cooled down casting 48h is kept the temperature, aluminum alloy blank is obtained, it is as shown in table 1 to measure comprehensive performance.

1 embodiment of table, 1 comprehensive performance evaluation table

Embodiment 2:

The mass percent of each element after composition adjustment are as follows: zirconium 0.05%, hafnium 0.02%, ytterbium 0.20%, iron are 0.11%, surplus is that Al and inevitable impurity element are warming up to 450 DEG C after 250 DEG C of heat preservation 8h after being quickly cooled down casting Heat preservation for 24 hours, obtains aluminum alloy blank, it is as shown in table 2 to measure comprehensive performance.

2 embodiment of table, 2 comprehensive performance evaluation table

Embodiment 3:

The mass percent of each element after composition adjustment are as follows: zirconium 0.05%, hafnium 0.01%, ytterbium 0.10%, iron are 0.11%, surplus is that Al and inevitable impurity element are warming up to 450 DEG C after 250 DEG C of heat preservation 8h after being quickly cooled down casting Heat preservation for 24 hours, obtains aluminum alloy blank, it is as shown in table 3 to measure comprehensive performance.

3 embodiment of table, 3 comprehensive performance evaluation table

Comparative example 1:

The mass percent of each element after composition adjustment are as follows: zirconium 0.18%, hafnium 0.02%, ytterbium 0.20%, iron are 0.11%, surplus is Al and inevitable impurity element, obtains aluminum alloy blank, is warming up to 450 DEG C after 250 DEG C of heat preservation 8h Heat preservation for 24 hours, it is as shown in table 4 to measure comprehensive performance.

4 comparative example of table, 1 comprehensive performance evaluation table

Comparative example 2:

The mass percent of each element after composition adjustment are as follows: zirconium 0.05%, hafnium 0.15%, ytterbium 0.20%, iron are 0.11%, surplus is Al and inevitable impurity element, obtains aluminum alloy blank, is warming up to 450 DEG C after 250 DEG C of heat preservation 8h Heat preservation for 24 hours, it is as shown in table 5 to measure comprehensive performance.

5 comparative example of table, 2 comprehensive performance evaluation table

It can be seen from comparative example 1 and comparative example 2 compared with Example 2, zirconium, any one in hafnium constituent element be not in this hair When in bright protection scope, the conductivity of gained aluminium alloy is remarkably decreased, this is well beyond estimated.

Comparative example 3:

The mass percent of each element after composition adjustment are as follows: zirconium 0.10%, hafnium 0.10%, ytterbium 0.20%, iron are 0.11%, surplus is that Al and inevitable impurity element are warming up to 400 DEG C after 250 DEG C of heat preservation 8h after being quickly cooled down casting 48h is kept the temperature, aluminum alloy blank is obtained, it is as shown in table 6 to measure comprehensive performance.

6 comparative example of table, 3 comprehensive performance evaluation table

Compared with Example 1, when the total content of zirconium and hafnium is greater than 0.15%, under the conductivity of gained aluminium alloy is significant Drop.

Comparative example 4

The mass percent of each element after composition adjustment are as follows: zirconium 0.05%, hafnium 0.02%, ytterbium 0.05%, iron are 0.11%, surplus is that Al and inevitable impurity element are warming up to 450 DEG C after 250 DEG C of heat preservation 8h after being quickly cooled down casting Heat preservation for 24 hours, obtains aluminum alloy blank, it is as shown in table 7 to measure comprehensive performance.

7 comparative example of table, 4 comprehensive performance evaluation table

When ytterbium, zirconium mass ratio are not more than 1, the intensity and conductivity of gained aluminium alloy are below

Embodiment 2.

Comparative example 5:

The mass percent of each element after composition adjustment are as follows: zirconium 0.05%, hafnium 0.02%, ytterbium 0.20%, iron are 0.11%, surplus is Al and inevitable impurity, after being quickly cooled down casting, carries out 350 DEG C of annealing 72h, obtains aluminum alloy blank, It is as shown in table 8 to measure comprehensive performance.

8 comparative example of table, 5 comprehensive performance evaluation table

Compared with Example 2, do not use twin-stage heat treatment that can drop low-alloyed conductivity and heat resisting temperature.

Comparative example 6:

In fusion process, aluminium boron intermediate alloy is not added, the mass percent of each element after composition adjustment are as follows: zirconium is 0.05%, hafnium 0.02%, ytterbium 0.20%, iron 0.11%, surplus is Al and inevitable impurity, is quickly cooled down casting Afterwards, it is warming up to 450 DEG C of heat preservations after 250 DEG C of heat preservation 8h for 24 hours, obtains aluminum alloy blank, it is as shown in table 9 to measure comprehensive performance.

9 comparative example of table, 6 comprehensive performance evaluation table

Compared with Example 2, it does not add aluminium boron intermediate alloy in fusion process, intensity and heat resistance is influenced not Greatly, but conductivity can be reduced.

Claims

1. a kind of transformer conductive material, it is characterised in that；The aluminium alloy is made of the alloying element of following mass percent: Zr:0.02~0.15%；Hf:0.02~0.15%；Yb:0.06~0.22%；Fe:0.05~0.15%；In the aluminium alloy, The mass ratio of Yb and Zr element is greater than 1, Zr and the content summation of Hf element is less than or equal to 0.15%, and the content of impurity Si is less than The content summation of 0.05%, Fe are less than 0.12%, and the content summation of impurity Ti, V, Cr, Mn are less than 0.01%, surplus Al.

2. a kind of transformer conductive material as described in claim 1, it is characterised in that: in the aluminium alloy, Yb and Zr element Mass ratio be 1.5~5:1.

3. a kind of transformer conductive material as described in claim 1, it is characterised in that:

The aluminium alloy is by mass percentage, composed of the following components: Zr:0.06~0.11%；Hf:0.03~0.06%； Yb:0.15~0.22%；Fe:0.08~0.10%；The content of impurity Si is less than 0.05%；The content summation of Fe is less than 0.12%；The content summation of impurity Ti, V, Cr, Mn are less than 0.01%；Surplus is Al.

4. a kind of transformer conductive material as described in claim 1, it is characterised in that: in the aluminium alloy containing Al3 (Hf, Zr, Yb) compound particle and divalent Fe and trivalent Fe functional group particle (Fe₂O₃)；Al3 (Hf, the Zr, Yb) compound particle Kernel is Al3Yb, and Zr, Hf enrichment of element are in Al3Yb particle outer layer；The partial size of Al3 (Hf, the Zr, Yb) compound particle is less than 50nm。

5. a kind of work of the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance prepared as described in claim 1-4 any one Skill, it is characterised in that: taking purity is 99.7% technical pure aluminium ingot remelting, or using electrolytic aluminium liquid as silicon source, control is molten Refining temperature is 760 DEG C -780 DEG C, and intermediate alloy is added, after intermediate alloy fusing, stirring, refining, stokehold fast analyzing constituent, Composition adjustment is carried out by the material component proportion of design, is stood in 700 DEG C of -750 DEG C of heat preservations, is then cast, is heat-treated, obtain aluminium Alloy blank.

6. a kind of application of the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance as described in claim 1-4 any one, Be characterized in that: the application includes being used as at least one of guide rod, bus, conducting wire；The guide rod is aluminum electrolyzing cell used Anode rod.

7. the preparation process of the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance as claimed in claim 5, it is characterised in that: institute It states and is cast into rapid cooling casting, the rapid cooling casting is including but not limited to water cooling casting；The ingot blank includes semicontinuous Ingot casting or continuous casting billet.

8. the preparation process of the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance as claimed in claim 5, it is characterised in that: institute Stating heat treatment is two-stage time effect；The first order aging temp of the two-stage time effect is 240~360 DEG C, and soaking time is 3~8h, The second level aging temp of the two-stage time effect is 400 DEG C~450 DEG C, and soaking time is 24~48h.

9. the preparation process of the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance as claimed in claim 5, it is characterised in that: press The 0.02~0.10% of commercial-purity aluminium gross mass used with taking B element, the B element in the form of Al-B intermediate alloy and prior to Other intermediate alloys are added, and stirring adds Al-Zr, Al-Hf, Al-Yb after standing, when the technical pure aluminium ingot or electrolysis When the content of Fe element designs content lower than it in molten aluminum, Al-Fe intermediate alloy is added.

10. the preparation process of the temperature sensitive high conductivity and heat heat resistance aluminium alloy of low resistance as claimed in claim 8, it is characterised in that: Prepared aluminium alloy is greater than 60%IACS in 20 DEG C of conductivity, is greater than 40%IACS in 150 DEG C of conductivities, at 200 DEG C Conductivity be greater than 36%IACS, when long heat resisting temperature be not less than 200 DEG C, in short-term heat resisting temperature be not less than 250 DEG C.